Amphoteric compounds

Patent metadata

Field	Value
Publication number	US-12516019-B2
Application number	US-202217864827-A
Country	US
Kind code	B2
Filing date	Jul 14, 2022
Priority date	Sep 17, 2015
Publication date	Jan 6, 2026
Grant date	Jan 6, 2026

Abstract

Disclosed are a variety of amphoteric compounds containing a quaternary nitrogen group, a covalently bound counterion, and an ester or amide group. These amphoteric compounds can be advantageously prepared via a chemoenzymatic green process, and exhibit good surfactant properties.

First claim

We claim:

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

wherein
R is a C 3 -C 24 hydrocarbyl group;
R 1 is a C 2 -C 8 hydrocarbyl group;
R 2 and R 3 are each independently a C 1 -C 6 alkyl or alkenyl group;
at least two of R 1 , R 2 , and R 3 may be connected with the N + to form a heterocyclic ring;
R 4 is a C 1 -C 8 hydrocarbyl group;
X is O or NH; and
Y − is CO 2 − , SO 3 − , SO 4 − , PO 3 −2 , or PO 4 −2 ,
the process comprising:
(a) contacting an amine or alcohol of formula 2 with an amino acid derivative 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 , R 3 , and X are as defined above and R 7 is hydrogen or a C 1 -C 4 alkyl group; and
(b) contacting the intermediate of formula 4 with a carboxylate, sulfonate, sulfate, phosphonate, or phosphate alkylating agent at conditions effective to form the compound of formula 1.

2 . The process according to claim 1 , wherein the enzyme is a lipase from Pseudomonas sp or Candida antarctica.

3 . The process according to claim 1 , wherein the alkylating agent is selected from the group consisting of sodium chloroacetate, 1,3-propanesultone, 1,4-butanesultone, sodium 2-chloroethanesulfonate, sodium 3-chloro-2-hydroxypropanesulfonate, 1,2-ethylene sulfate, 1,3-propylene sulfate, 3-bromopropanesulfate, sodium chloromethylphosphonate, sodium 3-chloro-2-hydroxypropylphosphate, sodium 2-chloroethylphosphate, sodium 3-chloro-2-propylphosphate, sodium 2-chloroethoxyethylphosphate, sodium 2,3-epoxypropylphosphate, and sodium 4-chlorobutylphosphate.

4 . The process according to claim 1 , wherein R 4 is substituted with a hydroxyl group.

5 . The process according to claim 1 , wherein
R is selected from the group consisting of C 6 -C 20 alkyl, C 6 -C 18 alkenyl, C 6 -C 18 dienyl, and C 3 -C 8 cycloalkyl; R 1 is a C 3 -C 4 alkylene group; 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; R 4 is selected from the group consisting of methylene, ethylene, propylene, butylene, and hydroxypropylene; X is O or NH; and Y − is CO 2 − or SO 3 − .

6 . The process according to claim 1 , wherein
R is selected from the group consisting of C 6 -C 20 alkyl, C 6 -C 18 alkenyl, and C 6 -C 18 dienyl; R 1 is 1,3-propylene or 1,4-butylene; R 2 and R 3 are both methyl; R 4 is 2-hydroxy-1,3-propylene; X is O or NH; and Y − is SO 3 − .

7 . The process according to claim 6 , wherein X is NH.

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

9 . The process 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 process according to claim 1 , wherein
R is lauryl, myristyl, cetyl, stearyl, or a C 6 to C 20 alkyl radical derived from a vegetable oil, a nut oil, or a seed oil; R 1 is ethylene, 1,3-propylene, or 1,4-butylene; R 2 and R 3 are both methyl; R 4 is methylene, ethylene, propylene, butylene, or hydroxypropylene; X is O or NH; and Y − is CO 2 − or SO 3 − .

11 . The process according to claim 1 , wherein
R is lauryl, myristyl, cetyl, stearyl, or a C 6 to C 20 alkyl radical derived from a vegetable oil, a nut oil, or a seed oil; R 1 and R 2 combine with the N + to form a 3-piperidinium, a 4-piperidinium, a 3-piperidiniummethyl, a 4-piperidiniummethyl, a 3-pyridinium, a 4-pyridinium, a 3-pyridiniummethyl, or a 4-pyridiniummethyl group; R 3 is methyl; R 4 is methylene, ethylene, propylene, butylene, or hydroxypropylene; X is O or NH; and Y − is CO 2 − or SO 3 − .

12 . The process according to claim 11 , wherein X is NH.

13 . The process according to claim 1 , wherein
R is lauryl, myristyl, or a C 6 to C 20 alkyl radical derived from a vegetable oil, a nut oil, or a seed oil; R 1 is 1,3-propylene or 1,4-butylene; R 2 and R 3 are both methyl; R 4 is 2-hydroxy-1,3-propylene; X is O or NH; and Y − is SO 3 − .

14 . The process according to claim 13 , wherein X is NH.

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

wherein
R is a C 3 -C 24 hydrocarbyl group;
R 1 is a C 2 -C 8 hydrocarbyl group;
R 2 and R 3 are each independently a C 1 -C 6 alkyl or alkenyl group;
at least two of R 1 , R 2 , and R 3 may be connected with the N + to form a heterocyclic ring;
R 4 is a C 1 -C 8 hydrocarbyl group;
X is O or NH; and
Y − is CO 2 − , SO 3 − , SO 4 − , PO 3 −2 , or PO 4 −2 , and

wherein the at least two compounds have at least one different R substituent,
the process comprising:
(a) contacting a mixture comprising at least two amines or alcohols of formula 2 with an amino acid derivative of formula 3:

in the presence of an enzyme at conditions effective to form at least two intermediates of formula 4:

wherein
R, R 1 , R 2 , R 3 , and X are as defined above,
R 7 is hydrogen or a C 1 -C 4 alkyl group,
the at least two amines or alcohols of the formula 2 have different R substituents, and
the at least two intermediates of the formula 4 have different R substituents; and
(b) contacting the at least two intermediates of formula 4 with a carboxylate, sulfonate, sulfate, phosphonate, or phosphate alkylating agent at conditions effective to form the mixture of at least two compounds of the formula 1.

16 . The process according to claim 15 , wherein
R is lauryl, myristyl, cetyl, stearyl, or a C 6 to C 20 alkyl radical derived from a vegetable oil, a nut oil, or a seed oil; R 1 is ethylene, 1,3-propylene, or 1,4-butylene; R 2 and R 3 are both methyl; R 4 is methylene, ethylene, propylene, butylene, or hydroxypropylene; X is O or NH; and Y − is CO 2 − or SO 3 − .

17 . The process according to claim 15 , wherein
R is lauryl, myristyl, cetyl, stearyl, or a C 6 to C 20 alkyl radical derived from a vegetable oil, a nut oil, or a seed oil; R 1 and R 2 combine with the N + to form a 3-piperidinium, a 4-piperidinium, a 3-piperidiniummethyl, a 4-piperidiniummethyl, a 3-pyridinium, a 4-pyridinium, a 3-pyridiniummethyl, or a 4-pyridiniummethyl group; R 3 is methyl; R 4 is methylene, ethylene, propylene, butylene, or hydroxypropylene; X is O or NH; and Y − is CO 2 − or SO 3 − .

18 . The process according to claim 15 , wherein
R is lauryl, myristyl, or a C 6 to C 20 alkyl radical derived from a vegetable oil, a nut oil, or a seed oil; R 1 is 1,3-propylene or 1,4-butylene; R 2 and R 3 are both methyl; R 4 is

Assignees

• Eastman Chem Co

Inventors

• Boaz Neil Warren
• Clendennen Stephanie Kay
• Zhang Yuan
• Fevola Michael James
• Fütterer Tobias Johannes

Classifications

• C12P13/02

  Amides, e.g. chloramphenicol {or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes (peptides C12P21/00 or C07K)} · CPC title

• C12P13/001

  Amines; Imines · CPC title

• C09K15/28

  containing nitrogen, oxygen and sulfur · CPC title

• C09K15/20

  containing nitrogen and oxygen · CPC title

• C07C303/08

  by reaction with halogenosulfonic acids · CPC title