WO2004007508A2

WO2004007508A2 - Nitrile production from ethylenically unsaturated compounds

Info

Publication number: WO2004007508A2
Application number: PCT/FR2003/002193
Authority: WO
Inventors: Jean-Christophe Galland; Blaise Didillon; Philippe Marion; Damien Bourgeois
Original assignee: Rhodia Polyamide Intermediates
Priority date: 2002-07-15
Filing date: 2003-07-11
Publication date: 2004-01-22
Also published as: FR2842195A1; FR2842195B1; AU2003273435A8; WO2004007508A3; AU2003273435A1

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.

Description

PROCESS FOR THE MANUFACTURE OF NITRILE COMPOUNDS FROM COMPOUNDS A

ETHYLENIC UNSATURATION

The present invention relates to a process for hydrocyanation of organic compounds containing ethylenic unsaturation into compounds comprising at least one nitrile function.

It relates more particularly to the hydrocyanation of diolefins such as butadiene or of substituted olefins such as alkenes nitrites such as pentenenitriles. The hydrocyanation of butadiene into pentenenitriles is an important reaction which has been implemented industrially for many years, in particular in the process for the synthesis of adiponitrile, a large chemical intermediate allowing in particular access to the monomers of many polymers, including mainly polyamides.

French Patent No. 1,599,761 describes a process for preparing nitriles by adding 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 carried out in the presence or not of a solvent.

When a solvent is used in this process of the prior art, it is preferably a hydrocarbon, such as benzene or xylenes or a nitrile such as acetonitrile.

The catalyst used is an organometallic nickel complex, containing ligands such as phosphines, arsines, stibines, antimonites, arsenites, phosphites, phosphinites or phosphonites.

The processes for hydrocyanating dienes generally comprise two stages: a first hydrocyanation leading to branched and linear unsaturated mononitriles and a second stage making it possible to obtain the dinitriles. Often only linear nitriles are of interest for the synthesis of new products such as adiponitrile for example. These methods therefore also include an intermediate step called isomerization step, consisting in treating the branched unsaturated mononitriles to transform them into linear unsaturated mononitriles.

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 out the second step. Patent FR-A-2 338 253 has proposed carrying out the hydrocyanation of compounds having at least one ethylenic unsaturation, in the presence of an aqueous solution of a compound of a transition metal, in particular nickel, palladium or iron, and a sulfonated phosphine.

The sulfonated phosphines described in this patent are sulfonated triarylphosphines and more particularly sulfonated triphenylphosphines. This process allows a correct hydrocyanation, in particular of butadiene and pentenenitriles, an easy separation of the catalytic solution by simple decantation and by Consequently, as much as possible avoids the discharge of effluents or waste containing the metals used as catalyst.

However, research is being carried out to find new catalytic systems which are more efficient both in catalytic activity and in selectivity and stability.

One of the aims of the present invention is to propose a new family of ligands which makes it possible to obtain, with the transition metals, catalytic systems having in particular an improved selectivity in linear nitriles compared to known systems.

To this end, the present invention provides a process for hydrocyanation of a hydrocarbon compound comprising at least one ethylenic unsaturation by reaction in a liquid medium with hydrogen cyanide in the presence of a catalyst comprising a metallic element chosen from the metals of transition and an organic ligand characterized in that the organic ligand corresponds to the following general formula I:

In which :

T, T-i, identical or different, represent a phosphorus, arsenic or antimony atom

Ri, R ₂ . _{3> 4} identical or different represent a carbonyl group or a substituted or unsubstituted aryl or cycloaliphatic group which may comprise heteroatoms and / or one or more rings in condensed form or not;

U ₁ , U ₂ , U ₃ , U _4, identical or different, represent an oxygen atom or a radical of formula NR in which R denotes a monovalent alkyl, aryl, cycloalkyl, sulfonyl or carbonyl radical, n is an integer equal to 0 or 1;

L |, L ₃ when n is equal to 0, represents a divalent radical chosen from the group comprising the groups NR ₇ , PR ₈ , SiR ₉ R ₁₀ , BRu, S, PORι ₂ , SO, CO in which R ₇ has the meaning of R indicated above, R ₈ and R-ι ₂ may represent the radical OR _13; and R _{8 |} R ₉ , Rι ₀ , Rn R-ι ₂ and R ₁₃ represent alkyl, aryl or cycloalkyl radicals; Li, L ₂ , L ₃ , L ₄ when n is equal to 1, identical or different represent a covalent bond, a radical chosen from the group comprising the groups O, NR ₇ , PR ₈ , SiR ₉ R ₁₀ , BRn, S , POR ₁₂ , SO ₂ , CO, -CR ₁₄ Rι ₅ -, in which R ₇ has the meaning of R indicated above, R ₈ and R ₁₂ may represent the radical OR ₁₃ , and R ₈ , Rg, R ₁₀ , u R- ₁₂ , Ri3 _> ι ₄ and R ₁₅ represent alkyl or aryl, cycloalkyl, R and R ₁₅ radicals which can also represent the hydrogen atom.

