WO2020079895A1 - Composé de 2-éthyl-2, 3-époxybutyloxy - Google Patents

Composé de 2-éthyl-2, 3-époxybutyloxy Download PDF

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WO2020079895A1
WO2020079895A1 PCT/JP2019/027032 JP2019027032W WO2020079895A1 WO 2020079895 A1 WO2020079895 A1 WO 2020079895A1 JP 2019027032 W JP2019027032 W JP 2019027032W WO 2020079895 A1 WO2020079895 A1 WO 2020079895A1
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ethyl
formula
group
diyl
epoxybutyloxy
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PCT/JP2019/027032
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Japanese (ja)
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正敏 川島
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Jnc株式会社
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Priority to CN201980065774.3A priority Critical patent/CN112805273A/zh
Priority to JP2020552523A priority patent/JPWO2020079895A1/ja
Publication of WO2020079895A1 publication Critical patent/WO2020079895A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
    • C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds

Definitions

  • the present invention is a 2-ethyl-2,3-epoxybutyloxy compound useful as an epoxy resin monomer.
  • Epoxy compounds are widely used in various materials as resin modifiers, cross-linking agents, etc., and glycidyl-based and cycloalkene oxide-based compounds have been developed, and heat resistance, flexibility, weather resistance, gas permeability, Physical properties according to each application such as heat-resistant yellowing, low viscosity, high Tg, transparency, UV curability, and halogen-free are required (Non-Patent Documents 1, 2, 3, 4, 5, 6).
  • the present inventor reduced the formyl of 2-ethyl-2,3-epoxybutanal obtained by epoxidizing 2-ethyl-2-butenal, which is one of the aldol condensation products of butyraldehyde and acetaldehyde. , 2-ethyl-2,3-epoxybutanol, and by esterification, sulfonylation, etherification, or urethane formation of these compounds, various novel 2-ethyl-2,3-epoxybutyloxy compounds can be obtained. Therefore, the present invention has been completed.
  • an ether containing an epoxy useful as an epoxy resin monomer is obtained by carrying out a conversion reaction of industrially easily available 2-ethyl-2-butenal in several steps which can be carried out on an industrial scale.
  • Various 2-ethyl-2,3-epoxybutyloxy compounds such as esters and urethanes can be provided.
  • a 2-ethyl-2,3-epoxybutyloxy compound represented by the formula (1) (In the formula, A is carbonyl or sulfonyl, Z is oxygen or imino, a and b are independently 0 or 1, c is an integer of 1 to 4, and R is a straight chain. , A branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a c-valent group in which these are combined, in which at least one carbon is oxygen or sulfur.
  • And may include carbonyl, oxycarbonyl, or sulfonyl, wherein at least one hydrogen of these groups is fluorine, chlorine, bromine, iodine, nitro, hydroxy, aryl, aralkyl, alkoxy, acyl. , Acyloxy, or alkoxycarbonyl, where at least one hydrogen bonded to a ring carbon is replaced by an alkyl having 1 to 6 carbons. May be replaced.
  • A is carbonyl, a is 1, b is 0, c is 1, and R is a linear, branched, or cyclic saturated or unsaturated hydrocarbon.
  • a group, a monocyclic or polycyclic aromatic group, or a monovalent group having 1 to 18 carbon atoms in which these groups are combined, and at least one hydrogen bonded to a ring carbon may be replaced with methyl.
  • A is carbonyl, a is 1, b is 0, c is 2 or 3, and R is linear, branched, or cyclic saturated or unsaturated.
  • A is sulfonyl
  • a is 1
  • b is 0,
  • c is 1
  • R is a linear saturated hydrocarbon group or a monocyclic aromatic group.
  • 2-ethyl-2 according to item [1] which is a monovalent group having 1 to 18 carbon atoms in which these are combined, and at least one hydrogen bonded to a carbon atom in the ring may be replaced with methyl.
  • 3-epoxybutyloxy compound is a monovalent group having 1 to 18 carbon atoms in which these are combined, and at least one hydrogen bonded to a carbon atom in the ring.
