Method for producing fluorine-containing dioxolane, and composition useful for producing same

Patent metadata

Field	Value
Publication number	US-2025382275-A1
Application number	US-202519303742-A
Country	US
Kind code	A1
Filing date	Aug 19, 2025
Priority date	Feb 22, 2023
Publication date	Dec 18, 2025
Grant date	—

Abstract

An object of the present disclosure is to provide a novel method for producing a 1,3-dioxolane compound having a 2-(difluoromethylene) structure (e.g., 2-(difluoromethylene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane) from a corresponding carboxylic acid salt, the method suppressing the production of HF adducts (e.g., 2-hydro-perfluoro(2,4-dimethyl-1,3-dioxolane)) as by-products. The present disclosure relates to a method for producing a compound represented by formula (1), the method comprising the following steps A, B, C, and D:
step A of reacting a compound represented by formula (2) with at least one base selected from the group consisting of hydroxides, carbonates, and alkoxides of alkali metals and alkaline earth metals to produce a compound represented by formula (3), thereby obtaining a reaction product having a pH range of more than 11.0; step B of adding carbon dioxide gas to the reaction product obtained in step A, or a liquid obtained by mixing the reaction product with water, to adjust the pH to 6.0 to 11.0, thereby obtaining a pH-adjusted liquid; step C of concentrating the pH-adjusted liquid obtained in step B to obtain a concentrate; and step D of heating the concentrate obtained in step C to thermally decompose the compound represented by formula (3), thereby producing the compound represented by formula (1):

wherein R 1 to R 4 are each independently a fluorine atom or a C1-C7 fluoroalkyl group optionally containing ethereal oxygen, X is a hydroxy group, a fluorine atom, a chlorine atom, or a C1-C3 alkoxy group in which one or more hydrogen atoms are optionally replaced by fluorine atoms, and M is an alkali metal atom or an alkaline earth metal atom.

First claim

1 . A method for producing a compound represented by formula (1):

wherein R 1 to R 4 are each independently a fluorine atom or a C1-C7 fluoroalkyl group optionally containing ethereal oxygen,
the method comprising the following steps A, B, C, and D:
step A of reacting a compound represented by formula (2):

wherein X is a hydroxy group, a fluorine atom, a chlorine atom, or a C1-C3 alkoxy group in which one or more hydrogen atoms are optionally replaced by fluorine atoms, and R 1 to R 4 are the same as above, with at least one base selected from the group consisting of hydroxides, carbonates, and alkoxides of alkali metals and alkaline earth metals to produce a compound represented by formula (3):

wherein M is an alkali metal atom or an alkaline earth metal atom, and R 1 to R 4 are the same as above, thereby obtaining a reaction product having a pH range of more than 11.0;
step B of adding carbon dioxide gas to the reaction product obtained in step A, or a liquid obtained by mixing the reaction product with water, to adjust the pH to 6.0 to 11.0, thereby obtaining a pH-adjusted liquid;
step C of concentrating the pH-adjusted liquid obtained in step B to obtain a concentrate; and
step D of heating the concentrate obtained in step C to thermally decompose the compound represented by formula (3), thereby producing the compound represented by formula (1).

2 . The production method according to claim 1 , wherein R 1 to R 4 are each independently a fluorine atom, a perfluoro C1-C7 alkyl group, or a perfluoro C1-C7 alkoxy group.

3 . The production method according to claim 1 , wherein R 1 is a trifluoromethyl group or a fluorine atom, and R 2 to R 4 are all fluorine atoms.

4 . The production method according to claim 1 , wherein X is a hydroxy group, a fluorine atom, a chlorine atom, methoxy, ethoxy, n-propoxy, i-propoxy, trifluoromethoxy, or 2,2,2-trifluoroethoxy.

5 . The production method according to claim 1 , wherein the base is at least one compound selected from the group consisting of potassium carbonate, sodium carbonate, magnesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium hydroxide, sodium hydroxide, magnesium hydroxide, potassium methoxide, sodium methoxide, magnesium methoxide, potassium ethoxide, sodium ethoxide, and magnesium ethoxide.

6 . The production method according to claim 1 , wherein the pH range of 6.0 to 11.0 in step B is 6.0 to 10.0.

7 . The production method according to claim 1 , wherein the amount of carbon dioxide gas added in step B is 100 to 10000 mol % based on the content of the compound represented by formula (3) in the reaction product obtained in step A.