Q represents a substituted or unsubstituted aromatic or cycloaliphatic radical comprising one or more rings in condensed form or not and which can comprise heteroatoms, or a radical of general formula II below:

in which: R _17l R ₁₈ , L ₅ , L ₆ and m have the meanings respectively of Ri, R ₂ , L- ,, L ₂ and n above.

As an example of structures

We can cite the following formulas listed in Table I below

In which R ₁₉ represents an alkyl, aryl, halogen, aikoxy, thiol, cyano, nitro, aryloxy, alkoxycarbonyl, acyl, formyl radical.

Similarly, the radical Q when it corresponds to the general formula:

advantageously corresponds to the structures listed in table I above.

Mention may be made, as ligands in accordance with the invention, of the following compounds, the formulas of which are listed in Table II below: Table II

According to the invention, the catalyst advantageously corresponds to the general formula (II):

M [L _f ] _t (II)

Where: M is a transition metal

L _f represents the organic ligand of formula (I) t represents a number between 1 and 4 (limits included)

The metals which can be complexed with the organic ligands of the invention are generally all the transition metals of groups 1b, 2b, 3b, 4b, 5b, 6b, 7b and 8 of the periodic table of the elements, as published in "Handbook of Chemistry and

Physics, 51 st Edition (1970-1971) "from The Chemical Rubber Company.

Among these metals, there may be mentioned more particularly the metals that may be mentioned by way of nonlimiting examples, nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum , copper, silver, gold, zinc, cadmium, mercury. The preparation of organometallic complexes comprising the organic ligands of the invention can be carried out by bringing a solution of a compound of the chosen metal into contact with a solution of the organic ligand of the invention.

The metal compound can be dissolved in a solvent.

The metal can be found in the compound used, either at the degree of oxidation that it will have in the organometallic complex, or at a higher degree of oxidation.

By way of example, it can be indicated that in the organometallic complexes of the invention, rhodium is at the degree of oxidation (I), ruthenium at the degree of oxidation (II), platinum at the degree of oxidation (0), palladium to the degree of oxidation (0), osmium to the degree of oxidation (II), iridium to the degree of oxidation (I), cobalt to the degree of oxidation (I), nickel to the degree of oxidation (0).

If, during the preparation of the organometallic complex, the metal is used at a higher degree of oxidation, it can be reduced in situ. The organometallic complexes comprising the organic ligands of the invention can be used as catalysts in the hydrocyanation reactions of olefins.

As transition metal, the compounds of the transition metals, more particularly the compounds of nickel, palladium, cobalt, iron or copper are preferably used. Among the aforementioned compounds, the most preferred compounds are those of nickel. As non-limiting examples, we can cite:

- compounds in which nickel is at zero oxidation state such as potassium tetracyanonickelate 4 [Ni (CN) 4], bis (acrylonitrile) zero nickel, bis

(cyclooctadiene-1,5) zero nickel (also called Ni (cod) ₂ ) and derivatives containing ligands such as tetrakis (triphenylphosphine) zero nickel. - nickel compounds such as carboxylates (especially acetate), carbonate, bicarbonate, borate, bromide, chloride, citrate, thiocyanate, cyanide, formate, hydroxide, hydrophosphite, phosphite, phosphate and derivatives, iodide, nitrate, sulfate, sulfite , aryl- and alkylsulfonates.

When the nickel compound used corresponds to an oxidation state of nickel greater than 0, a reducing agent for nickel reacting preferentially with the latter under the reaction conditions is added to the reaction medium. This reducing agent can be organic or mineral. As nonlimiting examples, borohydrides such as BH- ^ Na, BH4K, Zn powder, magnesium or hydrogen may be cited.

When the nickel compound used corresponds to the oxidation state of nickel, it is also possible to add a reducing agent of the type of those mentioned above, but this addition is not imperative.

When using an iron compound, the same reducers are suitable.

In the case of palladium, the reducing agents can also be elements of the reaction medium (phosphine, solvent, olefin).

