JP2007031355A - 3-oxa-2-thiatricyclo[4.2.1.04,8]nonane derivative - Google Patents
3-oxa-2-thiatricyclo[4.2.1.04,8]nonane derivative Download PDFInfo
- Publication number
- JP2007031355A JP2007031355A JP2005217631A JP2005217631A JP2007031355A JP 2007031355 A JP2007031355 A JP 2007031355A JP 2005217631 A JP2005217631 A JP 2005217631A JP 2005217631 A JP2005217631 A JP 2005217631A JP 2007031355 A JP2007031355 A JP 2007031355A
- Authority
- JP
- Japan
- Prior art keywords
- group
- halogen atom
- formula
- atom
- carbon atoms
- 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.)
- Granted
Links
- 0 C(C(*1)*C2)C3C1C2S*3 Chemical compound C(C(*1)*C2)C3C1C2S*3 0.000 description 33
- RBTZNUNPMAIXBV-UHFFFAOYSA-N CC(C(OC(C1OC2C3C1)C2OS3(=O)=O)=O)=C Chemical compound CC(C(OC(C1OC2C3C1)C2OS3(=O)=O)=O)=C RBTZNUNPMAIXBV-UHFFFAOYSA-N 0.000 description 1
- WRMFERKYCOHSIF-UHFFFAOYSA-N CC(C)C(O)OC(C1CC2C3C1)C3OS2(=O)=[O]=C Chemical compound CC(C)C(O)OC(C1CC2C3C1)C3OS2(=O)=[O]=C WRMFERKYCOHSIF-UHFFFAOYSA-N 0.000 description 1
- FNQWCJWWFJWXRX-UHFFFAOYSA-N CCC(C1CC2CC1)OCOS2(=O)=O Chemical compound CCC(C1CC2CC1)OCOS2(=O)=O FNQWCJWWFJWXRX-UHFFFAOYSA-N 0.000 description 1
Abstract
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３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体とその製造法、および該３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体の合成原料として有用な５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体とその製造法に関する。 The present invention relates to a novel 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative useful as a raw material for paints and functional polymers, a raw material for pharmaceuticals, agricultural chemicals and other fine chemicals. And its production method, and 5-hydroxy-3-oxa-2-thiatricyclo [4.2.4] useful as a raw material for synthesizing the 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative. 1.0 4,8 ] nonane derivative and a method for producing the same.
５位に重合性不飽和基を有する３−オキサトリシクロ［４．２．１．０4,8］ノナン−２−オン誘導体（＝９位に重合性不飽和基を有する２−オキサトリシクロ［４．２．１．０4,8］ノナン−３−オン誘導体）は、疎水性で嵩高く安定性の高い脂環式炭素環と、親水性で且つ加水分解性を示すラクトン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。また、その簡易な製造法も提案されている（特許文献１、２等）。しかし、上記の化合物において、ラクトン環はアルカリによって加水分解されるものの、加水分解速度はさほど速くない。そのため、その用途によっては所望の機能が十分に発揮されなかったり、加水分解後の生成物の水に対する溶解性が低く、性能や操作性に劣るなどの問題があった。 3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one derivative having a polymerizable unsaturated group at the 5-position (= 2-oxatricyclo having a polymerizable unsaturated group at the 9-position [4.2.1.0 4,8 ] nonan-3-one derivative) is a hydrophobic, bulky and highly stable alicyclic carbocycle and a lactone ring that is both hydrophilic and hydrolyzable. In addition to having a polymerizable unsaturated group, it is used as a raw material for paints and functional polymers utilizing its structural specificity. Moreover, the simple manufacturing method is also proposed (patent documents 1, 2, etc.). However, in the above compounds, the lactone ring is hydrolyzed by alkali, but the hydrolysis rate is not so fast. For this reason, there are problems such that the desired function is not sufficiently exhibited depending on the application, or the solubility of the product after hydrolysis in water is low and the performance and operability are poor.
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、加水分解性及び加水分解後の水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３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体とその効率のよい製造法を提供することにある。
本発明の他の目的は、前記３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体の合成原料として有用な新規な５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体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 to provide a monomer such as a high-functional polymer capable of improving hydrolyzability and solubility in water after hydrolysis while maintaining stability such as chemical resistance when derived into a polymer or the like. It is an object of the present invention to provide a novel 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative useful as a component and its efficient production method.
Another object of the present invention is to provide a novel 5-hydroxy-3-oxa-2-thiatricyclo [4.20.1.04,8] nonane derivative useful as a starting material for the synthesis of the 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative. 4.2.1.0 4,8 ] nonane derivative and its efficient production method.
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、３−オキサトリシクロ［４．２．１．０4,8］ノナン−２−オン誘導体よりも環の加水分解性が高く且つ加水分解後の水に対する溶解性を向上できる新規な３−オキサ−２−チア−トリシクロ［４．２．１．０4,8］ノナン誘導体とその効率のよい製造法を見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have found that when derived into a polymer or the like, a 3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one derivative is preferred. Novel 3-oxa-2-thia-tricyclo [4.2.1.0 4,8 ] nonane derivative having high ring hydrolyzability and improved water solubility after hydrolysis, and its efficient production The law was found and the present invention was completed.
すなわち、本発明は、下記式（１）
で表される３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体を提供する。
That is, the present invention provides the following formula (1):
The 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the formula:
本発明は、また、下記式（２）
で表される５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体と、下記式（３）
で表される不飽和カルボン酸又はその反応性誘導体を反応させて、下記式（１）
で表される３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体を得る３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体の製造法を提供する。
The present invention also provides the following formula (2):
A 5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by formula (3):
Is reacted with an unsaturated carboxylic acid represented by the following formula (1):
Of 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the following: Production of 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative Provide law.
本発明は、さらに、下記式（２′）
で表される５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体を提供する。
The present invention further provides the following formula (2 ′):
The 5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the formula:
本発明は、さらにまた、下記式（４）
で表される２，３−エポキシビシクロ［２．２．１］ヘプタン誘導体を環化反応に付して、下記式（２）
で表される５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体を得る５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体の製造法を提供する。
The present invention further provides the following formula (4):
A 2,3-epoxybicyclo [2.2.1] heptane derivative represented by the following formula (2)
5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the formula: 5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] A method for producing a nonane derivative is provided.
なお、３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン環における位置番号を下記に示す。
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、環の加水分解性及び加水分解後の水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３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体とその効率のよい製造法が提供される。また、前記３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体の合成原料として有用な新規な５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体とその効率のよい製造法が提供される。 According to the present invention, a highly functional polymer that can improve the hydrolyzability of the ring and the solubility in water after hydrolysis while maintaining stability such as chemical resistance when derived into a polymer or the like. The present invention provides a novel 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative useful as a monomer component and the like and an efficient production method thereof. In addition, novel 5-hydroxy-3-oxa-2-thiatricyclo [4.2.1., Useful as a raw material for the synthesis of the 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative. 0 4,8 ] nonane derivatives and their efficient production processes are provided.
