MXPA98002422A - Procedure of hydrocianuration of organic compounds of non saturation etilen - Google Patents

Abstract

The present invention relates to: a method of hydrocyanuration of ethylenically unsaturated organic compounds in nitriles, ie the hydrocyanuration of diolefins or substituted olefins such as alkane nitriles. More specifically, it is composed of a hydrocyanuration process of organic compounds composed of at least one ethylenic double bond by reaction with hydrogen cyanide, in the presence of an aqueous solution of a catalyst that is made up of at least one compound of a metal of transition and at least one water-soluble phosphine, characterized in that said water-soluble phosphine is a monodentate or bidentate phosphine

Description

PROCEDURE OF HYDROCIANURATION OF ORGANIC COMPOUNDS OF NON-SATURATION ETHYLENE DESCRIPTION OF THE INVENTION The present invention relates to a process for the hydrocyanination of ethylenically unsaturated organic compounds in nitriles, that is to say the hydrocyanuration of diolefins or of substituted olefins such as alkyl or t-rings. French Patent No. 1 599 761 describes a process for preparing nitriles by the addition of hydrocyanic acid to organic compounds having at least one ethylenic double bond, in the presence of a nickel catalyst and a triaryl phosphite. This reaction can be conducted in the presence or absence of a solvent. When a solvent is used in this prior art process, it is preferably a hydrocarbon, such as benzene or xylenes or a nitrile such as acetonitrile. The applied catalyst is an organic nickel complex, containing ligatures such as phosphines, arsines, stilbenes, phosphites, arsenites or antimonites.

The presence of a promoter to activate the catalyst, such as a boron compound or a metal salt, generally a Lewis acid, is in the same manner recommended in said patent. In this process, the medium is entirely organic and one of its main drawbacks lies in the difficulty of separating, at the end of the reaction, the products of hydrocyanuration, of the catalytic solution containing several constituents (nickel complexes, triaryl phosphite, promoter), mainly considering the recycling of the latter in a new hydrocyanuration reaction. Such separation is delicate, very complex and imperfect and a substantial loss of the catalyst is observed, as well as the presence of such a catalyst in the hydrocyanuration products. This loss of metallic catalyst, generally based on nickel, presents economic problems, but poses with more pressure questions about the future of such metals, since the rejection of the effluents or the storage of the waste are less and less acceptable for the environment . The patent 1 FR-A-2 338 253 proposes to carry out the hydrocyanuration of the compounds that have at least one ethylenically unsaturated, in the presence of an aqueous solution of a transition metal compound, ie nickel, palladium or iron, and a sulfonated phosphine. The sulfonated phosphines described in that patent are sulfonated fine triazoles and more particularly sulfonated tri-phenols. This procedure allows a good hydrocyanuration, mainly of butadiene and of pentane-ni tri, an easy separation of the catalytic solution by means of a simple decantation and therefore avoids to the maximum the rejection of effluents or wastes containing the metals that serve of catalyst. The results obtained during the hydrocyanuration reaction are relatively good with different substrates and mainly with olefins with a practical nature such as pentene-nitriles. However, it is found that the life of the catalyst could be improved in order to allow an industrial exploitation of this type of procedure. EP-A-0 650 959 discloses a hydrocyanuration process of unsaturated nitriles in dinitriles in the presence thereof sulfonated phosphines that the previous patent and of a Lewis acid. The patent EP-A-0 647 619 describes the i somer izc ion of methyl-2-butene-3 nitrile in pentane-in-linear terms using the catalytic system described in FR-A-2 338 253. EP-A-0 133 127 discloses novel sulfonated chiral phosphines. These chiral sulfur phosphines are used in the form of rhodium complexes in asymmetric catalysis, essentially in asymmetric hydrogenation of substituted acrylic acids. These possibilities of asymmetric catalysis and more particularly of asymmetric hydrogenation have no interest for the hydrocyanuration of ethylenic compounds. The application WO-95/22405 describes the BINAP catalysts (compounds 2, Water-soluble 2 '-bi s (di f-enyl-phosphino) -1, 1'-inafylsulfonated) for the asymmetric synthesis of the optically active compounds. The present invention relates to a process capable of providing a very efficient solution to this important hydrocyanuration reaction, which leads when it is applied, for example, to butadiene, then to pentane and tri of adiponitrile, one of the basic compounds necessary for the manufacture of pol-ida-6, 6. More specifically, it consists of a hydrocyanuration process of organic compounds constituted by at least one ethylenic double bond by reaction with the hydrogen cyanide, in the presence of an aqueous solution of a catalyst which is composed of at least one transition metal compound and at least one water-soluble phosphine characterized in that such water-soluble phosphine is a monodentate or bidentate phosphine corresponding to the formula general (Y): (Ar3) c wherein: Ar1 and Ar2, identical or different, represent the aryl or aryl groups consisting of one or more substituents such as: alkyl or alkoxy radical having 1 to 4 carbon atoms, - halogen atom, - hydrophilic group such as: -COOM, -SO3M, -PO3M, M representing a mineral or organic cationic moiety selected from the proton, cations derived from alkali or alkaline earth metals, ammonium cations -N (R 4 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, the other cations derived from metals whose salts of arylcarboxylic acids, arylsulfic acids The ionic or aromatic acids are soluble in water. -N (R) 3 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, -OH -Ar 3 represents an aryl group which is formed of one or more substituents such as: - alkyl or alkoxy radical having from 1 to 4 carbon atoms, - halogen atom, - hydrophilic group such as: -COOM, -PO3M, M representing a cationic mineral or organic residue selected from the proton, cations derived from alkali or alkaline-earth metals, ammonium cations -N (R) 4 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals whose salts of arylcarboxylic acids, arylsulfonic acids or phonic arylphonic acids are soluble in water. -N (R) 3 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, -OH, at least one of such substituents of Ar3 being a hydrophilic group as defined above, - a represents 0 or 1, - b represents 0 or 1, - c represents an integer from 0 to 3, D represents an alkyl group, a cycloalkyl group, an alkyl group or cycloalkyl which is constituted by one or more substituents such as: alkoxy radical having from 1 to 4 carbon atoms, - halogen atom, - hydrophilic group such as: -COOM, -S03M, -PO3M, M representing a mineral or organic cationic moiety selected from the proton, cations derived from alkali metals or alkaline-earth, the ammonium cations -N (R) 4 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, the other cations metal derivatives whose salts of arylcarboxylic acids, arylsulfonic acids or phosphonic acids are soluble in water. -N (R) 3 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, -OH-d represents an integer from 0 to 3 , - the sum (a + b + c + d) is equal to 3 or to the general formula (II): where: Arl, Ar2 and D have the meanings indicated above for the formula (I), - a, b, e and f represent each 0 or 1, dyg each represent an integer from 0 to 2, - the sum ( a + b + d) is equal to 2, - the sum (e + f + g) is equal to 2, - L represents a single valence bond or a divalent hydrocarbon radical such as an alkylene radical, a cycloalkylene radical, an arylene radical, a radical derived from a heterocycle consisting of one or two oxygen, nitrogen or sulfur atoms in the cycle, these different cyclic radicals being linked to one of the phosphorus atoms or to two phosphorus atoms or being linked to one of the phosphorus atoms or two by a linear or branched alkylene radical having from 1 to 4 carbon atoms, the cycle (s) finally parts of the radical divalent L may be constituted by one or more substituents such as the alkyl group having 1 to 4 carbon atoms. Mention may be made, as examples, of metals whose salts of arylcarboxylic acids, arylsulphonic acids or phonic acids are soluble in water, lead, zinc or tin. By the expression "soluble in water" is meant herein a compound soluble in at least 0.01 g per liter of water. The preferred water-soluble phosphines are the phosphines of the formula (I) or the formula (II) in which Arl and Ar 2 are phenyl or phenyl groups which are composed of one or two substituents such as those defined above, Ar 3 is a phenyl group which is composed of one or two substituents such as those defined above, D is an alkyl group having from 1 to 6 carbon atoms, a cycloalkyl group having from 5 to 8 carbon atoms, alkyl group of 1 to 6 carbon atoms or cycloalkyl having from 5 to 8 carbon atoms consisting of one or more substituents as defined above, L is a simple valence bond, an alkylene radical having from 1 to 6 carbon atoms, a monocyclic or bicyclic cycloalkylene radical having from 4 to 12 carbon atoms, a phenylene radical, a diphenylene radical, a naphthylene radical, a dinaphthylene radical, a radical derived from a heterocycle consisting of one or two oxygen atoms , of nitrogen or of sulfur in the cycle, those different cyclic radicals being directly linked to one of the phosphorus atoms or to the two phosphorus atoms or being linked to one of the phosphorus atoms or to both by means of a linear alkylene radical or branched having 1 to 4 carbon atoms, the cycle (s) finally parts of the divalent radical L may be composed of one or more substituents such as the alkyl group having 1 to 4 carbon atoms. Preferred water-soluble phosphines are the phosphines of the formula (I) or the formula (II) in which: - the substituent (s) of Arl and Ar2, identical or different, represent groups such as: alkyl or alkoxy radical having 1 to 2 carbon atoms, - chlorine atom, - hydrophilic group as: -COOM, -SO3M, -PO3M, M representing a mineral or organic cationic moiety selected from the proton, the cations derived from sodium, potassium, calcium or -baryl, ammonium cations, t re amethylammonium, tet rae t ilamonium , tetrapropylammonium, tetrabutylammonium, the cations derived from zinc, lead or tin, -N (R) 3 in the formula of which the R symbols, identical or different, represent a hydrogen atom or an alkyl radical having 1 to 4 atoms of carbon, -OH - or the substituents of Ar3, identical or different, represent such groups as: - alkyl or alkoxy radical having 1 to 2 carbon atoms, - chlorine atom, - hydrophilic group such as: -COOM, -PO3M, M representing a mineral or organic cationic residue selected from the proton, cations derived from sodium, potassium, calcium or barium, ammonium cations, t re ti ame lamonio, brings you t ilamonio, tetrapropylammonium, tetrabutilamonio, the cations derived from zinc, lead or tin, -N (R) 3 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, -OH in a global form, at least two such substituents of Arl, Ar2, Ar3 and D for the phosphines of the formula (I) and of Arl, Ar2 and D for the phosphines of the formula (II) being a hydrophilic group as defined above. By way of examples but not limiting the phosphines of the general formula (I), mention may be made principally of the tri s (idroximet i 1) phosphine, tris (2-hydroxyethyl) phosphine, tris (hydroxy-propyl 1) phos, t ri s (2-carboxymethyl) fos f ina, sodium salt of t (3-carboxy pheny1) fos f ina, tris (3-carboxyethyl 1) f or f ina, tris iodide (4- timamethylmethyl) phosphine, sodium salt of tris (2-phosphonate) phosphine, bis (2-carboxyethyl) phenylphosphine, sodium salt of the tris (parafens f onfyl) phosphine, sodium salt of the bi s (me t asul f of enyl) paracarboxi f eni 1 f os, the sodium salt of the bi s (me t asul f of eni 1) sul fo - 2 ethyl phosphine. By way of examples, but not limiting, the phosphines of the general formula (II) can be Name mainly the sodium salt of 2,2'-bis [di (sulfonatofenyl) fos] - 1,1'-dinaphyl, sodium salt of 1,2-bis [di (sulfonatofenyl) phosph. inomethyl] cyclobutane (CBDTS), 1,2-bis (dihydroxymethyl-1-ph) ethane, 1,3-bs (dihydroxymethylphosphine) propane, 2,2'-bis sodium salt [di (sulfonatophenyl) phosphinoacetyl] -1, dinaphthyl. Certain water-soluble phosphines of the formula (I) or (II) are for sale. For the preparation of others, reference may be made to the general or particular methods of synthesis of phosphines described in general works such as HOUBEN-WYEL, Method der organischen Chemie, organische Phosphor Verbindungen, teil 1 (1963). Finally, for the preparation of the water-soluble derivatives not described, it is possible to proceed with the introduction of one or more of these hydrophilic substituents from the phosphines which are not composed of water-soluble substituents defined previously. Thus sulphonate groups, for example, can be introduced by the reaction of S03 into sulfuric acid. The groups carbóxi latos, phosphonates, quaternary ammonium can in the same way be introduced when applying the chemical methods known for this type of synthesis. The nickel, palladium and iron compounds are preferably used as transition metal compounds. Water-soluble compounds are used or capable of passing in solution under the conditions of the reaction. The rest linked to the metal is not critical, from the moment it satisfies these conditions. Among the compounds mentioned, the most preferred compounds are those of nickel, which may be mentioned by way of examples but not limiting: the compounds in which nickel is at the zero oxidation degree such as tet racianoniquelat or potassium K4 [Ni (CN ) 4], bis (acri lonit rilo) i quel cero, bi s (c iclopent adieno - 1,5) 2 nickel and the derivatives containing ligatures of the group Va as the tet ra is (trif eni 1 - f os f ina) nickel zero (in in the latter case, the compound can be dissolved in a non-water miscible solvent such as toluene, since an aqueous sulfonated phosphine solution extracts a part of the nickel, developing a red coloration in the aqueous solution that decant); nickel compounds such as carboxylates (ie acetate), carbonate, bicarbonate, borate, bromide, chloride, citrate, thiocyanate, cyanide, formate, hydroxide, hydrofoam, phosphite, phosphate and derivatives, iodide, nitrate, sulfate, sulfite, aryl- and alkyl sulphates. It is not necessary for the nickel compound to be soluble in water. For example, nickel cyanide that is poorly soluble in water dissolves very well in an aqueous phosphine solution. When the nickel compound used corresponds to a nickel oxidation state higher than 0, a nickel reductant reactive with the nickel is added to the reaction medium under the reaction conditions. That reducer can be organic or mineral. Mention may be made, as non-limiting examples, of BH4Na, Zn powder, magnesium, BH4K and borohydrides, preferably soluble in water. The reducer is added in an amount such that the number of equivalents of rust-reducing ion is between 1 and 10. Values less than 1 and greater than 10 are not, however, excluded.

