Catalytic composition for hydroformylation of ethylene oxide, its preparation and method for producing 1,3 - propane diol and 3-aldehyde hydroxypropionate

 

(57) Abstract:

Use: in organic synthesis. The inventive product - 1,3-propandiol and 3-hydroxypropionate aldehyde. Reagent 1: ethylene oxide. Reagent 2: monoxide and hydrogen. Reaction conditions: catalyst composition containing anionic registergui complex with fosfatnym ligand in molar ratio of ligand to rhodium of 0.1-100: ion component connected other than covalent bonds with anionic registertask complex at a molar ratio of the ionic component to the rhodium of 0.1-10 and a cation other than hydrogen ions at a molar ratio of cation to rhodium of 0.1-100 3 C. and 12 C.p. f-crystals. 4 Il.

The invention relates to the production of 1,3-diols and/or 3-oxyaldehydes of epoxides. The invention relates to catalysts hydroformylation, the method of manufacturing catalysts hydroformylation and to methods of using the catalysts of hydroformylation to obtain such 1,3-diols and/or 3-oxyaldehydes of epoxides.

Glycols are typically valuable chemical compounds, which find diverse applications. Such compounds are used, for example, as an intermediate chemical products propandiol is particularly useful in some applications. 1,3-propandiol received acid catalyzed hydration of acrolein with the formation of 3-oxopropanal, which then was first made in the corresponding diol. Because of the relatively low reaction rate and outputs the obtained products this attempt did not lead to a viable process of obtaining 1,3-propane diol in large commercial quantities.

Obtaining 1,3-diols, such as 1,3-glycols by hydroformylation epoxides using modified phosphine complexes of cobalt carbonyl as the catalyst described by Smith with TCS. in U.S. patent N 3463819. In particular, this patent shows the derivation of the 1,3-propane diol by hydroformylation of ethylene oxide using a modified tertiary phosphine catalyst of cobalt carbonyl. To ensure good outputs 1,3-propane diol required very high concentrations of cobalt containing catalyst.

Lawrence with TCS. in U.S. patent N 3687981 described the process of obtaining 1,3-propane diol, which uses two separate stages. In the first stage, the ethylene oxide is subjected to reaction hydroformylation in the presence of a catalyst of hydroformylation containing a transition metal, especially a metal of Group VIII Drank)-4-hydroxy-1,3-dioxane. Dioxane connection together with minor kolichestvo 3-oxopropanenitrile separated from the solvent hydroformylation and catalytically hydronaut to obtain 1,3-propane diol.

Smith al. in U.S. patent N 3456017 described obtaining 1,3-propane diol by hydroformylation of ethylene oxide when used in A. import duties catalyst disabilitycontrolling complex which has two remaining contact point of the cobalt complex fragments associated with one or more tertiary phosphine ligands.

Horvitz with TCS. in U.S. patent N 4322355 described the reaction of an olefin with an aldehyde in the presence of a strong acid catalyst and socializaton chosen among oxides of antimony and bismuth and their salts, to obtain one or a mixture of 1,3-difunctional connections.

In European patent application N 0257967 describes a method for 1,3-glycols in the interaction of the epoxide with synthesis gas in an acid medium in the presence of rhodium and phosphine. Described the reaction mixture containing epoxide, rhodium, phosphine, water, carbon monoxide, hydrogen and acid. Describes a wide range malenich ratios of acid to rhodium, for example, from 10/1 to 1/10, this publication discloses predpochtitel or more takes place after the formation of the reaction mixture before the gas supply. This "induction period", which in itself is harmful, because it requires a greater volume of the reactor and/or a longer time to obtain a given quantity of 1,3-diol, is partly the result of combining a quantity of resin with rhodium and phosphine and possibly other components to obtain the true catalyst of hydroformylation. Therefore, a certain amount of resin included in the catalyst hydroformylation. Use epoxy resin to obtain a catalyst reduces the maximum yield of target products, such as 1,3-diol. Obviously, the more advantageous is registergui catalyst, which does not require an induction period and/or which are made without the inclusion of the epoxide.

Murphy with TCS. in U.S. patent N 4873378 describe essentially the same process as described in the aforementioned European patent publication. It also describes that in the reaction mixture also contains salt having a cation of an alkali metal and solubilizers anion. This patent describes that "induction period" is eliminated in some examples, contain relatively large amounts of salts of alkali metals.

Murphy with TCS. in the patent Dios, promoting salt of alkali metal, water, carbon monoxide and hydrogen. Not offered by other promoters than alkali metal salts.

Mayer with TCS. in U.S. patent N 4774361 described the solubilized rhodium-fosfatnyi complex that catalyzes the liquid process hydroformylation recycle to obtain the aldehyde in the interaction of olefinic unsaturated compounds with carbon monoxide and hydrogen. BILLIG with TCS. in the U.S. patents NN 4668651 and 4769498 described complex catalyst of a transition metal of group VIII with polyphosphates ligand and free polyphosphates ligand to obtain aldehydes, in which the olefinic compound is reacted with carbon monoxide and hydrogen. BILLIG with TCS. in U.S. patent N 4885401 described hydroformylation olefineverbund organic compounds with carbon monoxide and hydrogen in the presence of a rhodium catalyst complex is associated with bisphosphite ligand. BILLIG with TCS. in the U.S. patents NN 4717775 and 4599206 described hydroformylation refinanancing organic compounds carbon monoxide and hydrogen in the presence of registeruser catalyst complex is associated with diorganotin ligand.

1985), 171-179, some anionic rhodium complexes which have been studied as catalysts of hydroformylation formaldehyde. Were allocated to different crystalline materials containing alkali metals, such as [Na/C12H24O6][Rh(CO)3(PRh3)] and [K(C12H24O6)(Rh(CO)2/P(ORh3)2]

Not quoted hydroformylation epoxides.

In European patent publication N 0306094 described by way of hydroformylation some derivatives of acrylic acid in the presence of a homogeneous catalyst system consisting of rhodium compounds and one or more triphenylphosphite. Not quoted hydroformylation epoxides.

There remains a need in the new catalyst hydroformylation epoxides and method of its manufacture and use, as, for obtaining 1,3-diol and/or 3-oxyaldehydes.

Describes a new way of hydroformylation epoxides, the catalyst for use in such a method, and method for producing such catalysts. How hydroformylation epoxides provides a high final yield of the target products, such as 1,3-diols and/or 3-acetaldehyde. Nastoashe to the target product or products. Advantageously, it can be used less stringent reaction conditions of hydroformylation and/or lower concentration of catalyst. In addition, the induction period, which was typical of some of the previously proposed processes hydroformylation epoxides, can be reduced in length or even eliminated in the present invention. In addition, the inclusion of one or more specific promoting components provides superior results. These catalytic compositions and process of hydroformylating provide significant benefits, for example, provide economy and efficiency in the production of 1,3-diols and/or 3-oxyaldehydes.

The present invention relates to a method for producing 1,3-diol and/or 3-acetaldehyde. This process involves contacting a mixture of epoxide, carbon monoxide and hydrogen in the presence of radiogardase catalytic composition effective for promotion of hydroformylation epoxides in effective conditions for the formation of a 1,3-diol and/or 3-acetaldehyde. Registereda catalytic composition comprises anionic registergui complex and the electrophile. If there is one, is the product of 3-axiar CLASS="ptx2">

The contacting of the epoxide is preferably in the presence of N+ions in amounts effective to facilitate hydroformylation epoxides. Anionic registergui complex preferably includes fosforsoderzhashchie ligand, more preferably a phosphorus-oxygen-containing ligand, in particular at least one fosfatnyi ligand. In one useful embodiment, the catalytic composition comprises a different cation than N+and preferably a different cation than the alkali metal, in particular of organics-containing cation. The promoting component preferably include to increase the speed of hydroformylation epoxide and/or selectivity in 1,3-diol and/or 3-acetaldehyde.

Another broad aspect of the invention includes a composition which comprises a liquid medium, anionic registeruser complex comprising a ligand containing phosphorus and oxygen; N+other than covalently bound in the complex, and a cation other than H+. This composition has a catalytic activity for promotion of hydroformylation epoxide. The promoting component preferably include and it is effective to increase the rate and/or selectivity of reactualization of hydroformylation epoxide. This composition includes a liquid medium, registergui complex comprising a ligand containing phosphorus and oxygen; ion component having sufficient basicity to create anionic complex and includes a cation other than H+and N+. The composition has a catalytic activity promotion hydroformylation epoxides. The promoting component is preferably included and is effective to increase the rate and/or selectivity of the reaction of hydroformylation epoxides.

The present invention relates to a method for registergui compositions, for example, catalytic compositions for hydroformylation epoxides. This process consists in contacting, preferably in a liquid medium, a source of rhodium, the source of the ligand and the ion component, preferably an ionic component, including organics-containing cation, and preferably an acid under conditions effective to obtain anionic registergui complex comprising a ligand containing phosphorus and oxygen. This registereda composition, in particular anionic registergui complex, has activity promote hydroformylation epoxides.

the Xia precursors 1,3-diols, by hydroformylation epoxides. The target 1,3-diols and 3-acetaldehyde in their Monomeric form contains one carbon atom and one oxygen atom more than the epoxide. For example, when reacting the epoxide is ethylene oxide containing two atoms of carbon and one atom of oxygen-derived 1,3-diol is 1,3-propane diol and the resulting 3-acetaldehyde is a 3-oxopropylidene, each of which contains 3 atoms of carbon and two atoms of oxygen. As used herein, the term "1,3-diol and 3-acetaldehyde" refers not only to the Monomeric form of these compounds, but also oligomeric forms, for example, in which the degree of polymerization up to about 10, in particular dimers, trimers and tetramers. Mixed oligomers of 1,3-diols and 3-oxyaldehydes also possible and included within the scope of such terms.

Suitable epoxides have the formula:

CC where each R is selected among hydrogen, monovalent aliphatic or aromatic group containing 1-12 carbon atoms, a divalent aliphatic group containing 4-6 carbon atoms and communication with other R, which is bivalent. For example, when one R is a divalent saturated aliphatic group having 4 is m, then epoxide is cyclohexanediol. Examples of specific epoxides which are useful in the present invention include ethylene oxide, propylene oxide, 1,2-epoxyoctane, cyclohexanone and stimulated. The epoxide may be present at the time, especially in the early stages of hydroformylation of the present invention in widely varying amounts, for example, at concentrations in the range of from about 0.01 to about 95%, preferably from about 0.5 to about 75 wt. counting on the total weight of reactants, of a catalyst and a liquid medium present in this stage.

The reaction hydroformylation carried out in the presence of, for example, a suitable liquid medium, which preferably is a solvent for the epoxide and registereda catalytic composition. Suitable liquids are aliphatic hydrocarbon components, an aromatic hydrocarbon components, including benzene, toluene, xylenes, etc., ethers, including high molecular weight ethers, polyethers, especially simple polyglycolide ethers, and cyclic ethers, amides, sulfones, alcohols, ketones, esters and mixtures thereof. Specific esters of suitable liquid media include glyme (dimethoxyethane under the trade name YUKONRcompany Union carbide Corporation, which is a mixed glycolipopeptide ethylene and propylene glycols. The liquid medium preferably solubilities catalyst and epoxy reagent. The preferred liquid medium essentially does not react with any of the other components present during the reaction of hydroformylation. In a polar liquid medium, many of the components of the present catalyst compositions are often present in the form of individual charged particles, for example, complexes, ions, etc. In the non-polar liquid medium, these components are often present in the form of ion pairs. Such components are referred to here regardless of the type of the applied liquid medium as individual particles, it should be clear that one or more of these components may not be available as such, for example, may be present in the ion pair. For epoxides with a lower molecular weight, for example, ethylene oxide, is useful liquid medium, such as glyme, tetralin, tetrahydrofuran, etc., and mixtures thereof. For more high molecular weight epoxides can be suitable petroleum ethers and hydrocarbon materials, such as benzene, toluene and xylenes.

Important predeposited, in particular, low molecular weight epoxides, such as those that contain 2-5 carbon atoms, especially ethylene oxide, in which the product 1,3-diol and/or 3-acetaldehyde is insoluble or immiscible in the useful range of conditions. In particular, these catalysts have significant activity and selectivity in 1,3-diols and/or 3-acetaldehyde when hydroformylating low molecular weight epoxides using a liquid medium, which was less suitable for such hydroformylation. Such a liquid medium, in particular, hydrocarbons and their mixtures, especially aromatic hydrocarbons and their mixtures, are not only effective at the stage of hydroformylation epoxides, but also forms a two-phase mixture with the product 1,3-diola and/or 3-oxyaldehydes, in particular 3-oxyaldehydes, in these conditions, so that the product or products can be separated from the liquid medium, for example, when using traditional methods of phase separation, such as centrifugation, decantation, etc.,

Thus, in one embodiment, the present method of obtaining 1,3-diol and 3-acetaldehyde includes a step or stage in which the reaction mixture after hydroformylation, in particular, liquid medium and the product 3-about the Ohm particular useful embodiment, the reaction mixture is cooled from the reaction temperature of hydroformylation, to ensure the extraction of such phases. For example, cooling or keeping the reaction mixture at a temperature in the range of from about -50aboutWith up to about 50aboutIn some cases, causes the formation of the desired phase. You should use precautions to avoid temperatures at which cures a significant amount of liquid medium. Phase enriched liquid has a higher concentration of a liquid medium, and preferably a higher concentration of the components of the catalytic system than those that are in the common liquid reaction mixture and the product 3-acetaldehyde after hydroformylation. Similarly, enriched 3-oxyaldehydes phase has a higher concentration of 3-acetaldehyde than that available in total or combined liquid reaction mixture and the product 3-acetaldehyde after hydroformylation.

Enriched liquid phase and enriched 3-oxyaldehydes phase, which are in contact with each other, preferably divided, for example, when using traditional methods of phase separation to form a separated 3-oxyaldehydes material. This separated enriched oxyaldehydes material, which includes neatstaj in the reaction mixture, preferably then processed to obtain the target 1,3-diol. Separated enriched 3-oxyaldehydes material can be used directly on the stage hydrogenation to obtain 1,3-diol. Such "direct" hydrogenation is particularly useful when a liquid medium comprising enriched 3-oxyaldehydes material, separated from the hydrocarbons, in particular aromatic hydrocarbons, such as benzene, toluene and xylenes. Such materials are liquid medium essentially have no harmful effects on stage hydrogenation. After hydrogenation of the obtained 1,3-diol may be separated, for example, when using traditional methods to get the target 1,3-diol product of the desired purity. If desired, the material-enriched liquid medium, can be recollision for further use at the stage of hydroformylation.

The source of rhodium, which is used for manufacturing of the present catalytic compositions may be in the form of a metallic rhodium, rhodium salts and/or complexes of rhodium. Among the sources of rhodium, useful in the practice of the present invention are selected among one or more of: metal rhodium oxides, rhodium, RhI3, RhBr3, RhCl)3where ACAC means acetylacetonate. Rhodium can be used as a pre-formed anion, such as, for example, Rh6(CO)152-and other similar anionic cluster rhodium salt.

The concentration of rhodium in the reaction of hydroformylation may depend, for example, on the particular epoxy and apply a liquid medium and/or of the conditions of contact. This concentration is preferably range from about 100 PM per million (ppm) to about 10,000 ppm by weight, considering the elemental rhodium, based on the total weight of liquid medium and epoxide present during hydroformylation.

The term "complex" as it is used here and in the claims, means a coordination compound formed when connecting one or more enriched by the electrons of the molecules or atoms capable of independent existence with one or more electron-depleted molecules or atoms, each of which is also capable of independent existence. For example, applied here fosfatnye ligands include at least one donor atom of phosphorus, having one available or unshared pair of electrons and thus is: as a ligand) is also available to and forms a complex with rhodium. The finished composition anionic registeruser complex may also contain additional ligand, for example, hydrogen or an anion, filling focal points or nuclear charge of rhodium. Examples of additional ligands include, for example, halogen (Cl-, Br-I-), alkyl, aryl, substituted aryl, CF3-C2F5-CN-, R'3PO and R P(O)(OH)O), where each R' is alkyl or aryl), acetate, acetylacetonate, SO42-PF6-, NO2-, NO3-CH3O-CH2=CHCH2-C6N5CN, CH3CN, NO, NH3, pyridine, monoolefinic, diolefine and triolein, tetrahydrofuran, etc., of Course, it should be clear that the anionic radiogardase complex compounds preferably do not contain any additional organic ligands or anions, which can poison the catalytic composition and can have undesirable adverse effects on the performance of the catalytic composition. For example, it is known that the application of the traditional reactions of hydroformylation catalyzed by rhodium halide anions and sulfur compounds can poison the catalyst. Therefore, the preference is not absolutely necessary.

Therefore, anionic radiogardase complexes in their simplest form preferably contain a certain amount of ligand, other than carbon monoxide, more preferably phosphorus-containing ligand, and more preferably the phosphorus - and oxygen-containing ligand, in particular, Fofanova ligand, and the amount of carbon monoxide is a total of two /2/ three /3/ / four /4/ moles in complex combination with one mol of rhodium. Therefore, anionic registergui complex may represent a complex mixture of Monomeric, dimeric or higher forms of condensation, characterized by the presence of at least one legenday molecules other than carbon monoxide, complexly related to one atom of rhodium. Carbon monoxide may be and preferably is also available and comprehensively linked with rhodium in anionic registeruser complex connection.

Anionic registergui complex can be formed prior to introduction into the reaction zone of hydroformylation or anionic registergui complex can be prepared in situ during hydroformylation. Such pre-forming or obtaining preferably proishodili.

Any suitable ligand, other than or additional to carbon monoxide, can be applied in the present anionic registeruser complex. Of course, this ligand should not have a significant detrimental effect on the catalytic activity of the catalyst composition or process of hydroformylating epoxide as a whole. Phosphorus-containing ligands are preferred, more preferred fosfatnye ligands.

Anionic radiogardase complexes preferably have substantial stability in the context of the stage of hydroformylation epoxides. Thus, in one embodiment, anionic registergui complex is preferably such that at least about 50% of the complex remains after 2 h, more preferably after 5 h, and more preferably after 10 h in terms of hydroformylation epoxide, for example, in specified conditions of hydroformylation epoxide. As used here, these conditions hydroformylation epoxide are as follows: Epoxide ethylene oxide Liquid medium glyme

Original

the mass ratio

epoxide to the liquid medium 0,125 CO/H2(molar) 1:2 Pressure of 1000 lb/

/in2< / BR>
(703 kg/cm2 is Lennie phosphines, as it was discovered, are unstable in such usloviyah, for example, are formed phosphonium ions under such conditions of phosphine and available epoxide.

As noted earlier, more preferably, when the ligands contain both oxygen and phosphorus. examples of such ligands include phosphonites, phosphinite and phosphites.

The phosphonites, useful in the present invention preferably have the General formula

P(-OR")2(-CR"), while preferably useful in this case phosphinite have the General formula

P(-OR') (- CR')2where each R" is independently selected from among organic radicals, for example, hydrocarbon radicals and substituted hydrocarbon radicals, such as described herein elsewhere.

Examples organophosphine ligands that can be used in the present invention include organophosphate having the formula

ROX where R"' is a divalent organic radical, and X is a monovalent hydrocarbon radical, for example, as more particularly defined below.

Typical divalent radicals represented by R"' are those in which R"' may be divalent acyclic radicals or divalent uralkran-NX'-alkylen, where X' is a hydrogen or monovalent hydrocarbon radical, alkylene-S - alkylene and cycloalkyl, etc., such as more fully described for example in U.S. patents NN 3415906 and 4567306, etc., described here as prior art. Typical divalent aromatic radicals include Allen, di Allen, Allen-alkylen, Allen, alkylen-Allen, Allen-hydroxy-Allen, Allen-NX'-Allen, Allen-NX'-alkylene, where X' is a hydrogen or monovalent hydrocarbon radical, Allen-S-alkylene, Allen-S-Allen, etc., More preferably, when R"' is a divalent aromatic radical.

Among fofanah ligands used in the present invention are ligands of General formula

P O X where each Ar group is the same or different, substituted or unsubstituted aryl group; X is a monovalent hydrocarbon radical, where m is 1, and when m is other than 1, m-valent radical selected from the group consisting of alkylene alkylene-hydroxy-alkylene, arylene, Allen-(CH2)y-(Q)n-CH2)yarylene, each Allenby radical is the same or different, substituted or unsubstituted Allenby radical; each is Anna in the group, consisting of CR1R2-, -O-, -S-, -NR3-1-S/R4P5-1and-CO-, where each radical R1and R2individually is a radical selected from the group consisting of hydrogen, alkyl containing 1-12 carbon atoms, phenyl, talila, anisil, and each R3, R4and R5radical individually is hydrogen or stands; each n individually has a value of 0 or 1, and has a value of 1-6, preferably 1-4. In one embodiment, each y and each n has value 0. Where each n is equal to 1, the corresponding Q preferably is a bridging group of CR1R2as defined above, and more preferably a methylene (-CH2- or alkylidene (-CHR2-) c R2being alkyl containing 1-12 carbon atoms (for example, stands, ethyl, propylene, isopropyl, bootrom, Isodecyl, dodecyl, etc., especially the stands).

Typical examples of the monovalent hydrocarbon radicals represented by X, when m is 1 in the above formula include substituted or unsubstituted monovalent hydrocarbon radicals containing 1-30 carbon atoms selected from the group consisting of substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl and alicyclobacillus, selected from the group consisting of alkyl and aryl radicals.

More specific typical monovalent hydrocarbon radicals represented by X, include primary, secondary and tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, tert.-butylate, tert.-butylparaben, n-hexyl, amyl, sec.-amyl, tert. -amyl, ISO-octyl, 2-ethylhexyl, decyl, octadecyl, etc., aryl radicals such as phenyl, naphthyl, antracol etc. kalkilya radicals, such as tolyl, xylyl, etc., and alicyclic radicals, such as cyclopentyl, cyclohexyl, cyclooctyl, cyclohexylethyl, etc., Preferably unsubstituted alkyl radicals may contain 1-18 carbon atoms, more preferably 1-10 carbon atoms, whereas unsubstituted aryl, alkaline and alicyclic radicals preferably contain 6 to 18 carbon atoms.

