Title of Invention

METHOD FOR MAKING NITRILE COMPOUNDS FROM ETHYLENICALLY UNSATURATED COMPOUNDS

Abstract

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

Full Text

The present invenT1on concerns a process for hydrocyanaT1ng ethylenically unsaturated organic compounds to compounds containing at least one nitrile funcT1on. It relates more parT1cularly to the hydrocyanaT1on of diolefins such as butadiene or of subsT1tuted olefins such as alkenenitR1les, for instance pentenenitR1les. The hydrocyanaT1on of butadiene to pentenenitR1les is an important reacT1on which has been implemented industR1ally for a number of years, parT1cularly in the process for synthesizing adiponitR1le, a major chemical intermediate which allows access in parT1cular to the monomers of numerous polymers, foremost among which are the polyamides. French patent 1 599 761 descR1bes a process for prepaR1ng nitR1les by addiT1on 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 reacT1on 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 nitR1ie such as acetonitR1le. The catalyst employed is an organometalL1c complex of nickel, containing L1gands such as phosphines, arsines, sT1bines, anT1iaonites, arsenites, phosphites, phos-phinites or phosphonites. The processes for hydrocyanaT1ng dienes generally compR1se two steps: a first hydrocyanaT1on, leading to branched and L1near unsaturated mononitR1les, and a second step which allows the dinitR1les to be obtained. Often only the L1near 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 co as the isomeR1zation step and consists in treaT1ng the branched unsaturated mononitR1les to convert them into L1near unsaturated mononitR1les. The presence of a promoter to acT1vate the catalyst, such as a boron compound or a metal salt, generally a Lewis acid, is also recommended for carrying out the second step. Patent FR-A-2 33 8 253 proposed carrying out the hydrocyanaT1on of compounds having at least one ethylenic unsaturaT1on in the presence of an aqueous soluT1on of a compound of a transiT1on metal, parT1cularly nickel, palladium or iron, and of a sulphonated phosphine. The sulphonated phosphines descR1bed in said patent are sulphonated tR1arylphosphines and more parT1cularly sulphonated tR1phenylphosphines. This process permits proper hydrocyanaT1on, parT1cularly of the butadiene and the pentenenitR1les, easy separaT1on of the catalyT1c soluT1on, by simple decanT1ng, 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 catalyT1c systems which give greater performance in terms of catalyT1c acT1vity and of selecT1vity and stabiL1ty. One of the aims of the present invenT1on is to propose a new class of L1gands which with the transiT1on metals make it possible to obtain catalyT1c systems exhibiT1ng in parT1cular an improved selecT1vity to L1near nitR1les as compared with the known systems. The present invenT1on accordingly provides a process for hydrocyanaT1ng a hydrurxcn compound containing at least one ethylenic unsatrzrtan by reacT1ng it in a L1qU1d medium with hydrogen cyanide in the presence of a catalyst compR1sing a metalL1c element selected from transiT1on metals and an organic L1gand, characteR1zed in that the organic L1gand corresponds to the general in which: T and T1, which are idenT1cal or different, represent a phosphorus, arsenic or anT1mony atom, R1, R2, R3 and R4, which are idenT1cal or different, represent a subsT1tuted or unsubsT1tuted, aromaT1c, aL1phaT1c or cycloaL1phaT1c 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, U1, U2, U3 and U4, which are idenT1cal or different, represent an oxygen atom or a radical of fcrsula 5H in which R denotes a monovalent aL1yl, aryl cycloalkyl, sulphonyl or carbonyl radical R5 and R6, which are idenT1cal or different, represent an aryl or cycloaL1phaT1c group which may compR1se neteroatoms and/or one or more R1ngs, in fused form or not, and which are subsT1tuted or unsubsT1tuted, n is an integer equal to 0 or 1, L1, when n is 0, represents a divalent radical selected from the group consisT1ng of the groups NR7, PR8, SiRgR1o, BRn, S, POR12, S02 and CO, in which R7 is as defined for R above, R8 and R12 may represent the radical OR13, and R8, R9, R1o, Rn, R12 and R13 represent aL1yl, aryl or cycloalkyl radicals, Z.