Metal complexes for use in atom or group transfer and olefin exchange reactions

FIELD: chemistry.

SUBSTANCE: enhanced catalysts useful in a range of reactions in organic synthesis, such as olefin substitution and atom or group transfer reactions, are described. The catalysts are obtained by bringing a poly-coordination complex of a group VIII metal - ruthenium, including a Schiff base polydentate ligand and one or more other ligands, into contact with an acid under such conditions that the said acid can partially break the bond between the metal and the Schiff base polydentate ligand of the said metal complex, optionally through intermediate protonation of the said Schiff base ligand.

EFFECT: improved method.

17 cl, 43 ex, 3 tbl

 

The present invention relates to transition metal complexes which are useful as components of catalysts, or alone, or in combination with socialization or initiators, in a wide variety of reactions of organic synthesis, including exchange reactions (metathesis) of olefins, the exchange reaction of acetylene and reactions, including the transfer of atoms or groups in connection with ethylene or acetylene unsaturation or another reactive substrate, such as radical polymerization atom transport, joining radical atom transfer, ventiliruemye, cyclopropylamine ethyleneimine compounds, epoxidation, oxidative cyclization, aziridination, cyclopropenone alkynes, reactions, Diels-alder reaction, the accession Michael andolina condensation of ketones or aldehydes, annelation by Robinson, hydroporinae, hydrosilation, hidrotsianova olefins and alkynes, allyl alkylation, cross combination of the Grignard reagent, oxidation of organic compounds (including saturated hydrocarbons, sulfides, selenides, phosphines and aldehydes), gidrogenizirovanii, isomerization of alcohols into aldehydes, aminals olefins, hydroxylation of olefins, the restoration of the hydride, the reaction Hake, hydroamination olefins and alkynes and hydrogenation olefine is or ketones.

The present invention relates also to a method of obtaining the above metal complexes and to new intermediate compounds involved in such ways. More specifically, the present invention relates to derivatives of Schiff bases complexes of metals such as ruthenium, methods for their preparation and their use as catalysts for the metathesis of numerous unsaturated hydrocarbons, such as acyclic monoolefins, dieny and alkynes, in particular for substitution polymerization with ring opening of cyclic olefins and catalysts for radical polymerization of styrene or complex (meth)acrylic esters with the transfer of atoms to cyclopropylamine styrene and for the synthesis of quinoline.

BACKGROUND of the INVENTION

The exchange reaction of olefins is a catalytic process that includes as a key stage of the reaction between the olefin and the first alkylidene complex transition metal, obtaining thus an unstable intermediate metallacarboranes ring, which is then converted to the second olefin and the second alkylidene complex transition metal according to equation (1)below. Reactions of this type are reversible and competitive with each other, so the overall result is t strongly depends on their respective velocities, and, if there is a formation of volatile or insoluble products from the equilibrium displacement.

Some data for example, but not limiting of the types of reactions exchange for monoolefins or diolefins shown below in equations (2)-(5). Removal of the product, such as ethylene, in equation (2) from the system can dramatically change the course and/or speed desired exchange reaction, since the ethylene reacts with alkylidene complex with the formation of methylene (M=SN2) complex, which is the most reactive and the least stable alkylidene complexes.

Potentially representing greater interest than gonococcemia (equation 2), is crosssociety or cross-combination between two different terminal olefins. The reaction combinations involving dienes lead to linear and cyclic dimers, oligomers, and finally, a linear or cyclic polymers (equation 3). Usually the last reaction, called acyclic diene currency (here it is called as ADMET), is favorable in highly concentrated solutions or in the mass, whereas the cyclization is favorable at low concentrations. When intramolecular combination of the diene with the formation of the cyclic alkene is, the process is called metathesis with shorting rings (here referred to as RCM) (equation 4). Strained cyclic olefins can be opened and oligomerization or polymerization (exchange polymerization with ring opening (referred to below ROMP) shown in equation 5). When alkylidene catalyst reacts more quickly with the cyclic olefin (for example, norbornene or cyclobutanol)than with carbon-carbon double bond in the growing polymer chain, then the result can happen “live exchange polymerization with ring opening, i.e. almost no breakages circuit during or after the polymerization reaction.

Was obtained and was used in substitution of olefins huge number of systems of catalysts, including certain one-component metal-carbinole complexes. One of the major achievements in the exchange reaction of olefins was the discovery of ruthenium and osmaevyh of karbinovykh complexes author Grubbs (Grubbs) with employees. In U.S. patent No. 5977393 disclosed derivatives of such compounds based on Schiff's bases, which are useful as catalysts for the exchange reaction of olefins, in which the metal is coordinated with a neutral electron donor, such as triarylphosphine or three(cyclo)alkylphosphine, and an anionic ligand. Such catalysts show improved termicheskoe the stability while maintaining activity substitution even in proton polar solvents. They are also able to cilitate diallyldimethyl in dihydroprogesterone. The remaining problems to be solved for karbinovykh complexes of Grubbs are (i) to improve the stability of the catalyst (i.e. the slow decomposition), and activity-transfer reactions at the same time and (ii) the interval extension of organic products, activated with the use of such catalysts, for example ensuring that highly substituted dienes to the closure ring with obtaining tri - and Tetra-substituted olefins.

On the other hand, was reported living polymerization systems for anionic and cationic polymerization, however, their industrial use is limited by the need for monomers of high purity and solvents, reactive initiators and anhydrous conditions. In contrast, free-radical polymerization is the most popular industrial process for obtaining polymers with high molecular weight. A huge variety of monomers can drastically dry out and copolymerizate in a relatively simple experimental conditions, which require the absence of oxygen, but can be carried out in the presence of water. However, the processes of free radical polymerization often give polymers with hard-adjustable molecular the weights and high polydispersity. The combination of the advantages of living polymerization, and radical polymerization is therefore of great interest and has been achieved in the process of radical polymerization with the transfer of atoms (or groups) (referred to below ATRP), described in U.S. patent No. 5763548 and including (1) the path of migration of an atom or group, and (2) radical intermediate product. This type of living polymerization in which the reaction chain breaches, such as the transfer and interrupt the circuit, essentially absent, allows you to control various parameters of macromolecular structures such as molecular weight, distribution of molecular weight and end functionality or functional group. It also allows you to get all kinds of copolymers, including block and star (star) copolymers. Live/adjustable radical polymerization requires a low stationary concentration of radicals in equilibrium with diverse passive particles. It uses a new system of initiation is based on the reversible formation of growing radicals in oxidation-reduction reactions between different transition metal compounds and initiators, such as alkylhalogenide, aralkylated and halogenoalkane esters. ATRP is based on a dynamic equilibrium between propagating radicals and passive particles, which is due to reversible catalyzed by transition metal cleavage of covalent carbon-carbon links in the passive particles. Polymerization systems using this concept have been developed, for example, complexes of copper, ruthenium, Nickel, palladium, rhodium and iron to establish the desired equilibrium.

Thanks to the development of ATRP recently appeared further interest in the reactions of addition to Karasu (Kharash), consisting in joining polygalacturonase alkane transversely to the olefin via a radical mechanism (first published by the author Kharash et al. in Science (1945) 102:169) in accordance with the following scheme (where X can be hydrogen or chlorine or bromine, and R and R' may be each independently selected from hydrogen, C1-7of alkyl, phenyl and carboxylic acid, or a complex ester):

Due to the fact that ATRP is very similar to the reaction of accession on Karasu, the latter can also be called radical accession atom transfer (below referred to as ATRA) and attracts interest to the catalysis by transition metals. Research in this area focuses also on the use of new olefins and Tulegenov, and tested a wide range of domestic, end and cyclic olefins and diolefins with a wide range of polyhalogen is in, comprising fluorine, chlorine, bromine and iodine as halogen atoms, as described, for example, in Eur. Polym. J. (1980) 16:821 and Tetrahedron (1972) 28:29.

In the international patent application published as WO 03/062253, reveals five-coordinated metal complexes, and their salts, solvate, or enantiomers, comprising a carbene ligand, a polydentate ligand, and one or more other ligands in which at least one of these other ligands is intense ligand with a spatial difficulty with figure pKa of at least 15. More specifically, the document discloses five-coordinated metal complexes having one of the General formulas (IA) and (IB), referred to in figure 3, where

M represents a metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic table, preferably a metal selected from ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, Nickel and cobalt;

Z is selected from the group consisting of oxygen, sulfur, selenium, NR", PR"", AsR"" and SbR"";

- each of R", R"' and R"" represents a moiety independently selected from the group consisting of hydrogen, C1-6of alkyl, C3-8cycloalkyl,1-6alkyl-C1-6alkoxysilyl,1-6alkylresorcinol,1-6alkyl-C3-10the cycle is alkoxysilyl, aryl and heteroaryl, or R" and R"' together form an aryl or heteroaryl radical, each specified radical (when it is different from hydrogen) optionally substituted by one or more, preferably 1-3, substituents R5, each of which is independently selected from the group consisting of halogen atoms, C1-6of alkyl, C1-6alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate,1-6alkyl-C1-6alkoxysilyl,1-6alkylresorcinol,1-6alkyl-C3-10cycloalkenyl, alkylamine and arylamine;

- R' or has the meanings given for R", R"' and R""when it is included in the compound having General formula (IA), or when it is included in the compound having General formula (IB)selected from the group consisting of C1-6alkylene and C3-8cycloalkene, and specified Allenova or cycloalkenes group optionally substituted by one or more substituents R5;

- R1is deformed group with a spatial difficulty having a pKa of at least about 15;

- R2represents an anionic ligand;

- each of R3and R4represents hydrogen or a radical selected from the group consisting of C1-20of alkyl, C2-20alkenyl,2-20the quinil,1-20of carboxylate, With1-20 alkoxy, C2-20alkenylacyl,2-20alkyloxy, aryl, aryloxy,1-20alkoxycarbonyl,1-8alkylthio,1-20alkylsulfonyl,1-20alkylsulfonyl,1-20alkylsulfonate, arylsulfonate,1-20alkylphosphonate, arylphosphonate,1-20alkylamine and arylamine;

- R' and one R3and R4can be connected to each other, forming a bidentate ligand;

- R"' and R"" can be connected to each other to form an aliphatic ring system including a heteroatom selected from the group consisting of nitrogen, phosphorus, arsenic and antimony;

- R3and R4together may form a condensed aromatic ring system, and

- represents the number of carbon atoms sp2between M and the carbon atom bearing an R3and R4and is an integer from 0 to 3 inclusive,

their salts, solvate and enantiomers.

Data are five-coordinated metal complexes proved to be very effective catalysts for the replacement of olefins, as well as a very effective compounds in catalysis or initiating radical reactions with the transfer of atoms (or groups), such as ATRP, or ATRA, as well as reactions of vanilinovoi, for example synthesis of complex ester enol. In the same document reveals that the derivatives of ruthenium and osmium formed with the bases of the IFFA for U.S. patent No. 5977393, as well as the corresponding derivatives of other transition metals may also be used in catalysis or initiating radical reactions with the transfer of atoms (or groups), such as ATRP, or ATRA, as well as reactions of vanilinovoi, for example synthesis of complex ester enol.

However, in the technique still there is a need to improve the efficiency of catalysts, i.e. the improvement of the yield in the reaction catalyzed by the specified component of the catalyst after a certain period of time under given conditions (e.g. temperature, pressure, solvent and the ratio of the reagent/catalyst) or, when this reaction output, providing a milder conditions (lower temperature and pressure close to atmospheric pressure, the easier the separation and purification of the product from the reaction mixture) or in-demand a smaller quantity of catalyst (i.e. a higher ratio of reagent/catalyst) and in obtaining, thus, the result is a more economical and environmentally friendly working conditions. This need is even more mandatory for use in the processes of reaction-injection molding (RIM), such as, but not limited to, polymerization in bulk endo - or azodicarbonamide, or of his compositions.

In WO 93/20111 describes the osmium - and ruthenium-carbinole connection with f synonymy ligands as exclusively thermal catalysts for the exchange of polymerization with ring opening of tight cycloolefins, in which cyclodiene, such as Dicyclopentadiene, act as inhibitors of catalysts and can't cure. This is confirmed by, for example, example 3 of U.S. patent No. 6284852 in which the Dicyclopentadiene has not given any polymer even after days in the presence of some ruthenium-of karbinovykh complexes with phosphine ligands. However, in U.S. patent 6235856 says that the Dicyclopentadiene is available for heat exchange polymerization with single-component catalyst, if used available from ruthenium vinylcarbene(II)or osmium(II)-phosphine catalysts.

In U.S. patent No. 6284852 describes the increased catalytic activity of ruthenium-karbonovogo complex of the formula AxLyXzEN=CHR', where x=0, 1, or 2, y=0, 1, or 2, and z=1 or 2 and R' represents hydrogen or substituted or unsubstituted alkyl or aryl, L is any neutral electron donor, X is any anionic ligand, and a is a ligand having a covalent structure connecting the neutral electron donor and an anionic ligand, with the deliberate addition of specific amounts of acid are not present as a substrate or solvent, and the specified gain is intended for multiple exchange reactions of olefins, including ROMP RCM, ADMET and reaction cross-currency and dimerization. In the accordance with U.S. patent No. 6284852 organic or inorganic acid can be added to the catalyst or to, or during the reaction with the olefin, with a longer service life of the catalyst is observed when the catalyst is introduced into the acidic solution of olefin monomer. The amount of acid described in examples 3-7 U.S. patent No. 6284852 vary from 0.3 to 1 equivalent of the acid relative to alkylidene. In particular, the catalyst system of example 3 (in particular, catalysts, representing substituted Chiffonier base complexes including alkylidene the phosphine ligand and the ligand) in the presence of HCl as the acid reaches ROMP of Dicyclopentadiene in less than 1 minute at room temperature in the absence of solvent, and ROMP exonorbornenes monomer for 15 minutes at room temperature in the presence of proton solvent (methanol), however, when the ratio of monomer/catalyst, which are not listed.

In U.S. patent No. 6284852 also shows alkyliden-ruthenium complexes, which after activation in the water, a strong acid is rapidly and quantitatively initiate the living polymerization of water-soluble polymers, resulting in a significant improvement compared to existing ROMP catalysts. Further, in the patent States that the growing type (macro)radical is stable (type growing alkylidene was observed using proton nuclear magnetic resonance), and that the effect of the action CI the lots in the system is twofold: in addition to the elimination of hydroxide ions, which usually cause decomposition of the catalyst, the catalyst activity is also enhanced by protonation of phosphine ligands. The patent also States that, surprisingly, acids do not interact with the ruthenium-alkylidene connection.

Although the patent and provides improvements with respect to existing ROMP catalysts, the content of the disclosure of U.S. patent No. 6284852 limited in many aspects, namely:

since the mechanism of activation of the acid that is referenced patent, involves the protonation of phosphine ligands, it is limited to alkyliden-ruthenium complexes comprising at least one phosphine ligand;

- it is not revealed interaction of substituted Chiffonier base ruthenium complex with the acid under such conditions that this acid is at least partially uncoupled relationship between metal and ligand class of Schiff bases specified ruthenium complex.

In U.S. patent No. 6284852 not talking about the behavior, in the presence of acid, ruthenium complexes, in which the ruthenium is coordinated with vinylidene ligand, allenylidene ligand or N-heterocyclic carbene ligand.

Thus, U.S. patent No. 6284852 left an open field for the study of metal complexes, in particular, precoordination complex is in ruthenium and osmium acid, preferably strongly acidic environment when used for reactions of olefinic exchange, including ROMP, RCM, and ADMET reactions cross-currency and dimerization.

Therefore, one purpose of this invention is to provide a new and useful type of catalysts, especially on the basis of precoordination complexes of transition metals having unexpected properties and improved efficiency in the exchange reactions of olefins, as well as in other reactions with the transfer of atoms or groups, such as ATRP or ATRA.

Another objective of this invention is the effective implementation of the substitution reactions of olefins, in particular polymerization with ring opening of strained cyclic olefins (including cationic forms of such monomers, such as, but without limitation specified, strained cyclic olefins, including Quaternary ammonium salts), in the presence of precoordination complexes of transition metals, without limitation, the requirement of a phosphine ligand in these complexes.

In the art there is also a specific need, which is another purpose of this invention to improve processes, reaction-injection molding (RIM)processes, injection molding resins (RTM) and processes the reactive centrifugal molding (RRM), such as, what about without limitation specified, polymerization in bulk endo - or azodicarbonamide, or copolymerization with other monomers or his compositions, using precoordination transition metal complexes, particularly complexes of ruthenium with various combinations of ligands, but that may not necessarily include phosphine ligands. All of the above needs are different objectives to be achieved by the present invention, however, other advantages of this invention will be freely visible from the following description.

SUMMARY of INVENTION

The present invention is based on the unexpected finding, namely, that improved catalysts useful in a number of reactions of organic synthesis, as, for example, but without limitation specified, the exchange reaction of olefins and the reaction with the transfer of atoms or groups can be obtained by bringing into contact precoordination metal complexes, preferably at least tetracoordinated complex of the transition metal containing polydentate ligand class of Schiff bases and one or more other ligands, such as, without limitation specified, metal complexes WO 03/062253, acid under such conditions that this acid was capable of at least partially break down the connection between meth is llom and polydentate ligand class of Schiff's bases of the specified metal complex.

The present invention is based on the unexpected discovery that new and useful types of catalysts can be suitably obtained by the reaction of acid with precoordinated metal complex, preferably at least tetracoordinated complex of the transition metal containing polydentate ligand class of Schiff bases and optionally including one or more other ligands, such as, without limitation specified, anionic ligands, N-heterocyclic Kurbanova ligands, alkylidene ligands, vinylidene ligands, inteeligence ligands and allenylidene the ligand, under conditions that do not require protonation of phosphine ligand. In particular, this invention is based on the unexpected discovery that new and useful types of catalysts can be obtained in a suitable manner by the reaction of the acid with precoordinated complex metal, preferably at least tetracoordinated complex of the transition metal containing polydentate ligand class of Schiff bases and optionally including a number of other ligands, where the specified number of other ligands are free from any phosphine ligand. More specifically, this invention is based on the discovery that suitable conditions for the reaction with the activated acid is between the acid and precoordination complex metal are the conditions which allow one or more stages at least partially protoliterate polydentate ligand class of Schiff bases and at least partially tcoordinate polydentate ligand class of Schiff's bases by splitting kinoway connection with the metal center.

Thus, on the basis of these findings, the present invention provides a new catalytic objects or products, or a mixture of objects, the resulting reaction (referred to below as the “activation or activate”) between the source precoordination complex metal substituted Chiffonier base, preferably at least tetracoordinated complex of the transition metal containing polydentate ligand class of Schiff bases and optionally including one or more other ligands (these other ligands are preferably other than phosphine ligands), and the specified acid, preferably under conditions suitable for protonation polydentate ligand class of Schiff bases and/or decoordinated polydentate ligand class of Schiff bases in the decomposition of kinoway connection with the metal center. In a broader sense, these objects can be monometallic compounds represented by the General formula:

c)(L2)(X)(SB+)]X-

in which

- M is a metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic table, preferably a metal selected from ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, Nickel and cobalt;

- SB+is protonated ligand class of Schiff's bases, preferably protonated bidentate ligand class of Schiff bases;

- Lcrepresents a carbene ligand, preferably selected from the group consisting of alkylidene ligands, vinylidene ligands, indenyltitanium ligands and allenylidene ligands;

- L2represents a ligand, non-anionic, preferably other than the phosphine ligand;

- X represents an anionic ligand; and

- X-represents an anion;

including their salts, solvate and enantiomers.

These objects can also be bimetallic objects represented by the General formula:

[M(Lc)(SB+)(X1)(X2)(M')(X3)(L)]X-

in which

- each of M and M' represents a metal independently selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic table, preferably a metal, selected the C ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, Nickel and cobalt;

- SB+is protonated ligand class of Schiff's bases, preferably protonated bidentate ligand class of Schiff bases;

- Lcrepresents a carbene ligand, preferably selected from the group consisting of alkylidene ligands, vinylidene ligands, indenyltitanium ligands and allenylidene ligands;

L represents a ligand, non-anionic, preferably other than the phosphine ligand;

- X1, X2and X3each independently selected from anionic ligands; and

- X-represents an anion;

including their salts, solvate and enantiomers.

When coming from precoordination substituted Tiffanym the basis of the monometallic complex, such new objects or products can, for example, take the form of one or more cationic monometallic particles represented by the General formula (VI):

or one or more cationic monometallic particles represented by the General formula (VII):

in which

M represents a metal independently selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 If the second table, preferably the metal is selected from ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, Nickel and cobalt;

- W is selected from the group consisting of oxygen, sulfur, selenium, NR", PR"", AsR"" and SbR"";

- each of R", R"' and R"" represents a moiety independently selected from the group consisting of hydrogen, C1-6of alkyl, C3-8cycloalkyl,1-6alkyl-C1-6alkoxysilyl,1-6alkylresorcinol,1-6alkyl-C3-10cycloalkenyl, aryl and heteroaryl, or R" and R"' together form an aryl or heteroaryl radical, each specified radical (when it is different from hydrogen) optionally substituted by one or more, preferably 1-3, substituents R5, each of which is independently selected from the group consisting of halogen atoms, C1-6of alkyl, C1-6alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate,1-6alkyl-C1-6alkoxysilyl,1-6alkylresorcinol,1-6alkyl-C3-10cycloalkenyl, alkylamine and arylamine;

- R' or has the meanings given for R", R"' and R""when it is included in the compound having General formula (VI), or when it is included in the compound having General formula (VII)is selected from the group consisting of C1-6alkylen and 3-8cycloalkene, and specified Allenova or cycloalkenes group optionally substituted by one or more substituents R5;

- L2represents a ligand, non-anionic, preferably other than the phosphine ligand;

X represents an anionic ligand;

- each of R3and R4represents hydrogen or a radical selected from the group consisting of C1-20of alkyl, C2-20alkenyl,2-20the quinil,1-20of carboxylate, With1-20alkoxy, C2-20alkenylacyl,2-20alkyloxy, aryl, aryloxy,1-20alkoxycarbonyl,1-8alkylthio,1-20alkylsulfonyl,1-20alkylsulfonyl,1-20alkylsulfonate, arylsulfonate,1-20alkylphosphonate, arylphosphonate,1-20alkylamine and arylamine;

- R' and one R3and R4can be connected to each other, forming a bidentate ligand;

- R”' and R”” can be connected to each other to form an aliphatic ring system including a heteroatom selected from the group consisting of nitrogen, phosphorus, arsenic and antimony;

- R3and R4together may form a condensed aromatic ring system, and

- represents the number of carbon atoms sp2between M and the carbon atom bearing an R3and R4and is an integer from to 3 inclusive,

their salt, solvate, and enantiomers, and each of these cationic particles represented by the General formulas (VI) and (VII), associated with the anion derived from the acid used in this reaction is activated by acid.

When coming from precoordination substituted Chiffonier base bimetallic complex, such new objects or products may, for example, take the form of one or more cationic bimetallic particles represented by the General formula (X):

or one or more cationic bimetallic particles represented by the General formula (VII):

in which

- each of M and M' represents a metal independently selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic table, preferably a metal selected from ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, Nickel and cobalt;

- W, R', R", R"', R"", y, R3and R4have the meanings given above for formula (VI) and (VII);

- X1X2and X3each independently selected from anionic ligands; and

L represents a ligand, non-anionic, preferably non-phosphine ligand,

including their salts, solvate and enantiomers.

New the objects or products of the present invention may also take the form of one or more monometallic complexes, represented by the General formula (VIII):

in which

- M, X, y, R3and R4have the meanings given in formulas (VI) and (VII);

X' represents an anionic ligand; and

- L3represents a ligand, non-anionic, preferably other than the phosphine ligand,

including their salts, solvate and enantiomers.

New objects or products of the present invention may also take the form of one or more metal-monohydride complexes represented by the General formula (IX):

in which

- M and X have the meanings given in formulas (VI) and (VII);

- S is the solvent, for example water;

- Y represents a solvent or Y represents CO, when S is alcohol; and

- L1represents a ligand, non-anionic, preferably other than the phosphine ligand,

including their salts, solvate and enantiomers.

New catalytic objects according to the invention can be separately obtained, optionally separated, cleaned and conditioned for individual use in reactions of organic synthesis later, or they can be obtained in situ during the relevant chemical reactions (for example, exchange reactions) by introducing the acid into the reaction mixture prior to, simultaneously with or after the introduction of the introduction : the underwater metal complex of a class of Schiff's bases. The present invention also provides a catalytic system comprising in addition to these new catalytic species or reaction products of the second catalyst component (such as socialization - Lewis acid, or the initiator has the ability to transfer radical an atom or group, or the initiator radicals or bimetallic complex metal) and/or carrier suitable for applying to a specified catalytic species and reaction products.

The present invention also provides the use of such new catalytic species or reaction products, or any mixtures of such species, or of such catalytic systems in a wide variety of reactions of organic synthesis, such as exchange reactions of olefins, the exchange reaction of acetylene and some reactions involving the transfer of an atom or group in connection with ethylene or acetylene unsaturation or some other reactive substrate, such as a radical polymerization atom transfer radical accession atom transfer, ventiliruemye, cyclopropylamine compounds with ethylene unsaturation, and similar. In particular, this invention provides an improved process for the polymerization with ring opening of strained qi is symbolic of olefins, such as but not limited to, the Dicyclopentadiene.

BRIEF DESCRIPTION of DRAWINGS

Figure 1 shows the bidentate ligands of the class of Schiff bases having the General formula (IA) and (IB), which can be included in precoordinated metal complexes suitable for modification by acid according to the embodiment of the present invention.

Figure 2 shows tetradentate ligands of the class of Schiff bases having the General formula (II A) and (II B), which can be included in precoordinated metal complexes suitable for modification by acid according to another embodiment of the present invention.

Figure 3 shows tetradentate ligands of the class of Schiff bases having the General chemical formula (III A) and (III B), which can be included in precoordinated metal complexes suitable for modification by acid according to this invention.

Figure 4 shows tridentate ligands of the class of Schiff bases having the General chemical formula (IV D), which can be included in precoordinated metal complexes suitable for modification by acid according to the present invention, as well as bimetallic complexes having the General formula (IV A) and (IV B), which are suitable for modification of the acid according to the present invention, and condensed aromatic ring systems which, having the formula (IV C), which may be present in the carbene ligand of such metal complexes.

Figure 5 shows the scheme of obtaining precoordination complex metal, modified acid according to this invention.

6 shows monometallic complexes having the General formula (VA)derived from tetradentate ligand class of Schiff bases (IIIA), and General formula (VB), which are suitable for modification of the acid according to the present invention.

Fig.7 shows1H NMR spectrum in deuterated chloroform first substituted Chiffonier base ruthenium complex (example 12) before activating acid.

Fig shows1H NMR spectrum in deuterated chloroform product, the resulting 5-minute activation acid of the same first substituted Chiffonier base ruthenium complex.

Fig.9 shows1H NMR spectrum in deuterated chloroform product, the resulting 50-minute activation acid of the same first substituted Chiffonier base ruthenium complex.

Figure 10 shows1H NMR spectrum in deuterated chloroform product, the resulting 90-minute activation acid of the same first substituted Chiffonier base ruthenium complex.

11 shows1The NMR spectrum in deuterated chloroform product, the resulting 24-hour activation with acid of the same first substituted Chiffonier base ruthenium complex.

Fig shows1H NMR spectrum in deuterated chloroform product, the resulting 91-hour activation with acid of the same first substituted Chiffonier base ruthenium complex.

Fig shows1H NMR spectrum in deuterated chloroform mixture, the resulting 90-minute activation acid of the same first substituted Chiffonier base ruthenium complex with the subsequent addition cyclooctene and 30-minute polymerization.

Fig shows1H NMR spectrum in deuterated chloroform second substituted Chiffonier base ruthenium complex (example 43) before activating acid.

Fig shows1H NMR spectrum in deuterated chloroform product, the resulting 10-minute activation of the second acid substituted Chiffonier base ruthenium complex.

DEFINITION

Used herein, the term "complex" or "coordination compound" refers to the result of the reaction mechanism of donor-acceptor or reactions acid-base Lewis between metal (acceptor) and several neutral molecules ionic compounds, called ligands, containing, each of the second, atom or a nonmetal ion (donor). Ligands that have more than one atom with a single electron pair (i.e. more than one point of connection to the metal center) and therefore occupy more than one place (center) coordination, are called polydentate ligands. The latter, depending on the number of occupied focal points include bidentate, tridentate and tetradentate ligands.

Used herein, the term “monometallic” refers to a complex in which there is a single metal center. Used herein, the term “heterobimetallic” refers to the complex, which has two centres of various metals. Used herein, the term “homoskedasticity” refers to the complex having two centers of the same metals, which however do not necessarily have identical ligand or coordination number.

Used here to refer to the replacement radical, ligand or group, the term “C1-7alkyl” means a saturated acyclic hydrocarbon monovalent radicals with a straight or branched chain, having from 1 to 7 carbon atoms, such as, for example, methyl, ethyl, propyl, n-butyl, 1-methylethyl (isopropyl), 2-methylpropyl (isobutyl), 1,1-dimethylethyl (tert-butyl, 2-methylbutyl, n-pentyl, dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, n-GE is Teal, and similar; the length of the carbon chain of the group may not necessarily extend to 20 carbon atoms.

Used here to refer to a bridging group, the term “C1-7alkylene” means the divalent hydrocarbon radical corresponding to defined above With1-7the alkyl, such as methylene bis(methylene), Tris(methylene), tetramethylene, hexamethylene and similar.

Used here to refer to the replacement radical, ligand or group, the term “C3-10cycloalkyl” means a mono - or polycyclic saturated hydrocarbon monovalent radical having from 3 to 10 carbon atoms, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and analogous or7-10polycyclic saturated hydrocarbon monovalent radical having from 7 to 10 carbon atoms, such as, for example, norbornyl, fenchyl, trimethylcyclohexyl or substituted.

