Vinylether compounds and processes for preparing aldehyde compounds and a carboxylate compound therefrom

Patent metadata

Field	Value
Publication number	US-12415769-B2
Application number	US-202217861622-A
Country	US
Kind code	B2
Filing date	Jul 11, 2022
Priority date	Jul 13, 2021
Publication date	Sep 16, 2025
Grant date	Sep 16, 2025

Abstract

The present invention provides a vinylether compound of the following general formula (1), wherein R 1 represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, and the wavy line represents the E-form, the Z-form, or a mixture thereof. The present invention further provides a process for preparing 2,3,4,4-tetramethyl-1-cyclopentenecarbaldehyde of the following formula of the following formula (2), the process comprising subjecting the vinylether compound (1) to a hydrolysis reaction to form 2,3,4,4-tetramethyl-1-cyclopentenecarbaldehyde (2).

First claim

The invention claimed is:

1. A process for preparing 2,3,4,4-tetramethyl-1-cyclopentenecarbaldehyde of the following formula (2), the process comprising
subjecting a vinylether compound of the following general formula (1) to a hydrolysis reaction to form 2,3,4,4-tetramethyl-1-cyclopentenecarbaldehyde (2)

wherein in the general formula (1), R 1 represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, and the wavy line represents the E-form, the Z-form, or a mixture thereof.

2. A process for preparing 2,3,4,4-tetramethylcyclopentanecarbaldehyde of the following formula (3), the process comprising:
the process according to claim 1 for preparing 2,3,4,4-tetramethyl-1-cyclopentenecarbaldehyde (2), and
subjecting 2,3,4,4-tetramethyl-1-cyclopentenecarbaldehyde (2) thus obtained to a hydrogenation reaction to form 2,3,4,4-tetramethylcyclopentanecarbaldehyde (3)

3. The process for preparing a (2,3,4,4-tetramethylcyclopentyl)methyl carboxylate compound of the following general formula (5), the process comprising:
the process according to claim 2 for preparing 2,3,4,4-tetramethylcyclopentanecarbaldehyde (3),
subjecting 2,3,4,4-tetramethylcyclopentanecarbaldehyde (3) thus obtained to a reduction reaction with a reducing agent to form (2,3,4,4-tetramethylcyclopentyl)methanol of the following formula (4), and subjecting (2,3,4,4-tetramethylcyclopentyl)methanol (4) thus obtained to an esterification reaction to form the (2,3,4,4-tetramethylcyclopentyl)methyl carboxylate compound (5)

wherein in the general formula (5), R 2 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms.

4. The process for preparing the (2,3,4,4-tetramethylcyclopentyl)methyl carboxylate compound (5) according to claim 3 , wherein the carboxylate compound (5) is (2,3,4,4-tetramethylcyclopentyl)methyl acetate of the following formula (5A) and comprises (1R*,2R*,3S*)-(2,3,4,4-tetramethylcyclopentyl)methyl acetate of the following formula (5A′) in a diastereomeric ratio, dr, of 50% or more among four diastereomers of (2,3,4,4-tetramethylcyclopentyl)methyl acetate

wherein in the formulae (5A) and (5A′), Ac represents an acetyl group, and (R*), (S*), the bold bond, and the hashed bond represents a relative configuration.

5. The process according to claim 4 , wherein 2,3,4,4-tetramethylcyclopentanecarbaldehyde (3) is as (1RS,2R*,3S*)-2,3,4,4-tetramethylcyclopentanecarbaldehyde of the following formula (3′), the process further comprising
subjecting (1RS,2R*,3S*)-2,3,4,4-tetramethylcyclopentanecarbaldehyde (3′) to an isomerization reaction to form (1R*,2R*,3S*)-2,3,4,4-tetramethylcyclopentanecarbaldehyde of the following formula (3″);
wherein the reduction reaction is carried out on (1R*,2R*,3S*)-2,3,4,4-tetramethylcyclopentanecarbaldehyde (3″) thus obtained to form (1R*,2R*,3S*)-(2,3,4,4-tetramethylcyclopentyl)methanol (4′); and
wherein the esterification reaction is carried out on (1R*,2R*,3S*)-(2,3,4,4-tetramethylcyclopentyl)methanol (4′) thus obtained to form (1R*,2R*,3S*)-(2,3,4,4-tetramethylcyclopentyl)methyl acetate (5A′)

wherein the bold bond and the hashed bond represents a relative configuration.

6. The process for preparing 2,3,4,4-tetramethyl-1-cyclopentenecarbaldehyde (2) according to claim 1 , the process further comprising
subjecting 2,3,4,4-tetramethyl-2-cyclopentenone of the following formula (6) to a Wittig reaction with a phosphorus ylide compound of the following general formula (7) to form the vinylether compound (1)

wherein, in the general formula (7), R 1 represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, and Ph represents a phenyl group.

7. The process for preparing 2,3,4,4-tetramethylcyclopentanecarbaldehyde (3) according to claim 2 , the process further comprising
subjecting 2,3,4,4-tetramethyl-2-cyclopentenone of the following formula (6) to a Wittig reaction with a phosphorus ylide compound of the following general formula (7) to form the vinylether compound (1)

wherein, in the general formula (7), R 1 represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, and Ph represents a phenyl group.

8. The process according to claim 3 for preparing the (2,3,4,4-tetramethylcyclopentyl)methyl carboxylate compound (5), the process further comprising
subjecting 2,3,4,4-tetramethyl-2-cyclopentenone of the following formula (6) to a Wittig reaction with a phosphorus ylide compound of the following general formula (7) to form the vinylether compound (1)

wherein, in the general formula (7), R 1 represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, and Ph represents a phenyl group.

9. The process according to claim 4 for preparing the (2,3,4,4-tetramethylcyclopentyl)methyl carboxylate compound (5), the process further comprising
subjecting 2,3,4,4-tetramethyl-2-cyclopentenone of the following formula (6) to a Wittig reaction with a phosphorus ylide compound of the following general formula (7) to form the vinylether compound (1)

wherein, in the general formula (7), R 1 represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, and Ph represents a phenyl group.

10. A vinylether compound of the following general formula (1):

wherein R 1 represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, and the wavy line represents the E-form, the Z-form, or a mixture thereof.

11. 2,3,4,4-Tetramethyl-1-cyclopentenecarbaldehyde of the following formula (2):

Assignees

• Shinetsu Chemical Co

Inventors

• Watanabe Takeru
• Kinsho Takeshi

Classifications

• C07C45/513 Primary

  the singly bound functional group being an etherified hydroxyl group · CPC title

• C07C45/62

  by hydrogenation of carbon-to-carbon double or triple bonds · CPC title

• C07C29/14

  of a —CHO group · CPC title

• C07B2200/07

  Optical isomers · CPC title

• C07C67/08

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title