Typical m-valent radicals represented by X, when m is other than 1, the above formula include substituted and unsubstituted radicals selected from the group consisting of alkilinity, alkylen-hydroxy-alkilinity, filinovich, naftenovykh, phenylene-(CH2)y(Q)m(CH2)-filinovich and naphthyl is possible. More specific typical m-valent radicals represented by X, when m is other than 1, are alkylene radicals with a straight or branched chain, such as -(CH2)xwhere x has a value from 2 to about 18, preferably 2-12, pintaric, 1,2, 6-hexylen, etc.,- CH2CH2OCH2CH2-, 1,4-phenylene, 2,3-phenylene, 1,3,5-phenylene, 1,3-phenylene, 1,4-naftilan, 1,5-naftilan, 1,8-naftilan, 2,3-naftilan, 1,5-naftilan, 1,8-naftilan, 2,3-naftilan, 1,1'-biphenyl-2,2'-diyl, 2,2'-biphenyl-1,1'-diyl, 1,1'-biphenyl-4,4-diyl, 1,1-binaphthyl-2,2-diyl, 2,2-binaphthyl-1,1 - diyl, phenylene-CH2-phenylene, phenylene-S-phenylene, CH2-phenylene-CH2, phenylene-CH(CH3)-phenylene, etc.

So, when m is other than 1, X is a m-valent radical which may contain 2 to 30 carbon atoms, and alkylene and alkylene-hydroxy-alkylene radicals preferably containing 2-18 carbon atoms, and more preferably 2-12 carbon atoms, while the radicals ellenboro type can contain 6-18 carbon atoms. In this embodiment, X is preferably an ethylene radical or ellenboro type, and more preferably Neftyanoy or substituted or unsubstituted phenylene-(Q)nphenylenebis glad the Noah above formula include substituted, and unsubstituted aryl radicals. Such aryl radicals preferably contain 6 to 18 carbon atoms, such as phenylene (C6H4), naftilan (C10H6), Antratsit (C14H8), etc.

Typical substituted by groups which may be present in alkilinity or arenovich the radicals X and aryl groups represented by Ar in the above formula, are monovalent hydrocarbon radicals, such as substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or acyclic radicals, as well as silyl radicals such as -- Si(R6)3and-Si(OR6)3, an amino group, such as-N(R6)2, acyl radical, such as-C(O)R6carbonyloxy radicals such as-C(O)R6, oxycarbonyl radicals, such as-OC(O)R6, amide radicals, such as-C(O)N(R6)2and -(N)R6/C(O)6, sulfonylurea radicals, such as-S(O)2R6, sulfinyl radicals, such as-S(O)R6, ethers (e.g., alkoxy),- OR6, tinylove ethers, such as-SR6, fastonline radicals such as -- P(O)(R6)2and halogen, nitro, cyano, triptoreline and hydroxyl radicals, etc., the state Duma of the second radical, as defined here, in another place, provided that in amino substituents such as -- N(R6)2each R6taken together can also represent a divalent bridging group that forms a heterocyclic radical with the nitrogen atom in the amine and amide substituents, such as-N(R6)2, -C(O)N(R6)2and-N(R6)C(O)R6each R6associated with nitrogen, can also be hydrogen at the same time, as in postonline substituents, such as-P(O)(R6)2one R6can also be hydrogen. Preferably monovalent hydrocarbon replacement radicals, including the R6are unsubstituted alkyl or aryl radicals, although if desired they, in turn, can be substituted with any substitute who has not undoubtedly harmful effects on the process or the composition of the present invention, such as, for example, shown here hydrocarbon and non-radicals.

Among the more specific unsubstituted hydrocarbon replacement radicals, including those presented R6that can be attached to alkilinity and/or Allenby radicals X and/or the Ar groups II and tertiary radicals, such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert.-butyl, neo-pentyl, n-hexyl, amyl, sec. -amyl, tert. -amyl, ISO-octyl, decyl, etc., aryl radical such as phenyl, naphthyl, etc. aralkyl radicals, such as benzyl, phenylethyl, triphenylmethyl, etc., and alicyclic radicals, such as cyclopentyl, cyclohexyl, 1-methylcyclohexyl, cyclooctyl, cyclohexylethyl, etc., More non-specific substituents that may be present in alkilinity and/or arenovich the radicals X and/or the Ar groups of the above formula are, for example, halogen, preferably chlorine or fluorine, -NO2, -CN, -CF3, -OH, -Si(CH3)3, -Si(SON3)3, -Si(C3H7)3, -C(O)CH3, -C(O)C2H5, -OC(O)C6H5, -C(O)OCH3, -N(CH3)2, -NH2, -NHCH3, -NH(C2H5), -CONH2, -CON(CH3)2, -S(O)2C2H5, -OCH3, -OC2H5, -OC6H5, -C(O)C6H5, -O(tert. -C4H9), SC2H5, -(OCH2CH2)3OCH3, -(OCH2CH2)2OCH3, -(OCH2CH2)OCH3, -SCH3, -S(O)CH3, -SC6H5, -P(O)(C6H5)2, -P(O)(CH3)2, -P(O)(CUB>, -P(O)CH3(C6H5), -P(O)(H)(C6H5), -NHC(O)CH3etc. Replacement radicals present in alkilinity and/or arenovich the radicals X and/or the Ar groups of the above formulae can also contain 1-18 carbon atoms and may be connected with alkionovymi and/or allenbyi radicals X and/or the Ar groups in any suitable position, as it can be a linking group -(CH2)y-(Q)n-(CH2)y- connecting the two Ar groups or two allenbyi group X in the above formula. In addition, each Ar radical and/or alkalinity, and/or Allenby radical X may contain one or more substitutional groups, these substituting groups may be the same or different in any given phosphite. Preferred replacement radicals include alkyl and CNS radicals containing 1-18 carbon atoms, and more preferably 1-10 carbon atoms, especially tert.-butyl and methoxy.

Among the more preferred fofanah ligands are those in which two Ar groups are connected by bridging group represented by -(CH2)y-(Q)n-(CH2)yin the above formula and are connected through their ortho positions in relation to the oxygen atoms, to outstay in such groups Ar, was linked in the para and/or ortho-position of the aryl relative to the oxygen atom which connects this substituted Ar group to the phosphorus atom.

In one embodiment, fosfatnye ligands used in the present invention have formula

P-O X

-O X radical individually represents a radical selected from the group consisting of hydrogen, alkyl containing 1-12 carbon atoms (e.g. methyl, propyl, isopropyl, butyl, Isodecyl, dodecyl and etc.), phenyl, talila and anisil, and n has a value of 0-1; each y1,2, z2and z3individually represents a radical selected from the group consisting of hydrogen, alkyl radical containing 1-18 carbon atoms, substituted or unsubstituted aryl, alkaryl, aralkyl and alicyclic radicals as defined and confirmed by the examples here above (for example, phenyl, benzyl, cyclohexyl, 1-methylcyclohexyl and etc.), cyano, halogen, nitro, trifloromethyl, hydroxyl, and carbonyloxy, amino, acyl,phosphonyl, oxycarbonyl, amido, sulfinil, sulfonyl, Silla, alkoxy and tonila, as determined and confirmed by the examples here above, and m has a value of 2-6, more preferably 2-4, and more preferably 2. Site and more preferably tert.-butyl, or more. Preferably Q represents a methylene (CH2) bridge group, or alkylidene (-CH-R2-) bridge group, where R2is alkyl containing 1-12 carbon atoms, especially the stands. The preferred ligands are ligands of the formula (a) above, where both the1and2are branched alkilani having 3-5 carbon atoms, especially tert.-bootrom and z2and z3are hydrogen, alkyl, especially tert.-bootrom, hydroxyl or CNS radical, especially metaxylem.

Other preferred fosfatnye ligands include those in which X in the above formula is a divalent radical selected from the group consisting of alkylene, especially ethylene, alkylen-hydroxy-alkylene, especially-CH2CH2OCH2CH2-, and substituted or unsubstituted phenylene, naphthylene, naftilan-(Q)n-naphthylene and phenylene-(Q)n-phenylene, where Q and n are the same as in General and preferably defined above. Among the more preferred ligands bisphosphatase type, when m is 2, are those in which X is a divalent radical selected from the group consisting of 1,2-ethylene, naphthylene, substituted phenylene and Samashki filinovich and/or phenylene-(Q)n-filinovich radicals are preferably radicals, selected from the group consisting of alkyl and CNS radicals, most preferably correspond to the replacement radicals in1,2, z2and z3 are defined here.

Therefore another preferred class biphosphine ligands used here, are ligands of the formula:

P-O-X-O-P

and

-O-X-O-P where in the above formulae (C) and (D) each of the1,2, Q, X, z2, z3and n are the same as in General and preferably defined in formulas (a) and (b) above, and even more preferably n is equal to zero. Of course, it should be clear that each1,2, Q, z2, z3and n may be the same or different in any given phosphite. More preferably, each y1,2, z2and z3group individually represents a radical containing 1-8 carbon atoms, substituted or unsubstituted aryl, alkaryl, aralkyl and acyclic radicals as defined and confirmed by the examples here above (for example, phenyl, benzyl, cyclohexyl, 1-methylcyclohexyl and etc.), cyano, halogen, nitro, trifluoromethyl, oxyl, and carbonyloxy, amino, acyl, phosphonyl, oxycarbonyl, amido, sulfinil, sulfonyl, silyl, alkoxy and tional, what adically, having a steric hindrance of isopropyl, or more preferably tert.-butyl or more. The preferred ligands are those of the above with both the1and2are alkyl radicals are branched chain, having 3-5 carbon atoms, especially tert.bootrom and z2and z3are hydrogen, alkyl, especially tert.-bootrom, hydroxyl or alkoxy, especially methoxy.

Another group of phosphites that can be used in the present invention are tertiary organophosphate. Such phosphites may contain two or more of these tertiary (trivalent) phosphorus atoms, such as those that correspond to the formula

XP-O-X where X is a substituted or unsubstituted m-valent hydrocarbon radical, R' is the same as defined here, in another place, each Raindependently is a substituted or unsubstituted monovalent hydrocarbon radical, a and b each can have a value of 0-6, with the proviso that the sum a+b is equal to 2-6, and m is a+b. Typical tertiary organophosphate may include biphosphate, such as having the formula:

R-O-X where R"' is a divalent organic radical, as defined here, where each Raindependently is a substituted or unsubstituted monovalent hydrocarbon radical, and X is substituted or unsubstituted divalent hydrocarbon radical; and

R-O-X-O-P where R"' is a divalent organic radical, as defined here, in another place, each Raindependently is a substituted or unsubstituted monovalent hydrocarbon radical, and X is substituted or unsubstituted divalent hydrocarbon radical.

Representatives of one class of biophosphates, which can be used in the present invention are those in which

R-O in the above formula is replaced

P O where each Ar group, and X and Q groups are defined here in another place the appropriate context.

