JP2003034667A - Trifluoromethyl norbornene carboxylic acid-tert-butyl ester and its producing method - Google Patents
Trifluoromethyl norbornene carboxylic acid-tert-butyl ester and its producing methodInfo
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- JP2003034667A JP2003034667A JP2001219969A JP2001219969A JP2003034667A JP 2003034667 A JP2003034667 A JP 2003034667A JP 2001219969 A JP2001219969 A JP 2001219969A JP 2001219969 A JP2001219969 A JP 2001219969A JP 2003034667 A JP2003034667 A JP 2003034667A
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- butyl ester
- tertiary
- tert
- acid
- tbn
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、機能性高分子、医
農薬等の原料として有用と期待されるトリフルオロメチ
ルノルボルネンカルボン酸−第三級−ブチルエステル
（以下、Ｆ−ＴＢＮと略記する）とその製造方法に関す
る。TECHNICAL FIELD The present invention relates to trifluoromethylnorbornenecarboxylic acid-tertiary-butyl ester (hereinafter abbreviated as F-TBN), which is expected to be useful as a raw material for functional polymers, pharmaceuticals and agricultural chemicals. And its manufacturing method.
【０００２】[0002]
【従来の技術】近年、半導体の微細化に伴い種々のレジ
スト用モノマー及びポリマーが提案されている。例え
ば、ＡｒＦエキシマレーザー（１９３ｎｍ）用レジスト
モノマーとして、ドライエッチング耐性に優れたノルボ
ルネンカルボン酸系モノマーが提案されている（特開２
００１−９８０３１号広報）。一方、次世代Ｆ２エキシ
マレジスト（１５７ｎｍ）用レジストポリマーとして、
光透過性に優れたフッ素系ポリマーが提案されている
（特開２００１−１８３３３３号公報参照）。2. Description of the Related Art In recent years, various resist monomers and polymers have been proposed with the miniaturization of semiconductors. For example, as a resist monomer for ArF excimer laser (193 nm), a norbornene carboxylic acid-based monomer excellent in dry etching resistance has been proposed (Japanese Patent Laid-Open No. 2-212058)
No. 001-98031). On the other hand, as a resist polymer for the next-generation F2 excimer resist (157 nm),
Fluorine-based polymers having excellent light transmittance have been proposed (see Japanese Patent Laid-Open No. 2001-183333).
【０００３】本発明のＦ−ＴＢＮも、上記化合物と同
様、半導体レジスト用への展開が期待でき、特に遠紫外
線吸収特性、エッチング耐性等の物性が期待される化合
物である。本発明が提供するＦ−ＴＢＮは、文献未記載
の新規化合物であり、その製造方法についても知られて
いない。Like the above compounds, the F-TBN of the present invention is also a compound that can be expected to be applied to semiconductor resists, and is particularly expected to have physical properties such as deep ultraviolet absorption characteristics and etching resistance. The F-TBN provided by the present invention is a novel compound that has not been described in the literature, and its production method is not known.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、機能
性高分子、医農薬等の原料として有用と期待されるＦ−
ＴＢＮ、及びその製造方法を提供することにある。DISCLOSURE OF THE INVENTION The object of the present invention is F-, which is expected to be useful as a raw material for functional polymers, pharmaceuticals and agricultural chemicals.
It is to provide a TBN and a manufacturing method thereof.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、従来の問
題点を解決すべく鋭意検討した結果、下式（ＩＩ）Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the conventional problems, and as a result, the following formula (II)
【０００６】[0006]
【化３】
で示される２−トリフルオロメチルアクリル酸−第三級
−ブチルエステルをシクロペンタジエンと反応させるこ
とによりＦ−ＴＢＮが容易に得られることを見出し、本
発明を完成させるに至った。[Chemical 3] It was found that F-TBN can be easily obtained by reacting 2-trifluoromethylacrylic acid-tertiary-butyl ester represented by with cyclopentadiene, and completed the present invention.
【０００７】すなわち、本発明は、下式（Ｉ）That is, the present invention provides the following formula (I):
【０００８】[0008]
【化４】
で示されるトリフルオロメチルノルボルネンカルボン酸
−第三級−ブチルエステル、及び下式（ＩＩ）[Chemical 4] And a trifluoromethylnorbornenecarboxylic acid-tertiary-butyl ester represented by the following formula (II)
【０００９】[0009]
【化５】
で示される２−トリフルオロメチルアクリル酸−第三級
−ブチルエステルをシクロペンタジエンと反応させるこ
とを特徴とするトリフルオロメチルノルボルネンカルボ
ン酸−第三級−ブチルエステルの製造方法である。[Chemical 5] The method for producing trifluoromethylnorbornenecarboxylic acid-tertiary-butyl ester is characterized by reacting 2-trifluoromethylacrylic acid-tertiary-butyl ester represented by: with cyclopentadiene.
