Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
  • C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
  • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
  • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
  • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
  • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
  • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
  • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Definitions

• This disclosure relates to a method for producing a fluorinated organic compound.
• Fluorinated organic compounds are extremely important compounds as various chemical products such as functional materials, medical and agricultural chemical compounds, electronic materials, and their intermediates.
• Non-Patent Document 1 describes a method of reacting an alkene with hypohalite and BF 3 in a non-polar solvent of CH 2 Cl 2 or CCl 4 .
• Non-Patent Document 2 describes a method for reacting an alkene with hydrogen fluoride pyridine and N-halosuccinimide.
• Non-Patent Document 1 and N-halosuccinimide of Non-Patent Document 2 are expensive, and there is room for improvement in terms of manufacturing cost.
• the object of the present disclosure is to provide a novel method for producing a fluorinated organic compound.
• Equation (1) (During the ceremony, R 1 and R 2 may independently be hydrogen atoms, halogen atoms, or organic groups, or together with two adjacent carbon atoms to form a ring.
• n is 1 or 2 symbol: Is a double bond or a triple bond. however, When the symbol is a triple bond, n is 1. When the symbol is a double bond, n is 2.
• the two R1s may be the same or different from each other.
• the two R 2s may be the same or different from each other, or the two R 1s or the two R 2s together with adjacent carbon atoms form a ring. You may. )
• the compound represented by the formula (1) can be used as a compound.
• At least one fluorine source selected from the group consisting of hydrogen fluoride, hydrogen fluoride salt, and fluoride salt, and formula (B): R 3 (OX) m (in the formula, R 3 is a hydrogen atom. , A cation or an organic group, X is a halogen atom other than a fluorine atom, and m is an integer corresponding to the valence of R3) , and is reacted with a halogen source other than fluorine to form the double.
• a production method comprising a step of adding fluorine and a halogen other than fluorine to a bond or a triple bond. Item 2. Item 2.
• Item 3. Item 2. The production method according to Item 1 or 2, wherein the amount of the fluorine source (A) used is in the range of 0.1 to 1000 mol with respect to 1 mol of the compound represented by the formula (1).
• R 3 has an alkali metal, an alkaline earth metal, an alkyl group which may have one or more substituents, and one or more substituents.
• Item 6 May be a cycloalkyl group, an aryl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, or one or more substituents.
• Item 6. The production method according to any one of Items 1 to 3, which is a heteroaryl group which may be possessed. Item 5.
• Item 6. The production method according to any one of Items 1 to 4, wherein X is a chlorine atom in the halogen source (B) other than fluorine. Item 6. Item 6.
• the substituent is at least one selected from the group consisting of a halo group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an arylcarbonyloxy group, an aryloxycarbonyl group, and an aryl group.
• the compound represented by the formula (1) is the following formulas (1a) to (1c): (During the ceremony, R 1a may have an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or one or more substituents.
• R 1b and R 2b are independently an alkyl group which may have one or more substituents, or an aryl group which may have one or more substituents, or 1
• An aralkyl group that may have more than one substituent R 1c has a hydrogen atom, an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or one or more substituents.
• R 2c is an alkyl group which may have one or more substituents) Item 6.
• the production method according to any one of Items 1 to 9, which is any of the compounds represented by. Item 11. Item 6.
• Halogenating agents including the following (A) and (B): (A) At least one fluorine source selected from the group consisting of hydrogen fluoride, hydrogen fluoride salt, and fluoride salt, and formula (B): R 3 (OX) m (in the formula, R 3 is a cation or It is an organic group, X is a halogen atom other than a fluorine atom, and m is an integer corresponding to the valence of R3) , which is a halogen source other than fluorine.
• the exemplary group can function as a non-exclusive and representative group.
• room temperature can mean a temperature in the range of 10 to 40 ° C.
• C n- C m (where n and m are integers of 1 or more, respectively), as those skilled in the art usually understand, has n or more carbon atoms and m. Indicates that it is as follows.
• halogen atom can include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the term "organic group” means a group containing one or more carbon atoms.
• An example of the "organic group” is Alkyl groups, which may have one or more substituents, An alkenyl group which may have one or more substituents, An alkynyl group, which may have one or more substituents, A cycloalkyl group which may have one or more substituents, Cycloalkenyl groups, which may have one or more substituents, A cycloalkazienyl group which may have one or more substituents, Aryl groups, which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, Heteroaryl groups, which may have one or more substituents, Cyano group, Aldehyde group, Carboxyl group, R r O-, R r CO-, R r COO-, R r SO 2- , R
• examples of the "hydrocarbon group" in the present specification include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkazienyl group, an aryl group, an aralkyl group, and the like. Groups that are a combination of these can be included.
• alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl.
• Nonyl, and decyl can include linear or branched C1-16 alkyl groups (eg, C1-C14 alkyl groups, C1-C12 alkyl groups).
• alkenyl groups include vinyl, 1-propen-1-yl, 2-propen-1-yl, isopropenyl, 2-butene-1-yl, 4-. It can include linear or branched C2-C10 alkenyl groups such as pentene-1-yl and 5-hexene-1-yl.
• alkynyl groups include ethynyl, 1-propyne-1-yl, 2-propin-1-yl, 4-pentyne-1-yl, 5-hexin-. It can include linear or branched C2-C10 alkynyl groups such as 1-yl.
• cycloalkyl group can include C3-C7 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
• cycloalkenyl group can include C3-C7 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl.
• examples of the "cycloalkazienyl group” include cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, and cyclononadienyl.
• Cyclodecadienyl and the like can include C4-C10 cycloalkazienyl groups.
• aryl group can be monocyclic, bicyclic, tricyclic, or tetracyclic.
• aryl group can be a C6-C18 aryl group.
• aryl groups can include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthrill.
• aralkyl groups include benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-. Phenylbutyl, 5-phenylpentyl, 2-biphenylylmethyl, 3-biphenylylmethyl, and 4-biphenylylmethyl can be included.
• non-aromatic heterocyclic group can be monocyclic, bicyclic, tricyclic, or tetracyclic.
• non-aromatic heterocyclic group is, for example, 1 to 4 selected from oxygen atom, sulfur atom, and nitrogen atom in addition to a carbon atom as a ring-constituting atom. It can be a non-aromatic heterocyclic group containing a hetero atom.
• non-aromatic heterocyclic group can be saturated or unsaturated.
• non-aromatic heterocyclic groups include tetrahydrofuryl, oxazolidinyl, imidazolinyl (eg, 1-imidazolinyl, 2-imidazolinyl, 4-imidazolinyl), aziridinyl (eg: 1).
• azetidinyl eg 1-azetidinyl, 2-azetidinyl
• pyrrolidinyl eg 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl
• piperidinyl eg 1-piperidinyl, 2-piperidinyl, 3-piperidinyl
• azepanyl eg 1-azepanyl, 2-azepanyl, 3-azepanyl, 4-azepanyl
• azocanyl eg 1-azocanyl, 2-azocanyl, 3-azocanyl, 4-azocanyl
• piperazinyl eg) : 1,4-Piperazine-1-yl, 1,4-piperazine-2-yl
• diazepinyl eg 1,4-diazepine-1-yl, 1,4-diazepine-2-yl, 1,4- Dia
• heteroaryl groups include monocyclic aromatic heterocyclic groups (eg, 5- or 6-membered monocyclic aromatic heterocyclic groups), and aromatic condensations. Heterocyclic groups (eg, 5-18 member aromatic fused heterocyclic groups) can be included.
• examples of "5- or 6-membered monocyclic aromatic heterocyclic groups” include pyrrolyl (eg, 1-pyrrolyl, 2-pyrrolill, 3-pyrrolill), frills (eg, 1-pyrrolyl, 2-pyrrolill).
• 2-frill, 3-frill 2-frill, 3-frill
• thienyl eg 2-thienyl, 3-thienyl
• pyrazolyl eg 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl
• imidazolyl eg 1-imidazolyl, 2- Imidazolyl, 4-imidazolyl
• isooxazolyl eg, 3-isoxazolyl, 4-isooxazolyl, 5-isooxazolyl
• oxazolyl eg, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl
• isothiazolyl eg, 3-isothiazolyl, 4).
• examples of "5- to 18-membered aromatic fused heterocyclic groups” include isoindyl (eg, 1-isoindrill, 2-isoindrill, 3-isoindrill, 4-isoindrill, 5-isoindrill).
• furanyl eg 1-benzo [c] furanyl, 4-benzo [c] furanyl, 5-benzo [c] fur
• R rO- examples include alkoxy (eg, C1-C10 alkoxy such as methoxy, ethoxy, propoxy, butoxy) and cycloalkoxy (eg, C3-C7 such as cyclopentoxy and cyclohexoxy). Cycloalkoxy), aryloxy (eg, C6-C18 aryloxy such as phenoxy, naphthoxy), and aralkyloxy (eg, C7-C19 aralkyloxy such as benzyloxy, phenethyloxy) can be included.
