Title of Invention	CATALYST SYSTEM SUITABLE FOR THE HYDROCYANATION OF OLEFINICALLY UNSATURATED COMPOUNDS
Abstract	A system which is suitable as a catalyst for the hydrocyanation of olefinically unsatu¬rated compounds and comprises a) Ni(0) b) a compound which complexes Ni(0) as a ligand and contains trivalent phospho¬rus, c) a Lewis acid and d) a compound of the formula M Rn where M: Al or Ti R: identical or different monovalent alkoxy radicals, in which case a plurality of alko-xy radicals may be bonded together, and additionally, in the case that M = Al, R may be identical or different monovalent alkyl radicals, in which case a plurality of alkyl radicals may be bonded together or one or more alkyl radicals may be bonded to one or more of the abovementioned alkoxy radicals, n: valency of M, and processes for hydrocyanating an olefinically unsaturated compound in the pres¬ence of such a system.

Title of Invention

CATALYST SYSTEM SUITABLE FOR THE HYDROCYANATION OF OLEFINICALLY UNSATURATED COMPOUNDS

Abstract

A system which is suitable as a catalyst for the hydrocyanation of olefinically unsatu¬rated compounds and comprises a) Ni(0) b) a compound which complexes Ni(0) as a ligand and contains trivalent phospho¬rus, c) a Lewis acid and d) a compound of the formula M Rn where M: Al or Ti R: identical or different monovalent alkoxy radicals, in which case a plurality of alko-xy radicals may be bonded together, and additionally, in the case that M = Al, R may be identical or different monovalent alkyl radicals, in which case a plurality of alkyl radicals may be bonded together or one or more alkyl radicals may be bonded to one or more of the abovementioned alkoxy radicals, n: valency of M, and processes for hydrocyanating an olefinically unsaturated compound in the pres¬ence of such a system.

Full Text	System suitable as a catalyst for the hydrocyanation of olefinically unsaturated com-)ounds The present invention relates to a system which is suitable as a catalyst for the hydro- cyanation of olefinically unsaturated compounds and comprises a) Ni(0) b) a compound which complexes Ni(0) as a ligand and contains trivalent phospho-10 rus, c) a Lewis aC1d and 15 d) a compound of the formula M Rn where 20 M: Al or Ti R: identical or different monovalent alkoxy radicals, in which case a plurality of alko- xy radicals may be bonded together, and additionally, in the case that M = Al, R may be identical or different monovalent alkyl radicals, in which case a plurality 25 of alkyl radicals may be bonded together or one or more alkyl radicals may be bonded to one or more of the abovementioned alkoxy radicals, n: valency of M. 30 In addition, it relates to a process for hydrocyanating an olefinically unsaturated com¬pound in the presence of such a system. Processes for hydrocyanating an olefinically unsaturated nitrile, in particular the prepa¬ration of adipodinitrile by hydrocyanating an olefinically unsaturated compound such as 35 2-C1s-pentenenitrile, 2-trans-pentenenitrile, 3-C1s-pentenenitrile, 3-trans-pentenenitrile, 4-pentenenitrile, E-2-methyl-2-butenenitrile, Z-2-methyl-2-butenenitrile, 2-methyl-3-butenenitrle or mixtures thereof, in the presence of a catalyst system comprising a Lewis aC1d and a complex containing a phosphorus compound suitable as a ligand, such as a monodentate, preferably multidentate, in particular bidentate, compound 40 which coordinates to a central atom via a phosphorus atom which may be present as a phosphine, phosphite, phosphonite or phosphinite or mixture thereof, and a central 2- atom, preferably nickel, cobalt or palladium, in particular nickel, more preferably in the form of nickel(O), are known, for example from US 3,496,217, US 3,496,218, US 4,705,881, US 4,774,353, US 4,874,884, US 5,773,637, US 6,127,567, US 6,171,996 B1 and US 6,380,421 B1. It is an object of the present invention to provide a system which is suitable as a cata¬lyst for the hydrocyanation of olefinically unsaturated compounds and exhibits an im¬proved space-time yield of hydrocyanation products compared to the known systems. We have found that this object is achieved by the system defined at the outset and by a process for hydrocyanating an olefinically unsaturated compound in the presence of such a system. The preparation of Ni(0)-containing catalyst systems is known per se and, for the pur¬poses of the present invention, can be effected by processes known per se. The system also additionally comprises a compound which is suitable as a ligand for Ni(0) and contains at least one trivalent phosphorus atom, or a mixture of such com¬pounds. In a preferred embodiment, the compound used as a ligand may be one of the formula In the context of the present invention, this compound is a single compound or a mix¬ture of different compounds of the aforementioned formula. X1 X2, X3 may each independently be oxygen or a single bond. When all of the X1 X2 and X3 groups are single bonds, compound (I) is a phosphine of the formula P(R1 R2 R3) with the definitions of R1 R2 and R3speC1fied in this descrip¬tion. When two of the X1 X2 and X3 groups are single bonds and one is oxygen, compound (I) is a phosphinite of the formula P(OR1)(R2)(R3) or P(R1)(0R2)(R3) or P(R1)(R2)(OR3) with the definitions of R1 R2 and R3speC1fied in this description. When one of the X1 X2 and X3 groups is a single bond and two are oxygen, compound (I) is a phosphonite of the formulaP(OR1)(R2)(OR3) OR P(R1)(OR2)(OR3) or P(OR1)(R2)(OR3) with the definitions of R1 R2 AND R3speC1fied in this description. In a preferred embodiment, all of the X1 X2 and X3 groups should be oxygen, so that compound (I) is advantageously a phosphite of the formula P(OR1)(R2)(OR3) with the definitions of R1 R2 and R3speC1fied in this description. According to the invention, R1 R2, R3 are each independently identical or different or¬ganic radicals. R1 R2 and R3are each independently alky! radicals, advantageously having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, aryl groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, 2-naphthyl, or hydrocarbyl, advantageously having from 1 to 20 carbon atoms, such as 1,1'-biphenol, 1,r-binaphthol. The R1 R2 AND R3groups may be bonded together directly, i.e. not solely via the cen¬tral phosphorus atom. Preference is given to the R1 R2 and R3groups not being bonded together directly. In a preferred embodiment, the R1 R2 and R3groups are radicals selected from the group consisting of phenyl, o-tolyl, m-tolyl and p-tolyl. In a particularly preferred embodiment, a maximum of two of the R1 R2 and R3groups should be phenyl groups. In another preferred embodiment, a maximum of two of the R1 R2 and R3groups should be o-tolyl groups. Particularly preferred compounds which may be used are those of the formula :o-tolyl-0-)w (m-tolyl-O-)x (p-tolyl-O-)y (phenyl-O-)z P where w, x, y, z are each a natural number where w + x + y + z = 3 and w, z are each less than or equal to 2, such as (p-tolyl-0-)(phenyl)2P, (m-tolyl-0-)(phenyl)2P, (o-tolyl-0-)(phenyl)2P, p-tolyl-0-)2(phenyl)P, (m-tolyl-0-)2(phenyl)P, (o-tolyl-0-)2(phenyl)P, m-tolyl-0-)(p-tolyl-0-)(phenyl)P, (o-tolyl-0-)(p-tolyl-0-)(phenyl)P, (o-tolyl-0-) (m-tolyl-0-)(phenyl)P, (p-tolyl-0-)3P, (m-tolyl-0-)(p-tolyl-0-)2P, (o-tolyl-0-)(p-tolyl-0-)2P, (m-tolyl-0-)2(p-tolyl-0-)P, (o-tolyl-0-)2(p-tolyl-0-)P, (o-tolyl-0-)(m-tolyl-0-) (p-tolyl-O-)P, (m-tolyl-0-)3P, (o-tolyl-0-)(m-tolyl-0-)2P, (o-tolyl-0-)2(m-tolyl-0-)P or mix¬tures of such compounds. For example, mixtures comprising (m-tolyl-0-)3P, (m-tolyl-0-)2(p-tolyl-0-)P, (m-tolyl-0-)(p-tolyl-0-)2P and (p-tolyl-0-)3P may be obtained by reacting a mixture comprising m-cresol and p-cresol, in particular in a molar ratio of 2:1, as obtained in the distillative workup of crude oil, with a phosphorus trihalide, such as phosphorus trichlo¬ride. In the context of the present invention, such a compound is a single compound or a mixture of different compounds of the aforementioned formula. In a preferred embodiment, X11 X12, X13, X21 X22, X23 may each be oxygen. In such a case, the bridging group Y is bonded to phosphite groups. In another preferred embodiment, X11 and X12 may each be oxygen and X13 a single bond, or X11 and X13 oxygen and X12 a single bond, so that the phosphorus atom sur¬rounded by X11 X12 and X13 is the central atom of a phosphonite. In such a case, X21 X22and X23' may be oxygen, or X21 and X22 may each be oxygen and X21 a single bond, or X21 and X21 may each be oxygen and X21 a single bond, or X21 may be oxygen and X21 and X21 each a single bond, or X21 may be oxygen and X21 and X21 each a single bond, or X21 X21 and X21 may each be a single bond, so that the phosphorus atom sur¬rounded by X21 X21 and X21 may be the central atom of a phosphite, phosphonite, phosphinite or phosphlne, preferably a phosphonite. in another preferred embodiment, X21 may be oxygen and X11 and X21 each a single bond, or x11 may be oxygen and X21 and X21 each a single bond, so that the phospho¬rus atom surrounded by x11 X12 and X21 is the central atom of a phosphinite. In such a case, x11 X21 and X21 may each be oxygen, or X21 may be oxygen and X21 and X21 a single bond, or X21 may be oxygen and X21 and X21 each a single bond, or x11 X22 and X21 may each be a single bond, so that the phosphorus atom surrounded by x11 X21 and X21 may be the central atom of a phosphite, phosphinite or phosphlne, preferably a phosphinite. In another preferred embodiment, x11 X21 and X21 may each be a single bond, so that the phosphorus atom surrounded by x11, X21 and X21 is the central atom of a phosphlne. In such a case, x11 X21 and X21 may each be oxygen, or x11 X21 and X21 may each be a single bond, so that the phosphorus atom surrounded by x11 X}^ and X21 may be the central atom of a phosphite or phosphlne, preferably a phosphlne. The bridging group Y is advantageously an aryl group which is substituted, for example by C1-C4-alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or is unsubstituted, preferably a group having from 6 to 20 carbon atoms in the aromatic system, in particular pyrocatechol, bis(phenol) or bis(naphthol). The R21 and R'^ radicals may each independently be the same or different organic radicals. Advantageous R" and R21 radicals are aryl radicals, preferably those having from 6 to 10 carbon atoms, which may be unsubstituted or mono- or polysubstituted, in particular by C1-C4-alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups. The R21 and R21 radicals may each independently be the same or different organic radicals. Advantageous R21 and R21 radicals are aryl radicals, preferably those having from 6 to 10 carbon atoms, which may be unsubstituted or mono- or polysubstituted, in particular by C1-C4-alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups. The R21 and R21 radicals may each be separate or bridged. The R21 and R21 radicals may each be separate or bridged. The R11 R21, R21 and R21 radicals may each be separate, two may be bridged and two separate, or all four may be bridged, in the manner described. In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV and V speC1fied in US 5,723,641. In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV, V, VI and VII speC1fied in US 5,512,696, in particular the compounds used there in examples 1 to 31. In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV speC1fied in US 5,821,378, in par¬ticular the compounds used there in examples 1 to 73. In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV, V and VI speC1fied in US 5,512,695, in particular the compounds used there in examples 1 to 6. In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII and XIV speC1fied in US 5,981,772, in particular the compounds used there in examples 1 to 66. In a particularly preferred embodiment, useful compounds are those speC1fied in US 6,127,567 and the compounds used there in examples 1 to 29. In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV, V, VI, VII, VIII, IX and X speC1fied in US 6,020,516, in particular the compounds used there in examples 1 to 33. In a particularly preferred embodiment, useful compounds are those speC1fied in US 5,959,135, and the compounds used there in examples 1 to 13. In a particularly preferred embodiment, useful compounds are those of the formula I, II and III speC1fied in US 5,847,191. In a particularly preferred embodiment, useful compounds are those speC1fied in US 5,523,453, in particular the compounds illustrated there in formula 1, 2, 3, 4, 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 and 21. In a particularly preferred embodiment, useful compounds are those speC1fied in WO 01/14392, preferably the compounds illustrated there in formula V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XXI, XXII, XXIII. In a particularly preferred embodiment, useful compounds are those speC1fied in WO 98/27054. In a particularly preferred embodiment, useful compounds are those speC1fied in WO 99/13983. In a particularly preferred embodiment, useful compounds are those speC1fied in WO 99/64155. In a particularly preferred embodiment, useful compounds are those speC1fied in the German laid-open speC1fication DE 10038037. In a particularly preferred embodiment, useful compounds are those speC1fied in the German laid-open speC1fication DE 10046025. Such compounds and their preparation are known per se. In a further preferred embodiment, a mixture of one or more of the aforementioned compounds which are suitable as a ligand for Ni(0) and contain one phosphorus atom, and one or more compounds which are suitable as a ligand for Ni(0) and contain two phosphorus atoms may be used. In this case, the ratio of the first component to the second component may be in the range from 4/1 to 1/1 mol/mol. In a particularly preferred embodiment, useful systems are those which are speC1fied in the international patent application PCT/EP02/07888 and comprise Ni(0) and such mix¬tures. In addition, the system comprises a Lewis aC1d. In the context of the present invention, a Lewis aC1d is either a single Lewis aC1d or else a mixture of a plurality of, for example two, three or four, Lewis aC1ds. Useful Lewis aC1ds are inorganic or organic metal compounds in which the cation is selected from the group consisting of scandium, titanium, vanadium, chromium, man¬ganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, mo¬lybdenum, cadmium, rhenium and tin. Examples include ZnBra, Znl2, ZnC1a, ZnS04, CuCb, CuC1, Cu(03SCF3)2, C0C12, C0I2, Fel2, FeC1a, FeCb, FeCl2(THF)2, TiCl4(THF)2, TiCU, TiC1s, C1Ti(0-i-propyl)3, MnCb, ScCb, AIC13, (C8Hi7)AICl2, (C8Hi7)2AIC1, (i-C4H9)2AICl, (C6H5)2AIC1, (C6H5)AICl2, ReC1s, ZrCL, NbC1s, VC13, CrCb, M0C15, YC13, CdCl2, LaCl3, Er(03SCF3)3, Yb(02CCF3)3, SmCl3, B(C6H5)3, TaClg, as described, for example, in US 6,127,567, US 6,171,996 and US 6,380,421. Also useful are metal salts such as ZnCl2, C0I2 and SnCb, and organometallic compounds such as RAIC12, R2AIC1, RSnOsSCFs and R3B, where R is an alkyl or aryl group, as described, for ex¬ample, in US 3,496,217, US 3,496,218 and US 4,774,353. According to US 3,773,809, the promoter used may also be a metal in cationic form which is selected from the group consisting of zinc, cadmium, beryllium, aluminum, gallium, indium, thallium, tita¬nium, zirconium, hafnium, erbium, germanium, tin, vanadium, niobium, scandium, chromium, molybdenum, tungsten, manganese, rhenium, palladium, thorium, iron and cobalt, preferably zinc, cadmium, titanium, tin, chromium, iron, aluminium and cobalt, and the anionic moiety of the compound may be selected from the group consisting of halides such as fluoride, chloride, bromide and iodide, anions of lower fatty aC1ds hav¬ing from 2 to 7 carbon atoms, HPOs^', H3P0^", CF3COO", C7H15OSO2" or S04^'. Further suitable promoters disclosed by US 3,773,809 are borohydrides, organoborohydrides and boric esters of the formula R3B and B(0R)3, where R is selected from the group consisting of hydrogen, aryl radicals having from 6 to 18 carbon atoms, aryl radicals substituted by alkyl groups having from 1 to 7 carbon atoms and aryl radicals substi¬tuted by cyano-substituted alkyl groups having from 1 to 7 carbon atoms, advanta¬geously triphenylboron. Moreover, as described in US 4,874,884, it is possible to use synergistically active combinations of Lewis aC1ds, in order to increase the activity of the catalyst system. Suitable promoters may, for example, be selected from the group consisting of CdC^, FeClz, ZnCb, B(C6H5)3 and (C6H5)3SnX, where X=CF3S03, CH3C6H4SO3 or (C6H5)3BCN, and the preferred ratio speC1fied of promoter to nickel is from about 1:16 to about 50:1. In the context of the present invention, the term Lewis aC1d also Includes the promoters speC1fied in US 3,496,217, US 3,496,218, US 4,774,353, US 4,874,884, US 6,127,567, US 6,171,996 and US 6,380,421. Particularly preferred Lewis aC1ds among tliose mentioned are in particular metal salts, more preferably metal halides, such as fluorides, chlorides, bromides, iodides, in par¬ticular chlorides, of which particular preference is given to zinc chloride, iron(ll) chloride and iron(lll) chloride. According to the invention, the system comprises a compound d) of the formula M Rn where M: Al or Ti R: identical or different monovalent alkoxy radicals, in which case a plurality of alko-xy radicals may be bonded together, and additionally, in the case that M = Al, R may be identical or different monovalent alkyl radicals, in which case a plurality of alkyl radicals may be bonded together or one or more alkyl radicals may be bon¬ded to one or more of the abovementioned alkoxy radicals, n: valency of M. In the context of the present invention, a compound d) may be a single compound or else a mixture of different compounds of this type, and the different compounds may differ in the nature of M, the nature of R or both. According to the invention, M is aluminum or titanium, and the valency n of aluminum in compound d) should advantageously be three and the valency n of titanium in com¬pound d) should advantageously be three or four, in particular four. In the context of the definition of n, the valency refers to the number of R radicals on M, irrespective of the oxidation number of M which can be calculated for the particular structure M Rn in compound d). In the case that M is titanium, R is identical or different, preferably identical, monova¬lent alkoxy radicals, in which case a plurality of alkoxy radicals may be bonded to¬gether, preferably C1-C4-alkoxy radicals, such as methoxy, ethoxy, 1-propoxy, 2-propoxy, 1-n-butoxy, 2-n-butoxy, 1-isobutoxy or2-isobutoxy, preferably Ti(0Me)4, Ti(0Et)4, Ti(0-i-Pr)4, Ti(0-n-Pr)4, in particular Ti(0-i-Pr)4. In a preferred embodiment, compound d) may be a titanium tetraalkoxide, in particular Ti(0-i-Pr)4. In the case that M is aluminum, R is identical or different, preferably identical, monova¬lent alkoxy radicals, in which case a plurality of alkoxy radicals may be bonded to¬gether, preferably C1-C4-alkoxy radicals, such as methoxy, ethoxy, 1-propoxy, 2-propoxy, 1-n-butoxy, 2-n-butoxy, 1-isobutoxy or 2-isobutoxy, preferably AI(0Me)3, AI(0Et)3, AI(0-i-Pr)3, AI(0-s-Bu)3, in particular