JP2002205988A - Method for producing 5-hydroxy-3- oxatricyclo[4.2.1.04,8]nonan-2-one derivative - Google Patents
Method for producing 5-hydroxy-3- oxatricyclo[4.2.1.04,8]nonan-2-one derivativeInfo
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- JP2002205988A JP2002205988A JP2001002292A JP2001002292A JP2002205988A JP 2002205988 A JP2002205988 A JP 2002205988A JP 2001002292 A JP2001002292 A JP 2001002292A JP 2001002292 A JP2001002292 A JP 2001002292A JP 2002205988 A JP2002205988 A JP 2002205988A
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- acid
- oxatricyclo
- nonan
- hydroxy
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、感光性樹脂などの
機能性高分子の原料や、医薬、農薬その他の精密化学品
の原料などとして有用な５−ヒドロキシ−３−オキサト
リシクロ［４．２．１．０4,8］ノナン−２−オン誘導
体の製造法に関する。TECHNICAL FIELD The present invention relates to 5-hydroxy-3-oxatricyclo [4. useful as a raw material for functional polymers such as photosensitive resins and a raw material for pharmaceuticals, agricultural chemicals and other fine chemicals. 2.1.0 4,8 ] nonan-2-one derivative.
【０００２】[0002]
【従来の技術】５−ヒドロキシ−３−オキサトリシクロ
［４．２．１．０4,8］ノナン−２−オンの製造法とし
て、ジャーナル オブ モレキュラー キャタリシス
Ａ：ケミカル（Journal of Molecular Catalysis A: Ch
emical） 142(1999) 333-338には、メチルトリオキソレ
ニウムの存在下、５−ノルボルネン−２−カルボン酸を
過酸化水素と反応させる方法が提案されている。しか
し、この方法は高価で且つ毒性を有するレニウムを用い
るので工業的に有利な方法とは言えない。また、この方
法は機器が腐蝕しやすいという問題もある。2. Description of the Related Art A method for producing 5-hydroxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one is disclosed in Journal of Molecular Catalysis.
A: Chemical (Journal of Molecular Catalysis A: Ch
emical) 142 (1999) 333-338 proposes a method of reacting 5-norbornene-2-carboxylic acid with hydrogen peroxide in the presence of methyltrioxorhenium. However, this method is not industrially advantageous because it uses expensive and toxic rhenium. In addition, this method also has a problem that the equipment is easily corroded.
【０００３】[0003]
【発明が解決しようとする課題】従って、本発明の目的
は、５−ヒドロキシ−３−オキサトリシクロ［４．２．
１．０4,8］ノナン−２−オン誘導体を高い収率で効率
よく製造できる工業的に有利な製造法を提供することに
ある。本発明の他の目的は、コストが安く、しかも機器
の腐食を低減できる５−ヒドロキシ−３−オキサトリシ
クロ［４．２．１．０4,8］ノナン−２−オン誘導体の
製造法を提供することにある。Accordingly, an object of the present invention is to provide 5-hydroxy-3-oxatricyclo [4.2.
It is an object of the present invention to provide an industrially advantageous production method capable of efficiently producing a 1.0 4,8 ] nonan-2-one derivative in a high yield. Another object of the present invention is to provide a method for producing a 5-hydroxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one derivative which is inexpensive and can reduce equipment corrosion. To provide.
【０００４】[0004]
【課題を解決するための手段】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、５−ノルボルネン
−２−カルボン酸類又はそのエステルを特定の過酸と反
応させると、対応する５−ヒドロキシ−３−オキサトリ
シクロ［４．２．１．０4,8］ノナン−２−オン誘導体
が高い収率で効率よく製造できることを見出し、本発明
を完成させた。Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above-mentioned object. The present inventors have found that a 5-hydroxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one derivative can be efficiently produced in a high yield, and have completed the present invention.
