JP4940544B2 - Method for producing fluorine-containing organic compound with iodine pentafluoride - Google Patents

Description

  The present invention relates to a method for producing a fluorine-containing organic compound, characterized by using a fluorinating reagent mixed so that the molar ratio of IF5 to organic base hydrofluoric acid salt is in the range of 1: 1.25 to 1:10. It is.

  There have been some reports on the synthesis of fluorine-containing organic compounds using IF5 in the presence of organic base fluoride, and in particular, fluorinating agents in which IF5 and Et3N-3HF are mixed are well studied. It is known that various types of organic compounds can be fluorinated (Patent Documents 1 and 2, Non-Patent Documents 1 to 4). However, as described in Non-Patent Document 2, when the para-position is a substrate having an unsubstituted phenyl group, the side reaction in which the para-position of the phenyl group is substituted with iodine as shown in the following formula has a high yield. What happens at the rate is a problem.

WO01 / 096263 JP 2003-146965 A N.Yoneda and T.Fukuhara, Chemistry Letters, 2001, 222. S. Ayuba, N. Yoneda, T. Fukuhara, and S. Hara, Bull. Chem. Soc. Jpn., 2002, 75, 1597. S. Ayuba, T. Fukuhara, and S. Hara, Organic Letters, 2003, 5, 2873. N.Yoneda, J. Fluorine Chem., 2004, 125, 7.

  The object of the present invention is to suppress iodine substitution at the para-position of the aromatic ring in a fluorination of an aromatic ring that can be iodinated, particularly an organic compound containing a phenyl group that is unsubstituted at the para-position. The object is to produce a fluorine-containing organic compound.

As a result of repeated investigations in view of the above problems, the present inventors have used IF5 and a fluorinating reagent mixed so that the molar ratio of the organic base hydrofluoric acid salt is in the range of 1: 1.25 to 1:10. It has been found that in fluorination of an organic compound containing an aromatic ring that can be iodinated (particularly, a phenyl group that is unsubstituted in the para position), iodine substitution can be suppressed and a desired fluorine-containing organic compound can be produced in a high yield. That is, the present invention relates to the following items 1 to 8.
Item 1. An organic compound having at least one aromatic ring that can be iodinated and one or more hydrogen atoms bonded to a non-aromatic carbon atom is reacted with a fluorinating reagent to replace at least one of the hydrogen atoms with a fluorine atom. A method for producing an organic compound comprising:
The fluorinating reagent includes IF5 and an organic base hydrofluoric acid salt, and a fluorinating reagent mixed so that the molar ratio of IF5 to the organic base hydrofluoric acid salt is in the range of 1: 1.25 to 1:10 ,
The molar ratio of the organic base and hydrogen fluoride (HF) is 1: 1 to 1: wherein Rukoto using mixed the organic base hydrofluoric acid salts such as a range of 3.5,
A method for producing a fluorinated organic compound while suppressing iodine substitution of the aromatic ring.
Item 2. Item 2. The method according to Item 1, wherein the aromatic ring is at least one selected from the group consisting of a benzene ring and a naphthalene ring.
Item 3. Item 3. The method according to Item 1 or 2, wherein a fluorinating reagent mixed so that the molar ratio of IF5 and organic base hydrofluoric acid salt is in the range of 1: 2 to 1: 5 is used.
Item 4. Item 4. The method according to any one of Items 1 to 3, wherein an organic base hydrofluoric acid salt mixed so that a molar ratio of the organic base to hydrofluoric acid (HF) is in the range of 1: 2.5 to 1: 3.5 is used. .
Item 5. Item 5. The method according to any one of Items 1 to 4, wherein the organic base is a tertiary amine.
Item 6. Item 6. The method according to Item 5, wherein the organic base is a trialkylamine.
Item 7. Item 7. The method according to Item 6, wherein the organic base fluoride is (C ₂ H ₅ ) ₃ N · 3HF.
Item 8. The organic compound to be fluorinated is represented by the formula (1):
R ¹ R ² CH-SR ³ (1)
(R ¹ and R ² are the same or different, and are a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aralkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, aryl group, aryloxy group, aralkyloxy group. , An alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an acyl group, a heterocyclic group, —CONR ⁴ R ⁵ (R ⁴ and R ⁵ are independently a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. ), Alkylsulfinyl group, aralkylsulfinyl group, arylsulfinyl group, cycloalkylsulfinyl group, heterocycloalkylsulfinyl group, sulfinyl group to which a heterocyclic group is bonded, alkylsulfonyl group, aralkylsulfonyl group, arylsulfonyl group, cycloalkyl A sulfonyl group, a cyano group or a nitro group to which a heterocyclic group is bonded, and any group may have a substituent, and R ¹ and R ² are bonded. (R ³ is an aryl group in which the position on the orientation where iodine can be substituted is a hydrogen atom, and other positions may have a substituent.)
Item 8. The method according to any one of Items 1 to 7, having a sulfide group represented by:

  In the fluorination method of the present invention, that is, when a fluorinating reagent mixed so that the molar ratio of IF5 and organic fluoric acid salt is in the range of 1: 1.25 to 1:10 is used, the phenyl group in which the para position is unsubstituted In the fluorination of the substrate containing, the iodine substitution at the para-position of the phenyl group can be suppressed, and the desired fluorine-containing organic compound can be produced with a high yield.

  In the present invention, the organic base that is a constituent of the organic base hydrofluoric acid salt includes primary, secondary and tertiary aliphatic amines, secondary and tertiary alicyclic amines, primary and secondary and tertiary aromatic amines. And heterocyclic amines. Primary, secondary and tertiary aliphatic amines include methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, dimethylamine, diethylamine, dipropylamine, dihexylamine, dicyclohexylamine, trimethylamine, triethylamine, tripropyl Examples include amine, diisopropylethylamine, tributylamine, N, N-diethylmethylamine, N, N-dimethylisopropylamine, N, N-dimethylbutylamine, and trioctylamine. Secondary and tertiary alicyclic amines include piperidine, pyrrolidine, morpholine, N-methylpiperazine, N-methylpyrrolidine, 5-diazabicyclo [4.3.0] nonane-5-ene, 1,4-diazabicyclo [ 2.2.2] octane and the like. Primary, secondary and tertiary aromatic amines include aniline, N-methylaniline, N, N-dimethylaniline, N-ethylaniline, N, N-diethylaniline, N-ethyl-N-methylaniline, 1- Examples include phenylpiperidine, diphenylamine, and triphenylamine. Heterocyclic amines include pyridine, pyrimidine, piperazine, quinoline, imidazole and the like. Further examples include polymer-supported amine compounds such as polyaniline, polyallylamine, and polyvinylpyridine. Further, these amines may be arbitrarily mixed and used.

  Among these, tertiary compounds such as trimethylamine, triethylamine, tripropylamine, diisopropylethylamine, tributylamine, N, N-diethylmethylamine, N, N-dimethylisopropylamine, N, N-dimethylbutylamine, and trioctylamine Aliphatic amines are preferred.

  In the fluorinating reagent of the present invention, the higher the ratio of organic base hydrofluoric acid salt, the lower the generation of iodine-substituted products, and in particular, the ratio of IF5 to organic base hydrofluoric acid salt is not detected at all or is extremely low. Suppressed to level. On the other hand, when the ratio of the organic base fluoride is increased, the fluorination reaction is delayed.

  Therefore, from the viewpoint of suppressing iodine substitution and improving the fluorination reaction rate, the ratio of IF5 to organic base hydrofluoric acid salt should be in the range of 1: 1.25 to 1:10, preferably IF5 and organic base hydrofluoric acid salt. The ratio is from 1: 2 to 1: 5, more preferably from 1: 2.5 to 1: 3.5, in particular 1: 3.

  In the organic base hydrofluoric acid salt used in the present invention, the ratio of hydrofluoric acid (HF) to the organic base should be 1 equivalent or more and less than 5 equivalents, preferably 2.5 equivalents to 3.5 equivalents, Further, it is particularly preferable that the amount is 3 equivalents. Too much hydrofluoric acid relative to the organic base is not preferable because iodine substitution tends to occur.

  The reaction can be carried out without using a reaction solvent, but the following solvents can also be used. Aliphatic solvents such as pentane, hexane, heptane, cyclohexane, petroleum ether, dichloromethane, dichloroethane, chloroform, fluorotrichloromethane, 1,1,2-trichlorotrifluoroethane, 2-chloro-1,2-dibromo-1,1 , 2-trifluoroethane, 1,2-dibromohexafluoropropane, 1,2-dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, heptafluoro-2,3,3- Halogenated aliphatics such as trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1,1-trichlorotrifluoroethane, polychlorotrifluoroethylene, etc. Solvent, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, γ-butyl Ester solvents such as lolactone and propylene carbonate, nitrile solvents such as acetonitrile and propionitrile, aromatic solvents such as benzene, chlorobenzene, toluene, dichlorobenzene, fluorobenzene and nitrobenzene, diethyl ether, dipropyl ether, tetrahydrofuran and dimethoxyethane Ether solvents such as N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), nitromethane, N, N-diethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl -2-imidazolidinone (DMI), tetramethylurea, 1,3-dimethylpropyleneurea, hexamethylphosphoramide (HMPA) and the like. Although it may be used as the above mixed solvent, acetonitrile is particularly preferable.

  The reaction temperature is −20 ° C. to 200 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 5 minutes to 300 hours, and can be appropriately set according to the organic compound as a substrate.

  The substrate to be fluorinated is an organic compound having an aromatic ring that can be iodinated (for example, a benzene ring, a naphthalene ring, etc.), and the benzene ring can be included in the organic compound as a phenyl group, a phenylene group, etc. It can be contained in an organic compound as a naphthyl group, a naphthylene group or the like. Specifically, among the compounds described in Patent Documents 1 and 2 and Non-Patent Documents 1 to 4 described above as the substrate to be fluorinated, all of those corresponding to this are targets, but in particular the formula ( Application to a substrate having a sulfide group represented by 1) is preferred.

R ¹ R ² CH-SR ³ (1)
(R ¹ and R ² are the same or different, and are a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aralkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, aryl group, aryloxy group, aralkyloxy group. , An alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an acyl group, a heterocyclic group, —CONR ⁴ R ⁵ (R ⁴ and R ⁵ are independently a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. ), Alkylsulfinyl group, aralkylsulfinyl group, arylsulfinyl group, cycloalkylsulfinyl group, heterocycloalkylsulfinyl group, sulfinyl group to which a heterocyclic group is bonded, alkylsulfonyl group, aralkylsulfonyl group, arylsulfonyl group, cycloalkyl A sulfonyl group, a cyano group or a nitro group to which a heterocyclic group is bonded, and any group may have a substituent, and R ¹ and R ² are bonded. (R ³ is an aryl group in which the position on the orientation where iodine can be substituted is a hydrogen atom, and other positions may have a substituent.)
In the sulfides represented by the formula (1) of the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , Hexadecyl, heptadecyl, octadecyl, etc. having a straight chain or branched C _{1 to} C ₁₈ alkyl group, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl , A C ₁ -C ₆ alkyl group having a straight chain or a branch, such as hexyl, and the like, and a substituent may be bonded thereto.

The cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, include C ₃ -C ₈ cycloalkyl group such as cyclooctyl, C ₃ -C ₇ cycloalkyl group is preferably a substituted group is bonded It may be.

  Examples of the heterocycloalkyl group include those in which one or more carbon atoms forming the cyclic structure of the cycloalkyl group are substituted with a nitrogen atom, an oxygen atom, a sulfur atom, or the like. You may do it.