本発明の３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体は前記式（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、Ｒ1、Ｒ2、Ｒ3、Ｒ4は、同一又は異なって、水素原子、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、又はヒドロキシル基部分が保護基で保護されていてもよく且つ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を示し、Ｒ5、Ｒ6、Ｒ7は、同一又は異なって、水素原子、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、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、塩を形成していてもよいスルフィノ基、置換オキシスルフィニル基、塩を形成していてもよいスルホ基、置換オキシスルホニル基、又はシアノ基を示し、Ｘは炭素数１〜３のアルキル基が１又は２個置換していてもよいメチレン基、酸素原子又は硫黄原子を示す。ｎは１又は２を示す。 The 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative of the present invention is represented by the above formula (1). In Formula (1), 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, and R 1 , R 2 , R 3 and R 4 are the same. Or, differently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxyl group part may be protected with a protecting group and have a halogen atom. 1 to 6 represents a hydroxyalkyl group having 1 to 6 carbon atoms, and R 5 , R 6 and R 7 may be the same or different and each having a hydrogen atom, a halogen atom or a halogen atom and having 1 to 6 carbon atoms An alkyl group, a carboxyl group that may form a salt, a substituted oxycarbonyl group, a sulfino group that may form a salt, a substituted oxysulfinyl group, a sulfo group that may form a salt, a substituted oxysulfonyl group Or cyano Are shown, X is an alkyl group of 1 or 2 which may be substituted methylene group having 1 to 3 carbon atoms, an oxygen atom or a sulfur atom. n represents 1 or 2.
前記ハロゲン原子には、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。 Examples of the halogen atom 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.
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、スルフィノ基、スルホ基の塩としては、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 protective group for the hydroxyl group of a hydroxyalkyl group having 1 to 6 carbon atoms which may have a halogen atom include a protective group usually used as a protective group for a hydroxyl group in the field of organic synthesis, such as a methyl group, a 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, sulfino group, and sulfo 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。置換オキシスルフィニル基や置換オキシスルホニル基としては、上記置換オキシカルボニル基に対応する置換オキシスルフィニル基、置換オキシスルホニル基が挙げられる。Ｘにおいて、メチレン基に置換していてもよい炭素数１〜３のアルキル基としては、例えば、メチル、エチル、プロピル基などが挙げられる。炭素数１〜３のアルキル基が１又は２個置換したメチレン基には、例えば、メチルメチレン、ジメチルメチレン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. Examples of the substituted oxysulfinyl group and the substituted oxysulfonyl group include a substituted oxysulfinyl group and a substituted oxysulfonyl group corresponding to the above substituted oxycarbonyl group. In X, examples of the alkyl group having 1 to 3 carbon atoms which may be substituted with a methylene group include methyl, ethyl, and propyl groups. Examples of the methylene group substituted with 1 or 2 alkyl groups having 1 to 3 carbon atoms include methylmethylene and dimethylmethylene groups.
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。また、Ｒ1、Ｒ2、Ｒ3、Ｒ4としては、水素原子、メチル基やトリフルオロメチル基等の炭素数１〜３のアルキル基若しくはハロアルキル基、ヒドロキシ部分が保護基で保護されていてもよい炭素数１〜３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（特に、ヒドロキシメチル基、アセトキシメチル基等の保護基で保護されていてもよいヒドロキシメチル基）などが好ましい。Ｒ5、Ｒ6、Ｒ7としては、水素原子、メチル基やトリフルオロメチル基等の炭素数１〜３のアルキル基若しくはハロアルキル基（特に、メチル基、ハロメチル基）、置換オキシカルボニル基、シアノ基が好ましい。 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. R 1 , R 2 , R 3 and R 4 are each a hydrogen atom, an alkyl group having 1 to 3 carbon atoms such as a methyl group or a trifluoromethyl group, a haloalkyl group, or a hydroxy moiety protected with a protecting group. Preferred is a hydroxyalkyl group having 1 to 3 carbon atoms or a hydroxyhaloalkyl group (particularly a hydroxymethyl group which may be protected with a protective group such as a hydroxymethyl group or an acetoxymethyl group). R 5 , R 6 and R 7 are each a hydrogen atom, an alkyl group having 1 to 3 carbon atoms such as a methyl group or a trifluoromethyl group or a haloalkyl group (particularly a methyl group or a halomethyl group), a substituted oxycarbonyl group, a cyano group Groups are preferred.
式（１）で表される３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体の代表的な例として、下記式で表される５−（メタ）アクリロイルオキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン−２，２−ジオン化合物（各立体異性体を含む）、５−（メタ）アクリロイルオキシ−３，７−ジオキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン−２，２−ジオン化合物（各立体異性体を含む）、該５−（メタ）アクリロイルオキシ−３，７−ジオキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン−２，２−ジオン化合物の７位の酸素原子が硫黄原子に置き換わった対応する５−（メタ）アクリロイルオキシ−３−オキサ−２，７−ジチアトリシクロ［４．２．１．０4,8］ノナン−２，２−ジオン化合物（各立体異性体を含む）；及びこれらの化合物の２位の硫黄原子に酸素原子が２つではなく１つ結合した対応する化合物（各立体異性体を含む）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し、Ａｃはアセチル基を示す。 As a typical example of the 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the formula (1), 5- (meth) acryloyloxy- represented by the following formula 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane-2,2-dione compound (including each stereoisomer), 5- (meth) acryloyloxy-3,7-dioxa- 2-thiatricyclo [4.2.1.0 4,8 ] nonane-2,2-dione compound (including each stereoisomer), 5- (meth) acryloyloxy-3,7-dioxa-2-thiatricyclo The corresponding 5- (meth) acryloyloxy-3-oxa-2,7- in which the oxygen atom at the 7-position of the [4.2.1.0 4,8 ] nonane-2,2-dione compound is replaced with a sulfur atom. Dithiatricyclo [4.2.1.0 4,8 ] nonane-2,2- Dione compounds (including each stereoisomer); and corresponding compounds (including each stereoisomer) in which one oxygen atom is bonded to the sulfur atom at the 2-position of these compounds instead of two. In the formula, R represents an acryloyl group or a methacryloyl group, and Ac represents an acetyl group.
式（１）で表される３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体は、前記式（２）で表される５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体と、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、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｘ、ｎは、前記と同様である。 The 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the formula (1) is a 5-hydroxy-3-oxa-2- represented by the formula (2). It can be produced by reacting a thiatricyclo [4.2.1.0 4,8 ] nonane derivative with an unsaturated carboxylic acid represented by the formula (3) or a reactive derivative thereof. R a , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , 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５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体の代表的な例としては、前記式（１）で表される３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体の代表的な例として挙げた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。なお、式（２′）で表される化合物は式（２）で表される化合物に含まれる。 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. A typical example of a 5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the formula (2) is represented by the formula (1). As a typical example of a 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative, a compound (compound in which R is a hydrogen atom) is given. The compound represented by the formula (2 ′) is included in the compound represented by the formula (2).
上記式（１）で表される３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体は、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 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the above formula (1) is a solvent such as (a) tetrahydrofuran, toluene, methylene chloride or the like. In the compound represented by the formula (2), a (meth) acrylic acid halide such as (meth) acrylic acid chloride or (meta) in the presence of a base such as triethylamine, pyridine or 4-dimethylaminopyridine, if necessary. ) Reacting an active reactive derivative of an unsaturated carboxylic acid such as acrylic anhydride, or (b) an ester such as titanium isopropoxide in a compound represented by formula (2) in the same solvent as described above. In the presence of an exchange catalyst, an unsaturated carboxylic acid ester such as methyl (meth) acrylate is reacted, or (c) a compound represented by the formula (2) is mixed with hydrochloric acid, sulfuric acid, p in a solvent similar to the above. -Torr Can be obtained by reacting in the presence of a strong acid such as Nsuruhon acid and (meth) unsaturated carboxylic acids 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３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体は、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 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the formula (1) generated by the reaction is, for example, filtered, concentrated, distilled, extracted, crystallized, recrystallized. Separation and purification can be performed by separation means such as column chromatography, or a combination thereof.
前記式（２）で表される５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体は、前記式（４）で表される２，３−エポキシビシクロ［２．２．１］ヘプタン誘導体を環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Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｘ、ｎは前記と同様である。 The 5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the formula (2) is a 2,3-epoxy represented by the formula (4). It can be obtained by subjecting a bicyclo [2.2.1] heptane derivative to a cyclization reaction. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X, and n in the formula (4) are the same as described above.
Ｒbにおける有機基としては、カルボン酸エステルを構成する基であればよく、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、ｔ−ブチル基などのアルキル基（特に、Ｃ1-6アルキル基）；ビニル、アリル基等のアルケニル基（特に、Ｃ1-6アルケニル基）；シクロヘキシル基等のシクロアルケニル基；フェニル基等のアリール基；ピリジル基等の複素環式基などが挙げられる。Ｒbとしては、特に、水素原子のほか、メチル、エチル基等のＣ1-4アルキル基が好ましい。 The organic group for R b may be any group that constitutes a carboxylic acid ester, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and t-butyl groups (particularly, C 1-6 alkyl groups). Alkenyl groups such as vinyl and allyl groups (especially C 1-6 alkenyl groups); cycloalkenyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; heterocyclic groups such as pyridyl groups; R b is particularly preferably a hydrogen atom, or a C 1-4 alkyl group such as a methyl or ethyl group.
環化反応は、Ｒbが水素原子の場合は、例えば、式（４）で表される化合物を溶媒に溶解させるだけで進行する。Ｒbが有機基の場合は、式（４）で表される化合物を慣用の加水分解反応（アルカリ加水分解反応、酸加水分解反応等）に付してＲbが水素原子である化合物を生成させると、直ちに環化反応が進行して、式（２）で表される化合物が生成する。反応で生成した式（２）で表される５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体は、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。 When R b is a hydrogen atom, the cyclization reaction proceeds, for example, only by dissolving the compound represented by formula (4) in a solvent. When R b is an organic group, the compound represented by formula (4) is subjected to a conventional hydrolysis reaction (alkali hydrolysis reaction, acid hydrolysis reaction, etc.) to produce a compound in which R b is a hydrogen atom. As a result, the cyclization reaction proceeds immediately to produce the compound represented by the formula (2). The 5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the formula (2) produced by the reaction is, for example, filtered, concentrated, distilled, extracted, crystallized. Separation and purification can be performed by separation means such as precipitation, recrystallization, column chromatography, or a combination thereof.
なお、前記式（２）で表される化合物のうち、３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン環にフッ素原子が１以上結合している化合物は、３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン環に水素原子が少なくとも１つ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。 Of the compounds represented by the formula (2), a compound in which one or more fluorine atoms are bonded to the 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane ring is 3 A compound in which at least one hydrogen atom is bonded to the oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane ring is subjected to a conventional fluorination reaction using a fluorinating agent such as fluorine. Can also be manufactured.
前記式（４）で表される２，３−エポキシビシクロ［２．２．１］ヘプタン誘導体は、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、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｘ、Ｒb、ｎは前記と同様である。
すなわち、式（５）で表されるシクロペンタジエン誘導体、フラン誘導体又はチオフェン誘導体と式（６）で表される不飽和スルフィン酸若しくは不飽和スルホン酸又はそれらのエステルとをディールスアルダー反応に付して、式（７）で表されるビシクロ［２．２．１］ヘプタン−２−エン誘導体を得、これに過酸又は過酸化物を反応させることにより、式（４）で表される２，３−エポキシビシクロ［２．２．１］ヘプタン誘導体を得ることができる。なお、Ｒbが水素原子である場合等においては、式（７）で表される化合物に過酸又は過酸化物を作用させることにより、エポキシ化の後直ちに環化して、前記式（２）で表される化合物が主生成物として得られる場合もある。 That is, a cyclopentadiene derivative, a furan derivative or a thiophene derivative represented by formula (5) and an unsaturated sulfinic acid or unsaturated sulfonic acid represented by formula (6) or an ester thereof are subjected to Diels-Alder reaction. The bicyclo [2.2.1] heptan-2-ene derivative represented by the formula (7) is obtained, and by reacting this with a peracid or peroxide, 2,2 represented by the formula (4) is obtained. A 3-epoxybicyclo [2.2.1] heptane derivative can be obtained. In the case where R b is a hydrogen atom, the compound represented by formula (7) is cyclized immediately after epoxidation by acting a peracid or peroxide on the compound represented by formula (2). May be obtained as the main product.
式（５）で表されるシクロペンタジエン誘導体、フラン誘導体又はチオフェン誘導体の代表的な例として、例えば、１，３−シクロペンタジエン、１−メチル−１，３−シクロペンタジエン、２−メチル−１，３−シクロペンタジエン、５−メチル−１，３−シクロペンタジエン、１，２−ジメチル−１，３−シクロペンタジエン、１，４−ジメチル−１，３−シクロペンタジエン、２，３−ジメチル−１，３−シクロペンタジエン、１，２，３，４−テトラメチル−１，３−シクロペンタジエン、１，２，３，４，５−ペンタメチル−１，３−シクロペンタジエン、１−ヒドロキシメチル−１，３−ペンタジエン、１，４−ビス（ヒドロキシメチル）−１，３−シクロペンタジエン、２，３−ビス（ヒドロキシメチル）−１，３−シクロペンタジエン、１−アセトキシメチル−１，３−シクロペンタジエン、１，４−ビス（アセトキシメチル）−１，３−シクロペンタジエン、２，３−ビス（アセトキシメチル）−１，３−シクロペンタジエンなどのシクロペンタジエン誘導体（Ｘ＝ＣＨ2である化合物）、フラン、２−メチルフラン、３−メチルフラン、２，５−ジメチルフラン、３，４−ジメチルフラン、２，３，４，５−テトラメチルフラン、２−ヒドロキシメチルフラン、２，５−ビス（ヒドロキシメチル）フラン、２−アセトキシメチルフラン、２，５−ビス（アセトキシメチル）フランなどのフラン誘導体（Ｘ＝Ｏである化合物）、及びこれらのフラン誘導体に対応するチオフェン誘導体（Ｘ＝Ｓである化合物）などが例示される。式（６）で表される化合物の代表的な例として、例えば、ビニルスルホン酸、α−メチルビニルスルホン酸、β−メチルビニルスルホン酸、α−トリフルオロメチルビニルスルホン酸、β−トリフルオロメチルビニルスルホン酸、α−シアノビニルスルホン酸、β−シアノビニルスルホン酸、α−カルボキシビニルスルホン酸、β−カルボキシビニルスルホン酸などの不飽和スルホン酸；これらの化合物に対応する不飽和スルフィン酸；及びそれらのエステル（メチルエステル、エチルエステル等）などが挙げられる。 As typical examples of the cyclopentadiene derivative, furan derivative or thiophene derivative represented by the formula (5), for example, 1,3-cyclopentadiene, 1-methyl-1,3-cyclopentadiene, 2-methyl-1, 3-cyclopentadiene, 5-methyl-1,3-cyclopentadiene, 1,2-dimethyl-1,3-cyclopentadiene, 1,4-dimethyl-1,3-cyclopentadiene, 2,3-dimethyl-1, 3-cyclopentadiene, 1,2,3,4-tetramethyl-1,3-cyclopentadiene, 1,2,3,4,5-pentamethyl-1,3-cyclopentadiene, 1-hydroxymethyl-1,3 -Pentadiene, 1,4-bis (hydroxymethyl) -1,3-cyclopentadiene, 2,3-bis (hydroxymethyl) -1,3-cyclope Cyclones such as tadiene, 1-acetoxymethyl-1,3-cyclopentadiene, 1,4-bis (acetoxymethyl) -1,3-cyclopentadiene, 2,3-bis (acetoxymethyl) -1,3-cyclopentadiene Pentadiene derivative (compound in which X═CH 2 ), furan, 2-methylfuran, 3-methylfuran, 2,5-dimethylfuran, 3,4-dimethylfuran, 2,3,4,5-tetramethylfuran, Furan derivatives such as 2-hydroxymethylfuran, 2,5-bis (hydroxymethyl) furan, 2-acetoxymethylfuran, 2,5-bis (acetoxymethyl) furan (compounds where X = O), and these furans Examples include thiophene derivatives (compounds where X = S) corresponding to the derivatives. Representative examples of the compound represented by the formula (6) include, for example, vinyl sulfonic acid, α-methyl vinyl sulfonic acid, β-methyl vinyl sulfonic acid, α-trifluoromethyl vinyl sulfonic acid, β-trifluoromethyl. Unsaturated sulfonic acids such as vinylsulfonic acid, α-cyanovinylsulfonic acid, β-cyanovinylsulfonic acid, α-carboxyvinylsulfonic acid, β-carboxyvinylsulfonic acid; unsaturated sulfinic acids corresponding to these compounds; and Those esters (methyl ester, ethyl ester, etc.) can be mentioned.
式（５）で表される化合物と式（６）で表される化合物との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。 The reaction between the compound represented by formula (5) and the compound represented by formula (6) is performed 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.
反応速度や反応の選択性（立体選択性等）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、これらに限定されない。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。生成した式（７）で表されるビシクロ［２．２．１］ヘプタン−２−エン誘導体は、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。 In order to improve the reaction rate and reaction selectivity (stereoselectivity, etc.), 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 produced bicyclo [2.2.1] heptan-2-ene derivative represented by the formula (7) is separated by a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and the like. Or by combining them, it can be separated and purified.
式（７）で表される化合物と反応させる過酸又は過酸化物のうち、過酸としては、例えば、過ギ酸、過酢酸、トリフルオロ過酢酸、過安息香酸、ｍ−クロロ過安息香酸、モノペルオキシフタル酸などの有機過酸；過マンガン酸などの無機過酸が挙げられる。過酸は塩の形態で使用することもできる。有機過酸は平衡過酸（例えば、平衡過ギ酸、平衡過酢酸等）であってもよい。すなわち、例えば、ギ酸、酢酸などの有機酸と過酸化水素とを組み合わせて用い、系内で対応する有機過酸を生成させてもよい。平衡過酸を用いる場合、触媒として、硫酸などの強酸を少量添加してもよい。過酸の使用量は、例えば、式（７）で表される化合物１モルに対して、０．８〜２モル、好ましくは０．９〜１．５モル、さらに好ましくは０．９５〜１．２モル程度である。 Among peracids or peroxides to be reacted with the compound represented by the formula (7), examples of peracids include formic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, Organic peracids such as monoperoxyphthalic acid; inorganic peracids such as permanganic acid. Peracids can also be used in the form of salts. The organic peracid may be an equilibrium peracid (eg, equilibrium formic acid, equilibrium peracetic acid, etc.). That is, for example, organic acids such as formic acid and acetic acid may be used in combination with hydrogen peroxide to generate the corresponding organic peracid in the system. When using an equilibrium peracid, a small amount of a strong acid such as sulfuric acid may be added as a catalyst. The amount of peracid to be used is, for example, 0.8 to 2 mol, preferably 0.9 to 1.5 mol, more preferably 0.95 to 1 mol with respect to 1 mol of the compound represented by formula (7). About 2 moles.
式（７）で表される化合物と反応させる過酸化物としては、例えば、過酸化水素、ペルオキシド、ヒドロペルオキシド、ペルオキソ酸、ペルオキソ酸の塩などが挙げられる。過酸化水素としては、純粋な過酸化水素を用いてもよいが、取扱性の点から、通常、適当な溶媒、例えば水に希釈した形態（例えば、３０重量％過酸化水素水）で用いられる。過酸化水素等の過酸化物の使用量は、式（７）で表される化合物１モルに対して、例えば０．９〜５モル程度、好ましくは０．９〜３モル程度、さらに好ましくは０．９５〜２モル程度である。 Examples of the peroxide to be reacted with the compound represented by the formula (7) include hydrogen peroxide, peroxide, hydroperoxide, peroxo acid, and a salt of peroxo acid. As hydrogen peroxide, pure hydrogen peroxide may be used. However, from the viewpoint of handleability, it is usually used in a form diluted with an appropriate solvent, for example, water (for example, 30% by weight hydrogen peroxide). . The amount of peroxide such as hydrogen peroxide is, for example, about 0.9 to 5 mol, preferably about 0.9 to 3 mol, more preferably about 1 mol of the compound represented by formula (7). It is about 0.95 to 2 mol.
前記過酸化水素は金属化合物とともに用いる場合が多い。前記金属化合物としては、例えば、Ｗ、Ｍｏ、Ｖ、Ｍｎ、Ｒｅなどの金属元素を含む酸化物、オキソ酸又はその塩、硫化物、ハロゲン化物、オキシハロゲン化物、ホウ化物、炭化物、ケイ化物、窒化物、リン化物、過酸化物、錯体（無機錯体及び有機錯体）、有機金属化合物などが挙げられる。これらの金属化合物は単独で又は２種以上組み合わせて使用できる。 The hydrogen peroxide is often used together with a metal compound. Examples of the metal compound include oxides containing metal elements such as W, Mo, V, Mn, and Re, oxo acids or salts thereof, sulfides, halides, oxyhalides, borides, carbides, silicides, Examples thereof include nitrides, phosphides, peroxides, complexes (inorganic complexes and organic complexes), and organometallic compounds. These metal compounds can be used alone or in combination of two or more.
前記酸化物としては、例えば、酸化タングステン（ＷＯ2、ＷＯ3など）、酸化モリブデン（ＭｏＯ2、ＭｏＯ3など）、酸化バナジウム（ＶＯ、Ｖ2Ｏ3、ＶＯ2、Ｖ2Ｏ5など）、酸化マンガン（ＭｎＯ、Ｍｎ2Ｏ3、Ｍｎ3Ｏ4、ＭｎＯ2、Ｍｎ2Ｏ7など）、Ｗ、Ｍｏ、Ｖ、Ｍｎなどの金属元素を含む複合酸化物などが挙げられる。 Examples of the oxide include tungsten oxide (WO 2 , WO 3 etc.), molybdenum oxide (MoO 2 , MoO 3 etc.), vanadium oxide (VO, V 2 O 3 , VO 2 , V 2 O 5 etc.), Examples include manganese oxide (MnO, Mn 2 O 3 , Mn 3 O 4 , MnO 2 , Mn 2 O 7, etc.), composite oxides containing metal elements such as W, Mo, V, and Mn.
オキソ酸には、タングステン酸、モリブデン酸、バナジン酸、マンガン酸等のほか、イソポリタングステン酸、イソポリモリブデン酸、イソポリバナジウム酸などのイソポリ酸；リンタングステン酸、ケイタングステン酸、リンモリブデンサン、ケイモリブデン酸、リンバナドモリブデン酸等の前記金属元素と他の金属元素等とからなるヘテロポリ酸が含まれる。ヘテロポリ酸における他の金属元素等として、リン又はケイ素、特にリンが好ましい。 Oxo acids include tungstic acid, molybdic acid, vanadic acid, manganic acid, and other isopolyacids such as isopolytungstic acid, isopolymolybdic acid, isopolyvanadate; phosphotungstic acid, silicotungstic acid, phosphomolybdenum sun And heteropolyacids composed of the above metal elements such as silicomolybdic acid and phosphovanadmolybdic acid and other metal elements. As the other metal element in the heteropolyacid, phosphorus or silicon, particularly phosphorus is preferable.
オキソ酸の塩としては、前記オキソ酸のナトリウム塩、カリウム塩などのアルカリ金属塩；マグネシウム塩、カルシウム塩、バリウム塩などのアルカリ土類金属塩；アンモニウム塩；遷移金属塩などが挙げられる。オキソ酸の塩（例えば、ヘテロポリ酸の塩）は、カチオンに相当する水素原子の一部を他のカチオンに置換した塩であってもよい。 Examples of the salt of oxo acid include alkali metal salts such as sodium salt and potassium salt of oxo acid; alkaline earth metal salts such as magnesium salt, calcium salt and barium salt; ammonium salt; transition metal salt and the like. The salt of an oxo acid (for example, a salt of a heteropoly acid) may be a salt in which a part of the hydrogen atom corresponding to the cation is replaced with another cation.
金属元素を含む過酸化物としては、例えば、ペルオキソ酸（例えば、ペルオキソタングステン酸、ペルオキソモリブデン酸、ペルオキソバナジウム酸など）、ペルオキソ酸の塩（前記ペルオキソ酸のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、遷移金属塩など）、過酸（過マンガン酸など）、過酸の塩（前記過酸のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、遷移金属塩など）などが挙げられる。 Examples of the peroxide containing a metal element include peroxo acids (for example, peroxotungstic acid, peroxomolybdic acid, peroxovanadate, etc.), salts of peroxo acids (alkali metal salts, alkaline earth metal salts of the peroxo acids, Ammonium salts, transition metal salts, etc.), peracids (permanganic acid, etc.), peracid salts (alkali metal salts, alkaline earth metal salts, ammonium salts, transition metal salts, etc. of the peracids).
前記過酸化水素とともに用いる金属化合物の使用量は、例えば、式（７）で表される化合物１モルに対して、０．０００１〜２モル程度、好ましくは０．０００５〜０．５モル程度、さらに好ましくは０．００１〜０．２モル程度である。 The amount of the metal compound used together with the hydrogen peroxide is, for example, about 0.0001 to 2 mol, preferably about 0.0005 to 0.5 mol, with respect to 1 mol of the compound represented by the formula (7). More preferably, it is about 0.001-0.2 mol.
式（７）で表される化合物と過酸又は過酸化物との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、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；酢酸エチルなどのエステル；酢酸などの有機酸；水などが挙げられる。これらの溶媒は１種で、又は２種以上混合して用いられる。なお、不均一系で反応を行う場合には、溶媒として水、又は水を含む溶媒を用いる場合が多い。 The reaction between the compound represented by formula (7) and the peracid or peroxide is carried out in the presence or absence of a solvent. Examples of the solvent include alcohols such as t-butyl alcohol; halogenated hydrocarbons such as chloroform, dichloromethane, and 1,2-dichloroethane; aromatic hydrocarbons such as benzene; and 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; linear or cyclic ethers such as ethyl ether and tetrahydrofuran Esters such as ethyl acetate; organic acids such as acetic acid; water and the like. These solvents are used alone or in combination of two or more. Note that when the reaction is performed in a heterogeneous system, water or a solvent containing water is often used as the solvent.
反応温度は、反応速度及び反応選択性を考慮して適宜選択できるが、一般には０〜１００℃程度、好ましくは１０〜８０℃程度である。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。 Although reaction temperature can be suitably selected in view of reaction rate and reaction selectivity, it is generally about 0 to 100 ° C, preferably about 10 to 80 ° C. The reaction may be carried out by any method such as batch, semi-batch and continuous methods.
上記反応により、式（７）で表される化合物の二重結合のエポキシ化が起こり、式（４）で表されるエポキシ化合物が生成する。なお、例えば、Ｒbが水素原子である場合等には、続いてエポキシ環の開環を伴う分子内環化反応が進行して、式（２）で表される５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体が生成しうる。 By the said reaction, the epoxidation of the double bond of the compound represented by Formula (7) occurs, and the epoxy compound represented by Formula (4) produces | generates. For example, when R b is a hydrogen atom, an intramolecular cyclization reaction involving the opening of an epoxy ring proceeds, and a 5-hydroxy-3-oxa compound represented by the formula (2) is obtained. A 2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative can be formed.
反応で生成した式（４）で表されるエポキシ化合物や式（２）で表される化合物は、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 epoxy compound represented by the formula (4) and the compound represented by the formula (2) generated by the reaction are separated by means of separation such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc. Or by combining them, it can be separated and purified.
なお、式（１）において式中に示される３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン環にフッ素原子が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３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン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 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane ring represented by the formula is represented by the formula (1) A compound in which a hydrogen atom is bonded to the 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane ring represented by the formula in the formula, using a fluorinating agent such as fluorine. It can also be produced by subjecting to a reaction.
本発明の３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体は、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 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative of the present invention can be used as a raw material for paints, functional polymers, pharmaceuticals, agricultural chemicals and other fine chemicals. it can.
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。なお、化学式中のＭｅはメチル基を示す。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the chemical formula, Me represents a methyl group.
実施例１
下記の反応工程式に従って、５−メタクリロイルオキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン−２，２−ジオンを製造した。
According to the following reaction process formula, 5-methacryloyloxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane-2,2-dione was produced.
１，３−シクロペンタジエン（5a）２２５ｇ、ビニルスルホン酸メチル（6a）１００ｇ、およびトルエン２０００ｇの混合液を、還流下で３時間反応させた。その後、反応混合液を減圧下で濃縮することにより、式（7a）で表されるビシクロ［２．２．１］ヘプタン−２−エン−５−スルホン酸メチルを１３０ｇ得た。 A mixed solution of 225 g of 1,3-cyclopentadiene (5a), 100 g of methyl vinylsulfonate (6a) and 2000 g of toluene was reacted for 3 hours under reflux. Thereafter, the reaction mixture was concentrated under reduced pressure to obtain 130 g of methyl bicyclo [2.2.1] heptane-2-ene-5-sulfonate represented by the formula (7a).
上記で得られた式（7a）で表される化合物１３０ｇと塩化メチレン２Ｌの溶液を０℃まで冷却し、ｍ−ＣＰＢＡ（ｍ−クロロ過安息香酸）２００ｇを発熱に注意しながらゆっくり投入した。原料の消失を確認した後、亜硫酸ナトリウム水溶液を加え、その後、炭酸水素ナトリウム水溶液で３回有機層を洗浄した。有機層を濃縮することにより、式（4a）で表される２，３−エポキシビシクロ［２．２．１］ヘプタン−５−スルホン酸メチルを１３３ｇ得た。 A solution of 130 g of the compound represented by the formula (7a) obtained above and 2 L of methylene chloride was cooled to 0 ° C., and 200 g of m-CPBA (m-chloroperbenzoic acid) was slowly added while paying attention to heat generation. After confirming disappearance of the raw materials, an aqueous sodium sulfite solution was added, and then the organic layer was washed three times with an aqueous sodium hydrogen carbonate solution. By concentrating the organic layer, 133 g of methyl 2,3-epoxybicyclo [2.2.1] heptane-5-sulfonate represented by the formula (4a) was obtained.
上記で得られた式（4a）で表される化合物１３３ｇを５Ｎ−水酸化ナトリウム水溶液４００ｍｌへ滴下して加え、室温で５時間撹拌し、その後、冷却下で５Ｎ−塩酸４００ｍｌで中和し、塩化メチレンで抽出し、有機層を濃縮後、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（2a）で表される５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン−２，２−ジオンを４６ｇ得た。 133 g of the compound represented by the formula (4a) obtained above was added dropwise to 400 ml of 5N aqueous sodium hydroxide solution, stirred at room temperature for 5 hours, then neutralized with 400 ml of 5N hydrochloric acid under cooling, After extracting with methylene chloride and concentrating the organic layer, the concentrate is separated and purified by silica gel column chromatography, whereby 5-hydroxy-3-oxa-2-thiatricyclo [4.2. 1.0 4,8 ] 46 g of nonane-2,2-dione was obtained.
上記で得られた式（2a）で表される化合物２７ｇ、トリエチルアミン１８ｇ、４−ジメチルアミノピリジン（ＤＭＡＰ）０．２ｇをテトラヒドロフランに溶解した溶液２００ｇを冷却し、温度１０℃以下を保持しつつ、メタクリル酸クロリド（3a）２０ｇを滴下した。反応混合液に水５０ｍｌを加え、炭酸水素ナトリウム水溶液及び水で順次洗浄した後、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５−メタクリロイルオキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン−２，２−ジオンを１３ｇ得た。
［式（1a）で表される５−メタクリロイルオキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン−２，２−ジオンのスペクトルデータ］
1Ｈ−ＮＭＲ（CDCl3） δ：6.10(1H), 5.63-5.64(1H), 4.75-4.80(m, 2H), 3.48-3.60(m, 2H), 2.62-2.63(m, 1H), 2.08-2.63(m, 3H), 1.94(s,3H), 1.78-1.81(m, 1H)
ＭＳ：258, 189
While cooling 200 g of a solution obtained by dissolving 27 g of the compound represented by the formula (2a) obtained above, 18 g of triethylamine, 0.2 g of 4-dimethylaminopyridine (DMAP) in tetrahydrofuran, and maintaining the temperature at 10 ° C. or lower, 20 g of methacrylic acid chloride (3a) was added dropwise. 50 ml of water was added to the reaction mixture, and the mixture was washed successively with an aqueous sodium hydrogen carbonate solution and water, the organic layer was concentrated, and the concentrate was separated and purified by silica gel column chromatography to obtain 5 represented by the formula (1a). -13 g of methacryloyloxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane-2,2-dione was obtained.
[Spectral data of 5-methacryloyloxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane-2,2-dione represented by the formula (1a)]
1 H-NMR (CDCl 3 ) δ: 6.10 (1H), 5.63-5.64 (1H), 4.75-4.80 (m, 2H), 3.48-3.60 (m, 2H), 2.62-2.63 (m, 1H), 2.08 -2.63 (m, 3H), 1.94 (s, 3H), 1.78-1.81 (m, 1H)
MS: 258, 189
実施例２
下記の反応工程式に従って、５−メタクリロイルオキシ−３，７−ジオキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン−２，２−ジオンを製造した。
5-Methacryloyloxy-3,7-dioxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane-2,2-dione was produced according to the following reaction scheme.
実施例１において、一段目の反応を以下の方法で行った以外は、実施例１と同様の条件で反応を行い、目的化合物１０ｇを得た。
フラン（5b）３００ｇ（４．４モル）とヨウ化亜鉛３０ｇの混合液を５℃まで冷却し、ビニルスルホン酸メチル（6a）１００ｇ（０．６８モル）を滴下して加えた。そのままの温度で２日間撹拌を続けた。その後、水１Ｌで有機層を２回洗浄し、過剰の原料を減圧下で留去することにより、式（7b）で表される７−オキサビシクロ［２．２．１］ヘプタン−２−エン−５−スルホン酸メチルを７０ｇ得た。
In Example 1, the reaction was carried out under the same conditions as in Example 1 except that the first step reaction was carried out by the following method, to obtain 10 g of the objective compound.
A liquid mixture of 300 g (4.4 mol) of furan (5b) and 30 g of zinc iodide was cooled to 5 ° C., and 100 g (0.68 mol) of methyl vinylsulfonate (6a) was added dropwise. Stirring was continued for 2 days at the same temperature. Thereafter, the organic layer was washed twice with 1 L of water, and excess raw material was distilled off under reduced pressure, whereby 7-oxabicyclo [2.2.1] heptan-2-ene represented by the formula (7b) was obtained. 70 g of methyl -5-sulfonate was obtained.
［式（1b）で表される５−メタクリロイルオキシ−３，７−ジオキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン−２，２−ジオンのスペクトルデータ］
元素分析（ＣＨＳ）：Calculated % C 46.15, H 4.65, S 12.32
Found % C 46.11, H 4.62, S 12.36
ＭＳ：260, 191
ＩＲ（KBr）：1170, 1358, 1720 cm-1
[Spectral data of 5-methacryloyloxy-3,7-dioxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane-2,2-dione represented by the formula (1b)]
Elemental analysis (CHS): Calculated% C 46.15, H 4.65, S 12.32
Found% C 46.11, H 4.62, S 12.36
MS: 260, 191
IR (KBr): 1170, 1358, 1720 cm -1
Claims (4)
で表される３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体。 Following formula (1)
A 3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by:
で表される５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体と、下記式（３）
で表される不飽和カルボン酸又はその反応性誘導体を反応させて、下記式（１）
で表される３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体を得る３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体の製造法。 Following formula (2)
A 5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by formula (3):
Is reacted with an unsaturated carboxylic acid represented by the following formula (1):
In represented by 3-oxa-2-Chiatorishikuro [4.2.1.0 4, 8] nonane derivatives of 3-oxa-2-Chiatorishikuro [4.2.1.0 4, 8] Production of nonane derivatives Law.
で表される５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体。 Following formula (2 ')
A 5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by:
で表される２，３−エポキシビシクロ［２．２．１］ヘプタン誘導体を環化反応に付して、下記式（２）
で表される５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体を得る５−ヒドロキシ−３−オキサ−２−チアトリシクロ［４．２．１．０4,8］ノナン誘導体の製造法。
Following formula (4)
A 2,3-epoxybicyclo [2.2.1] heptane derivative represented by the following formula (2)
5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] nonane derivative represented by the formula: 5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 4,8 ] Method for producing nonane derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005217631A JP4212576B2 (en) | 2005-07-27 | 2005-07-27 | 3-oxa-2-thiatricyclo [4.2.1.04,8] nonane derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005217631A JP4212576B2 (en) | 2005-07-27 | 2005-07-27 | 3-oxa-2-thiatricyclo [4.2.1.04,8] nonane derivative |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2007031355A true JP2007031355A (en) | 2007-02-08 |
| JP2007031355A5 JP2007031355A5 (en) | 2008-05-29 |
| JP4212576B2 JP4212576B2 (en) | 2009-01-21 |
Family
ID=37791028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005217631A Active JP4212576B2 (en) | 2005-07-27 | 2005-07-27 | 3-oxa-2-thiatricyclo [4.2.1.04,8] nonane derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4212576B2 (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010001913A1 (en) * | 2008-06-30 | 2010-01-07 | 株式会社クラレ | Acrylate derivative, haloester derivative, polymer compound and photoresist composition |
| WO2010026974A1 (en) * | 2008-09-02 | 2010-03-11 | 株式会社クラレ | Process for production of sultone derivative |
| US7767379B2 (en) | 2007-09-07 | 2010-08-03 | Tokyo Ohka Kogyo Co., Ltd. | Polymer compound, positive resist composition, and method of forming resist pattern |
| JP2010210796A (en) * | 2009-03-09 | 2010-09-24 | Tokyo Ohka Kogyo Co Ltd | Positive resist composition, resist pattern forming method, high molecular compound, and compound |
| KR101038907B1 (en) | 2008-08-22 | 2011-06-03 | 도오꾜오까고오교 가부시끼가이샤 | Positive resist composition, method of forming resist pattern, and polymeric compound |
| JP2011219404A (en) * | 2010-04-08 | 2011-11-04 | Kuraray Co Ltd | Method for producing alicyclic sulfonate |
| US8088553B2 (en) | 2008-04-24 | 2012-01-03 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern, and polymeric compound |
| US8192915B2 (en) | 2008-08-22 | 2012-06-05 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern, and polymeric compound |
| US8206891B2 (en) | 2008-10-07 | 2012-06-26 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| US8227170B2 (en) | 2009-01-14 | 2012-07-24 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, method of forming resist pattern, polymeric compound, and compound |
| US8232041B2 (en) | 2009-02-16 | 2012-07-31 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern, and polymeric compound |
| US8236477B2 (en) | 2008-12-04 | 2012-08-07 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| US8257904B2 (en) | 2008-11-12 | 2012-09-04 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and method of forming resist pattern |
| US8268529B2 (en) | 2009-01-26 | 2012-09-18 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern using the same, and polymeric compound |
| US8283105B2 (en) | 2009-03-11 | 2012-10-09 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| US8323869B2 (en) | 2009-03-10 | 2012-12-04 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| US8329378B2 (en) | 2009-03-10 | 2012-12-11 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern, and polymeric compound |
| US8349534B2 (en) | 2009-03-09 | 2013-01-08 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| US8367296B2 (en) | 2008-09-29 | 2013-02-05 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern, and polymeric compound |
| US9023580B2 (en) | 2011-11-24 | 2015-05-05 | Tokyo Ohka Kogyo Co., Ltd. | Method of forming polymeric compound, resist composition and method of forming resist pattern |
| US9152042B2 (en) | 2010-09-08 | 2015-10-06 | Kuraray Co., Ltd. | Acrylic ester derivative, high-molecular compound and photoresist composition |
| US9170487B2 (en) | 2012-03-28 | 2015-10-27 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, method of forming resist pattern, and polymeric compound |
| CN107207457A (en) * | 2015-03-11 | 2017-09-26 | 株式会社大赛璐 | Cycloaliphatic epoxy and its manufacture method and the ring [4.2.1.0 of 2 hydroxyl, 4 oxa-, 5 thia three3,7] nonane derivatives manufacture method |
-
2005
- 2005-07-27 JP JP2005217631A patent/JP4212576B2/en active Active
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8105749B2 (en) | 2007-09-07 | 2012-01-31 | Tokyo Ohka Kogyo Co., Ltd. | Polymer compound, positive resist composition, and method of forming resist pattern |
| US7767379B2 (en) | 2007-09-07 | 2010-08-03 | Tokyo Ohka Kogyo Co., Ltd. | Polymer compound, positive resist composition, and method of forming resist pattern |
| US8088553B2 (en) | 2008-04-24 | 2012-01-03 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern, and polymeric compound |
| US8486606B2 (en) | 2008-06-30 | 2013-07-16 | Kuraray Co., Ltd. | Acrylate derivative, haloester derivative, polymer compound and photoresist composition |
| WO2010001913A1 (en) * | 2008-06-30 | 2010-01-07 | 株式会社クラレ | Acrylate derivative, haloester derivative, polymer compound and photoresist composition |
| US8192915B2 (en) | 2008-08-22 | 2012-06-05 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern, and polymeric compound |
| KR101038907B1 (en) | 2008-08-22 | 2011-06-03 | 도오꾜오까고오교 가부시끼가이샤 | Positive resist composition, method of forming resist pattern, and polymeric compound |
| US8182976B2 (en) | 2008-08-22 | 2012-05-22 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern, and polymeric compound |
| US8367849B2 (en) | 2008-09-02 | 2013-02-05 | Kuraray Co., Ltd. | Production method for sultone derivatives |
| WO2010026974A1 (en) * | 2008-09-02 | 2010-03-11 | 株式会社クラレ | Process for production of sultone derivative |
| JP2010083873A (en) * | 2008-09-02 | 2010-04-15 | Kuraray Co Ltd | Method for producing sultone derivative |
| US8367296B2 (en) | 2008-09-29 | 2013-02-05 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern, and polymeric compound |
| US8206891B2 (en) | 2008-10-07 | 2012-06-26 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| US8257904B2 (en) | 2008-11-12 | 2012-09-04 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and method of forming resist pattern |
| US8236477B2 (en) | 2008-12-04 | 2012-08-07 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| US8487056B2 (en) | 2008-12-04 | 2013-07-16 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| US8227170B2 (en) | 2009-01-14 | 2012-07-24 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, method of forming resist pattern, polymeric compound, and compound |
| US8268529B2 (en) | 2009-01-26 | 2012-09-18 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern using the same, and polymeric compound |
| KR101534356B1 (en) * | 2009-01-26 | 2015-07-06 | 도오꾜오까고오교 가부시끼가이샤 | Positive resist composition, method of forming resist pattern using the same, and polymeric compound |
| US8232041B2 (en) | 2009-02-16 | 2012-07-31 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern, and polymeric compound |
| JP2010210796A (en) * | 2009-03-09 | 2010-09-24 | Tokyo Ohka Kogyo Co Ltd | Positive resist composition, resist pattern forming method, high molecular compound, and compound |
| US8349534B2 (en) | 2009-03-09 | 2013-01-08 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| US8329378B2 (en) | 2009-03-10 | 2012-12-11 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition, method of forming resist pattern, and polymeric compound |
| US8323869B2 (en) | 2009-03-10 | 2012-12-04 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| US8283105B2 (en) | 2009-03-11 | 2012-10-09 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
| JP2011219404A (en) * | 2010-04-08 | 2011-11-04 | Kuraray Co Ltd | Method for producing alicyclic sulfonate |
| US9152042B2 (en) | 2010-09-08 | 2015-10-06 | Kuraray Co., Ltd. | Acrylic ester derivative, high-molecular compound and photoresist composition |
| US9023580B2 (en) | 2011-11-24 | 2015-05-05 | Tokyo Ohka Kogyo Co., Ltd. | Method of forming polymeric compound, resist composition and method of forming resist pattern |
| US9170487B2 (en) | 2012-03-28 | 2015-10-27 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, method of forming resist pattern, and polymeric compound |
| CN107207457A (en) * | 2015-03-11 | 2017-09-26 | 株式会社大赛璐 | Cycloaliphatic epoxy and its manufacture method and the ring [4.2.1.0 of 2 hydroxyl, 4 oxa-, 5 thia three3,7] nonane derivatives manufacture method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4212576B2 (en) | 2009-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4212576B2 (en) | 3-oxa-2-thiatricyclo [4.2.1.04,8] nonane derivative | |
| JP4740951B2 (en) | Polycyclic ester containing cyano group and lactone skeleton | |
| JP4781086B2 (en) | Polymer compound having alicyclic skeleton | |
| Hashimoto et al. | Total synthesis of the meso-triterpene polyether teurilene | |
| JP2003073321A (en) | Method for producing vinyl ether compound | |
| JP4740677B2 (en) | 3-oxa-7-oxa (or thia) tricyclo [4.2.1.04,8] nonan-2-one derivatives | |
| JP4718922B2 (en) | 3-Oxa-7-thiatricyclo [4.2.1.04,8] nonane derivative | |
| JP4748860B2 (en) | 2-Oxatricyclo [4.2.1.04,8] nonan-3-one derivative and process for producing the same | |
| EP1302469B1 (en) | Process for producing hydroxylactone | |
| JP4796794B2 (en) | Polycyclic ester containing lactone skeleton | |
| JP4832019B2 (en) | Polycyclic ester containing cyclic carbonate skeleton | |
| CN109232637B (en) | Preparation method of entecavir intermediate | |
| JP4993263B2 (en) | A method for producing 2- (meth) acryloyloxy-6-cyano-5-oxo-4-oxatricyclo [4.2.1.03,7] nonane. | |
| JP4953521B2 (en) | (Meth) acrylic acid ester having lactone skeleton | |
| WO2016141563A1 (en) | Alicyclic epoxide and preparation method therefor, and method for preparing 2-hydroxyl-4-oxa-5-thia tricycle[4.2.1.03,7] nonane derivative | |
| JP4748848B2 (en) | Process for producing 5-hydroxy-2,6-norbornanecarbolactone and its (meth) acrylic acid ester | |
| JP4919508B2 (en) | Photoresist monomer, polymer compound and photoresist composition | |
| Nahmany et al. | Studies on the synthesis of DNA-damaging part of leinamycin: regioselectivity in Ti (OiPr) 4 mediated opening of hydroxy epoxides with carboxylic acids | |
| JP5572127B2 (en) | Polymer compound having alicyclic skeleton | |
| US6509481B2 (en) | Tetrahydrofuran compounds having alicyclic structure | |
| EP0478803B1 (en) | Process for producing (S)-gamma-acyloxy-methyl-alpha-beta-butenolide | |
| JP2002226474A (en) | Method for manufacturing (meth)acrylic ester derivative containing lactone ring | |
| JP2007031354A (en) | Polycyclic ester | |
| JP2019513808A (en) | Preparation method of bimatoprost | |
| JPS63287780A (en) | Production of 3,7-dioxabicyclo(3.3.0)octane derivative |
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 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080414 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20080414 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20080509 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080520 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20080714 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20080717 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20080815 |
|
| 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: 20081028 |
|
| 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: 20081028 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111107 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4212576 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121107 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121107 Year of fee payment: 4 |
|
| 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: 20121107 Year of fee payment: 4 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121107 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131107 Year of fee payment: 5 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |