Method for producing glyceric acid ester

Patent metadata

Field	Value
Publication number	US-10829482-B2
Application number	US-201716473177-A
Country	US
Kind code	B2
Filing date	Dec 26, 2017
Priority date	Dec 27, 2016
Publication date	Nov 10, 2020
Grant date	Nov 10, 2020

Abstract

The present invention is to provide a method of producing a glyceric acid ester which is easy for production and high in yield, and in which a pyridine to be used for the reaction is easily reused. Provided is a method of producing a compound represented by the following formula (II), including a step of oxidatively esterifying Compound A represented by the following formula (I) with Compound B selected from an organic nitroxyl radical, an N-hydroxy form thereof, and a salt containing an oxo ammonium cation of them, and an oxidizing agent in the presence of a pyridine having an alkyl substituent, wherein the use amount of Compound B is 0.0001 or more and 0.1 or less in terms of a molar ratio relative to Compound A:

wherein, in the formulae (I) and (II), R 1 and R 2 each independently represent a hydrogen atom or a monovalent hydrocarbon group, or R 1 and R 2 are bonded to each other to form a divalent hydrocarbon group for constituting a ring structure.

First claim

The invention claimed is:

1. A method of producing a compound represented by the following formula (II), comprising a step of oxidatively esterifying Compound A, Compound A being represented by the following formula (I), with Compound B, Compound B being selected from an organic nitroxyl radical, an N-hydroxy form thereof, and a salt containing an oxo ammonium cation of them, and an oxidizing agent, and in the presence of a pyridine having an alkyl substituent, wherein the molar ratio of Compound B to Compound A (B:A) used in the oxidative esterification is in the range from 0.0001:1 through 0.1:1:

wherein, in the formula (I), R 1 and R 2 each independently represent a hydrogen atom or a monovalent hydrocarbon group, or R 1 and R 2 are bonded to each other to form a divalent hydrocarbon group for constituting a ring structure; and

wherein, in the formula (II), R 1 and R 2 each independently represent a hydrogen atom or a monovalent hydrocarbon group, or R 1 and R 2 are bonded to each other to form a divalent hydrocarbon group for constituting a ring structure.

2. The production method according to claim 1 , wherein in Compound A, R 1 is a hydrogen atom, and R 2 is a hydrogen atom or a monovalent hydrocarbon group.

3. The production method according to claim 1 , wherein in Compound A, R 1 and R 2 are each a monovalent hydrocarbon group.

4. The production method according to claim 1 , wherein the pyridine having an alkyl substituent is a pyridine having an alkyl substituent at at least one position selected from the 3-position, the 4-position, and the 5-position and not having an alkyl substituent at the 2-position and the 6-position; and Compound B is a compound selected from an organic nitroxyl radical and a salt containing an oxo ammonium cation thereof.

5. The production method according to claim 1 , wherein Compound B is an N-hydroxy form of an organic nitroxyl radical.

6. The production method according to claim 1 , wherein the alkyl substituent each independently has 1 or more and 4 or less carbon atoms.

7. The production method according to claim 1 , comprising a step of oxidatively esterifying a mixture of a compound represented by the following formula (I) and a compound represented by the following formula (V):

wherein, in the formulae (I) and (V), R 1 and R 2 each independently represent a hydrogen atom or a monovalent hydrocarbon group, or R 1 and R 2 are bonded to each other to form a divalent hydrocarbon group for constituting a ring structure.

8. The production method according to claim 1 , wherein the organic nitroxyl radical is a compound represented by the following formula (VIII), a compound represented by the following formula (IX), or a compound represented by the following formula (X):

wherein, in the formula (VIII), R 4 represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, art alkoxycarbonyl group, an amino group, an acylamino group, a sulfonyloxy group, an N-alkylcarbamoyloxy group, a carboxy group, a cyano group, an isocyanato group, an isothiocyanato group, or an oxo group; in the formula (IX), R 5 and R 6 each independently represent a hydrogen atom or a methyl group; and, in the formula (X), R 7 and R 8 each independently represent a hydrogen atom or a methyl group.

9. The production method according to claim 1 , wherein the oxidizing agent is an oxidizing agent composed of a compound containing chlorine.

10. The production method according to claim 1 , comprising, after the step of oxidatively esterifying the compound represented by the formula (I), a step of separating the compound represented by the formula (II).

11. The production method according to claim 10 , wherein the step of separating the compound represented by the formula (II) is separation through distillation.

Assignees

• Kao Corp

Inventors

• Aoki Takashi

Classifications

• C07C45/65

  by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups · CPC title

• C07D407/12 Primary

  linked by a chain containing hetero atoms as chain links · CPC title

• C07D317/72 Primary

  spiro-condensed with carbocyclic rings · CPC title

• C07B41/12

  of carboxylic acid ester groups · CPC title

• C07B61/00

  Other general methods · CPC title