| PATENT ASSIGNEE'S COUNTRY | USA |
| UPDATE | 09.00 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 19.09.00 |
| PATENT TITLE |
Supported bis(phosphorus) ligands |
| PATENT ABSTRACT |
Supported bis(phosphorus) ligands are disclosed for use in a variety of catalytic processes, including the hydrocyanation of unsaturated organic compounds. Catalysts are formed when the ligands are combined with a catalytically active metal (e.g., nickel). |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 08.07.98 |
| PATENT REFERENCES CITED |
Tolman et al., Advances in Catalysis, 33, 1, 1985. Baker, M.J. et al., J. Chem. Soc., 1292, 1991. Baker et al., J. Chem. Soc., 803, 1991. Cuny et al., J. Am. Chem. Soc., 115, 2066, 1993. Leeuwen et al., Macromol. Symp., 80 (1994) 241-256. Moroz et al., J. Molecular Catalysis A: Chemical, 112 (1996) 217-233. Behringer et al., Chem. Commun. (1996) 653-54. C.C. Leznoff et al., Canadian Journal of Chemistry, 51, 3756-3764, 1973. B. Altava et al., J. Org. Chem., 62, 3126-3134, 1997. C. U. Pittman Jr. Polymer Supported Catalysts in: Comprehensive Organometallic Chemistry, Pergamon Press, (1982) pp. 553-611 |
| PATENT PARENT CASE TEXT | This data is not available for free |
| PATENT CLAIMS |
What is claimed is: 1. A supported diol selected from the group consisting of the following structures: ##STR115## wherein x is 2, 3, or 4; and sup is a support. 2. The supported diol according to claim 1 wherein the support is an organic polymer resin. 3. The supported diol according to claim 2 wherein the organic polymer resin is a crosslinked polystyrene resin. 4. A supported bis(phosphorus) ligand according to formula (2): ##STR116## wherein: Q is any organic fragment which binds a OPX.sub.2 moiety to the support (Sup); and X is an alkoxide, aryloxide, alkyl, or aryl. 5. The ligand according to claim 4 wherein the support is an organic polymer resin. 6. The ligand according to claim 4 wherein X is aryloxide or aryl. 7. A supported catalyst composition according to formula (3): ##STR117## wherein: Q is any organic fragment which binds a OPX.sub.2 moiety to the support (Sup).; X is an alkoxide, aryloxide, alkyl or aryl; and M is a transition metal capable of carrying out catalytic transformations. 8. The supported catalyst composition of claim 7 wherein the support is an organic polymer resin. 9. The catalyst composition of claim 7 wherein X is aryloxide or aryl. 10. The catalyst composition of claim 7 wherein M is selected from the group consisting of Ni, Rh, Co, Ir, Pd, Pt, and Ru. 11. A catalytic hydrogenation or hydrosilation process utilizing the catalyst composition of claim 7. 12. A hydrocyanation process comprising reacting an acyclic, aliphatic, monoethylenically unsaturated compound in which the ethylenic double bond is not conjugated to any other olefinic group in the molecule, or a monoethylenically unsaturated compound in which the ethylenic double bond is conjugated to an organic ester group, with a source of hydrogen cyanide (HCN) in the presence of a supported catalyst composition according to formula (3): ##STR118## wherein: Q is any organic fragment which binds a OPX.sub.2 group to the support (Sup).; X is an alkoxide, aryloxide, alkyl or aryl; and M is nickel, wherein the process is run in a gas or a liquid phase. 13. The process of claim 12 wherein the support is an organic polymer resin. 14. The process of claim 12 wherein X is aryloxide or aryl. 15. The process of claim 12 wherein the reaction is run in the liquid phase. 16. A hydrocyanation process comprising reacting an acyclic aliphatic diolefinic compound with a source of hydrogen cyanide (HCN) in the presence of a supported catalyst composition according to formula (3): ##STR119## wherein: Q is any organic fragment which binds a OPX.sub.2 group to the support (Sup).; X is an alkoxide, aryloxide, alkyl or aryl; and M is nickel, wherein the process is run in a gas phase or a liquid phase. 17. The process of claim 16 wherein the support is an organic polymer resin. 18. The process of claim 16 wherein X is aryloxide or aryl. 19. The process of claim 16 wherein the reaction is run in the liquid phase. 20. The process of claim 16 wherein the reaction is run in the gas phase. 21. The process of claim 16 wherein the diolefinic compound is 1,3-butadiene. 22. The ligand according to claim 4 wherein the PX.sub.2 group forms a ring and X.sub.2 is a di(alkoxide), di(aryloxide), di(alkyl) or di(aryl). 23. The catalyst composition according to claim 7 wherein the PX.sub.2 group forms a ring and X.sub.2 is a di(alkoxide), di(aryloxide), di(alkyl) or di(aryl). 24. The process of claim 12 wherein the reaction is run in the gas phase. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
FIELD OF THE INVENTION The invention generally relates to supported bis(phosphorus) ligands useful for a variety of catalytic processes. In particular, the ligands are useful in the hydrocyanation of unsaturated organic compounds. BACKGROUND OF THE INVENTION Phosphorus ligands are ubiquitous in catalysis, finding use for a number of commercially important chemical transformations. Phosphorus ligands commonly encountered in catalysis include phosphines (A), and phosphites (B), shown below. In these representations R can be virtually any organic group. Monophosphine and monophosphite ligands are compounds which contain a single phosphorus atom which serves as a donor to a metal. Bisphosphine, bisphosphite, and bis(phosphorus) ligands in general, contain two phosphorus donor atoms and normally form cyclic chelate structures with transition metals. ##STR1## Two industrially important catalytic reactions using phosphorus ligands of particular importance are olefin hydrocyanation and olefin hydroformylation. Phosphite ligands are particularly good ligands for both of these transformations. For example, the hydrocyanation of ethylenically unsaturated compounds using transition metal complexes with monodentate phosphite ligands is well documented in the prior art. See, for example, U.S. Pat. Nos. 3,496,215, 3,631,191, 3,655,723 and 3,766,237, and Tolman et al., Advances in Catalysis, 33, 1, 1985. Bidentate bisphosphite ligands have been shown to be useful in the hydrocyanation of monoolefinic and diolefinic compounds, as well as for the isomerization of non-conjugated 2-alkyl-3-monoalkenenitriles to 3- and/or 4-monoalkene linear nitriles. See, for example, U.S. Pat. Nos. 5,512,695, 5,512,696 and WO 9514659. Bidentate phosphite ligands have also been shown to be particularly useful ligands in the hydrocyanation of activated ethylenically unsaturated compounds. See, for example, Baker, M. J., and Pringle, P. G., J. Chem. Soc., Chem. Commun., 1292, 1991; Baker et al., J. Chem. Soc., Chem. Commun., 803, 1991; WO 93,03839. Bidentate phosphite ligands are also useful for alkene hydroformylation reactions. For example, U.S. Pat. No. 5,235,113 describes a hydroformylation process in which an organic bidentate ligand containing two phosphorus atoms linked with an organic dihydroxyl bridging group is used in a homogeneous hydroformylation catalyst system also comprising rhodium. This patent describes a process for preparing aldehydes by hydroformylation of alkenically unsaturated organic compounds, for example 1-octene or dimerized butadiene, using the above catalyst system. Also, phosphite ligands have been disclosed with rhodium in the hydroformylation of functionalized ethylenically unsaturated compounds: Cuny et al., J. Am. Chem. Soc., 1993, 115, 2066. These prior art examples demonstrate the utility of bisphosphite ligands in catalysis. While these prior art systems represent commercially viable catalysts, they do suffer from significant drawbacks. Primarily, the catalyst, consisting of the ligand and the metal, must be separated from the reaction products. Typically this is done by removing the product and catalyst mixture from the reaction zone and performing a separation. Typical separation procedures involve extraction with an immiscible solvent, distillation, and phase separations. In all of these examples some of the catalyst, consisting of the ligand and/or the metal, is lost. For instance, distillation of a volatile product from a non-volatile catalyst results in thermal degradation of the catalyst. Similarly, extraction or phase separation results in some loss of catalyst into the product phase. These ligands and metals are often very expensive and thus it is important to keep such losses to a minimum for a commercially viable process. One method to solve the problem of catalyst and product separation is to attach the catalyst to an insoluble support. Examples of this approach have been previously described, and general references on this subject can be found in "Supported Metal Complexes", D. Reidel Publishing, 1985, Acta Polymer. 1996, 47, 1, and Comprehensive Organometallic Chemistry, Pergamon Press, 1982, Chapter 55. Specifically, monophosphine and monophosphite ligands attached to solid supports are described in these references and also in Macromol. Symp. 1994, 80, 241. Bisphosphine ligands have also been attached to solid supports and used for catalysis, as described in for example U.S. Pat. No. 5,432,289, J. Mol. Catal. A 1996, 112, 217, and J. Chem. Soc., Chem. Commun. 