Used here to refer to a bridging group, and unless otherwise specified, the term “C3-10cycloalkyl” means the divalent hydrocarbon radical corresponding to defined above With3-10cycloalkyl, such as 1,2-cyclohexene and 1,4-cyclohexene.

Used here to refer to the replacement radical, ligand or group, and unless otherwise specified, the term “aryl” denotes lubimoe - or polycyclic aromatic monovalent hydrocarbon radical, having from 6 to 30 carbon atoms, such as, for example, but without limitation specified, phenyl, naphthyl, anthracene, Finntroll, fluoranthene, Christel, pyrenyl, biphenylyl, terphenyl, Picanol, indenyl, biphenyl, indanyl, benzocyclobutene, benzocyclobutene and similar, comprising a condensed benzo-C4-8cycloalkyl radicals (the latter are such as defined above), such as, for example, indanyl, tetrahydronaphtyl, fluorenyl and similar, all of these radicals optionally substituted by one or more substituents selected from the group consisting of halogen, amino, nitro, hydroxyl, sulfhydryl and nitro, such as 4-forfinal, 4-chlorophenyl, 3,4-dichlorophenyl, 2,6-aminobutiramida 4-bromophenyl, and pentafluorophenyl 4-cyanophenyl.

Used here to refer to a bridging group, and unless otherwise specified, the term “Allen” means the divalent hydrocarbon radical corresponding to a particular one of the above aryl, such as phenylene, naftilan and similar.

Used here to refer to the combination of two replacement hydrocarbon radical, and unless otherwise specified, the term “homozygosity” means a mono - or polycyclic, saturated or monounsaturated or polyunsaturated hydrocarbon radical having from 4 to 15 carbon atoms, but does not include the heteroatom is in a specified ring; for example, this combination forms With2-6alkalinity radical, such as tetramethylene that cyclizes the carbon atoms to which are attached the two replacement hydrocarbon radical.

Used here to refer to the replacement of the radical (including the combination of the two substituting radical, ligand or group, and unless otherwise specified, the term “heterocyclic” means a mono - or polycyclic, saturated or monounsaturated or polyunsaturated monovalent hydrocarbon radical having from 2 to 15 carbon atoms and including one or more heteroatoms in one or more heterocyclic rings, each of these rings has from 3 to 10 atoms (and optionally additionally comprising one or more heteroatoms attached to one or more carbon atoms of the specified ring, for example, in the form of carbonyl, or thiocarbonyl, or selenocosmiinae group, and/or one or more heteroatoms specified ring, for example, in the form of sulfonic, sulfoxide, N-oxide, phosphate, phosphonate or selenocyanate group), each of these heteroatoms optionally selected from the group consisting of nitrogen, oxygen, sulfur, selenium and phosphorus, also including radicals where heterocyclic ring condenser the Vano with one or more aromatic hydrocarbon rings, for example in the form benzododecinium, dibenzoanthracene, oil-condensed heterocyclic radicals; within this definition are included heterocyclic radicals, such as, but without limitation specified, diazepines, oxadiazine, thiadiazine, detainer, triazolyl, diazepinones, thiazepines, diazepinones, tetraterpenes, benzoquinoline, benzothiazines, benzothiazinones, benzoxanthenes, benzodioxolyl, benzodithiol, benzoxazepine, benzodiazepines, benzodiazepines, benzodiazepines, benzodiapines, benzoxazolyl, benzothiazolyl, benzodiazipines, benzoxadiazole, benzodioxolyl, benzodioxepine, benzoxadiazole, benzodiazepines, benzothiadiazepine, benzotriazepine, benzoctamine, benzothiazinones, benzoxazolinone, azetidinone, azaspirones, getiasproperty, seleninyl, selenazoline, selenophene, hypoxanthine, asiapacificed, piperazinyl, piperidinyl, oxazolidinyl, decelerometer, benzodioxolyl, benzopyranyl, benzopyranones, benzofurazanyl, benzoquinoline, dibenzosuberyl, dibenzalacetone, dibenzothiazyl, dibenzothiophenes, dibenzoxepines, dibenzopyrene, dibenzodioxins, dibenzothiazepine, dibenzothiophenes, tetrathionate, teacherresearcher, accuracy, oxazinyl, dibenzothiophenes, d is benzofuranyl, oxazolines, oxazolones, isoindolyl, asolani, thiazolyl, thiazolyl, diazolidinyl, titanyl, pyrimidinyl, dipyrimidine, thiomorpholine, azlactones, martinazzoli, Martindale, negotiator, narcotically, naphtoquinones, naturasil, naphthopyrane, oxabicyclo, asianshemales, azacycloheptan, azocyclotin, azacyclonol, azabicycloalkanes, tetrahydrofuryl, tetrahydropyranyl, tetrahydropyranyl, tetrahydropyranyl, tetrahydrofuranyl and dioxide, dihydropteridine, dioxindole, dioxines, dioxines, dioxazines, dioxane, tixall, torezolid, titrisol, tiopronin, tiopronin, coumarinyl, chinoline, oxichinolinr, hinokitiol, xantinol, dihydropyran, benzodithiophene, benzodiapines benzothiophenes, benzoxazines, benzoxazolyl, benzodioxolyl, benzodioxane, benzothiadiazoles, benzotriazines, benzothiazolyl, benzoxazolyl, phenothiazinyl, phenothiazinyl, fentanyl (benzothiophenes), propionyl, phenoxetol, pyridinyl, dihydropyridines, tetrahydropyridine, piperidine, morpholine, thiomorpholine, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, tetrazines, thiazolyl, benzothiazolyl, tetrazolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolin, oxazolyl, oxadiazolyl, pyrrolyl, furyl, dihydrofuran, furoyl, hydantoinyl, DIOXOLANYL, d is oxalyl, ditional, dithienyl, dithienyl, thienyl, indolyl, indazoles, indolinyl, indolizinyl, benzofuran, hinely, hintline, honokalani, carbazolyl, phenoxazines, phenothiazines, xantener, purinol, benzothiazyl, naftotiekis, thianthrene, pyranyl, pyranyl, benzopyranyl, isobenzofuranyl, bromanil, phenoxathiin, indolizinyl, hemolysins, ethanolic, phthalazine, naphthyridine, cinnoline, pteridine, carbolines, acridines, pyrimidinyl, phenanthrolines, phenazines, phenothiazines, imidazolines, imidazolidinyl, benzimidazolyl, pyrazolyl, pyrazolidine, pyrrolidyl, pyrrolidinyl, piperazinil, original, thymidine, cytidine, azirines, aziridinyl, diazirines, diaziridines, oxiranyl, oxazolidinyl, dioxirane, thiiranes, azmil, dehydroabietyl, azetidine, axetil, oxetanyl, tatIl, titanyl, diazabicyclo, diacetyl, diaziridines, diaziridines, bromanil, chromanones, thiochroman, thiochroman, thiochroman, benzofuranyl, benzisothiazole, benzoylmethyl, Beskrovny, benzisothiazole, benzocoumarin, tokumine, framecontainer, proparacaine, phentrazine, thiadiazines, thiadiazolyl, indoxyl, toindex, benzodiazines (for example, phthalazine), phthalidyl, phtalimide, talasani, allocating, dibenzopyrene (i.e. cantonal), xanthinol, isatis, isoperator, isoperational, ursolic, azinil, retinal, uretidine, succinyl, succinimido, benzylsuccinic, benzylmethyl and similar, including all possible isomeric forms, in which each carbon atom is specified heterocyclic ring may be independently substituted by a Deputy selected from the group consisting of halogen, nitro, C1-7the alkyl (optionally containing one or more functional groups or radicals selected from the group consisting of carbonyl (oxo), alcohol (hydroxyl), simple ether (alkoxy), acetal, amino, imino, oximino, alkylamino, amino, cyano, ester or carboxylic acid amide, nitro, thio-C1-7of alkyl, thio-C3-10cycloalkyl,1-7alkylamino, cyclooctylamine, alkenylamine, cyclooctylamine, alkynylamino, arylamino, arylalkylamine, hydroxyethylamino, mercaptoethylamine, heterocyclic amino, hydrazino, acylhydrazone, phenylhydrazine, sulfonyl, sulfonamide and halogen-free)2-7alkenyl,2-7the quinil, halogen-C1-7of alkyl, C3-10cycloalkyl, aryl, arylalkyl, alkylaryl, alkylaryl, Ariella, hydroxyl, amino, C1-7alkylamino, cyclooctylamine, alkenylamine, cyclooctylamine, alkynylamino, arylamino, arylalkylamine, hydroxyethylamino, mercaptoethylamine, heterocyclic amino, hydrazino, acylhydrazone, phenylhydrazine, is sulfhydryl, With1-7alkoxy, C3-10cycloalkane, aryloxy, arylalkyl, oxygeneration radical, substituted heterocycle, alkyloxy, tio1-7of alkyl, thio-C3-10cycloalkyl, tiarella, togetherchicago radical, arylalkyl, substituted heterocycle, alkylthio, formyl, hydroxylamino, cyano, esters and thioesters of carboxylic acids or their amides, esters or thioesters thiocarbonic acid or their amides; depending on the number of nancysinatra 3-10-membered ring, heterocyclic radicals may be sub-divided into heteroaromatic (or “heteroaryl”) radicals and non-aromatic heterocyclic radicals; when a heteroatom of the specified non-aromatic heterocyclic radical is nitrogen, the latter may be substituted by the Deputy selected from the group consisting of C1-7of alkyl, C3-10cycloalkyl, aryl, arylalkyl and alkylaryl.

Used here to refer to the replacement radical, ligand or group, and unless otherwise specified, the terms “C1-7alkoxy”, “C2-7alkenylacyl”, “C2-7alkyloxy”, “C3-10cycloalkane”, “aryloxy”, “arylalkyl”, “exegetically”, “tio1-7alkyl”, “thio-C3-10cycloalkyl”, “aristeo”, “arylalkyl” and “togetherlike or togetherall” refers to the Deputy is m, which1-7alkyl, C2-7alkenyl or2-7quinil (not necessarily the length of the carbon chain such groups can extend up to 20 carbon atoms), respectively, With3-10cycloalkyl, aryl, arylalkyl or heterocyclic radical (each of them has the values defined here)attached to the oxygen atom or divalent atom of the sulfur through a single bond such as, but without limitation specified, methoxy, ethoxy, propoxy, butoxy, pentox, isopropoxy, sec-butoxy, tert-butoxy, isobutoxy, cyclopropylamine, cyclobutylamine, cyclopentyloxy, thiomethyl, thioethyl, thiopropyl, dibutyl, dipentyl, titilope, tittlebat, citicapital, thiophenyl, phenyloxy, benzyloxy, mercaptobenzyl, cresylate and similar.

Used here to refer to the replacement atom or ligand, the term "halogen" refers to any atom selected from the group consisting of fluorine, chlorine, bromine and iodine.

Used here to refer to the replacement of the radical or group, and unless otherwise indicated, the term “halogen-C1-7alkyl” means1-7alkyl radical (such as defined above, i.e. not necessarily the length of the carbon chain such groups can extend up to 20 carbon atoms), in which one or more hydrogen atoms are independently replaced by one or more halogen (predpochtitel is but fluorine, chlorine or bromine), such as, but without limitation specified, vermeil, deformity, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-triptorelin, 2-foretel, 2-chloroethyl, 2,2,2-trichlorethyl, octafluoropentyl, dodecafluoroheptyl, dichloromethyl and similar.

Used here to refer to the replacement radical, ligand or group, and unless otherwise specified, the term “C2-7alkenyl” means straight or branched acyclic hydrocarbon monovalent radical having one or more ethylene nancysinatra and having from 2 to 7 carbon atoms, such as, for example, vinyl, 1-propenyl, 2-propenyl (allyl), 1-butenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 3-methyl-2-butenyl, 3-hexenyl, 2-hexenyl, 2-heptenyl, 1,3-butadienyl, n-Penta-2,4-dienyl, hexadienyl, heptadienyl, heptatriene and similar, including all possible isomers; not necessarily the length of the carbon chain of the group can extend up to 20 carbon atoms (such as n-Oct-2-enyl, n-dodec-2-enyl, isododecane, n-octadec-2-enyl and n-octadec-4-enyl).

Used here to refer to the replacement radical, ligand or group, and unless otherwise specified, the term “C3-10cycloalkenyl” means a monocyclic mono - or polyunsaturated hydrocarbon monovalent radical having from 3 to 8 carbon atoms, such as, for example, cycloprop the Nile, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, cycloheptadiene, cycloheptatriene, cyclooctanol, cyclooctadiene, cyclooctatetraene, 1,3,5,7-cyclooctatetraene and analogous or7-10polycyclic mono - or polyunsaturated hydrocarbon monovalent radical having from 7 to 10 carbon atoms, such as dicyclopentadienyl, fenchene (including all their isomers, such as α-phenalenyl), bicyclo[2.2.1]hept-2-enyl (norbornyl), bicyclo[2.2.1]hepta-2,5-dienyl (norbornadiene), Cyclopentanol and similar.

Used here to refer to the replacement radical, ligand or group, the term “C2-7quinil” defines straight and branched chain hydrocarbon radicals containing one or more triple bonds (i.e acetylenic unsaturation and optionally at least one double bond and having from 2 to 7 carbon atoms, such as, for example, acetylenyl, 1-PROPYNYL, 2-PROPYNYL, 1-butynyl, 2-butynyl, 2-pentenyl, 1-pentenyl, 3-methyl-2-butenyl, 3-hexenyl, 2-hexenyl, 1-penten-4-inyl, 3-penten-1-inil, 1,3-hexadien-1-inyl and similar, including all possible isomers; not necessarily the length of the carbon chain of the group can extend up to 20 carbon atoms.

Used herein and unless otherwise indicated, the terms “arylalkyl”, “arylalkyl” and “Zam is on the heterocycle alkyl” refer to an aliphatic saturated or unsaturated hydrocarbon the monovalent radical (preferably 1-7alkyl or C2-7alkanniny radical such as defined above, i.e. not necessarily the length of the carbon chain of the group can extend up to 20 carbon atoms), which is already attached aryl or heterocyclic radical (such as defined above), and wherein said aliphatic radical and/or the aryl or heterocyclic radical may be optionally substituted by one or more substituents selected from the group consisting of halogen, amino, nitro, hydroxyl, sulfhydryl and nitro, such as but without limitation specified, benzyl, 4-Chlorobenzyl, phenylethyl, 3-phenylpropyl, α-methylbenzyl, terbutyl, α,α-dimethylbenzyl, 1-amino-2-phenylethyl, 1-amino-2-[4-hydroxyphenyl]ethyl, 1-amino-2-[indol-2-yl]ethyl, still, pyridylmethyl, pyridylethyl, 2-(2-pyridyl)isopropyl, oxazolidinyl, 2-thienylmethyl and 2-furylmethyl.

Used herein and unless otherwise indicated, the terms “alkylsilanes”, “alkenyl(hetero)aryl, alkyl(hetero)aryl” and “alkyl substituted heterocyclic” refer respectively to the aryl, heteroaryl, cycloalkyl or heterocyclic radical (such as defined above), which is already attached one or more aliphatic saturated or unsaturated hydrocarbon monovalent radicals, preferably one or more1- alkyl, C2-7alkenyl or3-10cycloalkyl radicals, such as, but without limitation specified, toluyl, m-toluyl, p-toluyl, 2,3-xylyl, 2,4-xylyl, 3,4-xylyl, cumenyl, m-cumenyl, p-cumenyl, simenel, m-simenel, p-simenel, mesityl, lutidines (i.e. dimethylpyridin), 2-methylaziridinyl, methylbenzimidazolyl, methylbenzofuran, methylbenzothiazole, methylbenzotriazole, methylbenzoxazolium, methylcyclohexyl and mental.

Used herein and unless otherwise indicated, the terms “alkylamino”, “cycloalkenyl”, “alkynylamino”, “cyclooctylamino”, “arylamino”, “arylalkylamine”, “heterocyclic amino”, “hydroxyethylamino”, “mercaptoethylamine and alkynylamino” mean respectively one (in the case of monosubstituted amino) or even two (in the case of a disubstituted amino)1-7alkyl, C3-10cycloalkyl,2-7alkenyl radical, With3-10cycloalkenyl, aryl, arylalkyl, heterocyclic, mono - or polyhydroxy-C1-7alkyl, mono - or polymercaptan-C1-7alkyl or C2-7etkinlik radical (each of them have respectively the meanings as defined above) is attached or joined to the nitrogen atom through a single bond, or, in the case of heterocyclic radicals include nitrogen atom, as, for example, but without limitation pointed to by the mi, of aniline, benzylamine, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, propanolamine, n-butylamino, tert-butylamino, dibutylamino, morpholinosydnonimine, morpholinyl, piperidinyl, piperazinil, hydroxyethylamino, β-hydroxyethylamino, ethynylene; this definition also includes mixed disubstituted amino radicals, in which the nitrogen atom is attached to two such radicals belonging to two different sub-groups of radicals, for example the alkyl radical and Alchemilla the radical, or to two different radicals in the same subgroup radicals, for example methylethylamine; among disubstituted amino radicals, it is generally preferable and more easily accessible symmetrically replaced.

Used herein and unless otherwise indicated, the terms “(thio)ester of (thio)carboxylic acid(thio)amide (thio)carboxylic acid” refers to substituents, in which carboxyl or dicarboxylate group attached to gidrokarbonatno residue of the alcohol, thiol, polyol, phenol, thiophenol, primary or secondary amine, polyamine, amerosport or ammonia, and specified hydrocarbonyl residue selected from the group consisting of C1-7of alkyl, C2-7alkenyl,2-7the quinil,3-10cycloalkyl,3-10cycloalkenyl, aryl, arylalkyl, alkylaryl, alkylamino, cyclooctylamine, alke is ylamino, cyclooctylamino, arylamino, arylalkylamine, heterocyclic amino, hydroxyethylamino, mercaptoethylamine or alkynylamino (everyone has the values defined above, respectively).

Used here in relation to the metal ligand of the terms "alkylamino" and "arylamine" means tetracoordinated the nitrogen atom associated with one or more1-7alkyl, C3-10cycloalkenyl, aryl or heteroaryl groups, each of which is respectively the same as defined above.

Used here to refer to a metal ligand, and unless otherwise specified, the term “Chippewa base”as the common, refers to the presence of aminogroup (usually the reaction of a primary amine with an aldehyde or ketone) in the specified ligand, which is part of the polydentate ligand (such as defined, for example, in http://www.ilpi.com/organomet/coordnum.html), and the ligand is coordinated to the metal, in addition to the nitrogen atom of the specified aminogroup, through at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium. Specified polydentate ligand can be, for example:

- N,O-bidentate ligand class of Schiff's bases, such as lunasin or substituted lumazine or 2-(2-hydroxyphenyl)benzoxazole or (2'-guide is oxyphenyl)-2-thiazolin, or

- N,S-bidentate ligand class of Schiff's bases, such as toumazis or substituted toumazis, or

Is N,Z is a bidentate ligand class of Schiff's bases, such as the one shown in figure 1, in which Z represents or includes an atom selected from the group consisting of oxygen, sulfur and selenium; may be favorable to the specified bidentate ligand class of Schiff's bases were additionally included a carbon-carbon double bond conjugated with a carbon-nitrogen double bond aminogroup, for example, as shown in figure 1, or

- N,N,O-tridentate ligand class of Schiff's bases, such as happens from 6-amino-5-formyl-1,3-dimethyluracil and semicarbazide or acetylhydrazine, or benzoylhydrazone, or such as occurs from 7-formyl-8-hydroxyquinoline solution(oxine) and 2-aminophenol or 2-aminopyridine, or

- O,N,O-tridentate ligand class of Schiff's bases, such as 6-amino-5-formyl-1,3-dimethylaminobenzylidene or as shown in the formula (IV) 5 or N-(2-methoxyphenyl)salicylidene or salicylaldehyde-2-hydroxyl or heterocyclic Chiffolo base resulting from the reaction of 1-amino-5-benzoyl-4-phenyl-1H-pyrimidine-2-one with 2-hydroxynaphthaldehyde, or thenoyltrifluoroacetone antipyrine Chiffolo base, the resulting reaction thenoyltrifluoroacetone 4-aminoand what Pirin, or

- O,N,S-tridentate ligand class of Schiff's bases, such as salicylaldehyde-2-mercaptophenyl, S-benzyl-2-[(2-hydroxyphenyl)methylene]dithiocarbonate or 2-[(2-hydroxyphenyl)methylene]-N-finishedrecording, or

- N,N,S-tridentate ligand class of Schiff's bases, such as 6-amino-5-formyl-1,3-diethylenetriaminepenta.

In a broad sense, the polydentate ligand can include more than one Chiffolo basis, for example two aminogroup, as shown in formulas (IIA) and (IIB) 2 and in formula (IIIA) 3, which can result in O,N,N,O-tetradentate or O,N,N,N-tetradentate ligands of the class of Schiff's bases.

Used herein, the terms “constrained spatial difficulty” describe the group or ligand, usually branched, or substituted groups, or ligands, which are limited in their movements, i.e. the group size which gives the molecular deformation (or angular deformation or elongation of the ties), measurable with the help of x-ray diraction processes.

Used herein and unless otherwise indicated, the term “stereoisomer” refers to all possible different isomeric as well as conformational forms which may have compound of the invention, in particular all possible stereochemical and conformationally isomeric forms, all diastereomers,enantiomers and/or conformers of the main molecular structure. Some compounds of the present invention may exist in different tautomeric forms, all of which are covered by the scope of the present invention.

Used herein and unless otherwise indicated, the term “enantiomer” means each individual or individual optically active form of compounds of the invention having an optical purity or enantiomeric excess (determined by methods standard in this area) at least 80% (i.e. at least 90% of one enantiomer and at most 10% of the other enantiomer), preferably at least 90% and more preferably at least 98%.

Used herein and unless otherwise indicated, the term “MES” includes any combination which may be formed by a compound of this invention with a suitable inorganic solvent (e.g. hydrates formed with water or an organic solvent, such as, but without limitation specified, alcohols (in particular, ethanol and isopropanol), ketones (in particular, methyl ethyl ketone and methyl isobutyl ketone), esters (particularly ethyl acetate) and similar.

DETAILED description of the INVENTION

In its broadest sense, the present invention firstly relates to a method of modifying precoordination complex metal salts thereof, MES or enantiomer, and pointed to by the th precoordination complex metal includes (i) at least one polydentate ligand class of Schiff's bases, including aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup, through at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium, and (ii) one or more other ligands, where the method is characterized by the fact that it includes the conversion of the specified precoordination metal complex into contact with an acid under such conditions that this acid is capable of at least partially cleave the bond between the metal and the specified at least one polydentate ligand class of Schiff bases (i), and in this way these other ligands (ii) are selected so that they were not capable of protonation of these acids under these conditions. Preferably, the conditions include one or more of the following:

- the molar ratio between these acids and the specified precoordination metal complex is higher than about 1.2, preferably more than about 2, more preferably more than about 3, and most preferably above about 5;

- the molar ratio between these acids and the specified precoordination metal complex is not more than about 40, preferably not more than about 30, more preferably not more than about 20 naibolee preferably not more than about 15;

- contact time over 5 seconds, preferably more than 30 seconds, more preferably at least 1 minute, for example at least 10 minutes.

- contact time below 100 hours, preferably not more than 24 hours, more preferably not more than 4 hours and most preferably not more than 90 minutes;

- contact temperature from about -50°to about 80°C., preferably from about 10°to about 60°C., more preferably from about 20°to about 50°C.

It should be clear that, as expected, any combination of the above reaction conditions covered by the scope of the present invention, and which is more suitable conditions depend on the acid used and the set of ligands around the metal center, especially from ligand class of Schiff's bases, and it can be easily determined by the expert on the basis of the information contained in this description.

Preferably also these other ligands (ii) is selected from the group consisting of amines, phosphines, arsinami and Stabenow, because all the latest capable of protonation by the acid in the above reaction conditions.

In a particular embodiment of the method according to the invention includes the additional step of determining (e.g., measurements) index pKa of the specified at least one polydentate ligand class Shift the s bases (i) and the choice of the specified acid thus to RCA specified acid was lower than the pKa of the specified polydentate ligand class of Schiff bases (ii), specific (for example, measured on specified measuring stage) in advance.

To perform the method of the invention suitable conditions are such that when one of the following situations:

at least one of these other ligands (ii) is a ligand with constrained spatial difficulty having a pKa of at least 15,

the number of carbon atoms in the specified at least one polydentate ligand class of Schiff bases (i) between the nitrogen atom of the specified aminogroup and specified coordinating heteroatom in at least one polydentate ligand class of Schiff bases (i) is 2 or 3,

the nitrogen atom of aminogroup polydentate ligand class of Schiff bases of (i) substituted by a group having significant spatial difficulties, such as substituted phenyl or preferably3-10cycloalkyl, such as substituted,

at least one of these other ligands (ii) is a carbene ligand, preferably a ligand selected from the group consisting of N-heterocyclic of karbinovykh ligands, alkylidene ligands, vinylidene ligands, indenyltitanium ligands and allenylidene ligands,

- at m is re one of these other ligands (ii) is an anionic ligand,

at least one of these other ligands (ii) is a ligand, non-anionic, such as a ligand, other than carbene ligand,

acid is a strong inorganic acid, such as, but without limitation specified, chloride-hydrogen acid, Hydrobromic acid, sulfuric acid or nitric acid, or strong organic acid, such as, but not limited to it, p-toluensulfonate acid.

It should be clear that, as expected, any combination of the above reaction conditions covered by the scope of the present invention, and which is more suitable conditions can be easily determined by the expert on the basis of the information contained in this description.

Secondly, the present invention relates to the reaction product

(a) precoordination complex metal salts thereof, MES or enantiomer, and specified precoordination complex metal includes (i) at least one polydentate ligand class of Schiff's bases, including aminogroup and coordinated with metal in addition to the nitrogen atom of the specified aminogroup through at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium, and (ii) one or more other ligands, and

(b) acid introduced into the reaction in a molar with who compared the above about 1.2, preferably in a molar ratio, defined here above) in relation to the specified precoordination metal complex (a)

provided that the said other ligands (ii) is selected so as to be incapable of protonation of the specified acid in the above reaction conditions.

For a more detailed definition of the reaction product of the invention preferably, when one of the following situations:

- these other ligands (ii) is selected from the group consisting of amines, phosphines, arsinami and Stabenow,

rock the specified acid (b) is lower than the pKa of the specified at least one polydentate ligand class of Schiff bases (i),

the number of carbon atoms in the specified at least one polydentate ligand class of Schiff bases (i) between the nitrogen atom of the specified aminogroup and specified the heteroatom of the specified at least one polydentate ligand class of Schiff bases (i) is 2 or 3,

at least one of these other ligands (ii) of the specified precoordination complex metal (a) is constrained spatial difficult ligand having a pKa of at least 15,

the nitrogen atom of aminogroup polydentate ligand class of Schiff bases of (i) substituted by a group having significant spatial difficulties, such as substituted phenyl or, prepact the tion, With3-10cycloalkyl, such as substituted,

at least one of these other ligands (ii) of the specified precoordination complex metal (a) is a carbene ligand, preferably a ligand selected from the group consisting of N-heterocyclic of karbinovykh ligands, alkylidene ligands, vinylidene ligands, indenyltitanium ligands and allenylidene ligands,

at least one of these other ligands (ii) of the specified precoordination complex metal (a) is an anionic ligand,

at least one of these other ligands (ii) of the specified precoordination complex metal (a) is a ligand, non-anionic, such as a ligand, other than carbene ligand,

at least one of these other ligands (ii) of the specified precoordination complex metal (a) is a solvent S, and the complex (a) is a cationic particle associated with anion And,

- the specified precoordination complex metal (a) is a bimetallic complex (two metals are the same or different), which is preferably (1) one metal specified bimetallic complex pentacoordinate with the specified at least one polydentate ligand class of Schiff bases (i) and at periodnum or more other ligands (ii), and other metal tetracoordinated with one or more neutral ligands and one or more anionic ligands, or (2) each metal specified bimetallic complex hexacoordinate with the specified at least one polydentate ligand class of Schiff bases (i) and with the specified one or more other ligands (ii);

- the specified precoordination complex metal (a) is a monometallic complex,

metal specified precoordination complex metal (a) is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic table, for example a metal selected from the group consisting of ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, Nickel and cobalt;

- specified precoordination complex metal (a) is pentacoordinated complex metal or tetracoordinated complex metal, for example, in which (1) the specified at least one polydentate ligand class of Schiff bases (i) is a bidentate ligand, and the specified precoordination complex metal (a) includes two other ligand (ii), or (2) the specified at least one polymetacrylate class of Schiff bases (i) is a tridentate ligand, as specified precoordination complex metal (a) includes one other ligand (ii);

- the specified at least one polydentate ligand class of Schiff bases (i) has one of the General formulas (IA) and (IB), referred to in figure 1, in which:

Z is selected from the group consisting of oxygen, sulfur and selenium;

- each of R" and R"' represents a radical independently selected from the group consisting of hydrogen, C1-7of alkyl, C3-10cycloalkyl,1-6alkyl-C1-6alkoxysilyl,1-6alkylresorcinol,1-6alkyl-C3-10cycloalkenyl, aryl and heteroaryl, or R" and R"' together form an aryl or heteroaryl radical, each specified radical optionally substituted by one or more, preferably 1-3, substituents R5, each of which is independently selected from the group consisting of halogen atoms, C1-6of alkyl, C1-6alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate,1-6alkyl-C1-6alkoxysilyl,1-6alkylresorcinol,1-6alkyl-C3-10cycloalkenyl, alkylamine and arylamine;

- R' or has the meanings given for R" and R"', when it is included in the compound having General formula (IA), or when it is included in the compound having General formula (IB)selected from the group consisting the th of 1-7alkylene and C3-10cycloalkene, and specified Allenova or cycloalkenes group optionally substituted by one or more substituents R5;

at least one of these other ligands (ii) of the specified precoordination complex metal (a) is a derivative in which one or more carbon atoms substituted by a group providing constrained spatial difficulty N-heterocyclic vinylcarbene selected from the group consisting of imidazol-2-ylidene; dihydroimidazole-2-ylidene, oxazol-2-ylidene, triazole-5-ylidene, triazole-2-ylidene, bis(imidazolin-2-ylidene), bis(imidazolidin-2-ylidene), pyrrolidine, pyrazolidine, dihydropyridine pyrrolidinedione and his benzododecinium derivative, or non-ionic profosmotrovaja Verhoeven;

at least one of these other ligands (ii) of the specified precoordination complex metal (a) is an anionic ligand selected from the group consisting of C1-20of alkyl, C1-20alkenyl,1-20the quinil,1-20of carboxylate, With1-20alkoxy, C1-20alkenylacyl,1-20alkyloxy, aryl, aryloxy,1-20alkoxycarbonyl,1-8alkylthio,1-20alkylsulfonyl,1-20alkylsulfonyl,1-20alkylsulfonate, arylsulfonate,1-20Ala is phosphonate, arylphosphonate,1-20alkylamine, arylamine, halogen, C1-20alkyldimethyl, iridecent, nitro and cyano;

at least one of these other ligands (ii) of the specified precoordination complex metal (a) is a carbene ligand represented by the General formula =[C=]yCR3R4where:

- y represents an integer from 0 to 3, inclusive, and

- each of R3and R4represents hydrogen or a hydrocarbon radical selected from the group consisting of C1-20of alkyl, C1-20alkenyl,1-20the quinil,1-20of carboxylate, With1-20alkoxy, C1-20alkenylacyl,1-20alkyloxy, aryl, aryloxy,1-20alkoxycarbonyl,1-8alkylthio,1-20alkylsulfonyl,1-20alkylsulfonyl1-20alkylsulfonate, arylsulfonate,1-20alkylphosphonate, arylphosphonate,1-20alkylamine and arylamine; or R3and R4together may form a condensed aromatic ring system such as, but without limitation specified, the system having the formula (IVC), referred to in figure 4, i.e. such as phenylindolizine ligand;

- indicated at least one polydentate ligand class of Schiff bases (i) is a tetradentate ligand, and the specified precoordination complex meth is the lia (a) includes one or two other ligand (ii), non-anionic ligands L7selected from the group consisting of aromatic and unsaturated cycloaliphatic groups, preferably aryl, heteroaryl and C4-20cycloalkenyl groups where the specified aromatic or unsaturated cycloaliphatic group optionally substituted by one or more1-7alkyl groups or electron-withdrawing groups such as, but not limited by them, halogen, nitro, cyano, (thio)carboxylic acid (thio)ester of (thio)carboxylic acid (thio)amide (thio)carboxylic acid, anhydride (thio)carboxylic acid halide (thio)carboxylic acid.