When the nickel compound used corresponds to the oxidation state 0 of the nickel, it is also possible to add a reductant of the type already mentioned, but such addition is not mandatory. When an iron compound is used, the same reducers are suitable. In the case of palladium, the reductants can also be the elements of the reaction medium (phosphine, solvent, olefin). The organic compounds containing at least one ethylenic double bond more particularly applied in the present process are the diofelins such as butadiene, isopropene, hexadiene-1, 5, cyclopentiene 1, 5, the aliphatic nitriles eti léni carne unsaturated, in particular the pentane - ni tr the linear ones such as pentene - 3 nitrile, pentene - 4 nitrile, monoolefins such as styrene, me ti t irene, vini lo - af taleno, cyclohexane, thiothicarbonhexane as well as mixtures of several of these compounds. Pentane-nitrosols may mainly contain large amounts, generally minor, of other compounds such as methyl-2-butene-3-nitrile, methyl-2-butene-2-nitrile, pentene-2-nitrile, valeroni-t-iyl, adiponitrile, methyl-2 glut aroni tyl, ethyl-2 suc c inoni t r i lo or butadiene, coming for example from the previous hydrocyanuration reaction of butadiene. The hydrocyanuration of butadiene is formed with linear pentylenitriles of the non-negligible amounts of methyl-2-butene-3-nitrile and methyl-2-butene-2-nitrile. The catalytic solution used for the hydrocyanuration according to the process of the invention can be prepared before its introduction into the reaction zone, for example by adding it to the aqueous solution of the water-soluble phosphine of the formula (I) or (II), the appropriate amount of the selected transition metal compound and finally the reductant. It is also possible to prepare the catalytic solution i n s i t u by a simple mixture of these various constituents. The amount of nickel compound or other transition metal used is selected such that there is per liter of reaction solution between 10"and 1, and preferably between 0.005 and 0.5 mol of nickel or other transition metal. api i cado.

The amount of water-soluble phosphine of the formula (1) or (11) used to prepare the reaction solution is selected such that the number of moles of that compound attributed to 1 mole of transition metal is from 0.5 to 2000. and preferably from 2 to 300. Although the reaction is generally conducted without a solvent third, it may be advantageous to add an inert organic solvent, not water miscible, which could be that of the previous extraction. As examples of such solvents, the aromatic, aliphatic or cycloaliphatic hydrocarbons which maintain the reaction medium in the biphasic state can be mentioned. Thus, from the end of the reaction, it is very easy to separate on the one hand an aqueous phase containing the phosphine or the water-soluble phosphines of the formula (1) or (11) and the transition metal compound and on the other hand, an organic phase consisting of reagents involved in the reaction of products of the reaction and according to the case of the organic solvent not miscible with water.

The hydrocyanuration reaction is generally carried out at a temperature of 10 ° C to 200 ° C and preferably 30 ° C to 120 ° C. The process of the invention can be applied continuously or discontinuously. The applied hydrogen cyanide can be prepared from the metal cyanides, that is to say the sodium cyanide, or the cyanhydrins. The hydrogen cyanide is introduced into the reactor in gaseous or liquid form. It can also be dissolved previously in an organic solvent. In the context of a discontinuous application, it can in practice be charged in a reactor, previously purified with the help of an inert gas (such as nitrogen, argon), either an aqueous solution containing all or a portion of the various constituents such as water-soluble phosphine, transition metal compound, reductants or eventual solvents, either separately from such constituents. In general, the reactor is brought to the selected temperature, then the penentone is introduced. The hydrogen cyanide is then introduced, preferably continuously and regularly.

When the reaction (whose evolution can be followed by the dosing of samples) is completed, the reaction mixture is extracted after cooling and the products of the reaction are isolated by decantation, finally followed by an extraction of the aqueous layer with the aid of a suitable solvent, such as, for example, the non-miscible solvents with water mentioned above. The aqueous catalyst solution can then be recycled in a new hydrocyanuration reaction of organic compounds that are composed of at least one ethylenic double bond. In the context of an application of the continuous process, only the organic phase can be extracted, while the aqueous catalytic phase remains in the reactor. This reaction in two-phase medium makes the application of an industrial process extremely easy. The easy separation of the whole of the catalyst from one part and from the products of the reaction by the other, makes a large number of operations such as the distillation of the reactants and the products of the reaction or the liquid / liquid extraction useless. with the help of a suitable solvent.

An improvement to the hydrocyanuration process of ethylenically unsaturated compounds according to the present invention refers to the hydrocyanuration of such ethylenically unsaturated compounds, by reaction with hydrogen cyanide, characterized in that it is carried out in the presence of an aqueous solution of a catalyst comprising at least minus a transition metal compound, at least one water-soluble phosphine of the formula (1) or (11) and a cocatalyst consisting of at least one Lewis acid. The ethylenically unsaturated compounds that can be applied in this improvement are generally those that have been cited for the basic process. However, it is more advantageous to apply ethylenically unsaturated aliphatic nitriles, ie linear pentene-nitriles such as pentene-3 nitrile, pentene-4 nitrile and mixtures thereof. These nitric compounds can contain amounts, usually minor, of other compounds, such as methyl-2-butene-3-nitrile, methyl-2-butene-2-nitrile, pentene-2-nitrile, valeroni tri-lo, adiponitrile, methyl-2. glut ar ini tri lo, etil-2 The succination of butadiene and / or the isomerization of methyl-2-butene-3-nitrile in pentane-nitryls. The water-soluble phosphines, the transition metal compounds, the operating conditions, the composition of the reaction medium are the same for the general hydrocyanination process according to the invention described above, but the reaction is further conducted in the presence of an acid of Lewis. The Lewis acid used as a cocatalyst mainly allows, in the case of the hydrocyanuration of the ethylenically unsaturated aliphatic nitriles, to improve the linearity of the dinitriles obtained, that is to say the percentage of linear dinitrile with respect to all of the dinitriles formed, and / or increase the life of the cat to the izador. By Lewis acid it is understood in the present text, according to the usual definition, the electric dipole acceptor compounds. The Lewis acids cited in the work edited by G.A. OLAH "Friedel-Crafts and related Reactions", volume 1, pages 191 to 197 (1963). The Lewis acids which can be applied as co-catalysts in the present process are selected from the compounds of the elements of groups Ib, IIb, Illa, IIIb, IVa, Ib, Va, Vb, Vlb, Vllb and HIV. of the periodic classification of the elements, insofar as such compounds are at least partially soluble and stable in water. These compounds are the most solvent of the salts, mainly the halides, preferably the chlorides and bromides, the sulphates, the carboxylates and the phosphates. By way of example but not limitation of such Lewis acids, mention may be made of zinc chloride, zinc bromide, zinc iodide, manganese chloride, manganese bromide, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, sulphate stannous, tartrate stannous, chlorides or bromides of rare earth elements such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holium, erbium, thulium, ytterbium and lutetium, chloride cobalt, ferrous chloride, yttrium chloride.

Of course, mixtures of several Lewis acids can be applied. It is also interesting, depending on the case, to stabilize the Lewis acid in an aqueous solution by the addition of an alkali metal chloride such as lithium chloride or sodium chloride, ie. The molecular ratio of lithium chloride or sodium / Lewis acid varies very widely, for example from 0 to 100, the particular ratio can be adjusted according to the water stability of Lewis acid. Among the Lewis acids, zinc chloride, zinc bromide, stannous chloride is particularly preferred., stannous bromide, stannous chloride stabilized by lithium chloride, stannous chloride stabilized by sodium chloride, zinc chloride / stannous chloride mixtures. The applied Lewis acid co-catalyst generally represents 0.01 to 50 moles per mole of transition metal compound, more particularly of the nickel compound, and preferably 1 to 10 mole per mole. Since for the application of the base process of the invention, the catalytic solution used for hydrocyanuration in the presence ofa Lewis acid can be prepared before its introduction into the reaction zone, for example by adding to the aqueous solution of the water-soluble phosphine of formula (1) or (11), the appropriate amount of the selected transition metal compound, Lewis acid and finally the reducer. It is also possible to prepare the catalytic solution in s i t u by simply mixing these various constituents. The separation of the catalyst in the aqueous phase is easy by simple decanting, as already indicated above for the basic process. This aqueous solution of the catalyst can thus be recycled in a new hydrochloride reaction of nitric oxide, this catalyst solution can be recycled, either in a new hydroentantion of pentane, or, more generally in the hydrocyanuration of butadiene that leads to the pentene-nitro groups that are immediately hydrogenated with the same catalyst. It is also possible under the conditions of the hydrocyanuration process of the present invention, and that is to say in the presence of the catalyst described above, that it is composed of at least one water-soluble phosphine of the formula (1) or (11) and at least one transition metal compound, perform, in the absence of hydrogen cyanide, the isomerization of methyl-2-butene-3-nitrile in pent-ene or tris. The methyl-2-butene-3-nitrile subjected to the isomerization according to the invention can be applied alone or in combination with other compounds. Thus, methyl-2-butene-3-nitrile can be introduced in combination with methyl-2-butene-2-nitrile, pentene-4-nitrile, pentene-3-nitrile, pentene-2-nitrile, butadiene, adiponitrile, methyl-2-glutononitrile, ethyl. -2 succinoni tr ilo or the vale roni tri lo. Thus, it is particularly interesting to treat the reaction mixture coming from the hydrocyanuration of butadiene by HCN in the presence of an aqueous solution of at least one water-soluble phosphine of the formula (1) or (11) and of at least one compound of a transition metal, preferably from a nickel compound to the degree of oxidation 0, as defined above. Within the framework of this preferred variant, the catalytic system is already present for the hydrocyanuration reaction of butadiene, with stopping any introduction of hydrogen cyanide, to stop producing the isomerization reaction. It is possible, according to the case, in this variant to make a light sweep of the reactor with the help of an inert gas such as nitrogen or argon for example, in order to expel the hydrocyanic acid that could still be present. The isomerization reaction is generally carried out at a temperature of 10 ° C to 200 ° C and preferably of 60 ° C to 120 ° C. In the preferred case of an isomerization immediately followed by the hydrocyanuration reaction of butadiene, it will be advantageous to operate at the temperature at which the hydrocyanuration was conducted. As for the hydrocyanuration process of ethylenically unsaturated compounds, the catalytic solution used for the isomerization can be prepared before its introduction into the reaction zone, for example by adding to the aqueous solution of the water-soluble phosphine of the formula (1) or ( 11), the appropriate amount of the selected transition metal compound and finally the reducer. Is It is also possible to prepare the catalytic solution i n s i t u by simply mixing these various constituents. The amount of the transition metal compound and more specifically of the nickel used, as well as the amount of water-soluble phosphine of the formula (1) or (11) are the same as for the hydrocyanuration reaction. Although the isomerization reaction is usually conducted without a solvent third, it may be advantageous to add an inert organic solvent, not miscible with water, which could be that of the previous extraction. It is specifically the case when a solvent like that has been applied in the isomerization reaction. Of these solvents, those mentioned above for hydrocyanuration can be chosen from among them. At the end of the reactionIt is very easy to separate the catalyst from the products of the isomerization reaction as indicated for hydrocyanuration and recycle it as the case may be in one of the hydrocyanuration reactions described above or in a new isomerization reaction. The following examples illustrate the present invention.

