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US 12,162,854 B2Granted
Production method for fluoromethyl derivative
AssigneesDaikin Industries, Ltd., Saga University
InventorsMasahiro Higashi, Yosuke Kishikawa, Tsugio Kitamura
Life of this patent
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Abstract
A method for producing a fluoromethyl derivative represented by formula (1), the method including step A of reacting an alkene compound represented by formula (2) with a fluorine source represented by formula MFn, in the presence of a hypervalent-iodine aromatic compound (1a), or in the presence of an aromatic iodine compound (1b) and an oxidant (A) to fluorinate the alkene compound.
Claims4
A method for producing a fluorinated organic compound represented by formula (1):
- wherein
- R1 represents an aromatic hydrocarbon group optionally having one or more substituents, or an aromatic heterocyclic group optionally having one or more substituents,
- R2 represents hydrogen, halogen, an alkyl group optionally having one or more substituents, an aryl group optionally having one or more substituents, a non-aromatic heterocyclic group optionally having one or more substituents, or a heteroaryl group optionally having one or more substituents,
- R3 represents hydrogen, or an alkyl group optionally having one or more substituents,
- L represents —CO—,
- R4 represents hydrogen, halogen, hydroxyl, an aliphatic hydrocarbon group optionally having one or more substituents, an aromatic hydrocarbon group optionally having one or more substituents, an aliphatic heterocyclic group optionally having one or more substituents, or an aromatic heterocyclic group optionally having one or more substituents, and
- RX represents fluoro,
- the method comprising step A of reacting an alkene compound represented by formula (2):
- wherein the steric configuration of a single bond indicated by a wavy line with respect to a double bond to which the single bond is connected is in E configuration or Z configuration, or a mixture of E configuration and Z configuration in any ratio, and other alphabetical symbols are as defined above,
- with a fluorine source that is a fluorine source (3a) represented by formula MFn wherein M represents 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
- in the presence of a hypervalent-iodine aromatic compound (1a), or
- in the presence of an aromatic iodine compound (1b) and an oxidant (A) to fluorinate the alkene compound,
- wherein the hypervalent-iodine aromatic compound (1a) is a compound represented by formula (p1):
- wherein
- Ar is an aromatic ring,
- Rp1 is independently in 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, or
- a sulfonic acid group;
- Rp2 is independently in 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 groups bonded to one iodine atom together optionally form ═O;
- n1 is a number greater than or equal to 0;
- n2 is a number greater than or equal to 1;
- and
- the sum of n1 and n2 is within the range of 1 to 11,
- wherein the aromatic iodine compound (1b) is a compound represented by formula (p1′):
- wherein
- Ar is an aromatic ring;
- Rp1 is independently in 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 independently, in each occurrence, 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, or
- a sulfonic acid group;
- n1 is 0 to the maximum substitutable number;
- and
- n2 is a number of 1 to 6, and
- wherein the oxidant (A) is one or more members selected from the group consisting of:
- (i) a compound represented by formula:
- RXCOOOM wherein, in formula RXCOOOM, RX is a hydrocarbon group optionally having one or more substituents, and
- M is a hydrogen atom or a metal atom;
- (ii) a compound represented by formula:
- RXOOM
- wherein, in formula RXOOM, RX is a hydrogen atom or a hydrocarbon group optionally having one or more substituents, and
- M is a hydrogen atom or a metal atom;
- and
- (iii) a metal oxide.
85 more elements
Dependencies are inferred from the claim text.