WO2019193846A1 - Production method for compound and compound - Google Patents

Production method for compound and compound Download PDF

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WO2019193846A1
WO2019193846A1 PCT/JP2019/005765 JP2019005765W WO2019193846A1 WO 2019193846 A1 WO2019193846 A1 WO 2019193846A1 JP 2019005765 W JP2019005765 W JP 2019005765W WO 2019193846 A1 WO2019193846 A1 WO 2019193846A1
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group
carbon
compound
atom
general formula
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PCT/JP2019/005765
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French (fr)
Japanese (ja)
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航太郎 林
昭佳 山内
悠希 鈴木
洋介 岸川
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ダイキン工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/72—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage

Definitions

  • the present disclosure relates to methods for producing compounds and compounds.
  • Patent Document 1 describes a reaction represented by the following formula.
  • An object of the present disclosure is to provide a method for producing a novel compound and a novel compound.
  • the present disclosure provides the following general formula (1): (Wherein R 1 and R 2 are each independently a fluorine atom or an organic group having 6 or less carbon atoms, and may be bonded to each other to form a cyclic structure. R 3 is carbon-carbon unsaturated. Which is an organic group having 7 or less carbon atoms having a bond).
  • step (1) is preferably carried out in the presence of a base (excluding amine (B)).
  • R 3 preferably contains one carbon-carbon double bond or one carbon-carbon triple bond.
  • R 3 is preferably a 2-propenyl group or a 2-propynyl group.
  • R 1 and R 2 are each independently a fluorine atom or an organic group having 6 or less carbon atoms, and may be bonded to each other to form a cyclic structure.
  • R 3 is carbon-carbon unsaturated. And an organic group having 7 or less carbon atoms having a bond).
  • a method for producing a novel compound and a novel compound can be provided.
  • R 1 and R 2 are each independently a fluorine atom or an organic group having 6 or less carbon atoms, and may be bonded to each other to form a cyclic structure.
  • R 3 is carbon-carbon unsaturated.
  • a compound (1) represented by the formula (1) is an organic group having 7 or less carbon atoms having a bond.
  • Compound (1) is a novel compound and the present disclosure also relates to compound (1).
  • R 1 and R 2 are each independently a fluorine atom or an organic group having 6 or less carbon atoms.
  • the organic group as R 1 and R 2 is a group containing at least one carbon atom, and is an atom other than a carbon atom, for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a halogen atom ( A fluorine atom, a chlorine atom, etc.).
  • the organic group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • Examples of the organic group as R 1 and R 2 include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, and these groups may have one or more substituents.
  • substituents include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
  • the alkyl group as R 1 and R 2 preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • the alkyl group may have a fluorine atom or a group containing a hetero atom such as a cyano group.
  • the alkyl group may be a cycloalkyl group. Examples of the alkyl group having no fluorine atom include a methyl group (—CH 3 ), an ethyl group (—CH 2 CH 3 ), a propyl group (—CH 2 CH 2 CH 3 ), and an isopropyl group (—CH (CH 3 ) 2.
  • Butyl group (—CH 2 CH 2 CH 2 CH 3 ), sec-butyl group (—CH (CH 3 ) CH 2 CH 3 ), tert-butyl group (—C (CH 3 ) 3 ), cyclopropyl group (—CHCH 2 CH 2 ), a cyanomethyl group (—CH 2 CN) and the like can be mentioned.
  • a methyl group (—CH 3 ), an ethyl group (—CH 2 CH 3 ), a propyl group (—CH 2 CH 2 CH 3 ), and a cyanomethyl group (—CH 2 CN) are preferable.
  • alkyl group having a fluorine atom examples include —CF 3 , —CF 2 H, —CFH 2 , —CF 2 CF 3 , —CH 2 CF 3 , —CH 2 CF 2 H, —CH 2 CFH 2 , —CF 2 CF 2 H, —CF 2 CFH 2 , —CF 2 CH 3 , —CH 2 CF 2 CF 3 , —CH 2 CF 2 CF 2 H, —CH 2 CF 2 CFH 2 , —CH 2 CFHCF 3 , —CH 2 CFHCF 2 H, —CH 2 CFHCFH 2 , —CF 2 CFHCF 3 , —CH (CF 3 ) 2 , —CF (CF 3 ) 2 , —C (CF 3 ) 3 , —CH 2 CF 2 CF 2 CF 3 , —CH 2 CH 2 CF 2 CF 3 and the like.
  • —CH 2 CF 3 , —CH 2 CF 2 H, —CH 2 CFH 2 , —CH 2 CF 2 CF 3 , —CH 2 CF 2 CF 2 H are preferable.
  • the alkyl group a methyl group (—CH 3 ), an ethyl group (—CH 2 CH 3 ), a cyanomethyl group (—CH 2 CN), and —CH 2 CF 3 are particularly preferable.
  • the alkenyl group as R 1 and R 2 is preferably an alkenyl group having 2 to 5 carbon atoms which may have one or more substituents.
  • the alkenyl group preferably has 2 to 4 carbon atoms.
  • Examples of the alkenyl group include an ethenyl group (—CH ⁇ CH 2 ), a 1-propenyl group (—CH ⁇ CH—CH 3 ), a 1-methylethenyl group (—C (CH 3 ) ⁇ CH 2 ), and a 2-propenyl group.
  • alkenyl group may have include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
  • alkenyl group examples include a 2-propenyl group (—CH 2 —CH ⁇ CH 2 ) and a 2-propenyl group (—CH 2 —CH ⁇ CH 2 ) wherein at least one hydrogen atom is a fluorine atom.
  • a substituted group is preferred, and a 2-propenyl group (—CH 2 —CH ⁇ CH 2 ) is more preferred.
  • the alkynyl group as R 1 and R 2 is preferably a C 2-6 alkynyl group optionally having one or more substituents.
  • the alkynyl group preferably has 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms.
  • alkynyl group examples include ethynyl group (—C ⁇ CH), 1-propynyl group (—C ⁇ C—CH 3 ), 2-propynyl group (—CH 2 —C ⁇ CH), 1-butynyl group (—C ⁇ C—CH 2 CH 3 ), 2-butynyl group (—CH 2 —C ⁇ C—CH 3 ), 3-butynyl group (—CH 2 CH 2 —C ⁇ CH), 1-pentynyl group (—C ⁇ C—CH 2 CH 2 CH 3 ), 2-pentynyl group (—CH 2 —C ⁇ C—CH 2 CH 3 ), 3-pentynyl group (—CH 2 CH 2 —C ⁇ C—CH 3 ), 4- Examples thereof include a pentynyl group (—CH 2 CH 2 CH 2 —C ⁇ CH) and a group in which at least one hydrogen atom of these groups is substituted with a substituent.
  • alkynyl group may have examples include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom and a silyl group are preferable, and a fluorine atom is more preferable.
  • alkynyl group examples include a 2-propynyl group (—CH 2 —C ⁇ CH) and a 2-propynyl group (—CH 2 —C ⁇ CH) in which at least one hydrogen atom is a fluorine atom or a silyl group. And a 2-propynyl group (—CH 2 —C ⁇ CH) is more preferable.
  • the aryl group as R 1 and R 2 is preferably an aryl group having 5 to 7 carbon atoms.
  • the aryl group preferably has 5 to 6 carbon atoms.
  • the aryl group preferably contains a 6-membered aromatic hydrocarbon ring or aromatic heterocycle.
  • Examples of the aryl group include a phenyl group, a benzyl group, a tolyl group, and a pyridyl group, and these groups may have one or more substituents.
  • substituents include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
  • a phenyl group, a benzyl group, and a pyridyl group are preferable, and a phenyl group and a pyridyl group are more preferable.
  • R 1 and R 2 may be bonded to each other to form a cyclic structure.
  • R 1 and R 2 are bonded to each other to form a 5-membered or 6-membered heterocyclic ring together with the nitrogen atom in the general formula (1) (the nitrogen atom in the amide bond in the general formula (1)).
  • a hydrogen group is preferred.
  • the heterocycle is preferably a non-aromatic heterocycle.
  • the heterocyclic ring preferably has 3 to 5 carbon atoms, and more preferably 4 to 5 carbon atoms.
  • the hydrocarbon group may contain at least one selected from the group consisting of O, S and N in the structure.
  • hydrocarbon group examples include the pyrrolidine ring, piperidine ring, oxazolidine ring, morpholine ring, thiazolidine ring, 2,5-dihydro-1H-pyrrole ring, pyrrole-2,5-dione together with the nitrogen atom in the general formula (1).
  • groups that form a ring, 4,5-dihydro-1H-imidazole ring, and the like are preferable.
  • a group which forms a pyrrolidine ring, piperidine ring or morpholine ring with the nitrogen atom in (1) is more preferred.
  • R 1 and R 2 are, among others, an alkyl group which may have a fluorine atom, a hydrocarbon which is bonded to each other to form a 5-membered or 6-membered heterocyclic ring together with the nitrogen atom in the general formula (1) Groups are preferred.
  • R 3 is an organic group having 7 or less carbon atoms having a carbon-carbon unsaturated bond.
  • the organic group as R 3 is a group containing at least one carbon-carbon unsaturated bond, and is an atom other than a carbon atom, for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a halogen atom ( A fluorine atom, a chlorine atom, etc.).
  • the carbon-carbon unsaturated bond is preferably a carbon-carbon double bond (—C ⁇ C—) or a carbon-carbon triple bond (—C ⁇ C—).
  • the organic group preferably has 2 to 6 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • Examples of the organic group as R 3 include an alkenyl group, an alkynyl group, and an aryl group, and these groups optionally have one or more substituents.
  • substituents include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
  • the alkenyl group as R 3 is preferably an alkenyl group having 2 to 5 carbon atoms which may have one or more substituents.
  • Examples of the alkenyl group include an ethenyl group (—CH ⁇ CH 2 ), a 1-propenyl group (—CH ⁇ CH—CH 3 ), a 1-methylethenyl group (—C (CH 3 ) ⁇ CH 2 ), and a 2-propenyl group.
  • alkenyl group may have include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
  • the alkenyl group is also preferably an alkenyl group having a fluorine atom.
  • the alkenyl group having a fluorine atom include an ethenyl group (—CH ⁇ CH 2 ), a 1-propenyl group (—CH ⁇ CH—CH 3 ), a 1-methylethenyl group (—C (CH 3 ) ⁇ CH 2 ), 2-propenyl group (allyl group, —CH 2 —CH ⁇ CH 2 ), 1-butenyl group (—CH ⁇ CH—CH 2 CH 3 ), 2-methyl-1-propenyl group (—CH ⁇ C (CH 3 ) —CH 3 ), 1-methyl-1-propenyl group (—C (CH 3 ) ⁇ CH—CH 3 ), 1-ethylethenyl group (—C (CH 2 CH 3 ) ⁇ CH 2 ), 2-butenyl group (—CH 2 —CH ⁇ CH—CH 3 ), 2-methyl-2-propenyl group (—CH 2 —C (CH
  • alkenyl groups those containing one carbon-carbon double bond are preferable.
  • the alkynyl group as R 3 is preferably a C 2-6 alkynyl group which may have one or more substituents.
  • Examples of the alkynyl group include an ethynyl group (—C ⁇ CH), a 1-propynyl group (—C ⁇ C—CH 3 ), a 2-propynyl group (propargyl group, —CH 2 —C ⁇ CH), and a 1-butynyl group.
  • alkynyl group may have examples include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom and a silyl group are preferable, and a fluorine atom is more preferable.
  • the alkynyl group is also preferably an alkynyl group having a fluorine atom.
  • alkynyl group having a fluorine atom examples include ethynyl group (—C ⁇ CH), 1-propynyl group (—C ⁇ C—CH 3 ), 2-propynyl group (—CH 2 —C ⁇ CH), 1-butynyl.
