Organic compounds

Patent metadata

Field	Value
Publication number	US-10544179-B2
Application number	US-201715726970-A
Country	US
Kind code	B2
Filing date	Oct 6, 2017
Priority date	Jan 24, 2014
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

Abstract

A process for the hydrogenation of a substrate comprising a carbon heteroatom double bond in the presence of a transition metal complex comprising a tridentate or bisdentate-ligand containing a nitrogen, sulphur and phosphorus atom, of which at least the N- and P- and optionally also the S-atom coordinates with the transition metal.

First claim

The invention claimed is:

1. A transition metal complex according to the formula:
MX 2 [SNP]Y
wherein M is a group VIII transition metal and SNP represents a tridentate or bisdentate ligand containing a nitrogen, sulphur and phosphorus atom, of which at least the N- and P- and optionally also the S-atom coordinates with the transition metal, each X is independently selected from a halide, hydroxyl, alkoxy, acyloxy and amido; and each Y is independently selected from a monodentate phosphine, a carbon monoxide (CO) ligand, a nitrosyl group and a RCN group, wherein R is alkyl or aryl,
wherein the tridentate or bisdentate ligand is represented by the formula

wherein
R 1 and R 2 are independently selected from H, or C 1 to C 20 alkyl and aryl, or R 1 and R 2 are connected such that together with the sulphur and carbon atoms to which they are attached, they form a heteroaliphatic or heteroaromatic ring;
R 3 through R 7 are independently selected from H; a C 1 to C 20 linear or branched alkyl group or alkenyl group; a C 3 to C 8 cyclic alkyl group; and a C 5 to C 10 aryl group; or R 2 and R 3; R 3 and R 4; or R 2 and R 4, together with the carbon atoms to which they are attached form a 5- or 6-membered aliphatic ring, which is optionally unsaturated; and/or R 5 and R 6; R 5 and R 7 ; or R 6 and R 7, together with the carbon atoms to which they are attached form a 5- or 6- membered aliphatic ring, which is optionally unsaturated;
R 8 and R 9 independently are selected from H; a C 1 to C 20 linear or branched alkyl group or alkenyl group; a C 3 to C 8 cyclic alkyl group; and a C 5 to C 10 aryl or heteroaryl group;
a and b are independently 0, 1 or 2;
n is 0 or 1; and
represents a single or a double bond, provided that when R 2 is H or C 4 to C 20 alkyl represents a single bond; and when n is 1 each N represents a carbon-nitrogen single bond; whereas when n is 0, one N is a carbon-nitrogen single bond and the other N is a carbon-nitrogen double bond.

2. A complex according to claim 1 wherein the nitrogen atom on the tridentate or bisdentate ligand forms part of an amine group or an imine group; the sulphur atom forms part of an aliphatic group or forms part of an aromatic ring; and the phosphorus atom forms part of a phosphine group.

3. A complex according to claim 1 , wherein the nitrogen atom-containing group is flanked on one side by the phosphorus atom-containing group, and on the other side by the sulphur atom-containing group.

4. A complex according to claim 1 , wherein the tridentate or bisdentate ligand is represented by the formula

wherein
R 1 and R 2 are independently selected from H, or C 1 to C 20 alkyl or aryl, or R 1 and R 2 are connected such that together with the sulphur and carbon atoms to which they are attached, they form a heteroaliphatic or heteroaromatic ring;
R 3 through R 7 are independently selected from H; a C 1 to C 20 linear or branched alkyl group or alkenyl group; a C 3 to C 8 cyclic alkyl group; and a C 5 to C 10 aryl group; or R 2 and R 3 ; R 3 and R 4 ; or R 2 and R4, together with the carbon atoms to which they are attached form a 5- or 6-membered aliphatic ring, which is optionally unsaturated; and/or R 5 and R 6 ; R 5 and R 7 ; or R 6 and R 7 , together with the carbon atoms to which they are attached form a 5- or 6-membered aliphatic ring, which is optionally unsaturated;
R 8 and R 9 independently are selected from H; a C 1 to C 20 linear or branched alkyl group or alkenyl group; a C 3 to C 8 cyclic alkyl group; and a C 5 to C 10 aryl or heteroaryl group;
a and b are independently 0, 1 or 2;
n is 0 or 1; and
represents a single or a double bond, provided that when R 2 is H or C 4 to C 20 alkyl represents a single bond; and when n is 1 each N represents a carbon-nitrogen single bond; whereas when n is 0, one N is a carbon-nitrogen single bond and the other N is a carbon-nitrogen double bond.

5. A complex according to claim 1 , wherein the tridentate or bisdentate ligand is represented by the formula selected from the group consisting of

wherein
R 10 is a moiety selected from C 1-10 alkyl, aryl, heteroaryl, alkenyl, nitrile and halide, and
m is 0, 1, 2 or 3.

6. A complex according to claim 1 , wherein the metal M is ruthenium or osmium.

7. A tridentate or bisdentate ligand L presented by the formula

wherein
R 1 and R 2 are independently selected from H, and C 1 to C 20 alkyl or aryl, or R 1 and R 2 are connected such that together with the sulphur and carbon atoms to which they are attached, they form a heteroaromatic or heteroaliphatic ring, and wherein said heteroaromatic ring is not a 5-membered heterocycle containing both S and N atoms;
R 3 through R 7 are independently selected from H; a C 1 to C 20 linear or branched alkyl group or alkenyl group; a C 3 to C 8 cyclic alkyl group; and a C 5 to C 10 aryl group; or R 2 and R 3 ; R 3 and R 4 ; or R 2 and R 4, together with the carbon atoms to which they are attached form a 5- or 6-membered aliphatic ring, which is optionally unsaturated; and/or R 5 and R 6; R 5 and R 7 ; or R 6 and R 7 , together with the carbon atoms to which they are attached form a 5- or 6-membered aliphatic ring, which is optionally unsaturated; R 8 and R 9 independently are selected from H; a C 1 to C 20 linear or branched alkyl group or alkenyl group; a C 3 to C 8 cyclic alkyl group; and a C 5 to C 10 aryl or heteroaryl group;
a and b are independently 0, 1 or 2;
n is 0 or 1; and
represents a single or a double bond, provided that when R 2 is H or C 4 to C 20 alkyl, represents a single bond; and when n is 1 each N represents a carbon-nitrogen single bond; whereas when n is 0, one N is a carbon-nitrogen single bond and the other N is a carbon-nitrogen double bond; with the proviso that the ligand L is not

wherein the tridentate or bisdentate ligand is represented by the formula selected from the group consisting of

wherein
R 10 is a moiety selected from C 1-10 alkyl, aryl, heteroaryl, alkenyl, nitrile and halide, and
m is 0,1,2 or 3.

8. A tridentate or bisdentate ligand according to claim 7 represented by the formula selected from the group consisting of

Assignees

• Givaudan Sa

Inventors

• Geisser Roger Wilhelm
• Oetiker Jürg Daniel
• Schröder Fridtjof

Classifications

• C07C33/20

  monocyclic · CPC title

• C07C2602/28

  Hydrogenated naphthalenes · CPC title

• C07C69/612

  Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety · CPC title

• C07C29/149

  with hydrogen or hydrogen-containing gases · CPC title

• C07C33/025

  with only one double bond · CPC title