WO2003040088A1 - Process for preparation of fluorinated sulfides with iodine pentafluoride - Google Patents

Abstract

A process for preparation of fluorinated sulfides, characterized by reacting a sulfide of the general formula (1) having at least one hydrogen atom with IF5 to thereby replace at least one hydrogen atom of the sulfide by a fluorine atom: (1) wherein X, X1, X2 and Y are each independently hydrogen, halogeno, alkyl, cycloalkyl, heterocycloalkyl, haloalkyl, aralkyl, aryl, alkoxy, aryloxy, aralkyloxy, alkoxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl, acyl, -CONR1R2 (wherein R1 and R2 are each independently hydrogen, alkyl, aryl, or aralkyl), alkylsulfinyl, aralkylsulfinyl, arylsulfinyl, cycloalkylsulfinyl, hetero- cycloalkylsulfinyl, alkylsulfonyl, aralkylsulfonyl, aryl- sulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, a heterocyclic group, cyano, or nitro; R is alkyl, cycloalkyl, haloalkyl, aralkyl, aryl or a heterocyclic group; and n is an integer of 1 to 20.

Description

 Production of fluorinated sulfides with iodine pentafluoride

 Technical field

The present invention relates to a method for producing fluorinated sulfides using iodine pentafluoride (IF ₅ ).

 Background art

A hydrogen atom bonded to a carbon atom of the side chain of sulfide with IF _5, as the example was replaced with a fluorine atom, (1) International Application No. PCT / JP 01Z05017, (2) ChemistryLetters, 2001, 222 reported Have been. However, in any of the reported examples, in the fluorination of sulfides, only the hydrogen atom on the carbon to which the electron-withdrawing group at the α-position of sulfur was bonded was substituted by fluorine, or the methyl group bonded to sulfur. There is no example of fluorinating a sulfide side chain other than a methyl group, in which an electron-withdrawing group is not bonded to the carbon at the α-position, and a carbon other than the α-position carbon in the sulfide side chain. a hydrogen atom bonded to an example in which was replaced with a fluorine atom in IF ₅ is not at all. Furthermore, no examples of such a fluorination reaction accompanied by rearrangement have been reported.

An object of the present invention, for a wide range of sulfides include, in the providing child generic process for the preparation of fluorinated sulfides replacing the hydrogen atom under IF ₅ co fluorine atom.

 Disclosure of the invention

The present inventor has repeated studies in view of the above problems, a wide range of sulfide compounds were found to be fluorinated under IF ₅ coexist. That is, the present invention relates to the following method for producing a fluorinated sulfide.

Item 1. Formula having at least one hydrogen atom (1)

(Where X, X ¹ , X ² and Y are the same or independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a heterocycloalkyl group, a haloalkyl group, Alkyl group, aryl group, alkoxy group, aryloxy group, aralkyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, acyl group, one CONRiR ² (R ¹ and R ² are independent Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,), an alkylsulfinyl group, an aralkylsulfinyl group, an arylsulfinyl group, a cycloalkylsulfinyl group, a heterocycloalkylsulfinyl group, an alkylsulfonyl group , An aralkylsulfonyl group, an arylsulfonyl group, a cycloalkylsulfonyl group, a heterocycloalkylsulfonyl group, a heterocyclic group, a cyano group or a nitro group, and R is an alkyl group, a cycloalkyl group, an octaalkyl group , Aralkyl group, aryl group or Represents a heterocyclic group. n represents an integer from 1 to 20. )

In the sulfides such as shown, is reacted in the presence of IF _5, producing how fluorinated sulfides, which comprises replacing at least one Tsunomizu atom to a fluorine atom.

Item 2. The method according to claim 1, wherein in the sulfides represented by the formula (1), a hydrogen atom is substituted with a fluorine atom at the α-position of the sulfur atom and / or at a reaction position other than the α-position of the sulfur atom.

Item 3. The method according to claim 1, wherein the fluorination of the sulfides represented by the formula (1) involves a rearrangement reaction.

Item 4. The method according to claim 1, wherein the reaction is performed in the presence of IF ₅ and HF.

Claim 5. IF _5, HF, and a method according to claim 1, wherein the performing the reaction in the presence of an organic base and Z or ambient temperature molten salt.