  • both a and b are 0, c is 1, and R is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, monocyclic or polycyclic aromatic 2-Ethyl-group according to item [1], which is a monovalent group having 1 to 18 carbon atoms in combination with these groups, and at least one hydrogen bonded to a ring carbon may be replaced with methyl. 2,3-epoxybutyloxy compound.
  • a and b are both 0, c is an integer of 2 to 4, and R is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a monocyclic ring or Item [1], which is a polycyclic aromatic group or a c-valent group having 1 to 18 carbon atoms in which they are combined, and at least one hydrogen bonded to a ring carbon may be replaced with methyl.
  • 2-ethyl-2,3-epoxybutyloxy compound is 2-ethyl-2,3-epoxybutyloxy compound.
  • A is carbonyl
  • Z is imino
  • both a and b are 1
  • c is 2
  • R is a linear, branched, or cyclic saturated hydrocarbon.
  • 2-Ethyl-2,3-epoxybutanol which can be used as the main raw material, is synthesized by the method of epoxidizing and then reducing 2-ethyl-2-butenal or the method of reducing and then epoxidizing as shown below. be able to.
  • 2-ethyl-2,3-epoxybutanol can also be used as a raw material by derivatization according to the following formula (wherein X represents a leaving group such as halogen and sulfonate).
  • a compound obtained by derivatizing 2-ethyl-2-butenol obtained by reducing 2-ethyl-2-butenal according to the following formula in the formula, G represents an organic group
  • G represents an organic group
  • Formula (1-1) (In the formula, c is an integer of 1 to 4, and R is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or these.
  • One hydrogen may be replaced by fluorine, chlorine, bromine, iodine, hydroxy, aryl, aralkyl, alkoxy, acyl, acyloxy, or alkoxycarbonyl, and at least one hydrogen bonded to a ring carbon has at least one carbon atom. It may be substituted with 1 to 6 alkyl.
  • Scheme 1 is a method of reacting 2-ethyl-2,3-epoxybutanol with carboxylic acid chloride or carboxylic acid anhydride, usually in the presence of a base, and as the base, pyridine, triethylamine, diisopropylethylamine, 4- Dimethylaminopyridine, 1,4-diazabicyclo [2.2.2] octane, N, N, N ', N'-tetramethylethylenediamine, sodium hydroxide, bismuth chloride, zinc oxide, aluminum oxide, zirconium oxychloride, oxidation Titanium, bismuth ferrite, cerium chloride, lithium perchlorate, etc. are used, but there is also a method using a microflow reactor without using a base.
  • Scheme 2 is a reaction of 2-ethyl-2,3-epoxybutanol and a carboxylic acid in the presence of a condensing agent, and as the condensing agent, N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole 1,1'-carbonyldi (1 , 2,4-Triazole), 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride n hydrate, trifluoromethanesulfonic acid (4, 6-dimethoxy-1,3,5-triazin-2-yl)-(2-octoxy-2-
  • Scheme 3 is a method of transesterifying 2-ethyl-2,3-epoxybutanol and a carboxylic acid ester in the presence of an acid, a base, or a neutral catalyst, such as sulfuric acid, p-toluenesulfonic acid.
  • Methanesulfonic acid sodium hydroxide, potassium hydroxide, sodium methoxide, potassium carbonate, potassium cyanide, 4-dimethylaminopyridine, zinc tetranuclear (ZnO 4 ) cluster, zinc-bismuth imidazole ligand complex, tetramethyl monomethyl carbonate Ammonium, lanthanum (III) isopropoxide / diethylene glycol monomethyl ether, iron salen complex, zinc hydroxide, various metal halides, various metal acetates and the like can be used.
  • Scheme 4 is a halide derived from 2-ethyl-2,3-epoxybutanol, p-toluenesulfonate, methanesulfonate, chloromethanesulfonate, trifluoromethanesulfonate, nonafluorobutanesulfonate, 3-nitrobenzenesulfonate, 4-bromobenzene.
  • a compound having a leaving group such as sulfonate is reacted with a carboxylate derived from carboxylic acid.
  • Chlorine, bromine, or iodine can be used as the halogen of the leaving group, and alkali metal, alkaline earth metal, tin, 1-ethyl-3-methylimidazolium, etc. can be used as the counterion of carboxylate. .
