JPH0680022B2 - Process for producing perfluorohexylmethylbenzene derivative - Google Patents
Process for producing perfluorohexylmethylbenzene derivativeInfo
- Publication number
- JPH0680022B2 JPH0680022B2 JP61072206A JP7220686A JPH0680022B2 JP H0680022 B2 JPH0680022 B2 JP H0680022B2 JP 61072206 A JP61072206 A JP 61072206A JP 7220686 A JP7220686 A JP 7220686A JP H0680022 B2 JPH0680022 B2 JP H0680022B2
- Authority
- JP
- Japan
- Prior art keywords
- perfluorohexylmethylbenzene
- derivative
- producing
- reaction
- perfluoro
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は界面活性剤の出発原料、並びに電気装置におけ
る絶縁油、精密機器に使用される不活性作動油として有
用なペルフルオロヘキシルメチルベンゼン誘導体の製造
法に関する。TECHNICAL FIELD The present invention relates to a starting material for a surfactant, a method for producing a perfluorohexylmethylbenzene derivative useful as an insulating oil in electric devices, and an inert hydraulic oil used in precision instruments. Regarding
従来技術および発明が解決しようとする問題点 ペルフルオロ−２−メチルペント−２−エンとベンジル
ブロマイドからペルフルオロヘキシルメチルベンゼンを
製造する方法は知られている［マカロフら（K.N.MAKARO
V et al）；ジャーナル・オブ・ブルオライン・ケミス
トリー（Journal of Fluorine Chemistry）第10巻、第1
57頁〜第158頁（1977）参照］。この合成法によれば、
反応溶媒としてジリムを使用し塩基性触媒としてフッ化
セシウムを使用することによって、室温、且つ短時間で
高収率でペルフルオロヘキシルメチルベンゼンが得られ
る。Problems to be Solved by Prior Art and Invention A method for producing perfluorohexylmethylbenzene from perfluoro-2-methylpent-2-ene and benzyl bromide is known [KNMAKARO et al.
V et al); Journal of Fluorine Chemistry, Volume 10, Volume 1.
See pages 57-158 (1977)]. According to this synthetic method,
By using dilim as the reaction solvent and cesium fluoride as the basic catalyst, perfluorohexylmethylbenzene can be obtained in high yield at room temperature and in a short time.
この反応は、次式のように中間状態として、ペルフルオ
ロ−tert−カルボアニオンを経由して進行すると考えら
れているが。It is believed that this reaction proceeds as an intermediate state via the perfluoro-tert-carbanion as shown in the following formula.
しかしながら、フッ化セシウムは高価且つ非常に吸湿性
の強い化合物の為、実用的でない。フッ化セシウムのか
わりにKF、NaFを用いて上と同様の条件下でこの反応を
行っても、目的化合物は極端に低い収率でしか得られな
い。これはフッ化ナトリウムやフッ化カリウムでは、安
定なカルボアニオンの生成が困難なために反応が進行し
難いものと考えられる。 However, cesium fluoride is an expensive and extremely hygroscopic compound and is not practical. Even when KF or NaF is used instead of cesium fluoride under the same conditions as above, the target compound can be obtained only in an extremely low yield. This is considered to be because it is difficult for sodium fluoride or potassium fluoride to generate a stable carbanion and thus the reaction is difficult to proceed.
この事は、従来、ヘキサフルオロオレフィン、又はテト
ラフルオロオレフィンの低分子量のオリゴマー（二量
体、三量体）のフッ素化剤としては、ほとんどフッ化セ
シウムに限られているという事実と対応する［例えば、
特開昭57−150625号公報およびヤコブソンら（G.G.YAKO
BSON et.al.）；シンセシス（Synthesis）第169頁（198
3）参照］。This corresponds to the fact that cesium fluoride has been mostly used as a fluorinating agent for low molecular weight oligomers (dimers, trimers) of hexafluoroolefin or tetrafluoroolefin. For example,
JP-A-57-150625 and Jacobson et al. (GGYAKO
BSON et.al.); Synthesis, page 169 (198)
See 3)].
本発明者らは高価なCsFの代わりにKFを使用し、反応溶
媒としてジグリムの代わりにジメチルホルムアミド（DM
F）を使用することによってペルフルオロヘキシルメチ
ルベンゼン誘導体が高収率で得られることを究明して本
発明を完成した。The present inventors used KF instead of expensive CsF, and used dimethylformamide (DMF) instead of diglyme as a reaction solvent.
The present invention has been completed by investigating that a high yield of a perfluorohexylmethylbenzene derivative can be obtained by using F).
