Heterocyclic amphoteric compounds

Patent metadata

Field	Value
Publication number	US-9533951-B2
Application number	US-201414518517-A
Country	US
Kind code	B2
Filing date	Oct 20, 2014
Priority date	Oct 20, 2014
Publication date	Jan 3, 2017
Grant date	Jan 3, 2017

Abstract

Disclosed are a variety of amphoteric compounds having a heterocyclic quaternary nitrogen group. The heterocycle includes pyridines, piperidines, and pyrrolidines, and is linked to the hydrophobe via either an amide or an ester linkage. These heterocyclic amphoteric compounds can be advantageously prepared in high yield and purity by a two-step chemoenzymatic process, and have excellent surfactant properties.

First claim

We claim:

1. A mixture comprising at least two compounds having the formula 1:

wherein
R is a C 3 -C 23 hydrocarbyl group;
R 1 is a C 1 -C 4 hydrocarbyl group;
HETN is piperidine;
X is O or NH
n is 0 or 1; and
m is 0 or 1 and is chosen to afford a quaternary heterocyclic nitrogen, and wherein the at least two compounds have at least one different R substituent.

2. The mixture according to claim 1 , wherein
RCO— is selected from octanoyl, decanoyl, lauroyl, myristoyl, and a C 6 to C 20 acyl radical derived from coconut oil, hydrogenated coconut oil, or hydrogenated and/or fractionated coconut oil fatty acids;
R 1 is methyl;
HETN is a 3-piperidine group or a 4-piperidine group; and
m is 1.

3. The mixture according to claim 2 , wherein the at least two compounds have different R substituents selected from C 6 to C 20 acyl radicals derived from coconut oil, hydrogenated coconut oil, or hydrogenated and/or fractionated coconut oil fatty acids.

4. The mixture according to claim 2 , wherein RCO— in one compound is lauroyl and RCO— in another compound is myristoyl.

5. The mixture according to claim 2 , wherein RCO— in one compound is octanoyl and RCO— in another compound is decanoyl.

6. The mixture according to claim 1 , wherein
RCO— is selected from octanoyl, decanoyl, lauroyl, myristoyl, and a C 6 to C 20 acyl radical derived from coconut oil, hydrogenated coconut oil, or hydrogenated and/or fractionated coconut oil fatty acids;
HETN is a 3-pyridine group or a 4-pyridine group; and
m is 0.

7. The mixture according to claim 6 , wherein the at least two compounds have different R substituents selected from C 6 to C 20 acyl radicals derived from coconut oil, hydrogenated coconut oil, or hydrogenated and/or fractionated coconut oil fatty acids.

8. The mixture according to claim 6 , wherein RCO— in one compound is lauroyl and RCO— in another compound is myristoyl.

9. The mixture according to claim 6 , wherein RCO— in one compound is octanoyl and RCO— in another compound is decanoyl.

10. A process for preparing a mixture comprising at least two compounds having the formula 1:

wherein
R is a C 3 -C 23 hydrocarbyl group;
R 1 is a C 1 -C 8 hydrocarbyl group;
HETN is piperidine;
X is O or NH;
n is 0 or 1; and
m is 0 or 1 and is chosen to afford a quaternary heterocyclic nitrogen, and wherein the at least two compounds have different R substituents,
the process comprising:
(a) contacting a mixture comprising at least two acids or esters of formula 2 with a heterocyclic alcohol of formula 3 or a heterocyclic amine of formula 4:
HO—(CH 2 ) n —HETN—(R 1 ) p    3

H 2 N—(CH 2 ) n —HETN—(R 1 ) p    4

in the presence of an enzyme at conditions effective to form at least two intermediates of formula 5:

wherein
R, R 1 , X, HETN, and n are as defined above,
R 4 is hydrogen or a C 1 -C 6 alkyl group,
p is 0 or 1 and is chosen to afford a tertiary heterocyclic amine,
the at least two acids or esters of the formula 2 have different R substituents, and
the at least two intermediates of the formula 5 have different R substituents; and
(b) contacting the intermediates of the formula 5 with an acetic acid alkylating agent at conditions effective to form the mixture of at least two compounds of the formula 1.

11. The process according to claim 10 , wherein the acetic acid alkylating agent is sodium chloroacetate or chloroacetic acid neutralized in situ with sodium hydroxide.

12. The process according to claim 10 , wherein
RCO— is selected from octanoyl, decanoyl, lauroyl, myristoyl, and a C 6 to C 20 acyl radical derived from coconut oil, hydrogenated coconut oil, or hydrogenated and/or fractionated coconut oil fatty acids;
R 1 is methyl;
HETN is a 3-piperidine group or a 4-piperidine group; and
m is 1.

13. The process according to claim 12 , wherein the at least two compounds have different R substituents selected from C 6 to C 20 acyl radicals derived from coconut oil, hydrogenated coconut oil, or hydrogenated and/or fractionated coconut oil fatty acids.

14. The process according to claim 12 , wherein RCO— in one compound is lauroyl and RCO— in another compound is myristoyl.

15. The process according to claim 12 , wherein RCO— in one compound is octanoyl and RCO— in another compound is decanoyl.

16. The process according to claim 10 , wherein
RCO— is selected from octanoyl, decanoyl, lauroyl, myristoyl, and a C 6 to C 20 acyl radical derived from coconut oil, hydrogenated coconut oil, or hydrogenated and/or fractionated coconut oil fatty acids;
HETN is a 3-pyridinium group or a 4-pyridinium group; and
m is 0.

17. The process according to claim 16 , wherein the at least two compounds have different R substituents selected from C 6 to C 20 acyl radicals derived from coconut oil, hydrogenated coconut oil, or hydrogenated and/or fractionated coconut oil fatty acids.

18. The process according to claim 16 , wherein RCO— in one compound is lauroyl and RCO— in another compound is myristoyl.

19. The process according to claim 16 , wherein RCO— in one compound is octanoyl and RCO— in another compound is decanoyl.

20. The process according to claim 10 , wherein
R 1 is a C 1 -C 4 hydrocarbyl group.

Assignees

• Eastman Chem Co

Inventors

• Boaz Neil Warren
• Boone Matthew Allen

Classifications

• A61Q19/00

  Preparations for care of the skin · CPC title

• C07D213/75

  Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates · CPC title

• C07D211/44 Primary

  attached in position 4 · CPC title

• C07D213/30

  Oxygen atoms · CPC title

• C07D211/58

  attached in position 4 · CPC title