Item 6. The method according to claim 5, wherein the organic base is triethylamine.

In the general formula (1), for example, when n = 3, the formula is as shown in the formula (2), and three X ¹ and three X ² may be the same or different.

Wherein R, X, X ¹ , X ² and Y are as defined above. ] The fluorinated product obtained by substituting at least one hydrogen atom with a fluorine atom according to the present invention is represented, for example, by the following formula (1A):

(1A)

(Wherein ^{x a, x la, x 2} a and Y ^a are the same or independently a hydrogen atom include a halogen atom (fluorine atom), fluorinated which may be an alkyl group, also be fluorinatedぃ cycloalkyl group, optionally fluorinated heterocycloalkyl group, optionally fluorinated ぃ alkyl group, optionally fluorinated aralkyl group, aryl group, alkoxy group , § Li one Ruokishi group, Ararukiruokishi group, § Le Koki deer Lupo group, § reel O carboxymethyl Cal Poni group, § Lal kill O propoxycarbonyl group, Ashiru group, one ^{C ON R 1! ^ 2 (} 1 ^ and 1 ² Independently represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.), An alkylsulfinyl group, an aralkylsulfinyl group, an arylsulfinyl group, a cycloalkylsulfenyl group Heterocycloalkyl sulfide El group, an alkylsulfonyl group, Ararukiru sulfonyl group, § reel sulfonyl group, a cycloalkyl sulfonyl group, Heteroshi black alkylsulfonyl group, a heterocyclic group, an Shiano group or a nitro group, R ^a is fluorinated R ^b represents an optionally substituted alkyl group, an optionally fluorinated cycloalkyl group, an optionally fluorinated haloalkyl group, an optionally fluorinated aralkyl group, an aryl group or a heterocyclic group. Represents a hydrogen atom or a fluorine atom, and n represents an integer of 1 to 20.)

 According to the production method of the present invention, the rearrangement of the substituents may occur, and thus the obtained fluorinated compound is represented by the above formula (1A), but the structure or skeleton is different from that of the raw material compound before fluorination. There can be.

 In addition, International Application No.PCTZ J P01 / 055017 and Chemistry Letters,

2001, if 222 sulfides present invention a partial structure which can occur various fluorination reaction by IF ₅ as reported in has, the present invention is such a fluorination reaction May occur simultaneously or stepwise.

Regarding the reaction of replacing a hydrogen atom with a fluorine atom in the present invention, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an acyl group, —CONR ¹ ! ^ ² ( R ¹ and R ² are as defined above, such as a substituent bonded through a carbonyl (C〇) group, or bonded through an oxygen atom such as an alkoxy group, an aryloxy group, or an aralkyloxy group. Hydrogen atoms on substituted substituents are not fluorinated.

 In the sulfides of the present invention represented by the formula (1) having at least one hydrogen atom, 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, noel, decyl, pendecyl, dodecyl, tridecyl, tetradecyl, It has a linear or branched chain such as pencil decyl, hexadecyl, heptyl decyl, and octadecyl (^ ~. ^ Alkyl group, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl Tert-butyl, pentyl, hexyl and the like, and a C i -C ₆ alkyl group having a straight or branched chain, and a substituent may be bonded.

The cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl cyclohexane, include 〇 ₃ ～〇 ₈ cycloalkyl Le group such Shikurookuchiru, c ₃ to c ₇ cycloalkyl groups are preferred, the substituent They may be combined.

 Examples of the heterocycloalkyl group include one in which one or more carbon atoms forming the cyclic structure of the above cycloalkyl group are substituted with a nitrogen atom, an oxygen atom, a sulfur atom, or the like, and the substituent is bonded. It may be.

Haloalkyl groups include trifluoromethyl group, trifluoroethyl group, trichloroethyl group, tetrafluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro port Hexyl group, perfluorooctyl group, perfluorodecyl group, 2- (perfluorooctyl) 'Having a straight or branched chain, such as a tyl group, a 1Η, 1Η, 3Η-tetrafluoropropyl group, a 1H, 1H, 5H-octafluoropentyl group, preferably a C ^ C e In the above-mentioned alkyl groups, those in which one to all hydrogen atoms have been replaced by halogen atoms can be mentioned.

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

 Examples of the phenyl 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.

The alkoxy group is a group represented by o- (the alkyl group and the alkyl group are the same as those described above). For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy , Pentyloxy, hexyloxy and the like, having a straight or branched chain (for example, ₆ to ₆ alkoxy groups, etc., and a substituent may be bonded.

Examples of the aryloxy group include a phenoxy group, a chlorophenoxy group, a methoxyphenoxy group, and a naphthyloxy group, and a substituent may be bonded. The Ararukiruokishi group, like 2-phenylalanine E chill O carboxymethyl, Benjiruokishi, 1-phenylalanine E chill O carboxymethyl, 3-phenylpropyl O carboxymethyl, etc. C ₇ ~ C _{2 0} Ararukiruokishi group such as 4-phenylbutyl Okishi is Can be

 Examples of the alkoxycarbonyl group include a C 0-(alkoxy) group in which the alkoxy group is the above-mentioned group. Specific examples include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, and n-butoxy. Cicarponyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl are exemplified.

Examples of the aryloxycarbonyl group include a CO— (aryloxy) group in which the aryloxy group is one of the above-mentioned groups, and specific examples thereof include a phenoxycarbonyl group, a chlorophenoxycarbonyl group, and a methoxyphenoxy group. Carbonyl group, naph Tiloxycarbonyl group and the like, and a substituent may be bonded.

 Examples of the aralkyloxycarbonyl group include a CO— (aralkyloxy) group in which the aralkyloxy group is one of the above-mentioned groups. Examples include 2-ethylpropoxycarbonyl, 3-phenylpropyloxypropyl, 4-phenylbutyloxycarbonyl, and naphthyloxycarbonyl, which may have a substituent.

 Examples of the acryl group include a linear or branched alkanoyl group having 1 to 6 carbon atoms, such as formyl, acetyl, propionyl, n-butyryl, isobutyryl, valeryl, isovaleryl, and pivaloyl, benzoyl and substituted acetyl groups. Examples of the substituted acetyl group 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-methylbenzoyl group, 41t Substituted benzoyl groups such as a monobutylbenzoyl group, a 4-methoxybenzoyl group, a 4-cyanobenzoyl group, and a 4-nitrobenzoyl group.

-CONR ^ ² ( ¹ and ² independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group) include carbamoyl, N-methylcarbamoyl,, N-dimethylcarbamoyl, N- Examples include a phenylcarbamoyl group, an N-cycloethylphenylcarbamoyl group, and an N, N-getylcarbamoyl group.

 Heterocyclic groups include piperidyl, furyl, chenyl, imidazolyl, oxazolyl, thiazolyl, pyrrolyl, pyrrolidinyl, triazolyl, benzothiazolyl, benzimidazolyl, oxaziazolyl, thiadiazolyl, indolyl, pyrazolinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl Examples thereof include pyridyl, benzofuryl, benzochenyl, and tetrazolyl, and a substituent may be bonded.

Alkylsulfinyl group (alkyl-SO—), aralkylsulfinyl group (α Aralkyl-S〇_), arylsulfinyl group (aryl-SO-), cycloalkylsulfinyl group (cycloalkyl-so-), heterocycloalkylsulfinyl group (heterocycloalkyl-so-), heterocyclic group Examples of the alkyl group, aralkyl group, aryl group, cycloalkyl group, heterocycloalkyl group, and heterocyclic group of the sulfiel group (one so-) are the same as those described above.

Alkylsulfonyl groups (alkyl one so ₂ -), § Lal Kill sulfonyl group (§ La alkyl - so ₂ -), § Li one Rusuruhoniru group (Ariru - so ₂ -), a cycloalkyl Rusuruhoniru group (cycloalkyl - so ₂ -), heterocycloalkyl alkylsulfonyl group (heterocycloalkyl - S_〇 ₂ -), bound sulfonyl group heterocyclic group (an S 〇 ₂ - alkyl group), Ararukiru group, Ariru group, a cycloalkyl group, heterocycloalkyl Examples of the alkyl group and the heterocyclic ring are as described above.

 Alkyl group having a substituent, alkoxy group having a substituent, aryl group having a substituent, aryloxy group having a substituent, aralkyloxy group having a substituent, cycloalkyl group having a substituent, heterocyclo having a substituent The number of substituents of the alkyl group and the heterocyclic group having a substituent is 1 to 5, preferably 1 to 3. Examples of the substituent include halogen, CiC alkoxy, CiC alkylthio, cyano, nitro, amino group, and hydroxyl group.As the alkyl group having a halogen, a part of hydrogen of the alkyl group or All substituted with fluorine or Z and chlorine or / and bromine or Z and iodine are included.

 In the fluorination reaction involving rearrangement, the skeleton of the structure may change as shown in Example 1. The following reaction mechanism I can be considered for this reaction. The stereochemistry of the double bond that is thought to be formed during the reaction is unknown.

(Reaction mechanism I)

That is, after the α-position hydrogen atom of the side chain of sulfide is fluorinated by IF _5, HF elimination occurs Orefin generates and then addition of the IF occurs that occurred in this in the system. It is presumed that the rearrangement reaction proceeds by opening the ring by attacking the three-membered thiophene salt formed by the elimination of iodine with F anion. After the rearrangement, the fluorination of the α-position of the sulfide proceeds. Hydrogen unsubstituted in the α-position Example 1 remains one is the possible to replace fluorine by increasing the number of equivalents of IF _5, also position shed by reducing the number of equivalents in the opposite It is also possible to leave two methylene hydrogens. In the compounds of formula (1), when the fluorine-substituted site is plural, thus, either adjust the amount of IF _5, the reaction conditions (reaction time, reaction temperature, presence or absence of the addition of HF, an organic base or room temperature By adjusting the presence or absence of the molten salt, only one fluorine substitution or two or more appropriate numbers and substitution positions of the fluorine substitution can be performed.

 Example 2 can be described in the same manner as Example 1.

Although the polyfluorination of the alkyl chain having 4 carbon atoms proceeds in Example 3, this fluorination reaction may also proceed by the same reaction mechanism II involving rearrangement as in Example 1. Sex is considered. The stereochemistry of the double bond that is thought to be formed during the reaction is unknown.

 (Reaction mechanism II)

 F

_{CI- S-CF 2 CF 2 CF} 2 CF 2 By changing the number of equivalents of HIF _5, it is also possible to control the degree of fluorination. Example 4 are conducted fluorine I匕reaction under coexistence of E t ₃ N-3HF is IF ₅ and ambient temperature molten salt, a similar rearrangement reaction proceeds, fluorinated sulfides is generated. The compound is just an intermediate in the middle of FIG. This is because the embodiment 3 4. While using IF ₅ of 8 moles, not only using IF ₅ of 1.2 moles in Example 4. This result by changing the number of equivalents of IF _5, shows that the number of fluorine substituents freely controls opening one le.

With IF ₅ ZE t ₃ N_ 3HF, on the reactivity of the IF ₅ becomes mild, implement a more select択的fluorination reaction, can result in successful.

The rearrangement reaction may take place at any position of the sulfide side chain, and various functional groups may be bonded to the rearranged side chain. 0 of progression of the fluorination is dependent on the number of equivalents of IF _5, the value is Kehhashi depending to the substrate to be fluorinated to replace the degree of hydrogen atoms with fluorine, IF ₅ the raw material compound. It is preferable to use at least 5 times the molar amount.

Fluorination of the present invention can be practiced using only IF _5, Ru can also be carried out in the presence of a presence or HF and organic bases and Z or ambient temperature molten salt HF.

 Organic bases include aliphatic amines (primary amines, secondary amines, tertiary amines), alicyclic amines (secondary amines, tertiary amines), and aromatic amines (primary amines, primary amines). Organic bases such as aminoamines, secondary amines, tertiary amines) and heterocyclic amines; wherein the aliphatic primary amines are methylamine, ethylamine, propylamine, butyramine, pentylamine, hexylamine, cyclohexylamine. And secondary aliphatic amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, and dihexylhexylamine. Examples of the amine include trimethylamine, triethylamine, and disopropylethylamine. , N, N, Ν ', N' - tetramethyl ethylene § Min, and the like;