Another group of phosphites that can be used in the present invention are the phosphites of the formula:

Z where z5is a trivalent organic radical, such as described in more detail, for example, in the previously mentioned U.S. patent N 4567306.

Finally, another group of phosphites that can be used in the present invention are triorganotin, such as Tris(ortho-phenyl)-phenylphosphate, Tris(ortho-m is esteem the invention, may be tertiary organophosphine ligand selected from the group consisting of monoethanolamide, georganopoulou, reorganistion and organophosphates, such as described above.

Additional typical examples fofanah ligands useful in the present invention, shown in Fig.1-4.

Fosfatnye ligands such types General class, applicable in the present invention and/or methods for their preparation are known. For example, fosfatnye ligands applicable in the present invention, can be easily obtained through a series of traditional reaction of phosphorus halides with alcohols. The condensation reaction of this type and methods for their implementation are well known in the prior art. Some of these ways to get shown in the U.S. patents of billiga with TCS. NN 4668651, 4717775, 4599207, 4769498 and in U.S. patent 4774361 Mayer with TCS.

The number of the applied ligand preferably is sufficient to provide targeted anionic registergui complex. Upon receipt or production of the target complex can be applied to the excess of the source of the ligand, for example, to increase the rate of formation of the complex. Additional free or uncomplexed. Alicia this free ligand can favorably act on the preservation of active anionic registeruser complex. The molar ratio of such a ligand (or source of ligand to rhodium (or the source of rhodium) is preferably in the range of from about 0.1 to about 100, more preferably from about 0.5 to about 50, and more preferably from about 0.5 to about 20. A very large excess of the source of the ligand and free ligand should be avoided as harmful. Also a very large excess can have a damaging effect on anionic registergui complex and/or the stage of hydroformylation.

This anionic registergui complex is associated with a cation other than H+and preferably a cation of an alkali metal, more preferably of organics-containing cation as described here.

In one embodiment, registergui the catalyst is of the anionic component that includes one or more of these cations, preferably, organics-containing cations. Such ionic components preferably have sufficient basicity, for example, include anion having sufficient basicity to facilitate , the button to deprotonate hydride rhodium, which may be provided or received, for example, as a precursor of the anionic registeruser complex described here. Specific anion is selected depending on, for example, from a specific source of rhodium, source, ligand, acid, if present, and the applied liquid medium. Preferably the ionic component is soluble in the liquid medium. The anions associated with the environment and a strong acid are one class of anions useful in the present ion components. Specific examples include halides, sulfates, phosphates, carboxylates, in particular, low molecular weight carboxylates, such as formats, acetates, etc.

Preferred organic contained the cation may include an element from group Va or group VIa of the Periodic system. One specifically useful group of organics-containing cations are those which have the formula selected from

Im RY where Y is a polyvalent element of group Va of the periodic system, in particular selected among nitrogen, phosphorus and arsenic, Y' is an element VIa group of the periodic system, each of R7, R8, R9and R10may be the same or different and can be merge the pre-selected among hydrogen and hydrocarbon radicals, which may be substituted or unsubstituted and may contain at least one carbon atom, preferably at least one and more preferably all of the hydrocarbon radicals R7, R8, R9and R10contain at least 4 carbon atoms, for example, from about 4 to 70 carbon atoms, and sometimes about 4-20 carbon atoms. However, at least one of R7, R8, R9and R10deputies must be hydrocarbon.

Hydrocarbon substituents can be aliphatic or aromatic and include, for example, n-hexyl, cyclohexyl, phenyl, benzyl, naphthyl, etc., Examples of Quaternary ammonium or Quaternary fofanah fragments are terapevticheskii fragments, for example, Tetramethylammonium, tetraethylammonium, Tetra-n-propylammonium, Tetra-n-butylammonium,Tetra-isobutylamine, trimethylbutyramide, tetragammaton, acetylcysteamine, tetraphenylarsonium, trimethylphenylammonium, Tetramethylammonium, tetradecyl - money, tetraoctylammonium etc. tripelenamine fragments, for example, ammonium, triethylammonium, triphenylamine, tridodetsilamin, trioctadecyl etc. Digue is ammonium, diphenylamine, dibenzylamine, deterimine, dioctadecyl etc. uglevodorodami fragments, for example, methylammonium, n-butylamine, Daudet - celemony, octadecylamine, phenylamine, benzylamine etc. terapevticheskii fragments, for example, tetramethylphosphonium, tetramethylphosphonium, Tetra-n-propylphosphine, Tetra-n-butylphosphonium, tetraisopalmitate, trimethylboroxine, tetracationic, tetraphenylphosphonium, tetrabutylphosphonium, tetradecylphosphonic, tetraoctylammonium etc. triple - vodorozpustnej fragments, for example, trimethylphosphine, triethylphosphine, triphenylphosphine, tricotillomania, triarticulate etc. Diplopoda - radiophonie fragments, for example, dimethylphosphino, diethylphosphino, di-n-butylphosphine, di-n-satifactory, diphenylphosphine, dibenzalacetone, didodecylphenol, dictatorshi etc. uglevodorodnaya fragments, for example, methylphosphonyl, n-butylphosphine, dodecylphosphonic, octadecylphosphonic, phenylphosphonic, benzylphosphonic etc.

Another group of organics-containing cations include bis(hydrocarbon-phosphine)imine General formula:

[(R311P)2N]+where each RIs-(uglevodorodov)eminiem are bis-(Trife - nilpotent) imine, bis-(tribenzylphosphine)imine, bis-(trimethylphosphine)imine, bis-(trimodality)imine, etc. and mixtures thereof.

Another group of organics-containing cation has the formula:

[(R13)r-y-R12-y-(R13r)2+where R12is alkylene with 1-6 carbon atoms, each R13independently selected from among hydrogen and hydrocarbon radicals which may be substituted or unsubstituted, and r is 3. Typical examples of this group include quaternion diamines, quaternion diphosphine, etc. Specific members of this group include

N,N'-bis(trimethyl)the propylene diammonium,

N,N'-bis(triphenyl)the propylene diammonium,

N,N'-bis(trioctadecyl)the propylene diammonium,

P,P'-bis(trimethyl)propylene diphosphane, etc. and mixtures thereof.

The number of ion component, for example, organics-containing cations used in the preparation of these catalyst compositions can really depend on, for example, a particular ion used component and from the target registeruser catalyst. The molar ratio of the ionic component to the rhodium used in the preparation of these catalyst compositions may vary within wide limits, for example, in the interval from when the m for merger or combination with registertask connection for example, registertask anion to retrieve the target catalyst. Can be used an excess of the cation, for example, of the order of at least about 50-100% or more.

In one embodiment, the present reaction hydroformylation epoxide occurs in the presence of an electrophile, for example, N+ions, proton acids, Lewis acids, etc., and their mixtures, in particular, N+ions, in an amount effective for the further promotion of hydroformylation epoxide. Some H+ions may be present as a result of deprotonization described here hydride compounds of rhodium. In some cases, the number of N+ions may be sufficient to ensure further promotion of hydroformylation epoxides. In a particularly useful embodiment, hydroformylation epoxide in the presence of acid, preferably a proton acid, which can be incorporated in the catalytic composition, or the composition of the catalyst precursor.

Medium or strong acids are preferred for use in the present invention. Suitable acids for the process of the present invention are strong to the I acid, triperoxonane acid, p-toluensulfonate, etc. and mixtures thereof. Middle acids suitable for the process include carboxylic acids such as benzoic acid, acetic acid, propionic acid, acidic salts such as dickishly sodium phosphate, etc. and mixtures thereof. Phosphoric acid is a specific example of a useful acid. The amount used of the acid is sufficient for the further promotion or facilitate hydroformylation epoxide. This number can vary depending on, for example, on the particular acid used anionic registeruser complex. The molar ratio of acid to rhodium can be in the range of from about 0.1 to about 10, preferably about 0.2 to 3.

These radiogardase catalysts preferably contain virtually no ions of the alkali metal. Indeed, this process of obtaining 1,3-diol/aldehyde, in particular the very stage of hydroformylation, preferably carried out practically in the absence of alkali metal ions.

The conditions under which receive the catalytic composition are such that a target registergui catalyst. It preferably has masatora more preferably acts as a solvent for the source of rhodium, the source of the ligand, ion and acid, if present, and other components, if any, in the predecessor used to obtain registeruser catalyst. In one particular advantageous embodiment, the liquid medium used in the composition of the catalyst precursor, has essentially the same chemical composition as the liquid medium used in the reaction of hydroformylation epoxide.

The conditions under which receive the catalytic composition may be similar to those used at the stage of hydroformylation. The catalytic composition may be prepared separately and outside stage hydroformylation epoxide, and then introduced at this stage to provide the desired promotion of catalytic hydroformylation. In one embodiment, form the composition of the catalyst precursor and the composition of the catalyst precursor is injected into hydroformylation epoxide. Conditions hydroformylation are effective for the formation of the catalytic compositions of this predecessor.

The molar ratio of carbon monoxide to hydrogen used at the stage of hydroformylation epoxide may znachitelnaya obtain 1,3-diol and/or 3-acetaldehyde is in contacting combinations of epoxide, of carbon monoxide and hydrogen in the presence of a catalytic composition effective for promotion of hydroformylation epoxide, and the promoting component under conditions effective for the formation of at least one 1,3-diol and 3-acetaldehyde. The catalytic composition consists of containing the anionic ligand registeruser complex and electrophile. The promoting component may be selected from among compounds, complexes, polymeric materials, mixtures thereof, etc., Such a promoting component is present in a quantity effective to increase the speed of hydroformylation epoxide and/or increasing the selectivity of formation of 1,3-diol and/or 3-acetaldehyde. Such increase or the increase is relative to an essentially identical to the process of hydroformylating epoxide carried out without or with little useful in this case the promoting component or components.

Any promoting component or components can be used in the present invention, provided that such component or components used in concentrations which provide one or more marked here increases, the concentration of their site is tion is in the material, used at this stage of the contact, for example, in the reaction mixture in molar concentration, for example, so much of moles per liter of liquid, which in theory or equivalent pH of the aqueous fluid with the 22aboutWith that contains only that the molar concentration of such a promoting component is in the range from about 1 to about 12, more preferably about 1.6 to 10.7. The promoting component is in a concentration that provides the above theoretical or equivalent pH were found to increase at least the speed of hydroformylation epoxide and selectivity in 1,3-diol and 3-acetaldehyde. Without wishing to limit the invention to any specific theory of operation, it is expected that such promoting components can act to facilitate education and/or maintain an effective concentration containing anionic ligand registeruser of a catalytic composition under conditions of contact. On the contrary, components or concentrations of components that result in either too high or too low theoretical or equivalent pH, as defined here, are not able to effectively facilitate and deistvitel complexes. In any case, the promoting component is present in amount to provide the above-mentioned theoretical or equivalent pH, as was found, should favor this phase contact reaction hydroformylation.