-_ and L2, -when n is 1, are idenT1cal or different and rsresent a covalent bond or a radical selected from the group consisting of the groups 0, NR7, PR8, SiR9R10, BRn, S, POR12, S02, CO and -CR14R3.5-, in which R7 is as defined for R above, R8 and R12 may represent the radical OR13, and RB, R9, R10, Rn, R12, R13/ R14 and R15 represent alkyl, aryl or cycloalkyl radicals, it being possible also for R14 and R15 to represent a hydrogen stom. include the following formulae L1sted in Table I below: Table I thiol, cyano, nitro, arylcsy, alkoxycarbonyl, acyl or formyl radical. Ligands in accordance with the invenT1on include the following compounds listed in Table II below: According to the invenT1on the catalyst corresponds advantageously to the general formula (II): M [L,]t (II) in which M is a transiT1on metal, Lf represents the organic ligand of formula (I) and t represents a number between 1 and 4 (inclusive). Metals which may be complexed by one organic ligands of the invenT1on are generally all transition metals of groups lb, 2b, 3b, 4b, 5b, 6b, 7b and of the PeR1odic Table of the Elements, as published in the ""Handbook of Chemistry and Physics", 51st EdiT1on (1970-1971) from The Chemical Rubber Company. Among these metals menT1on may be made more parT1cularly, as non-limiT1ng examples, of nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iR1dium, plaT1num, copper, silver, gold, zinc, cadmium and mercury. Organometallic complexes compR1sing the organic ligands of the invenT1on may be prepared by contacT1ng a soluT1on of a compound of the selected metal with a soluT1on of the organic ligand of the invenT1on. The metal compound may be dissolved in a solvent. The metal in the compound employed may be in the same oxidaT1on state which it will have in the organometallic complex or in a higiier oxidaT1on state. 3y way of example it is possible to indicate that in the organometallic complexes of the invenT1on rhodium is in oxidaT1on state (I), ruthenium in oxidaT1on state [II) , plaT1num in oxidaT1on state (0) , palladium in oxidaT1on state (0), osmium in oxidaT1on state (II), iR1dium in oxidaT1on state (I) , cobalt in oxidaT1on stage (I) and nickel in oxidaT1on state (0). If in the course of the preparaT1on of the organometallic complex the metal is employed in a higher oxidaT1on state it will be possible for it to be reduced in situ. The organometallic complexes compR1sing the organic ligands of the invenT1on may be used as catalysts in olefin hydrocyanation reacT1ons . is transition metal the transiT1on metal compounds, more parT1cularly the compounds of nickel, of palladium, of cobalt, of iron or of copper, are preferably used. Among the aforemenT1oned compounds the most preferred compounds are those of nickel. Non-limiT1ng examples include: compounds in which nickel is in oxidaT1on state zero, such as potassium tetracyanonickelate K4[Ni(CN)4], bis(acrylonitR1le)nickel zero, bis(cycloocta-1,5-diene)nickel zero (also called Ni(cod)2) and deR1vaT1ves containing ligands, such as tetrakis(tR1phenylphosphine)nickel zero; coinpoiinds of nickel such as carboxylates (especially the acetate), carbonate, bicarbonate, berate., bromide, chloR1de, citrate, thiocyanate, cyanide- formate, hydroxide, hydrophosphite, phosphite phosphate and deR1vaT1ves, iodide, nitrate, sulphate, sulphite, aryl- and alkylsulphonates. When the nickel conpound used corresponds to a nickel oxidaT1on state greater than next a nickel reducing agent which reacts preferentially with the nickel under the reacT1on condiT1ons is added to the reacT1on mixture. This reducing agent may be organic or inorganic. Non-limiT1ng examples include borohydR1des such as BH4Na and BH4K, Zn powder, magnesium or hydrogen. When the nickel compound used corresponds to the zero oxidaT1on state of nickel it is =L=-r possible to add a reducing agent of the aforfr-"! "■ ~~ —±. "cype, but such addiT1on is not mandatory. When an iron compound is used the ==—— reducing agents are sU1table. In the case of palladium the reducing agents may be, furthermore, elements of the reacT1on mixture (phosphine, solvent, olefin). The organic compounds containing at least one ethylenic double bond that are more parT1cularly employed in the present process are diolefins such as butadiene, isoprene, hexa-1,5-diene, cycloocta-1,5-diene, ethylenically unsaturated aliphaT1c 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 parT1cular may cantain amounts, generally minor amounts, of other coEapouraas such as 2-methylbut-3-enenitR1le, 2 -aetrylbut: - 2 -en-enitri1le, pent-2-enenitR1le, valeronitrile adiponicrile. 2-methylglutaronitR1le, 2-ethylsuccinonitR1le or butadiene, oR1ginaT1ng for example from the pR1or hydrocyanaT1on reacT1on of the butadiene to unsaturated nitR1les. The reason for this is that the hydrocyanaT1on of the butadiene is accompanied by the formaT1on, 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 hydrocyanaT1on according to the process of the invenT1on may be prepared before it is introduced into the reacT1on zone; for example by adding the appropR1ate amount of selected transiT1on metal compound and where appropR1ate of reducing agent to the ligand in accordance with the invenT1on, alone or in soluT1on in a solvent. It is also possible to prepare the catalyst system "in situ" by simply adding the ligand and the transiT1on metal compound to the hydrocyanaT1on reacT1on mixture before or after adding the compound to be hydrocyanated. The amount of compound of nickel or of another transiT1on metal used is selected so as to give a concentraT1on, in moles of transiT1on 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 transiT1on metal employed. The amount cf organic ligands of the invenT1on used to form the catalyst is selected such that the number of moles of this compound relaT1ve to 1 mol of transiT1on metal is from 0.5 to 50 and preferably from 1 to 10. Although the reacT1on is generally conducted without st1ven- 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 aromaT1c, aliphaT1c or cyclcalrphatic hydrocarbons. This solvent may also be parT1ally miscible with the compounds to be hydrocyanated, parT1cularly when the reacT1on mixture is at a temperature lower than the reacT1on temperature. Hence at such temperatures a two-phase system may be obtained. Where the catalyst system is soluble in said solvent its extracT1on from the reacT1on mixture is thereby facilitated. ParT1ally or immiscible solvents of this kind may be water or organic salts in melt form. wich an ionic character. Such solvents are used parT1cularly when rhe organic ligand contains anionic radicals which render it soluble in ionic media. These redicals are, for example, sulphonate, carbonate, carbcxylate, phosphate, ammonium, guanidinium and imidazoline groups which are subsT1tuents on the aromaT1c radicals of the ligand. The hydrocyanaT1on reacT1on is generally carR1ed out at a temperature from 10°C to 200oC and preferably from 3 0°C to 12 0°C. Advantageously it is carR1ed out in a single-phase medium at the reacT1on temperature. The process of the invenT1on may be implemented conT1nuously 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 implementaT1on it is possible in pracT1ce to charge a reactor, purged beforehand by means of an inert gas (such as nitrogen or argon) either with a soluT1on containing the enT1rety or a part of the vaR1ous consT1tuents, such as the organic ligand of the invenT1on, the transiT1on metal compound, the reducing agents and solvents where appropR1ate, or with said consT1tuents 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 conT1nuously and regularly. When the reacT1on (whose development can be monitored by assaying samples) is at an end the reacT1on mixture is wirhdrawn, after cooling, and the reacT1on products are isolated, by disT1llaT1on for example. An enhancement of the process for hydrocyanating ethylenically unsaturated compounds according to the present invenT1on relates in parT1cular to the hydrocyanation of said ethylenically unsaturated nitR1le compounds by reacT1on with hydrogen cyanide and consists in using a catalyst system in accordance with the present invenT1on 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 menT1oned for the basic process. However, it is more parT1cularly advantageous to apply it to the hydrocyanaT1on reacT1on to dinitR1les of the ethylenically unsaturated aliphaT1c mononitR1les, parT1cularly to apply it to linear pentenenitR1les such as pent-3-enenitR1le, pent-4-enenitR1le and mixtures T1-ese pertenenitriles may contain amounts, generally nzrer amounts. of other compounds, such as 2-methylbut- 3-enenitR1le, 2-methylbut-2-eneR1itR1le/ pent-2-ene-nitR1le, valeronitR1le, adiponitR1le, 2-methylglutaro-nitR1le, 2-ethylsuccinoR1itR1le or butadiene, oR1ginaT1ng from The prior hYdxocyaration reacT1on of the butadiene and/or from the simerizaT1on of 2 -methyibut-3 - enenitri1e to p=rr=r-aT~~r^rlles . The Lewis acid used as cocatalyst makes it possible in parT1cular, in the case where ethylenically unsaturated aliphaT1c nitR1les are hydrocyanated, to improve the lineaR1ty of the dinitR1les obtained, in other words the percentage of linear dinitR1les relaT1ve to the enT1rety of the dinitR1les formed, and/or to enhance the acT1vity and service life of r"~— raralyst. A Lewis acid in the present text.