【０００５】すなわち、本発明は、下記式（１）That is, the present invention provides the following formula (1)
【化３】 （式中、Ｒは水素原子又はメチル基を示す）で表される
５−ノルボルネン−２−カルボン酸類又はそのエステル
を、炭素数２〜５の脂肪族過カルボン酸又はベンゼン環
に置換基を有する過安息香酸と反応させて、下記式
（２）Embedded image (Wherein, R represents a hydrogen atom or a methyl group), a 5-norbornene-2-carboxylic acid or an ester thereof having a substituent on an aliphatic percarboxylic acid having 2 to 5 carbon atoms or a benzene ring. By reacting with perbenzoic acid, the following formula (2)
【化４】 （式中、Ｒは前記に同じ）で表される５−ヒドロキシ−
３−オキサトリシクロ［４．２．１．０4,8］ノナン−
２−オン誘導体を得ることを特徴とする５−ヒドロキシ
−３−オキサトリシクロ［４．２．１．０4,8］ノナン
−２−オン誘導体の製造法を提供する。Embedded image Wherein R is the same as defined above.
3-oxatricyclo [4.2.1.0 4,8 ] nonane-
There is provided a method for producing a 5-hydroxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one derivative, which comprises obtaining a 2-one derivative.
【０００６】[0006]
【発明の実施の形態】［反応原料］式（１）で表される
５−ノルボルネン−２−カルボン酸類には、５−ノルボ
ルネン−２−カルボン酸及び２−メチル−５−ノルボル
ネン−２−カルボン酸が含まれる。これらの化合物は、
シクロペンタジエンとアクリル酸又はメタクリル酸との
ディールスアルダー反応により得ることができる。DETAILED DESCRIPTION OF THE INVENTION [Reaction Raw Materials] The 5-norbornene-2-carboxylic acids represented by the formula (1) include 5-norbornene-2-carboxylic acid and 2-methyl-5-norbornene-2-carboxylic acid. Contains acids. These compounds are
It can be obtained by a Diels-Alder reaction between cyclopentadiene and acrylic acid or methacrylic acid.
【０００７】前記５−ノルボルネン−２−カルボン酸類
のエステルとしては、例えば、メチルエステル、エチル
エステル、プロピルエステル、イソプロピルエステル、
ブチルエステル、イソブチルエステル、ｓ−ブチルエス
テル、ｔ−ブチルエステル等のアルキルエステル（例え
ば、Ｃ1-4アルキルエステル）；シクロヘキシルエステ
ル等のシクロアルキルエステル；フェニルエステル等の
アリールエステル；ベンジルエステル等のアラルキルエ
ステルなどが挙げられるが、これらに限定されるもので
はない。The above-mentioned esters of 5-norbornene-2-carboxylic acid include, for example, methyl ester, ethyl ester, propyl ester, isopropyl ester,
Alkyl esters such as butyl ester, isobutyl ester, s-butyl ester and t-butyl ester (for example, C 1-4 alkyl ester); cycloalkyl esters such as cyclohexyl ester; aryl esters such as phenyl ester; aralkyl such as benzyl ester. Examples include, but are not limited to, esters.
【０００８】［過酸］本発明では、反応剤として炭素数
２〜５の脂肪族過カルボン酸又はベンゼン環に置換基を
有する過安息香酸を用いる。炭素数２〜５の脂肪族過カ
ルボン酸として、例えば、過酢酸、トリフルオロ過酢
酸、ペルオキシプロピオン酸、ペルオキシブタン酸、ペ
ルオキシペンタン酸などが挙げられる。また、ベンゼン
環に置換基を有する過安息香酸としては、例えば、ｍ−
クロロ過安息香酸、モノペルオキシフタル酸、３，５−
ジニトロ過安息香酸などが挙げられる。これらの中で
も、過酢酸やトリフルオロ過酢酸等の炭素数２の脂肪族
過カルボン酸が好ましい。[Peracid] In the present invention, an aliphatic percarboxylic acid having 2 to 5 carbon atoms or a perbenzoic acid having a substituent on a benzene ring is used as a reactant. Examples of the aliphatic percarboxylic acid having 2 to 5 carbon atoms include peracetic acid, trifluoroperacetic acid, peroxypropionic acid, peroxybutanoic acid, and peroxypentanoic acid. Examples of perbenzoic acid having a substituent on the benzene ring include, for example, m-
Chloroperbenzoic acid, monoperoxyphthalic acid, 3,5-
And dinitroperbenzoic acid. Among them, aliphatic percarboxylic acids having 2 carbon atoms such as peracetic acid and trifluoroperacetic acid are preferable.
【０００９】過酢酸等の炭素数２〜５の脂肪族過カルボ
ン酸は、取扱性の点から、通常、適当な溶媒、例えば酢
酸エチル等のエステル、酢酸等のカルボン酸などにより
希釈して用いられる。過酢酸等の炭素数２〜５の脂肪族
過カルボン酸は平衡過酸（平衡過酢酸等）であってもよ
い。すなわち、酢酸等の炭素数２〜５の脂肪族カルボン
酸と過酸化水素とを組み合わせて用い、系内で過カルボ
ン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。The aliphatic percarboxylic acid having 2 to 5 carbon atoms such as peracetic acid is usually used after being diluted with a suitable solvent, for example, an ester such as ethyl acetate, a carboxylic acid such as acetic acid, etc. from the viewpoint of handling. Can be The aliphatic percarboxylic acid having 2 to 5 carbon atoms such as peracetic acid may be an equilibrium peracid (equilibrium peracetic acid or the like). That is, an aliphatic carboxylic acid having 2 to 5 carbon atoms such as acetic acid and hydrogen peroxide may be used in combination to generate a percarboxylic acid 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.
【００１０】上記過酢酸等の過酸の使用量は、反応に用
いる５−ノルボルネン−２−カルボン酸類又はそのエス
テル１モルに対して、例えば０．８〜２モル程度、好ま
しくは０．９〜１．５モル程度、さらに好ましくは０．
９５〜１．２モル程度である。The amount of the peracid such as peracetic acid used is, for example, about 0.8 to 2 mol, preferably 0.9 to 2 mol per mol of 5-norbornene-2-carboxylic acid or ester thereof used in the reaction. About 1.5 mol, more preferably 0.1 mol.
It is about 95 to 1.2 mol.
【００１１】［反応］反応は、通常、溶媒の存在下で行
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；水などが挙げられる。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。[Reaction] The reaction is usually carried out in the presence 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; chloroform, dichloromethane, 1,
Halogenated hydrocarbons such as 2-dichloroethane; aromatic hydrocarbons such as benzene; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane; N, N-dimethylformamide, N, N- Amides such as dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; linear or cyclic ethers such as ethyl ether and tetrahydrofuran; and water. These solvents are used alone or in combination of two or more.
【００１２】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１０〜７０℃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。The reaction temperature can be appropriately selected in consideration of the reaction rate and the reaction selectivity.
Preferably it is about 10 to 70 ° C. The reaction is batch type,
It may be performed by any method such as a semi-batch type and a continuous type.
【００１３】上記反応により、式（２）で表される対応
する５−ヒドロキシ−３−オキサトリシクロ［４．２．
１．０4,8］ノナン−２−オン誘導体が生成する。すな
わち、５−ノルボルネン−２−カルボン酸又はそのエス
テルからは５−ヒドロキシ−３−オキサトリシクロ
［４．２．１．０4,8］ノナン−２−オンが生成し、２
−メチル−５−ノルボルネン−２−カルボン酸又はその
エステルからは５−ヒドロキシ−１−メチル−３−オキ
サトリシクロ［４．２．１．０4,8］ノナン−２−オン
が生成する。この反応では、まず５−ノルボルネン−２
−カルボン酸類又はそのエステルの二重結合のエポキシ
化が起こり、引き続き、エポキシ環の開環を伴う分子内
環化反応が進行して目的の５−ヒドロキシ−３−オキサ
トリシクロ［４．２．１．０4,8］ノナン−２−オン誘
導体が生成するものと推測される。By the above reaction, the corresponding 5-hydroxy-3-oxatricyclo [4.2.
1.0 4,8 ] nonan-2-one derivative is produced. That is, 5-hydroxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one is produced from 5-norbornene-2-carboxylic acid or its ester,
5-Hydroxy-1-methyl-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one is produced from -methyl-5-norbornene-2-carboxylic acid or an ester thereof. In this reaction, first, 5-norbornene-2
-The epoxidation of the double bond of the carboxylic acid or its ester occurs, followed by the intramolecular cyclization reaction involving the opening of the epoxy ring, and the desired 5-hydroxy-3-oxatricyclo [4.2. 1.0 4,8 ] nonan-2-one derivative is presumed to be produced.
【００１４】なお、５−ノルボルネン−２−カルボン酸
類のエステルを基質として用いた場合には、エステルに
対応するアルコールが副生する。反応で生成した５−ヒ
ドロキシ−３−オキサトリシクロ［４．２．１．
０4,8］ノナン−２−オン誘導体は、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 an ester of 5-norbornene-2-carboxylic acid is used as a substrate, an alcohol corresponding to the ester is by-produced. 5-Hydroxy-3-oxatricyclo [4.2.1.
The [ 04,8 ] nonan-2-one derivative can be separated and purified, for example, by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.
【００１５】こうして得られる５−ヒドロキシ−３−オ
キサトリシクロ［４．２．１．０4, 8］ノナン−２−オ
ン誘導体は感光性樹脂等の機能性材料の原料や、医薬、
農薬等の精密化学品の原料などとして使用できる。The thus obtained 5-hydroxy-3-oxa-tricyclo [4.2.1.0 4, 8] nonan-2-one derivatives materials and functional materials such as photosensitive resin, pharmaceutical,
It can be used as a raw material for fine chemicals such as pesticides.
【００１６】[0016]
【発明の効果】本発明の方法によれば、５−ヒドロキシ
−３−オキサトリシクロ［４．２．１．０4,8］ノナン
−２−オン誘導体を高い収率で効率よく製造できる。ま
た、過酢酸等の炭素数２〜５の脂肪族過カルボン酸又は
ｍ−クロロ過安息香酸等のベンゼン環に置換基を有する
過安息香酸を用いるので、製造コストが安く、しかも装
置や機器に対する腐食性が比較的低い。従って、本発明
の方法は５−ヒドロキシ−３−オキサトリシクロ［４．
２．１．０4,8］ノナン−２−オン誘導体の工業的な製
造法として極めて有用である。According to the method of the present invention, a 5-hydroxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one derivative can be efficiently produced in a high yield. Further, since a perbenzoic acid having a substituent on a benzene ring such as an aliphatic percarboxylic acid having 2 to 5 carbon atoms such as peracetic acid or m-chloroperbenzoic acid is used, the production cost is low, and furthermore, the apparatus and equipment are used. Relatively low corrosiveness. Therefore, the method of the present invention provides 5-hydroxy-3-oxatricyclo [4.
2.1.0 4,8 ] nonan-2-one derivative is extremely useful as an industrial production method.
【００１７】[0017]
【実施例】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。EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.
【００１８】実施例１ 滴下ロート、凝縮器及び攪拌機を備えたフラスコに５−
ノルボルネン−２−カルボン酸２０ｇ（０．１４５モ
ル）、酢酸エチル２０ｇを入れ、攪拌しながら５０℃ま
で昇温した。内温を５０〜６０℃に制御しながら、滴下
ロートから３０重量％過酢酸−酢酸エチル溶液４１ｇ
（０．１６モル）を３０分かけて滴下した。その後、５
０℃で５時間攪拌を続けた。反応液をガスクロマトグラ
フィーで分析したところ、５−ヒドロキシ−３−オキサ
トリシクロ［４．２．１．０4,8］ノナン−２−オンが
１７．９ｇ（０．１１６モル；収率８０％）生成してい
た。Example 1 A 5-neck flask was equipped with a dropping funnel, a condenser and a stirrer.
20 g (0.145 mol) of norbornene-2-carboxylic acid and 20 g of ethyl acetate were added, and the temperature was raised to 50 ° C. while stirring. While controlling the internal temperature to 50 to 60 ° C., 41 g of a 30% by weight peracetic acid-ethyl acetate solution from the dropping funnel.
(0.16 mol) was added dropwise over 30 minutes. Then 5
Stirring was continued at 0 ° C. for 5 hours. When the reaction solution was analyzed by gas chromatography, 17.9 g (0.116 mol; yield: 80) of 5-hydroxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one was obtained. %).
【００１９】実施例２ 滴下ロート、凝縮器及び攪拌機を備えたフラスコに５−
ノルボルネン−２−カルボン酸２０ｇ（０．１４５モ
ル）、酢酸８６ｇ、硫酸０．７ｇを入れ、攪拌しながら
５０℃まで昇温した。内温を５０〜６０℃に制御しなが
ら、滴下ロートから３０重量％過酸化水素水１７．３ｇ
（０．１５２モル）を２時間かけて滴下した。その後、
５０℃で５時間攪拌を続けた。反応液をガスクロマトグ
ラフィーで分析したところ、５−ヒドロキシ−３−オキ
サトリシクロ［４．２．１．０4,8］ノナン−２−オン
が１５．０ｇ（０．０９７モル；収率６７％）生成して
いた。Example 2 A 5-neck flask was equipped with a dropping funnel, a condenser and a stirrer.
20 g (0.145 mol) of norbornene-2-carboxylic acid, 86 g of acetic acid and 0.7 g of sulfuric acid were added, and the temperature was raised to 50 ° C. while stirring. While controlling the internal temperature to 50 to 60 ° C., 17.3 g of a 30% by weight aqueous hydrogen peroxide solution was dropped from the dropping funnel.
(0.152 mol) was added dropwise over 2 hours. afterwards,
Stirring was continued at 50 ° C. for 5 hours. When the reaction solution was analyzed by gas chromatography, 15.0 g (0.097 mol; yield: 67) of 5-hydroxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one was obtained. %).
Claims (1)
５−ノルボルネン−２−カルボン酸類又はそのエステル
を、炭素数２〜５の脂肪族過カルボン酸又はベンゼン環
に置換基を有する過安息香酸と反応させて、下記式
（２） 【化２】 （式中、Ｒは前記に同じ）で表される５−ヒドロキシ−
３−オキサトリシクロ［４．２．１．０4,8］ノナン−
２−オン誘導体を得ることを特徴とする５−ヒドロキシ
−３−オキサトリシクロ［４．２．１．０4,8］ノナン
−２−オン誘導体の製造法。[Claim 1] The following formula (1) (Wherein, R represents a hydrogen atom or a methyl group), a 5-norbornene-2-carboxylic acid or an ester thereof having a substituent on an aliphatic percarboxylic acid having 2 to 5 carbon atoms or a benzene ring. By reacting with perbenzoic acid, the following formula (2) Wherein R is the same as defined above.
3-oxatricyclo [4.2.1.0 4,8 ] nonane-
A method for producing a 5-hydroxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one derivative, which comprises obtaining a 2-one derivative.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001002292A JP2002205988A (en) | 2001-01-10 | 2001-01-10 | Method for producing 5-hydroxy-3- oxatricyclo[4.2.1.04,8]nonan-2-one derivative |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001002292A JP2002205988A (en) | 2001-01-10 | 2001-01-10 | Method for producing 5-hydroxy-3- oxatricyclo[4.2.1.04,8]nonan-2-one derivative |
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| Publication Number | Publication Date |
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| JP2002205988A true JP2002205988A (en) | 2002-07-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001002292A Pending JP2002205988A (en) | 2001-01-10 | 2001-01-10 | Method for producing 5-hydroxy-3- oxatricyclo[4.2.1.04,8]nonan-2-one derivative |
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| JP (1) | JP2002205988A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4828603A (en) * | 1988-03-21 | 1989-05-09 | E. I. Du Pont De Nemours And Company | Herbicidal oxatricyclo-nonane ethers |
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2001
- 2001-01-10 JP JP2001002292A patent/JP2002205988A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4828603A (en) * | 1988-03-21 | 1989-05-09 | E. I. Du Pont De Nemours And Company | Herbicidal oxatricyclo-nonane ethers |
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