Hydrogenation of esters with Fe/tridentate ligands complexes

Patent metadata

Field	Value
Publication number	US-10053475-B2
Application number	US-201415105927-A
Country	US
Kind code	B2
Filing date	Dec 10, 2014
Priority date	Dec 18, 2013
Publication date	Aug 21, 2018
Grant date	Aug 21, 2018

Abstract

The present invention relates to the field of catalytic hydrogenation and, more particularly, to the use of Fe complexes with tridentate ligands, having one amino or imino coordinating group and two phosphino coordinating groups, in hydrogenation processes for the reduction of ketones, aldehydes, esters or lactones into the corresponding alcohol or diol, respectively.

First claim

What is claimed is:

1. A process for the reduction by hydrogenation, using molecular H 2 , of a C 3 -C 70 substrate containing one or two carbonyl or carboxylic functional group into the corresponding alcohol, or diol, characterized in that said process is carried out in the presence of a base and at least one catalyst or pre-catalyst in the form of an iron complex of formula
[Fe(L3)(L′)Y a ](Z) b   (1)

wherein L3 is a compound of formula:

wherein in (A):
the dotted line indicates a single or double bond;
z is 0 or 1 when the carbon-nitrogen bond with the dotted line represents a double or single bond respectively;
R 1 and R 2 , when taken separately, represent, simultaneously or independently, a linear, branched or cyclic C 1 to C 10 alkyl or alkenyl group optionally substituted, a C 6 to C 10 aromatic group optionally substituted; said groups R 1 and R 2 , when taken together, may form a saturated or unsaturated ring optionally substituted, having 5 to 10 atoms and including the phosphorus atom to which said R 1 and R 2 groups are bonded;
R 6 and R 7 represent, simultaneously or independently, a hydrogen atom, a linear, branched or cyclic C 1 to C 6 alkyl or alkenyl group optionally substituted, a C 6 -C 10 aromatic group optionally substituted; when the dotted line represent a single bond, two R 6 taken together, may form a saturated heterocycle, optionally substituted and optionally containing one or two additional nitrogen or oxygen atoms, containing 5 to 10 atoms and including the N atom and the carbon atoms to which said R 6 groups are bonded respectively; and
Q represents:
a group of formula

wherein n is an integer from 1 to 3, and
R 4 and R 5 represent, simultaneously or independently, a hydrogen atom, a linear, branched or cyclic C 1 to C 6 alkyl or alkenyl group optionally substituted, a C 6 -C 10 aromatic group optionally substituted; two distinct R 4 and/or R 5 groups, taken together, may form a C 5 to C 8 , saturated ring optionally substituted, including the carbon atoms to which each of said R 4 or R 5 group is bonded; or
a diphenyl, dinaphthyl, C 5 -C 12 metallocediyl, phenylene or naphthylene group optionally substituted; and
the optional substituents of R 4 , R 5 , R 6 and R 7 are one or two halogen, C 1 to C 10 alkoxy groups, halo- or perhalo-hydrocarbon, COOR, NR 2 , quaternary amine or R groups, wherein R is a C 1 to C 6 alkyl, or a C 5 to C 12 cycloalkyl, aralkyl or aromatic group being also optionally substituted by one, two or three halogen, sulfonates groups or C 1 -C 8 alkyl, alkoxy, amino, nitro, sulfonates, halo- or perhalo-hydrocarbon or ester groups; and
the optional substituents of R 1 , R 2 and Q, when said groups are or contain phenyl or aromatic groups, are one to three C 1 to C 5 alkoxy groups, C 1 to C 4 alkyl groups, or NR groups, wherein R is a C 1 to C 6 alkyl C 5 to C 6 cycloalkyl;

L′ represents a CO or C 1-11 isonitrile compound;
each Y represents, simultaneously or independently, a hydrogen or halogen atom, a hydroxyl group, or a C 1 -C 6 alkoxy or carboxylic radical or a BH 4 or AlH 4 group;
Z represents a halogen atom, a hydroxyl group, or a C 1 -C 6 alkoxy or carboxylic radical or a BH 4 or AlH 4 group; and
(a+b)=2 with a being 1 or 2.