8 . The production method according to claim 1 , wherein steps C and D are performed continuously in the same reactor.

9 . The production method according to claim 1 , wherein
R 1 is a trifluoromethyl group or a fluorine atom, R 2 to R 4 are all fluorine atoms, X is a fluorine atom, methoxy, ethoxy, n-propoxy, or i-propoxy, the base is at least one compound selected from the group consisting of potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, M is a potassium atom or a sodium atom, the pH range of 6.0 to 11.0 in step B is 6.5 to 8.5, and the amount of carbon dioxide gas added in step B is 500 to 6000 mol % based on the content of the compound represented by formula (3) in the reaction product obtained in step A.

10 . The production method according to claim 1 , wherein
R 1 is a trifluoromethyl group or a fluorine atom, R 2 to R 4 are all fluorine atoms, X is a fluorine atom or methoxy, the base is at least one compound selected from the group consisting of potassium carbonate and potassium hydroxide, M is a potassium atom, the pH range of 6.0 to 11.0 in step B is 6.9 to 7.9, and the amount of carbon dioxide gas added in step B is 600 to 5000 mol % based on the content of the compound represented by formula (3) in the reaction product obtained in step A.

11 . A composition comprising:
at least one compound selected from the group consisting of a compound represented by formula (3):

wherein R 1 to R 4 are each independently a fluorine atom or a C1-C7 fluoroalkyl group optionally containing ethereal oxygen, and M is an alkali metal atom or an alkaline earth metal atom; and a compound represented by formula (4):

wherein Y is a hydrogen atom or a C1-C3 alkyl group in which one or more hydrogen atoms are optionally replaced by fluorine atoms, and R 1 to R 4 are the same as above; and
carbon dioxide gas,

wherein when the composition is an aqueous solution of at least one compound selected from the group consisting of the compounds represented by formulas (3) and (4), its pH is within the range of 6.0 to 11.0, and when the composition is a non-aqueous solution, the pH of an aqueous solution obtained by adding water to the composition is within the range of 6.0 to 11.0.

12 . The composition according to claim 11 , further comprising at least one base selected from the group consisting of hydroxides, carbonates, and alkoxides of alkali metals and alkaline earth metals.

13 . The composition according to claim 11 , wherein R 1 to R 4 are each independently a fluorine atom, a perfluoro C1-C7 alkyl group, or a perfluoro C1-C7 alkoxy group.

14 . The composition according to claim 11 , wherein R 1 is a trifluoromethyl group or a fluorine atom, and R 2 to R 4 are all fluorine atoms.

15 . The composition according to claim 11 , wherein Y is a hydrogen atom, methyl, ethyl, n-propyl, i-propyl, trifluoromethyl, or 2,2,2-trifluoroethyl.

16 . The composition according to claim 12 , wherein the base is at least one compound selected from the group consisting of potassium carbonate, sodium carbonate, magnesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium hydroxide, sodium hydroxide, magnesium hydroxide, potassium methoxide, sodium methoxide, magnesium methoxide, potassium ethoxide, sodium ethoxide, and magnesium ethoxide.

17 . The composition according to claim 11 , wherein the pH of the aqueous solution is within the range of 6.0 to 10.0.

18 . The composition according to claim 11 , wherein the pH of the aqueous solution is within the range of 6.5 to 10.0.

19 . The composition according to claim 12 , wherein
R 1 is a trifluoromethyl group or a fluorine atom, R 2 to R 4 are all fluorine atoms, the base is at least one compound selected from the group consisting of potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, Y is methyl, ethyl, n-propyl, or i-propyl, M is a potassium atom or a sodium atom, the aqueous solution has a pH within the range of 6.5 to 8.5, and the content of carbon dioxide gas is 0.2 to 30 mass % based on the mass of the composition.

20 . The composition according to claim 12 , wherein
R 1 is a trifluoromethyl group or a fluorine atom, R 2 to R 4 are all fluorine

Assignees

• Daikin Ind Ltd

Inventors

• Suzuki Yuki
• Kuroki Yoshichika
• Shirai Atsushi
• Mari Daichi
• Shinoki Noriyuki
• Okada Michiaki
• Ino Tadashi

Classifications

• C07D317/34

  Oxygen atoms · CPC title

• C07D317/42 Primary

  Halogen atoms or nitro radicals · CPC title

• C07D317/16

  Radicals substituted by halogen atoms or nitro radicals · CPC title

• C07D317/32

  with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms · CPC title