AI(0-s-Bu)3 or Identical or different, pref¬erably identical, monovalent alkyl radicals, in which case a plurality of alky! radicals may be bonded together or one or more alkyl radicals may be bonded to one or more of the abovementioned alkoxy radicals, preferably C1-C4-alkyl radicals such as methyl, ethyl, 1-propyl, 2-propyl, 1-n-butyl, 2-n-butyl, 1-isobutyl or 2-isobutyl, preferably MesAI, EtsAl, i-PrsAI, BU3AI, in particular Et3AI, or such mixed alkoxyalkyl radicals. In a preferred embodiment, compound d) may be an aluminum trialkoxide, in particular AI(0-s-Bu)3. In a further preferred embodiment, compound d) may be a trialkylaluminum, in particu¬lar EtsAI. Advantageously, compound d), based on Ni, may be used in amounts of from 0.01 to 2, preferably from 0.01 to 1.5, in particular from 0.01 to 1 mol/mol (w/w). The preparation of catalyst systems comprising the components a), b) and c) is known per se; the system according to the invention can be prepared in accordance with the¬se known processes. In processes for hydrocyanating olefinically unsaturated compounds in the presence of Ni(0)-containing catalyst systems, it is advantageous in accordance with the invention to use the present systems comprising compounds a), b), c) and d) as Ni(0)-containing catalysts. In the context of the present invention, olefinically unsaturated compound refers either to a single olefinically unsaturated compound or to a mixture of such olefinically unsatu¬rated compounds. Useful olefinically unsaturated compounds are compounds which have one or more, such as two, three or four, preferably one or two, in particular one, carbon-carbon dou¬ble bonds. The olefinically unsaturated compounds may advantageously be a branched or unbranched alkene, preferably having from 2 to 10 carbon atoms, or an arylalkene, such as a monoarylalkene or bisarylalkene, preferably having from 2 to 10 carbon at¬oms in the alkene backbone. Such olefinically unsaturated compounds may be unsubstituted. In a preferred embodiment, a substituted olefinically unsaturated compound is used, preferably an olefinically unsaturated compound which contains a functional group se¬lected from the group consisting of-CN, -COOR31 -CONR21R21 where R31 R21, R21: each independently, in the case that R21 and R21 are the same or different, H or alkyl, preferably C1-C4-alkyl, such as methyl, ethyl, 1-propyl, 2-propyl, 1-n-butyl, 2-n-butyl, 1-isobutyl or 2-isobutyl. In a further preferred embodiment, the substituted olefinically unsaturated compound used may be a compound of the formula (C4H7)-X where X: functional group selected from the group consisting of -CN, -COOR'^-CONR21R21 where R41 R42, R43: each independently, in the case that R42 and R43 are the same or different, H or alkyl, preferably C1-C4-alkyl, such as methyl, ethyl, 1-propyl, 2-propyl, 1-n-butyl, 2-n-butyl, 1-isobutyl or 2-isobutyl. In a further preferred embodiment, the olefinically unsaturated compound used may be a branched, preferably linear, pentenenitrile, such as 2-C1s-pentenenitrile, 2-trans-pentenenitrile, 3-C1s-pentenenitrile, 3-trans-pentenenitrile, 4-pentenenitrile, E-2-methyl-2-butenenitrile, Z-2-methyl-2-butenenitrlle, 2-methyl-3-butenenitrile or mixtures thereof. In a particularly preferred embodiment, the olefinically unsaturated compound used is 3-pentenenitrile, such as 3-C1s-pentenenitrile or 3-trans-pentenenitrile, 4-pentenenitrile or mixtures thereof. Such pentenenitriles can be obtained by processes known per se, for example by hy-drocyanation of butadiene in the presnce of Ni(0)-containing catalysts. Processes for hydrocyanating olefinically unsaturated compounds in the presence of Ni(0)-containing catalyst systems are known per se. The processes according to the invention can be carried out in accordance with these processes known per se. The adiponitrile ("ADN") obtainable as a product in such a hydrocyanation or the com¬pounds obtainable by hydrogenating ADN, 6-aminocapronitrile ("ACN") and hexame-thylenediamine ("HMD") can be used to prepare polyamides, in particular nylon-6 and nylon-6,6. The invention is illustrated by the nonlimiting examples which follow. All examples and comparative examples were carried out in an argon protective gas atmosphere. Nickel(0)(m-/p-tolyl phosphite)5.7 ("NTP") is a solution of 2.35% by weight of nickel(O) with 19% by weight of 3-pentenenitrile ("3PN") and 78.65% by weight of m-/p-tolyl phosphite with an m/p ratio of 2:1. In addition, "ADN" means adiponitrile, "4PN" means 4-pentenenitriie and "Ni(C0D)2" means Ni(0)-bis(cyclooctadiene) complex. Hydrocyanation of 3PN to ADN Example 1 (comparative), (0.42 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. In an Ar carrier gas stream, 277 eq. of HCN/hNi we¬re then injected. After 10 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatogra¬phy (GC percent by weight, internal standard: ethylbenzene): Example 2 (comparative) (0.42 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 1 eq. of EtsAI was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 276 eq. of HCN/hNi were then injected. After 20 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 60°C. 1 eq. of ZnCb was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 351 eq. of HCN/hNi were then injected. After 65 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 60°C. 1 eq. of EtsAI and 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 303 eq. of HCN/hNJ were then injected. After 140 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): 1 eq. of Ni(C0D)2 was admixed with 3 eq. of ligand 1 and 1000 eq. of 3PN, stirred at 25°C for one hour and heated to 73°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 271 eq. of HCN/hNI were then injected. After 120 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatogra¬phy (GC percent by weight, internal standard: ethylbenzene): Example 6 (inventive) (0.47 mmol of Ni(0)) 1 eq. of Ni(C0D)2 was admixed with 3 eq. of ligand 1 and 1000 eq. of 3PN, stirred at 25°C for one hour and heated to 73°C. 1 eq. of EtgAI and 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 268 eq. of HCN/hNi were then injected. After 150 min., the mixture tool 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 1 eq. of FeC1a was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 319 eq. of HCN/hNi were then injected. After 60 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 8 (inventive) (0.38 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 0.35 eq. of EtaAl and 1 eq. of FeC1a was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 324 eq. of HCN/hNi were then injected. After 110 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 9 (comparative) (0.46 mmol of Ni(0)) 1 eq. of Ni(C0D)2 was admixed witli 3 eq. of ligand 1 and 1000 eq. of 3PN, stirred at 25°C for one hour and heated to 73°C. 1 eq. of FeC1z was added to this mixture and it was stirred for a further 5 min. in an Ar carrier gas stream, 256 eq. of HCN/hNi were then injected. After 140 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatogra¬phy (GC percent by weight, internal standard: ethylbenzene): Example 10 (inventive) (0.4 mmol of Ni(0)) 1 eq. of Ni(C0D)2 was admixed with 3 eq. of ligand 1 and 1000 eq. of 3PN, stirred at 25°C for one hour and heated to 73°C. 0.35 eq. of EtgAI and 1 eq. of FeCb was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 300 eq. of HCN/hNi were then injected. After 150 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 11 (comparative) (0.43 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 10 eq. of AI(0-s-Bu)3 and 1 eq. of FeCb was added to this mixture and it was stirred for a further 5 min. In an Ar earner gas stream, 294 eq. of HCN/hNi were then injected. After 15 min., the mixture took up no more HCN; a sam¬ple was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 12 (inventive) (0.42 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 0.5 eq. of AI(0-s-Bu)3 and 1 eq. of ZnCb was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 361 eq. of HCN/hNi were then injected. After 80 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography ((3C percent by weight, internal standard: ethylbenzene): Example 13 (inventive) (0.42 mmol of Ni(0)) 1 eq. of NTP was adm xed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 1 eq. of Ti(0-Bu)4 and 1 eq. of ZnC^ was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 296 eq. of HCN/hNi were then injected. After 100 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography ((3C percent by weight, internal standard: ethylbenzene): Example 14 (comparative): (0.3 mmol of Ni(0)) 1 eq. of NTP was adm xed with 300 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 70°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 260 eq. of HCN/hNi were then injected. After 1, 2, 3, 4, 5 and 10 minutes, a sample was taken from the reaction mix¬ture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): i Example 15a (inventive) (0.3 mmol of Ni(0)) 1 eq. of NTP was admixed with 300 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 70°C. 1 eq. of EtsAI and 1 eq. of ZnCb was added to this mix¬ture and it was stirred for a further 5 min. In an Ar carrier gas stream, 260 eq. of HCN/hNi were then injected. After 1, 2, 3, 4, 5 and 10 minutes, a sample was taken from the reaction mixture and the following results were obtained by gas chromatogra¬phy (GC percent by weight, internal standard: ethylbenzene): Example 15b (inventive) (0.3 mmol of Ni(0)) 1 eq. of NTP was admixed with 300 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 70°C. 1 eq. of AI(0-s-Bu)3 and 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 265 eq. of HCN/hNi were then injected. After 1, 2, 3, 4, 5 and 10 minutes, a sample was taken from the reaction mixture and the following results were obtained by gas chromatogra¬phy (GC percent by weight, internal standard: ethylbenzene): The inventive additives tlius do not exiiibit any isomerization activity in the sense of US 4,874,884 within the measurement accuracy. The inventive additives thus exhibit no influence on the reaction rate of the hydrocyana-tion in the sense of US 4,874,884 within the measurement accuracy. Example 16 (comparative) (0.29 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 2, stirred at 25°C for one hour and heated to 60°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 314 eq. of HCN/hNi were then injected. After 50 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 17 (inventive); (0.29 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 2, stirred at 25°C for one hour and heated to 60°C. 1 eq. of EtgA! and 1 eq. of ZnCl2 were added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 340 eq. of HCN/hNi were then injected. After 135 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 18 (comparative) (0.43 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 3, stirred at 25°C for one hour and heated to 60°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 297 eq. of HCN/hNi were then injected. After 65 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 19 (inventive) (0.43 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 3, stirred at 25°C for one hour and heated to 60°C. 1 eq. of EtsAI and 1 eq. of ZnCb were added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 335 eq. of HCN/hNi were then injected. After 160 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 20 (comparative): (0.22 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 4, stirred at 25°C for one hour and heated to 60°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 272 eq. of HCN/hNi were then injected. After 30 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard; ethylbenzene): Example 21 (inventive) (0.23 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 4, stirred at 25°C for one hour and heated to 60°C. 1 eq. of Et3AI and 1 eq. of ZnCb were added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 298 eq. of HCN/hNi were then injected. After 100 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 22 (comparative) (0.4 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 3 eq. of ligand 5, stirred at 25°C for one hour and heated to 70°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 337 eq. of HCN/hNi were then injected. After 150 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 23 (inventive) (0.4 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 3 eq. of ligand 5, stirred at 25°C for one hour and heated to 70°C. 1 eq. of AI(0-s-Bu)3 and 1 eq. of ZnCl2 were added to this mixture and it was stirred for a furtlier 5 min. In an Ar carrier gas stream, 299 eq. of HCN/hNi were then injected. After 195 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 24 (comparative): (0.4 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 3 eq. of ligand 6, stirred at 25°C for one hour and heated to 70°C. 1 eq. of ZnCb was added to this mixture and It was stirred for a further 5 min. In an Ar carrier gas stream, 313 eq. of HCN/hNi were then injected. After 95 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 25 (inventive) (0.4 mmol of Ni(0)) 1 eq. of NTP was admixed with 1000 eq. of 3PN and 3 eq. of ligand 6, stirred at 25°C for one hour and heated to 7G°C. 1 eq. of AI(0-s-Bu)3 and 1 eq. of ZnCl2 were added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 303 eq. of HCN/hNi were then injected. After 130 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene): Example 26 (comparative) The procedure of example 14 was repeated with the difference that a mixture of 30 eq. of 4PN and 270 eq. of 3PN was used at the start. A sample was taken from the reac¬tion mixture after 1, 2, 3, 4, 5 and 10 minutes and the content of 4PN was determined by gas chromatography (GC percent by weight, internal standard: ethylbenzene) to determine the influence on the reaction rate of the hydrocyanation to the ADN of the inventive additives and the following results were obtained: MJn \ 4PN \ ADN - _ _- 2 3^4 57 3 3^3 7A 4 3^4 To 5 3A 1271 To 3 2475 Mh \ 4PN \ ADN - _ _- 2 3^4 57 3 3^3 7A 4 3A To 5 3A 1271 To 3 24^5 Example 27 (inventive) Tine procedure of example 15 was repeated with the difference that a mixture of 30 eq. of 4PN and 270 eq. of 3PN was used at the start. A sample was taken from the reac¬tion mixture after 1, 2, 3, 4, 5 and 10 minutes and the content of 4PN was determined by gas chromatography (GC percent by weight, internal standard: ethylbenzene) to determine the influence on the reaction rate of the hydrocyanation to give ADN of the inventive additives and the following results were obtained: Comparative Overview The inventive additives thus do not exhibit any isomerization activity in the sense of US 4,874,884 within the measurement accuracy. The inventive additives thus do not exhibit any influence on the reaction rate of the hy-drocyanation in the sense of US 4,874,884 within the measurement accuracy. We Claim, 1. A system which is suitable as a catalyst for the hydrocyanation of olefinically unsaturated compounds and comprises a) Ni(o) b) a compound which complexes Ni(o) as a ligand and comprises phosphites, phosphonites or mixtures thereof c) a Lewis acid and d) a compound of the formula MRn c) and d) being different, where M: A1 or Ti R: identical or different monovalent alkoxy radicals, in which case a plurality of alkoxy radicals may be bonded together, and additionally, in the case that M-Al, R may be identical or different monovalent alkyl radicals, in which case a plurality of alkyl radicals may be bonded together or one or more alkyl radicals may be bonded to one or more of the abovementioned alkoxy radicals, n: Valency of M, 2. The system as claimed in claim 1, wherein R, in the case of an alkoxy radical, is methoxy, ethoxy, 1-propoxy, 2-propoxy, 1-n-butoxy, 2-n-butoxy, 1-isobutoxy or 2-isobutoxy. 3. The system as claimed in claim 1, wherein R, in the case of an alkyl radical, is methyl, ethyl, 1-propyl, 2-propyl, 1-n-butyl, 2-n-butyl, 1-isobutyl or 2-isc butyl. 4. The system as claimed in claim 1 or 2, wherein compound d) is a titanium tetraalkoxide. 5. The system as claimed in claim 1 or 2, wherein compound d) is an aluminum trialkoxide. 6. The system as claimed in claim 1 or 3, wherein compound d) is a trialkylaluminum. 7. The system as claimed in any of claims 1 to 6, wherein the R radicals in compound d) are the same. A process for hydrocyanating an olefinically unsaturated compound in the presence of Ni(o) comprising catalyst system, which comprises using a system according to any of claims 1 to 7 as the Ni(0) comprising catalyst system. The process as claimed in claim 8, wherein the olefinically unsaturated compound comprises a functional group selected from the group consisting of-CN, -COOR1, -CONR2R3. where R1 R2, R3 each independently, in the case that R2 and R3 are the same or different, H or alkyl. The process as claimed in claim 8, wherein the olefinically unsaturated compound used is a compound of the formula (C4H7)-X where X; fimctional group selected from the group consistmg of-CN, -COOR , -CONR R . where R1 R2, R3 each independently, in the case that R2 and R3 are the same or different, H or alkyl. The process as claimed in claim 8, wherein the olefinically unsaturated compound used is a linear pentenenitrile. The process as claimed in claim 8, wherein the olefinically unsaturated compound used is 3-pentenenitrile or 4-pentenenitrile.

Full Text

System suitable as a catalyst for the hydrocyanation of olefinically unsaturated com-)ounds
The present invention relates to a system which is suitable as a catalyst for the hydro- cyanation of olefinically unsaturated compounds and comprises
a) Ni(0)
b) a compound which complexes Ni(0) as a ligand and contains trivalent phospho-10 rus,
c) a Lewis aC1d
and 15
d) a compound of the formula M Rn
where
20 M: Al or Ti
R: identical or different monovalent alkoxy radicals, in which case a plurality of alko-
xy radicals may be bonded together, and additionally, in the case that M = Al, R
may be identical or different monovalent alkyl radicals, in which case a plurality
25 of alkyl radicals may be bonded together or one or more alkyl radicals may be
bonded to one or more of the abovementioned alkoxy radicals,
n: valency of M.
30 In addition, it relates to a process for hydrocyanating an olefinically unsaturated com¬pound in the presence of such a system.
Processes for hydrocyanating an olefinically unsaturated nitrile, in particular the prepa¬ration of adipodinitrile by hydrocyanating an olefinically unsaturated compound such as
35 2-C1s-pentenenitrile, 2-trans-pentenenitrile, 3-C1s-pentenenitrile, 3-trans-pentenenitrile, 4-pentenenitrile, E-2-methyl-2-butenenitrile, Z-2-methyl-2-butenenitrile, 2-methyl-3-butenenitrle or mixtures thereof, in the presence of a catalyst system comprising a Lewis aC1d and a complex containing a phosphorus compound suitable as a ligand, such as a monodentate, preferably multidentate, in particular bidentate, compound
40 which coordinates to a central atom via a phosphorus atom which may be present as a phosphine, phosphite, phosphonite or phosphinite or mixture thereof, and a central
2-

