JP4832019B2 - Polycyclic ester containing cyclic carbonate skeleton - Google Patents

Polycyclic ester containing cyclic carbonate skeleton Download PDF

Info

Publication number
JP4832019B2
JP4832019B2 JP2005217633A JP2005217633A JP4832019B2 JP 4832019 B2 JP4832019 B2 JP 4832019B2 JP 2005217633 A JP2005217633 A JP 2005217633A JP 2005217633 A JP2005217633 A JP 2005217633A JP 4832019 B2 JP4832019 B2 JP 4832019B2
Authority
JP
Japan
Prior art keywords
formula
cyclic carbonate
represented
polycyclic
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP2005217633A
Other languages
Japanese (ja)
Other versions
JP2007031357A (en
Inventor
慶三 井上
隆裕 岩浜
隆司 久保
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daicel Corp
Original Assignee
Daicel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daicel Corp filed Critical Daicel Corp
Priority to JP2005217633A priority Critical patent/JP4832019B2/en
Publication of JP2007031357A publication Critical patent/JP2007031357A/en
Application granted granted Critical
Publication of JP4832019B2 publication Critical patent/JP4832019B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Description

本発明は、塗料や機能性高分子の原料、医薬、農薬その他の精密化学品の原料などとして有用な新規な環状カーボネート骨格を含む多環式エステルとその製造法、および該環状カーボネート骨格を含む多環式エステルの合成原料として有用な環状カーボネート骨格を含む多環式アルコールとその製造法に関する。   The present invention includes a polycyclic ester containing a novel cyclic carbonate skeleton useful as a raw material for paints and functional polymers, a raw material for pharmaceuticals, agricultural chemicals and other fine chemicals, and a method for producing the same, and the cyclic carbonate skeleton. The present invention relates to a polycyclic alcohol containing a cyclic carbonate skeleton useful as a raw material for synthesizing polycyclic esters and a method for producing the same.

ラクトン骨格や環状酸無水物骨格が縮合したノルボルナン環又はオキサノルボルナン環と重合性不飽和基を有する化合物は、疎水性で嵩高く安定性の高い環と親水性を示す環とを併有しているとともに、重合性不飽和基を有することから、その構造上の特異性を活かして塗料や機能性高分子の原料などとして用いられている(特許文献1参照)。しかし、用途によっては、全体として疎水性が高すぎて所望の機能が十分に発揮されなかったり、水性溶媒や有機溶媒に対する溶解性が低く操作性や取扱性に劣るなどの問題があった。   A compound having a norbornane ring or oxanorbornane ring condensed with a lactone skeleton or a cyclic acid anhydride skeleton and a polymerizable unsaturated group has both a hydrophobic, bulky, highly stable ring and a hydrophilic ring. In addition, since it has a polymerizable unsaturated group, it is used as a raw material for paints and functional polymers utilizing its structural specificity (see Patent Document 1). However, depending on the application, there are problems such that the hydrophobicity is too high as a whole and the desired function is not sufficiently exhibited, or the solubility in an aqueous solvent or an organic solvent is low and the operability and handleability are poor.

特開2004−51995号公報JP 2004-51995 A

本発明の目的は、ポリマー等に誘導した場合に耐薬品性等の安定性を保持しつつ親水性及び溶媒に対する溶解性を向上しうる、高機能性高分子等のモノマー成分等として有用な新規な重合性不飽和基を有する化合物を提供することにある。
本発明の他の目的は、前記重合性不飽和基を有する化合物の合成原料として有用な新規化合物とその効率のよい製造法を提供することにある。
An object of the present invention is a novel useful as a monomer component such as a high-functional polymer that can improve the hydrophilicity and solubility in a solvent while maintaining stability such as chemical resistance when derived into a polymer or the like. Another object of the present invention is to provide a compound having a polymerizable unsaturated group.
Another object of the present invention is to provide a novel compound useful as a raw material for synthesizing the compound having a polymerizable unsaturated group and an efficient production method thereof.

本発明者らは、上記目的を達成するため鋭意検討した結果、ポリマー等に誘導した場合に、ラクトン骨格や環状酸無水物骨格が縮合したノルボルナン環又はオキサノルボルナン環と重合性不飽和基を有する化合物よりも親水性及び溶媒に対する溶解性を向上できる新規な環状カーボネート骨格を含む多環式エステルとその効率的な製造法を見出し、本発明を完成した。   As a result of intensive studies to achieve the above object, the present inventors have a norbornane ring or oxanorbornane ring condensed with a lactone skeleton or a cyclic acid anhydride skeleton and a polymerizable unsaturated group when derived into a polymer or the like. The present inventors have found a polycyclic ester containing a novel cyclic carbonate skeleton capable of improving hydrophilicity and solubility in a solvent as compared with a compound and an efficient production method thereof, and completed the present invention.

すなわち、本発明は、下記式(1’)

Figure 0004832019
(式中、Raは水素原子、ハロゲン原子、又はハロゲン原子を有していてもよい炭素数1〜6のアルキル基を示し、X’はメチレン基を示す。nは0〜3の整数を示す。式中の環は置換基を有していてもよい)
で表される環状カーボネート骨格を含む多環式エステルを提供する。 That is, the present invention provides the following formula (1 ′)
Figure 0004832019
(In the formula, R a represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, X ′ represents a methylene group, and n represents an integer of 0 to 3. The ring in the formula may have a substituent)
The polycyclic ester containing the cyclic carbonate skeleton represented by these is provided.

本発明は、また、下記式(2’)

Figure 0004832019
(式中、X’はメチレン基を示す。nは0〜3の整数を示す。式中の環は置換基を有していてもよい)
で表される環状カーボネート骨格を含む多環式アルコールと、下記式(3)
Figure 0004832019
(式中、Raは水素原子、ハロゲン原子、又はハロゲン原子を有していてもよい炭素数1〜6のアルキル基を示す)
で表される不飽和カルボン酸又はその反応性誘導体を反応させて、下記式(1’)
Figure 0004832019
(式中、Ra、X’、nは前記に同じ。式中の環は置換基を有していてもよい)
で表される化合物を得る環状カーボネート骨格を含む多環式エステルの製造法を提供する。 The present invention also provides the following formula (2 ′)
Figure 0004832019
(In the formula, X ′ represents a methylene group . N represents an integer of 0 to 3. The ring in the formula may have a substituent . )
A polycyclic alcohol containing a cyclic carbonate skeleton represented by formula (3):
Figure 0004832019
(In the formula, Ra represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom)
Is reacted with an unsaturated carboxylic acid represented by the following formula (1 ′):
Figure 0004832019
(In the formula, R a , X ′ and n are the same as above . The ring in the formula may have a substituent)
The manufacturing method of the polycyclic ester containing the cyclic carbonate frame | skeleton which obtains the compound represented by these is provided.

本発明は、さらに、下記式(2’)

Figure 0004832019
(式中、X’はメチレン基を示す。nは0〜3の整数を示す。式中の環は置換基を有していてもよい)
で表される環状カーボネート骨格を含む多環式アルコールを提供する。 The present invention further includes the following formula (2 ′):
Figure 0004832019
(In the formula, X ′ represents a methylene group . N represents an integer of 0 to 3. The ring in the formula may have a substituent . )
The polycyclic alcohol containing the cyclic carbonate skeleton represented by these is provided.

本発明は、さらにまた、下記式(4’)

Figure 0004832019
(式中、X’はメチレン基を示す。nは0〜3の整数を示す。式中の環は置換基を有していてもよい)
で表される環状カーボネート骨格を含む多環式化合物をヒドロホウ素化−酸化反応に付して、下記式(2’)
Figure 0004832019
(式中、X’、nは前記に同じ。式中の環は置換基を有していてもよい)
で表される化合物を得る環状カーボネート骨格を含む多環式アルコールの製造法を提供する。尚、本明細書には、上記発明の他に、下記式(1)
Figure 0004832019
(式中、R a は水素原子、ハロゲン原子、又はハロゲン原子を有していてもよい炭素数1〜6のアルキル基を示し、Xはメチレン基、酸素原子又は硫黄原子を示す。nは0〜3の整数を示す。nが1以上の整数の場合、分子中の複数個のXは互いに同一でも異なっていてもよい。式中の環は置換基を有していてもよい)
で表される環状カーボネート骨格を含む多環式エステル、下記式(2)
Figure 0004832019
(式中、Xはメチレン基、酸素原子又は硫黄原子を示す。nは0〜3の整数を示す。nが1以上の整数の場合、分子中の複数個のXは互いに同一でも異なっていてもよい。式中の環は置換基を有していてもよい)
で表される環状カーボネート骨格を含む多環式アルコールと、下記式(3)
Figure 0004832019
(式中、R a は水素原子、ハロゲン原子、又はハロゲン原子を有していてもよい炭素数1〜6のアルキル基を示す)
で表される不飽和カルボン酸又はその反応性誘導体を反応させて、前記式(1)で表される化合物を得る環状カーボネート骨格を含む多環式エステルの製造法、前記式(2)で表される環状カーボネート骨格を含む多環式アルコール、下記式(4)
Figure 0004832019
(式中、Xはメチレン基、酸素原子又は硫黄原子を示す。nは0〜3の整数を示す。nが1以上の整数の場合、分子中の複数個のXは互いに同一でも異なっていてもよい。式中の環は置換基を有していてもよい)
で表される環状カーボネート骨格を含む多環式化合物をヒドロホウ素化−酸化反応に付して、前記式(2)で表される化合物を得る環状カーボネート骨格を含む多環式アルコールの製造法についても記載する。
The present invention further provides the following formula (4 ′):
Figure 0004832019
(In the formula, X ′ represents a methylene group . N represents an integer of 0 to 3. The ring in the formula may have a substituent . )
A polycyclic compound containing a cyclic carbonate skeleton represented by formula (2) is subjected to hydroboration-oxidation reaction.
Figure 0004832019
(In the formula, X ′ and n are the same as above . The ring in the formula may have a substituent)
The manufacturing method of the polycyclic alcohol containing the cyclic carbonate frame | skeleton which obtains the compound represented by these is provided. In this specification, in addition to the above invention, the following formula (1)
Figure 0004832019
(In the formula, Ra represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, X represents a methylene group, an oxygen atom or a sulfur atom. N represents 0. Represents an integer of ~ 3. When n is an integer of 1 or more, a plurality of X in the molecule may be the same or different from each other, and the ring in the formula may have a substituent.
A polycyclic ester containing a cyclic carbonate skeleton represented by formula (2):
Figure 0004832019
(In the formula, X represents a methylene group, an oxygen atom or a sulfur atom. N represents an integer of 0 to 3. When n is an integer of 1 or more, a plurality of X in the molecule may be the same or different from each other. The ring in the formula may have a substituent)
A polycyclic alcohol containing a cyclic carbonate skeleton represented by formula (3):
Figure 0004832019
(In the formula, Ra represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom)
A method for producing a polycyclic ester containing a cyclic carbonate skeleton, which is obtained by reacting an unsaturated carboxylic acid represented by the formula (I) or a reactive derivative thereof to obtain a compound represented by the formula (1), A polycyclic alcohol containing a cyclic carbonate skeleton, the following formula (4)
Figure 0004832019
(In the formula, X represents a methylene group, an oxygen atom or a sulfur atom. N represents an integer of 0 to 3. When n is an integer of 1 or more, a plurality of X in the molecule may be the same or different from each other. The ring in the formula may have a substituent)
About the manufacturing method of the polycyclic alcohol containing the cyclic carbonate skeleton which attaches | subjects the polycyclic compound containing the cyclic carbonate skeleton represented by this to hydroboration-oxidation reaction, and obtains the compound represented by the said Formula (2) Also described.

本発明によれば、ポリマー等に誘導した場合に耐薬品性等の安定性を保持しつつ親水性及び溶媒に対する溶解性を向上しうる、高機能性高分子等のモノマー成分等として有用な新規な環状カーボネート骨格を含む多環式エステルとその効率のよい製造法が提供される。また、前記環状カーボネート骨格を含む多環式エステルの合成原料として有用な新規な環状カーボネート骨格を含む多環式アルコールとその効率のよい製造法が提供される。   According to the present invention, when it is derived into a polymer or the like, it is useful as a monomer component such as a high-performance polymer that can improve the hydrophilicity and solubility in a solvent while maintaining stability such as chemical resistance. A polycyclic ester containing a cyclic carbonate skeleton and an efficient production method thereof are provided. Also provided are a novel polycyclic alcohol containing a cyclic carbonate skeleton useful as a raw material for synthesizing a polycyclic ester containing the cyclic carbonate skeleton and an efficient production method thereof.

本発明の環状カーボネート骨格を含む多環式エステルは前記式(1)で表される。式(1)中、Raは水素原子、ハロゲン原子、又はハロゲン原子を有していてもよい炭素数1〜6のアルキル基を示し、Xはメチレン基、酸素原子又は硫黄原子を示す。nは0〜3の整数を示す。nが1以上の整数の場合、分子中の複数個のXは互いに同一でも異なっていてもよい。式中の環は置換基を有していてもよい。なお、該置換基はXに結合していてもよい。 The polycyclic ester containing the cyclic carbonate skeleton of the present invention is represented by the formula (1). In formula (1), Ra represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, and X represents a methylene group, an oxygen atom or a sulfur atom. n represents an integer of 0 to 3. When n is an integer greater than or equal to 1, several X in a molecule | numerator may mutually be same or different. The ring in the formula may have a substituent. The substituent may be bonded to X.

前記Raにおけるハロゲン原子には、例えば、フッ素、塩素、臭素原子などが含まれる。炭素数1〜6のアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、s−ブチル、t−ブチル、ペンチル、ヘキシル基などが挙げられる。これらの中でも、C1-3アルキル基、特にメチル基が好ましい。ハロゲン原子を有する炭素数1〜6のアルキル基としては、例えば、クロロメチル基などのクロロアルキル基;トリフルオロメチル、2,2,2−トリフルオロエチル、ペンタフルオロエチル基などのフルオロアルキル基(好ましくは、C1-3フルオロアルキル基)などが挙げられる。Raとしては、水素原子、メチル基等のC1-3アルキル基、トリフルオロメチル基等のC1-3ハロアルキル基が好ましく、特に、水素原子又はメチル基が好ましい。 Examples of the halogen atom in R a include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl groups. Among these, a C 1-3 alkyl group, particularly a methyl group is preferable. Examples of the alkyl group having 1 to 6 carbon atoms having a halogen atom include chloroalkyl groups such as chloromethyl group; fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl groups ( Preferably, a C1-3 fluoroalkyl group) etc. are mentioned. R a is preferably a hydrogen atom, a C 1-3 alkyl group such as a methyl group, or a C 1-3 haloalkyl group such as a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

式(1)中の環が有していてもよい置換基としては、特に限定されないが、例えば、ハロゲン原子、ハロゲン原子を有していてもよい炭素数1〜6のアルキル基、ヒドロキシル基部分が保護基で保護されていてもよくハロゲン原子を有していてもよい炭素数1〜6のヒドロキシアルキル基、塩を形成していてもよいカルボキシル基、置換オキシカルボニル基、シアノ基などが挙げられる。ハロゲン原子、ハロゲン原子を有していてもよい炭素数1〜6のアルキル基としては、前記Raにおけるハロゲン原子等と同様のものが例示される。 The substituent that the ring in formula (1) may have is not particularly limited. For example, a halogen atom, an alkyl group having 1 to 6 carbon atoms that may have a halogen atom, and a hydroxyl group moiety. May be protected with a protective group and may have a halogen atom, a C1-C6 hydroxyalkyl group, a carboxyl group that may form a salt, a substituted oxycarbonyl group, a cyano group, etc. It is done. Examples of the halogen atom and the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include those similar to the halogen atom and the like in Ra .

炭素数1〜6のヒドロキシアルキル基としては、例えば、ヒドロキシメチル、2−ヒドロキシエチル、1−ヒドロキシエチル、3−ヒドロキシプロピル、2−ヒドロキシプロピル、4−ヒドロキシブチル、6−ヒドロキシヘキシル基などが挙げられる。ハロゲン原子を有する炭素数1〜6のヒドロキシアルキル基としては、例えば、ジフルオロヒドロキシメチル、1,1−ジフルオロ−2−ヒドロキシエチル、2,2−ジフルオロ−2−ヒドロキシエチル、1,1,2,2−テトラフルオロ−2−ヒドロキシエチル基などが挙げられる。ハロゲン原子を有していてもよい炭素数1〜6のヒドロキシアルキル基の中でも、炭素数1又は2(特に炭素数1)のヒドロキシアルキル基若しくはヒドロキシハロアルキル基が好ましい。ハロゲン原子を有していてもよい炭素数1〜6のヒドロキシアルキル基のヒドロキシル基の保護基としては、有機合成の分野でヒドロキシル基の保護基として通常用いられる保護基、例えば、メチル基、メトキシメチル基等のヒドロキシル基を構成する酸素原子とともにエーテル又はアセタール結合を形成する基;アセチル基、ベンゾイル基等のヒドロキシル基を構成する酸素原子とともにエステル結合を形成する基などが挙げられる。カルボキシル基の塩としては、アルカリ金属塩、アルカリ土類金属塩、遷移金属塩などが挙げられる。   Examples of the hydroxyalkyl group having 1 to 6 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl group and the like. It is done. Examples of the C1-C6 hydroxyalkyl group having a halogen atom include difluorohydroxymethyl, 1,1-difluoro-2-hydroxyethyl, 2,2-difluoro-2-hydroxyethyl, 1,1,2, Examples include 2-tetrafluoro-2-hydroxyethyl group. Among the hydroxyalkyl groups having 1 to 6 carbon atoms which may have a halogen atom, a hydroxyalkyl group or hydroxyhaloalkyl group having 1 or 2 carbon atoms (particularly 1 carbon atom) is preferable. Examples of the protecting group for the hydroxyl group of the hydroxyalkyl group having 1 to 6 carbon atoms which may have a halogen atom include protecting groups usually used as a protecting group for a hydroxyl group in the field of organic synthesis, such as a methyl group, methoxy group, and the like. Examples include groups that form an ether or acetal bond with an oxygen atom that constitutes a hydroxyl group such as a methyl group; groups that form an ester bond with an oxygen atom that constitutes a hydroxyl group such as an acetyl group or a benzoyl group. Examples of the carboxyl group salt include alkali metal salts, alkaline earth metal salts, and transition metal salts.

前記置換オキシカルボニル基としては、例えば、メトキシカルボニル、エトキシカルボニル、イソプロピルオキシカルボニル、プロポキシカルボニル基などのアルコキシカルボニル基(C1-4アルコキシ−カルボニル基等);ビニルオキシカルボニル、アリルオキシカルボニル基などのアルケニルオキシカルボニル基(C2-4アルコキシ−カルボニル基等);シクロヘキシルオキシカルボニル基などのシクロアルキルオキシカルボニル基;フェニルオキシカルボニル基などのアリールオキシカルボニル基などが挙げられる。 Examples of the substituted oxycarbonyl group include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, propoxycarbonyl group (C 1-4 alkoxy-carbonyl group, etc.); vinyloxycarbonyl, allyloxycarbonyl group, etc. Examples thereof include alkenyloxycarbonyl groups (C 2-4 alkoxy-carbonyl groups and the like); cycloalkyloxycarbonyl groups such as cyclohexyloxycarbonyl groups; aryloxycarbonyl groups such as phenyloxycarbonyl groups and the like.

式(1)で表される環状カーボネート骨格を含む多環式エステルの代表的な例として、下記式で表される8−(メタ)アクリロイルオキシ−3,5−ジオキサトリシクロ[5.2.1.02,6]デカン−4−オン及びその置換体、8−(メタ)アクリロイルオキシ−3,5,10−トリオキサトリシクロ[5.2.1.02,6]デカン−4−オン及びその置換体、8−(メタ)アクリロイルオキシ−3,5−ジオキサ−10−チアトリシクロ[5.2.1.02,6]デカン−4−オン及びその置換体、4−(メタ)アクリロイルオキシ−10,12−ジオキサペンタシクロ[6.5.1.13,6.02,7.09,13]ペンタデカン−11−オン及びその置換体、4−(メタ)アクリロイルオキシ−10,12,14−トリオキサペンタシクロ[6.5.1.13,6.02,7.09,13]ペンタデカン−11−オン及びその置換体、4−(メタ)アクリロイルオキシ−10,12,15−トリオキサペンタシクロ[6.5.1.13,6.02,7.09,13]ペンタデカン−11−オン及びその置換体、4−(メタ)アクリロイルオキシ−10,12,14,15−テトラオキサペンタシクロ[6.5.1.13,6.02,7.09,13]ペンタデカン−11−オン及びその置換体などが挙げられる。式中、Rはアクリロイル基又はメタクリロイル基を示す。式中に示される環は置換基を有していてもよい。 As a typical example of the polycyclic ester containing a cyclic carbonate skeleton represented by the formula (1), 8- (meth) acryloyloxy-3,5-dioxatricyclo [5.2 represented by the following formula: .1.0 2,6] decan-4-one and derivatives thereof, 8- (meth) acryloyloxy -3,5,10- trioxatridecane cyclo [5.2.1.0 2,6] decane - 4-one and substituted products thereof, 8- (meth) acryloyloxy-3,5-dioxa-10-thiatricyclo [5.2.1.0 2,6 ] decan-4-one and substituted products thereof, 4- ( (Meth) acryloyloxy-10,12-dioxapentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ] pentadecan-11-one and substituted products thereof, 4- (meth) acryloyloxy-10,12,14-trioxapentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ] pentadecan-11-one and substituted products thereof, 4- (meth) acryloyloxy-10,12,15-trioxapentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ] pentadecan-11-one and substituted products thereof, 4- (meth) acryloyloxy-10,12,14,15-tetraoxapentacyclo [6.5.1.1 3,6 . 0 2,7 . 0,13 ] pentadecan-11-one and substituted products thereof. In the formula, R represents an acryloyl group or a methacryloyl group. The ring shown in the formula may have a substituent.

Figure 0004832019
Figure 0004832019

式(1)で表される環状カーボネート骨格を含む多環式エステルは、前記式(2)で表される環状カーボネート骨格を含む多環式アルコールと、前記式(3)で表される不飽和カルボン酸又はその反応性誘導体とを反応させることにより製造することができる。式(2)及び式(3)におけるRa、X、nは、前記と同様である。 The polycyclic ester containing the cyclic carbonate skeleton represented by the formula (1) includes the polycyclic alcohol containing the cyclic carbonate skeleton represented by the formula (2) and the unsaturated represented by the formula (3). It can be produced by reacting a carboxylic acid or a reactive derivative thereof. R a , X, and n in Formula (2) and Formula (3) are the same as described above.

式(3)で表される不飽和カルボン酸の代表的な例として、アクリル酸、メタクリル酸、α−トリフルオロメチルアクリル酸などが挙げられる。式(3)で表される不飽和カルボン酸の反応性誘導体としては、酸ハライド、酸無水物、エステルなどが挙げられる。式(2)で表される環状カーボネート骨格を含む多環式アルコールの代表的な例としては、前記式(1)で表される環状カーボネート骨格を含む多環式エステルとして挙げた代表的化合物に対応する化合物(Rが水素原子である化合物)が挙げられる。   Typical examples of the unsaturated carboxylic acid represented by the formula (3) include acrylic acid, methacrylic acid, α-trifluoromethylacrylic acid and the like. Examples of the reactive derivative of the unsaturated carboxylic acid represented by the formula (3) include acid halides, acid anhydrides and esters. Typical examples of the polycyclic alcohol containing a cyclic carbonate skeleton represented by the formula (2) include the typical compounds mentioned as the polycyclic ester containing the cyclic carbonate skeleton represented by the formula (1). Corresponding compounds (compounds in which R is a hydrogen atom) can be mentioned.

上記式(1)で表される環状カーボネート骨格を含む多環式エステルは、より具体的には、(a)テトラヒドロフラン、トルエン、塩化メチレン等の溶媒中、式(2)で表される化合物に、必要に応じてトリエチルアミン、ピリジン、4−ジメチルアミノピリジン等の塩基の存在下、(メタ)アクリル酸クロリド等の(メタ)アクリル酸ハライドや(メタ)アクリル酸無水物などの不飽和カルボン酸の活性な反応性誘導体を反応させたり、(b)前記と同様の溶媒中、式(2)で表される化合物に、チタンイソプロポキシド等のエステル交換触媒の存在下、(メタ)アクリル酸メチル等の不飽和カルボン酸エステルを反応させたり、(c)前記と同様の溶媒中、式(2)で表される化合物を、塩酸、硫酸、p−トルエンスルホン酸等の強酸の存在下で(メタ)アクリル酸等の不飽和カルボン酸と反応させることにより得ることができる。   More specifically, the polycyclic ester containing a cyclic carbonate skeleton represented by the above formula (1) is more specifically (a) a compound represented by the formula (2) in a solvent such as tetrahydrofuran, toluene, methylene chloride or the like. If necessary, in the presence of a base such as triethylamine, pyridine, 4-dimethylaminopyridine, (meth) acrylic acid halide such as (meth) acrylic acid chloride or unsaturated carboxylic acid such as (meth) acrylic acid anhydride. (B) in the presence of a transesterification catalyst such as titanium isopropoxide in the same solvent as described above in the presence of a transesterification catalyst such as titanium isopropoxide. (C) In a solvent similar to the above, the compound represented by the formula (2) is reacted with a strong acid such as hydrochloric acid, sulfuric acid or p-toluenesulfonic acid. Down in standing (meth) can be obtained by reacting an unsaturated carboxylic acid such as acrylic acid.

これらの方法における反応条件は、通常のエステル製造法と同様である。例えば、前記(a)の方法において、不飽和カルボン酸の活性な反応性誘導体の使用量は、式(2)で表される化合物1モルに対して、例えば1〜1.5モル程度、塩基の使用量は、不飽和カルボン酸の活性な反応性誘導体1モルに対して、例えば1〜3モル程度(大過剰量であってもよい)であり、反応温度は、例えば、−20℃〜50℃程度である。また、前記(b)の方法において、不飽和カルボン酸エステルの使用量は、式(2)で表される化合物1モルに対して、例えば1〜10モル程度(大過剰量であってもよい)、エステル交換触媒の使用量は、式(2)で表される化合物1モルに対して、例えば0.0001〜1モル程度であり、反応温度は、例えば0〜150℃程度である。さらに、前記(c)の方法において、不飽和カルボン酸の使用量は、式(2)で表される化合物1モルに対して、例えば1〜5モル程度(大過剰量であってもよい)、強酸の使用量は、式(2)で表される化合物1モルに対して、例えば0.0001〜1モル程度であり、反応温度は、例えば0〜150℃程度である。なお、これらの反応の際、重合を抑制するため、ハイドロキノンモノメチルエーテルなどの重合禁止剤や酸素を導入することもできる。   The reaction conditions in these methods are the same as in the usual ester production method. For example, in the method (a), the amount of the active reactive derivative of the unsaturated carboxylic acid used is, for example, about 1 to 1.5 moles per 1 mole of the compound represented by the formula (2). Is used in an amount of, for example, about 1 to 3 mol (may be a large excess) with respect to 1 mol of the active reactive derivative of the unsaturated carboxylic acid, and the reaction temperature is, for example, from −20 ° C. to It is about 50 ° C. In the method (b), the amount of the unsaturated carboxylic acid ester used is, for example, about 1 to 10 mol (a large excess amount may be used) with respect to 1 mol of the compound represented by the formula (2). ), The amount of the transesterification catalyst used is, for example, about 0.0001 to 1 mol, and the reaction temperature is about 0 to 150 ° C., for example, with respect to 1 mol of the compound represented by the formula (2). Furthermore, in the method (c), the amount of the unsaturated carboxylic acid used is, for example, about 1 to 5 mol (may be a large excess amount) with respect to 1 mol of the compound represented by the formula (2). The amount of the strong acid used is, for example, about 0.0001 to 1 mol with respect to 1 mol of the compound represented by the formula (2), and the reaction temperature is about 0 to 150 ° C., for example. In addition, in order to suppress superposition | polymerization in these reactions, polymerization inhibitors, such as hydroquinone monomethyl ether, and oxygen can also be introduce | transduced.

反応で生成した式(1)で表される環状カーボネート骨格を含む多環式エステルは、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、カラムクロマトグラフィーなどの分離手段により、又はこれらを組み合わせることにより分離精製できる。   The polycyclic ester containing a cyclic carbonate skeleton represented by the formula (1) generated by the reaction is separated by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or the like. Can be separated and purified.

前記式(2)で表される環状カーボネート骨格を含む多環式アルコールは、前記式(4)で表される環状カーボネート骨格を含む多環式化合物をヒドロホウ素化−酸化反応に付すことにより得ることができる。式(4)におけるX、nは前記と同様である。   The polycyclic alcohol containing the cyclic carbonate skeleton represented by the formula (2) is obtained by subjecting the polycyclic compound containing the cyclic carbonate skeleton represented by the formula (4) to a hydroboration-oxidation reaction. be able to. X and n in the formula (4) are the same as described above.

前段のヒドロホウ素化反応(ハイドロボレーション)に用いるヒドロホウ素化試剤としては、特に制限はなく、例えば、BH3・THF、BH3・S(CH32などのボラン錯体;モノアルキルボラン;ジアルキルボラン;BH2Cl、BHCl2などが使用される。また、ヒドロホウ素化で生成した有機ホウ素化合物(中間体)の酸化反応(後段)に用いる酸化剤も、特に限定されず、例えば、過酸化水素(アルカリ条件下)、空気や酸素、第3級アミンのN−オキシド(例えば、トリメチルアミン−N−オキシド等)などが使用される。反応条件は一般的なヒドロホウ素化−酸化反応に準じて行うことができる。例えば、反応温度は、反応基質や反応試剤(ヒドロホウ素化試剤、酸化剤)の種類等によっても異なるが、一般に−50℃〜100℃程度である。反応試剤は、一般に、反応基質に対して当量以上用いられる。 The hydroboration reagent is used in front of the hydroboration reactions (hydroboration) is not particularly limited, for example, BH 3 · THF, BH 3 · S (CH 3) borane complexes such as 2; monoalkyl borane; Dialkylborane; BH 2 Cl, BHCl 2 and the like are used. Also, the oxidizing agent used for the oxidation reaction (after stage) of the organoboron compound (intermediate) generated by hydroboration is not particularly limited, and for example, hydrogen peroxide (under alkaline conditions), air, oxygen, tertiary N-oxides of amines (for example, trimethylamine-N-oxide and the like) are used. The reaction conditions can be performed according to a general hydroboration-oxidation reaction. For example, the reaction temperature is generally about −50 ° C. to 100 ° C., although it varies depending on the type of reaction substrate and reaction reagent (hydroboration reagent, oxidizing agent). The reaction reagent is generally used in an equivalent amount or more with respect to the reaction substrate.

反応で生成した式(2)で表される環状カーボネート骨格を含む多環式アルコールは、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、カラムクロマトグラフィーなどの分離手段により、又はこれらを組み合わせることにより分離精製できる。   The polycyclic alcohol containing the cyclic carbonate skeleton represented by the formula (2) generated by the reaction is separated by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or the like. Can be separated and purified.

なお、式(2)において式中に示される環にフッ素原子が1以上結合している化合物は、式(2)において式中に示される環に水素原子が結合している化合物をフッ素等のフッ素化剤を用いた慣用のフッ素化反応に付することにより製造することもできる。   In the formula (2), a compound in which one or more fluorine atoms are bonded to the ring shown in the formula is a compound in which a hydrogen atom is bonded to the ring shown in the formula in the formula (2) It can also be produced by subjecting it to a conventional fluorination reaction using a fluorinating agent.

前記式(4)で表される環状カーボネート骨格を含む多環式化合物のうちn=0である化合物は、例えば、下記反応工程式に従って製造することができる。式中、Yはメチレン基、酸素原子又は硫黄原子を示す。Xは前記と同じである。式中の各環は置換基を有していてもよい。

Figure 0004832019
Among the polycyclic compounds containing the cyclic carbonate skeleton represented by the formula (4), a compound where n = 0 can be produced, for example, according to the following reaction process formula. In formula, Y shows a methylene group, an oxygen atom, or a sulfur atom. X is the same as described above. Each ring in the formula may have a substituent.
Figure 0004832019

すなわち、式(5)で表される化合物(ジシクロペンタンジエン若しくはその置換体又はそれらの類縁体)又は式(6)で表される化合物(シクロペンタジエン、フラン若しくはチオフェン、又はそれらの置換体)と、式(7)で表される1,3−ジオキソール−2−オンとを反応させることにより、式(4a)で表される化合物(3,5−ジオキサトリシクロ[5.2.1.02,6]デカン−8−エン−4−オン若しくはその類縁体、又はそれらの置換体)を得ることができる。なお、式(5)で表される化合物と式(6)で表される化合物は混合して用いることができる。 That is, a compound represented by formula (5) (dicyclopentanediene or a substituted product thereof or an analog thereof) or a compound represented by formula (6) (cyclopentadiene, furan or thiophene, or a substituted product thereof) Is reacted with 1,3-dioxol-2-one represented by formula (7) to give a compound represented by formula (4a) (3,5-dioxatricyclo [5.2.1 .0 2,6] decan-8-en-4-one or its analogs, or their substituted derivatives) can be obtained. In addition, the compound represented by Formula (5) and the compound represented by Formula (6) can be mixed and used.

反応は溶媒の存在下又は非存在下で行われる。前記溶媒としては、例えば、酢酸エチルなどのエステル;酢酸などの有機酸;t−ブチルアルコールなどのアルコール;クロロホルム、ジクロロメタン、1,2−ジクロロエタンなどのハロゲン化炭化水素;ベンゼンなどの芳香族炭化水素;ヘキサン、ヘプタン、オクタンなどの脂肪族炭化水素;シクロヘキサンなどの脂環式炭化水素;N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミドなどのアミド;アセトニトリル、プロピオニトリル、ベンゾニトリルなどのニトリル;エチルエーテル、テトラヒドロフランなどの鎖状又は環状エーテルなどが挙げられる。これらの溶媒は単独で又は2種以上混合して用いられる。反応速度や反応の選択性を向上させるため、系内にルイス酸を添加してもよい。ルイス酸としては、例えば、AlCl3、SnCl4、TiCl4、BF3、ZnI2などが例示されるが、これに限定されない。反応温度は反応原料の種類等に応じて適宜選択できるが、一般には−80℃〜300℃程度、好ましくは−70℃〜250℃程度である。反応は常圧又は加圧下で行われる。反応はバッチ式、セミバッチ式、連続式などの何れの方法で行ってもよい。反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、カラムクロマトグラフィーなどの分離手段により、又はこれらを組み合わせることにより分離精製できる。 The reaction is carried out in the presence or absence of a solvent. Examples of the solvent include esters such as ethyl acetate; organic acids such as acetic acid; alcohols such as t-butyl alcohol; halogenated hydrocarbons such as chloroform, dichloromethane and 1,2-dichloroethane; aromatic hydrocarbons such as benzene. Aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile A linear or cyclic ether such as ethyl ether or tetrahydrofuran; These solvents are used alone or in combination of two or more. In order to improve the reaction rate and reaction selectivity, a Lewis acid may be added to the system. Examples of the Lewis acid include, but are not limited to, AlCl 3 , SnCl 4 , TiCl 4 , BF 3 , ZnI 2 and the like. Although reaction temperature can be suitably selected according to the kind etc. of reaction raw material, generally it is about -80 to 300 degreeC, Preferably it is about -70 to 250 degreeC. The reaction is carried out at normal pressure or under pressure. The reaction may be carried out by any method such as batch, semi-batch and continuous methods. The reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.

式(4)で表される環状カーボネート骨格を含む多環式化合物のうちn=1である化合物は、例えば、下記反応工程式に従って製造することができる。式中、Yはメチレン基、酸素原子又は硫黄原子を示す。Xは前記と同じである。式中の各環は置換基を有していてもよい。

Figure 0004832019
Among the polycyclic compounds containing a cyclic carbonate skeleton represented by the formula (4), a compound where n = 1 can be produced, for example, according to the following reaction process formula. In formula, Y shows a methylene group, an oxygen atom, or a sulfur atom. X is the same as described above. Each ring in the formula may have a substituent.
Figure 0004832019

すなわち、式(5)で表される化合物又は式(6)で表される化合物と、前記式(4a)で表される化合物とを反応させることにより、式(4b)で表される化合物(10,12−ジオキサペンタシクロ[6.5.1.13,6.02,7.09,13]ペンタデカン−4−エン−11−オン若しくはその類縁体、又はそれらの置換体)を得ることができる。なお、式(5)で表される化合物と式(6)で表される化合物は混合して用いることができる。反応条件は前記式(4a)で表される化合物を得る場合と同様である。 That is, the compound represented by Formula (4b) is reacted with the compound represented by Formula (5) or the compound represented by Formula (6) and the compound represented by Formula (4a) ( 10,12-di oxa penta cyclo [6.5.1.1 3,6 .0 2,7 .0 9,13] pentadecane-4-en-11-one or its analogs, or substituted versions thereof) Can be obtained. In addition, the compound represented by Formula (5) and the compound represented by Formula (6) can be mixed and used. The reaction conditions are the same as in the case of obtaining the compound represented by the formula (4a).

式(4)で表される環状カーボネート骨格を含む多環式化合物のうちn=2である化合物は、式(5)で表される化合物又は式(6)で表される化合物と前記式(4b)で表される化合物とを前記と同様にして反応させることにより得ることができ、また、式(4)で表される環状カーボネート骨格を含む多環式化合物のうちn=3である化合物は、式(5)で表される化合物又は式(6)で表される化合物と、こうして得られた式(4)で表される化合物のうちn=2である化合物とを前記と同様にして反応させることにより得ることができる。   Among the polycyclic compounds containing the cyclic carbonate skeleton represented by the formula (4), the compound where n = 2 is the compound represented by the formula (5) or the compound represented by the formula (6) and the above formula ( Compound obtained by reacting the compound represented by 4b) in the same manner as described above, and n = 3 among the polycyclic compounds containing a cyclic carbonate skeleton represented by formula (4) In the same manner as described above, the compound represented by the formula (5) or the compound represented by the formula (6) and the compound represented by the formula (4) thus obtained are compounds with n = 2. Can be obtained by reaction.

なお、式(1)において式中に示される環にフッ素原子が1以上結合している化合物は、式(1)において式中に示される環に水素原子が結合している化合物をフッ素等のフッ素化剤を用いた慣用のフッ素化反応に付することにより製造することもできる。   In the formula (1), a compound in which one or more fluorine atoms are bonded to the ring represented by the formula is a compound in which a hydrogen atom is bonded to the ring represented by the formula in the formula (1). It can also be produced by subjecting it to a conventional fluorination reaction using a fluorinating agent.

本発明の環状カーボネート骨格を含む多環式エステルは、塗料や機能性高分子の原料、医薬、農薬その他の精密化学品の原料などとして用いることができる。   The polycyclic ester containing a cyclic carbonate skeleton of the present invention can be used as a raw material for paints, functional polymers, pharmaceuticals, agricultural chemicals and other fine chemicals.

以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。   Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

実施例1
下記の反応工程式に従って、8−メタクリロイルオキシ−3,5−ジオキサトリシクロ[5.2.1.02,6]デカン−4−オンを製造した。

Figure 0004832019
Example 1
8-Methacryloyloxy-3,5-dioxatricyclo [5.2.1.0 2,6 ] decan-4-one was produced according to the following reaction scheme.
Figure 0004832019

J. Am. Chem. Soc., 1954, 76, 5400に記載の方法により、式(4c)で表される3,5−ジオキサトリシクロ[5.2.1.02,6]デカン−8−エン−4−オンを製造した。 3,5-dioxatricyclo [5.2.1.0 2,6 ] decane represented by the formula (4c) by the method described in J. Am. Chem. Soc., 1954, 76, 5400 8-en-4-one was prepared.

上記で得られた式(4c)で表される化合物76g(0.5モル)を脱水THF(テトラヒドロフラン)1Lに溶解させ、これにBH3のTHF溶液(0.2M)を氷冷下で1L加えた。5〜10℃で2時間撹拌後、トリメチルアミン−N−オキシド37.5gをゆっくり加え、ボラン中間体を酸化した。その後、反応混合液にメタノールをゆっくり加え、次いで水を加え、塩化メチレンで抽出した。有機層を濃縮し、濃縮物をシリカゲルカラムクロマトグラフィーに付すことにより、式(2a)で表される8−ヒドロキシ−3,5−ジオキサトリシクロ[5.2.1.02,6]デカン−4−オンを41g得た。 76 g (0.5 mol) of the compound represented by the formula (4c) obtained above was dissolved in 1 L of dehydrated THF (tetrahydrofuran), and 1 L of BH 3 in THF (0.2 M) was added to the solution under ice cooling. added. After stirring at 5-10 ° C. for 2 hours, 37.5 g of trimethylamine-N-oxide was slowly added to oxidize the borane intermediate. Thereafter, methanol was slowly added to the reaction mixture, water was then added, and the mixture was extracted with methylene chloride. The organic layer is concentrated, and the concentrate is subjected to silica gel column chromatography to give 8-hydroxy-3,5-dioxatricyclo [5.2.1.0 2,6 ] represented by the formula (2a). 41 g of decan-4-one was obtained.

上記で得られた式(2a)で表される化合物34g(0.2モル)を脱水THF800mlに溶解させ、これにトリエチルアミン24gを加え、0℃まで冷却後、メタクリル酸クロリド(3a)25gを滴下した。3時間後、水を加えて、塩化メチレンで目的物を抽出し、有機層を濃縮し、濃縮物をシリカゲルカラムクロマトグラフィーで分離精製することにより、式(1a)で表される8−メタクリロイルオキシ−3,5−ジオキサトリシクロ[5.2.1.02,6]デカン−4−オンを26g得た。
[式(1a)で表される8−メタクリロイルオキシ−3,5−ジオキサトリシクロ[5.2.1.02,6]デカン−4−オンのスペクトルデータ]
1H−NMR(CDCl3) δ:6.15(1H), 5.58(1H), 4.42-4.49(m, 2H), 3.90-3.92(m, 1H), 2.01-2.30(m, 2H), 1.93(s, 3H), 1.55-1.66(m, 4H)
34 g (0.2 mol) of the compound represented by the formula (2a) obtained above is dissolved in 800 ml of dehydrated THF, 24 g of triethylamine is added thereto, and after cooling to 0 ° C., 25 g of methacrylic acid chloride (3a) is added dropwise. did. After 3 hours, water was added, the target product was extracted with methylene chloride, the organic layer was concentrated, and the concentrate was separated and purified by silica gel column chromatography, whereby 8-methacryloyloxy represented by the formula (1a) was obtained. 26 g of -3,5-dioxatricyclo [5.2.1.0 2,6 ] decan-4-one was obtained.
[Spectral data of 8-methacryloyloxy-3,5-dioxatricyclo [5.2.1.0 2,6 ] decan-4-one represented by the formula (1a)]
1 H-NMR (CDCl 3 ) δ: 6.15 (1H), 5.58 (1H), 4.42-4.49 (m, 2H), 3.90-3.92 (m, 1H), 2.01-2.30 (m, 2H), 1.93 (s , 3H), 1.55-1.66 (m, 4H)

実施例2
実施例1において、式(7)で表される化合物(1,3−ジオキソール−2−オン=ビニリデンカーボネート)の代わりに、実施例1で得られた式(4c)で表される化合物を用いたこと以外は、すべて実施例1と同様の条件で反応を行い、下記式(1b)で表される4−メタクリロイルオキシ−10,12−ジオキサペンタシクロ[6.5.1.13,6.02,7.09,13]ペンタデカン−11−オンを12g得た。

Figure 0004832019
元素分析(CHS):Calculated % C 67.09, H 6.62
Found % C 67.10, H 6.63
MS:304, 235
Example 2
In Example 1, instead of the compound represented by the formula (7) (1,3-dioxol-2-one = vinylidene carbonate), the compound represented by the formula (4c) obtained in Example 1 was used. Except for the above, the reaction was carried out under the same conditions as in Example 1, and 4-methacryloyloxy-10,12-dioxapentacyclo [6.5.1.1 3, represented by the following formula (1b): 6 . 0 2,7 . 0,13 ] 12 g of pentadecan-11-one was obtained.
Figure 0004832019
Elemental analysis (CHS): Calculated% C 67.09, H 6.62
Found% C 67.10, H 6.63
MS: 304, 235

Claims (4)

下記式(1’)
Figure 0004832019
(式中、Raは水素原子、ハロゲン原子、又はハロゲン原子を有していてもよい炭素数1〜6のアルキル基を示し、X’はメチレン基を示す。nは0〜3の整数を示す。式中の環は置換基を有していてもよい)
で表される環状カーボネート骨格を含む多環式エステル。
Following formula (1 ')
Figure 0004832019
(In the formula, R a represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, X ′ represents a methylene group, and n represents an integer of 0 to 3. The ring in the formula may have a substituent)
The polycyclic ester containing the cyclic carbonate frame | skeleton represented by these.
下記式(2’)
Figure 0004832019
(式中、X’はメチレン基を示す。nは0〜3の整数を示す。式中の環は置換基を有していてもよい)
で表される環状カーボネート骨格を含む多環式アルコールと、下記式(3)
Figure 0004832019
(式中、Raは水素原子、ハロゲン原子、又はハロゲン原子を有していてもよい炭素数1〜6のアルキル基を示す)
で表される不飽和カルボン酸又はその反応性誘導体を反応させて、下記式(1’)
Figure 0004832019
(式中、Ra、X’、nは前記に同じ。式中の環は置換基を有していてもよい)
で表される化合物を得る環状カーボネート骨格を含む多環式エステルの製造法。
Following formula (2 ')
Figure 0004832019
(In the formula, X ′ represents a methylene group . N represents an integer of 0 to 3. The ring in the formula may have a substituent . )
A polycyclic alcohol containing a cyclic carbonate skeleton represented by formula (3):
Figure 0004832019
(In the formula, Ra represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom)
Is reacted with an unsaturated carboxylic acid represented by the following formula (1 ′):
Figure 0004832019
(In the formula, R a , X ′ and n are the same as above . The ring in the formula may have a substituent)
The manufacturing method of the polycyclic ester containing the cyclic carbonate frame | skeleton which obtains the compound represented by these.
下記式(2’)
Figure 0004832019
(式中、X’はメチレン基を示す。nは0〜3の整数を示す。式中の環は置換基を有していてもよい)
で表される環状カーボネート骨格を含む多環式アルコール。
Following formula (2 ')
Figure 0004832019
(In the formula, X ′ represents a methylene group . N represents an integer of 0 to 3. The ring in the formula may have a substituent . )
The polycyclic alcohol containing the cyclic carbonate skeleton represented by these.
下記式(4’)
Figure 0004832019
(式中、X’はメチレン基を示す。nは0〜3の整数を示す。式中の環は置換基を有していてもよい)
で表される環状カーボネート骨格を含む多環式化合物をヒドロホウ素化−酸化反応に付して、下記式(2’)
Figure 0004832019
(式中、X’、nは前記に同じ。式中の環は置換基を有していてもよい)
で表される化合物を得る環状カーボネート骨格を含む多環式アルコールの製造法。
Following formula (4 ')
Figure 0004832019
(In the formula, X ′ represents a methylene group . N represents an integer of 0 to 3. The ring in the formula may have a substituent . )
A polycyclic compound containing a cyclic carbonate skeleton represented by formula (2) is subjected to hydroboration-oxidation reaction.
Figure 0004832019
(In the formula, X ′ and n are the same as above . The ring in the formula may have a substituent)
The manufacturing method of the polycyclic alcohol containing the cyclic carbonate frame | skeleton which obtains the compound represented by these.
JP2005217633A 2005-07-27 2005-07-27 Polycyclic ester containing cyclic carbonate skeleton Expired - Fee Related JP4832019B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005217633A JP4832019B2 (en) 2005-07-27 2005-07-27 Polycyclic ester containing cyclic carbonate skeleton

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005217633A JP4832019B2 (en) 2005-07-27 2005-07-27 Polycyclic ester containing cyclic carbonate skeleton

Publications (2)

Publication Number Publication Date
JP2007031357A JP2007031357A (en) 2007-02-08
JP4832019B2 true JP4832019B2 (en) 2011-12-07

Family

ID=37791030

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2005217633A Expired - Fee Related JP4832019B2 (en) 2005-07-27 2005-07-27 Polycyclic ester containing cyclic carbonate skeleton

Country Status (1)

Country Link
JP (1) JP4832019B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5741340B2 (en) * 2010-09-29 2015-07-01 Jsr株式会社 Resist underlayer film forming composition, polymer, resist underlayer film, pattern forming method, and semiconductor device manufacturing method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2447370A1 (en) * 1974-10-04 1976-04-22 Basf Ag POLYMERIZES CONTAINING DIOXAZOLONE GROUPS
DE3528928A1 (en) * 1985-08-13 1987-02-26 Hoechst Ag POLYMERIZABLE CONNECTIONS AND METHOD FOR THEIR PRODUCTION
JPH01182310A (en) * 1988-01-12 1989-07-20 Nippon Oil & Fats Co Ltd Novel transparent resin and transparent optical resin having high refractive index
JPH08134060A (en) * 1994-11-02 1996-05-28 Daicel Chem Ind Ltd Continuous production of cyclic carbonate
JP4315756B2 (en) * 2002-07-19 2009-08-19 三菱レイヨン株式会社 (Co) polymer, resist composition, and pattern forming method

Also Published As

Publication number Publication date
JP2007031357A (en) 2007-02-08

Similar Documents

Publication Publication Date Title
JP4212576B2 (en) 3-oxa-2-thiatricyclo [4.2.1.04,8] nonane derivative
US20090156854A1 (en) Adamantane derivatives and process for producing the same
JP2000229911A (en) Production of 2-alkyl-2-adamantyl (meth)acrylates
JP4832019B2 (en) Polycyclic ester containing cyclic carbonate skeleton
EP3647304A1 (en) Method for preparing 2-fluoroacrylate
JP4896040B2 (en) Method for producing polymerizable hydroxydiamantyl ester compound
US20070249858A1 (en) Polymerizable fluorinated ester compounds and their preparing processes
JP6285825B2 (en) Method for producing compound containing N-acylcarbamoyl group and lactone skeleton
US20090076201A1 (en) (meth) acryloyloxytetrahydrofurans and process for production thereof
JP5005197B2 (en) Polycyclic ester
JP4740677B2 (en) 3-oxa-7-oxa (or thia) tricyclo [4.2.1.04,8] nonan-2-one derivatives
US20220162148A1 (en) Method of producing alpha,beta-unsaturated dicarboxylic acid ester
JP2007231002A (en) Manufacturing method of polymerizable diamantyl ester compound
JP4220888B2 (en) Adamantane derivative and method for producing the same
US6414167B1 (en) Octafluorotricyclodecane derivatives and processes for producing same
JP2009256307A (en) Adamantyl ester of unsaturated carboxylic acid and method for producing the same
JP2003146979A (en) Method for producing lactone
JPWO2005056512A1 (en) Method for producing polymerizable unsaturated carboxylic acid adamantyl esters
JP4718922B2 (en) 3-Oxa-7-thiatricyclo [4.2.1.04,8] nonane derivative
JP4659251B2 (en) Process for producing hydroxy-4-oxatricyclo [4.3.1.13,8] undecan-5-one and (meth) acrylic acid ester thereof
EP1731504A1 (en) Adamantane derivative and process for producing the same
JP4796794B2 (en) Polycyclic ester containing lactone skeleton
JP4815951B2 (en) New adamantyl ester compounds
JP2000344758A (en) Production of (meth)acrylic ester
JP2007254293A (en) METHOD FOR PRODUCING alpha-METHYLENE-beta-ALKYL-gamma-BUTYROLACTONE

Legal Events

Date Code Title Description
RD04 Notification of resignation of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7424

Effective date: 20070704

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20080401

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20110614

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20110803

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20110920

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20110920

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20140930

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20140930

Year of fee payment: 3

S533 Written request for registration of change of name

Free format text: JAPANESE INTERMEDIATE CODE: R313533

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20140930

Year of fee payment: 3

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

LAPS Cancellation because of no payment of annual fees