Amphoteric ester sulfonates

Patent metadata

Field	Value
Publication number	US-2018185801-A1
Application number	US-201815909653-A
Country	US
Kind code	A1
Filing date	Mar 1, 2018
Priority date	Oct 20, 2014
Publication date	Jul 5, 2018
Grant date	—

Abstract

Disclosed are a variety of amphoteric ester sulfonates, including 3-(N, N-dimethyl-cocoylpropylammonio-1-yl)-2-hydroxypropanesulfonate. These amphoteric ester sulfonates 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 compound having the formula 1:

wherein
R is C 3 -C 23 hydrocarbyl;
R 1 is C 3 -C 8 hydrocarbyl;
R 2 and R 3 are each independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 dienyl, C 1 -C 6 trienyl, and C 3 -C 8 cycloalkyl;
wherein at least two of R 1 , R 2 , and R 3 may be connected with the N + to form a heterocyclic ring; and
R 4 is C 1 -C 8 hydrocarbyl substituted with a hydroxyl group.

2 . The compound according to claim 1 , wherein the hydrocarbyl group of R is substituted with one to five substituents selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 carboxyl, C 1 -C 15 aminocarbonyl, C 1 -C 15 amido, cyano, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkanoyloxy, hydroxy, aryl, heteroaryl, thioether, C 2 -C 10 dialkylamino, C 3 -C 15 trialkylammonium, chlorine, and bromine.

3 . The compound according to claim 1 , wherein R is a C 3 -C 8 cycloalkyl group optionally substituted with one to five substituents selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 carboxyl, C 1 -C 15 aminocarbonyl, C 1 -C 15 amido, cyano, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkanoyloxy, hydroxy, aryl, heteroaryl, thioether, C 2 -C 10 dialkylamino, C 3 -C 15 trialkylammonium, chlorine, and bromine.

4 . The compound according to claim 1 , wherein R 1 is selected from branched or straight-chain C 1 -C 8 alkylene, branched- or straight-chain C 2 -C 8 alkenylene, and substituted or unsubstituted C 3 -C 8 cycloalkylene.

5 . The compound according to claim 1 , wherein at least one of R 2 and R 3 is substituted with one to three substituents selected from the group consisting of C 1 -C 6 alkoxy, carboxyl, C 1 -C 15 aminocarbonyl, C 1 -C 15 amido, cyano, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkanoyloxy, hydroxy, aryl, heteroaryl, thioether, C 2 -C 10 dialkylamino, C 3 -C 15 trialkylammonium, chlorine, and bromine.

6 . The compound according to claim 1 , wherein
R is selected from the group consisting of C 5 -C 19 alkyl, C 5 -C 17 alkenyl, C 5 -C 17 dienyl, and C 3 -C 8 cycloalkyl; R 1 is selected from the group consisting of C 3 -C 8 alkylene, C 3 -C 8 alkenylene, and C 3 -C 8 cycloalkylene; R 2 and R 3 are each independently selected from the group consisting of C 1 -C 6 alkyl and C 1 -C 6 alkenyl; wherein R 1 and R 2 may be connected with the N + to form a C 3 -C 8 heterocyclic structure; and R 4 is C 1 -C 8 alkylene substituted with a hydroxyl group.

7 . The compound according to claim 1 , wherein
RCO— is octanoyl, decanoyl, lauroyl, or a C 6 to C 20 acyl radical derived from coconut oil, hydrogenated coconut oil, hydrogenated and/or fractionated coconut oil fatty acids, palm kernel oil, hydrogenated palm kernel oil, or hydrogenated and/or fractionated palm kernel oil fatty acids; R 1 is 1,3-propylene or 1,3-butylene; R 2 and R 3 are methyl; and R 4 is 2-hydroxy-1,3-propylene.

8 . A compound having the formula 1:

wherein
R is C 3 -C 23 hydrocarbyl;
R 1 is C 1 -C 8 hydrocarbyl;
R 2 and R 3 are each independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 dienyl, C 1 -C 6 trienyl, and C 3 -C 8 cycloalkyl;
wherein at least two of R 1 , R 2 , and R 3 are connected with the N + to form a heterocyclic ring; and
R 4 is C 1 -C 8 hydrocarbyl.

9 . The compound according to claim 8 , wherein the heterocyclic ring is selected from the group consisting of pyrrolidinium, piperidinium, pyridinium, quinolinium, tetrahydroquinolinium, indolinium, octahydroindolinium, acridinium, octahydroacridinium, and tetradecahydroacridinium.

10 . The compound according to claim 8 , wherein
RCO— is octanoyl, decanoyl, lauroyl, or a C 6 to C 20 acyl radical derived from coconut oil, hydrogenated coconut oil, hydrogenated and/or fractionated coconut oil fatty acids, palm kernel oil, hydrogenated palm kernel oil, or hydrogenated and/or fractionated palm kernel oil fatty acids; R 1 and R 2 are connected with the N + to form a 3-piperidininum, a 4-piperidinium, a 3-piperidiniummethyl, a 4-piperidiniummethyl, a 3-pyridinum, a 4-pyridinium, a 3-pyridiniummethyl, or a 4-pyridiniummethyl group; R 3 is methyl; and R 4 is ethylene, 1,3-propylene, 1,4-butylene, or 2-hydroxy-1,3-propylene.

11 . A process for preparing a compound having the formula 1:

wherein
R is C 3 -C 23 hydrocarbyl;
R 1 is C 1 -C 8 hydrocarbyl;
R 2 and R 3 are each independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 dienyl, C 1 -C 6 trienyl, and C 3 -C 8 cycloalkyl;
wherein at least two of R 1 , R 2 , and R 3 may be connected with the N + to form a heterocyclic ring; and
R 4 is C 1 -C 8 hydrocarbyl,
the process comprising:
(a) contacting an acid or ester of formula 2 with a dialkylamino-alcohol of formula 3:

in the presence of an enzyme at conditions effective to form an intermediate of formula 4:

wherein R, R 1 , R 2 , and R 3 are as defined above and R 7 is hydrogen or C 1 -C 6 alkyl; and
(b) contacting the intermediate of formula 4 with a sulfonate alkylating agent at conditions effective to form the compound of formula 1.

12 . The process according to claim 11 , wherein the enzyme is a lipase from Pseudomonas sp or Candida antarctica.

13 . The process according to claim 11 , wherein step (a) is carried out at a temperature of 50 to 70° C. and a pressure of 10 Torr (1,333 Pa) to ambient pressure, and wherein step (b) is carried out at a temperature of 50 to 125° C.

14 . The process according to claim 11 , which further comprises removing water or alcohol by-product from the reaction mixture during step (a).

15 . The process according to claim 11 , wherein step (b) is carried out in the presence of a base selected from the group consisting of metal hydroxides, metal carbonates, and metal bicarbonates; and wherein step (b) is carried out in the presence of a solvent selected from the group consisting of water, C 2 -C 5 alcohols, ether-alcohols, and mixtures thereof.

16 . The process according to claim 11 , wherein the sulfonate alkylating agent is selected from the group consisting of 1,3-propanesultone, 1,4-butanesultone, sodium 2-chloroethanesulfonate, and sodium 3-chloro-2-hydroxypropanesulfonate.

17 . The process according to claim 11 , wherein
R is selected from the group consisting of C 5 -C 19 alkyl, C 5 -C 17 alkenyl, C 5 -C 17 dienyl, and C 3 -C 8 cycloalkyl; R 1 is selected from the group consisting of C 1 -C 8 alkylene, C 2 -C 8 alkenylene, and C 3 -C 8 cycloalkylene; R 2 and R 3 are each independently selected from the group consisting of C 1 -C 6 alkyl and C 1 -C 6 alkenyl; wherein R 1 and R 2 may be connected with the N + to form a C 3 -C 8 heterocyclic structure; and R 4 is C 1 -C 8 alkylene.

18 . The process according to claim 11 , wherein at least two of R 1 , R 2 , and R 3 are connected with the N + to form a heterocyclic ring

Assignees

• Eastman Chem Co

Inventors

• Boaz Neil Warren
• Boone Matthew Allen
• Lloyd Jennifer Michelle

Classifications

• C07D211/46

  having a hydrogen atom as the second substituent in position 4 · CPC title

• C07C309/14 Primary

  containing amino groups bound to the carbon skeleton · CPC title

• C07D211/22

  by oxygen atoms · CPC title

• C11D1/92

  Sulfobetaines {; Sulfitobetaines} · CPC title

• C12P13/001

  Amines; Imines · CPC title