問題点を解決するための手段 即ち、本発明は、ペルフルオロ−２−メチルペント−２
−エンおよび一般式［Ｉ］： （式中、ＲはＨ、ｐ−CN、ｍ−CN、ｏ−CN、ｐ−NO2、
ｍ−NO2、ｏ−NO2、ｐ−CH2Brまたはｍ−CH2Brを表わ
す） で表わされるベンジルブロマイド誘導体をジメチルホル
ムアミド溶媒中、フッ化カリウムの存在下で反応させる
ことを特徴とする、一般式［II］： （式中、Ｒ′はＨ、ｐ−CN、ｍ−CN、ｏ−CN、ｐ−N
O2、ｍ−NO2、ｏ−NO2、ｐ−CH2Rfまたはｍ−CH2Rf基を
表わし、 Rfは を表わす。） で表わされるペルフルオロヘキシルメチルベンゼン誘導
体の製造法に関する。Means for Solving the Problems That is, the present invention relates to perfluoro-2-methylpent-2
-Ene and the general formula [I]: (Wherein, R H, p-CN, m- CN, o-CN, p-NO 2,
dimethylformamide in a solvent of benzyl bromide derivative represented by representing the m-NO 2, o-NO 2, p-CH 2 Br or m-CH 2 Br), which comprises reacting in the presence of potassium fluoride , General formula [II]: (In the formula, R'is H, p-CN, m-CN, o-CN, p-N
Represents an O 2 , m-NO 2 , o-NO 2 , p-CH 2 Rf or m-CH 2 Rf group, and Rf represents Represents ) Relates to a process for producing a perfluorohexylmethylbenzene derivative.
ペルフルオロ−２−メチルペント−２−エンは例えばヘ
キサフルオロプロペンの２量化反応によって容易に得る
ことができる。Perfluoro-2-methylpent-2-ene can be easily obtained, for example, by a dimerization reaction of hexafluoropropene.
本発明に使用するベンジルブロマイド誘導体としては、
前記一般式［Ｉ］において置換基ＲがＨ、ｐ−CN、ｍ−
CN、ｏ−CN、ｐ−NO2、ｍ−NO2、ｏ−NO2、ｐ−CH2Brま
たはｍ−CH2Brを表す化合物が例示される。Examples of the benzyl bromide derivative used in the present invention include:
In the general formula [I], the substituent R is H, p-CN, m-
CN, o-CN, compounds representative of the p-NO 2, m-NO 2, o-NO 2, p-CH 2 Br or m-CH 2 Br may be mentioned.
ペルフルオロ−２−メチルペント−２−エンとベンジル
ブロマイド誘導体との反応モル比は特に限定的ではない
が通常は前者１モルに対して後者約0.5〜２モル、好ま
しくは約0.5〜１モルである。The reaction molar ratio of perfluoro-2-methylpent-2-ene and the benzyl bromide derivative is not particularly limited, but is usually about 0.5 to 2 mol, preferably about 0.5 to 1 mol for the latter with respect to 1 mol for the former.
KFの使用量も特に限定的ではないが通常はペルフルオロ
−２−メチルペント−２−エン１モルに対して約１〜３
モル、好ましくは約１〜２モルである。The amount of KF used is not particularly limited, but is usually about 1 to 3 with respect to 1 mol of perfluoro-2-methylpent-2-ene.
Mol, preferably about 1-2 mol.
上記の反応成分をDMF中、通常は約50〜150℃、好ましく
は約80〜130℃の温度において約２〜70時間反応させる
ことによって、前記一般式［II］によって表わされるペ
ルフルオロヘキシルメチルベンゼン誘導体が高収率で得
られる。By reacting the above reaction components in DMF at a temperature of usually about 50 to 150 ° C., preferably about 80 to 130 ° C. for about 2 to 70 hours, a perfluorohexylmethylbenzene derivative represented by the general formula [II] is obtained. Is obtained in high yield.
以下、本発明を実施例によって説明する。Hereinafter, the present invention will be described with reference to examples.
実施例１ ４−［2,2−ビス（トリフルオロメチル）−3,3,4,4,5,
5,5−ヘプタフルオロペンチル］ベンゾニトリル（IIa）
の合成。Example 1 4- [2,2-bis (trifluoromethyl) -3,3,4,4,5,
5,5-Heptafluoropentyl] benzonitrile (IIa)
Synthesis of.