atom, preferably nickel, cobalt or palladium, in particular nickel, more preferably in the form of nickel(O), are known, for example from US 3,496,217, US 3,496,218, US 4,705,881, US 4,774,353, US 4,874,884, US 5,773,637, US 6,127,567, US 6,171,996 B1 and US 6,380,421 B1.
It is an object of the present invention to provide a system which is suitable as a cata¬lyst for the hydrocyanation of olefinically unsaturated compounds and exhibits an im¬proved space-time yield of hydrocyanation products compared to the known systems.
We have found that this object is achieved by the system defined at the outset and by a process for hydrocyanating an olefinically unsaturated compound in the presence of such a system.
The preparation of Ni(0)-containing catalyst systems is known per se and, for the pur¬poses of the present invention, can be effected by processes known per se.
The system also additionally comprises a compound which is suitable as a ligand for Ni(0) and contains at least one trivalent phosphorus atom, or a mixture of such com¬pounds.
In a preferred embodiment, the compound used as a ligand may be one of the formula

In the context of the present invention, this compound is a single compound or a mix¬ture of different compounds of the aforementioned formula.
X1 X2, X3 may each independently be oxygen or a single bond.
When all of the X1 X2 and X3 groups are single bonds, compound (I) is a phosphine of the formula P(R1 R2 R3) with the definitions of R1 R2 and R3speC1fied in this descrip¬tion.
When two of the X1 X2 and X3 groups are single bonds and one is oxygen, compound (I) is a phosphinite of the formula P(OR1)(R2)(R3) or P(R1)(0R2)(R3) or P(R1)(R2)(OR3) with the definitions of R1 R2 and R3speC1fied in this description.

When one of the X1 X2 and X3 groups is a single bond and two are oxygen, compound (I) is a phosphonite of the formulaP(OR1)(R2)(OR3) OR P(R1)(OR2)(OR3) or P(OR1)(R2)(OR3) with the definitions of R1 R2 AND R3speC1fied in this description.
In a preferred embodiment, all of the X1 X2 and X3 groups should be oxygen, so that compound (I) is advantageously a phosphite of the formula P(OR1)(R2)(OR3) with the definitions of R1 R2 and R3speC1fied in this description.
According to the invention, R1 R2, R3 are each independently identical or different or¬ganic radicals.
R1 R2 and R3are each independently alky! radicals, advantageously having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, aryl groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, 2-naphthyl, or hydrocarbyl, advantageously having from 1 to 20 carbon atoms, such as 1,1'-biphenol, 1,r-binaphthol.
The R1 R2 AND R3groups may be bonded together directly, i.e. not solely via the cen¬tral phosphorus atom. Preference is given to the R1 R2 and R3groups not being bonded together directly.
In a preferred embodiment, the R1 R2 and R3groups are radicals selected from the group consisting of phenyl, o-tolyl, m-tolyl and p-tolyl.
In a particularly preferred embodiment, a maximum of two of the R1 R2 and R3groups should be phenyl groups.
In another preferred embodiment, a maximum of two of the R1 R2 and R3groups should be o-tolyl groups.
Particularly preferred compounds which may be used are those of the formula :o-tolyl-0-)w (m-tolyl-O-)x (p-tolyl-O-)y (phenyl-O-)z P where w, x, y, z are each a natural number where w + x + y + z = 3 and
w, z are each less than or equal to 2, such as (p-tolyl-0-)(phenyl)2P, (m-tolyl-0-)(phenyl)2P, (o-tolyl-0-)(phenyl)2P, p-tolyl-0-)2(phenyl)P, (m-tolyl-0-)2(phenyl)P, (o-tolyl-0-)2(phenyl)P, m-tolyl-0-)(p-tolyl-0-)(phenyl)P, (o-tolyl-0-)(p-tolyl-0-)(phenyl)P, (o-tolyl-0-)

(m-tolyl-0-)(phenyl)P, (p-tolyl-0-)3P, (m-tolyl-0-)(p-tolyl-0-)2P, (o-tolyl-0-)(p-tolyl-0-)2P, (m-tolyl-0-)2(p-tolyl-0-)P, (o-tolyl-0-)2(p-tolyl-0-)P, (o-tolyl-0-)(m-tolyl-0-) (p-tolyl-O-)P, (m-tolyl-0-)3P, (o-tolyl-0-)(m-tolyl-0-)2P, (o-tolyl-0-)2(m-tolyl-0-)P or mix¬tures of such compounds.
For example, mixtures comprising (m-tolyl-0-)3P, (m-tolyl-0-)2(p-tolyl-0-)P, (m-tolyl-0-)(p-tolyl-0-)2P and (p-tolyl-0-)3P may be obtained by reacting a mixture comprising m-cresol and p-cresol, in particular in a molar ratio of 2:1, as obtained in the distillative workup of crude oil, with a phosphorus trihalide, such as phosphorus trichlo¬ride.

In the context of the present invention, such a compound is a single compound or a mixture of different compounds of the aforementioned formula.
In a preferred embodiment, X11 X12, X13, X21 X22, X23 may each be oxygen. In such a case, the bridging group Y is bonded to phosphite groups.
In another preferred embodiment, X11 and X12 may each be oxygen and X13 a single bond, or X11 and X13 oxygen and X12 a single bond, so that the phosphorus atom sur¬rounded by X11 X12 and X13 is the central atom of a phosphonite. In such a case, X21

X22and X23' may be oxygen, or X21 and X22 may each be oxygen and X21 a single bond, or X21 and X21 may each be oxygen and X21 a single bond, or X21 may be oxygen and X21 and X21 each a single bond, or X21 may be oxygen and X21 and X21 each a single bond, or X21 X21 and X21 may each be a single bond, so that the phosphorus atom sur¬rounded by X21 X21 and X21 may be the central atom of a phosphite, phosphonite, phosphinite or phosphlne, preferably a phosphonite.
in another preferred embodiment, X21 may be oxygen and X11 and X21 each a single bond, or x11 may be oxygen and X21 and X21 each a single bond, so that the phospho¬rus atom surrounded by x11 X12 and X21 is the central atom of a phosphinite. In such a case, x11 X21 and X21 may each be oxygen, or X21 may be oxygen and X21 and X21 a single bond, or X21 may be oxygen and X21 and X21 each a single bond, or x11 X22 and X21 may each be a single bond, so that the phosphorus atom surrounded by x11 X21 and X21 may be the central atom of a phosphite, phosphinite or phosphlne, preferably a phosphinite.
In another preferred embodiment, x11 X21 and X21 may each be a single bond, so that the phosphorus atom surrounded by x11, X21 and X21 is the central atom of a phosphlne. In such a case, x11 X21 and X21 may each be oxygen, or x11 X21 and X21 may each be a single bond, so that the phosphorus atom surrounded by x11 X}^ and X21 may be the central atom of a phosphite or phosphlne, preferably a phosphlne.
The bridging group Y is advantageously an aryl group which is substituted, for example by C1-C4-alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or is unsubstituted, preferably a group having from 6 to 20 carbon atoms in the aromatic system, in particular pyrocatechol, bis(phenol) or bis(naphthol).
The R21 and R'^ radicals may each independently be the same or different organic radicals. Advantageous R" and R21 radicals are aryl radicals, preferably those having from 6 to 10 carbon atoms, which may be unsubstituted or mono- or polysubstituted, in particular by C1-C4-alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups.
The R21 and R21 radicals may each independently be the same or different organic radicals. Advantageous R21 and R21 radicals are aryl radicals, preferably those having from 6 to 10 carbon atoms, which may be unsubstituted or mono- or polysubstituted, in particular by C1-C4-alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups.