  • alkynyl groups those containing one carbon-carbon triple bond are preferable, Ethynyl group (—C ⁇ CH), 1-propynyl group (—C ⁇ C—CH 3 ), 2-propynyl group (—CH 2 —C ⁇ CH), 1-butynyl group (—C ⁇ C—CH 2 CH 3 ), 2-butynyl group (—CH 2 —C ⁇ C—CH 3 ), 2-pentynyl group (—CH 2 —C ⁇ C—CH 2 CH 3 ), and at least one hydrogen atom in these groups Is more preferably a group substituted by a fluorine atom or a silyl group, -C ⁇ C-TMS, -C ⁇ C-F, 1-propynyl group (-C ⁇ C-CH 3 ), -C ⁇ C-CF 3 , 2-propynyl group (-CH 2 -C ⁇ CH), A group in which at least one hydrogen atom is substituted with a fluorine atom or
  • the aryl group as R 3 is preferably an aryl group having 6 to 7 carbon atoms.
  • the aryl group preferably contains a 6-membered aromatic hydrocarbon ring.
  • aryl group examples include a phenyl group, a benzyl group, and a tolyl group, and these groups optionally have one or more substituents.
  • substituents include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
  • aryl groups a phenyl group and a benzyl group are preferable.
  • R 3 preferably contains one carbon-carbon double bond or one carbon-carbon triple bond, or an alkenyl group having 2 to 6 carbon atoms containing one carbon-carbon double bond, or a carbon-carbon triple bond. It is more preferably an alkynyl group having 2 to 6 carbon atoms containing one of them, more preferably a 2-propenyl group or a 2-propynyl group.
  • the compound represented by a following formula can be illustrated, for example.
  • the illustration of the compound in this specification shall also include the geometric isomer (when it exists) of the said compound, and is not limited to the specific example described.
  • a compound represented by the following formula is particularly preferable.
  • the production method of the present disclosure includes the following general formula (A): (Wherein R 3 is the same as described above. X is a halogen atom) and the following general formula (B): (In the formula, R 1 and R 2 are the same as above.)
  • a step (1) of obtaining compound (1) by reacting with amine (B) represented by the formula (1) is included.
  • amine (B) represented by the formula (1) may polymerize during the reaction.
  • a transesterification method is also conceivable as another method for synthesizing the compound (1).
  • a diamine compound may be formed (for example, the mechanism is described by Testa, Maria Luisa; Zaballos,von; Zaragoza).
  • the production method of the present disclosure includes the step (1), and surprisingly, there are few by-products such as a diamine body, the polymerization reaction due to the unsaturated bond hardly occurs, and high purity (for example, GC purity 95). 0.0% or more) of compound (1) can be produced.
  • X is a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom and a chlorine atom are preferable.
  • R 3 in the general formula (A) and R 1 and R 2 in the general formula (B) are as described for the general formula (1).
  • step (1) 1.0 to 1.5 mol of amine (B) is preferably used relative to 1 mol of compound (A), more preferably 1.0 to 1.2 mol. preferable.
  • the reaction in step (1) is preferably carried out in the presence of a base (excluding amine (B)).
  • a base excluding amine (B)
  • An amine however, except amine (B)), an inorganic base, etc. are mentioned.
  • the amine include tertiary amines and pyridines (pyridine and derivatives thereof).
  • DBU 1,8-diazabicyclo [5.4.0] -7-undecene
  • DBU 5-diazabicyclo [4.3.0] -5-nonene
  • Examples of the inorganic base include lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, cesium carbonate, cesium bicarbonate, and hydrogen carbonate.
  • Examples thereof include lithium, cesium fluoride, potassium fluoride, sodium fluoride, lithium chloride, and lithium bromide.
  • the above amine is preferable, at least one selected from the group consisting of tertiary amines and pyridines is more preferable, and at least one selected from the group consisting of triethylamine and pyridine is more preferable. .
  • the base is preferably used in an amount of 1.0 to 1.5 mol, more preferably 1.0 to 1.2 mol, per 1 mol of compound (A).
  • the reaction of step (1) can be carried out in a solvent.
  • the solvent is preferably an organic solvent, and examples thereof include non-aromatic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, nitrile solvents, sulfoxide solvents, and amide solvents. It is done.
  • non-aromatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, n-decane, isododecane and tridecane; benzene, toluene, xylene, tetralin, veratrol, diethylbenzene, methylnaphthalene, Aromatic hydrocarbon solvents such as nitrobenzene, o-nitrotoluene, mesitylene, indene, diphenyl sulfide; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, propiophenone, diisobutyl ketone, isophorone; dichloromethane, carbon tetrachloride, chloroform Halogenated hydrocarbon solvents such as chlorobenzene; dieth, chlor
  • the reaction temperature in step (1) is preferably ⁇ 78 to 25 ° C., more preferably ⁇ 20 to 10 ° C.
  • the reaction time in step (1) is preferably 0.5 to 24 hours, and more preferably 0.5 to 3 hours.
  • the above production method has the following general formula (C): (Wherein X is the same as above) and the following general formula (D): R 3 —OH (Wherein R 3 is the same as above), by reacting with the compound (D) represented by the formula (A), the step (2) of obtaining the compound (A) represented by the general formula (A) Further, it may be included.
  • step (2) can be carried out under known conditions.
  • the compound (A) obtained in the step (2) can be used for the reaction in the step (1).
  • the product after completion of each step, the product may be separated and purified by distilling off the solvent, distillation, column chromatography, recrystallization or the like.
  • Compound (1) is a novel compound and can be suitably used as various chemicals such as medical and agrochemical compounds, and intermediates thereof.
  • Example 1 ⁇ Synthesis of 2-propynyl (diethylcarbamoyl) fomate> 2-propynyl (chlorocarbonyl) fomate (1.47 g, 10 mmol) and 5 ml of dichloromethane were mixed and purged with nitrogen, and then diethylamine (0.73 g, 10 mmol) was added dropwise at 0 ° C. A solution obtained by mixing pyridine (0.87 g, 11 mmol) and 5 ml of dichloromethane was added dropwise to the solution. Then, it returned to room temperature and stirred. Celite filtration, washing with 1M aqueous hydrochloric acid solution, and liquid separation, followed by water washing and separation operation twice with water. The organic layer was dried and concentrated to obtain 1.20 g (GC purity: 98.3%) of the target compound represented by the following formula.
  • Example 2 ⁇ Synthesis of allyl (diethylcarbamoyl) formate> The synthesis was carried out with the same amount of substance as in Example 1 except that allyl (chlorocarbonyl) fomate was used instead of 2-propynyl (chlorocarbonyl) fomate, and 1.21 g of the desired product represented by the following formula (GC purity 96 .2%).
  • Example 3 Synthesis of 2-propynyl-2-morpholino-2-oxoacetate> The synthesis was carried out in the same amount of substance as in Example 1 except that morpholine was used instead of diethylamine to obtain 1.11 g (GC purity 98.0%) of the target compound represented by the following formula.
  • Example 4 Synthesis of 3- (trimethylsilyl) -2-propynyl (diethylcarbamoyl) fomate> Synthesis was carried out with the same amount of substance as in Example 1 except that 3- (trimethylsilyl) -2-propynyl (chlorocarbonyl) fomate was used instead of 2-propynyl (chlorocarbonyl) fomate. 1.30 g (GC purity 97.3%) was obtained.
  • Example 5 Synthesis of 2-propynyl (diallylcarbamoyl) fomate> The synthesis was performed with the same amount of substance as in Example 1 except that diallylamine was used in place of diethylamine to obtain 1.21 g of the target product represented by the following formula (GC purity 96.2%).
  • Example 6 Synthesis of 2-propynyl (di (2-propynyl) carbamoyl) fomate> The synthesis was carried out with the same amount of substance as in Example 1 except that di (2-propynyl) amine was used instead of diethylamine to obtain 1.09 g (GC purity 95.8%) of the target compound represented by the following formula. It was.
  • Example 7 Synthesis of 2-fluoroallyl (diallylcarbamoyl) fomate> The synthesis was carried out with the same amount of substance as in Example 5 except that 2-fluoroallyl (chlorocarbonyl) fomate was used instead of 2-propynyl (chlorocarbonyl) fomate, and 1.28 g of the desired product represented by the following formula ( GC purity 97.2%) was obtained.
  • Example 8 ⁇ Synthesis of allyl (diallylcarbamoyl) formate> The synthesis was carried out with the same amount of substance as in Example 5 except that allyl (chlorocarbonyl) fomate was used instead of 2-propynyl (chlorocarbonyl) fomate, and 1.20 g of the target compound represented by the following formula (GC purity 96 8%).
  • Example 9 ⁇ Synthesis of allyl (bis (2,2,2-trifluoroethyl) carbamoyl) fomate> The synthesis was carried out with the same amount of substance as in Example 2 except that bis (2,2,2-trifluoroethyl) amine was used instead of diallylamine, and 1.39 g of the desired product represented by the following formula (GC purity 96 8%).
  • Example 10 Synthesis of 2-fluoroallyl (diethylcarbamoyl) fomate> Synthesis was carried out with the same amount of substance as in Example 1 except that 2-fluoroallyl (chlorocarbonyl) fomate was used instead of 2-propynyl (chlorocarbonyl) fomate, and 1.22 g of the target compound represented by the following formula ( GC purity 96.8%) was obtained.
  • the compounds of the present disclosure can be used as various chemicals such as medical and agrochemical compounds, and intermediates thereof.

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Abstract

Provided is a novel production method for a compound. This production method for a compound (1) represented by the following general formula (1) (in the formula, R1 and R2 are independent of each other and are a fluorine atom or an organic group having a carbon number of 6 or less, and may be bonded to each other to form a cyclic structure. R3 is an organic group having a carbon number of 7 or less and a carbon-carbon unsaturated bond.), wherein said production method is characterized by comprising a step (1) for reacting a compound (A) represented by the following general formula (A) (in the formula, R3 is the same as previously described. X is a halogen atom.) and an amine (B) represented by the following general formula (B) (in the formula, R1 and R2 are the same as previously described.) to obtain the compound (1).

Description

化合物の製造方法及び化合物Method for producing compound and compound
本開示は、化合物の製造方法及び化合物に関する。 The present disclosure relates to methods for producing compounds and compounds.
特許文献１には、下記式で表される反応等が記載されている。
Figure JPOXMLDOC01-appb-C000005
 Patent Document 1 describes a reaction represented by the following formula.
Figure JPOXMLDOC01-appb-C000005
欧州特許出願公開第２９４００１０号明細書European Patent Application No. 294,010
本開示は、新規な化合物の製造方法及び新規な化合物を提供することを目的とする。 An object of the present disclosure is to provide a method for producing a novel compound and a novel compound.
本開示は、下記一般式（１）：
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ１及びＲ２は、互いに独立に、フッ素原子又は炭素数６以下の有機基であり、互いに結合して環状構造を形成してもよい。Ｒ３は、炭素－炭素不飽和結合を有する炭素数７以下の有機基である。）で表される化合物（１）を製造する方法であって、
下記一般式（Ａ）：
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｒ３は、前記と同じである。Ｘは、ハロゲン原子である。）で表される化合物（Ａ）と、下記一般式（Ｂ）：
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ１及びＲ２は、前記と同じである。）で表されるアミン（Ｂ）とを反応させることにより、化合物（１）を得る工程（１）を含むことを特徴とする製造方法に関する。 The present disclosure provides the following general formula (1):
Figure JPOXMLDOC01-appb-C000006
 (Wherein R 1 and R 2 are each independently a fluorine atom or an organic group having 6 or less carbon atoms, and may be bonded to each other to form a cyclic structure. R 3 is carbon-carbon unsaturated. Which is an organic group having 7 or less carbon atoms having a bond).
The following general formula (A):
Figure JPOXMLDOC01-appb-C000007
 (Wherein R 3 is the same as described above, X is a halogen atom), and the following general formula (B):
Figure JPOXMLDOC01-appb-C000008
 (Wherein R 1 and R 2 are the same as described above), which comprises reacting with the amine (B) represented by the step (1) to obtain the compound (1). It relates to a manufacturing method.
工程（１）の反応を、塩基（但し、アミン（Ｂ）を除く）の存在下に実施することが好ましい。 The reaction of step (1) is preferably carried out in the presence of a base (excluding amine (B)).
Ｒ３は、炭素－炭素二重結合又は炭素－炭素三重結合を１つ含むことが好ましい。 R 3 preferably contains one carbon-carbon double bond or one carbon-carbon triple bond.
Ｒ３は、２－プロペニル基又は２－プロピニル基であることが好ましい。 R 3 is preferably a 2-propenyl group or a 2-propynyl group.
本開示は、下記一般式（１）：
Figure JPOXMLDOC01-appb-C000009
 （式中、Ｒ１及びＲ２は、互いに独立に、フッ素原子又は炭素数６以下の有機基であり、互いに結合して環状構造を形成してもよい。Ｒ３は、炭素－炭素不飽和結合を有する炭素数７以下の有機基である。）で表されることを特徴とする化合物にも関する。 The present disclosure provides the following general formula (1):
Figure JPOXMLDOC01-appb-C000009
 (Wherein R 1 and R 2 are each independently a fluorine atom or an organic group having 6 or less carbon atoms, and may be bonded to each other to form a cyclic structure. R 3 is carbon-carbon unsaturated. And an organic group having 7 or less carbon atoms having a bond).
本開示によれば、新規な化合物の製造方法及び新規な化合物を提供することができる。 According to the present disclosure, a method for producing a novel compound and a novel compound can be provided.
以下、本開示を具体的に説明する。 Hereinafter, the present disclosure will be specifically described.
本開示の製造方法では、下記一般式（１）：
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ１及びＲ２は、互いに独立に、フッ素原子又は炭素数６以下の有機基であり、互いに結合して環状構造を形成してもよい。Ｒ３は、炭素－炭素不飽和結合を有する炭素数７以下の有機基である。）で表される化合物（１）を製造する。
化合物（１）は新規化合物であり、本開示は化合物（１）にも関する。 In the production method of the present disclosure, the following general formula (1):
Figure JPOXMLDOC01-appb-C000010
 (Wherein R 1 and R 2 are each independently a fluorine atom or an organic group having 6 or less carbon atoms, and may be bonded to each other to form a cyclic structure. R 3 is carbon-carbon unsaturated. A compound (1) represented by the formula (1) is an organic group having 7 or less carbon atoms having a bond.
Compound (1) is a novel compound and the present disclosure also relates to compound (1).
一般式（１）中、Ｒ１及びＲ２は、互いに独立に、フッ素原子又は炭素数６以下の有機基である。
Ｒ１及びＲ２としての上記有機基は、少なくとも１個の炭素原子を含む基であり、炭素原子以外の原子、例えば、水素原子、酸素原子、窒素原子、硫黄原子、ケイ素原子、ハロゲン原子（フッ素原子、塩素原子等）等を更に有していてもよい。
上記有機基の炭素数は、１～６であることが好ましく、１～５であることがより好ましく、１～３であることが更に好ましい。 In General Formula (1), R 1 and R 2 are each independently a fluorine atom or an organic group having 6 or less carbon atoms.
The organic group as R 1 and R 2 is a group containing at least one carbon atom, and is an atom other than a carbon atom, for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a halogen atom ( A fluorine atom, a chlorine atom, etc.).
The organic group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.
Ｒ１及びＲ２としての上記有機基としては、アルキル基、アルケニル基、アルキニル基、アリール基等が挙げられ、これらの基は１つ以上の置換基を有していてもよい。
上記置換基としては、ハロゲン原子、アルキル基、フッ素化アルキル基、ヘテロ原子を含む基等が挙げられ、ハロゲン原子が好ましく、フッ素原子がより好ましい。 Examples of the organic group as R 1 and R 2 include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, and these groups may have one or more substituents.
Examples of the substituent include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
Ｒ１及びＲ２としての上記アルキル基は、炭素数が１～６であることが好ましく、１～５であることがより好ましく、１～３であることが更に好ましい。
上記アルキル基は、フッ素原子を有していてもよく、シアノ基等のヘテロ原子を含む基を有していてもよい。また、上記アルキル基はシクロアルキル基であってもよい。
フッ素原子を有しないアルキル基としては、メチル基（－ＣＨ３）、エチル基（－ＣＨ２ＣＨ３）、プロピル基（－ＣＨ２ＣＨ２ＣＨ３）、イソプロピル基（－ＣＨ（ＣＨ３）２）、ブチル基（－ＣＨ２ＣＨ２ＣＨ２ＣＨ３）、ｓｅｃ－ブチル基（－ＣＨ（ＣＨ３）ＣＨ２ＣＨ３）、ｔｅｒｔ－ブチル基（－Ｃ（ＣＨ３）３）、シクロプロピル基（－ＣＨＣＨ２ＣＨ２）、シアノメチル基（－ＣＨ２ＣＮ）等が挙げられる。なかでも、メチル基（－ＣＨ３）、エチル基（－ＣＨ２ＣＨ３）、プロピル基（－ＣＨ２ＣＨ２ＣＨ３）、シアノメチル基（－ＣＨ２ＣＮ）が好ましい。
フッ素原子を有するアルキル基（フッ素化アルキル基）としては、－ＣＦ３、－ＣＦ２Ｈ、－ＣＦＨ２、－ＣＦ２ＣＦ３、－ＣＨ２ＣＦ３、－ＣＨ２ＣＦ２Ｈ、－ＣＨ２ＣＦＨ２、－ＣＦ２ＣＦ２Ｈ、－ＣＦ２ＣＦＨ２、－ＣＦ２ＣＨ３、－ＣＨ２ＣＦ２ＣＦ３、－ＣＨ２ＣＦ２ＣＦ２Ｈ、－ＣＨ２ＣＦ２ＣＦＨ２、－ＣＨ２ＣＦＨＣＦ３、－ＣＨ２ＣＦＨＣＦ２Ｈ、－ＣＨ２ＣＦＨＣＦＨ２、－ＣＦ２ＣＦＨＣＦ３、－ＣＨ（ＣＦ３）２、－ＣＦ（ＣＦ３）２、－Ｃ（ＣＦ３）３、－ＣＨ２ＣＦ２ＣＦ２ＣＦ３、－ＣＨ２ＣＨ２ＣＦ２ＣＦ３等が挙げられる。なかでも、－ＣＨ２ＣＦ３、－ＣＨ２ＣＦ２Ｈ、－ＣＨ２ＣＦＨ２、－ＣＨ２ＣＦ２ＣＦ３、－ＣＨ２ＣＦ２ＣＦ２Ｈが好ましい。
上記アルキル基としては、メチル基（－ＣＨ３）、エチル基（－ＣＨ２ＣＨ３）、シアノメチル基（－ＣＨ２ＣＮ）、－ＣＨ２ＣＦ３が特に好ましい。 The alkyl group as R 1 and R 2 preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.
The alkyl group may have a fluorine atom or a group containing a hetero atom such as a cyano group. The alkyl group may be a cycloalkyl group.
Examples of the alkyl group having no fluorine atom include a methyl group (—CH 3 ), an ethyl group (—CH 2 CH 3 ), a propyl group (—CH 2 CH 2 CH 3 ), and an isopropyl group (—CH (CH 3 ) 2. ), Butyl group (—CH 2 CH 2 CH 2 CH 3 ), sec-butyl group (—CH (CH 3 ) CH 2 CH 3 ), tert-butyl group (—C (CH 3 ) 3 ), cyclopropyl group (—CHCH 2 CH 2 ), a cyanomethyl group (—CH 2 CN) and the like can be mentioned. Of these, a methyl group (—CH 3 ), an ethyl group (—CH 2 CH 3 ), a propyl group (—CH 2 CH 2 CH 3 ), and a cyanomethyl group (—CH 2 CN) are preferable.
Examples of the alkyl group having a fluorine atom (fluorinated alkyl group) include —CF 3 , —CF 2 H, —CFH 2 , —CF 2 CF 3 , —CH 2 CF 3 , —CH 2 CF 2 H, —CH 2 CFH 2 , —CF 2 CF 2 H, —CF 2 CFH 2 , —CF 2 CH 3 , —CH 2 CF 2 CF 3 , —CH 2 CF 2 CF 2 H, —CH 2 CF 2 CFH 2 , —CH 2 CFHCF 3 , —CH 2 CFHCF 2 H, —CH 2 CFHCFH 2 , —CF 2 CFHCF 3 , —CH (CF 3 ) 2 , —CF (CF 3 ) 2 , —C (CF 3 ) 3 , —CH 2 CF 2 CF 2 CF 3 , —CH 2 CH 2 CF 2 CF 3 and the like. Of these, —CH 2 CF 3 , —CH 2 CF 2 H, —CH 2 CFH 2 , —CH 2 CF 2 CF 3 , —CH 2 CF 2 CF 2 H are preferable.
As the alkyl group, a methyl group (—CH 3 ), an ethyl group (—CH 2 CH 3 ), a cyanomethyl group (—CH 2 CN), and —CH 2 CF 3 are particularly preferable.
Ｒ１及びＲ２としての上記アルケニル基としては、１つ以上の置換基を有していてもよい炭素数２～５のアルケニル基が好ましい。上記アルケニル基の炭素数は、２～４であることが好ましい。
上記アルケニル基としては、エテニル基（－ＣＨ＝ＣＨ２）、１－プロペニル基（－ＣＨ＝ＣＨ－ＣＨ３）、１－メチルエテニル基（－Ｃ（ＣＨ３）＝ＣＨ２）、２－プロペニル基（アリル基、－ＣＨ２－ＣＨ＝ＣＨ２）、１－ブテニル基（－ＣＨ＝ＣＨ－ＣＨ２ＣＨ３）、２－メチル－１－プロペニル基（－ＣＨ＝Ｃ（ＣＨ３）－ＣＨ３）、１－メチル－１－プロペニル基（－Ｃ（ＣＨ３）＝ＣＨ－ＣＨ３）、１－エチルエテニル基（－Ｃ（ＣＨ２ＣＨ３）＝ＣＨ２）、２－ブテニル基（－ＣＨ２－ＣＨ＝ＣＨ－ＣＨ３）、２－メチル－２－プロペニル基（－ＣＨ２－Ｃ（ＣＨ３）＝ＣＨ２）、１－メチル－２－プロペニル基（－ＣＨ（ＣＨ３）－ＣＨ＝ＣＨ２）、３－ブテニル基（－ＣＨ２ＣＨ２－ＣＨ＝ＣＨ２）、１－メチレン－２－プロペニル基（－Ｃ（＝ＣＨ２）－ＣＨ＝ＣＨ２）、１，３－ブタジエニル基（－ＣＨ＝ＣＨ－ＣＨ＝ＣＨ２）、２，３－ブタジエニル基（－ＣＨ２－ＣＨ＝Ｃ＝ＣＨ２）、１－メチル－１，２－プロパジエニル基（－Ｃ（ＣＨ３）＝Ｃ＝ＣＨ２）、１，２－ブタジエニル基（－ＣＨ＝Ｃ＝ＣＨ－ＣＨ３）、２－ペンテニル基（－ＣＨ２－ＣＨ＝ＣＨ－ＣＨ２ＣＨ３）、及び、これらの基の少なくとも１つの水素原子が置換基により置換された基が挙げられる。 The alkenyl group as R 1 and R 2 is preferably an alkenyl group having 2 to 5 carbon atoms which may have one or more substituents. The alkenyl group preferably has 2 to 4 carbon atoms.
Examples of the alkenyl group include an ethenyl group (—CH═CH 2 ), a 1-propenyl group (—CH═CH—CH 3 ), a 1-methylethenyl group (—C (CH 3 ) ═CH 2 ), and a 2-propenyl group. (Allyl group, —CH 2 —CH═CH 2 ), 1-butenyl group (—CH═CH—CH 2 CH 3 ), 2-methyl-1-propenyl group (—CH═C (CH 3 ) —CH 3 ), 1-methyl-1-propenyl group (—C (CH 3 ) ═CH—CH 3 ), 1-ethylethenyl group (—C (CH 2 CH 3 ) ═CH 2 ), 2-butenyl group (—CH 2 -CH = CH-CH 3 ), 2-methyl-2-propenyl group (-CH 2 -C (CH 3 ) = CH 2 ), 1-methyl-2-propenyl group (-CH (CH 3 ) -CH = CH 2), 3- butenyl group (-CH 2 CH 2 -C = CH 2), 1- methylene-2-propenyl group (-C (= CH 2) -CH = CH 2), 1,3- butadienyl group (-CH = CH-CH = CH 2), 2,3- Butadienyl group (—CH 2 —CH═C═CH 2 ), 1-methyl-1,2-propadienyl group (—C (CH 3 ) ═C═CH 2 ), 1,2-butadienyl group (—CH═C ═CH—CH 3 ), 2-pentenyl group (—CH 2 —CH═CH—CH 2 CH 3 ), and groups in which at least one hydrogen atom of these groups is substituted with a substituent.
上記アルケニル基が有してもよい上記置換基としては、ハロゲン原子、アルキル基、フッ素化アルキル基、ヘテロ原子を含む基等が挙げられ、ハロゲン原子が好ましく、フッ素原子がより好ましい。 Examples of the substituent that the alkenyl group may have include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
上記アルケニル基としては、なかでも、２－プロペニル基（－ＣＨ２－ＣＨ＝ＣＨ２）、及び、２－プロペニル基（－ＣＨ２－ＣＨ＝ＣＨ２）において少なくとも１つの水素原子がフッ素原子により置換された基が好ましく、２－プロペニル基（－ＣＨ２－ＣＨ＝ＣＨ２）がより好ましい。 Examples of the alkenyl group include a 2-propenyl group (—CH 2 —CH═CH 2 ) and a 2-propenyl group (—CH 2 —CH═CH 2 ) wherein at least one hydrogen atom is a fluorine atom. A substituted group is preferred, and a 2-propenyl group (—CH 2 —CH═CH 2 ) is more preferred.
Ｒ１及びＲ２としての上記アルキニル基としては、１つ以上の置換基を有していてもよい炭素数２～６のアルキニル基が好ましい。上記アルキニル基の炭素数は、２～５であることが好ましく、２～４であることがより好ましい。
上記アルキニル基としては、エチニル基（－Ｃ≡ＣＨ）、１－プロピニル基（－Ｃ≡Ｃ－ＣＨ３）、２－プロピニル基（－ＣＨ２－Ｃ≡ＣＨ）、１－ブチニル基（－Ｃ≡Ｃ－ＣＨ２ＣＨ３）、２－ブチニル基（－ＣＨ２－Ｃ≡Ｃ－ＣＨ３）、３－ブチニル基（－ＣＨ２ＣＨ２－Ｃ≡ＣＨ）、１－ペンチニル基（－Ｃ≡Ｃ－ＣＨ２ＣＨ２ＣＨ３）、２－ペンチニル基（－ＣＨ２－Ｃ≡Ｃ－ＣＨ２ＣＨ３）、３－ペンチニル基（－ＣＨ２ＣＨ２－Ｃ≡Ｃ－ＣＨ３）、４－ペンチニル基（－ＣＨ２ＣＨ２ＣＨ２－Ｃ≡ＣＨ）、及び、これらの基の少なくとも１つの水素原子が置換基により置換された基が挙げられる。 The alkynyl group as R 1 and R 2 is preferably a C 2-6 alkynyl group optionally having one or more substituents. The alkynyl group preferably has 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms.
Examples of the alkynyl group include ethynyl group (—C≡CH), 1-propynyl group (—C≡C—CH 3 ), 2-propynyl group (—CH 2 —C≡CH), 1-butynyl group (—C ≡C—CH 2 CH 3 ), 2-butynyl group (—CH 2 —C≡C—CH 3 ), 3-butynyl group (—CH 2 CH 2 —C≡CH), 1-pentynyl group (—C≡ C—CH 2 CH 2 CH 3 ), 2-pentynyl group (—CH 2 —C≡C—CH 2 CH 3 ), 3-pentynyl group (—CH 2 CH 2 —C≡C—CH 3 ), 4- Examples thereof include a pentynyl group (—CH 2 CH 2 CH 2 —C≡CH) and a group in which at least one hydrogen atom of these groups is substituted with a substituent.
上記アルキニル基が有してもよい上記置換基としては、ハロゲン原子、アルキル基、フッ素化アルキル基、ヘテロ原子を含む基等が挙げられ、ハロゲン原子、シリル基が好ましく、フッ素原子がより好ましい。 Examples of the substituent that the alkynyl group may have include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom and a silyl group are preferable, and a fluorine atom is more preferable.
上記アルキニル基としては、なかでも、２－プロピニル基（－ＣＨ２－Ｃ≡ＣＨ）、及び、２－プロピニル基（－ＣＨ２－Ｃ≡ＣＨ）において少なくとも１つの水素原子がフッ素原子又はシリル基により置換された基が好ましく、２－プロピニル基（－ＣＨ２－Ｃ≡ＣＨ）がより好ましい。 Examples of the alkynyl group include a 2-propynyl group (—CH 2 —C≡CH) and a 2-propynyl group (—CH 2 —C≡CH) in which at least one hydrogen atom is a fluorine atom or a silyl group. And a 2-propynyl group (—CH 2 —C≡CH) is more preferable.
Ｒ１及びＲ２としての上記アリール基としては、炭素数５～７のアリール基が好ましい。上記アリール基の炭素数は、５～６であることが好ましい。
上記アリール基は、６員の芳香族炭化水素環又は芳香族複素環を含むことが好ましい。 The aryl group as R 1 and R 2 is preferably an aryl group having 5 to 7 carbon atoms. The aryl group preferably has 5 to 6 carbon atoms.
The aryl group preferably contains a 6-membered aromatic hydrocarbon ring or aromatic heterocycle.
上記アリール基としては、フェニル基、ベンジル基、トリル基、ピリジル基等が挙げられ、これらの基は１つ以上の置換基を有していてもよい。
上記置換基としては、ハロゲン原子、アルキル基、フッ素化アルキル基、ヘテロ原子を含む基等が挙げられ、ハロゲン原子が好ましく、フッ素原子がより好ましい。
上記アリール基としては、なかでも、フェニル基、ベンジル基、ピリジル基が好ましく、フェニル基、ピリジル基がより好ましい。 Examples of the aryl group include a phenyl group, a benzyl group, a tolyl group, and a pyridyl group, and these groups may have one or more substituents.
Examples of the substituent include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
Among them, a phenyl group, a benzyl group, and a pyridyl group are preferable, and a phenyl group and a pyridyl group are more preferable.
Ｒ１及びＲ２は、互いに結合して環状構造を形成してもよい。この場合、Ｒ１及びＲ２は、互いに結合して一般式（１）中の窒素原子（一般式（１）におけるアミド結合中の窒素原子）とともに５員又は６員の複素環を形成する炭化水素基であることが好ましい。上記複素環は、非芳香族複素環であることが好ましい。また、上記複素環は、炭素数が３～５であることが好ましく、４～５であることがより好ましい。
上記炭化水素基は、構造中にＯ、Ｓ及びＮからなる群より選択される少なくとも１種を含んでいてもよい。 R 1 and R 2 may be bonded to each other to form a cyclic structure. In this case, R 1 and R 2 are bonded to each other to form a 5-membered or 6-membered heterocyclic ring together with the nitrogen atom in the general formula (1) (the nitrogen atom in the amide bond in the general formula (1)). A hydrogen group is preferred. The heterocycle is preferably a non-aromatic heterocycle. The heterocyclic ring preferably has 3 to 5 carbon atoms, and more preferably 4 to 5 carbon atoms.
The hydrocarbon group may contain at least one selected from the group consisting of O, S and N in the structure.
上記炭化水素基としては、一般式（１）中の窒素原子とともにピロリジン環、ピペリジン環、オキサゾリジン環、モルホリン環、チアゾリジン環、２，５－ジヒドロ－１Ｈ－ピロール環、ピロール－２，５－ジオン環、４，５－ジヒドロ－１Ｈ－イミダゾール環等を形成する基が挙げられる。
なかでも、一般式（１）中の窒素原子とともにピロリジン環、ピペリジン環、モルホリン環、２，５－ジヒドロ－１Ｈ－ピロール環又はピロール－２，５－ジオン環を形成する基が好ましく、一般式（１）中の窒素原子とともにピロリジン環、ピペリジン環又はモルホリン環を形成する基がより好ましい。 Examples of the hydrocarbon group include the pyrrolidine ring, piperidine ring, oxazolidine ring, morpholine ring, thiazolidine ring, 2,5-dihydro-1H-pyrrole ring, pyrrole-2,5-dione together with the nitrogen atom in the general formula (1). And groups that form a ring, 4,5-dihydro-1H-imidazole ring, and the like.
Of these, a group which forms a pyrrolidine ring, piperidine ring, morpholine ring, 2,5-dihydro-1H-pyrrole ring or pyrrole-2,5-dione ring together with the nitrogen atom in the general formula (1) is preferable. A group which forms a pyrrolidine ring, piperidine ring or morpholine ring with the nitrogen atom in (1) is more preferred.
Ｒ１及びＲ２としては、なかでも、フッ素原子を有していてもよいアルキル基、互いに結合して一般式（１）中の窒素原子とともに５員又は６員の複素環を形成する炭化水素基が好ましい。 R 1 and R 2 are, among others, an alkyl group which may have a fluorine atom, a hydrocarbon which is bonded to each other to form a 5-membered or 6-membered heterocyclic ring together with the nitrogen atom in the general formula (1) Groups are preferred.
一般式（１）中、Ｒ３は、炭素－炭素不飽和結合を有する炭素数７以下の有機基である。
Ｒ３としての上記有機基は、少なくとも１つの炭素－炭素不飽和結合を含む基であり、炭素原子以外の原子、例えば、水素原子、酸素原子、窒素原子、硫黄原子、ケイ素原子、ハロゲン原子（フッ素原子、塩素原子等）等を更に有していてもよい。
上記炭素－炭素不飽和結合は、炭素－炭素二重結合（－Ｃ＝Ｃ－）、又は、炭素－炭素三重結合（－Ｃ≡Ｃ－）であることが好ましい。
上記有機基は、炭素数が２～６であることが好ましく、２～５であることがより好ましく、２～４であることが更に好ましい。 In the general formula (1), R 3 is an organic group having 7 or less carbon atoms having a carbon-carbon unsaturated bond.
The organic group as R 3 is a group containing at least one carbon-carbon unsaturated bond, and is an atom other than a carbon atom, for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a halogen atom ( A fluorine atom, a chlorine atom, etc.).
The carbon-carbon unsaturated bond is preferably a carbon-carbon double bond (—C═C—) or a carbon-carbon triple bond (—C≡C—).
The organic group preferably has 2 to 6 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably 2 to 4 carbon atoms.
Ｒ３としての上記有機基としては、アルケニル基、アルキニル基、アリール基等が挙げられ、これらの基は１つ以上の置換基を有していてもよい。上記置換基としては、ハロゲン原子、アルキル基、フッ素化アルキル基、ヘテロ原子を含む基等が挙げられ、ハロゲン原子が好ましく、フッ素原子がより好ましい。 Examples of the organic group as R 3 include an alkenyl group, an alkynyl group, and an aryl group, and these groups optionally have one or more substituents. Examples of the substituent include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
Ｒ３としての上記アルケニル基としては、１つ以上の置換基を有していてもよい炭素数２～５のアルケニル基が好ましい。
上記アルケニル基としては、エテニル基（－ＣＨ＝ＣＨ２）、１－プロペニル基（－ＣＨ＝ＣＨ－ＣＨ３）、１－メチルエテニル基（－Ｃ（ＣＨ３）＝ＣＨ２）、２－プロペニル基（アリル基、－ＣＨ２－ＣＨ＝ＣＨ２）、１－ブテニル基（－ＣＨ＝ＣＨ－ＣＨ２ＣＨ３）、２－メチル－１－プロペニル基（－ＣＨ＝Ｃ（ＣＨ３）－ＣＨ３）、１－メチル－１－プロペニル基（－Ｃ（ＣＨ３）＝ＣＨ－ＣＨ３）、１－エチルエテニル基（－Ｃ（ＣＨ２ＣＨ３）＝ＣＨ２）、２－ブテニル基（－ＣＨ２－ＣＨ＝ＣＨ－ＣＨ３）、２－メチル－２－プロペニル基（－ＣＨ２－Ｃ（ＣＨ３）＝ＣＨ２）、１－メチル－２－プロペニル基（－ＣＨ（ＣＨ３）－ＣＨ＝ＣＨ２）、３－ブテニル基（－ＣＨ２ＣＨ２－ＣＨ＝ＣＨ２）、１－メチレン－２－プロペニル基（－Ｃ（＝ＣＨ２）－ＣＨ＝ＣＨ２）、１，３－ブタジエニル基（－ＣＨ＝ＣＨ－ＣＨ＝ＣＨ２）、２，３－ブタジエニル基（－ＣＨ２－ＣＨ＝Ｃ＝ＣＨ２）、１－メチル－１，２－プロパジエニル基（－Ｃ（ＣＨ３）＝Ｃ＝ＣＨ２）、１，２－ブタジエニル基（－ＣＨ＝Ｃ＝ＣＨ－ＣＨ３）、２－ペンテニル基（－ＣＨ２－ＣＨ＝ＣＨ－ＣＨ２ＣＨ３）、及び、これらの基の少なくとも１つの水素原子が置換基により置換された基が挙げられる。 The alkenyl group as R 3 is preferably an alkenyl group having 2 to 5 carbon atoms which may have one or more substituents.
Examples of the alkenyl group include an ethenyl group (—CH═CH 2 ), a 1-propenyl group (—CH═CH—CH 3 ), a 1-methylethenyl group (—C (CH 3 ) ═CH 2 ), and a 2-propenyl group. (Allyl group, —CH 2 —CH═CH 2 ), 1-butenyl group (—CH═CH—CH 2 CH 3 ), 2-methyl-1-propenyl group (—CH═C (CH 3 ) —CH 3 ), 1-methyl-1-propenyl group (—C (CH 3 ) ═CH—CH 3 ), 1-ethylethenyl group (—C (CH 2 CH 3 ) ═CH 2 ), 2-butenyl group (—CH 2 -CH = CH-CH 3 ), 2-methyl-2-propenyl group (-CH 2 -C (CH 3 ) = CH 2 ), 1-methyl-2-propenyl group (-CH (CH 3 ) -CH = CH 2), 3- butenyl group (-CH 2 CH 2 -C = CH 2), 1- methylene-2-propenyl group (-C (= CH 2) -CH = CH 2), 1,3- butadienyl group (-CH = CH-CH = CH 2), 2,3- Butadienyl group (—CH 2 —CH═C═CH 2 ), 1-methyl-1,2-propadienyl group (—C (CH 3 ) ═C═CH 2 ), 1,2-butadienyl group (—CH═C ═CH—CH 3 ), 2-pentenyl group (—CH 2 —CH═CH—CH 2 CH 3 ), and groups in which at least one hydrogen atom of these groups is substituted with a substituent.
上記アルケニル基が有してもよい上記置換基としては、ハロゲン原子、アルキル基、フッ素化アルキル基、ヘテロ原子を含む基等が挙げられ、ハロゲン原子が好ましく、フッ素原子がより好ましい。 Examples of the substituent that the alkenyl group may have include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
上記アルケニル基は、フッ素原子を有するアルケニル基であることも好ましい。上記フッ素原子を有するアルケニル基としては、エテニル基（－ＣＨ＝ＣＨ２）、１－プロペニル基（－ＣＨ＝ＣＨ－ＣＨ３）、１－メチルエテニル基（－Ｃ（ＣＨ３）＝ＣＨ２）、２－プロペニル基（アリル基、－ＣＨ２－ＣＨ＝ＣＨ２）、１－ブテニル基（－ＣＨ＝ＣＨ－ＣＨ２ＣＨ３）、２－メチル－１－プロペニル基（－ＣＨ＝Ｃ（ＣＨ３）－ＣＨ３）、１－メチル－１－プロペニル基（－Ｃ（ＣＨ３）＝ＣＨ－ＣＨ３）、１－エチルエテニル基（－Ｃ（ＣＨ２ＣＨ３）＝ＣＨ２）、２－ブテニル基（－ＣＨ２－ＣＨ＝ＣＨ－ＣＨ３）、２－メチル－２－プロペニル基（－ＣＨ２－Ｃ（ＣＨ３）＝ＣＨ２）、１－メチル－２－プロペニル基（－ＣＨ（ＣＨ３）－ＣＨ＝ＣＨ２）、３－ブテニル基（－ＣＨ２ＣＨ２－ＣＨ＝ＣＨ２）、１－メチレン－２－プロペニル基（－Ｃ（＝ＣＨ２）－ＣＨ＝ＣＨ２）、１，３－ブタジエニル基（－ＣＨ＝ＣＨ－ＣＨ＝ＣＨ２）、２，３－ブタジエニル基（－ＣＨ２－ＣＨ＝Ｃ＝ＣＨ２）、１－メチル－１，２－プロパジエニル基（－Ｃ（ＣＨ３）＝Ｃ＝ＣＨ２）、１，２－ブタジエニル基（－ＣＨ＝Ｃ＝ＣＨ－ＣＨ３）及び２－ペンテニル基（－ＣＨ２－ＣＨ＝ＣＨ－ＣＨ２ＣＨ３）において、少なくとも１つの水素原子がフッ素原子により置換された基が挙げられる。 The alkenyl group is also preferably an alkenyl group having a fluorine atom. Examples of the alkenyl group having a fluorine atom include an ethenyl group (—CH═CH 2 ), a 1-propenyl group (—CH═CH—CH 3 ), a 1-methylethenyl group (—C (CH 3 ) ═CH 2 ), 2-propenyl group (allyl group, —CH 2 —CH═CH 2 ), 1-butenyl group (—CH═CH—CH 2 CH 3 ), 2-methyl-1-propenyl group (—CH═C (CH 3 ) —CH 3 ), 1-methyl-1-propenyl group (—C (CH 3 ) ═CH—CH 3 ), 1-ethylethenyl group (—C (CH 2 CH 3 ) ═CH 2 ), 2-butenyl group (—CH 2 —CH═CH—CH 3 ), 2-methyl-2-propenyl group (—CH 2 —C (CH 3 ) ═CH 2 ), 1-methyl-2-propenyl group (—CH (CH 3 ) -CH = CH 2), 3- butenyl group (- H 2 CH 2 -CH = CH 2 ), 1- methylene-2-propenyl group (-C (= CH 2) -CH = CH 2), 1,3- butadienyl group (-CH = CH-CH = CH 2 ), 2,3-butadienyl group (—CH 2 —CH═C═CH 2 ), 1-methyl-1,2-propadienyl group (—C (CH 3 ) ═C═CH 2 ), 1,2-butadienyl Examples of the group (—CH═C═CH—CH 3 ) and the 2-pentenyl group (—CH 2 —CH═CH—CH 2 CH 3 ) include groups in which at least one hydrogen atom is substituted with a fluorine atom.
上記アルケニル基としては、なかでも、炭素－炭素二重結合を１つ含むものが好ましく、
エテニル基（－ＣＨ＝ＣＨ２）、２－プロペニル基（－ＣＨ２－ＣＨ＝ＣＨ２）、２－ブテニル基（－ＣＨ２－ＣＨ＝ＣＨ－ＣＨ３）、３－ブテニル基（－ＣＨ２ＣＨ２－ＣＨ＝ＣＨ２）、並びに、２－プロペニル基（－ＣＨ２－ＣＨ＝ＣＨ２）、２－ブテニル基（－ＣＨ２－ＣＨ＝ＣＨ－ＣＨ３）及び２－ペンテニル基（－ＣＨ２－ＣＨ＝ＣＨ－ＣＨ２ＣＨ３）において少なくとも１つの水素原子がフッ素原子により置換された基がより好ましく、
エテニル基（－ＣＨ＝ＣＨ２）、２－プロペニル基（－ＣＨ２－ＣＨ＝ＣＨ２）、２－ブテニル基（－ＣＨ２－ＣＨ＝ＣＨ－ＣＨ３）、３－ブテニル基（－ＣＨ２ＣＨ２－ＣＨ＝ＣＨ２）、－ＣＨ２－ＣＦ＝ＣＨ２、－ＣＨ２－ＣＦ＝ＣＦ２、－ＣＨ２－ＣＨ＝ＣＦ２、－ＣＨ２－ＣＨ＝ＣＨ－ＣＦ３、－ＣＨ２－ＣＦ＝ＣＦ－ＣＦ３、－ＣＨ２－ＣＨ＝Ｆ－ＣＦ３、及び、－ＣＨ２－ＣＨ＝ＣＨ－ＣＦ２ＣＦ３が更に好ましく、
２－プロペニル基（－ＣＨ２－ＣＨ＝ＣＨ２）、－ＣＨ２－ＣＦ＝ＣＨ２、－ＣＨ２－ＣＨ＝ＣＨ－ＣＦ３、及び、－ＣＨ２－ＣＨ＝ＣＨ－ＣＦ２ＣＦ３が特に好ましく、
２－プロペニル基（－ＣＨ２－ＣＨ＝ＣＨ２）、－ＣＨ２－ＣＦ＝ＣＨ２及び－ＣＨ２－ＣＨ＝ＣＨ－ＣＦ３が最も好ましい。 Among the alkenyl groups, those containing one carbon-carbon double bond are preferable.
Ethenyl group (—CH═CH 2 ), 2-propenyl group (—CH 2 —CH═CH 2 ), 2-butenyl group (—CH 2 —CH═CH—CH 3 ), 3-butenyl group (—CH 2 CH 2 —CH═CH 2 ), and 2-propenyl group (—CH 2 —CH═CH 2 ), 2-butenyl group (—CH 2 —CH═CH—CH 3 ) and 2-pentenyl group (—CH 2 -CH═CH—CH 2 CH 3 ) is more preferably a group in which at least one hydrogen atom is replaced by a fluorine atom,
Ethenyl group (—CH═CH 2 ), 2-propenyl group (—CH 2 —CH═CH 2 ), 2-butenyl group (—CH 2 —CH═CH—CH 3 ), 3-butenyl group (—CH 2 CH 2 -CH = CH 2), - CH 2 -CF = CH 2, -CH 2 -CF = CF 2, -CH 2 -CH = CF 2, -CH 2 -CH = CH-CF 3, -CH 2 —CF═CF—CF 3 , —CH 2 —CH═F—CF 3 , and —CH 2 —CH═CH—CF 2 CF 3 are more preferable,
2-propenyl group (-CH 2 -CH = CH 2) , - CH 2 -CF = CH 2, -CH 2 -CH = CH-CF 3, and, is -CH 2 -CH = CH-CF 2 CF 3 Particularly preferred,
2-propenyl group (-CH 2 -CH = CH 2) , - CH 2 -CF = CH 2 and -CH 2 -CH = CH-CF 3 being most preferred.
Ｒ３としての上記アルキニル基としては、１つ以上の置換基を有していてもよい炭素数２～６のアルキニル基が好ましい。
上記アルキニル基としては、エチニル基（－Ｃ≡ＣＨ）、１－プロピニル基（－Ｃ≡Ｃ－ＣＨ３）、２－プロピニル基（プロパルギル基、－ＣＨ２－Ｃ≡ＣＨ）、１－ブチニル基（－Ｃ≡Ｃ－ＣＨ２ＣＨ３）、２－ブチニル基（－ＣＨ２－Ｃ≡Ｃ－ＣＨ３）、３－ブチニル基（－ＣＨ２ＣＨ２－Ｃ≡ＣＨ）、１－ペンチニル基（－Ｃ≡Ｃ－ＣＨ２ＣＨ２ＣＨ３）、２－ペンチニル基（－ＣＨ２－Ｃ≡Ｃ－ＣＨ２ＣＨ３）、３－ペンチニル基（－ＣＨ２ＣＨ２－Ｃ≡Ｃ－ＣＨ３）、４－ペンチニル基（－ＣＨ２ＣＨ２ＣＨ２－Ｃ≡ＣＨ）、及び、これらの基の少なくとも１つの水素原子が置換基により置換された基が挙げられる。 The alkynyl group as R 3 is preferably a C 2-6 alkynyl group which may have one or more substituents.
Examples of the alkynyl group include an ethynyl group (—C≡CH), a 1-propynyl group (—C≡C—CH 3 ), a 2-propynyl group (propargyl group, —CH 2 —C≡CH), and a 1-butynyl group. (—C≡C—CH 2 CH 3 ), 2-butynyl group (—CH 2 —C≡C—CH 3 ), 3-butynyl group (—CH 2 CH 2 —C≡CH), 1-pentynyl group ( -C≡C-CH 2 CH 2 CH 3 ), 2-pentynyl group (-CH 2 -C≡C-CH 2 CH 3 ), 3-pentynyl group (-CH 2 CH 2 -C≡C-CH 3 ) , A 4-pentynyl group (—CH 2 CH 2 CH 2 —C≡CH), and a group in which at least one hydrogen atom of these groups is substituted with a substituent.
上記アルキニル基が有してもよい上記置換基としては、ハロゲン原子、アルキル基、フッ素化アルキル基、ヘテロ原子を含む基等が挙げられ、ハロゲン原子、シリル基が好ましく、フッ素原子がより好ましい。 Examples of the substituent that the alkynyl group may have include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom and a silyl group are preferable, and a fluorine atom is more preferable.
上記アルキニル基は、フッ素原子を有するアルキニル基であることも好ましい。上記フッ素原子を有するアルキニル基としては、エチニル基（－Ｃ≡ＣＨ）、１－プロピニル基（－Ｃ≡Ｃ－ＣＨ３）、２－プロピニル基（－ＣＨ２－Ｃ≡ＣＨ）、１－ブチニル基（－Ｃ≡Ｃ－ＣＨ２ＣＨ３）、２－ブチニル基（－ＣＨ２－Ｃ≡Ｃ－ＣＨ３）、３－ブチニル基（－ＣＨ２ＣＨ２－Ｃ≡ＣＨ）、１－ペンチニル基（－Ｃ≡Ｃ－ＣＨ２ＣＨ２ＣＨ３）、２－ペンチニル基（－ＣＨ２－Ｃ≡Ｃ－ＣＨ２ＣＨ３）、３－ペンチニル基（－ＣＨ２ＣＨ２－Ｃ≡Ｃ－ＣＨ３）及び４－ペンチニル基（－ＣＨ２ＣＨ２ＣＨ２－Ｃ≡ＣＨ）において、少なくとも１つの水素原子がフッ素原子により置換された基が挙げられる。 The alkynyl group is also preferably an alkynyl group having a fluorine atom. Examples of the alkynyl group having a fluorine atom include ethynyl group (—C≡CH), 1-propynyl group (—C≡C—CH 3 ), 2-propynyl group (—CH 2 —C≡CH), 1-butynyl. Group (—C≡C—CH 2 CH 3 ), 2-butynyl group (—CH 2 —C≡C—CH 3 ), 3-butynyl group (—CH 2 CH 2 —C≡CH), 1-pentynyl group (—C≡C—CH 2 CH 2 CH 3 ), 2-pentynyl group (—CH 2 —C≡C—CH 2 CH 3 ), 3-pentynyl group (—CH 2 CH 2 —C≡C—CH 3) ) And 4-pentynyl group (—CH 2 CH 2 CH 2 —C≡CH), a group in which at least one hydrogen atom is substituted with a fluorine atom.
上記アルキニル基としては、なかでも、炭素－炭素三重結合を１つ含むものが好ましく、
エチニル基（－Ｃ≡ＣＨ）、１－プロピニル基（－Ｃ≡Ｃ－ＣＨ３）、２－プロピニル基（－ＣＨ２－Ｃ≡ＣＨ）、１－ブチニル基（－Ｃ≡Ｃ－ＣＨ２ＣＨ３）、２－ブチニル基（－ＣＨ２－Ｃ≡Ｃ－ＣＨ３）、２－ペンチニル基（－ＣＨ２－Ｃ≡Ｃ－ＣＨ２ＣＨ３）、及び、これらの基において少なくとも１つの水素原子がフッ素原子又はシリル基により置換された基がより好ましく、
－Ｃ≡Ｃ－ＴＭＳ、－Ｃ≡Ｃ－Ｆ、１－プロピニル基（－Ｃ≡Ｃ－ＣＨ３）、－Ｃ≡Ｃ－ＣＦ３、２－プロピニル基（－ＣＨ２－Ｃ≡ＣＨ）、－Ｃ≡Ｃ－ＣＦ２ＣＦ３、２－プロピニル基（－ＣＨ２－Ｃ≡ＣＨ）において少なくとも１つの水素原子がフッ素原子又はシリル基により置換された基、２－ブチニル基（－ＣＨ２－Ｃ≡Ｃ－ＣＨ３）において少なくとも１つの水素原子がフッ素原子により置換された基、並びに、２－ペンチニル基（－ＣＨ２－Ｃ≡Ｃ－ＣＨ２ＣＨ３）において少なくとも１つの水素原子がフッ素原子により置換された基が更に好ましく、
２－プロピニル基（－ＣＨ２－Ｃ≡ＣＨ）、－ＣＨ２－Ｃ≡Ｃ－ＴＭＳ、－ＣＨ２－Ｃ≡Ｃ－Ｆ、－ＣＨ２－Ｃ≡Ｃ－ＣＦ３及び－ＣＨ２－Ｃ≡Ｃ－ＣＦ２ＣＦ３が特に好ましく、
２－プロピニル基（－ＣＨ２－Ｃ≡ＣＨ）及び－ＣＨ２－Ｃ≡Ｃ－ＴＭＳが最も好ましい。
なお、上記式中、－ＴＭＳは、トリメチルシリル基を意味する。 Among the above alkynyl groups, those containing one carbon-carbon triple bond are preferable,
Ethynyl group (—C≡CH), 1-propynyl group (—C≡C—CH 3 ), 2-propynyl group (—CH 2 —C≡CH), 1-butynyl group (—C≡C—CH 2 CH 3 ), 2-butynyl group (—CH 2 —C≡C—CH 3 ), 2-pentynyl group (—CH 2 —C≡C—CH 2 CH 3 ), and at least one hydrogen atom in these groups Is more preferably a group substituted by a fluorine atom or a silyl group,
-C≡C-TMS, -C≡C-F, 1-propynyl group (-C≡C-CH 3 ), -C≡C-CF 3 , 2-propynyl group (-CH 2 -C≡CH), A group in which at least one hydrogen atom is substituted with a fluorine atom or a silyl group in a —C≡C—CF 2 CF 3 , 2-propynyl group (—CH 2 —C≡CH), a 2-butynyl group (—CH 2 — A group in which at least one hydrogen atom is substituted with a fluorine atom in C≡C—CH 3 ) and at least one hydrogen atom in a 2-pentynyl group (—CH 2 —C≡C—CH 2 CH 3 ) More preferred are groups substituted by atoms,
2- propynyl (-CH 2 -C≡CH), - CH 2 -C≡C-TMS, -CH 2 -C≡C-F, -CH 2 -C≡C-CF 3 and -CH 2 -C ≡C—CF 2 CF 3 is particularly preferred,
2-propynyl groups (—CH 2 —C≡CH) and —CH 2 —C≡C-TMS are most preferred.
In the above formula, -TMS means a trimethylsilyl group.
Ｒ３としての上記アリール基としては、炭素数６～７のアリール基が好ましい。上記アリール基は、６員の芳香族炭化水素環を含むことが好ましい。 The aryl group as R 3 is preferably an aryl group having 6 to 7 carbon atoms. The aryl group preferably contains a 6-membered aromatic hydrocarbon ring.
上記アリール基としては、フェニル基、ベンジル基、トリル基等が挙げられ、これらの基は１つ以上の置換基を有していてもよい。
上記置換基としては、ハロゲン原子、アルキル基、フッ素化アルキル基、ヘテロ原子を含む基等が挙げられ、ハロゲン原子が好ましく、フッ素原子がより好ましい。
上記アリール基としては、なかでも、フェニル基、ベンジル基が好ましい。 Examples of the aryl group include a phenyl group, a benzyl group, and a tolyl group, and these groups optionally have one or more substituents.
Examples of the substituent include a halogen atom, an alkyl group, a fluorinated alkyl group, a group containing a hetero atom, a halogen atom is preferable, and a fluorine atom is more preferable.
Among these aryl groups, a phenyl group and a benzyl group are preferable.
Ｒ３は、炭素－炭素二重結合又は炭素－炭素三重結合を１つ含むことが好ましく、炭素－炭素二重結合を１つ含む炭素数２～６のアルケニル基、又は、炭素－炭素三重結合を１つ含む炭素数２～６のアルキニル基であることがより好ましく、２－プロペニル基又は２－プロピニル基であることが更に好ましい。 R 3 preferably contains one carbon-carbon double bond or one carbon-carbon triple bond, or an alkenyl group having 2 to 6 carbon atoms containing one carbon-carbon double bond, or a carbon-carbon triple bond. It is more preferably an alkynyl group having 2 to 6 carbon atoms containing one of them, more preferably a 2-propenyl group or a 2-propynyl group.
化合物（１）としては、例えば、下記式で表される化合物が例示できる。なお、本明細書中の化合物の例示は、当該化合物の幾何異性体（存在する場合）も含むものとし、記載した具体例に限定されるものではない。 As compound (1), the compound represented by a following formula can be illustrated, for example. In addition, the illustration of the compound in this specification shall also include the geometric isomer (when it exists) of the said compound, and is not limited to the specific example described.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
化合物（１）としては、なかでも、下記式で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
 As the compound (1), a compound represented by the following formula is particularly preferable.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
本開示の製造方法は、下記一般式（Ａ）：
Figure JPOXMLDOC01-appb-C000052
 （式中、Ｒ３は、上記と同じである。Ｘは、ハロゲン原子である。）で表される化合物（Ａ）と、下記一般式（Ｂ）：
Figure JPOXMLDOC01-appb-C000053
 （式中、Ｒ１及びＲ２は、上記と同じである。）で表されるアミン（Ｂ）とを反応させることにより、化合物（１）を得る工程（１）を含む。
化合物（１）のような、不飽和結合を有する化合物は、一般に、反応時に重合する可能性がある。
また、化合物（１）を合成する別手法としてエステル交換法も考えられるが、その際に、ジアミン体が生成する可能性がある（メカニズムについては、例えば、Ｔｅｓｔａ，Ｍａｒｉａ　Ｌｕｉｓａ；Ｚａｂａｌｌｏｓ，Ｅｌｅｎａ；Ｚａｒａｇｏｚａ，Ｒａｍｏｎ　Ｊ．，Ｔｅｔｒａｈｅｄｒｏｎ，２０１２，ｖｏｌ．６８，４７，ｐ．９５８３－９５９１，９を参照）。更に、目的物とジアミン体とを分ける際に加熱蒸留が必要となり、加熱により上述のような重合反応が起こる可能性もある。
本開示の製造方法は、工程（１）を含むことにより、驚くべきことに、ジアミン体等の副生成物が少なく、また、不飽和結合による重合反応も起こりにくく、高純度（例えばＧＣ純度９５．０％以上）の化合物（１）を製造することができる。 The production method of the present disclosure includes the following general formula (A):
Figure JPOXMLDOC01-appb-C000052
 (Wherein R 3 is the same as described above. X is a halogen atom) and the following general formula (B):
Figure JPOXMLDOC01-appb-C000053
 (In the formula, R 1 and R 2 are the same as above.) A step (1) of obtaining compound (1) by reacting with amine (B) represented by the formula (1) is included.
In general, a compound having an unsaturated bond, such as compound (1), may polymerize during the reaction.
In addition, a transesterification method is also conceivable as another method for synthesizing the compound (1). In this case, a diamine compound may be formed (for example, the mechanism is described by Testa, Maria Luisa; Zaballos, Elena; Zaragoza). Ramon J., Tetrahedron, 2012, vol. 68, 47, p. 9583-9591, 9). Furthermore, when the target product and the diamine compound are separated, heating distillation is required, and the above-described polymerization reaction may occur due to heating.
Surprisingly, the production method of the present disclosure includes the step (1), and surprisingly, there are few by-products such as a diamine body, the polymerization reaction due to the unsaturated bond hardly occurs, and high purity (for example, GC purity 95). 0.0% or more) of compound (1) can be produced.
一般式（Ａ）中、Ｘはハロゲン原子である。上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、なかでもフッ素原子、塩素原子が好ましい。 In general formula (A), X is a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom and a chlorine atom are preferable.
一般式（Ａ）中のＲ３、一般式（Ｂ）中のＲ１及びＲ２は、一般式（１）について説明したとおりである。 R 3 in the general formula (A) and R 1 and R 2 in the general formula (B) are as described for the general formula (1).
工程（１）の反応では、化合物（Ａ）１モルに対して、アミン（Ｂ）を１．０～１．５モル使用することが好ましく、１．０～１．２モル使用することがより好ましい。 In the reaction of step (1), 1.0 to 1.5 mol of amine (B) is preferably used relative to 1 mol of compound (A), more preferably 1.0 to 1.2 mol. preferable.
工程（１）の反応は、塩基（但し、アミン（Ｂ）を除く）の存在下に実施することが好ましい。上記塩基としては特に限定されないが、アミン（但し、アミン（Ｂ）を除く）、無機塩基等が挙げられる。
上記アミンとしては、第三級アミンやピリジン類（ピリジン及びその誘導体）が挙げられ、例えば、トリエチルアミン、トリ（ｎ－プロピル）アミン、トリ（ｎ－ブチル）アミン、ジイソプロピルエチルアミン、シクロヘキシルジメチルアミン、ピリジン、ルチジン、γ－コリジン、Ｎ，Ｎ－ジメチルアニリン、Ｎ－メチルピペリジン、Ｎ－メチルピロリジン、Ｎ－メチルモルホリン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセン（ＤＢＵ）、１，５－ジアザビシクロ［４．３．０］－５－ノネン、１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）、４－ジメチルアミノピリジン（ＤＭＡＰ）、プロトンスポンジ等が挙げられる。
上記無機塩基としては、例えば、水酸化リチウム、水酸化カリウム、水酸化ナトリウム、水酸化カルシウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸セシウム、炭酸水素セシウム、炭酸水素リチウム、フッ化セシウム、フッ化カリウム、フッ化ナトリウム、塩化リチウム、臭化リチウム等が挙げられる。
上記塩基としては、なかでも、上記アミンが好ましく、第三級アミン及びピリジン類からなる群より選択される少なくとも１種がより好ましく、トリエチルアミン及びピリジンからなる群より選択される少なくとも１種が更に好ましい。 The reaction in step (1) is preferably carried out in the presence of a base (excluding amine (B)). Although it does not specifically limit as said base, An amine (however, except amine (B)), an inorganic base, etc. are mentioned.
Examples of the amine include tertiary amines and pyridines (pyridine and derivatives thereof). For example, triethylamine, tri (n-propyl) amine, tri (n-butyl) amine, diisopropylethylamine, cyclohexyldimethylamine, pyridine , Lutidine, γ-collidine, N, N-dimethylaniline, N-methylpiperidine, N-methylpyrrolidine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1 , 5-diazabicyclo [4.3.0] -5-nonene, 1,4-diazabicyclo [2.2.2] octane (DABCO), 4-dimethylaminopyridine (DMAP), proton sponge, and the like.
Examples of the inorganic base include lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, cesium carbonate, cesium bicarbonate, and hydrogen carbonate. Examples thereof include lithium, cesium fluoride, potassium fluoride, sodium fluoride, lithium chloride, and lithium bromide.
Among the above bases, the above amine is preferable, at least one selected from the group consisting of tertiary amines and pyridines is more preferable, and at least one selected from the group consisting of triethylamine and pyridine is more preferable. .
上記塩基は、化合物（Ａ）１モルに対して、１．０～１．５モル使用することが好ましく、１．０～１．２モル使用することがより好ましい。 The base is preferably used in an amount of 1.0 to 1.5 mol, more preferably 1.0 to 1.2 mol, per 1 mol of compound (A).
工程（１）の反応は、溶媒中で実施できる。上記溶媒としては、有機溶媒が好ましく、非芳香族炭化水素溶媒、芳香族炭化水素溶媒、ケトン溶媒、ハロゲン化炭化水素溶媒、エーテル溶媒、エステル溶媒、ニトリル溶媒、スルホキシド系溶媒及びアミド溶媒等が挙げられる。具体的には、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、デカヒドロナフタレン、ｎ－デカン、イソドデカン、トリデカン等の非芳香族炭化水素溶媒；ベンゼン、トルエン、キシレン、テトラリン、ベラトロール、ジエチルベンゼン、メチルナフタレン、ニトロベンゼン、ｏ－ニトロトルエン、メシチレン、インデン、ジフェニルスルフィド等の芳香族炭化水素溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、プロピオフェノン、ジイソブチルケトン、イソホロン等のケトン溶媒；ジクロロメタン、四塩化炭素、クロロホルム、クロロベンゼン等のハロゲン化炭化水素溶媒；ジエチルエーテル、テトラヒドロフラン、ジイソプロピルエーテル、メチル ｔ－ブチルエーテル、ジオキサン、ジメトキシエタン、ジグライム、フェネトール、１，１－ジメトキシシクロヘキサン、ジイソアミルエーテル等のエーテル溶媒；酢酸エチル、酢酸イソプロピル、マロン酸ジエチル、３－メトキシ－３－メチルブチルアセテート、γ－ブチロラクトン、エチレンカーボネート、プロピレンカーボネート、炭酸ジメチル、α－アセチル－γ－ブチロラクトン等のエステル溶媒；アセトニトリル、ベンゾニトリル等のニトリル溶媒；ジメチルスルホキシド、スルホラン等のスルホキシド系溶媒；及びＮ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、１，３－ジメチル－２－イミダゾリジノン、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジメチルアセトアセトアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ－ジエチルアセトアミド等のアミド溶媒等が挙げられる。 The reaction of step (1) can be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include non-aromatic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, nitrile solvents, sulfoxide solvents, and amide solvents. It is done. Specifically, non-aromatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, n-decane, isododecane and tridecane; benzene, toluene, xylene, tetralin, veratrol, diethylbenzene, methylnaphthalene, Aromatic hydrocarbon solvents such as nitrobenzene, o-nitrotoluene, mesitylene, indene, diphenyl sulfide; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, propiophenone, diisobutyl ketone, isophorone; dichloromethane, carbon tetrachloride, chloroform Halogenated hydrocarbon solvents such as chlorobenzene; diethyl ether, tetrahydrofuran, diisopropyl ether, methyl tert-butyl ether, dioxane, Ether solvents such as methoxyethane, diglyme, phenetole, 1,1-dimethoxycyclohexane, diisoamyl ether; ethyl acetate, isopropyl acetate, diethyl malonate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, ethylene carbonate, propylene Ester solvents such as carbonate, dimethyl carbonate and α-acetyl-γ-butyrolactone; nitrile solvents such as acetonitrile and benzonitrile; sulfoxide solvents such as dimethyl sulfoxide and sulfolane; and N, N-dimethylformamide and N, N-dimethylacetamide N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacrylamide, N, N-dimethylacetoacetamide, N, N-diethylformamide, N, N -Amide solvents such as diethylacetamide and the like.
工程（１）の反応の温度としては、－７８～２５℃が好ましく、－２０～１０℃がより好ましい。 The reaction temperature in step (1) is preferably −78 to 25 ° C., more preferably −20 to 10 ° C.
工程（１）の反応の時間としては、０．５～２４時間が好ましく、０．５～３時間がより好ましい。 The reaction time in step (1) is preferably 0.5 to 24 hours, and more preferably 0.5 to 3 hours.
上記製造方法は、下記一般式（Ｃ）：
Figure JPOXMLDOC01-appb-C000054
 （式中、Ｘは上記と同じである。）で表される化合物（Ｃ）と、下記一般式（Ｄ）：
Ｒ３－ＯＨ
（式中、Ｒ３は上記と同じである。）で表される化合物（Ｄ）とを反応させることにより、上記一般式（Ａ）で表される化合物（Ａ）を得る工程（２）を更に含んでもよい。 The above production method has the following general formula (C):
Figure JPOXMLDOC01-appb-C000054
 (Wherein X is the same as above) and the following general formula (D):
R 3 —OH
(Wherein R 3 is the same as above), by reacting with the compound (D) represented by the formula (A), the step (2) of obtaining the compound (A) represented by the general formula (A) Further, it may be included.
工程（２）の反応は、公知の条件下で実施することができる。工程（２）を実施する場合は、工程（２）の後に、工程（１）を実施することが好ましい。工程（２）で得られた化合物（Ａ）を、工程（１）の反応に用いることができる。 The reaction of step (2) can be carried out under known conditions. When implementing a process (2), it is preferable to implement a process (1) after a process (2). The compound (A) obtained in the step (2) can be used for the reaction in the step (1).
上記製造方法においては、各工程の終了後、溶媒の留去、蒸留、カラムクロマトグラフィー、再結晶等により生成物を分離・精製してもよい。 In the above production method, after completion of each step, the product may be separated and purified by distilling off the solvent, distillation, column chromatography, recrystallization or the like.
化合物（１）は新規化合物であり、医農薬化合物等の各種化学薬品、及びそれらの中間体等として好適に使用できる。 Compound (1) is a novel compound and can be suitably used as various chemicals such as medical and agrochemical compounds, and intermediates thereof.
次に実施例を挙げて本開示を更に詳しく説明するが、本開示はこれらの実施例のみに限定されるものではない。 Next, the present disclosure will be described in more detail with reference to examples. However, the present disclosure is not limited only to these examples.
化合物の同定及び、反応の進行度の確認はＮＭＲ測定にて実施した。 Identification of the compound and confirmation of the progress of the reaction were carried out by NMR measurement.
実施例１
＜２－プロピニル（ジエチルカーバモイル）フォメートの合成＞
２－プロピニル（クロロカーボニル）フォメート（１．４７ｇ、１０ｍｍｏｌ）とジクロロメタン５ｍｌを混合し、窒素置換した後に、０℃でジエチルアミン（０．７３ｇ，１０ｍｍｏｌ）を滴下した。その溶液に、ピリジン（０．８７ｇ，１１ｍｍｏｌ）とジクロロメタン５ｍｌを混合した溶液を滴下した。その後、室温に戻し、撹拌を行った。セライトろ過、１Ｍ塩酸水溶液で水洗、及び分液した後、同じく水で２回水洗と分液操作を行った。有機層を乾燥、濃縮することで、下記式で表される目的物１．２０ｇ（ＧＣ純度９８．３％）を得た。
Figure JPOXMLDOC01-appb-C000055
 Example 1
<Synthesis of 2-propynyl (diethylcarbamoyl) fomate>
2-propynyl (chlorocarbonyl) fomate (1.47 g, 10 mmol) and 5 ml of dichloromethane were mixed and purged with nitrogen, and then diethylamine (0.73 g, 10 mmol) was added dropwise at 0 ° C. A solution obtained by mixing pyridine (0.87 g, 11 mmol) and 5 ml of dichloromethane was added dropwise to the solution. Then, it returned to room temperature and stirred. Celite filtration, washing with 1M aqueous hydrochloric acid solution, and liquid separation, followed by water washing and separation operation twice with water. The organic layer was dried and concentrated to obtain 1.20 g (GC purity: 98.3%) of the target compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000055
実施例２
＜アリル（ジエチルカーバモイル）フォメートの合成＞
２－プロピニル（クロロカーボニル）フォメートの代わりにアリル（クロロカーボニル）フォメートを用いること以外は実施例１と同様の物質量で合成を行い、下記式で表される目的物１．２１ｇ（ＧＣ純度９６．２％）を得た。
Figure JPOXMLDOC01-appb-C000056
 Example 2
<Synthesis of allyl (diethylcarbamoyl) formate>
The synthesis was carried out with the same amount of substance as in Example 1 except that allyl (chlorocarbonyl) fomate was used instead of 2-propynyl (chlorocarbonyl) fomate, and 1.21 g of the desired product represented by the following formula (GC purity 96 .2%).
Figure JPOXMLDOC01-appb-C000056
実施例３
＜２－プロピニル－２－モルフォリノ－２－オキソアセテートの合成＞
ジエチルアミンの代わりにモルフォリンを用いること以外は実施例１と同様の物質量で合成を行い、下記式で表される目的物１．１１ｇ（ＧＣ純度９８．０％）を得た。
Figure JPOXMLDOC01-appb-C000057
 Example 3
<Synthesis of 2-propynyl-2-morpholino-2-oxoacetate>
The synthesis was carried out in the same amount of substance as in Example 1 except that morpholine was used instead of diethylamine to obtain 1.11 g (GC purity 98.0%) of the target compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000057
実施例４
＜３－（トリメチルシリル）－２－プロピニル（ジエチルカーバモイル）フォメートの合成＞
２－プロピニル（クロロカーボニル）フォメートの代わりに３－（トリメチルシリル）－２－プロピニル（クロロカーボニル）フォメートを用いること以外は実施例１と同様の物質量で合成を行い、下記式で表される目的物１．３０ｇ（ＧＣ純度９７．３％）を得た。
Figure JPOXMLDOC01-appb-C000058
 Example 4
<Synthesis of 3- (trimethylsilyl) -2-propynyl (diethylcarbamoyl) fomate>
Synthesis was carried out with the same amount of substance as in Example 1 except that 3- (trimethylsilyl) -2-propynyl (chlorocarbonyl) fomate was used instead of 2-propynyl (chlorocarbonyl) fomate. 1.30 g (GC purity 97.3%) was obtained.
Figure JPOXMLDOC01-appb-C000058
実施例５
＜２－プロピニル（ジアリルカーバモイル）フォメートの合成＞
ジエチルアミンの代わりにジアリルアミンを用いること以外は実施例１と同様の物質量で合成を行い、下記式で表される目的物１．２１ｇ（ＧＣ純度９６．２％）を得た。
Figure JPOXMLDOC01-appb-C000059
 Example 5
<Synthesis of 2-propynyl (diallylcarbamoyl) fomate>
The synthesis was performed with the same amount of substance as in Example 1 except that diallylamine was used in place of diethylamine to obtain 1.21 g of the target product represented by the following formula (GC purity 96.2%).
Figure JPOXMLDOC01-appb-C000059
実施例６
＜２－プロピニル（ジ（２－プロピニル）カーバモイル）フォメートの合成＞
ジエチルアミンの代わりにジ（２－プロピニル）アミンを用いること以外は実施例１と同様の物質量で合成を行い、下記式で表される目的物１．０９ｇ（ＧＣ純度９５．８％）を得た。
Figure JPOXMLDOC01-appb-C000060
 Example 6
<Synthesis of 2-propynyl (di (2-propynyl) carbamoyl) fomate>
The synthesis was carried out with the same amount of substance as in Example 1 except that di (2-propynyl) amine was used instead of diethylamine to obtain 1.09 g (GC purity 95.8%) of the target compound represented by the following formula. It was.
Figure JPOXMLDOC01-appb-C000060
実施例７
＜２－フルオロアリル（ジアリルカーバモイル）フォメートの合成＞
２－プロピニル（クロロカーボニル）フォメートの代わりに２－フルオロアリル（クロロカーボニル）フォメートを用いること以外は実施例５と同様の物質量で合成を行い、下記式で表される目的物１．２８ｇ（ＧＣ純度９７．２％）を得た。
Figure JPOXMLDOC01-appb-C000061
 Example 7
<Synthesis of 2-fluoroallyl (diallylcarbamoyl) fomate>
The synthesis was carried out with the same amount of substance as in Example 5 except that 2-fluoroallyl (chlorocarbonyl) fomate was used instead of 2-propynyl (chlorocarbonyl) fomate, and 1.28 g of the desired product represented by the following formula ( GC purity 97.2%) was obtained.
Figure JPOXMLDOC01-appb-C000061
実施例８
＜アリル（ジアリルカーバモイル）フォメートの合成＞
２－プロピニル（クロロカーボニル）フォメートの代わりにをアリル（クロロカーボニル）フォメート用いること以外は実施例５と同様の物質量で合成を行い、下記式で表される目的物１．２０ｇ（ＧＣ純度９６．８％）を得た。
Figure JPOXMLDOC01-appb-C000062
 Example 8
<Synthesis of allyl (diallylcarbamoyl) formate>
The synthesis was carried out with the same amount of substance as in Example 5 except that allyl (chlorocarbonyl) fomate was used instead of 2-propynyl (chlorocarbonyl) fomate, and 1.20 g of the target compound represented by the following formula (GC purity 96 8%).
Figure JPOXMLDOC01-appb-C000062
実施例９
＜アリル（ビス（２，２，２－トリフルオロエチル）カーバモイル）フォメートの合成＞
ジアリルアミンの代わりにビス（２，２，２－トリフルオロエチル）アミンを用いること以外は実施例２と同様の物質量で合成を行い、下記式で表される目的物１．３９ｇ（ＧＣ純度９６．８％）を得た。
Figure JPOXMLDOC01-appb-C000063
 Example 9
<Synthesis of allyl (bis (2,2,2-trifluoroethyl) carbamoyl) fomate>
The synthesis was carried out with the same amount of substance as in Example 2 except that bis (2,2,2-trifluoroethyl) amine was used instead of diallylamine, and 1.39 g of the desired product represented by the following formula (GC purity 96 8%).
Figure JPOXMLDOC01-appb-C000063
実施例１０
＜２－フルオロアリル（ジエチルカーバモイル）フォメートの合成＞
２－プロピニル（クロロカーボニル）フォメートの代わりに２－フルオロアリル（クロロカーボニル）フォメートを用いること以外は実施例１と同様の物質量で合成を行い、下記式で表される目的物１．２２ｇ（ＧＣ純度９６．８％）を得た。
Figure JPOXMLDOC01-appb-C000064
 Example 10
<Synthesis of 2-fluoroallyl (diethylcarbamoyl) fomate>
Synthesis was carried out with the same amount of substance as in Example 1 except that 2-fluoroallyl (chlorocarbonyl) fomate was used instead of 2-propynyl (chlorocarbonyl) fomate, and 1.22 g of the target compound represented by the following formula ( GC purity 96.8%) was obtained.
Figure JPOXMLDOC01-appb-C000064
本開示の化合物は、医農薬化合物等の各種化学薬品、及びそれらの中間体等として使用可能である。 The compounds of the present disclosure can be used as various chemicals such as medical and agrochemical compounds, and intermediates thereof.

Claims (5)

  1. 下記一般式（１）：
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１及びＲ２は、互いに独立に、フッ素原子又は炭素数６以下の有機基であり、互いに結合して環状構造を形成してもよい。Ｒ３は、炭素－炭素不飽和結合を有する炭素数７以下の有機基である。）で表される化合物（１）を製造する方法であって、
    下記一般式（Ａ）：
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ３は、前記と同じである。Ｘは、ハロゲン原子である。）で表される化合物（Ａ）と、下記一般式（Ｂ）：
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ１及びＲ２は、前記と同じである。）で表されるアミン（Ｂ）とを反応させることにより、化合物（１）を得る工程（１）を含むことを特徴とする製造方法。     The following general formula (1):
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 and R 2 are each independently a fluorine atom or an organic group having 6 or less carbon atoms, and may be bonded to each other to form a cyclic structure. R 3 is carbon-carbon unsaturated. Which is an organic group having 7 or less carbon atoms having a bond).
    The following general formula (A):
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 3 is the same as described above, X is a halogen atom), and the following general formula (B):
    Figure JPOXMLDOC01-appb-C000003
     (Wherein R 1 and R 2 are the same as described above), which comprises reacting with the amine (B) represented by the step (1) to obtain the compound (1). Production method.
  2. 工程（１）の反応を、塩基（但し、アミン（Ｂ）を除く）の存在下に実施する請求項１記載の製造方法。 The process according to claim 1, wherein the reaction of step (1) is carried out in the presence of a base (excluding amine (B)).
  3. Ｒ３は、炭素－炭素二重結合又は炭素－炭素三重結合を１つ含む請求項１又は２記載の製造方法。 The production method according to claim 1 or 2, wherein R 3 contains one carbon-carbon double bond or one carbon-carbon triple bond.
  4. Ｒ３は、２－プロペニル基又は２－プロピニル基である請求項１、２又は３記載の製造方法。 4. The production method according to claim 1, wherein R 3 is a 2-propenyl group or a 2-propynyl group.
  5. 下記一般式（１）：
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ１及びＲ２は、互いに独立に、フッ素原子又は炭素数６以下の有機基であり、互いに結合して環状構造を形成してもよい。Ｒ３は、炭素－炭素不飽和結合を有する炭素数７以下の有機基である。）で表されることを特徴とする化合物。     The following general formula (1):
    Figure JPOXMLDOC01-appb-C000004
     (Wherein R 1 and R 2 are each independently a fluorine atom or an organic group having 6 or less carbon atoms, and may be bonded to each other to form a cyclic structure. R 3 is carbon-carbon unsaturated. It is an organic group having 7 or less carbon atoms having a bond.)
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