JP3143650B2 - Novel fluoroolefin ether and method for producing the same - Google Patents
Novel fluoroolefin ether and method for producing the sameInfo
- Publication number
- JP3143650B2 JP3143650B2 JP11082462A JP8246299A JP3143650B2 JP 3143650 B2 JP3143650 B2 JP 3143650B2 JP 11082462 A JP11082462 A JP 11082462A JP 8246299 A JP8246299 A JP 8246299A JP 3143650 B2 JP3143650 B2 JP 3143650B2
- Authority
- JP
- Japan
- Prior art keywords
- producing
- butene
- methoxyheptafluoro
- novel
- ppm
- 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 - Lifetime
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は新規なフルオロオレ
フィンエーテル及びその製造方法に関するものである。
さらに詳しくいえば、本発明は、代替フロン、界面活性
剤、農薬、医薬品などとして、あるいは代替フロン、界
面活性剤、農薬、医薬品などのフッ素含有製品の合成中
間体などとして有用な１−メトキシヘプタフルオロ−２
−ブテン（ｃｉｓ、ｔｒａｎｓミクスチャー）を、容易
に入手しうる原料を用いて、高収率で経済的に製造する
方法に関するものである。The present invention relates to a novel fluoroolefin ether and a method for producing the same.
More specifically, the present invention relates to 1-methoxyhepta useful as a substitute for CFCs, surfactants, agricultural chemicals, pharmaceuticals, or as a synthetic intermediate for fluorine-containing products such as CFC substitutes, surfactants, agricultural chemicals, and pharmaceuticals. Fluoro-2
The present invention relates to a method for economically producing butene (cis, trans mixture) in a high yield using easily available raw materials.
【０００２】[0002]
【従来の技術】近年、含フッ素オレフィンエーテル化合
物は、種々のフッ素含有製品の合成中間体や原料として
脚光を浴びており、例えば界面活性剤、農薬、医薬品な
どの合成中間体として広く用いられている。ところで、
既知の含フッ素オレフィンエーテル類としては、ＣＦ3
ＯＣＦ＝ＣＦ2[「ブリテイン・ケミカル・ソサイアティ
・オブ・ジャパン（Bull.Chem.Soc.Japan)」３５巻Ｎ
ｏ．４第５３２ページ(１９６２年)]、ＣＦ3ＯＣＦ＝Ｃ
Ｆ2［Zr.Org.Khim.(１９８２),１８（９），１８４６]
などが知られている。2. Description of the Related Art In recent years, fluorine-containing olefin ether compounds have been spotlighted as synthetic intermediates and raw materials for various fluorine-containing products. For example, they have been widely used as synthetic intermediates for surfactants, agricultural chemicals and pharmaceuticals. I have. by the way,
Known fluorine-containing olefin ethers include CF 3
OCF = CF 2 [Bulletin Chemical Society of Japan (Bull.Chem.Soc.Japan)] Volume 35 N
o. 4 page 532 (1962)], CF 3 OCF = C
F 2 [Zr. Org. Khim. (1982), 18 (9), 1846]
Etc. are known.
【０００３】[0003]
【発明が解決しようとする課題】本発明の課題は、合成
中間体や含フッ素重合体製造用単量体などとして有用な
１−メトキシヘプタフルオロ−２−ブテンを、容易に入
手しうる原料を用いて、簡単に製造する方法を提供する
ことにある。An object of the present invention is to provide 1-methoxyheptafluoro-2-butene, which is useful as a synthetic intermediate or a monomer for producing a fluoropolymer, from a raw material which can be easily obtained. To provide a simple manufacturing method.
【０００４】[0004]
【課題を解決するための手段】本発明者は前記課題を解
決すべく鋭意研究を重ねた結果、ＭｅＯＦとヘキサフル
オロ−１，３−ブタジエンを反応させることにより、１
−メトキシヘプタフルオロ−２−ブテンが得られること
を見出し、この知見に基づいて本発明を完成するに至っ
た。すなわち、本発明は、下記式（１）The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by reacting MeOF with hexafluoro-1,3-butadiene, 1 is obtained.
-Methoxyheptafluoro-2-butene was found to be obtained, and the present invention was completed based on this finding. That is, the present invention provides the following formula (1)
【化３】 で表される１−メトキシヘプタフルオロ−２−ブテン
（ｃｉｓ、ｔｒａｎｓミクスチャー）を提供するもので
ある。また、本発明は、ＣＨ3ＯＦとヘキサフルオロ−
１，３−ブタジエンを反応させることを特徴とする前記
化合物の製造方法を提供するものである。Embedded image 1-methoxyheptafluoro-2-butene (cis, trans mixture) represented by the formula: Further, the present invention relates to CH 3 OF and hexafluoro-
An object of the present invention is to provide a method for producing the compound, wherein 1,3-butadiene is reacted.
