1,4-HYDROGENATION OF DIENES WITH RU COMPLEXES

• US 20100099904A1
• Filed: 04/02/2008
• Published: 04/22/2010
• Est. Priority Date: 04/03/2007
• Status: Active Grant

• Current Assignee: Firmenich SA
• Original Assignee: Firmenich SA
• Inventors: Dupau, Philippe, Bonomo, Lucia
• Granted Patent: US 8,003,838 B2
• Time in Patent Office: Days
• US Class Current: 556/136
• CPC Class Codes: B01J 2231/645 of C=C or C-C triple bonds
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 31/2295 Cyclic compounds, e.g. cyclopentadienyls
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 5/05 Partial hydrogenation
• CPC Class Codes: C07F 17/02 of metals of Groups 8, 9 or 10 of the Periodic System

Abstract

The present invention relates to the use of Ruthenium complexes having cyclopentadienyl derivatives and a diene as ligands, together with some acidic additives for improving the selectivity in the 1,4-hydrogenation of conjugated dienes into the corresponding “cis”-alkene as major product, i.e. wherein the two substituents in position 2,3 of the diene are in a cis configuration in the corresponding alkene.

Claims

1-10. -10. (canceled)

11. A process for the catalytic reduction by 1,4-hydrogenation, using molecular H₂, of a C₅-C₂₂ conjugated diene of formula

wherein R¹, R², R³, R⁴, R⁵ and R⁶ represent, simultaneously or independently from each other, a hydrogen atom or a C₁-C₁₂ alkyl or alkenyl group optionally substituted;

one of R² or R⁶ may also represent a C₁-C₁₂ alkoxy or acyloxy group optionally substituted; and

R¹ and R³, or R³ and R⁴, or R² and R⁶, or R⁶ and R⁵, or R⁴ and R⁵, taken together, may form a C_2-16 alkanediyl or de-conjugated alkenediyl group, optionally substituted;

into the corresponding alkene, of formula

wherein R¹ to R⁶ have the same meaning as for the compound of formula (I), and wherein the isomer having the R¹ and R² groups in a cis configuration is predominant;

wherein said process is carried out in the presence of

at least one ruthenium catalyst or pre-catalyst of formula

[Ru(L)(Diene)(L′

)]X 

 

(III)

wherein L represents a C₅-C₂₅ substituted cyclopentadienyl ligand, Diene represents a C₄-C₂₂ diene and X represents a non coordinated anion, n represents 2, 1 or 0 and L′

represents a solvent; and

at least an acidic additive selected from the group consisting of;

a compound of formula R¹⁴_(3-x)MO(OH)_x, wherein R¹⁴ is a R^14′

or R^14′

group wherein R^14′

is a C₁-C₁₀ group, M is P or As and x is 1 or 2; and

a boron derivative of formula R¹⁴B(OH)₂, wherein R¹⁴ is as defined above; and

phenol or a phenol substituted by up to three C₁-C₄ alkyl, alkoxy or carboxylic groups, nitro groups or halogen atoms; and

a C₁-C₁₂ mono-carboxylic non-amino acid; and

a HOOCCH═

CHCOOH di-acid, and the tetronic acid;

provided that the processes wherein compound (I) is sorbol and compound (III) is of formula [Ru(Cp*)(COD)]X are excluded.

15. A process according to claim 11, wherein Diene is a conjugated or non conjugated cyclic C₆-C₁₂ alkadiene.

16. A process according to claim 11, wherein X is ClO₄⁻

, R¹²SO₃⁻

, wherein R¹² is a chlorine or fluorine atom or a C₁-C₈ fluoroalkyl or fluoroaryl group, BF₄⁻

, PF₆⁻

, SbCl₆⁻

, SbF₆⁻

, or BR¹³₄⁻

, wherein R¹³ is a phenyl group optionally substituted by one to five halide atoms or methyl or CF₃ groups.

17. A process according to claim 11, wherein said mono-carboxylic acid is selected from the group consisting of a carboxylic acid of formula R¹⁵COOH, wherein R¹⁵ represents:

a halogenated or per-halogenated C₁-C₈ hydrocarbon group;

a R¹⁶CH(OR¹⁶) group, R¹⁶ being a hydrogen atom or a C₁-C₆ hydrocarbon group;

a C₁-C₁₂ hydrocarbon group, optionally substituted by one or two ether or ester groups;

the optional substituent being one, two or three C₁-C₄ alkyl, alkoxy or carboxylic groups, or nitro groups or halogen atoms.

18. A process according to claim 17, wherein said acidic additive is selected from the group consisting of

a compound of formula R¹⁴₂MO(OH) or R¹⁴MO(OH)₂, wherein R¹⁴ is a C₁-C₆ alkyl or alkoxyl group or a C₆-C₈ phenyl or phenoxyl and M is P or As;

and

maleic or glycolic acid and an halogenated or per-halogenated C₁-C₇ mono-carboxylic acid.

19. A process according to claim 11, wherein the conjugated diene of formula (I) is a compound of formula (I′

)

wherein R^a represents a linear, branched or cyclic C₁-C₈ alkyl or alkenyl group; and

R^b represents a (CH₂)_nX group, n representing 0, 1, 2 or 3, X representing a CHO, OH, OCOR^c, OR^c or COOR^c group, R^c being a C₁-C₈ alkyl or alkenyl group;

or of formula (I″

);

wherein R^d and R^e represent a hydrogen atom or a C₁-C₈ alkyl or alkenyl group, optionally substituted by a OH, OCOR^f, OR^f or COOR^f group, R^f being a C₁-C₈ alkyl or alkenyl group,

provided that R^d and R^e do not represent each a hydrogen atom.

20. A ruthenium complex of formula

[Ru(L)(Diene)(L′

)_n]X 

 

(III)

wherein Diene represents a C₄-C₂₂ diene and X represents a non coordinated anion, n represents 2, 1 or 0 and L′

represents a solvent; and

L represents a C₆-C₂₅ compound of formula

wherein each R⁹ represents, simultaneously or independently from each other, a hydrogen atom, a phenyl group optionally substituted, or a C₁-C₁₀ alkyl or alkenyl group optionally substituted; and

one or two of said groups R⁹ is a OSiR¹¹₃ or OCOR¹⁰ group, R¹¹ representing a C₁-C₆ alkyl group, R¹⁰ representing a R¹¹ or CF₃ group or a phenyl group optionally substituted; and

at least one R⁹ is an alkyl group;

two adjacent R⁹ can be bound together to form a C₂-C₁₀ alkanediyl group.