2,6-bis-(aminomethyl)piperidine derivatives

Patent metadata

Field	Value
Publication number	US-9695121-B2
Application number	US-201414764010-A
Country	US
Kind code	B2
Filing date	Jan 27, 2014
Priority date	Jan 30, 2013
Publication date	Jul 4, 2017
Grant date	Jul 4, 2017

Abstract

The present invention relates to 2,6-bis(aminomethyl)piperidine derivatives as such (in the following text abbreviated to “2,6-BAMP derivatives”) which are defined by the general formula (I) shown in the following text. In addition, the present invention relates to a process for preparing such 2,6-BAMP derivatives by hydrogenation of the corresponding 2,6-dicyanopiperidine derivatives (hereinafter abbreviated to “2,6-DCP derivatives”) in the presence of a catalyst. The present invention further provides for the use of the 2,6-BAMP derivatives of the invention as hardeners for epoxy resins, as intermediate in the preparation of diisocyanates, which play an important role in the production of polyurethanes, as starters in the preparation of polyetherols and/or as monomers for polyamide production. The present invention further relates to the diisocyanates as such prepared from the 2,6-BAMP derivatives and also the corresponding preparative process.

First claim

The invention claimed is:

1. A 2,6-bis(aminomethyl)piperidine derivative (2,6-BAMP derivative) of the general formula (I),

where:
A, B and D are each, independently of one another, CH 2 , CHR 2 or CR 2 R 3 ;
R 1 is unsubstituted or at least monosubstituted C 1 -C 30 -alkyl, unsubstituted or at least monosubstituted C 2 -C 10 -alkenyl or unsubstituted or at least monosubstituted aryl,
where the substituents are selected from the group consisting of C 1 -C 4 -alkyl, aryl 2 , —OR 4 , —C(O)R 6 , —C(O)OR 4 , —O—C(O)R 6 , —NR 4 R 5 or halogen,
and aryl 2 can in turn be at least monosubstituted by C 1 -C 4 -alkyl, —OR 4 , —C(O)R 6 , —C(O)OR 4 , —O—C(O)R 6 , —NR 4 R 5 or halogen;
R 2 and R 3 are each, independently of one another, unsubstituted or at least monosubstituted C 1 -C 10 -alkyl or unsubstituted or at least monosubstituted aryl, where the substituents are selected from the group consisting of C 1 -C 4 -alkyl, —OR 4 , —C(O)OR 4 , —O—C(O)R 6 , —NR 4 R 5 or halogen;
R 4 and R 5 are each, independently of one another, hydrogen or unsubstituted C 1 -C 4 -alkyl;
R 6 is unsubstituted C 1 -C 10 -alkyl.

2. The 2,6-BAMP derivative according to claim 1 , wherein the 2,6-BAMP derivative is defined according to the general formula (la),

where:
R 1 is unsubstituted or at least monosubstituted C 1 -C 10 -alkyl, unsubstituted or at least monosubstituted C 2 -C 10 -alkenyl or unsubstituted or at least monosubstituted aryl, where the substituents are selected from the group consisting of C 1 -C 4 -alkyl, aryl 2 , —OR 4 , —NR 4 R 5 or halogen, and aryl 2 can in turn be at least monosubstituted by C 1 -C 4 -alkyl, —OR 4 , —NR 4 R 5 or halogen; and
R 4 and R 5 are each, independently of one another, hydrogen or unsubstituted C 1 -C 4 -alkyl.

3. The 2,6-BAMP derivative according to claim 1 , wherein:
R 1 is unsubstituted or at least monosubstituted C 1 -C 4 -alkyl and the substituent is —NR 4 R 5 ; and
R 4 and R 5 are each, independently of one another, hydrogen or unsubstituted C 1 -C 4 -alkyl.

4. A process for preparing a 2,6-bis-aminomethyl)piperidine derivative, a 2,6-BAMP-derivative, according to the general formula (I)

wherein the 2,6-BAIMP-derivative is obtained from the corresponding 2,6-dicyanopiperidine derivative, the 2,6-DCP-derivative, of the general formula (II) or (IIa)

by hydrogenation in the presence of a catalyst,
wherein
A, B and D are each, independently of one another, CH 2 , CHR 2 or CR 2 R 3 ;
R 1 is unsubstituted or at least monosubstituted C 1 C 30 -alkyl, unsubstituted or at least monosubstituted C 2 -C 10 -alkenyl or unsubstituted or at least monosubstituted aryl, where the substituents are selected from the group consisting of C 1 -C 4 -alkyl, aryl 2 , —OR 4 , —C(O)R 6 , —C(O)OR 4 , —O—C(O)R 6 , —NR 4 R 5 or halogen, and aryl 2 can in turn be at least monosubstituted by C 1 -C 4 alkyl, —OR 4 , —C(O)R 6 , —C(O)R 4 , —O—C(O)R 6 , —NR 4 R 5 or halogen;
R 2 and R 3 are each, independently of one another, unsubstituted or at least monosubstituted C 1 -C 10 -alkyl or unsubstituted or at least monosubstituted aryl, where the substituents are selected from the group consisting of C 1 -C 4 -alkyl, —OR 4 —C(O)R 6 , —C(O)OR 4 , —O—C(O)R 6 , —NR 4 R 5 or halogen;
R 4 and R 5 are each, independently of one another, hydrogen or unsubstituted C 1 -C 4 -alkyl; and
R 6 is unsubstituted C 1 -C 10 -alkyl.

5. The process according to claim 4 , wherein a Raney catalyst, preferably a Raney nickel catalyst or a Raney cobalt catalyst, in particular a Raney cobalt catalyst, which comprises at least one of the elements Fe, Ni or Cr as promoter is used as catalyst.

6. The process according to claim 4 , wherein the hydrogenation is carried out in a solvent which is an amide, an aromatic hydrocarbon, an alcohol, an amine, an ester or an ether.

7. The process according to claim 4 , wherein the hydrogenation is carried out at a pressure from 80 to 200 bar or at a temperature from 90 to 130° C.

8. The process according to claim 4 , wherein the 2,6-DCP derivative used for the hydrogenation is prepared by reaction of i) glutaraldehyde or a glutaraldehyde derivative with ii) hydrogen cyanide (HCN) and iii) an appropriate amine of the formula R 1 NH 2 .

9. A method comprising a step, wherein a 2,6-BAMP derivative according to the definition of the general formula (I) in claim 4 is employed as hardener for epoxy resins.

10. A diisocyanate of the general formula (III),

where:
A, B and D are each, independently of one another, CH 2 , CHR 2 or CR 2 R 3 ;
R 1 is hydrogen, unsubstituted or at least monosubstituted C 1 -C 30 -alkyl, unsubstituted or at least monosubstituted C 2 -C 10 -alkenyl or unsubstituted or at least monosubstituted aryl, where the substituents are selected from the group consisting of C 1 -C 4 -alkyl,aryl 2 , —OR 4 , —C(O)R 6 , —C(O)OR 4 , —O—C(O)R 6 , —NR 4 R 5 or halogen, and aryl 2 can in turn be at least monosubstituted by C 1 -C 4 -alkyl, —OR 4 , —C(O)R 6 , —C(O)OR 4 , —O—C(O)R 6 , —NR 4 R 5 or halogen;
R 2 and R 3 are each, independently of one another, unsubstituted or at least monosubstituted C 1 -C 10 -alkyl or unsubstituted or at least monosubstituted aryl, where the substituents are selected from the group consisting of C 1 -C 4 alkyl, —OR 4 —C(O)R 6 , —C(O)OR 4 , —O—C(O)R 6 , —NR 4 R 5 or halogen;
R 4 and R 5 are each, independently of one another, hydrogen or unsubstituted C 1 -C 4 -alkyl; and
R 6 is unsubstituted C 1 -C 10 -alkyl.

11. The diisocyanate according to claim 10 , wherein the diisocyanate is defined according to the general formula (IIIa),

where:
R 1 is hydrogen, unsubstituted or at least monosubstituted C 1 -C 10 -alkyl or unsubstituted or at least monosubstituted aryl, where the substituents are selected from the group consisting of C 1 -C 4 -alkyl, aryl 2 , —OR 4 , —NR 4 R 5 or halogen, and aryl 2 can in turn be at least monosubstituted by C 1 -C 4 -alkyl, —OR 4 , —NR 4 R 5 or halogen;
R 4 and R 5 are each, independently of one another, hydrogen or unsubstituted C 1 -C 4 -alkyl.

12. A process for preparing a diisocyanate according to claim 10 , wherein a 2,6-BAMP derivative according to the definition of the general formula (II) in claim 4 is reacted with phosgene.

13. A method comprising a step, wherein a 2,6-BAMP derivative according to the definition of the general formula (I) in claim 4 is employed as intermediate in the preparation of diisocyanates.

14. A method comprising a step, wherein a 2,6-BAMP derivative according to the definition of the general formula (I) in claim 4 is employed as starter in the preparation of polyetherol or as monomer for polyamide production.

15. The process according to claim 4 , wherein the hydrogenation is carried out at a pressure from 80 to 200 bar and

Assignees

• Basf Se

Inventors

• Jaegli Stephanie
• Schmidt Thomas
• Oftring Alfred
• Panchenko Alexander
• Dahmen Kirsten
• Molt Oliver

Classifications

• C07D211/60

  Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals · CPC title

• C07D211/26 Primary

  with hydrocarbon radicals, substituted by nitrogen atoms · CPC title

• C07C265/14

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