【０００５】[0005]
【発明の実施の形態】本発明によるＣＨ3ＯＦとヘキサ
フルオロ−１，３−ブタジエンを反応は、アセトニトリ
ル、プロピオニトリル、アセトン、ジクロロメタン、ク
ロロホルム、ベンゼン等の溶媒中、または無溶媒で行わ
れる。反応温度は−８０〜１００℃、好ましくは−５０
〜５０℃の範囲である。ＣＨ 3ＯＦの使用割合は、ヘキ
サフルオロ−１，３−ブタジエン１モル当り、０．１〜
１０モル、好ましくは０．５〜２モルの割合である。DETAILED DESCRIPTION OF THE INVENTION CH according to the inventionThreeOF and Hex
Reaction of fluoro-1,3-butadiene with acetonitrile
, Propionitrile, acetone, dichloromethane,
Performed in a solvent such as loroform or benzene or without solvent
It is. The reaction temperature is -80 to 100 ° C, preferably -50.
~ 50 ° C. CH ThreeThe usage rate of OF
0.1 to 0.1 mol per mole of safluoro-1,3-butadiene
The ratio is 10 mol, preferably 0.5 to 2 mol.
【０００６】[0006]
【発明の効果】本発明方法によると、新規な１−メトキ
シヘプタフルオロ−２−ブテン（ｃｉｓ、ｔｒａｎｓミ
クスチャー）を、容易に入手しうる原料から、極めて簡
単なプロセスにより高収率で得ることがである。また、
得られた１−メトキシヘプタフルオロ−２−ブテン（ｃ
ｉｓ、ｔｒａｎｓミクスチャー）は、代替フロン、界面
活性剤、農薬、医薬品などとして、あるいは代替フロ
ン、界面活性剤、農薬、医薬品などのフッ素含有製品の
合成中間体などとして、工業的価値の極めて高いもので
ある。According to the process of the present invention, a novel 1-methoxyheptafluoro-2-butene (cis, trans mixture) can be obtained in a high yield from an easily available raw material by an extremely simple process. It is. Also,
The obtained 1-methoxyheptafluoro-2-butene (c
is, trans mixture) is extremely high in industrial value as an alternative fluorocarbon, surfactant, agricultural chemical, pharmaceutical, etc., or as a synthetic intermediate of fluorine-containing products, such as fluorocarbon alternative, surfactant, agricultural chemical, pharmaceutical, etc. It is.
【０００７】[0007]
【実施例】以下、本発明について実施例を用いて説明す
るが、本発明は実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples.
【０００８】実施例１ 反応はモネル製のラインを組んで行った。メタノール
２．５ｍｌ、プロピオニトリル ２．５ｍｌをＳＵＳ製
２５ｍｌの反応器に入れ、−７８℃に冷却した。ここ
に、Ｈｅ ９０ｍｌ／ｍｉｎ、Ｆ2 １０ｍｌ／ｍｉｎ
を６０分間バブリングした（Ｆ2 ２６．８ｍｍｏ
ｌ）。その後、Ｈｅで追い出ししてＣＨ3ＯＦ２．６ｍ
ｍｏｌを得た。こうして得たＣＨ3ＯＦとヘキサフルオ
ロ−１，３−ブタジエンをプロピオニトリル溶媒中で反
応を行った合成法を以下に示す。ＣＨ3ＯＦ２．６ｍｍ
ｏｌとヘキサフルオロ−１，３−ブタジエン３．０ｍｍ
ｏｌを、プロピオニトリル０．４２ｇの入った内容積１
ｃｃのＮＭＲチューブに液体窒素冷却温度で入れた。そ
の後、徐々に室温に戻し、１５時間後に内容物をＮＭ
Ｒ、ＧＣＭＳで測定した。その結果、原料のヘキサフル
オロ−１，３−ブタジエンと、１−メトキシヘプタフル
オロ−ｔｒａｎｓ−２−ブテン（ｔｒａｎｓ−ＣＦ3Ｃ
Ｆ＝ＣＦＣＦ2ＯＣＨ 3）が２．１２ｍｍｏｌ(ＣＨ3ＯＦ
基準収率８４％)、１−メトキシヘプタフルオロ−ｃｉ
ｓ−２−ブテン（ｃｉｓ−ＣＦ3ＣＦ＝ＣＦＣＦ2ＯＣＨ
3）が０．２８ｍｍｏｌ(ＣＨ3ＯＦ基準収率１１％)、そ
の他ＣＨ3ＯＦの分解物と考えれるトリオキサン等が確
認された。これを蒸留したところ、ＣＦ3ＣＦ＝ＣＦＣ
Ｆ2ＯＣＨ 3（ｃｉｓ：ｔｒａｎｓ＝１：７．６)が１．
０ｍｍｏｌ(ＣＨ3ＯＦ基準収率４０％)得られた。Example 1 The reaction was carried out in a Monel line. Methanol
2.5ml, propionitrile 2.5ml made by SUS
Placed in a 25 ml reactor and cooled to -78 ° C. here
He 90ml / min, FTwo 10ml / min
Was bubbled for 60 minutes (FTwo 26.8mmo
l). After that, drive out with He and CHThree2.6m OF
mol was obtained. CH thus obtainedThreeOF and hexafluo
B-1,3-butadiene is reacted in a propionitrile solvent
The synthesis method used for the reaction is shown below. CHThreeOF2.6mm
ol and hexafluoro-1,3-butadiene 3.0 mm
ol, an internal volume 1 containing 0.42 g of propionitrile
The cc NMR tube was placed at liquid nitrogen cooling temperature. So
After that, gradually return to room temperature, and after 15 hours,
R was measured by GCMS. As a result, hexaflu
Oro-1,3-butadiene and 1-methoxyheptaful
Oro-trans-2-butene (trans-CFThreeC
F = CFCFTwoOCH Three) Is 2.12 mmol (CHThreeOF
Reference yield 84%), 1-methoxyheptafluoro-ci
s-2-butene (cis-CFThreeCF = CFCFTwoOCH
Three) Is 0.28 mmol (CHThree11% based on OF)
Other CHThreeTrioxane, which is considered to be a decomposition product of OF
It has been certified. When this was distilled, CFThreeCF = CFC
FTwoOCH Three(Cis: trans = 1: 7.6).
0 mmol (CHThreeOF reference yield: 40%).
【０００９】得られた精製物のＧＣ−ＭＳ分析、1Ｈ−
ＮＭＲ分析、19Ｆ−ＮＭＲ分析を行い次のような結果を
得た。これにより、本反応の合成物が１−メトキシヘプ
タフルオロ−２−ブテン（ｃｉｓ、ｔｒａｎｓミクスチ
ャー）であることを確認した。[0009] GC-MS analysis of the obtained purified product, 1 H-
NMR analysis and 19 F-NMR analysis were performed, and the following results were obtained. This confirmed that the synthesized product of this reaction was 1-methoxyheptafluoro-2-butene (cis, trans mixture).
【００１０】分析結果 １−メトキシヘプタフルオロ−２−ブテン、 １）ＧＣ−ＭＳ分析 ＭＳ(ｍ／ｚ，[fragment]，％ intensity relative to
the parent ion) ２１２,［CH3OCF2CFCFCF3］,１０.５ １９３,［CH3O
CF2CFCFCF2］,１３.６ １８１,［CF2CFCFCF3］,３０.１ １５９,［OCF2CFCF
CF］,４６.４ １４３,［CH3OCF2CFCF］,１７.３ １３１,［CFCFC
F3］,７７.６ １０９,［OCFCFCF］,１６.３ ９３,［CFCFCF］,２
３.１ ８１,［CFCF3］,８０.５ ６９,［CF3］,３９.０ ６２,［CH3OCF］,４７.４ ４７,［OCF］,１５.５ ３１,［CH3O］,３３.０ ２９,［CHO］,１７.２ ２８,［CO］,１４.９ １５,［CH3］,１００.０Analysis results 1-methoxyheptafluoro-2-butene, 1) GC-MS analysis MS (m / z, [fragment],% intensity relative to
the parent ion) 212, [CH 3 OCF 2 CFCFCF 3 ], 10.5 193, [CH 3 O
CF 2 CFCFCF 2 ], 13.6 181, [CF 2 CFCFCF 3 ], 30.1 159, [OCF 2 CFCF
CF], 46.4 143, [CH 3 OCF 2 CFCF], 17.3 131, [CFCFC
F 3 ], 77.6 109, [OCFCFCF], 16.3 93, [CFCFCF], 2
3.1 81, [CFCF 3 ], 80.5 69, [CF 3 ], 39.0 62, [CH 3 OCF], 47.4 47, [OCF], 15.5 31, [CH 3 O] , 33.0 29, [CHO], 17.2 28, [CO], 14.9 15, [CH 3], 100.0
【００１１】ＮＭＲ分析には、日本電子（株）製ＥＸ−
２７０を使用した。 １−メトキシヘプタフルオロ−２−ブテン ２）1Ｈ−ＮＭＲ分析 ケミカルシフト（ｐｐｍ：ＴＭＳ基準 カップリング定
数はＨｚ）３.７ｐｐｍ ｓFor NMR analysis, JEOL Ltd. EX-
270 was used. 1-methoxyheptafluoro-2-butene 2) 1 H-NMR analysis Chemical shift (ppm: TMS standard coupling constant is Hz) 3.7 ppm s
【００１２】３）19Ｆ−ＮＭＲ分析 ケミカルシフト（ｐｐｍ：ＣＦＣｌ3基準 カップリン
グ定数はＨｚ）１−メトキシヘプタフルオロ−ｃｉｓ−
２−ブテン3) 19 F-NMR analysis Chemical shift (ppm: coupling constant based on CFCl 3 is Hz) 1-methoxyheptafluoro-cis-
2-butene
【化４】 ａ −７４．８ｐｐｍ ｍ ｂ −１４７．１ｐｐｍ ｍ ｃ −１３９．５ｐｐｍ ｍ ｄ −６５．８ｐｐｍ ｍEmbedded image a-74.8 ppm mb-147.1 ppm mc-139.5 ppm md-65.8 ppm m
【００１３】１−メトキシヘプタフルオロ−ｔｒａｎｓ
−２−ブテン1-methoxyheptafluoro-trans
-2-butene
【化５】 ｅ −７６．５ｐｐｍ ｄ ２０．８Ｈｚ ｄ
９．８Ｈｚ ｆ −１６２．８ｐｐｍ ｄ １３８．０Ｈｚ ｇ −１５７．１ｐｐｍ ｄ １３８．０Ｈｚ ｈ −６８．９ｐｐｍ ｄ ２２．０Ｈｚ ｄ
９．８ＨｚEmbedded image e -76.5 ppm d 20.8 Hz d
9.8 Hz f-162.8 ppm d 138.0 Hz g-157.1 ppm d 138.0 Hz h-68.9 ppm d 22.0 Hz d
9.8Hz
───────────────────────────────────────────────────── フロントページの続き (72)発明者 黒河 勇治 東京都文京区本郷２−40−17本郷若井ビ ル６階 財団法人地球環境産業技術研究 機構 新規冷媒等プロジェクト室内 (72)発明者 村田 潤治 東京都文京区本郷２−40−17本郷若井ビ ル６階 財団法人地球環境産業技術研究 機構 新規冷媒等プロジェクト室内 (72)発明者 阿部 隆 愛知県名古屋市北区平手町１−１ 工業 技術院名古屋工業技術研究所内 (72)発明者 関屋 章 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 審査官 藤森 知郎 (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 43/17 C07C 41/06 ＣＡＯＬＤ（ＳＴＮ) ＣＡＰＬＵＳ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yuji Kurokawa 6F, Hongo Wakai Building 2-40-17 Hongo, Bunkyo-ku, Tokyo New Refrigerant Project Room, etc. (72) Inventor Junji Murata 6-floor Hongo Wakai Building, Hongo 2-40-17, Bunkyo-ku, Tokyo New Technology Project Room (72) Inventor Takashi Abe 1-1, Hiratecho, Kita-ku, Nagoya-shi, Aichi Nagoya industrial technology in the Laboratory (72) inventor Akira Sekiya Higashi, Tsukuba, Ibaraki 1 chome industrial technology Institute substance Institute of Advanced industrial Science and technology in the examiner Tomo Fujimori Ichiro (58) investigated the field (Int.Cl. 7, DB name) C07C 43/17 C07C 41/06 CAOLD (STN) CAPLUS (STN) REGISTRY (STN)
Claims (2)
テン。[Claim 1] The following formula (1) A novel 1-methoxyheptafluoro-2-butene represented by the formula:
ブタジエンとを反応させることを特徴とする下記式
（１） 【化２】 で表される１−メトキシヘプタフルオロ−２−ブテンの
製造方法。2. CH 3 OF and hexafluoro-1,3-
Reacting butadiene with the following formula (1): A method for producing 1-methoxyheptafluoro-2-butene represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11082462A JP3143650B2 (en) | 1999-03-25 | 1999-03-25 | Novel fluoroolefin ether and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11082462A JP3143650B2 (en) | 1999-03-25 | 1999-03-25 | Novel fluoroolefin ether and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000281612A JP2000281612A (en) | 2000-10-10 |
| JP3143650B2 true JP3143650B2 (en) | 2001-03-07 |
Family
ID=13775185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11082462A Expired - Lifetime JP3143650B2 (en) | 1999-03-25 | 1999-03-25 | Novel fluoroolefin ether and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3143650B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050014383A1 (en) * | 2003-07-15 | 2005-01-20 | Bing Ji | Use of hypofluorites, fluoroperoxides, and/or fluorotrioxides as oxidizing agent in fluorocarbon etch plasmas |
| JP6514695B2 (en) * | 2013-07-25 | 2019-05-15 | スリーエム イノベイティブ プロパティズ カンパニー | Nitrogen-containing hydrofluoroether and method for producing the same |
-
1999
- 1999-03-25 JP JP11082462A patent/JP3143650B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JP2000281612A (en) | 2000-10-10 |
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