1996, 653. The solid support in these prior art examples can be organic, e.g., a polymer resin, or inorganic in nature. These prior art systems have to date suffered from several drawbacks and have not reached commercial potential. Among the drawbacks noted in the literature are metal leaching and poor reaction rates. In addition, the prior art systems are often not readily amenable to precise control of the ligand coordination properties, e.g., electronics and steric size. What is needed is a supported bis(phosphorus) ligand system which overcomes the problems and deficiencies inherent in the prior art. Other objects and advantages of the present invention will become apparent to those skilled in the art upon reference to the detailed description which hereinafter follows. SUMMARY OF THE INVENTION The present invention provides for novel supported diols and chelating bis(phosphorus) ligands covalently bonded to a support. Preferably, the support is an insoluble polymer such as a crosslinked polystyrene resin or other organic polymer resin. The supported bis(phosphorus) ligand has the structure (2): ##STR2## wherein: Q is any organic fragment which binds a OPX.sub.2 moiety to the support (Sup); and X is an alkoxide, aryloxide, alkyl, or aryl. Preferably, X is aryloxide or aryl. The invention also provides for a supported catalyst composition having the structure (3): ##STR3## wherein: Q is any organic fragment which binds a OPX.sub.2 moiety to the support (Sup).; X is an alkoxide, aryloxide, alkyl or aryl; and M is a transition metal capable of carrying out catalytic transformations. X is preferably aryloxide or aryl and M is preferably Ni, Rh, Co, Ir, Pd, Pt or Ru. The invention also provides for a catalytic process utilizing the above-described supported catalyst compositions. Such processes include, inter alia, hydrocyanation, isomerization, hydrogenation and hydrosilation. In particular, the invention provides for a hydrocyanation process comprising reacting an acyclic, aliphatic, monoethylenically unsaturated compound in which the ethylenic double bond is not conjugated to any other olefinic group in the molecule, or a monoethylenically unsaturated compound in which the ethylenic double bond is conjugated to an organic ester group, with a source of HCN in the presence of a supported catalyst composition according to formula (3): ##STR4## wherein: Q is any organic fragment which binds a OPX.sub.2 moiety to the support (Sup).; X is an alkoxide, aryloxide, alkyl or aryl; and M is nickel. The invention further provides for the hydrocyanation of diolefinic compounds comprising reacting an acyclic aliphatic diolefinic compound with a source of HCN in the presence of a supported catalyst composition according to formula (3): ##STR5## wherein: Q is any organic fragment which binds a OPX.sub.2 moiety to the support (Sup).; X is an alkoxide, aryloxide, alkyl or aryl; and M is nickel. This process may be run in either the liquid or vapor phase. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A primary aim of this invention is to provide catalysts for a number of industrially important reactions characterized by the fact that these catalysts are covalently attached to an insoluble support. These catalysts are additionally characterized by the fact that they consist of a chelating ligand covalently attached to an insoluble support. The chelate ligand coordinates catalytically active transition metals. The advantages of this process are: These catalysts are insoluble and non-volatile, allowing ready separation from the reaction medium by filtration or other means, or use in fixed bed, flow-through reactors using either liquid or gas phase carrier streams. The chelating arrangement of donor atoms gives catalysts with commercially practical activity and selectivity. In particular, the chelates described herein are based on bisphosphite ligands, in which it is known that soluble derivatives give catalysts with significantly improved reaction rates and selectivities over monophosphite ligands. The chelating arrangement of donor atoms results in a much stronger ligand-metal interaction and thus greatly minimizes the potential for metal leaching. It is possible to methodically alter the spacing between the chelating atoms, the steric environment of these atoms, and the electronic properties of the donor atoms, thereby offering precise control of ligand coordination properties; this in turn allows significant opportunity to optimize catalyst performance. The chemical environment in the immediate vicinity of the catalytically active site is uniform throughout the solid support matrix. The catalyst therefore acts as a "single site" type of catalyst, as opposed to an ensemble of different catalysts. The supported bis(phosphorus) ligands described herein may be used as a component of a catalyst system for a number of catalytic processes, e.g., hydrocyanation, hydrogenation, hydroformylation, polymerization, isomerization, hydrosilation, carbonylation, cross-coupling, and metathesis. The supported bis(phosphorus) ligands described herein generally form the catalyst when combined with a catalytically active metal. The resulting supported catalyst forms a separate phase from the reaction medium, reacting substrates, and products. The reaction medium may be composed of a liquid solvent which does not interfere with the catalytic reaction of interest, or may be gaseous, e.g., an inert carrier gas and gaseous reactants and products. It has been found that the supported bis(phosphorus) ligands of the present invention are particularly suitable for use in the hydrocyanation of unsaturated organic compounds in combination with a transition metal compound, the