MXPA01001809A - Method for producing cyanovaleric acid or esters thereof - Google Patents

Abstract

The invention relates to a method for producing cyanovaleric acid or esters thereof by reacting 2-, 3- or 4-pentene nitrile or mixtures thereof with carbon monoxide and with a compound containing hydroxyl groups in the presence of a catalyst system. Said catalyst system comprises:(i) a palladium (II) compound, (ii) a bidentate diphosphine ligand and (iii) an anion source. The invention also relates to novel catalyst systems with diphosphine ligands of the bis(phosphinomethyl)amine type.

Description

PROCEDURE FOR THE ELABORATION OF ACID OR CIANOVALERIC STERES Description The present invention relates to a process for the preparation of cyanovaleric acid or its esters by the transformation of 2-, 3- or 4-pentenorutrilo or mixtures thereof, with carbon monoxide and a compound containing hydroxyl groups, in presence of a catalyst system. o 5-cyanovaleric acid and its esters are valuable starting substances for the production of dyes, pesticides, fibers, especially polyamide fibers, and synthetic substances. By hydrogenation to obtain 6-aminocaproic acid or. where appropriate, esters of 6-aminocaproic acid and separation of water or alcohol, caprolactam is obtained. The production of cyanovaleric acid and esters of cyanovaleric acid by carbonylation of pentenenitriles in the presence of catalysts is known. The known syntheses are carried out by transformation of a pentenenitrile with carbon monoxide, in the presence of water or alcohol, at elevated temperature and high pressure, in the presence of a catalyst system. Cobalt compounds such as C? 2 (CO) 8 or Co (OAc) 2 are used predominantly as a catalyst system, in addition using nitrogenous bases (see GB-1 497 046 and DE-2 541 640), special solvents such as sulfolane (see US 4 508 660), cyclic derivatives of amides or urea (see EP-373 579) or nitnets (see EP-377 838 and US 4 933 483). 5 a ^ ^ ^, ^^^^ a¡ ^ g¡ | g ^ ¡¡^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ pentenonitrile to obtain cyanovaleric acid.

Substances that contain groups? Y¡gj¡ often form complexes with transition metals. The catalytically active catalyst complexes tend to be deactivated by coordination with nitrile. This is especially true for palladium. since palladium very easily forms stable complexes with mtryl as, for example, (PhCN) 2PdCl2, (CH3CN) 2PdCl2. Therefore, the carbonylation of olefins containing nitrile groups, catalysed by palladium, generally takes place with an activity very low catalytic. Thus, US 4257 973 describes the carbonylation of 3-pentenenitrile with the catalyst system (Ph3P) 2PdCl2 / SnCl2. The reaction proceeds with an unknown selectivity and the yield of esters of unspecified cyanoacids precisely amounted to only 5% (see example 108 of US 4 257 973).

The EP 0 495 547 describes a process for the monocarbonylation of unsaturated compounds in the form of olefins, optionally substituted, in the presence of a catalyst system comprising Pd cations, a bivalent diphosphine binder and a source of anions According to the description of EP 0 495 547 the starting olefin can be substituted, for example, by cyano or nitrile groups. If derivatives are used In the case of alkenic acids, such as nitriles of alkenic acids, as starting substances, the alkenic acid derivative preferably must be a derivative of 2-alkenic acid. In the carbonylation of alkenic acid derivatives, the catalyst system preferably comprises a promoter, for example, quinones and nitro compounds. In In this case, Example 59 of EP 0 495 547 describes the carbonylation of acrylonitrile with carbon monoxide and methanol. in the presence of Pd (OAc) 2. TBPD (1,3-bis (di-n-butylphosphine)? Ropano, NiTFS (nickel di-trifluorometul sulphonate) and 1,4-naphthoquinone However, the transformation to obtain monomethylester mononitrile of maleic acid was only produced by 5%. with respect to the acrylonitrile used Knowing EP 0 495 547 the expert for the transformation of other olefins substituted by nitrile than acrylonitrile would have expected even lower yields, according to the procedure described therein.

Surprisingly it was now found that the carbonylation of 2-, 3- or 4-pentenenitrile is achieved with a catalyst system which is comparable to that of EP 0 495 547, with high yield and high selectivity. In addition, new catalyst systems and new diphosphin binders were found, with which the yield and selectivity can be further increased.

