阅读说明：本技术 2-乙基-2,3-环氧基丁氧基化合物 (2-ethyl-2, 3-epoxybutoxy compound ) 是由 川岛正敏 于 2019-07-08 设计创作，主要内容包括：本发明提供一种新颖的有效用作环氧树脂单体的2-乙基-2,3-环氧基丁氧基化合物。将使丁醛与乙醛的羟醛缩合生成物之一即2-乙基-2-丁烯醛加以环氧化而获得的2-乙基-2,3-环氧基丁醛的甲酰还原,制成2-乙基-2,3-环氧基丁醇,并将其加以酯化、醚化、或氨基甲酸酯化,由此提供各种新颖的2-乙基-2,3-环氧基丁氧基化合物。(The present invention provides a novel 2-ethyl-2, 3-epoxybutoxy compound which is useful as an epoxy resin monomer. A2-ethyl-2, 3-epoxybutanol obtained by epoxidizing 2-ethyl-2, 3-epoxybutyraldehyde, which is one of aldol condensation products of butyraldehyde and acetaldehyde, is reduced in formyl group to produce 2-ethyl-2, 3-epoxybutanol, which is esterified, etherified, or carbamated, thereby providing various novel 2-ethyl-2, 3-epoxybutoxy compounds.)

1. A2-ethyl-2, 3-epoxybutoxy compound represented by the formula (1),

(wherein A is a carbonyl group or a sulfonyl group, Z is an oxygen or an imino group, a and b are independently 0 or 1, c is an integer of 1 to 4, R is a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a c-valent group formed by combining these groups, at least one carbon of these groups may be substituted by oxygen or sulfur, and may contain a carbonyl group, an oxycarbonyl group, or a sulfonyl group, at least one hydrogen of these groups may be substituted by fluorine, chlorine, bromine, iodine, nitro group, a hydroxyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an acyloxy group, or an alkoxycarbonyl group, and at least one hydrogen of the carbons bonded to the ring may be substituted by an alkyl group having 1 to 6 carbon atoms).

2. The 2-ethyl-2, 3-epoxybutoxy compound according to claim 1, wherein in formula (1), A is a carbonyl group, a is 1, b is 0, c is 1, R is a monovalent group having 1 to 18 carbon atoms and being a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a combination thereof, and at least one hydrogen bonded to a carbon of the ring may be substituted with a methyl group.

3. The 2-ethyl-2, 3-epoxybutoxy compound according to claim 1, wherein in formula (1), A represents a carbonyl group, a represents 1, b represents 0, c represents 2 or 3, and R represents a c-valent group having 1 to 18 carbon atoms, which is a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a combination thereof.

4. The 2-ethyl-2, 3-epoxybutoxy compound according to claim 1, wherein in formula (1), A is a sulfonyl group, a is 1, b is 0, c is 1, R is a linear saturated hydrocarbon group, a monocyclic aromatic group, or a monovalent group having 1 to 18 carbon atoms formed by a combination thereof, and at least one hydrogen of carbons bonded to the ring may be substituted by a methyl group.

5. The 2-ethyl-2, 3-epoxybutoxy compound according to claim 1, wherein in formula (1), a and b are both 0, c is 1, R is a monovalent group having 1 to 18 carbon atoms and formed by a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a combination thereof, and at least one hydrogen of carbon atoms bonded to the ring may be substituted by a methyl group.

6. The 2-ethyl-2, 3-epoxybutoxy compound according to claim 1, wherein in formula (1), a and b are each 0, c is an integer of 2 to 4, R is a c-valent group having 1 to 18 carbon atoms, which is a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a combination thereof, and at least one hydrogen of carbons bonded to the ring may be substituted with a methyl group.

7. The 2-ethyl-2, 3-epoxybutoxy compound according to claim 1, wherein in formula (1), A represents a carbonyl group, Z represents an imino group, a and b are each 1, c represents 2, and R represents a linear, branched or cyclic saturated hydrocarbon group or a divalent group having 1 to 18 carbon atoms formed by a combination thereof.

8. The 2-ethyl-2, 3-epoxybutoxy compound according to claim 1, which is represented by any one of formulae (1-1-1) to (1-1-5), formulae (1-2-1) to (1-2-2), formulae (1-3-1) to (1-3-7), and formulae (1-5-1),

Technical Field

The present invention is a 2-ethyl-2, 3-epoxybutoxy compound which is useful as an epoxy resin monomer.

Background

Epoxy compounds are widely used as modifiers and crosslinking agents for resins in various materials, and glycidyl or cycloolefin oxide compounds have been developed, and physical properties according to the respective uses such as heat resistance, flexibility, weather resistance, air permeability, resistance to thermal yellowing, low viscosity, high Tg, transparency, Ultraviolet (UV) curability, and no halogen are required (non-patent document 1, non-patent document 2, non-patent document 3, non-patent document 4, non-patent document 5, and non-patent document 6).

Documents of the prior art

Non-patent document

Non-patent document 1: "DIC Technical Review" No.7,1-12(2001)

Non-patent document 2: "network Polymer" Vol.36, No.5,239-

Non-patent document 3: "network Polymer" Vol.36, No.5,211-222(2015)

Non-patent document 4: "network Polymer" Vol.31, No.3,113-124(2010)

Non-patent document 5: "network Polymer" Vol.31, No.4,177-190(2010)

Non-patent document 6: "network Polymer" Vol.32, No.1,35-42(2011)

Disclosure of Invention

Problems to be solved by the invention

Many compounds have been developed for glycidyl epoxy monomers, but glycidyl monomers in which the oxirane ring part is trisubstituted are limited (Japanese patent laid-open No. 8-165288, Japanese patent laid-open No. 51-016464), and 2-ethyl-2, 3-epoxybutoxy compounds are expected to show different reactivity or selectivity in acid-catalyzed or base-catalyzed reactions, and although there is a possibility that various materials can be provided in various physical properties such as mechanical properties, electrical properties, heat resistance, moisture resistance, and adhesion of epoxy resins, they have not been synthesized so far.

Means for solving the problems

The present inventors have found that: the present inventors have completed the present invention by reducing formyl of 2-ethyl-2, 3-epoxybutanal (butanal) obtained by epoxidizing 2-ethyl-2, 3-epoxybutanal (butanal) which is one of aldol (aldol) condensation products of butanal and acetaldehyde to produce 2-ethyl-2, 3-epoxybutanol, and subjecting the 2-ethyl-2, 3-epoxybutanol to esterification, sulfonylation, etherification, or carbamation to obtain various novel 2-ethyl-2, 3-epoxybutoxy compounds.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, various 2-ethyl-2, 3-epoxybutoxy compounds such as epoxy group-containing ethers, esters and carbamates, which are useful as epoxy resin monomers, can be provided by carrying out a conversion reaction from 2-ethyl-2-butenal, which is industrially easily available, in several steps which can be carried out on an industrial scale.