  • Scheme 5 is a method of epoxidizing 2-ethyl-2-butenylcarboxylate, and as the epoxidizing agent, hydrogen peroxide, performic acid, peracetic acid, perisobutyric acid, trifluoroperacetic acid, perbenzoic acid, m-Chloroperbenzoic acid, t-butyl hydroperoxide and the like can be used.
  • Scheme 6 is a method in which a base is allowed to act on 3-hydroxy-2-ethylbutyl carboxylate having a leaving group at the 2-position to close the epoxy ring.
  • the leaving group include chlorine, bromine, iodine, p-toluenesulfonate, methanesulfonate, chloromethanesulfonate, trifluoromethanesulfonate and the like.
  • Examples of the base include alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, pyridine, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undecene, diazabicyclo [ 2.2.2] Octane, 1,5-diazabicyclo [4.3.0] -5-nonene, 4-dimethylaminopyridine, 1,1,3,3-tetramethylguanidine, 1,8-bis (dimethyl)
  • Examples thereof include organic bases such as amino) naphthalene and 1,5,7-triazabicyclo [4.4.0] -5-decene.
  • Formula (1-2) (In the formula, c is an integer of 1 to 4, and R is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or these.
  • One hydrogen may be replaced by fluorine, chlorine, bromine, iodine, nitro, aryl, aralkyl, alkoxy, acyl, acyloxy, or alkoxycarbonyl, and at least one hydrogen bonded to a ring carbon has at least one carbon atom.
  • Examples of the method for synthesizing 2-ethyl-2,3-epoxybutyl sulfonate represented by the formula (1) to (6) may include the following skis: Represented by 7-Scheme 8, but not limited thereto. C and R in these schemes are the same as defined in formula (1-1).
  • Scheme 7 is a method of reacting 2-ethyl-2,3-epoxybutanol with sulfonyl chloride or sulfonic acid anhydride in the presence of a base, and as the base, pyridine, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [ 5.4.0] undecene, diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] -5-nonene, 4-dimethylaminopyridine, 1,1,3,3-tetra Examples thereof include organic bases such as methylguanidine, 1,8-bis (dimethylamino) naphthalene, and 1,5,7-triazabicyclo [4.4.0] -5-decene.
  • a base and as the base, pyridine, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [ 5.4.0] undec
  • sulfonyl chloride examples include p-toluenesulfonyl chloride, methanesulfonyl chloride, chloromethanesulfonyl chloride, trifluoromethanesulfonyl chloride, nonafluorobutanesulfonyl chloride, 3-nitrobenzenesulfonyl chloride, 4-bromobenzenesulfonyl chloride and the like.
  • sulfonic acid anhydride examples include methanesulfonic acid anhydride, chloromethanesulfonic acid anhydride, trifluoromethanesulfonic acid anhydride, nonafluorobutanesulfonic acid anhydride, and the like.
  • Scheme 8 is a method for epoxidizing 2-ethyl-2-butenyl sulfonate, and as an epoxidizing agent, hydrogen peroxide, performic acid, peracetic acid, perisobutyric acid, trifluoroperacetic acid, perbenzoic acid, m-Chloroperbenzoic acid, t-butyl hydroperoxide and the like can be used.
  • sulfonate examples include methane sulfonate, chloromethane sulfonate, trifluoromethane sulfonate, nonafluorobutane sulfonate, p-toluene sulfonate, 3-nitrobenzene sulfonate, 4-bromobenzene sulfonate and the like.
  • Formula (1-3) (In the formula, c is an integer of 1 to 4, and R is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or these.
  • One hydrogen may be replaced by fluorine, chlorine, bromine, iodine, hydroxy, aryl, aralkyl, alkoxy, acyl, acyloxy, or alkoxycarbonyl, and at least one hydrogen bonded to a ring carbon has at least one carbon atom.
  • Examples of the method for synthesizing 2-ethyl-2,3-epoxybutyl ether represented by (1 to 6 alkyl) may include the following skis. Represented by 9 to Scheme 12, but not limited thereto. C and R in these schemes are the same as defined in formula (1-1).
  • Scheme 9 is a method of carrying out a Williamson ether synthesis reaction of 2-ethyl-2,3-epoxybutanol and an organic halide or organic sulfonate in the presence of a base, and as the halide, iodide, bromide,
  • the sulfonate include p-toluene sulfonate, methane sulfonate, chloromethane sulfonate, trifluoromethane sulfonate, nonafluorobutane sulfonate, 3-nitrobenzene sulfonate, 4-bromobenzene sulfonate, and the like.
  • Examples of the base include hydroxides of alkali metals or alkaline earth metals, hydrides of alkali metals or alkaline earth metals, pyridine, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undecene, diazabicyclo [2. 2.2.2] octane, 1,5-diazabicyclo [4.3.0] -5-nonene, 4-dimethylaminopyridine, 1,1,3,3-tetramethylguanidine, 1,8-bis (dimethylamino) )
  • Organic bases such as naphthalene and 1,5,7-triazabicyclo [4.4.0] -5-decene.
  • Scheme 10 is a method of reacting a 2-ethyl-2.3-epoxybutyl compound having a leaving group with an alcoholate or a phenolate, and the leaving group is iodine, bromine, chlorine, p-toluenesulfonate, methane.
  • the leaving group is iodine, bromine, chlorine, p-toluenesulfonate, methane.
  • Examples include sulfonates such as sulfonate, chloromethane sulfonate, trifluoromethane sulfonate, nonafluorobutane sulfonate, 3-nitrobenzene sulfonate, and 4-bromobenzene sulfonate.
  • the alcoholate or phenolate may be prepared separately in advance or may be produced in the reaction system.
  • Scheme 11 is a method of epoxidizing 2-ethyl-2-butenyl ether, and as the epoxidizing agent, hydrogen peroxide, performic acid, peracetic acid, perisobutyric acid, trifluoroperacetic acid, perbenzoic acid, m-Chloroperbenzoic acid, t-butyl hydroperoxide and the like can be used.
  • Scheme 12 is a method in which a base is allowed to act on 3-hydroxy-2-ethylbutyl ether having a leaving group at the 2-position to close the epoxy ring.
  • the leaving group include chlorine, bromine, iodine, p-toluenesulfonate, methanesulfonate, chloromethanesulfonate, trifluoromethanesulfonate and the like.
  • Examples of the base include alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, pyridine, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undecene, diazabicyclo [ 2.2.2] Octane, 1,5-diazabicyclo [4.3.0] -5-nonene, 4-dimethylaminopyridine, 1,1,3,3-tetramethylguanidine, 1,8-bis (dimethyl)
  • Examples thereof include organic bases such as amino) naphthalene and 1,5,7-triazabicyclo [4.4.0] -5-decene.
  • ether synthesis using the Mukaiyama redox condensation reaction that reacts 2-ethyl-2,3-epoxybutanol with fluoranil after diphenylphosphorylation of alcohol can also be applied.
  • Formula (1-4) (In the formula, c is an integer of 1 to 4, and R is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or these.
  • One hydrogen may be replaced by fluorine, chlorine, bromine, iodine, hydroxy, aryl, aralkyl, alkoxy, acyl, acyloxy, or alkoxycarbonyl, and at least one hydrogen bonded to a ring carbon has at least one carbon atom.
  • Examples of the method for synthesizing 2-ethyl-2,3-epoxybutyl carbonate represented by (1 to 6 alkyl) may include the following steps. Although it is shown in over arm 13 to Scheme 15, but not limited to. C and R in these schemes are the same as defined in formula (1-1).
  • Scheme 13 is a method of reacting 2-ethyl-2,3-epoxybutanol and chloroformate in the presence of a base, and as the base, pyridine, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4 .0] undecene, diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] -5-nonene, 4-dimethylaminopyridine, 1,1,3,3-tetramethylguanidine, Organic bases such as 1,8-bis (dimethylamino) naphthalene and 1,5,7-triazabicyclo [4.4.0] -5-decene can be mentioned.
  • Scheme 14 is a method for epoxidizing 2-ethyl-2-butenyl carbonate, and as the epoxidizing agent, hydrogen peroxide, performic acid, peracetic acid, perisobutyric acid, trifluoroperacetic acid, perbenzoic acid , M-chloroperbenzoic acid, t-butyl hydroperoxide and the like can be used.
