Isomerization method for bis (aminomethyl) cyclohexane

Patent metadata

Field	Value
Publication number	US-9604905-B2
Application number	US-201414916882-A
Country	US
Kind code	B2
Filing date	Sep 17, 2014
Priority date	Sep 17, 2013
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

A method for isomerizing a bis(aminomethyl)cyclohexane, including an isomerization step of isomerizing the bis(aminomethyl)cyclohexane in the presence of an imine compound represented by the following general formula (1) and at least one compound 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, and an acyl group (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 substituted or unsubstituted hydrocarbon groups; and n represents an integer of 1 to 10.

First claim

The invention claimed is:

1. A method for isomerizing a bis(aminomethyl)cyclohexane, comprising:
an isomerization step of isomerizing the bis(aminomethyl)cyclohexane in the presence of:
an imine compound represented by formula (1) and
at least one compound 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 (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 substituted or unsubstituted hydrocarbon groups; and n represents an integer of 1 to 10.

2. The method for isomerizing the bis(aminomethyl)cyclohexane 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 the bis(aminomethyl)cyclohexane according to claim 1 , wherein the imine compound comprises a compound represented by the following general formula (2) and/or a compound represented by the following general 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 (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 (R 1 and R 2 may mutually bind to form a ring).

4. The method for isomerizing the bis(aminomethyl)cyclohexane according to claim 2 , wherein the aliphatic hydrocarbon group comprises a linear or branched and substituted or unsubstituted aliphatic hydrocarbon group.

5. The method for isomerizing the bis(aminomethyl)cyclohexane according to claim 2 , wherein the alicyclic hydrocarbon group comprises an alicyclic hydrocarbon group having an amino group.

6. The method for isomerizing the bis(aminomethyl)cyclohexane according to claim 2 , wherein the aromatic hydrocarbon group comprises a monovalent group selected from the group consisting of a substituted or unsubstituted benzyl group, a substituted or unsubstituted benzal group, a substituted or unsubstituted monovalent phenyl group and a substituted or unsubstituted monovalent naphthyl group.

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

8. The method for isomerizing the bis(aminomethyl)cyclohexane according to claim 1 , wherein the imine compound is obtained by dehydration condensation between the bis(aminomethyl)cyclohexane and an aldehyde and/or a ketone.

9. The method for isomerizing the bis(aminomethyl)cyclohexane according to claim 7 , wherein the aldehyde comprises at least one selected from the group consisting of an aliphatic aldehyde represented by the following general formula (6), an aromatic aldehyde represented by the following general formula (7) and an aromatic aldehyde represented by the following general formula (8):

wherein R 22 represents a hydrogen atom or a monovalent substituent selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted alicyclic hydrocarbon group;

wherein R 10′ , R 11′ , R 12′ , R 13′ and R 14′ each independently represent a hydrogen atom or at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group and an amino group; and X 1′ represents a single bond or a divalent alkyl group having 1 to 10 carbon atoms;

wherein R 15′ , R 16′ , R 17′ , R 18′ , R 19′ , R 20′ and R 21′ each independently represent a hydrogen atom or at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group and an amino group; and X 2′ represents a single bond or a divalent alkyl group having 1 to 10 carbon atoms.

10. The method for isomerizing the bis(aminomethyl)cyclohexane according to claim 8 , wherein the aldehyde comprises:
at least one aliphatic aldehyde selected from the group consisting of formaldehyde, acetaldehyde, isobutyraldehyde, n-decylaldehyde, methacrolein, cinnamaldehyde and glyoxal; and/or
at least one aromatic aldehyde selected from the group consisting of benzaldehyde, 4-methylbenzaldehyde, 4-ethylbenzaldehyde, 4-isopropylbenzaldehyde, 4-isobutylbenzaldehyde, 2,4-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde and 4-biphenylaldehyde.

11. The method for isomerizing the bis(aminomethyl)cyclohexane according to claim 8 , wherein the ketone comprises at least one selected from the group consisting of an aliphatic ketone, an aromatic ketone, an aliphatic aromatic ketone and a cyclic ketone.

12. The method for isomerizing the bis(aminomethyl)cyclohexane according to claim 8 , wherein the ketone comprises at least one selected from the group consisting of methyl ethyl ketone and acetophenone.

13. The method for isomerizing the bis(aminomethyl)cyclohexane 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.

14. The method for isomerizing the bis(aminomethyl)cyclohexane according to claim 1 , wherein the compound comprises at least one selected from the group consisting of metallic sodium, sodium amide and sodium hydride.

15. The method for isomerizing the bis(aminomethyl)cyclohexane according to claim 1 , wherein the bis(aminomethyl)cyclohexane comprises 1,4-bis(aminomethyl)cyclohexane and/or 1,3-bis(aminomethyl)cyclohexane.

16. The method for isomerizing

Assignees

• Mitsubishi Gas Chemical Co

Inventors

• Yamamoto Yoshiaki
• Sameshima Yuko
• Okamura Takuya

Classifications

• C07C209/86

  Separation · CPC title

• C07C251/24

  having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings · 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

• C07C2101/14

  Chemistry & Metallurgy · mapped topic

• C07C211/18

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