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  • C07C2601/14—The ring being saturated

Definitions

• the present disclosure relates to a method for producing an organic fluorine compound, and the like.
• Patent Documents 1 and 2 A method of applying a fluorinating agent such as IF5 to an organic compound containing a sulfur atom to produce an organic fluorine compound has been known (Patent Documents 1 and 2).
• the desired organic fluorine compound is produced, and at the same time, a sulfur-containing substance is produced as a by-product from the organic compound containing a sulfur atom (in other words, the raw material compound).
• An alkali treatment method has been known as a method for removing this sulfur-containing substance and purifying an organic fluorine compound (especially an organic fluorine compound produced by using a fluorinating agent containing IF5 ).
• An object of the present disclosure is to provide a method for producing an organic fluorine compound capable of removing sulfur-containing substances to a high degree, or to provide an organic fluorine compound-containing composition having a low content of sulfur-containing substances.
• Section 1 A method for producing an organic fluorine compound (p f ), comprising: [A] reaction step A in which an organic sulfur compound (s s ) is fluorinated with a fluorinating agent to obtain a composition ( ⁇ ) containing an organic fluorine compound (p f ); and [B] at a temperature of 40° C. or higher , a post-treatment step B of reacting the composition ( ⁇ ) with a nucleophilic reagent
• a manufacturing method including: Section 2.
• Item 1 The method according to Item 1, wherein the reaction of the post-treatment step B is carried out in the presence of water.
• Item 3. Item 3.
• the oxidizing agent is IF 5 , bromine trifluoride, formula (3a): X 2 -Z (3a) [In the formula, X2 is a halogen atom, Z is a halogen atom or NZ 1 Z 2 , Z 1 and Z 2 are each independently an organic group, or Z 1 and Z 2 are bonded together to form a ring. ] and a compound represented by formula (3a′): [In the formula, X3 is a halogen atom, ClO4 , or NO3 ; Q 1 to Q 4 are each independently H or an organic group, and any two of Q 1 to Q 4 may combine with each other to form a ring. ] Item 6.
• the oxidizing agent contains at least one selected from the group consisting of the compounds represented by: Item 7.
• the X 2 is an iodine atom, a bromine atom or a chlorine atom
• the Z is an iodine atom, a bromine atom, a chlorine atom or NZ 1 Z 2
• said X 3 is ClO 4 or NO 3 ; 7.
• the fluorinating agent is a fluorinating agent containing IF 5 , fluoride ion, and amine.
• the basic compound has the formula: M m X n [In the formula, M is a cation, X is OH, CN or CO3 , m is the valence of X and n is the valence of M. ] 12.
• Item 14. The production method according to Item 13, wherein M is a metal cation or optionally substituted ammonium.
• Item 15 Item 14.
• Item 16 Item 16.
• Item 17 The production method according to any one of Items 1 to 16, wherein the temperature of the post-treatment step B is 50°C or higher. Item 18. Item 18. The production method according to any one of Items 1 to 17, wherein the time for the post-treatment step B is 0.5 hours or more. Item 19. Item 19. The production method according to any one of Items 1 to 18, wherein the post-treatment step B is performed in an organic solvent WS having a water solubility of 10 [g/100 g-water (20°C)] or more. . Item 20.
• the post-treatment step B is It is carried out in a mixed solvent containing the organic solvent WS and an organic solvent WP whose solubility in water is less than 10 [g/100 g-water (20 ° C.)], and the mass of the organic solvent WS is the organic Item 20.
• Item 21. moreover, (1) the reaction solution obtained by reacting the composition ( ⁇ ) with a nucleophilic reagent or (2) the organic phase obtained by separating the reaction solution into a crystallization treatment, an adsorption treatment, and a distillation Item 21.
• Item 22 The production method according to any one of Items 1 to 20, wherein at least one treatment selected from the group consisting of treatments is performed.
• Item 22 Item 23.
• Item 23. containing an organic fluorine compound (p f ) and a sulfur-containing substance (b s ) (however, the organic fluorine compound (p f ) is excluded from the sulfur-containing substance (b s )), and the sulfur-containing substance
• the composition ( ⁇ ) wherein the content of (b s ) is 10000 mass ppm or less in terms of sulfur content.
• Item 24 Item 24.
• a method for producing an organic fluorine compound that can remove sulfur-containing substances to a high degree is provided.
• the present disclosure also provides an organic fluorine compound-containing composition having a low content of sulfur-containing substances.
• halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• organic group means a group formed by removing one hydrogen atom from an organic compound.
• an alkyl group optionally having one or more substituents, an alkenyl group optionally having one or more substituents, an alkynyl group optionally having one or more substituents, an aryl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, non-aromatic heterocyclic group optionally having one or more substituents heteroaryl group optionally having one or more substituents, cyano group, aldehyde group, RO-, RCO-, RCOO-, RSO2- , ROCO-, and ROSO 2- (wherein R is independently an alkyl group optionally having one or more substituents, an alkenyl group optionally having one or more substituents, an alkynyl group optionally having one or more substituents, an aryl group optionally having one or more substituents,
• an "alkyl group” can be a straight-chain alkyl group, a branched-chain alkyl group, or a cyclic alkyl group (eg, a cycloalkyl group).
• an "alkyl group” can be, for example, a C1-C20 alkyl group, a C1-C12 alkyl group, a C1-C6 alkyl group, a C1-C4 alkyl group, or a C1-C3 alkyl group.
• alkyl group includes, for example, methyl group, ethyl group, propyl group (n-propyl group, isopropyl group), butyl group (n-butyl group, isobutyl group, sec-butyl group, tert- butyl group), pentyl group, and hexyl group, linear or branched alkyl groups.
• alkyl group includes, for example, a cyclic alkyl group or cycloalkyl group (eg, C3-C8 cycloalkyl group) such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. be done.
• a cyclic alkyl group or cycloalkyl group eg, C3-C8 cycloalkyl group
• cyclopropyl group cyclobutyl group
• cyclopentyl group cyclohexyl group
• an "alkenyl group” can be, for example, a C2-C10 alkenyl group, a C2-C6 alkenyl group, and the like.
• the "alkenyl group” includes, for example, vinyl group, allyl group, 3-butenyl group, 1-propen-1-yl group, 2-propen-1-yl group, isopropenyl group, 2-butene Linear or branched alkenyl groups such as -1-yl, 4-penten-1-yl, and 5-hexen-1-yl groups are included.
• the "alkenyl group” includes, for example, a cyclic alkenyl group or cycloalkenyl group (e.g., C3-C8 cycloalkenyl group).
• an “alkynyl group” can be, for example, a C2-C10 alkynyl group.
• the "alkynyl group” includes, for example, ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 4-pentyn-1-yl, and 5-hexyn-1-yl. , linear or branched alkynyl groups.
• an "aryl group” can be, for example, monocyclic, bicyclic, tricyclic, or tetracyclic.
• the "aryl group” can be, for example, a C6-C18 aryl group, a C6-C16 aryl group, a C6-C14 aryl group, a C6-C12 aryl group, and the like.
• the "aryl group” includes, for example, a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, 2-anthryl group and the like.
• the "aryloxy group” can be a group in which an oxygen atom is bonded to an aryl group (aryl group -O-).
• the "aryloxy group” can be, for example, a C6-C18 aryloxy group, a C6-C16 aryloxy group, a C6-C14 aryloxy group, a C6-C12 aryloxy group, and the like.
• the "aryloxy group” includes, for example, a phenoxy group, a naphthyloxy group, and the like.