According to the first aspect of the present invention will now be described with respect to several preferred embodiments precoordination complex metal (a), modified through reaction with acid.

The first embodiment precoordination metal complex (a)suitable for reaction with acid, according to the present invention is patikointipaivan metal complex salt, MES or enantiomer, such as described in WO 03/062253, i.e. comprising a carbene ligand, a polydentate ligand, and one or more other ligands, in which

at least one of these other ligands is tight spatial regulation l the GAND, having a pKa of at least 15 (specified pKa is measured under standard conditions, i.e. at about 25°C, usually in dimethyl sulfoxide (DMSO) or in water, depending on the solubility of the ligand),

- polydentate ligand is a polydentate ligand of a class of Schiff's bases, including aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup, through at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium, and

- these other ligands are not capable of protonation of these acids under the reaction conditions.

Patikointipaivan metal complex of this first embodiment may be either monometallic complex, or bimetallic complex, in which one metal pentacoordinate, and other metal tetracoordinated with one or more neutral ligands and one or more anionic ligands. In the latter case, the two metals M and M' may be the same or different. Specific examples of such bimetallic complexes represented by the General formulas (IVA) and (IVB), referred to in figure 4, in which

Z, R', R" and R"' have the meanings previously defined in relation to formula (IA) and (IB),

- each of M and M' represents a metal independently selected from the group consisting of ruthenium, osmium, m is for molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, Nickel and cobalt;

- y represents the number of carbon atoms sp2between M and the carbon atom bearing an R3and R4and is an integer from 0 to 3 inclusive;

- each of R3and R4represents hydrogen or a radical selected from the group consisting of C1-20of alkyl, C2-20alkenyl,2-20the quinil,1-20of carboxylate, With1-20alkoxy, C2-20alkenylacyl,2-20alkyloxy, aryl, aryloxy,1-20alkoxycarbonyl,1-8alkylthio,1-20alkylsulfonyl,1-20alkylsulfonyl,1-20alkylsulfonate, arylsulfonate,1-20alkylphosphonate, arylphosphonate,1-20alkylamine and arylamine;

- R' and one R3and R4can be connected to each other, forming a bidentate ligand;

- X1, X2and X3are anionic ligands, defined below;

- L is a neutral electron donor; and

- R3and R4together may form a condensed aromatic ring system, i.e. phenylindolizine ligand,

including their salts, solvate and enantiomers.

Included polydentate ligand class of Schiff's bases can b the th or bidentate ligand class of Schiff's bases, in the case of which precoordination complex metal (a) of this first embodiment includes two other ligand or a tridentate ligand class of Schiff's bases, in which the metal complex comprises one another ligand.

Preferably the metal in patikointipaivan metal complex of the invention is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic table. More preferably, the specified metal selected from the group consisting of ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, Nickel and cobalt.

Carbene ligand in patikointipaivan metal complex of the invention can be alkylidene ligand, benzylidene ligand, vinylidene ligand, inteeligence ligand, phenylindolizine ligand, allenylidene ligand or cumulativity ligand, for example, buta-1,2,3-trainride, Penta-1,2,3,4-tetrahedrite and analogichnye, i.e. between the metal M and carrier group carbon atom may be present from 1 to 3 carbon atoms sp2.

According to one aspect, which is particularly useful when the complex is used in the presence of an organic solvent, one of these others is other ligands, present in patikointipaivan metal complex of the invention is an anionic ligand, and the meaning of the term anionic ligand is conventional in the art and preferably is covered by the definition given in U.S. patent No. 5977393, for example a ligand selected preferably, but not exclusively, from the group consisting of C1-20of alkyl, C2-20alkenyl,2-20the quinil,1-20of carboxylate, With1-20alkoxy, C2-20alkenylacyl,2-20alkyloxy, aryl, aryloxy,1-20alkoxycarbonyl,1-8alkylthio,1-20alkylsulfonyl,1-20alkylsulfonyl,1-20alkylsulfonate, arylsulfonate,1-20alkylphosphonate, arylphosphonate,1-20alkylamine, arylamine, halogen (preferably chlorine), nitro, C1-20alkyldimethyl (e.g., acetylacetonate), iridecent and cyano.

According to another aspect, which is particularly useful when the complex is used in the presence of water, one of these other ligands is the solvent, and the complex is a complex of cationic type, associated with the anion. Suitable anions for the latter purpose are selected from the group consisting of tetrafluoroborate, Tetra(pentafluorophenyl)borate, alkylsulfonate, in which the alkyl group may be substituted by one or more of the volumes of halogen, and arylsulfonate. Suitable solvents for coordination with the metal in such a cationic particle can be selected from the group consisting of proton solvents, polar aprotic solvents and nonpolar solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, esters, ketones, amides, and water.

Methods of obtaining five-coordination metal complexes according to the first embodiment of the invention having been broadly described in WO 03/062253.

The second embodiment precoordination complex metal (a)suitable for reaction with acid, according to the present invention is chetyrehkilometrovoy monometallic complex containing polydentate ligand, and one or more other ligands, in which

at least one of these other ligands is tight spatial hindered ligand having a pKa of at least 15, or a group selected from aromatic and unsaturated cycloaliphatic groups, preferably aryl and C4-20cycloalkenyl (such as cyclooctadiene, norbornadiene, cyclopentadienyl and cyclooctadiene) groups, with the specified group optionally substituted by one or more1-7alkyl groups,

- polydentate the m ligand is a polydentate ligand of a class of Schiff's bases, including aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup, through at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium, and

- these other ligands are not capable of protonation of the acid under the reaction conditions.

Similar to the first embodiment, one of these other ligands present in chetyrehmetrovaya monometallic complex of the second embodiment of the invention may be anionic ligand, such as that previously defined.

More specifically, constrained spatial difficult ligand having a pKa of at least 15, which may be included, as in the first embodiment and the second embodiment of the invention may be derived, in which one or more hydrogen atoms substituted by a group providing constrained spatial difficulty of the following groups:

- imidazol-2-ilidene (pKa=24),

- dihydroimidazole-2-ilidene (pKa higher than 24),

- oxazol-2-ilidene,

- triazole-5-ilidene,

- thiazol-2-ilidene,

- pyrrolidide (pKa=17,5),

- pyrazolidine,

- dihydropyrimidin,

- pyrrolidinone (pKa=44),

bis(imidazolin-2-ilidene) and bis(imidazolidin-2-ilidene),

- benzododecinium derivatives, such as indolicidin (pKa=16), and

- non-ionic protostar the new superocean, namely, as described in U.S. patent No. 5698737, preferably trimethylphosphate P(CH3NCH2CH2)3N, known as superocean Verkade.

Limited spatial hindered group may be, for example, branched or substituted group, for example, tert-bucilina group, substituted C3-10cycloalkyl group, aryl group, having two or more1-7alkyl substituents (such as 2,4,6-trimetilfenil (mesityl), 2,6-dimetilfenil, 2,4,6-triisopropylphenyl or 2,6-diisopropylphenyl), or heteroaryl group (such as pyridinyl)having two or more1-7alkyl substituent.

As mentioned earlier, the polydentate ligand class of Schiff bases included or patikointipaivan complex of a metal of the first embodiment, or in chetyrehkilometrovoy monometallic complex of the second embodiment, there may be a ligand of the General formula (IA) and (IB)referred to in figure 1, where Z, R', R” and R”' have the meanings given above. In determining ligands having the General formula (IA), the group R' is preferably selected from methyl, phenyl and substituted phenyl (for example, dimethylphenyl or diisopropylphenyl). In determining ligand having General formula (IB), R' preferably represents methylidene or benzylidene.

Methods of obtaining chetyrehtomnik the skilled monometallic complexes according to the second embodiment of the invention having been broadly described in WO 03/062253.

The third embodiment precoordination complex metal (a)suitable for reaction with acid, according to this invention is at least tetracoordinated complex of the metal, its salt, MES or enantiomer, including

- polydentate ligand class of Schiff's bases, including aminogroup and koordinirovannye with metal, in addition to the nitrogen atom of the specified aminogroup, through at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium;

- non unsaturated anionic ligand L1selected from the group consisting of aromatic and unsaturated cycloaliphatic groups, preferably aryl, heteroaryl and C4-20cycloalkenyl groups, and specified aromatic or unsaturated cycloaliphatic group optionally substituted by one or more1-7alkyl groups or electron-withdrawing groups such as, but not limited by them, halogen, nitro, cyano, (thio)carboxylic acid (thio)ester of (thio)carboxylic acid (thio)amide (thio)carboxylic acid, anhydride (thio)carboxylic acid halide (thio)carboxylic acid; and

- non-anionic ligand L2selected from the group consisting of C1-7of alkyl, C3-10cycloalkyl, aryl, arylalkyl, alkylaryl the heterocyclic group, moreover, this group optionally substituted by one or more electron-withdrawing substituents, such as, but not limited by them, halogen, nitro, cyano, (thio)carboxylic acid (thio)ester of (thio)carboxylic acid (thio)amide (thio)carboxylic acid, anhydride (thio)carboxylic acid halide (thio)carboxylic acid,

provided that these other ligands L1and L2not capable of protonation of these acids under the reaction conditions.

According to a third embodiment of the invention polydentate ligand is preferably N,O-bidentate ligand class of Schiff's bases or N,S-bidentate ligand class of Schiff's bases, most preferably bidentate ligand class of Schiff bases shown in formulas (IA) or (IB) in figure 1 and described here above in more detail, in the case of which the complex metal is tetracoordinated. Polydentate ligand can also be tridentate Chiffolo base, a complex metal is pentacoordinated.

At least tetracoordinated complex metal according to a third embodiment of the invention is preferably monometallic complex. Preferably the metal is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11And 12 of the Periodic table. More preferably, the specified metal selected from the group consisting of ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, Nickel and cobalt.

Each of the metal, the ligand L1and ligand L2may be, independently from each other, any of the above-mentioned metals or any of the above groups with any of the substituents listed for such groups, including any of the individual values for these groups or substituents as listed in the definitions above. Preferably non-anionic ligand L2has constrained spatial difficulties, such as, but not limited to them, tert-butyl, neopentyl and mono - or politeley phenyl, for example pentafluorophenyl. L2can also be linear With1-7alkyl, such as methyl, or aryl, such as phenyl. Preferably non unsaturated anionic ligand L1also has constrained spatial difficulties (such as, but not limited to them, alkylaryl and alkylglycerols, for example, xylyl, cumenyl or mesityl).

At least tetracoordinated complex metal according to a third embodiment of the invention, may for example, but without limitation pointed to by the m to be obtained in accordance with the following procedure: salt metal (e.g., thallium) polydentate ligand (e.g., bidentate, or tridentate, Chippewa Foundation) is first subjected to a reaction with preferably bimetallism complex of the desired metal, more preferably Mobiltelecom complex, in which the desired metal is coordinated with a non unsubstituted anionic ligand L1and at least one anionic ligand, such as [RuCl2(p-cumene)]2, [RuCl2(COD)]2or [RuCl2(NBD)]2where COD and NBD respectively denote cyclooctadiene and norbornadiene. After removal of the metal salt formed with anionic ligand, such as califlorida obtained intermediate complex, i.e. a complex in which the desired metal is coordinated with a non unsaturated anionic ligand L1, polydentate ligand (e.g., bidentate or tridentate Chiffonier base) and anionic ligand, undergoes reaction with a combination of non-anionic ligand L2and alcohol or alkaline earth metal, for example With1-7alkylate,1-7alkylate, finelite, or Grignard reagent, such as phenylmagnesium, phenylmagnesium or pantothenicacid. The selection of the desired at least tetracoordinated the th complex metal of the third embodiment of the invention can be achieved properly by removing alcohol or alkaline earth metal salt, formed with anionic ligand, followed by purification using conventional techniques. High net outputs at least tetracoordinated complex metal of this embodiment can thus be achieved using a simple two-step method.

The fourth embodiment precoordination complex metal (a)suitable for reaction with acid, according to this invention, is hexacoordination complex of the metal, its salt, MES or enantiomer, including

- polydentate ligand class of Schiff's bases, including aminogroup and koordinirovannye with metal, in addition to the nitrogen atom of the specified aminogroup, through at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium;

at least one non-anionic bidentate ligand L3different from polydentate ligand; and

- at most, two anionic ligand L4,

provided that these ligands L3and L4not capable of protonation of these acids under the reaction conditions.

Specified hexacoordination complex metal is preferably a bimetallic complex, in which each metal hexacoordination. Two metal may be the same or different. Preferably the each metal is a transition metal, selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic table. More preferably each specified metal independently selected from the group consisting of ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, Nickel and cobalt.

Polydentate ligand is preferably a ligand as defined in the previous embodiments of the invention, i.e. they preferably is a bidentate or tridentate Chiffolo basis. Peninim bidentate ligand L3is preferably polyunsaturated3-10cycloalkenyl group, such as, but not limited to them, norbornadiene, cyclooctadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene or cycloheptatrien, or Generalna group, such as defined here above (preferably, in which the heteroatom is nitrogen, phosphorus, arsenic or antimony, to avoid the risk of protonation by the acid used for the modification of complex metal), for example (but without limitation) 1-hetero-2,4-cyclopentadiene, such as furan or thiophene, or condensed with a ring its derivative, such as benzofuran, tianfuan or benzothiophen or six-membered heteroaromatic connection, such as Piran or Conde is servandae with ring its derivative, such as cyclopentadiene, chrome or Xanten. Each anionic ligand L4preferably selected from the group consisting of C1-20of carboxylate, With1-20alkoxy, C2-20alkenylacyl,2-20alkyloxy, aryloxy,1-20alkoxycarbonyl,1-7alkylthio,1-20alkylsulfonyl,1-20alkylsulfonyl,1-20alkylsulfonate, arylsulfonate,1-20alkylphosphonate, arylphosphonate,1-20alkylamine, arylamine,1-20alkyldimethyl (e.g., acetylacetonate), iridecent, halogen, nitro and cyano, each of these groups is the same as defined above. When the specified hexacoordination complex metal is monometallic, it preferably has only one anionic ligand L4.

Hexacoordination complex metal according to the fourth embodiment of the invention may, for example, but not limited, to be obtained with high yield and purity using a one-step procedure, according to which the salt of the metal (e.g., thallium) polydentate ligand (e.g., bidentate, or tridentate, Chippewa Foundation) is subjected to reaction with preferably a bimetallic complex of the desired metal, more preferably Mobiltelecom complex, in which the desired metal coordinated the Academy with non-anionic bidentate ligand L 3and at least one anionic ligand, such as [RuCl2L3]2for example, [RuCl2(COD)]2or [RuCl2(NBD)]2where COD and NBD respectively denote cyclooctadiene and norbornadiene. After removal of the metal salt formed with anionic ligand, such as califlorida desired hexacoordination complex metal can be purified using conventional techniques.

According to a particular embodiment, which is useful when the complex metal this fourth embodiment of the invention is to be used in the presence of water, can be beneficial when one or more anionic ligands L4specified hexacoordination metal complex is removed and replaced with a solvent S as a ligand. This removal and replacement of the anionic ligand can be, for example, by treatment, in the presence of solvent (S, hexacoordination complex metal this fourth embodiment of the invention the equivalent amount of the compounds having the formula a-E, in which E represents trimethylsilyloxy group or a metal, such as silver, thus giving a modified hexacoordination metal complex, a cationic complex with the solvent S as a ligand (the place L 4) and associated with the anion A. This processing leads to the formation of compound L4E (for example, silver chloride and chlorotrimethylsilane), which can be removed from the reaction mixture using conventional techniques. Suitable anions And for this purpose may be, without limitation, selected from the group consisting of hexaflurophosphate, hexafluoroantimonate, hexafluoroarsenate, perchlorate, tetrafluoroborate, Tetra(Penta-forfinal)borate, alkyl sulphonates in which the alkyl group may be substituted by one or more halogen atoms, and arylsulfonate (for example, toluensulfonate). Suitable solvents's to coordinate with the metal in such cationic types can be selected from the group consisting of proton solvents, polar aprotic solvents and nonpolar solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, esters, ketones, amides and water.

More specifically, as at least tetracoordinated complex of a metal of the third embodiment of the invention, and hexa-coordinated complex of a metal of the fourth embodiment of the invention may have as a polydentate ligand bidentate Chiffolo base, having one of the General formulas (IA) or (IB), apamin is administered in figure 1, in which Z, R', R" and R"' have the meanings previously defined. In this particular case, R" and R"' is preferably together form a phenyl group which may be substituted by one or more preferably branched alkyl groups such as isopropyl or tert-butyl. Class of bidentate Schiff bases having the General formula (IA), well known in the art, and they can be obtained, for example, by condensation of salicylaldehyde with appropriately substituted aniline. Class of bidentate Schiff bases having the General formula (IB)can be obtained, for example, by condensation of benzaldehyde with appropriate selection of aminosterol, such as o-hydroxyanisol (when Z is oxygen), aminothiols (when Z is sulfur).

The fifth embodiment precoordination complex metal (a)suitable for reaction with acid, according to this invention is at least pentacoordinated complex of the metal, its salt, MES or enantiomer, including

- tridentate ligand comprising two Schiff bases, in which the nitrogen atoms of these two Schiff bases are connected to each other through a1-7alkylenes or Allenova linking group; and

- one or more non-anionic ligands L7selected from the group consisting of aroma is practical and unsaturated cycloaliphatic groups, preferably aryl, heteroaryl and C4-20cycloalkenyl groups, and specified aromatic or unsaturated cycloaliphatic group optionally substituted by one or more1-7alkyl groups or electron-withdrawing groups such as, but not limited by them, halogen, nitro, cyano, (thio)carboxylic acid (thio)ester of (thio)carboxylic acid (thio)amide (thio)carboxylic acid, anhydride (thio)carboxylic acid halide (thio)carboxylic acid.

Each ligand L7and substituting groups may, independently from each other, being any of the aforementioned groups, including any of the individual values for these groups or substituents as listed in the definitions above. Preferably non-anionic ligand L7has constrained spatial difficulties, such as, but not limited to them, mono - or politeley phenyl, for example, xylyl, cumenyl, simenel or mesityl.

At least pentacoordinated complex metal according to the fifth embodiment of the invention is preferably monometallic complex. Preferably the metal is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic table. More preferably, the specified metal selected from the group consisting of ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, Nickel and cobalt.

More specifically, in such at least pentacoordinated complexes of a metal of the fifth embodiment of each of these non-anionic ligand L7can be Ziman, and C1-7Allenova or Allenova binder group may be substituted by one or more substituents, preferably selected from the group consisting of chlorine, bromine, trifloromethyl and nitro. Preferably1-7Allenova or Allenova binder group And, together with two linked nitrogen atoms is derived from o-phenylenediamine, Ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane or 1.7-diaminoheptane. Also preferably, each Chiffolo the basis of the tetradentate ligand derived from salicylaldehyde or acetylacetone, which salicylidene or acetilenovaja group included in each such Chiffolo base, can be substituted by one or more substituents, preferably selected from the group consisting of chlorine, bromine, trifloromethyl and nitro.

Suitable, but non-limiting examples of tetradentate ligands in the volume of this fifth embodiment and the attainment have one of the General formulas (IIA) and (IIB), shown in figure 2. More specific examples include the so-called Salins (i.e. bis(salicylaldehyde)ethylendiamine), Salop (i.e. bis(salicylaldehyde)o-phenylendiamine), hydroxyacetic and Assas (i.e. bis(acetylacetone)ethylendiamine) ligands and their substituted derivatives. In formulas (IIA) and (IIB), the substituents X are preferably selected from the group consisting of chlorine, bromine, trifloromethyl and nitro. In the formula (IIA), the substituents Y are preferably selected from the group consisting of hydrogen and methyl. Preferred tetradentate ligand is N,N'-bis(5-nitrosalicylic)Ethylenediamine. Other suitable ligands include N,N'-1,2-cyclohexanebis(2-hydroxyacetophenone), 1,2-diphenylethylene(2-hydroxyacetophenone) and 1,1'-binaphthalene-2,2'-diamines(2-hydroxyacetophenone), all described in Molecules (2002) 7:511-516.

At least pentacoordinated complex metal according to the fifth embodiment of the invention can be obtained by reaction of a suitable tetradentate ligand, such as defined above, preferably a bimetallic complex of the desired metal, more preferably Mobiltelecom complex, in which the desired metal is coordinated with a non-anionic ligand L7and at least one anionic ligand, such as [RuCl2(t-Zimen) 2, [RuCl2(COD)]2or [RuCl2(NBD)]2where COD and NBD respectively denote cyclooctadiene and norbornadiene.

In the second aspect of the present invention will now be described relative to the several preferred embodiments of the acid and the reaction conditions that are suitable for modification precoordination complex metal (a). In relation to this aspect important factor is the choice of acid. In particular, it is preferable that the RCA specified acid was lower than the RCA polydentate ligand class of Schiff's bases. While the indexes of the RCA main available organic and inorganic acids (usually measured at room temperature (about 25°C) in aqueous solutions) are widely covered in the literature (for example, in the Handbook of Chemistry and Physics 81stedition (2000), CRC Press, page 8-44 to 8-56), database rka different possible polydentate ligands class of Schiff's bases are not necessarily available in the technique (for example, table rka Bondwell gives data only for a limited number of Iminov). This implies a practical consequence, namely, that before the selection of the acid may be first necessary to identify, measure or estimate the pKa of the specified polydentate ligand class of Schiff's bases. This measurement RCA is well within the knowledge kvalifitsirovannyi and can be performed in accordance with standard practice, i.e. usually at room temperature (about 25°C) in dimethyl sulfoxide (DMSO) as solvent. As soon as the result of such a measurement is available, can be a reliable choice of the acid having a pKa lower than the pKa polydentate ligand class of Schiff's bases by at least 2 units.

In particular, it is preferable that pKa (measured at room temperature is about 25°C in aqueous solutions) of the said acid for modification precoordination complex metal (a) was lower than about 4, i.e. with the exception of the so-called weak acids. Taking into account the above criteria acids suitable for the practical implementation of the invention, consist mainly of inorganic acids, such as, but not limited to, hydrogen iodide, hydrogen bromide, hydrogen chloride, hydrogen fluoride, sulfuric acid, nitric acid, innovate acid, periodic acid and perchloro acid, and HOClO, HOClO2and HOIO3. For the practice of the invention are suitable also some organic acids, including

- sulfonic acid, such as, but not limited to, methansulfonate acid, aminobenzenesulfonic acid (all 3 of its isomer), benzolsulfonat acid, naphthalenesulfonate acid, sulfanilic acid and triftormetilfullerenov acid;

- monocarboxylic to the slots, such as, but not limited to, acetoacetic acid, barbituric acid, brooksyne acid, brabantia acid (and its ortho - and meta-isomers), Chloroacetic, chlorbenzene (all 3 of its isomer), chlorprothixene (all 3 of its isomer), chloropropionate (as α-and β-isomers), CIS-cinnamic, tsianuksusnym, cyanomelana, cyanoprokaryota (all 3 of its isomer), cyanopropionic, dichloracetic, dichloroacetylene, dihydroxybenzene, dihydroxypregna, dihydroxyphenyl, dinicotinate, diphenylarsine, fervently, formic, francebuy, Turova, glycolic acid, hippuric, youkana, Identica, dairy, luteina, almond, α-naphthoic, nitrobenzene, nitrophenylacetate (all 3 of its isomer, o-phenylbenzene, teoksessa, thiophene-carboxylic, and trichloroacetic trihydroxybenzoic acid; and

- other acidic substances, such as, but not limited to, picric acid (2,4,6-trinitrophenol) and uric acid (trihydroxy-2,6,8-purine or ketone form).

Acids suitable for the practice of the invention also include, as an alternative embodiment, one of the above acid, generated in situ by methods known in the art. For example, this includes the so-called motociclete generators, i.e. compounds capable of being converted into acid under the influence of the radiation, for example, visible light sources or deep ultraviolet (or UV)light sources at short wavelengths, such as in the range of from about 100 nm to about 350 nm, or ionizing radiation such as electron beam or x-rays. Examples of such generators motociclete well known in the field of transferring images to a substrate, particularly in the area photoresist compositions and processes of copying, and include, for example, Monomeric generators, such as biculturality, bis(cyclohexanesulfonyl)diazomethane, sulfonylmethane for U.S. patent No. 6689530, itaniemi salt and sulfonate salt (including mixtures Solonevich salts of U.S. patent No. 6638685, especially those in which two groups sulfonato cation together form a substituted alkylenes group), in which the anionic component is selected from the group consisting of performanceswithout, camphorsulfonate, bansilalpet, Las, fluoro-substituted benzosulfimide, fluoro-substituted and Las halogen (provided that the anion capable of forming an acid having a pKa lower than about 4), and/or in which the cationic component comprises one or more groups, such as naftiliaki and pentafluorophenyl. Such motociclete generators may also include polymeric generators, still is as polymers with a molecular weight of from about 500 to about 1000000, which have in their skeleton and/or in side chains sulfonate salt, and also have one or more organic groups, generating motocicleta, the side chains to generate acid when exposed to light; such polymers may be such as in preparative examples 1 and 2 of U.S. patent No. 6660479, in which salt can be p-toluensulfonate salt, naftalina salt or 9,10-dimethoxy-2-anthracenesulfonic salt.

For the practice of the invention may also be appropriate also two or more of the above-mentioned acids or in the form of mixtures, if such acids can under the reaction conditions to be used together (i.e. if their physical form allows simultaneous reaction with precoordinated complex metal) or for consecutive reactions with precoordinated complex metal in two or more stages.

Preferred reaction conditions between precoordination complex metal and acid include one or more of the following:

effective contact between the normally solid precoordination complex of a metal and one or more acids; for example, when this acid is a gas at the prevailing temperature conditions, it may be passed one or more times (i.e. possibly with recirculation) through a solid mass of metal with tako the speed to provide the opportunity for sufficient contact time is allowed for heterogeneous reaction; alternatively, when this acid is liquid or soluble in the same or a similar solvent system (i.e. one or more, preferably miscible solvents), and precoordination complex metal, the effective contact can be achieved by dissolving the specified precoordination complex in this solvent system and added to the acid solution in the given solvent (or when the solvent is an ionic liquid, particles (components)capable of generating an acid in situ in the presence of a specified solvent and stirring the mixture using a suitable means of mixing for a sufficient time for the flow of homogeneous reactions;

the time of contact between precoordination complex of a metal and one or more acids (which are both optional dissolved in the solvent system, such as defined above), preferably from about 5 seconds to about 100 hours; depending on the physical state of the reaction medium, including precoordination complex of a metal and one or more acids, depending on the polydentate ligand class of Schiff bases and reactivity SEL is Anna acid, as well as other reaction conditions, such as temperature, contact time may be varied within the preferred range from about 30 seconds to about 24 hours, most preferably from 1 minute to 4 hours;

- contact temperature in the range of from about -50°to about +80°C; it should be understood that the reaction temperature does not need to be constant throughout the time of contact, and it may gradually be increased above the limits in order to maintain control of the reaction by a method well-known to specialists in this field of technology. For example, one or more acids can be added to precoordination complex metal optionally in the presence of the solvent system (defined above), in a receptacle supported at a relatively low temperature (i.e. below room temperature but above the temperature of solidification of the specified system solvent) with suitable cooling means, and then the temperature gently rises when the monitoring of any local overheating, to a higher temperature, which may be room temperature.

The molar ratio between the acid and precoordination complex metal is also an important parameter in the practice of the invention. Contrary to the information of the prior art (patent When And No. 6284852) this ratio is selected so that that was the protonation of the ligand (because another characteristic of the invention is to avoid the presence of such protonium ligands) or to avoid decomposition of the catalyst and is selected so that at least partially split the bond between the metal center and at least one polydentate ligand class of Schiff's bases. Therefore, it was found desirable to select the molar ratio between the acid and precoordination complex metal above about 1.2. Preferably this ratio is above 2.0, more preferably above 3.0, and most preferably above 4.0. This ratio can be achieved preferably step (stage by stage) by the gradual addition of acid to precoordination complex metal, optionally in the presence of the solvent system mentioned above, during the contact time, defined above. The rate of addition of acid may vary, depending on the acid, polydentate ligand class of Schiff bases and the temperature selected according to the usual experimentation.

Over consumption of acid and the degree of leakage of its reaction with precoordinated complex metal can be monitored using one or more standard analysis, the definition of methods, such as, but without limitation specified, infrared spectroscopy, carbon nuclear magnetic resonance (NMR) spectroscopy and proton NMR. These techniques are also useful in determining the precise nature of the reaction product of the invention. The nature or character can also be confirmed after the separation of the reaction product from the reaction medium and after cleaning using suitable techniques such as, but without limitation specified, recrystallization), obtaining x-ray diffractogram crystalline powder reaction product. Careful inspection shows that the reaction product of the invention includes the product of at least partial cleavage of the connection between the metal center and polydentate ligand class of Schiff's bases. Communication, which is partially broken in the reaction, may be a covalent bond or a coordination bond; it may be a relationship between the metal center and the nitrogen atom of aminogroup Chippewa base, or it may be a relationship between the metal center and the heteroatom (oxygen, sulfur or selenium) ligand class of Schiff's bases, or can at least partially split both these links. The present invention does not require that the specified cleavage was complete, and thus, displacement of the inventions covered by the partial cleavage of St. the Z. leading to a mixture of the original precoordination complex of a metal and one or more reaction products. Due to the fact that, as described hereinafter, the reaction of the invention can be carried out in situ in the presence of organic molecules, or monomers, which are processed under the action of catalytic activity of the resulting reaction product, is not essential to the specified reaction product could be isolated in the form of a single pure chemical particles.

According to another aspect of the present invention provides a catalytic system containing

(a) as a main catalytic component, the reaction product

- precoordination complex metal salts thereof, MES or enantiomer, and specified precoordination complex metal includes (i) at least one polydentate ligand class of Schiff's bases, including aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup, through at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium, and (ii) one or more other ligands, and

- acid, reacted in a molar ratio of above about 1.2 with respect to the specified precoordination metal complex, provided that these drugoligasi (ii) chosen to be able to protonation of the specified acid in the above reaction conditions, and

(b) one or more second catalyst components selected from the group consisting of socialization - a Lewis acid (b1), activators of the catalyst (b2and initiators having a portable on the radical mechanism atom or a group (b3).

In the catalytic system of this another aspect of the invention the second component (b) is chosen in accordance with the views of catalyzed reactions. For example, socialization (b1may be useful to increase the rate of metabolic reaction polymerization with ring opening of cyclic olefins and can be selected without limitation from the group consisting of trihalogen boron; trialkylborane; trailmore; alyuminiiorganicheskikh compounds; magnesium halides, halides of aluminum; tin tetrachloride; trigliceridos, or tetrachloride, or tetraethoxide titanium or vanadium, preferably of titanium tetrachloride or tetraisopropoxide; pentachloride antimony and bismuth. For example, socialization (b1can be alyuminiiorganicheskikh a compound selected from the group consisting of tri-n-alkylamine; hydrides dialkylamino, trialkylamine, alkoxides alkylamine, alkoxides dialkylamino, aryloxides dialkyl INIA and halides dialkylamide. Catalyst activator (b2) can also be useful to increase the reaction rate of exchange polymerization with ring opening of cyclic olefins (such manner can be combined with socialization (b1), such as defined above) and can be diazoketones, such as, but without limitation specified, ethyl diazo acetate and trimethylsilyldiazomethane, or a radical initiator such as azobis(isobutyronitrile).

On the other hand, the initiator having a portable on the radical mechanism atom or a group (b3is usually required, along with a main catalytic component, to perform radical polymerization of the monomer, since ATRP catalyst system based on reversible formation of growing radicals in a redox reaction between the metal component and the initiator.

Suitable initiators include those compounds having the formula R35R36R37CX1in which

- X1selected from the group consisting of halogen, OR38(where R38selected from C1-20of alkyl, polyhalogen1-20of alkyl, C2-20the quinil (preferably acetylenyl)2-20alkenyl (preferably vinyl), phenyl, optionally substituted by 1-5 halogen atoms or With1-7alkyl groups, and phenylseleno1-7is lcil), SR39, OC(=O)R39, OP(=O)R39, OP(=O)(or SIG39)2, OP(=O)or SIG39, O-N(R39)2and S-C(=S)N(R39)2where R39represents aryl or1-20alkyl, or, when there is a group N(R39)2two R39groups can be combined to form a 5-, 6 - or 7-membered heterocyclic ring (in accordance with the definition of heteroaryl above), and

- each of R35, R36and R37independently selected from the group consisting of hydrogen, halogen, C1-20the alkyl (preferably1-6the alkyl), C3-8cycloalkyl, C(=O)R40(where R40selected from the group consisting of C1-20of alkyl, C1-20alkoxy, aryloxy or heteroaromatic), C(=O)NR41R42(where R41and R42independently selected from the group consisting of hydrogen and C1-20the alkyl, or R41and R42together can be connected with the formation of alkalinous group with 2-5 carbon atoms), COCl, OH, CN, C2-20alkenyl (preferably vinyl), C2-20the quinil, oxiranyl, glycidyl, aryl, heteroaryl, arylalkyl and aryl-substituted C2-20alkenyl.

In these initiators X1is preferably bromine, which provides a higher reaction rate and a lower polydispersity polymer.

When one of R35, R36and R37select al the ilen, cycloalkyl or alkyl substituted aryl group, the alkyl group may be optionally substituted by a group X1defined above. Thus, it is possible that the initiator has served as a starting molecule for the branched or star (co)polymers. One example of such initiator is 2,2-bis(halogenmethyl)-1,3-dehalogenated (for example, 2,2-bis(chloromethyl)-1,3-dichloropropane or 2,2-bis(methyl bromide)-1,3-dibromopropane), and a preferred example is one in which one of R35, R36and R37represents phenyl substituted by one to five With1-6alkyl substituents, each of which may be independently optionally substituted by a group X1(for example, α,α'-dibromostyrene, hexacis(α-chloro - or α-methyl bromide)benzene). Preferred initiators include 1-phenylethylene and 1-fenilatilamin, chloroform, carbon tetrachloride, 2-chloropropionitrile and C1-7the alkyl esters of 2-halogen-C1-7carboxylic acids (such as 2-chloropropionic acid, 2-bromopropionic acid, 2-horizonally acid, 2-brometalia acid and similar). Another example of a suitable initiator is dimethyl-2-chloro-2,4,4-trimethylpentane.

In the catalytic system according to another aspect of the invention precoordination metal complex mo is et to be for example, any of such complexes, respectively, first, second, third, fourth and fifth embodiments, described in detail above.

According to another aspect of the present invention also provides a catalyst on a substrate, preferably for use in heterogeneous catalytic reactions, including

(a) a catalytic system comprising a catalytically active reaction product

- precoordination complex metal salts thereof, MES or enantiomer, and specified precoordination complex metal includes (i) at least one polydentate ligand class of Schiff's bases, including aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup, through at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium, and (ii) one or more other ligands, and

- acid, reacted in a molar ratio of above about 1.2 with respect to the specified precoordination metal complex, provided that the said other ligands (ii) is selected so as to be capable of protonation of the specified acid in the above reaction conditions, and

(b) a sufficient number of media suitable for holding therein specified catalytic system (a).

The catalytic system (a)included in the composition of the catalyst on the substrate of this aspect of the invention, may, in addition to the reaction product precoordination complex metal and acid, to include one or more second catalyst components, such as socializaton types of Lewis acids (b1), activators of the catalyst (b2and initiators having a portable on the radical mechanism atom or group, (b3), which had already been discussed in the previous aspect of the invention.

In this catalyst, deposited on a substrate, the specified media (b) may be selected from the group consisting of porous inorganic solids (including silica, Zirconia and aluminummagnesium), such as amorphous or paracrystalline materials, crystalline molecular sieve and a modified layered material that includes one or more inorganic oxides, and organic polymer resins such as polystyrene resins and their derivatives.

Porous inorganic solids, which can be coated on a substrate catalysts of the invention have an open microstructure, which allows the molecules to have access to a relatively large surface area of these materials, which enhances their catalytic and sorption activity. Dunn is e porous materials can be divided into three broad categories with details of their microstructure as a basis for classification. These categories are amorphous and paracrystalline substrate, the crystalline molecular sieve and a modified layered materials. Detailed differences in the microstructures of these materials appear as important differences in the catalytic and sorption behavior of materials, as well as differences in various observable properties used for their characteristics, such as their surface area, pore size and the variability of their size, the presence or absence of x-ray diffraction patterns and the details of such patterns, and the appearance of the materials, when the microstructure is investigated using transmission electron microscopy and electron diffraction methods. Amorphous and paracrystalline materials represent an important class of porous inorganic solids that have been used for many years in industrial applications. Typical examples of these materials are amorphous silica, commonly used in the compositions of the catalysts, and paracrystalline transitional alumina used as solid acid catalysts and substrates catalysts for reforming of oil. The term “amorphous” is used here to indicate a material that does not have long-range order structure and can be somewhat misleading, PQS is LCU almost all materials to some extent ordered at least at the local scale. An alternative term used to describe these materials is “indifferent to x-rays”. The microstructure of the silica consists of dense amorphous silica particles 100-250 angstroms (Kirk-Othmer Encyclopedia of Chemical Technology, 3rd, ed. vol. 20, 766-781 (1982) with porosity resulting voids between the particles.

Paracrystalline materials such as transition alumina, also have a wide distribution of pore sizes, but it is better determined by x-ray diffraction patterns, usually consisting of several broad peaks. The microstructure of these materials consists of tiny crystalline regions of condensed phases of alumina, and the porosity of materials is the result of irregular voids between these areas (K. Wefers and Chanakya Misra, “Oxides and Hydroxides of Aluminium”, Technical Paper No. 19 Revised, Alcoa Research Laboraties, 54-59 (1987)). As in the case of any of these materials there is no long-range order structure, regulating the size of the pores in the material, the variation of the pore size is usually quite high. The pore sizes of these materials fall into a mode called mesoporous region, including, for example, pores with size in the range from about 15 to about 200 angstroms.

A sharp contrast to the data of structurally poorly defined solids are materials, RAS is the definition of pore size which is very narrow, because it is governed by exactly repeating the crystalline nature of the microstructure of materials. These materials are referred to as “molecular sieves”, the most important examples are zeolites. Zeolites, both natural and synthetic, as has been demonstrated in the past to have catalytic properties for various types conversion of hydrocarbons. Some zeolite materials are ordered and porous crystalline aluminosilicates have a definite crystalline structure as determined by x-ray diffraction patterns, in which there is a huge number of smaller voids or cavities that are mutually close contact still smaller channels or pores. These cavities and pores are uniform in size, in particular a zeolite material. Since the dimensions of these pores are such that allow for adsorption molecules of certain dimensions while rejecting molecules of larger dimensions, these materials are known as “molecular sieves” and are utilized in many areas, allowing you to take advantage of these properties. Such molecular sieves, both natural and synthetic, include a wide array containing a positive ion of crystalline silicates. These silicates can be described as hard tre the dimensional framework of SiO 4and oxide of an element of Group IIIB of the Periodic table, for example AlO4in which the tetrahedra are cross linked by participating oxygen atoms whereby the ratio of total atoms of the element of Group IIIB, for example, aluminum, and an element of Group IVB, such as silicon, atoms to oxygen is 1:2. Electrovalent or innosti tetrahedra containing an element of Group IIIB, for example aluminum, is balanced by the inclusion in the crystal of a cation, for example the cation of an alkali metal or alkaline earth metal. This can be expressed in a case in which the element of Group IIIB, for example, aluminum, to the number of various cations, such as Ca, Sr, Na, K or Li, is equal to 1. One type of cations can be replaced either in whole or in part by another type of cation using the techniques of ion exchange in a conventional manner. Using this replacement cation is possible to vary the properties of a given silicate suitable choice of cation. Many of these zeolites was designated by letter or other convenient symbols, as illustrated by zeolite A (U.S. patent No. 2882243); X (U.S. patent No. 2882244); Y (U.S. patent No. 3130007); ZK-5 (U.S. patent No. 3247195); ZK-4 (U.S. patent No. 3314752); ZSM-5 (U.S. patent No. 3702886); ZSM-11 (U.S. patent No. 3709979); ZSM-12 (U.S. patent No. 3832449), ZSM-20 (U.S. patent No. 3972983); ZSM-35 (U.S. patent No. 4016245); ZSM-23 (U.S. patent No. 4076842); MSM-22 (U.S. patent No. 4954325); MCM-35 (U.S. patent No. 4981663); MCM-49 (U.S. patent No. 5236575); and PSH-3 (U.S. patent No. 4439409). The latter refers to the composition of matter of crystalline molecular sieves, called PSH-3, and its synthesis in the reaction mixture containing hexamethylenimine, organic compound, which acts as a directing agent for synthesis of layered MCM-56. A similar composition, but with additional structural components, is described in European patent application No. 293032. Hexamethylenimine is also described for use in the synthesis of crystalline molecular sieves MCM-22 in U.S. patent No. 4954325; MCM-35 in U.S. patent No. 4981663; MCM-49 in U.S. patent No. 5236575; and ZSM-12 in U.S. patent No. 5021141. The composition of the molecular sieve SSZ-25 is described in U.S. patent No. 4826667 and European patent application No. 231860, and the specified zeolite synthesized from the reaction mixture containing the Quaternary ammonium ion adamantane. Materials molecular sieves selected from the group consisting of zeolite REY, USY, REUSY, desalinizing Y, ultrahydrophobic Y-enriched silicon desalinizing Y, ZSM-20, Beta, L, silicoaluminate SAPO-5, SAPO-37, SAPO-40, MCM-9, metalloaluminophosphates MAPO-36, aluminophosphate VPI-5 and mesoporous crystalline MCM-41, are suitable for inclusion in deposited on the catalyst substrate according to this invention.

Some laminates that contain the LOI, able to be accommodated separately from the swelling agent may be stitched (connected columnar jumpers, giving materials having a very high degree of porosity. Examples of such layered materials include clay. Such clays can swell upon addition of water, which accounts for the clay layers are separated from water molecules. Other layered materials do not swell from water, but can swell under the action of some organic swelling agents, such as amines and Quaternary ammonium compounds. Examples of such nanabhay in water laminates are described in U.S. patent No. 4859648 and include layered silicates, magadia, ceniai, criticality and perovskites. Another example nenarokomov in water layered material that can swell under the action of some organic agents that promote swelling is containing vacancies titaniumalloy material described in U.S. patent No. 4831006. After the layered material swelled, the material can be crosslinked by klineline thermally stable substances, such as silica or silicon dioxide, between separately located layers. The above-mentioned U.S. patent No. 4831006 and 4859648 describe ways to support nanabhay in water materials described in the patents, and is incorporated into this description by reference to them in relation to school is exciting and stitched materials. Other patents disclosing the stitching layered materials and the stitching products include U.S. patent No. 4216188; 4248739; 4176090; and 4367163; and European patent application No. 205711. X-ray diffraction pattern of stitched laminates can vary significantly depending on the extent to which dissolved from the swelling and the stitching is usually well ordered in other cases, the layered microstructure. The regularity of the microstructure in some stitched layered materials so destroyed to such a bad state that x-ray diffraction pattern is observed only one peak in nikolovo region, when d is a distance corresponding to the repetition of the intermediate layer of stitched material. Less destroyed materials can detect multiple peaks in this area, which are typically orders of this fundamental repetition. Sometimes there are also x-ray reflection from the crystal structure of the layers. The distribution of pore size in the data sewn layered materials than in amorphous and paracrystalline materials, but wider than the crystal frame materials.

According to another aspect of the present invention provides the use as catalysts of the reaction product

- precoordination complex metal salts thereof, MES or Enan is imera, moreover, the specified precoordination complex metal includes (i) at least one polydentate ligand class of Schiff's bases, including aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup, through at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium, and (ii) one or more other ligands, and

- acid introduced into the reaction in a molar ratio of above about 1.2 with respect to the specified precoordination metal complex, provided that the said other ligands (ii) is selected so as to be incapable of protonotariou specified acid in the above reaction conditions,

in the exchange reaction of olefins (the latter is explained in the section "Background of the invention" or defined in http://www.ilpi.com/organomet/olmetathesis.html), in particular the exchange of polymerization with ring opening of cyclic olefins, or in the exchange reaction of acetylene (the latter is defined inhttp://www.ilpi.com/organomet/acmetathesis.htmlas a reaction, in which all carbon-carbon triple bond in a mixture of alkynes are cut and rearranged statistical way, and involving metal-cyclobutadiene intermediate connection) or in the reaction with the transfer of an atom or group to the compound with ethylene or acetylenes is th unsaturation or any other reactive substrate, such as, but not limited by them, saturated hydrocarbons, aldehydes, ketones, alcohols, alkylhalogenide and similar. Specifically, this aspect of the invention relates to a method of carrying out the above reaction in the presence of catalytic component comprising the product of the specified response.

The reaction of transfer of an atom or group usually includes the stage of interaction of the compounds with ethylene or acetylene unsaturation or another reactive substrate with the second reactive substrate in a suitable reaction conditions and in the presence of a suitable catalytic component, and the second reaktsionnosposobnykh substrate is a suitable donor for the atom or group, subject to transfer.

More specifically, these reactions transfer of an atom or group (which will be disaggregated below) can be, without limitation, selected from the group consisting of

- radical polymerization atom transfer or groups of one or more radically (co)polymerized monomers, especially mono - and Diethyleneamine monomers;

radical accession atom transfer (the latter is explained in background of the invention), such as attaching POLYHALOGENATED having the formula CXnH4-nin which X represents halogen and n represents the aloe a number from 2 to 4, to ethyleneamines connection to obtain the corresponding saturated polygalacturonase adduct, including, for example, the accession of carbon tetrachloride or chloroform to α-olefin;

reaction of vanilinovoi, i.e. the reaction of mono - or dulcina (for example, phenylacetylene or 1.7-octadiene) with monocarboxylic acid (e.g. formic or acetic acid or dicarboxylic acid with obtaining ALK-1-anilovich esters, or rolovich esters, or Markovnikov adducts, or antiaddictive Markovnikov, or mixtures thereof;

- cyclopropylamine α-Ethylenediamine compounds to produce organic compounds having one or more gives rise to structural subdivisions;

synthesis of quinoline via oxidative cyclization of 2-aminobenzamide alcohol ketones;

- epoxidation of α-Ethylenediamine compounds to obtain epoxides;

- oxidation of organic compounds, including the oxidation of saturated hydrocarbons (such as, but not limited to, methane) to obtain alcohols, or sulfides to obtain sulfoxidov and sulfones, or phosphine to obtain phosphonates, or alcohols and aldehydes to obtain carboxylic acids;

- cyclopropenone alkyne to produce organic compounds having one or more cyclopropenoid structural Venev;

- hydrocyanide α-Ethylenediamine compounds to obtain saturated NITRILES, or alkynes to obtain unsaturated NITRILES, or α,β-unsaturated aldehydes or ketones to obtain β-cyanocobalamine compounds;

- hydrosilation of olefins to obtain saturated silanes, or alkynes to obtain unsaturated silanes, or ketone to obtain cyrilovich esters, or trimethylsilylacetamide aldehydes to obtain cyanovalerianic ethers;

- aziridination Iminov or alkenes to produce organic compounds having one or more aziridine structural subdivisions;

- gidrolizirovanny olefins to obtain saturated amides;

- hydrogenation of olefins to obtain alkanes, or ketone to obtain alcohols;

- aminolysis olefins to obtain saturated primary or secondary amines;

- isomerization of alcohols, preferably allyl alcohols, to obtain aldehydes;

- cross-combination of the Grignard alkyl or aryl halides to obtain alkanes or arylalkyl;

- hydroporinae olefins to obtain alkylboranes and trialkylborane;

hydride reduction of aldehydes and ketones to obtain alcohols;

- aldol condensation of saturated carboxylic compounds (ALD the guides or ketones) to obtain α,β-unsaturated carboxyl compounds or β-hydroxycarbonyl compounds and intramolecular aldol condensation of dialdehydes or diones to obtain cyclic α,β-unsaturated carboxyl compounds (aldehydes or ketones);

- join Michael ketone or β-dicarbonyl compounds to α,β-unsaturated carboxyl compound to obtain a saturated polycarboxylic compounds;

- annelation on Robinson, i.e. joining Michael and subsequent intramolecular Alderney condensation of the ketone to the α,β-unsaturated carboxyl compound to obtain a saturated polycyclic carboxylic compounds which are suitable intermediates for steroids and other natural products containing six-membered ring;

- the Heck reaction, i.e. reaction of helgaleena or 1-hetero-2,4-cyclopentadiene (or benzododecinium derived) with α-ethylene unsaturated compound to obtain arylalkenes or heteroarylboronic;

- codimerization alkenes for higher saturated hydrocarbons or alkynes for higher alkenes; hydroxylation of olefins to obtain alcohols;

- gidroaminirovaniya olefins and alkynes;

- alkylation, preferably allylic alkylation of ketones to obtain alkyl ketones, preferably allyl ketones; and

- Diels-alder reaction, such as, but not limited to them, the cycloaddition of a conjugated diene α-ethyleneamines connect the nity to obtain optionally substituted cyclohexanol, or cycloaddition of furan to α-ethyleneamines connection for receiving optional substituted 7-exonorbornenes.

Each of the above reactions of organic synthesis, which will be described in more detail below, is known in itself. As for additional details on each type of reactions, you can refer to, for example, to the publication of K. Vollhardt and N. Schore. Organic chemistry, the sructure and function (1999) W.H. Freeman (3rdedition) and B.Cornils and A. Herrmann. Applied homogeneous catalysis with organometallic compounds (2000) Wiley.

Each reaction of organic synthesis of this sixth aspect of the invention may be continuous, semi-continuous or periodic manner, and may include, if desired, the operation of the recirculation liquid and/or gas. The manner or order of addition of reactants, catalyst and solvent are usually not significant. Each of the reactions of organic synthesis can be carried out in a liquid reaction medium which contains a solvent for the active catalyst, preferably a solvent in which the reagents, including the catalyst being soluble at the reaction temperature.

In the first embodiment of this sixth aspect of the invention specified reaction is an exchange reaction of olefins to transform the first olefin in at least one second olefin, or a linear olefin-oligom the R or polymer, or cycloolefin. The invention relates therefore to a method of performing transfer reactions of olefins, comprising bringing into contact at least one of the first olefin with a catalytic component, optionally deposited on a suitable carrier, such as described here above in relation to the fifth aspect of the invention. The high activity of the metal complexes of the present invention causes the data connection to be coordinated with the reactions and catalyze the exchange reaction between the many types of olefins. Examples of exchange reactions of olefins, which are made possible by using the metal complexes of the present invention include, but are not limited to, the RCM acyclic dienes, reaction cross-fertilization, depolymerization of olefinic polymers and, more preferably, ROMP of strained cyclic olefins. In particular, the catalytic components of this invention can catalyze ROMP unsubstituted, monosubstituted and disubstituted intense mono-, bi - and polycyclic olefins with a ring size of at least 3, preferably 3-5 atoms; examples include norbornene, cyclobutene, norbornadiene, cyclopentene, Dicyclopentadiene, cycloheptene, cyclooctene, 7-Oxandrolone, 7-arsenalsgatan, cyclooctadiene, cyclododecene, their mono - and disubstituted derivatives, especially derivatives, to the verge Deputy can be 1-7alkyl, cyano, diphenylphosphine, trimethylsilyl, methylaminomethyl, carboxylic acid or ester, trifluoromethyl, maleic ester, maleimido and similar, such as described in U.S. patent No. 6235856, the entire contents of which is included in this description. The invention also considers ROMP mixtures of two or more such monomers in any proportion. Additional examples include water-soluble cyclic olefins, such as chloride Exo-N-(N',N',N'-trimethylammonio)ativista[2.2.1]-hept-5-ene-2,3-dicarboximide or chloride Exo-N-(N',N',N'-trimethylammonio)ethyl-bicyclo-7-oxabicyclo[2.2.1]-hept-5-ene-2,3-dicarboximide. As is well known to specialists, olefins, such as cyclohexene, which have little or no Hoop stress or deformation, can not cure, because there is no thermodynamic preference of the polymer compared to the monomer.

ROMP according to the invention can be carried out in an inert atmosphere, for example, by dissolving a catalytic amount of the catalytic component in a suitable solvent, and then adding one or more of the said strained cyclic olefins, optionally dissolved in the same or another solvent to the catalyst solution, preferably with stirring. Because ROMP-system is provided which allows the normal process of living polymerization, two or more different strained cyclic olefins can polymerizates in successive stages to create the diblock and triblock copolymers, thus ensuring the properties of the resulting material, provided that the appropriate image is selected, the ratio of initiation of chain and development chain. Solvents that can be used to perform ROMP, include all kinds of organic solvents, such as proton solvents, polar aprotic solvents and nonpolar solvents, and supercritical solvents, such as carbon dioxide (when running ROMP in supercritical conditions) and aqueous solvents, which are inert with respect to tense cyclic olefin and catalyst component used in the polymerization conditions. More specific examples of suitable organic solvents include ethers (e.g., disutility ether, tetrahydrofuran, dioxane, etilenglikolevye or dimethyl ether, etilenglikolevye or diethyl ether, dietilenglikoluretan ether or triethylenemelamine ether), halogenated hydrocarbons (e.g. methylene chloride, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane or 1,1,2,2-tetrachlorethane), esters of carboxylic acids and lactones (for example, ethyl acetate, metalpro Jonat, ethylbenzoic, 2-ethoxyethylacetate, γ-butyrolactone, δ-valerolactone or pivalate), amides of carboxylic acids and lactams (such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, tetramethylrhodamine, triamide hexamethylphosphoric acid, γ-butyrolactam, ε-caprolactam, N-organic N-acetylpyrrolidine or N-methylcaprolactam), sulfoxidov (e.g., dimethylsulfoxide), sulfones (for example, dimethyl sulfone, diethylsulfate, trimetilindolom or tetramethylsilane), aliphatic and aromatic hydrocarbons (for example, petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene or xylene), NITRILES (e.g. acetonitrile, propionitrile, benzonitrile or phenylacetonitrile).

When the solvent choose water or a water mixture, it is preferable to use cationic particles of metal complex as a catalytic component, and these cationic particles associated with anion As described here above.

The solubility of the polymer, the resulting ROMP, depends on the choice of a busy cyclic olefin, choice of solvent and the molecular weight and concentration of the obtained polymer. When strained cyclic olefin is polyunsaturated (e.g., dicyclo entation or norbornadiene), the resulting polymer can often be insoluble in any solvent used. The polymerization temperature may be in the range of from about 0°to about 120°C., preferably 20°C To 85°C, depending on the stress of cyclic olefin and solvent. The duration of polymerization can be at least about 1 minute, preferably at least 5 minutes, and more preferably at least 30 minutes; duration of polymerization can be at most about 24 hours (although due to economic conditions can be used over long periods of time), preferably at most about 600 minutes and even less than 60 minutes. The molar ratio busy cyclic olefin by catalytic component of the invention is not critical, and, depending on the subject of polymerization of the olefin, can be at least about 100, preferably at least 250, more preferably at least 500. The specified molar ratio is typically at least about 1,000,000, preferably at least 300,000, and more preferably at most 50000. Before the formed polymer solidifies in the reactor or form, or, if desired, is achieved when the desired molecular weight of the polymer (which may be controlled, for example, mo is hitoriga reactor temperature and/or viscosity of the reaction mixture), to the reaction mixture, if necessary, can be added oxidation inhibitor and/or the agent interrupts or transfer chain. Select the terminating agent or agent transfer circuit is not critical to the present invention, provided that the terminating agent interacts with the catalytic component and gives some other particles that are inactive, i.e. not able to continue to propagate the polymerization reaction under the prevailing conditions (e.g. temperature). For example, adding a molar excess (with respect to the catalytic component) carbonyl compounds to the reaction mixture capable of giving a group of Metallica and olefin (or polymer), completed this carbonyl functionality; split the polymer can then be separated from the catalyst by precipitation with methanol. Another way of detachment of the polymer from the catalyst may be adding vinylalcohol ether. Alternatively, another way to break the polymer chain is the reaction with several equivalents agent transfer circuit, such as a diene, which is not deactivates the catalytic component, allowing the polymerization of the additional monomer is, however, possible risk of expanding the distribution of molecular weight.