Although the water meets the criterion of equivalent pH and can be used as the promoting component, nalichii water can irreversibly decompose or degrade one or more components of the present catalyst composition under conditions of hydroformylation epoxides and/or otherwise degrade the effect of the present process and compositions, for example, is destructive to affect the activity and/or stability of the catalytic composition. These promoting components are preferably chosen so that the certainly not have a detrimental effect on the present process and composition, in particular, to avoid irreversible decomposition or deterioration of one or more components of the present catalyst composition under conditions of hydroformylation epoxides. So, the promoting component should preferably be other than water.

In one briante promoting component selected among those companiesone during the reaction hydroformylation epoxide.

As used herein, the term "promoting component" refers not only to the components that are effective to increase the speed of hydroformylation epoxides and/or selectivity of hydroformylation epoxides 1,3-diol and/or 3-acetaldehyde, but also to one or more materials capable of forming one or more of these compounds in terms of hydroformylation epoxides.

Especially useful promoting components are components that are selected from among (a) nitrogen-containing compounds, (b) compounds containing hydroxyl groups, (b) compounds containing carboxyl groups, (d) proton acids and mixtures thereof. The promoting component or components may include at least one component that is at least two of (a), (b), (C) and (d). Particularly useful results are obtained when the promoting component comprises one hydroxyl group and/or at least one carboxyl group.

Among the useful nitrogen-containing components include amines, amides, imine, imidazoles, etc., and mixtures thereof. Polymeric nitrogen-containing compounds and mixtures thereof, particularly those of the polymeric nitrogen-containing compounds, which are things the is used as the promoting components. The nitrogen atom or atoms of nitrogen-containing compounds can be part of a heterocycle or substituted heterocycle, for example, containing 4,5 or 6 or more carbon atoms, and/or can have one or more such cycles and/or one or more saturated, unsaturated or aromatic hydrocarbon groups or substituted hydrocarbon groups, such as covalent bonds with each other. Nitrogen-containing compound may contain one or more than one nitrogen atom. Useful nitrogen-containing Monomeric compounds of the number of nitrogen atoms is preferably in the range of 1-5, more preferably 1-3. Compounds with a single nitrogen atom provide useful results. Preferably at least two and more preferably all three bonds at least one of the nitrogen atoms associated with hydrocarbon or substituted hydrocarbon groups.

Such hydrocarbon groups and substituted hydrocarbon groups can contain any number of carbon atoms provided that the promoting component acts as described in the present invention. In one embodiment, such hydrocarbon and substituted hydrocarbon group containing 1-20, preferably 1-12 carbon atoms. Palkel, such as phenylmethyl, phenylethyl, phenylbutyl, phenylactic etc. aralkyl, such as phenylethenyl, phenylbutyl, phenylethenyl, etc. of alkenyl, such as ethynyl, propenyl, butenyl, octenyl, decenyl, etc. alkylene, such as methylene, ethylene, butylene, pentile, hexylen, etc. other divalent hydrocarbon group, aryl, such as phenyl, naphthyl, etc. alkaryl, such as were, ethylphenyl, butylphenyl, octylphenyl, etc. alkenyl, such as ethenylene, butylphenyl, acheninver, etc., and similar groups. Can be applied substituted counterparts of such hydrocarbon groups. Such substituents can include, for example, carbon, hydrogen, oxygen, nitrogen, sulfur, halogen, phosphorus, etc., and mixtures thereof.

Specific examples of useful nitrogen-containing promoting components, especially to increase the speed of hydroformylation of ethylene oxide include Tris(4-bromophenyl)Amin, triphenylamine, benzimidazole, 2,6-lutidine, 2-Mei, 1-Mei, 1,8-bis-(dimethyl-amino)naphthalene, triethanolamine, N-methyl - pyrrolidone, dimethylformamide, etc., and mixtures thereof.

Among the useful promoting components, which contain hydroxyl groups, are such compounds in which a hydroxyl group or Gruppo. Such hydrocarbon groups and substituted hydrocarbon groups can contain any number of carbon atoms, provided that the promoting component acts as described in the present invention. In one embodiment, such a hydrocarbon or substituted hydrocarbon group containing 1-20, preferably 1-12 carbon atoms. Examples of useful hydrocarbon groups include groups such as here provided in relation to nitrogen-containing compounds, useful as promoting components. Can be applied substituted duplicates of such hydrocarbon groups. Such substituents can include, for example, carbon, hydrogen, oxygen, nitrogen, sulfur, halogen, phosphorus, etc., and mixtures thereof.

Can also be useful as promoters analiziruem dicarbonyl compounds such as 1,4-pentandiol and ethylacetoacetate that there are two equilibrium tautomers (one of which includes a hydroxyl group).

Particularly useful compounds containing hydroxyl group, selected from among such compounds having at least one aromatic hydrocarbon group. Polymeric compounds and mixtures thereof that include one or more hydroxyl groups, especially aeroportimilano epoxide, can also be used as the promoting compounds. Compounds containing hydroxyl groups may include one or more than one hydroxyl group. In Monomeric compounds containing a hydroxyl group, cello hydroxyl groups is preferably in the range of from 1 to about 6; more preferably 1-4.

Specific examples of the compounds containing hydroxyl groups, are useful as promoting components include phenol and derivatives of phenol such as alkyl-, aryl - and aralkylamines derivatives, for example, o-, m - and p-Cresols, dimethylphenols, ethylphenol, bottled oxytrol, etc. diphenol and derivatives diphenol, such as alkyl - and aryl-substituted; substituted divinely, catechol and derivatives of catechol; resorcinol and derivatives of resorcinol, sensation and derivatives benzonitrile, such as 1,2,4-benzothia; oxidation, such as 2-naphthol; dioxynaphthalene, such as 1,3-dioxynaphthalene; etc. and mixtures thereof.

Among the useful promoting compounds, which contain a carboxyl group or groups, are such compounds in which the carboxyl group or groups connected with a saturated or unsaturated, or aromaticheskoi ugye groups can contain any number of carbon atoms, provided what the promoting component operates as described in the present invention. In one embodiment, such a hydrocarbon or substituted hydrocarbon group containing 1-20, preferably 1-12 carbon atoms. Examples of useful hydrocarbon groups include groups such as those cited as examples here in relation to nitrogen-containing compounds which are useful as promoting compounds. Can be used replaced by duplicates of such hydrocarbon groups. Such substituents can include, for example, carbon, hydrogen, oxygen, nitrogen, sulfur, halogen, phosphorus, etc., and mixtures thereof.

Particularly useful compounds containing carboxyl group, selected from among such compounds having at least one aromatic hydrocarbon group, for example, as described. Polymeric compounds and mixtures thereof that include one or more carboxyl groups, particularly those polymers which are essentially soluble in the liquid medium during the reaction of hydroformylation epoxide can also be used as the promoting compounds. Compounds containing carboxyl groups may contain one or more carboxyl groups. In Monomeric compounds containing the RNO 6, more preferably 1-4.

Specific examples of compounds containing carboxyl groups, are useful as promoting components include mnogokubovye acid, such as acetic acid, propionic acid, butyric acid, somalina acid, valeric acid, isovalerianic acid, hexanoic acid, cekanova acid, lauriola acid, stearic acid, acrylic acid, lactic acid, benzoic acid, p-ethoxybenzene acid, 3,5-dimethoxybenzoic acid, picolina acid, pipecolinate acid, cinnamic acid; dicarboxylic acids such as adipic acid, 1,2-cyclohexanecarbonyl acid, malonic acid, succinic acid, glutaric acid, tartaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid and 1,8-natalijagolosova acid; polycarboxylic acids such as polyacrylic acid and 1,3,5-benzotriazole acid, etc. and mixtures thereof.

Proton acid, preferably used in concentrations sufficient to meet the above criterion is equivalent to pH are effective as promoting components. Strong acids, other compounds, forming a proton acid, for example, in usloviyah contact. In the present invention can be used in a strong proton acid, in particular acids, which are as strong as phosphoric acid, or stronger. Suitable strong acids include sulfuric acid, phosphoric acid, idiscovered acid, hydrochloric acid, Hydrobromic acid, triperoxonane acid, p. toluensulfonate, etc. and mixtures thereof. Phosphoric acid is a concrete example of a useful acid.

Useful proton acid medium strength include the previously carboxylic acid, and phosphorous acid, sulfurous acid, phosphinic acid, phosphonic acid, nitric acid, etc., a Relatively high concentration of proton acid medium and weak forces are the best in comparison with the concentrations used strong acids. Examples of weak proton acids, which can be used include diphenol, phenol, bottled oxytrol, succinimide, carbonic acid, ammonium salt, etc.

The promoting component may include one or more than one other electroneutrality groups. Examples electronbeam include both substituted, or unsubstituted aromatic group; foralkyl, such as trifluoromethyl and defloratin; ferril, such as forfinal; nitro; chlorine; bromine; iodine; a carbonyl group; ester groups; amide groups; carboxyl groups; cyano; ammonium (including hydrocarbon and substituted hydrocarbon ammonium) groups; postname (including hydrocarbon and substituted hydrocarbon postname) group; sulfonamide (including hydrocarbon and substituted hydrocarbon) group, etc. and mixtures thereof.

Useful aromatic hydrocarbon group or groups include at least one aromatic hydrocarbon ring, for example, groups such as aryl, alkaline, alkenylamine, kalkilya, kalkaylkia, their substituted counterparts, mixtures thereof and similar groups, shown here in a different location. Groups that include one or more condensed aromatic cyclic structures are also included in the scope of the present invention.

The promoting component may include one or more electron-donating groups. Examples of electron-donating groups useful in this invention are alkyl groups such as methyl, ethyl, propyl and butyl; phenyl groups, Alie as methoxyphenyl, ethoxyphenyl and propoxyphenyl; aminoaniline groups, such as AMINOPHENYL, methylaminophenol, dimethylaminophenyl and methyl, acylaminoalkyl; oxyphenylic groups, such as oxiranyl and dioksifenil; AMINOPHENYL, etc. and mixtures thereof.

As used here, electroneutrality ability and electron-donating sposobnosti any given group or substituent is compared with the Deputy of the hydrogen atom in the process of hydroformylating epoxides. I.e. electroneutrality group is defined as being able to stronger repulsion of the electrons relative to the substituent of the hydrogen atom. Similarly electron-donating group is defined as being able to more easy returns one or more electrons towards the Deputy hydrogen atom, etc.

The inclusion of one or more electroneutrality groups and/or electron-donating groups can act to control the acidity (or basicity of a specific component, so that gives the opportunity to coordinate with acidity) basicity of these promoting components.

Especially useful promoting components are selected among triethanolamine, 2,6-lutidine, benzimidazole, 2-methylimidazole, is methylformamide, N-methylpyrrolidone and mixtures thereof.

The number of the promoting component should be sufficient to ensure the desired results and it is preferable to satisfy the following criterion is equivalent to rn. Care should be taken to avoid excessive amounts of the promoting component. Such excessive promoting component may provide little or no additional benefits and/or may have a General deteriorating effect on the real system. Also the cost of promoting component may facilitate its use in large quantities. In one useful embodiment, the promoting component is in such a quantity that the molar ratio of the promoting component to rhodium is in the range from about 0.1 to about 10. In particular, the molar ratio of nitrogen atoms, hydroxyl groups, carboxyl groups and/or N+available in the promoting component, the rhodium is in the range from about 0.1 to about 10.

3-Acetaldehyde obtained when hydroformylating epoxide, can be extracted, for example, using one or more of radicidation. Then 3-acetaldehyde may be subjected to hydrogenation, for example, when using the traditional process of hydrogenation, to obtain the target 1,3-diol.

Stage hydrogenation is usually carried out under certain conditions of time and temperature. Preferably the temperature of the hydrogenation is in the range from about 90 to about 170aboutWith, preferably in a period of time from about 0.5 to about 4 hours the hydrogenation Reaction can be conducted in the presence and in the absence of a liquid medium hydrogenation. Liquid hydrogenation is preferably water, although they can be used directionspanel polar organic solvents, such as dimethoxyethane, etc., the Pressure applied during the hydrogenation, preferably in the range of about 500 lb/in2( to 35.15 kg/cm2) to about 2000 lb/in2( 140,6 kg/cm2). The catalyst used in stage hydrogenation can be any well-known hydrogenation catalyst used in this prior art, such as Raney Nickel, palladium, platinum, ruthenium, rhodium, cobalt, etc., it is Desirable to use as catalyst for the hydrogenation metal or compound of the metal is anaut this activity for a long period of time. The hydrogenation catalyst may be used in finely ground form and dispersed in the reaction mixture, or it can be used on the media, such as hard-shelled earth, clay, alumina, coal, etc., the Number of used hydrogenating catalyst is preferably in the range of from about 0.1 to about 10%, more preferably about 1-8 wt. from gidrirovannogo 3-acetaldehyde.

In these examples the names used to refer to the following ligands:

Ligand I

Ligand II

Ligand III

Ligand IV

P R I m e R 1. Synthesize the catalyst precursor of hydroformylation when combining 0.52 g radiokarbonmethode (Rh(CO)2(ACAC)), 0,643 g tetrabutylphosphonium (Bu4P)(OAc) 1,693 g Ligand IV and 5 cm3water in 80 cm3dimethoxyethane. This predecessor of the catalyst was tested as follows.

Autoclave with a capacity of 300 cm3with stirring, made of a suitable resistant metal alloy, such as stainless steel or Hastelloy CRwith internal akladasim coil, thermocouple, and a device for measuring pressure, used for testing the ez valve in the upper part of the autoclave. Then the autoclave is installed in working position and enter the eligible amount monoacid carbon and hydrogen. Then the autoclave is heated to the desired temperature and set the pressure as necessary to maintain the desired pressure with the feed mixture WITH a/H2or by blowing. As the reaction of hydroformylation introduce additional amount of a mixture of CO/H2until then, until you reach the desired gas or reaction time. After completion of the reaction the autoclave ohlala, for example, -40aboutWith, and otdovat excess gas. After heating to 0aboutWith the autoclave opened and analyze its contents traditional methods.

When using the above catalyst precursor in contact 10 g of ethylene oxide in an autoclave at 110aboutC and a pressure of 1100 lbs/inch (77,3 kg/cm2) synthesis gas, WITH/N2mixture having a molar ratio of 1 to 2 H2. The feed gas is spent immediately and not observed induction period.

This reaction results in the selectivity of ethylene oxide to 3-oxopropionate and 1,3-PROPANEDIOL 44% mol. The rate of formation of 3-oxopropionate the factory worker catalyst synthesized without water and dimethoxyethane replaced tetragonum. This reaction results in a selectivity of ethylene oxide to 3-oxopropionate and 1,3-propandiol 38 mole. and to the rate of formation of 3-oxopropanenitrile and 1,3-propane diol to 0.19 mol/l/h These results show that the water may have a synergistic effect on the activity and selectivity of the catalytic composition or system.

P R I m e R 3. Repeat example 1 with the exception that they did not use tetrabutylphosphonium, (Bu4P)(OAc)). Practically not observed hydroformylation of ethylene oxide. These results show that the ionic component is essential for efficient catalytic system hydroformylation epoxides.

P R I m e R s 4 and 5. Twice repeating example 2 except that the use of Ligand III (example 4) and Ligand 1 (example 5) instead of the Ligand IV, and the reaction hydroformylation spend half the concentration of the catalyst precursor relative to the concentration in example 2.

The results of these tests are shown in table.1.

These results show that different bis-fosfatnye ligands are useful for the preparation of catalytic systems for hydroformylation epoxides.

P R I m e R 6. Povtorat in the reaction. As a result, in example 6 receive the selectivity of ethylene oxide to 3-oxopropionate and 1,3-propandiol 75% mole. and the rate of formation of 3-oxopropanenitrile and 1,3-propane diol 0.8 mol/l/h These results indicate that reduced conversion of epoxide provides increase the rate of formation of product and increase the selectivity to the target product or products.

P R I m e R 7. Repeat example 2, except that the use of toluene instead of tetraline, the reaction temperature is 115aboutWith and the reaction mixture was injected 2 mmole of 2,6-lutidine. Molar concentration of 2,6-lutidine is such that is equivalent to the pH of a solution of 2,6-lutidine/water will be approximately equal to 9.5. There is a significant hydroformylation of ethylene oxide, produce large amounts of 3-xiaopingdao. When opening the autoclave determines that the received 3-oxopropionate forms a separate phase from the toluene solution.

Separated from the toluene solution of 19.5 mol obtained 3-oxopropanenitrile. This separated 3-oxopropionate added to 10 ml of water and transferred to glass line in the autoclave with a capacity of 300 ml In the autoclave was added 0.27 g of the Raney 3100 molybdenum promoted nick who shape and create a pressure of 1000 lb/in2( 70,3 kg/cm2) of hydrogen at 20aboutC. the Contents are heated to 105aboutC and maintained at this temperature for 3 h Then the reaction mixture is cooled to 20aboutWith and analyze the contents. It was found that 1,3-propandiol is formed with a yield of 96%

A significant activity of this catalytic composition for promotion of hydroformylation of ethylene oxide in toluene was unexpected, because in other work, namely, Murphy with TCS. U.S. patent N 4873378 and 4873379, indicated that solvent, such as toluene, are ill befits for hydroformylation low molecular epoxides. This system, in particular, the present catalytic system is significantly different from this other work and provides unexpected advantages in comparison with her.

P R I m e R 8. Download 1.0 g Rh4(CO)12and 4.44 g of the Ligand IV in a Parr autoclave with a capacity of 300 cm3. The autoclave is pressurized and then rinsed with nitrogen. In an autoclave pressure of 40 cm3heptane through a suitable valve and washed with a strong flow of gas mixture 1:1 CO/H2before the pressure of this gas mixture to a pressure of 60 lb/in2. In the autoclave is stirred overnight at room temperature. is really as HRh(CO)2(Ligand IV).

To stir a mixture of 0.3 g of potassium hydroxide in 30 cm3methanol in nitrogen was added 1.0 g HRh(CO)2(Ligand IV), then 23 g of bis-(triphenylphosphine)imidicloprid, (PPN)(Cl). The mixture is stirred at room temperature for 5 h, after which the insoluble product is filtered off. It is washed with methanol, diethyl ether, and then dried in vacuum. This product is defined as (PPN)(Rh(CO)2(Ligand IV)).

Repeat example 2 with the exception that using 1 mmol (PPN)(Rh(CO)2(Ligand IV) as the catalyst precursor. There is practically no gas consumption after 50 minutes did not have of H+ ions during the reaction of hydroformylation.

P R I m e R 9. Repeat example 8 except that the autoclave is injected 0.06 g of acetic acid. Molar concentration of acetic acid is such that is equivalent to the pH of a solution of acetic acid/water is about 3.4. In realitate these tests receive the selectivity of ethylene oxide to 3-oxopropionate and 1,3-propandiol 26 mole. and the rate of formation of 3-oxopropanenitrile and 1,3-propane diol is 0.05 mol/l/h These results indicate that the presence of acetic acid in the above concentrations may O equivalent number (PPN)(Rh(CO)2(Ligand IV) and (HRh(CO)2(Ligand IV)) is used instead of (PPN)(Rh(CO)2(Ligand IV)) and the molar ratio of CO to H2equal to 0.25. The results of this experience give the selectivity of ethylene oxide to 3-oxopropionate and 1,3-propandiol equal to 37 mole. and the rate of formation of 3-oxopropanenitrile and 1,3-propane diol by 0.055 mol/l/h

P R I m e R 11 (comparative). Synthesize the catalyst precursor of hydroformylation when combining 0.51 g of decarbonylation rhodium, Rh(CO)2(ACAC), 0,53 g tricyclohexylphosphine, (Cy)3P, of 0.13 g of phosphoric acid, H3RHO4, 5 cm3water and 0.1 g of hydroquinone in 80 g tetragonoloba solvent. This formulation is essentially the same as described in example 6 of U.S. patent 4873378 Murphy with TCS.

Repeat example 1, prepared using the above catalyst precursor instead of the catalyst precursor prepared in example 1. There is an induction period of about 30 min before gas consumption. During this induction period, considered to be the predecessor of katalysator reacts with ethylene oxide to form the active catalyst hydroformylation of ethylene oxide, which itself includes molecules ethylenoxy the 1,3-propandiol 59% and speed (not including the induction period) education 3-oxopropanenitrile and 1,3-propane diol 0.08 mol/l/h In example 11 receive 1,3-propandiol more than 3-oxopropionate, whereas the reverse with preventive for example 1.

P R I m e R s 12-15. Prepare a series registergui precursors of the catalyst. Prepare each of these precursors of the catalyst when combining the components described below 80 cm3dimethoxyethane. Each of these precursors of the catalyst obtained using 2 mmol radiokarbonmethode, Rh(CO)2(ACAC), 2 mmol of tetrabutylphosphonium, (Bu4P)/(OAc), 2 mmol of phosphoric acid, H3RHO4and 5 cm3water. These precursors of the catalyst include the following ligands:

An example of the Ligand, the Number of ligand

12 Ligand II 2 mmole

13 P/Me3(1)2 mmole

14 P(OMe)3(2)2 mmole

15 ButNC(3)2 mmole

(1) Trimethylphosphine

(2) Trimethylphosphite

(3) Tertbutylphenyl.

Each of these precursors of the catalyst was tested in the reaction of hydroformylation of ethylene oxide using the procedure described generally in example 1. Molar concentration of phosphoric acid is such that is equivalent to the pH of the solution of phosphoric acid/water equal to about 1.8. To the RA 110aboutWITH/N2(molar - ing) 1:2 Conc tion rhodium 2000 h/million Mac.

The results of these tests are presented in table.2.

These results show that fosfatnye ligands (examples 12 and 14) provide enhanced selectivity in the product compared to nepohytnyj ligands (examples 13 and 15). Referring to example 1, bis-fosfatnye ligands provide highly effective the rate of formation of product and selectivity compared to other topicname ligands and nepohytnyj ligands.

P R I m e R s 16-31. Prepare another series registergui compositions. Each of these predecessors catalyst is prepared by combining the following components in 80 cm3tetragona. Each of the precursor catalyst was prepared using 2 mmol radiokarbonmethode, Rh(CO)2(ACAC), 2 mmol of tetrabutylphosphonium, (Bu4P)(OAc) 2 m mmol specified below ligand.

Each of the precursor catalyst was tested in the reaction of hydroformylation of ethylene oxide by the method of example 1.

For specifically stated exceptions, the contacting is carried out in the following conditions: a Pressure of 1000 lb/in2< / BR>
( 70,3 kg/cm2) T is the Results are given in table.3.

These results show that the choice of ligand is essential for the effective catalyst hydroformylation epoxide.

P R I m e R s 32-43. Repeat example 2 twelve times, with the exception that 2 mmole of various nitrogen-containing compounds, as listed below, include in the catalyst. These precursors of catalysts also experience in the reaction of hydroformylation of ethylene oxide at 115aboutAnd pressure of 900-1000 lbs/inch2( 63,3-70,3 kg/cm2) a mixture of synthesis gas having a molar ratio of 1: 4.3 H2.

Get the following results in these trials (table. 4).

The results show that some quantity of certain nitrogen-containing compounds affect the selectivity and/or the rate of formation of 3-oxopropanenitrile and 1,3-propane diol when hydroformylation of ethylene oxide. In particular, the presence of such compounds in such amounts that the equivalent pH was equal to about 12 or below, preferably about 10.7 or below, providing an increased rate of formation of 3-oxopropanenitrile and 1,3-propane diol. The presence of such quantities of certain nitrogen-containing compounds also provides increased selectivity of the invention to any particular theory of operation), that 1,3-bis-dimethylamino/naphthalene, for example, due to the inherent connection of steric acts as less primary component than was predicted using the equivalent pH. Therefore, although the equivalent of several pH above 12, 1,8-bis(dimethylamino)naphthalene should provide some degree of increase of the rate of formation of 3-oxopropanenitrile and 1,3-propane diol.

P R I m e R s 44-49. Conduct a series of experiments on hydroformylation of ethylene oxide in accordance with the General procedure of example 1 in the absence of water.

Used the catalyst precursor is:

2 mmole decarbonylation rhodium

5 mmol of the Ligand IV

3 mmole of tetrabutylphosphonium

3 mmole of 2,6-lutidine

Use 100 cm3tetragona as solvent.

Molar concentration of 2,6-lutidine is such that is equivalent to the pH of a solution of 2,6-lutidine in the water should be about a 9.6. Reaction conditions are: Pressure of 1000 lb/in2< / BR>
( 70,3 kg/cm2) Temperature: 115aboutWITH

The molar ratio of CO/H21:2

Ethylene oxide: changed as indicated below.

The following results are obtained ex is and the activity and selectivity of the catalytic system.

P R I m e R s 50 and 51. Conduct two experiments on hydroformylation of ethylene oxide in accordance with the General procedure of example 1 in the absence of water.

As the catalyst precursor used:

2 mmole decarbonylation rhodium

2 mmole Ligand IV

2 mmole of tetrabutylphosphonium

Phosphoric acid is changed as shown below.

Use 100 cm3tetragona as solvent. Reaction conditions are: Pressure: 1000 lb/in2< / BR>
( 70,3 kg/cm2) Temperature: 110aboutWITH/N2(molar - ing) 1:2 ethylene oxide 10 grams

Get the following results of experiments (table. 6).

These results show that, although a limited amount of phosphoric acid, in particular, such a quantity that will provide equivalent pH of about 1.6 or above is favorable for catalytic systems, for example, increases the rate and/or selectivity, an excessive amount of phosphoric acid can cause deterioration reaction of hydroformylation of ethylene oxide.

P R I m e R 52. Repeat example 50, except that the catalyst precursor includes 2 mmole of triethanolamine and not codestore triethanolamine is about 10.0. The results of this experiment are as follows.

The selectivity for 3-oxypropyl - the Rate of formation of 3-oxypropyl-

the aldehyde and 1,3-propane diol, aldehyde and 1,3-propane diol,

the mole. mol/l/h

73(74)(1)0,74(0,76)(1)< / BR>
(1) the Value in parentheses obtained from exact duplicate of the experiment.

These results show that the triethanolamine promotiom hydroformylation of ethylene oxide and that used experimental procedure provides almost reproducible results. In particular, the presence of triethanolamine in the above concentration provides increased speed hydroformylation of ethylene oxide and increase the selectivity to 3-oxopropionate and 1,3-propandiol.

P R I m e R s 53 and 54. Repeat example 2 twice, with the exception that the catalyst include 2 mmole of diphenol. Molar concentration of diphenol is such that is equivalent to the pH of the solution diphenol/water approximately equal to 5.4. In example 54 reaction hydroformylation carried out at 90aboutC.

The results of these tests are as follows (table. 7).

These results indicate that certain concentrations of some other substances, in customedid and 1,3-propane diol when hydroformylation of ethylene oxide.

In addition, the lower temperature hydroformylation can as a result increase the selectivity.

P R I m e R 55. 3-Oxopropionate from example 47 extract, for example, by distillation and subjected to further processing as follows. Add to 10.9 mmole 3-oxopropanenitrile to 9 ml of water and transferred to glass line in the autoclave with a capacity of 300 ml In the autoclave was added 0.14 g of the Raney 3100 Nickel catalyst promoted with molybdenum, in 30 ml of water. Establish a pH equal to 7, adding 3 N. sulfuric acid. The autoclave is pressurized and create a pressure of 1000 lb/in2( 70,3 kg/cm2) at 22aboutC. the Contents of the autoclave are heated to 105aboutWith and maintain this temperature for 2 hours After this time the temperature was raised to 160aboutC and maintained at this temperature for another 1 h and Then the reactor is cooled to 25aboutWith and analyze the contents. Found that the obtained 1,3-propandiol with access 95%

P R I m e R s 56-63. Repeat example 50 a few times with the exception that in each iteration the catalyst precursor contains 2 mmole of one of the various compounds, as listed below, and does not contain phosphoric acid. The results of these experiments are given below (table. 8 hydroformylation epoxides. In addition, the concentrations of these compounds provide increased selectivity in target 3-oxopropionate and 1,3-propandiol.

1. Catalytic composition for hydroformylation of ethylene oxide, comprising liquid medium, registergui complex, fosforsoderzhashchie connection, ion component and a cation, characterized in that it contains anionic registergui complex with fosfatnym ligand in molar ratio of ligand to rhodium of 0.1 to 100.0, ion component, not connected by covalent bonds with anionic registertask complex at a molar ratio of the ionic component to the rhodium of 0.1 to 10.0, and a cation other than hydrogen ions at a molar ratio of cation to rhodium of 0.1 to 100.0.

2.The composition according to p. 1, characterized in that it contains fosfatnyi ligand in molar ratio of ligand to rhodium 0,9-20,0.

3. The composition according to p. 1, characterized in that it contains organics-containing cation, including VA element or VI group of the Periodic system.

4. The composition according to p. 1, characterized in that it further comprises a promoting component selected from the group comprising nitrogen-containing compound, compounds containing hydroxyl, carboxyl group, dipozitsia on p. 4, characterized in that it contains the promoting component in such quantity that its molar concentration in the specified composition in the specified conditions of hydroformylation is such that equivalent to a pH in the aqueous fluid with the 22oWith containing only the same molar concentration specified promoting component is in the range of about 1 to 12.

6. The composition according to p. 4, characterized in that it contains the promoting component selected from the group consisting of triethanolamine, 2,6-lutidine, benzimidazole, 2-methylimidazole, diphenol, catechol, isophthalic, pikolinos, acetic acid, p-ethoxybenzoyl acid, dimethylformamide, N-methylpyrrolidone and mixtures thereof.

7. The method for the catalytic compositions for hydroformylation of ethylene oxide, including interaction in a liquid medium source of rhodium, a source of phosphorus-containing ligand and the ion component in the presence of carbon monoxide and hydrogen, characterized in that the interaction is carried out under conditions effective to obtain anionic registeruser complex with fosfatnym ligand in a molar ratio of the source of the ligand to the source of the rhodium of 0.1 to 100.0 and ionic component to the rhodium of 0.1 to 100.0.

9. The method according to p. 7, characterized in that the interaction is carried out in the presence of the promoting component at a molar ratio of the promoting component to the rhodium 0,1-10,0.

10. The method according to p. 9, characterized in that the promoting component selected from the group consisting of nitrogen-containing compounds, compounds containing hydroxyl, carboxyl group, proton acid, and mixtures thereof.

11. The method according to p. 9, characterized in that the promoting component selected from the group consisting of triethanolamine, 2,6-lutidine, benzimidazole, 2-methylimidazole, diphenol, catechol, isophthalic, pikolinos, acetic acid, p-ethoxybenzoyl acid, dimethylformamide, N-methylpyrrolidone and mixtures thereof.

12. The method according to p. 7, characterized in that the ionic component includes organics-containing cation, which contains an element from group VA or VI of the Periodic system.

13. The method of obtaining 1,3-propane diol and 3-hydroxypropionate aldehyde by the interaction of ethylene oxide, carbon monoxide and hydrogen in the presence of a catalytic composition comprising registergui complex, fosforsoderzhashchie connection, at elevated temperature and pressure, characterized in that the molar ratio of ligand to rhodium of 0.1 to 100.0, ion component, not connected by covalent bonds with anionic registertask complex at a molar ratio of the ionic component to the rhodium of 0.1 to 10.0, and a cation other than hydrogen ions at a molar ratio of cation to rhodium of 0.1 to 100.0.

14. The method according to p. 13, characterized in that the cation includes organics-containing cation containing element 43 group VA or VI of the Periodic system.

15. The method of obtaining 1,3-propane diol and 3-hydroxypropionate aldehyde by the interaction of ethylene oxide with carbon monoxide and hydrogen in the presence of a catalytic composition comprising a liquid medium, registergui complex, fosforsoderzhashchie connection, the ionic complex and cation at elevated temperature and pressure, characterized in that the use of a catalytic composition comprising anionic registergui complex with fosfatnym ligand in molar ratio of ligand to rhodium of 0.1 to 100.0, ion component, not connected by covalent bonds with anionic registertask complex at a molar ratio of the ionic component to the rhodium 0,1-10,0 and cations other than hydrogen ions, when the molar ratio of cation to rhodium of 0.1 to 100.0.

 

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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: organic synthesis catalysts.

SUBSTANCE: catalyst consists of complex [Nd(NO3)7][C5H5NH]4 constituted by neodymium nitrate, pyridine, and nitric acid taken in molar ratio 1:4:4, respectively.

EFFECT: achieved accessibility of catalyst.

1 tbl, 2 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst consists of complex [La(NO3)7][C5H10NH2]4 constituted by lanthanum nitrate, piperidine, and nitric acid taken in molar ratio 1:4:4, respectively.

EFFECT: achieved accessibility of catalyst.

1 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing olefins by the oligomerization reaction of olefins in the presence of a catalytic system for the oligomerization reaction of olefins that involves the following stages: a) contacting alkylmetal and pyrrole-containing compound in the presence of unsaturated hydrocarbon in inert atmosphere to form the solution alkylmetal/pyrrole; b) contacting the chrome source with the alkylmetal/pyrrole solution in inert atmosphere to form the catalytic system and the following contacting of catalytic system with alpha-olefin. The claimed method provides the more effective method for preparing the catalytic system and provides the improved thermoregulation of a method for preparing the catalytic system.

