JP2007191399A - Cycloaliphatic compound and method for producing the same - Google Patents
Cycloaliphatic compound and method for producing the same Download PDFInfo
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Abstract
Description
本発明は新規脂環式化合物およびその製造方法に関する。 The present invention relates to a novel alicyclic compound and a method for producing the same.
近年、電子材料、光学材料の分野では、各種性能を向上させるべく、種々の新規材料が検討されている。特に、脂環式化合物については、電子材料、光学材料等の分野で優れた特性が期待できるため、研究開発が行われている。
本願人も先に種々の新規脂環式化合物を提案している（例えば、特許文献１、２参照）が、さらなる高性能を付与しうる材料が求められている。一方、ペルフルオロアルキル基による電気的、光学的特長の付与は広く知られるところである。しかしながら、ペルフルオロアルキル基をもつ化合物については、分解性、蓄積性の面から毒性が懸念されており、特に、ペルフルオロオクタンスルホン酸やペルフルオロオクタン酸などの炭素数６をこえるものには何らかの残留性があるとされている。よって、炭素数の少ないペルフルオロアルキル基を使用する事は環境負荷および安全性の面から重要である。
In recent years, various new materials have been studied in the fields of electronic materials and optical materials in order to improve various performances. In particular, alicyclic compounds have been researched and developed because excellent properties can be expected in the fields of electronic materials and optical materials.
The present applicant has previously proposed various novel alicyclic compounds (see, for example, Patent Documents 1 and 2), but a material capable of imparting further high performance is required. On the other hand, imparting electrical and optical characteristics by a perfluoroalkyl group is widely known. However, compounds having a perfluoroalkyl group are concerned with toxicity from the viewpoint of degradability and accumulation, and in particular, those having more than 6 carbon atoms such as perfluorooctane sulfonic acid and perfluorooctanoic acid have some residual properties. It is said that there is. Therefore, the use of a perfluoroalkyl group having a small number of carbon atoms is important from the viewpoint of environmental load and safety.
本発明は、電子材料、光学材料等として良好な物性を有する新規な樹脂材料とその原料単量体となる新規の脂環式化合物および当該新規脂環式化合物の製造方法を提供することを目的とする。 An object of the present invention is to provide a novel resin material having good physical properties as an electronic material, an optical material, etc., a novel alicyclic compound as a raw material monomer, and a method for producing the novel alicyclic compound. And
本発明者は、脂環式化合物について鋭意検討したところ、電子材料、光学材料として良好な物性を有することが期待できる新規な樹脂材料の原料単量体となる化合物および当該化合物を製造する方法を見出し、本発明を完成させた。すなわち、本発明は、一般式（１）： As a result of diligent research on the alicyclic compound, the present inventors have found a compound as a raw material monomer for a novel resin material that can be expected to have good physical properties as an electronic material and an optical material, and a method for producing the compound. The headline and the present invention were completed. That is, the present invention relates to the general formula (1):
（式中、Ｒは、−ＣＨ２ＣＦ２ＣＦ３または−ＣＨ２ＣＨ２（ＣＦ２）３ＣＦ３で表される官能基を表す。）で表される新規脂環式化合物；シクロペンタジエンに一般式（２）：ＣＨ２＝ＣＨＣＯＯＲ（式中、Ｒは、−ＣＨ２ＣＦ２ＣＦ３または−ＣＨ２ＣＨ２（ＣＦ２）３ＣＦ３で表される官能基を表す。）で表される化合物を反応させることを特徴とする当該新規脂環式化合物の製造方法；一般式（３）： (Wherein R represents a functional group represented by —CH 2 CF 2 CF 3 or —CH 2 CH 2 (CF 2 ) 3 CF 3 ); a cyclopentadiene; General formula (2): CH 2 = CHCOOR (wherein R represents a functional group represented by —CH 2 CF 2 CF 3 or —CH 2 CH 2 (CF 2 ) 3 CF 3 ). A method for producing the novel alicyclic compound, which comprises reacting the compound with a general formula (3):
（式中、Ｒ１は、−ＯＨ、ハロゲン基または−ＯＲ２（Ｒ２は炭素数１〜４のアルキル基を表す。）で表される官能基を示す。）で表される脂環式化合物と、一般式（４）：Ｒ−ＯＨ（式中、Ｒは、−ＣＨ２ＣＦ２ＣＦ３または−ＣＨ２ＣＨ２（ＣＦ２）３ＣＦ３で表される官能基を表す。）で表されるアルコールを反応させることを特徴とする当該新規脂環式化合物の製造方法に関する。 (Wherein R 1 represents a functional group represented by —OH, a halogen group, or —OR 2 (R 2 represents an alkyl group having 1 to 4 carbon atoms)). Compound and general formula (4): R—OH (wherein R represents a functional group represented by —CH 2 CF 2 CF 3 or —CH 2 CH 2 (CF 2 ) 3 CF 3 ). The present invention relates to a method for producing the novel alicyclic compound characterized by reacting the alcohol represented.
本発明の新規脂環式化合物は、重合性官能基を有するため、従来の電子材料、光学材料等に新規な特性を容易に組み込むことができるものである。また、当該化合物の重合体は、電子材料、光学材料等として良好な物性を有するものと期待できる。 Since the novel alicyclic compound of the present invention has a polymerizable functional group, it can easily incorporate new characteristics into conventional electronic materials and optical materials. In addition, the polymer of the compound can be expected to have good physical properties as an electronic material, an optical material, or the like.
本発明の新規脂環式化合物は、前記一般式（１）で表されるものである。当該化合物は、Ｒが−ＣＨ２ＣＦ２ＣＦ３で表される化合物の場合は、常温（２０℃）で液体の化合物である。また、Ｒが、−ＣＨ２ＣＨ２（ＣＦ２）３ＣＦ３で表される化合物の場合は、常温（２０℃）で液体の化合物である。 The novel alicyclic compound of the present invention is represented by the general formula (1). In the case where R is a compound represented by —CH 2 CF 2 CF 3 , the compound is a liquid compound at room temperature (20 ° C.). In the case where R is a compound represented by —CH 2 CH 2 (CF 2 ) 3 CF 3, it is a compound that is liquid at room temperature (20 ° C.).
本発明の新規脂環式化合物は、例えば、シクロペンタジエンに一般式（２）：ＣＨ２＝ＣＨＣＯＯＲ（式中、Ｒは、−ＣＨ２ＣＦ２ＣＦ３または−ＣＨ２ＣＨ２（ＣＦ２）３ＣＦ３で表される官能基を表す。）で表される化合物を反応させることにより得られる。
一般式（２）で表される化合物は、特に限定されず公知の方法により合成したものを用いることができる。具体的には、例えば、ＣＨ２＝ＣＨＣＯＲ３（式中、Ｒ３は、−ＯＨ、ハロゲン基または−ＯＲ４（Ｒ４は炭素数１〜４のアルキル基を表す。）で表される官能基を表す。）とＲ−ＯＨ（式中、Ｒは、−ＣＨ２ＣＦ２ＣＦ３または−ＣＨ２ＣＨ２（ＣＦ２）３ＣＦ３で表される官能基を表す。）で表される化合物を反応させる方法などを採用することができる。
シクロペンタジエンと一般式（２）で表される化合物の反応は、ディールスアルダー反応であり、一般的なディールスアルダー反応の反応条件を採用することができる。具体的には、シクロペンタジエン１モルに対し、一般式（２）で表される化合物を、０．１〜１０．０モル程度使用し、反応温度を、−２０〜３００℃程度とすればよい。反応圧力は、特に限定されないが、通常、１〜２０ＭＰａ程度とすることが反応を速やかに進行させることができるため好ましい。得られた反応物を、公知の方法で精製することにより、本発明の新規脂環式化合物が得られる。
The novel alicyclic compound of the present invention is, for example, cyclopentadiene having the general formula (2): CH 2 ═CHCOOR (wherein R is —CH 2 CF 2 CF 3 or —CH 2 CH 2 (CF 2 ) 3 It represents the functional group represented by CF 3 ).
The compound represented by the general formula (2) is not particularly limited, and those synthesized by a known method can be used. Specifically, for example, CH 2 = CHCOR 3 (wherein R 3 represents —OH, a halogen group, or —OR 4 (R 4 represents an alkyl group having 1 to 4 carbon atoms). And R—OH (wherein R represents a functional group represented by —CH 2 CF 2 CF 3 or —CH 2 CH 2 (CF 2 ) 3 CF 3 ). A method of reacting a compound can be employed.
The reaction between the cyclopentadiene and the compound represented by the general formula (2) is a Diels-Alder reaction, and reaction conditions for general Diels-Alder reactions can be employed. Specifically, the compound represented by the general formula (2) is used in an amount of about 0.1 to 10.0 mol with respect to 1 mol of cyclopentadiene, and the reaction temperature is set to about −20 to 300 ° C. . Although reaction pressure is not specifically limited, Usually, it is preferable to set it as about 1-20 MPa since reaction can be advanced rapidly. By purifying the obtained reaction product by a known method, the novel alicyclic compound of the present invention is obtained.
また、本発明の新規脂環式化合物は、前記一般式（３）で表される脂環式化合物と、一般式（４）：Ｒ−ＯＨ（式中、Ｒは、−ＣＨ２ＣＦ２ＣＦ３または−ＣＨ２ＣＨ２（ＣＦ２）３ＣＦ３で表される官能基を表す。）で表されるアルコールを反応させることによっても得られる。 Further, the novel alicyclic compound of the present invention includes an alicyclic compound represented by the general formula (3) and a general formula (4): R—OH (wherein R is —CH 2 CF 2 CF). 3 or represents a functional group represented by —CH 2 CH 2 (CF 2 ) 3 CF 3 ).
一般式（３）で表される化合物（Ｒ１が−ＯＨまたは−ＯＲ２のもの）は、シクロペンタジエンと、アクリル酸またはアクリル酸アルキルエステルなどをディールスアルダー反応させることにより得られる。ディールスアルダー反応の条件としては、公知の方法を採用することができ、具体的には、例えば、シクロペンタジエン１モルに対し、アクリル酸またはアクリル酸アルキルエステルなどを、０．１〜１０．０モル程度使用し、反応温度を、−２０〜３００℃程度とすればよい。反応圧力は、特に限定されないが、通常、１〜２０ＭＰａ程度とすることが反応を速やかに進行させることができるため好ましい。なお、Ｒ１がハロゲン基である一般式（３）で表される化合物は、例えば、Ｒ１が−ＯＨである一般式（３）で表される化合物を調製した後に塩化チオニル等のハロゲン化剤を反応させることにより得られる。このようにして得られた一般式（３）で表される化合物は、そのまま次の反応に使用してもよいが、公知の方法により精製して用いてもよい。なお、精製する場合には、蒸留による方法を採用することが好ましい。 The compound represented by the general formula (3) (R 1 is —OH or —OR 2 ) can be obtained by reacting cyclopentadiene with acrylic acid or an acrylic acid alkyl ester or the like with a Diels-Alder reaction. As conditions for the Diels-Alder reaction, a known method can be used. Specifically, for example, 0.1 mol of acrylic acid or an alkyl acrylate is added to 1 mol of cyclopentadiene. The reaction temperature may be about -20 to 300 ° C. Although reaction pressure is not specifically limited, Usually, it is preferable to set it as about 1-20 MPa since reaction can advance rapidly. The compound represented by the general formula (3) in which R 1 is a halogen group is, for example, a halogenated compound such as thionyl chloride after preparing a compound represented by the general formula (3) in which R 1 is —OH. It is obtained by reacting the agent. The compound represented by the general formula (3) thus obtained may be used in the next reaction as it is, or may be purified by a known method and used. In the case of purification, it is preferable to employ a distillation method.
得られた一般式（３）で表される化合物と、一般式（４）で表されるアルコールとの反応は、一般式（３）のＲ１の官能基が何であるかにより、反応条件が変わるため、適宜、選択する必要がある。 The reaction between the obtained compound represented by the general formula (3) and the alcohol represented by the general formula (4) depends on what the functional group of R 1 in the general formula (3) is. Since it changes, it is necessary to select appropriately.
一般式（３）のＲ１がＯＨの場合、当該反応はエステル化反応となる。このときの反応条件としては、特に限定されず、公知のエステル化反応の反応条件を採用することができる。具体的には、例えば、一般式（３）で表されるカルボン酸１モルに対し、一般式（４）で表されるアルコール０．５〜１０モル程度を、公知のエステル化触媒と共に６０〜１５０℃程度に加熱し、生成する水を除去しながら反応させれば良い。エステル化触媒にはパラトルエンスルホン酸などの有機酸、塩酸、硫酸などの無機酸などが挙げられる。また、必要に応じてエステル化剤として、例えば、Ｎ，Ｎ´−ジシクロヘキシルカルボジイミド、Ｎ−エチル−Ｎ´−（３−ジメチルアミノプロピル）カルボジイミドなどを用いてもよい。なお、溶媒を使用する場合には、各成分と反応しないものを使用する必要がある。 When R 1 in the general formula (3) is OH, the reaction is an esterification reaction. The reaction conditions at this time are not particularly limited, and known reaction conditions for esterification reactions can be employed. Specifically, for example, about 0.5 to 10 mol of the alcohol represented by the general formula (4) is added to 60 mol of the carboxylic acid represented by the general formula (3) together with a known esterification catalyst. What is necessary is just to make it react, heating at about 150 degreeC and removing the water to produce | generate. Examples of the esterification catalyst include organic acids such as p-toluenesulfonic acid, inorganic acids such as hydrochloric acid and sulfuric acid, and the like. Further, for example, N, N′-dicyclohexylcarbodiimide, N-ethyl-N ′-(3-dimethylaminopropyl) carbodiimide or the like may be used as an esterifying agent as necessary. In addition, when using a solvent, it is necessary to use what does not react with each component.
一般式（３）のＲ１がハロゲンの場合、当該反応は酸塩化物とアルコールの求核置換反応となる。このときの反応条件としては、特に限定されず、公知の求核置換反応の反応条件を採用することができる。具体的には、例えば、一般式（３）で表される酸塩化物１モルに対し、一般式（４）で表されるアルコール１．０〜２．０モル程度を、−５０〜１００℃程度でトリエチルアミン、水素化ナトリウムなどの塩基の存在下で反応させれば良い。 When R 1 in the general formula (3) is halogen, the reaction is a nucleophilic substitution reaction between an acid chloride and an alcohol. The reaction conditions at this time are not particularly limited, and known reaction conditions for nucleophilic substitution reactions can be employed. Specifically, for example, about 1.0 to 2.0 mol of the alcohol represented by the general formula (4) is −50 to 100 ° C. with respect to 1 mol of the acid chloride represented by the general formula (3). The reaction may be performed in the presence of a base such as triethylamine or sodium hydride.
一般式（３）のＲ１が−ＯＲ２（Ｒ２は炭素数１〜４のアルキル基を表す。）の場合、当該反応はエステル交換反応となる。このときの反応条件としては、特に限定されず、公知のエステル化反応の反応条件を採用することができる。具体的には、例えば、一般式（３）で表されるエステル化合物１モルに対し、一般式（４）で表されるアルコール０．５〜１０モル程度を公知のエステル交換触媒と共に６０〜１５０℃程度に加熱し、反応させれば良い。エステル交換触媒としては、例えば、パラトルエンスルホン酸などの有機酸、塩酸、硫酸などの無機酸、水酸化ナトリウム、カリウムエチラート、トリエチルアミン、などの塩基性触媒、テトラアルコキシチタンなどが挙げられる。 When R 1 in the general formula (3) is —OR 2 (R 2 represents an alkyl group having 1 to 4 carbon atoms), the reaction is a transesterification reaction. The reaction conditions at this time are not particularly limited, and known reaction conditions for esterification reactions can be employed. Specifically, for example, about 0.5 to 10 mol of the alcohol represented by the general formula (4) and 60 to 150 together with a known transesterification catalyst with respect to 1 mol of the ester compound represented by the general formula (3). What is necessary is just to heat and react to about ℃. Examples of the transesterification catalyst include organic acids such as p-toluenesulfonic acid, inorganic acids such as hydrochloric acid and sulfuric acid, basic catalysts such as sodium hydroxide, potassium ethylate and triethylamine, and tetraalkoxytitanium.
このようにして得られた反応物を、公知の方法で精製することにより、本発明の新規脂環式化合物が得られる。 The novel alicyclic compound of the present invention can be obtained by purifying the reaction product thus obtained by a known method.
以下に、実施例をあげて本発明をさらに具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。また、各化合物のスペクトル測定には、次の装置を使用した。 Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. Moreover, the following apparatus was used for the spectrum measurement of each compound.
ＮＭＲ：ＧＥＭＩＮＩ−３００（Ｖａｒｉａｎ社製）
ＩＲ：ＮＥＸＵＳ６７０（サーモエレクトロン社製）
ガスクロマトフィー（ＧＣ）：ＧＣ６８９０（アジレント社製）
NMR: GEMINI-300 (manufactured by Varian)
IR: NEXUS670 (manufactured by Thermo Electron)
Gas chromatography (GC): GC6890 (manufactured by Agilent)
実施例１
加圧反応容器に２，２，３，３，３−ペンタフルオロプロピルアクリレート３０ｇと重合禁止剤４−メトキシフェノール０．０６ｇを仕込み、１７０℃まで加熱昇温した後に、内温１６７〜１７３℃を維持しながら、シクロペンタジエン９．７ｇを１時間２０分かけて反応容器に仕込んだ。その後、同温度で１２時間反応を行い、粗生成物を得た。精留塔を備えた蒸留装置に粗生成物を仕込んで圧力２７０Ｐａで減圧蒸留精製を行う事により２，２，３，３，３−ペンタフルオロプロピル−ビシクロ［２，２，１］ヘプト−５−エン−２−カルボキシレート１２．０ｇを得た（収率３０％）。得られた２，２，３，３，３−ペンタフルオロプロピル−ビシクロ［２，２，１］ヘプト−５−エン−２−カルボキシレートは純度９９．９８％であった（ＧＣ法）。
Example 1
A pressurized reaction vessel was charged with 30 g of 2,2,3,3,3-pentafluoropropyl acrylate and 0.06 g of a polymerization inhibitor 4-methoxyphenol, heated to 170 ° C. and then heated to an internal temperature of 167 to 173 ° C. While maintaining, 9.7 g of cyclopentadiene was charged into the reaction vessel over 1 hour and 20 minutes. Then, reaction was performed at the same temperature for 12 hours, and the crude product was obtained. 2,2,3,3,3-Pentafluoropropyl-bicyclo [2,2,1] hept-5 is prepared by charging the crude product into a distillation apparatus equipped with a rectifying column and performing vacuum distillation purification at a pressure of 270 Pa. -12.0 g of ene-2-carboxylate was obtained (yield 30%). The obtained 2,2,3,3,3-pentafluoropropyl-bicyclo [2,2,1] hept-5-ene-2-carboxylate had a purity of 99.98% (GC method).
１Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ3、δ（ｐｐｍ））：１．３１、１．４８、１．９４、２．３２、２．９３、３．０３、３．２５、４．４２、４．５６、５．９２、６．１５、６．２３ 1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 1.31, 1.48, 1.94, 2.32, 2.93, 3.03, 3.25, 4.42, 4 .56, 5.92, 6.15, 6.23
１３Ｃ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ3、δ（ｐｐｍ））： ２９．１７、３０．３９、４１．６７、４２．５２、４２．８２、４３．０１、４５．７９、４６．３３、４６．５９、４９．６７、５８．６２、５８．９９、５９．３６、１３１．９７、１３５．４８、１３８．１６、１７３．０６ 13 C-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 29.17, 30.39, 41.67, 42.52, 42.82, 43.01, 45.79, 46.33, 46 .59, 49.67, 58.62, 58.99, 59.36, 131.97, 135.48, 138.16, 173.06
ＩＲ（ｎｅａｔ、（ｃｍ-1））：７１２、７７６、８３８、９５３、１０２９、１０７５、１１０５、１１４８、１２０１、１２７３、１３３７、１３５８、１４５０、１７５６、２９７８ IR (neat, (cm −1 )): 712, 776, 838, 953, 1029, 1075, 1105, 1148, 1201, 1273, 1337, 1358, 1450, 1756, 2978
実施例２
冷却管、温度計、滴下ロート、攪拌機を備えた反応容器に、ビシクロ［２，２，１］ヘプト−５−エン−２−カルボキシリックアシッド１５．０ｇ、トルエン９０．０ｇ、ジメチルアミノピリジン２．７ｇ、Ｎ，Ｎ´−ジシクロヘキシルカルボジイミド２６．９ｇ、２，２，３，３，３−ペンタフルオロプロパノール１７．９ｇを加え、室温で１２時間攪拌した。反応終了後、ろ過し、ろ液を３％硫酸３０ｍｌ、５％水酸化ナトリウム水溶液３０ｍｌ、イオン交換水３０ｍｌで順次洗浄した。得られた有機層を、無水硫酸ナトリウムを用いて乾燥させた後、トルエンを減圧下で留去させ２５．０ｇの粗生成物を得た。
得られた反応粗生成物を、精留塔を備えた蒸留装置に粗生成物を仕込んで圧力２７０Ｐａで減圧蒸留精製を行う事により、２，２，３，３，３−ペンタフルオロプロピル−ビシクロ［２，２，１］ヘプト−５−エン−２−カルボキシレート１８．５ｇを得た（収率５７．３％）。１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＩＲ分析を行ったところ実施例１と同結果が得られた。
Example 2
In a reaction vessel equipped with a condenser, a thermometer, a dropping funnel, and a stirrer, 15.0 g of bicyclo [2,2,1] hept-5-ene-2-carboxylic acid, 90.0 g of toluene, dimethylaminopyridine, 2. 7 g, 26.9 g of N, N′-dicyclohexylcarbodiimide and 17.9 g of 2,2,3,3,3-pentafluoropropanol were added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the mixture was filtered, and the filtrate was washed successively with 3% sulfuric acid 30 ml, 5% aqueous sodium hydroxide 30 ml, and ion-exchanged water 30 ml. The obtained organic layer was dried using anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure to obtain 25.0 g of a crude product.
The obtained reaction crude product was purified by distillation under reduced pressure at a pressure of 270 Pa by charging the crude product into a distillation apparatus equipped with a rectifying column, thereby obtaining 2,2,3,3,3-pentafluoropropyl-bicyclo. 18.5 g of [2,2,1] hept-5-ene-2-carboxylate was obtained (yield 57.3%). When 1 H-NMR, 13 C-NMR, and IR analysis were performed, the same results as in Example 1 were obtained.
実施例３
冷却管、温度計、攪拌機を備えた反応容器に、ビシクロ［２，２，１］ヘプト−５−エン−２−カルボキシリックアシッド１０１．０ｇ、トルエン１０１．０ｇ、塩化チオニル１０４ｇを仕込み、８０℃まで昇温し４時間反応させた。反応終了後、さらに１２０℃まで昇温し、未反応の塩化チオニルを留去させ、［２，２，１］ヘプト−５−エン−２−カルボニルクロライドのトルエン溶液を得た。
温度計、攪拌機を備えた反応容器に窒素雰囲気下でトルエン３０３ｇ、２，２，３，３，３−ペンタフルオロプロパノール１２５ｇ、トリエチルアミン１２６ｇを仕込んだ。攪拌しながら、室温にて先に調製した［２，２，１］ヘプト−５−エン−２−カルボニルクロライドのトルエン溶液の全量を１時間かけて滴下し、そのまま２時間反応させた。この反応混合物を５％硫酸４００ｇ、５％炭酸水素ナトリウム水溶液４００ｇ、次いでイオン交換水４００ｇで洗浄した。得られた有機層を、無水硫酸ナトリウムを用いて乾燥させた後、トルエンを減圧下で留去させ９８ｇの粗生成物を得た。精留塔を備えた蒸留装置に粗生成物を仕込んで圧力２７０Ｐａで減圧蒸留精製を行う事により、８８ｇの２，２，３，３，３−ペンタフルオロプロピル−ビシクロ［２，２，１］ヘプト−５−エン−２−カルボキシレートを得た（収率３９．１％）。１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＩＲ分析を行ったところ実施例１と同結果が得られた。
Example 3
A reaction vessel equipped with a condenser, a thermometer, and a stirrer was charged with 101.0 g of bicyclo [2,2,1] hept-5-ene-2-carboxylic acid, 101.0 g of toluene, and 104 g of thionyl chloride at 80 ° C. The mixture was heated up to react for 4 hours. After completion of the reaction, the temperature was further raised to 120 ° C., and unreacted thionyl chloride was distilled off to obtain a toluene solution of [2,2,1] hept-5-ene-2-carbonyl chloride.
A reaction vessel equipped with a thermometer and a stirrer was charged with 303 g of toluene, 125 g of 2,2,3,3,3-pentafluoropropanol and 126 g of triethylamine under a nitrogen atmosphere. While stirring, the whole amount of the toluene solution of [2,2,1] hept-5-ene-2-carbonyl chloride prepared previously at room temperature was added dropwise over 1 hour and allowed to react for 2 hours. The reaction mixture was washed with 400 g of 5% sulfuric acid, 400 g of 5% aqueous sodium hydrogen carbonate solution, and then 400 g of ion-exchanged water. The obtained organic layer was dried using anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure to obtain 98 g of a crude product. 88 g of 2,2,3,3,3-pentafluoropropyl-bicyclo [2,2,1] was prepared by charging the crude product into a distillation apparatus equipped with a rectifying column and performing vacuum distillation purification at a pressure of 270 Pa. Hept-5-ene-2-carboxylate was obtained (yield 39.1%). When 1 H-NMR, 13 C-NMR, and IR analysis were performed, the same results as in Example 1 were obtained.
実施例４
加圧反応器に３，３，４，４，５，５，６，６，６−ノナフルオロヘキシルアクリレート３０．０ｇ、ハイドロキノン０．０６ｇを仕込み、１７０℃まで加熱昇温した後に、内温１６７〜１７３℃を維持しながら、シクロペンタジエン６．２ｇを１時間２０分かけて反応容器に仕込んだ。その後、同温度で１２時間反応を行い、粗生成物を得た。精留塔を備えた蒸留装置に粗生成物を仕込んで圧力１０Ｐａで減圧蒸留精製を行う事により３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル−ビシクロ［２，２，１］ヘプト−５−エン−２−カルボキシレート７．４ｇを得た（収率２０．４％）。得られた３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル−ビシクロ［２，２，１］ヘプト−５−エン−２−カルボキシレートは純度９９．８１％であった（ＧＣ法）。
Example 4
A pressurized reactor was charged with 30.0 g of 3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate and 0.06 g of hydroquinone, heated to 170 ° C. and heated to an internal temperature of 167 While maintaining ˜173 ° C., 6.2 g of cyclopentadiene was charged into the reaction vessel over 1 hour and 20 minutes. Then, reaction was performed at the same temperature for 12 hours, and the crude product was obtained. The crude product was charged into a distillation apparatus equipped with a rectifying column, and purified by distillation under reduced pressure at a pressure of 10 Pa, to obtain 3,3,4,4,5,5,6,6,6-nonafluorohexyl-bicyclo [2 , 2,1] hept-5-ene-2-carboxylate (7.4 g) was obtained (yield 20.4%). The resulting 3,3,4,4,5,5,6,6,6-nonafluorohexyl-bicyclo [2,2,1] hept-5-ene-2-carboxylate has a purity of 99.81%. (GC method).
１Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ3、δ（ｐｐｍ））：１．２７、１．４３、１．９３、２．２３、２．４５、２．９４、３．０５、３．２２、４．３４、５．９２、６．１５、６．２０ 1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 1.27, 1.43, 1.93, 2.23, 2.45, 2.94, 3.05, 3.22, 4 .34, 5.92, 6.15, 6.20
１３Ｃ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ3、δ（ｐｐｍ））： ２９．１５、３０．２４、３０．３０、３０．５２、３０．８１、４１．６４、４２．５６、４３．０３、４３．０３、４３．２０、４５．７０、４６．３３、４６．５２、４９．６８、５６．０６、１３２．０６、１３５．６１、１３７．９８、１３８．１３、１７４．３１ 13 C-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 29.15, 30.24, 30.30, 30.52, 30.81, 41.64, 42.56, 43.03, 43 .03, 43.20, 45.70, 46.33, 46.52, 49.68, 56.06, 132.06, 135.61, 137.98, 138.13, 174.31
ＩＲ（ｎｅａｔ、（ｃｍ-1））：７１２、７４７、８３８、８６２、８７８、１０１７、１０８１、１１１２、１１３３、１１６９、１１８５、１１９９、１２２１、１２９８、１３３７、１７４０、２９７９ IR (neat, (cm −1 )): 712, 747, 838, 862, 878, 1017, 1081, 1112, 1133, 1169, 1185, 1199, 1221, 1298, 1337, 1740, 2979
本発明の化合物は、透明性、耐熱性、耐水性、撥水性等に優れた特性を有し、電子材料、光学材料等に有用である。
The compound of the present invention has excellent properties such as transparency, heat resistance, water resistance and water repellency, and is useful for electronic materials, optical materials and the like.
Claims (3)
一般式（１）：
General formula (1):
一般式（３）：
（式中、Ｒ１は、−ＯＨ、ハロゲン基または−ＯＲ２（Ｒ２は炭素数１〜４のアルキル基を表す。）で表される官能基を示す。）
An alicyclic compound represented by the following general formula (3) and general formula (4): R—OH (wherein R is —CH 2 CF 2 CF 3 or —CH 2 CH 2 (CF 2 ) 3 ). 2. The method for producing an alicyclic compound according to claim 1, wherein an alcohol represented by CF 3 is reacted.
General formula (3):
(In the formula, R 1 represents a functional group represented by —OH, a halogen group, or —OR 2 (R 2 represents an alkyl group having 1 to 4 carbon atoms).)
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5999720A (en) * | 1982-11-30 | 1984-06-08 | Toshiba Corp | Forming method of resist image |
| JPS60195542A (en) * | 1984-03-19 | 1985-10-04 | Nippon Oil Co Ltd | Material used for resist |
| JP2006291177A (en) * | 2005-02-23 | 2006-10-26 | Promerus Llc | Norbornene-type polymer, composition thereof and lithographic process using the same composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5999720A (en) * | 1982-11-30 | 1984-06-08 | Toshiba Corp | Forming method of resist image |
| JPS60195542A (en) * | 1984-03-19 | 1985-10-04 | Nippon Oil Co Ltd | Material used for resist |
| JP2006291177A (en) * | 2005-02-23 | 2006-10-26 | Promerus Llc | Norbornene-type polymer, composition thereof and lithographic process using the same composition |
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