EXAMPLE 1 1) Preparation of the Ni / CBDTSNa4 catalytic solution.

In a 100 ml glass flask, with a magnetized bar and an upward coolant, pour 50 ml of a solution of 11.3 mmol of 1,2-bis-sodium salt [di (sul f onat of eni 1 ) f os f inome ti 1] cyclobutane (CBDTSNa4) in water, this solution is degassed. Immediately, 2 g (7.3 mmol) of Ni (cyclopentadiene) _ are introduced immediately, stirring and under the argon stream, since 35 ml of ortho-xylene are previously degassed. It is heated at 45 ° C for 15 h. After cooling, the biphasic system is decanted and a sample of the aqueous phase is strongly colored in red. The elemental analysis of the aqueous phase reveals a Ni concentration of 8 mmol / 100 g and P of 35.5 mmol / 100 g. 2) Hydrocyanuration of pentene-3 nitrile In a 150 ml glass reactor, stirred with the aid of a turbine, 37.4 g of the aqueous solution prepared in 1) are poured. It heats up , stirring at 60 ° C, then maintaining that temperature is injected successively: 3.2 ml of an aqueous solution containing 20 mmol of Zn chloride - 16.5 g (204 mmol) of pentene-3 nitrile (3PN) It is then injected with hydrogen cyanide at a rate of 1.2 g / h (44 mmol / h) for 0.5 h. At the end of the test, the obtained reaction mixture is cooled, neutralized with the help of a concentrated solution of soda, the eventual excess of injected hydrogen cyanide and the different constituents are dosed by means of gas chromatography (CPG): The following results are obtained: - transformation rate (TT) of 3PN 7% - yield (RT) in adiponitrile (DNA) with respect to the 3PN transformed 1% - RT in methyl-2 glut aroni t r i lo (MGN) with respect to the 3PN transformed 10 - RT in ethyl-2 succinoni tri lo (ESN) with respect to the 3PN transformed 1 RT in valeroni t rilo (VN) with respect to the 3PN transformed - linearity (*) 89% - catalyst activity (**) 4 - productivity in DNA (compared to the volume of the aqueous phase) 65 g / h.l (*) DNA formed / DNA + MGN + ESN formed (**) number of moles of 3 PN transformed per mole of Ni involved EXAMPLE 2 1) Preparation of the catalytic solution Ni / TPPPNa6. Into a 100 ml glass flask, with a magnetized bar and an upward coolant, pour 50 ml of a solution of 32.8 sodium salt of the t ri s (parafos f of eni 1) f os f ina ( TPPPNaS) in water; This solution is degassed. After stirring under a stream of argon, 2 g (7.3 mmol) of Ni (cycloalkyl adieno) 2 are introduced, then 35 ml of ortho-xylene, which has previously been degassed. Heat at 45 ° C for 15 h. After cooling, the biphasic system is decanted and a sample of the aqueous phase is strongly colored in red.

The elemental analysis of the aqueous phase reveals a concentration in Ni of 11.9 mmol / lOOg and in P of 216.2 mmol / 100 g. 2) Hydrocyanuration of pentene-3 nitrile In a 150 ml glass reactor, stirred with the aid of a turbine, 42.0 g of the aqueous solution prepared in 1) are poured. It is heated by stirring at 60 ° C, then maintaining that temperature is injected successively: 3.2 ml of an aqueous solution containing 20 mmol of Zn chloride 23.5 g (290 mmol) of pentene-3 nitrile (3 PN). Hydrogen cyanide is then injected at a rate of l, 8 g / h (67 mmol / h) for 0.6 h. At the end of the test, the obtained reaction mixture is cooled, neutralized with the help of a concentrated solution of soda, the eventual excess of injected hydrogen cyanide and the different constituents are dosed by means of gas chromatography (CPG): The following results are obtained: - transformation rate (TT) of 3PN 13% - yield (RT) in adiponitrile (DNA) with respect to 3 transformed PN 70 - RT in methyl-2 glut aroni t ri lo (MGN) with respect to trans 3PN formed 23-RT in ethyl-2 suc c inoni tri 1 o (ESN) with respect to 3PN transformed-RT in valeroni tri lo (VN) with respect to the 3PN transformed 4 linearity 73 - catalyst activity 7 - productivity in DNA (compared to the volume of aqueous phase) 125 g / h .1 EXAMPLE 3 1) Preparation of the Ni / DSPCPPNa3 catalytic solution.