The R21 and R21 radicals may each be separate or bridged.
The R21 and R21 radicals may each be separate or bridged.
The R11 R21, R21 and R21 radicals may each be separate, two may be bridged and two
separate, or all four may be bridged, in the manner described.
In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV and V speC1fied in US 5,723,641.
In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV, V, VI and VII speC1fied in US 5,512,696, in particular the compounds used there in examples 1 to 31.
In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV speC1fied in US 5,821,378, in par¬ticular the compounds used there in examples 1 to 73.
In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV, V and VI speC1fied in US 5,512,695, in particular the compounds used there in examples 1 to 6.
In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII and XIV speC1fied in US 5,981,772, in particular the compounds used there in examples 1 to 66.
In a particularly preferred embodiment, useful compounds are those speC1fied in US 6,127,567 and the compounds used there in examples 1 to 29.
In a particularly preferred embodiment, useful compounds are those of the formula I, II, III, IV, V, VI, VII, VIII, IX and X speC1fied in US 6,020,516, in particular the compounds used there in examples 1 to 33.
In a particularly preferred embodiment, useful compounds are those speC1fied in US 5,959,135, and the compounds used there in examples 1 to 13.
In a particularly preferred embodiment, useful compounds are those of the formula I, II and III speC1fied in US 5,847,191.

In a particularly preferred embodiment, useful compounds are those speC1fied in
US 5,523,453, in particular the compounds illustrated there in formula 1, 2, 3, 4, 5, 6, 7,
8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 and 21.
In a particularly preferred embodiment, useful compounds are those speC1fied in
WO 01/14392, preferably the compounds illustrated there in formula V, VI, VII, VIII, IX,
X, XI, XII, XIII, XIV, XV, XVI, XVII, XXI, XXII, XXIII.
In a particularly preferred embodiment, useful compounds are those speC1fied in WO 98/27054.
In a particularly preferred embodiment, useful compounds are those speC1fied in WO 99/13983.
In a particularly preferred embodiment, useful compounds are those speC1fied in WO 99/64155.
In a particularly preferred embodiment, useful compounds are those speC1fied in the German laid-open speC1fication DE 10038037.
In a particularly preferred embodiment, useful compounds are those speC1fied in the German laid-open speC1fication DE 10046025.
Such compounds and their preparation are known per se.
In a further preferred embodiment, a mixture of one or more of the aforementioned compounds which are suitable as a ligand for Ni(0) and contain one phosphorus atom, and one or more compounds which are suitable as a ligand for Ni(0) and contain two phosphorus atoms may be used.
In this case, the ratio of the first component to the second component may be in the range from 4/1 to 1/1 mol/mol.
In a particularly preferred embodiment, useful systems are those which are speC1fied in the international patent application PCT/EP02/07888 and comprise Ni(0) and such mix¬tures.
In addition, the system comprises a Lewis aC1d.

In the context of the present invention, a Lewis aC1d is either a single Lewis aC1d or else a mixture of a plurality of, for example two, three or four, Lewis aC1ds.
Useful Lewis aC1ds are inorganic or organic metal compounds in which the cation is selected from the group consisting of scandium, titanium, vanadium, chromium, man¬ganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, mo¬lybdenum, cadmium, rhenium and tin. Examples include ZnBra, Znl2, ZnC1a, ZnS04, CuCb, CuC1, Cu(03SCF3)2, C0C12, C0I2, Fel2, FeC1a, FeCb, FeCl2(THF)2, TiCl4(THF)2, TiCU, TiC1s, C1Ti(0-i-propyl)3, MnCb, ScCb, AIC13, (C8Hi7)AICl2, (C8Hi7)2AIC1, (i-C4H9)2AICl, (C6H5)2AIC1, (C6H5)AICl2, ReC1s, ZrCL, NbC1s, VC13, CrCb, M0C15, YC13, CdCl2, LaCl3, Er(03SCF3)3, Yb(02CCF3)3, SmCl3, B(C6H5)3, TaClg, as described, for example, in US 6,127,567, US 6,171,996 and US 6,380,421. Also useful are metal salts such as ZnCl2, C0I2 and SnCb, and organometallic compounds such as RAIC12, R2AIC1, RSnOsSCFs and R3B, where R is an alkyl or aryl group, as described, for ex¬ample, in US 3,496,217, US 3,496,218 and US 4,774,353. According to US 3,773,809, the promoter used may also be a metal in cationic form which is selected from the group consisting of zinc, cadmium, beryllium, aluminum, gallium, indium, thallium, tita¬nium, zirconium, hafnium, erbium, germanium, tin, vanadium, niobium, scandium, chromium, molybdenum, tungsten, manganese, rhenium, palladium, thorium, iron and cobalt, preferably zinc, cadmium, titanium, tin, chromium, iron, aluminium and cobalt, and the anionic moiety of the compound may be selected from the group consisting of halides such as fluoride, chloride, bromide and iodide, anions of lower fatty aC1ds hav¬ing from 2 to 7 carbon atoms, HPOs^', H3P0^", CF3COO", C7H15OSO2" or S04^'. Further suitable promoters disclosed by US 3,773,809 are borohydrides, organoborohydrides and boric esters of the formula R3B and B(0R)3, where R is selected from the group consisting of hydrogen, aryl radicals having from 6 to 18 carbon atoms, aryl radicals substituted by alkyl groups having from 1 to 7 carbon atoms and aryl radicals substi¬tuted by cyano-substituted alkyl groups having from 1 to 7 carbon atoms, advanta¬geously triphenylboron. Moreover, as described in US 4,874,884, it is possible to use synergistically active combinations of Lewis aC1ds, in order to increase the activity of the catalyst system. Suitable promoters may, for example, be selected from the group consisting of CdC^, FeClz, ZnCb, B(C6H5)3 and (C6H5)3SnX, where X=CF3S03, CH3C6H4SO3 or (C6H5)3BCN, and the preferred ratio speC1fied of promoter to nickel is from about 1:16 to about 50:1.
In the context of the present invention, the term Lewis aC1d also Includes the promoters speC1fied in US 3,496,217, US 3,496,218, US 4,774,353, US 4,874,884, US 6,127,567, US 6,171,996 and US 6,380,421.

Particularly preferred Lewis aC1ds among tliose mentioned are in particular metal salts, more preferably metal halides, such as fluorides, chlorides, bromides, iodides, in par¬ticular chlorides, of which particular preference is given to zinc chloride, iron(ll) chloride and iron(lll) chloride.
According to the invention, the system comprises a compound d) of the formula M Rn
where
M: Al or Ti
R: identical or different monovalent alkoxy radicals, in which case a plurality of alko-xy radicals may be bonded together, and additionally, in the case that M = Al, R may be identical or different monovalent alkyl radicals, in which case a plurality of alkyl radicals may be bonded together or one or more alkyl radicals may be bon¬ded to one or more of the abovementioned alkoxy radicals,
n: valency of M.
In the context of the present invention, a compound d) may be a single compound or else a mixture of different compounds of this type, and the different compounds may differ in the nature of M, the nature of R or both.
According to the invention, M is aluminum or titanium, and the valency n of aluminum in compound d) should advantageously be three and the valency n of titanium in com¬pound d) should advantageously be three or four, in particular four. In the context of the definition of n, the valency refers to the number of R radicals on M, irrespective of the oxidation number of M which can be calculated for the particular structure M Rn in compound d).
In the case that M is titanium, R is identical or different, preferably identical, monova¬lent alkoxy radicals, in which case a plurality of alkoxy radicals may be bonded to¬gether, preferably C1-C4-alkoxy radicals, such as methoxy, ethoxy, 1-propoxy, 2-propoxy, 1-n-butoxy, 2-n-butoxy, 1-isobutoxy or2-isobutoxy, preferably Ti(0Me)4, Ti(0Et)4, Ti(0-i-Pr)4, Ti(0-n-Pr)4, in particular Ti(0-i-Pr)4.
In a preferred embodiment, compound d) may be a titanium tetraalkoxide, in particular Ti(0-i-Pr)4.

In the case that M is aluminum, R is identical or different, preferably identical, monova¬lent alkoxy radicals, in which case a plurality of alkoxy radicals may be bonded to¬gether, preferably C1-C4-alkoxy radicals, such as methoxy, ethoxy, 1-propoxy, 2-propoxy, 1-n-butoxy, 2-n-butoxy, 1-isobutoxy or 2-isobutoxy, preferably AI(0Me)3, AI(0Et)3, AI(0-i-Pr)3, AI(0-s-Bu)3, in particular AI(0-s-Bu)3 or Identical or different, pref¬erably identical, monovalent alkyl radicals, in which case a plurality of alky! radicals may be bonded together or one or more alkyl radicals may be bonded to one or more of the abovementioned alkoxy radicals, preferably C1-C4-alkyl radicals such as methyl, ethyl, 1-propyl, 2-propyl, 1-n-butyl, 2-n-butyl, 1-isobutyl or 2-isobutyl, preferably MesAI, EtsAl, i-PrsAI, BU3AI, in particular Et3AI, or such mixed alkoxyalkyl radicals.
In a preferred embodiment, compound d) may be an aluminum trialkoxide, in particular AI(0-s-Bu)3.
In a further preferred embodiment, compound d) may be a trialkylaluminum, in particu¬lar EtsAI.
Advantageously, compound d), based on Ni, may be used in amounts of from 0.01 to 2, preferably from 0.01 to 1.5, in particular from 0.01 to 1 mol/mol (w/w).
The preparation of catalyst systems comprising the components a), b) and c) is known per se; the system according to the invention can be prepared in accordance with the¬se known processes.
In processes for hydrocyanating olefinically unsaturated compounds in the presence of Ni(0)-containing catalyst systems, it is advantageous in accordance with the invention to use the present systems comprising compounds a), b), c) and d) as Ni(0)-containing catalysts.
In the context of the present invention, olefinically unsaturated compound refers either to a single olefinically unsaturated compound or to a mixture of such olefinically unsatu¬rated compounds.
Useful olefinically unsaturated compounds are compounds which have one or more, such as two, three or four, preferably one or two, in particular one, carbon-carbon dou¬ble bonds. The olefinically unsaturated compounds may advantageously be a branched or unbranched alkene, preferably having from 2 to 10 carbon atoms, or an arylalkene, such as a monoarylalkene or bisarylalkene, preferably having from 2 to 10 carbon at¬oms in the alkene backbone.

Such olefinically unsaturated compounds may be unsubstituted.
In a preferred embodiment, a substituted olefinically unsaturated compound is used, preferably an olefinically unsaturated compound which contains a functional group se¬lected from the group consisting of-CN, -COOR31 -CONR21R21
where R31 R21, R21: each independently, in the case that R21 and R21 are the same or different, H or alkyl, preferably C1-C4-alkyl, such as methyl, ethyl, 1-propyl, 2-propyl, 1-n-butyl, 2-n-butyl, 1-isobutyl or 2-isobutyl.
In a further preferred embodiment, the substituted olefinically unsaturated compound
used may be a compound of the formula (C4H7)-X
where X: functional group selected from the group consisting of -CN, -COOR'^-CONR21R21
where R41 R42, R43: each independently, in the case that R42 and R43 are the same or different, H or alkyl, preferably C1-C4-alkyl, such as methyl, ethyl, 1-propyl, 2-propyl, 1-n-butyl, 2-n-butyl, 1-isobutyl or 2-isobutyl.
In a further preferred embodiment, the olefinically unsaturated compound used may be a branched, preferably linear, pentenenitrile, such as 2-C1s-pentenenitrile, 2-trans-pentenenitrile, 3-C1s-pentenenitrile, 3-trans-pentenenitrile, 4-pentenenitrile, E-2-methyl-2-butenenitrile, Z-2-methyl-2-butenenitrlle, 2-methyl-3-butenenitrile or mixtures thereof.
In a particularly preferred embodiment, the olefinically unsaturated compound used is 3-pentenenitrile, such as 3-C1s-pentenenitrile or 3-trans-pentenenitrile, 4-pentenenitrile or mixtures thereof.
Such pentenenitriles can be obtained by processes known per se, for example by hy-drocyanation of butadiene in the presnce of Ni(0)-containing catalysts.
Processes for hydrocyanating olefinically unsaturated compounds in the presence of Ni(0)-containing catalyst systems are known per se. The processes according to the invention can be carried out in accordance with these processes known per se.
The adiponitrile ("ADN") obtainable as a product in such a hydrocyanation or the com¬pounds obtainable by hydrogenating ADN, 6-aminocapronitrile ("ACN") and hexame-thylenediamine ("HMD") can be used to prepare polyamides, in particular nylon-6 and nylon-6,6.

The invention is illustrated by the nonlimiting examples which follow.

All examples and comparative examples were carried out in an argon protective gas atmosphere.
Nickel(0)(m-/p-tolyl phosphite)5.7 ("NTP") is a solution of 2.35% by weight of nickel(O) with 19% by weight of 3-pentenenitrile ("3PN") and 78.65% by weight of m-/p-tolyl phosphite with an m/p ratio of 2:1.

In addition, "ADN" means adiponitrile, "4PN" means 4-pentenenitriie and "Ni(C0D)2" means Ni(0)-bis(cyclooctadiene) complex.
Hydrocyanation of 3PN to ADN
Example 1 (comparative), (0.42 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. In an Ar carrier gas stream, 277 eq. of HCN/h*Ni we¬re then injected. After 10 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatogra¬phy (GC percent by weight, internal standard: ethylbenzene):

Example 2 (comparative) (0.42 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 1 eq. of EtsAI was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 276 eq. of HCN/h*Ni were then injected. After 20 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 60°C. 1 eq. of ZnCb was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 351 eq. of HCN/h*Ni were then injected. After 65 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 60°C. 1 eq. of EtsAI and 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 303 eq. of HCN/h*NJ were then injected. After 140 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

1 eq. of Ni(C0D)2 was admixed with 3 eq. of ligand 1 and 1000 eq. of 3PN, stirred at 25°C for one hour and heated to 73°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 271 eq. of HCN/h*NI were then injected. After 120 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatogra¬phy (GC percent by weight, internal standard: ethylbenzene):

Example 6 (inventive) (0.47 mmol of Ni(0))
1 eq. of Ni(C0D)2 was admixed with 3 eq. of ligand 1 and 1000 eq. of 3PN, stirred at 25°C for one hour and heated to 73°C. 1 eq. of EtgAI and 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 268 eq. of HCN/h*Ni were then injected. After 150 min., the mixture tool
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 1 eq. of FeC1a was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 319 eq. of HCN/h*Ni were then injected. After 60 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 8 (inventive) (0.38 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 0.35 eq. of EtaAl and 1 eq. of FeC1a was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 324 eq. of HCN/h*Ni were then injected. After 110 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 9 (comparative) (0.46 mmol of Ni(0))
1 eq. of Ni(C0D)2 was admixed witli 3 eq. of ligand 1 and 1000 eq. of 3PN, stirred at 25°C for one hour and heated to 73°C. 1 eq. of FeC1z was added to this mixture and it was stirred for a further 5 min. in an Ar carrier gas stream, 256 eq. of HCN/h*Ni were then injected. After 140 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatogra¬phy (GC percent by weight, internal standard: ethylbenzene):

Example 10 (inventive) (0.4 mmol of Ni(0))
1 eq. of Ni(C0D)2 was admixed with 3 eq. of ligand 1 and 1000 eq. of 3PN, stirred at 25°C for one hour and heated to 73°C. 0.35 eq. of EtgAI and 1 eq. of FeCb was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 300 eq. of HCN/h*Ni were then injected. After 150 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 11 (comparative) (0.43 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 10 eq. of AI(0-s-Bu)3 and 1 eq. of FeCb was added to this mixture and it was stirred for a further 5 min. In an Ar earner gas stream, 294 eq. of HCN/h*Ni were then injected. After 15 min., the mixture took up no more HCN; a sam¬ple was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 12 (inventive) (0.42 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 0.5 eq. of AI(0-s-Bu)3 and 1 eq. of ZnCb was added

to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 361 eq. of HCN/h*Ni were then injected. After 80 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography ((3C percent by weight, internal standard: ethylbenzene):

Example 13 (inventive) (0.42 mmol of Ni(0))
1 eq. of NTP was adm xed with 1000 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 73°C. 1 eq. of Ti(0-Bu)4 and 1 eq. of ZnC^ was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 296 eq. of HCN/h*Ni were then injected. After 100 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography ((3C percent by weight, internal standard: ethylbenzene):

Example 14 (comparative): (0.3 mmol of Ni(0))
1 eq. of NTP was adm xed with 300 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 70°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 260 eq. of HCN/h*Ni were then injected. After 1, 2, 3, 4, 5 and 10 minutes, a sample was taken from the reaction mix¬ture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

i

Example 15a (inventive) (0.3 mmol of Ni(0))
1 eq. of NTP was admixed with 300 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 70°C. 1 eq. of EtsAI and 1 eq. of ZnCb was added to this mix¬ture and it was stirred for a further 5 min. In an Ar carrier gas stream, 260 eq. of HCN/h*Ni were then injected. After 1, 2, 3, 4, 5 and 10 minutes, a sample was taken from the reaction mixture and the following results were obtained by gas chromatogra¬phy (GC percent by weight, internal standard: ethylbenzene):

Example 15b (inventive) (0.3 mmol of Ni(0))
1 eq. of NTP was admixed with 300 eq. of 3PN and 2 eq. of ligand 1, stirred at 25°C for one hour and heated to 70°C. 1 eq. of AI(0-s-Bu)3 and 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 265 eq. of HCN/h*Ni were then injected. After 1, 2, 3, 4, 5 and 10 minutes, a sample was taken from the reaction mixture and the following results were obtained by gas chromatogra¬phy (GC percent by weight, internal standard: ethylbenzene):

The inventive additives tlius do not exiiibit any isomerization activity in the sense of US 4,874,884 within the measurement accuracy.