  • Scheme 15 is a method in which a base is allowed to act on 3-hydroxy-2-ethylbutyl carbonate having a leaving group at the 2-position to close the epoxy ring.
  • the leaving group include chlorine, bromine, iodine, p-toluenesulfonate, methanesulfonate, chloromethanesulfonate, trifluoromethanesulfonate and the like.
  • Examples of the base include alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, pyridine, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undecene, diazabicyclo [ 2.2.2] Octane, 1,5-diazabicyclo [4.3.0] -5-nonene, 4-dimethylaminopyridine, 1,1,3,3-tetramethylguanidine, 1,8-bis (dimethyl)
  • Examples thereof include organic bases such as amino) naphthalene and 1,5,7-triazabicyclo [4.4.0] -5-decene.
  • Formula (1-5) (In the formula, c is an integer of 1 to 4, and R is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or these.
  • One hydrogen may be replaced by fluorine, chlorine, bromine, iodine, aryl, aralkyl, alkoxy, acyl, acyloxy, or alkoxycarbonyl, and at least one hydrogen bonded to the ring carbon has 1 to 1 carbon atoms.
  • 6 may be substituted with alkyl of 6), and a method for synthesizing 2-ethyl-2,3-epoxybutyl carbamate represented by But is the, not limited thereto.
  • C and R in these schemes are the same as defined in formula (1-1).
  • Scheme 16 is a method of reacting 2-ethyl-2,3-epoxybutanol and isocyanate, and as the base catalyst, pyridine, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undecene, diazabicyclo [2.2.2] Octane, 1,5-diazabicyclo [4.3.0] -5-nonene, 4-dimethylaminopyridine, 1,1,3,3-tetramethylguanidine, 1,8-bis ( Examples thereof include organic bases such as dimethylamino) naphthalene and 1,5,7-triazabicyclo [4.4.0] -5-decene, and metal compounds such as tin and zirconium are also used.
  • phase transfer catalyst examples include pyridinium salts, ammonium salts, phosphonium salts or sulfonates having a long chain alkyl, crown ethers and the like.
  • R is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a c-valent group in which these are combined, and at least one carbon of these groups is , May be replaced by oxygen or sulfur, and may include carbonyl, oxycarbonyl, or sulfonyl, and at least one hydrogen of these groups may be fluorine, chlorine, bromine, iodine, hydroxy, nitro, aryl, aralkyl. , Alkoxy, acyl, acyloxy, or alkoxycarbonyl may be substituted, and at least one hydrogen bonded to a ring carbon may be replaced with an alkyl having 1 to 6 carbons.
  • the carbon number of R is preferably 1-18.
  • the linear, branched, or cyclic saturated hydrocarbon group includes methyl, ethyl, propyl, 2-propyl, butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, heptyl, octyl.
  • cyclic saturated hydrocarbon group examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, menthyl, cholestanyl, bornyl, 1-adamantyl, 1-adamantylmethyl, 2-adamantyl, 2-methyl-2-adamantyl, adamantane- 1,3-diyl, adamantane-1,3,5-triyl, pinane-2,3-diyl, cyclobutane-1,3-diyl, cyclopentane-1,2-diyl, cyclopentane-1,3-diyl, Cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, cyclohexane-1,2-diylbis (methylene), cyclohexane-1,
  • the linear, branched, or cyclic unsaturated hydrocarbon group may be vinyl, allyl, 3-butenyl, 3-methyl-3-butenyl, citronellyl, geranyl, linalyl, neryl, farnesyl, 1-p-menthene-8- And 2-butene-1,4-diyl, 2-methyl-2-butene-1,4-diyl, 4-cyclopentene-1,3-diyl, 2-cyclohexene-1,4-diyl and the like.
