Title of Invention

A PROCESS FOR HYDROCYANATING A HYDROCARBON CONTAINING ETHYLENIC UNSATURATION

Abstract

The invention concerns a method for hydrocyanation of ethylenically unsaturated organic compounds into compounds comprising at least one nitrile function. It concerns particularly hydrocyanation of diolefins such as butadiene or substituted olefins such as alkenenitriles like pentenenitriles. The method is characterized in that the reaction is carried out in the presence of a metal complex catalyst comprising a transition metal such as nickel and an organic ligand.

Full Text

The present invention concerns" a process for hydrocyanating ethylenically unsaturated organic compounds to compounds containing at least one nitR1le function. It relates more particularly to the hydrocyanation of diolefins such as butadiene or of substituted olefins such as alkenenitR1les, for instance pentenenitR1les. The hydrocyanation of butadiene to pentenenitR1les is an important reaction which has been implemented industR1ally for a number of years, particularly in the process for synthesizing adiponitR1le, a major chemical intermediate which allows access- in particular to the monomers of numerous polymers, foremost among which are the polyamides. French patent 1 599 761 descR1bes a process for prepaR1ng nitR1les by addition of hydrocyanic acid with organic compounds having at least one ethylenic double bond, in the presence of a nickel catalyst and a tR1aryl phosphite. This reaction may be conducted in the presence or absence of a solvent. When a solvent is used in this pR1or art process it is preferably a hydrocarbon, such as benzene or xylenes, or a nitR1le such as acetonitR1le. The catalyst employed is an organometallic complex of nickel, containing ligands such as phosphines, arsines, stibines, antimonites, arsenites, phosphites, phos-phinites or phosphonites. The processes for hydrocyanating dienes generally compR1se two steps: a first hydrocyanation, leading to branched and linear unsaturated mononitR1les, and a second step which allows the dinitR1les to be obtained. Often only the linear nitR1les are of interest for the synthesis of new products ■ such as, for example, adiponitR1le. These processes therefore also include an intermediate step, which is referred to as the isomeR1zation step and consists in treating the branched unsaturated mononitR1les to convert them" into linear unsaturated mononitR1les. The presence of a promoter to activate the catalyst, such as a. boron compound or a metal salt, generally a Lewis acid, is also recommended for carrying oii"t the second step. Patent FR-A-2 333 253 proposed carrying out the hydrocyanation of compounds having at least one ethylenic unsaturacion in the presence of an aqueous solution of a compound of a transition metal, particularly nickel, palladium or iron, and of a sulphonated phosphine. The sulphonated phosphines descR1bed in said patent are sulphonated tR1arylphosphines and more particularly sulphonated tR1phenylphosphines. This process permits proper hydrocyanation, particularly of the butadiene and the pentenenitR1les, easy separation of the catalytic solution, by simple decanting, and, consequently, goes as far as possible to avoid the discharge of effluent or of waste containing the metals used as catalyst. Research has nevertheless been conducted in order to find new catalytic systems which give greater performance in terms of catalytic activity and of selectivity and stability. One of the aims of the present invention is to propose a new class of ligands which with the transition metals make it possible to obtain catalytic systems exhibiting in particular an improved selectivity to linear nitR1les as compared with the known systems. The present invention accordingly provides a process for hydrocyanating a hydrocarbon compound containing at least one ethylenic unsaturation by reacting it in a liquid medium with hydrogen cyanide in the presence of a catalyst compR1sing a metallic element selected from transition metals and an organic ligand, characteR1zed in that the organic ligand corresponds to the general formula I below: in which: T and T1, which are identical or different, represent a phosphorus, arsenic or antimony atom, U1, U2, U3, U4, U5, and U6, which are identical or different, represent an oxygen atom or a radical NR, R representing an alkyl, aryl, sulphonyl or carbonyl radical, R1; R2, R3 and R4, which are identical or different, represent a substituted or unsubstituted, aromatic, aliphatic or cycloaliphatic radical compR1sing one or more R1ngs, which are in fused form or not and which may contain one or more heteroatoms, where the radicals R1 and R2 on the one hand and R3 and R4 on the other hand may be interconnected by a covalent bond, a hydrocarbon chain or a heteroatom, and, when one of the radicals U1, U2, U3 and U4 includes an N atom, the associated radical R1, R2, R3 or R4 may form a R1ng including the N element of the said radical, m and n are identical or different integers between 0 and 6, where m + n must be greater than or equal to 1, Q1 and Q2, which are identical or different, represent a group corresponding to the general formulae II, III or IV below: in which R5, R6, R7 and R6, which are identical or different, represent aliphatic, cycloaliphatic or aromatic hydrocarbon radicals containing 1 to 12 carbon atoms, R5 and R€ also representing the hydrogen atom,-and t and u represent integers between 0 and 6, with a sum u + t greater than or equal to 1, Z representing a divalent radical selected from the group consisting of aromatic or cycloaliphatic radicals containing one or more R1ngs, which are in fused form or not and which may be substituted and may contain heteroatoms. Suitable substituents for Z include alkyl, halogen, aryl, alkoxy, aryloxy, nitro, thioalkyl, secondary amine and nitR1le groups. Preferred ligands of the invention include those with the following structure of the formula (I): in which R9 represent an alkyl, aryl, halogen, alkoxy, thiol, cyano, nitro, aryloxy, alkoxycarbonyl, acyl or formyl radical. As examples of ligands which are suitable for the invention, mention may be made of the following compounds listed in table I below: In which: Ts represents the tolyl radical, tBU represents the tert-butyl group, Me represents the methyl group, and Ph represents the phenyl group. According to the invention the catalyst corresponds advantageously to the general formula (V) : M[L£]V (V) in which M is a transition metal, L£ represents the organic ligand of formula (I) and ". v represents a number between 1 and 4 (inclusive). Metals which may be complexed by the organic ligands of the invention are generally all transition metals of groups lb, 2b, 3b, 4b, 5b, 6b, 7b and 8 of the PeR1odic Table of the Elements, as published in the "Handbook of Chemistry and Physics", 51" Edition (1970-1971) from The Chemical Rubber Company. Among these metals mention may be made more particularly, as non-limiting examples, of nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iR1dium, platinum, copper, silver, gold, zinc, cadmium and mercury. Organometallic complexes compR1sing the organic ligands of the invention may be prepared by contacting a solution of a compound of the selected metal with a solution of the organic ligand of the invention. The metal compound may be dissolved in a solvent. The metal in the compound employed may be in the same oxidation state which it will have in the . organometallic complex or in a higher oxidation state. 3y way of example it is possible to indicate that in the organometallic complexes of the invention rhodium is in oxidation state (I) , ruthenium in oxidation state (II) , platinum in oxidation state (0) , palladium in oxidation state (0), osmium in oxidation state (II), iR1dium in oxidation state (I) , cobalt in oxidation state (I) and nickel in oxidation state (0) . If in the course of the preparation of the organometallic complex the metal is employed in a higher oxidation state it will be possible for it to be reduced in situ. The organometallic complexes compR1sing the organic ligands of the invention may be used as catalysts in olefin hydrocyanation reactions. As transition metal the transition metal compounds, more particularly the compounds of nickel, of palladium, of cobalt, of iron or of copper, are preferably used. Among the aforementioned compounds the most preferred compounds are those of nickel. Non-limiting examples include: compounds in which nickel is in oxidation state zero, such as potassium tetracyanonickelate K1(Ni (CN)4) , bis(acrylonitR1le)nickel zero, bis(cycloocta-1, 5-diene)nickel zero (also called Ni(codh) and deR1vatives containing ligands, such as tetrakis (tR1phenylphosphine)nickel zero,- compounds of nickel such as carboxylates (especially the acetate), carbonate, bicarbonate, borate, bromide, chloR1de, citrate, thiocyanate, cyanide, formate, hydroxide, hydrophosphite, phosphite, phosphate and " deR1vatives, iodide, nitrate, sulphate, sulphite, aryl- and •alkylsulphonates. When the nickel compound used corresponds to a nickel oxidation state greater than zero a nickel reducing agent which reacts preferentially with the nickel under the reaction conditions is added to the reaction mixture. This reducing agent may be organic or inorganic. Non-limiting examples include borohydR1des such as BH4Na and BH4K, Zn powder, magnesium or hydrogen. When the nickel compound used corresponds to the zero oxidation state of nickel it is also possible to add a reducing agent of the aforementioned type, but such addition is not mandatory. when an iron compound is used the same reducing agents are suitable. In the case of palladium the reducing agents may be, furthermore, elements of the reaction mixture (phosphine, solvent, olefin). The organic compounds containing at least one ethylenic double bond that are more particularly employed in the present process" are diolefins such as butadiene, isoprene, hexa-1,5-diene, cycloocta-1,5-diene, ethylenically unsaturated aliphatic nitR1les, especially linear pentenenitR1les such as pent-3-ene-nitR1le and pent-4-enenitR1le, monoolefins such as styrene, methylstyrene, vinylnaphthalene, cyclohexene, methylcyclohexene and mixtures of two or more of these compounds. The pentenenitR1les in particular may contain amounts, generally minor amounts, of other compounds, "such as 2-methylbut-3-enenitR1le, 2-methylbut-2-enenitR1le, pent-2-enenitR1le, valeronitR1le, adiponitR1le, 2-iaethylglutaronitR1le, 2-ethylsuccinonitR1le or butadiene, oR1ginating for example from the pR1or hydrocyahation reaction of the butadiene to unsaturated nitR1les. The reason for this is that the hydrocyanation of the butadiene is accompanied by the formation, along with the linear pentenenitR1les, of not inconsiderable amounts of 2-methylbut-3-enenitR1le and 2-methylbut-2-enenitR1le. The catalyst system used for the hydrocyanation according to the process of the invention may be prepared before it is introduced into the reaction zone; for example by adding the appropR1ate amount of selected transition metal compound and where appropR1ate of reducing agent to ligand in accordance with the invention, alone or in solution in a solvent. It is also possible to prepare the catalyst system "in situ" by simply adding the ligand and the transition metal compound to the hydrocyanation reaction mixture before or after adding the compound to be hydrocyanated. The amount of compound of nickel or of another transition metal used is selected so as to" give a concentration, in moles of transition metal per mole of organic compounds to be hydrocyanated or isomeR1zed, of between 10-4 and 1, and preferably between 0.005 and 0.5 mol of nickel or of the other transition metal employed. The amount of organic ligands of the invention used to form the catalyst is selected such that the number of moles of this compound relative to 1 mol of transition metal is from 0.5 to 50 and preferably from 2 to 10. Although the reaction is generally conducted without solvent it may be advantageous to add an inert organic solvent. The solvent may be a solvent for the catalyst which is miscible with the phase compR1sing the compound to be hydrocyanated at the hydrocyanation temperature. Examples of such solvents include aromatic, aliphatic or cycloaliphatic hydrocarbons. This solvent may also be partially miscible with the compounds to be hydrocyanated, particularly when the reaction mixture is at a temperature lower than the reaction temperature. Hence at such temperatures a two-phase system may be obtained. Where the catalyst system is soluble in said solvent its extraction from the reaction mixture is thereby facilitated. Partially or immiscible solvents of this kind may be water or organic salts in melt form with an ionic character. Such solvents are used particularly when the organic ligand contains anionic radicals which render it soluble in ionic media. These radicals are, for example, sulphonate, carbonate, carboxylate, phosphate, ammonium, guanidinium and imidazolium groups which are substituents on the aromatic radicals of the ligand. The hydrocyanation reaction is generally carR1ed out at a temperature from 10°C to . 