Into a 100 ml glass flask, with a magnetized bar and an upward coolant, 50 ml of a solution of 32.8 mmol of sodium salt of the bi s (me t asul fof eni 1) aracarboxi feni 1 phosphine are poured. (DSPCPPNa3) in water; This solution is degassed. They are introduced immediately, shaking it and under argon stream, 2 g (7.3 mmol) of Ni (cyclopentadiene) 2, then 35 ml of ortho-xylene previously degassed. Heat at 45 ° C for 15 h. After cooling, the biphasic system is decanted and a sample of the aqueous phase is strongly colored in red. The elemental analysis of the aqueous phase reveals a concentration in Ni of 12 mmol / lOOg and in P of 53.9 mmol / 100 g. 2) Hydrocyanuration of pentene-3 nitrile In a 150 ml glass reactor, stirred with the aid of a turbine, 41.7 g of the aqueous solution prepared in 1) are poured. It is heated by stirring at 60 ° C, then maintaining that temperature is injected successively: 3.2 ml of an aqueous solution containing 20 mmol of Zn chloride 23.5 g (290 mmol) of pentene-3 nitrile (3 PN). Hydrogen cyanide is then injected at 1.8 g / h (67 mmol / h) for 0.75 h. At the end of the test, the obtained reaction mixture is cooled, neutralized with the help of _ a concentrated solution of soda the eventual excess of hydrogen cyanide injected and the different constituents are dosed by means of "gas chromatography (CPG): The following results are obtained: - transformation rate (TT) of 3P 19% - yield (RT) in adiponitrile (DNA) with respect to 3PN transformed 71% - RT in methyl-2 glutaronthyl (MGN) with respect to 3PN transformed 20% - RT in ethyl-2 succinoni t ri lo (ESN) with respect to 3PN transformed 3% RT in valeroni trilo (VN) with respect to 3PN transformed 6% - 76% linearity - catalyst activity 10 - productivity in DNA (compared to the volume of aqueous phase) 150 g / h.l EXAMPLE 4 1) Preparation of the catalytic solution Ni / DSPSEPNa3.

Into a 100 ml glass flask, with a magnetized bar and an upward coolant, 50 ml of a solution of 32.8 mmol of sodium salt of the bi s (me t asul f of eni 1) sul fo 2 ethyl phosphine (DSPSEPNa3) in water, - this solution is degassed. 2 g (7.3 mmol) of Ni (cyclopenthene) 2 are then introduced, under stirring and under argon current, then 35 ml of ortho-xylene, previously degassed. Heat at 45 ° C for 15 h. After cooling, the biphasic system is decanted and a sample of the aqueous phase is strongly colored in red. The elemental analysis of the aqueous phase reveals a concentration in Ni of 11.8 mmol / lOOg and in P of 54.5 mmol / 100 g. 2) Hydrocyanuration of pentene-3 nitrile In a glass reactor of 150 ml, stirred with the help of a turbine, 42.4 g of the ^ aqueous solution prepared in 1). It is heated by stirring at 60 ° C, then maintaining that temperature is injected successively: 3.2 ml of an aqueous solution containing 20 mmol of Zn chloride 23.5 g (290 mmol) of pentene-3 nitrile (3 PN). It is then injected with hydrogen cyanide at a rate of 1.8 g / h (67 mmol / h) for 0.5 h. At the end of the test, the obtained reaction mixture is cooled, neutralized with the help of a concentrated solution of soda, the eventual excess of injected hydrogen cyanide and the different constituents are dosed by means of gas chromatography (CPG): The following results are obtained: - transformation rate (TT) of 3PN 8% - yield (RT) in adiponitrile (DNA) with respect to 3PN transformed 69% - RT in methyl-2 glu t aroni tory (MGN) with respect to 3PN transformed 24% - RT in ethyl-2 succinonitrile (ESN) with respect to the 3PN transformed 3% RT in valeroni tri lo (VN) with respect to 3PN transformed 4% - linearity 72% - catalyst activity 4 - productivity in DNA (compared to the volume of aqueous phase) 90 g / h .1 COMPARATIVE TEST 1) Preparation of the Ni / TPPTSNa3 catalytic solution.

Into a 1000 ml glass flask, with a stirrer and an upward coolant, 500 ml of a solution of 300 mmol of sodium salt of the t r i s (me t asulf of enyl) phosphine (TPPTSNa3) in water are poured; This solution is degassed. Subsequently, 20 g (73 mmol) of Ni (c i c lo c t adieno) 2 are added, stirring and under a stream of argon, then 350 ml of ortho-xylene, previously degassed. Heat at 45 ° C for 15 h. After cooling, the biphasic system is decanted and a sample of the aqueous phase is strongly colored in red.

The elemental analysis of the aqueous phase reveals a concentration in Ni of 12.0 mmol / 100 g and in P of 49.7 mmol / 100 g. 2) Hydrocyanuration of pentene-3 nitrile In a 150 ml glass reactor, stirred with the aid of a turbine, 41.7 g of the aqueous solution prepared in 1) are poured. It is heated by stirring at 60 ° C, then maintaining that temperature is injected successively: - 3.2 ml of an aqueous solution containing 20 mmol of Zn-8 g chloride (105 mmol) of pentene-3 nitrile (3 PN). It is then injected with hydrogen cyanide at a rate of 1.8 g / h (67 mmol / h) during 2 h. At the end of the test, the obtained reaction mixture is cooled, neutralized with the help of a concentrated solution of soda the eventual excess of injected hydrogen cyanide and the different constituents are dosed by means of gas chromatography (CPG): The following results are obtained: - transformation rate (TT) of 3PN 89% - yield (RT) in Adiponitrile (DNA) with respect to 3PN transformed 66% - RT in methyl-2 glut aroni t ri lo (MGN) with respect to 3PN transformed 26% - RT in ethyl-2 succinoni trilo (ESN) with respect to 3PN transformed 5% RT in valeroni trilo (VN) with respect to 3PN t ras formed 3% - 68% linearity - catalyst activity 20 - productivity in DNA (compared to the volume of aqueous phase) 90 g / h .1

Claims (19)

1. Hydrocyanuration process of organic compounds consisting of at least one ethylenic double bond in reaction with hydrogen cyanide, in the presence of an aqueous solution of a catalyst comprising at least one transition metal compound and at least one water-soluble phosphine , characterized in that such a water-soluble phosphine is a monodentate or bidentate phosphine corresponding to the general formula (1): (Ar1) a (Ar3) c wherein: - Ar1 and Ar2, identical or different, represent aryl or aryl groups consisting of one or more substituents such as: alkyl or alkoxy radical having 1 to 4 carbon atoms, - halogen atom, - hydrophilic group such as: -COOM, -SO3M, -P03M, M representing a mineral or organic cationic moiety selected from the proton, cations derived from alkali or alkaline-earth metals, ammonium cations -N (R) 4 in the formula which symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals whose salts of ary 1 carboxylic acids, ary 1 sulphonic acids, Phonic or aryphosphonic acids are soluble in water. -N (R) 3 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, -OH -Ar 3 represents an aryl group which is formed of one or more substituents such as: - alkyl or alkoxy radical having 1 to 4 carbon atoms, - halogen atom, - hydrophilic group such as: -COOM, -PO3M, M representing a mineral or organic cationic moiety selected from the group proton, cations derived from alkali or alkaline earth metals, ammonium cations -N (R) 4 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals whose salts of arylcarboxylic acids or acidic acids are soluble in water, at least one of such substituents of Ar3 being a hydrophilic group as defined above. defined above, - a represents 0 or 1, - b represents 0 or 1, - c represents an integer from 0 to 3, D represents an alkyl group, a cycloalkyl group, an alkyl or cycloalkyl group that is made up of one or more substituents such as: alkoxy radical having from 1 to 4 carbon atoms, - halogen atom, - hydrophilic group such as: -COOM, -S03M, -PO3M, M representing a mineral or organic cationic moiety selected from the proton, the cations metal derivatives alkaline or alkaline-earth, the ammonium cations -N (R) 4 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals whose salts of arylcarboxylic acids, aric acid sulfides or arylphosphonic acids are soluble in water . -N (R) 3 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, -OH-d represents an integer from 0 to 3 , - the sum (a + b + c + d) is equal to 3 or to the general formula (II): (Art), (Arl) e wherein: Arl, Ar2 and D have the meanings indicated above for the formula (I), - a, b, e and f represent each 0 or 1, - dyg each represent an integer from 0 to 2, - the sum (a + b + d) equals 2, - the sum (e + f + g) equals 2, - L represents a valence bond simple or a divalent hydrocarbon radical such as an alkylene radical, a cycloalkylene radical, a phenylene radical, a diphenylene radical, a radical derived from a heterocycle consisting of one or two oxygen, nitrogen or sulfur atoms in the cycle, these cyclic radicals different being linked directly to one of the phosphorus atoms or two phosphorus atoms or being attached to one of the phosphorus atoms or both by a linear or branched alkylene radical having from 1 to 4 carbon atoms, the cycle (s) finally parts of the divalent radical L may be constituted by one or several substituents such as the alkyl group having from 1 to 4 carbon atoms.

2. The process according to claim 1, characterized in that the water-soluble phosphines are the phosphines of the formula (1) or the formula (11) in which Arl and Ar2 are phenyl groups or the "Phenyl groups which are constituted by one or two substituents such as those defined above, Ar3 is a phenyl group which is composed of one or two substituents such as those defined above, D is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having from 5 to 8 carbon atoms, an alkyl group of 1 to 6 carbon atoms or cycloalkyl having from 5 to 8 carbon atoms consisting of one or more substituents as defined previously. L is a simple valence bond, an alkylene radical having from 1 to 6 carbon atoms, a monocyclic or bicyclic cycloalkylene radical having from 4 to 12 carbon atoms, a phenylene radical, a diphenylene radical, a radical derived from a heterocycle consisting of one or two oxygen, nitrogen or sulfur atoms in the cycle, those different cyclic radicals being linked directly to one of the phosphorus atoms or to the two phosphorus atoms or being linked to one of the phosphorus atoms or both by means of a linear or branched alkylene radical having from 1 to 4 carbon atoms, the cycle (s) finally parts of the divalent radical L may be composed of one or more substituents such as the alkyl group having 1 to 4 carbon atoms.

3. The process according to one of claims 1 or 2, characterized in that the water-soluble phosphines are phosphines of the formula (1) or the formula (11) in which: - the substituent (s) of Arl and Ar2, identical or different, represent groups such as: - alkyl or alkoxy radical having 1 to 2 carbon atoms, - chlorine atom, - hydrophilic group co or: -COOM, -S03M, -P03M, M representing a mineral or organic cationic moiety selected from the proton, the cations derived from sodium, potassium, calcium or barium, the ammonium cations, t amethylammonium, brings you t-ammonium, tetrapropylammonium, tetrabutylammonium, the cations derived from zinc, lead or tin, -N (R) 3 in the formula of which the R symbols, identical or different, represent a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, -OH - the substituent (s) of Ar3, identical or different, represent such groups as: - alkyl or alkoxy radical having 1 to 2 carbon atoms, - chlorine atom, - hydrophilic group such as: -COOM, -P03M, M representing a mineral or organic cationic moiety selected from the proton, the cations derived from sodium, potassium, calcium or barium, the ammonium cations, t re amethylammonium, brings you lamonium, tetrapropylammonium, tetrabutylammonium, the cations derived from zinc , lead or tin, globally at least two such substituents of Arl, Ar2, Ar3 and D for the phosphines of the formula (I) and Arl, Ar2 and D for the phosphines of the formula (II) being a hydrophilic group as the one defined above.

4. The process according to one of claims 1 to 3, characterized in that the compounds of the transition metals are selected from the nickel, palladium and iron compounds, soluble in water or capable of passing in solution under the conditions of the reaction.

5. The process according to one of claims 1 to 4, characterized in that the preferred transition metal compounds are those of nickel and are selected from: the compounds in which the nickel is at the zero oxidation degree such as potassium thio ratiate monophosphate K4 [ (Ni (CN) 4], bis (acrylonitrile) nickel zero, bis (ci c lopenthene-1, 2) 2 nickel and derivatives containing group Va ligations such as tetrakis (trif enylphosphine) zero ion; nickel compounds such as carboxylates, carbonate, bicarbonate, borate, bromide, chloride, citrate, thiocyanate, cyanide, formate, hydroxide, hydrophobic acid, phosphite, phosphate and derivatives, iodide, nitrate, sulfate, sulfite, aryl- and alkali 1 - sul fonat os.

6. The process according to one of claims 1 to 5, characterized in that the organic compounds containing at least one ethylenic double bond are selected from the diofelines such as butadiene, isoprene, hexadiene-1,5, ci c lopenthene 1,5, the aliphatic ethylenically unsaturated nitriles, in particular those ? PENT ENE-NINE linear ones such as pentene-3 nitrile, pentene-4 nitrile, monoolefins such as styrene, useful tireno, vinyl-naphthalene, cyclohexene, me-1-cyclohexene as well as mixtures of several of these compounds

7. The process according to one of claims 1 to 6, characterized in that the amount of nickel compound or other transition metal used is selected such that there is per liter of reaction solution between 10"and 1, and preferably between 0.005 and 0.5 mole of nickel or other transition metal applied and because the amount of water-soluble phosphine of formula (1) or (11) used is selected such that the number of moles of that compound attributed to a mole of transition metal is from 0.5 to 2000 and preferably from 2 to 300.

8. The process according to one of claims 1 to 7, characterized in that the hydrocyanuration reaction is carried out at a temperature of 10 ° C to 200 ° C and preferably of 30 ° C to 120 ° C.

9. The process according to one of claims 1 to 8 of hydrocyanuration of ethylenically unsaturated compounds, by reaction with hydrogen cyanide, characterized in that it is carried out in the presence of an aqueous solution of a catalyst composed of at least one compound of a transition metal , at least one water-soluble phosphine of the formula (1) or (11) and a cocatalyst consisting of at least one Lewis acid.

10. The process according to claim 9, characterized in that the ethylenically unsaturated compounds are selected from ethylenically unsaturated aliphatic nitriles, preferably linear pentylenitrile such as pentene-3 nitrile, pentene-4 nitrile and mixtures thereof.

11. The process according to claim 10, characterized in that the linear pentane-3-nitrobents contain amounts, usually minorities, of other compounds, such as methyl-2-butene-3-nitrile, methyl-2-butene-2-nitrile, pentene-2. nitrile, valeroni tri lo, adiponitrile, methyl-2 glu taroni tyl, ethyl-2 succ inoni t or butadiene.

12. The process according to one of claims 9 to 11, characterized in that the Lewis acid applied as co-catalyst is selected from the compounds of the elements of groups Ib, llb, Illa, IIIb, IVa, lVb, Va, Vb, Vlb , Vllb and HIV of the periodic classification of the elements, insofar as such compounds are at least partially soluble and stable in water.

13. The process according to one of claims 9 to 12, characterized in that the Lewis acid is selected from the salts, ie halides, sulfates, carboxylates and phosphates.

14. The process according to one of claims 9 to 13, characterized in that the Lewis acid is selected from zinc chloride, zinc bromide, zinc iodide, manganese chloride, manganese bromide, cadmium chloride, cadmium bromide, chloride stalwart, »Stannous bromide, stannous sulfate, tartrate stannous, chlorides or bromides of rare earth elements such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium , cobalt chloride, ferrous chloride, yttrium chloride and their mixtures.

15. The process according to one of the re-divisions 9 to 14, characterized in that the applied Lewis acid represents from 0.01 to 50 moles per mole of transition metal compound, more specifically of the nickel compound, and preferably from 1 to 10 mol per mol.

16. The process according to one of claims 1 to 15, characterized in that it is carried out in the absence of hydrogen cyanide, the isomerization in pentylne nor tri-s of the methyl-2-butene-3 nitrile present in the reaction mixture coming from the hydrocyanuration of the butadiene, when carried out in the presence of a catalyst consisting of at least one water-soluble phosphine of the formula (1) or (11) and at least one compound of a transition metal.

% 17. The procedure according to the claim 16, characterized in that the methyl-2-butene-3-nitrile subjected to the isomerization is applied alone or in combination with methyl-2-butene-2-nitrile, pentene-4-nitrile, pentene-3-nitrile, pentene-2-nitrile, butadiene, adiponitrile , methyl-2 glu t aroni tri lo, ethyl-2 succinoni tri lo or valeronitrile.

18. The process according to one of claims 16 or 17, characterized in that the isomerization reaction is carried out at a temperature of 10 ° C to 200 ° C and preferably of 60 ° C to 120 ° C.

19. The process according to one of claims 16 to 18, characterized in that the isomerization in pentene -not tri-those of methyl-2-butene-3-nitrile is carried out in the presence of an aqueous solution of a catalyst consisting of at least one compound of a metal of transition, at least one water-soluble phosphine of formula (1) or (11) and a co-catalyst consisting of at least one Lewis acid.