Method for producing reduced halide compound having undergone reduction of carbon-carbon unsaturated bond

Patent metadata

Field	Value
Publication number	US-10676417-B2
Application number	US-201916388309-A
Country	US
Kind code	B2
Filing date	Apr 18, 2019
Priority date	Apr 19, 2018
Publication date	Jun 9, 2020
Grant date	Jun 9, 2020

Abstract

A halide compound having one or more carbon-carbon unsaturated bonds is catalytically reduced with substantially no dehalogenation to produce a reduced halide compound in which at least one of the one or more unsaturated bonds is reduced. Specifically provided is a method for producing a reduced halide compound including steps of: reacting a nickel compound, a zinc compound, and a borohydride compound in a solvent to obtain a reduction catalyst; and subjecting a halide compound having one or more carbon-carbon unsaturated bonds to catalytic reduction in the presence of the reduction catalyst to reduce at least one of the one or more carbon-carbon unsaturated bonds to thereby obtain a reduced halide compound.

First claim

The invention claimed is:

1. A method for producing a reduced halide compound, comprising steps of:
reacting a nickel compound, a zinc compound, and a borohydride compound in a solvent to obtain a reduction catalyst; and
subjecting a halide compound having one or more carbon-carbon unsaturated bonds to catalytic reduction in the presence of the reduction catalyst to reduce at least one of the one or more carbon-carbon unsaturated bonds to thereby obtain a reduced halide compound.

2. The method for producing a halide compound according to claim 1 , wherein the halide compound having one or more carbon-carbon unsaturated bonds is denoted by General Formula (1):
X—Z 1 —[(CR 1 ═CR 2 ) a —(CH 2 ) b —(C═C) c —(CR 3 ═CR 4 ) d —(CH 2 ) e —(C≡C) f ] g —Z 2 —Y 1   (1),

wherein
X is a halogen atom;
R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 18 carbon atoms, or an acyl group having 1 to 18 carbon atoms beside a carbon atom of a carbonyl group, or are bonded together to form a divalent hydrocarbon group, R 1 -R 2 , R 1 -R 3 , R 1 -R 4 , R 2 -R 3 , R 2 -R 4 or R 3 -R 4 , having 1 to 18 carbon atoms;
Z 1 and Z 2 are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, or a single bond;

Y 1 is a hydrogen atom, a halogen atom, a protected formyl group, a hydroxy group, an acyl group, an acyloxy group, an alkoxy group, an alkoxyalkoxy group, a carboxyl group, an amino group, an amino group monosubstituted with a monovalent hydrocarbon group having 1 to 18 carbon atoms, an amino group disubstituted with two monovalent hydrocarbon groups each having 1 to 18 carbon atoms, an acylamino group, a silyl group, or an alkoxycarbonyloxy group; and
a, b, c, d, e and f are each an integer of 0 to 8 with the proviso that not all of a, c, d and fare 0, and g is an integer of 1 to 8; and

the reduced halide compound in which at least one of the one or more carbon-carbon unsaturated bonds is reduced is denoted by General Formula (2):
X—Z 3 —[(CHR 5 —CHR 6 ) a —(CH 2 ) b —(CH 2 —CH 2 ) c —(CHR 7 —CHR 8 ) d —(CH 2 ) e —(CH 2 —CH 2 ) f ] g —Z 4 —Y 2    (2),

wherein
X is a halogen atom;
R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 18 carbon atoms, or an acyl group having 1 to 18 carbon atoms beside a carbon atom of a carbonyl group, or are bonded together to form a divalent hydrocarbon group, R 5 -R 6 , R 5 -R 1 , R 5 -R 8 , R 6 -R 7 , R 6 -R 8 or R 7 -R 8 , having 1 to 18 carbon atoms;
Z 3 and Z 4 are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, or a single bond;
Y 2 is a hydrogen atom, a halogen atom, a protected formyl group, a hydroxy group, an acyl group, an acyloxy group, an alkoxy group, an alkoxyalkoxy group, a carboxyl group, an amino group, an amino group monosubstituted with a monovalent hydrocarbon group having 1 to 18 carbon atoms, an amino group disubstituted with two monovalent hydrocarbon groups each having 1 to 18 carbon atoms, an acylamino group, a silyl group, or an alkoxycarbonyloxy group; and
a, b, c, d, e and fare each an integer of 0 to 8 with the proviso that not all of a, c, d and f are 0, and g is an integer of 1 to 8.

3. The method for producing a reduced halide compound according to claim 1 , wherein the solvent is an alcohol.

4. The method for producing a reduced halide compound according to claim 1 , wherein the nickel compound is a nickelous compound.

5. The method for producing a reduced halide compound according to claim 1 , wherein the zinc compound is a divalent zinc compound.

6. The method for producing a reduced halide compound according to claim 1 , wherein the borohydride compound is an alkali metal borohydride.

7. The method for producing a reduced halide compound according to claim 1 , wherein the protected formyl group is protected by a protective group to form O,O-acetal denoted by General Formula (3):
—CHOR 9 (OR 10 )  (3),

wherein R 9 and R 10 are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms or are bonded together to form a divalent hydrocarbon group, R 9 -R 10 , having 1 to 18 carbon atoms.

Assignees

• Shinetsu Chemical Co

Inventors

• Miyake Yuki
• Kinsho Takeshi
• Nagae Yusuke

Classifications

• B01J23/80 Primary

  with zinc, cadmium or mercury · CPC title

• C07C29/172

  with the obtention of a fully saturated alcohol · CPC title

• B01J37/18

  with gases containing free hydrogen · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• C07F7/127

  by reactions not affecting the linkages to the silicon atom · CPC title