JPS62106036A - Hexafluoroisobutenyl ether and its production - Google Patents
Hexafluoroisobutenyl ether and its productionInfo
- Publication number
- JPS62106036A JPS62106036A JP24575385A JP24575385A JPS62106036A JP S62106036 A JPS62106036 A JP S62106036A JP 24575385 A JP24575385 A JP 24575385A JP 24575385 A JP24575385 A JP 24575385A JP S62106036 A JPS62106036 A JP S62106036A
- Authority
- JP
- Japan
- Prior art keywords
- ether
- hydride
- hexafluoroisobutenyl
- formula
- production
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規物質たるヘキサフルオロイソブテニルエ
ーテルおよびその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new substance, hexafluoroisobutenyl ether, and a method for producing the same.
〔従来の技術〕および〔発明の課題〕
オクタフルオロイソブチンは、含フツ素共重合体の重要
な原料の一種であるヘキサフルオロプロペン製造時の副
生成物であり、この毒性の強いオクタフルオロイソブチ
ンは、一般に低級アルコール、例えばメタノール、エタ
ノール、ｎ−プロパツール、イソプロパツール、ｎ−ブ
タノールなどのアルコール付加物を容易に形成する性質
を有している。[Prior Art] and [Problem of the Invention] Octafluoroisobutyne is a by-product during the production of hexafluoropropene, which is an important raw material for fluorine-containing copolymers. Butyne generally has the property of easily forming alcohol adducts such as lower alcohols, such as methanol, ethanol, n-propanol, isopropanol, and n-butanol.
このアルコール付加物たるオクタフルオロインブチルア
ルキルエーテルは、第４級アンモニウム塩などの相間移
動触媒の存在下に、アルカリ金属またはアルカリ土類金
属の炭酸塩または水酸化物あるいはトリアルキルアミン
などの塩基と共に攪拌することにより脱フツ化水素化さ
れ、ヘプタフルオロイソブテニルエーテルを４える。This alcohol adduct, octafluoroin butyl alkyl ether, is combined with an alkali metal or alkaline earth metal carbonate or hydroxide or a base such as a trialkylamine in the presence of a phase transfer catalyst such as a quaternary ammonium salt. By stirring, the mixture is dehydrofluorinated to yield 4 heptafluoroisobutenyl ether.
本発明音らは、かかるヘプタフルオロイソブテニルアル
キルエーテルの有効利用法についての種々の検討を行な
い、例えば
アルカリ金属またはアルカリ土類金属の炭酸塩または水
酸化物存在下での過酸化水素との反応による３、３．３
− トリフルオロ−２−ヒドロキシ−２−トリノルオロ
メチルプロピオン酸エステル（ＣＦ、 ）２Ｃ（ＯＨ）
Ｃ００Ｒの製造（特願昭６０−１２５２４２号）第４級
アンモニウム塩、第４級ホスホニウム塩または第３級ホ
スホニウム塩存在下での異性化反応による３、３．３−
トリフルオロ−２−トリフルオロメチル−２−置換プ
ロピオン酸フロライド（ＣＦ、 ）２ＣＲＣＯＦの製造
（特願昭６０−６５５４６号）
アルコールとの反応によるヘキサフルオロイソブタン酸
エステル（ＣＦ、 ）ｚ ＣＨＣＯＯＲの製造（特願昭
５９−１９２７９４号）
などを既に提案している。The inventors of the present invention have conducted various studies on the effective use of such heptafluoroisobutenyl alkyl ether, such as combining it with hydrogen peroxide in the presence of an alkali metal or alkaline earth metal carbonate or hydroxide. 3, 3.3 by reaction
- Trifluoro-2-hydroxy-2-trinorolomethylpropionic acid ester (CF, )2C(OH)
Production of C00R (Japanese Patent Application No. 60-125242) 3,3.3- by isomerization reaction in the presence of quaternary ammonium salt, quaternary phosphonium salt or tertiary phosphonium salt.
Production of trifluoro-2-trifluoromethyl-2-substituted propionic acid fluoride (CF, )2CRCOF (Japanese Patent Application No. 60-65546) Production of hexafluoroisobutanoic acid ester (CF, )z CHCOOR by reaction with alcohol ( Patent Application No. 59-192794) has already been proposed.
今回は更に、ヘプタフルオロインブテニルアルキルエー
テルを特定の還元剤の存在下で還元せしめることにより
、新規なヘキサフルオロイソブテニルアルキルエーテル
を得ることに成功した。また、この還元反応は、アルキ
ルエーテルばかりではなく、フェニルエーテルなどのア
リールエーテルやベンジルエーテルなどのアラルキルエ
ーテルなどにも等しく適用される。This time, we further succeeded in obtaining a new hexafluoroisobutenyl alkyl ether by reducing heptafluoroin butenyl alkyl ether in the presence of a specific reducing agent. Furthermore, this reduction reaction is equally applicable not only to alkyl ethers but also to aryl ethers such as phenyl ether and aralkyl ethers such as benzyl ether.
従って、本発明は、一般式（ＣＦ、 ）２Ｃ＝ Ｃｌ−
１０Ｒ（ここで、Ｒは炭化水素基である〕で表わされる
、新規物質たるヘキサフルオロインブテニルエーテルに
係る。Therefore, the present invention provides the general formula (CF, )2C=Cl-
The present invention relates to a new substance, hexafluoroin butenyl ether, represented by 10R (where R is a hydrocarbon group).
本発明はまた。かかるヘキサフルオロインブテニルエー
テルの製造法に係り、それの製造は、一般式（ＣＦ、）
２Ｃ＝ＣＦＯＲ（ここで、Ｒは炭化水素基である〕で表
わされるヘプタフルオロイソブテニルエーテルを金属水
素化物と反応させることにより行われる。The present invention also includes: The method for producing hexafluoroin butenyl ether is based on the general formula (CF,)
It is carried out by reacting a heptafluoroisobutenyl ether represented by 2C=CFOR (where R is a hydrocarbon group) with a metal hydride.
還元反応は、ヘプタフルオロイソブテニルエーテルにア
セトニトリル、ベンゼン、テトラヒドロフラン、ジエチ
ルエーテルなどの有機溶媒を８縫で約０．５〜５倍量程
度加え、水素化ナトリウム、水素化ジイソブチルアルミ
ニウム、水素化アルミニウムリチウム、水素化ホウ素す
Ｉ〜ツリウムどの金属水素化物をモル比で約０．２５〜
５となる量で存在させながら、約−２０〜６０℃、好ま
しくは約Ｏ〜２０℃の温度という温和な反応条件下で行
われる。For the reduction reaction, approximately 0.5 to 5 times the amount of an organic solvent such as acetonitrile, benzene, tetrahydrofuran, or diethyl ether is added to heptafluoroisobutenyl ether in 8 stitches, and sodium hydride, diisobutylaluminum hydride, or aluminum hydride is added. The molar ratio of metal hydrides such as lithium, boron hydride I to thulium is about 0.25 to
The reaction is carried out under mild reaction conditions at a temperature of about -20 to 60°C, preferably about 0 to 20°C.
本発明によれば、ヘプタフルオロイソブテニルエーテル
の有効利用の一つとして、新規の重合性単量体あるいは
反応中間体などとして使用することができるヘキサフル
オロイソブテニルエーテルが新規な物質として提供され
る。According to the present invention, as one of the effective uses of heptafluoroisobutenyl ether, hexafluoroisobutenyl ether, which can be used as a new polymerizable monomer or a reaction intermediate, is provided as a new substance. be done.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例
ジムロート冷却管、温度計および攪拌装置を備えた容ｆ
ｉｔ３００ｎｌのフラスコに、ヘプタフルオロインブテ
ニルメチルエーテル１００ ｇおよびアセトニ［−リル
１００ＩｌＩＱを仕込み、そこに水素化ホウ素ナトリウ
ム１６ｇを約０〜ＩＯ’Ｃの温度に保ちながら約３時間
にわたって加え、その温度で更に１時間反応させた。反
応路で後、反応混合物を２Ｑの水中に注ぎ、有機層を分
離した後蒸留し、沸点１１７〜１２０℃の留分としてヘ
キサフルオロイソブテニルメチルエーテル８５ｇ（収’
ｔｌ ９２ 、９％）を得た。Example: A container equipped with a Dimroth condenser, a thermometer and a stirring device
A 300 nl flask was charged with 100 g of heptafluoroin butenyl methyl ether and acetonyl[-lyl 100IlIQ, and 16 g of sodium borohydride was added thereto over a period of about 3 hours while maintaining the temperature between about 0 and IO'C. The reaction was further continued for 1 hour. After the reaction process, the reaction mixture was poured into 2Q water, and the organic layer was separated and distilled to obtain 85 g of hexafluoroisobutenyl methyl ether (yield) as a fraction with a boiling point of 117-120°C.
tl 92 , 9%).