The organic compounds comprising at least one ethylenic double bond more particularly used in the present process are the diolefins such as butadiene, isoprene, hexadiene-1, 5, cyclooctadiene-, 5, aliphatic nitriles with ethylenic unsaturation , particularly linear pentenenitriles such as pentene-3-nitrile, pentene-4-nitrile, monoolefins such as styrene, methylstyrene, vinylnaphthalene, cyclohexene, methylcyclohexene as well as mixtures of several of these compounds. Pentenenitriles in particular may contain amounts, generally in the minority, of other compounds, such as methyl-2-butene-3-nitrile, methyl-2-butene-2-nitrile, pentene-2-nitrile, valeronitrile, l adiponitrile, methyl-2-glutaronitrile, ethyl-2-succinonitrile or butadiene, originating for example from the previous hydrocyanation reaction of butadiene to unsaturated nitriles.

In fact, during the hydrocyanation of butadiene, non-negligible amounts of methyl-2-butene-3-nitrile and of methyl-2-butene-2-nitrile are formed with the linear pentenenitriles.

The catalytic system used for hydrocyanation according to the process of the invention can be prepared before its introduction into the reaction zone, for example by adding to the ligand according to the invention alone or dissolved in a solvent, the appropriate amount of compound of the transition metal chosen and optionally of the reducing agent. It is also possible to prepare the catalytic system "in situ" by simple addition of the ligand and of the transition metal compound in the hydrocyanation reaction medium before or after the addition of the compound to be hydrocyanated.

The amount of nickel compound or of another transition metal used is chosen to obtain a concentration in mole of transition metal per mole of organic compounds to be hydrocyanated or isomerized between 10 "4 and 1, and preferably between 0.005 and 0.5 mole of nickel or of the other transition metal used.

The amount of organic ligands of the invention used to form the catalyst is chosen such that the number of moles of this compound, based on 1 mole of transition metal, is from 0.5 to 50 and preferably from 1 to 10.

Although the reaction is generally carried out without solvent, it may be advantageous to add an inert organic solvent. The solvent can be a catalyst solvent which is miscible in the phase comprising the compound to be hydrocyanated at the hydrocyanation temperature. Examples of such solvents that may be mentioned are aromatic, aliphatic or cycloaliphatic hydrocarbons.

This solvent can also be partially miscible with the compounds to be hydrocyanated, in particular when the reaction medium is at a temperature below the reaction temperature. Thus, it is possible, at such temperatures, to obtain a two-phase system. In the case where the catalytic system is soluble in said solvent, its extraction from the reaction medium is facilitated. Such partially miscible or immiscible solvents can be water or molten organic salts of an ionic nature. Such solvents are used in particular when the organic ligand comprises anionic radicals making it soluble in ionic media. These radicals are, for example, sulfonate, carbonate, carboxylate, phosphate, ammonium, guanidinium, imidazolium groups, substituting the aromatic radicals of the ligand. The hydrocyanation reaction is generally carried out at a temperature of 10 ° C to 200 ^C C and preferably from 30 ° C to 120 ° C. It is advantageously carried out in a single-phase medium, at the reaction temperature.

The method of the invention can be implemented continuously or discontinuously. The hydrogen cyanide used can be prepared from metallic cyanides, in particular sodium cyanide, or cyanhydrins, such as acetone cyanohydrin or by any other known synthesis process.

The hydrogen cyanide is introduced into the reactor in gaseous, gas mixture or liquid form. It can also be previously dissolved in an organic solvent. In the context of a discontinuous implementation, it is in practice possible to charge into a reactor, previously purged using an inert gas (such as nitrogen, argon), either a solution containing all or part of the various constituents such as the organic ligand of the invention, the transition metal compound, any reducing agents and solvents, or separately said constituents. Generally the reactor is then brought to the chosen temperature, then the compound to be hydrocyanated is introduced. The hydrogen cyanide is then itself introduced, preferably continuously and regularly.

