RU2001101148A - THE CATALYST, INCLUDING THE COMPLEX OF METAL VIII OF THE UNDERSTANDING GROUP, BASED ON ONE OF THE BIDENTATE PHOSPHONITE LIGANDS AND METHOD FOR PRODUCING NITRILES - Google Patents

Claims (13)

1. A catalyst comprising a complex of a metal of group VIII of a side group with one of the bidentate ligands of the general formula I

_ where the residues R ¹ and R ² , respectively, R ^{1 '} and R ² ', are not connected by a bridge to each other; A is an alkylene bridge with 2-7 carbon atoms, which may contain one, two or three double bonds and / or one, two or three substituents selected from the group consisting of alkyl, cycloalkyl and aryl, while the aryl substituent may additionally have one, two or three substituents selected from the group consisting of alkyl, alkoxy, halogen, trifluoromethyl, nitro, alkoxycarbonyl or cyano, and / or an alkylene bridge with 2-7 carbon atoms may be interrupted by one, two or three non-adjacent, in some cases substituted heteroatoms, and / or an alkylene bridge with 2-7 carbon atoms can be interrupted one, two or three times non-adjacent, in some cases substituted heteroatoms, and / or an alkylene bridge with 2-7 carbon atoms can be one, two or three times annelated with aryl and / or hetaryl, while annelated aryl and hetaryl groups may carry one, two or three substituents each selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, acyl, halogen , trifluoromethyl, nitro, cyano, carboxyl, alko sikarbonil or NE ¹ E ^2, wherein E ¹ and E ² may be identical or different and are alkyl, cycloalkyl or aryl; R ¹ and R ^{1 ′} , independently of one another, are alkyl, cycloalkyl, aryl or hetaryl which may have one, two or three substituents each selected from the group consisting of alkyl, cycloalkyl and aryl, R ² and R ^{2 '} , independently of one another, are alkyl, cycloalkyl, aryl or hetaryl, while the aryl and hetaryl groups may have one, two or three substituents each selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, acyl, halogen, trifluoromethyl, nitro, cyano, carboxyl, alkoxycarbonyl or (and) NE ¹ E ² , while E ¹ and E ² may have the meanings indicated above, or their salts and mixtures thereof. 2. The catalyst according to claim 1, in which a represents the remainder of the formulas II.1-II.5

where X represents O, S, NR ⁵ , while R ⁵ represents alkyl, cycloalkyl or aryl, or X represents an alkylene bridge with 1-3 carbon atoms, which may contain a double bond and / or alkyl, cycloalkyl or aryl substituents wherein the aryl substituent may have one, two or three substituents selected from the group consisting of alkyl, alkoxy, halogen, trifluoromethyl, nitro, alkoxycarbonyl or cyano, or X represents an alkylene bridge with 2-3 carbon atoms, which is interrupted by O , S or NR ⁵ ; R ³ , R ^{3 ′} , R ^{3 ″} , R ^{3 ″} , R ⁴ , R ^{4 ’} , R ^{4 ″} R ^{4 ″} , independently of one another, are hydrogen, alkyl, alkoxy, halogen, trifluoromethyl, nitro, alkoxycarbonyl or cyano. 3. The catalyst according to one of claim 1 or 2, in which R ¹ and R ^{1 '} , independently from each other, are alkyl or aryl, preferably phenyl, 1-naphthyl or 2-naphthyl. 4. The catalyst according to one of the above paragraphs, in which R ¹ and R ² , independently of one another, are phenyl substituents, which in some cases may have one or two substituents that are selected from the group consisting of alkyl, alkoxy, halogen, trifluoromethyl, nitro, cyano, alkoxycarbonyl or carboxyl. 5. The catalyst according to one of the above paragraphs, in which the phosphonite ligand of the formula I is selected from ligands of the formulas Ia-Ic

while in the formula Ia, the substituents R ³ , R ⁴ , R ⁷ and R ⁸ have the following meanings:

in the formula Ib, the substituents R ⁴ , R ⁷ , R ⁸ and R ⁹ have the following meanings:

in the formula Ib, the substituents R ⁴ , R ⁷ , R ⁸ and R ⁹ have the following meanings:

6. The catalyst according to one of the preceding paragraphs, which further comprises at least one more ligand selected from the group consisting of cyanide, halides, amines, carboxylates, acetylacetone, aryl or alkyl sulfonates, hydride, CO (carbon monoxide), olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatic and heteroaromatic compounds, ethers, PF ₃ (phosphorus trifluoride), as well as mono-, bi- and polydentate phosphine, phosphite and phosphite ligands. 7. The catalyst according to one of the preceding paragraphs, in which in the case of a metal of the VIII side group, it is about cobalt, rhodium, ruthenium, palladium or nickel. 8. Phosphonite ligands of the general formula I _

as defined in claims 1-5, where R ² and R ^{2 '} , independently from each other, represent alkyl, cycloalkyl, aryl or hetaryl, while aryl and hetaryl groups may have one or two substituents selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, acyl, halogen, trifluoromethyl, nitro, cyano, carboxyl, alkoxycarbonyl or NE ¹ E ² , while E ¹ and E ² may be the same or different and represent alkyl, cycloalkyl or aryl. 9. A method of producing mixtures of monoolefin mononitriles with 5 carbon atoms with non-conjugated C = C and C≡N bonds by catalytic hydrocyanation of butadiene or hydrocarbon mixtures containing 1,3-butadiene, characterized in that the hydrocyanation occurs in the presence of a catalyst according to one of claims .1-7. 10. The method of catalytic isomerization of branched aliphatic monoalkenitriles with non-conjugated C = C and C≡N bonds into linear monoalkenitriles, characterized in that the isomerization occurs in the presence of a catalyst according to one of claims 1 to 7. 11. The method of producing adipic acid dinitrile by catalytic hydrocyanation of linear monoolefin mononitriles with 5 carbon atoms, characterized in that hydrocyanation occurs in the presence of a catalyst according to one of claims 1 to 7. 12. A method of producing adipic acid dinitrile, comprising a) obtaining a mixture of monoolefin mononitriles with 5 carbon atoms with non-conjugated C = C and C≡N bonds by catalytic hydrocyanation of butadiene or a hydrocarbon mixture containing 1,3-butadiene, b) catalytic isomerization of the mixture from a), c) catalytic hydrocyanation of the isomerized mixture from b), characterized in that stages a), b) and c) occur in the presence of at least one catalyst according to one of claims 1 to 7 and without isolating the product / products in stage a) and / or b). 13. The use of catalysts according to one of claims 1 to 7 for hydrocyanation and / or and isomerization of the position of the double bond of olefins.