Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/20—Processes
  • C25B3/27—Halogenation
  • C25B3/28—Fluorination
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/01—Products
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/01—Products
  • C25B3/07—Oxygen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/01—Products
  • C25B3/09—Nitrogen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/01—Products
  • C25B3/11—Halogen containing compounds

Definitions

• This disclosure relates to a method for producing a fluorine-containing organic compound.
• electrolytic fluorination As a method for producing a fluorine-containing organic compound, for example, electrolytic fluorination is known.
• electrolytic fluorination for example, the method described in Non-Patent Document 1 is known.
• An object of the present disclosure is to provide a new method for producing a fluorine-containing organic compound by electrolytic fluorination.
• Item 1 A method for producing a fluorine-containing organic compound (1).
• Organic compound (2) Step A of electrolytic fluorination in the presence of metal fluoride of 0.2 M or more and fluoroalcohol Manufacturing method including.
• the fluorine-containing organic compound (1) has a formula (1): R 1- (F) n [During the ceremony, R 1 represents an organic group and n represents an integer greater than or equal to 1. ] It is a fluorine-containing organic compound represented by, and the organic compound (2) is represented by the formula (2) :.
• the organic group is A (hetero) hydrocarbyl group which may have one or more substituents, Item 2.
• Item 4. n is An integer greater than or equal to 2 Item 2.
• R 1 is It is a polyether group, Item 8. The manufacturing method according to any one of Items 2 to 4.
• Item 6. The production method according to Item 1, wherein the fluorine-containing organic compound (1) is a ketone, an imine, a sulfide, an aromatic compound, a thiocarbonyl compound, or a polyether.
• the metal fluoride is One or more metal fluorides selected from the group consisting of metal fluorides belonging to Group 1 of the Periodic Table and fluorides of metals belonging to Group 2 of the Periodic Table.
• Item 8. The production method according to any one of Items 1 to 6.
• the metal fluoride is One or more metal fluorides selected from the group consisting of lithium fluoride, sodium fluoride, potassium fluoride, and cesium fluoride.
• Item 7. The manufacturing method according to Item 7.
• the fluoroalcohol is C 1-14 fluoroalcohol, Item 8.
• the fluoroalcohol is A fluoroalcohol whose fluorine content is in the range of 50-80% by mass.
• Item 9. The manufacturing method according to Item 9.
• Item 11. The total volume of the fluoroalcohol and the organic solvent per mole of the organic compound (2) at the time when the step A was carried out in the presence of the organic solvent and at the start of the electrolytic fluorination of the step A was 0.1 to Within the range of 100L, Item 8.
• the step A is carried out in the presence of an organic solvent, and the volume ratio of the fluoroalcohol to the organic solvent at the start of the electrolytic fluorination of the step A is 1/100 (v / v) or more.
• Item 8. The production method according to any one of Items 1 to 11. Item 13. The concentration of the metal fluoride (concentration of the metal fluoride with respect to the entire liquid component in the system) in the step A is determined. Within the range of 0.2-5M, Item 8. The production method according to any one of Items 1 to 12. Item 14. The temperature of step A is Above 0 ° C, Item 8. The production method according to any one of Items 1 to 13. Item 15. A composition containing 0.2 M or more of metal fluoride, a fluoroalcohol, and an organic solvent.
• a new method for producing a fluorine-containing organic compound and the like are provided.
• halo (group) can include fluoro (group), chloro (group), bromo (group), and iodine (group).
• halogen (atom) can include fluorine (atom), chlorine (atom), bromine (atom), and iodine (atom).
• the "organic group” means a group containing one or more carbon atoms (or a group formed by removing one hydrogen atom from an organic compound).
• heteroatom may mean an atom other than hydrogen and carbon.
• heteroatom includes a nitrogen atom, an oxygen atom, and a sulfur atom.
• organic group means a group containing one or more carbon atoms as its constituent atoms.
• examples of “organic groups” are used herein.
• Hydrocarbyl which may have one or more substituents
• substituents include halo, nitro, cyano, oxo, tioxo, sulfo, sulfamoyl, sulfinamoyl, and sulfenamoyl.
• hydrocarbyl (group) means a group containing one or more carbon atoms and one or more hydrogen atoms as its constituent atoms.
• (1) hydrocarbyl is substituted with an aliphatic hydrocarbyl group (eg, a benzyl group) which may be substituted with one or more aromatic hydrocarbyl groups, and one or more aliphatic hydrocarbyl groups. It includes an aromatic hydrocarbyl group (aryl group in a narrow sense) which may be used.
• the (hetero) aryl group includes an aryl group in a narrow sense and a heteroaryl group.
• a 5- to 6-membered heteroaryl group and the 5- to 6-membered heteroaryl group have a benzene ring. Includes fused groups, alkoxy groups, ester groups, ether groups, and heterocyclic groups.
• the "aliphatic hydrocarbyl (group)” can be linear, branched, cyclic, or a combination thereof. Unless otherwise specified herein, the “aliphatic hydrocarbyl (group)” can be saturated or unsaturated. Unless otherwise specified herein, examples of “aliphatic hydrocarbyl (group)” include alkyl groups, alkenyl groups, alkynyl groups, and cycloalkyl groups.
• alkyl (group) are methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, sec-butyl, tert-butyl). , Pentyl, isopentyl, neopentyl, and hexyl, which are linear or branched, and include alkyl groups having 1 to 10 carbon atoms.
• alkenyl (group) are linear or branched alkenyl groups having 1 to 10 carbon atoms (eg, 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, 5-hexenyl, etc.).
• alkynyl (group) are linear or branched alkynyl groups having 2 to 6 carbon atoms (eg, ethynyl, 1-propynyl, 2-propynyl, 1). -Includes (butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, and 5-hexynyl) To do.
• cycloalkyl (group) in the present specification include cycloalkyl groups having 3 to 8 carbon atoms (eg, cyclopentyl, cyclohexyl, and cycloheptyl).
• aromatic hydrocarbyl (group) [aryl (group)] examples include phenyl, naphthyl, phenanthryl, anthryl, and pyrenyl.
• aralkyl (group) can mean an alkyl group substituted with one aryl group, as is usually understood.
• alkoxy (group) is, for example, a group represented by RO- (in the formula, R is an alkyl group).
• RCO 2- in the formula, R is an alkyl group
• Ra- CO 2- R b- in the formula, R a is an alkyl group
• R b is an alkylene group
• ether group means a group having an ether bond (-O-).
• ether groups include polyether groups.
• polyether groups are of the formula: Ra ⁇ (OR b ) n ⁇ (in the formula, Ra is an alkyl group, R b is the same or different in each appearance, is an alkylene group, and n is an integer greater than or equal to 1).
• the alkylene group is a divalent group formed by removing one hydrogen atom from the alkyl group.
• ether groups also include hydrocarbyl ether groups. Hydrocarbyl ether group means a hydrocarbyl group having one or more ether bonds.
• a “hydrocarbyl group having one or more ether bonds” can be a hydrocarbyl group into which one or more ether bonds are inserted. Examples include the benzyloxy group. Examples of “hydrocarbyl groups having one or more ether bonds” include alkyl groups having one or more ether bonds. The "alkyl group having one or more ether bonds” can be an alkyl group into which one or more ether bonds are inserted. In the present specification, such a group may be referred to as an alkyl ether group.
• acyl (group) includes an alkanoyl group.
• alkanoyl (group) is, for example, a group represented by RCO- (in the formula, R is an alkyl group).
• 5- to 6-membered heteroaryl (group) is A 5- to 6-membered heteroaryl group having at least one (eg: 1, 2, or 3) heteroatoms selected from the group consisting of oxygen, sulfur, and nitrogen as ring-constituting atoms [eg, pyrrolyl.
• the manufacturing method which is one aspect of the present disclosure, is A method for producing a fluorine-containing organic compound (1).
• examples of the organic compound (2) as a reaction substrate include, for example.
• Ketones eg, diketones such as 1,3-diketone, ⁇ -ketocarboxylic acid, ⁇ -ketoester), imines (eg, Schiff base, hydrazone),
• Sulfides (2-3)
• Aromatic compounds eg, aromatic hydrocarbons, phenylhydrazine derivatives, phenol derivatives, 2-naphthol derivatives, aniline derivatives
• Examples thereof include thiocarbonyl compounds.
• an alkyl group which may have a substituent means an alkyl group (that is, an unsubstituted alkyl group) and an alkyl group having a substituent (that is, a substituted alkyl group).
• Heterocycloalkyl group which may have 1 or more substituents, heterocyclic group which may have 1 or more substituents, alkoxy group which may have 1 or more substituents, 1 piece.
• An aryloxy group which may have the above substituents, an amino group, a monoalkylamino group which may have one or more substituents, and a dialkylamino group which may have one or more substituents.
• R 2 is an alkyl group which may have one or more substituents, an aralkyl group which may have one or more substituents, an aryl group which may have one or more substituents, and 1
• An alkenyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, and a heterocycloalkyl group which may have one or more substituents, one or more.
• a heterocyclic group which may have a substituent of 1 or more, an alkoxy group which may have one or more substituents, an aryloxy group which may have one or more substituents, and one or more substituents.
• R 2a and R 2b are the same or different hydrogen atoms, an alkyl group which may have one or more substituents, an aralkyl group which may have one or more substituents, and one or more substituents.
• R 2 and R 2a may be combined with each other to form an annular structure.
• Examples of the cyclic structure include an aliphatic 4- to 7-membered ring which may have one or more substituents.
• R 2 is an alkyl group, an aralkyl group, an aryl group, an alkenyl group, a heterocyclic group, an alkoxy group, an aryloxy group, or is preferably a monoalkylamino group.
• R', R 2a , and R 2b are preferably hydrogen atoms, alkyl groups, aralkyl groups, aryl groups, alkenyl groups, heterocyclic groups, alkoxy groups, aryloxy groups, or monoalkylamino groups, respectively.
• Ketones include dialkyl ketones (eg acetone, methyl ethyl ketone), diketones (eg acetylacetone, acetoacetic acid, acetoacetate ester), cycloalkanones (eg cyclohexanone), alkylarylketones (eg acetophenone, propiophenone). ), Diarylketones (eg benzophenone), 4-piperidone, 1-oxo-1,2-dihydronaphthalene, aryl (arylalkenyl) ketones (eg benzylideneacetphenone (calcon)), and arylaralkyl ketones (eg deoxo). Benzoin), as well as these ketals and the like.
• dialkyl ketones eg acetone, methyl ethyl ketone
• diketones eg acetylacetone, acetoacetic acid, acetoacetate ester
• imines such as Schiff base and hydrazone
• examples of imines include condensates of ketones or aldehydes with appropriate primary amines and hydrazines.
• fluorination for example, one or two hydrogen atoms of methylene next to the S atom [or -CHQ- (Q is an organic group).
• a reaction is carried out in which one of the hydrogen atoms of) is replaced with a fluorine atom or -SQ (Q is an organic group) is replaced with fluorine.
• any of the following reactions (2-2-1) to (2-2-7) is carried out.
• R 3a , R 3a' , and R 3a'' are the same or different alkyl groups which may have one or more substituents, and aralkyl groups which may have one or more substituents, 1
• R 3 and R 3b are the same or different alkyl groups which may have one or more substituents, aralkyl groups which may have one or more substituents, and one or more substituents. It may have an aryl group, an alkenyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, and one or more substituents.
• Oxy group amino group, monoalkylamino group which may have one or more substituents, dialkylamino group which may have one or more substituents, acyl group, acylamino group, cyano group, one Alkyl sulfinyl group which may have the above substituents, aralkylsulfinyl group which may have one or more substituents, arylsulfinyl group which may have one or more substituents, one or more A cycloalkylsulfinyl group which may have a substituent, a heterocycloalkylsulfinyl group which may have one or more substituents, and a sulfinyl which is a heterocyclic group which may have one or more substituents.
• the ring has a halogen atom, an oxo group, an alkyl group which may have one or more substituents, an aralkyl group which may have one or more substituents, and one or more substituents. It may be substituted with one or more substituents selected from the group consisting of an aryl group which may have one or more substituents, an alkenyl group which may have a alkenyl group, a cyano group, and an amino group).
• R 3c and R 3d are the same or different hydrogen atoms, an alkyl group which may have one or more substituents, an aralkyl group which may have one or more substituents, and one or more substituents.
• An aryl group which may have a group, an alkenyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, and one or more substituents. It may have a heterocycloalkyl group, a heterocyclic group which may have one or more substituents, an alkoxy group which may have one or more substituents, and one or more substituents.
• R 3c and R 3d are bonded together with adjacent carbon atoms to form an aliphatic 4- to 7-membered ring with one or more saturated or unsaturated substituents.
• the ring may contain a halogen atom, an oxo group, an alkyl group which may have one or more substituents, an aralkyl group which may have one or more substituents, and one or more substituents.
• R 3a , R 3a' , and R 3a ′′ are preferably alkyl, aryl, or alkenyl groups, respectively.
• R 3 , R 3b , R 3c , and R 3d are preferably 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, respectively. ..
• sulfides include dialkyl sulfide (eg, methyl ethyl sulfide), alkyl aralkyl sulfide (eg, methyl benzyl sulfide), 2-arylthioacetic acid ester (eg, 2-phenylthioacetic acid ester), alkyl (arylthio) ketone (eg, 2).
• alkyl (alkylthio) ketone eg 2- (methylthio) acetophenone
• 2-aryloxy-2- (arylthio) acetonitrile eg 2-phenoxy-2- (phenylthio) acetonitrile
• bis (Alkylthio) Alkyl arene eg, bis (methylthio) methylbenzene
• bis (arylthio) diarylmethane eg, bis (phenylthio) diphenylmethane
• 1,3-dithian with one or more substituents at the 2-position (eg) : 2-octyl-1,3-dithian
• 1,3-dithiolane having one or more substituents at the 2-position (eg 2-phenyl-2-trifluoromethyl-1,3-dithiolane, 2,2) -Diphenyl-1,3-dithiolane), tris (alkylthio)
• R 5a , R 5b , R 5c , R 5d , and R 5e are the same or different, hydrogen atom, alkyl group, aralkyl group, aryl group, alkoxy group, nitro group, cyano group, halogen atom, It shows an alkanoyl group, an arylcarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkanoylamino group, an arylcarbonylamino group, and an alkylthio group.
• the phenol derivative has, for example, the difluoroylated quinonoid structure shown below, and then by reduction, fluorine is added to the ortho or para position of the hydroxyl group. The introduced phenol derivative is produced.
• R 5a , R 5b , R 5c , and R 5d are the same or different, hydrogen atom, alkyl group, aralkyl group, aryl group, alkoxy group, nitro group, cyano group, halogen atom, alkanoyl group, Indicates an arylcarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkanoylamino group, an arylcarbonylamino group, or an alkylthio group.
• R 5a , R 5b , R 5c , and R 5d are the same or different, hydrogen atom, alkyl group, aralkyl group, aryl group, alkoxy group, nitro group, cyano group, halogen atom, alkanoyl group, Indicates an arylcarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkanoyla
• a fluorine atom is introduced into the ortho or para position to produce a compound having a fluorinated quinonoid structure.
• phenol which may have one or more substituents is used as the phenol derivative, but a benzene-based derivative which has an electron-donating group such as a hydroxyl group or an alkoxy group and may be further substituted.
• a fluorine atom can be introduced into an aromatic compound or a condensed polycyclic hydrocarbon.
• R 5a , R 5b , R 5c , R 5d , R 5e , and R 5f are the same or different, hydrogen atom, alkyl group, aralkyl group, aryl group, alkoxy group, nitro group, cyano group, halogen atom, alkanoyl.
• R 5g contains 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, and an arylcarbonyl. Indicates an amino group or an alkylthio group. ]
• aniline derivative In the fluorination , the aniline derivative also has, for example, the difluoroylated quinonoid structure shown below, and then reduces to the ortho-position or para-position. Aniline derivatives with fluorine introduced into them are produced.
• R 5a , R 5b , R 5c , and R 5d are the same or different, hydrogen atom, alkyl group, aralkyl group, aryl group, alkoxy group, nitro group, cyano group, halogen atom, alkanoyl group, Arylcarbonyl group, amino group, monoalkylamino group, dialkylamino group, alkanoylamino group, arylcarbonylamino group and alkylthio group are shown. ]
• aniline which may have one or more substituents is used as the aniline derivative, but naphthylamine which may have one or more substituents also introduces a fluorine atom into the aromatic ring. be able to.
• Example: 5- to 6-membered aromatic ring group showing a (hetero) aryl group which may have.
• aryl group which may have a substituent (hetero) aryl group: indicates (examples 5-6 membered aromatic ring group), and R s, at each occurrence, the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl Indicates a group, aryl group, alkoxy group, nitro group, cyano group, halogen atom, alkanoyl group, arylcarbonyl group, amino group, monoalkylamino group, dialkylamino group, alkanoylamino group, arylcarbonylamino group or alkylthio group. .. ]
• the 5- to 6-membered aromatic ring group can be a phenyl group or a 5- to 6-membered heteroaryl group.
• Examples of the (hetero) arylmethyl part-containing compound include triarylmethane (eg, triphenylmethane), aryldialkylmethane (eg, 4-bromocumene), and arylacetate (eg, (4-methoxyphenyl) ethyl acetate). Can be mentioned.
• triarylmethane eg, triphenylmethane
• aryldialkylmethane eg, 4-bromocumene
• arylacetate eg, (4-methoxyphenyl) ethyl acetate
• An aryl group which may have a group, an alkenyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, and one or more substituents. It may have a heterocycloalkyl group, a heterocyclic group which may have one or more substituents, an alkoxy group which may have one or more substituents, and one or more substituents.
• R 6 and R 6a may be combined with each other to form an annular structure.
• R 6b is an alkyl group which may have one or more substituents, an aralkyl group which may have one or more substituents, an aryl group which may have one or more substituents, and 1
• An alkenyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, and a heterocycloalkyl group which may have one or more substituents, one or more. Indicates a heterocyclic group which may have a substituent of. ]
• R 6 , R 6a , and R 6b are preferably alkyl groups, aralkyl groups, aryl groups, or alkenyl groups, respectively.
• thiocarbonyl compound examples include O-arylS-alkyl dithiocarbonate (eg, O- (4-isopropylphenyl) dithiocarbonate S-methyl, O- (4-bromophenyl) S-methyl dithiocarbonate), ((alkylthio).
• O-arylS-alkyl dithiocarbonate eg, O- (4-isopropylphenyl) dithiocarbonate S-methyl, O- (4-bromophenyl) S-methyl dithiocarbonate
• ((alkylthio) examples include O-arylS-alkyl dithiocarbonate (eg, O- (4-isopropylphenyl) dithiocarbonate S-methyl, O- (4-bromophenyl) S-methyl dithiocarbonate), ((alkylthio).
• Carbonoti oil) oxybenzoic acid ester eg 4-(((methylthio) carbonothio oil) oxy) ethyl benzoate
• dithiocarbonate O-alkyl S-alkyl eg dithiocarbonate O-decyl S-methyl
• Dithiocarbonate O-aralkyl S-alkyl eg dithiocarbonate O- (3-phenylpropyl) S-methyl
• cycloalkanocarbothioate O-alkyl eg cyclohexanecarbothioate O-methyl
• heteroarene carbothio Acid O-alkyl eg 1-piperidin carbotiate O-propyl
• dithiobenzoic acid ester eg methyl dithiobenzoate
• diarylthioketone eg thiobenzophenone
• thiobenzoic acid ester eg thiobenzoate
• Acid O-phenyl N,
• fluorination of Polyether for example, a hydrogen atom bonded to a carbon atom adjacent to an oxygen atom constituting an ether bond can be replaced with a fluorine atom, but the fluorination is not limited to this.
• the number of fluorine atoms introduced in the fluorination is not particularly limited, but is, for example, one.
• the polyether is not particularly limited, but for example, the formula (1A): R 7a- (OR 7b ) p -OR 7c
• R 7a and R 7c represent the same or different organic groups.
• R 7b represents an alkylene group, and p is an integer greater than or equal to 0 or 1.
• R 7a and R 7c are preferably alkyl groups, alkenyl groups, aryl groups, or aralkyl groups, respectively.
• R 7b is preferably a C 2-4 alkylene group.
• p can be, for example, 50 or less, 40 or less, 30 or less, or 20 or less.
• Examples of the compound represented by the formula (1A) include ethylene glycol di C 1-4 alkyl ether (eg monoglyme), polyethylene glycol di C 1-4 alkyl ether (eg diglyme, triglyme) and the like.
• the fluorine-containing organic compound (1) has a formula (1): R 1- (F) n [During the ceremony, R 1 represents an organic group and n represents an integer greater than or equal to 1. ] It is a fluorine-containing organic compound represented by, and the organic compound (2) is represented by the formula (2) :.
• R 1 and n have the same meaning as described above, and R 1a to R 1c are the same or different organic groups.
• It is an organic compound represented by.
• the organic group represented by R 1 and R 1a may contain one or more fluoro groups therein.
• the organic group is Preferably, it is a (hetero) hydrocarbyl group which may have one or more substituents.
• n is preferably an integer of 2 or more.
• n is an integer equal to or less than the maximum number that can be replaced with the organic compound (2).
• the organic group represented by R 1 has an n-valence formed by further removing n-1 hydrogen atoms from the monovalent group described in "Terms". Is the basis of. In the manufacturing method of the present disclosure, for example, both an object having one F introduced therein and an object having two F introduced therein can be obtained.
• Formula (2) is R 1 -H, R 1 is preferably a triarylmethane residues (or triarylmethyl group).
• Formula (2) is R 1 -H, R 1 is preferably a polyether group.
• Q 1 and Q 2 are the same or different, hydrogen atom, hydroxyl group, or organic group (eg, alkyl group, alkenyl group, aryl group, or aralkyl group).
• Q 3 and Q 4 are the same or different, a hydrogen atom or an organic group: a (e.g. alkyl group, an alkenyl group, an aryl group, or an aralkyl group).
• Formula (2) is R 1 - is (SR 1a) 2, R 1 is preferably > CQ 5 Q 6
• Q 5 and Q 6 are the same or different organic groups: a (e.g. alkyl group, an alkenyl group, an aryl group, or an aralkyl group).
• R 1a is preferably an organic group (eg, an alkyl group, an alkenyl group, an aryl group, or an aralkyl group) independently at each appearance.
• R 1a may be bonded to each other to form a ring structure.
• Q 7 and Q 8 are the same or different organic groups: a (e.g. alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, or an aralkyl group). ] Is.
• the formula (2) is R 1 -NH-NH 2 , where R 1 is preferably an alkyl group, an alkenyl group, an aryl group, or an aralkyl group.
• R 1 is preferably an alkyl group, an alkenyl group, an aryl group, or an aralkyl group
• R 1b is preferably alkyl A group, an alkenyl group, an aryl group, or an aralkyl group.
• the metal fluoride can function as a supporting salt (supporting electrolyte) in step A.
• the metal fluoride is It is preferably one or more metal fluorides selected from the group consisting of metal fluorides belonging to Group 1 of the Periodic Table and fluorides of metals belonging to Group 2 of the Periodic Table; and more preferably lithium fluoride. , Sodium fluoride, potassium fluoride, rubidium fluoride, and cesium fluoride, and one or more metal fluorides selected from the group consisting of calcium fluoride.
• the fluoroalcohol can function as an electrolytic solution in step A.
• the fluoroalcohol is Preferably, it is a C 1-14 fluoroalcohol.
• the fluoroalcohol is preferably It is a fluoroalcohol represented by RfCH 2 OH or Rf 2 CHOH (in the formula, Rf independently represents a perfluoroalkyl group having 1 to 6 carbon atoms at each appearance).
• Rf independently represents a perfluoroalkyl group having 1 to 6 carbon atoms at each appearance.
• Specific examples of the 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 Includes 3,3-pentafluoro-1-propanol, and suitable examples thereof are 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3-3. Includes pentafluoro-1-propanol.
• the fluoroalcohol is Preferably, a fluoroalcohol having a fluorine content of 50% by mass or more, More preferably, it is a fluoroalcohol having a fluorine content of 55% by mass or more, and even more preferably, a fluoroalcohol having a fluorine content of 60% by mass or more.
• the fluoroalcohol is Preferably, a fluoroalcohol having a fluorine content of 80% by mass or less, More preferably, it is a fluoroalcohol having a fluorine content of 75% by mass or less, and even more preferably, a fluoroalcohol having a fluorine content of 70% by mass or less.
• the fluoroalcohol is Preferably, a fluoroalcohol having a fluorine content in the range of 50-80% by mass, More preferably, it is a fluoroalcohol having a fluorine content in the range of 55 to 75% by mass, and even more preferably, a fluoroalcohol having a fluorine content in the range of 60 to 70% by mass.
• the fluorine content means the ratio of the mass of fluorine in one molecule of fluoroalcohol.
• the reaction of step A can be carried out in the presence or absence of an organic solvent. Specific examples of the organic solvent will be described later.
• the step A is carried out in the presence of an organic solvent.
• the total volume of the fluoroalcohol and the organic solvent per mole of the organic compound (2) at the start of the electrolytic fluorination in the step A is Preferably, 0.1 L or more; More preferably, it is 1 L or more: and even more preferably, it is 2 L or more.
• the total volume of the fluoroalcohol and the organic solvent per mole of the organic compound (2) at the start of the electrolytic fluorination in the step A is It is preferably 100 L or less, more preferably 50 L or less, and even more preferably 30 L or less.
• the total volume of the fluoroalcohol and the organic solvent per mole of the organic compound (2) at the start of the electrolytic fluorination in the step A is Preferably within the range of 0.1-100 L; More preferably, it is in the range of 1 to 50 L: and even more preferably, it is in the range of 1 to 30 L.
• the volume ratio of the fluoroalcohol to the organic solvent at the start of electrolytic fluorination in step A is Preferably 1/100 (v / v) or more, More preferably, it is in the range of 0.2 to 2 (v / v): and even more preferably, it is in the range of 0.5 to 1 (v / v).
• the concentration of the metal fluoride (concentration of the metal fluoride with respect to the entire liquid component in the system) in the step A is determined.
• 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 2 M (mol / L): and even more preferably in the range of 0.2 to 1 M (mol / L). ).
• the lower limit of the temperature in step A is Preferably at 0 ° C. More preferably, 5 ° C. And even more preferably 10 ° C.
• the upper limit of the temperature in step A is Preferably at 150 ° C. More preferably 120 ° C. And even more preferably 100 ° C.
• the temperature of step A is Preferably in the range of 0-150 ° C, More preferably in the range of 0 to 120 ° C. More preferably, it is in the range of 0 to 100 ° C. By being at that temperature
• the lower the upper limit of the temperature in step A the more likely it is that side reactions can be suppressed.
• the higher the lower limit of the temperature in step A the more likely it is that the desired reaction will proceed.
• Step A can be performed at room temperature.
• Step A can be performed in an atmosphere of air, an inert gas (eg, nitrogen, argon), or a combination thereof.
• an inert gas eg, nitrogen, argon
• the lower limit of the reaction time in step A is Preferably for 0.5 hours More preferably, it can be 1 hour.
• the upper limit of the reaction time of the step A is Preferably for 72 hours It can be more preferably 48 hours, and even more preferably 24 hours.
• the reaction time of the step A is Preferably within the range of 0.5-72 hours, More preferably, within the range of 1 to 48 hours, And even more preferably, it can be in the range of 1 to 24 hours.
• the shorter the upper limit of the reaction time in step A the more likely it is that side reactions can be suppressed.
• the higher the lower limit of the reaction time in step A the more likely it is that the progress of the desired reaction will be promoted.
• the reaction can be carried out in the presence or absence of an organic solvent.
• organic solvents examples are referred to as An example of the solvent is
• Alcohol solvent Example: 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, hexanetriol
• Non-aromatic hydrocarbon solvents eg pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, n-decane, isododecane, tridecane
• Aromatic hydrocarbon solvents eg, benzene, toluen
• an inert solvent such as an aprotic solvent is preferable.
• examples thereof include nitrile solvents (eg, acetonitrile, propionitrile) and nitro solvents (eg, nitromethane, nitroethane). These solvents may be used alone or in combination of two or more.
• the electrolytic cell used in the electrolytic fluorination for example, a diaphragmless type or a diaphragm type electrolytic cell can be used, but a diaphragmless type electrolytic cell can be preferably used.
• the electrolysis method for example, constant current electrolysis or constant potential electrolysis can be used, but constant current electrolysis can be preferably used.
• the electrode a platinum electrode, a carbon electrode, a BDD (boron-doped diamond) electrode, a glassy carbon electrode, a silver electrode, a copper electrode and the like can be used, but a platinum electrode can be preferably used.
• the raw material conversion rate can be preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more.
• the yield of the target compound is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, and the target compound into which one or more Fs are introduced. Even more preferably, it can be 80% or more.
• the yield of the target compound is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, and more, for the target product into which two or more Fs have been introduced. More preferably, it can be 25% or more.
• compositions contains 0.2 M or more of metal fluoride, a fluoroalcohol, and an organic solvent.
• the metal fluoride, fluoroalcohol, and organic solvent of 0.2 M or more contained in the composition can be the same as those in the production method of the present disclosure. Therefore, those skilled in the art can understand the details of the composition and its specific embodiments based on the description of the production method of the present disclosure.
• Example 1 2,2,2-Trifluoroethanol (2 mL), acetonitrile (8 mL), cesium fluoride (608 mg), and triphenylmethane (244 mg) were added to a non-diaphragm cell to which a platinum plate was connected as an electrode, and under an air atmosphere, Constant current electrolysis was performed at 5 mA / cm 2 so that the total energization amount was 2 F / mol at room temperature. After completion of electrolysis, quantification by 19 F NMR revealed that the yield of fluorotriphenylmethane was 15%.
• Example 2 1,1,1,3,3,3-hexafluoro-2-propanol (2 mL), acetonitrile (8 mL), potassium fluoride (116 mg), triphenylmethane (11 mg) to a non-diaphragm cell to which a platinum plate was connected as an electrode. 244 mg) was added, and constant current electrolysis was performed at 5 mA / cm 2 so that the total energization amount was 2 F / mol at room temperature in an air atmosphere. After completion of electrolysis, quantification by 19 F NMR revealed that the yield of fluorotriphenylmethane was 80%.
• Example 3 1,1,1,3,3,3-hexafluoro-2-propanol (2 mL), nitromethane (8 mL), cesium fluoride (608 mg), (phenylthio) acetate to a non-diaphragm cell connected to a platinum plate as an electrode Ethyl (196 mg) was added, and constant current electrolysis was performed at 5 mA / cm 2 so that the total energization amount was 2 F / mol at room temperature in an air atmosphere.
• Example 4 1,1,1,3,3,3-hexafluoro-2-propanol (2 mL), nitromethane (8 mL), cesium fluoride (608 mg), (phenylthio) acetate to a non-diaphragm cell connected to a platinum plate as an electrode Ethyl (196 mg) was added, and constant current electrolysis was performed at 5 mA / cm 2 so that the total energization amount was 4 F / mol at room temperature in an air atmosphere.
• Example 5 1,1,1,3,3,3-hexafluoro-2-propanol (2 mL), acetonitrile (8 mL), cesium fluoride (304 mg), bis (phenylthio) to a non-diaphragm cell to which a platinum plate was connected as an electrode.
• Diphenylmethane (385 mg) was added, and constant current electrolysis was performed at 5 mA / cm 2 so that the total energization amount was 4 F / mol at room temperature in an air atmosphere. After the electrolysis was completed, the amount of difluorodiphenylmethane was 28% when quantified by 19 F NMR.
• Example 6 1,1,1,3,3,3-hexafluoro-2-propanol (2 mL), acetonitrile (8 mL), cesium fluoride (304 mg), 2,2- Diphenyl-1,3-dithiolane (258 mg) was added, and constant current electrolysis was performed at 5 mA / cm 2 so that the total energization amount was 4 F / mol at room temperature in an air atmosphere. After completion of electrolysis, quantification by 19 F NMR revealed that the yield of difluorodiphenylmethane was 20%.
• Example 7 1,1,1,3,3,3-hexafluoro-2-propanol (2 mL), acetonitrile (8 mL), cesium fluoride (304 mg), (4-methoxy) to a non-diaphragm cell to which a platinum plate was connected as an electrode.
• Ethyl (phenyl) acetate (194 mg) was added, and constant current electrolysis was performed at 5 mA / cm 2 so that the total energization amount was 4 F / mol at room temperature in an air atmosphere.
• Example 8 1,1,1,3,3,3-hexafluoro-2-propanol (2 mL), acetonitrile (8 mL), cesium fluoride (304 mg), 2-phenoxy- 2- (Phenylthio) acetonitrile (60 mg) was added, and constant current electrolysis was performed at 5 mA / cm 2 so that the total energization amount was 4 F / mol at room temperature in an air atmosphere. After completion of electrolysis, quantification by 19 F NMR revealed that the yield of 2-fluoro-2-phenoxy-2- (phenylthio) acetonitrile was 40%.
• Example 9 1,1,1,3,3,3-hexafluoro-2-propanol, acetonitrile, cesium fluoride, and 4-bromocumene are added to a non-diabolic cell to which a platinum plate is connected as an electrode, and constant current electrolysis is performed in an air atmosphere. As a result, 1-bromo-4- (1-fluoro-1-methylethyl) benzene was obtained.
• Example 10 1,1,1,3,3,3-hexafluoro-2-propanol (2 mL), acetonitrile (8 mL), cesium fluoride (304 mg), jiglime (70 mg) to a non-diaphragm cell to which a platinum plate was connected as an electrode.
• acetonitrile 8 mL
• cesium fluoride 304 mg
• jiglime 70 mg
• a non-diaphragm cell to which a platinum plate was connected as an electrode.
• constant current electrolysis was performed at 5 mA / cm 2 so that the total energization amount was 4 F / mol at room temperature in an air atmosphere.
• a peak of fluorinated diglyme was detected by mass spectrometry.

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