When the reaction (the progress of which can be followed by dosing of samples) is complete, the reaction mixture is withdrawn after cooling and the products of the reaction are isolated, for example, by distillation. An improvement to the process for hydrocyanation of ethylenically unsaturated compounds according to the present invention relates in particular to the hydrocyanation of said ethylenically unsaturated nitrile compounds, by reaction with hydrogen cyanide and consists in using a catalytic system in accordance with the present invention with a cocatalyst consisting of at least one Lewis acid. The ethylenically unsaturated compounds which can be used in this improvement are generally those which have been mentioned for the basic process. However, it is more particularly advantageous to apply it to the hydrocyanation reaction in dinitriles of aliphatic mononitriles with ethylenic unsaturation, in particular to linear pentenenitriles such as pentene-3-nitrile, pentene-4-nitrile and their mixtures. These pentenenitriles may contain quantities, generally in the minority, of other compounds, such as methyl-2-butene-3-nitrile, methyl-2-butene-2-nitrile, pentene-2-nitrile, valeronitrile, adiponitrile, methyl-2-glutaronitrile, ethyl-2-succinonitrile or butadiene, originating from the previous hydrocyanation reaction of butadiene and / or from the isomerization of methyl-2-butene-3-nitrile into pentenenitriles. The Lewis acid used as cocatalyst allows in particular, in the case of the hydrocyanation of aliphatic nitriles containing ethylenic unsaturation, to improve the linearity of the dinitriles obtained, that is to say the percentage of linear dinitriles relative to all of the dinitriles formed, and / or to increase the activity and the lifetime of the catalyst.

By Lewis acid is meant in the present text, according to the usual definition, compounds that accept electronic doublets. It is possible to use in particular the Lewis acids cited in the work edited by G.A.

OLAH "Friedel-Crafts and related Reactions", volume I, pages 191 to 197 (1963).

The Lewis acids which can be used as cocatalysts in the present process are chosen from the compounds of the elements of groups Ib, llb, llla, lllb, IVa, IVb, Va, Vb, Vlb, Vllb and VIII of the periodic table elements. These compounds are most often salts, in particular halides, such as chlorides or bromides, sulfates, sulfonates, haloalkylsulfonates, perhaloalkylsulfonates, in particular fluoroalkylsulfonates or perfluoroalkylsulfonates.

By way of nonlimiting examples of such Lewis acids, mention may be made of zinc chloride, zinc bromide, zinc iodide, manganese chloride, manganese bromide, cadmium chloride, bromide cadmium, stannous chloride, stannous bromide, stannous sulfate, stannous tartrate, indium trifluoromethylsulfonate, indium trifluoroacetate, zinc trifluoroacetate, chlorides or bromides of rare earth elements such as lanthanum, cerium , praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, hafnium, erbium, thallium, ytterbium and lutetium, cobalt chloride, ferrous chloride, yttrium chloride.

Organometallic compounds such as triphenylborane or titanium isopropylate can also be used as the Lewis acid. It is of course possible to use mixtures of several Lewis acids. Among the Lewis acids, zinc chloride, zinc bromide, stannous chloride, stannous bromide, triphenylborane and zinc chloride / stannous chloride mixtures, indium trifluoromethylsulfonate and indium trifluoroacetate are particularly preferred. , zinc trifluoroacetate.

The Lewis acid cocatalyst used generally represents from 0.01 to 50 moles per mole of transition metal compound, more particularly of nickel compound, and preferably from 0.5 to 10 moles per mole.

As for the implementation of the basic process of the invention, the catalytic solution used for hydrocyanation in the presence of Lewis acid can be prepared before its introduction into the reaction zone, for example by adding to the reaction medium the ligand of formula (I), of the appropriate amount of chosen transition metal compound, of Lewis acid and possibly the reducer. It is also possible to prepare the catalytic solution "in situ" by simple mixing of these various constituents.

It is also possible under the conditions of the hydrocyanation process of the present invention, and in particular by operating in the presence of the catalyst described above comprising at least one ligand of formula (I) and at least one compound of a transition metal, of perform, in the absence of hydrogen cyanide, the isomerization of methyl-2-butene-3-nitrile into pentenenitriles, and more generally of unsaturated nitriles branched into linear unsaturated nitriles.

The methyl-2-butene-3-nitrile subjected to the isomerization according to the invention can be used alone or as a mixture with other compounds. So we can use methyl-2-butene-3-nitrile in admixture with methyl-2-butene-2 nitrile, pentene-4-nitrile, pentene-3-nitrile, pentene-2-nitrile, butadiene , adiponitrile, methyl-2-glutaronitrile, ethyl-2-succinonitrile or valeronitrile. it is particularly advantageous to treat the reaction mixture originating from the hydrocyanation of butadiene with HCN in the presence of at least one ligand of formula (I) and at least one compound of a transition metal, more preferably a composed of nickel with an oxidation state of 0, as defined above.

In the context of this preferred variant, the catalytic system already being present for the hydrocyanation reaction of butadiene, it suffices to stop any introduction of hydrogen cyanide, to allow the isomerization reaction to take place. One can, if necessary, in this variant make a light sweeping of the reactor using an inert gas such as nitrogen or argon for example, in order to remove the hydrocyanic acid which could still be present.