2. A process according to claim 1 , wherein said ligand L3 is a compound of formula

wherein the R 1 , R 2 , R 6 and R 7 have the same meaning as recited in claim 1 .

3. A process according to claim 1 , wherein said substrate is a C 5 -C 30 compound of formula

wherein n represents 0 or 1;
R a and R b , taken together, represent a C 3 -C 20 hydrocarbon group, optionally substituted and optionally comprising one, two or three oxygen or nitrogen atoms; or, when said
R a and R b are taken separately,
R a represents a hydrogen atom or R b group;
R b represents a C 1 -C 30 hydrocarbon group, optionally substituted and optionally comprising one, two or three oxygen or nitrogen atoms; and
the optional substituents of R a and R b are one, two or three halogen, COOR c , OR c , NR c 2 or R c groups, in which R c is a hydrogen atom, a halogenated C 1 -C 2 group or a C 1 to C 10 cyclic, linear or branched alkyl, or alkenyl group.

4. A process according to claim 3 , wherein said substrate is a compound of formula (I) wherein R a represent a hydrogen atom or R b group, and R b group represents a linear, branched or cyclic C 3 -C 18 aromatic, alkyl, alkenyl or alkanedienyl group optionally substituted; or R a and R b are bonded together and form a C 5 -C 20 saturated or unsaturated linear, branched, mono-, di- or tri-cyclic group, optionally substituted.

5. A process according to claim 3 , wherein said substrate is a compound of formula (I) as defined in claim 3 , wherein
when n is 1 and R a is an alkenyl or alkadienyl group, that said group is not an alk-1-enyl or an alka-1,3-dienyl group; or
when n is 0 and R a is an alkenyl or alkadienyl group, that said group is an alk-1-enyl or an alka-1,3-dienyl group; or
when n is 0 and R a is a hydrogen atom, R b represent a branched or cyclic hydrocarbon group wherein the branching is in the alpha position relative to the CHO group of the substrate.

6. A process according to claim 3 , wherein in said substrate n is 1.

7. A process according to claim 3 , wherein R a and R b , taken together, represent a C 4 -C 20 , hydrocarbon group, optionally substituted and optionally comprising one, two or three oxygen or nitrogen atoms.

8. A process according to claim 3 , wherein R c is a C 1 to C 4 linear or branched alkyl or alkenyl group.

9. A process according to claim 1 , wherein said base has a pK a above 10.

10. A process according to claim 1 , wherein said base is a alkaline or alkaline-earth metal carbonates, an alkaline or alkaline-earth metal hydroxides, C 1-10 amidures, C 10-26 phosphazene or an alcoholate of formula (R 13 O) 2 M or R 13 OM′, wherein M is an alkaline-earth metal, M′ is an alkaline metal or an ammonium NR 14 4 + , R 13 stands for hydrogen or a C 1 to C 6 linear or branched alkyl radical and R 14 stands for a C 1 to C 10 linear or branched alkyl radical.

11. A process according to claim 1 , wherein said substrate is a C 5 -C 30 compound of formula

wherein n represents 0 or 1;
R a and R b , taken together, represent a C 3 -C 20 hydrocarbon group, optionally substituted and optionally comprising one, two or three oxygen or nitrogen atoms; or, when said
R a and R b are taken separately,
R a represents a hydrogen atom or R b group;
R b represents a C 1 -C 30 hydrocarbon group, optionally substituted and optionally comprising one, two or three oxygen or nitrogen atoms; and
the optional substituents of R a and R b are one, two or three halogen, COOR c , OR c , NR c 2 or R c groups, in which R c is a hydrogen atom, a halogenated C 1 -C 2 group or a C 1 to C 10 cyclic, linear or branched alkyl, or alkenyl group.

12. A process according to claim 11 , wherein R

Assignees

• Firmenich & Cie

Inventors

• Quintaine Julie
• Saudan Lionel

Classifications

• C07F15/02

  Iron compounds · CPC title

• C07F9/5004

  Acyclic saturated phosphines · CPC title

• C07F9/5045 Primary

  Complexes or chelates of phosphines with metallic compounds or metals · CPC title

• C07C35/18

  with unsaturation at least in the ring · CPC title

• C07F9/5018

  Cycloaliphatic phosphines · CPC title