JP2002193883A - Method for producing 2-alkyl-2-adamantyl(meth)acrylates - Google Patents
Method for producing 2-alkyl-2-adamantyl(meth)acrylatesInfo
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- JP2002193883A JP2002193883A JP2000389631A JP2000389631A JP2002193883A JP 2002193883 A JP2002193883 A JP 2002193883A JP 2000389631 A JP2000389631 A JP 2000389631A JP 2000389631 A JP2000389631 A JP 2000389631A JP 2002193883 A JP2002193883 A JP 2002193883A
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- alkyl
- meth
- adamantyl
- acrylates
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は２−アルキル−２−
アダマンチル（メタ）アクリレート類の製造法に関す
る。２−アルキル−２−アダマンチル（メタ）アクリレ
ート類はレジスト、インキ用レジン、塗料、接着剤、粘
着剤などの原料として有用である。TECHNICAL FIELD The present invention relates to 2-alkyl-2-alkyl-2-alkyl-2-alkyl-2-alkyl-2-alkyl-2-alkyl-2-alkyl-2- even
The present invention relates to a method for producing adamantyl (meth) acrylates. 2-Alkyl-2-adamantyl (meth) acrylates are useful as raw materials for resists, resins for inks, paints, adhesives, and adhesives.
【０００２】[0002]
【従来の技術】２−アルキル−２−アダマンチル（メ
タ）アクリレート類の製造法として、特開平１０−１８
２５５２号公報には、２−アダマンタノンと（メタ）ア
クリル酸ハライドとをグリニヤール試薬等の有機金属化
合物の存在下で反応させる方法が開示されている。ま
た、特開２０００−２２９９１１号公報には、特定の製
造法により得られた（メタ）アクリル酸クロリドと２−
アルキル−２−アダマンタノール類とを反応させて２−
アルキル−２−アダマンチル（メタ）アクリレート類を
得る方法が開示されている。しかしながら、これらの方
法は収率や工程の簡略さ等の点で必ずしも工業的方法と
して十分満足できるものではない。2. Description of the Related Art JP-A-10-18 discloses a method for producing 2-alkyl-2-adamantyl (meth) acrylates.
No. 2552 discloses a method of reacting 2-adamantanone with a (meth) acrylic halide in the presence of an organometallic compound such as a Grignard reagent. Japanese Patent Application Laid-Open No. 2000-229911 discloses that (meth) acrylic acid chloride obtained by a specific production method
Reaction with alkyl-2-adamantanols to give 2-
A method for obtaining alkyl-2-adamantyl (meth) acrylates is disclosed. However, these methods are not always satisfactory as industrial methods in terms of yield, simplification of steps, and the like.
【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、２−アルキル−２−アダマンチル（メタ）アクリレ
ート類を簡略化された工程で、しかも高い収率で、工業
的に効率よく製造できる方法を提供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to produce 2-alkyl-2-adamantyl (meth) acrylates in a simplified process, at a high yield, and industrially efficiently. It is to provide a method.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意検討の結果、２−アダマンタノン
類を有機金属化合物と反応させて対応する２−アルキル
−２−アダマンタノール類を生成させ、次いでこの生成
した２−アルキル−２−アダマンタノール類を単離する
ことなく（メタ）アクリル酸ハライドと反応させると、
対応する２−アルキル−２−アダマンチル（メタ）アク
リレート類を簡易に且つ収率よく得ることができること
を見出し、本発明を完成した。Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, reacted 2-adamantanones with an organometallic compound to form a corresponding 2-alkyl-2-adamantanol. And then reacting the resulting 2-alkyl-2-adamantanols without isolation with a (meth) acrylic halide,
The inventors have found that the corresponding 2-alkyl-2-adamantyl (meth) acrylates can be obtained easily and in good yield, and have completed the present invention.
【０００５】すなわち、本発明は、（Ａ）下記式（１）That is, the present invention provides (A) the following formula (1)
【化４】 （アダマンタン環は置換基を有していてもよい）で表さ
れる２−アダマンタノン類を、下記式（２） Ｒ1−Ｍ （２） ［式中、Ｒ1はアルキル基を示す。Ｍは配位子を有して
もよい金属原子、または下記式（３） −ＭｇＹ （３） （式中、Ｙはハロゲン原子を示す）で表される基を示
す］で表される有機金属化合物と反応させて、下記式
（４）Embedded image (The adamantane ring may have a substituent.) A 2-adamantanone represented by the following formula (2) R 1 -M (2) wherein R 1 represents an alkyl group. M represents a metal atom which may have a ligand, or an organic metal represented by the following formula (3) -MgY (3) (wherein, Y represents a halogen atom). After reacting with the compound, the following formula (4)
【化５】 （式中、Ｒ1は前記に同じ。アダマンタン環は置換基を
有していてもよい）で表される２−アルキル−２−アダ
マンタノール類を生成させる工程、及び（Ｂ）前記工程
で生成した２−アルキル−２−アダマンタノール類を単
離することなく（メタ）アクリル酸ハライドと反応させ
て、下記式（５）Embedded image (Wherein, R 1 is the same as described above; the adamantane ring may have a substituent); and (B) a step of forming the 2-alkyl-2-adamantanol The isolated 2-alkyl-2-adamantanols were reacted with (meth) acrylic acid halide without isolation to obtain the following formula (5)
【化６】 （式中、Ｒ2は水素原子又はメチル基を示す。Ｒ1は前記
に同じ）で表される２−アルキル−２−アダマンチル
（メタ）アクリレート類を生成させる工程を含む２−ア
ルキル−２−アダマンチル（メタ）アクリレート類の製
造法を提供する。この製造法において、工程（Ｂ）の反
応溶媒として、例えば少なくとも芳香族炭化水素を含む
溶媒などを使用できる。Embedded image (Wherein, R 2 represents a hydrogen atom or a methyl group; R 1 is the same as described above), and the method comprises the step of producing 2-alkyl-2-adamantyl (meth) acrylates Provided is a method for producing adamantyl (meth) acrylates. In this production method, as the reaction solvent in the step (B), for example, a solvent containing at least an aromatic hydrocarbon can be used.
【０００６】[0006]
【発明の実施の形態】［工程（Ａ）］本発明の製造法に
おいて、工程（Ａ）では、前記式（１）で表される２−
アダマンタノン類を、前記式（２）で表される有機金属
化合物と反応させて、前記式（４）で表される２−アル
キル−２−アダマンタノール類を生成させる。式（１）
で表される２−アダマンタノン類のアダマンタン環は置
換基を有していてもよい。このような置換基として、例
えば、ハロゲン原子（臭素、塩素、フッ素原子など）、
アルキル基（メチル、エチル、ブチル、ｔ−ブチル基な
どのＣ 1-4アルキル基など）、保護基で保護されたヒド
ロキシル基、保護基で保護されたアミノ基、保護基で保
護されたカルボキシル基などが挙げられる。前記保護基
としては有機合成の分野で通常用いられる保護基が例示
される。BEST MODE FOR CARRYING OUT THE INVENTION [Step (A)]
Here, in the step (A), 2-
The adamantanones are replaced with an organic metal represented by the formula (2).
Reacting with a compound to form a 2-alkane represented by the formula (4).
Produces kill-2-adamantanols. Equation (1)
The adamantane ring of 2-adamantanones represented by
It may have a substituent. Examples of such substituents include
For example, halogen atoms (bromine, chlorine, fluorine atoms, etc.),
Alkyl groups (e.g., methyl, ethyl, butyl, t-butyl groups)
Which C 1-4An alkyl group, etc.),
Loxyl group, amino group protected by a protecting group, protected by a protecting group
Protected carboxyl groups. The protecting group
Examples are protecting groups commonly used in the field of organic synthesis.
Is done.
【０００７】前記式（２）で表される有機金属化合物に
おいて、Ｍにおける金属原子としては、例えば、リチウ
ムなどのアルカリ金属、セリウム、チタン、銅などの還
移金属原子などが挙げられる。前記金属原子は配位子を
有していてもよい。前記配位子としては、塩素原子など
のハロゲン原子、イソプロポキシ基などのアルコキシ
基、ジエチルアミノ基などのジアルキルアミノ基、シア
ノ基、アルキル基、リチウム原子などのアルカリ金属原
子などが挙げられる。In the organometallic compound represented by the formula (2), examples of the metal atom in M include an alkali metal such as lithium and a transition metal atom such as cerium, titanium and copper. The metal atom may have a ligand. Examples of the ligand include a halogen atom such as a chlorine atom, an alkoxy group such as an isopropoxy group, a dialkylamino group such as a diethylamino group, a cyano group, an alkyl group, and an alkali metal atom such as a lithium atom.
【０００８】Ｒ1はアルキル基を示し、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−ブチル基などのＣ1-6アルキル
基などが挙げられる。前記式（３）において、Ｙで表さ
れるハロゲン原子としては、塩素、臭素、ヨウ素原子が
挙げられる。R 1 represents an alkyl group, for example, a C 1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl and the like. In the formula (3), examples of the halogen atom represented by Y include chlorine, bromine and iodine atoms.
【０００９】前記式（２）で表される有機金属化合物の
代表的な例として、ジメチルジイソプロポキシチタンな
どの有機チタン化合物（有機チタンのアート錯体な
ど）；メチルマグネシウムブロミド、エチルマグネシウ
ムブロミド、ブチルマグネシウムブロミドなどの有機マ
グネシウム化合物（Ｇｒｉｇｎａｒｄ試薬など）；メチ
ルリチウム、ブチルリチウムなどの有機リチウム化合物
などが挙げられる。有機マグネシウム化合物はハロゲン
化銅と組み合わせて用いることもできる。Representative examples of the organometallic compounds represented by the above formula (2) include organic titanium compounds such as dimethyldiisopropoxytitanium (art complexes of organic titanium); methylmagnesium bromide, ethylmagnesium bromide, butyl Organic magnesium compounds such as magnesium bromide (Grignard reagent); and organic lithium compounds such as methyllithium and butyllithium. The organomagnesium compound can be used in combination with a copper halide.
【００１０】前記式（２）で表される有機金属化合物の
使用量は、前記式（１）で表される２−アダマンタノン
類１モルに対して、例えば１〜２モル程度である。The amount of the organometallic compound represented by the formula (2) is, for example, about 1 to 2 mol per 1 mol of the 2-adamantanones represented by the formula (1).
【００１１】反応は、通常、有機溶媒中で行われる。有
機溶媒としては、反応に不活性な溶媒であればよく、例
えば、ジエチルエーテル、１，２−ジメトキシエタン、
テトラヒドロフランなどのエーテル類、ヘプタン、ヘキ
サン、オクタンなどの脂肪族炭化水素などを使用でき
る。The reaction is usually performed in an organic solvent. The organic solvent may be any solvent that is inert to the reaction, for example, diethyl ether, 1,2-dimethoxyethane,
Ethers such as tetrahydrofuran and the like, and aliphatic hydrocarbons such as heptane, hexane and octane can be used.
【００１２】反応温度は、有機金属化合物の種類などに
より、例えば−１００℃〜１５０℃程度の範囲内で適宜
選択できる。例えば、前記式（２）で表される有機金属
化合物において、Ｍが金属原子（例えば、リチウム）の
場合には、反応温度は、例えば−１００℃〜３０℃程度
である。また、式（２）の化合物として、Ｍが式（３）
で表される基を示す化合物を用いる場合には、反応温度
は、例えば０℃〜１５０℃程度、好ましくは２０℃〜１
００℃程度である。The reaction temperature can be appropriately selected, for example, in the range of about -100 ° C. to 150 ° C. depending on the kind of the organometallic compound. For example, in the organometallic compound represented by the formula (2), when M is a metal atom (for example, lithium), the reaction temperature is, for example, about −100 ° C. to 30 ° C. Further, as a compound of the formula (2), M is a compound of the formula (3)
When a compound showing a group represented by is used, the reaction temperature is, for example, about 0 ° C to 150 ° C, preferably 20 ° C to 1 ° C.
It is about 00 ° C.
【００１３】反応は、回分式、半回分式、連続式などの
慣用の方法により行うことができる。反応終了後、反応
中間体を水などでクエンチ（加水分解等）することによ
り前記式（４）で表される２−アルキル−２−アダマン
タノール類が生成する。前記加水分解の際には、希塩
酸、希硫酸などの酸の水溶液を用いる場合が多い。The reaction can be carried out by a conventional method such as a batch system, a semi-batch system, and a continuous system. After completion of the reaction, the reaction intermediate is quenched (hydrolyzed or the like) with water or the like to produce a 2-alkyl-2-adamantanol represented by the formula (4). In the hydrolysis, an aqueous solution of an acid such as dilute hydrochloric acid or dilute sulfuric acid is often used.
【００１４】［工程（Ｂ）］工程（Ｂ）では、前記工程
（Ａ）で生成した２−アルキル−２−アダマンタノール
類を単離することなく（メタ）アクリル酸ハライドと反
応させて、前記式（５）で表される２−アルキル−２−
アダマンチル（メタ）アクリレート類を生成させる。[Step (B)] In the step (B), the 2-alkyl-2-adamantanol produced in the step (A) is reacted with a (meth) acrylic halide without isolation. 2-alkyl-2- represented by the formula (5)
This produces adamantyl (meth) acrylates.
【００１５】通常、前記クエンチ処理後の反応混合液
を、液性調整（中和など）、溶媒交換、分液（抽出）、
濃縮、希釈等の適宜な操作を施した後、工程（Ｂ）に供
する。より具体的には、例えば、工程（Ａ）において反
応溶媒として水と混和する溶媒（例えば、テトラヒドロ
フランなど）を用いた場合には、クエンチ処理後の反応
混合液に、必要に応じて水酸化ナトリウムなどの塩基性
物質を含むアルカリ性水溶液を添加して中和した後、前
記反応溶媒を留去する操作を施し、その残液に水と分液
可能な有機溶媒を添加し、有機層と水層とを分液させ、
得られた有機層を工程（Ｂ）に供する。なお、該有機層
を濃縮及び／又は冷却することにより、２−アルキル−
２−アダマンタノール類をスラリー化して、若しくは該
スラリーを加熱により再溶解させて工程（Ｂ）に供して
もよい。また、工程（Ａ）における反応溶媒の種類によ
り、溶媒交換等の操作を省略することができる。Usually, the reaction mixture after the quenching treatment is adjusted for liquidity (neutralization, etc.), solvent exchange, liquid separation (extraction),
After performing appropriate operations such as concentration and dilution, the mixture is subjected to the step (B). More specifically, for example, when a water-miscible solvent (for example, tetrahydrofuran or the like) is used as the reaction solvent in the step (A), if necessary, sodium hydroxide may be added to the reaction mixture after the quenching treatment. After adding and neutralizing an alkaline aqueous solution containing a basic substance such as the above, an operation of distilling off the reaction solvent is performed, and an organic solvent capable of separating water and water is added to the remaining liquid, and an organic layer and an aqueous layer are added. And liquid separation,
The obtained organic layer is subjected to the step (B). In addition, by concentrating and / or cooling the organic layer, 2-alkyl-
The 2-adamantanol may be made into a slurry, or the slurry may be redissolved by heating to be subjected to the step (B). In addition, operations such as solvent exchange can be omitted depending on the type of the reaction solvent in the step (A).
【００１６】前記水と分液可能な溶媒としては、例え
ば、トルエン、キシレン等の芳香族炭化水素；ヘキサ
ン、ヘプタン等の脂肪族炭化水素；シクロヘキサン、メ
チルシクロヘキサン等の脂環式炭化水素；エチルエーテ
ル、イソプロピルエーテル、ジブチルエーテル等の鎖状
エーテル類；これらの混合液などが挙げられる。好まし
い溶媒には、トルエン等の芳香族炭化水素を少なくとも
含む溶媒が含まれる。これらの溶媒は工程（Ｂ）におけ
る反応溶媒として用いられる。なお、反応溶媒としては
上記の溶媒に限らず、反応を損なわないような溶媒であ
れば特に限定されない。Examples of the solvent capable of being separated from water include: aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Chain ethers such as isopropyl ether, dibutyl ether and the like; mixtures thereof. Preferred solvents include solvents containing at least an aromatic hydrocarbon such as toluene. These solvents are used as a reaction solvent in the step (B). The reaction solvent is not limited to the above solvents, and is not particularly limited as long as the solvent does not impair the reaction.
【００１７】（メタ）アクリル酸ハライドとしては、例
えば、アクリル酸クロリド、アクリル酸ブロミド等のア
クリル酸ハライド；メタクリル酸クロリド、メタクリル
酸ブロミド等のメタクリル酸ハライドが例示される。
（メタ）アクリル酸ハライドの使用量は、例えば、２−
アルキル−２−アダマンタノール類１モルに対して、１
〜４モル程度である。Examples of the (meth) acrylic halide include acrylic acid halides such as acrylic acid chloride and acrylic acid bromide; and methacrylic acid halides such as methacrylic acid chloride and methacrylic acid bromide.
The amount of the (meth) acrylic halide used is, for example, 2-
1 mole per mole of alkyl-2-adamantanols
About 4 mol.
【００１８】２−アルキル−２−アダマンタノール類と
（メタ）アクリル酸ハライドとの反応は、通常、塩基の
存在下で行われる。塩基としては、例えば、トリエチル
アミン、Ｎ−メチルピペリジン等の第３級アミン、ピリ
ジン等の窒素原子含有芳香族複素環化合物、ナトリウム
メトキシド等のアルカリ金属アルコキシド、酢酸ナトリ
ウムなどの有機塩基；水酸化ナトリム等のアルカリ金属
水酸化物、炭酸ナトリウム等のアルカリ金属炭酸塩、炭
酸水素ナトリウム等のアルカリ金属炭酸水素塩などの無
機塩基などが挙げられる。これらの塩基は単独で又は２
種以上組み合わせて使用できる。塩基の使用量は、例え
ば、２−アルキル−２−アダマンタノール類１モルに対
して、１〜５モル程度である。塩基は大過剰量用いるこ
ともできる。The reaction between 2-alkyl-2-adamantanols and (meth) acrylic halide is usually carried out in the presence of a base. Examples of the base include tertiary amines such as triethylamine and N-methylpiperidine; nitrogen-containing aromatic heterocyclic compounds such as pyridine; alkali metal alkoxides such as sodium methoxide; organic bases such as sodium acetate; sodium hydroxide; And inorganic bases such as alkali metal hydroxides such as sodium carbonate, alkali metal carbonates such as sodium carbonate and the like. These bases can be used alone or
It can be used in combination of more than one species. The amount of the base used is, for example, about 1 to 5 mol per 1 mol of the 2-alkyl-2-adamantanols. The base can be used in large excess.
【００１９】２−アルキル−２−アダマンタノール類と
（メタ）アクリル酸ハライドとを反応させる際の反応温
度は、通常−５０℃〜１００℃程度、好ましくは０〜７
０℃程度である。反応は、回分式、半回分式、連続式な
どの慣用の方法により行うことができる。一般には、２
−アルキル−２−アダマンタノール類のスラリー中に
（メタ）アクリル酸ハライドを逐次添加する方法が行わ
れる。The reaction temperature when the 2-alkyl-2-adamantanol is reacted with the (meth) acrylic halide is usually about -50 ° C to 100 ° C, preferably 0 to 7 ° C.
It is about 0 ° C. The reaction can be carried out by a conventional method such as a batch system, a semi-batch system, and a continuous system. Generally, 2
A method of sequentially adding (meth) acrylic acid halide to a slurry of -alkyl-2-adamantanols.
【００２０】反応終了後、例えば、液性調整（中和な
ど）、濾過、濃縮、抽出、洗浄、蒸留、晶析、再結晶、
カラムクロマトグラフィーなどの分離精製手段により、
前記式（５）で表される２−アルキル−２−アダマンチ
ル（メタ）アクリレート類を得ることができる。After completion of the reaction, for example, adjustment of liquid properties (neutralization, etc.), filtration, concentration, extraction, washing, distillation, crystallization, recrystallization,
By separation and purification means such as column chromatography,
A 2-alkyl-2-adamantyl (meth) acrylate represented by the formula (5) can be obtained.
【００２１】こうして得られた２−アルキル−２−アダ
マンチル（メタ）アクリレート類は、レジスト、インキ
用レジン、塗料、接着剤、粘着剤などの原料として有用
である。特に、酸によってアルコール部位が脱離し、遊
離のカルボン酸を生成させる化合物は、酸感応性化合物
として感光性樹脂のモノマー原料に使用できる。The thus obtained 2-alkyl-2-adamantyl (meth) acrylates are useful as raw materials for resists, resins for inks, paints, adhesives, and adhesives. In particular, a compound in which an alcohol moiety is eliminated by an acid to generate a free carboxylic acid can be used as a monomer material for a photosensitive resin as an acid-sensitive compound.
【００２２】[0022]
【発明の効果】本発明の方法によれば、２−アルキル−
２−アダマンタノール類を単離しないので、晶析、分
離、乾燥工程を省略でき、工程が簡略化されると共に、
２−アルキル−２−アダマンチル（メタ）アクリレート
類を高い収率で得ることができる。従って、本発明の製
造法は、工業的な２−アルキル−２−アダマンチル（メ
タ）アクリレート類の製法として極めて優れている。According to the method of the present invention, 2-alkyl-
Since 2-adamantanols are not isolated, crystallization, separation, and drying steps can be omitted, and the steps are simplified.
2-alkyl-2-adamantyl (meth) acrylates can be obtained in a high yield. Therefore, the production method of the present invention is extremely excellent as an industrial production method of 2-alkyl-2-adamantyl (meth) acrylates.
【００２３】[0023]
【実施例】以下、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 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００２４】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２−
アダマンタノン３０ｇ（０．２０モル）とテトラヒドロ
フラン６０ｇを入れ、５０℃以下に温度制御しながらメ
チルマグネシウムブロミド（ＣＨ3ＭｇＢｒ）のテトラ
ヒドロフラン溶液１２２ｇ（ＣＨ3ＭｇＢｒ：０．２２
５モル）をおよそ１時間で滴下した。その後６０℃で１
時間攪拌を続け、内容物を室温まで冷却した。滴下ロー
ト、凝縮器及び攪拌機を備えたフラスコに１０重量％硫
酸水溶液を入れ、窒素ガス雰囲気下、１０℃以下に温度
制御しながら、上記で得られた反応混合物を約１時間か
けて滴下した。その後、５重量％苛性ソーダ水溶液で中
和し、エバポレーターで常圧にて濃縮した。残液にトル
エン４５０ｇを添加し、攪拌した。トルエン層を分離採
取し、減圧下で残液が約２５０ｇになるまで濃縮し、２
−メチル−２−アダマンタノールのスラリーを得た。滴
下ロート、凝縮器及び攪拌機を備えたフラスコに上記の
スラリーを入れ、さらにトリエチルアミン７０ｇ（０．
６９モル）を加え、メタクリル酸クロリド５０ｇ（０．
４８モル）を、反応温度を３０℃以下に制御しながら約
２時間で滴下した。滴下終了後、さらに５０℃で１０時
間攪拌を続けた。冷却後、２０℃以下の温度で水１７０
ｇを滴下した。その後、炭酸ソーダ水溶液で中和し、食
塩水で洗浄後、有機層を液体クロマトグラフィーで分析
したところ、２−メタクリロイルオキシ−２−メチルア
ダマンタンが４２．１ｇ（０．１８モル）生成してい
た。２−メタクリロイルオキシ−２−メチルアダマンタ
ンの収率は、２−アダマンタノン基準で９０％であっ
た。Example 1 In a flask equipped with a dropping funnel, a condenser and a stirrer,
30 g (0.20 mol) of adamantanone and 60 g of tetrahydrofuran are added, and 122 g of a solution of methylmagnesium bromide (CH 3 MgBr) in tetrahydrofuran (CH 3 MgBr: 0.22) while controlling the temperature to 50 ° C. or less.
5 mol) in about 1 hour. Then at 60 ° C for 1
Stirring was continued for an hour and the contents were cooled to room temperature. A 10% by weight aqueous solution of sulfuric acid was placed in a flask equipped with a dropping funnel, a condenser and a stirrer, and the reaction mixture obtained above was added dropwise over about 1 hour while controlling the temperature at 10 ° C. or lower under a nitrogen gas atmosphere. Thereafter, the mixture was neutralized with a 5% by weight aqueous solution of caustic soda, and concentrated with an evaporator at normal pressure. 450 g of toluene was added to the remaining liquid, followed by stirring. The toluene layer was separated and collected, and concentrated under reduced pressure until the residual liquid was about 250 g.
A slurry of -methyl-2-adamantanol was obtained. The above slurry was placed in a flask equipped with a dropping funnel, a condenser and a stirrer, and further 70 g of triethylamine (0.
69 mol), and 50 g of methacrylic chloride (0.
48 mol) was added dropwise over about 2 hours while controlling the reaction temperature to 30 ° C. or lower. After completion of the dropwise addition, stirring was further continued at 50 ° C. for 10 hours. After cooling, water 170
g was added dropwise. Thereafter, the mixture was neutralized with an aqueous solution of sodium carbonate and washed with a saline solution, and the organic layer was analyzed by liquid chromatography. As a result, 42.1 g (0.18 mol) of 2-methacryloyloxy-2-methyladamantane was produced. . The yield of 2-methacryloyloxy-2-methyladamantane was 90% based on 2-adamantanone.
【００２５】比較例１ 滴下ロート、凝縮器及び攪拌機を備えたフラスコに２−
アダマンタノン３０ｇ（０．２０モル）とテトラヒドロ
フラン６０ｇを入れ、５０℃以下に温度制御しながらメ
チルマグネシウムブロミド（ＣＨ3ＭｇＢｒ）のテトラ
ヒドロフラン溶液１２２ｇ（ＣＨ3ＭｇＢｒ：０．２２
５モル）をおよそ１時間で滴下した。その後６０℃で１
時間攪拌を続け、内容物を室温まで冷却した。滴下ロー
ト、凝縮器及び攪拌機を備えたフラスコに１０重量％硫
酸水溶液を入れ、窒素ガス雰囲気下、１０℃以下に温度
制御しながら、上記で得られた反応混合物を１時間かけ
て滴下した。その後、５重量％苛性ソーダ水溶液で中和
し、エバポレーターで常圧にて内部温度が１００℃にな
るまで濃縮した。析出した結晶を濾過後、乾燥すること
により３５ｇの結晶が得られた。上記で得られた結晶と
トルエン３００ｇ、及びトリエチルアミン７０ｇ（０．
６９モル）を、滴下ロート、凝縮器及び攪拌機を備えた
フラスコに入れ、反応温度を３０℃以下に制御しなが
ら、メタクリル酸クロリド５０ｇ（０．４８モル）を約
２時間で滴下した。滴下終了後、さらに５０℃で１０時
間攪拌を続けた。冷却後、２０℃以下の温度で水１７０
ｇを滴下した。その後、炭酸ソーダ水溶液で中和し、食
塩水で洗浄後、有機層を液体クロマトグラフィーで分析
したところ、２−メタクリロイルオキシ−２−メチルア
ダマンタンが３５．１ｇ（０．１５モル）生成してい
た。２−メタクリロイルオキシ−２−メチルアダマンタ
ンの収率は、２−アダマンタノン基準で７５％であっ
た。COMPARATIVE EXAMPLE 1 In a flask equipped with a dropping funnel, a condenser and a stirrer,
30 g (0.20 mol) of adamantanone and 60 g of tetrahydrofuran are added, and 122 g of a solution of methylmagnesium bromide (CH 3 MgBr) in tetrahydrofuran (CH 3 MgBr: 0.22) while controlling the temperature to 50 ° C. or lower
5 mol) in about 1 hour. Then at 60 ° C for 1
Stirring was continued for an hour and the contents were cooled to room temperature. A 10% by weight aqueous solution of sulfuric acid was placed in a flask equipped with a dropping funnel, a condenser and a stirrer, and the reaction mixture obtained above was added dropwise over 1 hour while controlling the temperature at 10 ° C. or lower under a nitrogen gas atmosphere. Thereafter, the mixture was neutralized with a 5% by weight aqueous solution of sodium hydroxide and concentrated by an evaporator at normal pressure until the internal temperature reached 100 ° C. The precipitated crystals were filtered and dried to obtain 35 g of crystals. The crystals obtained above, 300 g of toluene, and 70 g of triethylamine (0.
(69 mol) was placed in a flask equipped with a dropping funnel, a condenser and a stirrer, and 50 g (0.48 mol) of methacrylic chloride was added dropwise over about 2 hours while controlling the reaction temperature to 30 ° C. or lower. After completion of the dropwise addition, stirring was further continued at 50 ° C. for 10 hours. After cooling, water 170
g was added dropwise. Thereafter, the mixture was neutralized with an aqueous solution of sodium carbonate and washed with a saline solution, and the organic layer was analyzed by liquid chromatography. As a result, 35.1 g (0.15 mol) of 2-methacryloyloxy-2-methyladamantane was produced. . The yield of 2-methacryloyloxy-2-methyladamantane was 75% based on 2-adamantanone.
Claims (2)
れる２−アダマンタノン類を、下記式（２） Ｒ1−Ｍ （２） ［式中、Ｒ1はアルキル基を示す。Ｍは配位子を有して
もよい金属原子、または下記式（３） −ＭｇＹ （３） （式中、Ｙはハロゲン原子を示す）で表される基を示
す］で表される有機金属化合物と反応させて、下記式
（４） 【化２】 （式中、Ｒ1は前記に同じ。アダマンタン環は置換基を
有していてもよい）で表される２−アルキル−２−アダ
マンタノール類を生成させる工程、及び（Ｂ）前記工程
で生成した２−アルキル−２−アダマンタノール類を単
離することなく（メタ）アクリル酸ハライドと反応させ
て、下記式（５） 【化３】 （式中、Ｒ2は水素原子又はメチル基を示す。Ｒ1は前記
に同じ）で表される２−アルキル−２−アダマンチル
（メタ）アクリレート類を生成させる工程を含む２−ア
ルキル−２−アダマンチル（メタ）アクリレート類の製
造法。(A) The following formula (1): (The adamantane ring may have a substituent.) A 2-adamantanone represented by the following formula (2) R 1 -M (2) wherein R 1 represents an alkyl group. M represents a metal atom which may have a ligand, or an organic metal represented by the following formula (3) -MgY (3) (wherein, Y represents a halogen atom). By reacting with a compound, the following formula (4) (Wherein, R 1 is the same as described above; the adamantane ring may have a substituent); and (B) a step of forming the 2-alkyl-2-adamantanol The resulting 2-alkyl-2-adamantanols are reacted with (meth) acrylic halide without isolation to give the following formula (5): (Wherein, R 2 represents a hydrogen atom or a methyl group; R 1 is the same as described above), and the method comprises the step of producing 2-alkyl-2-adamantyl (meth) acrylates A method for producing adamantyl (meth) acrylates.
も芳香族炭化水素を含む溶媒を用いる請求項１記載の２
−アルキル−２−アダマンチル（メタ）アクリレート類
の製造法。2. The method according to claim 1, wherein a solvent containing at least an aromatic hydrocarbon is used as a reaction solvent in the step (B).
-A method for producing alkyl-2-adamantyl (meth) acrylates.
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| JP2000389631A JP4667593B2 (en) | 2000-12-21 | 2000-12-21 | Process for producing 2-alkyl-2-adamantyl (meth) acrylates |
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Cited By (5)
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| JP2005112824A (en) * | 2003-10-10 | 2005-04-28 | Daicel Chem Ind Ltd | Fluorine-containing polymerizable adamantane derivative, method for producing the same and polymer compound |
| WO2009041204A1 (en) | 2007-09-28 | 2009-04-02 | Konica Minolta Opto, Inc. | Method for manufacturing optical device |
| WO2009116371A1 (en) | 2008-03-19 | 2009-09-24 | コニカミノルタオプト株式会社 | Method for producing wafer lens |
| WO2009116448A1 (en) | 2008-03-19 | 2009-09-24 | コニカミノルタオプト株式会社 | Method for producing molded body or wafer lens |
| WO2011136138A1 (en) | 2010-04-27 | 2011-11-03 | コニカミノルタオプト株式会社 | Image capture lens, wafer lens, wafer lens laminate, method of manufacturing image capture lens, image capture lens intermediate product, method of manufacturing image capture lens intermediate product |
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| WO2009116448A1 (en) | 2008-03-19 | 2009-09-24 | コニカミノルタオプト株式会社 | Method for producing molded body or wafer lens |
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