Due to the fact that the metal complexes of this and the finding are stable in the presence of various functional groups, they can be used for catalysis of a wide variety of olefins in a wide variety of conditions processes. In particular, the olefinic compound that is intended for transformation using the metathesis reaction may include one or more, preferably at most 2, the functional atoms or groups chosen, for example, from the group consisting of hydroxyl, thiol (mercapto), ketone, aldehyde, ether complex (carboxylate), complex tiefer, cyano, cyanate, epoxy, Silla, silyloxy, silanol, siloxane, boronate, barila, stanila, disulfide, carbonate, imine, carboxyl, amine, amide, carboxyl, isocyanate, thioisocyanate, carbodiimide, simple ether (preferably1-20alkoxy or aryloxy), tiefer (preferably1-20dialkoxy or diarylike), nitro, nitroso, halogen (preferably chlorine), ammonium, phosphonate, fostoria, phosphino, posvanila,1-20alkylsulfanyl, arylsulfonyl,1-20alkylsulfonyl, arylsulfonyl,1-20alkylsulfonyl, arylsulfonyl, sulfonamide and sulfonate (preferably toluensulfonate, methanesulfonate or triftoratsetata). These functional atom or group of olefin can be or be part of a substitute group of the olefin, or a part of the carbon chain of the olefin.

Metal complexes of this is bretania are also useful components for catalysis, at relatively low temperatures (approximately 20°C to 80°C), in the presence or in the absence of solvent exchange reactions with shorting rings acyclic dienes, such as, for example, diallylamine connection (valleroy ether, dellroy tiefer, diallylphthalate, diallylmethylamine, such as diallylamine, diallylmalonate, diarylpyrazole esters), 1,7-octadiene, substituted 1,6-heptadiene and similar.

Metal complexes of this invention may also be useful as a catalytic component for receiving telehealth polymers, i.e. macromolecules with one or more reactive end groups, which are useful materials for the process of chain elongation, synthesis of block copolymers, reaction injection molding and formation of polymeric reticulated structure. An example is hydroxyalkylated polybutadiene, which can be obtained from 1,5-cyclooctadiene, 1,4-diacetoxy-CIS-2-butene and vinyl acetate. For most applications require vyisokofunktsionalnyih polymer, i.e. a polymer with at least two functional groups on the chain. The reaction scheme for the synthesis telehealth polymers, using the exchange polymerization with ring opening is well known to specialists in this field: in this scheme acyclic olefins on setout as agents of transfer circuit, to regulate the molecular weight of the obtained telehealth polymer. When as agents of transfer circuits are α,ω-bifunctional olefins, can be synthesized really bifunctional thelegality polymers.

According to the sixth aspect of the invention, the combination of olefins can be carried out by cross currency, including the state of contact of the first olefinic compounds with such a metal complex in the presence of the second olefin or functionalized olefin. A first olefinic compound may be diolefin or cyclic monoolefins with a ring size of at least 3 atoms, and a specified cross-coupled by exchange is preferably carried out under conditions suitable for conversion of the specified cyclic monoolefins in linear olefin oligomer or polymer or specified diolefine in the mixture of cyclic monoolefins and aliphatic alpha-olefin.

Depending on the choice of initial substrates for the exchange reaction of olefins and organic molecules that want to get the reaction of the olefin can give a very wide range of end products, including biologically active compounds. For example, the reaction may also be used to transform a mixture of two dissimilar olefins and at least one cat is dedicated alpha-olefin, selected from (i) cyclodienes, containing from 5 to 12 carbon atoms, and (ii) olefins having the formula:

XHC=CH-(CH2)r-(CH=CH)a-(CHX')c-(CH2)t-X"(IV)

in unsaturated biologically active compound having the formula:

H(CH2)z-(CH=CH)a-(CH2)m-(CH=CH)b-(CH2)pX"(V)

in which a represents an integer from 0 to 2; b is selected from 1 and 2; c is selected from 0 and 1; m and p are such that the hydrocarbon chain of the formula (V) contains from 10 to 18 carbon atoms; r and t are such that in General the total number of carbon atoms in the hydrocarbon chains of the two dissimilar olefins of the formula (IV) is from 12 to 40; z represents an integer from 1 to 10, and X, X' and X" represent atoms or groups, or each each of which is independently selected, (a) hydrogen, halogen, methyl, acetyl, -Cho and-OR12where R12selected from hydrogen and alcohol protecting group selected from the group consisting of tetrahydropyranyl, tetrahydrofuranyl, tert-butyl, trityl, ethoxyethyl and SiR13R14R15where R13, R14and R15each independently selected from C1-7alkyl groups and aryl groups.

The specified unsaturated biologically active compound having the formula (V)may be eroman or predecessor pheromone, insecticide or predecessor insecticide, pharmaceutically active compound or pharmaceutical intermediate product, perfume or predecessor odorants. Some examples of these biologically active compounds include 1-chloro-5-mission, 8,10-dodecadienol, 3,8,10-dodecadienol, 5-destillat, 11-tetradecanoate, 1,5,9-tetradecane and 7,11-hexadecanoate. The latter is a pheromone, industrial available under the trade name of Gossyplure, useful in the control of pests in connection with the fact that it destroys the maturation and reproductive cycles of specific target insect species, which can be obtained from 1,5,9-tetraacetate, the latter can be obtained from cyclooctadiene and 1-hexene in accordance with the present invention.

When performing the reaction of olefinic exchange of the present invention, although in most cases this reaction proceeds very quickly, can be beneficial for several specific olefins, to improve speed and/or exit of the reaction, optionally enter the olefin into contact with socialization - Lewis acid (b1) and/or activator of the catalyst (b2). Acetalization (b1type Lewis acid may be selected from the group consisting of trihalogen boron; trialkylborane; trailmore; alyuminiiorganicheskikh compounds; halides magni is; the aluminum halides, halides of titanium or vanadium, preferably of titanium tetrachloride; pentachloride antimony and bismuth. For example, socialization - Lewis acid (b1can be alyuminiiorganicheskikh a compound selected from the group consisting of tri-n-alkylamines; dialkylaminoalkyl, trialkylaluminium, alkoxides alkylamine, alkoxides dialkylamino, aryloxides diallylamine and halides dialkylamide. Activator catalyst (b2may be, for example, vatsayana, such as, but not limited to, ethyl diazo acetate and trimethylsilyldiazomethane.

In contrast, the exchange reaction of polymerization with ring opening (ROMP) using catalytic components of the invention can for olefinic monomers such as Dicyclopentadiene or its oligomers (i.e. adducts Diels-alder reaction formed with approximately 1-20 cyclopentadienyl links) or their mixtures with strained monocyclic or condensed polycyclic olefins (such as defined in U.S. patent No. 6235856, the content of which is incorporated in this description by reference thereto), take place so quickly that the control of the polymerization could be a problem in the absence of appropriate measures. With this type of problem may also be encountered during the molding t is maturedaily polymers, liquid olefin monomer and catalyst are mixed and poured, cast or injections in shape, and in which upon completion of the polymerization (i.e. the “curing” of the product) of the molded part is removed from the form before any processing after curing, which may be required, as, for example, the reaction injection molding (“RIM”). It is well known that the ability to control the reaction rate, i.e. the viability of the reaction mixture becomes more important when molding large parts or parts with the use of this technique. Using the catalytic components of this invention prolongation of viability and/or controlling the speed of curing of the exchange reaction of olefins can be carried out in various ways, such as increasing the ratio of catalyst/olefin and/or adding a polymerization retarder to the reaction mixture. In addition, this can be achieved by using the improved embodiment in practice including

(a) the initial stage of contacting the catalytic component (optional on the substrate) metathesis of olefins according to the invention with the olefin in the reactor at the initial temperature at which the specified catalyst component of the metathesis reaction of olefins is essentially directionspanel (inactive), and

(b) the second stage of bringing the reactor temperature (for example, heating the contents of the specified reactor) to a second temperature above the first temperature, at which the specified catalytic active component, until complete the polymerization.

In a more specific embodiment, this improved embodiment, the heat activation occurs intermittently, not continuously, for example, by repeating a sequence of stages (a) and (b).

In the framework of this method the controlled polymerization should be understood that directionspanel catalytic component in the first stage depends not only on the first temperature, but also on the nature of the olefin (olefin)used in the technology RIM, and the ratio of olefin/catalyst component. Preferably the first temperature is about 20°C, but for some olefins or some ratio of olefin/catalyst component may even be appropriate cooling of the reaction mixture below room temperature, for example up to about 0°C. the Second temperature is preferably above 40°C and can be up to 90°C.

In ROMP with the use of catalytic components of this invention are easily derived linear or transverse cross-linked polymers mentioned above strained cyclic olefins, such to the to polynorbornene and polydicyclopentadiene, with well-controlled characteristics, i.e. the average molecular weight and distribution of molecular weight (polydispersity). In particular, can be obtained norbornene polymers with an average molecular weight ranging from about 200,000 up to 2,000,000 and distribution of molecular weight (polydispersity) of about from 1.1 to 2.2. Polymerization, in particular when it takes the form, such as in the method of the RIM, can occur in the presence of one or more auxiliary substances, such as antistatics, antioxidants, ceramic materials, light stabilizers, plasticizers, dyes, pigments, fillers, reinforcing fibers, lubricants, adhesion promoters, reinforcing viscosity agents and agents that contribute to the recess of forms, all of these support materials are well known in the technique.

Depending on the particular reaction involved in this sixth aspect of the present invention, and particularly when the specified response is a ROMP of strained cyclic olefins, the reaction can also favorably be carried out in conditions of radiation of visible light or ultraviolet light, for example using a source of visible light or ultraviolet light, capable of delivering sufficient energy to the reaction system.

In yet another embodiment of the sixth aspect of the present invention, the catalytic component is used for the reaction of the radical connection with the transfer of atoms (ATRA) polyhalomethanes alkane CXCl 3in which X represents hydrogen, C1-7alkyl, phenyl or halogen, olefin or diolefin. This reaction is preferably conducted in the presence of organic solvent in a molar excess polyhalomethanes alkane, and in the temperature range between about 30°and 100°C. Suitable examples polyhaloidorganic alkanes are carbon tetrachloride, chloroform, trichloromethane and chetyrehhloristy carbon. Examples of suitable olefins for this reaction radical accession include internal and cyclic olefins, and terminal olefins having the formula RR'C=CH2in which R and R', each independently, can be selected from hydrogen, C1-7of alkyl, phenyl and carboxylic acids or ether complex, for example vinylaromatic monomers, such as styrene or vinyltoluene, esters of α,β-ethylene unsaturated acids, such as C1-7alkylacrylate and methacrylates, Acrylonitrile and similar.

In yet another embodiment of the sixth aspect of the present invention the catalytic component is used for the radical polymerization atom transfer or groups (ATRP) of one or more radically (co)polymerized monomers. For the success of living/controlled radical polymerization described in this embodiment, it is important to achieve a rapid exchange between growing for Alami, present at low stationary concentration (in the range of about 10-8mol/l to 10-6mol/l), and dormant chains that are present at higher concentrations (typically in the range of about 10-4mol/l to 1 mol/l). Therefore, it may be desirable to select the appropriate amount of the catalytic component of the invention and radically (co)polymerized monomer(monomers) in such a way as to achieve these limits concentrations. If the concentration of growing radicals exceeds about 10-6mol/l, possibly in reaction to too many active particles, which can lead to undesirable increase in the rate of adverse reactions (for example, radical-radical quenching, radical separation from other particles than the catalyst, and so on). If the concentration of growing radicals is less than about 10-8mol/l, the rate of polymerization may be desirable slow. Similarly, if the concentration of dormant chains is less than about 10-4mol/l, the molecular weight of the obtained polymer can dramatically increase, thus leading to potential loss of control over its polydispersity. On the other hand, if the concentration of dormant chains is higher than 1 mol/l, the molecular weight of the reaction product can is likely to become too small and result in properties, the corresponding oligomer with no more than about 10 Monomeric units. In the mass concentration of dormant chains of about 10-2mol/l gives a polymer having a molecular weight of about 100,000 g/mol.

Various catalytic components of the present invention are suitable for radical polymerization of any radically polymerized ethylene or acetylanthracene compounds including acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid, amides of acrylic acid, amides of methacrylic acid, imides (such as N-cyclohexylmaleimide and N-phenylmaleimide), sterols, diene or mixtures thereof. Through the use of these compounds in single-stage or multi-stage procedure, they are able to provide controlled or regulated copolymers having different structures, including block copolymers, statistical, gradient, star, graft, comb-shaped, hyperbranched and dendritic (co)polymers of different monomer compositions, and respectively having desired properties such as heat resistance, scratch resistance, solvent resistance, etc.

More specifically, monomers suitable for ATRP include monomers of the formula R31R32C=CR33R34in which

- R31and R32independently selected and is a group, consisting of hydrogen, halogen, CN, CF3With1-20the alkyl (preferably1-6the alkyl), α,β-unsaturated C2-20the quinil (preferably acetylenyl), α,β-unsaturated C2-20alkenyl (preferably vinyl), optionally substituted (preferably at the α-position) halogen, C3-8cycloalkyl, phenyl, optionally bearing 1-5 substituents;

- R33and R34independently selected from the group consisting of hydrogen, halogen (preferably fluorine or chlorine), C1-6the alkyl and R35(where R35selected from hydrogen, alkali metal or With1-6the alkyl), and

at least two of R31, R32, R33and R34represent hydrogen or halogen.

Accordingly vinylethylene monomers suitable for ATRP in this embodiment of the sixth aspect of the invention, include, but are not limited to, 2-vinylpyridine, 6-vinylpyridine, 2-vinylpyrrole, 5-vinylpyrrole, 2-vinyloxy, 5-vinylacetal, 2-vinylthiazole, 5-vinylthiazole, 2-vinylimidazole, 5-vinylimidazole, 3-vinylphenol, 5-vinylphenol, 3-vinylpyridine, 6-vinylpyridine, 3-virilization, 3-virilization, 2-vinylpyridine, 4-vinylpyridine, 6-vinylpyridin and any vinylpyrazine, most preferred is 2-vinylpyridine.

Other preferred monomers include:

- (meth)acrylic EPE is s 1-20spirits

- Acrylonitrile,

- cyanoacrylate esters With1-20spirits

- complex diesters - delegitimate1-7spirits

- vinylketones, and

- styrene, optionally bearing From1-7alkyl group on the vinyl fragment (preferably at the α carbon atom) and/or bearing from 1 to 5 substituents on the phenyl ring, and these substituents selected from the group consisting of C1-7of alkyl, C1-7alkenyl (preferably vinyl or allyl), C1-7the quinil (preferably acetylenyl)1-7alkoxy, halogen, nitro, carboxy, C1-7alkoxycarbonyl, hydroxy, protected1-7acyl group, cyano and phenyl.

The most preferred monomers for ATRP are methyl acrylate, methyl methacrylate, butyl acrylate, 2-ethyl hexyl acrylate, Acrylonitrile, maleimide and styrene.

In this embodiment the catalytic component of the invention preferably is used in combination with one or more initiators having a portable radial mechanism atom or group, since ATRP catalyst system based on reversible formation of growing radicals in a redox reaction between the metal component and the initiator. Suitable initiators can be selected from the group consisting of compounds of the region have the General formula R 35R36R37CX1in which

- X1selected from the group consisting of halogen, OR38(where R38selected from the group consisting of C1-20of alkyl, polyhalogen-C1-20of alkyl, C2-20the quinil (preferably acetylenyl)2-20alkenyl (preferably vinyl or allyl, phenyl, optionally substituted by 1-5 substituents selected from the group consisting of halogen and C1-7the alkyl and phenylseleno1-7the alkyl), SR39, OC(=O)R39, OP(=O)R39, OP(=O)(or SIG39)2, OP(=O)or SIG39, O-N(R39)2and S-C(=S)N(R39)2where R39represents aryl or1-20alkyl, or, when there is a group N(R39)2at the specified X1two R39groups can be combined to form a 5-, 6 - or 7-membered heterocyclic ring (in accordance with the definition above), and

- each of R35, R36and R37independently selected from the group consisting of hydrogen, halogen, C1-20the alkyl (preferably1-7the alkyl), C3-10cycloalkyl, C(=O)R40(where R40selected from the group consisting of C1-20of alkyl, C1-20alkoxy, aryloxy or heteroaromatic), C(=O)NR41R42(where R41and R42independently selected from the group consisting of hydrogen and C1-20the alkyl, or R41and R42may be the b connected together, forming a 5-, 6 - or 7-membered heterocyclic ring (in accordance with the definition given above), COCl, OH, CN, C2-20alkenyl (preferably vinyl), C2-20the quinil, oxiranyl, glycidyl, aryl, heteroaryl, arylalkyl and aryl-substituted C2-20alkenyl.

In the last initiators X1is preferably bromine, which provides a higher reaction rate and a lower polydispersity polymer.

When one of the groups R35, R36and R37selected alkyl, cycloalkyl or alkyl substituted aryl group, the alkyl group may be optionally substituted by a group X1defined above, in particular a halogen atom. Thus, it is possible that the initiator has served as a source of molecules for branched, comb-shaped or star (co)polymers of virtually any type or geometry. One example of such initiator is 2,2-bis(halogenmethyl)-1,3-dehalogenated (for example, 2,2-bis(chloromethyl)-1,3-dichloropropane or 2,2-bis(methyl bromide)-1,3-dibromopropane), and a preferred example is one in which one of R35, R36and R37represents phenyl substituted by one to five With1-7alkyl substituents, each of which may be independently optionally substituted by a group X1for example, α,α'-bromocyclen, hexacis(α-chloro - or α-methyl bromide)benzene.

Preferred initiators include 1-phenylethylene and 1-fenilatilamin, chloroform, carbon tetrachloride, 2-chloropropionitrile and C1-7alkalemia esters of 2-halogen-C1-7saturated monocarboxylic acid (such as 2-chloropropionic acid, 2-bromopropionic acid, 2-horizonally acid, 2-brometalia acid and similar). Another example of a suitable initiator is dimethyl-2-chloro-2,4,4-trimethylpentane.

For use in this embodiment of the invention is any suitable complex of the transition metal, which can participate in a redox cycle with the initiator and dormant polymer chain, but which does not form a direct bond to the carbon-metal with carbon chain, such as a complex of ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, technetium, lanthanum, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, Nickel or cobalt. The number and relative molar proportions of the initiator and of the complex of the transition metal of the invention are those which are effective for holding ATRP. The molar ratio of the complex transition metal with respect to the initiator may be from 0.0001:1 to 10:1, preferably from 0.1:1 to 5:1, more preferably from 0.3:1 to 2:1, and most predpochtite the flax from 0.9:1 to 1.1:1.

ATRP according to the invention can be carried out in the absence of a solvent, i.e. in the mass. However, when a solvent is used, suitable solvents include ethers, cyclic ethers, alkanes, cycloalkanes, aromatic hydrocarbons, halogenated hydrocarbons, acetonitrile, dimethylformamide and mixtures thereof, and supercritical solvents (such as CO2). ATRP can be carried out in accordance with known suspension, emulsion methods or by deposition. Suitable ethers include diethyl ether, ethylpropyl ether, DIPROPYLENE ether, methyl tert-butyl ether, di-tert-butyl ether, glyme (dimethoxyethane), diglyme (diethylethylenediamine ether), etc. Suitable cyclic ethers include tetrahydrofuran and dioxane. Suitable alkanes include pentane, hexane, cyclohexane, octane and dodecane. Suitable aromatic hydrocarbons include benzene, toluene, o-xylene, m-xylene, p-xylene and cumene. Suitable halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane and benzene substituted by 1-6 fluorine atoms and/or chlorine, although you should make sure that selected halogenated hydrocarbon is not acting as the initiator in the reaction conditions.

ATRP can be carried out in the gas phase (for example, by passing a gaseous monomer(monomers) above the layer CA is aliciously system), in a sealed vessel or autoclave. (Co)polymerization can be carried out at a temperature of from about 0 to 160°C, preferably from about 60 to 120°C. Typically, the average reaction time is about 30 minutes to 48 hours, more preferably from 1 to 24 hours. (Co)polymerization can be carried out under a pressure of from about 0.1 to 100 atmospheres, preferably from 1 to 10 atmospheres.

According to another embodiment of the ATRP can be carried out in emulsion or suspension in suspendida environment for the suspension of the monomer(s) and using the metal complex of the invention in combination with a surface active agent to form an emulsion or suspension (co)polymer. Suspendida environment is usually inorganic liquid, preferably water. As suspendida elects water or an aqueous mixture, it is preferable to use as the catalytic component of cationic particles of a complex of the metal, and these cationic particles associated with anion And, as described above. In this embodiment of the invention the weight ratio of organic phase to suspendida environment is usually between 1:100 and 100:1, preferably between 1:10 and 10:1. If desired suspendida environment can supererogate. Preferably, the surface-active agent is selected to control the financial stability of the emulsion, i.e. for the formation of a stable emulsion.

In order to carry out the polymerization in a heterogeneous environment (when the monomer/polymer is insoluble or only slightly soluble in the suspension medium, i.e. water or CO2), metal catalytic component must be at least partially soluble in the monomer/polymer. Thus, only when the ligands are chosen properly, in order to allow the catalyst to meet this requirement, such as ligands, containing long alkyl chains to increase the solubility of the catalyst in the hydrophobic monomers subjected to polymerization, the process is successfully controlled ATRP polymerization in aqueous systems of this embodiment. Based on the above description of ligands that coordinate the metal in the catalytically active metal complexes of the invention, specialists in the art will be able to make the suitable selection.

A key component in obtaining stable emulsions of the present embodiment is the use of surface-active agent to stabilize the initial suspension/emulsion of the monomer and the particle growing polymer, and to prevent unwanted coagulation/flocculation or flocculation of the particles. In order, however, to conduct ATRP in emulsion, after which the duty to regulate to take precautions in the choice of surface-active agent, which does not interfere with the catalytic component or the inactive end of the chain. Suitable surfactants for this purpose include nonionic, anionic and cationogenic surfactants, and cationogenic and nonionic surfactants are preferred in nezasorennyh solutions. Especially preferred nonionic surfactants include polyethylene glycol, polyoxyethylenesorbitan esters and polyoxyethylenesorbitan. Preferred cationogenic surface-active substance is dodecyltrimethylammonium. Regardless of the used surfactant for obtaining good dispersions or latexes preferably efficient mixing.

Surfactants are usually present in concentrations of about 0.01-50% by weight calculated on the total weight of all components, is introduced into the polymerization reactor, i.e. suspendida environment, monomer(monomers), surfactant and catalyst system.

High solubility in the suspension medium is not a necessary condition for the initiator, as can be demonstrated by the use of poorly soluble in water, ethyl 2-bromoisobutyrate, to initiate emulsion polymerization. Even though IP is to olsavica any order of addition of the initiator and other reaction components, however, if the initiator is added to the pre-emulsified reaction mixture, usually obtained stable latexes. Suitable initiators are described here above in relation to embodiments relating to the solvent of the ATRP process. The initiators can be macromolecules that contain radically portable atoms or groups. A particular type of such macroinitiator may be water-soluble or even amphiphilic and can, after initiation of the reaction, be introduced into the polymer particle, and can stabilize the growing particles due to the hydrophilic segment of the macroinitiator.

After the completion of stage ATRP copolymerization process of this invention formed by the polymer can be isolated by known methods, such as, but not limited by them, the precipitation in a suitable solvent, filtering the precipitated polymer, and then washing and drying the filtered polymer. The deposition can be carried out usually using a suitable alkangovolo or cycloalkanones solvent, such as pentane, hexane, heptane, cyclohexane, or white spirits, or using alcohol, such as methanol, ethanol or isopropanol, or any mixture of suitable solvents. Besieged (co)polymer can be filtered by gravity or vacuum filtration, i.e. using the funnel Buhne the a and the suction pump. The polymer may then be washed with the solvent used for the deposition of the polymer, if desired. Stage sedimentation, filtration and washing may be repeated, if desired. Dedicated (co)polymer may be dried by passing air through (co)polymer, with the help of vacuum. Dried (co)polymer can then be analyzed and/or characterized, for example, by gel permeation chromatography or NMR spectroscopy.

(Co)polymers obtained by ATRP catalytic process of the present invention may be useful mainly as a molding material (e.g. polystyrene) and as a barrier or surface materials (e.g., polymethylmethacrylate). However, since they usually have more uniform properties (in particular, the distribution of molecular weight)than the polymers produced conventional radical polymerization, they will be most suitable for use in specialized applications. For example, block copolymers of polystyrene (PSt) and polyacrylate (PA), such as PSt-PA-PSt triblock copolymers are useful thermoplastic elastomers. The polymethyl methacrylate/acrylic triblock copolymers (for example, PMMA-PA-PMMA) are useful, fully acrylic, thermoplastic elastomers. Homo - and copolymers of styrene, (meth)acrylates and/and and Acrylonitrile are useful plastic materials, elastomers and adhesives. And statistical or block copolymers of styrene and (meth)acrylate or Acrylonitrile are useful thermoplastic elastomers having a high resistance to solvents. In addition, block copolymers, in which alternating blocks of polar monomers and non-polar monomers, obtained by the present invention are useful amphiphilic surfactants or dispersing agents for the production of highly homogeneous polymer mixtures. Star (co)polymers, for example, styrene-butadiene star block copolymers are useful as materials having high impact resistance.

(Co)polymers obtained by ATRP catalytic process, usually have an average numerical molecular weight of from about 5000 to 1000000, preferably approximately from 10,000 to 250,000, and more preferably from about 25,000 to 150000.

Since ATRP is a process of living polymerization, it can start and stop almost at will. Further, the polymer product has functional group X1necessary to initiate further polymerization. Thus, in a particular embodiment, once the first monomer is consumed in the initial stage of polymerization, then you can add a second monomer for the formation of Deuteronomy is the first block on the growing polymer chain in the second stage polymerization. Next, to obtain poly-block copolymers can be further polymerization processes with the same or different monomer(monomers). In addition, since ATRP is also radical polymerization, the data blocks can be essentially in any order.

(Co)polymers obtained by ATRP catalytic process of the present invention have a very low index polydispersity, i.e. the ratio of Mw/Mntheir average-weight molecular weight to their srednecenovom molecular weight is usually about from 1.1 to 2,4, preferably from 1.15 to 2.0, more preferably from 1.2 to 1.6.

Because living (co)polymer chains retain a fragment of the initiator, including X1as of the end groups, or in one of the embodiments as Deputy in the monomer link in the polymer chain, they can be (co)polymers with terminal functional groups or functional groups in the chain. Such (co)polymers can thus be transformed into the (co)polymers with different functional groups (for example, the halogen may turn into a hydroxy or amino with known methods, and the nitrile or ester of carboxylic acids can be either hydrolyzed to carboxylic acids known methods) for further reactions, including the stitching, the elongation of the chain with reactio nesposobnyi monomers (for example, for the formation of long-chain polyamides, polyurethanes and/or polyesters), reactive injection molding, and similar.

To facilitate the use of metal complexes according to the invention in the above-mentioned heterogeneous catalytic reactions, the present invention further provides a silyl derivatives of such complexes, which are suitable for covalent binding with the media, especially those of the complexes with polydentate ligand is a bidentate or tridentate Chiffolo base, such as base having the General formula (IA) or (IB)shown in figure 1, or tetradentate ligand, including two Chippewa reasons, such as having General formula (IIA) or (IIB) or (IIC), indicated in figure 2, or the General formula (IIIA) or (IIIB)shown on figure 3. In such silyl derivatives of R' and/or R" specified General formula replaced or substituted by a group having the formula:

-R20-(CH2)n-D-Si-R21R22R23(VIII)

in which

- R20represents a radical selected from the group consisting of C1-7alkylene, arylene, heteroaryl and C3-10cycloalkene, and the specified radical optionally substituted by one or more substituents R24, each of which is independently selected from the group status is the present from C 1-20of alkyl, C2-20alkenyl,2-20the quinil,1-20of carboxylate, With1-20alkoxy, C2-20alkenylacyl,2-20alkyloxy,2-20alkoxycarbonyl,1-20alkylsulfonyl,1-20alkylsulfonyl,1-20alkylthio, aryloxy and aryl;

- D represents a divalent atom or a radical selected from the group consisting of oxygen, sulfur, silicon, arylene, methylene, CHR24C(R24)2, NH, NR24and PR24;

- R21, R22and R23each independently selected from the group consisting of hydrogen, halogen and R24; and

n represents an integer from 1 to 20;

provided that at least one of R21, R22and R23selected from the group consisting of C1-20alkoxy, C2-20alkenylacyl,2-20alkyloxy,2-20alkoxycarbonyl,1-20alkylsulfonyl,1-20alkylsulfonyl,1-20alkylthio, aryloxy.

Preferable in the above group are silyl derivatives, in which R' is replaced or substituted 3-(triethoxysilyl), sawn or 2-(triethoxysilyl)ethyl group. Alternatively, suitable derivatives include molded organosiloxane products copolycondensation, such as described in EP-A-484755.

According to another embodiment of the invention provides a catalyst on the substrate, obinna for use in the above-mentioned catalytic reactions, includes product covalent binding (a) a silyl derivative of a complex of a metal, such as defined here above, and (b) a carrier comprising one or more inorganic oxides or organic polymeric material. Preferably specified inorganic carrier is selected from silica, alumina-silica, Zirconia, natural and synthetic zeolites and mixtures thereof, or the specified organic polymer carrier is a polystyrene resin or its derivative, in which the aromatic ring is substituted by one or more groups selected from C1-7of alkyl, C3-10cycloalkyl, aryl and heteroaryl. More detailed examples of suitable carriers (b) for this purpose already described in the fifth aspect of the invention.

