Process for producing amine compounds

Patent metadata

Field	Value
Publication number	US-9376372-B2
Application number	US-201314412633-A
Country	US
Kind code	B2
Filing date	Jul 8, 2013
Priority date	Jul 6, 2012
Publication date	Jun 28, 2016
Grant date	Jun 28, 2016

Abstract

The present invention provides processes for producing amine compounds. The amine compounds include diammonium compounds and amino acid derivatives.

First claim

The invention claimed is:

1. A process for producing an amino acid salt or derivative thereof comprising the steps of:
providing an unsaturated amine salt or derivative thereof; and
wherein the unsaturated amine salt is a compound of Formula I

wherein
each R 1 is independently selected from the group consisting of H, optionally C 1 -C 12 alkyl, optionally substituted C 2 -C 12 alkenyl, optionally substituted C 2 -C 12 alkynyl, optionally substituted C 2 -C 12 heteroalkyl, optionally substituted C 3 -C 12 cycloalkyl, optionally substituted C 3 -C 12 cycloalkenyl, optionally substituted C 2 -C 12 heterocycloalkyl, optionally substituted C 2 -C 12 heterocycloalkenyl, optionally substituted C 6 -C 18 aryl, optionally substituted C 1 -C 18 heteroaryl, optionally substituted C 1 -C 12 alkyloxy, optionally substituted C 2 -C 12 alkenyloxy, optionally substituted C 2 -C 12 alkynyloxy, optionally substituted C 2 -C 10 heteroalkyloxy, optionally substituted C 3 -C 12 cycloalkyloxy, optionally substituted C 3 -C 12 cycloalkenyloxy, optionally substituted C 2 -C 12 heterocycloalkyloxy, optionally substituted C 2 -C 12 heterocycloalkenyloxy, optionally substituted C 6 -C 18 aryloxy, optionally substituted C 1 -C 18 heteroaryloxy and optionally substituted C 1 -C 12 alkylamino;
R 2 and R 3 are each independently selected from the group consisting of H and C 1 -C 12 alkyl;
R 4 and R 5 are each independently selected from the group consisting of H, and C 1 -C 20 alkyl,
n is an integer selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20;
X − is a counterion; and
subjecting the unsaturated amine salt to
cross-metathesis with a compound of Formula II

wherein
R 7 is selected from the group consisting of OH, OR 7a and NR 7a R 7b ;
R 8 is selected from the group consisting of H and C 1 -C 12 alkyl;
R 9 and R 10 are each independently selected from the group consisting of H, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl and C(═O)R 7 ; and
R 7 and R 7b are each independently selected from the group consisting of H, optionally substituted C 1 -C 12 alkyl, optionally substituted C 2 -C 12 alkenyl, optionally substituted C 2 -C 12 alkynyl, optionally substituted C 2 -C 12 heteroalkyl, optionally substituted C 3 -C 12 cycloalkyl, optionally substituted C 3 -C 12 cycloalkenyl, optionally substituted C 2 -C 12 heterocycloalkyl, optionally substituted C 2 -C 12 heterocycloalkenyl, optionally substituted C 6 -C 18 aryl, optionally substituted C 1 -C 18 heteroaryl, optionally substituted C 1 -C 12 alkyloxy, optionally substituted C 2 -C 12 alkenyloxy, optionally substituted C 2 -C 12 alkynyloxy, optionally substituted C 2 -C 10 heteroalkyloxy, optionally substituted C 3 -C 12 cycloalkyloxy, optionally substituted C 3 -C 12 cycloalkenyloxy, optionally substituted C 2 -C 12 heterocycloalkyloxy, optionally substituted C 2 -C 12 heterocycloalkenyloxy, optionally substituted C 6 -C 18 aryloxy, optionally substituted C 1 -C 18 heteroaryloxy and optionally substituted C 1 -C 12 alkylamino;
in the presence of a metathesis catalyst to give the amino acid salt or derivative thereof.

