RU2000106067A - METHOD FOR PRODUCING MIXTURES OF MONOOLEPHIN MONONITRILES WITH FIVE FUNCTIONS OF CARBON CARBON BY CATALYTIC HYDROCYANATION IN THE PRESENCE OF A CATALYST CONTAINING AT LEAST ONE FINE AND SMALL FILTER) - Google Patents

Claims (19)

1. A method of obtaining mixtures of monoolefin mononitriles with 5 carbon atoms, including non-conjugated double carbon-carbon and triple carbon-nitrogen bonds, by catalytic hydrocyanation of 1,3-butadiene or a mixture of 1,3-butadiene hydrocarbons, characterized in that the hydrocyanation is carried out a the presence of a catalyst containing at least one metallocene complex with trivalent phosphorus and zero valence nickel, including at least one monodentate or bidentate metallocene Andes with trivalent phosphorus of general formula (I)

where R ¹ means the remainder of the formula PL ₂ , and the residues L may be the same or different and mean alkyl, cycloalkyl or aryl;
R ^{1 ′} represents a hydrogen atom, an alkyl or a residue of the formula PL ₂ , wherein the residues L have the above meaning;
R ² , R ^{2 ′} , R ³ , R ^{3 ′} , R ⁴ , R ^{4 ′} , R ⁵ , R ^{5 ′} , independently of one another, are selected from the group consisting of a hydrogen atom, cycloalkyl, aryl or alkyl, which may be interrupted by an oxygen atom or may be substituted by a residue of the formula NE ¹ E ² , wherein E ¹ and E ² may be the same or different and mean alkyl, cycloalkyl or aryl, or, as the case may be, two of the substituents R ² , R ³ , R ^4, R ^5, and ^', R ^5' in adjacent positions / or R ^{2 ',} R ^3', R ⁴ together with their binding part tsiklodentadienilnogo ring may form an aromatic or nonaromatic of toe - to seven-membered carbocycle or heterocycle which may contain one, two or three heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur;
M means an atom of iron, cobalt, nickel, ruthenium, osmium, rhodium, manganese, chromium or vanadium;
or their salts and mixtures.  2. The method according to claim 1, characterized in that a catalyst of the formula (I) is used, wherein M is an iron atom. 3. The method according to any one of claim 1 or 2, characterized in that the use of a catalyst of formula (I), where R ¹ means the remainder of the formula PL ₂ , and the residues L mean phenyl; R ^{1 ′} represents a hydrogen atom or a residue of the formula PL ₂ , wherein L residues mean phenyl; one of the substituents R ² , R ^{2 ′} , R ³ , R ^{3 ′} , R ⁴ , R ^{4 ′} , R ⁵ and R ^{5 ′} , preferably one in the α-position to R ¹ or R ^{1 ′} , means a hydrogen atom or an alkyl which can be interrupted by an oxygen atom or not or can be replaced by a residue of the formula NE ¹ E ² , wherein E ¹ and E ² can be the same or different and mean alkyl, and the remaining substituents R ² , R ^{2 ′} , R ³ , R ^{3 ′} , R ⁴ , R ^{4 ′} , R ⁵ , R ^{5 ′} , independently of one another, mean a hydrogen atom or alkyl.  4. The method according to any one of claims 1 to 3, characterized in that a catalyst is used comprising a ligand of formula (I) and at least one other ligand selected from the group consisting of halides, amines, carboxylates, acetylacetonate, aryl- or alkyl sulfonates, hydride, carbonyl, olefins, dienes, cycloolefins, nitriles, nitrogen-containing heterocycles, aromatic hydrocarbons and heteroaromatic hydrocarbons, ethers, phosphorus trifluoride, as well as monodentate, bidentate and polydentate phosphine, phosphinite, pho fonitnyh and phosphite ligands.  5. The method according to any one of claims 1 to 4, characterized in that the metallocene ligand comprising phosphorus (III), formula (I) is selected from the group consisting of 1,1'-bis (diphenylphosphino) ferrocene, 1,1 ' bis (dicyclohexylphosphino) ferrocene or 1,1'-bis (diisopropylphosphino) ferrocene.  6. The method according to any one of claims 1 to 5, characterized in that a mixture of hydrocarbons with a content of 1,3-butadiene of at least 10 vol.%, Preferably at least 25 vol.%, In particular at least 40 vol. .%.  7. The method according to any one of claims 1 to 6, characterized in that the hydrocarbon fraction with 4 carbon atoms from the oil refining process is used as the 1,3-butadiene mixture of hydrocarbons.  8. The method according to any one of claims 1 to 7, characterized in that the hydrocyanation is carried out semi-continuously, and a) a mixture of hydrocarbons is introduced into the reactor, if necessary, the in situ obtained catalyst, if necessary, part of the cyanide, as well as, if solvent needed; b) the mixture is converted at elevated temperature and elevated pressure and hydrogen cyanide is introduced as it is consumed; and c) if necessary, to achieve the fullness of the transformation leave to react for additional time and then process.  9. The method according to any one of claims 1 to 7, characterized in that the hydrocyanation is carried out periodically, and in the method according to claim 8, the entire amount of hydrogen cyanide is introduced in stage a). 10. The method according to any one of claims 1 to 9, characterized in that the hydrocyanation is carried out at a temperature of 0-200 ^o C, preferably 50-150 ^o C, in particular 70-120 ^o C.  11. The method according to any one of claims 1 to 10, characterized in that the hydrocyanation is carried out at a pressure of 1-200 bar, preferably 1-100 bar, in particular 1-50 bar and, in particular, 1-16 bar.  12. The method according to any one of claims 1 to 11, characterized in that the degree of conversion, based on hydrogen cyanide, is at least 95%, preferably at least 97%, particularly preferably at least 99%.  13. The method according to any one of claims 1 to 12, characterized in that a mixture of products is obtained, including isomeric pentenitriles and methylbutenitriles.  14. The method according to p. 13, characterized in that the quantitative ratio of 3-pentenitrile to 2-methyl-3-butennitrile is at least 5: 1, preferably at least 10: 1, in particular at least 20: 1.  15. The method according to any one of claims 1 to 14, characterized in that the catalyst is used, in addition to the hydrocyanation of 1,3-butadiene, also for isomerization of the position and double bond of monoolefin mononitriles with 5 carbon atoms.  16. A method of producing adipic acid dinitrile, characterized in that obtained according to paragraphs. 1-14 a mixture of monoolefin mononitriles with 5 carbon atoms, if necessary, after further processing and / or isomerization, catalytically hydrocyanate.  17. The method according to clause 16, wherein the hydrocyanation of 1,3-butadiene or a mixture of 1,3-butadiene containing hydrocarbons is carried out to obtain adipic acid dinitrile in one step, without separate processing and isomerization of monoolefin mononitriles with 5 carbon atoms.  18. The use of catalysts comprising ligands of the formula (I) for hydrocyanation of olefins.  19. The use of catalysts comprising ligands of the formula (I) for hydrocyanation and / or isomerization of the position and double bond of monoolefin mononitriles with 5 carbon atoms.