The inventive additives thus exhibit no influence on the reaction rate of the hydrocyana-tion in the sense of US 4,874,884 within the measurement accuracy.
Example 16 (comparative) (0.29 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 2, stirred at 25°C for one hour and heated to 60°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 314 eq. of HCN/h*Ni were then injected. After 50 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 17 (inventive); (0.29 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 2, stirred at 25°C for one hour and heated to 60°C. 1 eq. of EtgA! and 1 eq. of ZnCl2 were added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 340 eq. of HCN/h*Ni were then injected. After 135 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 18 (comparative) (0.43 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 3, stirred at 25°C for one hour and heated to 60°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 297 eq. of HCN/h*Ni were then injected. After 65 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 19 (inventive) (0.43 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 3, stirred at 25°C for one hour and heated to 60°C. 1 eq. of EtsAI and 1 eq. of ZnCb were added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 335 eq. of HCN/h*Ni were then injected. After 160 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 20 (comparative): (0.22 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 4, stirred at 25°C for one hour and heated to 60°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 272 eq. of HCN/h*Ni were then injected. After 30 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard; ethylbenzene):

Example 21 (inventive) (0.23 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 2 eq. of ligand 4, stirred at 25°C for one hour and heated to 60°C. 1 eq. of Et3AI and 1 eq. of ZnCb were added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 298 eq. of HCN/h*Ni were then injected. After 100 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 22 (comparative) (0.4 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 3 eq. of ligand 5, stirred at 25°C for one hour and heated to 70°C. 1 eq. of ZnCl2 was added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 337 eq. of HCN/h*Ni were then injected. After 150 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 23 (inventive) (0.4 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 3 eq. of ligand 5, stirred at 25°C for one hour and heated to 70°C. 1 eq. of AI(0-s-Bu)3 and 1 eq. of ZnCl2 were added to

this mixture and it was stirred for a furtlier 5 min. In an Ar carrier gas stream, 299 eq. of HCN/h*Ni were then injected. After 195 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 24 (comparative): (0.4 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 3 eq. of ligand 6, stirred at 25°C for one hour and heated to 70°C. 1 eq. of ZnCb was added to this mixture and It was stirred for a further 5 min. In an Ar carrier gas stream, 313 eq. of HCN/h*Ni were then injected. After 95 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 25 (inventive) (0.4 mmol of Ni(0))
1 eq. of NTP was admixed with 1000 eq. of 3PN and 3 eq. of ligand 6, stirred at 25°C for one hour and heated to 7G°C. 1 eq. of AI(0-s-Bu)3 and 1 eq. of ZnCl2 were added to this mixture and it was stirred for a further 5 min. In an Ar carrier gas stream, 303 eq. of HCN/h*Ni were then injected. After 130 min., the mixture took up no more HCN; a sample was taken from the reaction mixture and the following results were obtained by gas chromatography (GC percent by weight, internal standard: ethylbenzene):

Example 26 (comparative)
The procedure of example 14 was repeated with the difference that a mixture of 30 eq. of 4PN and 270 eq. of 3PN was used at the start. A sample was taken from the reac¬tion mixture after 1, 2, 3, 4, 5 and 10 minutes and the content of 4PN was determined by gas chromatography (GC percent by weight, internal standard: ethylbenzene) to determine the influence on the reaction rate of the hydrocyanation to the ADN of the inventive additives and the following results were obtained:

MJn \ 4PN \ ADN
- _ _-
2 3^4 57
3 3^3 7A
4 3^4 To
5 3A 1271 To 3 2475
Mh \ 4PN \ ADN
- _ _-
2 3^4 57
3 3^3 7A
4 3A To
5 3A 1271
To 3 24^5
Example 27 (inventive)
Tine procedure of example 15 was repeated with the difference that a mixture of 30 eq. of 4PN and 270 eq. of 3PN was used at the start. A sample was taken from the reac¬tion mixture after 1, 2, 3, 4, 5 and 10 minutes and the content of 4PN was determined by gas chromatography (GC percent by weight, internal standard: ethylbenzene) to determine the influence on the reaction rate of the hydrocyanation to give ADN of the inventive additives and the following results were obtained:

Comparative Overview

The inventive additives thus do not exhibit any isomerization activity in the sense of US 4,874,884 within the measurement accuracy.

The inventive additives thus do not exhibit any influence on the reaction rate of the hy-drocyanation in the sense of US 4,874,884 within the measurement accuracy.

We Claim,
1. A system which is suitable as a catalyst for the hydrocyanation of olefinically unsaturated compounds and comprises
a) Ni(o)
b) a compound which complexes Ni(o) as a ligand and comprises phosphites, phosphonites or mixtures thereof
c) a Lewis acid
and
d) a compound of the formula MRn
c) and d) being different,
where
M: A1 or Ti
R: identical or different monovalent alkoxy radicals, in which case a plurality of alkoxy radicals may be bonded together, and additionally, in the case that M-Al, R may be identical or different monovalent alkyl radicals, in which case a plurality of alkyl radicals may be bonded together or one or more alkyl radicals may be bonded to one or more of the abovementioned alkoxy radicals,
n: Valency of M,
2. The system as claimed in claim 1, wherein R, in the case of an alkoxy radical, is methoxy, ethoxy, 1-propoxy, 2-propoxy, 1-n-butoxy, 2-n-butoxy, 1-isobutoxy or 2-isobutoxy.
3. The system as claimed in claim 1, wherein R, in the case of an alkyl radical, is methyl, ethyl, 1-propyl, 2-propyl, 1-n-butyl, 2-n-butyl, 1-isobutyl or 2-isc butyl.
4. The system as claimed in claim 1 or 2, wherein compound d) is a titanium tetraalkoxide.
5. The system as claimed in claim 1 or 2, wherein compound d) is an aluminum trialkoxide.
6. The system as claimed in claim 1 or 3, wherein compound d) is a trialkylaluminum.
7. The system as claimed in any of claims 1 to 6, wherein the R radicals in compound d) are the same.

A process for hydrocyanating an olefinically unsaturated compound in the presence of Ni(o) comprising catalyst system, which comprises using a system according to any of claims 1 to 7 as the Ni(0) comprising catalyst system.
The process as claimed in claim 8, wherein the olefinically unsaturated compound comprises a functional group selected from the group consisting of-CN, -COOR1, -CONR2R3.
where R1 R2, R3 each independently, in the case that R2 and R3 are the same or different, H or alkyl.
The process as claimed in claim 8, wherein the olefinically unsaturated compound used is a compound of the formula (C4H7)-X
where X; fimctional group selected from the group consistmg of-CN, -COOR , -CONR R .
where R1 R2, R3 each independently, in the case that R2 and R3 are the same or different, H or alkyl.
The process as claimed in claim 8, wherein the olefinically unsaturated compound used is a linear pentenenitrile.
The process as claimed in claim 8, wherein the olefinically unsaturated compound used is 3-pentenenitrile or 4-pentenenitrile.

Documents:

2815-chenp-2005 abstract-duplicate.pdf

2815-chenp-2005 asbtract.pdf

2815-chenp-2005 claims-duplicate.pdf

2815-chenp-2005 claims.pdf

2815-chenp-2005 correspondence-others.pdf

2815-chenp-2005 correspondence-po.pdf

2815-chenp-2005 descripition(completed)-duplicate.pdf

2815-chenp-2005 description(complete).pdf

2815-chenp-2005 form-1.pdf

2815-chenp-2005 form-18.pdf

2815-chenp-2005 form-26.pdf

2815-chenp-2005 form-3.pdf

2815-chenp-2005 form-5.pdf

2815-chenp-2005 pct search report.pdf

2815-chenp-2005 pct.pdf

« Previous Patent

Next Patent »

Patent Number

229397

Indian Patent Application Number

2815/CHENP/2005

PG Journal Number

12/2009

Publication Date

20-Mar-2009

Grant Date

17-Feb-2009

Date of Filing

31-Oct-2005

Name of Patentee

BASF AKTIENGESELLSCHAFT

Applicant Address

D-67056, Ludwigshafen,

Inventors:

#	Inventor's Name	Inventor's Address
1	SCHEIDEL, Jens	Buttemer Weg 12, 69493 Hirschberg,
2	SIEGEL, Wolfgang	Goethestr. 34b, 67117 Limburgerhof,
3	MOLNAR, Ferenc	Keplerstrasse 5, 67346 Speyer,
4	BARTSCH, Michael	Konrad-Adenauer-Strasse 38, 67433 Neustadt,
5	BAUMANN, Robert	E 7,23, 68159 Mannheim,
6	HADERLEIN, Gerd	Hochgewanne 93a, 67269 Grunstadt,
7	FLORES, Miguel Angel	Acequia 27, E-28300 Aranjuez,
8	JUNGKAMP, Tim	Friedrichstrasse 19, 69207 Sandhausen,
9	LUYKEN, Hermann	Brusseler Ring 34, 67069 Ludwigshafen,

PCT International Classification Number

B01J27/14

PCT International Application Number

PCT/EP2004/003103

PCT International Filing date

2004-03-24

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	103 14 761.6	2003-03-31	Germany