RU2807182C1 - Method for producing fluorine-containing organic compound - Google Patents

Abstract

FIELD: organic compounds.

SUBSTANCE: invention is related to a method for producing a fluorine-containing organic compound (1). The method includes step A, in which the organic compound (2) is subjected to electrolytic fluorination in presence of 0.2 M or more of a metal fluoride and a fluorine-alcohol characterized by a fluorine content ranging from 50 to 80% by weight, step A is carried out in presence of an organic a solvent, and the fluorine-containing organic compound (1) is a fluorine-containing organic compound corresponding to the formula (1): in which R¹ means an organic group, and n is an integer of 1 or more; and the organic compound (2) is an organic compound corresponding to the formula (2): in which R¹ and n are as above, R^1a means an organic group provided that n/2 is an integer of 1 or more. The invention is also related to a system. The proposed method is novel.

EFFECT: method for producing fluorine-containing organic compound is proposed.

13 cl, 10 ex

(1) R¹-(F)_n

(2) R¹-(H)_n, R¹-(SR^1a)_n, or R¹(=S)_n/2

Description

TECHNICAL FIELD

[0001] The present invention relates to a method for producing a fluorine-containing organic compound

BACKGROUND OF THE ART

[0002] It is known to use electrolytic fluorination as a method for producing a fluorine-containing organic compound. For electrolytic fluorination, for example, the method described in Non-Patent Literature Document 1 is used.

List of cited literature

Non-patent literature

[0003] NPL 1: Sawamura et al., Angew. Chem. Int. Ed. 2012, 51, 4413

SUMMARY OF THE INVENTION

Technical problem

[0004] An object of the present invention is to provide a new method for producing a fluorine-containing organic compound by electrolytic fluorination and the like.

Solving a technical problem

[0005] 1. A method for producing a fluorinated organic compound (1), comprising a step A of subjecting the organic compound (2) to electrolytic fluorination in the presence of 0.2M or more of a metal fluoride and a fluorinated alcohol.

2. The production method according to claim 1, wherein the fluorine-containing organic compound (1) is a fluorine-containing organic compound corresponding to the formula (1):

R ¹ -(F) _n

in which R ¹ means an organic group, and n is an integer of 1 or more; And

organic compound (2) is an organic compound corresponding to formula (2):

R ¹ -(H) _n , R ¹ -(SR ^1a ) _n , or R ¹ (=S) _n/2

in which R¹ and n are as above, R^1a means an organic group provided that n/2 is an integer of 1 or more.

3. The production method according to claim 2, wherein the organic group is a (hetero)hydrocarbon radical, optionally with one or more substituents.

4. The production method according to claim 2 or 3, in which n is an integer of 2 or more.

5. Production method according to any one of paragraphs. 2-4, in which R ¹ is a polyether group.

6. The production method according to claim 1, wherein the fluorine-containing organic compound (1) is a ketone, an imine, a sulfide, an aromatic compound, a thiocarbonyl compound or a polyether.

7. Production method according to any one of paragraphs. 1-6, wherein the metal fluoride is at least one metal fluoride selected from the group consisting of Group 1 metal fluorides and Periodic Table 2 metal fluorides.

8. The production method according to claim 7, wherein the metal fluoride is at least one metal fluoride selected from the group consisting of lithium fluoride, sodium fluoride, potassium fluoride and cesium fluoride.

9. Production method according to any one of paragraphs. 1-8, in which the fluoroalcohol is a C _1-14 fluoroalcohol.

10. The production method according to claim 9, in which the fluorinated alcohol is a fluorinated alcohol characterized by a fluorine content ranging from 50 to 80 wt%.

11. Production method according to any one of paragraphs. 1 to 10, in which step A is carried out in the presence of an organic solvent, and the total volume of fluoroalcohol and organic solvent per mole of organic compound (2) at the beginning of electrolytic fluorination in step A is in the range of 0.1 to 100 L.

12. Production method according to any one of paragraphs. 1-11, in which step A is carried out in the presence of an organic solvent, and the volume ratio of fluorinated alcohol to organic solvent at the beginning of electrolytic fluorination in step A is 1/100 (v/v) or more.

13. Production method according to any one of paragraphs. 1-12, in which the metal fluoride concentration (the concentration of metal fluoride relative to all liquid components of the system) in stage A is in the range from 0.2 to 5 M.

14. Production method according to any one of paragraphs. 1-13, in which the temperature in stage A is 0°C or more.

15. A composition containing 0.2 M or more of a metal fluoride, a fluorinated alcohol and an organic solvent.

Advantages of the invention

[0006] The present invention provides a new method for producing a fluorine-containing organic compound and the like.

DESCRIPTION OF OPTIONS FOR IMPLEMENTING THE INVENTION

[0007] Although the details and embodiment of the production method and the like are described below. In accordance with the present invention, it is understood that various modifications in detail and form are possible without departing from the spirit and scope of the claims.

[0008] Given the generally known technical knowledge, those skilled in the art will understand that combinations of elements of the embodiments described below and alternative embodiments of the invention are possible.

[0009] Terminology

Unless otherwise indicated, the symbols and abbreviations used herein are to be taken in this context to have the meaning commonly used in the technical field to which the manufacturing method, etc., of the present invention relates.

As used herein, the terms “includes” and “comprises” are intended to include the terms “consisting essentially of” and “consisting of”.

In the context of the present description, room temperature may correspond to a temperature in the range from 10 to 40°C.

In the present description, the expression "C _n -C _m " (each of n and m is an integer of 1 or more, and n<m) means that the number of carbon atoms is n or more and m or less, as is generally understood expression specialists in the field.

[0010] In the present specification, unless otherwise specified, examples of the “halogen group” may include a fluorine group, a chlorine group, a bromine group, and an iodine group.

In the present specification, unless otherwise specified, examples of “halogen atom” may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0011] As used herein, the term “organic group” means a group comprising one or more carbon atoms (or a group formed by removing one hydrogen atom from an organic compound).

[0012] As used herein, unless otherwise indicated, the term “heteroatom” can mean any atom other than hydrogen and carbon.

In the present specification, unless otherwise specified, examples of “heteroatom” include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0013] As used herein, unless otherwise indicated, the term “organic group” means a group containing one or more carbon atoms as its constituent atom.

As used herein, unless otherwise indicated, examples of an "organic group" include (1) a hydrocarbon radical (optionally with one or more substituents) and (2) a group in which one or more heteroatoms (optionally with one or several substituents) (which in the present description may be called a “heterohydrocarbon radical”).

Examples of substituents are halogen, nitro-, cyano-, oxo-, thioxo-, sulfo-, sulfamoyl- and sulfenamoyl- groups.

[0014] As used herein, unless otherwise indicated, the term “hydrocarbon radical” means a group having as its constituent atoms one or more carbon atoms and one or more hydrogen atoms.

[0015] Examples of "(1) hydrocarbon radical" are an aliphatic hydrocarbon group optionally substituted by one or more aromatic hydrocarbon groups (for example, a benzyl group), and an aromatic hydrocarbon group optionally substituted by one or more aliphatic hydrocarbon groups (in the narrow sense, aryl group).

As used herein, the term “(hetero)hydrocarbon radical” includes an aryl group in the narrow sense and a heteroaryl group.

[0016] Examples of the "(2) group in which one or more heteroatoms are introduced into the hydrocarbon radical" (heterohydrocarbon radical) include a 5- and 6-membered heteroaryl group, a group in which a benzene ring is fused with a 5- and 6-membered heteroaryl group group, an alkoxy group, an ester group, an ether group and a heterocyclic group.

[0017] As used herein, unless otherwise indicated, an "aliphatic hydrocarbon radical" may be linear, branched, cyclic, or a combination of these forms.

As used herein, unless otherwise indicated, an "aliphatic hydrocarbon radical" may be saturated or unsaturated.

As used herein, unless otherwise specified, examples of an "aliphatic hydrocarbon radical" include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group.

[0018] As used herein, unless otherwise noted, examples of an "alkyl group" include C _1-10 linear or branched alkyl groups such as methyl, ethyl, propyl (n-propyl and isopropyl), butyl (n-butyl, isobutyl, sec-butyl and tert-butyl), pentyl, isopentyl, neopentyl and hexyl.

[0019] As used herein, unless otherwise noted, examples of an "alkyl group" include C _1-10 linear or branched alkenyl groups (e.g., vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl , 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3 -hexenyl, 4-hexenyl and 5-hexenyl).

[0020] As used herein, unless otherwise noted, examples of an "alkynyl group" include C _2-6 linear or branched alkynyl groups (e.g., ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3 -butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl and 5-hexynyl).

[0021] As used herein, unless otherwise indicated, examples of a “cycloalkyl group” include C _3-8 cycloalkyl groups (eg, cyclopentyl, cyclohexyl, and cycloheptyl).

[0022] As used herein, unless otherwise indicated, examples of an “aromatic hydrocarbon group (aryl group)” include phenyl, naphthyl, phenanthryl, anthryl and pyrenyl.

[0023] As used herein, unless otherwise indicated, the term “aralkyl group” may mean an alkyl group substituted with an aryl group as commonly understood.

[0024] As used herein, unless otherwise indicated, the term “alkoxy group” means, for example, a group represented by the formula RO- (wherein R is an alkyl group).

[0025] As used herein, unless otherwise indicated, the term “ester group” means an organic group comprising an ester linkage (i.e., -C(=O)-O- or -O-C(=O) -). Examples of "ester group" are the group represented by the formula RCO ₂ - (where R is an alkyl group) and the group represented by the formula R ^a -CO ₂ -R ^b - (where R ^a is an alkyl group and R ^b is an alkylene group) .

[0026] As used herein, unless otherwise indicated, the term “ether group” means a group including an ester bond (-O-).

Examples of "ether group" are polyether groups.

Examples of polyether groups are the group represented by the formula R ^a -(O-R ^b )n- (where R ^a means an alkyl group, and R ^b , in each case, the same or different and means an alkylene group, n is an integer from 1 or more).

An alkylene group is a divalent group formed by removing one hydrogen atom from the alkyl group described above.

Examples of "ether group" also include hydrocarbon ether groups.

A hydrocarbon ether group is a hydrocarbon group containing one or more ether bonds. A “hydrocarbon group having one or more ether linkages” may be a hydrocarbon group into which one or more ether linkages have been introduced. An example of this is the benzyloxy group.

An example of a "hydrocarbon group having one or more ether bonds" is an alkyl group having one or more ether bonds.

An "alkyl group having one or more ether linkages" may be an alkyl group into which one or more ether linkages have been introduced. In the present context, such a group may be called an "alkyl ether group".

[0027] As used herein, unless otherwise indicated, the term "acyl group" includes an alkanoyl group. As used herein, unless otherwise indicated, the term “alkanoyl group” means, for example, the group represented by the formula RCO- (where R is an alkyl group).

[0028] As used herein, examples of a "5- and 6-membered heteroaryl group" include 5- and 6-membered heteroaryl groups comprising at least one heteroatom (e.g., one, two, or three heteroatoms) selected from the group , consisting of oxygen, sulfur and nitrogen as a ring-forming atom, such as pyrrolyl (such as 1-pyrrolyl, 2-pyrrolyl and 3-pyrrolyl), furyl (such as 2-furyl and 3-furyl), thienyl ( e.g. 2-thienyl and 3-thienyl), pyrazolyl (e.g. 1-pyrazolyl, 3-pyrazolyl and 4-pyrazolyl), imidazolyl (e.g. 1-imidazolyl, 2-imidazolyl and 4-imidazolyl) isoxazolyl (e.g. 3- isoxazolyl, 4-isoxazolyl and 5-isoxazolyl), oxazolyl (e.g. 2-oxazolyl, 4-oxazolyl and 5-oxazolyl), isothiazolyl (e.g. 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl), thiazolyl (e.g. 2 -thiazolyl, 4-thiazolyl and 5-thiazolyl), triazolyl (for example, 1,2,3-triazol-4-yl and 1,2,4-triazol-3-yl), oxadiazolyl (for example, 1,2,4 -oxadiazol-3-yl and 1,2,4-oxadiazol-5-yl), thiadiazolyl (e.g. 1,2,4-thiadiazol-3-yl and 1,2,4-thiadiazol-5-yl), tetrazolyl , pyridyl (for example, 2-pyridyl, 3-pyridyl and 4-pyridyl), pyridazinyl (for example, 3-pyridazinyl and 4-pyridazinyl), pyrimidinyl (for example, 2-pyrimidinyl, 4-pyrimidinyl and 5-pyrimidinyl) and pyrazinyl.

[0029] Production method

According to one embodiment of the present invention, the production method is a method for producing a fluorine-containing organic compound (1), comprising a step A in which the organic compound (2) is subjected to electrolytic fluorination in the presence of 0.2M or more of a metal fluoride and fluorinated alcohol.

[0030] In the context of the present invention, examples of the organic compound (2) being the basis of the reaction include

(2-1) ketones (for example, diketones such as 1,3-diketone, β-ketocarboxylic acids and β-ketoesters) and imines (for example, Schiff bases and hydrazones),

(2-2) sulfides,

(2-3) aromatic compounds (for example, aromatic hydrocarbons, phenylhydrazine derivatives, phenol derivatives, 2-naphthol derivatives and aniline derivatives) and

(2-4) thiocarbonyl compounds.

In the context of the present invention, fluorination of an organic compound, in addition to replacing a hydrogen atom with a fluorine atom, means replacing (or replacing) with a fluorine atom, for example, the following atom or group (as shown in parentheses below): a hydrogen atom (CH→CF) or a hydrazine group ( С-NHNH ₂ →CF; C=N-NH ₂ →CF ₂ ).

Examples of fluoridation according to the production method of the present invention are described below. Examples of the fluorine-containing organic compound (1) produced by the production method of the present invention are also described below.

[0031] In the context of the present invention, the expression "optionally substituted" covers both cases when a substituent is present (ie, a substituted compound) and when it is not (ie, an unsubstituted compound). For example, an optionally substituted alkyl group includes an alkyl group (ie, an unsubstituted alkyl group) and a substituted alkyl group.

[0032] (2-1) Fluorination of ketones (including diketones, β-ketocarboxylic acids and β-ketoesters) and imines such as Schiff bases and hydrazones

In fluorination, for example, any of the following reactions (2-1-1)-(2-1-4) are carried out.

in which

X in each case is the same or different and is O or NR' (R' is a hydrogen atom, an alkyl group, optionally with one or more substituents, an aralkyl group, optionally with one or more substituents, an aryl group, optionally with one or several substituents, an alkenyl group, optionally with one or more substituents, a cycloalkyl group, optionally with one or more substituents, a heterocycloalkyl group, optionally with one or more substituents, a heterocyclic group, optionally with one or more substituents, an alkoxy group, optionally, with one or more substituents, an aryloxy group, optionally, with one or more substituents, an amino group, a monoalkylamino group, optionally with one or more substituents, a dialkylamino group, optionally with one or more substituents, an acyl group or an acylamino group);

R ² means an alkyl group, optionally with one or more substituents, an aralkyl group, optionally with one or more substituents, an aryl group, optionally with one or more substituents, an alkenyl group, optionally with one or more substituents, a cycloalkyl group, optionally with one or more substituents, a heterocycloalkyl group, optionally with one or more substituents, a heterocyclic group, optionally with one or more substituents, an alkoxy group, optionally with one or more substituents, an aryloxy group, optionally with one or more substituents, an amino group, a monoalkylamino group, optionally with one or more substituents, a dialkylamino group, optionally with one or more substituents, an acyl group or an acylamino group;

R ^2a and R ^2b are the same or different, and each of them represents a hydrogen atom, an alkyl group, optionally with one or more substituents, an aralkyl group, optionally with one or more substituents, an aryl group, optionally with one or more substituents, an alkenyl group, optionally with one or more substituents, a cycloalkyl group, optionally with one or more substituents, a heterocycloalkyl group, optionally with one or more substituents, a heterocyclic group, optionally with one or more substituents, an alkoxy group, optionally with one or several substituents, an aryloxy group, optionally with one or more substituents, a monoalkylamino group, optionally with one or more substituents, a dialkylamino group, optionally with one or more substituents, an acyl group or an acylamino group; and R ² and R ^2a are optionally connected to each other to form a cyclic structure.

[0033] Examples of the cyclic structure include aliphatic rings formed from 4 to 7 atoms, optionally with one or more substituents, and the like.

[0034] R ² is preferably an alkyl group, aralkyl group, aryl group, alkenyl group, heterocyclic group, alkoxy group, aryloxy group or monoalkylamino group. R', R ^2a and R ^2b each preferably represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkenyl group, a heterocyclic group, an alkoxy group, an aryloxy group or a monoalkylamino group.

[0035] Examples of ketones include dialkyl ketones (for example, acetone and methyl ethyl ketone), diketones (for example, acetylacetone, acetoacetic acid and acetoacetic acid esters), cycloalkanones (for example, cyclohexanone), alkylaryl ketones (for example, acetophenone and propiophenone), diaryl ketones (for example, benzophenone ), 4-piperidone, 1-oxo-1,2-dihydronaphthalene, aryl(arylalkenyl)ketones (e.g. benzylideneacetophenone (chalcone)), arylaralkyl ketones (e.g. deoxybenzoin) and their ketals, etc.

[0036] Examples of imines such as Schiff bases and hydrazones include ketone-aldehyde condensates with an appropriate primary amine or an appropriate hydrazine.

[0037] (2-2) Fluorination of sulfides (including dithioacetals and dithioketals)

In fluorination, for example, a reaction is carried out in which one or two methylene hydrogen atoms adjacent to a sulfur atom (or one -CHQ- (Q stands for organic group) hydrogen atom) are replaced by fluorine atom(s), or -SQ (Q stands for organic group) is replaced by a fluorine atom. In fluorination, for example, any of the following reactions (2-2-1)-(2-2-7) are carried out.

in which

R ^3a , R ^3a' and R ^3a'' are the same or different, and each of them means an alkyl group, optionally with one or more substituents, an aralkyl group, optionally with one or more substituents, an aryl group, optionally with one or more substituents, several substituents, an alkenyl group, optionally with one or more substituents, a cycloalkyl group, optionally with one or more substituents, a heterocycloalkyl group, optionally with one or more substituents, a heterocyclic group, optionally with one or more substituents,

R ^3a and R ^3a' or R ^3a' and R ^3a'' together represent an aliphatic ring formed by 4-7 atoms, optionally with one or more substituents;

R ³ and R ^3b are the same or different, and each of them represents an alkyl group, optionally with one or more substituents, an aralkyl group, optionally with one or more substituents, an aryl group, optionally with one or more substituents, an alkenyl group, optionally, with one or more substituents, cycloalkyl group, optionally, with one or more substituents, heterocycloalkyl group, optionally, with one or more substituents, heterocyclic group, optionally, with one or more substituents, alkoxy group, optionally, with one or more substituents , aryloxy group, optionally, with one or more substituents, amino group, monoalkylamino group, optionally, with one or more substituents, dialkylamino group, optionally, with one or more substituents, acyl group, acylamino group, cyano group, alkylsulfinyl group, optionally, with one or more substituents , an aralkylsulfinyl group, optionally with one or more substituents, an arylsulfinyl group, optionally with one or more substituents, a cycloalkylsulfinyl group, optionally with one or more substituents, a heterocycloalkylsulfinyl group, optionally with one or more substituents, a sulfinyl group with which linked heterocyclic group, optionally, with one or more substituents, an alkylsulfonyl group, optionally, with one or more substituents, an aralkylsulfonyl group, optionally, with one or more substituents, an arylsulfonyl group, optionally, with one or more substituents, a cycloalkylsulfonyl group, optionally, with one or more substituents, a heterocycloalkylsulfonyl group, optionally with one or more substituents, or a sulfonyl group to which a heterocyclic group, optionally with one or more substituents, is linked, or

R ³ and R ^3b , together with the carbon atom to which they are attached, optionally form a ring of 4-7 atoms through or without a heteroatom (the ring is optionally substituted with at least one substituent selected from the group consisting of a halogen, an oxo group, an alkyl group, optionally with one or more substituents, an aralkyl group, optionally with one or more substituents, an aryl group, optionally with one or more substituents, an alkenyl group, optionally with one or more substituents, a cyano group and amino groups); and R ^3c and R ^3d are the same or different, and each of them represents a hydrogen atom, an alkyl group, optionally with one or more substituents, an aralkyl group, optionally with one or more substituents, an aryl group, optionally with one or more substituents , an alkenyl group, optionally with one or more substituents, a cycloalkyl group, optionally with one or more substituents, a heterocycloalkyl group, optionally with one or more substituents, a heterocyclic group, optionally with one or more substituents, an alkoxy group, optionally with one or more substituents, an aryloxy group, optionally with one or more substituents, an amino group, a monoalkylamino group, optionally with one or more substituents, a dialkylamino group, optionally with one or more substituents, an acyl group, an acylamino group or a cyano group, or

R ^3c and R ^3d together with an adjacent carbon atom optionally form a saturated or unsaturated aliphatic ring of 4-7 atoms (the ring is optionally substituted with at least one substituent selected from the group consisting of a halogen atom, an oxo group, an alkyl group, optionally with one or more substituents, an aralkyl group, optionally with one or more substituents, an aryl group, optionally with one or more substituents, an alkenyl group, optionally with one or more substituents, a cyano group and an amino group).

[0038] R ^3a , R ^3a' and R ^3a'' are each preferably an alkyl group, an aryl group or an alkenyl group. R ³ , R ^3b , R ^3c and R ^3d each preferably represent an alkyl group, an aralkyl group, an aryl group, an alkenyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a cyano group.

[0039] Examples of sulfides include dialkyl sulfides (for example, methyl ethyl sulfide), alkyl aralkyl sulfides (for example, methyl benzyl sulfide), 2-arylthioacetic acid esters (for example, 2-phenylthioacetic acid ester), alkyl(arylthio)ketones (for example, 2-(phenylthio)acetophenone) , alkyl(alkylthio)ketones (e.g. 2-(methylthio)acetophenone), 2-aryloxy-2-(arylthio)acetonitrile (e.g. 2-phenoxy-2-(phenylthio)acetonitrile), bis(alylthio)alkylarenes (e.g. bis(methylthio)methylbenzene), bis(arylthio)diarylmethanes (e.g. bis(phenylthio)diphenylmethane), 1,3-dithiane with one or more substituents in the 2-position (e.g. 2-octyl-1,3-dithiane), 1,3-dithiolane with one or more substituents in the 2-position (for example, 2-phenyl-2-trifluoromethyl-1,3-dithiolane and 2,2-diphenyl-1,3-dithiolane), tris(alkylthio)alkanes ( for example, tris(ethylthio)hexane), tris(alkylthio)alkylarenes (for example, α,α,α-tris(methylthio)toluene), etc.

[0040] (2-3) Fluorination of aromatic compounds

In fluorination, for example, any of the following reactions (2-3-1)-(2-3-5) are carried out. In reactions (2-3-1)-(2-3-4), one or more fluorine substituents are introduced into the aromatic fragment. As shown in reaction (2-3-2) or (2-3-4), fluorination of the aromatic ring of a phenol derivative or an aniline derivative can be carried out by fluorinating it followed by reduction with a reducing agent such as zinc dust to obtain the desired fluorinated compound.

[0041] (2-3-1) Fluorination of ferylhydrazine derivatives

In fluorination, the phenylhydrazine residue (-NHNH ₂ ), optionally with one or more substituents, may be replaced by a fluorine atom.

where R ^5a , R ^5b , R ^5c , R ^5d and R ^5e are the same or different, and each of them represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, an alkanoyl group, an arylcarbonyl group , amino group, monoalkylamino group, dialkylamino group, alkanoylamino group, arylcarbonylamino group or alkylthio group.

[0042] (2-3-2) Fluorination of phenol derivatives

In fluorination, a phenol derivative forms, for example, the difluorinated quinoid structure shown below, followed by reduction, thereby obtaining a phenol derivative with fluorine in the ortho or para position relative to the hydroxyl group.

[0043]

where R ^5a , R ^5b , R ^5c and R ^5d are the same or different, and each of them represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, an alkanoyl group, an arylcarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkanoylamino group, an arylcarbonylamino group or an alkylthio group.

[0044] When a starting material substituted at all ortho and para positions is used, a fluorine atom is introduced into the ortho position or para position, thereby obtaining a fluorinated compound with a quinoid structure.

[0045] In the above example, phenol is used as the phenol derivative, optionally with one or more substituents; however, it is also possible to introduce a phenol atom into benzene-based aromatic compounds or fused polycyclic hydrocarbons containing an electron-donating group, such as a hydroxy group or an alkoxy group, and optionally substituted.

[0046] (2-3-3) Fluorination of 2-naphthol derivatives

In fluorination, mono- or difluorination can be carried out at the 1-position of naphthol.

where R ^5a , R ^5b , R ^5c , R ^5d , R ^5e and R ^5f are the same or different, and each of them represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, an alkanoyl group , arylcarbonyl group, amino group, monoalkylamino group, dialkylamino group, alkanoylamino group, arylcarbonylamino group or alkylthio group; And

R ^5g means an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, an alkanoyl group, an arylcarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkanoylamino group, an arylcarbonylamino group or an alkylthio group.

[0047] (2-3-4) Fluorination of aniline derivatives

In fluorination, as in the case of a phenol derivative, the aniline derivative produces, for example, the difluorinated quinoid structure shown below, which is then reduced, thereby producing an aniline derivative with fluorine in the ortho position or para position.

where R ^5a , R ^5b , R ^5c and R ^5d are the same or different, and each of them represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, an alkanoyl group, an arylcarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkanoylamino group, an arylcarbonylamino group or an alkylthio group.

[0048] In the above example, aniline is used as the aniline derivative, optionally with one or more substituents; however, it is also possible to introduce a phenol atom into aromatic compounds if naphthylamine is used, optionally with one or more substituents.

[0049] (2-3-5) Fluorination of compounds containing a (hetero)arylmethyl moiety

As shown below, the carbon at the 1-position of a (hetero)arylmethyl moiety in a compound comprising a (hetero)arylmethyl moiety (eg, at the benzyl position of a compound comprising a benzyl moiety) may be replaced by one or two fluorine atoms.

Ar-CHR'-R → Ar-CFR'-R and/or Ar-CF ₂ -R

where Ar denotes a (hetero)aryl group (eg a 5- or 6-membered aromatic ring), optionally with one or more substituents; R is an alkyl group, -C(=O)-OR ^s , -NR ^s , -C(=O)-R ^s , -C(=O)-R ^s , -CN or a (hetero)aryl group (e.g. 5- or 6-membered aromatic ring), optionally with one or more substituents;

R' is -H, an alkyl group, -C(=O)-OR ^s , -NR ^s , -C(=O)-R ^s , -C(=O)-R ^s , -CN or (hetero)aryl a group (eg a 5- or 6-membered aromatic ring), optionally with one or more substituents; And

R ^s is, in each case, the same or different and is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, an alkanoyl group, an arylcarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkanoylamino group, an arylcarbonylamino group, or alkylthio group.

[0050] The 5- or 6-membered aromatic ring may be a phenyl group or a 5-6 membered heteroaryl group.

[0051] Examples of compounds containing a (hetero)arylmethyl moiety include triarylmethanes (eg, triphenylmethane), aryldialkylmethanes (eg, 4-bromocumene), and aryl acetic acid esters (eg, ethyl (4-methoxyphenyl) acetate).

[0052] (2-4) Fluorination of thiocarbonyl compounds (including thioketone, thioester, thiocarboxylic acid ester, thioamide, dithiocarboxylic acid ester and dithiocarbamate)

During fluorination, for example, the following reactions (2-4-1) or (2-4-2) are carried out:

where R ⁶ and R ^6a are the same or different, and each of them represents a hydrogen atom, an alkyl group, optionally with one or more substituents, an aralkyl group, optionally with one or more substituents, an aryl group, optionally with one or more substituents , an alkenyl group, optionally with one or more substituents, a cycloalkyl group, optionally with one or more substituents, a heterocycloalkyl group, optionally with one or more substituents, a heterocyclic group, optionally with one or more substituents, an alkoxy group, optionally with one or more substituents, an aryloxy group, optionally with one or more substituents, a monoalkylamino group, optionally with one or more substituents, a dialkylamino group, optionally with one or more substituents, an acyl group or an acylamino group; and R ⁶ and R ^6a are optionally connected to each other to form a cyclic structure; And

R ^6b means an alkyl group, optionally with one or more substituents, an aralkyl group, optionally with one or more substituents, an aryl group, optionally with one or more substituents, an alkenyl group, optionally with one or more substituents, a cycloalkyl group, optionally with one or more substituents, a heterocycloalkyl group, optionally with one or more substituents, a heterocyclic group, optionally with one or more substituents.

[0053] Preferably, R ⁶ , R ^6a and R ^6b are each an alkyl group, an aryl group or an alkenyl group.

[0054] Examples of thiocarbonyl compounds include O-aryl-S-alkyldithiocarbonates (for example, O-(4-isopropylphenyl)S-methyldithiocarbonate and O-(4-bromophenyl)S-methyl)dithiocarbonate), ((alkylthio)carbonthioyl)oxybenzoic esters acids (e.g. ethyl 4-((methylthio)carbonothioyl)oxy)benzoate), O-alkyl-S-alkyldithiocarbonates (e.g. O-decyl-S-methyldithiocarbonate), O-aralkyl-S-alkyldithiocarbonates (e.g. O- (3-finylpropyl)S-methyl)dithiocarbonate), O-alkylcycloalkanecarbothioates (e.g. O-methylcyclohexanecarbothioate), O-alkylheteroarenecarbothioates (e.g. O-propyl-1-piperidinecarbothioate), dithiobenzoic acid esters (e.g. methyldithiobenzoate), diarylthioketones (e.g. , thiobenzophenone), thiobenzoic acid esters (e.g. O-phenylthiobenzoate), N, N-dialkylarylthioamides (e.g. N, N-dimethylphenylthioamide), dithiocarboxylic acid esters (e.g. ethyl 3-quinoline dithiocarboxylate), fluoroalkanecarbothioylarenes (e.g. trifluoromethanecarbothioylnaphthalene), N-alkyl-N-arylfluoroalkanethioamides (e.g. N-methyl-N-fetyltrifluoromethanethioamide), N-aralkyl-N-arylfluoroalkanethioamides (e.g. N-benzyl-N-phenylheptafluoropropanethioamide), O-cycloalkyl-S-alkyldithiocarbonates (e.g. O- (4'-pentyl-[1,1'-di(cyclohexane)]-4-yl)S-methyl)dithiocanbonate),

and so on.

[0055] (2-5) Fluorination of polyethers

In fluorination, for example, the hydrogen atom(s) connected to the carbon atom(s) adjacent to the oxygen atom forming the ether bond may be replaced by fluorine atom(s); however, fluoridation is not limited to this. The number of fluorine atoms introduced during fluorination has no specific restrictions and is equal, for example, to one.

[0056] Polyether is not particularly limited and is, for example, the compound represented by formula (1A): R ^7a -(OR ^7b ) _p -OR ^7c

wherein

R ^7a and R ^7c are the same or different, and each of them represents an organic group;

R ^7b means an alkylene group; And

p equals 0 or is an integer of 1 or more.

R ^7a and R ^7c each preferably represent an alkyl group, an alkenyl group, an aryl group or an aralkyl group. R ^7b is preferably a C _2-4 alkylene group.

p may be, for example, 50 or less, 40 or less, 30 or less, or 20 or less.

Examples of compounds corresponding to formula (1A) include ethylene glycol di-C _1-4 alkyl ethers (eg, monoglyme), polyethylene glycol di-C _1-4 alkyl ethers (eg, diglyme and triglyme), and the like.

[0057] As one of the preferred examples of one embodiment of the invention, the fluorine-containing organic compound (1) is a fluorine-containing organic compound corresponding to the formula (1):

R ¹ -(F) _n

wherein

R ¹ means an organic group; And

n is an integer of 1 or more; And

Organic compound (2) is an organic compound corresponding to formula (2):

R ¹ -(H) _n , R ¹ -(SR ^1a ) _n , R ¹ -(NH-NH ₂ ) _n , R ¹ -(N=NR ^1b ) _n , R ¹ (=N-NHR ^1c ) _{n/ 2} , or R ¹ (=S) _n/2

wherein

R ¹ and n are as defined above; And

R ^1a - R ^1c are the same or different and each of them represents an organic group.

When formula (2) is R ¹ (=N-NHR ^1c ) _n/2 or R ¹ (=S) _n/2 , n/2 is an integer of 1 or more, that is, n is a multiple of 2.

[0058] The organic group corresponding to each of R ¹ and R ^1a may include one or more fluorine groups.

[0059] Preferably, the organic group is a (hetero)hydrocarbon radical, optionally with one or more substituents.

[0060] According to the method of the present invention, one or more fluorine atoms, preferably two or more fluorine atoms are introduced into the organic compound (2) as a base. In this regard, in formula (1) and formula (2), n is preferably an integer of 2 or more. n is an integer less than or equal to the maximum number of possible substituents in the organic compound (2). When n is an integer of 2 or more, the organic group corresponding to R ¹ is an n-valent group formed by removing n-1 hydrogen atoms from the monovalent group described in the Terminology section.

According to the method of the present invention, for example, both a predetermined compound into which one fluorine atom is introduced and a predetermined compound into which two fluorine atoms are introduced can be produced.

[0061] In one embodiment, formula (2) is R ¹ -H, in which R ¹ is preferably a triarylmethane moiety (or triarylmethyl group).

[0062] In one embodiment of the invention, formula (2) is R ¹ -H, in which R ¹ is preferably a polyether group.

[0063] In one embodiment of the invention, formula (2) is R ¹ -(H) ₂ in which R ¹ is preferably

>C(C(=O)Q ¹ )(C(=O)Q ² ), in which Q ¹ and Q ² are the same or different, and each of them represents a hydrogen atom, a hydroxyl group or an organic group (for example, an alkyl group , alkenyl group, aryl group or aralkyl group) or

>C(CO ₂ Q ³ )(SQ ⁴ ), in which Q ³ and Q ⁴ are the same or different, and each of them represents a hydrogen atom or an organic group (for example, an alkyl group, an alkenyl group, an aryl group or an aralkyl group).

[0064] In one embodiment of the invention, formula (2) is R ¹ -(SR ^1a ) ₂ in which R ¹ is preferably

>CQ ⁵ Q ⁶ , in which Q ⁵ and Q ⁶ are the same or different, and each of them is an organic group (for example, an alkyl group, an alkenyl group, an aryl group or an aralkyl group), and

R^1a, preferably, independently, in each case means an organic group (for example, an alkyl group, an alkenyl group, an aryl group or an aralkyl group), or R^1a can be connected to every other group to form a ring structure.

[0065] In one embodiment of the invention, formula (2) is R ¹ =S, in which R ¹ is preferably

=CQ ⁷ Q ⁸ wherein Q ⁷ and Q ⁸ are the same or different and each is an organic group (eg, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, or an aralkyloxy group).

[0066] In one embodiment, formula (2) is R ¹ -NH-NH ₂ , in which R ¹ is preferably an alkyl group, alkenyl group, aryl group or aralkyl group.

[0067] In one embodiment, formula (2) is R ¹ -NH=NR ^1b , in which R ¹ is preferably an alkyl group, an alkenyl group, an aryl group or an aralkyl group; and R ^1b is preferably an alkyl group, an alkenyl group, an aryl group or an aralkyl group.

[0068] In one embodiment of the invention, formula (2) is R ¹ =NH-NHR ^1c , in which R ¹ is preferably

=CQ ⁹ Q ¹⁰ , in which Q ⁹ and Q ¹⁰ are the same or different, and each of them represents an organic group (eg, an alkyl group, an alkenyl group, an aryl group or an aralkyl group).

[0069] The metal fluoride in step A may function as a supporting salt (maintaining electrolyte).

The metal fluoride is preferably at least one metal fluoride selected from the group consisting of periodic table group 1 metal fluorides and periodic table group 2 metal fluorides; more preferably at least one metal fluoride selected from the group consisting of lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride and calcium fluoride.

[0070] The fluoroalcohol in step A may function as an electrolyte solution. Preferably, the fluoroalcohol is a C _1-14 fluoroalcohol.

[0071] Preferably, the fluoroalcohol is a fluoroalcohol corresponding to the formula RfCH ₂ OH or Rf ₂ CHOH, in which Rf is independently, in each case, a C _1-6 perfluoroalkyl group.

Specific examples of fluoroalcohol include 2,2,3,3-tetrafluoro-1-propanol, 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3 ,3,3-pentafluoro-1-propanol. Preferred examples of the fluoroalcohol are 1,1,1,3,3,3-hexafluoro-2-propanol and 2,2,3,3,3-pentafluoro-1-propanol.

Preferably, the fluorinated alcohol is a fluorinated alcohol characterized by a fluorine content of 50% by weight. or more, more preferably, a fluorinated alcohol characterized by a fluorine content of 55 wt%. or more, even more preferably, a fluorinated alcohol characterized by a fluorine content of 60 wt%. or more.

Preferably, the fluorinated alcohol is a fluorinated alcohol having a fluorine content of 80% by weight. or less, more preferably, a fluorinated alcohol characterized by a fluorine content of 75 wt%. or less, even more preferably, a fluorinated alcohol characterized by a fluorine content of 70 wt%. or less.

Preferably, the fluoroalcohol is a fluoroalcohol having a fluorine content of 50 to 80% by weight, more preferably a fluoroalcohol having a fluorine content from 55 to 75% by weight, even more preferably a fluoroalcohol having a fluorine content from 60 to 75% by weight. 70% wt.

Fluorine content (% wt.) means the percentage of the mass of fluorine in the molecule of a fluorine-substituted alcohol.

[0072] Reaction step A is carried out in the presence or absence of an organic solvent. Specific examples of the organic solvent are described below.

Preferably, reaction step A is carried out in the presence of an organic solvent.

The total volume of fluorinated alcohol and organic solvent per mole of organic compound (2) at the beginning of the electrolytic fluorination in step A is preferably 0.1 L or more, more preferably 1 L or more, even more preferably 2 L or more.

The total volume of fluorinated alcohol and organic solvent per mole of organic compound (2) at the beginning of the electrolytic fluorination in step A is preferably 100 L or less, more preferably 50 L or less, even more preferably 30 L or less.

The total volume of fluorinated alcohol and organic solvent per mole of organic compound (2) at the beginning of the electrolytic fluorination in step A is preferably from 0.1 L to 100 L, more preferably from 1 to 50 L, even more preferably from 1 to 30 l.

[0073] If step A is carried out in the presence of an organic solvent, the volume ratio of fluoroalcohol to organic solvent at the start of electrolytic fluorination in step A is preferably 1/100 (v/v) or more, more preferably in the range of 0.2 to 2 (v/v), even more preferably in the range of 0.5 to 1 (v/v).

[0074] The metal fluoride concentration (concentration of metal fluoride relative to all liquid components of the system) in step A is preferably 0.2 M (mol/L) or more, more preferably in the range of 0.2 to 5 M (mol/L ), even more preferably in the range of 0.2 to 2M (mol/L), and even more preferably in the range of 0.2 to 1M (mol/L).

[0075] The lower temperature limit in step A may be preferably 0°C, more preferably 5°C, even more preferably 10°C.

The upper temperature limit in step A may be preferably 150°C, more preferably 120°C, even more preferably 100°C.

The temperature of step A is preferably in the range from 0 to 150°C, more preferably in the range from 0 to 120°C, even more preferably in the range from 0 to 100°C.

With regard to the specified temperature ranges, the lower the upper temperature limit in stage A, the more likely it is that adverse reactions will be suppressed. The higher the lower temperature limit in stage A, the more likely it is to stimulate the target response.

Stage A can be carried out at room temperature.

[0076] Step A can be carried out under an atmosphere of air, an inert gas (eg, nitrogen or argon), or a mixture thereof.

[0077] The lower limit of the reaction time in step A may be preferably 0.5 hour, more preferably 1 hour.

The upper limit of the reaction time in step A may be preferably 72 hours, more preferably 48 hours, even more preferably 24 hours.

The reaction time in step A may preferably be in the range of 0.5 to 72 hours, more preferably in the range of 1 to 48 hours, even more preferably in the range of 1 to 24 hours.

The shorter the upper reaction time limit in stage A, the more likely it is that adverse reactions will be suppressed.

The longer the lower limit of reaction time at stage A, the more likely it is that the target response will be stimulated.

[0078] As stated above, this reaction can be carried out in the presence or absence of an organic solvent.

In the present specification, examples of the organic solvent include

(1) alcohol solvents (eg, methanol, ethanol, n-propanol, isopropanol, n-butanol, pentanol, hexanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylene glycol and hexanetriol);

(2) non-aromatic hydrocarbon solvents (eg, pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, n-decane, isodecane and tridecane);

(3) aromatic hydrocarbon solvents (eg, benzene, toluene, xylene, tetralin, veratrole, ethylbenzene, diethylbenzene, naphthalene, methylnaphthalene, anisole, mesethylene, indene, diphenyl sulfide);

(4) ketone solvents (eg, acetone, methyl ethyl ketone, diethyl ketone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, acetonylacetone, methylhexanone, acetophenone, cyclohexanone, diacetone alcohol, propiophenone and isophorone);

(5) halogenated hydrocarbon solvents (eg, dichloromethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, chloroform and chlorobenzene);

(6) ethers (e.g. diethyl ether, tetrahydrofuran (THF), diisopropyl ether, methyl t-butyl ether (MTBE), dioxane, dimethoxyethane, diglyme, triglyme, tetraglyme, anisole, phenetol, 1,1-dimethoxycyclohexane, diisoamyl ether and cyclopentyl methyl ether (CPME));

(7) esters (eg, ethyl acetate, isopropyl acetate, butyl acetate, diethyl malonate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone and α-acetyl-γ-butyrolactone);

(8) nitrile solvents (eg, acetonitrile, propionitrile and benzonitrile);

(9) sulfoxide solvents (eg, dimethyl sulfoxide and sulfolane);

(10) amide solvents (e.g. N,N-dimethylformamide (DMF), N,N-dimethylacetamide, N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), N,N-dimethylacrylamide, N , N-dimethylacetamide (DMA), N, N-diethylformamide and N, N-diethylacetamide);

(11) nitrosolvents (eg, nitromethane, nitroethane, nitrobenzene, 4-nitrophenetol and o-nitrotoluene); And

(12) carbonate solvents (eg, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate and propylene carbonate).

Particularly preferred are inert solvents such as aprotic solvents. Examples of these are nitrile solvents (eg, acetonitrile and propionitrile) and nitrosolvents (eg, nitromethane and nitroethane).

These solvents can be used individually or in combination of two or more.

[0079] The electrolytic cell used in electrolytic fluorination may be, for example, a diaphragmless or diaphragm-type electrolytic cell, preferably a diaphragmless electrolytic cell is used.

The electrolysis method may be, for example, constant current electrolysis or controlled potential electrolysis, preferably constant current electrolysis is used.

Examples of suitable electrodes include platinum electrodes, carbon electrodes, boron doped diamond (BDD) electrodes, glassy carbon electrodes, silver electrodes, copper electrodes and the like. Preferably, platinum electrodes are used.

[0080] According to the production method of the present invention, the conversion rate of the starting material may be preferably 10% or more, more preferably 30% or more, even more preferably 50% or more.

According to the production method of the present invention, the yield of a given compound into which one or more fluorine atoms are introduced may be preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, and further more preferably 80% or more.

[0081] According to the production method of the present invention, the yield of a given compound into which two or more fluorine atoms are introduced may be preferably 10% or more, more preferably 15% or more, even more preferably 20% or more , and even more preferably 25% or more.

[0082] Composition

The composition according to one embodiment of the present invention includes 0.2 M or more of a metal fluoride, a fluorinated alcohol and an organic solvent.

The metal fluoride at a concentration of 0.2M or more, the fluorine alcohol and the organic solvent contained in the composition may be the same as those in the production method of the present invention.

Accordingly, those skilled in the art will understand specific details regarding the composition and embodiments thereof based on the description of the production method according to the present invention.

EXAMPLES

[0083] Next, the present invention is described in more detail with reference to examples; however, the present invention is not limited to these examples.

[0084] Example 1

2,2,2-trifluoroethanol (2 ml), acetonitrile (8 ml), cesium fluoride (608 mg) and triphenylmethane (244 mg) were placed in a diaphragmless cell with platinum plates installed in it as electrodes, and electrolysis was carried out at constant a current of 5 mA/cm ² in an air atmosphere at room temperature so that the total amount of energy supplied was 2 F/mol. At the end of the electrolysis, quantitative analysis by ¹⁹ F NMR showed that the yield of fluorotriphenylmethane was 15%.

[0085] Example 2

1,1,1,3,3,3-hexafluoro-2-propanol (2 ml), acetonitrile (8 ml), potassium fluoride (116 mg) and triphenylmethane (244 mg) were placed in a diaphragmless cell with platinum plates mounted in as electrodes, and electrolysis was carried out at a constant current of 5 mA/cm ² in an air atmosphere at room temperature so that the total amount of energy input was 2 F/mol. At the end of the electrolysis, quantitative analysis by ¹⁹ F NMR showed that the yield of fluorotriphenylmethane was 80%.

[0086] Example 3

1,1,1,3,3,3-hexafluoro-2-propanol (2 ml), nitromethane (8 ml), cesium fluoride (608 mg) and ethyl(phenylthio)acetate (196 mg) were placed in a diaphragmless cell with platinum plates installed in it as electrodes, and electrolysis was carried out at a constant current of 5 mA/cm ² in an air atmosphere at room temperature so that the total amount of energy supplied was 2 F/mol. At the end of the electrolysis, quantitative analysis by ¹⁹ F NMR showed that the yield of ethyl α-fluoro(phenylthio)acetate was 45%, and the yield of ethyl α,α-difluoro(phenylthio)acetate was 2%.

[0087] Example 4

1,1,1,3,3,3-hexafluoro-2-propanol (2 ml), nitromethane (8 ml), cesium fluoride (608 mg) and ethyl(phenylthio)acetate (196 mg) were placed in a diaphragmless cell with platinum plates installed in it as electrodes, and electrolysis was carried out at a constant current of 5 mA/cm ² in an air atmosphere at room temperature so that the total amount of energy supplied was 4 F/mol. At the end of the electrolysis, quantitative analysis by ¹⁹ F NMR showed that the yield of ethyl α-fluoro(phenylthio)acetate was 7%, and the yield of ethyl α,α-difluoro(phenylthio)acetate was 23%.

[0088] Example 5

1,1,1,3,3,3-hexafluoro-2-propanol (2 ml), acetonitrile (8 ml), cesium fluoride (304 mg) and bis(phenylthio)diphenylmethane (385 mg) were placed in a diaphragmless cell with platinum plates installed in it as electrodes, and electrolysis was carried out at a constant current of 5 mA/cm ² in an air atmosphere at room temperature so that the total amount of energy supplied was 4 F/mol. At the end of the electrolysis, quantitative analysis by ¹⁹ F NMR showed that the yield of difluorodiphenylmethane was 28%.

Example 6

1,1,1,3,3,3-hexafluoro-2-propanol (2 ml), acetonitrile (8 ml), cesium fluoride (608 mg) and 2,2-diphenyl-1,3-dithiolane (258 mg) placed in a diaphragm-less cell with platinum plates installed in it as electrodes, and electrolysis was carried out at a constant current of 5 mA/cm ² in an air atmosphere at room temperature so that the total amount of energy supplied was 4 F/mol. At the end of the electrolysis, quantitative analysis by ¹⁹ F NMR showed that the yield of difluorodiphenylmethane was 20%.

[0089] Example 7

1,1,1,3,3,3-hexafluoro-2-propanol (2 ml), acetonitrile (8 ml), cesium fluoride (304 mg) and ethyl (4-methoxyphenyl) acetate (194 mg) were placed in a non-diaphragm cell with platinum plates installed therein as electrodes, and electrolysis was carried out at a constant current of 5 mA/cm ² in an air atmosphere at room temperature such that the total amount of energy input was 4 F/mol. At the end of the electrolysis, quantitative analysis by ¹⁹ F NMR showed that the yield of ethyl α-fluoro(4-methoxyphenyl)acetate was 5%, and the yield of ethyl α,α-difluoro(4-methoxyphenyl)acetate was 20%.

[0090] Example 8

1,1,1,3,3,3-hexafluoro-2-propanol (2 ml), acetonitrile (8 ml), cesium fluoride (304 mg) and 2-phenoxy-2(phenylthio)acetonitrile (60 mg) were placed in a diaphragmless cell with platinum plates installed therein as electrodes, and electrolysis was carried out at a constant current of 5 mA/cm ² in an air atmosphere at room temperature so that the total amount of energy input was 4 F/mol. At the end of the electrolysis, quantitative analysis by ¹⁹ F NMR showed that the yield of 2-fluoro-2-phenoxy-2(phenylthio)acetonitrile was 40%.

[0091] Example 9

1,1,1,3,3,3-hexafluoro-2-propanol (2 ml), acetonitrile, cesium fluoride and 4-bromocumene were placed in a diaphragmless cell with platinum plates installed in it as electrodes, and electrolysis was carried out at constant current in an air atmosphere, thereby obtaining 1-bromo-4(1-fluoro-1-methylethyl)benzene.

[0092] Example 10

1,1,1,3,3,3-hexafluoro-2-propanol (2 ml), acetonitrile (8 ml), cesium fluoride (304 mg) and diglyme (70 mg) were placed in a diaphragmless cell with platinum plates mounted in as electrodes, and electrolysis was carried out at a constant current of 5 mA/cm ² in an air atmosphere at room temperature so that the total amount of energy input was 4 F/mol. At the end of electrolysis, a peak of fluorinated diglyme was detected by mass spectrometry.

Claims (19)

1. A method for producing a fluorine-containing organic compound (1), comprising a step A of subjecting the organic compound (2) to electrolytic fluorination in the presence of 0.2M or more of a metal fluoride and a fluorinated alcohol, characterized by a fluorine content ranging from 50 to 80% wt., while stage A is carried out in the presence of an organic solvent, and wherein the fluorine-containing organic compound (1) is a fluorine-containing organic compound corresponding to the formula (1): R ¹ -(F) _n , in which R ¹ means an organic group, and n is an integer of 1 or more; And organic compound (2) is an organic compound corresponding to formula (2): R ¹ -(H) _n , R ¹ -(SR ^1a ) _n , or R ¹ (=S) _n/2 , in which R¹ and n are as above, R^1a means an organic group provided that n/2 is an integer of 1 or more. 2. The production method according to claim 1, wherein the organic group is a (hetero)hydrocarbon radical, optionally with one or more substituents. 3. The production method according to claim 1, in which n is an integer of 2 or more. 4. The production method according to claim 1, in which R ¹ is a polyester group. 5. The production method according to claim 1, wherein the fluorine-containing organic compound (1) is a ketone, an imine, a sulfide, an aromatic compound, a thiocarbonyl compound or a polyether. 6. The production method according to claim 1, wherein the metal fluoride is at least one metal fluoride selected from the group consisting of metal fluorides of group 1 of the periodic table of elements and metal fluorides of group 2 of the periodic table of elements. 7. The production method according to claim 6, wherein the metal fluoride is at least one metal fluoride selected from the group consisting of lithium fluoride, sodium fluoride, potassium fluoride and cesium fluoride. 8. The production method according to claim 1, in which the fluorinated alcohol is a C _1-14 fluorinated alcohol. 9. Production method according to any one of paragraphs. 1-8, in which the total volume of fluorinated alcohol and organic solvent per mole of organic compound (2) at the beginning of electrolytic fluorination in step A is in the range from 0.1 to 100 l. 10. Production method according to any one of paragraphs. 1-8, in which the volume ratio of fluorinated alcohol to organic solvent at the beginning of electrolytic fluorination in step A is 1/100 (v/v) or more. 11. Production method according to any one of paragraphs. 1-8, in which the concentration of metal fluoride in step A is in the range from 0.2 to 5M. 12. Production method according to any one of paragraphs. 1-8, in which the temperature in stage A is 0°C or more. 13. A composition for the production of a fluorine-containing organic compound, containing 0.2 M or more of metal fluoride, a fluorinated alcohol and an organic solvent.