metal of which is for example nickel, platinum, palladium, or cobalt. Of the transition metals useful for hydrocyanation, nickel is especially preferred. The polymer-supported bis(phosphorus) ligands of the present invention are also suitable for use in the hydrogenation and hydrosilation of double bonds in combination with a transition metal. Rhodium is especially preferred for phosphine-promoted hydrogenation and hydrosilation. DESCRIPTION OF THE SUPPORT Virtually any solid material may be used as a support in the context of this invention as long as it meets the following criteria: The material is insoluble in organic, aqeuous, or inorganic solvents. Organic polymer supports are acceptable in this regard but they generally need to be crosslinked. Inorganic supports, such as metal oxides (silicas, etc.) are generally insoluble in these solvents and also may be used as supports. The support contains reactive sites which can be used for the covalent attachment of organic fragments containing a diol group (as described below) or a protected diol group. The reactive sites are isolated to prevent additional crosslinking during further chemical transformations. The reactive sites are exposed to the reaction medium. With a polymer resin support this is achieved through the use of resins which swell in a reaction solvent or is sufficiently porous to allow transport of the reaction medium through the polymer matrix. The term "solid support" or "support" (sup) refers to a material having a rigid or semi-rigid surface which contain or can be derivatized to contain functionality which covalently links a compound to the surface thereof. Such materials are well known in the art and include, by way of example, polystyrene supports, polyacrylamide supports, polyethyleneglycol supports, and the like. Such supports will preferably take the form of small beads, pellets, disks, or other conventional forms, although other forms may be used. The supports described in this application are functionalized poly(styrene) resins. Other suitable polymers include polyolefins, polyacrylates, polymethacrylates, and copolymers thereof that meet the general criteria described above. Specifically, poly(styrene) resins commonly used for solid phase synthesis have been used. These particular resins are crosslinked with from 1 to 10 wt % divinylbenzene. The styrene moieties are substituted in the para or meta positions. Only a portion of the styrene moieties are substituted, typically resulting in functional group loadings of approximately 0.2 to 2.0 mmole per gram of resin, although this value may be higher or lower. DESCRIPTION AND PREPARATION OF SUPPORTED DIOLS The aims of this invention are achieved by construction of a chelating ligand covalently bonded to an insoluble support (Sup), preferably a polymer support (Pol). The first step of this procedure involves the preparation of a diol group covalently attached to an insoluble support as exemplified by the following structure: ##STR6## wherein, Sup represents the insoluble support. As used herein, Q means any organic fragment which binds the diol moiety to the support. For example, Q may consist of from 2 to 50 carbon atoms, in addition to heteroatoms such as nitrogen, oxygen, and the like. Q may additionally contain functional groups such as ether, acetal, ketal, ester, amide, amine, imine, etc., and combinations thereof. Q may also contain saturated or unsaturated carbon-carbon bonds. Q may or may not be symmetrical. The number of atoms present in Q and used to separate the two OH moieties of the diol is generally limited to between 2 and 10, although any number and arrangement which ultimately allows the formation of a chelating ring is acceptable. A preferred number is 2 to 5 atoms. These atoms may be carbon or heteratoms such as oxygen and nitrogen. The atoms may further comprise a chain or cyclic structure, the latter of which may be saturated or unsaturated, e. g., aromatic. The preparation of materials of Formula 1 follows methods known to those skilled in the art. The procedure may involve one reaction step or multiple reaction steps. Preferred methods are those which proceed in high yield, high selectivity, are inexpensive, and are simple to conduct. For example, Can. J. Chem. 1973, 51, 3756, describes the synthesis of the material of formula SD6. The synthesis occurs in two reaction steps from inexpensive materials and in high yield. Other materials described in this invention have not been previously reported in the literature but follow reaction steps known for soluble, non-polymer supported analogues. For instance, reaction of the polymer-supported benzaldehyde pol-CHO, prepared by the method described in J. Polym. Sci.1975, 13, 1951 and J. Polym. Sci., Polym. Lett. 1965, 3, 505, with pentaerythritol gives polymer-supported diol SD1. The analogous reaction of soluble, non-polymer supported benzaldehyde with pentaerythritol is described in Org. Syn. Vol 38, 65. Alternatively, reaction