The present invention therefore relates to a process for the preparation of cyanovaleric acid or its esters by the transformation of 2-, 3 or 4-pentenenitrile or mixtures thereof, with carbon monoxide and a hydroxyl group-containing compound. in the presence of a catalyst system comprising: (i) a palladium (II) compound (ii) a bivalent diphosphinic binder and (iii) a source of anions. 2-, 3- or 4-pentenenitrile or mixtures thereof are used as starting materials for the carbonylation according to the invention. It is preferable to use 3- and / or 4-pentenenitrile or, where appropriate, mixtures containing 3- and / or 4-pentenenitrile j ^^ i ^^^^^^^^^^^^^^^^^^^^^^^^ as main components. Of greater pretersf fa are the 3-pentenot? Itrilo or mixtures with 3-pentenonitrilo like main component. The 3-pentenenitrile can be prepared. for example, by adding hydrocyanic acid to butadiene, for example, in the presence of complex compounds containing nickel, or copper (I) chloride. according to the ways of proceeding described in the German publications 1 593 277, 2 344 767 and 2 009 470.

In the process according to the invention, 5-cyanovaleric acid with high selectivity is obtained, regardless of whether 2-, 3- or 4-pentenenitrile or a mixture thereof is used. that first one occurs isomerization giving 4-pentenenitrile. The carbonylation of 4-pentenenitrile to give 5-cyanovaleric acid (ester) acid, according to the process according to the invention, occurs in a highly regioselective manner, with selectivities that are generally above 70%, preferably above 80% with reference to the cyanovaleric acid (acid ester) formed. In the case of the palladium (II) compound, it is preferably a palladium salt. Examples of suitable palladium salts are, inter alia, salts of nitric acid, sulfuric acid, sulfonic acids, for example chlorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, t-butylsulfonic acid, p-20 toluenesulfonic acid or a sulfonated ion exchange resin, or a carboxylic acid, for example, an alkanoic acid such as acetic acid or trifluoroacetic acid. It is understood that if in the case of the palladium (II) compound it is a palladium salt of an appropriate acid, this compound at the same time can represent the source of anions to be used according to the invention. The palladium (II) compound can also be in the form of a palladium complex, for example, a complex with a bivalent diphosphinic binder. In this case the palladium (II) compound at the same time contains the bivalent diphosphinic binder, used according to the invention. The palladium compound (II) can also be formed in situ. starting from the elementary state.

The amount of palladium (II) compound is not critical. Preferably the amount amounts to 10'7 to 10"1 mol of Pd per mol of pentenonitrile used, especially from W6 to 10'2.

The bivalent diphosphinic binder can be used as such or in the form of a complex with the palladium (II) compound. Preferably, the diphosphinic binder has the following general structural formula: R'R ^ -X-PR where R1, R2, R3 and R4, independently of each other, represent Cx- to C20-alkyl, C3-a C?-Cycloalkyl, aryl or heteroaryl with up to 4 condensed aromatic rings or C7- a Cio-aralkyl, which, if appropriate, can be substituted, or R1 and R2 together and / or R3 and R4 together represent C2- to C20-alkylene, arylene or heteroarylene with up to 4 aromatic rings, C7- to C20-aralkylene, which, if necessary, can be substituted, and X represents a bivalent moiety forming a bridge, by which the phosphorus atoms that flank it are separated by 1 to 10 atoms.

The most preferred diphosphinic binders are characterized by R1. R.

R "and R4, independently of each other, each represents an unsubstituted alkyl radical, optionally branched, optionally cyclic of 1 to 10 carbon atoms or R1 and R: together> or R3 and R4 together form an alkylene radical, optionally branched, optionally cyclic, of 1 to 10 carbon atoms.

In particularly preferred embodiments R1, R2. R3 and R4 are chosen from methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl and / or cyclohexyl radicals or R1 and R2 together and / or R3 and R4 together form a pentamethylene, hexamethylene or cyclooctylene radical . When it is indicated above that the radicals R.sub.1, R.sub.2, R.sub.3 and R.sub.4, if appropriate, can be substituted, they can be any substituents which do not impair the catalytic activity of the system. Appropriate substituents are. among others, halogen atoms, alkoxy groups, haloalkyl groups, halogenoalkoxy, acyl residues, acyloxy, amino, hydroxyl, nitrile, acylamino and aryl groups.

The diphosphinic binder to be used according to the invention is bivalent, that is, it must have the two phosphine phosphors at a distance and in an intramolecular configuration that allow the formation of a coordinated bond of both phosphorus atoms with a single palladium atom. . Therefore, in the structural formula of preference shown above, X represents a bivalent bridge-forming residue, whereby the phosphorus atoms that flank it are separated by 1 to 10 atoms. The bridging group preferably does not contain substituents that aesthetically impede coordination. Preferably X represents an alkylene chain which, if appropriate, contains heteroatoms, such as a bivalent carbon, an ether residue or a thioether radical. m > * '- 1' ^ iJi á2S ^ »^ i? ^ Il & ^^ Examples of groups of bridge formers X are. for example: -CH2-í -C? 2CH.-. CH2CH2CH2-. -CH2OCH2-. -CH2SCH2-. -CH2CH: CH2CH: -. -CH2CH üCH: CH: -. -CH2CH2SCH2CH2-. -CH2CH: OCHiCH:? CH2CH: -. -CH, C (CH3) 2-CH2-. -CH2-CH (CH3) -0-CH (CH3) -CH2-.