The isomerization reaction is generally carried out at a temperature of 10 ° C to 200 ° C and preferably from 60 ° C to 160 ° C. In the preferred case of isomerization immediately following the hydrocyanation reaction of butadiene, it will be advantageous to operate at the temperature at which the hydrocyanation has been carried out.

As for the hydrocyanation process for ethylenically unsaturated compounds, the catalytic system used for isomerization can be prepared before its introduction into the reaction zone, for example by adding the ligand of formula (I), the appropriate amount of compound of the transition metal chosen and optionally the reducing agent. It is also possible to prepare the catalytic system "in situ" by simple addition of these various constituents in the reaction medium. The amount of transition metal compound and more particularly of nickel used, as well as the amount of ligand of formula (I) are the same as for the hydrocyanation reaction. Although the isomerization reaction is generally carried out without solvent, it may be advantageous to add an inert organic solvent which may be that of the subsequent extraction. This is particularly the case when such a solvent has been used in the hydrocyanation reaction of the butadiene which served to prepare the medium subjected to the isomerization reaction. Such solvents can be chosen from those which have been mentioned above for hydrocyanation.

The preparation of dinitrile compounds by hydrocyanation of an olefin such as butadiene can be carried out using a catalytic system in accordance with the invention for the stages of formation of the unsaturated mononitriles and the stage of isomerization above, the reaction of hydrocyanation of mononitriles unsaturated with dinitriles which can be used with a catalytic system according to the invention or any other catalytic system already known for this reaction.

Likewise, the hydrocyanation reaction of the olefin into unsaturated mononitriles and the isomerization of these can be carried out with a catalytic system different from that of the invention, the step of hydrocyanation of the mononitriles unsaturated into dinitriles being implemented with a catalytic system according to the invention.

The subject of the invention is also organophosphorus compounds corresponding to the following general formula I:

In which :

T, Ti identical or different represent an atom of phosphorus, arsenic or antimony

Ri. R ₂ . R _3> P, which may be identical or different, represent a carbonyl group or a substituted or unsubstituted aryl or cycloaliphatic group which may comprise heteroatoms and / or one or more rings in condensed form or not;

Ui, U ₂ , U ₃ , U _4, identical or different, represent an oxygen atom or a radical of formula NR in which R denotes a monovalent alkyl, aryl, cycloalkyl, sulfonyl or carbonyl radical, n is an integer equal to 0 or 1; Li, L ₃ when n is equal to 0, represents a divalent radical chosen from the group comprising the groups NR ₇ , PR ₈ , SiR ₉ R ₀ , BR ^, S, POR ₁₂ , S0 ₂ , CO in which R ₇ has the meaning of R indicated above, R _{8 and} R ₁₂ may represent the radical OR _13; and R ₈ , Rg, R-10, Ru R ₁₂ and Ri ₃ represent alkyl, aryl or cycloalkyl radicals;

Li, L ₂ , L ₃ , L ₄ when n is equal to 1, identical or different represent a covalent bond, a radical chosen from the group comprising the groups O, NR ₇ , PR ₈ , SiR ₉ R ₁₀ , BR-n , S, POR ₁₂ , S0 ₂ , CO, -CRι ₄ Rι ₅ -, in which R ₇ has the meaning of R indicated above, R _{8 and} R ₁₂ may represent the radical OR ₁₃ , and R ₈ , R ₉ , R ₁₀ , Ru R ₁₂ , R ₁₃ , R and R ₁₅ represent alkyl or aryl, cycloalkyl, R ₁₄ and R ₁₅ radicals which may also represent the hydrogen atom. Q represents a substituted or unsubstituted aromatic or cycloaliphatic radical comprising one or more rings in condensed form or not and which can comprise heteroatoms, or a radical of general formula II below:

in which: Rι ₇ , Rι ₈ , L5, L6 and m have the meanings respectively of R _{1 f} R ₂ , Li, L ₂ and n above. A subject of the invention is also the compounds whose formulas are listed in Table II above.

These compounds are obtained in particular by mixing a solution in toluene of a diphenol compound corresponding to the structure of the following formula:

HO OH

\ /

Q With a toluene solution of a chlorophosphite of the following formula:

In the formulas above the symbols have the same meanings as in formula 1.

The mixture is kept stirring for several hours (of the order of 8 to 15 hours) at room temperature (between 15 ° C and 30 ° C). The organophosphorus compound is recovered for example by filtration of the mixture.

This preparation procedure is given solely by way of example and indicative. Other manufacturing methods can be used without departing from the scope of the invention.

Furthermore, the phenols and chlorophosphites are generally commercially available or can be synthesized by the conventional and described methods for obtaining these compounds.

The following examples illustrate the invention. In the examples, the abbreviations used have the meanings indicated below, cod:, 5-cyclooctadiene. eq: equivalent. 3PN: 3-pentenenitrile. 4PN: 4-pentenenitrile. 3 + 4PN: 3PN + 4PN.

TT (Y): transformation rate of the product to be hydrocyanated Y corresponding to the ratio of the number of transformed moles of Y to the number of initial moles of Y. Linearity (L): ratio of the number of moles of adiponitrile (AdN) formed at number of moles of dinitriles formed (sum of moles of AdN, ethylsuccinonitrile (ESN) and methylglutaronitrile (MGN)).

GPC: gas chromatography, ml: milliliter. mol: mole. mmol: millimole.

EXAMPLE 1 Preparation of the Liαand A of Following Structure

A solution of 2,2'-thiobis (4-tert-octylphenol) (100 mmol) and hexamethylphosphoramide (P (NMe ₂ ) ₃ ) (100 mmol) in toluene is brought to reflux for 5 h. The mixture is then concentrated under reduced pressure and the phosphoramidite with the following structure is obtained:

This intermediate is used for the preparation of ligand A according to the following procedure:

Under argon, 6 mmol of phosphoramidite in 20 ml of anhydrous toluene are introduced into a 100 ml reactor. The solution is stirred at 0 ° C., and 7.5 ml of a 2M solution of hydrochloric acid in ether is added thereto over 30 min. The formation of a white precipitate is observed, and the mixture is stirred for 1 h at room temperature. A solution of 3 mmol of bis (2-hydroxyphenyl) methane and 10 mmol of triethylamine in 20 ml of anhydrous toluene is then introduced dropwise into the reaction medium cooled to -10 ° C. The suspension is kept under vigorous stirring for 18 h at 25 ° C., then filtered under argon on a bed of basic alumina. After rinsing with toluene, the filtrate is concentrated under reduced pressure to yield the desired product, used without further purification.

Example 2: Hydrocyanation of 3-pentenenitrile (3PN) to adiponitrile (AdN). Under an argon atmosphere, in a 60 ml Shott type glass tube fitted with a septum cap, are successively charged - ligand A (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

- 141 mg (0.5 mmol; 1 eq) of lutetium chloride (III). The mixture is brought, with stirring, to 70 ° C. The acetone cyanohydrin is injected into the reaction medium by a syringe pump at a flow rate of 0.45 ml per hour. After 3 hours of injection, the syringe pump is stopped. The mixture is cooled to room temperature, diluted with acetone and analyzed by gas chromatography.

The following results are obtained: TT (3PN) = 12%, L = 79%

Claims

. Process for hydrocyanating a hydrocarbon compound comprising at least one ethylenic unsaturation by reaction in a liquid medium with hydrogen cyanide in the presence of a catalyst comprising a metallic element chosen from transition metals and an organic ligand characterized in that the organic ligand corresponds to the following general formula I:

In which :

T, Ti identical or different represent a phosphorus, arsenic or antimony atom Ri, R ₂ , R ₃ , R ₄ identical or different represent a carbonyl group or a substituted or unsubstituted aryl or cycloaliphatic group which may include heteroatoms and / or one or more cycles in condensed form or not;

Ui, U ₂ , U ₃ , U _4, identical or different, represent an oxygen atom or a radical of formula NR in which R denotes a monovalent alkyl, aryl, cycloalkyl, sulfonyl or carbonyl radical, n is an integer equal to 0 or 1;

L |, L ₃ when n is equal to 0, represents a divalent radical chosen from the group comprising the groups NR ₇ , PR ₈ , SiR ₉ R _10l BRn, S, PORι ₂ , S0 ₂ , CO in which R ₇ has the meaning of R indicated above, R _{8 and} Rι ₂ may represent the radical OR _13; and Rβ. Rg, R ₁₀ , Rn R ₁₂ and R-ι ₃ represent alkyl, aryl or cycloalkyl radicals;

Li, L ₂ , L ₃ , L when n is equal to 1, identical or different represent a covalent bond, a radical chosen from the group comprising the groups O, NR ₇ , PR ₈ , SiR ₉ R ₁₀ , BR ₁₁ , S , PORι ₂ , S0 ₂ , CO, -CR ₁ R ₁₅ -, in which R ₇ has the meaning of R indicated above, R _{8 and} Ri2 can represent the radical OR13, and R ₈ , R _g , R ₁₀ , Rn Rι ₂ , R13, R14 and R ₁₅ represent alkyl or aryl, cycloalkyl, R ₁ and R ₁₅ radicals which can also represent the hydrogen atom. Q represents a substituted or unsubstituted aromatic or cycloaliphatic radical comprising one or more rings in condensed form or not and which can comprise heteroatoms, or a radical of general formula II below:

in which: Ru, Ris, L ₅ , L ₆ and m have the meanings of R ₁ respectively _; R ₂ , Li, L ₂ and n above.

2. Method according to claim 1, characterized in that the organic ligand of general formula I comprises a structure:

chosen from the group comprising the following structures:

In which R19 represent an alkyl, aryl, halogen, aikoxy, thiol, cyano, nitro, aryloxy, aikoxycarbonyl, acyl, formyl radical.

3. Method according to claim 1 or 2, characterized in that the organic ligand of formula comprises a structure:

Chosen from the group including

. Process according to claim 1 or 2, characterized in that the organic ligand of formula is chosen from the group comprising:

5. Method according to one of claims 1 to 3 characterized in that the metallic element is chosen from the group comprising nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium, mercury.

6. Method according to one of the preceding claims, characterized in that the reaction is carried out in a single-phase medium.

7. Method according to one of the preceding claims, characterized in that the catalyst corresponds to the general formula (II):

M [1 (II)

In which: M is a transition metal. L _f represents the organic ligand of formula (I) t represents a number between 1 and 4 (limits included)

8. Method according to one of the preceding claims, characterized in that the reaction medium comprises a solvent for the catalyst miscible in the phase comprising the compound to be hydrocyanated at the hydrocyanation temperature.

9. Method according to one of the preceding claims, characterized in that the transition metal compounds are those of nickel and are chosen from the group comprising: compounds in which nickel is at zero oxidation state such as tetracyanonickelate potassium K4 [(Ni (CN) 4J, bis (acrylonitrile) zero nickel, bis (1,5-cyclooctadiene) zero nickel and derivatives containing ligands such as tetrakis (triphenylphosphine) zero nickel; nickel compounds such as carboxylates, carbonate, bicarbonate, borate, bromide, chloride, citrate, thiocyanate, cyanide, formate, hydroxide, hydrophosphite, phosphite, phosphate and derivatives, iodide, nitrate, sulfate, sulfite, aryl and alkyl sulfonates .

10. Method according to one of the preceding claims, characterized in that the organic compounds comprising at least one ethylene double bond are chosen from diolefins such as butadiene, isoprene, hexadiene-1, 5, cyclooctadiene-1 , 5, ethylenically unsaturated aliphatic nitriles, particularly linear pentenenitriles such as pentene-3-nitrile, pentene-4-nitrile, monoolefins such as styrene, methylstyrene, vinylnaphthalene, cyclohexene, methylcyclohexene as well as mixtures of several of these compounds.

11. Method according to one of the preceding claims, characterized in that the quantity of nickel compound or of another transition metal used is chosen so that there is per mole of organic compound to be hydrocyanated or isomerized between 10 ^{~ 4} and 1 mole of nickel or of the other transition metal used and in that the amount of organic ligand of formula (I) used is chosen so that the number of moles of this compound relative to 1 mole of transition metal is 0.5 to 50.

12. Method according to one of the preceding claims, characterized in that the hydrocyanation reaction is carried out at a temperature of 10 ° C to 200 ° C.

13. Method according to one of the preceding claims for hydrocyanation into dinitriles of ethylenically unsaturated nitrile compounds, by reaction with hydrogen cyanide, characterized in that one operates in the presence of a catalytic system comprising at least one composed of a transition metal, at least one organic compound of formula (I) and a cocatalyst consisting of at least one Lewis acid.

14. The method of claim 13, characterized in that the ethylenically unsaturated nitrile compounds are chosen from aliphatic ethylenically unsaturated nitriles comprising linear pentenenitriles such as pentene-3-nitrile, pentene-4-nitrile and their mixtures.

15. The method of claim 14, characterized in that the linear pentenenitriles contain amounts of other compounds selected from the group comprising methyl-2-butene-3-nitrile, methyl-2-butene-2-nitrile, pentene-2-nitrile, valeronitrile, adiponitrile, methyl-2-glutaronitrile, ethyl-2-succinonitrile or butadiene.

16. Method according to one of claims 13 to 15, characterized in that the Lewis acid used as cocatalyst is chosen from the compounds of the elements of groups Ib, llb, llla, lllb, IVa, IVb, Va, Vb, Vlb, Vllb and VIII of the Periodic Table of the Elements.

17. Method according to one of claims 13 to 16, characterized in that the Lewis acid is chosen from the salts chosen from the group of halides, sulfates, sulfonates, halogenoalkylsulfonates, perhaloalkylsulfonates, haloalkylacetates, perhalogenoalkylacetates, carboxylates and phosphates.

18. Method according to one of claims 13 to 17, characterized in that the Lewis acid is chosen from zinc chloride, zinc bromide, zinc iodide, manganese chloride, manganese bromide , cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulfate, stannous tartrate, indium trifluoromethylsulfonate, indium trifluoroacetate, zinc trifluoroacetate, chlorides or bromides of the elements rare earths such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, hafnium, Terbium, thallium, ytterbium and lutetium, chloride cobalt, ferrous chloride, yttrium chloride and mixtures thereof.

19. Method according to one of claims 13 to 18, characterized in that the Lewis acid used represents from 0.01 to 50 moles per mole of transition metal compound.

20. Method according to one of claims 1 to 17, characterized in that is carried out in the absence of hydrogen cyanide isomerization into pentenenitriles, methyl-2-butene-3-nitrile present in the reaction mixture originating hydrocyanation of butadiene, operating in the presence of a catalyst comprising at least one organic ligand of general formula (I) and at least one compound of a transition metal.

21. The method of claim 20, characterized in that the methyl-2-butene-3-nitrile subjected to isomerization is used alone or in admixture with methyl-2-butene-2-nitrile, pentene- 4-nitrile, pentene-3-nitrile, pentene-2-nitrile, butadiene, adiponitrile, methyl-2-glutaroronithle, ethyl-2-succinonitrile or valeronitrile.

22. Method according to one of claims 20 or 21, characterized in that the isomerization reaction is carried out at a temperature of 10 ° C to 200 ° C.

23. Method according to one of claims 20 to 22, characterized in that the isomerization into pentenenitriles of methyl-2-butene-3-nitrile is carried out in the presence of at least one compound of a transition metal, d 'at least one organic phosphorus ligand of formula (I) and a cocatalyst consisting of at least one Lewis acid.

24. Organophosphorus compounds corresponding to the following general formula (!):

In which: T, Ti identical or different represent a phosphorus, arsenic or antimony atom

Ri, R _{2 l 3} , ₄ identical or different represent a carbonyl group or a substituted or unsubstituted aryl or cycloaliphatic group which may include heteroatoms and / or one or more rings in condensed form or not; U _h U ₂ , U ₃ , U _4, identical or different, represent an oxygen atom or a radical of formula NR in which R denotes a monovalent alkyl, aryl, cycloalkyl, sulfonyl or carbonyl radical, n is an integer equal to 0 or 1;

Li, L ₃ when n is equal to 0, represents a divalent radical chosen from the group comprising the groups NR ₇ , PR ₈ , SiRg Rio, BR _11t S, POR-ι ₂ , S0 ₂ , CO in which R ₇ has the meaning of R indicated above, R ₈ and R ₂ may represent the radical OR _13; and R ₈ , Rg, Rio, Ru Rι ₂ and R ₁ 3 represent alkyl, aryl or cycloalkyl radicals; L, L ₃ , L when n is equal to 1, identical or different represent a covalent bond, a radical chosen from the group comprising the groups O, NR ₇ , PR _B , SiR ₉ R- | ₀ , BRn, S, PORι ₂ , S0 ₂ , CO, -CR ₁₄ R ₁₅ -, in which R ₇ has the meaning of R indicated above above, R _{8 and} R ₁₂ may represent the radical 0R ₁₃ , and R ₈ , R ₉ , Rio, Rn R ₁₂ , R ₁ 3, ι and R _1g represent alkyl or aryl, cycloalkyl, R ₁₄ and R ₁₅ radicals which may also represent the hydrogen atom. Q represents a substituted or unsubstituted aromatic or cycloaliphatic radical comprising one or more rings in condensed form or not and which can comprise heteroatoms, or a radical of general formula II below:

in which: R ₁₇ , R ₁₈ , L ₅ , L ₆ and m have the meanings respectively of Ri, R ₂ , L ₁ , L ₂ and n above.

25. Compounds corresponding to the following formulas: