JP2006069897A - Oxygen atom-containing polycyclic compound, polymerizable composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new oxygen-containing polycyclic compound, a polymerizable composition comprising the same and a cured product thereof. <P>SOLUTION: The oxygen-containing polycyclic compound is represented by formula (I) (ring Z is a polycyclic nonaromatic ring containing one oxygen atom on a part of a ring; X and RO-(W)<SB>n</SB>-group is a substituent group bonded to a carbon atom constituting ring Z; X is a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a sulfo group, an oxo group, a nitro group, a cyano group or a hydroxy group which may be protected with a protective group or the like; W is a bifunctional organic group; R is a hydrogen atom or a group represented by formula (2); p is an integer of ≥0; n is 0 or 1; m is an integer of 1-5; s and t are each an integer of 0-7 or the like; R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each the same or different and a hydrogen atom or a 1-4C alkyl group). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a polymerizable compound that is polymerized or cured by light or heat, and is useful in the fields of pharmaceuticals, agricultural chemicals, coating agents, inks, paints, adhesives, resists, plate making materials, oxygen atom-containing polycyclic compounds, polymerization The present invention relates to a composition and a cured product thereof.

  Polymerizable compounds that are polymerized or cured by light or heat are widely used as polymer raw materials for coating agents, inks, paints, adhesives, resists, platemaking materials and the like. Conventionally, an epoxy compound has been used as a polymerizable compound in order to obtain a cured product having excellent chemical resistance and adhesion. However, since the epoxy compound has low polymerization reactivity (curability) and extremely high skin irritation and toxicity, safety in handling is regarded as a problem. On the other hand, vinyl ether compounds are attracting attention as polymerizable compounds having low toxicity and skin irritation, excellent safety, and excellent curability. However, in the market, since vinyl ether compounds are few in kind and expensive in price, the present situation is that they cannot sufficiently meet the needs.

  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 oxygen atom-containing polycyclic compound, a polymerizable composition containing the same, and a cured product thereof.
Another object of the present invention is to provide an oxygen atom-containing polycyclic 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 found that when a vinyl ether compound having an oxygen atom-containing polycyclic group in the molecule is used as a comonomer of the polymer, the curing rate is remarkably improved and the hardness is increased. The present invention was completed by finding that a cured product having a high hardness was obtained.

［式中、環Ｚは環の一部に１つの酸素原子を含む多環の非芳香族性環を示し、Ｘ及びＲＯ−（Ｗ）_n−基は環Ｚを構成する炭素原子に結合している置換基であって、Ｘは、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。Ｗは２価の有機基を示し、Ｒは、水素原子又は下記式（２）

（式中、Ｒ¹、Ｒ²及びＲ³は、同一又は異なって、水素原子又は炭素数１〜４のアルキル基を示す）
で表される基を示し、Ｗは２価の有機基を示す。ｐは０以上の整数を示し、ｎは０又は１を示し、ｍは１〜５の整数を示し、ｓ及びｔは、それぞれ、０〜７の整数を示す。ｐ、ｎ、ｍ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。Ｘが２以上の場合、それらは互いに結合して、環Ｚ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］
で表される酸素原子含有多環式化合物を提供する。 The present invention provides the following formula (1)

[Wherein, ring Z represents a polycyclic non-aromatic ring containing one oxygen atom as a part of the ring, and X and RO- (W) _n -groups are bonded to the carbon atoms constituting ring Z. X is a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group that may be protected with a protecting group, a hydroxymethyl group that may be protected with a protecting group, or a protecting group Protected with an amino group which may be protected with, a carboxyl group which may be protected with a protective group, a sulfo group which may be protected with a protective group, an oxo group, a nitro group, a cyano group, or a protective group An acyl group that may be present is shown. W represents a divalent organic group, R represents a hydrogen atom or the following formula (2)

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
W represents a divalent organic group. p shows an integer greater than or equal to 0, n shows 0 or 1, m shows the integer of 1-5, s and t show the integer of 0-7, respectively. When p, n and m are 2 or more, the substituents in parentheses may be the same or different. When X is 2 or more, they may be bonded to each other to form a 4-membered or more ring with the carbon atoms constituting the ring Z.]
The oxygen atom containing polycyclic compound represented by these is provided.

  The present invention also provides a polymerizable composition comprising a polymerization initiator and the oxygen atom-containing polycyclic compound of the present invention.

  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 oxygen atom-containing polycyclic compound of the present invention has little toxicity and skin irritation, it can be used as a raw material for coating agents, inks, paints, adhesives, resists, plate making materials and the like. In particular, when a vinyl ether compound having an oxygen atom-containing polycyclic group is used as a polymer raw material monomer, the curing rate by heating or light irradiation is extremely high, and a cured product having high hardness can be formed.

The oxygen atom-containing polycyclic compound of the present invention is a compound represented by the formula (1). In the formula (1), ring Z represents a polycyclic non-aromatic ring containing one oxygen atom in a part of the ring. s and t are each an integer of 0 to 7, preferably an integer of 0 to 6, and more preferably an integer of 0 to 5. Moreover, the sum total of s and t is an integer of 0-14, for example, Preferably it is an integer of 1-10, More preferably, it is an integer of 1-6. That is, the ring Z can be composed of at least 4 or more carbon atoms. For example, the carbon atoms constituting the ring Z are 4 to 18, preferably 5 to 14, and more preferably 5 to 10. Representative examples of ring Z include 5-oxabicyclo [1.1.1] pentane, 6-oxabicyclo [2.1.1] hexane, 7-oxabicyclo [2.2.1] heptane (7 -Oxanorbornane), 7-oxabicyclo [2.2.1] -2-heptene (7-oxa-2-norbornene), 7-oxabicyclo [3.1.1] heptane, 7-oxabicyclo [3. 1.1] -2-heptene, 8-oxabicyclo [3.2.1] octane, 8-oxabicyclo [3.2.1] -2-octene, 8-oxabicyclo [3.2.1]- 6-octene, 8-oxabicyclo [4.1.1] octane, 8-oxabicyclo [4.1.1] -3-octene, 9-oxabicyclo [3.3.1] nonane, 9-oxabicyclo [3.3.1] -2-Nonene, 9- Xabicyclo [4.2.1] nonane, 9-oxabicyclo [4.2.1] -3-nonene, 9-oxabicyclo [4.2.1] -7-nonene, 3-oxatricyclo [4. 2.1.0 ^4,8] bicyclo ring such as nonane, 4-oxa-tricyclo [5.2.10 ^2,6] tricyclo ring such as decane, 11-oxa tetracyclo [4.4.0.1 ^{2 , 5} . 0 ^7,10 ] Polycyclic non-aromatic rings such as tetracyclo ring such as dodecane. 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). The same group as X).

X in the formula (1) represents a substituent bonded to the carbon atom constituting the ring Z. Preferably, X is bonded to the carbon atom constituting the ring Z other than the bridgehead position constituting the ring Z. As a halogen atom in X, a fluorine, chlorine, a bromine atom etc. are mentioned, for example. Examples of the alkyl group for X include C _1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, and decyl groups (preferably C _{1- 5} alkyl group). Examples of the haloalkyl group for X 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 for X 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.
It is.

Examples of the protecting group for hydroxyl group and hydroxymethyl group in X include protecting groups commonly used in the field of organic synthesis, such as alkyl groups (for example, C _1-4 alkyl groups such as methyl and t-butyl groups), alkenyl groups, and the like. (For example, an allyl group), a cycloalkyl group (for example, a cyclohexyl group), an aryl group (for example, a 2,4-dinitrophenyl group), an aralkyl group (for example, a benzyl group); a substituted methyl group (for example, Methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group, etc.), substituted ethyl groups (for example, 1-ethoxyethyl group, etc.), tetrahydropyranyl group, tetrahydrofuranyl group, 1-hydroxy Hydroxyl groups such as alkyl groups (eg 1-hydroxyethyl group etc.) A group capable of forming an acetal or hemiacetal group with an acyl; an acyl group (for example, a C _1-6 aliphatic acyl group such as formyl, acetyl, propionyl, butyryl, isobutyryl, pivaloyl group; an acetoacetyl group; an aromatic group such as a benzoyl group Acyl groups, etc.), alkoxycarbonyl groups (eg, C _1-4 alkoxy-carbonyl groups such as methoxycarbonyl groups), aralkyloxycarbonyl groups, substituted or unsubstituted carbamoyl groups, substituted silyl groups (eg, trimethylsilyl groups), 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, cyclopentylidene) which may have a substituent. Cyclohexylidene, benzylidene group, etc.) It can be shown.

  Examples of the amino-protecting group for X include an alkyl group, an aralkyl group, an acyl group, and an alkoxycarbonyl group exemplified as the hydroxyl-protecting group.

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

Examples of the acyl group in X include C _1-6 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, and pivaloyl groups; acetoacetyl groups; aromatic acyl groups such as 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 is 2 or more, they are bonded to each other to form a 4-membered or more ring formed together with the carbon atom constituting the ring Z in the formula (1), for example, cyclopentane ring, cyclohexane ring, perhydronaphthalene Examples thereof include alicyclic carbocycles such as rings (decalin rings); lactone rings such as γ-butyrolactone rings and δ-valerolactone rings.

  p is, for example, an integer of 0 to 5, preferably an integer of 0 to 3.

The RO- (W) _n -group represents a substituent bonded to the carbon atom constituting the ring Z. Preferably, the RO— (W) _n — group is bonded to a carbon atom other than the bridgehead constituting the ring Z. 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、Ｒ⁴及びＲ⁵は、同一又は異なって、水素原子又は炭化水素基を示す。Ｒ⁴及びＲ⁵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 (3)

(In the formula, R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or a hydrocarbon group. R ⁴ and R ⁵ are bonded to each other to form an alicyclic ring together with adjacent carbon atoms. May be)
The group represented by these is included.

The hydrocarbon group in R ⁴ and R ⁵ 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.

Preferred R ⁴ and R ⁵ include a hydrogen atom; a C _1-10 alkyl group (particularly a C _1-5 alkyl group) such as a methyl, ethyl, propyl, isopropyl, or butyl group; a substituent such as a cyclopentyl group or 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—O— group is bonded to the ring Z via W or not. Particularly in the present invention, it is preferable that at least one R—O— group is directly bonded to the ring Z.

R represents a hydrogen atom or a group represented by the formula (2). In formula (2), R < ¹ >, R < ² > and R < ³ > show a hydrogen atom or a C1-C4 alkyl group, respectively. Examples of the alkyl group include linear C _1-4 (preferably C _1-3 ) alkyl groups such as methyl, ethyl, propyl, and butyl; branched chains such as isopropyl, isobutyl, s-butyl, and t-butyl. C _1-4 (preferably C _1-3 ) alkyl group and the like. R ¹ , R ² and R ³ are particularly preferably 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 1-5. When m is 2 or more, the groups in parentheses may be the same or different. m is preferably an integer of 2 to 4, more preferably an integer of 2 to 3.

The oxygen atom-containing polycyclic compound represented by the formula (1) is an oxygen atom-containing polycyclic hydroxy compound in which all R in the formula (1) are hydrogen atoms, and at least one R in the formula (1) is The oxygen atom containing polycyclic vinyl ether compound which is the said Formula (2) is included. 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 oxygen atom-containing polycyclic vinyl ether compound includes a monovinyl body in which m is 1 and R is R ² in formula (1), and divinyl in which m is 2 and both R are R ^2. And a half vinyl body in which m is 2 or more and hydrogen atoms and R ² are mixed among a plurality of R.

  Typical examples of the oxygen atom-containing polycyclic vinyl ether compound include the following compounds. As the oxygen atom-containing polycyclic vinyl ether compound (monovinyl body) in which the ring Z in the formula (1) is a bicyclo ring having 7 carbon atoms and m is 1, for example, 2-vinyloxy-7-oxabicyclo [2.2 .1] Heptane, 6-vinyloxy-7-oxabicyclo [2.2.1] heptane, 6-vinyloxy-7-oxabicyclo [2.2.1] -2-heptene, 2-vinyloxymethyl-7- Oxabicyclo [2.2.1] heptane, 6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane, 6-vinyloxymethyl-7-oxabicyclo [2.2.1] -2- Heptene and its positional isomers, mixtures thereof; and the corresponding isopropenyl ethers.

  As the oxygen atom-containing polycyclic vinyl ether compound in which the ring Z in the formula (1) is a bicyclo ring having 7 carbon atoms and m = 2, for example, 2,6-bis (vinyloxy) -7-oxabicyclo [2. 2.1] Heptane, 3,6-bis (vinyloxy) -7-oxabicyclo [2.2.1] heptane, 2-vinyloxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane 3-vinyloxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane, 2,6-bis (vinyloxy) -3-methoxy-7-oxabicyclo [2.2.1] heptane, 3,6-bis (vinyloxy) -2-methoxy-7-oxabicyclo [2.2.1] heptane, 2-vinyloxy-3-methoxy-6-vinyloxymethyl-7-oxa Divinyl compounds such as cyclo [2.2.1] heptane, 2-methoxy-3-vinyloxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane, 2-vinyloxy-6-hydroxy-7 -Oxabicyclo [2.2.1] heptane, 2-hydroxy-6-vinyloxy-7-oxabicyclo [2.2.1] heptane, 2-hydroxy-5-vinyloxy-7-oxabicyclo [2.2. 1] Heptane, 2-vinyloxy-5-hydroxy-7-oxabicyclo [2.2.1] heptane, 3-vinyloxy-6-hydroxy-7-oxabicyclo [2.2.1] heptane, 2-vinyloxy- 6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane, 3-vinyloxy-6-hydroxymethyl-7-oxabicyclo 2.2.1] Half vinyl material such as heptane, and positional isomers thereof, mixtures thereof; and the like isopropenyl ether corresponding to thereof.

  As the oxygen atom-containing polycyclic vinyl ether compound in which ring Z in formula (1) is a bicyclo ring having 9 carbon atoms and m = 2, for example, 2,6-bis (vinyloxy) -9-oxabicyclo [3. 3.1] Nonane, 2-vinyloxy-6-vinyloxymethyl-9-oxabicyclo [3.3.1] nonane, 2,5-bis (vinyloxy) -9-oxabicyclo [3.3.1] nonane 2-vinyloxy-5-vinyloxymethyl-9-oxabicyclo [3.3.1] nonane, 2,6-bis (vinyloxy) -9-oxabicyclo [4.2.1] nonane, 2-vinyloxy- 6-vinyloxymethyl-9-oxabicyclo [4.2.1] nonane, 2,5-bis (vinyloxy) -9-oxabicyclo [4.2.1] nonane, 2-vinyloxy-5-bi Divinyl compounds such as ruoxymethyl-9-oxabicyclo [4.2.1] nonane, 2-hydroxy-6-vinyloxy-9-oxabicyclo [3.3.1] nonane, 2-hydroxy-6-vinyloxymethyl- 9-oxabicyclo [3.3.1] nonane, 2-hydroxy-6-vinyloxy-9-oxabicyclo [4.2.1] nonane, 2-hydroxy-6-vinyloxymethyl-9-oxabicyclo [4 2.1] half vinyl forms such as nonane, and their positional isomers, mixtures thereof; and the corresponding isopropenyl ethers.

As the oxygen atom-containing polycyclic vinyl ether compound (having a lactone ring) in which the ring Z in the formula (1) is a tricyclo ring having 9 carbon atoms and X is an oxo group, for example, 5-vinyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 4-vinyloxy-9-methyl-3oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one and its position Isomers, mixtures thereof; and the corresponding isopropenyl ethers.

  Examples of the oxygen atom-containing polycyclic hydroxy compound include primary alcohols, secondary alcohols, and tertiary alcohols. 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.

  Typical examples of the oxygen atom-containing polycyclic hydroxy compound include the following compounds. As the oxygen atom-containing polycyclic hydroxy compound in which the ring Z in the formula (1) is a bicyclo ring having 7 carbon atoms and m is 1, for example, 2-hydroxy-7-oxabicyclo [2.2.1] heptane 2-hydroxymethyl-7-oxabicyclo [2.2.1] heptane, 6-hydroxy-7-oxabicyclo [2.2.1] -2-heptene, 2-methoxy-6-hydroxy-7-oxa Bicyclo [2.2.1] heptane, 2-methoxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane, 6-hydroxymethyl-7-oxabicyclo [2.2.1] -2 -Heptene and its positional isomers, mixtures thereof and the like.

  As the oxygen atom-containing polycyclic hydroxy compound in which the ring Z in the formula (1) is a bicyclo ring having 7 carbon atoms and m = 2, for example, 2,6-dihydroxy-7-oxabicyclo [2.2.1 ] Heptane, 3,6-dihydroxy-7-oxabicyclo [2.2.1] heptane, 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane, 3-hydroxy-6 Hydroxymethyl-7-oxabicyclo [2.2.1] heptane, 2,6-dihydroxy-3-methoxy-7-oxabicyclo [2.2.1] heptane, 3,6-dihydroxy-2-methoxy-7 -Oxabicyclo [2.2.1] heptane, 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane, 3-hydroxy-6-hydroxy Tyl-7-oxabicyclo [2.2.1] heptane, 2-hydroxy-3-methoxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane, 2-methoxy-3-hydroxy-6 -Hydroxymethyl-7-oxabicyclo [2.2.1] heptane, and its positional isomers, mixtures thereof and the like.

  As the oxygen atom-containing polycyclic hydroxy compound in which the ring Z in the formula (1) is a bicyclo ring having 9 carbon atoms and m = 2, for example, 2,6-dihydroxy-9-oxabicyclo [3.3.1]. ] Nonane, 2-hydroxy-6-hydroxymethyl-9-oxabicyclo [3.3.1] nonane, 2,5-dihydroxy-9-oxabicyclo [3.3.1] nonane, 2-hydroxy-5 Hydroxymethyl-9-oxabicyclo [3.3.1] nonane, 2,6-dihydroxy-9-oxabicyclo [4.2.1] nonane, 2-hydroxy-6-hydroxymethyl-9-oxabicyclo [4 2.1] nonane, 2,5-dihydroxy-9-oxabicyclo [4.2.1] nonane, 2-hydroxy-5-hydroxymethyl-9-oxabicyclo [4.2.1] Emissions and its regioisomer, mixtures thereof and the like.

As the oxygen atom-containing polycyclic hydroxy compound (having a lactone ring) in which the ring Z in the formula (1) is a tricyclo ring having 9 carbon atoms and X is an oxo group, for example, 5-hydroxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 4-hydroxy-9-methyl-3oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one and its position Isomers, mixtures thereof; and the corresponding isopropenyl ethers.

  The oxygen atom-containing polycyclic vinyl ether compound in the present invention can be produced by utilizing a known reaction as a method for producing a vinyl ether compound. A preferred embodiment includes a method for producing an oxygen atom-containing polycyclic vinyl ether compound by reacting the oxygen atom-containing polycyclic hydroxy compound with a vinyl ester compound in the presence of a transition element compound.

（式中、Ｒ¹、Ｒ²及びＲ³は、同一又は異なって、水素原子又は炭素数１〜４のアルキル基を示し、Ｒ⁶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 oxygen atom-containing polycyclic hydroxy compound 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 (4)

(Wherein R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ represents an organic group)
The vinyl ester compound represented by these is mentioned.

In the vinyl ester compound represented by the formula (4), R ^{1 to} R ³ are the same as described above. Alkyl group having 1 to 4 carbon atoms in the R ⁶ may be any organic group which does not inhibit the reaction, can be utilized for illustrative as alkyl group having 1 to 4 carbon atoms in the R ¹ or the like. Representative examples of the vinyl ester compound represented by the formula (4) include vinyl acetate, isopropenyl acetate, 1-propenyl acetate, 2-methyl-1-propenyl acetate, 1,2-dimethyl 1-propenyl acetate, 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 between the vinyl ester compound represented by formula (4) and the oxygen atom-containing polycyclic hydroxy compound is carried out 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 vinyl ester compound represented by the formula (4) is used in an amount of, for example, 0.8 to 10 equivalents, preferably 1 to 8 equivalents, more preferably 1 to 1 equivalent of the oxygen atom-containing polycyclic hydroxy compound. About 5 to 5 equivalents. A large excess of the vinyl ester compound represented by the formula (4) 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 oxygen atom-containing polycyclic hydroxy compounds); alkali metal phenoxides such as sodium phenoxide; triethylamine, Examples thereof include amines such as 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 oxygen atom containing polycyclic hydroxy compounds represented by Formula (4), 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 progress of the vinylation reaction can be controlled by adjusting the reaction time. For example, a dihydroxy compound having two hydroxyl groups in the molecule produces a monovinyl compound in which one hydroxyl group remains and one vinyloxy is introduced in a short-time reaction (for example, about 2 hours). A divinyl compound into which two vinyloxy groups are introduced can be produced by a reaction for a period of time (for example, about 5 hours).

The above reaction produces an oxygen atom-containing polycyclic vinyl ether compound 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 oxygen atom-containing polycyclic hydroxy compound in the present invention can be produced by utilizing a known reaction as a method for producing a hydroxy compound having a cyclic group. For example, a hydroxyl compound having an oxygen atom-containing polycyclic group can be produced according to the following steps.

  The above step is a step of obtaining a mixture of the compound represented by the formula (1a-1) and the formula (1a-2) by reacting the compound represented by the formula (A) with dicyclohexylborane and hydrogen peroxide. Is shown.

In formula (A), ring Z ¹ represents a polycyclic non-aromatic bridged ring having one oxygen atom and one double bond in a part of the ring. Examples of the polycyclic non-aromatic ring having one oxygen atom and one double bond in a part of the ring include, for example, at least one part of the ring among the non-aromatic rings in the ring Z. And a ring having two double bonds. Examples of such ring Z ¹ include 6-oxabicyclo [2.1.1] -2-hexene, 7-oxabicyclo [2.2.1] -2-heptene (7-oxanorbornane), 8 -Oxabicyclo [3.2.1] -2-octene, 8-oxabicyclo [4.1.1] -3-octene, 9-oxabicyclo [3.3.1] -2-nonene, 9-oxa Bicyclo [4.2.1] -3-nonene, 9-oxabicyclo [4.2.1] -7-nonene and the like are included. In formula (1a-1) and formula (1a-2), ring Z ² is non-aromatic corresponding to a ring in which one double bond of ring Z ¹ in formula (A) is converted to a single bond A ring is shown, and the same ring as the ring Z is exemplified. X and p are the same as described above.

  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, about -40 to 25 ° C, preferably about -30 to 10 ° 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.

According to the above reaction, a hydroxyl group is introduced into the double bond site of ring Z ¹ in formula (A) by the action of dicyclohexylborane and hydrogen peroxide, and the corresponding formula (1a-1) and formula (1a -2) is produced. After completion of the reaction, the reaction product can be separated and purified by the separation means exemplified above.

Moreover, the hydroxyl compound which has an oxygen atom containing polycyclic group can also be manufactured according to the process shown below.

The above steps include a pre-step for obtaining a compound represented by the formula (B) by reaction of a compound represented by the formula (A) and a peracid, and a formula (B) obtained in the pre-step in the presence of an acid catalyst. And a subsequent step of obtaining a mixture of the compounds represented by formula (1b-1) and formula (1b-2) by reacting the compound represented by formula (R1) with the hydroxy compound represented by R ¹ —OH. The

The compound represented by the formula (A) in the previous step is the same as described above. Examples of the peracid include performic acid, peracetic acid, m-chloroperbenzoic acid (mCPBA), and the like. The peracid may be generated in the system using an organic acid such as formic acid or acetic acid and hydrogen peroxide, or may be generated in the system using a metal compound and hydrogen peroxide. Metal peroxides can also be used. Rings Z ² , X and p in the formula (B) are the same as described above. 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. In addition, the same reaction conditions as those in the above steps can be adopted as long as the progress of the reaction is not inhibited.

According to the above reaction, the double bond site of ring Z ¹ in formula (A) is epoxidized by the action of peracid 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, the rings Z ² , X, p, and R ¹ in formula (1b-1) and formula (1b-2) 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. 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. In addition, the same reaction conditions as those in the above steps can be adopted 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 formula (B) is opened by the action of the acid catalyst, and the corresponding formula (1b-1) and A mixture of the compounds represented by formula (1b-2) is formed. After completion of the reaction, the reaction product can be separated and purified by the separation means exemplified above.

Furthermore, the dihydroxyl compound having an oxygen atom-containing polycyclic group can also be produced according to the steps shown below.

  In the above step, a diepoxy compound represented by the formula (D) is formed by a reaction between a cyclic compound having a diene in a part of the ring represented by the formula (C) and a peracid, and the reaction is further performed by raising the temperature. It shows the step of proceeding to obtain the desired mixture of compounds represented by formula (1c-1) and formula (1c-2).

The compound represented by the formula (C) is a cyclic compound having a diene in a part of the ring, and the ring Z ³ in the formula has at least one or more double bonds in each part of the ring. A monocyclic or polycyclic ring arranged via a single bond is shown. Examples of such ring Z ³ include monocyclic rings such as 1,4-cyclohexadiene and 1,5-cyclooctadiene; bridged rings such as 2,5-norbornadiene, and bicyclo [3.2.1]- Polycyclic non-aromatic cyclic group-containing compounds such as condensed rings such as 2,6-octadiene; and compounds having substituents on these rings are included. As these substituents, those exemplified as the substituent in Z can be used. As the peracid, the same one as in the above step can be used. The ring Z ⁴ in the formula (D) corresponds to a ring in which two double bond sites of the ring are single bonds with respect to the ring Z ³ in the formula (C). X, p, and R ¹ are the same as described above. Rings Z ² and R ¹ in formula (1c-1) and formula (1c-2) are the same as described above.

  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 according to the type of reaction components, and is, for example, −40 to 100 ° C., preferably −30 to 80 ° C. In the above step, the reaction is usually carried out at a temperature of about -40 to 25 ° C, preferably about -30 to 10 ° C, and then heated to 25 to 100 ° C, preferably about 30 to 70 ° C. It is preferable. In addition, the same reaction conditions as those in the above steps can be adopted as long as the progress of the reaction is not inhibited.

  According to the above reaction, an oxacyclo ring and two hydroxyl groups are introduced into two double bond sites constituting part of the ring of the compound represented by formula (C), and the corresponding formula (1c-1) And a mixture of the compounds represented by formula (1c-2) 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 contains a polymerization initiator and an oxygen atom-containing polycyclic compound represented by the formula (1) of the present invention. The polymerizable composition generally contains a polymerization initiator and an oxygen atom-containing polycyclic vinyl ether compound as constituent components. 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 oxygen atom-containing polycyclic group-containing vinyl ether compound.

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

  According to the present invention, since the oxygen atom-containing polycyclic 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. it can. 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
Furan (100 g, 1.48 mol), methyl acrylate (129 g, 1.50 mol) and aluminum chloride (19.4 g, 0.145 mol) as starting materials were added to dichloromethane solvent (300 ml), and Diels- Alder reaction was performed. After quenching the reaction solution with dilute hydrogen chloride aqueous solution, washing with water, washing with alkali, and concentration were performed, methyl 7-oxabicyclo [2.2.1] -2-heptene-6-carboxylate was obtained almost quantitatively. . The methyl 7-oxabicyclo [2.2.1] -2-heptene-6-carboxylate (100 g, 0.65 mol) and LiAlH ₄ (25 g, 0.65 mol) were added to a tetrahydrofuran (THF) solvent. The reduction reaction was performed in an ice bath. Then, after quenching with methanol in an ice bath, diluting with THF and filtering, the filtrate obtained was concentrated to obtain 6-hydroxymethyl-7-oxabicyclo [2.2.1] -2-heptene. .

The obtained 6-hydroxymethyl-7-oxabicyclo [2.2.1] -2-heptene (60 g, 0.48 mol) and 2.1 equivalent of dicyclohexylborane were added to a THF solvent (300 ml) at 0 ° C. The reaction was performed for about 3 hours. Next, the reaction solution was treated with 5N aqueous sodium hydroxide solution (600 ml) and 30 wt% aqueous hydrogen peroxide (340 ml). Analysis by GC-MS revealed that 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane and 3-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1]. A mixture of heptanes was formed with a yield of 72%. The reaction solution was distilled under reduced pressure to obtain the above compound.
[Spectral data of a mixture of 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane and 3-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 0.78-1.13 (m, 2H), 1.4-1.78 (m, 2H), 1.78-1.90 (m, 2H) ), 2.23-2.26 (m, 1H), 3.26-3.37 (m, 2H), 3.62-3.89 (m, 2H), 4.23-4.44 (m) , 1H)

Example 2
Of the mixture obtained in Example 1, 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane was subjected to the following vinylation step. That is, 4 equivalents of vinyl propionate, 0.7 mol% of di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ with respect to the dihydroxy compound, and carbonic acid Sodium toluene equivalent of 1.5 equivalents was added 4.5 times by weight and reacted at 105 ° C. for 2 hours. When analyzed by GC-MS, 2-hydroxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane was produced in a yield of 67%. The reaction solution was distilled under reduced pressure to obtain the above compound.
[Spectral data of 2-hydroxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.31-2.21 (m, 5H), 3.42 (m, 1H), 3.92-4.12 (m, 5H), 5. 13-5.27 (m, 1H), 6.24-6.29 (dd, 1H)

［２−ビニルオキシ−６−ビニルオキシメチル−７−オキサビシクロ［２．２．１］ヘプタンと３−ビニルオキシ−６−ビニルオキシメチル−７−オキサビシクロ［２．２．１］ヘプタンとの混合物のスペクトルデータ］
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：０．９４−２．５９（ｍ，５Ｈ），３．４２−３．５６（ｍ，２Ｈ），３．９９−４．２４（ｍ，５Ｈ），４．５６−４．６５（ｍ，２Ｈ），６．３４−６．４７（ｍ，２Ｈ） Example 3
Of 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane and 3-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane obtained in Example 1 The mixture was subjected to the following vinylation step. That is, 4 equivalents of vinyl propionate, 2 mol% of di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ , and carbonic acid, based on the mixture of dihydroxy compounds Sodium toluene equivalent of 1.5 equivalents was added 4.5 times by weight and reacted at 105 ° C. for 5 hours. When analyzed by GC-MS, 2-vinyloxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane represented by the following formula (5) and 3 represented by the following formula (6). A mixture with -vinyloxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane was formed in a yield of 84%. The reaction solution was distilled under reduced pressure to obtain the above compound.

Of a mixture of [2-vinyloxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane and 3-vinyloxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane Spectral data]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 0.94 to 2.59 (m, 5H), 3.42 to 3.56 (m, 2H), 3.99 to 4.24 (m, 5H) ), 4.56-4.65 (m, 2H), 6.34-6.47 (m, 2H)

Example 4
To 6-hydroxymethyl-7-oxabicyclo [2.2.1] -2-heptene (50 g, 0.40 mol), dichloromethane solvent (850 ml) was added and stirred, and m-chloroperbenzoic acid having a purity of 60%. (MCPBA: 276.8 g, 0.96 mol) was slowly added. The mixture was aged for about 2 hours at room temperature with stirring, and then washed with a 5 wt% aqueous sodium thiosulfate solution until the peroxide disappeared. 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. As analyzed by GC-MS, 2-hydroxy-3-methoxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane and 2-methoxy-3-hydroxy-6-hydroxymethyl-7-oxa A mixture of bicyclo [2.2.1] heptane was produced with a yield of 92%. The reaction solution was distilled under reduced pressure to obtain the above compound.
[2-Hydroxy-3-methoxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane and 2-methoxy-3-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] ] Spectral data of mixture with heptane]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.23-2.14 (m, 5H), 3.20-3.49 (m, 6H), 4.24-4.46 (m, 1H) ), 5.11-5.14 (m, 1H), 5.78-5.86 (m, 1H)

Example 5
2-Hydroxy-3-methoxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane obtained in Example 4 and 2-methoxy-3-hydroxy-6-hydroxymethyl-7-oxabicyclo [ 2.2.1] The mixture with heptane was subjected to the same vinylation step as in Example 2. When this reaction solution was analyzed by GC-MS, 2-hydroxy-3-methoxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane and 2-methoxy-3-hydroxy-6-vinyl were analyzed. A mixture of oxymethyl-7-oxabicyclo [2.2.1] heptane was produced with a yield of 68%. The reaction solution was distilled under reduced pressure to obtain the above compound.
[2-Hydroxy-3-methoxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane and 2-methoxy-3-hydroxy-6-vinyloxymethyl-7-oxabicyclo [2.2 .1] Spectral data of a mixture with heptane]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.19-2.14 (m, 4H), 3.20-3.24 (m, 4H), 3.92-4.56 (m, 5H) ), 5.02-5.14 (m, 1H), 5.78-5.86 (m, 1H), 6.43 (dd, 1H)

［２−ビニルオキシ−３−メトキシ−６−ビニルオキシメチル−７−オキサビシクロ［２．２．１］ヘプタンと２−メトキシ−３−ビニルオキシ−６−ビニルオキシメチル−７−オキサビシクロ［２．２．１］ヘプタンとの混合物のスペクトルデータ］
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：１．２３−１．７８（ｍ，３Ｈ），３．２４−３．４８（ｍ，４Ｈ），３．９２−４．４９（ｍ，７Ｈ），５．２１−５．２４（ｍ，１Ｈ），６．１３−６．２１（ｍ，１Ｈ），６．３４−６．４８（ｍ，２Ｈ） Example 6
2-Hydroxy-3-methoxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane obtained in Example 4 and 2-methoxy-3-hydroxy-6-hydroxymethyl-7-oxabicyclo [ 2.2.1] The mixture with heptane was subjected to the same vinylation step as in Example 3. When this reaction solution was analyzed by GC-MS, 2-vinyloxy-3-methoxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane represented by the following formula (7) and the following formula A mixture of 2-methoxy-3-vinyloxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane represented by (8) was produced in a yield of 74%. The reaction solution was distilled under reduced pressure to obtain the above compound.

[2-Vinyloxy-3-methoxy-6-vinyloxymethyl-7-oxabicyclo [2.2.1] heptane and 2-methoxy-3-vinyloxy-6-vinyloxymethyl-7-oxabicyclo [2.2 .1] Spectral data of a mixture with heptane]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.23-1.78 (m, 3H), 3.24-3.48 (m, 4H), 3.92-4.49 (m, 7H ), 5.21-5.24 (m, 1H), 6.13-6.21 (m, 1H), 6.34-6.48 (m, 2H)

Example 7
Formic acid (188 ml, 5 mol) and 1,5-cyclooctadiene (1.2 L, 10 mol) are placed in a reaction vessel, and 30% by weight hydrogen peroxide (2.6 L, 23 mol) is added dropwise in an ice bath while stirring. did. After completion of the dropping, the liquid temperature was kept at 50 ° C., and stirring was continued for about 8 hours until the system became uniform. When this reaction solution was analyzed by GC-MS, 2,6-dihydroxy-9-oxabicyclo [3.3.1] nonane and 2,5-dihydroxy-9-oxabicyclo [4.2.1] nonane were analyzed. A mixture was formed with a yield of 90%. Water was added until the reaction solution became cloudy, then cooled in an ice bath, and the precipitated solid was separated by filtration. As a result, a high-purity product consisting of the above mixture having a purity of 95% could be obtained.
[Spectral data of a mixture of 2,6-dihydroxy-9-oxabicyclo [3.3.1] nonane and 2,5-dihydroxy-9-oxabicyclo [4.2.1] nonane]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.79-2.16 (m, 10H), 3.22-3.46 (m, 2H), 3.67-3.72 (m, 2H) )

Example 8
The mixture of 2,6-dihydroxy-9-oxabicyclo [3.3.1] nonane and 2,5-dihydroxy-9-oxabicyclo [4.2.1] nonane obtained in Example 7 was The same vinylation process as in No. 2 was applied. When the reaction solution was analyzed by GC-MS, 2-hydroxy-6-vinyloxy-9-oxabicyclo [3.3.1] nonane and 2-hydroxy-5-vinyloxy-9-oxabicyclo [4.2. 1] A mixture of nonane was produced with a yield of 66%.
[Spectral data of a mixture of 2-hydroxy-6-vinyloxy-9-oxabicyclo [3.3.1] nonane and 2-hydroxy-5-vinyloxy-9-oxabicyclo [4.2.1] nonane]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.56-1.93 (m, 8H), 2.2 (br, 1H), 3.32-3.89 (m, 4H), 3. 67-3.72 (m, 2H)

［２，６−ビス（ビニルオキシ）−９−オキサビシクロ［３．３．１］ノナンと２，５−（ビニルオキシ）−９−オキサビシクロ［４．２．１］ノナンのスペクトルデータ］
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）５００ＭＨｚ δ：１．７８−２．３２（ｍ，８Ｈ），３．９６−４．６４（ｍ，８Ｈ），６．３２−６．４７（ｍ，２Ｈ） Example 9
The mixture of 2,6-dihydroxy-9-oxabicyclo [3.3.1] nonane and 2,5-dihydroxy-9-oxabicyclo [4.2.1] nonane obtained in Example 7 was The same vinylation process as in No. 3 was applied. When the reaction solution was analyzed by GC-MS, it was represented by 2,6-bis (vinyloxy) -9-oxabicyclo [3.3.1] nonane represented by the following formula (9) and the following formula (10). Of 2,5- (vinyloxy) -9-oxabicyclo [4.2.1] nonane produced in a yield of 78%.

[Spectral data of 2,6-bis (vinyloxy) -9-oxabicyclo [3.3.1] nonane and 2,5- (vinyloxy) -9-oxabicyclo [4.2.1] nonane]
¹ H-NMR (CDCl ₃ , TMS) 500 MHz δ: 1.78-2.32 (m, 8H), 3.96-4.64 (m, 8H), 6.32-6.47 (m, 2H) )

Comparative Example 1
As the vinyl ether compound having a cyclic group, 1,4-bis (vinyloxymethyl) cyclohexane represented by the following formula (11) was used.

Examples 10 to 12 and Comparative Example 2
For the oxygen atom-containing polycyclic vinyl ether compound obtained in Examples 3, 6, and 9 and the cyclic group-containing vinyl ether compound of Comparative Example 1, respectively, a photopolymerization initiator (propylene carbonate of triallylsulfonium hexafluorophosphate) was used. Solution: 3% by weight of a 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 200 μm, and irradiated with a UV lamp (wavelength configuration: 365 nm, 405 nm, 436 nm, intensity: 250 W) at a focal length of 15 cm, and the surface was not sticky. The irradiation time until 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 (3)

Following formula (1)

[Wherein, ring Z represents a polycyclic non-aromatic ring containing one oxygen atom as a part of the ring, and X and RO- (W) _n -groups are bonded to the carbon atoms constituting ring Z. X is a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group that may be protected with a protecting group, a hydroxymethyl group that may be protected with a protecting group, or a protecting group Protected with an amino group which may be protected with, a carboxyl group which may be protected with a protective group, a sulfo group which may be protected with a protective group, an oxo group, a nitro group, a cyano group, or a protective group An acyl group that may be present is shown. W represents a divalent organic group, R represents a hydrogen atom or the following formula (2)

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
W represents a divalent organic group. p shows an integer greater than or equal to 0, n shows 0 or 1, m shows the integer of 1-5, s and t show the integer of 0-7, respectively. When p, n and m are 2 or more, the substituents in parentheses may be the same or different. When X is 2 or more, they may be bonded to each other to form a 4-membered or more ring with the carbon atoms constituting the ring Z.]
The oxygen atom containing polycyclic compound represented by these.   A polymerizable composition comprising a polymerization initiator and the oxygen atom-containing polycyclic compound according to claim 1.   A cured product obtained by curing the polymerizable composition according to claim 2.