The catalytic component according to the sixth aspect of the present invention is also useful in cyclopropylamine ethyleneimine compounds, or intramolecular cyclopropanation α-diazo ketones or α-diazo-β-ketoesters to obtain compounds having one or more gives rise to structural units in the hydrocarbon chain. This embodiment of the invention is useful, therefore, in one or more stages to obtain the following natural and synthetic cyclopropylacetic compounds. Cyclopropylalanine soedineniya to be found in found in nature the terpenes, steroids, amino acids, fatty acids, alkaloids and nucleic acids. For example, derivatives khrizantemova acid (such as pyrethrins)produced in plants, are precursors of strong insecticides. The invention is applicable also to the production of synthetic PYRETHROID insecticides such as deltamethrin and SIRENIA, aristona, sesquiterpene and cyclopropyl derivatives, which are intermediates in the synthesis of steroid giratina or antibiotic seromycin. Cyclopropylalanine unnatural compounds also possess biological activity, such as cipro is a strong remedy for anthrax, or cyclopropanecarboxylate (for example, 2,3-melaniemelanie, a cure for Parkinson's disease - 2,3-methane-m-tyrosine, coronation and cornamona acid). Politicophobia derivatives of fatty acids isolated from fungi, U-106305 (transfer inhibitor protein cholesterolemia of ester) and FR-900848 (nucleoside analogue), are also candidates for such synthetic production. Compounds with ethylene unsaturation, which can cyclopropaneacetic according to this invention, respectively cyclopropylamine compounds is not specifically limited and include, without limitation, compounds having terminal ethylene ninasimone is, such as styrene (which in the presence of ethyl diazo acetate can be converted to ethyl-2-phenylcyclopropanecarboxylic) and its substituted derivatives (for example, 4-chloresterol, α-methylsterols and ministeral), 2-vinylnaphthalene, 1,1-diphenylethylene, 1-mission functional α-olefins, in which the functional group is preferably contiguous with ethylene unsaturation and preferably represents a protected alcohol, such as in protected allyl alcohols, such as simple acyclic allylsilanes esters (which can be converted into cyclopropanecarbonitrile esters) or carboxypropyl, such as acrylic and methacrylic acids (as well as their esters, thioethers, Amidah or anhydrides), cinnamate esters, alkenylboronic esters (such as 2-mailinator-4,5-bis[methoxycarbonylmethyl]-1,3,2-dioxaborolane or derivatives thereof, in which a methyl group protected by a protective group, such as, but not limited by them, tert-butyldimethylsilyloxy, tert-butyldiphenylsilyl, benzyloxy, methoxyethoxy or benzoyloxy, which can be transformed into the corresponding cyclopropylboronic esters), 2-phenylsulfonyl-1,3-diene and cycloolefin, such as cyclooctene. This reaction preferably occurs in the presence of diazocompounds, such as, but not limited by them, ativates the tat, cinnamylpiperazine, dicyclohexylthiourea, fenildiazoetanom, methyldiazonium or 1-diazo-6-methyl-5-hepten-2-he, at moderate temperatures in the range of from about 0 to 80°C., preferably 20-60°C., the reaction time in the range of about 1 to 12 hours, and in a relatively low-boiling solvent, such as methylene chloride, tetrahydrofuran, ethanol, isopropanol, tert-butanol, L-menthol or water or mixtures thereof. Diazoketone can be added as such, or to eliminate the risk of handling due to its explosive nature, can be generated in situ through reaction acetamino salt with sodium nitrite in the presence of Ethylenediamine connection. When the solvent for the reaction choose water or a water mixture, it is preferable to use as the catalytic component of the complex metal cation type, and the specified cationic type associated with anion And, as described above. Preferably the molar ratio Ethylenediamine connection to the catalytic component is in the range from 200 to 2000, more preferably from 250 to 1500. The molar ratio Ethylenediamine connection to diazoketone is common for this type of reaction, i.e. the molar excess of the first connection. Cyclopropylamine Ethylenediamine connection of the clusters may not necessarily be carried out in the presence of a tertiary aliphatic amine, such as triethylamine or tri-n-butylamine, or a heterocyclic amine such as pyridine or lutidine, as socializaton. Intramolecular cyclopropanation α-diazocarbonyl compounds, such as α-diazo ketones or α-diazo-β-ketoesters, may also be carried out under similar reaction conditions (temperature, reaction time, the ratio substrate/catalyst) and may result in bicyclic molecules in which cyclopropyl group may be condensed with another cycloaliphatic group, such as Cyclopentanone, such as in the synthesis of intermediate compounds of giratina or sarcolysin, or cyclopentenone group when coming from acetylene α-diazoketones. However, it should be noted that in accordance with the recommendations Padwa in Molecules (2001) 6:1-12 cyclization of acetylenic α-diazoketone in the presence of catalytic component of the present invention may also lead to the formation of other polycyclic ring systems such as, but not limited to them, Cyclopentanone, condensed with furan, alkenylsilanes indene, cyclopropylmethyl indene, cyclopentadiene or cyclopentadiene, condensed with indenones.

Catalytic component of the sixth aspect of the present invention is also useful in cyclopropylamine alkynes to gaining the compounds with one or more cyclopentenone structural units in the hydrocarbon chain. This applies in particular to alkynes having From2-7alkylamino group, such as, but not limited by them, 1-hexyne, 3,3-dimethyl-1-butyn, phenylacetylene, cyclohexylacetate, methoxyethylamine and acetoxylation that can be transformed with good outputs in ethylcyclopropane-3-carboxylates in the presence of diazocompounds, such as, but not limited to, ethyl diazo acetate, cinnamylpiperazine, dicyclohexylthiourea, fenildiazoetanom, 1-diazo-6-methyl-5-hepten-2-he or methyldiazonium. It is also useful when the intramolecular cyclopropenone acetylene α-diazoketones, leading, for example, to cyclopropylmagnesium compounds, such as cyclopropylamine indanone.

Catalytic component of the sixth aspect of the present invention are also useful in the synthesis of quinoline via oxidative cyclization of 2-aminobenzamide alcohol ketones (i.e. the so-called reaction Friedlander). This reaction preferably takes place with a molar excess of a specified ketone in alkaline conditions (such as in the presence of alkali metal hydroxide), at moderate temperatures usually in the range of from about 20 to about 100°C. and optionally in the presence of a solvent. Preferably Rel is the solution of 2-aminobenzamide alcohol by catalytic component is in the range from 100 to 2000, preferably from about 200 to about 1000. In the process of the invention can be used a number of alkylalcohol, alkylchlorosilanes, dialkylamino and benzododecinium cyclic ketones, including C1-7alkylene, in which the second hydrocarbon attached to oxoprop can be methyl, pentyl, isopropyl, phenethyl, phenyl, tolyl, anisyl, nitrophenyl, hydroxyphenyl, forfinal, triptoreline, cyanophenyl, naphthyl, furanyl, thiophenyl, pyridyl and similar. Exemplary ketones, which can cilitates in quinoline, according to this embodiment of the invention include, but are not limited to, acetophenone, 3-methylacetophenone, cyclohexanone, 4-phenylcyclohexanone and propiophenone. Other suitable alcohols for this purpose are described by the authors Cho et al. in Chem. Commun. (2001) 2576-2577. Surprisingly, some ketones, such as cyclohexanone, can be transformed into the corresponding quinoline with the release of significantly higher under equivalent reaction conditions, than is achieved with ruthenium catalyst used in recent publications.

Catalytic component of the sixth aspect of the present invention is also useful in intramolecular epoxydecane, including asymmetric epoxidation ethyleneimine compounds, i.e. alkenes, to obtain the corresponding epoxides (i.e. oxa is ecoprojection compounds). Such alkenes include, for example, but without limitation specified, styrene and its analogs (such as α-methylsterols, p-chloresterol, p-cryptomaterial and similar) or cholesterylester. Illustrative olefinic source reagents useful in asymmetric epoxydecane of the present invention include reagents that can be unsaturated at the end or inside and consist of a straight chain, branched chain or cyclic structure. Such olefinic reagents can contain from 3 to about 40 carbon atoms and may contain one or more Ethylenediamine groups. In addition, such olefinic reagents may contain groups or substituents which do not have a significant adverse impact on the asymmetric epoxidation, such as carbonyl, carbonyloxy, oxy, hydroxy, oxycarbonyl, halogen, alkoxy, aryl, halogenated and similar. Illustrative olefinic unsaturated compounds include substituted and unsubstituted alpha-olefins, internal olefins, alkylalcohol, alkenylamine, alkenylsilanes esters, alkanol and similar, for example propylene, 1-butene, 1-penten, 1-hexene, 1-octene, 1-mission 1-dodecene, 1 octadecene, 2-butene, isoamylene, 2-penten, 2-hexene, 3-hexene, 2-hepten, cyclohexene, 2-ethylhexane, 3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadien, 1,5,9-dodecatrien,3-cyclohexyl-1-butene, allyl alcohol, Gex-1-EN-4-ol, Oct-1-EN-4-ol, acetate, ZIOC scientists, arylate, such as vinylbenzoate, and similar, 3-butylacetat, finalproject, arylpropionate, allylmalonate, methyl methacrylate, 3-butylacetat, unilateraly ether, vinylmations ether, arelatively ether, n-propyl-7-octenoate, substituted and unsubstituted the chromenes, 2,2-dimethylcyclopropane, 3-butenonitrile, 5-hexanamide, inden, 1,2-dihydronaphthalene, 2-vinylnaphthalene, norbornene, CIS-stilbene, TRANS-stilbene, p-isobutylester, 2-vinyl-6-methoxy-naftilan, 3-ethenylene-phenylketone, 4-ethylphenyl-2-titillation, 4-ethynyl-2-fluoro-biphenyl, 4-(1m,3-dihydro-1-oxo-2H-isoindole-2-yl)styrene, 2-ethyl-5-benzoylthiophene, 3-ethynyl-finalfantasy ether, isobutyl-4-propenylbenzene, phenyleneoxy ether, 2-cyclohexene-1,1-dioxolane, vinyl chloride, connection benzopyranones and benzofuranol type, and substituted arelatively, such as described in U.S. patent No. 4329507, the entire contents of which is included in this description by reference no. Epoxidation according to the invention can be applied to the synthesis of biologically active molecules, such as oxide, CIS-stilbene (substrate for microsome and cytosol of epoxyphenols) and isoprostane.

This epoxidation reaction preferably occurs in the presence of at least stoichiometric quantity (relative to e is rinnensysteme connection) source, an oxygen atom or reagent transfer of oxygen, being a relatively directionspanel to olefins in the absence of the catalytic system under the prevailing conditions (e.g. temperature and pressure). The specified source of the oxygen atom or reagent transfer of oxygen can be, without limitation, selected from the group consisting of H2About2(hydrogen peroxide), NaOCl, biodosimetry, NaIO4The MBC4IO4, peroxymonosulfate potassium, monoperoxyphthalate magnesium, N-oxide 2,6-dichloropyridine and hexacyanoferrate ion. Can also be used mixtures of such sources of oxygen or agents of oxygen transport. This epoxidation reaction preferably takes place under the conditions and within such period of time that is required for the epoxidation of olefinic unsaturated compounds. Such conditions include, without limitation specified,

the reaction temperature is usually in the range of from about -20°C. to about 120°C., preferably from 0 to 90°C, more preferably from 20 to about 40°C., and/or

- the reaction pressure in the range of from about 0.1 to about 70 bar, and/or

- carrying out the reaction in the presence of a solvent for the catalyst system, preferably a relatively low-boiling organic solvent selected from the group consisting of saturated alcohols, amines, alkanes, ethers, complex EPE is s, aromatic compounds and similar, and/or

- molar ratio Ethylenediamine connection to the catalytic component in the range from about 200 to about 20,000, preferably from 500 to 10,000, and/or

- molar excess of the reagent transfer of oxygen relative to the olefinic unsaturated compound.

Catalytic component of the sixth aspect of the present invention are also useful in the oxidation of hydrocarbons to alcohols, such as, but not limited to them, the oxidation of methane (which is known to be more difficult to oxidize than other alkanes) in methanol. Although this process is effective for a wide variety of hydrocarbons, it is particularly effective for the oxidation of alkanes with straight chain and branched chain and cycloalkanes with 1-15 oxygen atoms, and arylalkyl, such as toluene, xylene and ethylbenzene. Preferred aliphatic hydrocarbons have 1-10 carbon atoms, including ethane, propane, butane, isobutane, hexane and heptane; and preferred cyclic hydrocarbons have 5 to 10 carbon atoms, such as cyclopentane, cyclohexane, Cycloheptane, cyclooctane and adamantane. This invention is applicable also to a broad range of hydrocarbons containing different substituents to enhance the rate of oxidation. The oxidation according to this invention can be carried out in the liquid phase, in which the mixed solvent system, such as water/acetone, water/acetonitrile and/or acetic acid, which is inert to the reaction conditions and the oxidation by molecular oxygen. The temperature can be between 20 and 60°C. the Pressure may be in the range of 5 to 20 atmospheres. Depending on whether the hydrocarbon solid, liquid or gas, he or dissolved in the mixed solvent system, or barbatiruem through the solvent together with air or oxygen before adding the catalytic component of the invention. Concentration in the range from 10-3up to 10-6mol catalytic component in the solution is usually sufficient to achieve the desired oxidation. The reaction time is preferably from 30 minutes to 30 hours, more preferably from 1 to 5 hours. According to another embodiment of the catalytic component of the sixth aspect of the present invention are also useful in the oxidation of allyl and benzyl alcohols to carbonyl compounds.

The sixth aspect of the present invention also applies to other transfer reactions atom or group, such as asymmetric synthesis, in which pokerline or chiral compound is subjected to reaction in the presence of an optically active metal-ligand complex catalyst, active enantiomeric form, to obtain optically active compounds. Given the reaction, which are useful for many classes of products, for example, sulfoxidov, aziridines, rolovich esters, NITRILES, silanes, cyrilovich ethers, alkanes, phosphonates, alkylboranes, hydroxycarbonyl compounds, β-cyanocobalamine compounds, carboxyl compounds, arylalkenes, heteroarylboronic, cyclohexanol, 7-exonorbornenes, aldehydes, alcohols, primary or secondary amines, amides and similar, listed here previously and will be described in detail below.

For example, the catalytic oxidation of sulfides (sulfoxidov and sulfones), phosphines (phosphonates), and alcohols or aldehydes to carboxylic acids can be carried out in accordance with generally accepted procedures oxidation, known in the art. For example, without limitation, the optically active carboxylic acid can be obtained by the reaction of racemic aldehyde and source of the oxygen atom in the presence of catalytic systems based on optically active complex of metal (or optically active metal complex catalytic system as described here. Using this stage of the process can be obtained a number of sulfoxidov which finds application in the pharmaceutical industry, such as sulfoxide quinolone, described by the authors Matsugi et al., in Tetrahedron (2001) 57:2739 (inhibitor of ADH is Ziya platelets), or sulfoxide pyrazoloacridine described by Naito et al., in Yakugaku Zasshi (2001) 121:989 (a drug for treatment of hyperuricemia and ischemic reperfusion injury), or methylphenylsulfonyl (metilfenidato of tiefer).

Catalytic hidrotsianova (or ciangherotti) α - compounds with ethylene unsaturation to obtain saturated NITRILES, or alkynes to obtain unsaturated NITRILES, or α,β-unsaturated aldehydes or ketones to obtain β-cyanocobalamine compounds can be carried out in accordance with conventional procedures known in the art. For example, 1-phenylpropanol can be transformed into 4-oxo-4-phenylbutyrate, or optically active nitrile compounds can be obtained by the reaction prehiring of olefin and hydrogen cyanide in the presence of catalytic systems based on optically active complex metal described here.

Catalytic hydrosilation of olefins to obtain saturated silanes, or alkynes to obtain unsaturated silanes, or ketone to obtain a simple cyrilovich esters, or triallylisocyanurate aldehydes (e.g. benzaldehyde) to obtain cyanovalerianic esters (which can then be either hydrolyzed in cyanohydrine) can be carried out in accordance with generally accepted procedure is AMI, known in the art. For example, optically active silanes or Silovye esters can be obtained by the reaction prehiring of olefin, or a ketone or aldehyde with a suitable silyl compound in conventional conditions hydrosilation in the presence of catalytic systems based on optically active complex metal described here.

Catalytic aziridination Iminov or alkenes to produce organic compounds having one or more aziridine structural links can be carried out in accordance with conventional procedures known in the art. For example, probiralsya olefins can become optically active aziridine in the conventional terms of aziridine in the presence of catalytic systems based on optically active complex metal described here.

Catalytic gidrogenizirovanii olefins to obtain saturated amides can be carried out in accordance with conventional procedures known in the art. For example, optically active amides can be obtained by the reaction prehiring of olefin, carbon monoxide and a primary or secondary amine or ammonia in the conventional terms of gidrolizirovanny in the presence of catalytic systems based on optically active complex metal described here.

Rolled the practical hydrogenation of olefins to alkanes or ketones to alcohols can be carried out in accordance with conventional procedures, known in the art. For example, the ketone can turn into an optically active alcohol in the conventional reaction conditions of the hydrogenation in the presence of catalytic systems based on optically active complex metal described here. Substrates that can gidrirovaniya in accordance with this embodiment of the invention, include, but are not limited to, α-(acylamino)acrylic acid (obtaining thus enantioselective chiral amino acid), α-acetamidocinnamic acid, α-benzamidomethyl acid derivative dehydrolinalool and its methyl esters, imine, complex β-ketoesters (such as methylacetoacetate) and ketones.

Catalytic aminals olefins to obtain saturated primary or secondary amines can be carried out in accordance with conventional procedures known in the art. For example, optically active amines can be obtained by the reaction prehiring olefins with primary or secondary amine in the conventional reaction conditions of aminolysis in the presence of catalytic systems based on optically active complex metal described here.

Catalytic isomerization of alcohols, preferably allyl alcohols, to obtain aldehydes can be carried out in accordance with conventional procedures known in the art. For example, alllow the e alcohols can be isomerized in the conventional reaction conditions of somerdale obtaining optically active aldehydes in the presence of catalytic systems based on optically active complex of the metal, are described here.

Catalytic reaction of crosslinking by Grignard alkyl - or aryl halides to obtain alkanes or arylalkyl can be carried out in accordance with conventional procedures known in the art. For example, optically active alkanes or arylalkyl can be obtained by the reaction of chiral Grignard reagent with an alkyl or helgaleena in the conventional reaction conditions stitching on the Grignard reagent in the presence of catalytic systems based on optically active complex metal described here.

Catalytic hydroporinae olefins (such as, but not limited to them, 4-methyl-1-penten) to obtain alkylboranes and trialkylborane (which can then be oxidized or to either hydrolyzed to alcohols) may be carried out in accordance with conventional procedures known in the art. For example, optically active alkylborane or alcohols can be obtained by the reaction prehiring of olefin and borane in the conventional reaction conditions of hydroporinae in the presence of an optically active metal complex catalytic system as described here.

Catalytic hydride recovery of aldehydes and ketones to obtain alcohols can be carried out in accordance with conventional procedures known in the art, i.e. by processing the indicated aldehyde or ketone HYDR who dnim reagent, such as sodium borohydride or aluminiumhydride lithium. For example, pentanal can recover in 1-pentanol, cyclobutanone in cyclobutanol, and cyclohexane-1,4-dione 1,4-cyclohexanediol.

Catalytic andolina condensation of saturated carboxylic compounds (aldehydes or ketones) to obtain α,β-unsaturated carboxyl compounds or β-hydroxycarbonyl compounds, and intramolecular andolina condensation of dialdehydes or diones to obtain cyclic α,β-unsaturated carboxyl compounds (aldehydes or ketones) may be carried out in accordance with conventional procedures known in the art. For example, optically active alday can be obtained by the reaction prehiring ketone or aldehyde and protected enol, such as silyl-enology ether in the usual conditions of condensation in the presence of an optically active metal complex catalytic system as described here.

Catalytic codimerization alkenes for higher saturated hydrocarbons, or alkynes for higher alkenes can be carried out in accordance with conventional procedures known in the art. For example, optically active hydrocarbons can be obtained through reaction prehiring alkene and one alkene in the reaction conditions of codimerization in the presence of the tvii optically active metal complex catalytic system, are described here.

Catalytic alkylation, preferably allylic alkylation of ketones to obtain alkyl ketones, preferably allyl ketones can be carried out in accordance with conventional procedures known in the art in the presence of a metal complex catalytic system as described here. Similarly, 1,3-diphenyl-2-propylacetate can alkylaromatic a nucleophile, such as CH2(CO2CH3)2in the presence of catalytic component of the invention.

Catalytic Diels-alder reaction, such as, but not limited to, the cycloaddition of a conjugated diene α-ethylene-unsaturated compound to obtain optionally substituted cyclohexanol, or cycloaddition of furan to α-ethylene-unsaturated compound to obtain optionally substituted 7-exonorbornenes can be carried out in accordance with conventional procedures known in the art, in the presence of a metal complex catalytic system as described here.

Catalytic joining Michael ketone or β-dicarbonyl compounds to α,β-unsaturated carboxyl compound to obtain a saturated polycarboxylic compounds can be carried out in accordance with conventional procedures known in the art, prisutstvie metal complex catalytic system, described here, i.e, for example, idolatry ion can be paired connection to α,β-unsaturated aldehyde or ketone, such as, for example, attaching acrolein to 2,4-pentanedione (acetylacetone) or 2-methylcyclohexanone. With some Michael acceptors, such as 3-butene-2-it, products of primary accession capable of subsequent intramolecular aldol condensation, the so-called annelation by Robinson, i.e. connecting 3-butene-2-it 2-methylcyclohexanone.

Catalyst for the Heck reaction can be carried out in accordance with conventional procedures known in the art, in the presence of a metal complex catalytic system as described here. Standard reaction Hake, particularly when the catalytic metal component is palladium, involves the reaction of aryl - or heteroarylboronic, for example 3-brainline, alkene, usually acrylate. Oxidative variant of the Heck reaction proceeds of certain heterocyclic compounds, such as indoles, furans and tifany, such as, but not limited to, N-acetyl-3-methylindole) are studied. Restorative option for the Heck reaction stems from some 3-allerigies, 4-allerigies and cilindrov, for example the reaction of 3-acetylpyridine with triethoxysilane.

Catalytic hydroamination olefins and alkynes to n the receipt of amines can be carried out in accordance with conventional procedures, known in the art, in the presence of a metal complex catalytic system as described here. Namely, this type of reaction is useful for the direct amination of conventional raw materials such as ethylene, ammonia to obtain ethylamine, and to attach aromatic and aliphatic amines to dianam, and to attach aromatic amines to vinieron.

Valid probiralsya and chiral starting reagents covered by the processes of this invention, are selected, of course, depending on the specific synthesis of the desired product. Such starting materials are well known in the art and can be used in conventional amounts in accordance with conventional methods. Illustrative source reagents include, for example, aldehydes (for example, for the intramolecular gidroalkilirovaniya, aldol condensation and oxidation in acid), probiralsya olefins (for example, epoxidation, hydrocyanide, hydrosilation, aziridination, gidrolizirovanny, aminolysis, cyclopropylamine, hydroporinae, the Diels-alder reaction, gidroaminirovaniya and codimerization), ketones (for example, hydrogenation, hydrosilation, aldol condensation, annelation by Robinson, hydrogenation with transfer and allylic alkylation), alkynes (e.g., on the I cyclopropenone and gidroaminirovaniya), the epoxides (for example, for hydrocyanide or nucleophilic reaction with ring opening), alcohols (for example, carbonyl, aryl halides (for example, for decarbonylation and reactions Hake) and chiral Grignard reagents (for example, the crosslinking of the Grignard reagent).

The present invention will now be further explained by reference to the following examples, which should be understood only as an illustration of various embodiments of the invention without limiting them its volume.

EXAMPLES 1-a - 1-E

Getting ligands of the class of Schiff bases

The ligands of the class of Schiff bases were obtained and purified as follows. Condensation of salicylaldehyde (10 mmol) with the appropriate substituted aniline was carried out with stirring in 40 ml of methanol at the boiling point under reflux for 4 hours. After cooling at -18°C for 24 hours, the resulting crystals were filtered and were washed with cold ethanol, then dried in vacuum at 40°C for 4 hours, giving the following outputs desired salicylaldimine ligands. Each ligand (formula given here below) was characterized using proton nuclear magnetic resonance (hereinafter indicated as NMR (NMR), carried out at 300 MHz using C6D6at 25°C), carbon NMR (held at 75 MHz is by using C 6D6) and infrared spectrophotometry (IR), performed using Cl4), as follows:

- N-(2,6-diisopropylphenyl)-2-hydroxy-3-tert-butyl-1-phenylmethanone (Chippewa base 1-A) received (butter yellow-orange, 2.9 g, yield 87%) of 1,71 ml of 3-tert-butyl-2-hydroxybenzaldehyde and a 1.88 ml of 2,6-diisopropylaniline.

1H-NMR: δ 12,24 (s, 1H), 9,19 (s, 1H), 7,34 is 6.67 (m, 6H), 2,96 (Sept., 2H), and 1.56 (s, 9H) and 1.31 (d, 12H) ppm;13C-NMR: δ 167,4, 160,3, 146,0, 138,8, 137,5, 130,4, 125,3, 123,0, 118,6, 118,3, 109,2, 34,9, 28,0 and 23.2 ppm; IR: 3451 (OH), 3056, 2962 (tBu), 2927, 2870, 1626 (C=N), 1579, 1494, 1437, 1396, 1385, 1359, 1318, 1278, 1109, 1060, 906, 844, 813, 781, 759, 741, 701, 560 and 462 cm-1.

- N-(4-bromo-2,6-dimethyl)-2-hydroxy-3-tert-butyl-1-phenylmethanone (Chippewa base 1-C) obtained (yellow oil, 2.8 g, yield 79%) of 1,71 ml of 3-tert-butyl-2-hydroxybenzaldehyde and 2 g of 4-bromo-2,6-dimethylaniline.

1H-NMR: δ to 12.35 (s, 1H), and 8.3 (s, 1H), 7,45 (d, 1H), 7,25 (s, 2H), 7,18 (d, 1H), 6,9 (t, 1H), 2,15 (s, 6H) and 1.6 (s, 9H) ppm;13C-NMR: δ 168,2, 161,3, 147,3, 139,0, 138,0, 130,9, 126,3, 123,9, 118,7, 118,0, 110,1, 35,1, 28,5, 23,8 ppm; IR: 3450 (OH), 3057, 2964 (tBu), 2928, 2888, 1627 (C=N), 1578, 1496, 1438, 1386, 1360, 1320, 1280, 1212, 1174, 1109, 1097, 1061, 989,7, 844, 813, 800, 782, 759, 739, 701, 623, 560, 534, 462 and 418 cm-1.

- N-(4-bromo-2,6-dimetilfenil)-2-hydroxy-1-phenylmethanone (Chippewa base 1-C) obtained (powder yellow, 2.83 g, yield 93%) of 1,065 ml salicylaldehyde and 2 g of 4-bromo-2,6-dimethylaniline the A.

1H-NMR: δ is 12.85 (s, 1H), 8,32 (s, 1H), 7,30-to 7.15 (m, 6H) and of 2.21 (s, 6H) ppm;13C-NMR: δ 167,0, 160,9, 148,3, 138,9, 133,4, 132,1, 130,8, 130,3, 119,0, 117,6, 117,2 and 19.0 ppm; IR: 3350, 3065, 3031, 2942, 2930, 2860, 1620 (C=N), 1570, 1526, 1489, 1461 and 1109 cm-1.

- N-(4-bromo-2,6-dimetilfenil)-2-hydroxy-4-nitro-1-phenylmethanone (Chiffolo the basis of the 1-D) obtained in powder form dark yellow color of the rate of 1.67 g of 4-hydroxy-3-nitrobenzaldehyde and 2 g of 4-bromo-2,6-dimethylaniline.

1H-NMR: δ 13,96 (s, 1H), to 8.41 (s, 1H), 8,35 (d, 1H), 8.30 to (d, 1H), 7,28 (s, 2H), 7,13 (d, 1H) and are 2.19 (s, 6H) ppm;13C-NMR: δ 166,4, 165,5, 145,6, 139,8, 132,0, 130,4, 128,7, 128,5, 118,6, 118,3, 117,1 and 18.1 ppm; IR: 3459 (OH), 3086, 3059, 2987, 2967, 2932, 1619 (C=N), 1581, 1523, 1480, 1458, 1340 (NO2), 1300, 1177, 1095, 983, 937, 853, 832, 798, 772, 751, 731, 716, 659, 633, 567 and 464 cm-1.

- N-(2,6-diisopropylphenyl)-2-hydroxy-4-nitro-1-phenylmethanone (Chippewa base 1-E) were obtained in the form of a yellow powder of 1,065 ml salicylaldehyde and a 1.88 ml of 2,6-diisopropylaniline.

1H-NMR: δ 13,16 (s, 1H), 8.34 per (s, 1H), 7,46 (d, 1H), 7,40 (t, 1H), 7,22 (Sirs, 3H), 7,10 (d, 1H), 6,99 (t, 1H), 3,20 (Sept., 2H) and 1.20 (d, 12H) ppm;13C-NMR: δ 166,4, 161,0, 145,9, 138,4, 133,0, 132,0, 125,3, 123,0, 118,8, 118,4, 117,1, 27,9 and 23.3 ppm; IR 3330 (OH), 3080, 3055, 2982, 2970, 2930, 1608 (C=N), 1581, 1520, 1477, 1454, 1323, 1301, 1170, 1090, 980, 935, 850, 835, 796, 770 and 751 cm-1.

EXAMPLES 2-8

Obtaining ruthenium complexes, substituted Chiffonier base

Ruthenium complexes with Shift the th basis of examples 1-A - 1-E were obtained in three stages and was purified as follows. In the first stage to a solution of the appropriate Chippewa base (3 mmol) in (15 ml) THF, at room temperature, was added dropwise a solution of ethoxide thallium (5 ml) of THF. Immediately after adding the formed solid pale yellow color and the reaction mixture is stirred for 2 hours at 20°C.

To a solution of the specified salicylaldiminato salt (5 ml) in THF was added a solution of [RuCl2(p-timal)]2in (5 ml), THF, and then the reaction mixture was stirred at room temperature (20°C) for 6 hours. A byproduct of the thallium chloride was removed by filtration. After evaporation of the solvent the residue was precrystallization at 0°C from dichloromethane/pentanol mixture. The resulting product was then dissolved in dry simple ether (15 ml) and cooled to 0°C.

In the third and last stage to the specified simple solution of ether was slowly added a solution of metallyte (2.3 ml, 1.4m in ether) or chloride vinylmania (1.75 ml, 2M in THF) or chloride panafcortelone (7 ml, 0.5m in simple ether), respectively. The reaction mixture was then slowly heated to room temperature and stirred for 4 hours. The formed salt was filtered and the solvent was removed. After recrystallization from a mixture of simple EPE is/pentane, complexes having the following formula was obtained with a yield in the range of 60 to 70% and was characterized by proton nuclear magnetic resonance (hereinafter indicated as NMR (NMR), carried out at 300 MHz using C6D6at 25°C), carbon NMR (carried out at 75 MHz using C6D6) and infrared spectrophotometry (IR), carried out using Cl4), as follows:

- Example 2 (obtained from Chippewa base 1 and metallicy):

1H-NMR: 9,81 (s, 1H), 7,10-to 6.80 (m, 6 H), of 1.33 (s, 6H); of 5.48 (d, 1H), of 5.34 (d, 1H), 4,48 (d, 1H), 4,36 (d, 1H), 2,90 (Sept., 1H), 2,16 (s, 3H), 1.26 in (d, 6H) and 0.10 (s, 3H) ppm; IR (KBr) 3051, 2957, 2923, 2853, 1920, 1670, 1596, 1564, 1516, 1462, 1447, 1372, 758 cm-1.

- Example 3 (obtained from Chippawa the Foundation of the 1st and metallicy):

1H-NMR: to 9.70 (s, 1H), 7.3 to 7,0 (m, 7 H)of 3.00 (Sept., 2H), 1,12 (d, 12H); 5,43 (d, 1H), and 5.30 (d, 1H), 4,47 (d, 1H), 4,33 (d, 1H), 3,10 (Sept., 1H), 2,11 (s, 3H), 1,22 (d, 6H) and 0.22 (s, 3H) ppm; IR: 3052, 2980, 2970, 2924, 1602, 1583, 1514, 1470, 1451, 1333, 1300, 1087, 976, 930, 850, 830, 796 and 750 cm-1.

- Example 4 (obtained from Chippawa the base 1 and metallicy):

1H-NMR: 9,27 (s, 1H), 7,2 to 7.75 (m, 6H), 3.00 today (Sept., 2H), 1,12 (d, J=6.5 Hz, 12H); 5,43, 4,70 of 4.44, 4,37 (d, 4H), 3,14 (Sept., 1H), 2,08 (s, 3H), of 1.30 (d, 6H) and 0.13 (s, 3H) ppm; IR: 3052, 2980, 2970, 2924, 1602, 1583, 1514, 1470, 1451, 1333, 1300, 1087, 976, 930, 850, 830, 796 and 750 cm-1.

Example 5 (obtained is g Chippewa the base 1 and formanilide):

1H-NMR: to 9.70 (s, 1H), 7.3 to a 7.0 (m, 7H), 3.00 today (Sept., 2H), 1,12 (d, J=6.5 Hz, 12H); 5,43 (d, 2H), and 5.30 (d, 2H), 3,10 (Sept., 1H), 2,11 (s, 3H), 1,22 (d, 6H) and 0.22 (s, 3H) ppm; IR: 3052, 2980, 2970, 2924, 1602, 1583, 1514, 1470, 1451, 1333, 1300, 1087, 976, 930, 850, 830, 796 and 750 cm-1.

Example 6 (obtained from Chippawa the base 1 And in the second stage):

1H-NMR of 7.69 (s, 1H), 7,07-6,12 (m, 6H), 2,99 (Sept., 2H), 1,40 (s, 9H), of 1.28 (d, 12H); 5,10, 4,55, 4,46, 4,39 (d, 1H), 2,72 (Sept., 1H), 1,60 (s, 6H) and 1.09 (d, 6H) ppm;13C-NMR: 161,4, 152,9, 138,96, 133,36, 130,85, 125,74, 123,43, 118,7, 114,42, 35,34, 28,42, 26,52, 23,47, 104,14, 93,64, 86,38, 83,74, 80,69, 78,61, 30,20, 22,40 and 17,86 ppm; IR: 3050, 3032, 2956, 2923, 2853, 1920, 1672, 1594, 1536, 1467, 1447, 1376, 1347 and 757 cm-1.

Example 7 (obtained from Chippawa the base 1 and metallicy):

1H-NMR: δ 7,693 (s, 1H); 7,047-x 6.15 (m, 6H); 2,723 (Sept., 2H); 1,404 (s, 9H); to 1.31 (d, 12H); of 4.95 (d, 1H); 4,55 (d, 1H); 4,48 (d, 1H); was 4.42 (d, 1H); at 2,426 (Sept., 1H); 1,596 (s, 3H); 1,050 (d, 6H) and 0.04 (s, 3H) ppm;13C-NMR: δ 163,047; 152,815; 137,314; 134,565; 131,872; 127,227; 124,148; 122,06; 115,546; 35,619; 26,934; 103,04; 91,77; 88,36; 85,972; 79,485; 77,121; 30,837; 21,986 and to 18.01 ppm

Example 8 (obtained from Chippawa the base 1 and pantothenicacid):

1H-NMR: 7,71 (s, 1H), 6,99-6,14 (m, 6H), 2,77 (Sept., 2H), a 1.46 (s, 9H), of 1.30 (d, 12H); 5,20, 4,72, 4,58, 4,36 (all d, 1H), 2,61 (Sept., 1H), 1,62 (s, 6H) and of 1.10 (d, 6H) ppm;13C-NMR 161,4, 152,9, 138,96, 133,36, 130,85, 125,74, 123,43, 118,7, 114,42, 35,34, 28,42, 26,52, 23,47, 104,14, 93,64, 86,38, 83,74, 80,69, 78,61, 30,20, 22,40, 17,86, 109,94 (d), 136,51 (d), 133,19 (who) and 147,73 (d) ppm; IR: 3050, 3032, 2956, 2923, 2853, 1920, 1648, 1605, 1537, 1503, 1465, 1433, 1410, 1376, 1347, 1263, 1078, 1030, 801, 749, 720 and 566 cm-1.

EXAMPLES 9 and 10

Obtaining bimetallic ruthenium complexes, substituted Chiffonier base

The ruthenium precursor [RuCl2L3]2in which L3represents norbornadiene (example 9) or cyclooctadiene (example 10) was dissolved in methylene chloride (15 ml)to which was added 3 ml tallic salt Chippewa the base 1 (10 ml, 0.3 m) and the reaction mixture is stirred for 10 hours. After filtering califlorida and removal of the solvent the residue was rinsed with methylene chloride and was characterized by proton nuclear magnetic resonance (hereinafter indicated as NMR (NMR), carried out at 300 MHz using C6D6at 25°C), carbon NMR (carried out at 75 MHz using C6D6) and infrared spectrophotometry (IR), carried out using Cl4), as follows:

Example 9:

1H-NMR: of 7.70 (s, 1H), 7,14 of 6.66 (m, 6H), 2,70 (Sept., 2H), of 1.34 (s, 9H), 1.27mm (d, 12H); 6,59 (d, 1H), 6,47 (d, 1H), 4,1 (s, 1H), 3,98 (s, 1H), 3,91 (s, 1H), 3,86 (s, 1H) and is 1.82 (s, 2H) ppm;13C-NMR δ 160,98, 151,36, 140,15, 135,14, 130,91, 126,68, 123,88, 120,52, 113,92, 34,49, 31,17, 27,84, 24,59, 145,88, 140,15, 139,84, 135,14, 72,7, 54,94 and 50,10 ppm; IR; 3098, 3025, 3032, 2956, 2923, 2853, 1920, 1672, 1594, 1536, 1467, 1409, 1310, 1240, 1180, 1160, 1085, 1035, 1000, 941, 863, 805 and 757 cm-1.

- Use the 10:

1H-NMR of 7.69 (s, 1H), 7,07-6,12 (m, 6H), 2,99 (Sept., 2H), 1,40 (s, 9H), of 1.28 (d, 12H); 5,10, 4,55, 4,46, 4,39 (all d, 1H), 2,72 (Sept., 1H), 1,60 (s, 6H), of 1.09 (d, 6H);13C-NMR: 161,4, 152,9, 138,96, 133,36, 130,85, 125,74, 123,43, 118,7, 114,42, 35,34, 28,42, 26,52, 23,47, 104,14, 93,64, 86,38, 83,74, 80,69, 78,61, 30,20, 22,40 and 17,86 ppm; IR: 3050, 3032, 2956, 2923, 2853, 1920, 1672, 1594, 1536, 1467, 1447, 1376, 1347 and 757 cm-1.

EXAMPLE 11

Production precoordination ruthenium complexes Chippewa base

This example illustrates an alternative way of production for ruthenium complexes, substituted Chiffonier base represented by the formula (VII.a) - (VII.f) in example 6 and 1 WO 03/062253 (i.e. with the carbene ligand with a condensed aromatic ring system having the formula (VI)shown in figure 3 WO 03/062253). This alternative method is shown schematically in figure 5, which uses the following abbreviations:

- Ph denotes phenyl,

- Cy represents cyclohexyl,

- Me denotes methyl,

- iPr represents isopropyl and

- tBu represents tert-butyl.

The scheme is quite clear and shows how that is done in five stages and in which the desired ruthenium complexes, substituted Chiffonier base, obtained with better yields than in the method described in examples 1-6 and figure 1 WO 03/062253.

EXAMPLE 12 (comparative)

Obtaining ruthenium complex, Samusenko what about Chiffonier base for use in polymerization with ring opening of cyclooctadiene without acid activation

Ruthenium complex, substituted Chiffonier base, similar to the connection 70, shown in figure 5 (i.e., R1= NO2, R2= methyl and R3= bromine), with the only exception that the carbene ligand with a condensed aromatic ring system substituted =SNA6H5carbene ligand was carried out according to the procedure of example 11.

Exchange polymerization with ring opening of cyclooctadiene was carried out for 17 hours at 60°C in tetrahydrofuran (THF) as solvent, using this ruthenium complex, substituted Chiffonier base as a catalyst in a molar ratio of cyclooctadiene/catalyst equal to 500/1. The polymer having srednetsenovoj molecular weight 59000 and a polydispersity of 1.4, was obtained with 96%yield.

EXAMPLE 13

Polymerization with ring opening of cyclooctadiene acid-activated ruthenium complex Shiftwork base

Ruthenium complex, substituted Chiffonier base obtained in example 12 was dissolved in THF. Then the catalyst solution was cooled to -78°C using an acetone bath and liquid nitrogen. Then to the cooled solution of the catalyst was added to 6 equivalents of hydrochloric acid in THF and the mixture is stirred for about 1 hour until until it reaches room is based temperature and the stirring continued for additional 1 hour.

Exchange polymerization with ring opening of cyclooctadiene was conducted for 2 hours at room temperature in THF as solvent, with the use of this ruthenium complex, substituted Chiffonier base, modified acid as catalyst in a molar ratio of cyclooctadiene/catalyst equal to 500/1. The polymer having srednetsenovoj molecular weight 57500 and a polydispersity of 1.4, was obtained with 100%output. It is noteworthy that due to the acid activation of the catalyst is ruthenium complex can be obtained a polymer with very similar characteristics as the polymer of example 12, reducing the reaction temperature from 60°C to room temperature and simultaneous separation of the reaction time by a factor equal to 51.

EXAMPLE 14 (comparative)

The exchange reaction of 1,9-decadiene without acid activated ruthenium complex Shiftwork base

The exchange reaction of acyclic diene (D) 1,9-decadiene was carried out in mass under conditions of partial vacuum for 17 hours at 60°C, using this ruthenium complex, substituted Chiffonier base of example 12 as a catalyst in a molar ratio of 1,9-decadiene/catalyst equal to 500/1. Could not get any polymer of polecenie period of this reaction, i.e. specified ruthenium complex catalyzes ADMET in such conditions.

EXAMPLE 15

The exchange reaction of 1,9-decadiene acid-activated ruthenium complex Shiftwork base

Ruthenium complex, substituted Chiffonier base obtained in example 12 was dissolved in THF. Then the catalyst solution was cooled to -78°C using an acetone bath and liquid nitrogen. Then to the cooled solution of the catalyst was added to 6 equivalents of hydrochloric acid in THF and the mixture is stirred for about 1 hour, until then, until reaching the room temperature, and stirring was continued for additional 1 hour.

The exchange reaction of acyclic diene (D) 1,9-decadiene was carried out in mass under conditions of partial vacuum for 2 hours at 60°C, using this ruthenium complex, substituted Chiffonier base, modified acid as catalyst in a molar ratio of 1,9-decadiene/catalyst equal to 500/1.

Was obtained a polymer having srednetsenovoj molecular weight 57500 and a polydispersity of 1.2. It is noteworthy that due to activation of the acid catalyst ruthenium complex polymer can be obtained by reducing the reaction time from 17 hours to 2 hours, all other reaction conditions are equivalent to those that do not perfectly the axis of the polymer in the absence of acid activation of the metal complex.

EXAMPLE 16

Polymerization with ring opening of the Dicyclopentadiene with the acid activation of the ruthenium complex Shiftwork base

Ruthenium complex, substituted Chiffonier base obtained in example 12 was dissolved in THF. Then the catalyst solution was cooled to -78°C using an acetone bath and liquid nitrogen. Then to the cooled solution of the catalyst was added to 6 equivalents of hydrochloric acid in THF, and the mixture is stirred for about 1 hour until until it reaches room temperature, and stirring was continued for additional 1 hour.

Exchange polymerization with ring opening of Dicyclopentadiene was carried out in bulk using standard conditions the reaction injection molding (RIM) for 5 minutes at room temperature, using this modified acid ruthenium complex, substituted Chiffonier base as a catalyst in a molar ratio of Dicyclopentadiene/catalyst equal 50000/1. Was transparent glassy polymer.

EXAMPLE 17

Polymerization with ring opening of other monomers with acid activation of the ruthenium complex Shiftwork base

Ruthenium complex, substituted Chiffonier base obtained in example 12 was dissolved in THF. Then restoredirectory was cooled to -78°C using an acetone bath and liquid nitrogen. Then to the cooled solution of the catalyst was added to 6 equivalents of hydrochloric acid in THF and the mixture is stirred for about 1 hour until until it reaches room temperature, and stirring was continued for additional 1 hour.

Exchange polymerization with ring opening of various monomers was carried out for 5 minutes at room temperature in THF as solvent, using this modified acid ruthenium complex, substituted Chiffonier base as catalyst in the following molar ratios of the monomer/catalyst:

Ethylidene-norbornene: 50000/1

Cycloocten: 150000/1

Ethylmethylketone: 50000/1

In each case, the complete conversion of the monomer into the corresponding polymer was achieved in less than 5 minutes.

EXAMPLE 18

Acid activation precoordination ruthenium complexes

Monometallic ruthenium complexes, substituted Tiffanym the basis of examples 2-8 and bimetallic ruthenium complexes, substituted Chiffonier base, examples 9 and 10 was activated with hydrogen chloride (hydrochloric acid) in the experimental conditions used in example 13, i.e. the molar ratio of the specified acid to the specified ruthenium complex, equal to 6/1. Modified so ruthenium is omplex then tested in polymerization with ring opening of various strained cyclic olefins in the experimental conditions, the same conditions of examples 13, 16 and 17. Received superior outputs of the polymer in a shorter period of reaction time and/or at lower reaction temperatures than non-activated acid ruthenium complex.

EXAMPLE 19

Study of the reaction of the acid with ruthenium complex, substituted Chiffonier base

Stable in air ruthenium complexes coordinated with Chippewa-basic ligands, are effective catalysts for ROMP of strained cyclic olefins, such as Dicyclopentadiene. As shown in the previous examples, more effective catalysts can be generated in situ (in place) after adding a significant molar excess of a strong acid to said ruthenium complexes, substituted Chiffonier base. In order to better understand the reaction between a specified acid and ruthenium complex, substituted Chiffonier base, and to characterize the intermediate connection and end ruthenium types involved in this reaction was monitored by acid activation of the ruthenium complex, substituted Chiffonier base obtained in example 12, using1H-NMR spectroscopy.1H-NMR spectra were recorded on solutions of ruthenium complex, substituted Chiffonier base, before and after the acid is activated at different time intervals, in deuterated chloroform. Acid activation of the free ligand class of Schiff bases in the same conditions were also subjected to study by using the same technology for comparison purposes.

Fig.7 shows1H-NMR spectrum in deuterated chloroform, in the range of chemical shifts from 0 to 9 ppm, ruthenium complex, substituted Chiffonier base obtained in example 12, before any acid activation. This spectrum shows several groups of signals corresponding to the protons of the coordinated ligands. There were two singlet at δ of 1.03 1.48 ppm corresponding to the methyl groups of the ligand class of Schiff's bases, then between δ 2.0 and 2.8 ppm is observed 6 singlets, characteristic for the methyl groups dihydroimidazolium ligand. The following signals between δ of 3.9 and 4.3 ppm are attributed to the methylene protons groups dihydroimidazolium ligand. Between δ of 6.2 and 8.2 ppm is observed multiplet corresponding to the phenyl protons of all ligands and protons associated with the carbon atom included in kinoway group. Finally, when δ 18,51 ppm (not shown in Fig.7) was observed singlet characterizing the proton benzylidene ligand.

Continuous1H-NMR monitoring has allowed the inventors to observe the results of the reaction of the acid-ruthenium complex. For example, Fig p is found 1H-NMR spectrum in deuterated chloroform, in the range of chemical shifts from 8 to 19 ppm, product, resulting from the 5-minute acid activation of the same ruthenium complex, substituted Chiffonier base (obtained in example 12), with 10 molar equivalents DCl (deuterium chloride) at 20°C. In this spectrum is characterized by a wide signal of the proton for the protonated ligand class of Schiff's bases, still associated with the ruthenium was determined at δ 8,72 ppm as well as the signals at δ 10,01 and 8,56 ppm, which is typical for nitrosalicylaldehyde. Thus, the spectrum clearly demonstrates that acid activation after 5 minutes under these conditions (acid/complex, the molar ratio is 10:1) leads to (i) protonation of the ligand class of Schiff's bases with partial decoordinated the nitrogen atom of Chippewa base, and (ii) partial discoordinating oxygen atom of the ligand class of Schiff bases from the center of the metal with subsequent cleavage of kinoway communication. However, this interaction of deuterium chloride with a nitrogen atom of the ligand class of Schiff's bases can clearly be observed only during the first few minutes of the reaction, prior to the manifestation and increase the intensity of signals at δ 10,01 and 8,56 ppm due to the formation of nitrosalicylaldehyde. Prothero is the use of ligand class of Schiff bases results in the presence of an intermediate type, which can be represented by the following formula:

Fig.9 shows1H-NMR spectrum in deuterated chloroform, in the range of chemical shifts from 10 to 19 ppm, product, resulting from a 50-minute acid activation of the same ruthenium complex, substituted Chiffonier base (obtained in example 12), 10 molar equivalents DCl (deuterium chloride) at 20°C. In this spectrum, the authors found the formation of at least one new ruthenium-karbonovogo complex, which is characterized by a weak broad signal from benzylidene ligand coordinated to the metal center at δ 16,91 and 17,62 ppm, respectively. This at least one new ruthenium-carbene complex was probably formed during the previous stage of decoordinated Chippewa basis, i.e. probably was present at an early stage (between 5 and 50 minutes of reaction), but in concentrations too low to be determined by NMR analysis. Without intending to be bound to any theory, the authors believe that at least one new ruthenium-carbene complex is perhaps the active catalytic species, which contributes to the promotion of the exchange reactions of olefin and can be represented by the following formula (where Ph is phenyl):

This type should therefore be referred to as [dichloro][phenylmethylene][1,3-dimethylimidazolidin-2-ilidene]ruthenium. It should be noted that as will now be shown, this species is very unstable and reactive, being subject to rapid decomposition.

Figure 10 shows1H-NMR spectrum in deuterated chloroform, in the range of chemical shifts from -5 to +19 ppm, product, resulting from a 90-minute acid activation of the same ruthenium complex, substituted Chiffonier base (obtained in example 12), 10 molar equivalents DCl (deuterium chloride) at 20°C. In this spectrum, the authors identified the presence of new chemical shifts when -0,2 and to-4.0 ppm, respectively. Not wishing to be bound by any theory, we believe that these signals can possibly be attributed to at least one new monohydride complex of ruthenium, which can be represented by the following formula:

where L represents the water (H2O).

From figure 10, it can be estimated that the conversion in the reaction of acid activation was 60% after 90 minutes.

Fig. 11 and 12 show1H-NMR spectra in deuterated chloroform, in the range of chemical shifts from -5 to +19 ppm, products resulting from 24-hour and 91 hours, respectively, islotes activation of the same ruthenium complex, substituted Chiffonier base (obtained in example 12), 10 molar equivalents DCl (deuterium chloride) at 20°C. After 24 hours reaction time, the signals caused by the proton source ruthenium complex, substituted Chiffonier base, was still present together with the signals from 5-nitrosalicylaldehyde (when δ of 10.01 ppm, δ of 11.61 ppm, δ 8.6 out of 8.4 ppm and 7,13 ppm), from the protonated 4-bromo-2,6-dimethylaniline (δ 2,56 ppm and 7,27 ppm) and the signals assigned to the new ruthenium monohydride complex (when δ -4 ppm, δ -0,2 ppm, δ ppm 1,2, δ 2,1 ppm and δ of 3.2 ppm, and a multiplet between 6.5 and 8 ppm). Of the 11 possible to estimate that the conversion in the reaction of acid activation was about 90% after 24 hours.

After 91 hours of reaction time, all the signals caused by the proton source ruthenium complex, substituted Chiffonier base, disappeared. You still see only the signals from the protons of the new ruthenium monohydride complex, from 5-nitrosalicylaldehyde and protonated 4-bromo-2,6-dimethylaniline.

EXAMPLE 20

Polymerization cyclooctene in the presence of activated acid ruthenium complex, substituted Chiffonier base

After a 90-minute activation acid under the conditions of example 19 (i.e. acid activation at 20°C, in a mixture of acid complex at a molar ratio that is equal to the 10, source ruthenium complex substituted Chiffonier base obtained according to example 12), 100 molar equivalents cyclooctene (relative to the ruthenium complex, substituted Chiffonier base) was added to the NMR tube. This led to a very rapid polymerization of the monomer, and the polymer immediately appeared at the top of the tube. Fig shows1H-NMR spectrum in deuterated chloroform, in the range of chemical shifts from -5 to +19 ppm, the mixture present in the test tube after 2 hours (i.e. 90-minute acid activation and 30 minutes of polymerization). Detected signals of olefinic protons politicalaction when to 5.4 ppm and could be easily seen on Fig. This experiment also allows inventors to trace the formation of propagating the species, which produces a signal at δ 18,0 ppm

EXAMPLES 21-27

Polymerization of Dicyclopentadiene in the presence of activated acid ruthenium complex, substituted Chiffonier base (first)

In order to investigate the influence of various parameters on the polymerization of Dicyclopentadiene in the presence of certain activated acid ruthenium complex, substituted Tiffanym basis, was carried out the following procedure on the basis of the complex obtained in example 12. Exchange the polymerization of Dicyclopentadiene with a ring opening was carried out in 16 ml polypropylene container, using this complex as a catalyst in a molar ratio of Dicyclopentadiene/catalyst equal 30000/1, unless otherwise noted. First, the catalyst (dissolved in 0.1 ml of methylene chloride and hydrochloric acid (in a molar ratio of acid/catalyst r1specified in the table below) was introduced into the reactor at room temperature, optionally with the addition (in molar ratio acid/catalyst r2specified in the table below), and then after some time t3activation (expressed in minutes in the table below) in the reactor were successively introduced Dicyclopentadiene at room temperature in the above-mentioned molar ratio as long as the volume of reagents of less than 10 ml, and the reaction was given the opportunity to proceed for some time tr(expressed in minutes in the table below). Then the temperature was rapidly decreased. The polymerization reaction was very exothermic and the maximum temperature Tmax(expressed in °C in the table below) duly registered by the probe. In several embodiments of the experiment (examples 24 and 25) was performed dynamic mechanical analysis (hereinafter indicated as DMA) obtained by pentadiene in order to determine the glass transition temperature Tg. The DMA results would be the following:

Example 24: 149,9°C

Example 25: USD 151.6°C

These DMA data show that Tmaxis in full compliance with Tg.

The following table 1 shows the maximum temperature Tmaxobtained by changing various parameters of the reaction.

TABLE 1
Exampler1r2tatrTmax
2110007,4129
2210011,8151
23100,2514,0153
2420518,7150
25 30514,1153
263010*9,3142
27200*4,2155

In all the examples above used the Dicyclopentadiene monomer includes 0.2% by weight vinylnorbornene (hereinafter indicated as VNB), acting as the agent of the transfer chain. The additive used in example 23, is ruthenium dimer, represented by the following formula:

The additive used in examples 24 and 25, is azobis(isobutyronitrile) (hereinafter cited reduction as AIBN)represented by the formula:

The additive used in example 26, is tribromide phosphorus PBr3.

The data presented in table 1 show that, provided that it remains short time of activation for the interaction of the catalyst and hydrochloric acid before adding the monomer is subjected to polymerization in accordance with this from what Britanie can reproducibly be obtained polydicyclopentadiene with the glass transition temperature T gabove 140°C.

EXAMPLES 28-31

Polymerization of Dicyclopentadiene in the presence of activated acid ruthenium complex, substituted Chiffonier base (second)

The experimental procedure of examples 21-27 was repeated, except that in this second conduction was used 100-ml polypropylene vessel, the catalyst (obtained from example 12) was dissolved in 1 ml of methylene chloride, Dicyclopentadiene was introduced into the reactor at room temperature as long as the volume of all reagents did not reach 80 ml, the activation time was fixed to 1 minute, and the molar ratio R of the Dicyclopentadiene/catalyst was also used as a parameter of the reaction.

The following table 2 shows the maximum temperature Tmaxobtained by changing various parameters of the reaction. The additive used in the examples 30 and 31, is AIBN. The data presented in table 1 show that polydicyclopentadiene with the highest temperature ectothermy (previously it was determined that it corresponds to the glass transition temperature Tgabove 140°C and up to 166°C, can reproducibly be obtained according to this invention even at higher molar ratios, the Dicyclopentadiene/catalyst than in the first implementation.

TABLE 2
ExampleRR1r2trTmax
28300001005,6193
296000030014,6143
3060000302019,4160
3160000303016,5166

EXAMPLES 32-42

Polymerization of Dicyclopentadiene in the presence of activated acid ruthenium complex, substituted Chiffonier base and in a solvent (third)

Exchange polymerization of Dicyclopentadiene with a ring opening was carried out using the complex obtained in example 12 (dissolved in 1 ml dissolve the La's, or tetrahydrofuran or methylene chloride, respectively designated as THF or MX (MS) in the following table 3), as a catalyst, at a molar ratio of the Dicyclopentadiene/catalyst indicated as R. First at room temperature to 80 ml of Dicyclopentadiene was added hydrochloric acid (in a molar ratio r1acid/catalyst indicated in the table below) and VNB (0.2% by weight relative to the Dicyclopentadiene). Then this mixture was added to a solution of the catalyst, optionally together with AIBN as an additive (in a molar ratio of additive/catalyst r2indicated in the table below). Reactions were given the opportunity to continue for some time tr(measured in minutes in the table below), after which the reactor was cooled. Dynamic mechanical analysis (hereinafter indicated as DMA) was performed on the resulting polydicyclopentadiene in order to determine the glass transition temperature Tg.

The following table 3 shows the temperature measured by DMA (specified in °C) when changing various parameters of the reaction.

TABLE 3
ExampleRR1r 2trSDMA
3260000303058,6THF154,7
3330000103017,7CM165,2
34300003007,7THF163,8
35300003007,9CM170,2
3630000103046,9THF166,7
3760000303030,6 CM158,2
3830000303018,0THF165,3
393000010028,9CM167,4
406000030056,0THF151,1
41600000of 21.9THF169, 5mm
4230000303012,5CM159,6

The data presented in table 3 show that polydicyclopentadiene with the glass transition temperature Tgbetween approximately 150°C and 170°C can reproducibly be obtained under different conditions in this province of the attachment of the invention.

EXAMPLE 43

Study of the reaction of the acid with ruthenium complex, substituted Chiffonier base

The study of example 19 was repeated, but on the other ruthenium complex, substituted Tiffanym the basis having the following formula:

i.e. ruthenium complex, similar to the complex of example 12, except that the substituted phenyl group on the nitrogen atom of Chippewa base was replaced with more complicated spatial Adamantine group. The corresponding ligand class of Schiff bases is easily accessible from adamantylamine. Proton NMR spectrum of this complex in deuterated chloroform presented on Fig. The authors observed a group of signals between δ of 1.5 and 2.8 ppm, which are characteristic for the methyl groups of the ligand of dihydroimidazolium and protons adamantly group, coordinated with nitrogen. The signals between δ of 3.9 and 4.3 ppm are attributed to the methylene protons dihydroimidazolium ligand. Between δ of 6.2 and 8.2 ppm is observed multiplet corresponding to the phenyl protons of all ligands and the protons attached to the carbon atom included in kinoway communication. In conclusion, when δ to 17.7 ppm authors observed a singlet characterizing the proton benzylidene ligand.

When carrying out the acid activation under the same conditions, h is about and in example 19, except for the acid activation only for 10 minutes, the proton NMR spectrum of the resulting product are shown in Fig. This experiment allows inventors to observe a very rapid and complete (100%) conversion of the original complex after 10 minutes (the disappearance of the signal at δ to 17.7 ppm). During this time period we observed formation of a new complex (signal at 16,91 ppm). Similar to the experiment of example 19, when δ to 8.62 ppm was also found wide proton signal characteristic of the protonated ligand class of Schiff's bases, still coordinated to the ruthenium.

1. Modification precoordination complex metal salts thereof, MES or enantiomer, and specified precoordination complex metal includes (i) at least one bidentate ligand class of Schiff's bases, including aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup through one additional heteroatom which is oxygen, and (ii) one or more other ligands, wherein the method comprises bringing the specified precoordination complex metal in contact with the acid under such conditions, under which this acid is capable of at least partially cleave the bond between the metal and the specified on m is Nisha least one bidentate ligand class of Schiff bases (i), and the fact that the said other ligands (ii) is selected so as to be incapable of protonation of these acids in these conditions, but they are not selected from the group consisting of phosphines, amines, arsinami and Stabenow, and characterized in that the specified precoordination complex metal selected so that as a result of its modification of this method are the reaction product, which is a monometallic particles (molecules)represented by the structural formula:

in which M represents a metal selected from group 8 of the Periodic table, which is ruthenium;
SB+is protonated bidentate ligand class of Schiff bases;
Lcrepresents the carbene ligand selected from the group consisting of N-heterocyclic carbenes, alkylidene ligands, vinylidene ligands, indenyltitanium ligands and allenylidene ligands;
Lcis non-anionic ligand;
X represents an anionic ligand; and
X-represents an anion;
its salt, solvate and enantiomers, or
bimetallic particles (molecules)represented by the General formula:

in which each of M and M' represents a metal selected from group 8 of the Periodic table, which is what I ruthenium;
SB+is protonated bidentate ligand class of Schiff bases;
Lcrepresents the carbene ligand selected from the group consisting of N-heterocyclic carbenes, alkylidene ligands, vinylidene ligands, indenyltitanium ligands and allenylidene ligands;
L represents a non-anionic ligand;
each of X1X2and X3independently selected from anionic ligands; and
X-represents an anion;
its salt, solvate and enantiomers.

2. The method according to claim 1, wherein the specified conditions include
the molar ratio between these acids and the specified precoordination complex of the metal constituting more than 1.2 and less than 40, and/or
the contact time from 5 to 100 h, and/or
contact temperature from about -50°to about +80°C.

3. The method according to claim 1, characterized in that the pKa of the specified acid is lower than the pKa of the specified bidentate ligand class of Schiff bases (i).

4. The method according to claim 1, characterized in that at least one of these other ligands (ii) is a ligand with constrained spatial difficulty having a pKa of at least 15.

5. The method according to claim 1, wherein the number of carbon atoms in the specified at least one bidentate ligand class of Schiff bases (i) between the nitrogen atom of the specified them is nography and specified coordinating heteroatom in at least one specified bidentate ligand class of Schiff bases (i) is from 2 to 4.

6. The method according to claim 1, characterized in that the specified acid is chloride-hydrogen acid or Hydrobromic acid.

7. The method according to claim 1, characterized in that the above conditions are able to provide
protonation of bidentate ligand class of Schiff bases and decoordinated the nitrogen atom of aminogroup specified polydentate ligand class of Schiff's bases with respect to the metal, and/or decoordinated additional heteroatom specified bidentate ligand class of Schiff bases against the metal.

8. The reaction product
(a) precoordination complex metal salts thereof, MES or enantiomer, and specified precoordination complex metal includes (i) at least one bidentate ligand class of Schiff's bases, including aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup through one additional heteroatom which is oxygen, and (ii) one or more other ligands, and
(b) acid introduced into the reaction in a molar ratio of above about 1.2 with respect to the specified precoordination metal complex (a), provided that the said other ligands (ii) is not capable of protonation of these acids and is not selected from the group consisting of amines, phosphines, arsinami and article the bins, where the reaction product is a monometallic particles (molecules)represented by the structural formula:

in which M represents a metal selected from group 8 of the Periodic table, which is ruthenium;
SB+is protonated bidentate ligand class of Schiff bases;
Lcrepresents the carbene ligand selected from the group consisting of N-heterocyclic carbenes, alkylidene ligands, vinylidene ligands, indenyltitanium ligands and allenylidene ligands;
L2is non-anionic ligand;
X represents an anionic ligand; and
X-represents an anion;
its salt, solvate and enantiomers, or
bimetallic particles (molecules)represented by the General formula:

in which each of M and M' represents a metal selected from group 8 of the Periodic table, which is ruthenium;
SB+is protonated bidentate ligand class of Schiff bases;
Lcrepresents the carbene ligand selected from the group consisting of N-heterocyclic carbenes, alkylidene ligands, vinylidene ligands, indenyltitanium ligands and allenylidene ligands;
L represents a non-anionic ligand;
each of X 1, X2and X3independently selected from anionic ligands; and
X represents an anion;
its salt, solvate and enantiomers.

9. Product of claim 8, wherein the pKa of the specified acids (b) is lower than the pKa of the specified at least one polydentate ligand class of Schiff bases (i).

10. Product of claim 8, wherein the number of carbon atoms in the specified at least one bidentate ligand class of Schiff bases (i) between the nitrogen atom of the specified aminogroup and specified the heteroatom of the specified at least one bidentate ligand class of Schiff bases (i) is from 2 to 4.

11. Product of claim 8, wherein at least one of these other ligands (ii) of the specified precoordination complex metal (a) is constrained spatial-difficult ligand having a pKa of at least 15.

12. Product of claim 8, representing monometallic particles (molecules)containing cationic monometallic particles (molecules)represented by structural formula (VI):

or cationic monometallic particles (molecules)represented by the General formula (VII):

in which M represents a metal selected from group 8 of the Periodic table, which is ruthenium;
W is selected the C group, consisting of oxygen;
each of R", R"' and R"" represents a moiety independently selected from the group consisting of hydrogen, C1-6of alkyl, C3-8cycloalkyl,1-6alkyl-C1-6alkoxysilyl, C1-6alkylresorcinol, C1-6alkyl-C3-10cycloalkenyl, aryl and heteroaryl, or R" and R"' together form an aryl or heteroaryl radical, each specified radical (when it is different from hydrogen) optionally substituted by one or more, preferably 1-3, substituents R5, each of which is independently selected from the group consisting of halogen atoms, C1-6of alkyl, C1-6alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, C1-6alkyl-C1-6alkoxysilyl, C1-6alkylresorcinol, C1-6alkyl-C3-10cycloalkenyl, alkylamine and arylamine;
R' has any of the values defined for R", R"' and R""when it is included in the compound having General formula (VI)
or, when it is included in the compound having General formula (VII)is selected from the group consisting of C1-6alkylene and C3-8cycloalkene, and specified Allenova or cycloalkenes group optionally substituted by one or more substituents R5;
L2is non-anionic ligand;
X represents anions the first ligand;
each of R3and R4represents hydrogen or a radical selected from the group consisting of C1-20of alkyl, C2-20alkenyl,2-20the quinil,1-20of carboxylate, With1-20alkoxy, C2-20alkenylacyl,2-20alkyloxy, aryl, aryloxy, C1-20alkoxycarbonyl, C1-alkylthio, C1-20alkylsulfonyl, C1-20alkylsulfonyl,1-20alkylsulfonate, arylsulfonate, C1-20alkylphosphonate, arylphosphonate,1-20alkylamine and arylamine;
R' and one R3and R4can be connected to each other, forming a bidentate ligand;
R"' and R"" can be connected to each other to form an aliphatic ring system including a heteroatom selected from the group consisting of nitrogen, phosphorus, arsenic and antimony;
R3and R4together may form a condensed aromatic ring system, and
y represents the number of sp2 carbon atoms between M and the carbon atom bearing an R3and R4and is an integer from 0 to 3 inclusive,
his salt, solvate, and enantiomers, and these cationic particles associated with anion,
or cationic bimetallic particles (molecules),
represented by structural formula (X):

or cationic bimetallic particles (molecules), represented structurally the formula (XI):

in which each of M and M' represents a metal selected from group 8 of the Periodic table, which is ruthenium;
W is selected from the group consisting of oxygen;
each of R", R"' and R""' represents a radical independently selected from the group consisting of hydrogen, C1-6of alkyl, C3-8cycloalkyl, C1-6alkyl-C1-6alkoxysilyl,1-6alkylresorcinol,1-6alkyl-C3-10cycloalkenyl, aryl and heteroaryl, or R" and R"' together form an aryl or heteroaryl radical, each specified radical (when it is different from hydrogen) optionally substituted by one or more, preferably 1-3, substituents R5, each of which is independently selected from the group consisting of halogen atoms, C1-6of alkyl, C1-6alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, C1-6alkyl-C1-6alkoxysilyl,1-6alkylresorcinol, C1-6alkyl-C3-10cycloalkenyl, alkylamine and arylamine;
R' has any of the values defined for R", R"' and R""when it is included in the compound having General formula (X), or, when it is included in the compound having General formula (XI)is selected from the group consisting of C1-6alkylene and C3-8cycloalkene, and specified Allenova or recloak the Lenovo group optionally substituted by one or more substituents R 5;
each of R3and R4represents hydrogen or a radical selected from the group consisting of C1-20of alkyl, C2-20alkenyl,2-20the quinil,1-20of carboxylate, With1-20alkoxy, C2-20alkenylacyl,2-20alkyloxy, aryl, aryloxy, C1-20alkoxycarbonyl, C1-8alkylthio,1-20alkylsulfonyl, C1-20alkylsulfonyl,1-20alkylsulfonate, arylsulfonate, C1-20alkylphosphonate, arylphosphonate,1-20alkylamine and arylamine;
R' and one R3and R4can be connected to each other, forming a bidentate ligand;
R"' and R"" can be connected to each other to form an aliphatic ring system including a heteroatom selected from the group consisting of nitrogen, phosphorus, arsenic and antimony;
R3and R4may together form a condensed aromatic ring system, and
y represents the number of sp2 carbon atoms between M and the carbon atom bearing an R3and R4and is an integer from 0 to 3 inclusive,
each of X1X2and X3independently selected from anionic ligands; and
L represents a non-anionic ligand, including its salts, solvate, and enantiomers, and these cationic particles associated with the anion.

13. Product of claim 8, characterized in that specified by m is Nisha least one bidentate ligand class of Schiff bases (i) has one of structural formulas (IA) and (IB):

in which Z is selected from the group consisting of oxygen, sulfur and selenium;
each of R" and R"' represents a radical independently selected from the group consisting of hydrogen, C1-7of alkyl, C3-10cycloalkyl,1-6alkyl-C1-6alkoxysilyl, C1-6alkylresorcinol, C1-6alkyl-C3-10cycloalkenyl, aryl and heteroaryl, or R" and R"' together form
aryl or heteroaryl radical, each specified radical (when it is different from hydrogen) optionally substituted by one or more,
preferably 1-3, substituents R5, each of which is independently selected from the group consisting of halogen atoms, C1-6of alkyl, C1-6alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate,1-6alkyl-C1-6alkoxysilyl, C1-6alkylresorcinol, C1-6alkyl-C3-10cycloalkenyl, alkylamine and arylamine;
R' has any of the meanings given for R" and R"', when it is included in the compound having General formula (IA), or when it is included in the compound having General formula (IB)selected from the group consisting of C1-7alkylene and C3-10cycloalkene, and specified Allenova or cycloalkenes group optionally substituted by one or more for what estately R 5.

14. Product of claim 8, wherein at least one of these other ligands (ii) of the specified precoordination complex metal (a) is a derivative in which one or more hydrogen atoms substituted by a group providing constrained spatial difficulty N-heterocyclic vinylcarbene selected from the group consisting of imidazol-2-ylidene, dihydroimidazole-2-ylidene, oxazol-2-ylidene, triazole-5-ylidene, thiazol-2-ylidene, bis(imidazolin-2-ylidene), bis(imidazolidin-2-ylidene), pyrrolidine,
pyrazolidine, dihydropyridine, pyrrolidinedione and their benzododecinium derivatives, or non-ionic profosmotrovaja Verhoeven.

15. Product of claim 8, wherein at least one of these other ligands (ii) of the specified precoordination complex metal (a) is an anionic ligand selected from the group consisting of C1-20of alkyl, C2-20alkenyl,2-20the quinil,1-20of carboxylate, C1-20alkoxy, C2-20alkenylacyl,2-20alkyloxy, aryl, aryloxy,1-20alkoxycarbonyl,1-8alkylthio, C1-20alkylsulfonyl,1-20alkylsulfonyl, C1-20alkylsulfonate, arylsulfonate,1-20alkylphosphonate, arylphosphonate, C1-20alkylamine, arylamine, halogen atoms and cyano,
and the and carbene ligand, represented by the General formula =[=]yCR3R4in which
y represents an integer from 0 to 3, inclusive, and
each of R3and R4represents hydrogen or a hydrocarbon radical selected from the group consisting of C1-20of alkyl, C2-20alkenyl,2-20the quinil,1-20of carboxylate, With1-20alkoxy, C2-20alkenylacyl,2-20alkyloxy, aryl, aryloxy,1-20alkoxycarbonyl, C1-8alkylthio, C1-20alkylsulfonyl,1-20alkylsulfonyl, C1-20alkylsulfonate, arylsulfonate,1-20alkylphosphonate, arylphosphonate, C1-20alkylamine and arylamine; or R3and R4together may form a condensed aromatic ring system.

16. Product of claim 8, including product at least partial cleavage of the link between metal and at least one bidentate ligand class of Schiff bases (i).

17. The method of carrying out the reaction of exchange (metathesis) of the olefin or acetylene or reaction, in which there is a transfer of an atom or group to the compound with ethylene or acetylene unsaturation or any other reactive substrate in the presence of catalytic component, characterized in that the catalytic component includes the product, as claimed in any of PP-16, obazatelno supported on a carrier, and where this reaction, in which there is a transfer of an atom or group that is the reaction of substitution polymerization with ring opening of cyclic olefins, in particular mono - and dimensioned cyclic olefins, and the reaction of exchange (metathesis) of olefins is, in particular, the reaction of exchange (metathesis) DIMENSIONI cyclic olefins.



 

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FIELD: chemistry.

SUBSTANCE: invention relates to a polyolefin synthesis method and more specifically to a polyethylene synthesis method. Polyethylene is a copolymer of ethylene with 1-alkenes. The invention also relates to polyethylene synthesis catalyst systems. The catalyst system is a mixture of metallocenes: hafnocene and an iron-based complex, an activating compound and a support. The invention also relates to films made from polyethylene and packets made from the said films.

EFFECT: disclosed catalyst system enables production of polyethylene with given molecular weight distribution in a single reactor.

16 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of polymerisation and regulation of rheological characteristics of polymeric compositions. Method includes introduction of polymer with high molecular weight into polymer with low molecular weight. Polymeric compositions are obtained by polymerisation of monomers in gas-phase polymerisation reactor with the use of bimetal catalytic composition and at least one regulating agent. Regulating agent such as alcohol, simple ether, oxygen or amin, is added or removed in amount necessary to regulate the level of introduction of polymer with high molecular weight, level of polymer with low molecular weight or both of them. Polymerisation takes place in pseudoliquefied layer with fluidising medium, which includes alkan, selected from group including C4-C20 alkans. With increase of alkan content in reactor, amount of regulating agent is increased for supporting polymeric composition at target value of flow-behaviour index I21.

EFFECT: improvement of regulation of rheological characteristics.

20 cl, 2 dwg, 2 tbl, 5 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention describes a method for synthesis of fluorinated catalytically active compound, catalytic compositions and methods for polymerization comprising such compound. Method for synthesis of fluorinated catalytically active compound involves contacting metallocene catalyst component of catalyst with fluorinated inorganic salt for time sufficient for preparing fluorinated metallocene component of catalyst, such as describes in the following example: wherein R represents substituting groups chosen from group comprising (C1-C10)-alkyls in the specific preferable variant; p represents 0 or a whole number from 1 to 5. Fluorinated inorganic salt in the specific preferable variant is described as a compound that generates fluoride ions in contacting with a diluting agent containing at least 50 wt.-% of water. Invention provides increasing yield of the end product and high output of fluorinated catalytically active compound.

EFFECT: improved method of synthesis, enhanced and valuable chemical properties of catalysts.

9 cl, 14 ex

FIELD: chemistry of metalloorganic compounds.

SUBSTANCE: invention describes organotellurium compounds of the general formula (I): wherein R1 means (C1-C8)-alkyl; each among R2 and R3 means hydrogen atom (H) or (C1-C8)-alkyl; R4 means substituted phenyl, aromatic heterocyclic group or cyano-group. Proposed compounds can be used as initiating agents in "live" radical polymerization that provides possibility for precise regulation of molecular masses and molecular-mass distributions under mild conditions.

EFFECT: improved and valuable properties of compounds.

22 cl, 51 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to metallocenes, method for copolymerization of propylene and ethylene and static copolymers of propylene with ethylene. Invention describes metallocenes comprising different substitutes at positions 2 and 4 and system of ligands, in particular, metallocenes of the formula (I): and metallocenes of the formula (II): Also, invention describes a method for copolymerization of propylene and ethylene in the presence of catalytic system comprising at least one metallocene of the formula (I) and at least one co-catalyst and static copolymers of propylene with ethylene. Invention provides high effectiveness of catalyst, synthesis of copolymers of propylene with ethylene showing high molecular mass and high content of ethylene links.

EFFECT: improved method for copolymerization.

11 cl, 14 tbl, 119 ex

FIELD: polymerization processes and polymerization catalysts.

SUBSTANCE: catalytic system including chromium compound deposited on silicon oxide/titanium oxide carrier, which is preliminarily reduced by carbon monoxide, and co-catalyst selected from group consisting of (i) alkyl lithium, (ii) dialkylaluminum alkoxides combined with at least one alkyl metal selected from group consisted of alkylzinc, alkylaluminum, alkylboron, and mixtures thereof, and (iii) their mixtures, can be used for polymerization of olefins to form low-density polymer with reduced melt index and/or greatly loaded melt index. Such catalyst may be used jointly with olefin polymerization Ziegler-Natta catalytic system. Polymerization processes involving above-defined catalytic systems are also disclosed. Polymers obtained via processes according to invention also show elevated volume viscosity values and find use as components in preparation of bimodal high-molecular weight resins for production of films and/or in pneumatic molding processes.

EFFECT: expanded olefin polymerization possibilities.

31 cl, 3 tbl, 3 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalyst is composed of double metal cyanide compound, organic ligand, and two complexing components other than precedent organic ligand and selected from group including: polyethers and polyesters, glycidyl ethers, esters from carboxylic acids and polyatomic alcohols, bile acids, bile acid salts, bile acid esters, bile acid amides, and phosphorus compounds, provided that selected complexing components belong to different classes.

EFFECT: substantially increased catalytic activity.

5 cl, 1 tbl, 16 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to novel organometallic compounds and to olefin polymerization catalytic systems including such organometallic compounds, and also to a method for polymerization of olefins conduct in presence of said catalytic system. Novel organometallic compound is prepared by bringing into contact (i) compound of general formula I: (I), where Ra, Rb, Rc, and Rd, identical or different, represent hydrocarbon groups; and (ii) Lewis acid of general formula MtR

13
, where Mt represents boron atom and R1, identical or different, are selected from halogen and halogenated C6-C30-aryl groups.

EFFECT: enabled preparation of novel olefin polymerization cocatalysts, which reduce use of excess cocatalyst relative to alkylalumoxanes, do not lead to undesired by-products after activation of metallocene, and form stable catalytic compositions.

14 cl, 1 tbl, 32 ex

FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.

EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

FIELD: chemistry.

SUBSTANCE: method involves reacting triethanol ammonium salts of o-cresoxyacetic and p-chloro-o-cresoxyacetic acid with the corresponding metal salt in alcohol or aqueous medium preferably at room temperature for 1-48 hours. The three-component complexes are extracted through solvent distillation with subsequent washing of the formed powder with ether and drying in a vacuum. The said complexes can be used as a base for making medicinal drugs.

EFFECT: design of a method of preparing complexes of o-cresoxy- and p-chloro-o-cresoxyacetic acid, triethanolamine and metals having formula n[R(o-CH3)-C6H3-OCH2COO-•N+H(CH2CH2OH)3]•MXm, where R = H, p-Cl; M = Mg, Ca, Mn, Co, Ni, Cu, Zn, Rh, Ag; X = CI, NO3, CH3COO; n = 1, 2; m = 1-3.

2 cl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis and preparation of dicyclopentadiene metathesis polymerisation catalysts. The metathesis polymerisation catalyst has the formula: , where L is a substitute selected from the group: , , . Several methods of preparing the catalyst are disclosed. The method of preparing the catalyst having formula , where , , is characterised by that, a second generation Grubbs catalyst is reacted with N,N-dialkyl-(2-vinylbenzyl)amine or 4-(2-vinylbenzyl)morpholine in an inert atmosphere at 60-85°C in the presence of a solvent, where the dialkyl- is methylethyl- or methyl(2-methoxyethyl). The method of preparing the catalyst formula , where L is a substitute selected from the group: , , , , involves reacting a ruthenium triphenylphosphine complex with 1,1-diphenyl-2-propyn-1-ol in tetrahydrofuran at boiling point of the solvent in an inert atmosphere and then with tricyclohexylphosphine at room temperature in an inert atmosphere. The ruthenium indenylidene complex formed is extracted and then, successively in the same reactor, reacted with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 2-(N,N-dialkylaminomethyl)styrene or 1-(2-vinylbenzyl)pyrrolidine or 4-(2-vinylbenzyl)morpholine in toluene while heating to 60-70°C in an inert atmosphere. The dialkyl- is diethyl-, methylethyl- or methyl(2-methoxyethyl)-. A dicyclopentadiene metathesis polymerisation method is disclosed, which involves polymerisation using the catalyst in paragraph 1 in molar ratio substrate: catalyst ranging from 70000:1 to 200000:1.

EFFECT: invention increases catalyst output and simplifies synthesis by reducing the number of steps, and also enables to obtain polydicyclopentadiene with good application properties.

4 cl, 1 tbl, 22 ex

FIELD: chemistry.

SUBSTANCE: invention relates to obtaining physiologically active compounds, particularly to a new water-soluble complex of cis-diaminodichloroplatinum (2+) with isonicotinic acid hydrazide of formula Pt(NH3)2Cl2·2L, where L=INH is isoniaside, isonicotinic acid hydrazide. The method of preparing the complex involves reacting cis-diaminodichloroplatinum (2+) with isonicotinic acid hydrazide with subsequent extraction of the end product.

EFFECT: compound widens the range of water-soluble anti-tumour and anti-metastatic preparations; can be used in medical practice as an analogue of cisplatin on therapeutic effect, but in a more convenient form of administration due to its high solubility and low toxicity.

3 cl, 6 dwg, 1 ex

FIELD: process engineering.

SUBSTANCE: invention relates to complete methane oxidation catalysts and can be used in industries using diesel fuel. Invention covers complete methane oxidation catalysts based on strontium hexaferrites of the following composition: SrMnxFe12-xO19, where x=0, 1, 2, 6. Proposed method comprises settling catalyst components with the help of NH4HCO3 solution at constant pH equal to (7.1 to 8.0) and temperature not lower than 70°C with subsequent stages of filtration, rinsing, drying and roasting. Proposed method comprises also the stage of heat treatment at 800° to 1000° C and is realised in the presence of above described catalysts.

EFFECT: high degree of methane conversion at relatively low temperatures.

6 cl, 2 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: method of obtaining palladium acetate involves dissolving palladium metal in concentrated nitric acid, evaporation of the obtained solution and reaction with acetic acid, where the palladium nitrate solution after evaporation, before crystallisation of palladium (II) nitrate salt, is treated with nitrogen (II) oxide or a mixture of nitrogen (II) and (IV) oxides containing not more than 30% nitrogen (IV) oxide and acetic acid at temperature of the solution of 40-90°C with glacial acetic acid consumption of 1.5-2.5 l per kg of palladium in the solution and nitrogen (II) oxide or mixture of nitrogen (II) and (IV) oxides consumption of 1.0-2.0 m3 at normal conditions per 1 l of the initial palladium nitrate solution for 0.5-1.5 hours and the formed solution is heated in a nitrogen atmosphere at 110-140°C for not less than 2 hours with consumption of elementary nitrogen of approximately 30 m3 per 1 m3 of the formed solution.

EFFECT: obtaining palladium acetate in monophase state and avoding formation of impurities of insoluble palladium catena-poly-acetate.

3 cl, 35 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a polyolefin synthesis method and more specifically to a polyethylene synthesis method. Polyethylene is a copolymer of ethylene with 1-alkenes. The invention also relates to polyethylene synthesis catalyst systems. The catalyst system is a mixture of metallocenes: hafnocene and an iron-based complex, an activating compound and a support. The invention also relates to films made from polyethylene and packets made from the said films.

EFFECT: disclosed catalyst system enables production of polyethylene with given molecular weight distribution in a single reactor.

16 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polyolefin synthesis method and more specifically to a polyethylene synthesis method. Polyethylene is a copolymer of ethylene with 1-alkenes. The invention also relates to polyethylene synthesis catalyst systems. The catalyst system is a mixture of metallocenes: hafnocene and an iron-based complex, an activating compound and a support. The invention also relates to films made from polyethylene and packets made from the said films.

EFFECT: disclosed catalyst system enables production of polyethylene with given molecular weight distribution in a single reactor.

16 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: method involves reaction in aqueous medium of a diaquaplatinum or bis(nitrato)platinum complex in a mixture with dihalogenoplatinum with a block-copolymer of formula (1): or (2):, where R1 represents hydrogen or C1-C12-alkyl, L1 and L2 - connecting groups, R3 - hydrogen, a protective group for amino groups, a hydrophobic or polymerised group, R4 represents hydroxy-, carboxy- or a hydrophobic group, R5 represents hydrogen, an alkali metal ion or a protective group for the carboxylic group, m=5-20000, n=10-60, under the condition that, R5 - hydrogen or an alkali metal ion constitutes 50% or more in n links.

EFFECT: obtaining a conjugate which does not contain silver ions, the solution of which has lower particle-size distribution.

17 cl, 11 dwg, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic chemistry, specifically to a method of preparing a catalyst for metathesis polymerisation of dicyclopentadiene -[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-N,N-dimethylaminomethylphenyl methylene)ruthenium. The method involves reacting a triphenylphosphine complex of ruthenium with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran while boiling in an inert atmosphere, and then with tricyclohexylphosphine at room temperature in an inert atmosphere. The indenylidene ruthenium complex formed is separated and successively reacted in a single reactor with 1,3-bis(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 2-(N,N-dimethylaminomethyl)styrene in toluene while heating in an inert atmosphere.

EFFECT: method increases output of product.

3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing iron (II) oxalate by directly reacting metal with acid in the presence of atmospheric oxygen and a liquid phase while stirring. The process is carried out in a bead mill. The liquid phase solvent used is water with mass ratio of the liquid phase to glass beads equal to 1:1, content of oxalic acid in the initial load is between 0.5 and 2.0 mol/kg, and content of stimulating sodium chloride additive is between 0.02 and 0.10 mol/kg. Crushed grey cast iron which is stirred by a blade mixer is taken in amount of 30% of the mass of the rest of the load. The process is started and carried out at temperature in the interval from (50±2) to (93±2)°C while bubbling air under conditions for stabilising temperature using a heated liquid bath and controlling using a sample taking method and determination of content of iron (II) and (III) salts in the samples, and residual quantity of acid up to virtually complete conversion of the latter into salt. After that air bubbling, external heat supply for stabilising temperature and stirring are stopped. The suspension of the reaction mixture is separated from the glass beads and particles of unreacted metal alloy and filtered. The filtration residue is washed with distilled water and taken for further purification through recrystallisation, while the filtrate and the washing water are returned to the load for the repeated process. Iron (II) oxalate, which is separated from the reaction mixture by traditional filtering, is virtually the only product of conversion.

EFFECT: liquid phase used together with the sodium chloride additive can be repeatedly returned to the process.

10 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing highly pure terephthalic acid which involves the following steps: (a) an oxidation reaction, where p-xylene is oxidised in an acetic acid solution in the presence of a catalyst to form terephthalic acid, (b) obtaining crystals of crude terephthalic acid, where the suspension containing the precipitate of the obtained terephthalic acid is separated into a solid phase and a liquid to obtain crystals of crude terephthalic acid, (c) hydrogenation step, where crystals of crude terephthalic acid are dissolved in water to form an aqueous solution which is hydrogenated, (d) crystallisation of highly pure terephthalic acid, where terephthalic acid is crystallised from the hydrogenated aqueous solution to form a suspension of highly pure terephthalic acid, (e) obtaining crystals of highly pure terephthalic acid, where the suspension of highly pure terephthalic acid is separated into a solid phase and a liquid to obtain crystals of highly pure terephthalic acid and a primary mother solution, and (f) extraction of p-toluic acid from the primary mother solution and taking it to the oxidation reaction step, where the p-toluic acid extraction step includes the following steps: (I) adsorption step, where primary or secondary mother solution, obtained by cooling the primary mother solution in order to separate the solid phase and liquid, is fed in form of treated liquid into an adsorption column filled with an adsorption agent, where the p-toluic acid breakthrough time is greater than that of benzoic acid, for adsorption of p-toluic acid and benzoic acid from the treated liquid on the adsorption agent, (II) cutting supply of the treated liquid into the adsorption column for at a certain moment in time when concentration of benzoic acid in the effluent from the adsorption column reaches at least 10% of the concentration of benzoic acid in the treated liquid, (III) desorption step, where a desorption agent in form of acetic acid, methylacetate or their mixture is fed into the adsorption column for desorption of the adsorbed p-toluic acid and (IV) circulation step, where p-toluic acid contained in the desorption agent flows from the adsorption column and taken to the oxidation reaction step.

EFFECT: design of a method of obtaining highly pure terephthalic acid through selective extraction of p-toluic acid from waste water currently released, and use of the waste water as raw material for producing terephthalic acid.

19 cl, 6 dwg, 5 ex, 1 tbl

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