Catalyst complex for metathesis of olefins, method for preparation thereof and use thereof

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of preparing a catalyst complex of formula , where R1, R2, R3 and R4 are independently selected from a group consisting of hydrogen, C1-C20alkyl, C2-C20alkoxy group, halogen and amino group, where if R1 or R3 is an amino group, the amino group is optionally substituted with one or more fragments which are alkyl, if R2 or R4 is an amino group, the amino group is optionally substituted with one or more fragments which are C1-C20alkyl. The method includes a step of reacting a ruthenium catalyst precursor with one or two bidentate ligands of the Schiff base class in a nonpolar solvent and in the presence of a weak base, where the bidentate ligands of the Schiff base class are independently in amount of 1.0-3.0 equivalents relative to the amount of the catalyst precursor (formulae of the precursors and ligands are given in claim 1 of the invention). The invention also discloses a catalyst complex, a supported catalyst for metathesis of olefins and use thereof in olefin metathesis reactions.

EFFECT: invention enables to obtain a catalyst having high activity after activation, monomer stability and a simple and cheap method.

11 cl, 2 tbl

 

The technical field to which the invention relates

The present invention relates to catalytic complex for metathesis reactions of olefins, its preparation and its use in the metathesis reactions of olefins, in particular in reactions metathetical polymerization disclosure cycle (ROMP).

The level of technology

In recent years, the metathesis of olefins has been widely developed and has become a versatile and efficient tool in organic synthesis.

The success of the reaction of metathesis of olefins is mainly due to the versatility and development of well-characterized ruthenium catalysts that are resistant to the required reaction conditions. Due to the fact that these catalysts were commercially available and were used in a large number of potentially interesting applications in the field of new problems have emerged, for example the latency of the catalysts. Ideal latent catalyst for the metathesis of olefins does not exhibit catalytic activity in the presence of the monomer or the media, at room temperature, but can be quantitatively stimulated in a highly active form by thermal, chemical or photochemical activation to initiate the metathesis reaction. In addition, the stability of the catalyst to the decomposition or thermal decomposition should be guaranteed a thorough p�dbaron ligand environment.

For industrial use in the polymerization of Dicyclopentadiene (DCPD) requires latent catalysts exhibiting lower initial speed, allowing longer to store the mixture of the monomer-catalyst prior to the polymerization.

Van der Schaaf with the staff has developed a thermally-activated, slowly initiating the metathesis of olefins, the catalyst (PR3)(Cl)2Ru(CH(CH2)2-C,N-2-C5H4(N) (Scheme 1), while the initiation temperature were adjusted by changing the equivalent circuit of the pyridine ring (Van der Schaaf, R. A.; Kolly, R.; Kirner, H.-J.; Rime, F.; Muhlebach, A.; Hafner, A. J. Organomet. Chem. 2000, 606, 65-74). Unfortunately, the activity of the complexes were proposed undesirably low; limited to 12000 EQ. DCPD. Later Ung suggested similar custom catalytic system obtained by partial isomerization of TRANS-(SIMes)(Cl)2Ru(CH(CH2)2-C,N-2-C5H4(N) (2) in CIS analogue (, T.; Hejl, A.; Grubbs, R. H.; Schrodi, Y. Organometallics 2004, 23, 5399-5401). However, none of these catalysts could not be stored in the DCPD monomer for a long time, because the reaction metathetical polymerization disclosure cycle (ROMP) of Dicyclopentadiene (DCPD) was completed in 25 minutes after injection of the catalyst.

In another approach to rationally designed thermally stable catalyst for metathesis olef�new for the polymerization of Dicyclopentadiene (DCPD) efforts have been focused on the development of Ru-carbene catalysts containing O,N-bidentate ligand class Schi bases developed by Verpoort et al (Scheme 2, 4, 5, L=SIMes). It has been shown that such complexes are extremely inactive at room temperature in the polymerization of cyclic olefins with low deformation, can be stored in DCPD for months and can be thermally activated to produce high activity for polymerization in the mass of DCPD, but activity, comparable with the corresponding complexes without Schiff's base, achieved can not be (EP 1 468 004; Allaert, B.; Dieltiens, N.; Ledoux, N.; Vercaemst, C; Van Der Voort, P.; Stevens, C. V.; Linden, A.; Verpoort, F. J. Mol. Cat. A: Chem. 2006, 260, 221-226).

In addition, activation of the catalyst promotes the addition of large amounts of acids Branstad (e.g., HCl), leading to high catalytic activity towards the reaction of the ROMP of Dicyclopentadiene (DCPD) (EP 1 577 282; EP 1 757 613; V. De Clercq, F. Verpoort, Tetrahedron Lett., 2002, 43, 9101-9104; (b) B. Allaert, N. Dieltens, N. Ledoux, C. Vercaemst, P. Van Der Voort, C. V. Stevens, A. Linden, F. Verpoort, J. Mol. Catal. A: Chem., 2006, 260, 221-226; (c) N. Ledoux, B. Allaert, D. Schaubroeck, S. Monsaert, R. Drozdzak, P. Van Der Voort, F. Verpoort, J. Organomet. Chem., 2006, 691, 5482-5486). However, the need for large amounts of HCl, due to its high volatility and corrosion problems, is unacceptable for industrial applications.

Were recently synthesized series of latent catalysts for metathesis of olefins bearing bidentate to2-(O,O)ligands (Scheme 2, 3). It turned out that complex 3 is inactive for polymerization without solvent Dicyclopentadiene (DCPD). Moreover, it was shown that the complex 3 (Scheme 2, L=DCS3, SIMes) is easily activated by irradiation of a mixture of the catalyst/monomer containing motocicletas generator and suitable for the reactions ROMP of Dicyclopentadiene (DCPD) (D. M. Lynn, E. L. Dias, R N. Grubbs, V. Mohr, 1999, WO 99/22865). Despite the fact that irradiation of a solution of Dicyclopentadiene (DCPD) 3 (L=SIMes) in minimum amount of CH2Cl2led to a complete gelation within 1 hour, cured and cross-linked monomer was not received. This indicates a low catalytic activity and low amounts of active particles. Moreover, the Protocol of synthesis for catalyst 3 has a serious drawback, namely the use of T1(alkyl-ASAS). Thallium and its derivatives are extremely toxic, so this method is not acceptable for industrial applications. In addition, the use of Ag(Me6acac) led to a complete ligand exchange, but the desired product 3 was resistant to further treatment, only ligand exchange with the use of thallium as a more effective element of parameterone allowed to obtain the desired pure complex 3 in high yield (K. Keitz, R. N. Grubbs, J. Am. Chem. Soc., 2009,131, 2038-2039).

Thus, the latent catalysts are important for meta�eisney polymerization disclosure cycle of cyclic olefins with low deformation, allowing the mixing of the monomer and catalyst without the accompanying gelation or microencapsulation of precatalysts. Obtaining latent catalyst is stable in the monomer, is highly active when suitable for the production of the activation method and made harmless to the environment, remains an open issue.

Disclosure of the invention

The aim of the present invention to provide a catalytic complex for use in the metathesis reactions of olefins, which overcomes the above deficiencies latent catalysts with Schiff base, a stable consisting of DCPD monomer, easily and effectively activates the quantitative amounts of a weak Lewis acid with high activity after activation and the simple, efficient, safe manner with a high yield.

This object is achieved by a method of preparation of the catalytic complex consisting of:

a. of metal atom selected from the group consisting of ruthenium and osmium;

b. two bidentate class of ligands of Schiff bases containing aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup, via at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium associated with the specified metal

c. nucleophilic carbene ligand associated with the specified metal; and

d. carbon-containing ligand associated with said metal, wherein said carbon-containing ligand is a substituted or unsubstituted alkylidene, vinylidene or inteeligence ligand;

the method includes the stage of interaction of the precursor ruthenium or osmium catalyst, consisting of:

a. of metal atom selected from the group consisting of ruthenium and osmium;

b. two anionic ligands;

c. nucleophilic carbene ligand associated with the specified metal;

d. carbon-containing ligand associated with said metal, wherein said carbon-containing ligand is a substituted or unsubstituted alkylidene, vinylidene or inteeligence ligand; and

e. neutral ligand or

predecessor ruthenium or osmium catalyst, consisting of:

a. of metal atom selected from the group consisting of ruthenium and osmium;

b. one anionic ligand;

c. one bidentate ligand class Schi bases containing aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup at least one additional heteroatom selected from the group consisting of oxygen, CoE�s, and selenium, associated with the specified metal;

d. nucleophilic carbene ligand associated with the specified metal; and

E. carbon-containing ligand associated with said metal, wherein said carbon-containing ligand is a substituted or unsubstituted alkylidene, vinylidene or inteeligence ligand;

1.0-3.0 equivalents of bidentate ligand class of Schiff bases in nonpolar solvent and in the presence of weak bases.

In addition, the present invention relates to catalytic complex, which can be obtained this way, i.e. catalytic complex consisting of:

a. of metal atom selected from the group consisting of ruthenium and osmium;

b. two bidentate class of ligands of Schiff bases containing aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium associated with the specified metal;

c. nucleophilic carbene ligand associated with the specified metal; and

d. carbon-containing ligand associated with said metal, wherein said carbon-containing ligand is a substituted or unsubstituted alkylidene, vinylidene or inteeligence whether�of the Andes.

In addition, the present invention relates to a catalyst containing the above catalyst complex.

Thus, the present invention relates to the use of the above catalytic complex and a catalyst in the metathesis reactions of olefins and, in particular, in metathetical polymerization disclosure cycle.

Preferred embodiments of the present invention are described in dependent claims.

The implementation of the invention

The catalytic complex according to the present invention contains a metal atom selected from the group consisting of ruthenium and osmium, as the base metal. Preferably, the catalyst comprises ruthenium.

In addition, the catalytic complex contains two bidentate ligand class Schi bases containing aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium associated with the specified metal. Preferably, the heteroatom was oxygen.

Suitable bidentate ligands of the class of Schiff bases is described for example in European patent 1468004. These ligands of the class of Schiff's bases have the General formula:

where Z is selected from the group consisting of oxygen, sulfur and selenium, and where each R', R" and R'" represents a radical independently selected from the group consisting of hydrogen, C1-6alkyl, C3-8cycloalkyl, 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 of R5, each of which is independently selected from the group consisting of halogen atoms, C1-6alkyl, C1-6alkoxygroup, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, alkylammonium and arylamine.

In addition, the bidentate ligands of the class of Schi bases for use in the catalytic complex according to the present invention are disclosed in the pending European patent applications EP 08290747 and 08290748.

These ligands of the class of Schiff bases derived from derivatives salicylaldimine of the General formula shown below:

where S1to S4represent substituents which are selected so that the connection had RKand≥6.2, and where

But it is aheteroaryl, substituted or unsubstituted alkyl, heteroalkyl or cycloalkyl;

In is a in�Gorod, With1-C20alkyl, C1-C20heteroalkyl or heteroaryl, where each is different from hydrogen, the group may be optionally substituted with one or more groups selected from the group consisting of C1-C10of alkyl and aryl;

each Ro1, Ro2, Rm1, Rm2and Rpselected from the group consisting of hydrogen, C1-C20alkyl, C1-C20heteroalkyl, S1-C20alkoxygroup, aryl, aryloxy groups, heteroaryl, heteroseksualci, disulfide, carbonate, isocyanate, carbodiimide, carbalkoxy, carbamate and halogen, thioether, ketone, aldehyde, ester, ether, amino, amide, nitro, carboxylic acid, and is other than hydrogen groups optionally substituted with one or more groups selected from the group consisting of C1-C20alkyl, C1-C20alkoxy and aryl, and Ro1, Ro2, Rm1, Rm2and Rptogether may form a condensed cyclic aliphatic or aromatic ring, optionally substituted with one or more groups selected from the group consisting of C1-C20alkyl, C1-C20heteroalkyl, S1-C20alkoxygroup, aryl, aryloxy groups, heteroaryl, heteroseksualci, disulfide, carbonate, Isola�ATA carbodiimide, carbalkoxy, carbamate and halogen, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, and is other than hydrogen groups optionally substituted with one or more groups selected from the group consisting of C1-C20alkyl, C1-C20alkoxygroup and aryl.

Preferably, the substituents from S1to S4were selected from the group consisting of hydrogen, amino group, substituted or unsubstituted mono - and dialkylamino, S1-C20of alkyl, thioalkyl, aryl and aryloxy groups.

More preferably, the substituents from S1to S4were selected from the group consisting of hydrogen, methoxy groups, methylthiourea, amino, dimethylaminopropyl, trifloromethyl, cryptometer, tert-butyl, phenyl, fenoxaprop, chlorine, bromine, piperidinyl, 1-pyrrolidino, 4-tert-butylphenoxy and 2-pyridyl.

Preferably, Ro1, Ro2, Rm1, Rm2and Rpwere selected from the group consisting of hydrogen, methyl, isopropyl, tert-butyl, methoxy groups, dimethylaminopropyl and nitro group.

Presents specific examples of such ligands of the class of Schiff's bases of the above General formula in which a represents hydrogen,

A p�establet a and S1to S4and Ro1, Ro2, Rm1, Rm2and Rpare as defined below.

The catalytic complex according to the present invention additionally contains a nucleophilic carbene ligand associated with the metal ruthenium or osmium.

Suitable nucleophilic karbanova ligands described in European patent 1468004.

Preferably, the nucleophilic carbene ligand represented a substituted or unsubstituted, saturated or unsaturated 1,3-deleteroute cyclic compound in which the heteroatoms are nitrogen atoms.

Such 1,3-deleteroute cyclic compound may have the formula

where Y and Y1independently selected from the group consisting of hydrogen, C1-C20alkyl, C2-C20alkenyl, S2-C20alkynyl, S2-C20alkoxycarbonyl, aryl, C1-C20carboxylate, C1-C20alkoxygroup, S2-C20alkenylacyl, S2-C20alkyloxy or aryloxy groups; each Y and Y1optionally is substituted With1-C5by alkyl, halogen, (C1-C6alkoxygroup or phenyl group substituted by halogen, C1-C5the alkyl or C1-C5and�maksigrupp and;

Z and Z1independently selected from the group consisting of hydrogen, C1-C20alkyl, C2-C20alkenyl, S2-C20alkynyl, S2-C20alkoxycarbonyl, aryl, C1-C20carboxylate, C1-C20alkoxygroup, S2-C20alkenylacyl, S2-C20alkyloxy or aryloxy groups, each Z and Z1optionally is substituted With1-C5by alkyl, halogen, (C1-C6alkoxygroup or phenyl group substituted by halogen, C1-C5the alkyl or C1-C5alkoxygroup, and wherein the ring may be optionally aromatic, through the introduction of additional double bonds in the ring.

Preferably, the nucleophilic carbene ligand represented SIMES or IMES, and most preferably, the nucleophilic carbene ligand represented SIMES.

The catalytic complex according to the present invention further contains a carbon-containing ligand associated with the metal ruthenium or osmium. This carbon-containing ligand selected from the group consisting of substituted or unsubstituted alkylidene, vinylidene or indenyltitanium ligands.

Such alkylidene, vinylidene or Ingenierie ligands are described for example in WO 00/15339.

Alternates for �quiet ligands selected from the group consisting of C1-C10alkyl, C2-C20alkynyl, S1-C20alkoxygroup, S2-C20alkoxycarbonyl and aryl.

Most preferably, the carbon-containing ligand represented familygenealogy ligand.

Suitable carbon-containing ligands are also described in European patent 1468004.

A preferred family of catalytic complexes according to the present invention has the formula:

where R1, R2, R3and R4independently selected from the group consisting of hydrogen, halogen, C1-C20alkyl, C2-C20alkenyl, C2-C20alkenyl, C2-C20alkoxycarbonyl, aryl, C1-C20carboxylate, C1-C20alkoxygroup, C2-C20alkenylacyl, C2-C20alkyloxy, aryloxy groups, C1-C20allylthiourea, C1-C20alkylsulfonyl, C1-C20alkylsulfonyl, and wherein each of R1, R2, R3and R4can be substituted With1-C5by alkyl, halogen, (C1-C10alkoxygroup or aryl group, substituted C1-C5the alkyl, C1-C5arroceros, halogen or a functional group.

Particularly preferred complex according� the present invention has the formula:

The catalytic complex of the present invention can be applied as such or in the form of a catalyst containing the catalyst complex and the media.

The carrier can be selected from the group consisting of porous inorganic solids, such as amorphous or paracrystalline materials, crystalline molecular sieves and modified layered materials including one or more inorganic oxides, and organic polymer resins.

The catalytic complex prepared by the method which includes the stage of interaction of the precursor ruthenium or osmium catalyst, consisting of:

a. of metal atom selected from the group consisting of ruthenium and osmium;

b. two anionic ligands;

c. nucleophilic carbene ligand associated with the specified metal;

d. carbon-containing ligand associated with said metal, wherein said carbon-containing ligand is a substituted or unsubstituted alkylidene, vinylidene or inteeligence ligand; and

e. neutral ligand;

or the precursor to ruthenium or osmium catalyst, consisting of:

a. of metal atom selected from the group consisting of ruthenium and osmium;

b. one anionic ligand;

c. one�about bidentate ligand class Schi bases, containing aminogroup and coordinated with the metal, in addition to the nitrogen atom of the specified aminogroup at least one additional heteroatom selected from the group consisting of oxygen, sulfur and selenium associated with the specified metal;

d. nucleophilic carbene ligand associated with the specified metal; and

e. carbon-containing ligand associated with said metal, wherein said carbon-containing ligand is a substituted or unsubstituted alkylidene, vinylidene or inteeligence ligand;

from 1.0 to 3.0 equivalents of bidentate ligand class of Schiff bases in nonpolar solvent and in the presence of weak bases.

Suitable for use in the present invention anionic ligands selected from the group consisting of C1-20alkyl, C1-20alkenyl, S1-20alkynyl, S1-20carboxylate, C1-20alkoxygroup, S1-20alkenylacyl, S1-20alkyloxy, aryl, aryloxy groups, With1-20alkoxycarbonyl, C1-8allylthiourea, S1-20alkylsulfonyl, S1-20alkylsulfonyl, C1-20alkylsulfonate, arylsulfonate, S1-20alkylphosphonate, arylphosphonate, S1-20alkylamine, arylamine, halogen atoms and cyanide groups. Preferably, the anionic ligand represented �lorenia ligands.

Preferably, the neutral ligand represented a phosphine of the formula PR3R4R5where R3is a secondary alkyl or cycloalkyl, and each of R4and R5represents aryl, C1-C10primary alkyl, secondary alkyl or cycloalkyl, each independently of the other. More preferably, the neutral ligand was one of P(cyclohexyl)3P(cyclopentyl)3, P(isopropyl)3or P(phenyl)3.

Since the catalytic complex according to the present invention and compounds used in the method for its preparation, are sensitive to air, moisture and impurities, you should be certain that the used starting materials, reagents and solvents do not contain impurities and dried.

Suitable weak bases for use in the method according to the present invention have the value of the pKbin the range from 3.5 to 7. Examples of suitable bases for use in the present invention include Li2CO3, Na2CO3, K2CO3, CuCO3and Ag2CO3. Ag2CO3with the magnitude of the pKb3,68 is especially preferred.

Additional examples of weak bases, which are used in the method of the present invention include carboxylates.

For when�otopleniya catalytic complex of the present invention the catalyst precursor, ligand class Schi bases and weak base, for example Ag2CO3preferably premixed and then added a suitable non-polar solvent which does not interact with any of the components of the preliminary mixture. In the present invention it is preferable to use aprotic solvents, which do not have acidic hydrogen, with a dielectric constant above 3.

In General, the dielectric constant of the solvent provides a rough estimation of the polarity of the solvent. Solvents with dielectric constants less than 15 are generally considered nonpolar. Technically, using dielectric permittivity to evaluate the ability of a solvent to reduce the electric field surrounding a charged particle immersed in this field. Examples are shown in Table 1 below.

As indicated above, the preferred solvents for use in the present invention have a dielectric constant higher than 3, and such solvents include tetrahydrofuran, methylenechloride, chloroform and diethyl ether.

Most preferably, as a non-polar solvent tetrahydrofuran was applied.

The reaction mixture was then heated and stirred. To�to the rule, the reaction is conducted at a temperature in the range from 20°C to the temperature of the boiling point of the used non-polar solvent, preferably in the range from 40°C to 60°C, particularly preferably at about 40°C.

Generally, the reaction time ranges from 2 to 72 h.

After completion of the reaction, the reaction mixture was cooled to about 0°C to remove any by-products formed during filtration. Then the solvent was removed by evaporation, typically under reduced pressure.

The amount of weak base, which is used in the method according to the present invention typically is in the range from 0.5 to 2.0 equivalents.

It is preferable to use a weak base in an amount of from 0.5 to 1 equivalents, more preferably about 0.6 equivalents relative to the amount of catalyst precursor in the case where the precursor contains one anionic ligand and uses a single bidentate ligand of a class of Schiff's bases.

In the case where the precursor contains two anionic ligand, a weak base is preferably used in an amount of from 1.0 to 2.0 equivalents, preferably about 1.1 equivalents relative to the amount of catalyst precursor.

The number of ligand class Schi bases used in the method according to the present invented�Yu, as a rule, is from 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, and particularly preferably about 1.1 equivalent relative to the amount of catalyst precursor in the case where the precursor contains one ligand class Schi bases, and from 2.0 to 2.5 equivalents, and particularly preferably about 2.1 equivalent relative to the amount of catalyst precursor in the case where the precursor contains two anionic ligand.

The optimal outputs of the catalyst according to the present invention are achieved when 1 equivalent of catalyst precursor interacts with 2.1 equivalents of ligand class of Schiff bases in the presence of 1.1 equivalent of a weak base, preferably Ag2CO3in the case where the precursor contains two anionic ligand.

The optimal outputs of the catalyst according to the present invention are achieved when 1 equivalent of catalyst precursor interacts with 1.1 equivalent of ligand class of Schiff bases in the presence of 0.6 equivalents of weak base, preferably Ag2CO3in the case where the precursor contains one anionic ligand and one ligand class of Schiff's bases.

The catalytic complex according to the present invention exhibits excellent latent�industry in the reaction metathetical polymerization disclosure cycle of Dicyclopentadiene (DCPD) in comparison with ruthenium catalysts in this field. Moreover, the catalyst according to the present invention is inactive at room temperature and even after heating to 200°C, which is confirmed by measurements by the method of differential scanning calorimetry (DSC). Moreover, the catalyst according to the present invention can be activated by a smaller amount of a Lewis acid or Bronsted than catalysts of the prior art.

A more detailed description of the present invention presents the following examples, in which the manipulation is sensitive to oxygen and moisture materials were performed using the methods Slanka in an argon atmosphere. As illustrative of the solvent used THF.

General method of preparation of the catalytic complexes of phenylindolin-Schiff base-ruthenium (Scheme 3)

Stoichiometric amount of the precursor phenylenedimaleimide catalyst 1 (Scheme 3, Method A) or precursors of monoolefinic Schiff 2 (Scheme 3, Method B), the corresponding ligand class Schi bases, sodium carbonate, silver (I) is added to the flask Slanka (50-250 ml). The flask is evacuated and filled with argon. Then in the flask Slanka (still in the atmosphere of argon) was added dry THF (20 ml) and stirred for occurs 6-72 h. the Reaction mixture was cooled to 0°C, the white precipitate PCy3AgCl (side ol�the product) is removed by filtration. The filtrate is collected in the flask Slanka (250 ml) and the solvent removed by evaporation under reduced pressure. The crude product is suspended in hexane, stirred well and filtered. The final product was dried under reduced pressure.

Complex 3. Method A. Predecessor phenylenedimaleimide catalyst 1 (Scheme 3) (0.54 mmol), 2-[(4-tertbutylbenzylamine)methyl]-4-methoxyphenol (1.134 mmol), silver carbonate(I) (0.594 mmol) and THF (10 ml) is introduced into the reaction as described above for 72 h at room temperature. A study of the reaction mixture by NMR nuclei1N and31P revealed a quantitative conversion in a complex of 3.

Complex 3. Method B. Ruthenium[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinone]-[2-[[(4-tertbutylbenzylamine)methyl]-4-methoxyphenyl]-[3-phenyl-1H-indene-1-Illidan] ruthenium(II) chloride (0.54 mmol), 2-[(4-tertbutylbenzylamine)methyl]-4-methoxyphenol (0.594 mmol), silver carbonate(I) (0.324 mmol) and THF (10 ml) is introduced into the reaction as described above, for 24 h at room temperature. A study of the reaction mixture by NMR nuclei1N and31P revealed a quantitative conversion in a complex of 3.

Complex 4. Method A. Predecessor phenylenedimaleimide catalyst 1 (Scheme 3) (0.54 mmol), 2-[(4-tertbutylbenzylamine)methyl]-5-methoxyphenol (1.134 mmol), silver carbonate(I) (0.594 mmol) THF (10 ml) is introduced into the reaction, as described above, for 72 h at room temperature. A study of the reaction mixture by NMR nuclei1N and31P revealed a quantitative conversion in a complex of 4.

Complex 4. Method B. Ruthenium [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinone] - [2-[[(4-tertbutyl phenylimino)methyl]-5-methoxyphenyl] - [3-phenyl-1H-indene-1-Illidan] ruthenium(II) chloride (0.54 mmol), 2-[(4-tertbutylbenzylamine)methyl]-5-methoxyphenol (0.594 mmol), silver carbonate(I) (0.324 mmol) and THF (10 ml) is introduced into the reaction as described above for 72 h at room temperature. A study of the reaction mixture by NMR nuclei1N and31P revealed a quantitative conversion in a complex of 4.

Complex 5. Method A. Predecessor phenylenedimaleimide catalyst 1 (Scheme 3) (0.54 mmol), 2-[(4-methylphenylimino)methyl]-5-methoxyphenol (1.134 mmol), silver carbonate(I) (0.594 mmol) and THF (10 ml) is introduced into the reaction as described above for 72 h at room temperature. A study of the reaction mixture by NMR nuclei1N and31P revealed a quantitative conversion in a complex of 5.

Complex 5. Method B. Ruthenium[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinone] - [2-[[(4-tertbutyl phenylimino)methyl]-5-methoxyphenyl] - [3-phenyl-1H-indene-1-Illidan] ruthenium(II) chloride (0.54 mmol), 2-[(4-methylphenylimino)methyl]-5-methoxyphenol (0.594 mmol), silver carbonate(I) (0.324 m�ol) and THF (10 ml) is introduced into the reaction, as described above, for 72 h at room temperature. A study of the reaction mixture by NMR nuclei1N and31P revealed a quantitative conversion in a complex of 6.

Complex 6. Method A. Predecessor phenylenedimaleimide catalyst 1 (Scheme 3) (0.54 mmol), 2-[(4-methylphenylimino)methyl]-5-methoxyphenol (0.54 mmol), silver carbonate(I) (0.594 mmol) and THF (10 ml) is introduced into the reaction as described above for 72 h at room temperature, then added 2-[(4-methylphenylimino)methyl]-4-methoxyphenol (0.594 mmol). The resulting mixture reacts within 48 h. a Study of the reaction mixture by NMR nuclei1N and31P revealed a quantitative conversion in a complex of 6.

Complex 6. Method B. Ruthenium [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinone]-[2-[[(4-methylphenylimino)methyl]-5-methoxyphenyl]-[3-phenyl-1H-indene-1-Illidan] ruthenium(II) chloride (0.54 mmol), 2-[(4-methylphenylimino)methyl]-4-methoxyphenol (0.594 mmol), silver carbonate(I) (0.324 mmol) and THF (10 ml) is introduced into the reaction, as described above, for 24 h at room temperature. A study of the reaction mixture by NMR nuclei1N and31P revealed a quantitative conversion in a complex of 6.

Complex 7. Method A. Predecessor phenylenedimaleimide catalyst 1 (Scheme 3) (0.54 mmol), 2-[(4-outPROPYLENEIMINE)methyl]-5-methoxyphenol (1.134 mmol), carb�Nate silver(I) (0.594 mmol) and THF (10 ml) is introduced into the reaction, as described above, for 72 h at room temperature. A study of the reaction mixture by NMR nuclei1N and31P revealed a quantitative conversion of the complex 7.

Complex 7. Method B. Ruthenium [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinone] - [2-[[(4-outPROPYLENEIMINE)methyl]-5-methoxyphenyl] - [3-phenyl-1H-indene-1-Illidan] ruthenium(II) chloride (0.54 mmol), 2-[(4-outPROPYLENEIMINE)methyl]-5-methoxyphenol (0.594 mmol), silver carbonate(I) (0.324 mmol) and THF (10 ml) is introduced into the reaction as described above, for 24 h at room temperature. A study of the reaction mixture by NMR nuclei1N and31P revealed a quantitative conversion of the complex 7.

Properties of the catalyst

The ruthenium catalyst complex (4) according to the present invention, as shown above, was tested in ROMP reactions of Dicyclopentadiene (DCPD). The ruthenium catalyst (2A), containing only one bicentenary ligand class Schi bases, was used as the reference catalyst:

The results are presented in Table 2 below.

Salicylaldimine ligand of the reference catalyst (2A) carries a substituent in the ortho-position of the aniline fragment and ruthenium catalysts of this type, having�e salicylaldimine ligand such ortho-substituent exhibit good latency in reactions metathetical polymerization disclosure cycle of Dicyclopentadiene.

Despite the absence of such Deputy, it was found that the ruthenium catalyst complex 4 according to the present invention is the exceptional latent catalyst in the reaction ROMP of Dicyclopentadiene (DCPD) ratio (catalyst/monomer 1:15000), inactive at room temperature and even after heating above 200°C, as confirmed by DSC measurement method. The stability of the bis-substituted catalytic complex 4 of the present invention is superior to the stability of the more reactive monosubstituted analog and similar stability of the reference catalyst (2A) (see Table 2). The stability of the ruthenium catalyst 4 of the present invention in ROMP reactions of Dicyclopentadiene (DCPD) improved partly due to the increase in steric hindrance around the ruthenium center.

When chemical activation of bis-salicylaldimine catalytic complex 4 according to the present invention demonstrates increased initiation compared with the reference catalyst (2A), because only less than 1 equivalent PhSiCl3to generate a highly active system. During the catalysis reaction ROMP of Dicyclopentadiene (DCPD) chemically activated complex 2A in the same conditions (less than 1 equivalent PhSiCl3) there is a low catalytic activity. Even after chemical activation using 45 equivalents PhSiCl3the benchmark catalyst (2A) still exhibits a slower initiation compared with the ruthenium complex 4 according to the present invention.

Thus, after activation, the ruthenium complex 4 according to the present invention is significantly superior to the reference catalyst (2A) to form a polymer having improved properties, such as the glass transition temperature of 171°C and 178°C, the superior properties of other latent catalysts.

1. Method of preparation of the catalytic complex having the formula

where R1, R2, R3and R4independently selected from the group consisting of hydrogen, C1-C20alkyl, C2-C20alkoxygroup, halogen and amino, where if R1or R3represents an amino group, the amino group optionally substituted by one or more fragments that represents alkyl, if R2or R4represents an amino group, the amino group optionally substituted by one or more fragments, representing the C1-C20alkyl;
where the method includes the stage of interaction of predestiny�and ruthenium catalyst, having the formula:

where Mes means mesitylene, su means cycloalkyl;
with two bidentate ligands of the class of Schiff bases in nonpolar solvent and in the presence of weak bases, where the bidentate ligands of the class of Schiff's bases are independently in an amount of from 1.0 to 3.0 equivalents relative to the amount of catalyst precursor, where one bidentate ligand class of Schiff bases has the formula:

and another bidentate ligand class of Schiff bases has the formula

where R1, R2, R3and R4independently selected from the group consisting of hydrogen, C1-C20alkyl, C1-C20alkoxygroup, halogen and amino, where if R1or R3represents an amino group, the amino group optionally substituted by one or more fragments that represents alkyl, if R2or R4represents an amino group, the amino group optionally substituted by one or more fragments, representing the C1-C20alkyl;
or the stage of interaction of the precursor of the ruthenium catalyst having the formula:

where R1, R2independently selected from the group, with�modern from hydrogen, C1-C20alkyl, C1-C20alkoxygroup, halogen and amino, where if R1represents an amino group, the amino group optionally substituted by one or more fragments that represents alkyl, if R2represents an amino group, the amino group optionally substituted by one or more fragments, representing the C1-C20alkyl;
with bidentate ligand of a class of Schiff bases in nonpolar solvent and in the presence of weak bases, where the bidentate ligand of a class of Schiff's bases is present in an amount of from 1.0 to 3.0 equivalents relative to the amount of catalyst precursor, where bidentate ligand class of Schiff bases has the formula:

where R3and R4independently selected from the group consisting of hydrogen, C1-C20alkyl, C1-C20alkoxygroup, halogen and amino, where if R3represents an amino group, the amino group optionally substituted by one or more fragments that represents alkyl, if R4represents an amino group, the amino group optionally substituted by one or more fragments, representing the C1-C20alkyl.

2. A method according to claim 1, wherein CL�bym base is Ag 2Co3.

3. A method according to claim 1, wherein the weak base is used in an amount of 1 to 2 equivalents, preferably about 1.1 equivalents relative to the amount of catalyst precursor, for the case when the precursor contains two chloride ligand, and used two bidentate ligand of a class of Schiff's bases.

4. A method according to claim 1, wherein the weak base is used in an amount of from 0.5 to 1 equivalents, preferably about 0.6 equivalents relative to the amount of catalyst precursor, for the case when the precursor contains one chloride ligand and uses a single bidentate ligand of a class of Schiff's bases.

5. A method according to claim 1, wherein the nonpolar solvent is tetrahydrofuran.

6. A method according to claim 1, wherein the reaction step is carried out at a temperature in the range from 20°C to the temperature of the boiling point non-polar solvent, preferably at about 40°C.

7. The catalytic complex obtained by the method according to claim 1 having the formula:

where R1, R2, R3and R4independently selected from the group consisting of hydrogen, halogen, C1-C20alkyl, C1-C20alkoxygroup and amino groups, where if R1or R3represents an amino group, the amino group of n�necessarily substituted by one or more fragments, represents alkyl, if R2or R4represents an amino group, the amino group optionally substituted by one or more fragments, representing the C1-C20alkyl.

8. The catalyst for metathesis reactions of olefins, containing a catalytic complex according to claim 7 and a carrier.

9. The catalyst according to claim 8, wherein the carrier is selected from the group consisting of porous inorganic solids, such as amorphous or paracrystalline materials, crystalline molecular sieves and modified layered materials including one or more inorganic oxides and organic polymers.

10. The use of a catalytic complex according to claim 7 or a catalyst according to claim 8 or 9 as a catalyst in the metathesis reactions of olefins.

11. The use according to claim 10, in which metathetical polymerization of olefins is metatezisnaya polymerization disclosure cycle.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a ligand of metal complex. A ligand of metal complex having the following structure or wherein Z is CH2=; m=0 or 1, n=0 or 1; when m=0, X is HN, C1-C20-alkylimino or C6-C20-arylamino; when m=1, X is CH2; X is HN or C1-C20-alkylimino; is a single bond; when n=1, X1 is CH2 or carbonyl; Y1 is oxygen or carbonyl; R1 is hydrogen; R2 is C1-C20-alkyl or C6-C20-aryl; E is hydrogen, halogen, nitro, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or C1-C8-alkylaminosulfonyl; E1 and E2 are each independently selected from the group consisting of H and halogen; E3 is hydrogen; E4 is hydrogen or C1-C4-alkyl; E5 and E6 are either hydrogen or halogen, C1-C4-alkyl or C1-C6-alkoxy; E7 is hydrogen or C1-C4-alkyl. A transition metal complex, a method of carrying out a metathesis reaction with olefin substrate, use of a transition metal complex for rubber depolymerisation and rubber hydrogenation.

EFFECT: transition metal complexes offering high activity and selectivity for ROMP and RCM reactions.

11 cl, 13 tbl, 118 ex

FIELD: chemistry.

SUBSTANCE: catalyst of dicyclopentadiene polymerisation in the form of a ruthenium complex represents [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(2-((2-dimethylaminoethylmethylamino)methyl))benzylidene)ruthenium of formula (I) The catalyst is obtained by the interaction of a ruthenium triphenylphosphine complex with 1,1-diphenyl-2-propin-1-ol in tetrahydrofurane or dioxane at a temperature of the solvent boiling in an inert atmosphere, then with tricyclohexylphosphine at room temperature in an inert atmosphere the formed indenylidene complex of ruthenium is extracted. The latter is successively subjected to interaction with 1,3-bis-(2,4,6-trimethylphenyl)-2-tricloromethylimidazolidine and 2-vinylbenzylamine, the formed product is extracted and dried.

EFFECT: extension of technological abilities in the process of polymerisation, and improvement of rheological, mechanical and thermal indices of the obtained polycyclopentadiene.

2 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: catalyst of polymerisation has the general formula (I)

where a novel substituent is selected from the group of aminostyrenes. It ensures fundamentally novel properties of the catalyst. The catalyst is obtained by the interaction of a triphenylphosphine complex of ruthenium with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran or dioxane at a temperature of the solvent boiling in an inert atmosphere, and then with tricyclohexylphospine at room temperature in an inert atmosphere, the formed ruthenium indenylidenic complex is extracted. The latter is successively subjected to interaction with 1,3-bis-(2,4,6-trimethylphenyl)-2- tricloromethylimidazolidine and respective aminostyrene with the formation of a target product.

EFFECT: reduction of the catalyst consumption, reduction of the time before beginning of the polymerisation process and improvement of rheological, mechanical and thermal indices of the obtained polydicyclopentadiene, which ensures obtaining the product from polydicyclopentadiene with high consumer properties.

2 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: method includes the dissolution of metallic palladium in concentrated nitric acid, evaporation of an obtained palladium nitrate solution. The palladium nitrate solution is evaporated at a temperature of (40-80)°C until palladium nitrate crystallisation starts, into the formed solution added is carboxylic acid in the form of a water-free or a water solution, in a liquid or crystalline state in an amount of (600-800)% of a molar amount of palladium in the initial palladium nitrate solution, or carboxylic acid anhydrite in an amount of (350-450)% of a molar amount of palladium in the initial palladium nitrate solution until crystallisation of polymer palladium carboxylate stops.

EFFECT: invention makes it possible to improve the method of obtaining polymer palladium carboxylates, increase the synthesis stability, and achieve a high output of the target product.

8 cl, 5 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: method includes dissolving palladium metal in concentrated nitric acid and evaporating the obtained solution. The palladium nitrate solution is evaporated at (40-80)°C until palladium nitrate begins to crystallise. The formed solution at (30-80)°C is mixed with trifluoroacetic acid in amount of (600-800)% of the molar amount of palladium in the starting palladium nitrate solution or trifluoroacetic acid anhydride in amount of (350-450)% of the molar amount of palladium in the starting palladium nitrate solution until the end of crystallisation of polymeric palladium trifluoroacetate. The method also includes filtering the formed compound and conversion thereof into the end product by adding acetonitrile at (10-30)°C with weight ratio of the compound to acetonitrile of 1:(0.5-2).

EFFECT: invention improves the method of producing palladium trifluoroacetate in a crystalline monophase state, improves synthesis stability and enables to achieve high output of the desired compound.

2 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing palladium (II) beta-diketonates or beta-ketoiminates. The method involves reacting a beta-diketone with a palladium salt solution in an organic solvent, followed by cooling the end product and separation thereof from the solution. The beta-diketone or beta-ketoimine used is the compound R'C(O)CH2C(O)R or R'C(O)CH2C(NH)R, respectively, where R', R denote alkyl or perfluoroalkyl or an alkoxy group, containing 1-4 carbon atoms, an aryl containing 4-10 carbon atoms, in different combinations. The palladium salt used is palladium (II) chloride. The reaction is carried out in a solvent selected from nitriles or amides of organic acids, in which starting components are dissolved, and which is infinitely miscible with water, in the presence of an equivalent amount of sodium or potassium hydroxide, or sodium or potassium carbonate. The end product is precipitated from the solution with water.

EFFECT: invention enables to obtain an isomerically pure product with high output directly in a single-step synthesis process without using additional separation processes.

3 cl, 5 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: method involves reacting bis(acetylacetonato)palladium, 1,5-cyclooctadiene and boron trifluoride etherate BF3·OEt2, in a medium of benzene or toluene as an organic solvent.

EFFECT: invention increases efficiency of producing a palladium complex.

2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing palladium (II) beta-ketoiminates. The method involves reacting palladium dichloride with a beta-ketoiminate. The palladium dichloride in aqueous solution of concentrated ammonia (NH3(concentrated):H2O - 25:25 ml) is transferred into an ampoule which is then placed in a microwave oven reactor and excess beta-ketoimine (in ratio of 1:(2-3)) dissolved in ethanol is then added. The mixture is exposed to 100-150 W microwaves to heat the solution for 2-30 minutes at temperature of 90-110°C. The end product is separated by filtration and the residue is dried on air.

EFFECT: simple method, shorter duration of the method, high output of end products.

2 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acetylacetonates of platinum group metals. The method involves reacting a chloride of a corresponding metal with acetylacetonate, followed by neutralisation of the reaction mixture and separation of the end product. A calculated amount of metal chloride is placed into a container and 0.1 M HCl is added until obtaining a solution with concentration of 0.12-0.15 M by metal. The container with the metal chloride solution is placed into the reactor of a microwave apparatus and exposed to microwaves with power of 100-200 W in order to heat the solution for 15-30 minutes at temperature of 100-120°C. The activated solution is then mixed with acetylacetone in ratio of 1:(3-4) and the mixture is further exposed to microwaves for 5-15 minutes. The reaction mixture is then neutralised to pH 6-7, after which the mixture is further exposed to microwaves for 5-10 minutes and the end product is separated by filtering.

EFFECT: invention simplifies and cuts the duration of the method of producing acetylacetonates of platinum group metals.

3 cl, 3 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to a complex compound of a magnetisable metal and salen. The complex compound is presented by formula (I) , wherein M represents Fe, Cr, Mn, Co, Ni, Mo, Ru, Rh, Pd, W, Re, Os, Ir or Pt, and a-f and Y represents hydrogen, or -NHR3-, -NHCOR3 respectively provided a-f and Y are not hydrogen simultaneously, wherein -R3 represents a pharmaceutical molecule with R3 provides the transport of a charge equivalent to max. 0.5 electron (e); or by formula (II) , wherein M represents Fe, Y, a, c, d, f, g, i, j, 1 represent hydrogen respectively; b and k represent -NH2, h and e represent -NHR3, wherein -R3 represents taxol (paclitaxel), or M represents Fe, Y, a, c, d, f, g, i, j, 1 represent hydrogen respectively; b, e, h and k represent -NHR3-, wherein -R3 represent gemfibrozil. There are also presented a local anaesthetic, an antineoplastic agent, a complex metal molecule, an intermediate compound, methods for preparing the magnetic substance, methods for preparing the magnetisable compound. The present invention enables preparing the therapeutic agent using the magnetic properties of the complex of metal and salen for the purpose of magnetising the specific therapeutic agent by chemical binding of the therapeutic agent to the complex of metal and salen so that to deliver the therapeutic agent to an affected area.

EFFECT: preparing the complex compound of the magnetisable metal and salen.

16 cl, 20 dwg, 10 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of converting a stream of C4 olefins containing isobutene, but-1-ene and butadiene to propylene and octenes. The method involves a) selective hydrogenation of the stream of C4 olefins in the presence of a catalyst to remove butadiene via partial hydrogenation to butenes, and converting but-1-ene to but-2-ene to obtain a partially hydrogenated effluent; b) separating the partially hydrogenated effluent through distillation into a head fraction containing but-1-ene and hydrocarbon compounds which boil at a lower temperature than but-1-ene, and a bottom fraction containing compounds which boil at a higher temperature than but-1-ene; c) feeding at least a portion of the head fraction from step (b) as dimerisation material into a dimerisation reactor, wherein the dimerisation material undergoes dimerisation in the presence of a dimerisation catalyst to form a dimerisation reaction product; d) separating at least a portion of the dimerisation reaction product to form a liquid stream rich in octene and a vapour stream rich in C4; e) feeding the octene-rich liquid stream from step (d) to distillation step (b) and removing the bottom product from the distillation step (b) which contains almost all octene from the liquid stream rich in octene; f) removing a middle fraction product containing but-2-ene from the distillation step (b) from an intermediate point between points where the head and bottom fractions are extracted; and g) the middle fraction product undergoes metathesis with ethylene in the presence of a metathesis catalyst to obtain a metathesis reaction product containing propylene. The invention also relates to an apparatus realising said method.

EFFECT: use of the present invention reduces capital and operating costs and improves characteristics of the metathesis material.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to oil and gas chemistry and specifically to catalysts and processes for synthesis of light alkenes, particularly propylene. Described is a catalyst for single-step synthesis of propylene from ethylene, containing rhenium oxide Re2O7 and nickel oxide NiO, attached to the surface of a carrier in form of borate-containing aluminium oxide with the following ratio of components in wt %: Re2O7 - 5-13; NiO - 4-8; B2O3 - 15-18; Al2O3 - the rest. Described is a method of preparing said catalyst, which involves preliminary production of borate-containing aluminium oxide by mixing a hydrate of aluminium oxide having a pseudo-boehmite structure with ortho-boric acid, drying at 120°C and calcination at 550°C in an air current for 16 hours, followed by saturation of the borate-containing aluminium oxide with an aqueous solution containing perrhenic acid and nickel nitrate, drying at 120°C and calcination at 550°C for 16 hours. Described also is a method for single-step synthesis of propylene from ethylene which involves passing a stream of pure (100%) ethylene through a fixed layer of the disclosed catalyst at temperature 40-150°C, pressure close to atmospheric pressure and mass flow rate of feeding ethylene equal to 1 h-1.

EFFECT: high efficiency of single-step synthesis of propylene from ethylene owing to high selectivity of formation and output of propylene.

3 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: method of producing olefins via a metathesis reaction, involving supply of gaseous olefin for passage through a catalyst bed in the presence of hydrogen gas, for converting olefin to another type of olefin, the catalyst bed containing a catalyst which contains at least one metal selected from a group comprising tungsten, molybdenum, rhenium, niobium, tantalum and vanadium, and a cocatalyst which contains a basic composition containing at least one metal selected from groups Ia (alkali metals), IIa (alkali-earth metals), IIb and IIIa of the periodic table. The improvement lies in controlling the reduced velocity of gas passing through the catalyst bed which ranges from 0.01 to 2.0 m/s, wherein the reaction pressure ranges from 0.01 to 20 MPa and the amount of the cocatalyst relative the catalyst ranges from 0.1 to 20 of the weight.

EFFECT: use of the method increases efficiency of the metathesis reaction for producing olefins in the presence of hydrogen along with suppression of secondary production of paraffins.

3 cl, 4 ex, 1 dwg

FIELD: explosives.

SUBSTANCE: one of methods includes the following stages: a. steam-phase cracking of ethane or mainly ethane initial raw materials, containing 70% or more of ethane, with production of, thereby, cracking product, containing ethylene, hydrogen, ethane, methane, acetylene and C3 and heavier carbohydrates; b. processing of mentioned cracking product in extraction section of ethylene plant, also removal of mentioned hydrogen, methane and C3 and heavier carbohydrates from it and conversion of mentioned acetylene available in it mainly into ethylene with production of, thereby, cracking product exposed to processing, containing mainly ethylene and ethane, and also fractioning of specified cracking product that has been processed into C2 fractioning column and production of ethylene fraction, consisting of chemical ethylene and characterized with level of ethylene content below 99% (vol.), and ethane fraction in the form of distillation residue; c. sending of specified ethane fraction in the form of distillation fraction for recycle to specified steam-phase cracking; d. performance of reaction by mechanism of dimerisation in dimerisation section for the first part of specified ethylene fraction with thereby production of butene-enriched flow; e. performance of reaction by metathesis mechanism in metathesis section between butene in specified flow enriched with butene, and the second part of specified ethylene fraction with thereby production of flow enriched with propylene, ethylene and ethane; f. separation of propylene from specified ethylene and ethane in specified flow enriched with propylene and g. sending of at least part of specified ethylene and ethane from specified flow enriched with propylene for recycle into mentioned C2 fractioning plant. Besides invention is related to method for production of propylene from carbohydrate raw materials.

EFFECT: application of proposed methods makes it possible to improve and make process of propylene production from carbohydrate initial raw materials more profitable.

39 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of converting a C4 stream, containing 1-butene and 2-butene, preferably into 2-butene, involving: mixture of the said C4 stream with the first hydrogen stream to form the input stream, hydroisomerisation of the said input stream in the presence of first hydroisomerisation catalyst, so as to convert at least part of the said 1-butene to 2-butene and obtain an output hydroisomerisation product, separation of the output hydroisomerisation product in a catalytic distillation column, with a top end and a bottom end, to obtain a mixture of 1-butene at the said top end, a top output stream which contains isobutene and isobutylene, and a bottom stream which contains 2-butene, and hydroisomerisation of the said mixture of 1-butene at the said top end of the catalytic distillation column using a second hydroisomerisation catalyst to obtain additional 2-butene in the said bottom stream; where location of the said second hydroisomerisation catalyst in the top section of the column as a separate reaction zone is chosen to achieve maximum concentration of 1-butene, under the condition that, the hydroisomerisation stage with participation of the second isomerisation catalyst does not take place. The invention also relates to an apparatus for realsing this method and a method of producing propylene from a C4 stream.

EFFECT: selective hydrogenation of 1-butene to 2-butene which is more efficient than existing technologies.

30 cl, 7 dwg, 4 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method of olefins preparation by metathesis reaction includes the interreaction of homological or heterological olefines with formation of olefins having other structure whereat the reaction is carried out in compresence of gaseous hydrogen and catalyst containing at least one element - metal selected from tungsten and molybdenum and having the structure of catalyst applied to carrier - silicon dioxide and in presence (in addition to catalyst) of the compound containing at least one element -metal selected from metals of the group Ia (alkali metals), group IIa (alkali-earth metals), group IIb and group IIIa as cocatalyst with cocatalyst/catalyst mass ratio being in the range from 0.1 to 20 wt. The amount of gaseous hydrogen taken in compresence with starting materials loaded to reactor is 0.1-80% by volume of total gas amount (taking into account the gaseous state of starting materials).

EFFECT: method of olefines preparation possesses the significant safety, operation and economic advantages.

10 cl, 16 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: raw material composition based on fatty acids or esters of fatty acids, obtained by hydrolysis of oil from seeds or by re-etherification of oil from seeds with C1-8-alkanol, contains more than 70 wt % of unsaturated fatty oleic acid, and less than 1.5 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of composition, after purification with adsorbent. Admixture contains one or more organic hydroperoxides. Method of olefin methathesis lies in contacting of raw composition, obtained from seed oil and containing one or more unsaturated fatty acids or esters of unsaturated fatty acids, with lower olefin in presence of catalyst based on phosphororganic transition metal complex. Used raw material composition contains less than 25 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of raw material composition, able to inhibit methathesis catalyst. As a result of reaction olefin with shortened chain and unsaturated acid or unsaturated ester with shortened chain is obtained. Method of obtaining complex polyether polyepoxide lies in carrying out the following stages. At the first stage raw material compositiojn, obtained from seed oil, containing one or more unsaturated fatty acids or esters of fatty acids, contacts with lower olefin in presence of olefin methathesis catalyst. Used raw material composition contains less than 25 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of composition. At the second stage (re)etherification of obtained unsaturated acid with shortened chain or unsaturated ester with shortened chain with polyol is carried out. At the third stage epoxidation of obtained complex polyether polyolefin is carried out with epoxidising agent optionally in presence of catalyst. Method of obtaining α,ω-oxoacid, complex α,ω-oxyester and/or α,ω-diol with shortened chain lies in carrying out the following stages. At the first stage raw material composition, obtained from seed oil, containing one or more unsaturated fatty acids or esters of fatty acids contacts with lower olefin in presence of olefin methathesis catalyst. Used raw material composition contains less than 25 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of composition. At the second stage hydroformilation is carried out with hydrating of obtained unsaturated acid or ester with shortened chain in presence of hydroformiolation/hydration catalyst.

EFFECT: increase of catalyst serviceability and obtaining chemical compounds with high productivity.

25 cl, 3 tbl, 12 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides rhenium oxide catalyst on anion-containing gamma-alumina-based support: 0.1-10.0% Re2O3 and 0.2-4.0% fluorine based on the weight of alumina. Catalyst is prepared by impregnating alumina, including 0.2-4.0 wt % fluorine, with rhenium compound solution, drying resulting mass, and subjecting it to heat treatment in oxidative and/or inert medium at 600-900°C. Propylene synthesis process including metathesis of C2-C4-olefinic hydrocarbon blend or ethylene alone is also described.

EFFECT: increased catalytic activity and simplified technology.

7 cl, 2 tbl, 8 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention relates to supported olefin metathesis catalyst and to a olefin metathesis process using the latter. Catalyst is essentially composed of transition metal or oxide thereof, or a mixture of such metals, or oxides thereof deposited on high-purity silicon dioxide containing less than: 150 ppm magnesium, 900 ppm calcium, 900 ppm sodium, 200 ppm aluminum, and 40 ppm iron. When pure 1-butene comes into interaction with this catalyst under metathesis reaction conditions, reaction proceeds with 2-hexene formation selectivity at least 55 wt %. Use of catalyst according to invention in olefin metathesis process minimizes double bond isomerization reactions.

EFFECT: increased olefin metathesis selectivity regarding specific products.

17 cl, 2 tbl, 2 ex

FIELD: petrochemical processes.

SUBSTANCE: narrow-range hydrocarbon stock is fed into reaction-distillation tower at a level located between lower and upper tower parts to perform isomerization and disproportionation of hydrocarbons. Reaction mixture is maintained in vapor-liquid equilibrium state to concentrate lighter reaction products in vapor phase and higher ones in liquid phase by means of controlling temperature profile and in-tower pressure. Higher olefins are withdrawn as bottom product and lighter olefins from the top of tower.

EFFECT: increased yield of desired product.

41 cl, 4 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing pentacyclo[8.4.0.03.7.04.14.06.11]tetradeca-8,12-diene of formula The method is characterised by catalytic dimerisation of 1,3,5-cycloheptatriene (CHT). The catalyst used is Ni(acac)2-Et2AlCl. The reaction is carried out with molar ratio CHT:Ni(acac)2:Et2AlCl=10:(0.1-0.3):4, in an argon atmosphere, at 20-100°C, in benzene for 8-48 hours.

EFFECT: method enables to obtain the end product separately.

7 ex, 1 tbl

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