元素分析値（ＣＳＨ４０Ｆ６とシテ）
計算値 Ｃ：３０．９４％、ｌＩ：２．０８％、Ｆ：５
８．７３％実測値 Ｃ：３１．０６％、ＩＩ：２．２０
％、Ｆ：５８．３８％赤外線吸収スペクトル
ＣＨ： ２９５０■−１
ｃ＝ｃ ： １６７０■−１
ＣＦ ： １１３５ａｎ−’
１９Ｆ ＮＭＲスペクトル
ＣＦｂ３０ＣＨ３
ＣＦａ、 ： ＣＦ３ＣＯＯＨより １５．２ｐｐｍＪ
Ｆａ−Ｆｂ ６．４ｃｐｓ
Ｊ Ｆａ−）１ ｚＯｃｐｓ
ＣＦｂ、： ＣＦ、ＣＯＯ１１より １３．２ｐｐｍＪ
Ｆａ−Ｆｂ ６．４ｃｐｓ
Ｊ Ｆａ−Ｉｆ ｌ 、 ５ｃｐｓ’ＨＮＭＲスペ
クトルElemental analysis value (CSH40F6 and shite) Calculated value C: 30.94%, lI: 2.08%, F: 5
8.73% actual value C: 31.06%, II: 2.20
%, F: 58.38% Infrared absorption spectrum CH: 2950■-1 c=c: 1670■-1 CF: 1135an-' 19F NMR spectrum CFb30CH3 CFa, : 15.2ppmJ from CF3COOH
Fa-Fb 6.4cps J Fa-)1 zOcps CFb,: CF, from COO11 13.2ppmJ
Fa-Fb 6.4cps J Fa-If l, 5cps'H NMR spectrum
Claims (1)
は炭化水素基である〕で表わされるヘキサフルオロイソ
ブテニルエーテル。 ２、一般式（ＣＦ＿３）＿２Ｃ＝ＣＦＯＲ〔ここで、Ｒ
は炭化水素基である〕で表わされるヘプタフルオロイソ
ブテニルエーテルを金属水素化物と反応させることを特
徴とする一般式（ＣＦ＿３）＿２Ｃ＝ＣＨＯＲ〔ここで
、Ｒは炭化水素基である〕で表わされるヘキサフルオロ
イソブテニルエーテルの製造法。[Claims] 1. General formula (CF_3)_2C=CHOR [where R
is a hydrocarbon group] hexafluoroisobutenyl ether. 2. General formula (CF_3)_2C=CFOR [where, R
is a hydrocarbon group] is reacted with a metal hydride. A method for producing hexafluoroisobutenyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24575385A JPS62106036A (en) | 1985-11-01 | 1985-11-01 | Hexafluoroisobutenyl ether and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24575385A JPS62106036A (en) | 1985-11-01 | 1985-11-01 | Hexafluoroisobutenyl ether and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62106036A true JPS62106036A (en) | 1987-05-16 |
| JPH0580460B2 JPH0580460B2 (en) | 1993-11-09 |
Family
ID=17138282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24575385A Granted JPS62106036A (en) | 1985-11-01 | 1985-11-01 | Hexafluoroisobutenyl ether and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62106036A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994017023A1 (en) * | 1993-01-22 | 1994-08-04 | Daikin Industries, Ltd. | Fluorinated hydrocarbon compound, process for producing the same, and refrigerator oil and magnetic recording medium lubricant |
-
1985
- 1985-11-01 JP JP24575385A patent/JPS62106036A/en active Granted
Non-Patent Citations (3)
| Title |
|---|
| IZV.AKAD KAUK SSSR SER=1972 * |
| IZV.AKAD NAUK SSSR SER KHIM=1973 * |
| J.ORG CHEM=1967 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994017023A1 (en) * | 1993-01-22 | 1994-08-04 | Daikin Industries, Ltd. | Fluorinated hydrocarbon compound, process for producing the same, and refrigerator oil and magnetic recording medium lubricant |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0580460B2 (en) | 1993-11-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |