Process for producing α-fluoroaldehydes

Patent metadata

Field	Value
Publication number	US-9284248-B2
Application number	US-201514667753-A
Country	US
Kind code	B2
Filing date	Mar 25, 2015
Priority date	Aug 3, 2011
Publication date	Mar 15, 2016
Grant date	Mar 15, 2016

Abstract

A production process of an α-fluoroaldehyde according to the present invention includes reaction of an α-fluoroester with hydrogen gas (H 2 ) in the presence of a ruthenium complex. It is possible in the present invention to allow relatively easy industrial production of the α-fluoroaldehyde and to directly obtain, as stable synthetic equivalents of the α-fluoroaldehyde, not only a hydrate (as obtained by conventional techniques) but also a hemiacetal that is easy to purify and is of high value in synthetic applications. The present invention provides solutions to all problems in the conventional techniques and establishes the significantly useful process for production of the α-fluoroaldehyde.

First claim

The invention claimed is:

1. A process for producing an α-fluoroaldehyde of the general formula [3]

comprising the step of: reacting an α-fluoroester of the general formula [1] with hydrogen gas (H 2 ) in the presence of a homogeneous ruthenium catalyst and a base,

where R 1 represents a halogen atom or a haloalkyl group; and R 2 represents an alkyl group or a substituted alkyl group

2. The process according to claim 1 , wherein the base is an alkali metal alkoxide and is used in an amount of 0.005 to 5 mol per 1 mol of the α-fluoroester of the general formula [1].

3. The process according to claim 1 , wherein the α-fluoroaldehyde of the general formula [3] is in the form of an α-fluoroaldehyde equivalent of the following formula

where R 1 and R 2 have the same meanings as in the general formula [1].

4. The process according to claim 1 , wherein the reaction is performed at a hydrogen pressure of 2 MPa or lower.

5. The process according to claim 4 , wherein the reaction is performed at a hydrogen pressure of 1 MPa or lower.

6. The process according to claim 5 , wherein the reaction is performed at a hydrogen pressure of 0.5 MPa or lower.

7. The process according to claim 1 , wherein the reaction is performed at a temperature of +125 to −50° C.

8. The process according to claim 1 , wherein the reaction is performed with the use of an alcohol reaction solvent.

9. The process according to claim 8 , wherein the reaction solvent is used in an amount of 0.03 to 10 L per 1 mol of the α-fluoroester of the general formula [1].

10. The process according to claim 1 , further comprising the steps of:
neutralizing a reaction solution obtained after the completion of the reaction with at least one kind of organic acid selected from the group consisting of formic acid, acetic acid, citric acid, oxalic acid, benzoic acid, methanesulfonic acid, and paratoluenesulfonic acid, or at least one kind of inorganic acid selected from the group consisting of hydrogen chloride, hydrogen bromide, nitric acid, and sulfuric acid; and
subjecting the neutralized reaction solution to recovery distillation.

11. A process for producing an α-fluoroaldehyde of the general formula [3]

comprising the step of: reacting an α-fluoroester of the general formula [1] with hydrogen gas (H 2 ) in the presence of a homogeneous ruthenium catalyst and a base,

where R 1 represents a fluorine atom, a chlorine atom, a CF 3 group or a CF 2 H group; and R 2 represents an alkyl group

12. The process according to claim 11 , wherein the base is lithium methoxide, sodium methoxide or potassium methoxide and is used in an amount of 0.01 to 3 mol per 1 mol of the α-fluoroester of the general formula [1].

13. The process according to claim 11 , wherein the α-fluoroaldehyde of the general formula [3] is in the form of an α-fluoroaldehyde equivalent of the following formula

where R 1 and R 2 have the same meanings as in the general formula [1].

14. The process according to claim 11 , wherein the reaction is performed at a hydrogen pressure of 1 MPa or lower.

15. The process according to claim 14 , wherein the reaction is performed at a hydrogen pressure of 0.5 MPa or lower.

16. The process according to claim 11 , wherein the reaction is performed at a temperature of +100 to −25° C.

17. The process according to claim 1 , wherein the reaction is performed with the use of methanol, ethanol or n-propanol as a reaction solvent.

18. The process according to claim 17 , wherein the reaction solvent is used in an amount of 0.05 to 7 L per 1 mol of the α-fluoroester of the general formula [1].

19. The process according to claim 11 , further comprising the steps of:
neutralizing a reaction solution obtained after the completion of the reaction with at least one kind of organic acid selected from the group consisting of formic acid, acetic acid, citric acid, oxalic acid, benzoic acid, methanesulfonic acid, and paratoluenesulfonic acid, or at least one kind of inorganic acid selected from the group consisting of hydrogen chloride, hydrogen bromide, nitric acid, and sulfuric acid; and
subjecting the neutralized reaction solution to recovery distillation.

Assignees

• Central Glass Co Ltd

Inventors

• Ishii Akihiro
• Ootsuka Takashi
• Imamura Mari
• Nishimiya Takayuki
• Kimura Kazuto

Classifications

• C07C45/41 Primary

  by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof · CPC title

• C07C41/50

  by reactions producing [IMAGE cpc-sch-C07C-0958.gif] groups · CPC title

• B01J2231/641

  Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes · CPC title

• B01J31/189

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title

• B01J2531/821

  Ruthenium · CPC title