Isomerization method for cyclohexanediamine

Patent metadata

Field	Value
Publication number	US-10407380-B2
Application number	US-201615556416-A
Country	US
Kind code	B2
Filing date	Feb 25, 2016
Priority date	Mar 9, 2015
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

Abstract

The present invention provides a method for isomerizing a cyclohexanediamine, which simply and highly actively realizes an isomerization reaction of a cyclohexanediamine, without passing through a high-pressure reaction and a complicated multi-stage process. The isomerization method has an isomerization step of isomerizing a cyclohexanediamine in the presence of a compound represented by the following formula (1) and at least one selected from the group consisting of an alkali metal, an alkali metal-containing compound, an alkaline earth metal or an alkaline earth metal-containing compound.

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 (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 the group consisting of a substituted or unsubstituted hydrocarbon group; and n represents, an integer of 1 to 10.

First claim

The invention claimed is:

1. A method for isomerizing a cyclohexanediamine, comprising:
isomerizing the cyclohexanediamine in the presence of an imine compound represented by formula (1) and
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:

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 bond 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 a cyclohexanediamine according to claim 1 , wherein 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 a cyclohexanediamine according to claim 1 , wherein the imine compound comprises a compound represented by formula (2) and/or a compound represented by formula (3):

wherein in formula (2), 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 bond to form a ring;

wherein in formula (3), 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 bond to form a ring.

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

wherein in formula (2a), 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 bond to form a ring,

wherein in formula (3a), 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 bond to form a ring.

5. The method for isomerizing a cyclohexanediamine 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 a cyclohexanediamine according to claim 1 , wherein the imine compound is obtained by dehydration condensation between the cyclohexanediamine and an aldehyde and/or a ketone.

7. The method for isomerizing a cyclohexanediamine according to claim 1 , wherein the cyclohexanediamine is 1,4-cyclohexanediamine.

8. The method for isomerizing a cyclohexanediamine according to claim 1 , 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 a cyclohexanediamine according to claim 1 , wherein an isomerization reaction temperature in the isomerizing is 100 to 140° C.

10. The method for isomerizing a cyclohexanediamine according to claim 9 , wherein, in the isomerizing, a solvent having a boiling point equal to or lower than the isomerization reaction temperature is used.

11. The method for isomerizing a cyclohexanediamine according to claim 1 , wherein, in the isomerizing, bubbling is performed by an inert gas.

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

• C07B61/00

  Other general methods · CPC title

• C07C2601/14

  The ring being saturated · 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

• C07C209/88 Primary

  Separation of optical isomers · CPC title