- according to the usual definiT1on, refers to compounds which accept electron pairs. Use may be made in parT1cular of the Lewis acids cited in the work edited by G.A. Olah. "FR1edel-Crafts and related ReacT1ons", 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 perfluoroalkylacetates, carboxylates and phosphates. Non-limiting examples of such Lewis acids include zinc chloR1de, zinc bromide, zinc iodide- manganese chloR1de, manganese bromide, cadmiur CHLORIDE. cadrium bromide, stannous chloR1de, stannous bromide, stannous sulphate, stannous tartrate, indium tri1fluoromethyl-sulphonate, indium trifluoroacetate, 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 luteT1um, and cobalt chloR1de, ferrous chloR1de and yttR1um chloR1de. As a Lewis acid it is also possible to use organometallic compounds such as tR1phenylborane or T1tanium isopropoxide. It will be appreciated that mixtures of two or more Lewis acids may be employed. among Lewis acids parT1cular preference is given to zinc chloR1de, zinc bromide, stannous chloR1de, stammous bromide and tR1phenylborane and to zinc chloR1de/stannous chloR1de mixtures, indium tR1-fluoromethylsulphonate, indium tR1f luoroacetate and " zinc trifluoroacetate. The Lewis acid cocatalyst employed represents generally from 0.01 to 50 mol per mole of transiT1on metal compound, more parT1cularly of nickel compound, and preferably from 0.5 to 10 mol per mole. As for the implementaT1on of the basic process of the invenT1on, the catalyst soluT1on used for the hydrocyanation in the presence of Lewis acid may be prepared pR1or to its introducT1on into the reacT1on zone; for example, by adding the ligand of formula (I), the appropR1ate amount of selected transiT1on metal compound, Lewis acid and, where appropR1ate, reducing 35 agent to the reacT1on mixture. It is also possible to prepare the catalyst soluT1on "in situ" by simply mixing these vaR1ous consT1tuents. Zz is else possible, under the condiT1ons of the hydrocyanaT1on process of the present invenT1on, 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 meral compound, to carry out the isomerization of 2-methylbut-3-ene-nitR1le to pentenenitries. and more generally of branched unsaturated nitries to linear unsaturated nitR1les, in the absence of hydrogen cyanide. The 2-methylbut-3-enenitR1le subjected to the isomeR1zaT1on according to the invenT1on may be employed alone or in a mixture with other compounds. Thus 2-methylbut-3-enenitrile may be deployed as a mixture with 2-methylbut-2—ererrrrrle, pent-4-ene-nitR1le, pent-3-enenitR1le, penr-2-enenirrR1le, buta¬diene, adiponitR1le, 2-metbylglurartrile, 2-ethyl-succinonitR1le or valeronitrile. It is parT1cularly advantageous to treat the reacT1on mixture oR1ginaT1ng from rre hydrocyanation of butadiene by HCN in the presence of ax least one ligand of formula (I) and at least one transiT1on metal compound, more preferably a compound of nickel in oxidaT1on state 0, as defined above. In the context of this preferred version the catalyst system is already present for the butadiene hydrocyanaT1on reacT1on and it is therefore sufficient to stop any introducT1on of hydrogen cyanide in order to allow the isomeR1zaT1on reacT1on 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 sT1ll be present. The isomeR1zaT1on reacT1on is generally carR1ed our at a temperature from 10°C to 200°C and preferably from 60°C to 160°C. in the preferred case of an isomeR1zaT1on immediately following the butadiene hydrocyanaT1on reacT1on it will be advantageous to operate at the temperature at- which the hydrocyanaT1on was conducted. As for the process of hydrocyanating ethylenically unsaturated compounds, the catalyst system used for the isomeR1zaT1on may be prepared pR1or to its introducT1on into the reacT1on zone; for example, by adding the ligand of formula (I), the appropR1ate amount of selected transiT1on 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 consT1tuents to the reaction mixture. The amount of transiT1on metal compound, and more parT1cularly of nickel compound, that is used, and the amount of ligand of formula (I), are the same as for the hydrocyanaT1on reacT1on. Although the isomeR1zaT1on reacT1on is conducted generally without solvent it may be advantageous to add an inert organic solvent, which may be that of the subsequent extracT1on. This is the case parT1cularly when such a solvent has been employed in the butadiene hydrocyanaT1on reacT1on that was used to prepare the mixture which is subjected to the isomeR1zaT1on reacT1on. Such solvents may be selected from those which were idenT1fied above for the hydrocyanaT1on. The preparaT1on of dinitR1le compounds by hydrocyanaT1on of an olefin such as butadiene may be carR1ed out using a catalyst system in accordance with the invenT1on for the above steps of formaT1on of unsaturated moncnitR1les and the isomeR1zaT1on step; the hydrocyatation reacT1on of unsaturated mononitR1les to dinitR1les can be implemented with a catalyst system in accordance with the invenT1on or any other catalyst system already known for this reacT1on. Similarly the hydrocyanaT1on reacT1on of the olefin to unsaturated mononitR1les and T1e i-scxnaR1zaT1on thereof may be carR1ed out with a catalyst system other than that of the invenT1on; the hydrocyanaT1on step of the unsaturated mononitR1les to dinitR1les is employed with a catalyst system in accordance with the invenT1on. The invenT1on likewise provides organophosphorus compounds corresponding to the general formula I below: in which: T and T1, which are idenT1cal or different, represent a phosphorus, arsenic or anT1mony atom, Ra, R2, R3 and R4, which are idenT1cal or different, represent a subsT1tuted or unsubsT1tuted, aromaT1c, aliphaT1c or cycloaliphaT1c 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, U1, U2, U3 and U4, which are identical or different represent an oxygen atom or a radical, of formula NR in. which R denotes a monovalent alkyl, aryl, cycloalkyl, sulphonyl or carbonyl radical, 2.5 and R6, which are idenT1cal or different, represent an aryl or cycloaliphaT1c group which may compR1se heteroatoms and/or one or more R1ngs, in fused form or not, and which are subsT1tuted or unsubsT1tuted, n is an integer equal to 0 or 1, L1, when n is. 0, represents a divalent radical selected from the group consisT1ng of the groups NR7, PR8, SiR9R10, BR11, S, POR12, S02 and CO, in which R7 is as defined for R above, R8 and R12 may represent the radical OR13, and R8, R9, R10, Ru, R12 and R13 represent alkyl, sxyl or cycloalkyl radicals, L1 and L-2, when n is 1, are idenT1cal or different and represent a covalent bond or a radical selected from the group consisT1ng of the groups 0, NR7, PR8, SiR9R10, 3Rn, S, POR12, SO2, CO and -CR14R15-, in which R7 is as defined for R above, R8 and R12 may represent the radical OR13, and R8, R9, R10/ R11, R12/ R13 / R14 and R15 represent alkyl, aryl or cycloalkyl radicals, it being possible also for R14 and R15 to represent a hydrogen atom. The invenT1on relates in parT1cular to the organophosphorus compounds listed in Table II above. These compounds are obtained in parT1cular by mixing a soluT1on in toluene of a diphenol compound corresponding to the structure of the following fomula: with a toluenic soluT1on of a chlorophosphite of following formula(e): and/or In the above formulae the symbelss havs the same meanings as in formula 1. The mixture is sT1rred for a number of hours (of the order of 8 to 15 hours) at ambient: tesperatrure (between 15°C and 30°C) . The organophcsphoras compound is recovered, for example, by filteR1ng the mixture. This preparaT1on procedure is given solely by way of example and indicaT1on. Other preparaxion processes may be used without deparT1ng from the scope of the invenT1on. Moreover, the phenols and chlorophosphites are generally available commercially or may be synthesized by convenT1onal processes descR1bed for obtaining these compounds. The examples which follow illustrate the invenT1on. In the examples the abbreviaT1ons used have the meanings indicated below. cod: 1,5-cyclooctadiene eq: eqU1valent 3PN: 3-pentenenitR1le 4PN: 4-pentenenitR1le 3+4PN: 3PN + 4FN DC(Y): degree of conversion of the product to be hydrocyanated, Y, corresponding to the raT1o of the number of moles of Y converted to the iniT1al number of moles of Y LineaR1ty (L) : raT1o 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 (MGN)) GC: gas chromatography n1: millilitre mol: mole(s) nmol: millimole (s) . The vaR1ous products in accordance with the invenT1on may be prepared by one of the two following procedures: Procedure I: A phosphochloR1dite is used which is prepared from a phenol or biphenol deR1vaT1ve and PC13 according to a convenT1onal procedure (see, for example, the method descR1bed by G. BU1sman et al. in Tetrahedron, Asymmetry, vol. 4, (7), pp. 