JP2006069896A - Alkoxy group-containing cyclic compound, polymerizable composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new alkoxy group-containing cyclic compound, a polymerizable composition comprising the same and a cured product thereof. <P>SOLUTION: The alkoxy group-containing cyclic compound is represented by formula (1) [wherein the ring Z is a monocyclic or polycyclic non-aromatic ring; the R<SP>1</SP>O-group and the R<SP>2</SP>O-(W)<SB>n</SB>-group are each a substituent group bonded to an atom constituting the ring Z; R<SP>1</SP>is a 1-5C straight chain or branched chain alkyl group; R<SP>2</SP>is a hydrogen atom or a group represented by formula (2) (wherein R<SP>3</SP>, R<SP>4</SP>and R<SP>5</SP>are the same or different, and are each a hydrogen atom or an organic group); W is a bivalent organic group; n is 0 or 1; m is an integer of 1-8; and k is an integer of 1-5, or the like]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides an alkoxy group-containing cyclic compound, a polymerizable composition, and a curing thereof useful as a polymerizable compound that is polymerized or cured by light or heat, such as coating agents, inks, paints, adhesives, resists, and platemaking materials. Related to things.

  Conventionally, acrylic compounds have been widely used. However, since they have odor and skin irritation, handling properties are inferior, and there are several problems associated with the polymerization inhibiting action by oxygen. Therefore, recently, vinyl ether compounds that have low skin irritation, low odor, and little influence of oxygen during polymerization have attracted attention. In addition, vinyl ether compounds are cationically polymerizable, have a high curing rate, and are superior to acrylic materials, and therefore, supply of vinyl ether materials is required. However, in the market, since vinyl ether compounds are less in number than acrylic compounds and are expensive in price, it is not possible to meet the needs sufficiently.

  On the other hand, JP-A-10-25262 and JP-A-2003-73321 disclose several alicyclic vinyl ether compounds. Although these compounds are improved in workability in terms of low skin irritation, when these compounds are used as coatings or ink materials, the curing rate and hardness are insufficient and improvement is required.

Japanese Patent Laid-Open No. 10-25262 JP 2003-73321 A

An object of the present invention is to provide a novel alkoxy group-containing cyclic compound, a polymerizable composition containing the same, and a cured product thereof.
Another object of the present invention is to provide an alkoxy group-containing cyclic compound capable of forming a cured product having a high curing rate and high hardness, a polymerizable composition containing the same, and a cured product thereof.

  As a result of intensive studies to achieve the above object, the present inventors have significantly improved the curing rate when a vinyl ether compound having an alicyclic group bonded with an alkoxy group in the molecule is used as a comonomer of the polymer. In addition, the present inventors have found that a cured product having a high hardness can be obtained, thereby completing the present invention.

［式中、環Ｚは単環又は多環の非芳香族性環を示し、Ｒ¹Ｏ−基及びＲ²Ｏ−（Ｗ）_n−基は環Ｚを構成する原子に結合している置換基であって、Ｒ¹は炭素数１〜５のアルキル基を示し、Ｒ²は、水素原子又は下記式（２）

（式中、Ｒ³、Ｒ⁴及びＲ⁵は、同一又は異なって、水素原子又は有機基を示す）
で表される基を示し、Ｗは２価の有機基を示す。ｎは０又は１を示し、ｍは１〜８の整数を示し、ｋは１〜５の整数を示す。ｍ、ｋが２以上の場合、括弧内の置換基は同一であってもよく、異なっていてもよい。但し、環Ｚにおける少なくとも１つのＲ¹−Ｏ−基は、環ＺにおけるＲ²Ｏ−（Ｗ）_n−基が結合する構成原子に対してα位又はβ位の構成原子に結合している。また、ｍが１のときＲ²は式（２）で表される基である］
で表されるアルコキシ基含有環状化合物を提供する。 The present invention provides the following formula (1)

[Wherein, ring Z represents a monocyclic or polycyclic non-aromatic ring, and the R ¹ O— group and the R ² O— (W) _n — group are bonded to the atoms constituting ring Z. R ¹ represents an alkyl group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or the following formula (2)

(Wherein R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or an organic group)
W represents a divalent organic group. n represents 0 or 1, m represents an integer of 1 to 8, and k represents an integer of 1 to 5. When m and k are 2 or more, the substituents in parentheses may be the same or different. However, at least one R ¹ —O— group in the ring Z is bonded to the constituent atom at the α-position or the β-position with respect to the constituent atom to which the R ² O— (W) _n — group in the ring Z is bonded. . When m is 1, R ² is a group represented by the formula (2)]
The cyclic group containing cyclic compound represented by these is provided.

（式中、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、Ｘ⁵は、各環を構成する原子に結合している置換基であり、ハロゲン原子、アルキル基、ハロアルキル基、アリール基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシメチル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいカルボキシル基、保護基で保護されていてもよいスルホ基、オキソ基、ニトロ基、シアノ基、又は保護基で保護されていてもよいアシル基を示す。Ｘ¹が２以上の場合、それらは互いに結合して、式中のシクロアルカン環を構成する炭素原子と共に４員以上の環を形成していてもよい。ａ、ｂ、ｃ、ｄ、ｅは０以上の整数を示す。ａ、ｂ、ｃ、ｄ又はｅが２以上の場合、括弧内の置換基は同一であってもよく異なっていてもよい。ｐは１〜８の整数を示し、ｑは０〜３の整数を示し、ｒは１〜３の整数を示す）
で表される脂環式環が挙げられる。 The alkoxy group-containing cyclic compound of the present invention includes a compound in which ring Z is an alicyclic ring. Examples of the ring Z include the following formulas (3) to (7).

(In the formula, X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are substituents bonded to the atoms constituting each ring, and are halogen atoms, alkyl groups, haloalkyl groups, aryl groups, protecting groups. A hydroxyl group that may be protected with a hydroxyl group, a hydroxymethyl group that may be protected with a protecting group, an amino group that may be protected with a protecting group, a carboxyl group that may be protected with a protecting group, or a protecting group; An optionally protected sulfo group, an oxo group, a nitro group, a cyano group, or an acyl group that may be protected with a protecting group, when X ¹ is 2 or more, A 4-membered ring or more may be formed together with the carbon atoms constituting the cycloalkane ring, wherein a, b, c, d and e represent an integer of 0 or more, and a, b, c, d or e is In the case of 2 or more, the substituents in parentheses may be the same or different. (P represents an integer of 1 to 8, q represents an integer of 0 to 3, and r represents an integer of 1 to 3)
The alicyclic ring represented by these is mentioned.

The present invention also provides a polymerization initiator and the alkoxy group-containing cyclic compound of the present invention, wherein at least one R ² out of m R ² is a group represented by the formula (2). A polymerizable composition is provided.

  Furthermore, this invention provides the hardened | cured material obtained by hardening | curing the polymeric composition of the said invention.

  In addition, the vinyl ether compound and the vinyl ester compound in this specification include compounds in which a hydrogen atom of a vinyl group is substituted with a substituent.

  Since the alkoxy group-containing cyclic compound of the present invention has low odor and little skin irritation, it can be used as a raw material for coating agents, inks, paints, adhesives, resists, platemaking materials and the like. In particular, since it has a non-aromatic ring to which an alkoxy group is bonded, when used as a raw material monomer for a polymer, a curing rate by heating or light irradiation is extremely fast, and a cured product having high hardness can be formed. Moreover, when used as a raw material monomer for a resist, a resist having excellent transparency and dry etching properties can be formed.

The alkoxy group-containing cyclic compound of the present invention is a compound represented by the formula (1). Ring Z in formula (1) represents a monocyclic or polycyclic non-aromatic ring, which may be a heterocyclic ring or a condensed heterocyclic ring, but is often a hydrocarbon ring. Preferred examples of the ring Z include, for example, a cycloalkane ring which may have a substituent such as a cyclohexane ring, a cycloalkene ring which may have a substituent such as a cyclohexene ring, a substitution such as a norbornane ring and an adamantane ring. Examples thereof include an alicyclic ring such as a bridged ring which may have a group and a condensed ring which may have a substituent in which two or more rings are condensed. The ring is a substituent such as an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, a substituted oxycarbonyl group, an acyl group, an acyloxy group, a nitro group, a cyano group, an amino group, or a halogen atom (for example, described later). X ¹ etc. may have the same group).

Typical examples of the ring Z include alicyclic rings represented by the formulas (3) to (7). X ¹ , X ² , X ³ , X ⁴ , and X ⁵ in formulas (3) to (7) are each ring (ring represented by the formula, for example, cyclopentane ring, tricyclo [5.2.1.0 ^{2, 6} ] decane ring, tetracyclo [4.4.0.1 ^2,5 .1, ^7,10 ] dodecane ring, adamantane ring, bicyclo [4.4.0] decane ring, etc.) Indicates a substituent. Examples of the halogen atom in X ^{1 and the} like include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group in X ^{1 and the} like include, for example, C _1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl groups (preferably C 1 _1-5 alkyl group) and the like. Examples of the haloalkyl group in X ^{1 and the} like include C _1-10 haloalkyl groups (preferably, C _1-5 haloalkyl groups) such as chloromethyl, trifluoromethyl, trifluoroethyl, and pentafluoroethyl groups. Examples of the aryl group in X ^{1 and the} like include phenyl and naphthyl groups. The aromatic ring of the aryl group includes, for example, a halogen atom such as a fluorine atom, a C _1-4 alkyl group such as a methyl group, a C _1-5 haloalkyl group such as a trifluoromethyl group, a C _1-4 such as a hydroxyl group and a methoxy group. It may have a substituent such as an alkoxy group such as an alkoxy group, amino group, dialkylamino group, carboxyl group or methoxycarbonyl group, an acyl group such as nitro group, cyano group or acetyl group.

Examples of the protecting group for hydroxyl group and hydroxymethyl group in X ^{1 and the} like include protecting groups commonly used in the field of organic synthesis, such as alkyl groups (eg, C _1-4 alkyl groups such as methyl and t-butyl groups), An alkenyl group (such as an allyl group), a cycloalkyl group (such as a cyclohexyl group), an aryl group (such as a 2,4-dinitrophenyl group), an aralkyl group (such as a benzyl group); a substituted methyl group (such as For example, methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (for example, 1-ethoxyethyl group, etc.), tetrahydropyranyl group, tetrahydrofuranyl group, 1 -Hydroxy, such as a hydroxyalkyl group (eg 1-hydroxyethyl group etc.) A group capable of forming a group with acetal or hemiacetal group; an acyl group (e.g., formyl, acetyl, propionyl, butyryl, isobutyryl, C _1-6 aliphatic acyl group such as pivaloyl group; an aromatic such as benzoyl group; acetoacetyl group Aromatic acyl group), alkoxycarbonyl group (eg C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group), aralkyloxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted silyl group (eg trimethylsilyl group etc.) And when there are two or more hydroxyl groups (including hydroxymethyl groups) in the molecule, a divalent hydrocarbon group (for example, methylene, ethylidene, isopropylidene, cyclopentyl) which may have a substituent. Ridene, cyclohexylidene, benzylidene group, etc.) Can be illustrated.

Examples of the amino-protecting group for X ^{1 and the} like include the alkyl groups, aralkyl groups, acyl groups, alkoxycarbonyl groups and the like exemplified as the hydroxyl-protecting group.

Examples of the protecting group for the carboxyl group and the sulfo group in X ¹ include, for example, an alkoxy group (for example, a C _1-6 alkoxy group such as methoxy, ethoxy, and butoxy groups), a cycloalkyloxy group, an aryloxy group, and an aralkyloxy group. Group, trialkylsilyloxy group, optionally substituted amino group, hydrazino group, alkoxycarbonylhydrazino group, aralkylcarbonylhydrazino group and the like.

Examples of the acyl group in X ¹ include C _1-6 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, and pivaloyl groups; aromatic acyl groups such as acetoacetyl groups; benzoyl groups, and the like. . As the protecting group for the acyl group, a protecting group conventionally used in the field of organic synthesis can be used. Examples of the protected form of the acyl group include acetal (including hemiacetal).

When X ¹ is 2 or more, the 4-membered or more ring formed by combining them together with the carbon atom constituting the cycloalkane ring in the formula (3) includes, for example, a cyclopentane ring, cyclohexane ring, Examples thereof include alicyclic carbon rings such as hydronaphthalene ring (decalin ring); lactone rings such as γ-butyrolactone ring and δ-valerolactone ring.

  a, b, c, d, and e are integers of, for example, 0 to 5, preferably 0 to 3.

  W represents a divalent organic group. As the divalent organic group, a group having a carbon atom at a bonding site with an adjacent oxygen atom is usually used. Preferred divalent organic groups are (i) a divalent hydrocarbon group, (ii) a divalent hydrocarbon group, and at least one linking group selected from an oxygen atom, a sulfur atom, a carbonyl group and an amino group. And a divalent group consisting of

  The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent hydrocarbon group in which two or more of these are bonded. Is included.

  Typical examples of the divalent hydrocarbon group include 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) such as methylene, methylmethylene, ethylmethylene, dimethylmethylene, ethylmethylmethylene, ethylene, trimethylene, and tetramethylene groups. , More preferably about 1 to 6) linear or branched alkylene group; straight chain having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 6) such as propenylene group or Branched chain alkenylene group; 3 to 20 members (preferably 3 to 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene group, etc. 15-membered, more preferably 5-8-membered) cycloalkylene group; 3-20 membered (such as cyclopropylene, cyclopentylidene, cyclohexylidene group) Mashiku 3-15 membered, more preferably cycloalkylidene group having about 5-8 membered); and the like benzylidene group; an arylene group such as phenylene group.

  The divalent hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group which may be protected with a protective group, a hydroxymethyl group which may be protected with a protective group, an amino group which may be protected with a protective group, and a protective group. And a carboxyl group, a sulfo group optionally protected by a protecting group, a halogen atom, an oxo group, a cyano group, a nitro group, a heterocyclic group, a hydrocarbon group, a haloalkyl group, and the like. As the protecting group, a protecting group conventionally used in the field of organic synthesis can be used.

  The heterocyclic group as the substituent is a heterocyclic group of about 3 to 15 members (in particular, 5 to 8 membered heterocycles) containing at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom. Cyclic group).

The hydrocarbon group as the substituent includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded. As an aliphatic hydrocarbon group, it is a C1-C20 (preferably 1-10, more preferably 1-3) alkyl group; C2-C20 (preferably 2-10, more preferably 2-3). Alkenyl group having about 2 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 3). The alicyclic hydrocarbon group is a cycloalkyl group of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members); 3 to 20 members (preferably 3 to 15 members, more preferably About 5 to 8 membered cycloalkenyl group; perhydronaphthalen-1-yl group, norbornyl, adamantyl, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] bridged cyclic hydrocarbon groups such as dodecan-3-yl groups. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms. The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20 cycloalkyl- C _1-4 alkyl group and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to about 4). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

Examples of the haloalkyl group as the substituent include haloalkyl groups having about 1 to 10 carbon atoms such as chloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl groups (particularly, C _{1- 3} haloalkyl group).

  As the divalent organic group, a linear or branched alkylene group having 1 to 6 carbon atoms or a group in which the alkylene group is bonded to an oxygen atom or a sulfur atom is particularly preferable.

（式中、Ｒ⁶及びＲ⁷は、同一又は異なって、水素原子又は炭化水素基を示す。Ｒ⁶及びＲ⁷は、互いに結合して、隣接する炭素原子と共に脂環式環を形成していてもよい）
で表される基が含まれる。 Preferred examples of W include, for example, the following formula (8)

(In the formula, R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom or a hydrocarbon group. R ⁶ and R ⁷ are bonded to each other to form an alicyclic ring together with adjacent carbon atoms. May be)
The group represented by these is included.

Examples of the hydrocarbon group for R ⁶ and R ⁷ include the same groups as the hydrocarbon groups for R ¹ and the like. The hydrocarbon group includes a hydrocarbon group having a substituent. Examples of the substituent include the same group as the substituent that the hydrocarbon group in R ¹ and the like may have, or the same group as the substituent X ₁ and the like of the ring Z and the like.

Preferred R ⁶ and R ⁷ include a hydrogen atom; a C _1-10 alkyl group such as methyl, ethyl, propyl, isopropyl and butyl groups (particularly a C _1-5 alkyl group); a substituent such as a cyclopentyl group and a cyclohexyl group. A cycloalkyl group optionally having a substituent; a bridged cyclic group optionally having a substituent such as a norbornan-2-yl group and an adamantan-1-yl group. Examples of the substituent that the cycloalkyl group or the bridged cyclic group may have are, for example, the same as the above-described substituent X ₁ and the like, protected with a halogen atom, an alkyl group, a haloalkyl group, an aryl group, or a protective group. May be a hydroxyl group that may be protected with a protecting group, an amino group that may be protected with a protecting group, a carboxyl group that may be protected with a protecting group, or a group that is protected with a protecting group Examples thereof include a good sulfo group, an oxo group, a nitro group, a cyano group, and an acyl group which may be protected with a protecting group.

n represents 0 or 1. That is, the R ² —O— group is bonded to ring Z with or without W. Particularly in the present invention, it is preferable that at least one R ² —O— group is directly bonded to the ring Z.

R ¹ represents an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include linear C _1-5 (preferably C _1-3 ) alkyl groups such as methyl, ethyl, propyl, butyl and pentyl; isopropyl, isobutyl, s-butyl, t-butyl and the like. _Examples include branched C _1-5 (preferably C _1-3 ) alkyl groups. Of these, a linear C _1-3 alkyl group, particularly a methyl group is preferred.

R ² represents a hydrogen atom or a group represented by the formula (2). In formula (2), R ³ , R ⁴ and R ⁵ each represent a hydrogen atom or an organic group. Examples of the organic group include a halogen atom, a hydrocarbon group, a heterocyclic group, a substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, cycloalkyloxycarbonyl group, etc.), a carboxyl group, and a substituted group. Or an unsubstituted carbamoyl group, a cyano group, a nitro group, a sulfur acid group, a sulfur acid ester group, an acyl group (an aliphatic acyl group such as an acetyl group; an aromatic acyl group such as a benzoyl group), an alkoxy group (a methoxy group, C _1-6 alkoxy group such as ethoxy group), N, N-disubstituted amino group (N, N-dimethylamino group, piperidino group, etc.), and a group in which two or more of these are bonded. The carboxyl group and the like may be protected with a protecting group known or commonly used in the field of organic synthesis. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Of these organic groups, a hydrocarbon group, a heterocyclic group, and the like are preferable.

  The hydrocarbon group and the heterocyclic group also include a hydrocarbon group and a heterocyclic group having a substituent. The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded. Examples of the aliphatic hydrocarbon group include 1 to 20 carbon atoms (preferably 1 to 1) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups. 10, more preferably an alkyl group of about 1 to 3); an alkenyl group of about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as vinyl, allyl, 1-butenyl group; Examples thereof include alkynyl groups having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as propynyl groups.

As the alicyclic hydrocarbon group, a cycloalkyl group having about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl groups; Cycloalkenyl groups of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as pentenyl and cyclohexenyl groups; perhydronaphthalen-1-yl group, norbornyl, adamantyl, tetracyclo [4 4.0.1, ^2,5 . 1 ^7,10 ] bridged cyclic hydrocarbon groups such as dodecan-3-yl groups. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as phenyl and naphthyl groups.

The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20 cycloalkyl- C _1-4 alkyl group and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to about 4). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

Preferred hydrocarbon groups include C _1-10 alkyl groups, C _2-10 alkenyl groups, C _2-10 alkynyl groups, C _3-15 cycloalkyl groups, C _6-10 aromatic hydrocarbon groups, C _3-15 A cycloalkyl-C _1-4 alkyl group, a C _7-14 aralkyl group and the like are included.

  The hydrocarbon group includes various substituents such as halogen atoms, oxo groups, hydroxyl groups, substituted oxy groups (for example, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, etc.), carboxyl groups, substituted oxycarbonyls. Group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc. May be. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis. In addition, an aromatic or non-aromatic heterocycle may be condensed with the ring of the alicyclic hydrocarbon group or aromatic hydrocarbon group.

The heterocyclic ring constituting the heterocyclic group in R ^{3 and the} like includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. Examples of such a heterocyclic ring include a heterocyclic ring containing an oxygen atom as a hetero atom (for example, 5-membered ring such as furan, tetrahydrofuran, oxazole, isoxazole, and γ-butyrolactone ring, 4-oxo-4H-pyran, tetrahydro 6-membered ring such as pyran, morpholine ring, condensed ring such as benzofuran, isobenzofuran, 4-oxo-4H-chromene, chroman, isochroman ring, 3-oxatricyclo [4.3.1.1 ^4,8 ] undecane 2-one ring, a bridged ring such as 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring), a heterocycle containing a sulfur atom as a hetero atom (for example, thiophene, 5-membered ring such as thiazole, isothiazole, thiadiazole ring, 6-membered ring such as 4-oxo-4H-thiopyran ring, benzothiophene ring Any condensed ring), heterocycles containing nitrogen atoms as heteroatoms (eg, 5-membered rings such as pyrrole, pyrrolidine, pyrazole, imidazole, and triazole rings, 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, piperidine, and piperazine rings) Ring, indole, indoline, quinoline, acridine, naphthyridine, quinazoline, a condensed ring such as a purine ring, etc.). In addition to the substituents that the hydrocarbon group may have, the heterocyclic group includes an alkyl group (eg, a C _1-4 alkyl group such as a methyl or ethyl group), a cycloalkyl group, an aryl group It may have a substituent such as (for example, phenyl, naphthyl group).

Preferred R ³ , R ⁴ and R ⁵ include a hydrogen atom and a hydrocarbon group (for example, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _2-10 alkynyl group, a C _3-15 cycloalkyl group, C _6-10 aromatic hydrocarbon group, C _3-12 cycloalkyl-C _1-4 alkyl group, C _7-14 aralkyl group, etc.). More preferable R ³ , R ⁴ and R ⁵ include a C _1-3 alkyl group such as a hydrogen atom or a methyl group.

  Typical examples of the group represented by the formula (2) include vinyl group, isopropenyl group, 1-propenyl group, 2-methyl-1-propenyl group, 1,2-dimethyl-1-propenyl group and the like. .

  m shows the integer of 1-8. When m is 2 or more, the groups in parentheses may be the same or different. m is preferably an integer of 1 to 6, more preferably an integer of 1 to 3.

In formula (1), at least one R ¹ —O— group in ring Z is a constituent atom at the α-position or β-position with respect to the constituent atom to which the R ² O— (W) _n — group in ring Z is bonded. Are connected.

The alkoxy group-containing cyclic compound represented by the formula (1) is a hydroxy compound having an alkoxy group-containing cyclic group in which all R ² in the formula (1) is a hydrogen atom, and m Rs in the formula (1). ^At least one R ² out of ² includes a vinyl ether compound having an alkoxy group-containing cyclic group represented by the formula (2). Among these, the alkoxy group-containing cyclic compound in which m in Formula (1) is 1 represents a compound in which R ² is a group represented by Formula (2), that is, a vinyl ether compound having an alkoxy group-containing cyclic group. ing. In addition, these compounds may be a single compound when stereoisomers (for example, geometrical isomers such as cis / trans isomers and endo-exo isomers, optical isomers, etc.) exist. A mixture of a plurality of stereoisomers may be used.

The vinyl ether compound having an alkoxy group-containing cyclic group is a vinyl ether compound in which m R ² are all represented by the formula (2), and at least one R ² of m R ² is represented by the formula (2). In addition, a compound in which one or a plurality of R ² is a hydrogen atom, that is, a vinyl ether compound having both a hydroxyl group in the molecule and a vinyloxy group is included. Typical examples of the vinyl ether compound having an alkoxy group-containing cyclic group include the following compounds. Examples of vinyl ether compounds having an alkoxy group-containing cyclic group in which ring Z is an alicyclic ring represented by formula (3) include 1-methoxy-2-vinyloxycyclohexane and 1-methoxy-3-vinyloxycyclohexane. 1-methoxy-2-vinyloxycyclopentane, 1-methoxy-3-vinyloxycyclopentane, 1-methoxy-2-vinyloxycyclooctane, 1-methoxy-3-vinyloxycyclooctane, 1-methoxy-2 -Vinyloxycyclododecane, 1-methoxy-3-vinyloxycyclododecane, 2-methoxy-1,4-bis (vinyloxy) cyclohexane, 2-methoxy-1,3-bis (vinyloxy) cyclohexane, 5-methoxy-1 , 3-bis (vinyloxy) cyclohexane, 2-methoxy-1-bi Ruoxy-4- (vinyloxymethyl) cyclohexane and its positional isomers, mixtures thereof, 1,4-dimethoxy-2,5-bis (vinyloxy) cyclohexane, 1-methoxy-1-methyl-2-vinyloxy-4- (1-methoxy-1-methyl-2-vinyloxyethyl) cyclohexane, 1-vinyloxy-2-methoxy-4- (1-methoxy-2-vinyloxyethyl) cyclohexane, 1-methoxy-2-vinyloxy-4- (1-methoxy-2-vinyloxyethyl) cyclohexane, 2-methoxy-2-methyl-5- (1-methoxy-1-methyl-2-vinyloxyethyl) cyclohexanol, 1-methoxy-1-methyl-2 -Vinyloxy-4- (1-methoxy-1-methyl-2-hydroxyethyl) cyclohexane, Regioisomers benefactor, mixtures thereof; and the like isopropenyl ether corresponding to thereof. In addition to the above, terpenes such as 1-methoxy-1-vinyloxy-4-isopropenylcyclohexane and 1-methoxy-1,4-bis (vinyloxy) -4-isopropylcyclohexane and derivatives thereof; ring Z is an alkylcyclohexane ring, etc. And the like, which are alkylcycloalkane rings. Among the vinyl ether compounds in which the ring Z is an alicyclic ring represented by the formula (3), a compound in which p = 1 to 4 or 8 is particularly preferable, and a compound in which a = 0 to 3 is preferable. .

Examples of vinyl ether compounds having an alkoxy group-containing cyclic group in which ring Z is an alicyclic ring represented by formula (4) include 5-methoxy-6- (vinyloxy) -3a, 4, 5, 6, 7 , 7a-Hexahydro-1H-4,7-methano-indene, 1-methoxy-2- (vinyloxy) octahydro-4,7-methano-indene, 5-methoxy-6- (vinyloxy) octahydro-4,7-methano Indene, 1-methoxy-2,5-bis (vinyloxy) octahydro-4,7-methano-indene {3-methoxy-4,8-bis (vinyloxy) tricyclo [5.2.1 ^1,7 . 0 ^2,6 ] decane}, 1,6-dimethoxy-2,5-bis (vinyloxy) octahydro-4,7-methano-indene, 1-methoxy-2-vinyloxy-5- (vinyloxymethyl) octahydro-4 , 7-methano-indene and its positional isomers, mixtures thereof; and the corresponding isopropenyl ethers. Among the vinyl ether compounds in which the ring Z is an alicyclic ring represented by the formula (4), a compound in which b = 0 to 3 is particularly preferable.

Examples of vinyl ether compounds having an alkoxy group-containing cyclic group in which ring Z is an alicyclic ring represented by formula (5) include 2-methoxy-3- (vinyloxy) bicyclo [2.2.1] heptane, 5-methoxy-6- (vinyloxy) bicyclo [2.2.1] heptane-2-carboxylic acid methyl ester, 2-methoxy-3,5-bis (vinyloxy) bicyclo [2.2.1] heptane, 2- Methoxy-3-vinyloxy-5- (vinyloxymethyl) bicyclo [2.2.1] heptane, 3-methoxy-4-vinyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3-methoxy-4,9-bis (vinyloxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane; and the corresponding isopropenyl ethers. The compounds exemplified above also include these positional isomers and mixtures thereof. Among the vinyl ether compounds in which the ring Z is an alicyclic ring represented by the formula (5), a compound in which q = 0 to 3 and a compound in which c = 0 to 3 are particularly preferable.

  Examples of vinyl ether compounds having an alkoxy group-containing cyclic group in which ring Z is an alicyclic ring represented by formula (6) include 1-methoxy-2-vinyloxyadamantane and 1-methoxy-3-vinyloxyadamantane. 1-methoxy-1-methyl-2-vinyloxyadamantane, 3-methoxy-5-vinyloxy-1-adamantanol, 1-methoxy-2,6-bis (vinyloxy) adamantane, 1-methoxy-3,5- Bis (vinyloxy) adamantane, 3-methoxy-5,7-bis (vinyloxy) -1-adamantanol, 1-methoxy-3,5,7-tris (vinyloxy) adamantane, and corresponding isopropenyl ethers, etc. Is mentioned. The compounds exemplified above also include these positional isomers and mixtures thereof. Among the vinyl ether compounds in which the ring Z is an alicyclic ring represented by the formula (6), a compound in which d = 0 to 3 is particularly preferable.

  Examples of vinyl ether compounds having an alkoxy group-containing cyclic group in which ring Z is an alicyclic ring represented by formula (7) include 2-methoxy-3-vinyloxydecalin, 2-methoxy-3,6-bis. (Vinyloxy) decalin, 1-methyl-2-methoxy-3,7-bis (vinyloxy) decalin, 1-methoxy-3-vinyloxyperhydroanthracene, 1-methoxy-2,7-bis (vinyloxy) perhydroanthracene And corresponding isopropenyl ethers. The compounds exemplified above also include these positional isomers and mixtures thereof. Among the vinyl ether compounds in which the ring Z is an alicyclic ring represented by the formula (7), a compound in which r = 0 to 3 and a compound in which e = 0 to 3 are particularly preferable.

  The hydroxy compound having an alkoxy group-containing cyclic group includes a primary alcohol, a secondary alcohol, a tertiary alcohol and the like. The hydroxyl compound may have a plurality of hydroxyl groups, and may be any of monohydric alcohol, dihydric alcohol, trihydric alcohol, polyhydric alcohol and the like.

  Representative examples of the hydroxy compound having an alkoxy group-containing cyclic group include the following compounds. Examples of the hydroxy compound having an alkoxy group-containing cyclic group in which the ring Z is an alicyclic ring represented by the formula (3) include 1-methoxy-2-hydroxycyclohexane, 1-methoxy-3-hydroxycyclohexane, 1 1-methoxy-2-hydroxycyclopentane, 1-methoxy-3-hydroxycyclopentane, 1-methoxy-2-hydroxycyclooctane, 1-methoxy-3-hydroxycyclooctane, 1-methoxy-2-hydroxycyclododecane, 1 -Methoxy-3-hydroxycyclododecane, 2-methoxy-1,4-dihydroxycyclohexane, 2-methoxy-1,3-dihydroxycyclohexane, 6-methoxy-1,4-dihydroxycyclohexane, 5-methoxy-1,3- Dihydroxycyclohexane and its position difference Body, mixtures thereof; 1,4-dimethoxy-2,5-dihydroxy cyclohexane and its regioisomer, mixtures thereof and the like. In addition to the above, terpenes such as 2-methoxy-2-methyl-5- (1-methoxy-1-methyl-2-hydroxyethyl) cyclohexanol and derivatives thereof, and ring Z is an alkylcycloalkane ring such as an alkylcyclohexane ring And the like are also included. Among the hydroxy compounds in which the ring Z is an alicyclic ring represented by the formula (3), a compound in which p = 1 to 4 or 8 is particularly preferable, and a compound in which a = 0 to 3 is preferable. .

Examples of the hydroxy compound having an alkoxy group-containing cyclic group in which the ring Z is an alicyclic ring represented by the formula (4) include 1-methoxy-2- (hydroxy) octahydro-4,7-methano-indene, 1-methoxy-2,5- (dihydroxy) octahydro-4,7-methano-indene {3-methoxy-4,8- (dihydroxy) tricyclo [5.2.1 ^1,7 . 0 ^2,6 ] decane} and their positional isomers, mixtures thereof and the like. Among the hydroxy compounds in which the ring Z is an alicyclic ring represented by the formula (4), a compound in which b = 0 to 3 is particularly preferable.

Examples of the hydroxy compound having an alkoxy group-containing cyclic group in which the ring Z is an alicyclic ring represented by the formula (5) include 2-methoxy-3- (hydroxy) bicyclo [2.2.1] heptane, 2-methoxy-3,5-dihydroxybicyclo [2.2.1] heptane, 2-methoxy-3-hydroxy-5- (hydroxymethyl) bicyclo [2.2.1] heptane, 3-methoxy-4-hydroxy Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and 3-methoxy-4,9-dihydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane and the like. The compounds exemplified above also include these positional isomers and mixtures thereof. Among the hydroxy compounds in which the ring Z is an alicyclic ring represented by the formula (5), a compound in which q = 0 to 3 and a compound in which c = 0 to 3 are particularly preferable.

  Examples of the hydroxy compound having an alkoxy group-containing cyclic group in which the ring Z is an alicyclic ring represented by the formula (6) include 2-methoxy-1-adamannol, 3-methoxy-1-adamantanol, 1 -Methoxy-2-methyl 2-hydroxyadamantane, 1-methoxy-2,6-dihydroxyadamantane, 1-methoxy-3,5-dihydroxy-1-adamantane, 1-methoxy-3,5,7-trihydroxyadamantane, And 2-methyl-2-hydroxyadamantane. The compounds exemplified above also include these positional isomers and mixtures thereof. Among the hydroxy compounds in which the ring Z is an alicyclic ring represented by the formula (6), a compound in which d = 0 to 3 is particularly preferable.

  Examples of hydroxy compounds having an alkoxy group-containing cyclic group in which ring Z is an alicyclic ring represented by formula (7) include 2-methoxy-3-hydroxydecalin and 2-methoxy-3,6-dihydroxydecalin. 1-methyl-2-methoxy-3,7-dihydroxydecalin, 1-methoxy-3-vinyloxyperhydroanthracene, 1-methoxy-2,7-dihydroxyperhydroanthracene and the like. The compounds exemplified above also include these positional isomers and mixtures thereof. Among the hydroxy compounds in which the ring Z is an alicyclic ring represented by the formula (7), a compound in which r = 0 to 3 and a compound in which e = 0 to 3 are particularly preferable.

  The vinyl ether compound having an alkoxy group-containing cyclic group in the present invention can be produced by utilizing a known reaction as a method for producing a vinyl ether compound (for example, Japanese Patent Application No. 2003-73321). A preferred embodiment includes a method for producing a vinyl ether compound having an alkoxy group-containing cyclic group by reacting the hydroxy compound having an alkoxy group-containing cyclic group with a vinyl ester compound in the presence of a transition element compound. . In this case, when a vinyl ether compound having an alkoxy group-containing cyclic group containing one or more hydroxyl groups in the molecule is used instead of the hydroxy compound having an alkoxy group-containing cyclic group, a plurality of vinyloxy groups are introduced into the molecule. A vinyl ether compound having an alkoxy group-containing cyclic group can be produced.

（式中、Ｒ³、Ｒ⁴及びＲ⁵は、同一又は異なって、水素原子又は有機基を示し、Ｒ⁸は有機基を示す）
で表されるビニルエステル化合物が挙げられる。 The hydroxy compound having an alkoxy group-containing cyclic group may be any compound that does not inhibit the reaction, and those exemplified above can be used. As a typical example of the vinyl ester compound, the following formula (9)

(Wherein R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or an organic group, and R ⁸ represents an organic group)
The vinyl ester compound represented by these is mentioned.

In the vinyl ester compound represented by the formula (9), R ^{3 to} R ⁵ are the same as described above. The organic group in R ⁸ may be an organic group that does not inhibit the above reaction, and the exemplified organic groups in R ^{3 and the} like can be used. Representative examples of the vinyl ester compound represented by the formula (9) include vinyl acetate, isopropenyl acetate, 1-propenyl acetate, 2-methyl-1-propenyl acetate, 1,2-dimethyl 1-propenyl acetate, and formic acid. Examples include vinyl, vinyl propionate, and vinyl benzoate.

  In the above method, since a transition element compound (including a single transition element) is used as a catalyst, the reaction can proceed under mild conditions. The transition element compounds can be used alone or in combination of two or more. Transition elements include group IIIA elements (particularly lanthanoid elements), group VA elements, group VIA elements, group VIIA elements, group VIII elements such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, IB Group elements are included. Among these, group VIII elements are preferable, and platinum group elements (ruthenium, rhodium, palladium, osmium, iridium and platinum), and particularly iridium are particularly preferable.

  Examples of transition element compounds include transition element simple substances (metals), oxides, sulfides, hydroxides, halides (fluorides, chlorides, bromides, iodides), sulfates, and oxo acids containing transition elements. Or an inorganic compound such as a salt or an inorganic complex thereof; an organic compound such as a cyanide, an organic acid salt (such as an acetate salt), or an organic complex. Among these, an organic complex is particularly preferable. The ligand of the complex includes a known ligand. The valence of the transition element in the transition element compound is about 0 to 6, preferably 0 to 3. In particular, in the case of an iridium compound, monovalent or trivalent is preferable. The transition element compound can be used as it is or in a form supported on a carrier.

  The amount of the transition element compound used is, for example, 0.0001 to 1 mol, preferably 0.001 to 0.3 mol, more preferably 0.005 to 0.1 mol, with respect to 1 mol of the hydroxy compound used as the reaction component. Degree.

  The reaction of the vinyl ester compound represented by formula (9) and the hydroxy compound having an alkoxy group-containing cyclic group is performed in the presence or absence of a solvent. Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, dichloromethane, 1,2- Halogenated hydrocarbons such as dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate; N, N-dimethylformamide; Amides such as N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile. These solvents are used alone or in admixture of two or more.

  The amount of the vinyl ester compound represented by the formula (9) is, for example, 0.8 to 10 equivalents, preferably 1 to 8 equivalents, more preferably 1 equivalent to 1 equivalent of the hydroxy compound having an alkoxy group-containing cyclic group. Is about 1.5 to 5 equivalents. A large excess of the vinyl ester compound represented by the formula (9) may be used.

  The presence of a base in the reaction system generally increases the reaction rate significantly. Bases include inorganic and organic bases. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, and barium hydroxide. Alkaline metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; alkaline earth metal carbonates such as magnesium carbonate; alkali metal carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and cesium hydrogen carbonate Examples thereof include hydrogen salt.

  Examples of the organic base include alkali metal organic acid salts such as lithium acetate, sodium acetate, potassium acetate and cesium acetate (particularly alkali metal acetate); alkaline earth metal organic acid salts such as magnesium acetate; lithium methoxide, Alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide (alkali metal alkoxides corresponding to the hydroxy compounds having an alkoxy group-containing cyclic group); alkali metal phenoxides such as sodium phenoxide; Examples include amines such as triethylamine and N-methylpiperidine (tertiary amine and the like); nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2′-bipyridyl and 1,10-phenanthroline. Among the above bases, a base containing sodium is preferable.

  The usage-amount of a base is 0.001-3 mol with respect to 1 mol of hydroxy compounds which have an alkoxy-group containing cyclic group represented by Formula (9), Preferably it is about 0.005-2 mol.

  The reaction may be performed in the presence of a polymerization inhibitor. The reaction temperature can be appropriately selected according to the reaction components and the type of catalyst, and is, for example, about 20 to 200 ° C, preferably about 50 to 150 ° C, and more preferably about 70 to 120 ° C. The reaction may be carried out at normal pressure or under reduced pressure or increased pressure. The atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.

The above reaction produces a vinyl ether compound having an alkoxy group-containing cyclic group in which at least one of R ² in the corresponding formula (1) is a group represented by the formula (2) under mild conditions. After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.

The hydroxy compound having an alkoxy group-containing cyclic group in the present invention can be produced by utilizing a known reaction as a method for producing a hydroxy compound having a cyclic group. As an example of a hydroxy compound having an alkoxy group-containing cyclic group, R ² in formula (1) is a hydrogen atom, n is 0, and the R ¹ —O— group is a constituent atom to which the HO— group in ring Z is bonded. On the other hand, a hydroxy compound having an alkoxy group-containing cyclic group bonded to the constituent atom at the α-position [the following formula (1a)] can be produced according to the following steps.

The above steps were obtained in the previous step in which a compound represented by the formula (B) was obtained by reaction of the compound represented by the formula (A) with peracid or hydrogen peroxide, and in the presence of an acid catalyst. And a post-process for obtaining the target compound represented by the formula (1a) by the reaction of the compound represented by the formula (B) and the hydroxy compound represented by R ¹ —OH.

In formula (A) in the previous step, ring Z ¹ represents a non-aromatic ring having at least one double bond in a part of the ring. Examples of the non-aromatic ring having at least one double bond in a part of the ring (hereinafter sometimes referred to as “cyclic olefin”) include, among the non-aromatic rings in the ring Z, a ring A ring having at least one double bond as a part of the formula ring may be mentioned. Such cyclic olefins include, for example, monocyclic rings such as cycloalkene such as cyclopentene and cyclohexene, bridged rings such as 2-norbornene, and condensed rings such as bicyclo [3.2.1] -2-octene. It is. Examples of the peracid include performic acid, peracetic acid, m-chloroperbenzoic acid (mCPBA), and the like. In formula (B), ring Z ² represents a non-aromatic ring corresponding to a ring in which one double bond of ring Z ¹ in formula (A) is converted to a single bond, The same ring is illustrated.

  The reaction is carried out in the presence or absence of a solvent. As the solvent, those exemplified above can be used as long as the reaction is not inhibited. The reaction temperature can be appropriately selected depending on the type of reaction components, and is, for example, 0 to 70 ° C., preferably 5 to 50 ° C., and may be room temperature. The reaction may be carried out at normal pressure or under reduced pressure or increased pressure. The atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.

According to the above reaction, the double bond site of ring Z ¹ in formula (A) is epoxidized by the action of peracid or hydrogen peroxide to produce the corresponding compound represented by formula (B). After completion of the reaction, the reaction product can be separated and purified by the separation means exemplified above.

In the subsequent step, rings Z ² and R ¹ in formula (1a) are the same as described above. The reaction is carried out in the presence of an acid catalyst. As the acid catalyst, for example, an organic acid such as sulfonic acid such as p-toluenesulfonic acid, an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid, a strong acid cation exchange resin, or the like is used. In addition, the same reaction conditions as in the previous step can be employed as long as the progress of the reaction is not inhibited.

According to the above reaction, an R ¹ O-group derived from R ¹ OH is introduced into the site where the epoxy site in the formula (B) is opened by the action of the acid catalyst, and is represented by the corresponding formula (1a). Is formed. After completion of the reaction, the reaction product can be separated and purified by the separation means exemplified above.

The polymerizable composition of the present invention is a polymerization initiator and an alkoxy group-containing cyclic compound represented by the formula (1) of the present invention, wherein at least one R ² out of m R ² is represented by the formula (2). ), That is, a vinyl ether compound having an alkoxy group-containing cyclic group. Examples of the polymerization initiator include those capable of causing radical polymerization such as thermal polymerization initiator, photo radical or photo cation polymerization initiator, radical polymerization such as ionic (cation) polymerization initiator, and ionic (cation) polymerization. The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. For example, as thermal polymerization initiator, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile, azobis-2-4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, etc. 2,4-diethylthioxanthone, benzophenone, 4-dimethylaminoisoamylbenzoate, 4-dimethylaminoethylbenzoate, triallylsulfonium hexafluorophosphate, etc. can be used as a photopolymerization initiator.

  The polymerization initiator is usually used in an amount of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the vinyl ether compound having an alkoxy group-containing cyclic group.

  The cured product of the present invention can be obtained by subjecting a polymerizable composition comprising a polymerization initiator and an alkoxy group-containing cyclic compound represented by formula (1) to electron beam or radiation irradiation or heating.

  According to the present invention, since the alkoxy group-containing cyclic compound represented by the formula (1) of the present invention is used, a cured product having a very high curing rate and a high hardness can be formed during the curing reaction. For this reason, it can be widely used as a polymerizable compound that is polymerized or cured by light or heat in the fields of coating agents, inks, paints, adhesives, resists, plate-making materials and the like.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
Example 1
Production of Hydroxy Compound Having Alkoxy Group-Containing Cyclic Group A 1000 ml reactor was charged with 50 g (0.45 mol) of 3-cyclohexene-1-methanol as a starting material, 850 ml of dichloromethane was added as a solvent and stirred, purity 60% Of m-chloroperbenzoic acid (mCPBA) was added slowly. After aging for about 2 hours at room temperature with stirring, an aqueous sodium thiosulfate solution was added. The aqueous layer was removed, and the collected organic layer was washed successively with a 5 wt% aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, and the organic layer was concentrated to obtain a crude epoxy product. This crude epoxy product was dissolved in 100 times by weight of methanol, 2% by weight of concentrated sulfuric acid was added, and the mixture was stirred at room temperature for about 2 hours to remove methanol. When the reaction solution was analyzed by GC-MS, a mixture of 2-methoxy-1-hydroxy-4- (hydroxymethyl) cyclohexane and 6-methoxy-1-hydroxy-3- (hydroxymethyl) cyclohexane was obtained in a yield of 80%. It was generated.

［２−メトキシ−１−ヒドロキシ−４−（ヒドロキシメチル）シクロヘキサン及び６−メトキシ−１−ヒドロキシ−３−（ヒドロキシメチル）シクロヘキサンの混合物のスペクトルデータ］
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：１．４０−１．５７（ｍ，７Ｈ），２．１６（ｂｒ，２Ｈ），２．８７（ｍ，１Ｈ），３．２４（ｓ，３Ｈ），３．４９（ｍ，３Ｈ）
［２−メトキシ−１−ビニルオキシ−４−（ビニルオキシメチル）シクロヘキサン及び６−メトキシ−１−ビニルオキシ−３−（ビニルオキシメチル）シクロヘキサンの混合物のスペクトルデータ］
ＧＣ−ＭＳ ｍ／ｅ：２１２，９３，５７
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：１．３１−１．９７（ｍ，７Ｈ），３．３２（ｓ，３Ｈ），３．４５（ｍ，３Ｈ），３．９１−３．９８（ｍ，３Ｈ），４．１１（ｄ，１Ｈ），４．２８（ｄ，１Ｈ），６．３５（ｄｄ，２Ｈ） Production of vinyl ether compound having alkoxy group-containing cyclic group Mixture (dihydroxy) of 2-methoxy-1-hydroxy-4- (hydroxymethyl) cyclohexane and 6-methoxy-1-hydroxy-3- (hydroxymethyl) cyclohexane obtained Compound) was subjected to the following vinylation step. That is, with respect to the dihydroxy compound, 4 equivalents of vinyl propionate, di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ 2 mol%, and sodium carbonate 1 .5 equivalents of toluene mixture was added 4.5 times by weight and stirred at 105 ° C. for 3 hours. When the reaction solution was analyzed by GC-MS, 2-methoxy-1-vinyloxy-4- (vinyloxymethyl) cyclohexane and 6-methoxy-1-vinyloxy-3 in which two hydroxyl groups were substituted with vinyloxy groups. A mixture of-(vinyloxymethyl) cyclohexane was formed. This reaction solution was distilled under reduced pressure to give 2-methoxy-1-vinyloxy-4- (vinyloxymethyl) cyclohexane represented by the following formula (11a) and 6-methoxy-1 represented by the following formula (11b). A mixture of -vinyloxy-3- (vinyloxymethyl) cyclohexane was obtained with a yield of 72%. Moreover, 2-methoxy-1-hydroxy-4- (vinyloxymethyl) cyclohexane, 2-methoxy-1-vinyloxy-4- (hydroxymethyl) cyclohexane in which one of the two hydroxyl groups is substituted with a vinyloxy group, A small amount of 6-methoxy-1-hydroxy-3- (vinyloxymethyl) cyclohexane and 6-methoxy-1-vinyloxy-3- (hydroxymethyl) cyclohexane were also produced.

[Spectral data of a mixture of 2-methoxy-1-hydroxy-4- (hydroxymethyl) cyclohexane and 6-methoxy-1-hydroxy-3- (hydroxymethyl) cyclohexane]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.40-1.57 (m, 7H), 2.16 (br, 2H), 2.87 (m, 1H), 3.24 (s, 3H), 3.49 (m, 3H)
[Spectral data of a mixture of 2-methoxy-1-vinyloxy-4- (vinyloxymethyl) cyclohexane and 6-methoxy-1-vinyloxy-3- (vinyloxymethyl) cyclohexane]
GC-MS m / e: 212, 93, 57
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.31-1.97 (m, 7H), 3.32 (s, 3H), 3.45 (m, 3H), 3.91-3. 98 (m, 3H), 4.11 (d, 1H), 4.28 (d, 1H), 6.35 (dd, 2H)

Example 2
Production of Hydroxy Compound Having Alkoxy Group-Containing Cyclic Group 2-Methoxyhydroquinone was subjected to a normal high pressure hydrogenation reaction with Raney nickel. When the reaction solution was analyzed by GC-MS, a mixture (geometric isomer mixture) composed of a cis isomer and a trans isomer of 2-methoxy-1,4-cyclohexanediol represented by the following formula (12) was generated. .

［２−メトキシ−１，４−シクロヘキサンジオールの幾何異性体混合物の混合物のスペクトルデータ］
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：１．３７−１．９７（ｍ，８Ｈ），２．２８（ｍ，１Ｈ），３．３７（ｓ，３Ｈ），３．４４（ｍ，２Ｈ）
［２−メトキシ−１，４−ビス（ビニルオキシ）シクロヘキサンの幾何異性体混合物のスペクトルデータ］
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：１．３７−２．１０（ｍ，６Ｈ），３．１６−３．２４（ｍ，１Ｈ），３．３９（ｓ，３Ｈ），３．６７（ｍ，１Ｈ），３．７９（ｍ，１Ｈ），４．０２−４．０４（ｍ，２Ｈ），４．２９−４．３７（ｍ，２Ｈ），６．２９−６．３９（ｍ，２Ｈ） Production of Vinyl Ether Compound Having Alkoxy Group-Containing Cyclic Group A vinylation step similar to that in Example 1 was performed using the obtained geometric isomer mixture of 2-methoxy-1,4-cyclohexanediol. When the reaction solution was analyzed by GC-MS, 2-methoxy-1,4-bis (vinyloxy) cyclohexane geometric isomer represented by the following formula (13) in which both hydroxyl groups were substituted with vinyloxy groups. A mixture was formed with a yield of 75%. A small amount of 2-methoxy-1-hydroxy-4-vinyloxycyclohexane and 2-methoxy-1-vinyloxy-4-hydroxycyclohexane in which one of the two hydroxyl groups was substituted with a vinyloxy group was also produced.

[Spectral data of a mixture of geometrical isomers of 2-methoxy-1,4-cyclohexanediol]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.37-1.97 (m, 8H), 2.28 (m, 1H), 3.37 (s, 3H), 3.44 (m, 2H)
[Spectral data of geometrical mixture of 2-methoxy-1,4-bis (vinyloxy) cyclohexane]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.37-2.10 (m, 6H), 3.16-3.24 (m, 1H), 3.39 (s, 3H), 3. 67 (m, 1H), 3.79 (m, 1H), 4.02-4.04 (m, 2H), 4.29-4.37 (m, 2H), 6.29-6.39 ( m, 2H)

Example 3
Production of hydroxy compound having an alkoxy group-containing cyclic group In Example 1, except that 0.45 mol of 5-norbornen-2-ol was used instead of 3-cyclohexene-1-methanol as a starting material. The same reaction as in Example 1 was performed. When the reaction solution was analyzed by GC-MS, a mixture of 2-methoxy-3,5-norbornanediol and 2-methoxy-3,6-norbornanediol was produced. In addition, when the acetic ester of 5-norbornen-2-ol is used instead of 5-norbornen-2-ol, the mixture can be generated by performing hydrolysis after performing the same reaction.

［２−メトキシ−３，５−ノルボルナンジオール及び２−メトキシ−３，６−ノルボルナンジオールの混合物のスペクトルデータ］
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：１．４３−２．１３（ｍ，８Ｈ），２．８６（ｍ，１Ｈ），３．１６（ｍ，１Ｈ），３．２７（ｓ，３Ｈ），３．４８（ｍ，１Ｈ）
［２−メトキシ−３，５−ビス（ビニルオキシ）ノルボルナン、２−メトキシ−３，６−ビス（ビニルオキシ）ノルボルナン及びこれらのエンド・エキソ混合物のスペクトルデータ］
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：１．３７−２．０４（ｍ，６Ｈ），３．０８−３．７５（ｍ，６Ｈ），４．０４（ｍ，２Ｈ），４．１８（ｍ，２Ｈ），６．８９（ｄｄ，２Ｈ） Production of vinyl ether compound having alkoxy group-containing cyclic group A mixture of the obtained 2-methoxy-3,5-norbornanediol and 2-methoxy-3,6-norbornanediol was subjected to the same vinylation step as in Example 1. It was attached. When the reaction solution was analyzed by GC-MS, positional isomers of methoxy-bis (vinyloxy) norbornane in which two hydroxyl groups were substituted with vinyloxy groups, and mixtures of these endo and exo forms (endo exo). Mixture) was formed. By distilling this reaction liquid under reduced pressure, 2-methoxy-3,5-bis (vinyloxy) norbornane represented by the following formula (14a), 2-methoxy-3,6- represented by the following formula (14b) Bis (vinyloxy) norbornane and these endo-exo mixtures were obtained in a yield of 72%. Also, 2-methoxy-3-hydroxy-5- (vinyloxy) norbornane, 2-methoxy-3-vinyloxy-5-hydroxynorbornane, 2-methoxy-3, wherein one of the two hydroxyl groups is substituted with a vinyloxy group Small amounts of -hydroxy-6- (vinyloxy) norbornane and 2-methoxy-3-vinyloxy-6-hydroxynorbornane were also produced.

[Spectral data of a mixture of 2-methoxy-3,5-norbornanediol and 2-methoxy-3,6-norbornanediol]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.43 to 2.13 (m, 8H), 2.86 (m, 1H), 3.16 (m, 1H), 3.27 (s, 3H), 3.48 (m, 1H)
[Spectral data of 2-methoxy-3,5-bis (vinyloxy) norbornane, 2-methoxy-3,6-bis (vinyloxy) norbornane and their endo-exo mixtures]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.37-2.04 (m, 6H), 3.08-3.75 (m, 6H), 4.04 (m, 2H), 4. 18 (m, 2H), 6.89 (dd, 2H)

Example 4
Production of Hydroxy Compound Having Alkoxy Group-Containing Cyclic Group In Example 1, except that 0.45 mol of cyclohexane-2,5-diene was used as a starting material instead of 3-cyclohexene-1-methanol. The same reaction as in Example 1 was performed. When the reaction solution was analyzed by GC-MS, a mixture of 2,5-dimethoxy-1,4-cyclohexanediol and 4,6-dimethoxy-1,3-cyclohexanediol was produced.

［２，５−ジメトキシ−１，４−ビス（ビニルオキシ）シクロヘキサン及び４，６−ジメトキシ−１，３−ビス（ビニルオキシ）シクロヘキサンの混合物のスペクトルデータ］
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：１．８９−１．９５（ｍ，４Ｈ），３．０８−３．２５（ｍ，８Ｈ），３．７９（ｍ，２Ｈ），４．０５（ｍ，２Ｈ），４．２３（ｍ，２Ｈ），６．８７（ｄｄ，２Ｈ） Production of vinyl ether compound having alkoxy group-containing cyclic group The obtained mixture of 2,5-dimethoxy-1,4-cyclohexanediol and 4,6-dimethoxy-1,3-cyclohexanediol was the same as in Example 1. To the vinylation step. When the reaction solution was analyzed by GC-MS, 2,5-dimethoxy-1,4-bis (vinyloxy) cyclohexane and 4,6-dimethoxy-1,3- in which both hydroxyl groups were substituted with vinyloxy groups. Bis (vinyloxy) cyclohexane was produced. This reaction solution was distilled under reduced pressure to give 2,5-dimethoxy-1,4-bis (vinyloxy) cyclohexane represented by the following formula (15a) and 4,6-dimethoxy- represented by the following formula (15b). A mixture of 1,3-bis (vinyloxy) cyclohexane was obtained with a yield of 63%. Also, 2,5-dimethoxy-1-hydroxy-4- (vinyloxy) cyclohexane, 2,5-dimethoxy-1-vinyloxy-4-hydroxycyclohexane in which one of the two hydroxyl groups is substituted with a vinyloxy group, 4 Small amounts of 1,6-dimethoxy-1-hydroxy-3- (vinyloxy) cyclohexane and 4,6-dimethoxy-1-vinyloxy-3-hydroxycyclohexane were also formed.

[Spectral data of a mixture of 2,5-dimethoxy-1,4-bis (vinyloxy) cyclohexane and 4,6-dimethoxy-1,3-bis (vinyloxy) cyclohexane]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.89-1.95 (m, 4H), 3.08-3.25 (m, 8H), 3.79 (m, 2H), 4. 05 (m, 2H), 4.23 (m, 2H), 6.87 (dd, 2H)

Example 5
Production of Hydroxy Compound Having Alkoxy Group-Containing Cyclic Group In Example 1, the same reaction as in Example 1 except that 0.45 mol of norbornadiene was used as a starting material instead of 3-cyclohexene-1-methanol. Went. When the reaction solution was analyzed by GC-MS, an endo-exo mixture of 2,4-dimethoxy-3,5-norbornanediol and 2,5-dimethoxy-3,4-norbornanediol was formed.

［２，５−ジメトキシ−３，４−ビス（ビニルオキシ）ノルボルナン及び２，６−ジメトキシ−３，５−ビス（ビニルオキシ）ノルボルナン及びこれらのエンド・エキソ混合物のスペクトルデータ］
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：１．４３−１．４９（ｍ，２Ｈ），２．０８−２．２１（ｍ，２Ｈ），３．０６−３．２５（ｍ，８Ｈ），３．７５（ｍ，２Ｈ），４．０７（ｍ，２Ｈ），４．２１（ｍ，２Ｈ），６．７９（ｄｄ，２Ｈ） Production of vinyl ether compound having an alkoxy group-containing cyclic group. Using the obtained endo-exo mixture of 2,4-dimethoxy-3,5-norbornanediol and 2,5-dimethoxy-3,4-norbornanediol. The same vinylation process as in Example 1 was applied. When the reaction solution was analyzed by GC-MS, 2,5-dimethoxy-3,4-bis (vinyloxy) norbornane in which two hydroxyl groups were substituted with vinyloxy groups, 2,6-dimethoxy-3,5- Bis (vinyloxy) norbornane and these endo-exo mixtures were formed. This reaction solution was distilled under reduced pressure to give 2,5-dimethoxy-3,4-bis (vinyloxy) norbornane represented by the following formula (16a) and 2,6-dimethoxy- represented by the following formula (16b). 3,5-Bis (vinyloxy) norbornane and these endo-exo mixtures were obtained in a yield of 58%. In addition, 2,5-dimethoxy-3-hydroxy-4- (vinyloxy) norbornane, 2,5-dimethoxy-3-vinyloxy-4-hydroxynorbornane, wherein one of the two hydroxyl groups is substituted with a vinyloxy group, , 6-Dimethoxy-3-hydroxy-5- (vinyloxy) norbornane and 2,6-dimethoxy-3-vinyloxy-5-hydroxynorbornane were also produced in small amounts.

[Spectral data of 2,5-dimethoxy-3,4-bis (vinyloxy) norbornane and 2,6-dimethoxy-3,5-bis (vinyloxy) norbornane and their endo-exo mixtures]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.43-1.49 (m, 2H), 2.08-2.21 (m, 2H), 3.06-3.25 (m, 8H) ), 3.75 (m, 2H), 4.07 (m, 2H), 4.21 (m, 2H), 6.79 (dd, 2H)

Example 6
Production of hydroxy compound having alkoxy group-containing cyclic group In Example 1, 0.45 mol of hexahydro-4,7-methano-indene-6-ol was used as a starting material instead of 3-cyclohexene-1-methanol. The same reaction as in Example 1 was performed except for the points described above. When the reaction solution was analyzed by GC-MS, an endo-exo mixture of 1-methoxy-2,5-dihydroxy-octahydro-4,7-methano-indene was formed.

［１−メトキシ−２，５−ビス（ビニルオキシ）−オクタヒドロ−４，７−メタノ−インデンのエンド・エキソ混合物のスペクトルデータ］
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：１．４５−１．８２（ｍ，９Ｈ），３．１５−４．２５（ｍ，１０Ｈ），６．８６（ｄｄ，２Ｈ） Production of Vinyl Ether Compound Having Alkoxy Group-Containing Cyclic Group Vinyl as in Example 1 was obtained by using the obtained 1-methoxy-2,5-dihydroxy-octahydro-4,7-methano-indene endo-exo mixture. It was attached to the conversion process. When the reaction solution was analyzed by GC-MS, 1-methoxy-2,5-bis (vinyloxy) -octahydro-4 represented by the following formula (17) in which both hydroxyl groups were substituted with vinyloxy groups, A 7-methano-indene endo-exo mixture was formed. Also, 1-methoxy-2-hydroxy-5-vinyloxy-octahydro-4,7-methano-indene, 1-methoxy-2-vinyloxy-5-hydroxy, wherein one of the two hydroxyl groups is substituted with a vinyloxy group Small amounts of octahydro-4,7-methano-indene and their endo-exo mixtures were also formed.

[Spectral data of endo-exo mixture of 1-methoxy-2,5-bis (vinyloxy) -octahydro-4,7-methano-indene]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.45 to 1.82 (m, 9H), 3.15 to 4.25 (m, 10H), 6.86 (dd, 2H)

Comparative Example 1
As the vinyl ether compound having a cyclic group, 1,4-bis (vinyloxymethyl) cyclohexane represented by the following formula (18) was used.

Example 7
Production of Hydroxy Compound Having Alkoxy Group-Containing Cyclic Group In Example 1, the same reaction as in Example 1 was carried out except that limonene was used as a starting material instead of 3-cyclohexene-1-methanol. When the reaction solution was analyzed by GC-MS, 2-methoxy-2-methyl-5- (1-methoxy-1-methyl-2-hydroxyethyl) cyclohexanol represented by the following formula (19) was formed. It was.

［１−メトキシ−１−メチル−２−ビニルオキシ−４−（１−メトキシ−１−メチル−２−ビニルオキシエチル）シクロヘキサンのスペクトルデータ］
ＧＣ−ＭＳ ｍ／ｅ：２８４，２５３，２４０ Production of Vinyl Ether Compound Having Alkoxy Group-Containing Cyclic Group Similar to Example 1 using the obtained 2-methoxy-2-methyl-5- (1-methoxy-1-methyl-2-hydroxyethyl) cyclohexanol To the vinylation step. When the reaction solution was analyzed by GC-MS, 1-methoxy-1-methyl-2-vinyloxy-4- (1-) represented by the following formula (20) in which two hydroxyl groups were both substituted with vinyloxy groups. Methoxy-1-methyl-2-vinyloxyethyl) cyclohexane was formed. Also, 2-methoxy-2-methyl-5- (1-methoxy-1-methyl-2-vinyloxyethyl) cyclohexanol and 1-methoxy-1 in which one of two hydroxyl groups is substituted with a vinyloxy group A small amount of -methyl-2-vinyloxy-4- (1-methoxy-1-methyl-2-hydroxyethyl) cyclohexane was also produced.

[Spectral data of 1-methoxy-1-methyl-2-vinyloxy-4- (1-methoxy-1-methyl-2-vinyloxyethyl) cyclohexane]
GC-MS m / e: 284, 253, 240

Example 8
Production of hydroxy compound having alkoxy group-containing cyclic group In Example 1, the same reaction as in Example 1 was carried out except that 2-norbornene was used instead of 3-cyclohexene-1-methanol as the starting material. It was. When the reaction solution was analyzed by GC-MS, 2-methoxy-3- (hydroxy) bicyclo [2.2.1] heptane represented by the following formula (21) was produced.

［２−メトキシ−３−（ビニルオキシ）ビシクロ［２．２．１］ヘプタンのスペクトルデータ］
ＧＣ−ＭＳ ｍ／ｅ：１６８，１３７，９４ Production of vinyl ether compound having alkoxy group-containing cyclic group The obtained 2-methoxy-3- (hydroxy) bicyclo [2.2.1] heptane was subjected to the same vinylation step as in Example 1. When the reaction solution was analyzed by GC-MS, 2-methoxy-3- (vinyloxy) bicyclo [2.2.1] represented by the following formula (22) in which both hydroxyl groups were substituted with vinyloxy groups. Heptane was generated.

[Spectral data of 2-methoxy-3- (vinyloxy) bicyclo [2.2.1] heptane]
GC-MS m / e: 168, 137, 94

Examples 9 to 14 and Comparative Example 2
For the vinyl ether compound having an alkoxy group-containing cyclic group obtained in Examples 1 to 6 and the vinyl ether compound having a cyclic group of Comparative Example 1, respectively, a photopolymerization initiator (propylene of triallylsulfonium hexafluorophosphate) was obtained. 3% by weight of a carbonate solution: trade name “UVACURE” manufactured by Daicel Chemical Industries, Ltd. was mixed to obtain a polymerizable composition.
The obtained polymerizable composition was applied on quartz glass to a thickness of about 50 μm, irradiated with a UV lamp at a focal length of 15 cm, and the irradiation time until the surface was not sticky was measured. About the formed hardened | cured material, pencil hardness was measured by the test based on JISK5400. These results are shown in Table 1.

Claims (5)

Following formula (1)

[Wherein, ring Z represents a monocyclic or polycyclic non-aromatic ring, and the R ¹ O— group and the R ² O— (W) _n — group are bonded to the atoms constituting ring Z. R ¹ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and R ² represents a hydrogen atom or the following formula (2)

(Wherein R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or an organic group)
W represents a divalent organic group. n represents 0 or 1, m represents an integer of 1 to 8, and k represents an integer of 1 to 5. When m and k are 2 or more, the substituents in parentheses may be the same or different. However, at least one R ¹ —O— group in the ring Z is bonded to the constituent atom at the α-position or the β-position with respect to the constituent atom to which the R ² O— (W) _n — group in the ring Z is bonded. . When m is 1, R ² is a group represented by the formula (2)]
An alkoxy group-containing cyclic compound represented by the formula:   The alkoxy group-containing cyclic compound according to claim 1, wherein the ring Z is an alicyclic ring. Ring Z is represented by the following formulas (3) to (7)

(In the formula, X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are substituents bonded to the atoms constituting each ring, and are halogen atoms, alkyl groups, haloalkyl groups, aryl groups, protecting groups. A hydroxyl group that may be protected with a hydroxyl group, a hydroxymethyl group that may be protected with a protecting group, an amino group that may be protected with a protecting group, a carboxyl group that may be protected with a protecting group, or a protecting group; An optionally protected sulfo group, an oxo group, a nitro group, a cyano group, or an acyl group that may be protected with a protecting group, when X ¹ is 2 or more, A 4-membered ring or more may be formed together with the carbon atoms constituting the cycloalkane ring, wherein a, b, c, d and e represent an integer of 0 or more, and a, b, c, d or e is In the case of 2 or more, the substituents in parentheses may be the same or different. (P represents an integer of 1 to 8, q represents an integer of 0 to 3, and r represents an integer of 1 to 3)
The alkoxy group-containing cyclic compound according to claim 1, which is an alicyclic ring represented by the formula: The alkoxy group-containing cyclic compound according to any one of claims 1 to 3, wherein at least one R ² out of m R ² is a group represented by the formula (2): A polymerizable composition comprising a compound.   A cured product obtained by curing the polymerizable composition according to claim 4.