IP Library Granted Patent US 12,590,047
Granted Patent B2
US 12,590,047 · App. 17/891,336 · Granted Mar 31, 2026

Method for producing fluorine-containing olefin

Inventors: Kyoko Nozaki (Bunkyo-ku, JP); Midori Akiyama (Bunkyo-ku, JP); Kenta Mori (Bunkyo-ku, JP); Takashi Okazoe (Chiyoda-ku, JP); Yuichiro Ishibashi (Chiyoda-ku, JP); Ko Inada (Chiyoda-ku, JP)
Assignees: THE UNIVERSITY OF TOKYO; AGC INC.
C07C41/22B01J31/2217B01J31/2278C07C17/2637C07C319/20C07D209/86B01J2231/4288B01J2531/821
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Quick Facts
Patent No.
US 12,590,047
App. No.
17/891,336
Granted
Mar 31, 2026
Kind
B2
Abstract

A production method of producing a fluorine-containing olefin by allowing a first olefin represented by the following Formula (1) and a second olefin to react with each other in the presence of a ruthenium compound represented by the following Formula (X) is provided.

Claims (27)

1 . A production method of producing a fluorine-containing olefin comprising:

allowing a first olefin represented by the following Formula (1) and a second olefin different from Formula (1) of the first olefin to react with each other in the presence of a ruthenium compound represented by the following Formula (X):

wherein, in Formula (X),

A represents an atom group necessary for forming a 6- or 7-membered nitrogen-containing heterocyclic ring comprising two nitrogen atoms, an aromatic or aliphatic ring may be condensed to the nitrogen-containing heterocyclic ring, and A and the aromatic or aliphatic ring condensed to the nitrogen-containing heterocyclic ring may comprise a substituent,

each of R 1 and R 2 independently represents an alkyl group, an aryl group, or an aralkyl group,

each of Y 1 and Y 2 independently represents an anionic ligand,

L′ represents a neutral electron-donating ligand,

p represents 0 or 1, and

each of Z 1 and Z 2 independently represents a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having a carbon number of from 1 to 20, or a monovalent hydrocarbon group having a carbon number of from 1 to 20 and comprising one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom, Z 1 and Z 2 may be bonded to each other to form a ring, and either or both of Z 1 and Z 2 , and L 1 may be chemically bonded to each other,

wherein, in Formula (1), each of A 1 , A 2 , and A 3 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, or a fluorine-containing alkyl group having a carbon number of from 1 to 10.

2 . The production method according to claim 1 , wherein the second olefin is represented by the following Formula (2):

wherein, in Formula (2),

at least one of A 4 to A 7 represents a functional group AA comprising an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom at a linkage position to vinyl carbon, each of A 4 to A 7 , other than the functional group AA, independently represents a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having a carbon number of from 1 to 20, or a monovalent hydrocarbon group having a carbon number of from 1 to 20 and comprising one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom, and A 4 and A 5 , A 4 and A 6 , A 5 and A 7 , or A 6 and A 7 may be bonded to each other to form a ring, and

in a case in which one of A 4 or A 5 is a halogen atom, another one of A 4 or A 5 represents a hydrogen atom, a monovalent hydrocarbon group having a carbon number of from 1 to 20, or a monovalent hydrocarbon group having a carbon number of from 1 to 20 and comprising one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom, and in a case in which one of A 6 or A 7 is a halogen atom, another one of A 6 or A 7 represents a hydrogen atom, a monovalent hydrocarbon group having a carbon number of from 1 to 20, or a monovalent hydrocarbon group having a carbon number of from 1 to 20 and comprising one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.

3 . The production method according to claim 2 , wherein, in Formula (2), the functional group AA is an alkoxy group having a carbon number of from 1 to 20 or an aryloxy group having a carbon number of from 6 to 20.

4 . The production method according to claim 1 , wherein, in Formula (1), at least two of A 1 , A 2 , or A 3 are fluorine atoms.

5 . The production method according to claim 1 , wherein the second olefin is a monosubstituted olefin or a 1,2-disubstituted olefin.

6 . The production method according to claim 1 , wherein an amount of the ruthenium compound used is from 0.001% by mol to 1.0% by mol with respect to a substance amount of the second olefin.

7 . The production method according to claim 1 , wherein, in Formula (X), each of R 1 and R 2 is independently 2,4,6-trimethylphenyl group, 2,6-diisopropylphenyl group, o-tolyl group, 3,5-di-tert-butylphenyl group, 2,6-dimethyl-4-methoxyphenyl group, or 2,6-difluorophenyl group.

8 . The production method according to claim 1 , wherein A is an atom group that forms a 6-membered nitrogen-containing heterocyclic ring.

9 . The production method according to claim 1 , wherein A is an atom group that forms a 7-membered nitrogen-containing heterocyclic ring.

10 . The production method according to claim 1 , wherein the first olefin and the second olefin react with each other under an olefin back pressure of 1 to 2 atm.

11 . The production method according to claim 1 , wherein the first olefin and the second olefin react with each other in the presence of the ruthenium compound to form the fluorine-containing olefin with a reaction conversion rate of 19.1 to 71.6%.

12 . The production method according to claim 1 , wherein the first olefin and the second olefin react with each other in the presence of the ruthenium compound to form the fluorine-containing olefin with a reaction conversion rate of 58.8 to 98.8%.

13 . The production method according to claim 1 , wherein the first olefin and the second olefin react with each other in the presence of the ruthenium compound to form the fluorine-containing olefin with a selective rate of 3.05 to 10.8.

14 . The production method according to claim 1 , wherein the first olefin and the second olefin react with each other in the presence of the ruthenium compound to form the fluorine-containing olefin with a selective rate of 0.3 to 17.7.

15 . The production method according to claim 1 , wherein the functional group AA is selected from the group consisting of an alkoxy group, an aryloxy group, an acetoxy group, an amino group, an alkythio group, an arylthio group, a dialkyphosphino group and a diarylphosphino group.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 19, 2022
From: NOZAKI, KYOKO; AKIYAMA, MIDORI; MORI, KENTA; OKAZOE, TAKASHI; ISHIBASHI, YUICHIRO; INADA, KO
To: THE UNIVERSITY OF TOKYO; AGC INC.
Reel/Frame 061234/0359 →
Priority Claims (2)
JP 2020-034736 · Mar 2, 2020 · national
JP 2020-132483 · Aug 4, 2020 · national
Continuity (2)
Continuation PCTJP2021005343 · Feb 12, 2021
Related Publication 20230016405A1 · Jan 19, 2023
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