• the "aralkyl group” can be, for example, a C7-C19 aralkyl group, a C7-C17 aralkyl group, a C7-C15 aralkyl group, a C7-C13 aralkyl group, a C7-C10 aralkyl group, and the like.
• aralkyl group includes, for example, benzyl group, phenethyl group, diphenylmethyl group, 1-phenylethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 2,2-diphenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group, 5-phenylpentyl group, 2-biphenylylmethyl group, 3-biphenylylmethyl group, 4-biphenylylmethyl group and the like.
• a “non-aromatic heterocyclic group” can be, for example, monocyclic, bicyclic, tricyclic, or tetracyclic.
• the term “non-aromatic heterocyclic group” refers to, for example, a non- It can be an aromatic heterocyclic group.
• the "non-aromatic heterocyclic group” can be saturated or unsaturated.
• non-aromatic heterocyclic group includes, for example, a tetrahydrofuryl group, an oxazolidinyl group, an imidazolinyl group, an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, an azepanyl group, an azocanyl group, a piperazinyl group, and a diazepinyl group.
• diazocanyl group tetrahydropyranyl group, morpholinyl group, thiomorpholinyl group, 2-oxazolidinyl group, dihydrofuryl group, dihydropyranyl group, dihydroquinolyl group and the like.
• heteroaryl group refers to, for example, a monocyclic aromatic heterocyclic group (e.g., a 5- or 6-membered monocyclic aromatic heterocyclic group), and an aromatic condensed heterocyclic group (e.g., 5- to 18-membered aromatic condensed heterocyclic groups).
• 5- or 6-membered monocyclic aromatic heterocyclic group includes, for example, pyrrolyl group, furyl group, thienyl group, pyrazolyl group, imidazolyl group, isoxazolyl group, oxazolyl group, isothiazolyl group, thiazolyl group , triazolyl group, oxadiazolyl group, thiadiazolyl group, tetrazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group and the like.
• "5- to 18-membered aromatic condensed heterocyclic group” includes, for example, isoindolyl group, indolyl group, benzofuranyl group, benzothienyl group, indazolyl group, benzimidazolyl group, 1,2-benzisoxazolyl benzoxazolyl group, 1,2-benzisothiazolyl group, benzothiazolyl group, isoquinolyl group, quinolyl group, cinnolinyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, pyrazolo[1,5-a]pyridyl group, imidazo[1,2-a]pyridyl groups and the like can be included.
• RO- refers to an alkoxy group, an aryloxy group (e.g., a C6-C18 aryloxy group such as a phenoxy group and a naphthoxy group), and an aralkyloxy group (e.g., a benzyloxy group, a phenethyloxy group, etc.). (C7-C19 aralkyloxy groups).
• an "alkoxy group” can be a group in which an oxygen atom is bonded to an alkyl group (alkyl-O-).
• alkoxy group refers to, for example, a C1-C20 alkoxy group, a C1-C12 alkoxy group, a C1-C6 alkoxy group, a C1-C4 alkoxy group, a C1-C3 alkoxy group, or a straight or branched chain It can be a cyclic alkoxy group such as a linear alkoxy group, a C3-C8 cycloalkoxy group, a C3-C7 cycloalkoxy group, a C4-C7 cycloalkyl group.
• alkoxy group includes, for example, methoxyl group, ethoxy group, propoxy group (n-propoxy group, isopropoxy group), butoxy group (n-butoxy group, isothoxy group, sec-butoxy group, tert -butoxy group), linear or branched alkoxy groups such as pentyloxy group and hexyloxy group, and cyclic alkoxy groups such as cyclopropoxy group, cyclobutoxy group, cyclopentoxy group and cyclohexoxy group.
• RCO- means, for example, an alkylcarbonyl group (e.g., an acetyl group, a propionyl group, a (C1-C10 alkyl)carbonyl group such as a butyryl group), an arylcarbonyl group (e.g., a benzoyl group, a naphthoyl group). (C6-C18 aryl)carbonyl groups such as ), and aralkylcarbonyl groups (eg, (C7-C19 aralkyl)carbonyl groups such as a benzylcarbonyl group and a phenethylcarbonyl group).
• alkylcarbonyl group e.g., an acetyl group, a propionyl group, a (C1-C10 alkyl)carbonyl group such as a butyryl group
• arylcarbonyl group e.g., a benzoyl group, a naphthoy
• RCOO- is, for example, an alkylcarbonyloxy group (e.g., (C1-C10 alkyl)carbonyloxy group such as an acetyloxy group, propionyloxy group, butyryloxy group), an arylcarbonyloxy group (e.g., (C6-C18 aryl)carbonyloxy groups such as benzoyloxy group and naphthoyloxy group), and aralkylcarbonyloxy groups (e.g. (C7-C19 aralkyl)carbonyloxy groups such as benzylcarbonyloxy group and phenethylcarbonyloxy group) can include
• RSO 2 - is, for example, an alkylsulfonyl group (e.g., a C1-C10 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group), an arylsulfonyl group (e.g., a phenylsulfonyl group) , C6-C18 arylsulfonyl groups such as naphthylsulfonyl groups), and aralkylsulfonyl groups (eg, C7-C19 aralkylsulfonyl groups such as benzylsulfonyl groups and phenethylsulfonyl groups).
• alkylsulfonyl group e.g., a C1-C10 alkylsulfonyl group such as a methylsulf
• ROCO- is, for example, an alkoxycarbonyl group (e.g., a (C1-C10 alkoxy)carbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group), an aryloxycarbonyl group (e.g., phenoxy carbonyl group, (C6-C18 aryloxy) carbonyl group such as naphthoxycarbonyl group), and aralkyloxycarbonyl group (e.g., benzyloxycarbonyl group, (C7-C19 aralkyloxy) carbonyl group such as phenethyloxycarbonyl group) can be included.
• alkoxycarbonyl group e.g., a (C1-C10 alkoxy)carbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group
• aryloxycarbonyl group e.
• ROSO 2 - is, for example, an alkoxysulfonyl group (e.g. C1-C10 alkoxysulfonyl group such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group), aryloxysulfonyl group (e.g.
• phenoxysulfonyl groups C6-C18 aryloxysulfonyl groups such as naphthoxysulfonyl groups
• aralkyloxysulfonyl groups eg, C7-C19 aralkyloxysulfonyl groups such as benzyloxysulfonyl groups and phenethyloxysulfonyl groups.
• an alkyl group optionally having one or more substituents an alkenyl group optionally having one or more substituents
• an alkynyl group optionally having one or more substituents aryl group optionally having one or more substituents
• an aralkyl group optionally having one or more substituents “Non-aromatic heterocyclic group optionally having one or more substituents”
• heteroaryl group optionally having one or more substituents”
• substituents in are, respectively, halo, nitro, cyano, oxo, thioxo, carboxyl, sulfo, sulfamoyl, sulfinamoyl, sulfenamoyl, RO-, RCO-, RCOO-, RSO 2 -, ROCO-, and ROSO 2 - (wherein R r has the same meaning as defined above) can be included.
• halo groups can include fluoro, chloro, bromo, and iodo groups.
• the number of substituents may be in the range of 1 to the maximum substitutable number (eg, 1, 2, 3, 4, 5, 6).
• heterocycloalkyl group includes, for example, one or more carbon atoms forming a cyclic structure of a cycloalkyl group substituted with a nitrogen atom, an oxygen atom, a sulfur atom, or the like. mentioned.
• a "monoalkylamino group” can be, for example, an amino group mono-substituted with a C1-C6 alkyl group.
• a "dialkylamino group” can be, for example, an amino group disubstituted with the same or different C1-C6 alkyl groups.
• the dialkylamino group includes, for example, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, dibutylamino group, dipentylamino group, dihexylamino group and methylethylamino group.
• methylpropylamino group methylbutylamino group, methylpentylamino group, methylhexylamino group, ethylpropylamino group, ethylbutylamino group, ethylpentylamino group, ethylhexylamino group, propylbutylamino group, propylpentylamino group, propyl
• Examples thereof include amino groups disubstituted with C1-C6 alkyl groups such as hexylamino group, butylpentylamino group, butylhexylamino group and pentylhexylamino group.
• acylamino group includes acylamino groups having 1 to 8 carbon atoms such as formylamino group, benzoylamino group, acetylamino group, propionylamino group, n-butyrylamino group (e.g., formylamino group, alkanoyl amino group, arylcarbonylamino group).
• alkylthio group includes -S- (C1-C6 alkyl group) and the like (the C1-C6 alkyl group is the same as described above).
• the "heterocyclic group” includes, for example, a piperidyl group, a furyl group, a thienyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a pyrrolyl group, a pyrrolidinyl group, a triazolyl group, a benzothiazolyl group, a benzimidazolyl group, and an oxadiazolyl group.
• thiadiazolyl group indolyl group, pyrazolyl group, pyridazinyl group, cinolinyl group, quinolyl group, isoquinolyl group, quinoxalyel group, pyrazinyl group, pyridyl group, benzofuryl group, benzothienyl group, tetrazolyl group, 5- to 10-membered Examples include monocyclic or bicyclic heterocyclic groups having one or more heteroatoms selected from nitrogen, oxygen, and sulfur as ring-constituting atoms.
• the "aromatic heterocyclic group” includes furyl, thienyl, imidazolyl, oxazolyl, thiazolyl, pyrrolyl, triazolyl, benzothiazolyl, benzimidazolyl, oxadiazolyl, thiadiazolyl, indolyl, pyrazolyl, pyridazinyl, cinnolinyl, quinolyl, isoquinolyl, 5- to 10-membered, monocyclic or bicyclic rings comprising one or more heteroatoms selected from nitrogen, oxygen, and sulfur, such as quinoxalinyl, pyrazinyl, pyridyl, benzofuryl, benzothienyl, tetrazolyl, etc.
• a heteroaryl group having as an atom can be mentioned.
• acyl group includes a formyl group; a linear or branched C 2- an alkanoyl group of 6; and an arylcarbonyl group of 7 to 15 carbon atoms such as a benzoyl group.
• alkylsulfinyl group examples include “alkylsulfinyl group”, “aralkylsulfinyl group”, “arylsulfinyl group”, “cycloalkylsulfinyl group”, “heterocycloalkylsulfinyl group”, and “sulfinyl group with heterocyclic group”
• alkyl group, aralkyl group, aryl group, cycloalkyl group, heterocycloalkyl group, and heterocyclic group examples include those described above.
• alkylsulfonyl group examples include “alkylsulfonyl group”, “aralkylsulfonyl group”, “arylsulfonyl group”, “cycloalkylsulfonyl group”, “heterocycloalkylsulfonyl group”, and “heterocyclic group-bonded sulfonyl group”
• alkyl group, aralkyl group, aryl group, cycloalkyl group, heterocycloalkyl group, and heterocyclic group examples include those described above.
• ester group includes, for example, an acyl-O- group and an alkoxy-CO- group.
• acyl and alkoxy include the aforementioned “acyl group” and “alkoxy group”.
• groups having substituents such as “an alkyl group having one or more substituents”, “alkoxy groups having one or more substituents”, and “alkenyl groups having one or more substituents”
• the number of substituents in can be, for example, 1 to the maximum number of substitutable, 1 to 10, 1 to 8, 1 to 6, 1 to 5, preferably 1 to 3 can.
• the substituent is not particularly limited as long as it is inert in the fluorination reaction with the fluorinating agent described below.
• substituents include halogen atoms, C1-C6 alkoxy groups, C1-C6 alkylthio groups, cyano groups, nitro groups, amino groups, hydroxyl groups, C1-C6 alkyl-carbonyloxy groups (eg, acetoxy), C1-C6 Alkoxy-carbonyl groups (eg, isopropyloxycarbonyl), C3-C6 cycloalkyl groups (eg, cyclohexyl), and the like.
• Alkyl groups having halogen include those in which some or all of the hydrogen atoms in an alkyl group are substituted with fluorine atoms.
• aralkyl group having one or more substituents aryl group having one or more substituents
• aryloxy group having one or more substituents one or more cycloalkyl group having a substituent
• heterocycloalkyl group having one or more substituents heterocyclic group having one or more substituents
• monoalkylamino having one or more substituents group
• dialkylamino group having one or more substituents dialkylamino group having one or more substituents
• acylamino group having one or more substituents alkylsulfinyl group having one or more substituents
• one or more substituted aralkylsulfinyl group having a group arylsulfinyl group having one or more substituents
• cycloalkylsulfinyl group having one or more substituents heterocycloalkylsulfinyl group having one or more substituents
• group sulfiny
• the substituent is not particularly limited as long as it is inert in the fluorination reaction with the fluorinating agent described below.
• the number of substituents in the "aliphatic 4- to 7-membered ring having one or more substituents" is 1-5, preferably 1-3.
• the substituent is not particularly limited as long as it is inert in the fluorination reaction with the fluorinating agent described below.
• Substituents include C1-C6 alkyl groups, halogen atoms, C1-C6 alkoxy groups, C1-C6 alkylthio groups, cyano groups, nitro groups, amino groups, hydroxyl groups, carboxyesters and the like.
• Compounds represented by the following formulas are also included in aliphatic 4- to 7-membered rings having substituents.
• the number of substituents in the "acyl group having one or more substituents" is 1 to 5, preferably 1 to 3.
• the substituent is not particularly limited as long as it is inert in the fluorination reaction with the fluorinating agent described below.
• substituents include halogen atom-substituted acetyl groups such as chloroacetyl group, bromoacetyl group, dichloroacetyl group and trifluoroacetyl group; alkoxy-substituted acetyl groups such as methoxyacetyl group and ethoxyacetyl group; and alkylthio-substituted groups such as methylthioacetyl group.
• acetyl group phenoxyacetyl group, phenylthioacetyl group, 2-chlorobenzoyl group, 3-chlorobenzoyl group, 4-chlorobenzoyl group, 4-methylbenzoyl group, 4-t-butylbenzoyl group, 4-methoxy
• benzoyl groups such as benzoyl group, 4-cyanobenzoyl group, 4-nitrobenzoyl group and the like can be mentioned.
• the method for producing an organic fluorine compound (p f ) comprises: [A] reaction step A in which an organic sulfur compound (s s ) is fluorinated with a fluorinating agent to obtain a composition ( ⁇ ) containing an organic fluorine compound (p f ); and [B] at a temperature of 40° C. or higher , a post-treatment step B of reacting the composition ( ⁇ ) with a nucleophilic reagent including.
• the composition ( ⁇ ) is not particularly limited as long as it is produced from the organic sulfur compound (s s ) by a fluorinating agent and contains an organic fluorine compound (p f ) corresponding to the organic sulfur compound (s s ).
• the composition ( ⁇ ) can be, for example, a crude organic fluorine compound containing a sulfur-containing substance (b s ) as an impurity. Note that organic fluorine compounds (p f ) are excluded from the sulfur-containing substances (b s ).