2. The process according to claim 1 , wherein R 1 is H, R 2 is H and R 3 is H.

3. The process according to claim 1 , wherein n is selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.

4. The process according to claim 1 , wherein R 4 is H and R 5 is H.

5. The process according to claim 1 , wherein X − is selected from the group consisting of BF 4 − , TsO − , Cl − , TfO − , TFA − , Adipate 2− , BSA − , MsO − , HSO 4 − , F − , Br − , I − , H 2 AsO 4 − , H 2 PO 4 − , H 2 AsO 3 − , HPO 4 2− , H 2 PO 4 − , SO 4 2− , NO 3 − , NO 2 − , S 2 O 3 2− , HSO 3 − , ClO 4 − , IO 3 − , ClO 3 − , BrO 3 − , ClO 2 − , CrO 4 2− , HCO 3 − , Cr 2 O 7 2− , ClCH 2 COO − , HCOO − , OCN − , HC 2 O 4 − , B(OR) 4 − , B(OH) 4 − , CF 2 HSO 2 —O − , CFH 2 SO 2 —O − and alkyl aryl sulfonates.

6. The process according to claim 5 , wherein X − is selected from the group consisting of BF 4 − , TsO − and TfO − .

7. The process according to claim 1 , wherein R 7 is selected from the group consisting of OH and OC 1 -C 6 alkyl.

8. The process according to claim 1 , wherein R 8 is H, R 9 is H and R 10 is H.

9. The process according to claim 1 , wherein the compound of Formula II is a compound of Formula III

wherein R 7 is selected from the group consisting of OH, OR 7a and NR 7a R 7b ; and
R 7a and R 7b are each independently selected from the group consisting of H, optionally substituted C 1 -C 12 alkyl, optionally substituted C 2 -C 12 alkenyl, optionally substituted C 2 -C 12 alkynyl, optionally substituted C 2 -C 12 heteroalkyl, optionally substituted C 3 -C 12 cycloalkyl, optionally substituted C 3 -C 12 cycloalkenyl, optionally substituted C 2 -C 12 heterocycloalkyl, optionally substituted C 2 -C 12 heterocycloalkenyl, optionally substituted C 6 -C 18 aryl, optionally substituted C 1 -C 18 heteroaryl, optionally substituted C 1 -C 12 alkyloxy, optionally substituted C 2 -C 12 alkenyloxy, optionally substituted C 2 -C 12 alkynyloxy, optionally substituted C 2 -C 10 heteroalkyloxy, optionally substituted C 3 -C 12 cycloalkyloxy, optionally substituted C 3 -C 12 cycloalkenyloxy, optionally substituted C 2 -C 12 heterocycloalkyloxy, optionally substituted C 2 -C 12 heterocycloalkenyloxy, optionally substituted C 6 -C 18 aryloxy, optionally substituted C 1 -C 18 heteroaryloxy and optionally substituted C 1 -C 12 alkylamino.

10. A process according to claim 1 , wherein the catalyst is a metal complex wherein the metal in the metal complex is selected from the group consisting of ruthenium, molybdenum and tungsten.

11. A process according to claim 1 , wherein the catalyst is a ruthenium-alkylidene catalyst, a Grubbs catalyst or a later generation analogue, or a Hoveyda Grubbs second generation catalyst.

12. The process according claim 1 , further comprising the step of hydrogenating the amino acid salt or derivative thereof; formed from cross-metathesis to give a saturated amino acid salt.

13. The process according to claim 12 , wherein the cross-metathesis step and the hydrogenating step are performed in series without isolation of the amino acid salt or derivative thereof; after cross-metathesis.

Assignees

• Univ Monash

Inventors

• Robinson Andrea J
• Spiccia Nicolas
• Jackson William Roy
• Woodward Clint

Classifications

• C07B35/02

  Reduction · CPC title

• C07C227/16 Primary

  by reactions not involving the amino or carboxyl groups · CPC title

• C07D213/127

  Preparation from compounds containing pyridine rings · CPC title

• C07B37/08

  Isomerisation · CPC title

• C07C209/68

  from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton · CPC title