Detailed Description

The present invention includes the following items [1] to [8], and the like.

[1] A2-ethyl-2, 3-epoxybutoxy compound represented by formula (1).

(wherein A is a carbonyl group or a sulfonyl group, Z is an oxygen or an imino group, a and b are independently 0 or 1, c is an integer of 1 to 4, R is a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a c-valent group formed by combining these groups, at least one carbon of these groups may be substituted by oxygen or sulfur, and may contain a carbonyl group, an oxycarbonyl group, or a sulfonyl group, at least one hydrogen of these groups may be substituted by fluorine, chlorine, bromine, iodine, nitro, hydroxyl, aryl, aralkyl, alkoxy, acyl, acyloxy, or alkoxycarbonyl, and at least one hydrogen of the carbons bonded to the ring may be substituted by an alkyl group having 1 to 6 carbon atoms.)

[2] The 2-ethyl-2, 3-epoxybutoxy compound according to the above [1], wherein in the formula (1), A represents a carbonyl group, a represents 1, b represents 0, c represents 1, R represents a monovalent group having 1 to 18 carbon atoms and being a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a combination thereof, and at least one hydrogen bonded to a carbon of the ring may be substituted by a methyl group.

[3] The 2-ethyl-2, 3-epoxybutoxy compound according to the above [1], wherein in the formula (1), A represents a carbonyl group, a represents 1, b represents 0, c represents 2 or 3, and R represents a c-valent group having 1 to 18 carbon atoms, which is a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a combination thereof.

[4] The 2-ethyl-2, 3-epoxybutoxy compound according to the item [1], wherein in the formula (1), A is a sulfonyl group, a is 1, b is 0, c is 1, R is a linear saturated hydrocarbon group, a monocyclic aromatic group, or a monovalent group having 1 to 18 carbon atoms formed by combining these groups, and at least one hydrogen of the carbon bonded to the ring may be substituted by a methyl group.

[5] The 2-ethyl-2, 3-epoxybutoxy compound according to the above [1], wherein in the formula (1), a and b are both 0, c is 1, R is a monovalent group having 1 to 18 carbon atoms and being a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a combination thereof, and at least one hydrogen of carbon atoms bonded to the ring may be substituted with a methyl group.

[6] The 2-ethyl-2, 3-epoxybutoxy compound according to the item [1], wherein in the formula (1), a and b are each 0, c is an integer of 2 to 4, R is a c-valent group having 1 to 18 carbon atoms, which is a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a combination thereof, and at least one hydrogen of carbons bonded to the ring may be substituted by a methyl group.

[7] The 2-ethyl-2, 3-epoxybutoxy compound according to the above [1], wherein in the formula (1), A represents a carbonyl group, Z represents an imino group, a and b are each 1, c represents 2, and R represents a linear, branched or cyclic saturated hydrocarbon group or a divalent group having 1 to 18 carbon atoms which is a combination of these groups.

[8]

The 2-ethyl-2, 3-epoxybutoxy compound according to the item [1], which is represented by any one of the formulae (1-1-1) to (1-1-6), the formulae (1-2-1) to (1-2-2), the formulae (1-3-1) to (1-3-7), and the formula (1-5-1).

< about raw materials >

2-Ethyl-2, 3-epoxybutanol, which can be used as a main raw material, can be synthesized by a method of epoxidizing 2-ethyl-2-butenal followed by reduction, a method of carrying out reduction followed by epoxidation, or the like, as shown below.

Further, 2-ethyl-2, 3-epoxybutanol may be derivatized according to the following formula (wherein X represents a leaving group such as halogen or sulfonate) and used as a raw material.

Further, a compound obtained by derivatizing 2-ethyl-2-butenol obtained by reducing 2-ethyl-2-butenal according to the following formula (wherein G represents an organic group) can also be used as a raw material.

< 2-ethyl-2, 3-epoxybutyl acylate >

The method for synthesizing a 2-ethyl-2, 3-epoxybutyl acylate represented by the formula (1-1) (wherein c is an integer of 1 to 4, R is a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a c-valent group formed by a combination thereof, at least one carbon of these groups may be substituted by oxygen or sulfur, and may include a carbonyl group, an oxycarbonyl group, or a sulfonyl group, at least one hydrogen of these groups may be substituted by fluorine, chlorine, bromine, iodine, a hydroxyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an acyloxy group, or an alkoxycarbonyl group, and at least one hydrogen of the carbons bonded to the ring may be substituted by an alkyl group having 1 to 6 carbon atoms) is represented by, for example, the following schemes 1 to 6, but is not limited thereto. C and R in these schemes are as defined for formula (1-1).

Scheme 1 is a method of reacting 2-ethyl-2, 3-epoxybutanol with a carboxylic acid chloride or a carboxylic acid anhydride in the presence of a base, and as the base, pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, 1, 4-diazabicyclo [2.2.2] octane, N' -tetramethylethylenediamine, sodium hydroxide, bismuth chloride, zinc oxide, aluminum oxide, zirconium oxychloride, titanium oxide, bismuth ferrite, cerium chloride, lithium perchlorate, or the like can be used, and a method using a microflow reactor without using a base can also be used.

Scheme 2 is a scheme in which 2-ethyl-2, 3-epoxybutanol is reacted with a carboxylic acid in the presence of a condensing agent, and examples of the condensing agent include: n, N '-dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide, 1- [3- (dimethylamino) propyl ] -3-ethylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N '-carbonyldiimidazole 1,1' -carbonylbis (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-octyloxy-2-oxoethyl) dimethylammonium, sodium bicarbonate, 2,4, 6-trichlorobenzoyl chloride, 2-methyl-6-nitrobenzoic anhydride, ditrimethylanilinium pentafluorosulfonate, diphenylphosphorylazide, 2-chloro-4, 6-dimethoxy-1, 3, 5-triazine/N-methylmorpholine and the like, and a method using a hill-ward reagent (2-halo-N-alkylpyridinium salt), a mitsunobu method (azodicarboxylate/triphenylphosphine), a hill-ward quinone method (diphenylphosphorylation reagent/dimethylbenzoquinone) and the like can be used.

Scheme 3 is to react 2-ethyl-2, 3-epoxybutanol with a carboxylic acid ester in the presence of an acid, base, or neutral catalystThe transesterification reaction may be carried out using sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium carbonate, potassium cyanide, 4-dimethylaminopyridine, zinc tetranuclear (ZnO)₄) Clusters, zinc-bismuth imidazole ligand complexes, tetramethylammonium monomethylcarbonate, lanthanum (III) isopropoxide/diethylene glycol monomethyl ether, ferrosalen (salen) complexes, zinc hydroxide, various metal halides, various metal acetates, and the like.