of polymer-supported aldehyde pol-CHO with diethyl tartrate, followed by reduction, leads to the class of polymer-supported diols SD2, 3, 4. SD3 is described in J. Org. Chem., 1997, 62, 3126. The analogous reactions of the soluble, non-polymer supported compounds are described in Helv. Chim. Acta 1983, 66, 2308 and J. Org. Chem. 1993, 58, 6182. Supported alkylene-bridged bisaryl alcohols can be prepared by methods found in J. Chem. Soc., Perkin I, 1980, 1978-1985; Indian J. Chem. 1995, 34B, 6-11, and Chem. Ber. 1985,118, 3588-3619. Other examples may be prepared by known organic transformations, and representative structures are shown below. ##STR7## DESCRIPTION AND PREPARATION OF POLYMER-SUPPORTED BIS(PHOSPHORUS) LIGANDS The polymer-supported bis(phosphorus) ligands may be prepared by a variety of methods known in the art, for example, see descriptions in WO 93,03839; U.S. Pat. Nos. 4,769,498 and 4,668,651. In general, the transformation involves the reaction of a phosphorus halide, typically but not limited to chloride, with the diol to form P-O bonds. The phosphorus halide may be any compound of the type PY.sub.n X.sub.3-n, where Y=halide, X=alkoxide, aryloxide, alkyl, aryl, and n=3, 2, or 1. The phosphorus halides most useful for the present invention are those where Y.dbd.Cl; X=alkoxide, aryloxide, alkyl, or aryl; and n=1. The group X may contain from 1 to 50 carbon atoms. It may also optionally contain heteroatoms such as oxygen, nitrogen, halogen, and the like, and also functional groups such as ethers, alcohols, esters, amides, as well as others. The groups X may or may not be linked to form a cyclic structure. The PX.sub.2 moiety may form a ring and X.sub.2 may be a di(alkoxide), di(aryloxide), di(alkyl) or di(aryl). Many dialkylchlorophosphines and diarylchlorophosphines are commercially available, or may be prepared by methods known in the art, for example, J. Am. Chem. Soc. 1994, 116, 9869. Phosphorochloridites, may be prepared by a variety of methods known in the art, for example, see descriptions in Polymer 1992, 33, 161; Inorg. Syn. 1966, 8, 68; U.S. Pat. No. 5,210,260; Z. Anorg. Allg. Chem. 1986, 535, 221. For example, the reaction of 2,2'-biphenol with phosphorus trichloride gives 1,1'-2,2'-diylphosphorochloridite. The reaction of these chlorophosphorus reagents with a material of Formula 1 in the presence of a base gives a polymer-supported bis(phosphorus) ligand exemplified by the structure shown: ##STR8## where X and Q are as defined above. Other examples may be prepared by similar transformations, and representative structures are also shown below. ##STR9## DESCRIPTION AND PREPARATION OF POLYMER-SUPPORTED TRANSITION METAL CATALYSTS The transition metal catalysts which are a subject of this invention are defined by the formula shown below: ##STR10## wherein Q and X are as defined above. M is a transition metal capable of carrying out catalytic transformations. M may additionally contain labile ligands which are either displaced during the catalytic reaction, or take an active part in the catalytic transformation. Any of the transition metals may be considered in this regard. The preferred metals are those comprising groups 8, 9, and 10 of the Periodic Table. The catalytic transformations possible with these catalysts comprise, but are not limited to, hydrocyanation, hydroformylation, hydrogenation, hydrosilation, cross-coupling, isomerization, carbonylation, and metathesis. The most preferred metal for hydrocyanation is nickel, and the preferred metals for hydrosilation, hydrogenation, and hydroformylation are rhodium, cobalt, iridium, palladium and platinum, the most preferred being rhodium. The zero-valent nickel compounds, suitable for hydrocyanation, can be prepared or generated according to techniques well known in the art, as described, for example, U.S. Pat. Nos. 3,496,217; 3,631,191; 3,846,461; 3,847,959; and 3,903,120. Zero-valent nickel compounds that contain ligands which can be displaced by the organophosporus ligands are a preferred source of zero-valent nickel. Two such preferred zero-valent nickel compounds are Ni(COD).sub.2 (COD is 1,5-cyclooctadiene) and Ni{P(O-o-C.sub.6 H.sub.4 CH.sub.3).sub.3 }.sub.2 (C.sub.2 H.sub.4), both of which are known in the art. Alternatively, divalent nickel compounds may be combined with a reducing agent, to serve as a source of zero-valent nickel in the reaction. Suitable divalent nickel compounds include compounds of the formula NiY.sub.2 where Y is halide, carboxylate, or acetylacetonate. Suitable reducing agents include metal borohydrides, metal aluminum hydrides, metal alkyls, Li, Na, K, or H.sub.2. Rhodium catalysts suitable for hydrogenation and hydrosilation can be prepared by techniques well known in the art as described, for example, in J. Amer. Chem. Soc. 1976, 98, 2134, J. Org. Chem. 1977, 42, 1671, and J. Amer. Chem. Soc. 1973, 95, 8295. For example, monovalent rhodium compounds that contain ligands which can be displaced by the supported organophosphorus ligands are a preferred source of monovalent rhodium. Examples of such preferred monovalent rhodium compounds are Rh(COD).sub.2 X (where COD is as defined above and X is negatively charged counterion such as halide, BF.sub.4 -, PF.sub.6 -, OTf (OTF=O.sub.3 SCF.sub.3), ClO.sub.4 -, and the like), Rh(PPh.sub.3).sub.3 Cl, and Rh(CO).sub.2 (acac) (acac=acetylacetonate). DESCRIPTION OF CATALYTIC PROCESSES--HYDROCYANATION OF DIOLEFINIC COMPOUNDS The diolefinic compound reactants used in this study include primarily conjugated diolefins containing from 4 to 10 carbon atoms; for example, 1,3-butadiene and cis and trans-2,4-hexadienes. Butadiene is especially preferred by reason of its commercial importance in the production of adiponitrile. Other suitable diolefinic compounds include diolefinic compounds substituted with groups which do not deactivate the catalyst, for example, cis and trans-1,3-pentadienes. The following Formulas.dagger.I and II illustrate suitable representative starting diolefinic compounds; and Formulas III, IV, and V represent the products obtained from 1,3-butadiene and HCN. ##STR11## wherein each one of R.sup.1 and R.sup.2, independently, is H or a C.sub.1 to C.sub.3 alkyl. ##STR12## It will be recognized that Compound I is a special case of Formula II, where each one of R.sup.1 and R.sup.2 is hydrogen. The hydrocyanation reaction can be carried out with or without a solvent. The solvent should be a liquid at room temperature and inert towards the unsaturated compound and the catalyst. Generally, such solvent are hydrocarbons such as benzene, xylene, or nitriles such as acetonitrile, benzonitrile or adiponitrile. The reaction may also be carried out with the reactants and products present in the gas phase. The exact temperature used is dependent, to a certain extent, on the particular catalyst being used, the particular unsaturated compound being used, the volatility of the reactants and products, and the desired rate. Generally, temperatures of from -25.degree. C. to 200.degree. C., can be used with from 0.degree. C. to 175.degree. C. being the preferred range. The mole ratio of unsaturated compound to catalyst generally is varied from about 10:1 to 100,000 to:1, preferably 100:1 to 5,000:1, unsaturated compound to catalyst for a batch operation. In a continuous operation such as when using a fixed bed catalyst type of operation, a higher proportion of catalyst may be used such as 5:1 to 100,000:1, preferably 100:1 to 5,000:1, unsaturated compound to catalyst. Preferably, when a liquid reaction medium is used, the reaction mixture is agitated, such as by stirring or shaking. The cyanated product can be recovered by conventional techniques such as crystallization of the product from the solution or by distillation. One can either isolate the 2-alkyl-3-monoalkenenitriles produced by the hydrocyanation of the diolefin or proceed continuously with the isomerization under similar reaction conditions. The hydrocyanation process may also be conducted in the vapor phase wherein an acyclic aliphatic diolefinic compound, preferably butadiene, is reacted with HCN in the vapor phase. This process is similar to that described in U.S. Pat. Nos. 5,449,807 and 5,440,067 (both to Druliner) and U.S. Provisional Application No. 60/014,618, filed Apr. 2, 1996, with the exception that the catalyst employed is the same as that described in this invention. The temperature of such a gas phase process can vary from about 135.degree. C. to about 170.degree. C. The supported nickel catalysts of formula 3 (M=Ni(0)) are loaded into tubular reactors, and a gaseous diolefinic compound, e.g., butadiene, and HCN is passed continuously over the solid catalysts at temperatures sufficiently high to maintain the starting materials as well as the reaction products in the vapor phase. The temperature range is generally from about 135.degree. C. to about 300.degree. C. and preferably from about 145.degree. C. to 200.degree. C. The temperature must be high enough to maintain all of the reactants and products in the vapor phase but low enough to prevent deterioration of the catalyst. The particular preferred temperature depends to some extent on the catalyst being used, the diolefinic compound being used, and the desired reaction rate. The operating pressure is not particularly critical and can conveniently be from about 1-10 atmospheres (101.3 to 1013 kPa). No practical benefit is obtained when operating above the upper limit of this pressure range. HCN and/or the diolefinic starting materials can be delivered as a neat vapor or as a preheated solution in a solvent, such as acetonitrile or toluene. Under atmospheric pressure, using nitrogen or other inert gas as carrier, temperatures of from about 140-160.degree. C. are typically used. Nitrogen is preferred because of its low cost. Gaseous oxygen, water vapor, or other gaseous substance which could react with HCN, the catalyst, or the starting diolefinic compound should be avoided. The