Fluorinated organic compound production method

Patent metadata

Field	Value
Publication number	US-11667600-B2
Application number	US-201917042377-A
Country	US
Kind code	B2
Filing date	Mar 29, 2019
Priority date	Mar 30, 2018
Publication date	Jun 6, 2023
Grant date	Jun 6, 2023

Abstract

An object of the present invention is to provide a method for producing a fluorinated organic compound, whereby an iodosylbenzene derivative can be easily separated and recovered. The above object can be achieved by a method for producing a fluorinated organic compound, comprising step A of fluorinating an organic compound (1) by reaction with a fluorine source (3) in the presence of a hypervalent iodine aromatic ring compound (2a), or in the presence of an iodine aromatic ring compound (2b) and an oxidant (2bo); wherein the fluorine source (3) is a fluorine source (3a) represented by formula: MFn, wherein M is H, a metal of Group 1 of the periodic table, or a metal of Group 2 of the periodic table; and n is 1 or 2; and step B of separating the iodine aromatic ring compound from a reaction liquid after step A is started.

First claim

The invention claimed is:

1. A method for producing a fluorinated organic compound, comprising:
step A of fluorinating an organic compound (1) by reaction with a fluorine source (3)

in the presence of a hypervalent iodine aromatic ring compound (2a), or
in the presence of an iodine aromatic ring compound (2b) and an oxidant (2bo);
wherein the fluorine source (3) is a fluorine source (3a) represented by formula: MF n , wherein M is H, a metal of Group 1 of the periodic table, or a metal of Group 2 of the periodic table; and n is 1 or 2;
step B of separating the iodine aromatic ring compound from a reaction liquid after step A is started; and
step C of oxidizing the iodine-substituted aromatic ring compound separated from the reaction liquid in step B with an oxidant (C),

wherein the organic compound (1) is:
an organic compound represented by formula (1a):

wherein
A is a hydrogen atom, an aromatic group optionally having one or more substituents, an alkyl group optionally having one or more substituents, a halogen atom, —OR, or —NR 2 ,
R 1 is a hydrogen atom, an organic group, or a halogen atom,
R 2 is a hydrogen atom, an organic group, or a halogen atom, and
R is independently at each occurrence a hydrogen atom or an organic group; or
an organic compound represented by formula (1b):

wherein
R 3 is a hydrogen atom, an aromatic group optionally having one or more substituents, an alkyl group optionally having one or more substituents, a halogen atom, —OR, or —NR 2 ,
R 4 is a hydrogen atom, an aromatic group optionally having one or more substituents, an alkyl group optionally having one or more substituents, a halogen atom, —OR, or —NR 2 ,
R 5 is a hydrogen atom, an aromatic group optionally having one or more substituents, an alkyl group optionally having one or more substituents, a halogen atom, —OR, or —NR 2 , and
R is independently at each occurrence a hydrogen atom or an organic group; and
wherein the hypervalent iodine aromatic ring compound (2a) is an organic compound represented by formula (2a1):

wherein
Ar is an aromatic ring,
R p1 is independently at each occurrence
a group: —O—(CH 2 ) q —NR 3 X, wherein q is a number greater than or equal to 1; R is H or a C 1 -C 20 alkyl group; and X is a halogen atom, an arylsulfonyloxy group, or an alkylsulfonyloxy group,
a group: —(CH 2 ) q —NR 3 X, wherein q is a number greater than or equal to 1; R is H or a C 1 -C 20 alkyl group; and X is a halogen atom, an arylsulfonyloxy group, or an alkylsulfonyloxy group,
a group: —O—(CH 2 ) q -A, wherein q is a number greater than or equal to 1; A is —SO 3 Y or —COOY; Y is independently at each occurrence H, a metal atom, or NR 5 4 ; and R 5 is independently at each occurrence H or an organic group,
a group: —(CH 2 ) q -A, wherein q is a number greater than or equal to 1; A is —SO 3 Y or —COOY; Y is independently at each occurrence H, a metal atom, or NR 5 4 ; and R 5 is independently at each occurrence H or an organic group,
a carboxylic acid group, or
a sulfonic acid group;

R p2 is independently at each occurrence
an alkyl group,
an alkoxy group,
a group: —O—(CH 2 ) q —NR 3 X, wherein q is a number greater than or equal to 1; R is H or a C 1 -C 20 alkyl group; and X is a halogen atom, an arylsulfonyloxy group, or an alkylsulfonyloxy group,
a group: —(CH 2 ) q —NR 3 X, wherein q is a number greater than or equal to 1; R is H or a C 1 -C 20 alkyl group; and X is a halogen atom, an arylsulfonyloxy group, or an alkylsulfonyloxy group,
a halogen atom,
a cyano group,
a nitro group,
a carboxylic acid group,
a sulfonic acid group,
a hydroxy group, or
a phosphoryloxy group; or

two R p2 bonded to one iodine atom optionally together form ═O;
n1 is a number greater than or equal to 1;
n2 is a number greater than or equal to 1; and
the sum of n1 and n2 is in the range of 2 to 11; and
the iodine aromatic ring compound (2b) is an organic compound represented by formula (2b1):

wherein
Ar is an aromatic ring;
R p1 is independently at each occurrence
a group: —O—(CH 2 ) q —NR 3 X, wherein q is a number greater than or equal to 1; R is H or a C 1 -C 20 alkyl group; and X is a halogen atom, an arylsulfonyloxy group, or an alkylsulfonyloxy group,
a group: —(CH 2 ) q —NR 3 X, wherein q is a number greater than or equal to 1; R is H or a C 1 -C 20 alkyl group; and X is a halogen atom, an arylsulfonyloxy group, or an alkylsulfonyloxy group,
a group: —O—(CH 2 ) q -A, wherein q is a number greater than or equal to 1; A is —SO 3 Y or —COOY; Y is independently at each occurrence H, a metal atom, or NR 5 4 ; and R 5 is independently at each occurrence H or an organic group,
a group: —(CH 2 ) q -A, wherein q is a number greater than or equal to 1; A is —SO 3 Y or —COOY; Y is independently at each occurrence H, a metal atom, or NR 5 4 ; and R 5 is independently at each occurrence H or an organic group,
a carboxylic acid group, or
a sulfonic acid group;

n1 is a number greater than or equal to 1;
n2 is a number greater than or equal to 1; and
the sum of n1 and n2 is in the range of 2 to 11.

2. The production method according to claim 1 , wherein R p1 in formulas (2a1) and (2b1) is independently at each occurrence a carboxylic acid group, or a sulfonic acid group.

3. The production method according to claim 1 , wherein R p2 in formula (2a1) is independently at each occurrence a halogen atom, an acetic acid group, a trifluoroacetic acid group, a tosic acid group, a hydroxy group, a phosphoryloxy group, a trifluoromethanesulfonic acid group, a propionic acid group, a 3,3,3-trifluoropropionic acid group, a perfluoropropionic acid group, a perfluorobutyric acid group, or a methanesulfonic acid group.

4. The production method according to claim 1 , wherein the oxidant (2bo) is one or more members selected from the group consisting of metachloroperbenzoic acid, hydrogen peroxide, peracetic acid, perbenzoic acid, tert-butyl hydroperoxide, cumene hydroperoxide, potassium persulfate, and a potassium hydrogen persulfate-potassium hydrogen sulfate-potassium sulfate mixture.

5. The method according to claim 1 , wherein the oxidant (C) is one or more members selected from the group consisting of metachloroperbenzoic acid, hydrogen peroxide, peracetic acid, perbenzoic acid, tert-butyl hydroperoxide, cumene hydroperoxide, potassium persulfate, and a potassium hydrogen persulfate-potassium hydrogen sulfate-potassium sulfate mixture.

Assignees

• Daikin Ind Ltd
• Univ Saga

Inventors

• Higashi Masahiro
• Kishikawa Yosuke
• Kitamura Tsugio

Classifications

• C07C45/63 Primary

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title

• C07C67/307 Primary

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title

• C07C231/12

  by reactions not involving the formation of carboxamide groups · CPC title

• C07C51/363

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title

• C07C17/02

  to unsaturated hydrocarbons · CPC title