Scheme 4 is a method of reacting a compound having a leaving group such as a halide derived from 2-ethyl-2, 3-epoxybutanol, p-toluenesulfonate, methanesulfonate, chloromethanesulfonate, trifluoromethanesulfonate, nonafluorobutanesulfonate, 3-nitrobenzenesulfonate, 4-bromobenzenesulfonate, with a carboxylic ester derived from a carboxylic acid. As the halogen of the leaving group, chlorine, bromine or iodine can be used, and as the counter ion (counter ion) of the carboxylate, alkali metal, alkaline earth metal, tin, 1-ethyl-3-methylimidazolium or the like can be used.

Scheme 5 is a method for carrying out the epoxidation of 2-ethyl-2-butenyl carboxylate, and as the epoxidizing agent, hydrogen peroxide, performic acid, peracetic acid, isobutyric acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, t-butyl hydroperoxide and the like can be used.

Scheme 6 is a method of ring-closing a 3-hydroxy-2-ethylbutyl carboxylate having a leaving group at the 2-position to an epoxy ring by allowing a base to act thereon. Examples of the leaving group include: chlorine, bromine, iodine, p-toluenesulfonate, methanesulfonate, chloromethanesulfonate, trifluoromethanesulfonate and the like. As the base, there may be mentioned: an organic base such as an alkali metal or alkaline earth metal hydroxide, an alkali metal or alkaline earth metal hydride, 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, 1,3, 3-tetramethylguanidine, 1, 8-bis (dimethylamino) naphthalene, 1,5, 7-triazabicyclo [4.4.0] -5-decene, or the like.

< 2-ethyl-2, 3-epoxybutylsulfonate >)

The method for synthesizing 2-ethyl-2, 3-epoxybutyl sulfonate represented by the formula (1-2) (wherein c is an integer of 1 to 4, R is a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a c-valent group formed by a combination thereof, at least one carbon of these groups may be substituted by oxygen or sulfur, and may include a carbonyl group, an oxycarbonyl group, or a sulfonyl group, at least one hydrogen of these groups may be substituted by fluorine, chlorine, bromine, iodine, nitro group, aryl group, aralkyl group, alkoxy group, acyl group, acyloxy group, or alkoxycarbonyl group, and at least one hydrogen of carbon bonded to the ring may be substituted by an alkyl group having 1 to 6 carbon atoms) is represented by, for example, the following schemes 7 to 8, but is not limited thereto. C and R in these schemes are as defined for formula (1-1).

Scheme 7 is a method of reacting 2-ethyl-2, 3-epoxybutanol with sulfonyl chloride or sulfonic anhydride in the presence of a base, which may be exemplified by: an organic base such as 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, 1,3, 3-tetramethylguanidine, 1, 8-bis (dimethylamino) naphthalene, 1,5, 7-triazabicyclo [4.4.0] -5-decene, etc. Examples of sulfonyl chlorides include: p-toluenesulfonyl chloride, methanesulfonyl chloride, chloromethanesulfonyl chloride, trifluoromethanesulfonyl chloride, nonafluorobutanesulfonyl chloride, 3-nitrobenzenesulfonyl chloride, 4-bromobenzenesulfonyl chloride and the like. Examples of the sulfonic anhydride include: methanesulfonic anhydride, chloromethanesulfonic anhydride, trifluoromethanesulfonic anhydride, nonafluorobutanesulfonic anhydride, and the like.

Scheme 8 is a method for epoxidizing 2-ethyl-2-butenyl sulfonate, and as the epoxidizing agent, hydrogen peroxide, performic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, t-butyl hydroperoxide, etc. can be used. Examples of the sulfonic acid ester include: methanesulfonate, chloromethanesulfonate, trifluoromethanesulfonate, nonafluorobutanesulfonate, p-toluenesulfonate, 3-nitrobenzenesulfonate, 4-bromobenzenesulfonate and the like.

< 2-ethyl-2, 3-epoxybutyl ether >)

The method for synthesizing 2-ethyl-2, 3-epoxybutyl ether represented by the formula (1-3) (wherein c is an integer of 1 to 4, R is a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a c-valent group formed by a combination thereof, at least one carbon of these groups may be substituted by oxygen or sulfur, and may include a carbonyl group, an oxycarbonyl group, or a sulfonyl group, at least one hydrogen of these groups may be substituted by fluorine, chlorine, bromine, iodine, a hydroxyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an acyloxy group, or an alkoxycarbonyl group, and at least one hydrogen of carbons bonded to the ring may be substituted by an alkyl group having 1 to 6 carbon atoms) is represented by, for example, the following schemes 9 to 12, but is not limited thereto. C and R in these schemes are as defined for formula (1-1).

Scheme 9 is a method of carrying out Williamson (Williamson) ether synthesis reaction of 2-ethyl-2, 3-epoxybutanol with an organic halide or organic sulfonate in the presence of a base, and examples of the halide include: iodides, bromides, chlorides, and sulfonic acid esters include: p-toluenesulfonate, methanesulfonate, chloromethanesulfonate, trifluoromethanesulfonate, nonafluorobutanesulfonate, 3-nitrobenzenesulfonate, 4-bromobenzenesulfonate and the like. As the base, there may be mentioned: an organic base such as an alkali metal or alkaline earth metal hydroxide, an alkali metal or alkaline earth metal hydride, 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, 1,3, 3-tetramethylguanidine, 1, 8-bis (dimethylamino) naphthalene, 1,5, 7-triazabicyclo [4.4.0] -5-decene, or the like.

Scheme 10 is a method of reacting a 2-ethyl-2, 3-epoxybutyl compound having a leaving group with an alkoxide or phenoxide, and examples of the leaving group include: sulfonates such as iodine, bromine, chlorine, p-toluenesulfonate, methanesulfonate, chloromethanesulfonate, trifluoromethanesulfonate, nonafluorobutanesulfonate, 3-nitrobenzenesulfonate and 4-bromobenzenesulfonate. The alkoxide or phenoxide is produced separately in advance and is 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, isobutyric acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, t-butyl hydroperoxide, etc. can be used.

Scheme 12 is a method of ring-closing a 3-hydroxy-2-ethylbutyl ether having a leaving group at the 2-position to an epoxy ring by allowing a base to act thereon. Examples of the leaving group include: chlorine, bromine, iodine, p-toluenesulfonate, methanesulfonate, chloromethanesulfonate, trifluoromethanesulfonate and the like. As the base, there may be mentioned: an organic base such as an alkali metal or alkaline earth metal hydroxide, an alkali metal or alkaline earth metal hydride, 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, 1,3, 3-tetramethylguanidine, 1, 8-bis (dimethylamino) naphthalene, 1,5, 7-triazabicyclo [4.4.0] -5-decene, or the like.

Further, ether synthesis using a hill-oriented redox condensation reaction in which 2-ethyl-2, 3-epoxybutanol is reacted with tetrafluorop-benzoquinone (fluoroanil) after diphenylphosphorylation of an alcohol can also be used.

< 2-ethyl-2, 3-epoxybutyl carbonate >)

The method for synthesizing 2-ethyl-2, 3-epoxybutyl carbonate represented by the formula (1-4) (wherein c is an integer of 1 to 4, R is a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a c-valent group formed by a combination thereof, at least one carbon of these groups may be substituted by oxygen or sulfur, and may include a carbonyl group, an oxycarbonyl group, or a sulfonyl group, at least one hydrogen of these groups may be substituted by fluorine, chlorine, bromine, iodine, a hydroxyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an acyloxy group, or an alkoxycarbonyl group, and at least one hydrogen of carbons bonded to the ring may be substituted by an alkyl group having 1 to 6 carbon atoms) is represented by, for example, the following schemes 13 to 15, but is not limited thereto. C and R in these schemes are as defined for formula (1-1).

Scheme 13 is a method of reacting 2-ethyl-2, 3-epoxybutanol with a chloroformate in the presence of a base, which may be: an organic base such as 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, 1,3, 3-tetramethylguanidine, 1, 8-bis (dimethylamino) naphthalene, 1,5, 7-triazabicyclo [4.4.0] -5-decene, etc.

Scheme 14 is a method for epoxidizing 2-ethyl-2-butenyl carbonate, and as the epoxidizing agent, hydrogen peroxide, performic acid, peracetic acid, isobutyric acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, t-butyl hydroperoxide, etc. can be used.

Scheme 15 is a method of ring-closing an epoxy ring by allowing a base to act on 3-hydroxy-2-ethylbutyl carbonate having a leaving group at the 2-position. Examples of the leaving group include: chlorine, bromine, iodine, p-toluenesulfonate, methanesulfonate, chloromethanesulfonate, trifluoromethanesulfonate and the like. As the base, there may be mentioned: an organic base such as an alkali metal or alkaline earth metal hydroxide, an alkali metal or alkaline earth metal hydride, 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, 1,3, 3-tetramethylguanidine, 1, 8-bis (dimethylamino) naphthalene, 1,5, 7-triazabicyclo [4.4.0] -5-decene, or the like.

< 2-ethyl-2, 3-epoxybutyl carbamate >)

The method for synthesizing 2-ethyl-2, 3-epoxybutylcarbamate represented by formula (1-5) (wherein c is an integer of 1 to 4, R is a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a c-valent group formed by a combination thereof, at least one carbon of these groups may be substituted with oxygen or sulfur, and may include a carbonyl group, an oxycarbonyl group, or a sulfonyl group, at least one hydrogen of these groups may be substituted with fluorine, chlorine, bromine, iodine, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an acyloxy group, or an alkoxycarbonyl group, and at least one hydrogen of the carbons bonded to the ring may be substituted with an alkyl group having 1 to 6 carbon atoms) is represented by, for example, scheme 16 below, but is not limited thereto. C and R in these schemes are as defined for formula (1-1).

Scheme 16 is a method for reacting 2-ethyl-2, 3-epoxybutanol with an isocyanate, and examples of the base catalyst include: organic bases such as 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, 1,3, 3-tetramethylguanidine, 1, 8-bis (dimethylamino) naphthalene, 1,5, 7-triazabicyclo [4.4.0] -5-decene, and metal compounds such as tin and zirconium may be used.

In the above-mentioned reactions 1 to 16, a method of using a transfer catalyst or an ionic liquid is also used to promote the reaction. As the relevant transfer catalyst, there may be mentioned: pyridinium salts, ammonium salts, phosphonium salts, sulfonates, and the like having a long-chain alkyl group, crown ethers, and the like.

< about R >

R is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, or a c-valent group formed by combining these groups, at least one carbon of these groups may be substituted by oxygen or sulfur, and may include a carbonyl group, an oxycarbonyl group, or a sulfonyl group, at least one hydrogen of these groups may be substituted by fluorine, chlorine, bromine, iodine, a hydroxyl group, a nitro group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an acyloxy group, or an alkoxycarbonyl group, and at least one hydrogen of the carbons bonded to the ring may be substituted by an alkyl group having 1 to 6 carbon atoms. The number of carbon atoms in R is preferably 1 to 18.

Examples of the linear, branched, or cyclic saturated hydrocarbon group include: methyl, ethyl, propyl, 2-propyl, butyl, 2-methylpropyl, 1-dimethylethyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 3, 7-dimethyloctyl, methylene, ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, octane-1, 8-diyl, decane-1, 10-diyl, dodecane-1, 12-diyl, tetradecane-1, 14-diyl, hexadecane-1, 16-diyl, octadecane-1, 18-diyl, Oxybis (ethane-2, 1-diyl), oxybis (propane-3, 1-diyl), oxybis (butane-4, 1-diyl), oxybis (pentane-5, 1-diyl), oxybis (hexane-6, 1-diyl), oxybis (octane-8, 1-diyl), (ethane-1, 2-diylbis (oxy)) bis (ethane-2, 1-diyl), (propane-1, 3-diylbis (oxy)) bis (propane-3, 1-diyl), (butane-1, 4-diylbis (oxy)) bis (ethane-1, 1-diyl), 3,6,9, 12-tetraoxatetradecane-2, 13-diyl, and the like.

Examples of the cyclic saturated hydrocarbon group 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-diyl, 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, 3-diylbis (methylene), Cyclohexane-1, 4-diylbis (methylene), [1,1 '-bis (cyclohexane) ] -4,4' -diylbis (methylene), propane-2, 2-diylbis (cyclohexane-4, 1-diyl), carbonylbis (cyclohexane-4, 1-diyl), oxybis (cyclohexane-4, 1-diyl), decahydronaphthalene-2, 6-diyl, octahydro-1H-4, 7-methanobridge indene (methanoindene) -2, 5-diyl, (octahydro-1H-4, 7-methanobridge indene-2, 5-diyl) bis (methylene), bicyclo [2.2.1] heptane-2, 5-diyl, bicyclo [2.2.2] octane-1, 4-diyl, 2,2,4, 4-tetramethylcyclobutane-1, 3-diyl, (cyclohexane-1, 4-diylbis (methylene)) bis (oxy)) bis (ethane-1, 1-diyl), and the like.

Examples of the linear, branched, or cyclic unsaturated hydrocarbon group include: vinyl, allyl, 3-butenyl, 3-methyl-3-butenyl, citronellyl, geranyl, linalyl (linalyl), neryl (neryl), farnesyl (farnesyl), 1-p-menthene (menthene) -8-yl, 2-buten-1, 4-diyl, 2-methyl-2-buten-1, 4-diyl, 4-cyclopenten-1, 3-diyl, 2-cyclohexen-1, 4-diyl, and the like.

Examples of monocyclic or polycyclic aromatic groups 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' -binaphthyl ] -2,2' -diyl, methylenebis (naphthalene-1, 2-diyl), 1' -ferrocenediyl, 1, 4-naphthalenediyl, 1, 5-naphthalenediyl, 2, 6-naphthalenediyl, 2, 7-naphthalenediyl, 1, 6-naphthalenediyl, anthracene-2, 6-diyl, anthracene-9, 10-diyl, [1, 1': 4', 1' -terphenyl ] -4,4' -diyl, anthracene-9, 10-diylbis (4, 1-phenylene), anthracene-9, 10-diylbis ([1,1' -biphenyl ] -4', 4-diyl), (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (naphthalene-6, 2-diyl), (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (naphthalene-4, 1-diyl), anthracene-9, 10-diylbis (naphthalene-6, 2-diyl),

[2,2 '-binaphthyl ] -6,6' -diyl, 9H-fluorene-2, 7-diyl, 9-dimethyl-9H-fluorene-2, 7-diyl, 9-oxo-9H-fluorene-2, 7-diyl, dibenzo [ b, d ] furan-3, 7-diyl, 7H-dibenzo [ c, g ] fluorene-5, 9-diyl, 7-dimethyl-7H-dibenzo [ c, g ] fluorene-5, 9-diyl, 7-oxo-7H-dibenzo [ c, g ] fluorene-5, 9-diyl, dinaphtho [2, 1-b: 1',2-d ] furan-5, 9-diyl, 13H-dibenzo [ a, j ] fluorene-3, 10-diyl, 13-dimethyl-13H-dibenzo [ a, j ] fluorene-3, 10-diyl, 13-oxo-13H-dibenzo [ a, j ] fluorene-3, 10-diyl, dinaphtho [1, 2-b: 2',1' -d ] furan-3, 10-diyl, 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl, 9, 10-dioxo-9, 10-dihydroanthracene-1, 5-diyl, benzene-1, 3, 5-diyl, benzene-1, 2,4, 5-diyl, naphthalene-2, 3,6, 7-diyl, naphthalene-1, 4,5, 8-diyl, [1,1 ': 4',1": 4', 1' -quaterphenyl ] -4,4' -diyl, (naphthalene-2, 6-diylbis (oxy)) bis (4, 1-phenylene), naphthalene-2, 6-diylbis (4, 1-phenylene), and the like.

Specific examples of the Compound represented by the formula (1)

Specific examples of the 2-ethyl-2, 3-epoxybutoxy compound represented by the formula (1) are shown below, but not limited to the compounds represented by the following exemplified formulae (1-1-1) to (1-1-83), formulae (1-2-1) to (1-2-10), formulae (1-3-1) to (1-3-178), formulae (1-4-1) to (1-4-15), and formulae (1-5-1) to (1-5-11).

Examples

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The measurement conditions of the gas chromatography were as follows.

Gas Chromatograph (GC) apparatus: GC-2014 from Shimadzu

Pipe column: agilent J & W GC column DB-1ms (L60 m x phi 0.250mm, D: 0.25 μm)

Temperature of the pipe column: 50 ℃ (5 min hold) → 10 ℃/min → 250 ℃ (5 min hold)

Injection temperature: 280 deg.C

Carrier gas: pure helium G1

A detector: flame Ionization Detector (FID)

< Synthesis example 1 >Synthesis of 2-ethyl-2, 3-epoxybutyraldehyde

A mixture of 2-ethyl-2-butenal (50g), sodium 4-dodecylbenzenesulfonate (89mg) and 10% sodium hydroxide (55ml) was cooled in an ice bath under a nitrogen atmosphere, and 30% hydrogen peroxide water (62ml) was added dropwise over 1 hour at a temperature of not more than 10 ℃. After stirring for 17 hours under cooling in an ice bath, salt (32g) was added thereto, and the mixture was stirred for 5 minutes, and then allowed to stand still for liquid separation. The organic layer was washed with saturated brine (3 times, total 100ml) and dried over sodium sulfate, thereby obtaining 2-ethyl-2, 3-epoxybutyraldehyde (40g, 91% by GC and 63: 37(GC), 6: 4(NMR (nuclear magnetic resonance))).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：9.44(s,0.4H),8.86(s,0.6H),3.30(q,J＝5.5Hz,0.6H),3.23(q,J＝6.0Hz,0.4H),2.04～1.93(m,0.8H),1.68～1.60(m,1.2H),1.47(d,J＝6.0Hz,1.2H),1.44(d,J＝5.5Hz,1.8H)),1.04(t,J＝7.5Hz,1.8H),0.96(t,J＝7.5Hz,1.2H).

< Synthesis example 2 >Synthesis of 2-ethyl-2, 3-epoxybutanol

Methanol (11ml) and methylene chloride (97ml) were added to 2-ethyl-2, 3-epoxybutanal (10.8g) obtained in synthetic example 1 under a nitrogen atmosphere, and cooled in an ice bath, and sodium borohydride (1.8g) was added in small amounts in succession at 5 ℃ to 15 ℃. After stirring for 30 minutes under ice-bath cooling, water was added and liquid separation was performed, the organic layer was washed 2 times with water, dried with sodium sulfate and filtered, and the filtrate was concentrated under reduced pressure and at room temperature with an evaporator. To the concentrated residue was added methylene chloride, followed by addition of sodium sulfate, drying and filtration, and the filtrate was concentrated at room temperature using an evaporator to obtain 2-ethyl-2, 3-epoxybutanol (6.6g, 87% by GC, 58: 42(GC), 6: 4 (NMR)).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：3.78～3.59(m,2H),3.18(q,J＝5.6Hz,0.66H),3.01(q,J＝5.7Hz,0.34H),2.31(br,1H),1.87～1.44(m,2H),1.35(d,J＝5.6Hz,1.1Hz),1.33(d,J＝5.7Hz,1.9H),1.01(t,J＝Hz,1.9H),0.97(t,J＝Hz,1.1H)

< example 1 >Synthesis of (formula 1-2-1)

Pyridine (10ml) was added to 2-ethyl-2, 3-epoxybutanol (1.0g) obtained in synthetic example 2 under a nitrogen atmosphere and cooled in an ice bath, and methanesulfonyl chloride (0.8ml) was added dropwise. After stirring for 1 hour with ice-cooling, water and tert-butyl methyl ether were added to separate the phases, the organic layer was washed with water, a saturated aqueous sodium bicarbonate solution, water, and a saturated brine in this order, dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure and at 40 ℃ by an evaporator. The concentrated residue was dried under reduced pressure at room temperature using a vacuum pump, to obtain methanesulfonic acid 2-ethyl-2, 3-epoxybutyl ester (0.64g, isomer ratio 6: 4 (NMR)).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：4.4～4.1(m,2H),3.1～3.0(m,1H),3.09(s,1.2H),3.07(s,1.8H),1.9～1.5(m,2H),1.37(d,J＝5.7Hz,1.2H),1.35(d,J＝5.6Hz,1.8H),1.05(t,J＝7.7Hz,1.8H),0.98(t,J＝7.6Hz,1.2H)

< example 2 >Synthesis of (formula 1-2-2)

Pyridine (10ml) was added to 2-ethyl-2, 3-epoxybutanol (1.0g) obtained in synthetic example 2 under a nitrogen atmosphere and cooled in an ice bath, and p-toluenesulfonyl chloride (2.1g) was added. After stirring for 1 hour under cooling in an ice bath and then for 30 minutes at room temperature, water and tert-butyl methyl ether were added and liquid-separated, the organic layer was washed with water, a saturated aqueous sodium bicarbonate solution, water and a saturated common salt solution in this order, dried with sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure and at 40 ℃ by an evaporator. The concentrated residue was dried under reduced pressure at room temperature using a vacuum pump, thereby obtaining 2-ethyl-2, 3-epoxybutyl p-toluenesulfonate (0.98g, isomer ratio 6: 4 (NMR)).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：7.81～7.78(m,2H),7.37～7.35(m,2H),4.10～3.95(m,2H),2.95(q,J＝5.6Hz,0.4H),2.92(q,J＝5.6Hz,0.6H),2.46(s,1.2H),2.45(s,1.8H),1.46～1.75(m,2H),1.27(d,J＝5.6Hz,1.8H),1.22(d,J＝5.7Hz,1.2H),0.94(t,J＝7.6Hz,1.8H),0.86(t,J＝7.6Hz,1.2H)

< example 3 >Synthesis of (formula 1-1-1)

Pyridine (10ml) was added to 2-ethyl-2, 3-epoxybutanol (1.0g) obtained in synthetic example 2 under a nitrogen atmosphere, cooled in an ice bath, and methacryloyl chloride (1.0ml) was added dropwise. After stirring for 1 hour with ice-cooling, water and tert-butyl methyl ether were added to separate the phases, the organic layer was washed with water, a saturated aqueous sodium bicarbonate solution, water, and a saturated brine in this order, dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure and at 40 ℃ by an evaporator. The concentrated residue was dried under reduced pressure at room temperature using a vacuum pump, to obtain 2-ethyl-2, 3-epoxybutyl methacrylate (0.82g, isomer ratio 6: 4 (NMR)).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：6.15～6.14(m,1H),5.61～5.60(m,1H),4.34～4.04(m,2H),3.05(q,J＝5.5Hz,0.6H),3.00(q,J＝5.6Hz,0.4H),1.97(s,3H),1.66～1.83(m,2H),1.36(d,J＝5.7Hz,1.2H),1.34(d,J＝5.6Hz,1.8H),1.04(t,J＝7.6Hz,1.8H),0.97(t,J＝7.6Hz,1.2H)

< example 4 >Synthesis of (formula 1-1-4)

Pyridine (10ml) was added to 2-ethyl-2, 3-epoxybutanol (1.4g) obtained in synthetic example 2 under a nitrogen atmosphere and cooled in an ice bath, and phthaloyl chloride (1.2g) was added dropwise. After stirring for 1 hour with ice-cooling, water and tert-butyl methyl ether were added to separate the phases, the organic layer was washed with water, a saturated aqueous sodium bicarbonate solution, water, and a saturated brine in this order, dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure and at 40 ℃ by an evaporator. The concentrated residue was dried under reduced pressure at room temperature using a vacuum pump, to obtain 2-ethyl-2, 3-epoxybutyl phthalate (1.9g, isomer ratio 6: 4 (NMR)).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：7.76～7.74(m,2H),7.59～7.53(m,2H),4.52～4.19(m,4H),3.09(q,J＝5.6Hz,1.2H),3.01(q,J＝5.7Hz,0.8H),1.52～1.85(m,4H),1.39(d,J＝5.6Hz,2.4H),1.34(d,J＝5.5Hz,3.6H),1.06(t,J＝7.6Hz,3.6H),0.98(t,J＝7.5Hz,2.4H)

< example 5 >Synthesis of (formula 1-1-5)

Pyridine (10ml) was added to 2-ethyl-2, 3-epoxybutanol (1.4g) obtained in synthetic example 2 under a nitrogen atmosphere and cooled in an ice bath, and terephthaloyl chloride (1.2g) was added. After stirring for 1 hour under ice-bath cooling, toluene (60ml) was added and stirred at room temperature for 24 hours. Water and tert-butyl methyl ether were added to separate the phases, and the organic layer was washed with water, a saturated aqueous sodium bicarbonate solution, water, and a saturated brine in this order, dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure at 40 ℃. The concentrated residue was dried under reduced pressure at room temperature using a vacuum pump, thereby obtaining 2-ethyl-2, 3-epoxybutyl terephthalate (1.6 g).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：8.14～8.11(m,4H),4.57～4.23(m,4H),3.13(q,J＝5.5Hz,1.2H),3.06(q,J＝5.6Hz,0.8H),1.91～1.63(m,4H),1.41(d,J＝5.7Hz,2.4H),1.37(d,J＝5.6Hz,3.6H),1.09(t,J＝7.7Hz,3.6H),1.02(t,J＝7.5Hz,2.4H)

< example 6 >Synthesis of (formula 1-1-3)

A mixture of 2-ethyl-2, 3-epoxybutanol (1.5g), 1, 4-cyclohexanedicarboxylic acid (0.74g), 4-dimethylaminopyridine (53mg) and dichloromethane (15ml) obtained in Synthesis example 2 was cooled in an ice bath under a nitrogen atmosphere, and N, N' -dicyclohexylcarbodiimide (2.7g) was added in small amounts. Stirring was carried out for 5 minutes under ice-bath cooling and then for 17 hours at room temperature. The precipitate was filtered, and the filtrate was washed with 0.1N hydrochloric acid, water, an aqueous sodium hydrogencarbonate solution, water, and a saturated saline solution, then dried over sodium sulfate and filtered, and the residue obtained by concentrating the filtrate was purified by silica gel column chromatography (silica gel michk (Merck)60, heptane/ethyl acetate 4/1), thereby obtaining bis (2-ethyl-2, 3-epoxybutyl) 1, 4-cyclohexanedicarboxylate (0.65 g).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：4.30～3.96(m,4H),3.02(q,J＝5.6Hz,1.2H),2.97(q,J＝5.6Hz,0.8H),2.53～1.46(m,14H),1.34(d,J＝5.7Hz,2.2H),1.32(d,J＝5.5Hz,3.8H),1.02(t,J＝7.7Hz,3.8H),0.95(t,J＝7.6Hz,2.2H)

< example 7 >Synthesis of (formula 1-1-2)

Pyridine (10ml) was added to 2-ethyl-2, 3-epoxybutanol (1.0g) obtained in Synthesis example 2 under a nitrogen atmosphere, cooled in an ice bath, and 1, 4-butanedicarboxylic acid chloride (0.75g) was added dropwise. After stirring for 1 hour with ice-bath cooling, water and tert-butyl methyl ether were added and liquid separation was performed. The organic layer was washed with water, 0.1N hydrochloric acid, water, a saturated aqueous sodium bicarbonate solution, water, and a saturated common salt solution in this order, dried over sodium sulfate, filtered, and the filtrate was concentrated. The concentrated residue was purified by silica gel column chromatography (silica gel michek (Merck)60, heptane/ethyl acetate 7/3) to obtain bis (2-ethyl-2, 3-epoxybutyl) 1, 4-butanedicarboxylic acid (0.1 g).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：4.28～3.96(m,4H),3.02(q,J＝5.6Hz,1.5H),2.98(q,J＝5.6Hz,0.5H),2.39～2.36(m,4H),1.83～1.46(m,8H),1.34(d,J＝5.7Hz,1.5H),1.32(d,J＝5.6Hz,4.5H),1.02(t,J＝7.6Hz,4.5H),0.95(t,J＝7.6Hz,1.5H)

< example 8 >Synthesis of (formula 1-3-1)

60% sodium hydride (0.52g) was put into a flask under a nitrogen atmosphere, washed 2 times with dry heptane, added with 8ml of tetrahydrofuran and cooled in an ice bath, and a solution of 2-ethyl-2, 3-epoxybutanol (1.5g) obtained in Synthesis example 2 in 1-methyl-2-pyrrolidone (8ml) was added dropwise at an inner temperature of not more than 10 ℃. After stirring for 30 minutes under ice-bath cooling, 1, 6-dibromohexane was added, and stirring was performed at room temperature for 2 hours and then at 45 ℃ for 1 hour. Water and toluene were added thereto under cooling in an ice bath to separate the phases, and the organic layer was washed with water and saturated brine in this order, dried over sodium sulfate, filtered, and the filtrate was concentrated. The concentrated residue was purified by silica gel column chromatography (silica gel michek (Merck)60, heptane/ethyl acetate 4/1) to obtain hexamethylenediol bis (2-ethyl-2, 3-epoxybutyl) ether (0.56 g).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：3.54～3.38(m,8H),2.98(q,J＝5.6Hz,1.3H),2.93(q,J＝5.6Hz,0.7H),1.80～1.36(m,12H),1.32(d,J＝5.7Hz,2.3H),1.31(d,J＝5.6Hz,3.7H),1.01(t,J＝7.6Hz,3.7H),0.95(t,J＝7.5Hz,2.3H)

< example 9 >Synthesis of (formula 1-5-1)

To 2-ethyl-2, 3-epoxybutanol (1.0g) obtained in Synthesis example 2 were added 10ml of toluene, 0.66g of 1, 6-hexamethylene diisocyanate and 0.03ml of pyridine under a nitrogen atmosphere, and the mixture was stirred with heating at an internal temperature of 45 ℃ for 13 hours. After cooling to room temperature, heptane was added, and the precipitated solid was washed with heptane, heptane/ethyl acetate (9/1), heptane/toluene (1/1) in this order and dried by a vacuum pump, thereby obtaining bis (2-ethyl-2, 3-epoxybutyl) hexane-1, 6-diyldicarbamic acid ester (0.7 g).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：7.27～7.14(m,2H),4.27～3.95(m,4H),3.16(t,J＝6.2Hz,4H),3.02(q,J＝5.5Hz,1.4H),2.97(q,J＝5.6Hz,0.6H),1.81～1.26(m,18H),1.02(t,J＝7.6Hz,4.0H),0.95(t,J＝7.5Hz,2.0H)

< example 10 >Synthesis of (formula 1-3-2)

60% sodium hydride (0.30g) was put in a flask under a nitrogen atmosphere, washed 2 times with dry heptane, added with 1-methyl-2-pyrrolidone (10ml) and cooled in an ice bath, and a tetrahydrofuran (5ml) solution of cyclohexane-1, 4-dimethanol was added dropwise. After stirring for 30 minutes under ice-bath cooling, a solution of 2-ethyl-2, 3-epoxybutyl p-toluenesulfonate (2.0g) obtained in example 2 in tetrahydrofuran (5ml) was added dropwise. The ice bath was removed and stirred at room temperature for 18 hours followed by stirring at 40 ℃ for 20 hours. Water and ethyl acetate were added and liquid separation was performed. The aqueous layer was extracted with ethyl acetate, and the ethyl acetate layers were combined and washed with water, dried over sodium sulfate, and concentrated to obtain a residue, which was purified by silica gel column chromatography (silica gel michk (Merck)60, heptane/ethyl acetate 4/1) to obtain 1, 4-bis (((2-ethyl-3-methyloxiran-2-yl) methoxy) methyl) cyclohexane (0.38 g).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：3.55～3.22(m,8H),2.97(q,J＝5.5Hz,1H)),2.92(q,J＝5.5Hz,1H),1.81～1.47(m,14H),1.33～1.30(m,6H),1.01(t,J＝7.5Hz,3H),0.945(t,J＝7.5Hz,3H)

< example 11 >(formula 1-3-5) is a groupBecome into

60% sodium hydride (0.30g) was put in a flask under a nitrogen atmosphere, and after washing 2 times with dry heptane, tetrahydrofuran (5ml) and 1-methyl-2-pyrrolidone (10ml) were added and cooled in an ice bath, and [1,1 '-biphenyl ] -4,4' -diol (0.66g) was added in small amounts in succession. After stirring for 30 minutes under ice-bath cooling, a solution of 2-ethyl-2, 3-epoxybutyl p-toluenesulfonate (2.0g) obtained in example 2 in tetrahydrofuran (5ml) was added dropwise. The ice bath was removed and stirred at room temperature for 18 hours followed by stirring at 40 ℃ for 26 hours. Water and ethyl acetate were added and liquid separation was performed. The aqueous layer was extracted with ethyl acetate, and the ethyl acetate layers were combined and washed with water, dried over sodium sulfate, and concentrated to obtain a residue, which was purified by silica gel column chromatography (silica gel michek (Merck)60, heptane/ethyl acetate 4/1) to obtain 4,4 '-bis ((2-ethyl-3-methyloxiran-2-yl) methoxy) -1,1' -biphenyl (0.62 g).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：7.48～7.44(m,4H),7.00～6.95(m,4H),4.12～4.01(m,4H),3.14(q,J＝5.6Hz,1.2H),3.06(q,J＝5.6Hz,0.8H),1.92～1.64(m,4H),1.38(d,J＝5.7Hz,2.4H),1.37(d,J＝5.5Hz,3.6H),1.08(t,J＝7.6Hz,3.6H),1.00(t,J＝7.6Hz,2.4H)

< example 12 >Synthesis of (formula 1-3-6)

60% sodium hydride (0.30g) was put in a flask under a nitrogen atmosphere, and after washing 2 times with dry heptane, tetrahydrofuran (5ml) and 1-methyl-2-pyrrolidone (10ml) were added and cooled in an ice bath, and naphthalene-1, 5-diol (0.56g) was added in small amounts in succession. After stirring for 30 minutes under ice-bath cooling, a solution of 2-ethyl-2, 3-epoxybutyl p-toluenesulfonate (2.0g) obtained in example 2 in tetrahydrofuran (5ml) was added dropwise. The ice bath was removed and stirred at room temperature for 18 hours followed by stirring at 40 ℃ for 24 hours. Water and ethyl acetate were added and liquid separation was performed. The aqueous layer was extracted with ethyl acetate, and the ethyl acetate layers were combined and washed with water, dried over sodium sulfate, and concentrated to obtain a residue, which was purified by silica gel column chromatography (silica gel michek (Merck)60, heptane/ethyl acetate 4/1) to obtain 1, 5-bis ((2-ethyl-3-methyloxiran-2-yl) methoxy) naphthalene (0.50 g).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：7.89～7.86(m,2H),7.39～7.34(m,2H),6.87～6.82(m,2H),4.27～4.12(m,4H),3.23～3.19(m,1.3H),3.10(q,J＝5.6Hz,0.7H),2.02～1.69(m,4H),1.41(d,J＝5.5Hz,3.9H),1.40(d,J＝5.5Hz,2.1H),1.11(t,J＝7.5Hz,3.9H),1.04(t,J＝7.5Hz,2.1H)

< example 13 >Synthesis of (formula 1-3-7)

After 60% sodium hydride (0.30g) was put into a flask under a nitrogen atmosphere and washed 2 times with dry heptane, tetrahydrofuran (5ml) and 1-methyl-2-pyrrolidone (10ml) were added and cooled in an ice bath, and 4,4' - (propane-2, 2-diyl) diphenol (0.80g) was added in small amounts in succession. After stirring for 30 minutes under ice-bath cooling, a solution of 2-ethyl-2, 3-epoxybutyl p-toluenesulfonate (2.0g) obtained in example 2 in tetrahydrofuran (5ml) was added dropwise. The ice bath was removed and stirred at room temperature for 18 hours followed by stirring at 40 ℃ for 20 hours. Water and ethyl acetate were added and liquid separation was performed. The aqueous layer was extracted with ethyl acetate, and the ethyl acetate layers were combined and washed with water, dried over sodium sulfate, and concentrated to obtain a residue, which was purified by silica gel column chromatography (silica gel michk (Merck)60, heptane/ethyl acetate 4/1) to obtain 2,2' - (((propane-2, 2-diylbis (4, 1-phenylene)) bis (oxy)) bis (methylene)) bis (2-ethyl-3-methyloxirane) (0.68 g).

¹H-NMR (Varian 500MHz, CDCl)₃/TMS)δ(ppm)：7.15～7.11(m,4H),6.84～6.79(m,4H),4.06～3.92(m,4H),3.10(q,J＝5.6Hz,1.3H),3.03(q,J＝5.6Hz,0.7H),1.89～1.60(m,10H),1.353(d,J＝5.5Hz,3.9H),1.351(d,J＝5.7Hz,2.1H),1.05(t,J＝7.6Hz,3.9H),0.975(t,J＝7.5Hz,2.1H)

< example 16 >Synthesis of (formula 1-3-3)

60% sodium hydride (0.31g) was put in a flask under a nitrogen atmosphere, washed 2 times with dry heptane, added with 1-methyl-2-pyrrolidone (6ml) and cooled in an ice bath, and 2- (hydroxymethyl) -2-methylpropane-1, 3-diol (0.3g) was added in small amounts in succession. After stirring for 30 minutes under ice-bath cooling, a solution of 2-ethyl-2, 3-epoxybutyl p-toluenesulfonate (2.1g) obtained in example 2 in tetrahydrofuran (3ml) was added dropwise. The ice bath was removed, heated to 40 ℃ and stirred for 15 hours. Water and ethyl acetate were added and liquid separation was performed. The aqueous layer was extracted with ethyl acetate, and the ethyl acetate layers were combined and washed with water, dried over sodium sulfate, and concentrated to obtain a residue, which was purified by silica gel column chromatography (silica gel michk (Merck)60, heptane/ethyl acetate 2/1) to obtain 2,2' - ((((2- (((2-ethyl-3-methyloxirane-2-yl) methoxy) methyl) -2-methylpropane-1, 3-diyl) bis (oxy)) bis (methylene)) bis (2-ethyl-3-methyloxirane) (0.43 g).

¹H-NMR (Varian 500MHz, CDCl3/TMS) delta (ppm): 3.50 to 3.28(m,8H),2.95 to 2.90(m,3H),1.77 to 1.46(m,6H),1.32 to 1.31(m,9H),1.02 to 0.92(m,12H)

< example 17 >Synthesis of (formula 1-3-4)

60% sodium hydride (0.37g) was put in a flask under a nitrogen atmosphere, washed 2 times with dry heptane, added with 1-methyl-2-pyrrolidone (6ml) and cooled in an ice bath, and small amounts of pentaerythritol (0.3g) were added successively. After stirring for 30 minutes under ice-bath cooling, a solution of 2-ethyl-2, 3-epoxybutyl p-toluenesulfonate (2.5g) obtained in example 2 in tetrahydrofuran (3ml) was added dropwise. The ice bath was removed and stirred at 40 ℃ for 18 h. Water and ethyl acetate were added and liquid separation was performed. The aqueous layer was extracted with ethyl acetate, and the ethyl acetate layers were combined and washed with water, dried over sodium sulfate, and concentrated to obtain a residue, which was purified by silica gel column chromatography (silica gel michek (Merck)60, heptane/ethyl acetate ═ 4/1) to obtain 2,2' - (((2, 2-bis (((2-ethyl-3-methyloxirane-2-yl) methoxy) methyl) propane-1, 3-diyl) bis (oxy)) bis (methylene)) bis (2-ethyl-3-methyloxirane) (0.25 g).

¹H-NMR (Varian 500MHz, CDCl3/TMS) delta (ppm): 3.66 to 3.35(m,16H),3.00 to 2.90(m,4H),1.84 to 1.46(m,8H),1.37 to 1.27(m,16H),1.02 to 0.92(m,16H)

Industrial applicability

According to the present invention, a novel 2-ethyl-2, 3-epoxybutoxy compound which is effective as an epoxy resin monomer can be provided.