Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
  • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/04—Saturated ethers
  • C07C43/12—Saturated ethers containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/14—Unsaturated ethers
  • C07C43/17—Unsaturated ethers containing halogen
  • C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

• the present disclosure relates to a method for producing fluoroether.
• Fluoroethers in which the ⁇ -carbon is fluorinated are useful as refrigerants, solvents, medicines, agricultural chemicals, functional materials, etc.
• Methods for producing ⁇ -fluoroether are broadly divided into methods for etherifying fluorine-containing compounds and methods for fluorinating hydrocarbon ethers.
• the former method has advantages over the latter method, such as milder reaction conditions, no need for special equipment, and easier control of the fluorine introduction position. Examples of the former method include a method of reacting a fluoroolefin with an alcohol.
• the method includes method 1 using KOH or the like (for example, Patent Document 1) as a method using a strong base, method 2 using a Pd catalyst (for example, Patent Document 2) as a method not using a strong base, and method 2 using a Pd catalyst (for example, Patent Document 2) as a method using a strong base.
• a method using a liquid for example, Patent Document 3) is known.
• Method 1 has room for improvement in terms of safety and environmental impact.
• Method 2 requires the use of the rare metal Pd, which is expensive and difficult to sustain.
• Method 3 requires the use of expensive ionic liquids that are difficult to handle on an industrial scale.
• the main objective of the present disclosure is to provide a method for producing ⁇ -fluoroether using a predetermined phosphine and/or amine.
• R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group substituted with one or more fluorine atoms, or an alkoxy group substituted with one or more fluorine atoms
• R 3 is a fluorine atom, an alkyl group substituted with one or more fluorine atoms, or an alkoxy group substituted with one or more fluorine atoms
• R 2 and R 3 may be bonded to each other to form a ring
• R 4 is an alkyl group which may have one or more substituents or an aryl group which may have one or more substituents.
• R 5 , R 6 , and R 7 each independently represent an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, and one an alkoxy group which may have the above substituents, or an aryloxy group which may have one or more substituents, Any two of R 5 , R 6 and R 7 may be bonded to each other to form a ring, R 8 , R 9 , and R 10 are each independently an alkyl group that may have one or more substituents, or an aryl group that may have one or more substituents; , Item 2.
• Step A According to any one of Items 1 to 7, Step A is carried out in the presence of at least one solvent selected from the group consisting of ether solvents, sulfoxide solvents, nitrile solvents, and amide solvents. manufacturing method.
• R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group substituted with one or more fluorine atoms, or an alkoxy group substituted with one or more fluorine atoms
• R 3 is a fluorine atom, an alkyl group substituted with one or more fluorine atoms, or an alkoxy group substituted with one or more fluorine atoms
• R 2 and R 3 may be bonded to each other to form a ring
• R 4 is an alkyl group which may have one or more substituents or an aryl group which may have one or more substituents.
• a method for producing ⁇ -fluoroether is provided, for example, using a predetermined phosphine and/or amine.
• room temperature can mean a temperature within the range of 10-40°C.
• C nm (where n and m are each positive integers, and n ⁇ m) represents that the number of carbon atoms is n or more and m or less .
• halogen atom examples include fluorine atom, chlorine atom, bromine atom, and iodine atom.
• organic group means a group containing one or more carbon atoms.
• examples of the “organic group” are: A hydrocarbon group that may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a heteroaryl group optionally having one or more substituents, cyano group, aldehyde group, carboxyl group, R r O-, R r CO-, R r COO-, R r SO 2 ⁇ , R r OCO-, and R r OSO 2 - (In these formulas, R r is independently, A hydrocarbon group that may have one or more substituents, It is a non-aromatic heterocyclic group which may have one or more substituents, or a heteroaryl group which may have one or more substituents. ) can be included.
• hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
• hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and combinations of two or more of these (e.g. aralkyl groups).
• alkyl group examples include linear or branched C 1-12 alkyl groups, and specific examples thereof include methyl group, ethyl group, propyl group (e.g. n- propyl group, isopropyl group), butyl group (e.g. n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. include.
• alkenyl group examples include linear or branched C 2-20 alkenyl groups, and specific examples thereof include vinyl group, 1-propen-1-yl group, 2 -propen-1-yl group, isopropenyl group, 2-buten-1-yl group, 4-penten-1-yl group, and 5-hexen-1-yl group.
• alkynyl group examples include linear or branched C 2-20 alkynyl groups, and specific examples thereof include ethynyl group, 1-propyn-1-yl group, 2-propyn-1-yl group, -propyn-1-yl, 4-pentyn-1-yl, and 5-hexyn-1-yl.
• cycloalkyl group examples include C3-10 cycloalkyl group, and specific examples thereof include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group. do.
• examples of "cycloalkenyl group” include C3-10 cycloalkenyl group, and specific examples thereof include cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, and cycloheptenyl group. include.
• examples of "cycloalkadienyl group” include C 4-10 cycloalkadienyl group, and specific examples thereof include cyclobutadienyl group, cyclopentadienyl group, cyclohexadienyl group. and cycloheptadienyl groups.
• aryl group can be monocyclic or polycyclic (eg, bicyclic, tricyclic, tetracyclic).
• aryl group include C 6-14 aryl group, and specific examples thereof include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group. and 2-anthryl groups.
• heteroaryl group refers to a monocyclic aromatic heterocyclic group (e.g., a 5- or 6-membered monocyclic aromatic heterocyclic group), and an aromatic fused heterocyclic group (e.g., a 5- or 6-membered monocyclic aromatic heterocyclic group). 18-membered aromatic fused heterocyclic group).
• examples of "5- or 6-membered monocyclic aromatic heterocyclic group” include pyrrolyl (e.g. 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (e.g. 2-furyl, 3-pyrrolyl), -furyl), thienyl (e.g. 2-thienyl, 3-thienyl), pyrazolyl (e.g. 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (e.g. 1-imidazolyl, 2-imidazolyl, 4-imidazolyl) , isoxazolyl (e.g.
• 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxadiazolyl Example: 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl), Thiadiazolyl (Example: 1,2,4-thiadiazol-3-yl, 1,2 , 4-thiadiazol-5-yl), tetrazolyl, pyridyl (e.g. 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridazinyl (e.g. 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (e.g. 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), pyrazinyl, and the like.
• pyridyl e.g. 2-pyridyl, 3-pyridyl, 4-pyridyl
• pyridazinyl e.
• examples of "5- to 18-membered aromatic fused heterocyclic group” include isoindolyl (e.g., 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl), indolyl (e.g. 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), benzo[b]furanyl (e.g.
• 1-benzo[c] thienyl, 4-benzo[c]thienyl, 5-benzo[c]thienyl), indazolyl e.g. 1-indazolyl, 2-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl
• benzimidazolyl e.g. 1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl
• 1,2-benzisoxazolyl e.g.
• 1,2-benzisoxazol-3-yl, 1,2 -benzisoxazol-4-yl, 1,2-benzisoxazol-5-yl, 1,2-benzisoxazol-6-yl, 1,2-benzisoxazol-7-yl), benzoxazolyl Example: 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl
• 1,2-benzisothiazolyl example: 1,2-benzisothiazol-3-yl, 1,2-benzisothiazol-4-yl, 1,2-benzisothiazol-5-yl, 1,2-benzisothiazol-6-yl, 1, 2-benzoisothiazol-7-yl
• benzothiazolyl e.g.
• pyrazolo[1,5-a]pyridin-2-yl pyrazolo[1,5-a]pyridin-3-yl
• pyrazolo[1,5-a]pyridin-4- pyrazolo[1,5-a]pyridin-5-yl
• pyrazolo[1,5-a]pyridin-6-yl pyrazolo[1,5-a]pyridin-7-yl
• imidazo[1,2 -a]pyridyl e.g.
• imidazo[1,2-a]pyridin-2-yl imidazo[1,2-a]pyridin-3-yl, imidazo[1,2-a]pyridin-5-yl, imidazo [1,2-a]pyridin-6-yl, imidazo[1,2-a]pyridin-7-yl, imidazo[1,2-a]pyridin-8-yl), and the like.
• -CH 2 - that may exist in the hydrocarbon group in "hydrocarbon group optionally having one or more substituents" is -O-, -S-, or -NH- may be replaced by Examples of substituents that can be substituted on the hydrocarbon group include a halogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, and a cyano group.
• substituents that can be substituted on the hydrocarbon group include a halogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, and a cyano group.
• the number of substituents can be selected from the range from 1 to the maximum number that can be substituted, for example, 1, 2, 3, 4, or 5. can be individual. When the number of substituents is two or more, each substituent may be the same or different from each other.
• substituents in "alkyl group which may have one or more substituents” include halogen atom, hydroxy group, R A O- (wherein R A is an alkyl group or ), (R B ) 2 N- (wherein each R B is independently a hydrogen atom, an alkyl group, or an aryl group), (R C ) 2 P- (R C ) 2 P- (wherein each R B is independently a hydrogen atom, an alkyl group, or an aryl group) (wherein, each R C is independently a hydrogen atom, an alkyl group, or an aryl group), and a combination of two or more thereof (eg, a haloalkoxy group).
• the number of substituents can be selected from 1 to the maximum number that can be substituted, for example, 1, 2, 3, 4, or 5. can be.
• the number of substituents is two or more, each substituent may be the same or different from each other.
• alkyl group which may have one or more substituents examples include alkyl groups which may be substituted with one or more fluorine atoms.
• An alkyl group substituted with one or more fluorine atoms may be referred to as a "fluoroalkyl group".
• the "fluoroalkyl group” may be a perfluoroalkyl group or a non-perfluoroalkyl group.
• Examples of “fluoroalkyl group” include linear or branched fluoroC 1-12 alkyl groups, and specific examples thereof include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group (e.g.
• perfluoro n-propyl group perfluoroisopropyl group
• perfluorobutyl group perfluoropentyl group
• perfluorohexyl group etc., including linear or branched fluoroC 1-12 alkyl groups.
• the alkyl group has one or more substituents other than fluorine atoms (e.g., fluoroalkoxy group), such as CF 3 -O-CF 2 -, CF 3 -O-CF(CF 3 )-, CF 3 -O-CH 2 -CH 2 -, CF 3 -O-CH(CF 3 )-CH 2 -, CF 3 -O-CF 2 -CF 2 -, CF 3 -CF 2 -O-CF 2 - , CF 3 -CF 2 -O-CF 2 -CF 2 -, CF 3 -O-CF 2 -O-CF 2 -, CF 3 -CF 2 -CF 2 -O-CF 2 -, CF 3 -CF 2 -CF 2 -O-CH 2 -CF 2 -, CF 3 -CF 2 -CF 2 -O-CF 2 -CF 2 -, CF 3 -CF 2 -CF 2 -O-CH 2
• substituents in "aryl group which may have one or more substituents” include halogen atom, hydroxy group, alkyl group, R A O- (where R A is ), (R B ) 2 N- (wherein each R B is independently a hydrogen atom, an alkyl group, or an aryl group), (R C ) 2 P - (wherein each R C is independently a hydrogen atom, an alkyl group, or an aryl group), and combinations of two or more of these (eg, haloalkyl groups).
• the number of substituents can be selected from 1 to the maximum number that can be substituted, for example, 1, 2, 3, 4, or 5. can be.
• each substituent may be the same or different from each other.
• alkoxy groups include linear or branched C 1-12 alkoxy groups, and specific examples thereof include methoxy groups, ethoxy groups, propoxy groups (e.g. n- propoxy group, isopropoxy group), butoxy group, pentyloxy group, and hexyloxy group.
• alkoxy group which may have one or more substituents
• substituents in "alkoxy group which may have one or more substituents” include halogen atoms, hydroxy groups, alkyl groups, alkoxy groups, and combinations of two or more of these (e.g. : haloalkyl group, haloalkoxy group).
• the number of substituents can be selected from 1 to the maximum number that can be substituted, for example, 1, 2, 3, 4, or 5. can be.
• each substituent may be the same or different from each other.
• alkoxy group which may have one or more substituents examples include alkoxy groups which may be substituted with one or more fluorine atoms.
• An alkoxy group substituted with one or more fluorine atoms may be referred to as a "fluoroalkoxy group.”
• the "fluoroalkoxy group” may be a perfluoroalkoxy group or a non-perfluoroalkoxy group.
• fluoroalkoxy groups include linear or branched fluoroC 1-12 alkoxy groups, and specific examples thereof include perfluoromethoxy groups, perfluoroethoxy groups, perfluoropropoxy groups (e.g.
• linear or branched fluoro C 1-12 alkoxy groups such as perfluoro n-propoxy group, perfluoroisopropoxy group), perfluorobutoxy group, perfluoropentyloxy group, and perfluorohexyloxy group.
• the alkoxy group has one or more substituents other than fluorine atoms (e.g., fluoroalkoxy group), such as CF 3 -O-CF 2 -O-, CF 3 -O-CF 2 -CF 2 -CF 2 -O-, CF 3 -O-CH 2 -CF 2 -CF 2 -O-, CF 3 -CF 2 -O-CF 2 -CF 2 -O-, CF 3 -CF 2 -CF 2 - O-CH 2 -CF 2 -CF 2 -O-, CF 3 -CF 2 -CF 2 -O-CF 2 -CF 2 -CF 2 -O-, CF 3 -CF 2 -CF 2 -O-CF ( CF 3 )-CF 2 -O-, CF 3 -CF 2 -CF 2 -O-[CF(CF 3 )-CF 2 -O-] 2 -, and CF 3 -CF 2 -CF 2 -
• aryloxy groups include C 6-12 aryloxy groups, and specific examples thereof include phenoxy groups, naphthoxy groups, and the like.
• substituents in "aryloxy group which may have one or more substituents” include halogen atoms, hydroxy groups, alkyl groups, alkoxy groups, and combinations of two or more of these ( Examples: haloalkyl group, haloalkoxy group).
• the number of substituents can be selected from 1 to the maximum number that can be substituted, for example, 1, 2, 3, 4, or 5. can be individual.
• each substituent may be the same or different from each other.
• R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group substituted with one or more fluorine atoms, or an alkoxy group substituted with one or more fluorine atoms
• R 3 is a fluorine atom, an alkyl group substituted with one or more fluorine atoms, or an alkoxy group substituted with one or more fluorine atoms
• R 2 and R 3 may be bonded to each other to form a ring
• R 4 is an alkyl group which may have one or more substituents or an aryl group which may have one or more substituents.
• R 1 and R 2 are each independently preferably a halogen atom, an alkyl group substituted with one or more fluorine atoms, or an alkoxy group substituted with one or more fluorine atoms, and fluorine More preferably, it is an alkyl group substituted with an atom, an alkyl group substituted with one or more fluorine atoms, or an alkoxy group substituted with one or more fluorine atoms; More preferably, it is an alkyl group.
• Both R 1 and R 2 may be halogen atoms (e.g., one is a chlorine or bromine atom, the other is a fluorine atom), and both R 1 and R 2 are substituted with one or more fluorine atoms. or an alkoxy group substituted with one or more fluorine atoms, but an alkyl group in which one of R 1 and R 2 is substituted with one or more fluorine atoms, or an alkoxy group substituted with one or more fluorine atoms, and the other is preferably a fluorine atom.
• it is preferable that one of R 1 and R 2 is an alkyl group substituted with one or more fluorine atoms, and the other is a fluorine atom.
• R 1 or R 2 is "an alkyl group substituted with one or more fluorine atoms", fluoroC 1- such as trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, etc. 10 alkyl group or (fluoroC 1-4 alkoxy)fluoroC 1-4 alkyl group such as CF 3 -O-CF 2 -, CF 3 -O-(CF 2 ) 2 -.
• R 1 or R 2 is "an alkoxy group substituted with one or more fluorine atoms", fluoroC 1- such as trifluoromethoxy group, perfluoroethoxy group, perfluoropropoxy group, perfluorobutoxy group, etc. 10 alkoxy group or (fluoroC 1-4 alkoxy)fluoroC 1-4 alkoxy groups such as CF 3 -O-CF 2 -O- and CF 3 -O-(CF 2 ) 2 -O-.
• R 3 is preferably a fluorine atom or an alkyl group substituted with one or more fluorine atoms, more preferably a fluorine atom, a fluoroC 1-10 alkyl group, or (fluoroC 1-4 alkoxy)fluoro It is a C 1-4 alkyl group, and more preferably a fluorine atom.
• examples of the ring include cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene.
• the ring may have one or more substituents (eg, a halogen atom such as a fluorine atom).
• R 4 is an alkyl group which may have one or more substituents, and is represented by the following formula (A):
• R 4a and R 4b are each independently a hydrogen atom, an alkyl group that may have one or more substituents, or an aryl group that may have one or more substituents. (The wavy line indicates the bonding point with the hydroxyl group.)
• a group represented by is more preferable.
• the group represented by formula (A) may be any of the following (A-1) to (A-5): (A-1) Both R 4a and R 4b are hydrogen atoms, (A-2) R 4a is a hydrogen atom, and R 4b is an alkyl group that may have one or more substituents or an aryl group that may have one or more substituents, (A-3) Both R 4a and R 4b are alkyl groups that may have one or more substituents, (A-4) R 4a is an alkyl group which may have one or more substituents, and R 4b is an aryl group which may have one or more substituents, (A-5) Both R 4a and R 4b are aryl groups which may have one or more substituents.
• the alkyl group may be, for example, a C 1-10 alkyl group, and may include a halogen atom (e.g. fluorine atom), R A O-, (R B ) 2 N-, (R C ) 2 P-, aryl group (e.g. C 6-12 aryl group such as phenyl group), and a combination of two or more of these (e.g. 1, 2 (2, 3, 4, 5) substituents.
• a halogen atom e.g. fluorine atom
• the aryl group may be, for example, a C 6-12 alkyl group such as a phenyl group, a halogen atom, an alkyl group (e.g. a C 1-10 alkyl group). group), R A O-, (R B ) 2 N-, (R C ) 2 P-, and combinations of two or more of these (e.g., 1, 2, 3, 4 or 5) substituents.
• R 4 is an aryl group which may have one or more substituents, and a C 6-12 aryl group which may have one or more substituents. More preferably, it is a phenyl group which may have one or more substituents.
• the aryl group is, for example, a halogen atom, an alkyl group (e.g., a C 1-10 alkyl group), R A O-, (R B ) 2 N-, (R C ) 2 P-, and a combination of two or more of these. It may be substituted with one or more (eg, 1, 2, 3, 4, 5) substituents selected from the following.
• the amount of the compound represented by formula (2) to be used is not particularly limited, but is, for example, 0.1 mol or more, 0.2 mol or more, 0.2 mol or more, per 1 mol of the compound represented by formula (1). It may be 3 mol or more, 0.4 mol or more, or 0.5 mol or more, and 5 mol or less, 4 mol or less, 3 mol or less, 2 mol or less, 1.5 mol or less, or 1 mol or less. The amount may be approximately equimolar, for example within the range of 0.5 to 1.5 moles.
• R 5 , R 6 , and R 7 each independently represent a hydrocarbon group that may have one or more substituents, a heteroaryl group that may have one or more substituents ( Examples: furyl group, thienyl group), or R X -O- (wherein R X is a hydrocarbon group that may have one or more substituents), and one A hydrocarbon group that may have the above substituents, or an alkyl group that may have one or more substituents, more preferably R x -O-, one or more substituents a cycloalkyl group that may have one or more substituents, an aryl group that may have one or more substituents, an alkoxy group that may have one or more substituents, or one or more substituents More preferably, it is an aryloxy group which may have a group, an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, It is even more prefer
• C 1-6 alkyl group which may have one or more substituents
• C 6-12 aryl group which may have one or more substituents (e.g. phenyl group, tolyl group, biphenyl group), one or more substituents
• Particularly preferred is a C 1-6 alkoxy group which may have one or more substituents, or a C 6-12 aryloxy group (eg, phenoxy group) which may have one or more substituents.
• the substituent include a halogen atom, R A O-, and (R C ) 2 P-, and more preferable examples include a C 1-4 alkoxy group such as a methoxy group, and a diphenylphosphino group. and diC 6-12 arylphosphino groups.
• examples of the ring include phosphetane, phosphorane, phospholinane, phosphepane, and the like.
• the compound represented by formula (4) may be a phosphine ligand capable of coordinating to a transition metal (e.g., Pd), but the production method of the present disclosure can be carried out in the absence of or substantially in the absence of a transition metal. It can be suitably carried out under conditions where no such conditions exist.
• a transition metal e.g., Pd
• Examples of the compound represented by formula (4) include tri-n-butylphosphine, tri-t-butylphosphine, di-t-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, isopropyldiphenylphosphine, 2- (di-t-butylphosphino)biphenyl, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenyl) phosphino)butane, 1,5-bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, tricyclohexylphosphine, dicyclohexylphenylphosphine, dicyclohexyl(2',
• R 8 , R 9 , and R 10 are each independently a hydrocarbon group that may have one or more substituents or a heteroaryl group that may have one or more substituents ( Example: pyridyl group), more preferably a hydrocarbon group which may have one or more substituents, an alkyl group which may have one or more substituents, More preferably, it is a cycloalkyl group which may have one or more substituents, or an aryl group which may have one or more substituents, and which has one or more substituents.
• Preferred examples of the substituents include R A O-, (R B ) 2 N-, and (R C ) 2 P-, and more preferred examples include C 1-4 alkoxy groups such as methoxy groups. , diC 1-4 alkylamino groups such as dimethylamino, and diC 6-12 arylphosphino groups such as diphenylphosphino.
• R 8 , R 9 , and R 10 combine with each other to form a ring
• examples of the ring include pyridine, imidazole, morpholine, diazabicyclononene, diazabicyclononene, and diazabicyclononene. Desene etc. can be mentioned.
• the compound represented by formula (5) may be an amine ligand capable of coordinating with a transition metal (e.g., Pd), but the production method of the present disclosure can be performed without or with substantially no transition metal. It can be carried out under non-existing conditions.
• a transition metal e.g., Pd
• Examples of the compound represented by formula (5) include triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, pyridine, 4-dimethylaminopyridine, 1-methylimidazole, N,N,N,N -tetramethyl-1,3-diaminopropane, N,N,N,N-tetraethylethylenediamine, N,N,N,N-tetramethyl-1,4-diaminobutane, 1-(diphenylphosphino)-N, Examples include N-dimethyl-2-propanamine, diazabicyclononene, diazabicycloundecene, and the like.
• the amount of at least one selected from the group consisting of the compound represented by formula (4) and the compound represented by formula (5) is not particularly limited, but is preferably a catalytic amount.
• the usage amount is preferably 0.5 mol or less, more preferably 0.4 mol or less, and 0.5 mol or less, more preferably 0.4 mol or less, per 1 mol of the compound represented by formula (1). It is more preferably 3 mol or less, even more preferably 0.2 mol or less, and particularly preferably 0.1 mol or less.
• the amount used may be, for example, 0.0001 mol or more, 0.0005 mol or more, or 0.001 mol or more, and 0.0001 to 0.0001 mol or more, per 1 mol of the compound represented by formula (1). It may be within the range of 0.5 mol, within the range of 0.0005 to 0.2 mol, or within the range of 0.001 to 0.1 mol.
• Step A is carried out in the presence of a solvent.
• the solvent include hydrocarbon solvents, halogen solvents, ether solvents, nitrile solvents, amide solvents, ketone solvents, sulfoxide solvents, and the like.
• hydrocarbon solvent examples include aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, and decane, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.
• halogen-based solvent examples include dichloromethane, dichloroethane, chloroform, and chlorobenzene.
• ether solvents include diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether (DME), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), 1,4-dioxane, Examples include tetrahydrofuran.
• nitrile solvents examples include acetonitrile, propionitrile, benzonitrile, and the like.
• amide solvent examples include formamide, N,N-dimethylformamide, and N-methylpyrrolidone.
• ketone solvents include acetone and methyl ethyl ketone.
• Examples of the sulfoxide solvent include dimethyl sulfoxide.
• At least one selected from the group consisting of ether solvents, sulfoxide solvents, nitrile solvents, and amide solvents is preferred.
• the amount of the solvent to be used is not particularly limited, but for example, 0.1 mL or more, 0.15 mL or more, 0.2 mL or more, 0.25 mL or more, 0. It may be 5 mL or more, 1 mL or more, or 1.5 mL or more, it may be 5 mL or less, 3 mL or less, 2.5 mL or less, or 2 mL or less, and it may be within the range of 0.2 mL to 3 mL. .
• Step A is preferably carried out in the absence of a transition metal catalyst, or in the presence of more than 0 mol and not more than 0.01 mol of a transition metal catalyst per 1 mol of the compound represented by formula (1).
• transition metal catalysts include Pd and the like.
• step A is carried out in the absence of a Pd catalyst, or in the presence of more than 0 mol and 0.01 mol or less of a Pd catalyst per 1 mol of the compound represented by formula (1). is preferred.
• Step A is preferably carried out in the absence of an inorganic base, or in the presence of more than 0 mol and not more than 2 mol of an inorganic base per 1 mol of the compound represented by formula (2).
• the inorganic base include alkali metal hydroxides such as KOH and NaOH, and alkaline earth metal hydroxides such as Ca(OH) 2 .
• step A is performed in the absence of an alkali metal hydroxide or an alkaline earth metal hydroxide, or in an amount of more than 0 mol and not more than 2 mol per mol of the compound represented by formula (2).
• it is carried out in the presence of a metal hydroxide or an alkaline earth metal hydroxide.
• Step A is preferably carried out in the absence of an ionic liquid, or in the presence of more than 0 mL and less than 0.1 mL of the ionic liquid per mol of the compound represented by formula (1).
• the ionic liquid include imidazolium salts such as 1-ethyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium chloride, and pyridinium salts.
• step A is performed in the absence of an imidazolium salt or pyridinium salt, or in the presence of more than 0 mL and less than 0.1 mL of an imidazolium salt or pyridinium salt per 1 mol of the compound represented by formula (1). It is preferable to carry out below.
• reaction temperature and reaction time are not particularly limited as long as the reaction proceeds.
• the reaction temperature can be, for example, 0°C to 60°C.
• the reaction time is, for example, within the range of 10 minutes to 72 hours, preferably within the range of 15 minutes to 48 hours.
• compositions according to an embodiment of the present disclosure contains a compound represented by formula (3) and water.
• the content of the compound represented by formula (3) is not particularly limited, but for example, 60 parts by mass or more, 65 parts by mass or more, 70 parts by mass or more, or 73 parts by mass or more, based on 100 parts by mass of the composition. may be less than 100 parts by mass, 99.99 parts by mass or less, 99.9 parts by mass or less, 99 parts by mass or less, or 95 parts by mass or less, within the range of 60 to 95 parts by mass. There may be.
• the content can be measured, for example, by 1 H-NMR, gas chromatography (GC), or gas chromatography-mass spectrometry (GC-MS).
• the content of water is not particularly limited, but is, for example, 0.3 parts by mass or less, 0.2 parts by mass, 0.2 parts by mass or less, based on 100 parts by mass of the composition or 100 parts by mass of the compound represented by formula (3). It may be 1 part by mass or less, 0.05 part by mass or less, 0.02 part by mass or less, 0.01 part by mass or less, or 0.001 part by mass or less, more than 0 part by mass, 0.0001 part by mass or more. , 0.0002 parts by mass or more, or 0.0003 parts by mass or more, and may be within the range of 0.0003 to 0.001 parts by mass.
• the content can be measured, for example, by the Karl Fischer method.
• Composition A may further contain other optional components.
• other optional components may include by-products of the Step A reaction.
• nBu normal butyl
• Cy means cyclohexyl
• tBu means tert-butyl
• Et means ethyl
• Ph means phenyl

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (2)

Family

ID=88419961

Family Applications (1)

Country Status (7)

Citations (7)

Family Cites Families (6)

• 2022
  • 2022-04-20 JP JP2022069520A patent/JP7473826B2/ja active Active
• 2023
  • 2023-04-10 CN CN202380034843.0A patent/CN119053581A/zh active Pending
  • 2023-04-10 EP EP23791715.8A patent/EP4512793A1/en active Pending
  • 2023-04-10 WO PCT/JP2023/014486 patent/WO2023204066A1/ja not_active Ceased
  • 2023-04-10 KR KR1020247038114A patent/KR20250005310A/ko active Pending
  • 2023-04-19 TW TW112114573A patent/TW202404931A/zh unknown
• 2024
  • 2024-01-09 JP JP2024001511A patent/JP2024041869A/ja active Pending
  • 2024-10-18 US US18/919,833 patent/US20250034069A1/en active Pending

Patent Citations (8)

Also Published As

Similar Documents

Legal Events