ペルフルオロ−２−メチルペント−２−エン（4.50g、1
5mmol）、フッ化カリウム（1.16g、20mmol）、α−ブロ
モ−ｐ−トルニトリル（1.96g、10mmol）とN,N−ジメチ
ルホルムアミド（10ml）を反応容器に加え、よく撹拌し
ながら、100℃で10時間反応を行う。反応終了後、反応
液をエーテル溶媒中に移し、水、５％NaHCO3水溶液、水
の順序でよく洗浄する。その後、エーテルを除去して、
黄色オイル状液体を得る。未反応のベンジルブロマイド
を除去する為に、黄色混合物をエーテル／ピリジン混合
溶液中に加え、室温で３時間良く撹拌する。引き続き、
水、５％HCl水溶液、水の順序で洗浄する。その後、有
機溶媒相を取り出し、無水硫酸マグネシウムで乾燥、溶
媒を除去後、蒸留によって、無色透明液体の標記化合物
（4.26g;収率98％）を得た。この化合物の物性を表３に
示す。Perfluoro-2-methylpent-2-ene (4.50 g, 1
5 mmol), potassium fluoride (1.16 g, 20 mmol), α-bromo-p-tolunitrile (1.96 g, 10 mmol) and N, N-dimethylformamide (10 ml) were added to a reaction vessel, and the mixture was stirred well at 100 ° C. Incubate for 10 hours. After completion of the reaction, the reaction solution is transferred into an ether solvent and washed well with water, 5% NaHCO 3 aqueous solution and water in this order. Then remove the ether,
A yellow oily liquid is obtained. In order to remove the unreacted benzyl bromide, the yellow mixture is added to the ether / pyridine mixed solution and well stirred at room temperature for 3 hours. Continuing,
Wash with water, 5% aqueous HCl, then water. Then, the organic solvent phase was taken out, dried over anhydrous magnesium sulfate, the solvent was removed, and the residue was distilled to obtain the title compound (4.26 g; yield 98%) as a colorless transparent liquid. Table 3 shows the physical properties of this compound.
実施例２〜９ 実施例１の手順に準拠し、表１の反応条件下で化合物II
aを合成した。収率を表１に示す。Examples 2-9 According to the procedure of Example 1, under the reaction conditions of Table 1, compound II
a was synthesized. The yield is shown in Table 1.
比較例１〜５ 実施例１の手順に準拠し、表１の反応条件下で化合物II
aを合成した。収率を表１に示す。Comparative Examples 1-5 According to the procedure of Example 1, compound II under the reaction conditions of Table 1 was used.
a was synthesized. The yield is shown in Table 1.
実施例10〜17 実施例１の手順に準拠し、表２の合成条件によって化合
物IIa〜g,j,kを合成した。これらの化合物の収率および
物性を表３に示す。 Examples 10 to 17 According to the procedure of Example 1, compounds IIa to g, j, k were synthesized under the synthesis conditions shown in Table 2. Table 3 shows the yield and physical properties of these compounds.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 253/30 255/50 Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display area C07C 253/30 255/50
Claims (2)
ンおよび一般式［Ｉ］： （式中、ＲはＨ、ｐ−CN、ｍ−CN、ｏ−CN、ｐ−NO2、
ｍ−NO2、ｏ−NO2、ｐ−CH2Brまたはｍ−CH2Brを表わ
す） で表わされるベンジルブロマイド誘導体をジメチルホル
ムアミド溶媒中、フッ化カリウムの存在下で反応させる
ことを特徴とする、一般式［II］： （式中、Ｒ′はＨ、ｐ−CN、ｍ−CN、ｏ−CN、ｐ−N
O2、ｍ−NO2、ｏ−NO2、ｐ−CH2Rfまたはｍ−CH2Rf基を
表わし、 Rfは を表わす。） で表わされるペルフルオロヘキシルメチルベンゼン誘導
体の製造法。1. Perfluoro-2-methylpent-2-ene and the general formula [I]: (Wherein, R H, p-CN, m- CN, o-CN, p-NO 2,
dimethylformamide in a solvent of benzyl bromide derivative represented by representing the m-NO 2, o-NO 2, p-CH 2 Br or m-CH 2 Br), which comprises reacting in the presence of potassium fluoride , General formula [II]: (In the formula, R'is H, p-CN, m-CN, o-CN, p-N
Represents an O 2 , m-NO 2 , o-NO 2 , p-CH 2 Rf or m-CH 2 Rf group, and Rf represents Represents ) A method for producing a perfluorohexylmethylbenzene derivative represented by
の方法。2. The method according to claim 1, wherein the reaction temperature is about 50 to 150 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61072206A JPH0680022B2 (en) | 1986-03-28 | 1986-03-28 | Process for producing perfluorohexylmethylbenzene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61072206A JPH0680022B2 (en) | 1986-03-28 | 1986-03-28 | Process for producing perfluorohexylmethylbenzene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62226932A JPS62226932A (en) | 1987-10-05 |
| JPH0680022B2 true JPH0680022B2 (en) | 1994-10-12 |
Family
ID=13482530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61072206A Expired - Fee Related JPH0680022B2 (en) | 1986-03-28 | 1986-03-28 | Process for producing perfluorohexylmethylbenzene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0680022B2 (en) |
-
1986
- 1986-03-28 JP JP61072206A patent/JPH0680022B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62226932A (en) | 1987-10-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |