WO2020246612A1 - Composé fluoré - Google Patents

Composé fluoré Download PDF

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Publication number
WO2020246612A1
WO2020246612A1 PCT/JP2020/022446 JP2020022446W WO2020246612A1 WO 2020246612 A1 WO2020246612 A1 WO 2020246612A1 JP 2020022446 W JP2020022446 W JP 2020022446W WO 2020246612 A1 WO2020246612 A1 WO 2020246612A1
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group
substituents
hydrogen
ring
groups
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PCT/JP2020/022446
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English (en)
Japanese (ja)
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昌弘 東
洋介 岸川
二雄 北村
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ダイキン工業株式会社
国立大学法人佐賀大学
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Priority to JP2021524944A priority Critical patent/JP7373809B2/ja
Publication of WO2020246612A1 publication Critical patent/WO2020246612A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D347/00—Heterocyclic compounds containing rings having halogen atoms as ring hetero atoms

Definitions

  • the present disclosure relates to a fluoride compound (particularly, a vinyl fluoride group-containing cyclic hypervalent iodine compound).
  • Non-Patent Documents 1 and 2 disclose iodotoluene difluoride and the steric and regioselective addition of fluorine using the iodine toluene difluoride.
  • the object of the present disclosure is to provide a fluoride compound (particularly, a cyclic hypervalent iodine compound containing a vinyl fluoride group) and a method for producing the same.
  • Item 1 Equation (2): [During the ceremony, Wavy lines represent cis or transformer arrangements; Ring A represents an aromatic ring that may have one or more substituents; and R 1 and R 2 represent the same or different hydrogen or organic groups. ] A cyclic hypervalent iodine compound containing a vinyl fluoride group represented by. Item 2. R 1 and R 2 are the same or different, hydrogen, Alkyl groups, which may have one or more substituents, An aromatic group that may have one or more substituents, or a heterocyclic group that may have one or more substituents. Item 2. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to Item 1. Item 3. Item 2.
  • Item 4. Item 2. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to Item 2, wherein R 1 is an alkyl group which may be substituted with one or more cycloalkyl groups.
  • Item 5. Have R 2 is hydrogen, or one or more substituents is also an alkyl group, fluorinated vinyl group-containing cyclic hypervalent iodine compound according to any one of claims 1-4.
  • Item 7. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to any one of Items 1 to 6, wherein ring A is an aromatic carbocyclic ring which may have one or more substituents.
  • a production method comprising a step B of reacting with an alkyne compound represented by. Item B2.
  • a fluorinated compound particularly, a vinyl fluoride group-containing cyclic hypervalent iodine compound
  • a method for producing the same is provided.
  • organic compound is understood in the usual sense and can be a compound having one or more carbon atoms and one or more hydrogen atoms.
  • the fluorinated organic compound means a compound that can be produced by fluorinating an organic compound, and does not have to contain a hydrogen atom.
  • 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).
  • aromatic ring can include an aromatic carbocycle and an aromatic heterocycle.
  • aromatic carbocycle can include an aromatic hydrocarbon ring having 6 to 14 carbon atoms, and specific examples thereof include benzene, naphthalene, anthracene, and phenanthrene. And biphenyl can be included.
  • aromatic heterocycles can include 5- or 6-membered aromatic heterocycles, and specific examples thereof include furan ring, thiophene ring, pyrrole ring, and oxadiazole ring.
  • aromatic heterocycle is fused rings of one or more of the five or six-membered aromatic heterocycles and one or more of the aromatic carbocycles. Can be included.
  • organic group means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound.
  • the organic group may contain one or more atoms other than a carbon atom and a hydrogen atom (eg, nitrogen, oxygen, sulfur, phosphorus, silicon, halo).
  • Examples of organic groups can include (pel) fluoroorganic groups and (pel) fluoroorganic groups.
  • the suffix "perhalogeno” means that all hydrogen atoms are substituted with halo groups.
  • the suffix "perfluoro” means that all hydrogen atoms are substituted with fluorogroups.
  • An example of the "organic group” is Alkyl groups that may have one or more substituents ⁇ eg: (pel) halogenoalkyl groups [eg: (pel) fluoroalkyl groups] ⁇ , 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, R r O-, R r CO-, R r SO 2- , R r OCO- and
  • the "organic group” is, for example, a hydrocarbon group which may have one or more substituents
  • One or more moieties selected from the group consisting of 3- (in these equations, Ro is independently a hydrogen atom or an organic group) may be inserted. ] Can be.
  • examples of hydrocarbon groups into which heteroatoms are inserted in this way can include non-aromatic heterocyclic groups and heteroaryl groups.
  • the carbon number of the "hydrocarbon group" in the “hydrocarbon group which may have one or more substituents” is, for example, 1 to 100, 1 to 80, 1 to 60, 1 to 1. It can be 40, 1-30, 1-20, or 1-10 (eg: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10).
  • “Hydrocarbon groups which may have one or more substituents” can include halo groups, nitro groups, cyano groups, oxo groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, and sulfenamoyl groups, respectively.
  • the number of the substituents can include halo groups, nitro groups, cyano groups, oxo groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, and sulfenamoyl groups, respectively.
  • the number of the substituents can include halo groups, nitro groups, cyano groups, oxo groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, and sulfenamoyl groups, respectively.
  • examples of the "hydrocarbon group” are 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 a group thereof. 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, which are linear or branched, can include C1-C10 alkyl groups.
  • the "fluoroalkyl group” is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
  • the number of fluorine atoms contained in the “fluoroalkyl group” is 1 or more (example: 1 to 3, 1 to 6, 1 to 12, 1 to the maximum number that can be replaced). be able to.
  • the "fluoroalkyl group” can include a perfluoroalkyl group.
  • a "perfluoroalkyl group” is an alkyl group in which all hydrogen atoms are substituted with fluorine atoms.
  • Specific examples of the perfluoroalkyl group can include a trifluoromethyl group (CF 3- ) and a pentafluoroethyl group (C 2 F 5- ).
  • the "fluoroalkyl group” has, for example, 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 6 carbon atoms, and a carbon number of carbon atoms. It can be a fluoroalkyl group having 5, carbon number 4, carbon number 3, carbon number 2, or carbon number 1.
  • the "fluoroalkyl group” can be a linear or branched fluoroalkyl group.
  • the "fluoroalkyl group” specifically, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group (CF 3- ), a 2,2,2-trifluoroethyl group, a pentafluoro Ethyl group (C 2 F 5- ), tetrafluoropropyl group (eg HCF 2 CF 2 CH 2- ), hexafluoropropyl group (eg (CF 3 ) 2 CH-), nonafluorobutyl group, octafluoropentyl Groups (eg, HCF 2 CF 2 CF 2 CF 2 CH 2- ), tridecafluorohexyl groups, and 3,3,4,4,5,5,6,6,7,7,8,8,8- Examples thereof include a tridecafluorooctyl group (
  • 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-propine-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 in the present specification can include C3-C7 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl and the like.
  • examples of the "cyclo-alkazienyl group” include cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, and cyclononazienyl.
  • Cyclodecadienyl and the like can include C4-C10 cycloalkazienyl groups.
  • the "aromatic group” can include an “aryl group” and a "heteroaryl group”.
  • the "aryl group” can be monocyclic, bicyclic, tricyclic, or tetracyclic. In the present specification, unless otherwise specified, the “aryl group” can be a C6-C18 aryl group. Unless otherwise specified herein, examples of “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.
  • the "non-aromatic heterocyclic group” can be monocyclic, bicyclic, tricyclic, or tetracyclic.
  • the “non-aromatic heterocyclic group” is, for example, 1 to 4 atoms selected from oxygen atom, sulfur atom, and nitrogen atom in addition to carbon atom as ring-constituting atoms. It can be a non-aromatic heterocyclic group containing a hetero atom.
  • the "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-piperazin-2-yl
  • diazepinyl eg 1,4-diazepine-1-yl, 1,4-diazepine-2-yl, 1,4-
  • 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 group” include pyrrolyl (eg, 1-pyrrolyl, 2-pyrrolill, 3-pyrrolyl), frill (eg). : 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-isooxazolyl, 4-isooxazolyl, 5-isoxazolyl), oxazolyl (eg 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (eg 3-isothiazolyl, 4) -Isotiazolyl, 5-isothiazolyl), thiazolyl (eg 3-isothi
  • examples of "5- to 18-membered aromatic condensed heterocyclic groups” include isoindyl (eg, 1-isoindrill, 2-isoindrill, 3-isoindrill, 4-isoindrill, 5-isoindrill).
  • Non-aromatic heterocyclic group which may have one or more substituents
  • Benzene ring which may have one or more substituents
  • Heteroaryl group which may have one or more substituents
  • Pyridine ring which may have one or more substituents
  • Examples of each "substituent” in the above are hydrocarbon groups, halo groups, nitro groups, cyano groups, oxo groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, which may have one or more substituents.
  • sulfenamoyl groups can be included.
  • the number of the substituents can be in the range of 1 to the maximum number of substituents that can be substituted (eg: 1, 2, 3, 4, 5, 6).
  • R 1 and R 2 are preferably Same or different, hydrogen, Alkyl group which may have one or more substituents (eg: C1-C20 alkyl group which may have one or more substituents and may have one or more substituents. C1-C6 alkyl group), Aromatic groups that may have one or more substituents (eg: C6-C20 aryl groups that may have one or more substituents, even if they have one or more substituents.
  • a good C6-C10 aryl group), or a heterocyclic group which may have one or more substituents can be More preferably, it can be the same or different alkyl group which may have hydrogen or one or more substituents. More preferably, it can be an alkyl group that is the same or different and may have one or more substituents. Even more preferably, they can be the same or different alkyl groups.
  • R 1 is more preferably Alkyl groups which may have one or more substituents (eg: C1-C10 alkyl groups which may have one or more substituents, and one or more substituents. Good C1-C6 alkyl group) Can be.
  • the number of carbon atoms of the alkyl group of the "alkyl group which may have one or more substituents" for R 1 is 1 to 20 is preferred 1 to 15 are more preferred 1 to 10 are more preferred 1 to 6 are even more preferred, and 1 to 4 are particularly preferred.
  • R 1 is also more preferred, Alkyl groups optionally substituted with one or more cycloalkyl groups (eg: C1-C6 alkyl groups optionally substituted with one or more C3-C6 cycloalkyl groups) Can be.
  • cycloalkyl groups eg: C1-C6 alkyl groups optionally substituted with one or more C3-C6 cycloalkyl groups
  • R 2 is Preferably, it is hydrogen, or an alkyl group which may have one or more substituents (eg: a C1-C20 alkyl group which may have one or more substituents). More preferably, it is hydrogen, or an alkyl group, and most preferably hydrogen.
  • R 1 and R 2 may be linked together with the carbon atoms to which they are bonded to form a ring that may have one or more substituents.
  • the structure of the "ring that may have one or more substituents" can be understood from the structures of R 1 and R 2 .
  • Ring A is preferably Aromatic carbocycles which may have one or more substituents (eg: aromatic carbocycles having 6 to 14 carbon atoms which may have one or more substituents) Can be.
  • substituents eg: aromatic carbocycles having 6 to 14 carbon atoms which may have one or more substituents
  • Ring A is preferably Aromatic heterocycles that may have one or more substituents (eg: 5- to 10-membered aromatic heterocycles that may have one or more substituents) Can be.
  • substituents eg: 5- to 10-membered aromatic heterocycles that may have one or more substituents
  • Ring A is preferably Aromatic monocycles which may have one or more substituents (eg: a benzene ring which may have one or more substituents; and may have one or more substituents.
  • a 5- to 6-membered aromatic heterocycle which may have one or more substituents, such as a pyridine ring and a thiophene ring which may have one or more substituents).
  • the production method according to one aspect of the present disclosure is the formula (2): [The symbols in the formula have the same meaning as above. ] It is a method for producing a cyclic hypervalent iodine compound containing a vinyl fluoride group represented by. Equation (1): [In the formula, R 1 and R 2 represent hydrogen or an organic group, which are the same or different. ] The compound represented by In the presence of 2-iodobenzoic acid, which may have a substituent, and an oxidizing agent. This is a production method including step A of reacting with a fluorine source.
  • the production method can be a method for producing a compound, which is one aspect of the present disclosure. Therefore, for the understanding of the production method, the description of the preferred embodiment of the compound can also be referred to.
  • R 1 and R 2 represent hydrogen or an organic group, which are the same or different.
  • It can be a compound represented by.
  • R 1 and R 2 are preferably the same or different hydrogen, Alkyl groups, which may have one or more substituents, It can be an aromatic group that may have one or more substituents, or a heterocyclic group that may have one or more substituents.
  • R 2 can be preferably hydrogen.
  • Ring A can be an aromatic carbocycle, which may preferably have one or more substituents.
  • Equation (2) [The symbols in the formula have the same meaning as above. ] It can be a cyclic hypervalent iodine compound containing a vinyl fluoride group represented by.
  • the R 1 and R 2 alignment rings A for the target object can be the same or different from those for the target object, respectively, but are usually the same.
  • R 1 and R 2 are preferably the same or different hydrogen, Alkyl groups, which may have one or more substituents, It can be an aromatic group that may have one or more substituents, or a heterocyclic group that may have one or more substituents.
  • R 1 and R 2 are preferably It can be hydrogen or a C1-C20 alkyl group.
  • step A The compound represented by the formula (1) is In the presence of 2-iodobenzoic acid, which may have one or more substituents, and an oxidizing agent. React with a fluorine source.
  • Ring A can be a benzene ring which may preferably have one or more substituents, a pyridine ring which may have one or more substituents, and more preferably a benzene ring. ..
  • 2-Iodine benzoic acid which may have one or more substituents
  • 2-iodobenzoic acid which may have one or more substituents
  • 2-Iodine benzoic acid can be included.
  • the amount of the above-mentioned "2-iodine benzoic acid which may have a substituent" is for compound (1) which is a substrate Usually in the range of 0.2 to 10 equals, preferably in the range of 0.5 to 5 equals, It can be more preferably in the range of 0.8 to 3 equals, and even more preferably in the range of 1 to 2 equals.
  • the "oxidizing agent" used in step A is preferably, for example, for example.
  • oxidizing agent is Metachloroperbenzoic acid, hydrogen peroxide, peracetic acid, perbenzoic acid, tert-butyl hydroperoxide, cumene hydroperxide, potassium persulfate, potassium hydrogen persulfate-potassium hydrogen sulfate-potassium sulfate mixture, permanganate, dichromic acid , Tungsten oxide, ruthenium oxide, antimony oxide, osmium oxide, and sulfur trioxide can be included.
  • a good example of the oxidizing agent is Included are meta-chloroperbenzoic acid, hydrogen peroxide, peracetic acid, perbenzoic acid, tert-butyl hydroperoxide, cumene hydroperxide, potassium persulfate, and potassium hydrogen peroxide-potassium hydrogensulfate-potassium sulfate mixture.
  • a more preferred example of the oxidizing agent can include m-chloroperbenzoic acid. These may be used alone or in combination of two or more.
  • the amount of the oxidizing agent is, for example, For compound (1) which is a substrate Usually in the range of 0.1 to 40 equals, preferably in the range of 0.5 to 30 equals, It can be more preferably in the range of 0.8 to 10 equals, and even more preferably in the range of 1 to 5 equals.
  • the "fluorine source” used in the step A can preferably be a hydrogen fluoride source.
  • An example of the "fluorine source” is Formula: A fluorine source represented by MF n (where M is H, a Group 1 metal of the Periodic Table, or a metal of Group 2 of the Periodic Table; and n is 1 or 2). Can be included.
  • M is Preferably, it can be H, Li, Na, K, Ca, or Cs. More preferably, it can be H, Na, K, or Ca, and even more preferably, it can be H.
  • the example of the "fluorine source” also includes Hydrofluoric acid anhydride, Hydrofluoric acid aqueous solution (eg, hydrofluoric acid aqueous solution having a concentration of 10 to 70% by weight), A mixture or complex of hydrofluoric acid and an organic base, It can include a mixture or complex of hydrofluoric acid and an inorganic base.
  • the mixture or complex of hydrofluoric acid and an organic base is, for example, HF-KF (KHF 2 ) Etc., or can be derived from this.
  • the fluorine source can be used alone or in combination of two or more.
  • the amount of the fluorine source is, for example, As hydrogen fluoride for compound (1) which is a substrate Usually in the range of 1-70 mol, Preferably in the range of 3-50 mol, It can be more preferably in the range of 5-40 mol, and even more preferably in the range of 10-30 mol. Within the range of 0.1 to 1000 mol, preferably within the range of 0.2 to 500 mol, more preferably within the range of 0.3 to 100 mol, still more preferably within the range of 0.4 to 50 mol, and even more. It can preferably be in the range of 0.5-30 mol.
  • the reaction of acid step A can be preferably carried out in the presence of acid.
  • the lower limit of the amount of the acid used can be, for example, 0.5, 0.6, 0.8, 1, 3, or 5 with respect to the substrate compound (1).
  • the upper limit of the amount of the acid used can be, for example, 50, 30, 20, or 15 with respect to the substrate compound (1).
  • the amount of the acid used is For example For compound (1) which is a substrate Usually in the range of 0.5 to 50 equals, preferably in the range of 0.5 to 30 equals, It can be more preferably in the range of 0.6 to 20 equals, and even more preferably in the range of 0.8 to 15 equals.
  • Hydrogen halide or hydrohalic acid hypochlorous acid, chlorous acid, halogen acid, or perhalogen acid
  • sulfuric acid, nitrate, phosphoric acid, polyphosphate hydrogen fluoride, hydrofluoric acid, hydrochloric acid, hydrogen bromide , Hydrogen iodide, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, perbromic acid, and periodic acid
  • Sulfonic acid or polymer-supported sulfonic acid such as polystyrene sulfonic acid, fluorinated sulfonic acid resin [Nafion-H (trade name)]
  • the reaction of Step A 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.
  • a specific example is The solvent may be either a non-polar solvent or a polar solvent.
  • the solvent is an ester, a ketone, an aromatic compound, 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 any of these. It can be a combination.
  • ester as the solvent can include ethyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and preferred examples thereof can include ethyl acetate.
  • ketones as the solvent can include, and are suitable, acetone, methyl ethyl ketone, diethyl ketone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, acetonyl acetone, methyl hexanone, and acetophenone, cyclohexanone, diacetone alcohol.
  • Examples can include acetone.
  • aromatic compound as the solvent can include anisole, benzene, toluene, xylene, and ethylbenzene, and suitable examples thereof can 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 can 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, and propylene.
  • PGME glycol monomethyl ether
  • propylene glycol monoethyl ether triethylene glycol dimethyl ether
  • triethylene glycol diethyl ether triethylene glycol diethyl ether
  • tetraethylene glycol dimethyl ether tetraethylene glycol dimethyl ether
  • tetraethylene glycol diethyl ether tetrahydrofuran
  • Examples of amines as the solvent can 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 can include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone.
  • nitrile as the solvent can include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and adiponitrile, and preferred examples thereof can include acetonitrile.
  • halogenated hydrocarbons as the solvent can include dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene, and preferred examples thereof include dichloromethane and chloroform. Can be included.
  • Examples of aliphatic hydrocarbons as the solvent can include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirit, and preferred examples thereof can include cyclohexane, heptane.
  • fluorosolvent examples include perfluorobenzene, trifluorotoluene, ditrifluorobenzene and trifluoroethanol, and suitable examples thereof can include perfluorobenzene and trifluoroethanol.
  • carbonate as the solvent can include tetralin dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate, and preferred examples thereof can include ethylene carbonate and propylene carbonate.
  • Examples of the other solvents can include acetic acid, pyridine, dimethyl sulfoxide, sulfolane, and water.
  • the solvent may be used alone or in combination of two or more.
  • the amount of solvent used is, for example, With respect to 1 part by mass of the organic compound (1) which is a substrate It is usually in the range of 0 to 200 parts by mass, 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 step A is Usually in the range of ⁇ 78 to 200 ° C., preferably in the range of ⁇ 10 to 100 ° C. More preferably, it can be in the range of ⁇ 65 to 100 ° C., and even more preferably in the range of 0 to 100 ° C.
  • the time of step A is It is usually in the range of 0.1 to 72 hours, preferably in the range of 0.1 to 48 hours, and more preferably in the range of 0.1 to 36 hours.
  • the obtained compound (2) can be isolated or purified by a conventional method such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, or chromatography, or a combination thereof, if desired.
  • the raw material conversion rate is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, still more preferably 70% or more, and particularly preferably 80% or more. be able to.
  • the selectivity of the target compound is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, still more preferably 70% or more, and particularly preferably 80% or more.
  • the yield of the target compound is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, still more preferably 70% or more, and particularly preferably 80% or more. Can be.
  • Equation (1') [During the ceremony, Wavy lines represent cis or transformer arrangements; R 1 and R 2 represent hydrogen or an organic group; and R represents an organic group. ] It is a method for producing a compound represented by Equation (2): [During the ceremony, Wavy lines represent cis or transformer arrangements; Ring A represents an aromatic ring that may have one or more substituents; and R 1 and R 2 represent the same or different hydrogen or organic groups.
  • Step B to react with the alkyne compound represented by It is a manufacturing method including. The reaction of step B is optionally carried out in the presence of a metal catalyst and / or base.
  • the metal in the metal catalyst is It can be preferably a transition metal, and more preferably one or more metals selected from the group consisting of Cu, Pd, Fe, Zr, Co, Ni, Ru, and Rh.
  • the metal catalyst may have a ligand.
  • a metal catalyst with a ligand is Palladium catalysts (eg palladium acetate, [1,1'-bis (diphenylphosphine) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, and bis (triphenylphosphine) palladium Dichloride) Can be included.
  • the metal catalyst may be used alone or in combination of two or more.
  • the metal catalyst can preferably be used in combination with a copper compound.
  • a copper compound is It can include copper chloride, copper bromide, and copper iodide.
  • the copper compound may be used alone or in combination of two or more.
  • the lower limit of the amount of the metal catalyst used with respect to the vinyl fluoride group-containing cyclic hypervalent iodine compound (2) can be, for example, 0.001 equivalent.
  • the upper limit of the amount can be, for example, one equivalent.
  • Organic bases eg triethylamine, tributylamine, isopropylamine, diethylamine, diisopropylamine, diisopropylethylamine
  • inorganic bases eg sodium carbonate, potassium carbonate, and cesium carbonate
  • the base can be used alone or in combination of two or more.
  • the upper limit of the amount of the base used with respect to the vinyl fluoride group-containing cyclic hypervalent iodine compound (2) can be, for example, 1 equivalent.
  • the lower limit of the amount can be, for example, 50 equivalents.
  • the liquid organic base can also be used as a solvent in the reaction of step B.
  • step B may be carried out in the presence of a solvent.
  • the solvent can include those exemplified for the step A.
  • the amount of solvent used is, for example, With respect to 1 part by mass of the organic compound (1) which is a substrate It is usually in the range of 0 to 200 parts by mass, 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 step B is It is usually in the range of ⁇ 78 to 200 ° C., preferably in the range of ⁇ 10 to 100 ° C., and more preferably in the range of 0 to 100 ° C.
  • the time of process B is It is usually in the range of 0.1 to 72 hours, preferably in the range of 0.1 to 48 hours, and more preferably in the range of 0.1 to 36 hours.
  • the obtained compound (2) can be isolated or purified by a conventional method such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, or chromatography, or a combination thereof, if desired.
  • the raw material conversion rate is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, still more preferably 70% or more, and particularly preferably 80% or more. be able to.
  • the selectivity of the target compound is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, still more preferably 70% or more, and particularly preferably 80% or more.
  • the yield of the target compound is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, still more preferably 70% or more, and particularly preferably 80% or more. Can be.
  • Pr Pyridine
  • mCPBA Metachloroperbenzoic acid
  • Example 1 2-Iodine benzoic acid (1.5 eq.), MCPBA (1.5 eq.), Dichloromethane, Py ⁇ HF (20 eq.), 1-Octyne 1a (0.5 mmol) were added. Then, BF 3 ⁇ OEt 2 (10 eq.) was added at ⁇ 65 ° C., and the mixture was further stirred at room temperature. Then, quenching, liquid separation, solvent distillation, and purification were carried out to obtain the desired product 2a in a yield of 84% (Table 1, Entry 1).
  • Examples 2-9 The same operation was performed except that 1-Octyne was changed to the following alkynes 1b to 1f , and the corresponding objects 2b to 2f were obtained. The results are shown in Table 1 (Entry 2-7).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un composé fluoré (en particulier un composé d'iode hypervalent cyclique contenant un groupe vinyle fluoré). La solution selon l'invention concerne un composé d'iode hypervalent cyclique contenant un groupe vinyle fluoré représenté par la formule (2). (Dans la formule, le cycle A représente un cycle aromatique qui peut avoir un ou plusieurs substituants ; R1 et R2 peuvent être identiques ou différents, et chacun représente un atome d'hydrogène ou un groupe organique.)
PCT/JP2020/022446 2019-06-07 2020-06-05 Composé fluoré WO2020246612A1 (fr)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN106631680A (zh) * 2016-12-20 2017-05-10 江南大学 一种三氟甲基芳香族化合物的合成方法
US20170233420A1 (en) * 2014-08-07 2017-08-17 Eth Zurich Hypervalent iodine cf2cf2x reagents and their use
US20170298008A1 (en) * 2014-10-10 2017-10-19 The Research Foundation For The State University Of New York Trifluoromethoxylation of arenes via intramolecular trifluoromethoxy group migration

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US20170233420A1 (en) * 2014-08-07 2017-08-17 Eth Zurich Hypervalent iodine cf2cf2x reagents and their use
US20170298008A1 (en) * 2014-10-10 2017-10-19 The Research Foundation For The State University Of New York Trifluoromethoxylation of arenes via intramolecular trifluoromethoxy group migration
CN106631680A (zh) * 2016-12-20 2017-05-10 江南大学 一种三氟甲基芳香族化合物的合成方法

Non-Patent Citations (1)

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Title
WU JUNLIANG, DENG XIAOZHOU, YOSHIKAI NAOHIKO: "Stereocontrolled Synthesis of Halovinylbenziodoxoles by Hydro- and Iodochlorination of Ethynylbenziodoxoles", CHEMISTRY - A EUROPEAN JOURNAL, vol. 25, no. 33, 24 April 2019 (2019-04-24), pages 7839 - 7842, XP055768648 *

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