They are therefore examples of bivalent diphosphinic binders: 1,2-bis (di-n-butylphosphine) ethane, 1,3-bis (dimethylphosphin) propane, 1,3-bis (di-i-propylphosphine) propane, 1,3- bis (di-n-propylphosphine) propane, 1,3-bis (di-i-butyphosphine) propane, 1,3-bis (di-n-butylphosphin) propane, 1, -bis (di-s-butylphosphine) propane , 1,3-bis (di-t-butylphosphine) propane, 1,3-bis (di-n-hexylphosphine) propane, 1,2-bis (di-cyclohexylphosphine) ethane, 1,3-bis (n-butylmethylphosphine) propane , l, 3-bis (n-butyethylphosphin) propane, l, 3-bis (l, 5-cyclooctylenephosphine) propane and its mixture of isomers containing 1,4-cyclooctylene groups; l, 4-bis (di-i-propylphosphine) butane, 1,5-bis (dimethylphosphin) -3-oxapentane, 1,8-bis (di-n-butylphosphin) -3,6-dioxaoctane and 1,4-bis (di-n-butylphosphin) -2,2,3,3-tetramethylbutane.

In particularly preferred embodiments X represents -CH2-N (R5) -CH2-, where RJ represents hydrogen, Ci- to C20-straight or branched chain alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t -butyl, pentyl, hexyl, octyl, C3- to o-cycloalkyl, optionally substituted by - a Cfi-alkyl, including bicycloalkyl, such as cyclopropyl, cyclopentyl, cyclohexyl, nor-bomyl, pinanyl, bomyl, biciclononyl, C6- to C20-aryl, optionally substituted by C to C6-alkyl, such as phenyl, tolyl, naphthyl, C7- to C20-aralkyl. if necessary, substituted by Ci- a Cß-alkyl, for example, with 1 to 6 JMMB ^ ÉÉS ^ aJfa C atoms in the alkyl moiety and from 6 to 14 C atoms in the aryl moiety. as benzyl. C_ a o-heteroaryl. if necessary, replaced by - a CValquilo. as pyridyl. pinmidil. pyrazil triazinyl and C2- to C21-acyl.

Provided that the stated radicals can be substituted by C to C6-alkyl. they can be substituted by one or more alkyl groups, for example, methyl or ethyl.

C The moieties listed above may be substituted by one or more, for example, from 1 to 5 substituents chosen from -NO, -NO2, -CN, -CO2", -CO2R6, -CORR2, halogen, ie, F, Cl, Br, I, -NR62, -ORd, -NR6 + 3, -SO3 \ -SO3R6, -SO2R, SO2NR62 and SLR73, where R6 can represent hydrogen, Cj- a C? O-alkyl, especially methyl, ethyl or i-propyl, or C6- a C? -Aryl, especially phenyl. and R7 may represent -Cio-alkyl, especially methyl, ethyl or i-propyl, or C6 to C? 4 -aryl, especially phenyl. Also, in the remains mentioned above, 1 can be exchanged, 2, 3 or 4 carbon atoms per N or O.

R5 may represent, for example, a group - (CH2) "- Q which, if appropriate, may be substituted and may contain heteroatoms such as oxygen or nitrogen, or arylene units, such as phenylene, in the alkylene chain, where Q represents -SO3-, CO2 ', C02R6, -CONR62, halogen, -NR62, -OR6, NR6 + 3 and n = 1-20, especially preferably 1- 10. Rf can also represent SiR73, such as thiimethylsilyl, t-butyldimethylsilyl, triphenylsilyl.

It is preferred that R3 represents a moiety that attracts electrons, since this increases the stability of the diphosphinic compound. As R5 remains that attract g83ttB Sm electrons are suitable for C2o-linear or branched alkyl which is substituted by at least one electron-withdrawing group, where the group that attracts electrons is preferably in position a-, β-. y- and o d, especially in position y or ß, with respect to the nitrogen atom. C6- to C4-aryl substituted by at least one electron withdrawing group, as well as nitrile, sulfinyl groups (-S02R). sulfonyl (-SO3R) and nitro groups. In addition R5 can represent -C (O) R8. where R8 represents C to C: linear or branched o-d-alkyl, C6- to Ci4-aryl or aralkyl with 1 to 10 C atoms in the alkyl and from 6 to 14 C atoms in the arith, - to C20-linear alkyl or branched which is replaced by at least one electron-attracting group, where the group that attracts electrons is preferably in position a-, β-, β- and / od with respect to group C (O) -. as well as C6- to C ^ -aryl which is substituted by at least one electron withdrawing group. R8 moieties are preferably, inter alia, methyl, ethyl, i-propyl. phenyl, trifluoromethylphenyl, trifluoromethyl or pentafluoroethyl.

Substituents which attract electrons in an alkyl or aryl radical Rs are halogen atoms, such as fluorine, chlorine or bromine, preferably fluorine and chlorine, and especially fluorine. The alkyl and aryl moieties may be partially halogenated, and may also be perhalogenated. In addition, the nitro, nitrile, ester, amide, sulfinyl, sulfonamide and sulfonyl groups are suitable as substituents for the alkyl and aryl moieties. The aryl moieties can also be substituted by trifluoror- or trichloromethyl groups, as well as ammonium moieties. By way of example, we mention as suitable alkyl radicals Rs: trifluoromethyl, trichloromethyl, difluoromethyl, 2,2,2-t-ifluoroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl, pentafluoroethyl, nitromethyl, 2- nitromethyl, 2-nitroethyl and cyanomethyl. They are preferably trifluoromethyl and 2,2,2-trifluoroethyl. As an example, mention aryl glycols R "appropriate- p- .m- or o-fluorine or chloro-phenyl 2,4-difluorophenyl 2,4-dichlorophenol, 2,4,6-trifluorophenyl, pentafluorophenyl, 2,4,6-trichlorophenyl. nitrophenyl, 2,4-dinitroferulum, 2-chloro-5-nitrophenyl, 2-bromo-5-nitrophenyl, methylsulfinylphenyl and methylsulfonylphenyl.

The invention further relates to a catalyst composition comprising a palladium (II) compound and a diphosphine compound of general structural formula R'R2P-CH2-N (R5) -CH2-PR3R4, wherein from R1 to R have the meanings and meanings of preference already indicated. In particularly preferred embodiments of the catalyst composition according to the invention R1 and R2 together and R3 and R4 together, independently of one another, represent 1,3 and / or 1,4-cyclooctylene and R 3 represents 2,4-difluorophenyl, pentafluorophenyl or 2.4.6-trifluorophenyl.

As for the palladium compound (II), reference is made to the specifications made at the beginning of this description. The catalyst composition may contain a source of anions or may be used together with a source of amons. When the palladium (II) compound is the palladium salt with an appropriate acid, then this at the same time 'can represent the source of amones. Such diphosphine compounds are also referred to as bis (phosphinomethyl) amines. The preparation of some representatives was described by J. Fawcett, P.A.T. Hoye et al. in J. Chem. Soc. Dalton Trans. 1993, 2563-2567.

Some of the bis (fosfmomethyl) amines as such are new. Therefore, the invention also relates to diphosphinic compounds of general structural formula R'R P-CH NíR 'ILPR'R4. where R1 to R "have the meanings and meanings of preference are indicated, except that the compounds in which R1, R3 and R4 are equal and represent phenyl and R5 represent CHMePh, CHMeCO2? le, are excepted. CH? LeC02Et, endo- (lR) -l, 7,7-trimetubiciclo [2.2.1] heptano-2-yl, CH2CH2OH or CH2CH = CH2; R1, R2, RJ and R4 are identical and represent cyclohexyl and R5 represents CHMePh or CHMeCO2H, R1 and R2 together, as also R3 and R4 together represent cyclooctylene and R5 represents CHVIePh (Me means a methyl residue, Et an ethyl moiety and Ph means a phenyl moiety).

The elaboration of the bis (fosfinometü) apunas is achieved, for example, according to the following general scheme X PH + ñP + 2 CH20 + R5NH2 i ^ " • ^ "^^ 15 D L R5 t RL 3 / -CH2-N-CH2-P R4 Conventional reaction conditions analogous to the 20 dignts can be conveniently chosen in J. Fawcett, P. A. Hoye, et al., J. Chem. Soc. Dalton Trans. 1993, 2563-2567. Thus bis (phosphinomethyl) amines can be easily made in a single vessel reaction by converting the secondary phosphine with formaldehyde and ammonia or a piimana amine, for example, in a solvent such as toluene, to a temperature of preferably 80 ° C to 150 ° C. 25 l > Preferably the molar ratio of the diphosphinic compound to the palladium (II) compound, with reference to palladium. is in the range of 0.5 to 20: 1. especially in the field of 1 to 5: 1.

Levvis and protonic acids and their mixtures are considered as anion source. Preferably as weak anion sources, organic acids are used, for example, with a Pka value of 3.5 or higher, especially sterically hindered organic acids. Preferred organic acids are, for example, benzoic acid, 2,4,6-trimethylbenzoic acid, 2,6-dichlorobenzoic acid. 9-anthracene acid, pivalic acid, 1,2,3-benzenetricarboxylic acid and its partial esters, 2-ethoxy-1-naphthalenecarboxylic acid, 2,6-dimethoxybenzoic acid, acetic acid, propionic acid, butyric acid and / or cyanovaleric acid .

In addition, strong mineral acids such as sulfuric acid, perchloric acids, as well as strong organic acids such as sulfonic acids can be used, for example, methanesulfonic acid, p-toluenesulfonic acid and benzenesulfonic acids, as well as trichloroacetic and trifluoroacetic acid.

The molar ratio of the source of anions to the palladium (II) compound is not critical. Preferably the molar ratio of the source of anions to the palladium compound (II) is in the range of 0.5-100: 1, especially in the range of 1-10: 1, equivalent per mole of Pd.

The use of cyanovaleric acid is especially preferred because the esterification of the organic acid used as a source of anions, with the compound containing hydroxyl groups, For example, an alcohol, which is produced as a secondary reaction, then does not lead to a contamination of the product of the reaction obtained.

In the case of the compound containing hydroxyl groups which is used in the process according to the invention, it can be treated, for example, with water or an alcohol, especially an alcohol with 1-6 carbon atoms. any primary, secondary or tertiary alcohol Examples of alcohols are, inter alia, methanol, ethanol, propanol, i-propanol, butanols, n-hexanol, n-octanol, i-octanol, 2-ethylhexanol, cyclohexanol, alcohol benzyl, phenylethyl alcohol, ethylene glycol, 1,2 and 1,3-propylene glycol, neopentyl glycol, trimethylolpropane and pentaerythritol Methanol and ethanol are particularly preferred.

The process according to the invention is conveniently carried out at a temperature of 40-200 ° C, preferably 75-170 ° C. The process according to the invention can be carried out conveniently at a pressure of 1-200 bar, preferably 5-70 bar. The transformation can be carried out in discontinuous, continuous or semi-continuous conditions. Reaction times in general amount to 0.5 hour up to 10 hours.

The catalyst system to be used according to the invention can be homogeneous or heterogeneous. The catalyst system can also be used in immobilized form. ßmßsu a Appropriate supports are. for example, ion exchangers, where, for example, it produces an interaction between ionic groups in the diphosphinic compound. for example. certain substitutes Q in the re in the ion exchanger. The immobilization can be effected by adding a solution of the catalyst system to the ion exchanger, where the catalyst system remains attached.

The process according to the invention is preferably carried out in the liquid phase. The liquid phase may be formed by the pentenonitrile used or by the hydroxy-containing compound used. Alternatively or additionally it may also consist of a solvent. Any inert solvent can be used. Examples of these are sulfoxides and sulfones. for example, dimethylsulphide, diisopropylsulphone or tetrahydrothiophene 2,2-dioxide, 2-methylsulfolane, 3-methylsulfolane, 2-methyl-4-butylsulfolane; aromatic hydrocarbons, such as benzene, toluene, xylene; esters, such as methyl acetate and butyrolactone; ketones, such as acetone or methyl isobutyl ketone; alcohols, such as methanol and ethanol, ethers, such as tetrahydrofuran, anisole, 2,5,8-trioxanonane, diphenyl ether and diisopropyl ether; amides, such as dimethylacetamide and N-methylpyrrolidone.

The process according to the invention is preferably carried out under high oxygen exclusion. To this end the reaction vessel, for example, is evacuated several times and then ventilated with a protective gas, for example, nitrogen. The reactants, the solvent and the catalyst system are added under exclusion of air.

The process according to the invention can be carried out, for example, in the following manner: 2-pentenenitrile is poured. 3-? Entenonitrilo. 4-Pentenenitrile or a mixture thereof, the compound containing hydroxyl groups. the catalyst system and, if necessary, a solvent, in a pressure-resistant reactor. Then carbon monoxide is added under pressure and the reactor is brought to the desired reaction temperature. If necessary, the pressure of the reaction can be adjusted by additionally adding carbon monoxide under pressure or, if necessary, removing carbon monoxide. After the transformation, the pressure of the mixture can be cooled and lowered. The cyanovaleric acid or its esters can be isolated from the mixtures according to customary methods, for example, by fractional distillation.

The catalyst system used can be formed in situ under the conditions of the reaction. But alternatively and preferably the catalyst system is prepared previously. For this purpose, for example, the palladium (II) compound, the bivalent diphosphinic binder and, if appropriate, a source of anions, are dissolved or suspended respectively in solvents mutually miscible with each other and the solutions or suspensions are combined. The complex compound of palladium (I?) - diphosphine can then be isolated, if appropriate, after the addition of a diluent that lowers the solubility, for example, by filtration.

The invention is explained in more detail by the following examples. gSgj ^^^^ i ^ ji ^^^^^^^^^ ii? B ^^^^^^^ J ^ Sfe ^ • * Example 1 28 mg (0.125 mmol) of palladium (II) acetate were incorporated. 155 mg (0.5 mmol) of a mixture of 1,3-bis (1,5-cyclooCythylenephosphine) ethane and 1,2-bis (1,4-cyclooctylenphosphine) ethane and of the compounds mixed with groups 1.5 and 1,4-cycloocti (bcope), 445 mg (2.0 mmol) of 9-anthracenecarboxylic acid and 3 ml (31 mmol) of 3-pentenenitrile in 10 ml of diphenyl ether and 5 ml of methanol and poured into an autoclave - * » , of 100 ml. After closing the autoclave a carbon monoxide pressure of 40 bar was exerted. The autoclave was heated to 150 ° C and the total pressure was adjusted to 60 bar. After the reaction time indicated in table 1 the transformation was finished by cooling the autoclave. The overpressure of the autoclave was removed and the liquid product was analyzed by gas chromatography.

Example 2 Example 1 was repeated, but carrying out the transformation in an autoclave of 300 t mi and adding the following reactants in the indicated quantities: 112 mg (0.5 mmol) of palladium (II) acetate, 845 mg (2.0 mmoles) of l, 2-bis (dicyclohexy] phosphine) ethane, 2.2 g (10 mmoles) of 9-anthracenecarboxylic acid, 12 ml (124 mmoles) of 3-pentenenitrile. 20 ml of methanol and 40 ml of diphenyl ether. twenty Example 3 Example 1 was repeated, but using the following reactants in the indicated amounts: 28 mg (0.125 mmol) of palladium (II) acetate, 116 mg (0.375 mmol) of bcope, 445 mg (2.0 mmol) of acid 9-anthracenecarboxylic acid. 10 ml (103 mmol) of 3-pentenenitrile and 15 ml of methanol.

Example 4 For this example, the palladium (I?) - diphosphine complex was previously prepared. 1.0 g (4.4 mmol) of palladium (II) acetate was dissolved in 50 ml of acetone, stirred for 2 hours at room temperature and filtered through celite. To the filtrate was added a suspension of 2.1 g (4.4 mmol) of bcope in 50 ml of acetone and stirred for 1 h at room temperature. The pale yellow solid substance that formed [(bcope) Pd (OAc) 2] was filtered off and dried in vacuo. Yield: 2.2 g (94%).

Example 1 was repeated, but using the following reactants in the indicated amounts: 67 mg (0.125 mmol) of (bcope) Pd (OAc) 2, 445 mg (2.0 mmoles) of anthracenecarboxylic acid, 10 ml (103 mmoles) of 3-pentenenitrile and 15 ml of methanol. The results are indicated in the following table.

^^ ^ J ^ i ^^^ s & ^ ^ k ^ S ^^^ Example Time of 1 Transformation TOX TOF Selectivity Selectivity CVE = cyanovaleric acid ester TON = replacement number TOF = replacement frequency The comparison of example 4 with example 3 shows that using the defined complex (bcopeJPd OAc ^ previously prepared, an improvement in catalyst activity is achieved.) Another advantage of using the defined complex, prepared previously, is that no excess is necessary of diphosphinic compound.

Example 5 This example explains the preparation of a mixture of 1, 3-bis- (1, 4-cyclooctüenfosfmometü) f enylamine, 1, 3-bis- (1, 5-cyclooctüenfosfínometü) fenña rtina, 1 - (1, 4-ciclooctilenfosfinomethyl) ) -3- (1, 5-cyclooctüenfosfinometü) phenylamine. 1.2 g (0.035 mol) is suspended in 100 ml of toluene and the suspension is heated to 65 ° C. 1.6 ml (0.0175 mol) of aniline and 5 g (0.035 mol) of a mixture of 1,4-cyclo-ruthenyl-phosphine and 1-cyclooctenyl-phosphine are added. After 5 hours a clear solution is obtained which is concentrated after cooling. The residue is taken up in 50 ml of dichloromethane and the phosphine chelate is precipitated by the addition of ethanol. After filtering, the white residue is dried under vacuum. Yield: 4.8 g (68%).

Example 6 This example explains the preparation of 1, 3-bis- (1, 4-cyclooctylene-phosphinomethyl) (2,4-difluorfenu) amine, 1,3-bis- (1, 5-cyclooctylene-phosphinomethyl) (2,4-difluoride). ü) amine, 1 - (1, 4-cyclooctüenfosfinometü) -3- (1, 5-ciclooctüenfosfinometü) (2,4-difluorfenü) ap? ina (aza-bcope). 1.2 g (0.035 mol) of paraformaldehyde is suspended in 100 ml of toluene and the suspension is heated to 65 ° C. Add 1, 8 ml (0.0175 mol) of 2,4-difluoroaniline and 5 g (0.035 mol) of a mixture of 1,4-cyclooctenylphosphine and 1,5-cyclooctenylphosphine and stir the solution at 65 ° C. overnight. After cooling, the solvent is removed in vacuo, the residue is taken up in 20 ml of dichloromethane and the product is precipitated by the addition of ether. The white solid substance is separated by filtration and dried under vacuum. Yield: 5.4 g (70%). ..... "; ./ ..- j ^ SaattaáÉM-ai ^ ei ^^ g ^^ tea ^ MiS ^^ a ^^ ^ Example 7 This example explains the elaboration of a mixture of the complexes 1,3-bis- (1,4- cyclooctilenfosfmometü) (2,4-difluorfer?) Arnin-Pd (OAc) 2, 1, 3-bis- (1.5- 5 cyclooctüertfosfinometü) (2 , 4-difluorophenyl) amin-Pd (OAc) 2 and 1- (1,4-cyclooctüenfosfmometü) -3- (1, 5-cycloctüenfosfmometü) (2,4-difluo? Fenü) amin-Pd (OAc) 2. 0.45 g (2.0 mmol) of palladium (II) acetate were dissolved in 50 ml of acetone, stirred for 2 h at room temperature and filtered through celite. A suspension of 0.88 g (2.2 mmol) of aza-bcope in 50 ml of acetone was added to the filtrate and stirred for 1 h at room temperature. The light yellow solid formed was separated by filtration and dried in vacuo. Yield: 1.1 g (88%).

Example 8 15 This example explains the carbonylation of 3-pentenenitrile, using the complex (aza-bcope) Pd (OAc) 2. Example 1 was repeated, but using the following reactants in the indicated amounts: 79 mg (0.125 mmol) of (aza-bcope) Pd (OAc) 2 (see example 7), 445 mg (2.0 mmoles) of anthracenecarboxylic acid , 10 ml (103 mmol) of 3- 20 pentenenitrile and 15 ml of methanol. ^ fc ^ ggg ^^^^^^^^ ggagggg fig ^ ----. - ~ »> - ^ - »..... ~. Fc-ajL- $ £ a £ j ^^^^^^ dm ^^^^ j & & amp; mB * Example Time i Transfor- -V - SelectiviSelectivi¬ The comparison of example 8 with example 4 shows that the catalyst system (aza-bcope) Pd (OAc) 2 has a clearly higher catalytic activity. 10 c twenty

Claims (6)

1. Claims 1. Process for making cyanovaleric acid or its esters, by transforming 2-, 3- or 4-pentenenitrile or mixtures thereof, with carbon monoxide and a compound containing hydroxyl groups, in the presence of a catalyst system comprising: (i) a palladium (II) compound (ii) a bivalent diphosphinic binder and (ii) a source of anions.
2. 2. Process according to claim 1, characterized in that the diphosphinic binder has the following general structural formula: R ^ P-X-PR'R4 where R1, R2, R3 and R4, independently of each other, represents - a C20-alkyl, C3- a or -cycloalkyl, aryl or heteroaryl with up to 4 condensed aromatic rings, C7- to C20-aralkyl, which, if appropriate, may be substituted, or R1 and R2 together and / or R3 and R4 together represent C2- to C2o-alkylene, arylene or heteroarylene with up to 4 aromatic rings or C7- to C20-aralkylene, which, if appropriate, may be substituted, and X represents a bivalent moiety forming ¡G | 3a? Tí ^ r: 1 ^ .z. ^ FS £? S¿ ^ i ^? ^ ~ Bridge, where the phosphorus atoms that flank it are separated by 1 to 10 atoms.
3. 3. Process according to claim 2, characterized in that R1. R \ R3 and R4. Independently of each other, each represents an unsubstituted alkyl moiety. where appropriate, branched, optionally, cyclic with 1 to 10 carbon atoms, or R1 and R2 together and / or R3 and R4 together form an alkylene radical, optionally branched, optionally cyclic with 1 to 10 carbon atoms.
4. 4. Process according to claim 3, characterized in that R1, R2, R3 and R4 are chosen from methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl and / or cyclohexyl radicals or R1 and R2 together and / or R3 and R4 together form a pentamethylene, hexamethylene or cyclooctylene moiety.
5. 5. Process according to one of claims 2 to 4, characterized in that X r represents an alkylene chain which, if appropriate, contains heteroatoms.
6. 6. Process according to claim 5, characterized in that X represents twenty - . 20-CH2-N (R5) -CH2- wherein R5 represents hydrogen, Ci- to C20-alkyl, C3- to C-0-cycloalkyl, optionally, substituted by C to C6-alkyl, C6- to C4- aryl, if appropriate, substituted by Ci- a Ce-alkyl, C7- to C20-aralkyl. if necessary, substituted by Ci- to C6-alkyl, 25 C3- to C20-heteroaryl. if necessary, substituted by - to C6-alkyl, C2- to C2? -acilo. where the residues stated above can be substituted by substituents chosen from -NO. -NO2, -CN. -C02 ' -CO: R6. -CONR62, halogen, -NRd2, -OR6. -NR63". -SO3 '. -SO3R6, -SO2R6, SO2NR62 and SiR 3 or, where appropriate, in the residues listed above, 1, 2, 3, or 4 carbon atoms may be exchanged for N or O, as well as it may represent a nitro, nitrile, sulfinyl, sulphonyl or SiR73 group, where R6 represents hydrogen, - to C10-alkyl or C- to C1-aryl and R7 may represent - to C10-alkyl or C6- to Cw-aryl. Process according to one of the preceding claims, characterized in that the source of anions is an organic acid with a pKa value of 3.5 or greater. Diphosphinic compound of general structural formula R1R2P-CH2-N (Ri) ^ CH2-PR3R4, where R1, R2, R3 and R4, independently of each other, represent C? - a C20-alkyl, C3- to C? o-cycloalkyl, aryl or heteroaryl with up to 4 condensed aromatic rings, C7- to C ^ -aralkyl, which if appropriate, they can be substituted, or R1 and R2 together and / or R3 and R4 together represent C2 to C20-alkylene, arylene or heteroarylene with up to 4 aromatic rings or C7- to C20 aralkylene, which can optionally be be substituted, and R5 represents hydrogen, - a C20-alkyl, C3- to C? o-cycloalkyl, optionally substituted by Ci- to C6-alkyl, C6- to C20-aryl, given the case, substituted by d- to C6-alkyl. C- to C 0-aralkyl. optionally substituted by C? - a C6-alkyl, C3- to C20-heteroaryl. if necessary, replaced by - a C6- alkyl, C2-C2? -acyl, where the residues listed above can be substituted by substituents chosen from -NO. -N'02 -CN -C02"-C02R6, CONR62, halogen, -NR62, -OR6, -NR63 +, -SO3", -SO3R6. -SO2R6. SO2NR62 and SiR73 or, where appropriate, in the residues listed above 1, 2, 3, or 4 carbon atoms may be exchanged for N or O, as may also represent nitro, nitrile, sulfinyl, sulfonyl or SiR73 groups, where R6 can represent hydrogen, d- to C? o-alkyl or C6- to Cw-aryl and R7 can represent d- to C10-alkyl or C6- to C? 4-aryl, with the exception that the compounds in the which R1, R2, R3 and R4 are equal and represent phenyl and R1 represents CHMePh, CHMeCO2Me, CHMeCO2Et, endo- (lR) -1.7.7- trimethylbicyclo [2.2.1] heptane-2-io, CH2CH2OH or CH2CH = CH2; R1, R2, R3 and R4 are identical and represent cyclohexyl and R3 represents CHMePh or CHMeCO2H; R1 and R2 together, as also R3 and R4 together represent cyclooctylene and R3 represents CHMePh. ' 9. Catalyst composition comprising a palladium (II) compound and a diphosphinic compound of general structural formula RXR2P-CH2-N (R3) -CH2-PR3R4, where R1, R2, R3 and R4, independently of each other, represent - a C20-alkyl, C3- a or -cycloalkyl, aryl or heteroaryl with up to 4 aromatic rings áj & * - 4 »aiM« ifaa condensed, T- to C20-aralkyl, which. if appropriate, they may be substituted, or R1 and R2 together or R3 and R4 together represent C2- to C2o-alkylene. arylene or heter-arylene with up to 4 aromatic rings or C- to C20- < ? ralquilene. what. where appropriate, they may be substituted, and R5 may represent hydrogen, d- to do- alkyl, C3- to C- or cycloalkyl, optionally substituted by Ci- a Ce-alkyl, C6- to do-aryl, If necessary, substituted by C6-C6-alkyl, Ct- to C20-aralkyl, if appropriate, substituted by C to C6-alkyl, C3- to C20-heteroaryl, optionally substituted by d- a Ce -alkyl, C2- to C2? -acyl, where the radicals mentioned above can be substituted by substituents chosen from -NO, -NO2, -CN, -CO2 ', -CO2R6, -CONR62, halogen, -NR62, -OR6 , -NR63 +, -SO3-, -SO3R6, -SO2R6, SO2NR62 and SiR73 or, as the case may be, in the abovementioned radicals 1, 2, 3 or 4 carbon atoms can be exchanged for heteroatoms, as can also be represented by a group nitro, nitrile, sulfinyl, sulfonyl or SiR73, where R6 represents hydrogen, Ci- a C10-alkyl or Ce- a Ch¬ Allyl and R7 can represent Ci- a Cio-alkyl or C6- a C? 4-aryl. c twenty 25 H¡jj * - "AS-