Isomerization method for 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane

Patent metadata

Field	Value
Publication number	US-10287235-B2
Application number	US-201615556535-A
Country	US
Kind code	B2
Filing date	Feb 25, 2016
Priority date	Mar 9, 2015
Publication date	May 14, 2019
Grant date	May 14, 2019

Abstract

An isomerization reaction of a predetermined compound, without passing through a high pressure reaction and a complicated multi-stage process. The isomerization method includes isomerizing, 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane in the presence of a compound represented by formula (1) and at least one compound selected from no alkali metal, an alkali metal-containing compound, an alkaline earth metal and an alkaline earth metal-containing compound:

where R 1 and R 2 each independently represent a hydrogen atom or a monovalent group selected from a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group and an acyl group, R 1 and R 2 may mutually bind to form a ring, R 3 represents a hydrogen atom and an n-valent group selected from a substituted or unsubstituted hydrocarbon group, and n represents as integer of 1 to 10.

First claim

The invention claimed is:

1. A method for isomerizing a 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane represented by the following formula (9):

the method comprising:
isomerizing the 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane in the presence of:
at least one selected from the group consisting of an alkali metal, an alkali metal-containing compound, an alkaline earth metal and an alkaline earth metal-containing compound, and
an imine compound represented by the following formula (1):

wherein:
R 1 and R 2 each independently represent a hydrogen atom or a monovalent group selected from the group consisting of a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group and an acyl group, wherein R 1 and R 2 may mutually bind to form a ring;
R 3 represents a hydrogen atom or an n-valent group selected from the group consisting of a substituted or unsubstituted hydrocarbon group; and
n represents an integer of 1 to 10.

2. The method for isomerizing 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane according to claim 1 , wherein
R 1 , R 2 , and R 3 each independently represent a substituted or unsubstituted hydrocarbon group, and
the substituted or unsubstituted hydrocarbon group represented by each of R 1 and R 2 comprises a monovalent group selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group; and
the substituted or unsubstituted hydrocarbon group represented by R 3 comprises an n-valent group selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group.

3. The method for isomerizing 1,3,3-trimethyl-1-(aminomethypaminocyclohexane according to claim 1 , wherein the imine compound comprises a compound represented by the following formula (2) and/or a compound represented by the following formula (3):

wherein R 1 and R 2 each independently represent a hydrogen atom or a monovalent group selected from the group consisting of a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group and an acyl group, wherein R 1 and R 2 may mutually bind to form a ring;

wherein R 1 and R 2 each independently represent a hydrogen atom or a monovalent group selected from the group consisting of a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group and an acyl group, wherein R 1 and R 2 may mutually bind to form a ring.

4. A method for isomerizing 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane, comprising:
isomerizing the 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane in the presence of:
at least one selected from the group consisting of an alkali metal, an alkali metal-containing compound, an alkaline earth metal and an alkaline earth metal- containing compound, and
an imine compound,
wherein the imine compound comprises a compound represented by the following formula (2a) and/or a compound represented by the following formula (3a):

wherein R 1 and. R 2 each independently represent a hydrogen atom or a monovalent group selected from the group consisting of a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group and an acyl group, wherein R 1 and R 2 may mutually bind to form a ring,

wherein R 1 and R 2 each independently represent a hydrogen atom or a monovalent group selected from the group consisting of a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group and an acyl group, wherein R 1 and R 2 may mutually bind to form a ring.

5. The method for isomerizing 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane according to claim 1 , wherein the imine compound is obtained by dehydration condensation between a primary amine and an aldehyde and/or a ketone.

6. The method for isomerizing 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane according to claim 1 , wherein the imine compound is obtained by dehydration condensation between the 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane and an aldehyde and/or a ketone.

7. The method for isomerizing 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane according to claim 1 , wherein the 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane is 1,3,3-trimethyl-1-(aminomethyl)-5-aminocyclohexane.

8. The method for isomerizing 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane according to claim 1 , comprising isomerizing the 1,3,3-trimethvl-1-(aminomethyl)aminocyclohexane in the presence of an alkali metal-containing compound, wherein the alkali metal-containing compound comprises at least one selected from the group consisting of an alkali metal hydride and an alkali metal amide.

9. The method for isomerizing 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane according to claim 1 , comprising performing isomer separation for separating a trans-isomer and a cis-isomer of 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane by distillation, during and/or after the isomerizing.

10. The method for isomerizing 1,3,3trimethyl-1-(aminomethyl)aminocyclohexane according to claim 1 , wherein an isomerization reaction temperature of the isomerizing is 100 to 140° C.

11. The method for isomerizing 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane according to claim 10 , wherein, in the isomerizing, a solvent having a boiling point equal to or lower than the isomerization reaction temperature is used.

12. The method for isomerizing 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane according to claim 1 , wherein, in the isomerizing, bubbling is performed by an inert gas.

13. The method for isomerizing 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane according to claim 4 , wherein the imine compound comprises a compound represented by formula (2a).

14. ; The method for isomerizing 1,3;3-trimethyl-1-(aminomethyl)aminocyclohexane according to claim 4 , wherein the imine compound comprises a compound represented by formula (3a).

15. The method for isomerizing 1,3,3-trimethyl-1-(aminomethyl)aminocyclohexane according to claim 4 , wherein the imine compound comprises a compound represented by formula (2a) and a compound represented by formula (3a).

Assignees

• Mitsubishi Gas Chemical Co

Inventors

• Shimizu Yuko
• Yamamoto Yoshiaki

Classifications

• C07C211/36

  containing at least two amino groups bound to the carbon skeleton · CPC title

• C07C209/68 Primary

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

• C07B61/00

  Other general methods · CPC title

• C07C2601/14

  The ring being saturated · CPC title