EFFECT: improved preparing method.

15 cl, 3 tbl, 4 ex

FIELD: processes catalyzed by metal-phosphoro-organic ligand complexes when target product may be selectively extracted and separated from liquid product.

SUBSTANCE: Specification gives description of methods of separation of one or several products of decomposition of phosphoro-organic ligand, one or several reaction byproducts and one or several products from liquid reaction product synthesized continuously and containing one or several non-consumed reagents, catalyst in form of complex of metal-phosphoro-organic ligands, not obligatory free phosphoro-organic ligand, one or several said decomposition products of phosphoro-organic ligand, one or several said reaction byproducts, one or several said products, one or several non-polar solvents and one or several polar solvents by separation of phases where (i) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several products expressed by ratio of distribution coefficient Ef1 whose magnitudes exceeds about 2.5; (ii)is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several decomposition products expressed by ratio of distribution coefficients Ef2 whose magnitude exceeds proximately 2.5; and (iii) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several reaction byproducts expressed by ratio of distribution coefficients Ef3 whose magnitude exceeds approximately 2.5 (versions). Description is also given of continuous methods of obtaining one or several products (versions) and reaction mixture containing one or several aldehyde products.

EFFECT: increased conversion of initial materials and selectivity by product; avoidance or exclusion of deactivation of catalyst.

20 cl, 2 tbl

FIELD: main organic synthesis.

SUBSTANCE: proposed method is used for production of ketones, for example dimethyl ketone (CH3COCH3), methyl ethyl ketone (CH3COC2H5) by direct catalytic oxidation of respective alkenes, for example propylene, n-butenes, as well as catalysts for realization of this method. Oxidation of alkenes is performed in the presence of metallocomplex catalysts containing organic component where nitrogen oxide (I) is used as oxidant. Used for process is catalyst on base of peroxopolyoxo metallate complexes of terakis (oxo diperoxo metallate)-phosphate (3-) together with quaternary ammonium cationes having formula Q3{PO4[MeO(O2)2]4}, where Me-Mo, W,V; Q3 is quaternary ammonium catione containing alkyl chains C4-C8 or N-hexadecyl pyridinium.

EFFECT: enhanced selectivity of process.

10 cl, 14 ex

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention provides alternative bimetallic catalyst composition comprising a cobalt component and a iron component alloyed with ligand selected from group consisting of T-heterocycle residue, phosphine, and porphyrin. 1,3-Butanediol production process comprises providing reaction mixture containing ethylene oxide, carbon monoxide, hydrogen (H2/CO molar ratio being between 2:1 and 6:1), inert solvent, and above-defined catalyst composition, and heating this reaction mixture to temperature from 30 to 150°C at pressure from 1500 to 2500 psig (1034 to 17420 kPa) to form biphasic mixture of reaction products composed of (i) upper phase including at least wt 50% of solvent, at least 50 wt % of catalyst composition plus unreacted ethylene oxide and (ii) lower phase containing more than 50% of 1,3-butanediol.

EFFECT: achieved single-stage production of 1,3-butanediol with minimum amounts of impurities and by-products, and increased stability of catalyst.

10 cl, 4 dwg, 4 tbl, 20 ex

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention provides alternative bimetallic catalyst composition comprising a cobalt component constituted by a number of non-alloyed cobalt carbonyl compounds and a ruthenium component including ruthenium carbonyl compound alloyed with N-heterocyclic ligand selected from group of bidentate and multidentate N-heterocyclic ligands. 1,3-Butanediol production process comprises providing reaction mixture containing ethylene oxide, carbon monoxide, hydrogen, inert organic solvent, and above-defined catalyst, and heating this reaction mixture to temperature from 30 to 150°C at pressure from 100 to 4000 psig (690 to 27580 kPa) over a period of time long enough to obtain biphasic mixture of products composed of (i) upper phase including major part of solvent, at least wt 50% of catalyst composition plus unreacted ethylene oxide and (ii) lower phase containing major part of 1,3-butanediol.

EFFECT: increased yield of product under mild conditions and increased stability of catalyst.

8 cl, 5 dwg, 19 tbl, 98 ex

FIELD: polymerization catalysts.

SUBSTANCE: supported olefin trimerization and oligomerization catalyst is characterized by molar productivity equal to 50% of that shown by the same but non-supported catalyst. Catalyst comprises: source of transition group 6 metal; ligand depicted by formula (R1)(R2)X-Y-X(R3)(R4) or X(R1)(R2)(R3), wherein X represents phosphorus, arsenic, or antimony atom, Y is linking group, and each of R1, R2, R3, R4, independently of each other, represents optionally substituted hydrocarbon group, optionally substituted heterohydrocarbon group, wherein each of the formulas has polar substituent, which is other than phosphane, arsane, or stibane group; and optionally activator. Polymerization of olefins or olefin blends is an integrated process in one or different reactors, in particular olefin monomer or olefin blend is brought into contact with above-described catalyst under trimerization conditions and then with additional catalyst suitable for olefin polymerization, which results in that trimerization products are incorporated into higher-molecular weight polymer. Process may be accomplished in a reaction circuit. Invention also claims supported α-olefin trimerization and polymerization catalyst comprising above-indicated components and optionally one or several olefin polymerization suitable catalysts.

EFFECT: excluded loss of catalyst activity in supported form.

36 cl, 25 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to improved method for preparing 1,3-dioles comprising (i) bringing into contact oxirane, carbon monoxide, and hydrogen at 30 to 150°C and pressure 3 to 25 MPa in essentially water-immiscible solvent in presence of effective amount of homogenous bimetallic hydroformylation cobalt carbonyl-containing catalyst and cocatalyst based on metal selected from ruthenium group and which is bound to phosphine ligand optionally in presence of promoter, wherein molar ratio of ligand to this cocatalyst metal atom is within a range of 0.2:1.0 to 0.4:1.0, under reaction conditions effective to obtain reaction products mixture containing aliphatic 1,3-diol; (ii) adding aqueous solution to reaction product mixture obtained and extracting major part of aliphatic 1,3-diol into said aqueous solution at temperature below 100°C to form aqueous phase containing aliphatic 1,3-diol in higher concentration that that of aliphatic 1,3-diol in reaction product mixture and organic phase containing at least part of bimetallic hydroformylation catalyst; (iii) separating aqueous phase from processing phase; and (iv) optionally recycling at least part of catalyst-containing organic phase to stage (i). Invention also relates to catalyst composition for hydroformylation of ethylene oxide into aliphatic 1,3-propanediol, which composition is obtained via a method comprising (i) preparation of complex A by bringing cocatalyst ruthenium-group metal compound into contact with phosphine ligand at ligand-to-cocatalyst metal atom from 0.2:1.0 to 0.4:1.0; (ii) preparation of complex B by subjecting complex A to redox reaction with cobalt carbonyl.

EFFECT: enabled less costly single-step hydroformylation process.

8 cl, 2 dwg, 4 tbl, 52 ex

FIELD: chemistry of metalloorganic compounds, chemical industry.

SUBSTANCE: invention relates to preparing compounds of tetrapyrazinoporphyrazine order, namely, to cobalt octasulfooctaphenyltetrapyrazinoporphyrazine of the formula:

that can be used as a catalyst in oxidation reactions of sulfur-containing compounds, in particular, cysteine and thioureas, and diethylamine also being both in acid and neutral media.

EFFECT: valuable properties of compound.

2 cl, 2 dwg, 4 ex

FIELD: chemistry, pharmacology.

SUBSTANCE: present invention relates to method for production of indolo-pyrrolo-carbazole derivative according to formula (I) , or its pharmaceutically acceptable salt, that have antitumour activity. Invention also relates to method for production of indole compound according to formula (XII) , or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, distinguished by conducting interreaction between compound with formula (XIII) , or its pharmaceutically acceptable salt, where R1 is definitely above, Ra and Rb are either separately C1-C7-alkyl, or together form C3-C6-alkylene group, and hydrogen gas at 1 to 5 atmospheres, in presence of hydrogenation catalyst (applied as novel catalyst as well), which consist of rhodium compound, metal compound, and optionally amine, in inert solvent at room temperature; the rhodium compound being 1 to 10% rhodium on carbon, aluminium oxide, calcium carbonate, or barium sulphate, and metal compound being nickel (II), iron (II), iron (III), cobalt (II), or cobalt (III). Method is also submitted for production of bis-indole compound by formula (VIII) , or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, Y is hydrogen, C1-C7-alkyl, phenyl, benzyloxymethyl, or C7-C12-aralkyl, consisting in reaction of indole compound by formula (XII), or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, with ethylmagnesium chloride, or butylmagnesium chloride, or magnesium compound by formula (X) RdMgRd, where Rd is butyl, in inert solvent, followed by conducting interreaction between product obtained and maleimide compound by formula (IX) , where X is halogen, and Y as above, in inert solvent.

EFFECT: improved method for indolo-pyrrolo-carbazole production.

15 cl, 68 ex, 12 tbl

FIELD: chemistry.

SUBSTANCE: method involves catalytic telomerisation of butadiene with diethylamine in the presence of a catalyst based on cationic complexes of palladium (II) of general formula [(acac)Pd(L)2]BF4 (where acac is an acetylacetonate ligand, L=PPh3, P'Pr3, P"Bu3 P(p-Tol)3 or (L)2=diphosphine ligands, selected from bis(diphenylphosphino)methane(dppm), bis(diphenylphosphino)propane(dppp), bis(diphenylphosphino)butane(dppb), bis(diphenylphosphino)ferrocene(dppf)). The process is carried out in a substrate medium, specifically diethylamine and butadiene, at temperature of 50-90C. The method enables to obtain N,N-diethylocta-2,7-diene-1-amine with selectivity of 99.9% from the overall mixture of reaction products with high process output which reaches 4180 g of product per 1 g Pd. The catalysts used are more readily available compared to those previously used for the process.

EFFECT: improved method.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the field of organic chemistry, in particular to a method of obtaining alkylethers of 1- and 2-naphthalenecarboxylic acids, which are used in the synthesis of herbicides, plant growth hormones, dyes, photomaterials and polymers. The method of obtaining compounds of formula (1a-b) or (2a-b) in which R=CH3, C2H5, n-C3H7,consists in the fact that naphthalene is subjected to interaction with CCl4 and alcohol (methanol, ethanol, n-propanol) in the presence of metallic iron, activated HCl, and acetylacetone with the molar ratio of [Fe0(met.)]:[acetylacetone]:[naphthalene]:[CCl4]:[alcohol]=5-50:5:100:100-1000:100-1000, at a temperature of 130C for 4-12 h in the argon atmosphere.

EFFECT: total output of alkyl ethers of 1- and 2-naphthalenecarboxylic acids reaches 75%.

1 tbl, 21 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 20-100C, in benzene for 8-48 hours.

EFFECT: method enables to obtain the end product separately.

7 ex, 1 tbl

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