• the fluorination in the production method of the present disclosure is exemplified below. This also exemplifies the organofluorine compound (p f ) obtained by the production method of the present disclosure.
• Organic sulfur compounds include, for example, sulfide compounds (thioether compounds), thiocarbonyl compounds, and the like.
• Sulfide compounds are organic Producing sulfur compounds (s s ): (a-1) R 3 —CH 2 —S—R 3a ⁇ R 3 —CFH—S—R 3a ⁇ R 3 -CF 2 -SR 3a (a-2) R 3 -CHR 3b -SR 3a ⁇ R 3 -CFR 3b -SR 3a (b-1) R 3 —CO—CH 2 —S—R 3a ⁇ R 3 —CO—CFH—S—R 3a ⁇ R 3 -CO-CF 2 -SR 3a (b-2) R 3 -CO-CHR 3b -SR 3a ⁇ R 3 -CO-CFR 3b -SR 3a (c) R 3c R 3d C ⁇ C(SR 3a ) 2 ⁇ R 3c R 3d CH—CF 2 —SR 3a ( d ) R3cR3dC ( SR3a ')( SR3
• R 3a , R 3a ', and R 3a '' are the same or different, an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, 1 aryl group optionally having one or more substituents, alkenyl group optionally having one or more substituents, cycloalkyl group optionally having one or more substituents, one or more substituents a heterocycloalkyl group optionally having a group, or a heterocyclic group optionally having one or more substituents, or R 3a and R 3a ' together represent one or more substituents It represents an aliphatic 4- to 7-membered ring which may have a group.
• R 3 and R 3b are the same or different, an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or one or more substituents aryl group optionally having one or more substituents, alkenyl group optionally having one or more substituents, cycloalkyl group optionally having one or more substituents, optionally having one or more substituents Heterocycloalkyl group optionally having one or more substituents, heterocyclic group optionally having one or more substituents, alkoxy group optionally having one or more substituents, aryl optionally having one or more substituents oxy group, amino group, monoalkylamino group optionally having one or more substituents, dialkylamino group optionally having one or more substituents, acyl group, acylamino group, cyano group, one an alkylsulfinyl group optionally having one or more substituents, an aralkylsulfin
• the ring may be a halogen atom, an oxo group, an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or one or more substituents optionally substituted with one or more substituents selected from the group consisting of an aryl group optionally having one or more substituents, an alkenyl group optionally having one or more substituents, a cyano group, and an amino group.
• R 3c and R 3d are the same or different and are a hydrogen atom, an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, one or more aryl groups optionally having substituents, alkenyl groups optionally having one or more substituents, cycloalkyl groups optionally having one or more substituents, heterocycloalkyl group optionally having one or more substituents, heterocyclic group optionally having one or more substituents, alkoxy group optionally having one or more substituents, having one or more substituents an aryloxy group, a monoalkylamino group optionally having one or more substituents, a dialkylamino group optionally having one or more substituents, an acyl group, or an acylamino group, or R3c and R3d, together with the carbon atoms adjacent to them, may be bonded together to form an aliphatic 4- to 7-membered ring having one or more
• Sulfide compounds include methylethylsulfide, methylbenzylsulfide, 2-phenylthioacetate, 2-phenylthioacetophenone, C 6 H 5 —CO—CH 2 SCH 3 , bis(methylthio)methylbenzene, 2-octyl-1, 3-dithiane, 2-phenyl-2-trifluoromethyl-1,3-dithiolane, tris(ethylthio)hexane, 4-tris(methylthio)toluene, 2,2-diphenyl-1,3-dithiolane, the following compounds etc.
• R 6 and R 6a are the same or different and are a hydrogen atom, an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, one or more substituents aryl group optionally having one or more substituents, alkenyl group optionally having one or more substituents, cycloalkyl group optionally having one or more substituents, having one or more substituents heterocycloalkyl group optionally having one or more substituents, heterocyclic group optionally having one or more substituents, alkoxy group optionally having one or more substituents, optionally having one or more substituents An aryloxy group, an amino group, a monoalkylamino group optionally having one or more substituents, a dialkylamino group optionally having one or more substituents, an acyl group, and an acylamino group.
• R 6 and R 6a may combine with each other to form a cyclic structure.
• R 6a is the same or different and is a hydrogen atom, an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or one or more substituents aryl group optionally having one or more substituents, alkenyl group optionally having one or more substituents, cycloalkyl group optionally having one or more substituents, optionally having one or more substituents heterocycloalkyl group, heterocyclic group optionally having one or more substituents, alkoxy group optionally having one or more substituents, aryloxy optionally having one or more substituents group, amino group, monoalkylamino group optionally having one or more substituents, dialkylamino group optionally having one or more substituents, optionally having one or more substituents It represents an acyl group, an acylamino group optionally having one or more substituents, and
• R 6b is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, an aryl group optionally having one or more substituents, 1 alkenyl group optionally having one or more substituents, cycloalkyl group optionally having one or more substituents, heterocycloalkyl group optionally having one or more substituents, one or more represents a heterocyclic group which may have a substituent of ].
• Thiocarbonyl compounds include thiobenzophenone, O-decyl S-methyl dithiocarbonate, O-(4'-pentyl-[1,1'-bi(cyclohexane)]-4-yl) S-methyl dithiocarbonate, N- Butyl-N-(methylthio(thiocarbonyl))propanamide, O-(3,4,5-trifluorophenyl) 4-chloro-2,6-difluorobenzothioate, O-(3,4,5-tri fluorophenyl) 2',3,5-trifluoro-4''-propyl-[1,1':4',1''-terphenyl]-4-carbothioate, O-(3,4,5 -trifluorophenyl) 2',3,5-trifluoro-4''-pentyl-[1,1':4',1'-terphenyl]-4-carbothioate, dithiocarbonate O-(4 -is
• the fluorinating agent can be, for example, a fluorinating agent containing fluoride ions.
• the fluorinating agent containing fluoride ions is preferably an oxidizing agent and a fluorinating agent containing fluoride ions, more preferably IF5 , bromine trifluoride, a compound represented by the following formula (3a), and It may be at least one oxidizing agent selected from the group consisting of compounds represented by the following formula (3a') and a fluorinating agent containing fluoride ions.
• the fluorinating agent containing IF5 and fluoride ion can preferably be a fluorinating agent containing IF5 , fluoride ion (preferably HF), and an amine.
• X 2 -Z (3a) [In the formula, X2 is a halogen atom, Z is a halogen atom or NZ 1 Z 2 , Z 1 and Z 2 are each independently an organic group, or Z 1 and Z 2 are bonded together to form a ring. ].
• the oxidizing agent is preferably a halogen-based oxidizing agent or an ammonium salt-based oxidizing agent, and may be used alone or in combination of two or more.
• An oxidant is classified as a halogen-based oxidant when it contains both a halogen atom and an ammonium cation.
• the halogen-based oxidizing agent may be an oxidizing agent containing a halogen atom.
• the halogen-based oxidizing agent include IF 5 , bromine trifluoride, compounds represented by the above formula (3a), compounds represented by the above formula (3a′) containing a halogen atom, and the like.
• IF 5 , bromine trifluoride or compounds represented by formula (3a) are preferred.
• X2 is preferably an iodine atom, a bromine atom or a chlorine atom, more preferably a bromine atom.
• Z is preferably an iodine atom, a bromine atom, a chlorine atom or NZ 1 Z 2 .
• Z 1 and Z 2 are each independently an organic group, or Z 1 and Z 2 are bonded together to form a ring. Examples of the organic group include an alkyl group which may have one or more substituents, an acyl group which may have one or more substituents, and the like, and an alkylcarbonyl group and an arylcarbonyl group are preferable.
• the ring formed by combining Z 1 and Z 2 may have one or more substituents.
• ring examples include pyrrolidine ring, imidazolidine ring, oxopyrrolidine ring, pyridine ring, piperidine ring, isoquinoline ring, quinoline ring, pyrazole ring, imidazole ring, imidazoline ring, benzimidazole ring, triazole ring, hydantoin ring and the like. , pyrrolidine ring, imidazolidine ring and oxopyrrolidine ring are preferred.
• substituents on the ring include an oxo group, a C1-C10 alkyl group (preferably a C1-C4 alkyl group) and the like, and an oxo group and a C1-C3 alkyl group are preferred.
• the number of substituents can be 0-4, 0-3, 0-2, 1, 0, 2-4, and the like.
• Examples of compounds represented by formula (3a) include N-bromosuccinimide (sometimes abbreviated as NBS) and 1,3-dibromo-5,5-dimethylhydantoin (sometimes abbreviated as DBH). ), ClF, BrF, ICl, and IBr, and N-bromosuccinimide and 1,3-dibromo-5,5-dimethylhydantoin are preferred.
• NBS N-bromosuccinimide
• DBH 1,3-dibromo-5,5-dimethylhydantoin
• X3 is preferably an iodine atom, a bromine atom, ClO4 or NO3 , more preferably ClO4 or NO3 .
• Q 1 to Q 4 are each independently H or an organic group, and any two of Q 1 to Q 4 may combine with each other to form a ring.
• Organic groups include alkyl groups, alkenyl groups, aryl groups, aralkyl groups, cycloalkyl groups, and the like, which may have one or more substituents.
• the organic group includes an alkyl group optionally having one or more substituents, an alkenyl group optionally having one or more substituents, and an aryl group optionally having one or more substituents. preferable.
• any two of Q 1 to Q 4 may have one or more substituents in a ring formed by bonding with each other.
• the ring include a pyridine ring, a quinolium ring, an isoquinolium ring, a pyrrolidine ring, an imidazolidine ring, a pyrazole ring, an imidazole ring and the like, and a pyridine ring, an imidazolidine ring and a pyrazole ring are preferred.
• substituents on the ring include alkyl groups, alkenyl groups, aryl groups, aralkyl groups, cycloalkyl groups and the like.
• the number of substituents can be 0 to 4, 0 to 3, 0 to 2, 1, 0, etc., preferably 0 to 2.
• Q 1 to Q 4 are each independently more preferably H or a C1-C4 alkyl group optionally substituted with one phenyl group.
• Examples of compounds represented by formula (3a′) include NH 4 Br, NH 4 I, MeNH 3 Br, MeNH 3 I, Me 4 NBr, Me 4 NI, Et 4 NBr, Et 4 NI, Bu 4 NBr , Bu4NI , PhMe3NBr , PhMe3NI , PhCH2NMe3I , NH4ClO4 and other halogen - based oxidants, NH4NO3 and other ammonium salt - based oxidants, and NH4ClO4 , NH4NO3 are preferred.
• Fluoride ions may be compounds containing fluoride ions, such as HF, KF, KHF2 , NaF, CsF, TiF4 , LiF, MgF2 , CaF2 , NH4F , NHMe3F , NHEt3 . F, NMe4F , NEt4F , NHBu3F , NBu4F and the like, preferably HF, KHF2 and the like.
• fluoride ions such as HF, KF, KHF2 , NaF, CsF, TiF4 , LiF, MgF2 , CaF2 , NH4F , NHMe3F , NHEt3 .
• F, NMe4F , NEt4F , NHBu3F , NBu4F and the like preferably HF, KHF2 and the like.
• Amines include primary amines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, ethylenediamine; dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dicyclohexyl Secondary amines such as amine; trimethylamine, triethylamine (sometimes abbreviated as Et 3 N), diisopropylethylamine, tributylamine, N,N,N',N'-tetramethylethylenediamine, triphenylamine, diphenylmethyl tertiary amines such as amines; piperidine, piperazine, pyrrolidine, morpholine, N-methylpiperazine, N-methylpyrrolidine, 5-diazabicyclo[4.3.0]nonan-5-ene, 1,4-diazabicyclo[
• Alicyclic amines such as octane
• Aromatic amines such as aniline, methylaniline, dimethylaniline, N,N-dimethylaniline, haloaniline and nitroaniline
• Heterocycles such as pyridine, pyromidine, piperazine, quinoline and imidazole Formula amines and the like.
• fluorinating agents examples include IF5 - Et3N-3HF, IF5 - Et3N-5HF, IF5 -pyridine-HF, NBS(N-bromosuccinimide)-pyridine-9HF, DBH(1,3 -dibromo-5,5-dimethylhydantoin)-pyridine-9HF, BrF3 - KHF2 , 4-tert-butyl-2,6-dimethylphenyl sulfur trifluoride (e.g.
• Et2NSF3 (abbreviation: DAST), (MeOCH 2 CH 2 ) 2 NSF 3 (abbreviation: Deoxo-Fluor), 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octanebis(tetrafluoroborate) ) (e.g., SelectFluor (registered trademark), etc.), preferably IF 5 -Et 3 N-3HF, IF 5 -Et 3 N-5HF, IF 5 -pyridine-HF, NBS-pyridine-9HF, DBH- Pyridine-9HF, BrF3 - KHF2 .
• the amount of the fluorinating agent used in the reaction step A is preferably in the range of 0.01 to 20 mol, more preferably 0.1 mol, per 1 mol of the organic sulfur compound (s s ) as the starting compound. It is in the range of to 10 mol, more preferably in the range of 0.1 to 5 mol.
• the reaction temperature in the reaction step A is generally about -70°C to 200°C, preferably about -20°C to 120°C, more preferably about 0°C to 100°C.
• the reaction time of the reaction step A is usually within the range of 0.1 hour to 300 hours, preferably within the range of 0.5 hours to 100 hours, more preferably within the range of 2 hours to 48 hours.
• Reaction step A can be carried out in the presence or absence of a solvent, preferably in the presence of a solvent.
• the solvent include aliphatic solvents such as pentane, hexane, heptane, cyclohexane, and 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-trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoroprop
• Halogenated aliphatic solvents such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ⁇ -butyrolactone, propylene carbonate, nitrile solvents such as acetonitrile and propionitrile, benzene, Aromatic solvents such as chlorobenzene, toluene, dichlorobenzene, fluorobenzene, and nitrobenzene, ether solvents such as monoglyme, diglyme, diethyl ether, dipropyl ether, and tetrahydrofuran, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), Water, nitromethane, N,N-diethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone (DM)
• Preferred solvents are acetonitrile (MeCN), dichloromethane, ethyl acetate (AcOEt), monoglyme, and the like.
• the amount of solvent used in reaction step A is preferably in the range of 0.1 to 50 parts by mass, more preferably 0.5 to 1 part by mass, relative to 1 part by mass of the organic sulfur compound (s s ) as the starting compound. It is within the range of 20 parts by mass.
• Fluorination in reaction step A yields a composition ( ⁇ ) containing an organic fluorine compound (p f ).
• the composition ( ⁇ ) may contain one or more other substances in addition to the organic fluorine compound (p f ) and the sulfur-containing substance (b s ).
• Other substances include, for example, substances used in the production of organic fluorine compounds (eg, catalysts, bases), by-products, and the like.
• the product liquid containing the organic fluorine compound (p f ) obtained in the reaction step A can be subjected to the post-treatment step B as it is.
• Post-treatment process B In the post-treatment step B, the composition ( ⁇ ) containing the crude organic fluorine compound (p f ) obtained in the reaction step A is reacted with a nucleophilic reagent at a temperature of 40° C. or higher. This step reduces the sulfur-containing substances (b s ) contained in the crude product.
• nucleophilic reagents include anion source compounds.
• the anion source compound may be a compound capable of providing an anion in post-treatment step B.
• anion source compounds include carbanion source compounds, halogen ion source compounds, basic compounds, and the like.
• Anion source compounds can be used singly or in combination of two or more.
• Carbanion source compounds include NaCN, KCN, CuCN, Zn(CN) 2 , n-BuLi, sec-BuLi, t-BuLi, PhLi, EtMgBr, EtMgCl, MeMgBr, MeMgCl, Et2Zn , Me2Zn , Ph 2 Zn, PhMgBr, PhMgCl, etc.
• Halogen ion source compounds include sodium chloride, potassium chloride, lithium chloride, hydrochloric acid, sodium bromide, potassium bromide, lithium bromide, hydrobromic acid, sodium fluoride, potassium fluoride, lithium fluoride, hydrogen fluoride. acid, sodium iodide, potassium iodide, lithium iodide, hydroiodic acid, ammonium chloride, ammonium bromide, ammonium iodide, ammonium fluoride and the like.
• Examples of basic compounds include (1) alkali or alkaline earth metal acetates, carbonates, hydrogen carbonates, sulfates, sulfites, phosphates, hydrogen phosphates, alkoxide salts, hydroxides At least one selected from the group consisting of salts, hydride salts, thiosulfates, or amide salts, (2) alkali metals, and (3) amines.
• Acetates include sodium acetate, potassium acetate, lithium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, barium acetate and the like.
• Carbonates include sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, barium carbonate and the like.
• Examples of hydrogencarbonate include sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydrogencarbonate, rubidium hydrogencarbonate, cesium hydrogencarbonate, magnesium hydrogencarbonate, calcium hydrogencarbonate, and barium hydrogencarbonate.
• Sulfates include sodium sulfate, potassium sulfate, lithium sulfate, rubidium sulfate, cesium sulfate, magnesium sulfate, calcium sulfate, and barium sulfate.
• Sulfites include sodium sulfite, potassium sulfite, lithium sulfite, rubidium sulfite, cesium sulfite, magnesium sulfite, calcium sulfite, and barium sulfite.
• Phosphates include trisodium phosphate, tripotassium phosphate, trilithium phosphate, trirubidium phosphate, tricesium phosphate, trimagnesium phosphate, tricalcium phosphate, and tribarium phosphate.
• Hydrogen phosphates include sodium hydrogen phosphate, potassium hydrogen phosphate, lithium hydrogen phosphate, rubidium hydrogen phosphate, cesium hydrogen phosphate, magnesium hydrogen phosphate, calcium hydrogen phosphate, barium hydrogen phosphate, and the like. .
• Alkoxide salts include sodium methoxide, sodium ethoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium butoxide, lithium methoxide, lithium ethoxide, and the like.
• Hydroxide salts include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide and the like.
• Hydride salts include sodium hydride, potassium hydride, lithium hydride, and calcium hydride.
• Thiosulfates include sodium thiosulfate, potassium thiosulfate, lithium thiosulfate, rubidium thiosulfate, cesium thiosulfate, magnesium thiosulfate, calcium thiosulfate, and barium thiosulfate.
• Sulfites include sodium sulfite, potassium sulfite, lithium sulfite, rubidium sulfite, cesium sulfite, magnesium sulfite, calcium sulfite, and barium sulfite.
• Amide salts include sodium amide, potassium amide, lithium amide, rubidium amide, cesium amide, magnesium amide, calcium amide, and barium amide.
• Alkali metals include sodium, potassium, and lithium.
• Amines include aliphatic amines, alicyclic amines, aromatic amines, heterocyclic amines, and the like.
• the amine can suitably be a tertiary amine.
• Amines include triethylamine, tri(n-propyl)amine, tri(n-butyl)amine, diisopropylethylamine, cyclohexyldimethylamine, pyridine, lutidine, ⁇ -collidine, N,N-dimethylaniline, N-methylpiperidine, N -methylpyrrolidine, N-methylmorpholine and the like.
• the basic compound is preferably lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium carbonate, potassium sulfite ( K2SO 3 ), sodium sulfite ( Na2SO3 ) , sodium thiosulfate, potassium thiosulfate, ammonia and the like.
• the basic compound is more preferably potassium hydroxide, sodium hydroxide, potassium hydrogen carbonate, sodium hydrogen carbonate, potassium carbonate, potassium sulfite ( K2SO3 ) , sodium carbonate and the like.
• Basic compounds include, for example, inorganic bases.
• inorganic bases include lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium carbonate, potassium sulfite ( K2SO3 ), sodium sulfite (Na 2 SO 3 ), sodium thiosulfate, potassium thiosulfate, ammonia and the like.
• Basic compounds include, for example, the formula: M m X n [wherein M is a cation, X is OH, CN or CO3 , m is the valence of X, and n is is the valence of M. ]
• M may be, for example, a metal cation or optionally substituted ammonium, preferably alkali metal, alkaline earth metal or quaternary ammonium.
• M is more preferably one or more metal cations selected from the group consisting of sodium, lithium and potassium, more preferably one or more metal cations selected from the group consisting of sodium and potassium.
• the quaternary ammonium includes tetraalkylammonium (eg, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, hexadecyltriethylammonium, etc.), benzyltrialkylammonium (preferably benzyltriC1-C4 alkylammonium), and the like. is mentioned. )
• tetraalkylammonium eg, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, hexadecyltriethylammonium, etc.
• benzyltrialkylammonium preferably benzyltriC1-C4 alkylammonium
• the amount of nucleophile in the post-treatment step B can be, for example, in the range of 0.5 to 100 mol, preferably in the range of 1 to 70 mol, per 1 mol of the organic sulfur compound (S S ). and more preferably in the range of 2 to 50 mol.
• the treatment temperature in the post-treatment step B can be preferably 50° C. or higher, more preferably 60° C. or higher.
• the treatment temperature in the post-treatment step B can be, for example, 200° C. or lower, preferably 170° C. or lower, and more preferably 150° C. or lower.
• the lower limit and upper limit may be combined as appropriate.
• the treatment temperature in the post-treatment step B can be, for example, within the range of 40°C to 200°C, within the range of 40°C to 170°C, within the range of 60°C to 170°C, and preferably within the range of 50°C to 170°C. , more preferably in the range of 60°C to 150°C.
• the treatment time of the post-treatment step B can be, for example, 0.5 hours or longer, preferably 1 hour or longer, and more preferably 3 hours or longer.
• the treatment time of the post-treatment step B can be, for example, 72 hours or less, preferably 48 hours or less, and more preferably 24 hours or less.
• the lower limit and upper limit may be combined as appropriate.
• the treatment time of the post-treatment step B can be, for example, within the range of 0.5 hours to 72 hours, within the range of 0.5 hours to 48 hours, within the range of 0.5 hours to 24 hours, etc., preferably 1 hour. It can be in the range of ⁇ 48 hours.
• the post-treatment step B can be suitably carried out in the presence of water.
• the composition ( ⁇ ) obtained in reaction step A for example, the reaction solution obtained in reaction step A
• water in which a nucleophilic reagent is dissolved or dispersed are mixed to obtain desired temperature conditions.
• a post-treatment step B can be performed.
• the amount of water is not particularly limited as long as the reaction with the nucleophilic reagent proceeds.
• the post-treatment step B can be suitably carried out in an organic solvent.
• the composition ( ⁇ ) obtained in reaction step A for example, the reaction solution obtained in reaction step A
• water in which a nucleophilic reagent is dissolved or dispersed are mixed to obtain desired temperature conditions.
• the post-treatment step B can be carried out.
• the organic solvent may not be added in the post-treatment step B, but it is preferable to add it.
• Post-treatment step B can be more preferably carried out in the presence of water and an organic solvent.
• the composition ( ⁇ ) obtained in reaction step A for example, the reaction solution obtained in reaction step A
• water in which a nucleophilic reagent is dissolved or dispersed, and an organic solvent are mixed to obtain desired temperature conditions.
• the post-treatment step B can be carried out. Stirring is preferred in the post-treatment step B in order to promote the reaction.
• the organic solvent may be the organic solvent WS, the organic solvent WP, or a solvent containing the organic solvent WS and the organic solvent WP.
• the amount of the organic solvent used is not particularly limited as long as the post-treatment step B can be carried out, and may be an amount that dissolves the crude organic fluorine compound (p f ) at a temperature of 40° C. or higher.
• the organic solvent is preferably an organic solvent WS having a solubility in water of 10 [g/100 g-water (20° C.)] or more. By using such an organic solvent, the effect of reducing sulfur-containing substances (b s ) is further improved. Solubility in water is the maximum amount of organic solvent that will dissolve in 100 g of water at a water temperature of 20°C. Table 1 shows an example of the solubility of organic solvents at a water temperature of 20°C.
• the solubility of the organic solvent WS in water can be, for example, 10 or higher, preferably 15 or higher, and more preferably 20 or higher. More preferably, the solubility of the organic solvent WS in water is infinite.
• the organic solvent WS can be used in combination as appropriate.
• the solubility of the organic solvent WS in water can be, for example, 10 to infinity, preferably 15 to infinity, more preferably 20 to infinity.
• organic solvent WS examples include monoglyme, acetonitrile, acetone, dioxane (preferably 1,4-dioxane), N-methylpyrrolidone (abbreviation: NMP), diethylene glycol, 3-butene, 2-butanol, tetrahydrofuran (abbreviation: THF), 2-Methyl THF, N,N-dimethylformamide (abbreviation: DMF), dimethylacetamide (abbreviation: DMAc) and the like are preferred, and monoglyme, acetonitrile, acetone, dioxane (preferably 1,4-dioxane), THF and the like are more preferred. .
• the organic solvent can be a mixed solvent of an organic solvent WS and an organic solvent WP whose solubility in water is less than 10 [g/100 g-water (20°C)].
• the solubility of the organic solvent WP in water can be, for example, less than 10, preferably 5 or less, more preferably 3 or less.
• the solubility of the organic solvent WP in water can be, for example, 0.01 or more.
• the lower limit and upper limit may be combined as appropriate.
• the solubility of the organic solvent WP in water can be, for example, within the range of 0.001 to less than 10, preferably within the range of 0.001 to 5, and more preferably within the range of 0.001 to 3.
• organic solvent WP As the organic solvent WP, toluene, dichloromethane, hexane, heptane, xylene, benzene, diethyl ether, methyl tert-butyl ether (abbreviation: MTBE), ethyl acetate, chloroform, cyclopentyl methyl ether (CPME) and the like are preferable, and toluene, dichloromethane, Heptane and the like are more preferred.
• MTBE methyl tert-butyl ether
• CPME cyclopentyl methyl ether
• the mass of the organic solvent WS in the mixed solvent can be, for example, 0.1 g or more, preferably 0.5 g or more, per 1 g of the organic solvent WP.
• the mass of the organic solvent WS in the mixed solvent can be, for example, 20 g or less, preferably 10 g or less per 1 g of the organic solvent WP in the mixed solvent.
• the lower limit and upper limit may be combined as appropriate.
• the mass of the organic solvent WS in the mixed solvent can be, for example, within the range of 0.1 g to 20 g, preferably within the range of 0.5 g to 10 g, per 1 g of the mass of the organic solvent WP in the mixed solvent. .
• the reaction liquid obtained in the post-treatment step B is subjected to a conventional method such as liquid separation, extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof.
• a crude organofluorine compound (p f ) with a reduced content of sulfur-containing substances (b s ) is obtained.
• the reaction solution obtained by reacting the composition ( ⁇ ) with a nucleophilic reagent in step B or (2) the organic phase obtained by separating the reaction solution is concentrated to obtain a solid.
• the step of obtaining the solid can be carried out by a known method, for example, a method of concentrating the reaction solution or organic phase under reduced pressure.
• the step of obtaining the solution can be carried out by a known method, for example, a method of dissolving the solid in an excess amount of a solvent capable of dissolving it.
• the solvent used in the step of obtaining the solution is not particularly limited as long as it can dissolve the solid, and examples thereof include heptane, hexane, methanol, and ethanol.
• the step of precipitating the organic fluorine compound (p f ) can be carried out, for example, by adding a poor solvent to the solution to precipitate the organic fluorine compound (p f ).
• the poor solvent is not particularly limited as long as it can precipitate the organic fluorine compound (p f ).
• the reaction solution or organic phase may be treated with silica gel, celite, activated carbon, or the like, and then subjected to the subsequent concentration step.
• the solution may be treated with silica gel, celite, activated carbon, or the like, and subjected to the subsequent step of precipitating the organofluorine compound (p f ).
• the treatment with silica gel or the like can be carried out by a known appropriate method. liquid), and a method of obtaining a distillate obtained by subjecting the reaction liquid or the organic phase to column chromatography using silica gel, celite, activated carbon, or the like.
• composition ( ⁇ ) Since the composition ( ⁇ ) has a reduced content of sulfur-containing substances (b s ), the composition ( ⁇ ) is useful as a source of organic fluorine compounds (p f ). Composition ( ⁇ ) can be suitably produced by the method for producing an organic fluorine compound of the present disclosure.
• the lower limit of the content of the organic fluorine compound (p f ) in the composition ( ⁇ ) is preferably 80% by mass, more preferably 90% by mass, and still more preferably 95% by mass.
• the upper limit of the content of the organic fluorine compound in the composition ( ⁇ ) is preferably 99.9% by mass, more preferably 99.5% by mass, and still more preferably 99% by mass.
• the lower limit and upper limit may be combined as appropriate.
• the content of the organic fluorine compound in the composition ( ⁇ ) is preferably in the range of 80 to 99.9% by mass, more preferably in the range of 90 to 99.5% by mass, still more preferably 95 to 99% by mass. can be in the range of
• the upper limit of the content of the sulfur-containing substance (b s ) in the composition ( ⁇ ) is preferably 10000 ppm by mass, more preferably It can be 7000 ppm by weight, more preferably 6000 ppm by weight.
• the lower limit of the content of the sulfur-containing substance in the composition ( ⁇ ) is preferably 0.01 mass ppm, more preferably 0.01 ppm by mass, in terms of sulfur content, relative to the mass of the composition ( ⁇ ). It can be 1 ppm by weight, more preferably 0.5 ppm by weight.
• the lower limit and upper limit may be combined as appropriate.
• the content of the sulfur-containing substance in the composition ( ⁇ ) is preferably in the range of 0.01 to 10000 ppm by mass, more preferably 0.1 to It can be in the range of 7000 mass ppm, more preferably in the range of 0.5 to 6000 mass ppm.
• the content of the sulfur-containing substance (b s ) is preferably 1/10 or less in terms of sulfur content to the content of the organic fluorine compound (p f ), and more It is preferably 1/50 or less, more preferably 1/100 or less.
• the mass ratio of the sulfur content of the sulfur-containing substance (b s ) to the content of the organic fluorine compound (p f ) is preferably 1/1000000 or more, More preferably, it is 1/500,000 or more, and still more preferably 1/300,000 or more. The lower limit and upper limit may be combined as appropriate.
• the mass ratio of the sulfur content of the sulfur-containing substance (b s ) to the content of the organic fluorine compound (p f ) is preferably in the range of 1/1000000 to 1/10. , more preferably in the range of 1/500000 to 1/50, more preferably in the range of 1/300000 to 1/100.
• the method for analyzing the amount of sulfur includes, for example, the oxidative decomposition/ultraviolet absorption method.
• the method described in the Examples can be mentioned.
• the sulfur content in the examples was measured by the following method.
• measuring device Trace sulfur analyzer (ultraviolet fluorescence method) (Mitsubishi Chemical Analytech TS-100)
• Preparation of sample solutions Accurately weighed 10-15 mg of sample and 10 mL of acetone were placed in a glass vial to dissolve the sample. In addition, 10 to 15 mg of an accurately weighed sample can be used as it is for measuring the amount of sulfur without dissolving.
• Preparation of blank solution 10 mL of acetone was placed in a glass vial. measurement: (1) 100 ⁇ L of the blank solution was placed in a quartz boat that had been pre-baked twice, and acetone was volatilized.
• Example 1 3,5,2'-Trifluoro-4''-propyl[1,1';4',1'']terphenyl-4-carbothioic acid 3,4,5-trifluorophenyl ester (185 g, 0.35 mol), Dissolve in MeCN (143 g) and monoglyme (103 g), fluorinate with IF 5 -Et 3 N-3HF (150.9 g, 0.39 mol), add toluene (206 g) to the resulting product solution. , KOH (176.9 g, 3.16 mol), and K2SO3 ( 187.1 g, 1.18 mol) dissolved in water (925.1 g) were added and mixed. The resulting mixture was stirred at 80° C. for 24 hours.
• Example 2 3,5,2'-Trifluoro-4''-pentyl[1,1';4',1'']terphenyl-4-carbothioic acid 3,4,5 -trifluorophenyl ester to 4-[Difluoro(3,4,5-trifluorophenoxy)methyl]-3,5,2'-trifluoro-4''-pentyl[1,1';4',1'']terphenyl
• a crude product (186 g; target fluorinated compound content: 182 g) was obtained.
• Example 3 4-Chloro-2,6-difluorothiobenzoic acid 3,4,5-trifluorophenyl ester (255.6 g, 0.75 mol) was dissolved in MeCN (364.2 g) and IF 5 -Et 3 N-3HF (231.3 g, 0.60 mol) toluene (322.5 g), KOH (271.0 g, 4.84 mol), and K 2 SO 3 (286.6 g, 1.81 mol) were dissolved in water (1417.6 g). Aqueous solutions were added and mixed. The resulting mixture was stirred at 85° C. for 13 hours.
• Example 6 Diphenylmethanethione (5 g, 25.3 mmol) was dissolved in CH 2 Cl 2 (100 g) and fluorinated with IF 5 -Et 3 N-3HF (11.6 g, 30.3 mmol). (120 g), KOH (13.6 g, 242 mmol), and K2SO3 (19.1 g, 121.2 mmol) in water (65 g) were added. After the mixture was stirred at 40°C for 24 hours and separated, the resulting organic layer was filtered, and the solvent was distilled off under reduced pressure to obtain crude difluorodiphenylmethane (4.4 g; desired fluorinated compound content 3.74 g). Its sulfur content is shown in Table 4.
• Example 7 Methyl N-butyl-N-(1-oxopropyl)carbamodithioate (0.5 g, 2.28 mmol) was dissolved in dichloromethane (10 g) and fluorinated with IF 5 -Et 3 N-3HF (0.87 g, 2.28 mmol). After that, an aqueous solution of MeCN (40 g), KOH (6.5 g, 115.2 mmol), and K2SO3 ( 9.1 g, 57.6 mmol) dissolved in water (30 g) was added to the resulting solution. The mixture was stirred at 75-80 ° C.
• Example 8 By the same molar amount and operation as in Example 7, from O-decyl S-methyl carbonodithioate, crude 1-Trifluoromethoxydecane and 1-(Difluoro(methylthio)methoxy)decane (490 mg; target fluorinated compound content 440 mg ). Its sulfur content is shown in Table 4.
• Example 9 Crude 4-pentyl-4'-trifluoromethoxybicyclohexyl was obtained from S-methyl O-(4'-pentylbicyclohexyl-4-yl)carbonodithioate in the same manner as in Example 7, except that the solvent used in the reaction was changed from dichloromethane to AcOEt. (378 mg; target fluorinated compound content: 310 mg). Its sulfur content is shown in Table 4.
• Example 10 Using the same molar amount and operation as in Example 6, crude difluorodiphenylmethane (5.2 g; target fluorinated compound content: 4.7 g) was obtained from 2,2-diphenyl-[1,3]dithiolane. Its sulfur content is shown in Table 4.
• Example 11 4'-(difluoro(methylthio)methoxy)-4 - pentylbicyclohexyl was converted to , crude 4-pentyl-4'-trifluoromethoxybicyclohexyl (650 mg; target fluorinated compound content: 550 mg) was obtained. Its sulfur content is shown in Table 4.
• Example 12 Silica gel (20 g) was added to the organic layer obtained in Example 1 after separation and filtration, and the mixture was stirred at room temperature for 30 minutes and then filtered. The obtained organic layer was concentrated under reduced pressure to obtain a crude product (158 g; (target fluorinated compound content: 156 g, sulfur content: 99 ppm). Further, heptane (555 g) was added to the obtained crude product. 4-[Difluoro(3,4,5-trifluorophenoxy)methyl]-3,5,2'-trifluoro-4''-propyl[1,1';4',1'' ]terphenyl (126 g, sulfur content 23 ppm) was obtained.
• Example 13 The organic layer obtained in Example 1 after liquid separation and filtration was concentrated under reduced pressure, and the solid obtained was dissolved in heptane (555 g) and purified with a silica gel column. After heptane was concentrated under reduced pressure from the obtained distillate, a crystallization step was performed using ethanol (516 g) to give 4-[Difluoro(3,4,5-trifluorophenoxy)methyl]-3,5,2'-trifluoro-4''-propyl[1,1';4',1'']terphenyl (172 g, sulfur content 1 ppm) was obtained.
• Example 14 4-Chloro-2,6-difluorothiobenzoic acid 3,4,5-trifluorophenyl ester (50 mg, 0.147 mmol) was dissolved in dichloromethane (1 g) and BrF 3 -1.5(KHF 2 ) (74.9 mg, 0.295 mmol). After the fluorination reaction at , MeCN (4 g), KOH (99.1 mg, 1.770 mmol), and K 2 SO 3 (186.4 mg, 1.180 mmol) were dissolved in water (3 g) to the resulting solution. Aqueous solutions were added and mixed. The resulting mixture was stirred at 60° C. for 3 hours.

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