reaction products are liquid at room temperature and are conveniently recovered by cooling. Branched 2-methyl-3-butenenitrile can be separated from linear 3- and 4-pentenenitrile by distillation. DESCRIPTION OF CATALYTIC PROCESSES--HYDROCYANATION OF MONOOLEFINIC COMPOUNDS The present invention also provides a process for hydrocyanation, comprising reacting a nonconjugated, acyclic, aliphatic, monoethylenically unsaturated compound or 2-pentenenitrile or an alkyl-2-pentenoate with a source of HCN in the presence of a Lewis acid promoter catalyst composition formed by the supported nickel catalysts described previously and depicted by Formula 3. Representative ethylenically unsaturated compounds which are useful in the process of this invention are shown in Formula VI or VIII, and the corresponding terminal nitrile compounds produced are illustrated by Formula VII or IX, respectively, wherein like reference characters have same meaning. ##STR13## wherein R.sup.4 is H, CN, CO.sub.2 R.sup.5, or perfluoroalkyl; y is an integer of 0 to 12; x is an integer of 0 to 12 when R.sup.4 is H, CO.sub.2 R.sup.5 or perfluoroalkyl; x is an integer of 1 to 12 when R.sup.4 is CN; and R.sup.5 is alkyl. The nonconjugated acyclic, aliphatic, monoolefinically unsaturated starting materials useful in this invention include unsaturated organic compounds containing from 2 to approximately 30 carbon atoms. The 3-pentenenitrile and 4-pentenenitrile are especially preferred. As a practical matter, when the nonconjugated acyclic aliphatic monoethylenically unsaturated compounds are used in accordance with this invention, up to about 10% by weight of the monoethylenically unsaturated compound may be present in the form of a conjugated isomer, which itself may undergo hydrocyanation. For example, when 3-pentenenitrile is used, as much as 10% by weight thereof may be 2-pentenenitrile. As used herein, the term "pentenenitrile" is intended to be identical with "cyanobutene". Suitable unsaturated compounds include unsubstituted hydrocarbons as well as hydrocarbons substituted with groups which do not attack the catalyst, such as cyano. These unsaturated compounds include monoethylenically unsaturated compounds containing from 2 to 30 carbons such as ethylene, propylene, butene-1, pentene-2, hexene-2, etc.; nonconjugated diethylenically unsaturated compounds such as allene; and substituted compounds such as 3-pentenenitrile, 4-pentenenitrile, methyl pent-3-enoate; and ethylenically unsaturated compounds having perfluoroalkyl substituents such as, for example, C.sub.z F.sub.2z+1, where z is an integer of up to 20. The monoethylenically unsaturated compounds may also be conjugated to an ester group such as methyl pent-2-enoate. The starting olefinically unsaturated compounds useful in this invention and the hydrocyanation products thereof are those shown above in Formulas VI through VIII. Those of Formula VI yield terminal nitrites of Formula VII, while those of Formula VIII yield terminal nitrites of Formula IX. Preferred are nonconjugated linear alkenes, nonconjugated linear alkenenitriles, nonconjugated linear alkenoates, linear alk-2-enoates and perfluoroalkyl ethylenes. Most preferred substrates include 3- and 4-pentenenitrile, alkyl 2-, 3-, and 4-pentenoates, and C.sub.z F.sub.2z+1 CH.dbd.CH.sub.2 (where z is 1 to 12). The preferred products are terminal alkanenitriles, linear dicyanoalkylenes, linear aliphatic cyanoesters, and 3-(perfluoroalkyl)propionitrile. Most preferred products are adiponitrile, alkyl 5-cyanovalerate, and C.sub.z F.sub.2z+1 CH.sub.2 CH.sub.2 CN, where z is 1 to 12. The hydrocyanation of monoolefinic compounds may be carried out by charging a reactor with all of the reactants, or preferably on a commercial scale, the reactor is charged with the catalyst components, the unsaturated organic compound, the promoter, and the solvent to be used, and the hydrogen cyanide is added slowly. HCN may be delivered as a liquid or as a vapor to the reaction. Another technique is to charge the reactor with the catalyst, promoter, and the solvent to be used, and to feed both the unsaturated organic compound and the HCN slowly to the reaction mixture. The molar ratio of unsaturated monoolefinic compound to catalyst is generally varied from about 10:1 to 2000:1. The molar ratio of phosphorus compound to nickel is in the range 0.5:1 to 20:1. Preferably, the reaction medium is agitated, such as by stirring or shaking. The cyanated product can be recovered by conventional techniques, such as by distillation. The reaction may be run batchwise or in a continuous manner. The hydrocyanation reaction can be carried out with or without a solvent. The solvent, if used, should be liquid at the reaction temperature and pressure and inert towards the unsaturated compound and to the catalyst. Suitable such solvents include hydrocarbons such as benzene or xylene and nitrites such as acetonitrile or benzonitrile. In some cases, the unsaturated compound to be hydrocyanated may itself serve as the solvent. The exact temperature is dependent to a certain extent on the particular catalyst being used, the particular unsaturated compound being used and the desired rate. Normally, temperatures of from -25.degree. C. to 200.degree. C. can be used, the range of 0.degree. C. to 150.degree. C. being preferred. Atmospheric pressure is satisfactory for carrying out the present invention and hence pressure of from about 0.05 to 10 atmospheres (50.6 to 1013 kPa) are preferred. Higher pressures, up to 10,000 kPa or more, can be used, if desired, but any benefit that may be obtained thereby would not justify the increased cost of such operations. HCN can be introduced to the reaction as a vapor or liquid. As an alternative, a cyanohydrin can be used as the source of HCN. See, for example, U.S. Pat. No. 3,655,723. The process of this invention is carried out in the presence of one or more Lewis acid promoters which affect both the activity and the selectivity of the catalyst system. The promoter may be an inorganic or organometallic compound in which the cation is selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium and tin. Examples include ZnBr.sub.2, ZnI.sub.2, ZnCl.sub.2, ZnSO.sub.4, CuCl.sub.2, CuCl, Cu(O.sub.3 SCF.sub.3).sub.2, CoCl.sub.2, CoI.sub.2, FeI.sub.2, FeCl.sub.2, FeCl.sub.3, FeCl.sub.2 (THF).sub.2, TiCl.sub.4 (THF).sub.2, TiCl.sub.4, TiCl.sub.3, ClTi(OiPr).sub.3, MnCl.sub.2, ScCl.sub.3, AlCl.sub.3, (C.sub.8 H.sub.17)AlCl.sub.2, (C.sub.8 H.sub.17) AlCl.sub.2, (iso-C.sub.4 H.sub.9).sub.2 AlCl, Ph.sub.2 AlCl, Ph.sub.2 AlCl, ReCl.sub.5, ZrCl.sub.4, NbCl.sub.5, VCl.sub.3, CrCl.sub.2, MoCl.sub.5, YCl.sub.3, CdCl.sub.2, LaCl.sub.3, Er(O.sub.3 SCF.sub.3).sub.3, Yb(O.sub.2 CCF.sub.3).sub.3, SmCl.sub.3, BPh.sub.3, TaCl.sub.5. Suitable promoters are further described in U.S. Pat. Nos. 3,496,217; 3,496,218,; 4,774,353. These include metal salts (such as ZnCl.sub.2, CoI.sub.2, and SnCl.sub.2), and organometallic compounds (such as RAlCl.sub.2, R.sub.3 SnO.sub.3 SCF.sub.3, and R.sub.3 B, where R is an alkyl or aryl group). U.S. Pat. No. 4,874,884 describes how synergistic combinations of promoters can be chosen to increase the catalytic activity of the catalyst system. Preferred promoters are CdCl.sub.2, ZnCl.sub.2, B(C.sub.6 H.sub.5).sub.3, and (C.sub.6 H.sub.5).sub.3 SnX, where X.dbd.CF.sub.3 SO.sub.3, CH.sub.3 C.sub.6 H.sub.5 SO.sub.3, or (C.sub.6 H.sub.5).sub.3 BCN. The mole ratio of promoter to nickel present in the reaction can be within the range of 1:16 to 50: 1. DESCRIPTION OF CATALYTIC PROCESSES--HYDROGENATION Olefinic compounds of the type shown below are converted to the corresponding saturated alkane by the catalysts of the title invention. ##STR14## R.sup.5, R.sup.6, R.sup.7, and R.sup.8 represent hydrogen or hydrocarbyl groups of up to 20 carbon atoms. R.sup.5, R.sup.6, R.sup.7, and R.sup.8 may be aromatic or saturated, and may be the same or different. The hydrogenation process may be carried out at a temperature of from about room temperature, e.g., 20.degree. C., to about 150.degree. C. A preferable range is from about 30.degree. C. to about 100.degree. C. The hydrogen pressure may be varied from about 15 psia to 2000 psia. A preferred range is from about 15 psia to about 300 psia. The reaction time can vary and normally depends on the temperature and pressure. Generally, with the preferred temperatures and pressures, the reactions are complete within 1-10hours. Rhodium is the preferred metal for hydrogenation of carbon-carbon double bonds, but ruthenium, platinum, and palladium may also be used. The ratio of substrate to catalyst dependes primarily on the reactor configuration but can range from about 50:1 to 50,000:1. DESCRIPTION OF CATALYTIC PROCESSES--HYDROSILATION Unsaturated compounds can be converted to silanes with the catalysts of the title invention. Ketones, alkenes, and alkynes may be converted to silanes, as shown in the Scheme below. Scheme: ##STR15## R.sup.9, R.sup.10, R.sup.11, and R.sup.12 represent hydrogen or hydrocarbyl groups of up to 20 carbon atoms. R.sup.9, R.sup.10, R.sup.11, and R.sup.12 may be aromatic or saturated, and may be the same or different. R.sup.13, R.sup.14, and R.sup.15 represent hydrogen, hydrocarbyl, or alkoxy groups of up to 20 atoms. R.sup.13, R.sup.14 and R.sup.15 may be aromatic or saturated, and may be the same or different. The hydrosilation process may be carried out at from about 0.degree. C. to about 150.degree. C., and a preferable range is from about 20.degree. C. to 100.degree. C. The ratio of substrate to olefin can range from about 1:10 to about 10:1, and a preferred range is from about 1:2 to 2:1. Rhodium is the preferred metal for the phosphine-promoted hydrosilation of double bonds, but ruthenium, platinum, and palladium may also be used. The ratio of substrate to catalyst depends primarily on the reactor configuration but can range from about 50:1 to 50,000:1. |
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