【００１０】以下、本発明について詳細に説明する。The present invention will be described in detail below.
【００１１】本発明の方法において使用される２−トリ
フルオロメチルアクリル酸−第三級−ブチルエステル
は、（１）触媒存在下、２−トリフルオロメチルアクリ
ル酸をイソブチレンと反応させる方法、（２）２−トリ
フルオロメチルアクリル酸クロライドをｔ−ブチルアル
コールと反応させる方法、（３）２−トリフルオロメチ
ルアクリル酸メチルをｔ−ブチルアルコールとエステル
交換させる方法、等により容易に調製できる。The 2-trifluoromethylacrylic acid-tertiary-butyl ester used in the method of the present invention is (1) a method of reacting 2-trifluoromethylacrylic acid with isobutylene in the presence of a catalyst, (2) ) A method of reacting 2-trifluoromethylacrylic acid chloride with t-butyl alcohol, (3) a method of transesterifying methyl 2-trifluoromethylacrylic acid with t-butyl alcohol, and the like can be easily prepared.
【００１２】本発明の方法では、上記の方法で調製した
２−トリフルオロメチルアクリル酸−第三級−ブチルエ
ステルを、シクロペンタジエンと反応させることによ
り、Ｆ−ＴＢＮを効率良く製造することが可能となる。In the method of the present invention, 2-trifluoromethylacrylic acid-tertiary-butyl ester prepared by the above method is reacted with cyclopentadiene, whereby F-TBN can be efficiently produced. Becomes
【００１３】本発明の方法で用いるシクロペンタジエン
の量は、特に限定するものではないが、２−トリフルオ
ロメチルアクリル酸−第三級−ブチルエステルに対し、
１〜１０モル比の範囲が好ましい。このモル比が１より
小では、２−トリフルオロメチルアクリル酸−第三級−
ブチルエステルの十分な転化率が得られない場合があ
り、１０より大では、シクロペンタジエンの量が著しく
増加して経済的でない。The amount of cyclopentadiene used in the method of the present invention is not particularly limited, but it is based on 2-trifluoromethylacrylic acid-tertiary-butyl ester.
A range of 1 to 10 molar ratio is preferable. When this molar ratio is less than 1, 2-trifluoromethylacrylic acid-tertiary-
In some cases, a sufficient conversion of butyl ester may not be obtained, and when it is higher than 10, the amount of cyclopentadiene increases remarkably, which is not economical.
【００１４】また、上記の方法は、通常０℃〜１００
℃、好ましくは１０℃〜５０℃の条件下で実施される。Further, the above method is usually carried out at 0 ° C to 100 ° C.
It is carried out under the condition of C, preferably 10C to 50C.
【００１５】反応終了後は、第三級−ブチルカテコ−ル
等の重合禁止剤を添加して蒸留することにより、目的と
するＦ−ＴＢＮを得る。After completion of the reaction, a desired F-TBN is obtained by adding a polymerization inhibitor such as tertiary-butyl catechol and distilling.
【００１６】[0016]
【実施例】以下に、本発明の方法を実施例により具体的
に説明するが、本発明はこれら実施例のみに限定される
ものではない。EXAMPLES The method of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
【００１７】調製例１（２−トリフルオロメチルアクリ
ル酸−第三級−ブチルエステルの製造）
温度計、攪拌翼を有する１０００ｍｌフラスコに、２−
トリフルオロメチルアクリル酸１００．０ｇ（０．７１
ｍｏｌ）、硫酸１．２ｇ（０．０１ｍｏｌ）、トルエン
１５０．０ｇを仕込み、１０℃でイソブチレンガス７
９．５ｇ（１．４２ｍｏｌ）を約４時間かけて吹き込ん
だ。更に、１０℃で１６時間攪拌した。Preparation Example 1 (Production of 2-trifluoromethylacrylic acid-tertiary-butyl ester) In a 1000 ml flask equipped with a thermometer and a stirring blade, 2-
Trifluoromethylacrylic acid 100.0 g (0.71
mol), 1.2 g (0.01 mol) of sulfuric acid, and 150.0 g of toluene were charged, and isobutylene gas 7 was added at 10 ° C.
9.5 g (1.42 mol) was bubbled in over about 4 hours. Furthermore, it stirred at 10 degreeC for 16 hours.
【００１８】反応終了後、反応液に２０％−炭酸水素ナ
トリウム水溶液５０．０ｇ（０．１２ｍｏｌ）を加え
た。さらに有機層を水５０．０ｇで洗浄した。得られた
有機層に重合禁止剤を加えて減圧蒸留を行い、３７℃／
３．０ｋＰａ留分として無色液体１３９．２ｇ（収率８
８．０％）を得た。After completion of the reaction, 50.0 g (0.12 mol) of 20% -aqueous sodium hydrogen carbonate solution was added to the reaction solution. Further, the organic layer was washed with 50.0 g of water. A polymerization inhibitor was added to the obtained organic layer, and vacuum distillation was carried out at 37 ° C /
As a 3.0 kPa fraction, 139.2 g of a colorless liquid (yield 8
8.0%) was obtained.
【００１９】核磁気共鳴分析、質量分析による分析の結
果、該無色液体は２−トリフルオロメチルアクリル酸−
第三級−ブチルエステルであることを確認した。また、
ガスクロマトグラフィーで分析した結果、２−トリフル
オロメチルアクリル酸−第三級−ブチルエステルの純度
は９９．１％であった。As a result of analysis by nuclear magnetic resonance analysis and mass spectrometry, the colorless liquid was found to be 2-trifluoromethylacrylic acid-
It was confirmed to be a tertiary-butyl ester. Also,
As a result of analysis by gas chromatography, the purity of 2-trifluoromethylacrylic acid-tertiary-butyl ester was 99.1%.
【００２０】（分析結果）
１−ＮＭＲ（ＣＤＣｌ3）
δ（ｐｐｍ）＝６．６２（ｍ，１Ｈ），６．３５（ｍ，
１Ｈ），１．５５（ｓ，９Ｈ）
質量分析（ｍ／ｚ）：１９６（ｍ+）。(Analysis result) 1-NMR (CDCl 3 ) δ (ppm) = 6.62 (m, 1H), 6.35 (m,
1H), 1.55 (s, 9H) mass spectrum (m / z): 196 (m + ).
【００２１】実施例１（Ｆ−ＴＢＮの製造）
温度計、攪拌翼を有する５００ｍｌフラスコに、２−ト
リフルオロメチルアクリル酸−ｔ−ブチルエステル１０
０．０ｇ（０．５１ｍｏｌ）、トルエン１００．０ｇを
仕込み、３０℃でシクロペンタジエン３３．７ｇ（０．
５１ｍｏｌ）を約３０分かけて添加した。更に、３０℃
で３時間攪拌した。Example 1 (Production of F-TBN) 2-Trifluoromethylacrylic acid-t-butyl ester 10 was placed in a 500 ml flask equipped with a thermometer and a stirring blade.
0.0g (0.51 mol) and 100.0 g of toluene were charged, and 33.7 g of cyclopentadiene (0.
51 mol) was added over about 30 minutes. Furthermore, 30 ℃
And stirred for 3 hours.
【００２２】反応終了後、得られた反応液に重合禁止剤
を加えて減圧蒸留を行い、５６℃／０．１３ｋＰａ留分
として無色液体１１９．７ｇ（収率８９．５％）を得
た。After the completion of the reaction, a polymerization inhibitor was added to the obtained reaction solution and vacuum distillation was carried out to obtain 119.7 g (yield 89.5%) of a colorless liquid as a 56 ° C./0.13 kPa fraction.
【００２３】質量分析、元素分析による分析の結果、該
無色液体はＦ−ＴＢＮであることを確認した。また、ガ
スクロマトグラフィーで分析した結果、Ｆ−ＴＢＮの純
度は９９．０％であった。
（分析結果）
質量分析（ｍ／ｚ）：２６２（ｍ+）
元素分析
計算値：Ｃ＝５９．５％，Ｈ＝６．５％，Ｆ＝２１．７
％
実測値：Ｃ＝５９．０％，Ｈ＝６．４％，Ｆ＝２１．０
％。As a result of analysis by mass spectrometry and elemental analysis, it was confirmed that the colorless liquid was F-TBN. As a result of analysis by gas chromatography, the purity of F-TBN was 99.0%. (Analysis result) Mass spectrum (m / z): 262 (m + ) Elemental analysis calculation values: C = 59.5%, H = 6.5%, F = 21.7
% Measured value: C = 59.0%, H = 6.4%, F = 21.0
%.
【００２４】実施例２（Ｆ−ＴＢＮの製造、２−トリフ
ルオロメチルアクリル酸から）
温度計、攪拌翼を有する１０００ｍｌフラスコに、２−
トリフルオロメチルアクリル酸１００．０ｇ（０．７１
ｍｏｌ）、硫酸１．２ｇ（０．０１ｍｏｌ）、ヘプタン
２００．０ｇを仕込み、１０℃でイソブチレンガス５
１．０ｇ（０．８９ｍｏｌ）を約４時間かけて吹き込ん
だ。更に、１０℃で１６時間攪拌した。Example 2 (Production of F-TBN, from 2-trifluoromethylacrylic acid) In a 1000 ml flask equipped with a thermometer and stirring blade, 2-
Trifluoromethylacrylic acid 100.0 g (0.71
mol), 1.2 g (0.01 mol) of sulfuric acid, and 200.0 g of heptane were charged, and isobutylene gas 5 was added at 10 ° C.
1.0 g (0.89 mol) was blown in over about 4 hours. Furthermore, it stirred at 10 degreeC for 16 hours.
【００２５】反応終了後、反応液に５％−水酸化ナトリ
ウム水溶液５０．０ｇ（０．０６ｍｏｌ）を加えた。さ
らに有機層を水５０．０ｇで洗浄した。After completion of the reaction, 50.0 g (0.06 mol) of 5% -sodium hydroxide aqueous solution was added to the reaction solution. Further, the organic layer was washed with 50.0 g of water.
【００２６】得られた有機層を、温度計、攪拌翼を有す
る５００ｍｌフラスコに移し、２０℃でシクロペンタジ
エン３３．７ｇ（０．５１ｍｏｌ）を約１時間かけて添
加した。更に、２０℃で５時間攪拌した。The obtained organic layer was transferred to a 500 ml flask having a thermometer and a stirring blade, and 33.7 g (0.51 mol) of cyclopentadiene was added at 20 ° C. over about 1 hour. Furthermore, it stirred at 20 degreeC for 5 hours.
【００２７】反応終了後、ガスクロマトグラフィ−で分
析したところ、Ｆ−ＴＢＮが８７．９％（Ｆ−ＴＢＮ
１６３．７ｇ）の収率で生成していた。After completion of the reaction, analysis by gas chromatography revealed that F-TBN was 87.9% (F-TBN
It was produced in a yield of 163.7 g).
【００２８】[0028]
【発明の効果】本発明によれば、機能性高分子、医農薬
等の原料として有用と期待されるＦ−ＴＢＮ、及びその
製造方法を提供することができ、工業的に極めて有用で
ある。Industrial Applicability According to the present invention, it is possible to provide F-TBN, which is expected to be useful as a raw material for functional polymers, pharmaceuticals and agricultural chemicals, and a method for producing the same, and it is industrially very useful.
Claims (3)
−第三級−ブチルエステル。1. The following formula (I): A trifluoromethylnorbornenecarboxylic acid-tertiary-butyl ester represented by:
−ブチルエステルをシクロペンタジエンと反応させるこ
とを特徴とするトリフルオロメチルノルボルネンカルボ
ン酸−第三級−ブチルエステルの製造方法。2. The following formula (II): A method for producing trifluoromethylnorbornenecarboxylic acid-tertiary-butyl ester, which comprises reacting 2-trifluoromethylacrylic acid-tertiary-butyl ester represented by: with cyclopentadiene.
ソブチレンを反応させて２−トリフルオロメチルアクリ
ル酸−第三級−ブチルエステルを合成し、得られた２−
トリフルオロメチルアクリル酸−第三級−ブチルエステ
ルをシクロペンタジエンと反応させることを特徴とする
請求項２に記載の製造方法。3. 2-Trifluoromethylacrylic acid and isobutylene are reacted to synthesize 2-trifluoromethylacrylic acid-tertiary-butyl ester, and the obtained 2-
The method according to claim 2, wherein trifluoromethylacrylic acid-tertiary-butyl ester is reacted with cyclopentadiene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001219969A JP2003034667A (en) | 2001-07-19 | 2001-07-19 | Trifluoromethyl norbornene carboxylic acid-tert-butyl ester and its producing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001219969A JP2003034667A (en) | 2001-07-19 | 2001-07-19 | Trifluoromethyl norbornene carboxylic acid-tert-butyl ester and its producing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003034667A true JP2003034667A (en) | 2003-02-07 |
Family
ID=19053863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001219969A Pending JP2003034667A (en) | 2001-07-19 | 2001-07-19 | Trifluoromethyl norbornene carboxylic acid-tert-butyl ester and its producing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003034667A (en) |
-
2001
- 2001-07-19 JP JP2001219969A patent/JP2003034667A/en active Pending
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