As the haloalkyl group, trifluoromethyl group, trifluoroethyl group, trichloroethyl group, tetrafluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, C ₁ -C having a straight chain or branched chain, such as a perfluorodecyl group, a 2- (perfluorooctyl) ethyl group, a 1H, 1H, 3H-tetrafluoropropyl group, or a 1H, 1H, 5H-octafluoropentyl group ₁₈ , preferably a C ₁ -C ₆ alkyl group in which one to all hydrogen atoms are substituted with halogen atoms.

Examples of the aralkyl group include C _{7 to} C ₂₀ aralkyl groups such as 2-phenylethyl, benzyl, 1-phenylethyl, 3-phenylpropyl and 4-phenylbutyl.

  Examples of the aryl group include a phenyl group, a methylphenyl group, a chlorophenyl group, a methoxyphenyl group, a diphenyl group, and a naphthyl group, and a substituent may be bonded thereto.

The alkoxy group is a group represented by O- (alkyl group, alkyl group is the same as described above). For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert- Examples thereof include straight-chain or branched C ₁ -C ₆ alkoxy groups such as butoxy, pentyloxy, and hexyloxy, and a substituent may be bonded thereto.

  Examples of the aryloxy group include a phenoxy group, a chlorophenoxy group, a methoxyphenoxy group, a naphthyloxy group, and the like, and a substituent may be bonded thereto.

Examples of the aralkyloxy group include C _{7 to} C ₂₀ aralkyloxy groups such as 2-phenylethyloxy, benzyloxy, 1-phenylethyloxy, 3-phenylpropyloxy, 4-phenylbutyloxy and the like.

  Examples of the alkoxycarbonyl group include CO- (alkoxy) groups in which the alkoxy group is the group shown above, specifically, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, Examples include isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl.

  Examples of the aryloxycarbonyl group include a CO- (aryloxy) group in which the aryloxy group is the group shown above, and specifically include a phenoxycarbonyl group, a chlorophenoxycarbonyl group, a methoxyphenoxycarbonyl group, and a naphthyloxycarbonyl group. Group and the like, and a substituent may be bonded thereto.

  Examples of the aralkyloxycarbonyl group include a CO- (aralkyloxy) group in which the aralkyloxy group is the group shown above, specifically 2-phenylethyloxycarbonyl, benzyloxycarbonyl, 1-phenylethyloxycarbonyl , 3-phenylpropyloxycarbonyl, 4-phenylbutyloxycarbonyl, naphthyloxycarbonyl group and the like, and a substituent may be bonded thereto.

  Examples of the acyl group include linear or branched alkanoyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, n-butyryl, isobutyryl, valeryl, isovaleryl, and pivaloyl, benzoyl, and substituted acyl groups.

  Examples of the acyl group having a substituent include a substituted acetyl group such as a chloroacetyl group, a bromoacetyl group, a dichloroacetyl group, and a trifluoroacetyl group, an alkoxy-substituted acetyl group such as a methoxyacetyl group and an ethoxyacetyl group, and a methylthioacetyl group. Alkylthio-substituted acetyl group, phenoxyacetyl group, phenylthioacetyl group, 2-chlorobenzoyl group, 3-chlorobenzoyl group, 4-chlorobenzoyl group, 4-methylbenzoyl group, 4-t-butylbenzoyl group, 4-methoxybenzoyl group Groups, substituted benzoyl groups such as 4-cyanobenzoyl group and 4-nitrobenzoyl group.

-CONR ¹ R ² (wherein R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group N-phenylcarbamoyl group, N-chlorophenylcarbamoyl group, N, N-diethylcarbamoyl group and the like.

  Heterocyclic groups include piperidyl, furyl, thienyl, imidazolyl, oxazolyl, thiazolyl, pyrrolyl, pyrrolidinyl, triazolyl, benzothiazolyl, benzoimidazolyl, oxadiazolyl, thiadiazolyl, indolyl, pyrazolyl, pyridazinyl, cinolinyl, quinolyl, isoquinolyl, quinoxalyl, pyrynyl Examples include benzofuryl, benzothienyl, tetrazolyl, and the like, and a substituent may be bonded thereto.

  Alkylsulfinyl group (alkyl-SO-), aralkylsulfinyl group (aralkyl-SO-), arylsulfinyl group (aryl-SO-), cycloalkylsulfinyl group (cycloalkyl-SO-), heterocycloalkylsulfinyl group (heterocyclo Alkyl-SO-), alkyl group, aralkyl group, aryl group, cycloalkyl group, heterocycloalkyl group, and heterocyclic group of the sulfinyl group to which a heterocyclic group is bonded (-SO-) are exemplified above. .

Alkylsulfonyl groups (alkyl _-SO 2 -), aralkyl sulfonyl group (aralkyl _-SO 2 -), an arylsulfonyl group (aryl _-SO 2 -), cycloalkyl sulfonyl group (cycloalkyl _-SO 2 -), heterocycloalkyl alkylsulfonyl As the group (heterocycloalkyl-SO ₂ —), the alkyl group, aralkyl group, aryl group, cycloalkyl group, heterocycloalkyl group, and heterocyclic group of the sulfonyl group (—SO ₂ —) to which the heterocyclic group is bonded are as described above. Are exemplified.

An alkyl group having a substituent, an alkoxy group having a substituent, an aryl group having a substituent, an aryloxy group having a substituent, an aralkyloxy group having a substituent, a cycloalkyl group having a substituent, and a hetero having a substituent The number of substituents of the cycloalkyl group and the heterocyclic group having a substituent is 1 to 5, preferably 1 to 3. Examples of the substituent include halogen, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, cyano, nitro, amino group, hydroxyl group, etc. As the alkyl group having halogen, a part of hydrogen of the alkyl group or All substituted with fluorine or / and chlorine or / and bromine or / and iodine.

  For example, the following compounds are exemplified, but not limited thereto.

(In the formula, a hydrogen atom that can be fluorinated is indicated as “—H”. When one structural formula has two or more hydrogen atoms, only one hydrogen atom may be substituted, and two or more fluorine atoms may be substituted. Atoms may be substituted simultaneously.)
The above 12 types of compounds are for indicating hydrogen atoms to be fluorinated, and similarly for more complex compounds having the above skeleton or a skeleton similar thereto as a partial structure, a substrate to be fluorinated. (Organic compound).

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by it at all.
Example 1

Compound 1 (1.14 g, 5.0 mmol), IF5 (3.9 g, 17.5 mmol) and Et3N-3HF (3.5 g, 21.9 mmol) were added to a 20 ml fluororesin container, and the mixture was stirred at room temperature for 18 hours and at 80 ° C. for 1.5 hours. After confirming the disappearance of Compound 1, the reaction solution was added to an aqueous KOH / K2SO3 solution in an ice bath and extracted with 20 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then 481 mg (5 mmol) of fluorobenzene was added as an internal standard, and the yield was determined by 19F-NMR.
Examples 2-12, Comparative Examples 1-2
The reaction was carried out in the same manner as in Example 1 using the reaction conditions described in Table 1.

Example 13
To a 20 ml fluororesin container, 1.14 g (5.0 mmol) of Compound 1, acetonitrile (0.83 ml), 6.6 g (30 mmol) of IF5 and 9.6 g (60 mmol) of Et3N-3HF were added and stirred at 75 ° C. for 4 hours. After confirming the disappearance of Compound 1, the reaction solution was added to an aqueous KOH / K2SO3 solution in an ice bath and extracted with 20 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then 481 mg (5 mmol) of fluorobenzene was added as an internal standard, and the yield was determined by 19F-NMR.

Example 14
The reaction was performed in the same manner as in Example 13 using the reaction conditions described in Table 2.
Comparative Example 3
To a 20 ml fluororesin container, 1.14 g (5.0 mmol) of Compound 1, 1.4 g (6.5 mmol) of IF5 and 2.6 g (13 mmol) of Et3N-5HF were added, and the mixture was stirred at room temperature for 18 hours and at 80 ° C. for 2 hours. After confirming the disappearance of Compound 1, the reaction solution was added to an aqueous KOH / K2SO3 solution in an ice bath and extracted with 20 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then 481 mg (5 mmol) of fluorobenzene was added as an internal standard, and the yield was determined by 19F-NMR.
Comparative Example 4
The reaction was carried out in the same manner as in Comparative Example 3 using the reaction conditions described in Table 3.

Example 15
In a 20 ml fluororesin container, 392.6 g (2.0 mmol) of compound 4, 799 mg (3.6 mmol) of IF5 and 726 mg (4.5 mmol) of Et3N-3HF were added, and the mixture was stirred at room temperature for 18 hours and at 80 ° C. for 5 hours. After confirming the disappearance of Compound 4, the reaction solution was added to an aqueous KOH / K2SO3 solution in an ice bath and extracted with 20 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, 96.1 mg (1 mmol) of fluorobenzene was added as an internal standard, and the yield was determined by 19F-NMR.

Examples 16 to 19, Comparative Example 5
The reaction was performed in the same manner as in Example 15 using the reaction conditions described in Table 4.

Claims (8)

An organic compound having at least one aromatic ring that can be iodinated and one or more hydrogen atoms bonded to a non-aromatic carbon atom is reacted with a fluorinating reagent to replace at least one of the hydrogen atoms with a fluorine atom. A method for producing an organic compound comprising:
The fluorinating reagent includes IF5 and an organic base hydrofluoric acid salt, and a fluorinating reagent mixed so that the molar ratio of IF5 to the organic base hydrofluoric acid salt is in the range of 1: 1.25 to 1:10 ,
The molar ratio of the organic base and hydrogen fluoride (HF) is 1: 1 to 1: wherein Rukoto using mixed the organic base hydrofluoric acid salts such as a range of 3.5,
A method for producing a fluorinated organic compound while suppressing iodine substitution of the aromatic ring. The method according to claim 1, wherein the aromatic ring is at least one selected from the group consisting of a benzene ring and a naphthalene ring. The method according to claim 1 or 2, wherein a fluorinating reagent mixed so that a molar ratio of IF5 and organic base hydrofluoric acid salt is in a range of 1: 2 to 1: 5 is used. The molar ratio of the organic base and hydrogen fluoride (HF) is 1: 2.5 to 1: according to claim 1, which comprises using a mixed organic bases hydrofluoric acid salts such as the range of 3.5 the method of. The method according to claim 1, wherein the organic base is a tertiary amine. 6. A process according to claim 5, wherein the organic base is a trialkylamine. The method according to claim 6, wherein the organic base fluoride is (C ₂ H ₅ ) ₃ N · 3HF. The organic compound to be fluorinated is represented by the formula (1):
R ¹ R ² CH-SR ³ (1)
(R ¹ and R ² are the same or different, and are a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aralkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, aryl group, aryloxy group, aralkyloxy group. , An alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an acyl group, a heterocyclic group, —CONR ⁴ R ⁵ (R ⁴ and R ⁵ are independently a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. ), Alkylsulfinyl group, aralkylsulfinyl group, arylsulfinyl group, cycloalkylsulfinyl group, heterocycloalkylsulfinyl group, sulfinyl group to which a heterocyclic group is bonded, alkylsulfonyl group, aralkylsulfonyl group, arylsulfonyl group, cycloalkyl A sulfonyl group, a cyano group or a nitro group to which a heterocyclic group is bonded, and any group may have a substituent, and R ¹ and R ² are bonded. (R ³ is an aryl group in which the position on the orientation where iodine can be substituted is a hydrogen atom, and other positions may have a substituent.)
The method in any one of Claims 1-7 which have a sulfide group represented by these.