1625-34 (1993)), and a diol available commercially. The following general procedure is representaT1ve: In a 100 ml reactor under argon 6 mmol of phosphochloR1dite are dissolved in 20 ml of anhydrous toluene. The soluT1on is sT1rred at -10°C. A soluT1on of 3 nmol of diol and 10 mmol of tR1ethylamine in 20 ml of anhydrous toluene is introduced dropwise into the reacT1on xixture, which is held at -10°C: a white precipitate forms. The suspension is sT1rred vigorously at 25oC 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 puR1ficaT1on. The following ligands were prspared acccrding to the procedure descR1bed above: Procedure II: A phosphoramidite is used which is prepared from Cl2PNEt2 (available commercially) and a subsT1tuted or unsubsT1tuted phenol according to the following procedure: A mixture of Cl2PNEt2 (0.20 mol) and tR1ethylamine (0.44 mol) in toluene (800 ml) at C°C is admixed slowly, with vigorous sT1rR1ng, with a soluT1on of phenol (0.40 mol) in toluene (100 ml) . The formaT1on of a white precipitate is observed. The mixture is allowed to climb to ambient temperature and is sT1rred, sT1ll vigorously, for 2 h. The mixture is subsequently filtered on a bed of silica and concentrated under vacuum to give the phosphoramidate (ArO)2PNEt2 with a puR1ty of more than 95%. AddiT1onally a commercially available diol is used. The following general procedure is representaT1ve: In a 100 ml reactor under argon 6 mmol of phosphoramidite are introduced in 2 0 ml of anhydrous toluene. The soluT1on is sT1rred at 0°C and 7.5 ml of a 2 M soluT1on of hydrochloR1c acid in ether are added thereto over 30 minutes. The formaT1on of a white precipitate is observed, and the mixture is sT1rred at ambient temperature for 1 hour. A soluT1on of 3 mmol of diol and 10 mmol of tR1ethylamine in 20 ml of anhydrous toluene is subsequently introduced dropwise into the reacT1on mixture, which is cooled at -10°C. The suspension is sT1rred 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 puR1ficaT1on. The following ligands were prepared according to the procedure descR1bed above: Examples of hydrocyanaT1on of 3-penterenitR1le (3PN) to adiponitR1le (AdN) The general procedure used is as follows: Under an argon atmosphere a 60 ml Schott glass tube eqU1pped with a septum stopper is charged in succession with the ligand (2.5 eq), 1.21 g (15 mmol; 3 0 eq) of anhydrous 3PN, 13 8 mg (0.5 mmol; 1 eq) of Ni(cod)2 and the Lewis acid (0.5 mmol; 1 eq). The mixture is taken to 7 0°C with sT1rR1ng. Acetone cyanohydR1n is injected into the reacT1on mixture by means of a syR1nge dR1ver at a rate of 0.45 ml per hour. After 3 hours of injecT1on 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 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 comprising a metallic element selected from transition metals and an organic ligand, characterized 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, R1, R2, R3 and R4, which are identical or different, represent a substituted or unsubstituted, aromatic, aliphatic or cycloaliphatic radical comprising one or more rings, 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, U1, U2, U3 and U4, which are identical or different, represent an oxygen atom or a radical of formula NR in which R denotes a monovalent alkyl, aryl, cycloalkyl, sulphonyl or carbonyl radical, R5 and R6, which are identical or different, represent an aryl or cycloaliphatic group which may comprise heteroatoms and/or one or more rings, in fused form or not, and which are substituted or unsubstituted, 2. Process according to Claim 1, wherein the organic ligand of general formula I comprises a structure: selected from the group consisting of the following structures: 3. Process according to Claim 1 or 2, wherein the organic ligand of formula I is selected from the group consisting of: 4. Process according to one of Claims 1 to 3, wherein the metallic element is selected from the group consisting of nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium and mercury. 5. Process according to one of the preceding claims, wherein the reaction is carried out in a single-phase medium. 6. Process according to one of the preceding claims, wherein the catalyst corresponds to the general formula (II): M [Lf]t (II) in which M is a transition metal, Lf represents the organic ligand of formula (I) and t represents a number between 1 and 4 (inclusive). 7. Process according to one of the preceding claims, wherein the reaction mixture comprises a solvent for the catalyst which is miscible with the phase comprising the compound to be hydrocyanated at the hydrocyanation temperature. 8. Process according to 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)4], bis(acrylonitrile)nickel zero, bis-(cycloocta-1,5-diene)nickel zero and derivatives containing ligands, such as tetrakis(tri-phenylphosphine)nickel zero; compounds of nickel such as carboxylates, carbonate, bicarbonate, borate, bromide, chloride, citrate, thiocyanate, cyanide, formate, hydroxide, hydrophosphite, phosphite, phosphate and derivatives, iodide, nitrate, sulphate, sulphite, aryl- and alkylsulphonates. 9. Process according to 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-1,5-diene, ethylenically unsaturated aliphatic nitriles, especially linear pentenenitriles such as pent-3-enenitrile and pent-4-enenitrile, monoolefins such as styrene, methylstyrene, vinylnaphthalene, cyclohexene and methylcyclohexene and also mixtures of two or more of these compounds. 10. Process according to 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 isomerized 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 (I) 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. Process according to one of the preceding claims, wherein the hydrocyanation reaction is carried out at a temperature from 10°C to 200°C. 12. Process according to one of the preceding claims for hydrocyanating ethylenically unsaturated nitrile compounds to dinitriles by reaction with hydrogen cycanide, characterized in that it is operated in the presence of a catalyst system comprising at least one transition metal compound, at least one organic compound of formula (I) and a cocatalyst composed of at least one Lewis acid. 13. Process according to Claim 12, wherein the ethylenically unsaturated nitrile compounds are selected from ethylenically unsaturated aliphatic nitriles comprising linear pentenenitriles such as pent-3-enenitrile and pent-4-enenitrile and mixtures thereof. 14. Process according to Claim 13, wherein the linear pentenenitriles contain amounts of other compounds selected from the group consisting of 2-methylbut-3-enenitrile, 2-methylbut-2-enenitrile, pent-2-enenitrile, valeronitrile, adiponitrile, 2-methylglutaronitrile, 2-ethylsuccinonitrile and buta¬diene. 15. Process according to one of Claims 12 to 14, wherein the Lewis acid employed as cocatalyst is selected from compounds of the elements of groups lb, llb, llla, lllb, IVa, IVb, Va, Vb, VIb, Vllb and VIII of the Periodic Table of the Elements. 16. Process according to 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. Process according to one of Claims 12 to 16, wherein the Lewis acid is selected from zinc chloride, zinc bromide, zinc iodide, manganese chloride, manganese bromide, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulphate, stannous tartrate, indium trifluoromethyl-sulphonate, indium trifluoroacetate, zinc trifluoro-acetate, the chlorides or bromides of rare earth elements such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, hafnium, erbium, thallium, ytterbium and lutetium, and cobalt chloride, ferrous chloride, yttrium chloride and mixtures thereof. 18. Process according to one of Claims 12 to 17, wherein the Lewis acid employed represents irom 0.01 to 50 mol per moie of transition metal compound. 19. Process according to one of Claims 1 to 18, wherein 2-methylbut-3-enenitrile, present in the reaction mixture originating from butadiene hydrocyanation, is isomerized to pentenenitriles in the absence of hydrogen cyanide, in the presence of a catalyst comprising at least one organic ligand of general formula (I) and at least one transition metal compound. 20. Process according to Claim 19, wherein the 2-methylbut-3-enenitrile subjected to isomerization is employed alone or in a mixture with 2-methylbut-2-enenitrile, pent-4-enenitrile, pent-3-enenitrile, pent-2-enenitrile, butadiene, adiponitrile, 2-methylglutaronitrile, 2-ethylsuccinonitrile or valeronitrile. 21. Process according to either of Claims 19 and 20, wherein the isomerization reaction is carried out at a temperature from 10°C to 200°C. 22. Process according to Claims 19 to 21, wherein the isomerization of 2-methylbut- 3-enenitrile to pentenenitriles is carried out in the presence of at least one transition metal compound, at least one organic phosphorous ligand of the formula (I) and a cocatalyst composed of at least one Lewis acid.

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