Examples of alicyclic secondary amines include piperidine, piperazine, pyrrolidine, and morpholine, and examples of alicyclic tertiary amines include メ チ ル -methylpiperazine, Ν-methylpyrrolidine, and 5-diazabicyclo. [4.3.0] 1 Nonan 5-en, 1, 4 Diazabicyclo [2.2.2] octane;

 Examples of the aromatic amine include aniline, methylaniline, dimethylaniline, N, N-dimethylaniline, haloaline, nitroaniline and the like;

 Examples of the heterocyclic amine include pyridine, pyrimidine, piperazine, quinoline, imidazole, and the like, and further include amine compounds supporting a polymer such as polyallylamine and polyvinylpyridine;

Or a mixture thereof can be exemplified.

 The amount of the organic base used in the present invention can be selected in a large excess from the amount of the catalyst, but is preferably 0.01 to 20 mol per mol of the hydrogen-containing organic compound to be fluorinated. And more preferably 0.1 mol to 10 mol.

 The amount of HF used in the present invention can be selected in a large excess range from the amount of the catalyst, but is preferably 0.01 to 100 mol, more preferably 1 mol, per 1 mol of the hydrogen-containing organic compound to be fluorinated. Is from 0.1 mol to 20 mol.

Examples of the room temperature molten salt include (C ₂ H ₅ ) ₄ NF, 1-ethyl-13-methylimidazonium fluoride, (C ₂ H ₅ ) ₃ N— (HF) _n , and (C ₂ H ₅ ) ₄ NF— ( _{HF) n, (n- C 4} H 9) 3 N- (HF) n, (n- C 4 H 9) 4 NF- (HF) n, BF 3 · E t 2 0- (HF) n , such as ( n == 1 to 20), and a room temperature molten salt having a fluorine anion or HF.

 The reaction solvent may or may not be used, but is preferably used. Examples of the reaction solvent include aliphatic solvents such as pentane, hexane, heptane, cyclohexane, and petroleum ether, dichloromethane, dichloroethane, chloroform, chlorotrifluoromethane, 1,1,2-trichloromethane, 2, 1,2-dibromohexafluoropropane, 1,2-dibromohexafluoropropane, 1,2-dibumotetrafluoroethane, 1,1 -Difluorotetrachloroethane, 1,2-difluoropertrachloroethane, heptafluor-2,3,3-trichlorobutane, 1,1,1,3-tetraura

1, trichloroethane, polychloromouth 1, polychlorinated octalogenated aliphatic solvents such as trifluoroethylene, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, aptyloractone, Propylene carbonate Ester solvents such as acetonitrile, nitrile solvents such as propionitrile, aromatic solvents such as benzene, cyclobenzene, toluene, dichlorobenzene, fluorobenzene, nitrobenzene, etc., such as Jethyl ether, dipropyl ether, tetrahydrofuran, etc. Ether solvent, N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), water, nitromethane, N, N-getylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1 , 3-dimethyl-2-imidazolidinone (DMI), tetramethylperyl, 1,3, etc., used alone or as a mixture of two or more.

 The reaction temperature is from —70 ° C. to 200 ° C., preferably from 120 ° C. to 100 ° C., and the reaction time can be from 5 minutes to 200 hours, It can be set appropriately according to the desired position of fluorination and the number of substituted fluorine atoms.

The post-treatment after the reaction, excess for the reduction of oxidized organic compounds, since there was or for reducing excess residual IF ₅ or IF ₅ from certain oxidative compounds, inorganic, a variety of organic A reducing agent may be added.

 Examples of the reducing agent include zinc powder, tin, tin chloride, iron, aluminum, sodium thiosulfate, dithionite, butyltin hydride, sodium polo hydride, and lithium aluminum hydride. Anything is fine.

 The fluorinated sulfides thus obtained can be converted into various derivatives by an organic synthesis reaction that can be usually performed. For example, it can be converted to the corresponding sulfoxide derivative, sulfone derivative, sulfoximine derivative, or thiophene salt by oxidation reaction. Furthermore, it is also possible to conduct a reaction such as the Pummere rearrangement to lead to another derivative, and to synthesize a thiol derivative, a sulfinic acid derivative, or a sulfonic acid derivative by cutting a sulfur-carbon bond. it can. Further, a desulfurization reaction may be performed.