  • Examples of the monocyclic or polycyclic aromatic group include phenyl, 4-methylphenyl, 5-isopropyl-2-methylphenyl, 6-isopropyl-3-methylphenyl, 1,2-phenylene, 1,3-phenylene, 1, 4-phenylene, oxybis (4,1-phenylene), propane-2,2-diylbis (4,1-phenylene), carbonylbis (4,1-phenylene), sulfonylbis (4,1-phenylene), [1 , 1'-biphenyl] -4,4'-diyl, [1,1'-binaphthalene] -2,2'-diyl, methylenebis (naphthalene-1,2-diyl), 1,1'-ferrocenediyl, 1 , 4-naphthalenediyl, 1,5-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,6-naphthalenediyl
  • Example 1 Synthesis of (Formula 1-2-1) Under a nitrogen atmosphere, pyridine (10 ml) was added to the 2-ethyl-2,3-epoxybutanol (1.0 g) obtained in Synthesis Example 2, ice-cooled, and methanesulfonyl chloride (0.8 ml) was added dropwise. . After stirring under ice-cooling for 1 hour, water and t-butyl methyl ether were added and the layers were separated. The organic layer was washed with water, saturated aqueous sodium hydrogen carbonate solution, water and saturated brine in that order, and sodium sulfate was added for drying. After that, it was filtered, and the filtrate was concentrated under reduced pressure at 40 ° C. by an evaporator.
  • Example 7 Synthesis of (Formula 1-1-2) Under a nitrogen atmosphere, pyridine (10 ml) was added to the 2-ethyl-2,3-epoxybutanol (1.0 g) obtained in Synthesis Example 2, and the mixture was ice-cooled to give 1,4-butanedicarboxylic acid chloride (0 0.75 g) was added dropwise. After stirring for 1 hour under ice cooling, water and t-butyl methyl ether were added to separate the layers. The organic layer was washed with water, 0.1N hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate solution, water and saturated brine in this order, dried over sodium sulfate, filtered, and the filtrate was concentrated.
  • Example 8 Synthesis of (Formula 1-3-1) Under a nitrogen atmosphere, 60% sodium hydride (0.52 g) was placed in a flask, washed twice with dry heptane, 8 ml of tetrahydrofuran was added, and the mixture was ice-cooled to give 2-ethyl-2,3 obtained in Synthesis Example 2. A solution of epoxybutanol (1.5 g) in 1-methyl-2-pyrrolidone (8 ml) was added dropwise at a rate such that the internal temperature did not exceed 10 ° C. After stirring for 30 minutes under ice cooling, 1,6-dibromohexane was added, and the mixture was stirred at room temperature for 2 hours and then at 45 ° C. for 1 hour.
  • Example 12 Synthesis of (formula 1-3-6) Under a nitrogen atmosphere, 60% sodium hydride (0.30 g) was placed in a flask, washed twice with dry heptane, tetrahydrofuran (5 ml) and 1-methyl-2-pyrrolidone (10 ml) were added, and the mixture was ice-cooled. Naphthalene-1,5-diol (0.56 g) was added in small portions. After stirring for 30 minutes under ice cooling, a solution of 2-ethyl-2,3-epoxybutyl p-toluenesulfonate (2.0 g) obtained in Example 2 in tetrahydrofuran (5 ml) was added dropwise.
  • Example 13 Synthesis of (formula 1-3-7) Under a nitrogen atmosphere, 60% sodium hydride (0.30 g) was placed in a flask, washed twice with dry heptane, tetrahydrofuran (5 ml) and 1-methyl-2-pyrrolidone (10 ml) were added, and the mixture was ice-cooled. 4,4 '-(Propane-2,2-diyl) diphenol (0.0.80g) was added in small portions. After stirring for 30 minutes under ice cooling, a solution of 2-ethyl-2,3-epoxybutyl p-toluenesulfonate (2.0 g) obtained in Example 2 in tetrahydrofuran (5 ml) was added dropwise.
  • 60% sodium hydride (0.30 g) was placed in a flask, washed twice with dry heptane, tetrahydrofuran (5 ml) and 1-methyl-2-pyrrolidone (10 ml)
  • Example 16 Synthesis of (formula 1-3-3) Under a nitrogen atmosphere, 60% sodium hydride (0.31 g) was placed in a flask, washed twice with dry heptane, 1-methyl-2-pyrrolidone (6 ml) was added, and the mixture was ice-cooled to give 2- (hydroxymethyl). ) -2-Methylpropane-1,3-diol (0.3 g) was added in small portions. After stirring for 30 minutes under ice cooling, a solution of 2-ethyl-2,3-epoxybutyl p-toluenesulfonate (2.1 g) obtained in Example 2 in tetrahydrofuran (3 ml) was added dropwise.
  • Example 17 Synthesis of (formula 1-3-4) Under a nitrogen atmosphere, 60% sodium hydride (0.37 g) was placed in a flask, washed twice with dry heptane, 1-methyl-2-pyrrolidone (6 ml) was added, and the mixture was ice-cooled and pentaerythritol (0. 3 g) was added in small portions. After stirring for 30 minutes under ice cooling, a solution of 2-ethyl-2,3-epoxybutyl p-toluenesulfonate (2.5 g) obtained in Example 2 in tetrahydrofuran (3 ml) was added dropwise. The ice bath was removed, and the mixture was stirred at 40 ° C. for 18 hours.
  • a novel 2-ethyl-2,3-epoxybutyloxy compound useful as an epoxy resin monomer can be provided.

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  • Epoxy Compounds (AREA)
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Abstract

La présente invention concerne un composé de 2-éthyl-2, 3-époxybutyloxy qui est utile en tant que nouveau monomère de résine époxy. La présente invention concerne divers nouveaux composés de 2-éthyl-2, 3-époxybutyloxy obtenus par estérification, éthérification ou uréthanisation de 2-éthyl -2, 3-époxybutanol qui est obtenu par réduction d'un formyle de 2-éthyl-2, 3-époxybutanal qui est obtenu par époxydation de 2-éthyl-2-buténal qui est l'un des produits de condensation aldolique de butyraldéhyde et d'acétaldéhyde.
PCT/JP2019/027032 2018-10-19 2019-07-08 Composé de 2-éthyl-2, 3-époxybutyloxy WO2020079895A1 (fr)

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CN201980065774.3A CN112805273A (zh) 2018-10-19 2019-07-08 2-乙基-2,3-环氧基丁氧基化合物
JP2020552523A JPWO2020079895A1 (ja) 2018-10-19 2019-07-08 ２−エチル−２，３−エポキシブチルオキシ化合物

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JP2018197434 2018-10-19
JP2018-197434 2018-10-19

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53146799A (en) * 1977-05-27 1978-12-20 Sumitomo Chem Co Ltd Novel epoxy resin and its preparation
WO2005061473A1 (fr) * 2003-12-24 2005-07-07 Sumitomo Chemical Company, Limited Composes epoxy et resines epoxy durcies obtenues a partir desdits composes
WO2006043608A1 (fr) * 2004-10-20 2006-04-27 Kansai Paint Co., Ltd. Composé de type polyépoxy, méthode de synthèse dudit composé, formulation de résine thermodurcissable contenant ledit composé, produit durci obtenu grâce à une telle formulation, et méthode de démoulage d'un tel produit durci
WO2012128325A1 (fr) * 2011-03-23 2012-09-27 日産化学工業株式会社 Composé époxy polyfonctionnel
WO2017077845A1 (fr) * 2015-11-05 2017-05-11 日産化学工業株式会社 Composé époxy multifonctionnel et composition durcissable le contenant

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007197518A (ja) * 2006-01-24 2007-08-09 Fujifilm Corp エポキシ樹脂化合物、熱硬化性樹脂組成物、及び感光性組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53146799A (en) * 1977-05-27 1978-12-20 Sumitomo Chem Co Ltd Novel epoxy resin and its preparation
WO2005061473A1 (fr) * 2003-12-24 2005-07-07 Sumitomo Chemical Company, Limited Composes epoxy et resines epoxy durcies obtenues a partir desdits composes
WO2006043608A1 (fr) * 2004-10-20 2006-04-27 Kansai Paint Co., Ltd. Composé de type polyépoxy, méthode de synthèse dudit composé, formulation de résine thermodurcissable contenant ledit composé, produit durci obtenu grâce à une telle formulation, et méthode de démoulage d'un tel produit durci
WO2012128325A1 (fr) * 2011-03-23 2012-09-27 日産化学工業株式会社 Composé époxy polyfonctionnel
WO2017077845A1 (fr) * 2015-11-05 2017-05-11 日産化学工業株式会社 Composé époxy multifonctionnel et composition durcissable le contenant

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CN112805273A (zh) 2021-05-14

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