200°C and preferably from 30°C to 120°C. Advantageously it is carR1ed out in a single-phase medium at the reaction temperature. The process of the invention may be implemented continuously or batchwise. The hydrogen cyanide employed may be prepared from metal cyanides, especially sodium cyanide, or from cyanohydR1ns, such as acetone cyanohydR1n, or by any other known synthesis process. The hydrogen cyanide is introduced into the reactor in gaseous form, as * a gas"" mixture or in liquid form. It . may also be dissolved beforehand in an organic solvent. In the context of a batchwise implementation it is possible in practice to charge a reactor, purged beforehand by means of an inert gas (such as nitrogen or argon) either with a solution containing the entirety or a part of the vaR1ous constituents, such as the- organic ligand of the invention, the" transition metal compound, the reducing agents and solvents where appropR1ate, or with said constituents separately. Generally the reactor is then taken to the selected temperature and then the compound to be hydrocyanated is introduced. The hydrogen cyanide is then itself introduced, preferably continuously and regularly. When the reaction (whose development can be monitored by assaying samples) is at an end the reaction mixture is withdrawn, after cooling, and the reaction products are isolated, by distillation for example. An enhancement of the process for hydrocyanating ethylenically unsaturated compounds according to the present invention relates in particular to the hydrocyanation of said ethylenically unsaturated nitR1le compounds by reaction with hydrogen cyanide and consists in using a catalyst system in accordance with the present invention with a cocatalyst composed of at least one Lewis acid.. The ethylenically unsaturated compounds which may be employed in this improvement are in general those which were mentioned for the basic process. However, it is more particularly advantageous to apply it to the hydrocyanation reaction to dinitR1les of the ethylenically unsaturated aliphatic mononitR1les, particularly to apply it to linear pentenenitR1les such as pent-3-enenitR1le, pent-4-enenitR1le and mixtures thereof. These pentenenitR1les may contain amounts, generally minor amounts, of other compounds, such as 2-methylbut-3-enenitR1le, 2-methylbut-2-enenitR1le, pent-2-ene-nitR1le, valeronitR1le, adiponitR1le, 2-methylglutaro-nitR1le, 2-ethylsuccinonitR1le or butadiene, oR1ginating from the pR1or hydrocyanation reaction of the butadiene and/or from the isomeR1zation of 2-methylbut-3-enenitR1le to pentenenitR1les. The Lewis acid used as cocatalyst makes it possible in particular, in the case where ethylenically unsaturated aliphatic nitR1les are hydrocyanated, to improve the lineaR1ty of the dinitR1les obtained, in other words the percentage of linear dinitR1les relative to the entirety of the dinitR1les formed, and/or to enhance the activity and service life of the catalyst. A Lewis acid in the present text, according to the usual definition, refers to compounds which accept electron pairs. Use may be made in particular of the Lewis acids cited in the work edited by G.A. Olah, "FR1edel-Crafts and related Reactions", volume I, pages 191 to 197 (1963). The Lewis acids which may be employed as cocatalysts in the present process are selected from compounds of the elements of groups Ib, IIb, IIIa, IIIb, Iva, Ivb, Va, Vb, VIb, VIIb and VIII of the PeR1odic Table of the Elements. These compounds are most often salts, especially halides, such as chloR1des or bromides, sulphates, sulphonates, haloalkylsulphonates, perhalo- alkylsulphonates, especially fluoroalkylsulphonates or perfluoroalkylsulphonates, haloalkylacetates, perhaloalkylacetates, especially fluoroalkylacetates or perfluoroalkyl&cetates, carboxylates and phosphates. Non-limiting examples of such Lewis acids include zinc chloR1de, zinc bromide, zinc iodide, manganese chloR1de, manganese bromide, cadmium chloR1de, cadmium bromide, stannous chloR1de, stannous bromide, stannous sulphate, stannous tartrate, indium tR1fluoromethyl-sulphonate, indium tR1fluoroacetate, zinc tR1fluoro-acetate, the chloR1des or bromides of rare earth elements such as lanthanum, ceR1um, praseodymium, neodymium, samaR1um, europium, gadolinium, terbium, dysprosium, hafnium, erbium, thallium, " ytterbium and lutetium, and cobalt chloR1de, ferrous chloR1de and yttR1um chloR1de. As a Lewis acid it is also possible to use organometallic compounds such as tR1phenylborane or titanium isopropoxide. It will be appreciated that mixtures of two or more Lewis acids may be employed. Among Lewis acids particular preference is given to zinc chloR1de, zinc bromide, stannous chloR1de, stannous bromide and tR1phenylborane and to zinc chloR1de/stannous chloR1de mixtures, indium tR1-fluoromethylsulphonate, indium tR1fluoroacetate and zinc tR1fluoroacetate. The Lewis acid cocatalyst employed represents generally from 0.01 to 50 mol per mole of transition metal compound, more particularly of nickel compound, and preferably from 0.5 to 10 mol per mole. As for the implementation of the basic process of the invention, the catalyst solution used for the hydrocyanation in the presence- of Lewis acid may be prepared pR1or to its introduction into the reaction zone; for example, by adding the ligand of formula (I), the appropR1ate amount of selected transition metal compound, Lewis acid and, where appropR1ate, reducing , agent to the reaction mixture. It is also possible to prepare the catalyst solution *in situ" by simply-mixing these vaR1ous constituents. It is also possible, under the conditions of the hydrocyanation process of the present invention, and especially when working in the presence of the above-descR1bed catalyst compR1sing at least one ligand of formula (I) and at least one transition metal compound, to carry out the isomeR1zation of 2-methylbut-3-ene-nitR1le to pentenenitR1les, and more generally of branched unsaturated nitR1les to linear unsaturated nitR1les, in the absence of hydrogen cyanide. The 2-methylbut-3-enenitR1le subjected to the isomeR1zation according to the invention may be employed alone or in a mixture with other compounds. Thus 2-methylbut-3-enenitR1le may be deployed as a mixture with 2-methylbut-2-enenitR1le, pent-4-ene-nitR1le, pent-3-enenitR1le, pent-2-enenitR1le, buta¬diene, adiponitR1le, 2-methylglutaronitR1le, 2-ethyl-succinonitR1le or valeronitR1le. It is particularly advantageous to treat the reaction mixture oR1ginating from the hydrocyanation of butadiene by KCN in the presence of at least one ligand of formula (I) and at least one transition metal compound, more preferably a compound of nickel" in oxidation state 0, as defined above. In the context of this preferred version the catalyst system is already present for the butadiene hydrocyanation reaction and it is therefore sufficient to stop any introduction of hydrogen cyanide in order to allow the isomeR1zation reaction to take place. It is possible, where appropR1ate, in this version to effect a gentle purging of the reactor by means of an inert gas, such as nitrogen or argon for example, in order to expel the hydrocyanic acid which might still be present. The isomeR1zation reaction is generally carR1ed out at a temperature from 10°C to 200°C and preferably from 60°C to 160°C. In the preferred case of an isomeR1zation immediately following the butadiene hydrocyanation reaction it will be advantageous to operate at the temperature at which the hydrocyanation was conducted. As for the process of hydrocyanating ethylenically unsaturated compounds, the catalyst system used for the isomeR1zation may be prepared pR1or to its introduction into the reaction zone; for example, by adding the ligand of formula (I), the appropR1ate amount of selected transition metal compound and, where appropR1ate, reducing agent to a solvent.- It is also possible to prepare the catalyst system "in situ" by simply adding these vaR1ous constituents to the reaction mixture. The amount of transition metal compound, and more particularly of nickel compound, that is used, and the amount of ligand of formula (I), are the same as for the hydrocyanation reaction. Although the isomeR1zation reaction is conducted, generally without solvent it may be advantageous to add an inert organic solvent, which may be that of the subsequent extraction. This is the case particularly when such a solvent has been employed in the butadiene hydrocyanation reaction that was used to prepare the mixture which is subjected to the isomeR1zation reaction. Such solvents may be selected from those which were identified above for the hydrocyanation. The preparation. of dinitR1le compounds by hydrocyanation of an olefin such as -butadiene may be carR1ed out using a catalyst system in accordance with the invention for the above steps of formation of unsaturated mononitR1les and the isomeR1zation step; the hydrocyanation reaction of unsaturated mononitR1les to dinitR1les car. be implemented with a catalyst system in accordance with the invention or any other catalyst system already known for this reaction. Similarly the hydrocyanation reaction of the olefin to unsaturated mononitR1les and the isomeR1zation thereof may be carR1ed out with a catalyst system other than that of the invention; the hydrocyanation step of the unsaturated mononitR1les to dinitR1les is employed with a catalyst system in accordance with the invention. The invention likewise provides organophosphorus compounds corresponding to the general formula (I) above. It likewise provides the organophosphorus compounds corresponding to the general formulae listed in Table I above. The examples which follow illustrate the invention. In the examples the abbreviations used have the meanings indicated below. cod: 1,5-cyclooctadiene eg: equivalent 3PN: 3-pentenenitR1le 4PN: 4-pentener.itR1le 3+4PN: 3PN + 4PK DC(Y): degree of conversion of the product to be hydrocyanated, Y, corresponding to the ratio of the number of moles of Y converted to the initial number of moles of Y LineaR1ty (L) : ratio of the number of moles of adiponitR1le (AdN) formed to the number of moles of dinitR1les formed (sum of the moles of AdN, ethylsuccinonitR1le (ESN) and methylglutaronitR1le (MGKT)} GC: gas chromatography ml: millilitre mol: mole(s) mmol: millimole(s). The vaR1ous products in accordance with the invention may be prepared by one of the two following procedures: Procedure I: A phosphochloR1dite is used which is prepared from a phenol or biphenol deR1vative and PCI3 according to a conventional procedure (see, for example, the method descR1bed by G. Buisman et al. in Tetrahedron, Asymmetry, vol. 4, (7), pp. 1625-34 (1993)), and a diol available commercially. The following general procedure is representative: In a 100 ml reactor under argon 6 mmol of phosphochloR1dite are dissolved in 2 0 ml of anhydrous toluene. The solution is stirred at -10°c: A solution of 3 mmol of diol and 10 mmol of tR1ethylamine in 20 ml of anhydrous toluene is introduced dropwise into the reaction mixture, which is held at -10°C: a white precipitate forms. The suspension is stirred vigorously at 25°C for 18 h and then filtered under argon over a bed of basic alumina. After R1nsing with toluene, the filtrate is concentrated under reduced pressure to give the desired product, which is used without further puR1fication. The following ligands were prepared according to the procedure descR1bed above: Procedure II: A phosphoramidite is used which is prepared from Cl2PNEt2 (available commercially) and a substituted or unsubstituted phenol according to the following procedure: A mixture of Cl2PNEtz (0-20 mol) and tR1 ethyl amine (0.44 mol) in toluene (800 ml) at 0°C is admixed slowly, with vigorous stirR1ng, with a solution of phenol (0.40 mol) in toluene (100 ml). The formation of a white precipitate is observed. The mixture is allowed to climb to ambient temperature and is stirred, still vigorously, for 2 h. The mixture is subsequently filtered on a bed of silica and concentrated under vacuum to give the phosphoramidite (ArO)2PNEt2 with a puR1ty of more than 95%. Additionally a commercially available diol is used. The following general procedure is representative: In a 100 ml reactor under argon 6 mmol of phosphoramidite are introduced in 20 ml of anhydrous toluene. The solution is stirred at 0°C and 7.5 ml of a 2 M solution of hydrochloR1c acid in ether are added thereto over 30 minutes. The formation of a white precipitate is observed, and the mixture is stirred at ambient temperature for 1 hour. A solution of 3 mmol of diol and 10 mmol of tR1ethylamine in 20 ml of anhydrous toluene is subsequently introduced dropwise into the reaction mixture, which is cooled at -10°C. The suspension is stirred vigorously at 25°C for 18 hours and then filtered under argon on a bed of basic alumina. After R1nsing with toluene, the filtrate is concentrated under reduced pressure to give the desired product, which is used without further puR1fication. Examples of hydrocyanation of 3-pentehenitR1le (3PN) to" adiponitR1le (AdK) The general procedure used is as follows: Under an argon atmosphere a 60 ml Schott glass tube equipped with a septum stopper is charged in succession with the ligand (2.5 eq), 1.21 g (15 mmol; 30 eq) of anhydrous 3PN, 138 mg (0.5 mmol,- 1 eq) of Ni(cod)2 and the Lewis acid (0.5 mmol; 1 eq). The mixture is taken to 70°C with stirR1ng. Acetone cyanohydR1n is injected into the reaction mixture by means of a syR1nge dR1ver at a rate of 0.45 ml per hour. After 3 hours of injection the syR1nge dR1ver is stopped. The mixture is cooled to ambient temperature, diluted with .acetone and analysed by gas chromatography. WE CLAIM: 1, Process for hydrocyaziatcing a hydrocarbon compound containing at least one ethylenic unsaturation by reacting it in a liguid medium with hydrogen cyanide in the presence of a catalyst compR1sing a metallic element selected from transition metals and an organic ligand, wherein said organic ligand corresponds to the general formula I below: in Which: T and Tl( which are identical or different, represent a phosphorus, arsenic or antimony atom, U1, -U2 U3, U4, U5, and U6- which are identical or different, represent an oxygen atom or a radical NR, R representing an alkyl, " aryl, sulphonyl or carbonyl radical, R1, " R2, R3 and R4, which are identical or different, represent a substituted or unsubstituted, aromatic, aliphatic or cycloaliphatic radical compR1sing one or more R1ngs, which are in fused form or not and which may contain one or more heteroatoms, where the radicals R1 and R2 on the one hand and R3 and R4 on the other hand may be interconnected by a covalent bond, a hydrocarbon chain or a heteroatom, and, when one of the radicals U1, U2, U3 and U4 includes an N atom, the associated radical R1, R2, R3 or R4 mey form a R1ng including the N element of the said radical, m"and n are identical or different integers between 0 and 6, where m + n must be greater than or equal to 1, Qi and Q2, which are. identical or different, represent a group corresponding to the general formulae II, III or IV below: in which R5, R6, R7 and R8, which are identical or different, represent aliphatic, cycloaliphatic or aromatic hydrocarbon radicals containing 1 to 12 carbon atoms, R5 and R6 also • representing the hydrogen atom, and t and u represent integers between 0 and 6, with a sum u + t greater than or equal to 1, Z representing a divalent radical selected from the group consisting of aromatic or cycloaliphatic radicals containing one or more R1ngs, which are in fused form of not and which may be substituted and may contain heteroatoms. 2. The process as claimed in claim 1, wherein 4. The process as claimed in any one of claims 1 to 3, wherein the metallic element is selected from the group consisting of nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iR1dium, platinum, copper, silver, gold, zinc, cadmium and mercury. 5. The process as claimed in any one of the preceding claims, wherein the reaction is carR1ed out in a single-phase medium. 6. The process as claimed in any one of the preceding claims, wherein the catalyst corresponds to the general formula (V): M[Lf]v (V) in Which M is, a transition metal, L£ represents the organic ligand of formula (I) and v represents a number between 1 and 4 (inclusive). 7. The process as claimed in any one of the preceding claims, wherein the reaction mixture compR1ses a solvent for the catalyst which is miscible with the phase compR1sing the compound to be hydrocyanated at the hydrocyanation temperature. 8. The process as claimed in any one of the preceding claims, wherein the transition metal compounds are nickel compounds selected from the group consisting of: compounds in which, nickel is in oxidation state zero, such as potassium tetracyanonickelate K4[Ni(CN)t], bis(acrylonitR1le)nickel zero, bis-(cycloocta-1,5-diene)nickel zero and deR1vatives containing ligands, such as tetrakis(tR1-phanylphosphine)nickel zero; compounds of nickel such as carboxylates, carbonate, bicarbonate, borate, bromide, chloR1de, citrate, thioeyanate, cyanide, formate, hydroxide, hydrophosphite, phosphite, phosphate and deR1vatives, iodide, nitrate, sulphate, sulphite, aryl- and alkylsulphonates. 9, The process as claimed in any one of the preceding claims, wherein the organic compounds containing at least one ethylenic double bond are selected from diolefins such as butadiene, isoprene, hexa-1,5-diene, cycloocta-l,5-diene, ethylenically unsaturated aliphatic nitR1les, especially linear pentenenitR1les such as pent-3-enenitR1le and pent-4-enenitR1le, monoolefins such as styrene, methylstyrene, vinylnaphthalene, cyclohexene and methyleyelohexene and also mixtures of two or more of these compounds. 10. The process as claimed in any one of the preceding claims, wherein the amount of compound of nickel or of another transition metal used is selected such that per mole of organic compound to be hydrocyanated • or isomeR1zed between 10"4 and 1 mol of nickel or of the other transition metal is employed and in that the amount of organic ligand of formula (V) used is selected such that the number of moles of this compound relative to 1 mol of transition metal is from 0.5 to 50. 11. The process as claimed in any one of the preceding claims, wherein the hydrocyanation. reaction is carR1ed out at a temperature from 10°C to 200CC. 12. The process as claimed in any one of the preceding claims for .hydrocyanating ethylenically unsaturated nitR1le compounds to dinitR1les by reaction with hydrogen cycanide, wherein it is operated in the presence of a catalyst system compR1sing at least one transition metal compound, at least one organic compound of formula (I) or (V) and a cocatalyst composed of at least one Lewis acid. 13. The process as claimed in claim 12, wherein the ethylenically unsaturated nitR1le compounds are selected from ethylenically unsaturated aliphatic nitR1les compR1sing linear pentenenitR1les such as pent-3-enenitR1le and pent-4-enenitR1le and mixtures thereof. 14. The process as claimed in claim 13, wherein the linear pentenenitR1les contain amounts of other compounds selected from the group consisting of 2-methylbut-3-enenitR1le, 2-methylbut-2-enenitR1le, pent-2-enenitR1le, valeronitR1le, adiponitR1le, 2-methylglutaronitR1le, 2-ethylsuccinonitR1le and buta¬diene . 15. The process as claimed in any one of claims 12 to 14, wherein the Lewis acid employed as cocatalyst is selected from compounds of the elements of groups lb, IIb, IIIa, IIb, IVa, IVb, Va, Vb, VIb, VIIb and VIII of" the PeR1odic Table of the Elements. 16. The process as claimed in any one of claims 12 to 15, wherein the Lewis acid is selected from salts selected from the group of halides, sulphates, sulphonates, haloalkylsulphonates, perhaloalkyl- sulphonates, haloalkylacetates, perhaloalkylacetates, carboxylates and phosphates. 17. The process as claimed in any one of claims 12 to 16, wherein the Lewis acid is selected from zinc chloR1de, zinc bromide, zinc iodide, manganese chloR1de, manganese bromide, cadmium chloR1de, cadmium bromide, stannous chloR1de, stannous bromide, stannous "sulphate, stannous tartrate, indium tR1fluoromethyl- sulphpnate, indium tR1fluoroacetate, zinc tR1fluoro- acetate, the chloR1des or bromides of rare earth elements such as lanthanum, ceR1um, praseodymium, neodymium, samaR1um, europium, gadolinium, terbium, dysprosium, hafnium, erbium, thallium, ytterbium and lutetium, and cobalt chloR1de, ferrous chloR1de, yttR1um chloR1de and mixtures thereof. 18. The process as claimed in any one of claims 12 to 17, wherein the Lewis acid employed represents from 0.01 to 50 mol per mole of transition metal compound, 19. The process as claimed in any one of claims 1 to 18, wherein 2-methylbut-3-enenitR1le, present in the reaction mixture oR1ginating from butadiene hydrocyanation; is isomeR1zed to pentenenitR1les in the absence of hydrogen cyanide, in the presence of a catalyst compR1sing at least one organic ligand of general formula (I) or (V) and at least one transition metal compound. 20. The process as claimed in claim 19, wherein the 2-methylbut-3-enenitR1le subjected to isomer!zation is employed alone or in a mixture with 2-methylbut-2-enenitR1le, pent-4-enenitR1le, pent-3-enenitR1le, pent-2-enenitR1le, butadiene, adiponitR1le, 2-methylglutaronitR1le, 2-ethylsuccinonitR1le or valeronitR1le. 21. The process as claimed in any one of claims 19 and 20, wherein the isomeR1zation reaction is carR1ed out at a temperature from 10°C to 200oC. 22. The process as claimed in claims 19 to 21, wherein the isomeR1zation of 2-methylbut-3-enenitR1le to pentenenitR1les is carR1ed out in the presence of at least one transition metal compound, at least one organi phosphorous ligand of the formula (I) and a cocatalyst composed of at least one Lewis acid.

Documents:

0183-chenp-2005 abstract.pdf

0183-chenp-2005 claims-duplicate.pdf

0183-chenp-2005 claims.pdf

0183-chenp-2005 correspondence-others.pdf

0183-chenp-2005 correspondence-po.pdf

0183-chenp-2005 description(complete)-duplicate.pdf

0183-chenp-2005 description(complete).pdf

0183-chenp-2005 form-1.pdf

0183-chenp-2005 form-18.pdf

0183-chenp-2005 form-26.pdf

0183-chenp-2005 form-3.pdf

0183-chenp-2005 form-5.pdf

0183-chenp-2005 pct search report.pdf

0183-chenp-2005 pct.pdf

0183-chenp-2005 petition.pdf