The fluorinated sulfides or various derivatives derived therefrom can be various pharmaceutical intermediates, agricultural chemical intermediates, and functional material intermediates. Functional materials include, for example, liquid crystal materials, surfactants, PAGs, resist leveling agents, ARCO I int -fr ÷ Y¾ (I ° ™ Γΐ) (% Ioui 9l) ^Z D¾) ^-S JI)

• 0886 V ^ffl : P-picture '9886 ^ 82: SIO'O'dY'O JOj a ^ inoiBO (ia) SH

 '(9) S

 ') OS' (6) 19 '(61) 69' (U) C9 '(6) 69' (S) 8A '(H)' (A) 28 '(ZI) 66' (9t) 80l OS '( 9) 60ΐ '(Π) ΟΠ' (Π) ΠΙ '(S9) 8tl' HI) ^ I '(0Z) 9fl') SSI '(OOl) SZI

^£ (6) 9Ai's) Ai'e% n) m '(Dm' (zz) m '(9) s' (II) S' (9) 8: si¾

'(6 Ό'ΖΖ' 9892 = / 'dl' ΡΡΡ) ll ^ n ί 'WZl Τ02' 9 * 892 = / 'άΐ' ΡΡΡ) S9- U ό '(ΖΗΓ0Ζ'Ο'ΖΖ'0'0S = / 'dl' ΡΡΡ) 8SH £>: ( ⁸ Ιθαθ 'hidden) trans-d _6I

-(ZH9

'HZ' Ρ) 9S

'(， · 6 Ί' ΖΙ '0 "03 = /' HI 'ΡΡΡ) 00 · 9' (Η8 '96' 8 Q-( ^s I0a3 'OQf) Awake—

(% Ζ 8) SHI ε ε ζ ¾Υ ^ ¾, 碡 * Unan ^ —: Roma ^ 0,

Ϊ3¾Ν m ^Ε 03Η¾Ν am ^S 0 ^Z S ^Z BN% 0I 繳 回 ΐ L ΐωθΖ Λ (^-οτ 、, / ^ /: ΐ く 氺 氺 ^ 氺 氺 ¾ 缀 ¾ ¾ ¾¾ί¾ ° ¾ ¾¾ ¾¾ ^ mine, 乙 t 乙a

2a, ^ 9 ^^ a S {, Soil ms army (iora ο · ΐ) §ιπτ ε z T (# ^> ¾n ^ ¾

(ζioΐ) (¾ioin Γ9ΐ) ^Ζ Ι3¾)-1 instrument

. ςα; $ ¾¾ <5Ί ^ コ ¾ book

, Soil w

° 9: ^^: 1: # ^ ΨΟ) 5ΐ; Ko ^ 9 ^ ^^ ¾! SOd: d, "Η

 ετ

LtmilHAillDA 8800read 0 OAV 259 mg (1.0 iMol) of the dissolved substrate was added dropwise at room temperature, and the fluorination reaction was carried out at room temperature for 72 hours with stirring.

After the reaction, the reaction solution was quenched with ice water and extracted four times with 20 ml of ether. Organic phase _{10% Na 2 S 2 0 3} aq, saturated NaHCO ₃ aq, washed with saturated NaCl aq, then isolated and purified by Karamuku port Matogurafi one, the A 224mg (76%) was obtained.

_ ^ Spectrum data

'H-NMR (400MHz, CDC1 3): δ 1.33 (t, 3H, 7.3Hz), 1.42 (d, 3H, /=7.1Hz), 3.51-3.65 (m, 1H), 4.21-4.41 (m, 2H ), 7.30 (d, 2H, 7-8.6Hz), 7.43 (d, 2H, /-8.6Hz).

^{19 F - NMR (376MHz, CDC1} 3): δ? 115.56 (dd, IF, 7 = 255.4, 18.9Hz),? 103.36 (dd, IF, 7 = 255.4, 9.2Hz).

Example 3

IF fluororesin container _{5 -CH 2 C1CH 2 C1 (16.7mol} %) (4.8 negation ol), a substrate, placed 0 lmg (1.0 thigh ol), 68 hours at room temperature with stirring, was carried out fluorination reaction.

After the reaction, the reaction solution was quenched with ice water and extracted four times with 20 ml of ether. Organic phase _{10% Na 2 S 2 0 3} aq, saturated NaHCO ₃ aq, washed with saturated NaCl, then isolated and purified by Karamuku port Matogurafi one, to give 103mg (30%).

 _ ^ Spectrum data

_{Ή-NMR (CDC1 3) (} 56.01 (1H, tt, J = 52.4 Hz, J = 5.4 Hz), 7.41 (2H; d, J = 7.8 Hz), 7.59 (2H, d, J = 7.8 Hz);

¹⁹ F- negation _{R (CDC1 3) δ-137.62} (2F, dm, J = 52.4 Hz), -129.71 (2F, m), -121.48 (2F, in), -87.46 (2F, m);

Example 4

7 Fluorine IF the resin vessel Bruno Et ₃ N_3HF (1.2 mmol), methylene (4 ml) chloride, substrate I, 2 0 put lmg (1.0 negation ol), stirring 22 hours at 40 ° C, the fluorination reaction line One, second.

After the reaction, the reaction solution was quenched with ice water and extracted four times with 20 ml of ether. The organic phase was _{10% Na 2 S 2 0 3} aq, saturated NaHCO ₃ aq, washed with saturated NaCl aq, it was isolated and purified by subsequent column chromatography to obtain 1 12mg (44%).

A spectrum data

_{Ή- MR (CDC1 3) 61.16 (} 3H, ί, J = 7.6 Hz), 1.88-2.19 (2H, m), 5.49 (1H, dt, J-2.2 Hz, J = 53.7 Hz), 7.35 (2H, d , J = 8.3 Hz), 7.53 (2H, d, J = 8.3 Hz); 19 F - NMR (CDC1 3) (5-144.93-144.77 (IF, ni), -135.74 (IF, ddd, J = 12.8Hz , J = 53.7 Hz, J = 283.8 Hz), -127.97 (IF, ddd, J = 283.8, J = 53.7, J = 12.8)

Claims

The scope of the claims

 1. Formula having at least one hydrogen atom (1)

(Wherein X, XX ² and Y each independently represent a hydrogen atom, a halogen atom, an alkyl group 5, a cycloalkyl group, a heterocycloalkyl group, an octaalkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryl group Roxy group, aralkyloxy group, alkoxyl propyl, 7 lyroxycarponyl group, aralkyloxycarponyl group, acryl group, -CON R ^ ² (R ¹ and R ² are independently hydrogen atom, alkyl Represents an alkyl group, an aryl group or an aralkyl group.), An alkylsulfinyl group, an aralkyl0 sulfinyl group, an arylsulfinyl group, a cycloalkylsulfinyl group, a heterocycloalkylsulfiel group, an alkylsulfonyl group, an aralkylsulfonyl group, Arylsulfonyl group, cycloalkylsulfonyl group, heterocycloalkyl R represents a rufonyl group, a heterocyclic group, a cyano group or a nitro group, and R represents an alkyl group, a cycloalkyl group, an octaalkyl group, an aralkyl group, an aryl group or a compound having 5 to 5 ring groups, and n represents 1 to 20. Indicates an integer up to.)

In the sulfides indicated, is reacted in the presence of IF _5, the preparation of fluorinated sulfides, characterized by replacing the fluorine atom at least one hydrogen atom.

 2. In the sulfides represented by the formula (1), a hydrogen atom is replaced with a fluorine atom at a reaction position other than the α-position of a sulfur atom and Z or the 0! -Position of a sulfur atom. Method for producing sulfides.

 3. The process for producing a fluorinated sulfide according to claim 1, wherein the fluorination of the sulfide represented by the formula (1) involves a rearrangement reaction.

4. IF ₅ and claim 1, characterized in that the reaction is carried out in the presence of HF, 2 and 3 the preparation of fluorinated sulfides described.

5 5. IF _5, HF, and organic bases, and Z or claim 1, characterized that you perform the reaction in the presence of a room temperature molten salt, 2 and 3 the preparation of fluorinated sulfides described.

6. The fluorinated sulfide according to claim 5, wherein the organic base is triethylamine. Manufacturing method.