WO1999006146A2 - Supported diols and supported bis(phosphorus) ligands - Google Patents

Supported diols and supported bis(phosphorus) ligands Download PDF

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Publication number
WO1999006146A2
WO1999006146A2 PCT/US1998/015199 US9815199W WO9906146A2 WO 1999006146 A2 WO1999006146 A2 WO 1999006146A2 US 9815199 W US9815199 W US 9815199W WO 9906146 A2 WO9906146 A2 WO 9906146A2
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WO
WIPO (PCT)
Prior art keywords
supported
resin
ligand
mmol
toluene
Prior art date
Application number
PCT/US1998/015199
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French (fr)
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WO1999006146A3 (en
Inventor
Joseph D. Druliner
Kenneth Gene Moloy
Manxue Wang
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E.I. Du Pont De Nemours And Company
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Priority to DE69820635T priority Critical patent/DE69820635T2/en
Priority to EP98935940A priority patent/EP1003607B1/en
Publication of WO1999006146A2 publication Critical patent/WO1999006146A2/en
Publication of WO1999006146A3 publication Critical patent/WO1999006146A3/en
Priority to HK00105639A priority patent/HK1026383A1/en

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    • C07F9/06—Phosphorus compounds without P—C bonds
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Definitions

  • the invention generally relates to supported bis(phosphorus) ligands useful for a variety of catalytic processes.
  • the ligands are useful in the hydrocyanation of unsaturated organic compounds.
  • 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.
  • Phosphite ligands are particularly good ligands for both of these transformations.
  • 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. 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, US 5,512,695, US 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.
  • 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.
  • phosphite ligands have been disclosed with rhodium in the hydroformylation of functionalized ethylenically unsaturated compounds: Cunv et al.. J. Am. Chem. Soc, 1993, 115, 2066.
  • These prior art examples demonstrate the utility of bisphosphite ligands in catalysis.
  • the catalyst consisting of the ligand and the metal
  • the catalyst 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.
  • Bisphosphine ligands have also been attached to solid supports and used for catalysis, as described in for example US 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.
  • the present invention provides for novel supported diols and chelating bis(phosphorus) ligands covalently bonded to a support.
  • 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):
  • Q is any organic fragment which binds a OPX2 moiety to the support (Sup); and X is an alkoxide, aryloxide, alkyl, or aryl.
  • X is aryloxide or aryl.
  • the invention also provides for a supported catalyst composition having the structure (3):
  • Q is any organic fragment which binds a OPX 2 moiety to the support
  • X is an alkoxide, aryloxide, alkyl or aryl
  • 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.
  • 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):
  • Q is any organic fragment which binds a OPX 2 moiety to the support (Sup).
  • X is an alkoxide, aryloxide, alkyl or aryl;
  • 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):
  • Q is any organic fragment which binds a OPX 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.
  • 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 chelating arrangement of donor atoms gives catalysts with commercially practical activity and selectivity.
  • 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 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.
  • a liquid solvent which does not interfere with the catalytic reaction of interest
  • gaseous e.g., an inert carrier gas and gaseous reactants and products.
  • 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
  • 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.
  • 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.
  • suitable polymers include polyolefins. polyacrylates, polymethacrylates, and copolymers thereof that meet the general criteria described above.
  • 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.
  • 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:
  • Sup represents the insoluble support.
  • Q means any organic fragment which binds the diol moiety to the support.
  • 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.
  • 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. 4,769,498 and U.S. 4,668,651.
  • the transformation involves the reaction of a phosphorus halide, typically but not limited to chloride, with the diol to form P-O bonds.
  • 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 2 moiety may form a ring and X 2 may be a di(alkoxide), di(aryloxide), di(alkyl) or di(aryl).
  • 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 ; lnorg. Syn. 1966, 8, 68; U.S. 5,210,260; Z. Anorg. Allg. Chem. 1986, 535, 221.
  • the reaction of 2,2'-biphenol with phosphorus trichloride gives 1 , 1 '-biphenyl-2,2'-diylphosphorochloridite.
  • transition metal catalysts which are a subject of this invention are defined by the formula shown below:
  • 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. 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) (COD is 1,5-cyclo- octadiene) and Ni ⁇ P(0-o-C6H CH 3 )3 ⁇ 2 (C 2 H 4 ), both of which are known in the art.
  • 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 2 where Y is halide, carboxylate, or acetylacetonate.
  • Suitable reducing agents include metal borohydrides, metal aluminum hydrides, metal alkyls, Li, Na, K, or H 2 .
  • Rhodium catalysts suitable for hydrogenation and hydrosilation can be prepared by techniques well known in the art as described, for example, in
  • the diolefinic compound reactants used in this study include primarily conjugated diolefms 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.
  • Formulasf 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.
  • each one of R 1 and R 2 independently, is H or a Ci to C3 alkyl.
  • Compound I is a special case of Formula II, where each one of R 1 and R 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.
  • 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.
  • temperatures of from -25°C to 200°C can be used with from 0°C to 175°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.
  • 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. Patents 5,449,807 and 5,440,067 (both to Druliner) and U.S. Provisional Application No. 60/014,618, filed April 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 C C to about 170°C.
  • the temperature range is generally from about 135°C to about 300°C and preferably from about 145°C to 200°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.
  • a solvent such as acetonitrile or toluene.
  • temperatures of from about 140-160°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.
  • the present invention also provides a process for hydrocyanation, comprising reacting a nonco ⁇ jugated, 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.
  • R 4 is H, CN, CO 2 R 5 , or perfluoroalkyl; y is an integer of 0 to 12; x is an integer of 0 to 12 when R 4 is H, C0 R 5 or perfluoroalkyl; x is an integer of 1 to 12 when R 4 is CN; and
  • R 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.
  • 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.
  • 3-pentenenitrile as much as 10% by weight thereof may be 2- pentenenitrile.
  • 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
  • the starting olefmically 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 nitriles of Formula VII, while those of Formula VIII yield terminal nitriles of Formula IX.
  • nonconjugated linear alkenes Preferred are nonconjugated linear alkenes, nonconjugated linear alkenenitriles, nonconjugated linear alkenoates, linear alk-2-enoates and perfluoroalkyl ethylenes.
  • the preferred products are terminal alkanenitriles, linear dicyanoalkylenes, linear aliphatic cyanoesters, and 3-(perfluoroalkyl)propio- nitrile. Most preferred products are adiponitrile, alkyl 5-cyanovalerate, and C 2 F 2z+ ⁇ CH2CH 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 monoolefmic 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.
  • 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 nitriles such as acetonitrile or benzonitrile.
  • 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 °C to 200 °C can be used, the range of 0°C to 150°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.
  • a cyanohydrin can be used as the source of HCN. See, for example, U.S. 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 2 , Znl 2 , ZnCl 2 , ZnSO 4 , CuCl 2 , CuCl, Cu(O 3 SCF 3 ) 2 , CoCl 2 , CoI 2 , Fel 2 , FeCl 2 , FeCl 3 , FeCl 2 (THF) 2 , TiCl 4 (THF) 2 , TiCl 4 , TiCl 3 , ClTi(OiPr) 3 , MnCl 2 , ScCl 3 , AICI3, (C 8 H ⁇ 7 )AlCl 2 , (C 8 H ⁇ 7 ) A1C1 2 , (iso-C 4 H 9 ) 2 AlCl, Ph 2 AlCl, Ph 2 AlCl, ReCl 5 , ZrCl 4 , NbCl 5 , VC1 3 , CrCl 2 , MoCl 5 , YC1 3 , CdCl 2 , LaCl 3
  • Suitable promoters are further described in U.S. 3,496,217; U.S. 3,496,218,; U.S. 4,774,353. These include metal salts (such as ZnCl 2 , CoI , and SnCl ), and organometallic compounds (such as RA1C1 , R3SnO3SCF3, and R3B, where R is an alkyl or aryl group).
  • metal salts such as ZnCl 2 , CoI , and SnCl
  • organometallic compounds such as RA1C1 , R3SnO3SCF3, and R3B, where R is an alkyl or aryl group.
  • U.S. 4,874,884 describes how synergistic combinations of promoters can be chosen to increase the catalytic activity of the catalyst system.
  • the mole ratio of promoter to nickel present in the reaction can be within the range of 1:16 to 50:1.
  • R 5 , R 6 , R 7 , and R 8 represent hydrogen or hydrocarbyl groups of up to
  • R 5 , R 6 , R 7 , and R s 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°C, to about 150°C. A preferable range is from about 30°C to about 100°C.
  • the hydrogen pressure may be varied from about
  • 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.
  • 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:
  • R 9 , R 10 , R 1 and R 12 represent hydrogen or hydrocarbyl groups of up to 20 carbon atoms.
  • R 9 , R 10 , R 1 J , and R 12 may be aromatic or saturated, and may be the same or different.
  • R 13 , R 14 , and R 15 represent hydrogen, hydrocarbyl, or alkoxy groups of up to 20 atoms.
  • R 13 , R 14 and R 15 may be aromatic or saturated, and may be the same or different.
  • the hydrosilation process may be carried out at from about 0°C to about 150°C, and a preferable range is from about 20°C to 100°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 .
  • the resin-supported bis(phosphite) SL3 (1.048 g) was suspended in 15 mL toluene and a solution of 0.243 g Ni(COD) 2 was added. The mixture was stirred at room temperature for 2 h. The resulting dark Ni(COD)-loaded resin was isolated by filtration, washed with toluene and pentane, and then dried under vacuum.
  • This catalyst was prepared from supported ligand SL4 and Ni(COD) 2 following the procedures described above.
  • Resin-supported diol SD2 (5.0 g) was suspended in a pyridine/toluene (3/1) mixture. 3.82 g bis(2-isopropyl-5-methylphenyl)phosphorochloridite was then added dropwise with stirring at room temperature. After several hours the resin was filtered and washed with pyridine (4 x 25 mL), diethyl ether (2 x 25 mL), and pentane (2 x 25 mL) before vacuum drying. IR: complete loss of O-H band.
  • Resin-supported ligand SL7 (1.235 g) was suspended in 15 mL toluene and 0.279 g Ni(COD) 2 was added. The mixture was stirred for 2 h at room temperature and then filtered. The dark solid was washed with toluene and pentane, and then vacuum dried.
  • Resin-supported diol SD3 (2.344 g) was suspended in 20 mL of pyridine/toluene (1/1). 1.12 g PPh 2 Cl was added dropwise; heat evolution was noted. After stirring for 3 days at room temperature the reaction was heated to 80°C overnight. The product was collected by filtration, washed with pyridine (3 x 15 mL), and pentane (3 x 15 mL) and then dried under vacuum. IR: loss of O-H band.
  • This material was prepared and isolated in a similar fashion using 2.250 g of supported diol SD3 and 1.769 g bis(2-isopropyl-5-methylphenyl)phosphoro- chloridite (as a toluene solution).
  • Resin-supported ligand SL8 (1.90 g) was suspended in 20 mL toluene. 0.445 g of Ni(COD) 2 was added. After 3 h the catalyst, a nearly black solid due to some precipitated Ni metal, was isolated by filtration and washed thoroughly with toluene, pentane, and then vacuum dried. A small amount of the resulting catalyst was suspended in toluene and treated with CO (1 atm) at room temperature for 3 h. The dark brown resin was isolated by filtration, washed with hexane and dried under vacuum. IR: 2067, 1996 cm- 1 . EXAMPLE 25
  • resin-supported ligand SL10 (1.60 g) was treated with 0.32 g Ni(COD) 2 in 20 mL toluene. Work-up provided the Ni(COD) catalyst as a brown solid.
  • Ni(COD)-loaded catalyst SCI 3 was prepared in the usual manner from supported ligand SL11 and characterized as the supported dicarbonyl derivative. IR (KBr, cm” 1 ): 2091 (weak), 2055, 2006.
  • This supported benzyl alcohol can be purchased commercially from
  • sulfoxyl-protected binaphthol acid chloride shown in 0.525 g of the resin-supported benzyl alcohol was suspended in 15 mL THF and then treated with 0.236 g of the sulfoxyl-protected binaphthol acid chloride shown.
  • the sulfoxyl-protected binaphthol acid chloride was prepared by oxidative coupling of 2-naphthol with 2-hydroxy-3-naphthoic acid followed by treatment with thionyl chloride. These transformations are well known to those skilled in the art. The mixture was stirred for 1 day at room temperature and then one day at 45°C.
  • the resin-supported diol SD5 (1.80 g) was suspended in 15 mL of THF along with 1 mL of pyridine and 2.70 g of l,l'-biphenyl-2,2'-diylphosphoro- chloridite (50 wt % solution in toluene). The mixture was stirred overnight at 50°C before filtration. The product was washed with CH 2 C1 2 (3 x 5 mL), THF (3 x 5 mL), toluene (3 x 5 mL), and pentane (2 x 5 mL), before vacuum drying. IR showed nearly complete loss of O-H at ca. 3400 cm -1 .
  • Resin SD5 (1.74 g) was suspended in 15 mL of THF. To this was added 0.91 g of 1,2-phenylenephosphorochloridite and 1 mL of pyridine, and the mixture was stirred overnight at 50°C. The resin was collected by filtration and washed with successive portions of CH 2 C1 2 , THF, toluene, and pentane before vacuum drying.
  • the resin-supported ligand SL12 (1.105 g) was suspended in 8 mL of toluene and then treated with 0.19 g Ni(COD) 2 .
  • the black Ni(COD)-loaded catalyst was isolated by filtration, washed with toluene and pentante, and then vacuum dried.
  • the resin-supported ligand SL13 (1.02 g) was suspended in 8 mL of toluene and then treated with 0.19 g Ni(COD) for 40 min at room temperature.
  • the Ni(COD)-loaded catalyst was filtered and washed with toluene and pentane, then vacuum dried, to give a black solid.
  • the supported ketal was deprotected by suspension in 200 mL of dioxane containing a small amount of 10% aq HCl. The mixture was stirred overnight at room temperature. Workup was accomplished by filtration and then washing with water, acetone, and THF before vacuum drying.
  • the product was filtered, washed with CH2CI2, toluene, and pentane, and then dried under vacuum.
  • Method 1 0.55 g of the bis(phosphite)-supported resin SL15 was suspended in 15 mL of toluene in a sintered glass suction filter. A toluene solution of 0.19 g Ni(COD) 2 (1.5 equiv) was added and the mixture was stirred with a spatula. After approximately 1 minute the resin began to turn brown. The solvent was filtered away and the resin was washed with toluene and pentane before vacuum drying to yield the catalyst as a brown solid.
  • Ni(COD)-loaded catalyst was suspended in 5 mL of toluene and then treated with 1 atm of CO. After 20 min the resin turned beige. The resin was collected by filtration, washed with acetone and then hexane before vacuum drying.
  • Method 1 The same procedure described in Example 39 Method 1 was followed using 0.46 g of resin SL14 and 0.144 g Ni(COD) 2 to give the Ni(COD)- loaded catalyst resin as a light purple solid. Treatment with CO by the method described yielded the Ni(CO) 2 -loaded resin as a colorless solid. IR (KBr, cm- 1 ): 2083 (very weak), 2042, 2015 (shoulder), 1988.
  • Method 1 The same procedure described for Example 39 Method 1 was followed using 0.497 g of resin SL 16 and 0.14 g Ni(COD) 2 to give the Ni(COD)- loaded catalyst resin as a brown solid.
  • the binaphthol-supported resin SD8 from Example 42-2 (2.0 g) was suspended in 10 mL of THF; 3 mL of pyridine and 2.5 g of a 50 wt % solution of 1 , 1 '-biphenyl-2,2'-diylphosphorochloridite in toluene were then added. The yellow resin decolorized immediately. The mixture was stirred overnight at room temperature and then worked up by filtration and washing the resin with pyridine, THF, and pentane. The light yellow supported ligand SL17 was dried under vacuum.
  • Ni(COD)-loaded catalysts were prepared and analyzed as the Ni(CO)2 derivatives by the methods described in previous examples.
  • Example 44 The same procedure described in Example 44 was employed with 10 g (6.9 mmol) of commercially available Wang resin (from Advanced Chemtech, Louisville, KY), 8.2 g (20.7 mmol) of the sulfoxyl-protected binaphthol acid chloride shown in Example 30, and 36 ml of DIEA.
  • Example 44 The same procedure described in Example 44 was used using 6 g (7 mmol) of resin-supported benzyl alcohol, 8.3 g (21 mmol) of sulfoxyl-protected binaphthol acid chloride, and 6.1 ml of DIEA.
  • This ligand was prepared according to the same procedure as that of Example 49 using 1.46 g (4.0 mmol) of bis(2-isopropyl-5-methylphenyl)- phosphorochloridite.
  • This ligand was synthesized according to the same procedure as that for
  • Example 49 using 2.17 g (1.0 mmol) of resin-supported diol SDl 1, 2 g of 1 , l'-biphenyl-2,2'-diylphosphorochloridite (50% weight in toluene, 4.0 mmol), 1.7 ml (10 mmol) of DIEA and 15 ml of anhydrous toluene.
  • IR (KBr) 1743 cm" 1 (vs), 1680 cm” 1 (m). Elemental Analysis: C% 86.34, H% 7.00, P% 0.77
  • Example 49 The same procedure described for Example 49 was followed using 2.17 g (1.0 mmol) of the resin SDl 1, 1.46 g (4.0 mmol) of bis(2-isopropyl-5-methyl- phenyl)phosphorochloridite, 1.7 ml (10 mmol) of DIEA and 15 ml of toluene.
  • Example 49 The same procedure described for Example 49 was followed using 2.17 g (1.0 mmol) of supported diol SDl l, 1.34 g (4.0 mmol) of bis(2-isopropylphenyl)- phosphorochloridite, 1.7 ml (10 mmol) of DIEA and 15 ml of toluene.
  • This ligand was made following same procedure described for Example 49 from 2.17 g (1.0 mmol) of the supported diol SDl l, 1.41 g ( 4.0 mmol) of bis(l-naphthyl)phosphorochloridite, 1.7 ml (10 mmol) of DIEA and 14 ml of toluene.
  • the ligand was prepared following the same procedure described for Example 49 using 1.17 g (1.0 mmol) of supported diol SDl 2, 2 g (50%) weight in toluene) (4.0 mmol) of l,l'-biphenyl-2,2'-diylphosphorochloridite, 1.7 ml (10 mmol) of DIEA and 10 ml of toluene.
  • Example 49 The same procedure described for Example 49 was followed using 1.17 g (1.0 mmol) of supported diol SD12, 884 mg (4.0 mmol) of ClPPh 2 , 1.7 ml (10 mmol) of DIEA and 10 ml of toluene.
  • This product was rynthesized according to the same procedure as that for Example 49 was from 2.35 g (2.0 mmol) of the resin supported diol SD12, 2.91 g (8.0 mmol) of bis(2-isopropyl-5-methylphenyl)phosphorochloridite, 3.4 ml (10 mmol) of DIEA and 20 ml of toluene.
  • Example 49 The same procedure described for Example 49 was followed using 2.17 g (2.0 mmol) of supported diol SDl 3, 2.91 g (8.0 mmol) of bis(2-isopropyl-5- methylphenyl)phosphorochloridite, 3.4 ml (10 mmol) of DIEA and 10 ml of toluene.
  • Example 49 The same procedure described for Example 49 was followed using 2.17 g (2.0 mmol) of the resin SD13, 2.69 g (8.0 mmol) of bis(2-isopropylphenyl)- phosphorochloridite, 3.4 ml (10 mmol) of DIEA and 10 ml of toluene. Elemental Analysis: C% 90.10, H% 7.15, P% 0.48
  • the ligand was prepared according to the procedure described for Example 49 from 2.17 g (2.0 mmol) of resin SDl 3, 2 g of 1 , 1 '-biphenyl-2,2'- diylphosphorochloridite (50 wt % solution in toluene, 8.0 mmol), 3.4 ml (10 mmol) of DIEA, and 20 ml of toluene. Elemental Analysis: C% 90.28, H% 6.97, P% 0.54
  • Example 49 The same procedure described for Example 49 was followed using 1.09 g (1.0 mmol) of resin SD13, 0.7 g (4.0 mmol) of 1,2-phenylenephosphorochloridite, 1.7 ml (10 mmol) of DIEA, and 10 ml of toluene. Elemental Analysis: C% 89.82, H% 6.35, P% 1.19
  • N 1 -naphthyl
  • Example 49 The same procedure described for Example 49 was followed using 1.79 g (1.35 mmol) of supported diol resin SD10, 1.9 g (5.4 mmol) of bis(l-naphthyl)- phosphorochloridite, 2.3 ml (10 mmol) of DIEA, and 15 ml of toluene.
  • Example 49 The same procedure described for Example 49 was followed using 2.35 g (2.0 mmol) of the supported diol resin SD12, 2.69 g (8.0 mmol) of bis(2-isopropylphenyl)phosphorochloridite, 3.4 ml (10 mmol) of DIEA, and 20 ml of toluene.
  • Example 49 The same procedure described for Example 49 was followed using 2.35 g (2.0 mmol) of resin SD12, 2.69 g (8.0 mmol) of 1 ,2-ppenylenephosphoro- chloridite, 3.4 ml (10 mmol) of DIEA and 20 ml of toluene.
  • This supported bis(phosphite) was prepared following the same procedure described in Example 36 using bis(l-naphthyl)phosphorochloridite and supported diol SD6.
  • This supported bis(phosphite was prepared from supported diol SD8 following the same general procedure described in Example 43-1 using bis(2-isopropyl-5-methylphenyl)phosphorochloridite. Elemental Analysis: C% 85.79, 85.55; H% 7.56; 7.48; P% 1.44
  • This ligand was prepared according to the procedure described for Example 49 using 1.5 g (3.15 mmol) of supported diol SD14, 6.3 g (50% weight in toluene, 12.6 mmol) of l,l'-biphenyl-2,2'-diylphosphorochloridite, 5.5 ml of DIEA and 15 ml of anhydrous toluene. Elemental Analysis: C% 85.33, H% 7.11, P% 1.94
  • This supported ligand was prepared according to the procedure described for Example 49 using 1.5 g (3.15 mmol) of supported diol SDH, 4.2 g (12.6 mmol) of bis(2-isopropylphenyl)phosphorochloridite, 5.5 ml of DIEA, and 15 ml of anhydrous toluene. Elemental Analysis: C%85.80, H% 7.67, P% 2.56
  • This supported ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of resin SDH, 4.6 g (12.6 mmol) of bis(2-isopropyl-5-methylphenyl)phosphorochloridite, 5.5 ml of DIEA, and 15 ml of anhydrous toluene.
  • This ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of resin SDH, 4.4 g (12.6 mmol) of bis(l-naphthyl)phosphorochloridite, 5.5 ml of DIEA and 15 ml of anhydrous toluene. Elemental Analysis: C% 85.94, H% 7.25, P% 1.91
  • This supported ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of resin SDH, 2.8 g (12.6 mmol) of ClPPh 2 , 5.5 ml of DIEA and 15 ml of anhydrous toluene. Elemental Analysis: C% 87.65, H% 7.57, P% 2.17
  • This supported ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of supported diol SDH, 2.2 g (12.6 mmol) of 1 ,2-phenylenephosphorochloridite, 5.5 ml of DIEA, and 15 ml of anhydrous toluene. Elemental Analysis: C% 84.16, H% 7.24, P% 2.41
  • This ligand was prepared according to the procedure described in
  • Example 49 using 1.5 g (3.15 mmol) of the resin, 3.88 g (12.6 mmol) of bis(2-ethylphenyl)phosphorochloridite, 5.5 ml of DIEA and 15 ml of anhydrous toluene. Elemental Analysis: C% 84.45, H% 7.09, P% 3.09
  • This ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of the supported diol SDH, 3.88 g (12.6 mmol) of bis(2,3-dimethylphenyl)phosphorochloridite, 5.5 ml of DIEA, and 15 ml of anhydrous toluene. Elemental Analysis: C% 84.97, H% 7.16, P% 2.98 EXAMPLE 85
  • This ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of the resin SDH, 4.23 g (12.6 mmol) of bis(2,3,5-trimethylphenyl)phosphorochloridite, 5.5 ml of DIEA, and 15 ml of anhydrous toluene.
  • This ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of the resin SDH, 4.60 g (12.6 mmol) of bis(2-tertbutylphenyl)phosphorochloridite, 5.5 ml of DIEA and 15 ml of anhydrous toluene. Elemental Analysis: C% 85.83, H% 7.68, P% 2.40 EXAMPLE 87
  • This ligand was prepared according to the procedure described in
  • EXAMPLE 88 The following is a general procedure for the preparation of supported nickel catalysts using the supported ligands described in previous examples. Information in Table 2 shows the generality of this procedure. The appropriate supported ligand (0.5-1.0 g, ca. 0.5 mmol) is suspended in
  • EXAMPLE 90 Butadiene Hydrocyanation with Supported Nickel Catalysts The resin supported ligand and nickel were charged as either the Ni(COD) loaded material, prepared as described above, or by separate addition of Ni(COD)2 and ligand. The amount of supported ligand charged was targeted at 5.4 micromoles and a 1 : 1 ratio of chelate ligand to nickel, except where noted. 5 mL of solvent (toluene or tetrahydrofuran) was used as the reaction solvent, and the experiments were conducted at 80°C. The reaction mixtures are made to a target HCN/Ni ratio of 500 and to a target HCN/BD ratio of 0.89.
  • EXAMPLE 92 3-Pentenenitrile Hydrocyanation with Supported Nickel Catalysts
  • the resin supported ligand and nickel were charged as the preformed .
  • nickel-loaded, supported catalyst The amount of supported ligand charged was 8.5 micromoles, and a 1:1 ratio of ligand to nickel was used.
  • ZnCl 2 was added as a promoter, using a ratio 1 : 1 ZnCl 2 :Ni.
  • To the catalyst and promoter was added 5 mL of a 40 mole % solution in HCN in trans -3 -pentenenitrile. The sample was analyzed by gas chromatography after 24 h at 25 °C.
  • % HCN conversion refers to the amount of HCN converted to hydrocyanation products
  • ADN refers to adiponitrile
  • MGN refers to methylglutaronitrile
  • ESN refers to ethylsuccinonitrile.
  • a comparative example using a commercial homogeneous catalyst based on pTTP (pTTP is para-tritolylphosphite) and nickel (0) is provided in the Table below, showing that the supported catalysts perform better than current commercial soluble catalysts.
  • a vial is charged with 2 mmol of olefin, the supported rhodium catalyst (0.014 mmol Rh), and 2 mL of THF.
  • the vial is placed in a shaker tube and then treated with hydrogen at the desired temperature, pressure, and time.
  • a 100 ⁇ L aliquot of the supernatant is removed, diluted with 500 ⁇ L THF, and analyzed by GC. The results are provided in Table 6.
  • EXAMPLE 94 Olefin Hydrogenation - Catalyst Recycle/Metal Leaching 100 mg of the rhodium-loaded resin from Example 8 was charged to a glass pressure vessel. 1 mL of cyclooctene and 10 mL of THF were added. The vessel was pressurized with 50 psig H2 and heated to 50°C, with stirring. After 2 h the pressure dropped to 25 psi. The liquid supernatant was removed with a syringe. GC analysis showed 100% conversion of the cyclooctene to cyclooctane. Analysis of the supernatant further showed 3 ppm Rh. Fresh cyclooctene (1 mL) and THF (10 mL) were added to the remaining rhodium-loaded resin remaining in the reactor and the hydrogenation process was repeated.
  • a vial was charged with 9.5 mg of the supported rhodium catalyst SC3, corresponding to 0.18 ⁇ mole of rhodium. The vial was then charged with 12 mg (0.1 mmol) of Et3SiH, 24 mg (0.2 mmol) of acetophenone, and 1 mL of toluene. The vial was then heated for the indicated time and temperature. The supernatant was then analyzed by GC, which showed a 36% conversion to

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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). Furthermore, supported diols are disclosed, said diols being based on a binaphthal, 2-naphthal or 2,4-dimethylphenol structure.

Description

TITLE
SUPPORTED DIOLS AND SUPPORTED BIS(PHOSPHORUS) LIGANDS
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.
R OR
I I
R R RO OR
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. 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, US 5,512,695, US 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, US 5,235,1 13 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: Cunv 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 US 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):
Sup
I
X PO OPX, 2 2 (2)
wherein:
Q is any organic fragment which binds a OPX2 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):
Sup
X ,pχ .
(3)
wherein:
Q is any organic fragment which binds a OPX2 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):
Figure imgf000006_0001
wherein:
Q is any organic fragment which binds a OPX2 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):
Sup
I
x2' p pχ2
M
(3)
wherein:
Q is any organic fragment which binds a OPX2 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:
Sup
I
HO OH
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 SDL 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. Ada 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 1, 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.
Figure imgf000010_0001
SD1 SD6
Figure imgf000010_0002
SD2 , 3 , 4
Figure imgf000010_0003
SD5 , 12
Figure imgf000010_0004
SD7 , 8 , 9
Figure imgf000011_0001
SDH SD10
Figure imgf000011_0002
SD13 SD14
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. 4,769,498 and U.S. 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 PYnX3_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 = 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 PX2 moiety may form a ring and X2 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 ; lnorg. Syn. 1966, 8, 68; U.S. 5,210,260; Z. Anorg. Allg. Chem. 1986, 535, 221. For example, the reaction of 2,2'-biphenol with phosphorus trichloride gives 1 , 1 '-biphenyl-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:
Pol
X2 PO -\ OPX'
(2)
where X and Q are as defined above. Other examples may be prepared by similar transformations, and representative structures are also shown below.
Figure imgf000012_0001
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:
Figure imgf000012_0002
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. 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) (COD is 1,5-cyclo- octadiene) and Ni{P(0-o-C6H CH3)3}2(C2H4), 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 NiY2 where Y is halide, carboxylate, or acetylacetonate. Suitable reducing agents include metal borohydrides, metal aluminum hydrides, metal alkyls, Li, Na, K, or H2.
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)2X (where COD is as defined above and X is negatively charged counterion such as halide, BF4", PFg", OTf (OTF = O3SCF3), CIO4-, and the like), Rh(PPh3)3Cl, and Rh(CO)2(acac) (acac = acetylacetonate).
DESCRIPTION OF CATALYTIC PROCESSES - HYDROCYANATION OF DIOLEFINIC COMPOUNDS
The diolefinic compound reactants used in this study include primarily conjugated diolefms 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 Formulasf 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.
CH2=CH-CH=CH2 R1CH=CH-CH=CHR2
(1, 3-butadiene) II
I
wherein each one of R1 and R2, independently, is H or a Ci to C3 alkyl.
CH2=CH-CH-CH3
I
NC-CH2 -CH=CH-CH3 CH =CH-CH2 -CH2 -CN CN
I I I IV V
( 3PN) ( 4 PN) ( 2M3BN )
It will be recognized that Compound I is a special case of Formula II, where each one of R1 and R2 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°C to 200°C, can be used with from 0°C to 175°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. Patents 5,449,807 and 5,440,067 (both to Druliner) and U.S. Provisional Application No. 60/014,618, filed April 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 135CC to about 170°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°C to about 300°C and preferably from about 145°C to 200°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°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 noncoηjugated, 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.
Catalyst
Composition
CH3-(CH2 ) y-CH=CH-(CH2)χ-R4 >■ NC- (CH2 ) y+x+3-R4
Promotor, HCN Formula VI Formula VII or
Catalyst
. Composition CH2=CH-(CH2)χ-R4 ». NC_(CH2)χ+2_R4
Promotor, HCN Formula VIII Formula IX
wherein
R4 is H, CN, CO2R5, or perfluoroalkyl; y is an integer of 0 to 12; x is an integer of 0 to 12 when R4 is H, C0 R5 or perfluoroalkyl; x is an integer of 1 to 12 when R4 is CN; and
R5 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, CZF2Z+ 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 olefmically 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 nitriles of Formula VII, while those of Formula VIII yield terminal nitriles 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 CzF2z+ ιCH = CH (where z is 1 to 12).
The preferred products are terminal alkanenitriles, linear dicyanoalkylenes, linear aliphatic cyanoesters, and 3-(perfluoroalkyl)propio- nitrile. Most preferred products are adiponitrile, alkyl 5-cyanovalerate, and C2F2z+ ιCH2CH2CN, 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 monoolefmic 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 nitriles 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 °C to 200 °C can be used, the range of 0°C to 150°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. 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 ZnBr2, Znl2, ZnCl2, ZnSO4, CuCl2, CuCl, Cu(O3SCF3)2, CoCl2, CoI2, Fel2, FeCl2, FeCl3, FeCl2(THF)2, TiCl4(THF)2, TiCl4, TiCl3, ClTi(OiPr)3, MnCl2, ScCl3, AICI3, (C8Hι7)AlCl2, (C8Hι7) A1C12, (iso-C4H9)2AlCl, Ph2AlCl, Ph2AlCl, ReCl5, ZrCl4, NbCl5, VC13, CrCl2, MoCl5, YC13, CdCl2, LaCl3, Er(O3SCF3)3, Yb(O2CCF3)3, SmCl3, BPh3, TaCl5. Suitable promoters are further described in U.S. 3,496,217; U.S. 3,496,218,; U.S. 4,774,353. These include metal salts (such as ZnCl2, CoI , and SnCl ), and organometallic compounds (such as RA1C1 , R3SnO3SCF3, and R3B, where R is an alkyl or aryl group). U.S. 4,874,884 describes how synergistic combinations of promoters can be chosen to increase the catalytic activity of the catalyst system. Preferred promoters are CdCl2, ZnCl , B(C6H5)3, and (CeHs^SnX, where X = CF3SO3, CH3C6H5SO3, or (C6H5)3BCN. 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.
( 4 ) ( 5 )
R5, R6, R7, and R8 represent hydrogen or hydrocarbyl groups of up to
20 carbon atoms. R5, R6, R7, and Rsmay 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°C, to about 150°C. A preferable range is from about 30°C to about 100°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 1-10 hours. 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:
Figure imgf000020_0001
R9, R10, R1 and R12 represent hydrogen or hydrocarbyl groups of up to 20 carbon atoms. R9, R10, R1 J, and R12 may be aromatic or saturated, and may be the same or different. R13, R14, and R15 represent hydrogen, hydrocarbyl, or alkoxy groups of up to 20 atoms. R13, R14 and R15 may be aromatic or saturated, and may be the same or different.
The hydrosilation process may be carried out at from about 0°C to about 150°C, and a preferable range is from about 20°C to 100°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 .
EXAMPLES The following non-limiting examples further illustrate the invention. All percentages are by weight, unless otherwise noted.
EXAMPLE 1
Figure imgf000021_0001
Supported diol SD1
10.2 g of pentaerythritol was dissolved in the minimum amount of dimethyl sulfoxide, and then toluene was added until the solution became slightly cloudy. 18.9 g of the polymer-supported benzaldehyde resin (prepared by oxidation of Merrifield's resin commercially available from Aldrich Chemical Co., Milwaukee, WI, or Polymer Laboratories, Ltd., Shropshire, England) and a few crystals of p-toluenesulfonic acid were then added. The suspension was brought to reflux and the condensate was passed through a bed of molecular sieves in a Soxhlet extractor before returning to the reaction flask. After 12 h the suspension was cooled to room temperature and the resin was isolated by filtration. After washing with warm 0.5% aq NaHC03, MeOH, and then hexane the resin was dried under vacuum. IR: O-H at 3400 cm- l ; complete loss of C=O at 1701 cm" l .
MAS 1 C{ !H} NMR (CDC13): δ 102.7 (acetal carbon); 70.7 (ring OCH2); 65.3, 63.7 (axial, equatorial CH2OH); 39.6 (quaternary carbon) , in addition to polymer backbone and ring resonances.
EXAMPLE 2
Figure imgf000021_0002
Supported Ligand SL1
1.0 g of resin-supported diol SD1 was suspended in 15 mL pyridine. 0.97 g PPh2Cl was added dropwise with stirring. After 2.5 days the resin was filtered, washed with 5 x 10 mL pentane and then dried under vacuum.
MAS 1 C{ !H} NMR (CDCI3): δ 102.7 (acetal carbon); 70.3 (ring OCH2); 70.0,
68.3 (axial, equatorial CH2OP), in addition to polymer backbone and ring resonances. MAS ^P^H NMR CDCh,): 114, l lό ppm. EXAMPLE 3
Figure imgf000022_0001
Supported Ligand SL2
In a manner similar to Example 2, 2.0 g of SD1 was suspended in 15 mL pyridine. 4.4 g of 1 , l'-biphenyl-2,2'-diylphosphorochloridite (50 wt % solution in toluene) was added dropwise. The resulting slurry was stirred overnight. The resin was filtered, washed with 2 x 15 mL of 50/50% CH2Cl2/pentane, then 3 x 15 mL pentane, and then dried under vacuum.
EXAMPLE 4
Figure imgf000022_0002
In a manner similar to Example 2, 2.0 g of SD1 was suspended in 15 mL pyridine, and 44 mL of a 0.2 M solution of bis(2-isopropyl-5-methylphenyl)phos- phorochloridite in toluene was added dropwise. After stirring overnight the resin was filtered, washed with 3 x 10 mL 50/50 pyridine/pentane, then 2 x 10 mL pentane, and finally dried under vacuum.
An identical experiment was performed using a 2% divinylbenzene crosslinked resin support to give supported ligand SL3-2. 3 1P{1H} (CDC13): 134 ppm.
EXAMPLE 5
Figure imgf000023_0001
Supported Ligand SL4
In a manner similar to Example 2, 4.20 g of SD1 was suspended in 20 mL pyridine. 1.616 g 1 ,2-phenylenephosphorochlodite was added dropwise at room temperature. The mixture was then stirred for three days at room temperature and the resulting resin isolated by filtration. After washing thoroughly with pyridine and pentane it was dried under vacuum.
IR: Loss of O-H band at 3400 cm-1.
EXAMPLE 6
Figure imgf000023_0002
Supported Ligand SL5
In a manner similar to Example 2, 0.98 g of SD1 was suspended in 15 mL of pyridine and then 1.1 g of bis(l-naphthyl)phosphorochloridite was added. The resulting mixture was agitated overnight at room temperature. The product was collected by filtration and then washed with CH2C12, THF (tetrahydrofuran), and pentane before vacuum drying. IR (KBr, cm"1): loss of O-H at 3400 cm"1. Elemental analysis: 81.63% C, 6.98% H, 2.78% P.
EXAMPLE 7
Figure imgf000023_0003
Supported Catalyst SCI
1.53 g of the supported bis(phosphinite) resin SL1 was suspended in 20 mL toluene. A solution of 0.426 g Ni(COD)2 in 10 mL toluene was added, whereupon the mixture turned orange. After 3 h the slurry was filtered to give an orange Ni(COD)-loaded resin which was washed (5 x 15 mL toluene, 2 x 15 mL pentane) and dried under vacuum.
0.10 g of the resulting Ni(COD)-supported resin was suspended in 8 mL toluene. The slurry was then treated with CO (1 atm). After 3 h the color changed to a light yellow. The Ni(CO)2-loaded resin was filtered and GC/MS analysis of the filtrate showed the presence of 1,5-cyclooctadiene. The resin was washed with toluene, then pentane, and then vacuum dried. IR Ccnr^ KBr): 2013, 1956.
EXAMPLE 8
ooctadiene,
Figure imgf000024_0001
Supported Catalyst SC2
3.0 g of the bis(phosphinite) resin SL1 was suspended in 60 mL of THF. 1.03 g of Rh(COD)2(O3SCF3) was added. The mixture was shaken overnight at room temperature. GC analysis of the supernatant showed the presence of COD. The now orange Rh(COD)(O3SCF3)-loaded resin was isolated by filtration, washed with 2 x 20 mL of THF and then vacuum dried. Yield = 3.275 g. Analysis: P, 0.83 wt %; Rh, 1.91 wt %. A small amount of the resulting Rh(COD)(03SCF3)-loaded resin was suspended in THF and treated with 1 atm CO. GC analysis of the supernatant after 30 min showed the presence of COD. The product was isolated by filtration and dried under vacuum. IR (KBr) showed a strong carbonyl absorption at 2002 cm- 1 indicative of the supported rhodium carbonyl complex. EXAMPLE 9
Figure imgf000024_0002
Supported Catalyst SC3
0.50 g of the bis(phosphinite) resin SL1 and 0.34 g of Rh(PPh3)3Cl were weighed into a vial; 20 mL of THF was then added. The suspension was shaken overnight at room temperature. The burgundy solution was filtered to yield an orange solid. The solid was washed with THF until the washings were colorless, and then dried under vacuum. Yield = 0.452 g of the orange chlororhodium- triphenylphosphine loaded resin (L = PPh3), catalyst SC3.
The catalyst was characterized as the rhodium-carbonyl derivative by infrared spectroscopy: 40 mg of the resulting chlororhodiumtriphenylphosphine - loaded resin was suspended in THF and treated with 1 atm of CO at room temperature. After 30 min the orange resin was filtered, washed with THF and dried under vacuum. IR showed a strong absorption at 1981 cm"1, consistent with formation of the chlororhodiumcarbonyl loaded resin (L = CO).
EXAMPLE 10
L = 1 ,5-cyclooctadiene,
Figure imgf000025_0001
Figure imgf000025_0002
Supported Catalyst SC4
The resin-supported bis(phosphite) SL3 (1.048 g) was suspended in 15 mL toluene and a solution of 0.243 g Ni(COD)2 was added. The mixture was stirred at room temperature for 2 h. The resulting dark Ni(COD)-loaded resin was isolated by filtration, washed with toluene and pentane, and then dried under vacuum.
100 mg of the resulting Ni(COD)-loaded resin was suspended in toluene and treated with 1 atm CO. After 3 h the resin was filtered, washed with toluene and hexane, and then vacuum dried. GC/MS analysis showed liberation of COD.
IR showed carbonyl absorptions consistent with formation of the Ni(CO)2-loaded resin.
IR: NiC-O at 2035, 1984 cm"1.
EXAMPLE 11
L = 1 ,5-cyclooctadiene,
Figure imgf000026_0001
Figure imgf000026_0002
Supported Catalyst SC5
1.030 g of the supported ligand SL2 was similarly treated with 0.280 g Ni(COD)2 in toluene to yield the Ni(COD)-supported catalyst.
50 mg of the resulting dark brown Ni(COD)-supρorted catalyst was treated with CO at 1 atm for 2.5 h. After filtration and washing with toluene and pentane the Ni(CO)2-supported resin was dried under vacuum. IR: 2046, 1987 cm"1.
EXAMPLE 12
e,
Figure imgf000026_0003
Supported Catalyst SC6
This catalyst was prepared from supported ligand SL4 and Ni(COD)2 following the procedures described above.
EXAMPLE 13
Figure imgf000026_0004
Supported Catalyst SC7
Approximately 1.5 g of the bis(phosphite) resin SL5 was suspended in
10 mL of toluene and treated with 0.28 g Ni(COD)2 in a sintered glass filter. The reaction was stirred with a spatula until the resin turned yellow, whereupon the reaction was quickly filtered. The resulting resin was washed with toluene and pentane and dried under vacuum as a yellow solid. 50 mg of the resulting Ni(COD) loaded resin was suspended in 5 mL toluene and treated with 1 atm CO for 20 min. The Ni(CO)2-loaded product was filtered, washed with acetaone and hexane, and then dried under vacuum. IR (KBr, cm"1): 2084 (weak), 2041, 1986. EXAMPLE 14
Figure imgf000027_0001
8.0 g of polymer-supported benzaldehyde resin (1% divinylbenzene cross- linked), 3.3 g diethyltartrate, and a few crystals of p-toluenesulfonic acid were combined in 50 mL toluene. The mixture was refluxed for 18 h, with the condensed vapors passing through a bed of molecular sieves before returning to the reaction flask. The resin was collected by filtration, washed with acetone (4 x 15 mL), CH2C12 (4 x 15 mL), hexane (2 x 15 mL), and CH2C12 before vacuum drying.
IR: -CO2Et at 1730 cm"1; complete loss of aldehyde C=0 at 1701 cm"1.
An identical experiment was conducted using 2% cross-linked resin (86094-57) to give a derivatized resin with an identical infrared spectrum.
EXAMPLE 15
Figure imgf000027_0002
R = CH3
Supported Diol SD2
7.3 g polymer-supported diester of Example 14 was suspended in 100 mL dry THF and then cooled to 0°C. 11.4 mL of a 3.0 M solution of CH3MgBr in diethyl ether was added dropwise. The mixture was warmed to room temperature and then heated to 60°C. After 3.5 h the mixture was cooled to 0°C and then quenched with aqueous HCl. The product was collected by filtration, washed with H20 (3 x 15 mL), acetone (3 x 15 mL), and diethyl ether (2 x 15 mL), and finally vacuum dried.
IR: O-H at 3400 cm"1; complete loss of the ester band at 1730 cm- 1.
An identical experiment was conducted using 2% cross-linked resin to give a derivatized resin with an identical infrared spectrum. EXAMPLE 16
Figure imgf000028_0001
Supported Ligand SL6
5.374 g of supported diol SD2 was suspended in 50 mL toluene and 15 mL pyridine. 8.04 g l,l'-biphenyl-2,2'-diylphosphorochloridite (50 wt % soln in toluene) was added dropwise. The mixture was heated overnight at 60°C. The product was filtered, washed with pyridine (2 x 15 mL), diethyl ether (3 x 15 mL), and hexane (15 mL) before vacuum drying. IR: complete loss of O-H at 3400 cm"1. 3 1P NMR (CDC13): 153 ppm.
EXAMPLE 17
Figure imgf000028_0002
Supported catalyst SC8
1.087 g of supported ligand SL6 was suspended in 25 mL toluene and 0.29 g Ni(COD)2 was added. After 3.5 h the product was isolated as a brown solid and washed with toluene (4 10 mL) and pentane (2x 10 mL) before vacuum drying.
50 mg of the supported Ni(COD) catalyst was suspended in 10 mL toluene and treated with 1 atm CO for 15 h at room temperature. The resin was then filtered and washed with toluene (3 x 15 mL) and hexane (2 x 5 mL). The resulting pale gray solid was then dried under vacuum. IR (KBr, cm-1): 2082 (weak), 2036, 1977. EXAMPLE 18
Figure imgf000029_0001
Supported Ligand SL7
Resin-supported diol SD2 (5.0 g) was suspended in a pyridine/toluene (3/1) mixture. 3.82 g bis(2-isopropyl-5-methylphenyl)phosphorochloridite was then added dropwise with stirring at room temperature. After several hours the resin was filtered and washed with pyridine (4 x 25 mL), diethyl ether (2 x 25 mL), and pentane (2 x 25 mL) before vacuum drying. IR: complete loss of O-H band.
EXAMPLE 19
ooctadiene,
Figure imgf000029_0002
Figure imgf000029_0003
Supported Catalyst SC9
Resin-supported ligand SL7 (1.235 g) was suspended in 15 mL toluene and 0.279 g Ni(COD)2 was added. The mixture was stirred for 2 h at room temperature and then filtered. The dark solid was washed with toluene and pentane, and then vacuum dried.
50 mg of the resulting Ni(COD)-loaded catalyst was placed in 10 mL toluene and treated with 1 atm CO at room temperature for 3 days. The product was washed with hexane (4 x 10 mL) and dried under vacuum. IR: NiC-O at 2032 and 1977 cm"1. EXAMPLE 20
Figure imgf000030_0001
Supported Diol SD3
The resin-supported diester of Example 14 (10.98 g) was suspended in
50 mL THF at 0°C. 18.4 mL of PhMgBr (3.0 M solution in diethyl ether) was then added, with stirring. When the addition was complete the suspension was gradually warmed to 60°C and maintained at this temperature for 15 h. After cooling to 0°C the reaction was quenched with dilute aqueous HCl and the product collected by filtration. After washing with H2O (5 x 25 mL), acetone
(5 x 25 mL), and hexane (3 x 25 mL), it was vacuum dried.
IR: O-H at 3400 cm"1; complete loss of ester CO at 1730 cm"1.
EXAMPLE 21
Figure imgf000030_0002
Supported Ligand SL8
Resin-supported diol SD3 (2.344 g) was suspended in 20 mL of pyridine/toluene (1/1). 1.12 g PPh2Cl was added dropwise; heat evolution was noted. After stirring for 3 days at room temperature the reaction was heated to 80°C overnight. The product was collected by filtration, washed with pyridine (3 x 15 mL), and pentane (3 x 15 mL) and then dried under vacuum. IR: loss of O-H band.
EXAMPLE 22
Figure imgf000031_0001
Supported Ligand SL9
This material was prepared and isolated in a similar fashion using 2.257 g of supported diol SD3 and 2.44 g l,l'-biphenyl-2,2'-diylphosphorochloridite
(50 wt % solution in toluene).
IR: loss of O-H band. EXAMPLE 23
Figure imgf000031_0002
Supported Ligand SL10
This material was prepared and isolated in a similar fashion using 2.250 g of supported diol SD3 and 1.769 g bis(2-isopropyl-5-methylphenyl)phosphoro- chloridite (as a toluene solution).
IR: loss of O-H band.
EXAMPLE 24
octadiene,
Figure imgf000031_0003
Supported catalyst SC10
Resin-supported ligand SL8 (1.90 g) was suspended in 20 mL toluene. 0.445 g of Ni(COD)2 was added. After 3 h the catalyst, a nearly black solid due to some precipitated Ni metal, was isolated by filtration and washed thoroughly with toluene, pentane, and then vacuum dried. A small amount of the resulting catalyst was suspended in toluene and treated with CO (1 atm) at room temperature for 3 h. The dark brown resin was isolated by filtration, washed with hexane and dried under vacuum. IR: 2067, 1996 cm-1. EXAMPLE 25
Figure imgf000032_0001
Supported Catalyst SCI 1
In a similar fashion, resin supported catalyst SCI 1 was prepared from
1.50 g of supported ligand SL9 and 0.340 g Ni(COD)2 to yield a light brown solid.
A portion of this material was similarly treated with CO in toluene to give a beige solid. IR: 2083; 2042; 2006; 1987 cm"1.
EXAMPLE 26
L = 1 ,5-cyclooctadiene,
Figure imgf000032_0002
Figure imgf000032_0003
Supported Catalyst SCI 2
Similarly, resin-supported ligand SL10 (1.60 g) was treated with 0.32 g Ni(COD)2 in 20 mL toluene. Work-up provided the Ni(COD) catalyst as a brown solid.
A small amount of this material was treated with CO in toluene per the above procedure.
IR: 2080; 2035; 2010; 1980 cm"1. EXAMPLE 27
Figure imgf000033_0001
Supported Diol SD4
6.66 g of the resin-supported diester of Example 14 in 60 mL of THF was treated with 34.3 mL of a 1.0 M solution of LiBHE-3 in THF. After 5 h at room temperature the reaction was quenched (95% ethanol or isopropanol) and the resulting resin isolated by filtration. The resin was dried under vacuum after washing with water, alcohol, and then diethyl ether.
IR: formation of O-H at 3400 cm"1; complete loss of ester C=O band at
1730 cm"1.
EXAMPLE 28
Figure imgf000033_0002
upported Ligand SL11 AA
1.54 g of resin-supported diol SD4 was suspended in 10 mL toluene and 0.788 g of 1 ,2-phenylene phosphorchloridite was added, followed by 1 mL pyridine. The suspension was stirred at room temperature for 3 days and 1 day at 40°C. The product was isolated by filtration, washed with three portions of pyridine, then with pentane, and dried under vacuum.
The corresponding Ni(COD)-loaded catalyst SCI 3 was prepared in the usual manner from supported ligand SL11 and characterized as the supported dicarbonyl derivative. IR (KBr, cm"1): 2091 (weak), 2055, 2006.
EXAMPLE 29
Figure imgf000033_0003
This supported benzyl alcohol can be purchased commercially from
Novabiochem Corp., LaJolla, California or prepared by the following method. 10.33 g of polymer-supported benzaldehyde resin was suspended in 100 mL THF and cooled to 0°C. 15.4 mL of a 1.0 M solution of LiBHEt3 in THF was added dropwise. The suspension was warmed to room temperature and stirred for 1.5 h. The reaction was quenched by the addition of isopropanol. The resin was isolated by filtration, washed with isopropanol and hexane, and dried under vacuum. The resin was then suspended in 20 mL EtOH and treated with aqueous NaOH (0.6 g in 5 mL water) and 15 mL 30% H2O2. After stirring overnight at room temperature the resin was filtered and washed with ethanol/aqueous HCl, ethonal, acetone, ether, and hexane, and then vacuum dried. IR: O-H at 3400 cm"1; complete loss of C=O at 1701 cm"1.
EXAMPLE 30
Figure imgf000034_0001
Supported Diol SD5
0.525 g of the resin-supported benzyl alcohol was suspended in 15 mL THF and then treated with 0.236 g of the sulfoxyl-protected binaphthol acid chloride shown. The sulfoxyl-protected binaphthol acid chloride was prepared by oxidative coupling of 2-naphthol with 2-hydroxy-3-naphthoic acid followed by treatment with thionyl chloride. These transformations are well known to those skilled in the art. The mixture was stirred for 1 day at room temperature and then one day at 45°C. The reaction was quenched with H2O/methanol, filtered, and the resin washed with toluene, acetone, methanol, water, acetone, and hexane before vacuum drying. IR: O-H at 3430 cm"1 ester C=O at 1729 cm"1. EXAMPLE 31
Figure imgf000035_0001
Supported Li SL12
The resin-supported diol SD5 (1.80 g) was suspended in 15 mL of THF along with 1 mL of pyridine and 2.70 g of l,l'-biphenyl-2,2'-diylphosphoro- chloridite (50 wt % solution in toluene). The mixture was stirred overnight at 50°C before filtration. The product was washed with CH2C12 (3 x 5 mL), THF (3 x 5 mL), toluene (3 x 5 mL), and pentane (2 x 5 mL), before vacuum drying. IR showed nearly complete loss of O-H at ca. 3400 cm-1.
31P{1H} MAS NMR (CDC13): broad resonances at δ 144.2 and 137.8, in addition to an unidentified component at δ 12.8.
EXAMPLE 32
Figure imgf000035_0002
Supported ligand SL13
Resin SD5 (1.74 g) was suspended in 15 mL of THF. To this was added 0.91 g of 1,2-phenylenephosphorochloridite and 1 mL of pyridine, and the mixture was stirred overnight at 50°C. The resin was collected by filtration and washed with successive portions of CH2C12, THF, toluene, and pentane before vacuum drying.
31P{1H} MAS NMR (CDC13): δ 130.6 (major), 127.0 (minor), in addition to several unidentified resonances at δ 74, 45, and 22 to -20. EXAMPLE 33
Ln = 1,5-cycIooctadiene
Figure imgf000036_0001
Figure imgf000036_0002
Supported Catalyst SCI 4
The resin-supported ligand SL12 (1.105 g) was suspended in 8 mL of toluene and then treated with 0.19 g Ni(COD)2. The black Ni(COD)-loaded catalyst was isolated by filtration, washed with toluene and pentante, and then vacuum dried.
0.1 g of the Ni(COD)-loaded catalyst SCI 4 was treated with 1 atm CO in 5 mL of toluene for 30 min. The black solid was isolated by filtration and washed with acetone and hexane before vacuum drying. IR (KBr, cm"1): 2083 (weak), 2047, 1998.
EXAMPLE 34
Figure imgf000036_0003
Supported catalyst SCI 5
The resin-supported ligand SL13 (1.02 g) was suspended in 8 mL of toluene and then treated with 0.19 g Ni(COD) for 40 min at room temperature. The Ni(COD)-loaded catalyst was filtered and washed with toluene and pentane, then vacuum dried, to give a black solid.
0.1 g of the resulting catalyst SCI 5 was suspended in 5 mL toluene and treated with 1 atm CO and stirring for 30 min. The resulting dark brown Ni(CO)2-loaded resin was filtered and then washed with acetone and hexane before vacuum drying. IR (KBr, cm"1): 2090 (weak), 2060, 2012. EXAMPLE 35
polCH 2CI OH
Figure imgf000037_0001
Supported diol SD6
This supported diol was prepared by the literature procedure in Can. J.
Chem., 1973, 51, 3756. 18.8 g of Merrifield resin was suspended in 50 mL of solketal containing 4.70 g of the sodium salt of solketal. The mixture was stirred overnight at 80°C. The intermediate ketal was collected by filtration, and then washed with water (3 x 20 mL), acetone (3 x 20 mL), and hexane (3 x 20 mL).
IR (KBr): C-O-C at 1151, 1211, 1249 cm"1.
13C{ !H} MAS NMR (CDC13): δ 110.1, 75.5, 74.6, 71.6, 67.7.
The supported ketal was deprotected by suspension in 200 mL of dioxane containing a small amount of 10% aq HCl. The mixture was stirred overnight at room temperature. Workup was accomplished by filtration and then washing with water, acetone, and THF before vacuum drying.
IR: (KBr): Loss of): C-O-C at 1156-1249 cm"1; formation of O-H at 3430 cm"1. l3C{lH} MAS NMR (CDC13): δ 74.2, 72.2, 71.6, 64.8, in addition to polymer resonances. EXAMPLE 36
polCH2-0
Figure imgf000037_0002
Supported Ligand SL14
1.185 g of the supported diol resin SD6 was suspended in 15 mL of THF.
1.8 g of l,l'-biphenyl-2,2'-diylphosphorochloridite (50 wt % solution in toluene) was added dropwise, followed by 1.0 mL of pyridine. The resulting mixture was stirred at room temperature for 3 days. The product was isolated by filtration and then washed with successive portions of CH3CN, CH2C12, and pentane. The product was then vacuum dried.
IR (KBr): disappearance of O-H at 3430 cm"1. 31P{JH} MAS NMR (CDC13): δ 144.4, 138.3, in addition to minor components between δ 25-7.
EXAMPLE 37
Figure imgf000038_0001
Supported ligand SL15
1.40 g of the resin-supported diol SD 6 was suspended in 15 mL of THF and then treated with 0.75 g 1,2-phenylenephosphorochloridite and 1 mL of pyridine. The resulting mixture was stirred for three days at room temperature.
The product was filtered, washed with CH2CI2, toluene, and pentane, and then dried under vacuum.
IR (KBr): disappearance of O-H at 3430 cm"1.
^P^H} MAS NMR (CDCI3): δ 144.2, 138.2. EXAMPLE 38
Figure imgf000038_0002
Supported Ligand SL16
1.40 g of supported diol resin SD6 was suspended in 15 mL of THF and then treated with 1.53 g of bis(2-isopropyl-5-methylphenyl)phosphorochloridite (as a toluene solution) and 1 mL of pyridine. The mixture was stirred for 3 days at room temperature. The product was filtered, washed with CH2C12, CH3CN, and pentane before vacuum drying. IR (KBr): disappearance of O-H at 3430 cm"1.
31P{ !H} MAS NMR (CDCI3): δ 131.0, 128.6, in addition to several minor components in the ranges δ 134-127 and δ 25-0. Elemental analysis: 81.44% C, 7.83% H, 3.09% P. EXAMPLE 39
'
Figure imgf000039_0001
Supported catalyst SCI 6
Method 1. 0.55 g of the bis(phosphite)-supported resin SL15 was suspended in 15 mL of toluene in a sintered glass suction filter. A toluene solution of 0.19 g Ni(COD)2 (1.5 equiv) was added and the mixture was stirred with a spatula. After approximately 1 minute the resin began to turn brown. The solvent was filtered away and the resin was washed with toluene and pentane before vacuum drying to yield the catalyst as a brown solid.
A small amount of the resulting Ni(COD)-loaded catalyst was suspended in 5 mL of toluene and then treated with 1 atm of CO. After 20 min the resin turned beige. The resin was collected by filtration, washed with acetone and then hexane before vacuum drying.
IR (KBr, cm"1): 2089 (very weak), 2056, 2004.
Method 2. In a small vial, 0.50 g of the bis(phosphte)-supported resin
SL15 was suspended in 5 mL toluene containing 0.18 g Ni(COD)2. The mixture was stirred for 20 min, during which time the resin turned black. The catalyst resin was filtered and then washed with toluene and pentane before vacuum drying.
A small amount of the resulting Ni(COD)-loaded catalyst was then treated with CO in the same manner described above to give the Ni(CO)2-loaded resin as a black material. IR (KBr, cm"1): identical to that derived in Method 1.
EXAMPLE 40
adiene
Figure imgf000039_0002
Figure imgf000039_0003
Supported catalyst SCI 7
Method 1. The same procedure described in Example 39 Method 1 was followed using 0.46 g of resin SL14 and 0.144 g Ni(COD)2 to give the Ni(COD)- loaded catalyst resin as a light purple solid. Treatment with CO by the method described yielded the Ni(CO)2-loaded resin as a colorless solid. IR (KBr, cm-1): 2083 (very weak), 2042, 2015 (shoulder), 1988.
Method 2. The same procedure described for Example 39 Method 2 was followed using 0.45 g of resin SL 14 and 0.144 g Ni(COD)2 to give the Ni(COD)- loaded catalyst resin as a dark brown solid.
Treatment with CO by the method described yielded the Ni(CO)2-loaded resin as a dark brown solid.
IR (KBr, cm-1): identical to that obtained by Method 1.
EXAMPLE 41
Ln = 1,5-
Figure imgf000040_0001
Figure imgf000040_0002
Supported catalyst SCI 8
Method 1. The same procedure described for Example 39 Method 1 was followed using 0.497 g of resin SL 16 and 0.14 g Ni(COD)2 to give the Ni(COD)- loaded catalyst resin as a brown solid.
Treatment with CO by the method described yielded the Ni(CO)2-loaded resin as a beige solid. IR (KBr, cm"1): 2080 (very weak), 2040, 1988.
Method 2. The same procedure described for Example 39 Method 2 was followed using 0.514 g of resin SL16 and 0.14 g Ni(COD)2 to give the Ni(COD)- loaded resin as a black solid.
Treatment with CO by the method described yielded the Ni(CO)2-loaded resin as a black solid.
IR (KBr, cm- 1): identical to that obtained by Method 1.
EXAMPLE 42
Figure imgf000041_0001
Example 42-1, x = 3, Supported diol SD7
2.33 g of the binaphthol ester shown (x = 3) was dissolved in DMF. 0.39 g (2.7 equiv) of NaH was added to give gas evolution and an orange solution. After 20 min at room temperature the solution was treated with 4.0 g of Merrifield's resin (4.8 mmol CH2CI). The mixture was stirred overnight at 98°C. The resulting resin was isolated by filtration and then washed with 95% EtOH, acetone, THF, toluene, and hexane before drying under vacuum. IR (KBr, cm"1): 3441 and 3223 (O-H), 1685 (C=O).
Example 42-2. x = 4, Supported diol SD8 In a similar manner, 5.83 g of the binaphthol monoester (x = 4), 0.94 g NaH, and 9.6 g of Merrifield's resin were reacted in 30 mL of DMF. After heating at 80°C overnight the resin was isolated and rinsed by the method described above. IR (KBr, cm-1): 3583, 3419 and 3223 (O-H), 1674 (C=O).
Example 42-3 , x = 2, Supported diol SD9 This resin was prepared and isolated similarly from 1.20 g of the binaphthol monoester (x = 2), 0.22 g of NaH, and 2.4 g of Merrifield's resin. IR (KBr, cm"1): 3451, 1690 (C=O).
EXAMPLE 43
Figure imgf000041_0002
The following is a general example for the synthesis of this class of supported bis(phosphite) ligands and catalysts. Examples of supported ligands and catalysts prepared by this generic route are provided in Table 1. Example 43-1. x = 4, X2 = l,l'-biphenoxy. The binaphthol-supported resin SD8 from Example 42-2 (2.0 g) was suspended in 10 mL of THF; 3 mL of pyridine and 2.5 g of a 50 wt % solution of 1 , 1 '-biphenyl-2,2'-diylphosphorochloridite in toluene were then added. The yellow resin decolorized immediately. The mixture was stirred overnight at room temperature and then worked up by filtration and washing the resin with pyridine, THF, and pentane. The light yellow supported ligand SL17 was dried under vacuum.
The Ni(COD)-loaded catalysts were prepared and analyzed as the Ni(CO)2 derivatives by the methods described in previous examples.
TABLE 1
Example X X2 Supported liqand code
43-2 x=3 1 ,1'-biphenoxy SL18
43-3 x=3 1,2-phenyienedioxy SL19
43-4 x=4 1 ,2-phenylenedioxy SL20
43-5 x=2 1 ,1'-biphenoxy SL21
43-6 x=2 1 ,2-phenylenedioxy SL22
43-7 x=3 SL18 + Ni(COD)2 SC19
43-8 x=4 SL17 + Ni(COD)2 SC20
43-9 x=3 SL19 + Ni(COD)2 SC21
43-10 x=4 SL20 + Ni(COD)2 SC22
43-11 x=2 SL21 + Ni(COD)2 SC23
43-12 x=2 SL22 + Ni(COD)2 SC24
EXAMPLE 44
Figure imgf000042_0001
Supported diol SD 10
The sulfoxyl-protected binaphthol acid chloride shown in Example 30
(5.9 g, 15 mmol) was dissolved in 150 mL of dry DMF. The commercially available benzyl amine resin (6.1 g, 6 mmol) from Novabiochem. Corp. and then diisopropyl ethyl amine (DIEA) (26 mL, 150 mmol) were added. The mixture was agitated on a Rotovap over night with exclusion of air. Water (4 mL, 220 mmol) was added to the reaction mixture and the suspension was rotated for another 3 h. The resin was filtered, washed with DMF thoroughly, then with CH2CI2 and hexanes before vacuum drying.
IR(KBr): OH and NH at 3422 cnr1 (br) and 3535 cm"1 (shoulder), amide at 1652 cm-1.
EXAMPLE 45
Figure imgf000043_0001
Supported Diol SD 11
The same procedure described in Example 44 was employed with 10 g (6.9 mmol) of commercially available Wang resin (from Advanced Chemtech, Louisville, KY), 8.2 g (20.7 mmol) of the sulfoxyl-protected binaphthol acid chloride shown in Example 30, and 36 ml of DIEA. IR (KBr): OH at 3443 cm"1 (br) ester at 1678 cm"1 (s) .
EXAMPLE 46
Figure imgf000043_0002
Supported Diol SD12
The same procedure described in Example 44 was used using 6 g (7 mmol) of resin-supported benzyl alcohol, 8.3 g (21 mmol) of sulfoxyl-protected binaphthol acid chloride, and 6.1 ml of DIEA.
IR (KBr): OH at 3448 cm"1 (br) and 3247 cnr^br), ester at 1740 cm"1 (m). EXAMPLE 47
Figure imgf000044_0001
The resin-supported benzaldehyde described in Example 1 (407 mg, 0.5 mmol), 2-naphthol (576-mg, 2 mmol), glacial acetic acid (5 ml) , CHCL3 (1 ml) and hydrochloric acid (0.5 ml) were mixed with a vortexer for 5 days. The product was filtered, washed with aqueous THF, and then THF thoroughly before vacuum drying.
EXAMPLE 48
Figure imgf000044_0002
Supported Diol SD 14
2,4-Dimethylphenol (6.95 ml, 57.6 mmol) and resin-supported benzaldehyde (5.85 g, 7.2 mmol) were added to an ice cold aqueous sulfuric acid solution (H2SO4: 15 ml; H2O 12 ml). The reaction mixture was shaken until no starting material was observed in the IR spectrum. The resin was collected by filtration, washed with aqueous acetone, aqueous THF, and thoroughly with THF before vacuum drying. IR (KBr): OH at 3444 cm"1 (br, s).
EXAMPLE 49
Figure imgf000045_0001
Supported Ligand SL23
DIEA (1.7 ml, 10 mmol) was added to the suspension containing the resin- supported diol SD10 (1.33 g,1.0 mmol), 2.0 g (4.0 mmol) of 1 , 1 "-biphenyl-2,21- diylphosphorochloridite (50% weight in toluene) and 10 ml of dry toluene. The resulting mixture was vortexed at room temperature overnight. The brown product was filtered, washed with toluene, DMF, CH2CI2, hexanes and vacuum dried to lead to a fluffy solid.
IR(KBr): NH at 3433 cm"1 (m), amide at 1659 cnr^s) Elemental Analysis: C% 83.27, H% 6.61, N% 1.06, P% 2.12
EXAMPLE 50
Figure imgf000045_0002
Supported Ligand SL24
This ligand was prepared according to the same procedure as that of Example 49 using 1.46 g (4.0 mmol) of bis(2-isopropyl-5-methylphenyl)- phosphorochloridite.
IR (KBr): NH at 3431 cm"1 (m), amide at 1666 cm"1 (s). Elemental Analysis: C% 84.01, H% 7.07, N% 1.25, P% 1.53 EXAMPLE 51
Figure imgf000046_0001
Supported Ligand SL25
This product was synthesized following the procedure described for Example 49 using 1.34 g of bis(2-isopropylphenyl)phosphorochloridite and the same amounts of the resin, DIEA and toluene. IR (KBr): NH at 3432 cm"1 (s), amide at 1656 cm"1 (s) Elemental Analysis: C% 83.25, H% 6.97, N% 1.30, P% 1.56
EXAMPLE 52
Figure imgf000046_0002
Supported Ligand SL26
The same procedure described for Example 49 was followed using 0.718 ml (4 mmol) of chlorodiphenylphosphine. IR (KBr): NH at 3422 cm"1 (s), amide at 1656 cm"1 (s) Elemental Analysis: C% 85.94, H% 6.57, N% 1.28, P% 2.01
EXAMPLE 53
Figure imgf000047_0001
Supported Ligand SL27
This ligand was synthesized according to the same procedure as that for
Example 49 using 698 mg (4.0 mmol) of 1 ,2-phenylenephosphorochloridite.
IR (KBr): NH at 3437 cm"1 (m), amide at 1667 cm"1 (s)
Elemental Analysis: C% 82.24, H% 6.26, N% 1.19, P% 2.54 EXAMPLE 54
Figure imgf000047_0002
Supported Ligand SL28
This product was obtained following the same procedure described for
Example 49 using 2.17 g (1.0 mmol) of resin-supported diol SDl 1, 2 g of 1 , l'-biphenyl-2,2'-diylphosphorochloridite (50% weight in toluene, 4.0 mmol), 1.7 ml (10 mmol) of DIEA and 15 ml of anhydrous toluene. IR (KBr): 1743 cm"1 (vs), 1680 cm"1 (m). Elemental Analysis: C% 86.34, H% 7.00, P% 0.77
EXAMPLE 55
Figure imgf000048_0001
Supported Ligand SL29
This compound was made according to the procedure described for Example 49 using 2.17 g (1.0 mmol) ofsupported diol SDl 1, 884 mg (4.0 mmol) of the chlorodiphenylphosphine, 1.7 ml (10 mmol) and 15 ml of toluene. IR (KBr): 1744 cm"1 (m), 1680 cm"1 (s) Elemental Analysis: C% 86.55, H% 6.85, P% 0.59
EXAMPLE 56
Figure imgf000048_0002
Supported Ligand SL30
The same procedure described for Example 49 was followed using 2.17 g (1.0 mmol) of the resin SDl 1, 1.46 g (4.0 mmol) of bis(2-isopropyl-5-methyl- phenyl)phosphorochloridite, 1.7 ml (10 mmol) of DIEA and 15 ml of toluene. IR (KBr): 1744 cm"1 (vs), 1680 cm"1 (m) Elemental Analysis: C% 85.49, H% 7.04, P% 0.64
EXAMPLE 57
Figure imgf000049_0001
Supported Ligand SL31
The same procedure described for Example 49 was followed using 2.17 g (1.0 mmol) of supported diol SDl l, 1.34 g (4.0 mmol) of bis(2-isopropylphenyl)- phosphorochloridite, 1.7 ml (10 mmol) of DIEA and 15 ml of toluene. IR (KBr): 1722 cπr1 (w), 1678 cnr1 (m) Elemental Analysis: C% 86.51, H% 7.12, P% 0.42
EXAMPLE 58
Figure imgf000049_0002
Supported Ligand SL32
This ligand was made following same procedure described for Example 49 from 2.17 g (1.0 mmol) of the supported diol SDl l, 1.41 g ( 4.0 mmol) of bis(l-naphthyl)phosphorochloridite, 1.7 ml (10 mmol) of DIEA and 14 ml of toluene.
IR (KBr): 1726 cm"1 (m), 1674 cm"1 (w) Elemental Analysis: C% 84.97, H% 8.23, P% 0.55 EXAMPLE 59
Figure imgf000050_0001
Supported Ligand SL33
The same procedure described for Example 49 was followed using 2.17 g
(1.0 mmol) of the resin-supported diol SDl 1, 884 mg (4.0 mmol) of
1,2-phenylenephosphorochloridite, 1.7 ml (10 mmol) of DIEA and 14 ml of toluene. IR (KBr): 1726 cm"1 (m), 1674 cm"1 (w)
Elemental Analysis: C% 85.35, H% 6.57, P% 0.51
EXAMPLE 60
Figure imgf000050_0002
Supported Ligand SL34
The ligand was prepared following the same procedure described for Example 49 using 1.17 g (1.0 mmol) of supported diol SDl 2, 2 g (50%) weight in toluene) (4.0 mmol) of l,l'-biphenyl-2,2'-diylphosphorochloridite, 1.7 ml (10 mmol) of DIEA and 10 ml of toluene. IR (KBr): 1742 cm"1 (vs), 1680 cm-1 (m) Elemental Analysis: C% 84.69, H% 6.51, P% 1.03 EXAMPLE 61
Figure imgf000051_0001
Supported Ligand SL35
The same procedure described for Example 49 was followed using 1.17 g (1.0 mmol) of supported diol SD12, 884 mg (4.0 mmol) of ClPPh2, 1.7 ml (10 mmol) of DIEA and 10 ml of toluene. IR (KBr): 1741 cm"1 (vs)
Elemental Analysis: C% 85.45, H% 6.74, P% 1.14
EXAMPLE 62
Figure imgf000051_0002
Supported Ligand SL36
This product was rynthesized according to the same procedure as that for Example 49 was from 2.35 g (2.0 mmol) of the resin supported diol SD12, 2.91 g (8.0 mmol) of bis(2-isopropyl-5-methylphenyl)phosphorochloridite, 3.4 ml (10 mmol) of DIEA and 20 ml of toluene. IR (KBr): 1741 cπr1 (vs), 1684 cm"1 (w) Elemental Analysis: C% 84.62, H% 6.92, P% 0.79
Figure imgf000052_0001
Supported Ligand SL37
The same procedure described for Example 49 was followed using 2.17 g (2.0 mmol) of supported diol SDl 3, 2.91 g (8.0 mmol) of bis(2-isopropyl-5- methylphenyl)phosphorochloridite, 3.4 ml (10 mmol) of DIEA and 10 ml of toluene.
Elemental Analysis: C% 90.40, H% 7.26, P% 0.61
EXAMPLE 64
Figure imgf000052_0002
Supported Ligand 38
The same procedure described for Example 49 was followed using 2.17 g (2.0 mmol) of the resin SD13, 2.69 g (8.0 mmol) of bis(2-isopropylphenyl)- phosphorochloridite, 3.4 ml (10 mmol) of DIEA and 10 ml of toluene. Elemental Analysis: C% 90.10, H% 7.15, P% 0.48
Figure imgf000053_0001
Supported Ligand SL39
The ligand was prepared according to the procedure described for Example 49 from 2.17 g (2.0 mmol) of resin SDl 3, 2 g of 1 , 1 '-biphenyl-2,2'- diylphosphorochloridite (50 wt % solution in toluene, 8.0 mmol), 3.4 ml (10 mmol) of DIEA, and 20 ml of toluene. Elemental Analysis: C% 90.28, H% 6.97, P% 0.54
EXAMPLE 66
Figure imgf000053_0002
Supported Ligand SL40
The same procedure described for Example 49 was followed using 1.09 g (1.0 mmol) of resin SD13, 0.7 g (4.0 mmol) of 1,2-phenylenephosphorochloridite, 1.7 ml (10 mmol) of DIEA, and 10 ml of toluene. Elemental Analysis: C% 89.82, H% 6.35, P% 1.19
Figure imgf000054_0001
Supported Ligand SL 41
This product was obtained according to the same procedure described for Example 49 using 2.17 g (2.0 mmol) of resin SDl 3, 1.77 g (8.0 mmol) of PPh2Cl, 3.4 ml (10 mmol) of DIEA, and 10 ml of toluene. Elemental Analysis: C% 89.90, H% 7.46, P% 0.81
EXAMPLE 68
N = 1 -naphthyl
Figure imgf000054_0002
Supported Ligand SL42
The same procedure described for Example 49 was followed using 2.17 g
(2.0 mmol) of resin SD13, 2.82 g (8.0 mmol) of bis(l-naphthyl)phosphoro- chloridite, 3.4 ml (10 mmol) of DIEA, and 20 ml of toluene. Elemental Analysis: C% 90.34, H% 7.38, P% 0.43
EXAMPLE 69
N = 1-naphthyl
Figure imgf000055_0001
Supported Ligand 43
The same procedure described for Example 49 was followed using 1.79 g (1.35 mmol) of supported diol resin SD10, 1.9 g (5.4 mmol) of bis(l-naphthyl)- phosphorochloridite, 2.3 ml (10 mmol) of DIEA, and 15 ml of toluene. IR (KBr): NH at 3436 cm"1 (m), amide at 1668 cm"1 (s) Elemental Analysis: C% 83.99, H% 6.65, N% 1.22, P% 1.60
EXAMPLE 70
Figure imgf000055_0002
Supported Ligand SL44
The same procedure described for Example 49 was followed using 2.35 g (2.0 mmol) of the supported diol resin SD12, 2.69 g (8.0 mmol) of bis(2-isopropylphenyl)phosphorochloridite, 3.4 ml (10 mmol) of DIEA, and 20 ml of toluene.
IR (KBr): 1738 cm"1 (s), 1676 cm"1 (s) Elemental Analysis: C% 83.78, H% 6.49, P% 1.00
EXAMPLE 71
Figure imgf000056_0001
Supported Ligand SL45
The same procedure described for Example 49 was followed using 2.35 g (2.0 mmol) of resin SD12, 2.69 g (8.0 mmol) of 1 ,2-ppenylenephosphoro- chloridite, 3.4 ml (10 mmol) of DIEA and 20 ml of toluene. IR (KBr): 1739 cm"1 (s), 1656 cm"1 (s) Elemental Analysis: C% 83.00, H% 6.26, P% 1.70
EXAMPLE 72
1 -naphthyl
Figure imgf000056_0002
Supported Ligand SL46
The same procedure described for E90113-16 was followed using 2.35 g (2.0 mmol) of resin SD12, 2.82 g (8.0 mmol) of bis(l-naphthyl)phosphoro- chloridite, 3.4 ml (10 mmol) of DIEA, and 20 ml of toluene. IR (KBr): 1739 cm"1 (vs), 1681 cm"1 (m) Elemental Analysis: C% 84.38, H% 6.94, P% 1.25
EXAMPLE 73
1-naphthyl
Figure imgf000056_0003
Supported Ligand SL47
Following the same procedure as that described in Example 28, 1.0 g of supported diol SD4 was treated with bis(l-naphthyl)phosphorochloridite in pyridine. After ca. 3 days at room temperature the product was filtered and washed with CH2CI2 and THF before vacuum drying. EXAMPLE 74
Figure imgf000057_0001
Supported Ligand SL48
This supported bis(phosphite) was prepared following the same procedure described in Example 36 using bis(l-naphthyl)phosphorochloridite and supported diol SD6.
Elemental Analysis: C% 85.81, 85.99; H% 7.16; 7.39; P% 0.96 EXAMPLE 75
Figure imgf000057_0002
Supported Ligand SL49
This supported bis(phosphite was prepared from supported diol SD8 following the same general procedure described in Example 43-1 using bis(2-isopropyl-5-methylphenyl)phosphorochloridite. Elemental Analysis: C% 85.79, 85.55; H% 7.56; 7.48; P% 1.44
EXAMPLE 76
Figure imgf000057_0003
Supported Ligand SL50
This supported bis(phosphite) was prepared following the same procedure described in Example 36 using supported diol SD6 and l,l'-biphenyl-2,2'- diylphosphorochloridite. EXAMPLE 77
Figure imgf000058_0001
Supported Ligand SL51
This ligand was prepared according to the procedure described for Example 49 using 1.5 g (3.15 mmol) of supported diol SD14, 6.3 g (50% weight in toluene, 12.6 mmol) of l,l'-biphenyl-2,2'-diylphosphorochloridite, 5.5 ml of DIEA and 15 ml of anhydrous toluene. Elemental Analysis: C% 85.33, H% 7.11, P% 1.94
EXAMPLE 78
Figure imgf000058_0002
Supported Ligand SL52
This supported ligand was prepared according to the procedure described for Example 49 using 1.5 g (3.15 mmol) of supported diol SDH, 4.2 g (12.6 mmol) of bis(2-isopropylphenyl)phosphorochloridite, 5.5 ml of DIEA, and 15 ml of anhydrous toluene. Elemental Analysis: C%85.80, H% 7.67, P% 2.56
Figure imgf000059_0001
Supported Ligand SL53
This supported ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of resin SDH, 4.6 g (12.6 mmol) of bis(2-isopropyl-5-methylphenyl)phosphorochloridite, 5.5 ml of DIEA, and 15 ml of anhydrous toluene.
Elemental Analysis: C% 85.04, H% 7.80, P% 2.06
EXAMPLE 80
Figure imgf000059_0002
Supported Ligand SL54
This ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of resin SDH, 4.4 g (12.6 mmol) of bis(l-naphthyl)phosphorochloridite, 5.5 ml of DIEA and 15 ml of anhydrous toluene. Elemental Analysis: C% 85.94, H% 7.25, P% 1.91
Figure imgf000060_0001
Supported Ligand SL55
This supported ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of resin SDH, 2.8 g (12.6 mmol) of ClPPh2, 5.5 ml of DIEA and 15 ml of anhydrous toluene. Elemental Analysis: C% 87.65, H% 7.57, P% 2.17
EXAMPLE 82
Figure imgf000060_0002
Ligand SL
This supported ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of supported diol SDH, 2.2 g (12.6 mmol) of 1 ,2-phenylenephosphorochloridite, 5.5 ml of DIEA, and 15 ml of anhydrous toluene. Elemental Analysis: C% 84.16, H% 7.24, P% 2.41
EXAMPLE 83
Figure imgf000061_0001
Supported Ligand SL57
This ligand was prepared according to the procedure described in
Example 49 using 1.5 g (3.15 mmol) of the resin, 3.88 g (12.6 mmol) of bis(2-ethylphenyl)phosphorochloridite, 5.5 ml of DIEA and 15 ml of anhydrous toluene. Elemental Analysis: C% 84.45, H% 7.09, P% 3.09
EXAMPLE 84
Figure imgf000061_0002
Supported Ligand SL58
This ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of the supported diol SDH, 3.88 g (12.6 mmol) of bis(2,3-dimethylphenyl)phosphorochloridite, 5.5 ml of DIEA, and 15 ml of anhydrous toluene. Elemental Analysis: C% 84.97, H% 7.16, P% 2.98 EXAMPLE 85
Figure imgf000062_0001
Supported Ligand SL59
This ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of the resin SDH, 4.23 g (12.6 mmol) of bis(2,3,5-trimethylphenyl)phosphorochloridite, 5.5 ml of DIEA, and 15 ml of anhydrous toluene.
Elemental Analysis: C% 84.65, H% 7.62, P% 2.70
EXAMPLE 86
Figure imgf000062_0002
Supported Ligand SL60
This ligand was prepared according to the procedure described in Example 49 using 1.5 g (3.15 mmol) of the resin SDH, 4.60 g (12.6 mmol) of bis(2-tertbutylphenyl)phosphorochloridite, 5.5 ml of DIEA and 15 ml of anhydrous toluene. Elemental Analysis: C% 85.83, H% 7.68, P% 2.40 EXAMPLE 87
Figure imgf000063_0001
Supported Ligand SL61
This ligand was prepared according to the procedure described in
Example 49 using 1.5 g (3.15 mmol) of the resin SDH, 4.95 g (12.6 mmol) of the corresponding bis(2-tertbutyl-4-methylphenyl)phosphorochloridite, 5.5 ml of
DIEA and 15 ml of anhydrous toluene. Elemental Analysis: C% 86.19, H% 7.80, P% 2.19
EXAMPLE 88 The following is a general procedure for the preparation of supported nickel catalysts using the supported ligands described in previous examples. Information in Table 2 shows the generality of this procedure. The appropriate supported ligand (0.5-1.0 g, ca. 0.5 mmol) is suspended in
15 mL of toluene in a sintered glass filter. A slight molar excess of Ni(COD)2 is added and the mixture stirred with a spatula, usually for less than 1 min. The supernatant was then removed by suction filtration, washed with toluene (3x), THF (3x), and pentane (3x), before drying under vacuum. This yielded the supported catalyst, useful for olefin hydrocyanation. The product was further characterized by conversion to the supported nickel carbonyl complex by treatment of a toluene slurry of the supported Ni(COD) catalyst with CO.
TABLE 2
Supported NiCCOϋ) Catalysts Prepared
Example Supported Ligand Used Supported Catalyst ID Ni-CO Infrared
88-1 SL23 SC25 2079w, 2045m, 1992s
88-2 SL24 SC26 2078w, 2043m, 1991s
88-3 SL25 SC27 2084w, 2045m, 1995s
88-4 SL26 SC28 2062w, 2012m, 1959s
88-5 SL27 SC29 2060m, 2010s
88-6 SL28 SC30 2049m, 1997s
Figure imgf000064_0001
Example Supported Ligand Used Supported Catalyst ID Ni-CO Infrared
88-7 SL29 SC31 2019m, 1964s
88-8 SL30 SC32 2041m, 1990s
88-9 SL31 SC33 2085m, 2012s
88-10 SL32 SC34 2086w, 2047m, 2007s
88-11 SL33 SC35 2062m, 2013s
88-12 SL34 SC35 2047m, 1994s
88-13 SL35 SC37 2073m, 1997s, 1964s
88-14 SL36 SC38 2082m, 2054m, 2008s, 1984s
88-15 SL37 SC39 2082m, 2013s
88-16 SL39 SC40
88-17 SL40 SC41 2059m, 2009s
88-18 SL41 SC42 2072w, 2010m, 1961s
88-19 SL43 SC43 2048m, 1998s
88-20 SL44 SC44 2085m, 2065m, 2010s
88-21 SL45 SC45
88-22 SL47 SC46 2086m, 2043m, 1991s
88-23 SL49 SC48 2080m, 2036m, 2003s
88-24 SL50 SC49 2083w, 2041m, 2017w, 1990s
88-25 SL51 SC50 2084vw, 2042s, 1989vs
88-26 SL52 SC51 2083vw, 2039s, 2013m, 1986s
88-27 SL53 SC52 2082m, 2040m, 2009s, 1981s
88-28 SL54 SC53 2083m, 2041m, 2022s, 1988s
88-29 SL55 SC54 2073m, 2012s, 1958s
88-30 SL56 SC55 2058m, 2010s
88-31 SL42 SC56
88-31 SL46 SC57
EXAMPLE 89
Supported ligand SL33 (0.489 g) was placed in 5 mL of toluene. To this solution was added 0.268 g of Ni(oTTP)3 (oTTP = ortho-tritolylphosphite). The mixture was stirred occasionally with a spatula and then filtered. The resulting orange, nickel supported catalyst SC58 was washed with toluene (3x) and CH2Cl2(3x) before vacuum drying.
A 50 mg aliquot of this sample was placed in 5 mL of toluene and then CO was bubbled through the solution at 1 atm. The orange color immediately dissipated to give a beige product. The resin was filtered, washed with solvent (toluene, CH2CI2) and dried in vacuum. Infrared analysis showed a single Ni-CO absorption at 2011 cm-1.
EXAMPLE 90 Butadiene Hydrocyanation with Supported Nickel Catalysts The resin supported ligand and nickel were charged as either the Ni(COD) loaded material, prepared as described above, or by separate addition of Ni(COD)2 and ligand. The amount of supported ligand charged was targeted at 5.4 micromoles and a 1 : 1 ratio of chelate ligand to nickel, except where noted. 5 mL of solvent (toluene or tetrahydrofuran) was used as the reaction solvent, and the experiments were conducted at 80°C. The reaction mixtures are made to a target HCN/Ni ratio of 500 and to a target HCN/BD ratio of 0.89. The resulting concentrations of HCN and BD are 2.3 M and 2.64 M, respectively. Valeronitrile acts as the internal standard. "Total PN, %" represents the sum of %3PN and %2M3. Aliquots were removed at the indicated reaction times for gas chromatographic analysis. As used below in Table 3, pTTP = para- tritolylphosphite.
TABLE 3 Butadiene Hydrocyanation
Time,
Example Supported Ligand/Catalyst hours Total PN, % 3PN/2M3 Ratio
Comparative pTTP + Ni(COD)2 1.5 10.7 0.51
Example 3.25 16.4 0.49
90-1 SL1 2.0 23.0 1.45
3.0 27.4 1.29
90-2 SL3-1 2.0 12.5 0.81
3.0 13.4 0.77
90-3 SL3-2 2.0 24.2 0.73
3.0 40.1 0.77
90-4 SL2 2.0 0.1 -
3.0 2.6 0.88
90-5A SL3/SC4 2.0 33.7 0.71
3.0 40.3 0.67
90-5B SL3/SC4 repeat with 2.0 2.2 0.83 half the Ni loading 3.0 16.3 0.75
90-6 SL4 1.5 0.8 0.65
90-7 SL50 1.5 3.9 0.75
3.0 12.1 0.73
90-8 SL7 1.5 0.8 0.9
2.8 1.2 0.87
90-9 SL8 1.5 0.3 1.96
2.8 0.6 2.02 Time,
Example Supported Ligand/Catalyst hours Total PN, % 3PN/2M3 Ratio
90-10 SL9 1.5 0.3 1.6
3.0 0.3 1.53
90-1 1 SL10 1.5 0.2 2.63
3.0 0.2 2.63
90-12 SL12 3.0 22.4 1.72
90-13 SL13 1.5 2.3 0.71
3.0 3.7 0.69
90-14 SL15 1.5 1.3 0.57
3.0 1.3 0.57
90-15 SL15 1.5 1.7 0.57
3.0 2.1 0.61
90-16 SL14 1.5 3.9 0.73
3.0 12.0 0.71
90-17 SL14 1.5 0.4 1.26
3.0 6.0 0.72
90-19 SL16 1.5 9.5 0.81
3.0 10.8 0.78
90-20 SL16 1.5 9.6 0.79
3.0 18.3 0.78
90-21 SL18 1.5 2.0 0.90
3.0 3.3 0.87
90-22 SL17 1.5 1.3 0.84
3.0 2.2 0.77
90-23 SL19 1.5 0.6 0.81
3.0 0.9 0.67
90-24 SL20 1.5 0.0 -
3.0 0.4 0.73
90-25 SL21 1.5 1.7 0.86
3.0 3.0 0.79
90-26 SL22 1.5 0.0 -
3.0 0.6 0.79
90-27 SL5 1.5 52.7 1.10
90-28 SL47/SC 1.5 1.1 0.83
3.0 0.7 1.04
90-29 SL48 1.5 2.3 1.41
3.0 2.5 1.44
90-30 SL49 1.5 2.7 1.02
3.0 5.1 1.02
90-31 SL23/SC25 1.58 13.3 0.94
3.0 11.7 0.97
90-32A SL26/SC28 1.58 14.7 0.39
3.0 10.7 0.40 Time,
Example Supported Ligand/Catalyst hours Total PN, % 3PN/2M3 Ratio
90-32B SL26/SC28 1.5 5.3 0.40
2.0 9.3 0.41
90-33A SL27/SC29 1.58 7.2 3.6
3.0 3.7 3.5
90-33B SL27/SC29 1.5 2.9 3.42
3.0 2.0 3.29
90-34 SL24/SC26 1.58 1.6 0.47
3.0 9.3 0.49
90-35A SL25/SC27 1.58 15.7 0.65
3.0 12.3 0.63
90-35B SL25/SC27 1.5 10.1 0.59
3.0 11.9 0.58
90-36A SL32/SC34 1.67 20.5 1.09
3.0 23.1 1.09
90-36B SL32/SC34 1.5 5.5 0.85
3.0 6.3 0.82
90-37A SL31/SC33 1.67 0.4 0.83
3.0 0.4 0.75
90-37B SL31/SC33 1.5 0.5 0.63
3.0 0.5 0.68
90-38A SL30/SC32 1.67 36.9 1.42
90-38B SL30/SC32 1.5 8.2 0.44
3.0 6.4 0.44
90-38C SL30/SC32 1.5 6.4 0.46
3.0 7.8 0.45
90-38D SL30/SC32 1.5 5.1 0.38
3.0 5.9 0.38
90-38E SL30/SC32 1.5 6.9 0.44
3.0 7.1 0.44
90-39 SL29/SC31 1.67 0.5 0.63
3.0 3.8 0.84
90-40A SL28/SC30 1.67 5.2 0.84
3.0 2.5 0.39
90-40B SL28/SC30 1.5 15.0 0.74
3.0 18.6 0.71
90-41 A SL37/SC39 1.5 1.8 0.55
3.0 2.7 0.57
90-4 IB SL37/SC39 1.5 3.1 0.54
3.0 4.0 0.53
90-42A SL41/SC42 1.5 3.7 0.44
3.0 4.3 0.46
90-42B SL41/SC42 1.5 4.0 0.44 3.0 3.4 0.46
90-43A SL34/SC36 1.5 20.4 0.69
3.0 25.1 0.65
90-43B SL34/SC36 1.5 28.7 0.69
3.0 28.2 0.64
90-43C SL34/SC36 1.5 16.8 0.70
3.0 27.0 0.63
90-44A SL35/SC37 1.5 7.7 0.32
3.0 8.5 0.32
90-44B SL35/SC37 1.5 9.2 0.31
3.0 8.7 0.31
90-45 SL43/SC43 1.5 17.9 0.95
3.0 26.5 0.89
90-46 SL44/SC44 1.5 2.5 0.44
3.0 2.9 0.44
90-47 SL36/SC38 1.5 7.1 0.37
3.0 8.7 0.36
90-48 SL51/SC50 1.5 29.8 1.60
3.0 30.7 1.61
90-49 SL52/SC51 1.5 15.8 0.64
3.0 18.8 0.65
90-50 SL53/SC52 1.5 16.7 0.53
3.0 14.5 0.59
90-51 SL54/SC52 1.5 21.2 1.06
3.0 22.9 1.09
90-52 SL55/SC54 1.5 46.7 0.43
3.0 46.3 0.44
90-53 SL56/SC55 1.5 0.9 1.16
3.0 1.0 1.24
EXAMPLE 91 Butadiene Hydrocyanation - Vapor Phase An empty 0.24 inch (0.64 cm) diameter, 15 inch (37.5) long stainless steel tubular reactor was placed in a nitrogen filled glove box. A plug of glass wool was placed in the bottom end of the reactor, followed by the amount and type of supported catalyst as shown in Table 4. A thermocouple was inserted into the top of the reactor. Both ends of the reactor were sealed with metal fittings, and the reactor was removed from the glove box and connected to stainless steel reactor feed lines purged with nitrogen. The feed streams consisted of approximately 2.2 vol %> gaseous HCN in nitrogen and gaseous butadiene (BD). The reactor was heated in a split tube furnace to H5°C. Gaseous effluent from the reactor passed through a heated sampling valve which permitted periodic on-line gas chromatographic analyses of products. GC analyses were done on a 30 m DB-23 capillary column of a 0.32 mm internal diameter, supplied by J&W Scientific, Folsom, California. The stationary phase was cyanopropyl (50%) methylpolysiloxane. Table 4 shows the specific reaction conditions and summarizes the results. Percent selectivity to (3PN + 4PN + 2M3BN) was determined as (GC area % for 3PN + 4PN + 2M3BN)/GC are % for PNs) x 100.
TABLE 4
Butadiene Hydrocyanation - Vapor 1 Phase (All experiments conducted at 145 °C)
Selectivity
Example Supported Catalyst Feed mmol/hour Elapsed Time, h GC Area % PNs DNs % 3PN Ratio
2M3 Kaπ°
91-1 SCI BD 1.13 0.5 8.2 100 1.4
0.87 g HCN 0.28 3.5 9.4 100 4.5
6.5 9.4 100 4.0
9.5 9.8 100 1.8
12.5 10.4 100 0.9
15.5 4.2 100 0.8
17.5 3.1 100 0.8
91-2 SC4 BD 1.13 2.75 1 1.5 88.7 12.5
0.96 g HCN 0.28 8.75 11.1 0.22 96.3 10.4 13.75 10.8 0.23 100 7.6 19.75 10.9 0.31 100 4.2 25.75 10.2 0.35 100 2.9 31.75 10.0 0.33 100 2.4 37.75 10.0 0.24 100 2.1 43.75 9.7 0.28 100 1.9 49.75 9.3 0.28 100 1.8 55.75 9.3 0.26 100 1.7 61.75 9.0 0.23 100 1.6 67.75 8.6 0.26 100 1.5
91-3 SC5 BD 1.13 1 10.8 79.4 13.0
0.89 g HCN 0.28 3 12.6 86.9 11.8
9 12.1 95.0 11.1
15 12.5 95.0 9.3
21 13.8 95.1 1.7
27 13.4 95.0 1.5
33 13.3 0.24 94.8 1.3
39 12.5 94.8 1.2
45 11.7 94.9 1-2
51 10.4 94.7 1.1
EXAMPLE 92 3-Pentenenitrile Hydrocyanation with Supported Nickel Catalysts The resin supported ligand and nickel were charged as the preformed . nickel-loaded, supported catalyst. The amount of supported ligand charged was 8.5 micromoles, and a 1:1 ratio of ligand to nickel was used. ZnCl2 was added as a promoter, using a ratio 1 : 1 ZnCl2:Ni. To the catalyst and promoter was added 5 mL of a 40 mole % solution in HCN in trans -3 -pentenenitrile. The sample was analyzed by gas chromatography after 24 h at 25 °C. In the Table below, % HCN conversion refers to the amount of HCN converted to hydrocyanation products, and % ADN distribution refers to the per cent amount of ADN relative to all isomeric dinitrile products (% ADN Distribution = 100 x ADN/(ADN + MGN + ESN)). ADN refers to adiponitrile, MGN refers to methylglutaronitrile, and ESN refers to ethylsuccinonitrile. A comparative example using a commercial homogeneous catalyst based on pTTP (pTTP is para-tritolylphosphite) and nickel (0) is provided in the Table below, showing that the supported catalysts perform better than current commercial soluble catalysts.
TABLE 5
Example Ligand Catalyst HCN Conversion ADN Distribution
(%) (%)
Comparative pTTP pTTP + 5.6 63.3
Example Ni(COD)2
92-1 SL12 SC14 69.3 66.6
92-2 SL41 SC42 32.0 80.1
92-3 SL28 SC30 23.5 67.9
92-4 SL43 SC43 20.8 63.5
92-5 SL25 SC27 15.5 80.1
92-6 SL35 SC37 14.0 74.7
92-7 SL32 SC34 13.5 86.9
92-8 SL32 SC34 5.0 80.1
92-9 SL26 SC28 12.8 75.7
92-10 SL37 SC39 12.5 87.9 Example Ligand Catalyst HCN Conversion ADN Distribution
(%1 (%)
92-11 SL27 SC29 11.3 69.2
92-12 SL44 SC44 10.0 87.0
92-13 SL30 SC32 8.0 85.4
92-14 SL26 SC32 8.3 87.2
92-15 SL51 SC50 83.5 59.0
92-16 SL40 SC41 73.5 59.4
92-17 SL52 SC51 48.3 77.2
92-18 SL45 SC45 29.0 71.6
92-19 SL42 SC56 25.8 42.2
92-20 SL39 SC40 23.5 64.2
92-21 SL46 SC57 17.8 51.7
92-22 SL53 SC52 14.3 84.2
92-23 SL54 SC53 14.0 73.9
92-24 SL55 SC54 10.5 85.8
92-25 SL56 SC55 8.8 61.5
92-26 SL33 SC35 17.8 40.3
92-27 SL33 SC58 7.8 75.8
EXAMPLE 93
Olefin Hydrogenation ■ - General Procedure
A vial is charged with 2 mmol of olefin, the supported rhodium catalyst (0.014 mmol Rh), and 2 mL of THF. The vial is placed in a shaker tube and then treated with hydrogen at the desired temperature, pressure, and time. A 100 μL aliquot of the supernatant is removed, diluted with 500 μL THF, and analyzed by GC. The results are provided in Table 6.
EXAMPLE 94 Olefin Hydrogenation - Catalyst Recycle/Metal Leaching 100 mg of the rhodium-loaded resin from Example 8 was charged to a glass pressure vessel. 1 mL of cyclooctene and 10 mL of THF were added. The vessel was pressurized with 50 psig H2 and heated to 50°C, with stirring. After 2 h the pressure dropped to 25 psi. The liquid supernatant was removed with a syringe. GC analysis showed 100% conversion of the cyclooctene to cyclooctane. Analysis of the supernatant further showed 3 ppm Rh. Fresh cyclooctene (1 mL) and THF (10 mL) were added to the remaining rhodium-loaded resin remaining in the reactor and the hydrogenation process was repeated.
TABLE 6
Olefin Hydrogenation with Resin Supported Rhodium Complexes
Pressure Temp Conversion
Example Substrate Catalyst (psig) (°C) Time Product (GC Area %)
93-1 cis-cyclooctene SC2 100 50 3 cyclooctane 100
93-2 cis-cyclooctene SC2 50 21 0.75 cyclooctane 11
93-3 cis-cyclooctene SC3 50 50 0.75 cyclooctane 21
93-4 cis-cyclooctene SC2 50 50 2 cyclooctane 100
93-5 styrene SC2 100 50 3 ethylbenzene 14
93-6 a-methylstyrene SC2 100 50 3 isopropylbenzene 12
93-7 trans- SC2 100 50 3 PhCH2CH(CH3)(CO2CH3) 2
PhCHC(CH3)(CO2CH3)
This overall process was repeated an additional two times and the results are shown in Table 7. The final example shows that metal leaching is below the detection limits and yet catalyst activity is maintained. To the supernatant from the final cycle was added 0.725 g of norbomylene. The resulting solution was treated with 50 psi H2 at 50°C. After 2 h no gas uptake was detected. GC analysis of the solution showed no hydrogenation of norbomylene to norbomane had occurred. This result shows that hydrogenation activity occurs with the rhodium-supported catalyst and can not be attributed to metal leached into solution. These results show that the resins of this invention are resistant to metal leaching and are amenable to recycle.
TABLE 7
Cyclooctene Hydrogenation/Catalyst Recycle and Metal Leaching
Conversion Turnovers [Rh] Supernatant Cycle # % (2 h) mol COE/mol Rh p_p_m
1 100 416 3
2 96 399 1
3 70 291 1
4 81 337 undetected
EXAMPLE 95 Hydrosilation Catalysis - General Procedure
A vial was charged with 9.5 mg of the supported rhodium catalyst SC3, corresponding to 0.18 μmole of rhodium. The vial was then charged with 12 mg (0.1 mmol) of Et3SiH, 24 mg (0.2 mmol) of acetophenone, and 1 mL of toluene. The vial was then heated for the indicated time and temperature. The supernatant was then analyzed by GC, which showed a 36% conversion to
PhCH(CH3)OSiE-3. The remaining examples shown in Table 8 were performed in a similar manner. The last entry in this table, Comparative Example 95-14 shows the results obtained with a known homogeneous catalyst for this reaction, RhTPP3Cl (TPP = triphenylphosphine). TABLE 8 Hydrosilation with Resin-Supported Rhodium Catalysts
Temp Time Conversion
Reference Catalyst Silane Substrate °C h Product GC Area %
95-1 SC2 E_3SiH acetophenone 60 0.3 5.2
95-2 SC2 acetophenone 85 30
Figure imgf000076_0001
o. 95-3 SC2 1-hexene 85 CH3(CH2)5SiEt3 20 ^
95-4 SC2 Me2PhSiH 85 CH3(CH2)5SiMe2Ph 100
95-5 SC2 E-3SiH phenylacetylene 85 2 .SiEt,
V
Ph
Ph SiEt3
74
Figure imgf000076_0002
Temp ) Time Conversion
Reference Catalyst Silane Substrate °C h Product GC Area %
95-6 SC3 Et3SiH acetophenone 85 0.25 0 Q -CH(CH3)OSiEt3
Figure imgf000077_0001
95-8 SC3 1-hexene 85 0.25 CH3(CH2)5SiEt3 0
t_Λ 95-9 SC3 85 2 2
95-10 SC3 Me2PhSiH 85 0.25 CH3(CH2)5SiMe2Ph 0.8
95-11 SC3 π 85 2 88
95-12 SC3 phenylacetylene 85 0.25
Figure imgf000077_0002
Ph / — Si.Et,
13
Figure imgf000077_0003
Temp Time Conversion
Reference Catalyst Silane Substrate °C h Product GC Area %
95-13 SC3 phenylacetylene 85 0.25 77
95-14 RhTPP3Cl Et3SiH acetophenone 60 0.25 38
(Compar.
Figure imgf000078_0001
Example)
-4
Although particular embodiments of the present invention have been described in the foregoing description, it will be understood by those skilled in the art that the invention is capable of numerous modifications, substitutions and rearrangements without departing from the spirit or essential attributes of the invention. Reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.

Claims

Claims:
1. A supported diol selected from the group consisting of the following structures:
Figure imgf000080_0001
SDl
Figure imgf000080_0002
SD5, 12
Figure imgf000080_0003
SD7, 8, 9
Figure imgf000080_0004
SDll SD10
Figure imgf000081_0001
SDl 3 SD14 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):
Sup
X,P0' OPX,
(2)
wherein:
Q is any organic fragment which binds a OPX2 moiety to the support (Sup); and
X is an alkoxide, aryloxide, alkyl, or aryl.
5. The ligand according to Claim 2 wherein the support is an organic polymer resin.
6. The ligand according to Claim 2 wherein X is aryloxide or aryl.
7. A supported catalyst composition according to formula (3):
Figure imgf000081_0002
wherein: Q is any organic fragment which binds a OPX2 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 process utilizing the catalyst composition of Claim 7.
12. The process of Claim 11 wherein the process is hydrogenation or hydrosilation.
13. 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):
Sup
X2P -PX,
* '
(3)
wherein:
Q is any organic fragment which binds a OPX2 moiety to the support
(Sup).; X is an alkoxide, aryloxide, alkyl or aryl; and M is nickel.
14. The process of Claim 13 wherein the support is an organic polymer resin.
15. The process of Claim 13 wherein X is aryloxide or aryl.
16. The process of Claim 13 wherein the reaction is run in the liquid phase.
17. A hydrocyanation process comprising reacting an acyclic aliphatic diolefinic compound with a source of HCN in the presence of a supported catalyst composition according to formula (3): Sup
./ \,
X^P . PX
M
(3)
wherein:
Q is any organic fragment which binds a OPX2 moiety to the support (Sup).;
X is an alkoxide, aryloxide, alkyl or aryl; and M is nickel.
18. The process of Claim 17 wherein the support is an organic polymer resin.
19. The process of Claim 17 wherein X is aryloxide or aryl.
20. The process of Claim 17 wherein the reaction is run in the liquid phase.
21. The process of Claim 17 wherein the reaction is run in the vapor phase.
22. The process of Claim 17 wherein the diolefinic compound is 1,3- butadiene.
23. The ligand according to Claim 4 wherein the PX moiety forms a ring and X2 is a di(alkoxide), di(aryloxide), di(alkyl) or di(aryl).
24. The catalyst composition according to Claim 7 wherein the PX2 moiety forms a ring and X2 is a di(alkoxide), di(aryloxide), di (alkyl) or di(aryl).
PCT/US1998/015199 1997-07-29 1998-07-23 Supported diols and supported bis(phosphorus) ligands WO1999006146A2 (en)

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999062855A1 (en) * 1998-05-29 1999-12-09 E.I. Du Pont De Nemours And Company Hydroformylation of olefins using supported bis(phosphorus) ligands
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US7977502B2 (en) 2008-01-15 2011-07-12 Invista North America S.A R.L. Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile
US8088943B2 (en) 2008-01-15 2012-01-03 Invista North America S.A R.L. Hydrocyanation of pentenenitriles
US8101790B2 (en) 2007-06-13 2012-01-24 Invista North America S.A.R.L. Process for improving adiponitrile quality
US8178711B2 (en) 2006-03-17 2012-05-15 Invista North America S.A R.L. Method for the purification of triorganophosphites by treatment with a basic additive
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US8338636B2 (en) 2009-08-07 2012-12-25 Invista North America S.A R.L. Hydrogenation and esterification to form diesters
US8373001B2 (en) 2003-02-10 2013-02-12 Invista North America S.A R.L. Method of producing dinitrile compounds
JP2014169259A (en) * 2013-03-05 2014-09-18 Toyoji Shimada Octahydrobinaphthyl derivative
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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US20030135014A1 (en) * 2001-11-26 2003-07-17 Radu Nora S. Polymeric, phosphorus-containing compositions and their use in hydrocyanation, isomerization and hydroformylation reactions
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US7709674B2 (en) 2006-07-14 2010-05-04 Invista North America S.A R.L Hydrocyanation process with reduced yield losses
US8906334B2 (en) 2007-05-14 2014-12-09 Invista North America S.A R.L. High efficiency reactor and process
JP5823967B2 (en) 2009-10-16 2015-11-25 ダウ テクノロジー インベストメンツ リミティド ライアビリティー カンパニー Gas-phase hydroformylation process
US9126906B2 (en) * 2012-02-21 2015-09-08 Celgene Corporation Asymmetric synthetic processes for the preparation of aminosulfone compounds

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0040891A1 (en) * 1980-05-28 1981-12-02 Stamicarbon B.V. Process and catalyst for performing hydroformylation reactions
US4897197A (en) * 1987-06-17 1990-01-30 Dow Corning Corporation Using liquid chromatography packing materials
US4937292A (en) * 1986-07-09 1990-06-26 Solavchem Enterprises Inc. Photosensitizer
EP0472071A1 (en) * 1990-08-21 1992-02-26 BASF Aktiengesellschaft Hydroformylation rhodium catalysts with biphosphite ligands
WO1996016022A1 (en) * 1994-11-18 1996-05-30 E.I. Du Pont De Nemours And Company Catalyzed vapor phase hydrocyanation of diolefinic compounds

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3496215A (en) * 1965-11-23 1970-02-17 Du Pont Hydrocyanation of olefins using selected nickel phosphite catalysts
US3655723A (en) * 1969-10-31 1972-04-11 Du Pont Hydrocyanation of olefins
US3631191A (en) * 1970-04-08 1971-12-28 Du Pont Synthesis of zero valent nickel-tetrakis triaryl phosphite complexes
US3766237A (en) * 1972-01-25 1973-10-16 Du Pont Hydrocyanation of olefins
EP0496700B1 (en) * 1991-01-25 1996-03-06 Ciba-Geigy Ag Diphosphines containing silane groups, immobilized diphosphines and their use as hydrogenation catalysts
TW213465B (en) * 1991-06-11 1993-09-21 Mitsubishi Chemicals Co Ltd
US5360938A (en) * 1991-08-21 1994-11-01 Union Carbide Chemicals & Plastics Technology Corporation Asymmetric syntheses
CA2177135C (en) * 1993-11-23 2005-04-26 Wilson Tam Processes and catalyst compositions for hydrocyanation of monoolefins
US5512695A (en) * 1994-04-14 1996-04-30 E. I. Du Pont De Nemours And Company Bidentate phosphite and nickel catalyst compositions for hydrocyanation of monoolefins
US5512696A (en) * 1995-07-21 1996-04-30 E. I. Du Pont De Nemours And Company Hydrocyanation process and multidentate phosphite and nickel catalyst composition therefor
TW343195B (en) * 1996-03-15 1998-10-21 Dsm Nv Process to prepare a terminal aldehyde

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0040891A1 (en) * 1980-05-28 1981-12-02 Stamicarbon B.V. Process and catalyst for performing hydroformylation reactions
US4937292A (en) * 1986-07-09 1990-06-26 Solavchem Enterprises Inc. Photosensitizer
US4897197A (en) * 1987-06-17 1990-01-30 Dow Corning Corporation Using liquid chromatography packing materials
EP0472071A1 (en) * 1990-08-21 1992-02-26 BASF Aktiengesellschaft Hydroformylation rhodium catalysts with biphosphite ligands
WO1996016022A1 (en) * 1994-11-18 1996-05-30 E.I. Du Pont De Nemours And Company Catalyzed vapor phase hydrocyanation of diolefinic compounds

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
B. ALTAVA ET AL.: "Polymer-Grafed Ti-TADDOL Complexes. Preparation and Use as Catalysts in Diels-Alder Reactions" J. ORG. CHEM., vol. 62, 1997, pages 3126-3134, XP002080846 cited in the application *
C. C. LEZNOFF AND J. Y. WONG: "The Use of Polymer Supports in Organic Synthesis. III: Selective Chemical Reactions on One Aldehyde Group of Symmetrical Dialdehydes" CANADIAN JOURNAL OF CHEMISTRY, vol. 51, 1973, pages 3756-3764, XP002080845 cited in the application *

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WO1999006146A3 (en) 1999-04-08
HK1026383A1 (en) 2000-12-15
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DE69833807D1 (en) 2006-05-11
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EP1003607A2 (en) 2000-05-31

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