US 11,667,600 B2
Fluorinated organic compound production method
Masahiro Higashi, Osaka (JP); Yosuke Kishikawa, Osaka (JP); and Tsugio Kitamura, Saga (JP)
Assigned to DAIKIN INDUSTRIES, LTD., Osaka (JP); and SAGA UNIVERSITY, Saga (JP)
Appl. No. 17/42,377
Filed by DAIKIN INDUSTRIES, LTD., Osaka (JP); and SAGA UNIVERSITY, Saga (JP)
PCT Filed Mar. 29, 2019, PCT No. PCT/JP2019/014278
§ 371(c)(1), (2) Date Sep. 28, 2020,
PCT Pub. No. WO2019/189862, PCT Pub. Date Oct. 3, 2019.
Claims priority of application No. JP2018-067382 (JP), filed on Mar. 30, 2018.
Prior Publication US 2021/0024450 A1, Jan. 28, 2021
This patent is subject to a terminal disclaimer.
Int. Cl. C07C 67/307 (2006.01); C07C 231/12 (2006.01); C07C 51/363 (2006.01); C07C 45/63 (2006.01); C07C 51/62 (2006.01); C07C 17/02 (2006.01)
CPC C07C 67/307 (2013.01) [C07C 17/02 (2013.01); C07C 45/63 (2013.01); C07C 51/363 (2013.01); C07C 51/62 (2013.01); C07C 231/12 (2013.01)] 5 Claims
 
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: 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;
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):

OG Complex Work Unit Chemistry
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 —NR2,
R1 is a hydrogen atom, an organic group, or a halogen atom,
R2 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):

OG Complex Work Unit Chemistry
wherein
R3 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 —NR2,
R4 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 —NR2,
R5 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 —NR2, 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):

OG Complex Work Unit Chemistry
wherein
Ar is an aromatic ring,
Rp1 is independently at each occurrence
a group: —O—(CH2)q—NR3X, wherein q is a number greater than or equal to 1; R is H or a C1-C20 alkyl group; and X is a halogen atom, an arylsulfonyloxy group, or an alkylsulfonyloxy group,
a group: —(CH2)q—NR3X, wherein q is a number greater than or equal to 1; R is H or a C1-C20 alkyl group; and X is a halogen atom, an arylsulfonyloxy group, or an alkylsulfonyloxy group,
a group: —O—(CH2)q-A, wherein q is a number greater than or equal to 1; A is —SO3Y or —COOY; Y is independently at each occurrence H, a metal atom, or NR54; and R5 is independently at each occurrence H or an organic group,
a group: —(CH2)q-A, wherein q is a number greater than or equal to 1; A is —SO3Y or —COOY; Y is independently at each occurrence H, a metal atom, or NR54; and R5 is independently at each occurrence H or an organic group,
a carboxylic acid group, or
a sulfonic acid group;
Rp2 is independently at each occurrence
an alkyl group,
an alkoxy group,
a group: —O—(CH2)q—NR3X, wherein q is a number greater than or equal to 1; R is H or a C1-C20 alkyl group; and X is a halogen atom, an arylsulfonyloxy group, or an alkylsulfonyloxy group,
a group: —(CH2)q—NR3X, wherein q is a number greater than or equal to 1; R is H or a C1-C20 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 Rp2 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):

OG Complex Work Unit Chemistry
wherein
Ar is an aromatic ring;
Rp1 is independently at each occurrence
a group: —O—(CH2)q—NR3X, wherein q is a number greater than or equal to 1; R is H or a C1-C20 alkyl group; and X is a halogen atom, an arylsulfonyloxy group, or an alkylsulfonyloxy group,
a group: —(CH2)q—NR3X, wherein q is a number greater than or equal to 1; R is H or a C1-C20 alkyl group; and X is a halogen atom, an arylsulfonyloxy group, or an alkylsulfonyloxy group,
a group: —O—(CH2)q-A, wherein q is a number greater than or equal to 1; A is —SO3Y or —COOY; Y is independently at each occurrence H, a metal atom, or NR54; and R5 is independently at each occurrence H or an organic group,
a group: —(CH2)q-A, wherein q is a number greater than or equal to 1; A is —SO3Y or —COOY; Y is independently at each occurrence H, a metal atom, or NR54; and R5 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.