• alkoxy eg, C1-C10 alkoxy such as methoxy, ethoxy, propoxy, butoxy
• cycloalkoxy eg, C3-C7 such as cyclopentoxy and cyclohexoxy
• Cycloalkoxy aryloxy (eg, C6-C18 aryloxy such as phenoxy, naphthoxy), and aralkyloxy (e
• R r CO- examples include alkylcarbonyls [eg, (C1-C10 alkyl) carbonyls such as acetyl, propionyl, butyryl], cycloalkylcarbonyls [eg, cyclopentanoyl, cyclohexanoyl, etc.].
• alkylcarbonyls eg, (C1-C10 alkyl) carbonyls such as acetyl, propionyl, butyryl
• cycloalkylcarbonyls eg, cyclopentanoyl, cyclohexanoyl, etc.
• arylcarbonyl eg, (C6-C18aryl) carbonyl such as benzoyl, naphthoyl
• aralkylcarbonyl eg, (C7-C19 aralkyl) carbonyl such as benzylcarbonyl, phenethylcarbonyl, etc.
• R r COO- examples include alkylcarbonyloxy [eg, (C1-C10 alkyl) carbonyloxy such as acetyloxy, propionyloxy, butyryloxy], cycloalkylcarbonyloxy [eg, cyclopentanoyl]. , (C3-C7 cycloalkyl) carbonyloxy such as cyclohexanoyloxy], arylcarbonyloxy [eg, (C6-C18aryl) carbonyloxy such as benzoyloxy, naphthoyloxy], and aralkylcarbonyloxy [eg benzyl]. (C7-C19 aralkyl) carbonyloxy] such as carbonyloxy and phenethylcarbonyloxy can be included.
• alkylcarbonyloxy eg, (C1-C10 alkyl) carbonyloxy such as acetyloxy, propionyloxy, butyryloxy
• examples of "R r SO 2-" include alkyl sulfonyls (eg, C1-C10 alkyl sulfonyls such as methyl sulfonyl, ethyl sulfonyl, propyl sulfonyl), cycloalkyl sulfonyls (eg cyclopentyl sulfonyl, cyclohexyl sulfonyl, etc.).
• alkyl sulfonyls eg, C1-C10 alkyl sulfonyls such as methyl sulfonyl, ethyl sulfonyl, propyl sulfonyl
• cycloalkyl sulfonyls eg cyclopentyl sulfonyl, cyclohexyl sulfonyl, etc.
• C4-C8 cycloalkylsulfonyl C4-C8 cycloalkylsulfonyl
• arylsulfonyl eg, C6-C18arylsulfonyl such as phenylsulfonyl, naphthylsulfonyl
• aralkylsulfonyl eg, C7-C19 aralkylsulfonyl such as benzylsulfonyl, phenethylsulfonyl.
• R r OCO- examples include alkoxycarbonyl [eg, (C1-C10 alkoxy) carbonyls such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl], cycloalkoxycarbonyl [eg, cyclopentoxycarbonyl, etc.].
• alkoxycarbonyl eg, (C1-C10 alkoxy) carbonyls such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl
• cycloalkoxycarbonyl eg, cyclopentoxycarbonyl, etc.
• (C3-C7 cycloalkoxy) carbonyls such as cyclohexoxycarbonyl]
• aryloxycarbonyls eg, (C6-C18aryloxy) carbonyls such as phenoxycarbonyl, naphthoxycarbonyl
• aralkyloxycarbonyls eg, benzyloxycarbonyl, (C7-C19 aralkyloxy) carbonyls such as phenethyloxycarbonyl
• examples of “R r OSO 2-" include alkoxysulfonyl (eg, C1-C10 alkoxysulfonyl such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl), cycloalkoxysulfonyl (eg cyclopentoxysulfonyl, cyclohexyl).
• alkoxysulfonyl eg, C1-C10 alkoxysulfonyl such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl
• cycloalkoxysulfonyl eg cyclopentoxysulfonyl, cyclohexyl.
• C3-C7 cycloalkoxysulfonyls such as soxysulfonyls
• aryloxysulphonyls eg, C6-C18aryloxysulphonyls such as phenoxysulphonyls and naphthoxysulphonyls
• aralkyloxysulphonyls egs benzyloxysulphonyls, phenethyloxysulphonyls and the like.
• C7-C19 aralkyloxysulfonyl can be included.
• Haldrocarbon groups which may have one or more substituents "Alkyl group which may have one or more substituents", “An alkenyl group which may have one or more substituents”, “Alkynyl group which may have one or more substituents”, “Cycloalkyl group which may have one or more substituents”, “Cycloalkenyl group which may have one or more substituents”, “Cycloalkazienyl group which may have one or more substituents", “Aryl groups may have one or more substituents", “Aralkyl group which may have one or more substituents", “A non-aromatic heterocyclic group which may have one or more substituents” and "a heteroaryl group which may have one or more substituents”.
• substituteduents in the above are halo group, nitro group, cyano group, oxo group, thioxo group, carboxyl group, sulfo group, sulfamoyl group, sulfinamoyl group, sulfenamoyl group, R r O-, R r CO-, respectively. , R r COO-, R r SO 2- , R r OCO-, and R r OSO 2- (in these equations, R r has the same meaning as described above).
• halo group can include a fluoro group, a chloro group, a bromo group, and an iodine group.
• the number of the substituents can be within the range of 1 to the maximum number of replaceable groups (eg: 1, 2, 3, 4, 5, 5, 6).
• Method for producing halogen adduct of compound (1) In the production method of the present disclosure, the compound (1) is reacted with a fluorine source (A) and a halogen source (B) other than fluorine to form a double bond or a triple bond of the compound (1) with fluorine and a halogen other than fluorine. Includes the step of adding.
• Reaction substrate Compound (1)
• R 1 and R 2 independently have a hydrogen atom, a halogen atom, an alkyl group which may have one or more substituents, and an alkoxy which may have one or more substituents.
• a group may have one or more substituents
• an alkylcarbonyl group may have one or more substituents
• an alkylcarbonyloxy group may have one or more substituents
• one or more substituents may be present.
• R 1 and R 2 may be independently substituted with a hydrogen atom, a halogen atom, an alkyl group which may be substituted with one or more halo groups, and one or more halo groups.
• An alkoxy group may be substituted with one or more halo groups
• an alkoxyalkyl group may be substituted with one or more halo groups
• an alkylcarbonyl group may be substituted with one or more halo groups
• the group may be substituted with one or more halo groups.
• alkylcarbonyloxy group an alkoxycarbonyl group optionally substituted with one or more halo groups, a cycloalkyl group optionally having one or more substituents, and one or more substituents. It is also a good aryl group, or an aralkyl group which may have one or more substituents.
• the substituent can be any group having a structure substitutable for the subject, for example, a halo group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an arylcarbonyloxy. It can be at least one selected from the group consisting of a group, an aryloxycarbonyl group, and an aryl group.
• the number of the substituents can be selected from 1 to the maximum number of substituents (eg: 1, 2, 3).
• R 1 and R 2 can be combined with two adjacent carbon atoms to form a ring.
• the ring is usually formed when the symbol is a double bond and n is 2.
• Examples of the ring correspond to the cycloalkene ring corresponding to the group exemplified in "cycloalkenyl group” and the group having a carbon-carbon double bond among the groups exemplified in "non-aromatic heterocyclic group”. Includes non-aromatic heterocycles.
• the ring may have one or more substituents.
• substituents are hydrocarbon group, halo group, nitro group, cyano group, oxo group, tioxo group, carboxyl group, sulfo group, sulfamoyl group, sulfinamoyl group, sulfenamoyl group, R r O-, R r CO-. , R r COO-, R r SO 2- , R r OCO-, and R r OSO 2- (in these equations, R r has the same meaning as described above).
• the number of the substituents can be selected from 1 to the maximum number of replaceable groups (eg: 1, 2, 3, 4, 5, 5).
• a good example of compound (1) is formula (1A) :.
• R 11 , R 12 , R 21 and R 22 are independently hydrogen atoms, halogen atoms, or organic groups, or R 11 and R 12 or R 21 and R 22 are one adjacent. Together with a carbon atom, they may form a ring, or R 11 and R 21 , R 11 and R 22 , R 12 and R 21 , or R 12 and R 22 are two adjacent carbons. Together with the atom, it may form a ring, symbol: Indicates a cis or transformer arrangement.
• R 13 and R 23 are independently hydrogen atoms, halogen atoms, or organic groups.
• R 11 , R 12 and R 21 independently have a hydrogen atom, a halogen atom, an alkyl group which may have one or more substituents, and one or more substituents.
• R 11 , R 12 , and R 21 are independently substituted with a hydrogen atom, a halogen atom, an alkyl group optionally substituted with one or more halo groups, and one or more halo groups.
• An alkylcarbonyloxy group that may be present, an alkoxycarbonyl group that may be substituted with one or more halo groups, a cycloalkyl group that may have one or more substituents, and one or more substituents. It is an aryl group which may have an aryl group or an aralkyl group which may have one or more substituents, and R 22 is a hydrogen atom.
• R 11 and R 21 independently have a hydrogen atom, a halogen atom, an alkyl group which may have one or more substituents, and an alkoxy which may have one or more substituents.
• a group may have one or more substituents
• an alkylcarbonyl group may have one or more substituents
• an alkylcarbonyloxy group may have one or more substituents
• one or more substituents may be present.
• R 12 and R 22 are hydrogen atoms. More preferably, R 11 and R 21 may be independently substituted with a hydrogen atom, a halogen atom, an alkyl group which may be substituted with one or more halo groups, and one or more halo groups.
• An alkoxy group may be substituted with one or more halo groups
• an alkoxyalkyl group may be substituted with one or more halo groups
• an alkylcarbonyl group may be substituted with one or more halo groups
• the group may be substituted with one or more halo groups.
• alkylcarbonyloxy group an alkoxycarbonyl group optionally substituted with one or more halo groups, a cycloalkyl group optionally having one or more substituents, and one or more substituents. It is also a good aryl group, or an aralkyl group which may have one or more substituents, and R 12 and R 22 are hydrogen atoms.
• R 11 is a hydrogen atom, a halogen atom, an alkyl group which may have one or more substituents, an alkoxy group which may have one or more substituents, and one or more substituents.
• An alkylcarbonyl group which may have a group, an alkylcarbonyloxy group which may have one or more substituents, an alkoxycarbonyl group which may have one or more substituents, and one or more.
• a cycloalkyl group which may have a substituent of 1 or more, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents, R.
• Reference numeral 21 has a hydrogen atom, an alkyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, and one or more substituents.
• R 21 has a hydrogen atom, an alkyl group which may have one or more substituents, and one or more substituents.
• a cycloalkyl group may be an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents, and R 12 and R 22 are , A hydrogen atom.
• the substituent can be any group having a substitutable structure, such as a halo group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl. It can be at least one selected from the group consisting of a group, an arylcarbonyloxy group, an aryloxycarbonyl group, and an aryl group.
• the number of the substituents can be selected from 1 to the maximum number of substituents (eg: 1, 2, 3).
• R 11 and R 12 or R 21 and R 22 can be combined with one adjacent carbon atom to form a ring.
• the ring include a cycloalkane ring (eg, a C5-C7 cycloalkane ring such as a cyclohexane ring) corresponding to the group exemplified in "cycloalkyl group”, and a group exemplified in "non-aromatic heterocyclic group”. Includes non-aromatic heterocycles corresponding to.
• the ring may have one or more substituents.
• substituents are hydrocarbon group, halo group, nitro group, cyano group, oxo group, tioxo group, carboxyl group, sulfo group, sulfamoyl group, sulfinamoyl group, sulfenamoyl group, R r O-, R r CO-. , R r COO-, R r SO 2- , R r OCO-, and R r OSO 2- (in these equations, R r has the same meaning as described above).
• the number of the substituents can be in the range of 1 to the maximum number of replaceable groups (eg: 1, 2, 3, 4, 5, 5).
• the ring are the cycloalkene ring (eg, C5-C7 cycloalkene ring such as cyclohexene ring) corresponding to the group exemplified in "cycloalkene group", and the group exemplified in "non-aromatic heterocyclic group”.
• a non-aromatic heterocycle corresponding to a group having a carbon-carbon double bond is included.
• the ring may have one or more substituents.
• substituents are hydrocarbon group, halo group, nitro group, cyano group, oxo group, tioxo group, carboxyl group, sulfo group, sulfamoyl group, sulfinamoyl group, sulfenamoyl group, R r O-, R r CO-. , R r COO-, R r SO 2- , R r OCO-, and R r OSO 2- (in these equations, R r has the same meaning as described above).
• the number of the substituents can be in the range of 1 to the maximum number of replaceable groups (eg: 1, 2, 3, 4, 5, 5).
• Suitable examples of compound (1A) include formulas (1a)-(1c) :.
• R 1a may have an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or one or more substituents. It is an aralkyl group, and R 1b and R 2b are independently an alkyl group which may have one or more substituents, or an aryl group which may have one or more substituents, or 1
• An aralkyl group that may have more than one substituent, R 1c has a hydrogen atom, an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or one or more substituents.
• R 2c is an alkyl group which may have one or more substituents) Includes compounds represented by.
• the substituent can be any group having a structure substitutable for the subject, for example, a halo group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an arylcarbonyloxy. It can be at least one selected from the group consisting of a group, an aryloxycarbonyl group, and an aryl group.
• the number of the substituents can be selected from 1 to the maximum number of substituents (eg: 1, 2, 3).
• R 1a is an alkyl group which may have one or more substituents or an aralkyl group which may have one or more substituents.
• R 1b and R 2b are aryl groups that may independently have one or more substituents.
• R 1c is a hydrogen atom, an alkyl group which may have one or more substituents, or an aryl group which may have one or more substituents, and R 2c is.
• R 13 and R 23 independently have a hydrogen atom, a halogen atom, an alkyl group which may have one or more substituents, and an alkoxy which may have one or more substituents.
• a group may have one or more substituents
• an alkylcarbonyl group may have one or more substituents
• an alkylcarbonyloxy group may have one or more substituents
• one or more substituents may be present.
• R 13 and R 23 may be independently substituted with a hydrogen atom, a halogen atom, an alkyl group which may be substituted with one or more halo groups, and one or more halo groups.
• An alkoxy group may be substituted with one or more halo groups
• an alkoxyalkyl group may be substituted with one or more halo groups
• an alkylcarbonyl group may be substituted with one or more halo groups
• the group may be substituted with one or more halo groups.
• alkylcarbonyloxy group an alkoxycarbonyl group optionally substituted with one or more halo groups, a cycloalkyl group optionally having one or more substituents, and one or more substituents. It is also a good aryl group, or an aralkyl group which may have one or more substituents.
• the substituent can be any group having a substitutable structure, such as a halo group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl. It can be at least one selected from the group consisting of a group, an arylcarbonyloxy group, an aryloxycarbonyl group, and an aryl group.
• the number of the substituents can be selected from 1 to the maximum number of substituents (eg: 1, 2, 3).
• the aqueous solution can be, for example, an aqueous solution having a hydrogen fluoride concentration of 10 to 70% by mass.
• hydrogen fluoride salts include hydrogen fluoride amine salts and hydrogen fluoride ammonium salts.
• the amine in the hydrogen fluoride amine salt, can be a chain amine or a cyclic amine.
• chain amines examples include aliphatic primary amines, aliphatic secondary amines, and aliphatic tertiary amines.
• aliphatic primary amines include C1-C6 alkylamines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and the like.
• aliphatic secondary amines include diC1-C6 alkylamines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine and the like.
• aliphatic tertiary amines include tri-C1-C6 alkylamines such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N, N, N', N'-tetramethylethylenediamine.
• cyclic amines include aliphatic cyclic amines and aromatic cyclic amines.
• aliphatic cyclic amines are piperidine, piperazine, pyrrolidine, morpholine, N-methylpiperazine, N-methylpyrrolidin, 5-diazabicyclo [4.3.0] nonane-5-ene, and 1,4-diazabicyclo [2.2.2]. ] Includes octane.
• aromatic cyclic amines include pyridine, pyrimidine, pyrazine, quinoline, and imidazole.
• ammonium fluoride salt is formula (A1) :. NQ4 ⁇ xHF (A1) (In the formula, each Q is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and x is an integer of 1 or more). Includes compounds represented by.
• Q is preferably an alkyl group, more preferably a C1-C6 alkyl group.
• x is preferably 1 to 10.
• Suitable examples of the compound (A1) are ammonium hydrogen fluoride ( NH 4F ⁇ HF), hydrogen fluoride-tetramethylammonium fluoride, hydrogen fluoride-tetraethylammonium fluoride, hydrogen fluoride-tetrapropylammonium fluoride. , And hydrogen fluoride-tetrabutylammonium fluoride.
• an example of a fluoride salt is the formula (A2) :.
• M 1 F m1 (A2) (During the ceremony, M 1 is an alkali metal or an alkaline earth metal; and m 1 is 1 or 2 depending on the valence of M 1 ). Includes compounds represented by.
• M 1 is Li, Na, K, Ca, or Cs. More preferably, M 1 is Na, K, or Ca. More preferably, M 1 is K.
• the fluoride salt can preferably be an alkali metal fluoride salt [compound (A2) in which M1 is an alkali metal and m1 is 1 ].
• the fluorine source (A) can be used alone or in combination of two or more.
• the amount of the fluorine source (A) used is not particularly limited.
• the lower limit of the amount of the fluorine source (A) used is, for example, 0.1 mol or more, preferably 0.2 mol or more, more preferably 0.3 mol or more, still more preferably 0, with respect to 1 mol of the compound (1). It can be .4 mol or more, particularly preferably 0.5 mol or more.
• the upper limit of the amount of the fluorine source (A) used is, for example, 1000 mol or less, preferably 500 mol or less, more preferably 300 mol or less, still more preferably 100 mol or less, still more preferably 100 mol or less, based on 1 mol of the compound (1).
• the amount of the fluorine source (A) used is, for example, in the range of 0.1 to 1000 mol, preferably in the range of 0.2 to 500 mol, more preferably in the range of 0.3 to 100 mol, and further preferably in the range of 0.3 to 100 mol. It can be in the range of 0.4 to 50 mol, particularly preferably in the range of 0.5 to 10 mol.
• the residual fluorine source (A) after the reaction may be trapped and discarded, but it is preferable to recover and reuse it from the viewpoint of manufacturing cost.
• the residual trap after the reaction may be washed with, for example, water or alkaline water.
• R 3 is an alkali metal, an alkaline earth metal, an alkyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, and one.
• alkali metal examples include Li, Na, K, and Cs.
• alkaline earth metals examples include Mg and Ca.
• the substituent can be any group having a structure substitutable for the target, and can be, for example, a halo group.
• the number of the substituents can be selected from 1 to the maximum number of substituents (eg: 1, 2, 3).
• R 3 is more preferably an alkali metal or an alkyl group which may have one or more substituents. More preferably, R 3 is an alkali metal or an alkyl group. Even more preferably , R3 is an alkali metal or a C1-C6 alkyl group. Particularly preferably , R3 is an alkali metal or a C1-C4 alkyl group.
• X is a chlorine atom, a bromine atom, or an iodine atom. More preferably, X is a chlorine atom or a bromine atom. More preferably, X is a chlorine atom.
• the halogen source (B) can be, for example, a hydrate.
• R 3a ClO (B1) (In the formula, R 3a is an alkali metal or a C1-C4 alkyl group) Includes compounds represented by.
• the halogen source (B) can be used alone or in combination of two or more.
• the amount of the halogen source (B) used is not particularly limited.
• the lower limit of the amount of the halogen source (B) used can be, for example, 0.1 mol or more, preferably 0.2 mol or more, and more preferably 0.3 mol or more with respect to 1 mol of the compound (1). ..
• the lower limit of the amount of the halogen source (B) used can be, for example, 10 mol or less, preferably 9 mol or less, more preferably 8 mol or less, relative to 1 mol of the compound (1).
• the amount of the halogen source (B) used is, for example, in the range of 0.1 to 10 mol, preferably in the range of 0.2 to 9 mol, and more preferably in the range of 0.3 with respect to 1 mol of the compound (1). It can be in the range of ⁇ 8 mol.
• the residual halogen source (B) after the reaction may be trapped and discarded, but it is preferable to recover and reuse it from the viewpoint of manufacturing cost.
• the residual trap after the reaction may be washed with, for example, water or alkaline water.
• the reaction of the above steps can be carried out in the presence or absence of BF 3 and / or N-halosuccinimide, but in the absence of BF 3 and N-halosuccinimide. It is preferable to do so.
• Each component may be charged into the reaction system of the above step at once, may be charged in several batches, or may be continuously charged.
• the reaction of the above steps can be carried out in the presence or absence of a solvent.
• the solvent may be either a non-polar solvent or a polar solvent.
• the solvent may be an ester, a ketone, an aromatic hydrocarbon, an alcohol, an ether, an amine, a nitrogen-containing polar organic compound, a nitrile, a halogenated hydrocarbon, an aliphatic hydrocarbon, a fluorine-based solvent, a carbonate, or another solvent, or these.
• ester as the solvent examples include ethyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and suitable examples thereof include ethyl acetate.
• Examples of the ketone as the solvent include acetone, methyl ethyl ketone, diethyl ketone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, acetonyl acetone, methyl hexanone, and acetophenone, cyclohexanone, diacetone alcohol, and suitable thereof.
• Examples include acetone.
• aromatic hydrocarbons as the solvent include benzene, toluene, xylene, and ethylbenzene, and suitable examples thereof include benzene, and toluene.
• alcohol examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, pentanol, hexanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol and dipropylene glycol.
• Tripropylene glycol, polypropylene glycol, trimethylene glycol, and hexanetriol and suitable examples thereof include methanol, and ethanol.
• ether examples include diethyl ether, dibutyl ether, tetrahydrofuran, tetrahydropyran, dioxane, dimethoxyethane, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene.
• glycol monomethyl ether also known as 1-methoxy-2-propanol
• propylene glycol monoethyl ether triethylene glycol dimethyl ether
• triethylene glycol diethyl ether triethylene glycol diethyl ether
• tetraethylene glycol dimethyl ether triethylene glycol diethyl ether
• anisole tetrahydrofuran
• amines as the solvent examples include monoethanolamine, diethanolamine, and triethanolamine.
• nitrogen-containing polar organic compound as the solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidi.
• suitable examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone.
• nitrile as the solvent examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and adiponitrile, and suitable examples thereof include acetonitrile.
• halogenated hydrocarbons examples include dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene, and suitable examples thereof include dichloromethane, and chloroform. Include.
• aliphatic hydrocarbons examples include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirit, and suitable examples thereof include cyclohexane, heptane.
• fluorinated solvent examples include perfluorobenzene, trifluorotoluene, ditrifluorobenzene and trifluoroethanol, and suitable examples thereof include perfluorobenzene and trifluoroethanol.
• carbonate as the solvent examples include tetralin dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate, and suitable examples thereof include ethylene carbonate and propylene carbonate.
• Examples of the other solvents include acetic acid, pyridine, dimethyl sulfoxide, sulfolane, and water.
• the solvent can preferably be at least one selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters, nitriles, and water, more preferably aliphatic hydrocarbons. It can be at least one selected from halogenated hydrocarbons, ethers, and water, more preferably halogenated hydrocarbons.
• the solvent can be used alone or in combination of two or more.
• the amount of solvent used is, for example, Compound (1) For 1 part by mass Usually in the range of 0 to 200 parts by mass, It can be preferably in the range of 0 to 100 parts by mass, and more preferably in the range of 0 to 50 parts by mass.
• the temperature of the above process is Usually in the range of -78 to 200 ° C, Preferably, in the range of -10 to 100 ° C. It can be more preferably in the range of 0 to 100 ° C, and even more preferably in the range of 10 to 40 ° C.
• the time of the above process is Generally, it can be in the range of 0.1 to 72 hours, preferably in the range of 0.5 to 48 hours, and more preferably in the range of 1 to 36 hours.
• the production method of the present disclosure may further include a step of isolating or purifying compound (1).
• Isolation or purification of compound (1) can be carried out by methods such as filtration, extraction, dissolution, concentration, precipitation, dehydration, adsorption, or chromatography, or a combination thereof.
• the halogenating agents of the present disclosure include a fluorine source (A) and a halogen source other than fluorine (B).
• the fluorine source (A) and the halogen source (B) are as described in [Method for producing a halogen adduct of compound (1)].
• the molar ratio of the fluorine source (A) and the halogen source (B) is not particularly limited.
• the lower limit of the content of the fluorine source (A) can be, for example, 1 mol or more, preferably 1.5 mol or more, and more preferably 2 mol or more with respect to 1 mol of the halogen source (B).
• the upper limit of the content of the fluorine source (A) can be, for example, 1000 mol or less, preferably 500 mol or less, and more preferably 300 mol or less with respect to 1 mol of the halogen source (B).
• the content of the fluorine source (A) is, for example, in the range of 1 to 1000 mol, preferably in the range of 1.5 to 500 mol, and more preferably in the range of 2 to 300 mol with respect to 1 mol of the halogen source (B). Can be within range.
• the halogenating agents of the present disclosure may contain BF 3 and / or N-halosuccinimide, but preferably do not contain BF 3 and N-halosuccinimide.
• the halogenating agent of the present disclosure can be suitably used for adding fluorine and a halogen other than fluorine to the double bond or triple bond of the compound (1).
• the above examples show an example in which the compound (1) having a double bond is used as a substrate, but the present invention is not limited thereto.
• the compound (1) having a triple bond basically has a strong tendency to have a small steric hindrance and tends to have a higher reactivity than the compound (1) having a double bond. It can be said that the reaction proceeds in the same manner even if the compound (1) having a triple bond is used.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=82057830

Family Applications (1)

Country Status (5)

Cited By (1)

Families Citing this family (1)

Citations (3)

Family Cites Families (6)

• 2021
  • 2021-12-17 CN CN202180085050.2A patent/CN116583494A/zh active Pending
  • 2021-12-17 WO PCT/JP2021/046869 patent/WO2022131378A1/ja not_active Ceased
  • 2021-12-17 JP JP2022570085A patent/JP7704380B2/ja active Active
  • 2021-12-17 EP EP21906736.0A patent/EP4265589A4/en active Pending
• 2023
  • 2023-06-16 US US18/210,750 patent/US20230322649A1/en active Pending

Patent Citations (3)

Non-Patent Citations (7)

Also Published As

Similar Documents

Legal Events