JPS64390B2 - - Google Patents
Info
- Publication number
- JPS64390B2 JPS64390B2 JP13534685A JP13534685A JPS64390B2 JP S64390 B2 JPS64390 B2 JP S64390B2 JP 13534685 A JP13534685 A JP 13534685A JP 13534685 A JP13534685 A JP 13534685A JP S64390 B2 JPS64390 B2 JP S64390B2
- Authority
- JP
- Japan
- Prior art keywords
- peroxodisulfate
- acid
- bistrifluoromethylalkanol
- ammonium
- peroxosulfate
- 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
Links
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 claims 1
- DAFQZPUISLXFBF-UHFFFAOYSA-N tetraoxathiolane 5,5-dioxide Chemical compound O=S1(=O)OOOO1 DAFQZPUISLXFBF-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- FQDXJYBXPOMIBX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-methylpropan-2-ol Chemical compound FC(F)(F)C(O)(C)C(F)(F)F FQDXJYBXPOMIBX-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000004791 alkyl magnesium halides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- -1 heptafluoroisobutenyl alkyl ether Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- RQRAWIBGGIBWAT-UHFFFAOYSA-M potassium;3,3,3-trifluoro-2-methyl-2-(trifluoromethyl)propanoate Chemical compound [K+].[O-]C(=O)C(C)(C(F)(F)F)C(F)(F)F RQRAWIBGGIBWAT-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、１，１―ビストリフルオロメチルア
ルカノールの製法に関する。１，１―ビストリフ
ルオロメチルアルカノールは、通常のアルコール
に比べて酸性度および揮発性が高く、各種反応試
薬、反応溶媒、動作流体、溶剤などとして有用で
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing 1,1-bistrifluoromethylalkanol. 1,1-bistrifluoromethylalkanol has higher acidity and volatility than ordinary alcohols, and is useful as various reaction reagents, reaction solvents, working fluids, solvents, and the like.
１，１―ビストリフルオロメチルアルカノール
の製法としては、ヘキサフルオロアセトンとヨウ
化メチルマグネシウム等のハロゲン化アルキルマ
グネシウム（グリニヤール試薬）を反応させて合
成する製法が知られているが、ヘキサフルオロア
セトンは非常に高価な化合物であり、グリニヤー
ル試薬は大量合成に不向きであるなど工業的な製
法としては種々の欠点があつた。
A known method for producing 1,1-bistrifluoromethylalkanol is to react hexafluoroacetone with an alkylmagnesium halide such as methylmagnesium iodide (Grinard reagent), but hexafluoroacetone is extremely difficult to synthesize. It has various drawbacks as an industrial production method, such as being an expensive compound and the Grignard reagent being unsuitable for large-scale synthesis.
本発明の目的は、１，１―ビストリフルオロメ
チルアルカノールを低価格でかつ工業的規模で得
る方法を提供することにある。
An object of the present invention is to provide a method for obtaining 1,1-bistrifluoromethylalkanol at low cost and on an industrial scale.
本発明の要旨は、
一般式：RC（CF3）2CO2M（）
〔式中、Ｒは炭素数１〜５のアルキル基、Ｍは
水素、アルカリ金属またはアンモニウムを表わ
す。〕
で示される化合物とペルオキソ硫酸またはペルオ
キソ硫酸塩を反応させて
一般式：RC（CF3）2OH
〔式中、Ｒは前記と同意義。〕
で示される１，１―ビストリフルオロメチルアル
カノールの製法に存する。
The gist of the present invention is as follows: General formula: RC( CF3 ) 2CO2M () [In the formula, R represents an alkyl group having 1 to 5 carbon atoms, and M represents hydrogen, an alkali metal, or ammonium. ] A compound represented by the above is reacted with peroxosulfuric acid or peroxosulfate to form a compound represented by the general formula: RC(CF 3 ) 2 OH [wherein R has the same meaning as above. ] The method consists in the production of 1,1-bistrifluoromethylalkanol shown below.
化合物（）は、たとえばオクタフルオロイソ
ブチルアルキルエーテルを脱フツ化水素してヘプ
タフルオロイソブテニルアルキルエーテルとし、
これを相間移動触媒を用いて転位反応させて２，
２―ビストリフルオロメチルアルカノイルフルオ
ライドとして、これをアルカリ処理等をすること
によつて得られる。 Compound () is, for example, dehydrofluorinated octafluoroisobutyl alkyl ether to form heptafluoroisobutenyl alkyl ether,
This is rearranged using a phase transfer catalyst, and 2,
2-bistrifluoromethylalkanoyl fluoride can be obtained by treating this with an alkali or the like.
ペルオキソ硫酸としては、ペルオキソー硫酸ま
たはペルオキソ二硫酸が、ペルオキソ硫酸塩とし
ては、ペルオキソ二硫酸カリウム、ペルオキソ二
硫酸ナトリウム、ペルオキソ二硫酸アンモニウム
またはペルオキソ二硫酸バリウム等を使用するこ
とができる。使用量は、化合物（）１モルに対
して0.5〜５モルの割合である。 As the peroxosulfuric acid, peroxosulfuric acid or peroxodisulfate can be used, and as the peroxosulfate, potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, barium peroxodisulfate, etc. can be used. The amount used is 0.5 to 5 mol per 1 mol of compound ().
PHは、通常水酸化カリウムまたは水酸化ナトリ
ウム水溶液等を用いて調節し、５〜９、好ましく
は６〜８とする。 The pH is usually adjusted to 5 to 9, preferably 6 to 8, using an aqueous potassium hydroxide or sodium hydroxide solution.
反応温度は、通常60〜100℃、好ましくは80〜
90℃で、反応時間は通常0.5〜６時間、好ましく
は１〜３時間である。 The reaction temperature is usually 60-100℃, preferably 80-100℃.
At 90°C, the reaction time is usually 0.5 to 6 hours, preferably 1 to 3 hours.
反応には通常水を溶媒として用いる。 Water is usually used as a solvent for the reaction.
次に実施例を示し、本発明を更に詳しく説明す
る。 EXAMPLES Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
温度計、滴下漏斗およびコンデンサーを備えた
1000ml四つ口フラスコに、２，２―ビストリフ
ルオロメチルプロピオン酸カリウム19.8ｇ（80ミ
リモル）、ペルオキソ二硫酸カリウム64.8ｇ（240
ミリモル）および水400mlを仕込み、40重量％水
酸化カリウム水溶液67.0mlを系内のPH６〜８にな
るように滴下しながら、90℃で２時間反応させ
た。Example 1 Equipped with thermometer, addition funnel and condenser
In a 1000 ml four-necked flask, add 19.8 g (80 mmol) of potassium 2,2-bistrifluoromethylpropionate and 64.8 g (240 mmol) of potassium peroxodisulfate.
millimoles) and 400 ml of water were charged, and 67.0 ml of a 40% by weight aqueous potassium hydroxide solution was added dropwise to adjust the pH of the system to 6 to 8, while reacting at 90°C for 2 hours.
反応後蒸留により、１，１―ビストリフルオロ
メチルエタノール6.6ｇ（収率45％）を得た。沸
点60.5℃。 After the reaction, 6.6 g (yield: 45%) of 1,1-bistrifluoromethylethanol was obtained by distillation. Boiling point 60.5℃.
実施例 ２
実施例１で使用したペルオキソ二硫酸カリウム
の代わりにペルオキソ二硫酸アンモニウム54.7ｇ
（240ミリモル）を使用し、他は実施例１と同一条
件で反応させた。Example 2 54.7 g of ammonium peroxodisulfate was used in place of the potassium peroxodisulfate used in Example 1.
(240 mmol) was used, and the other conditions were the same as in Example 1.
反応後蒸留により、１，１―ビストリフルオロ
メチルエタノール7.6ｇ（収率52％）を得た。 After the reaction, 7.6 g (yield: 52%) of 1,1-bistrifluoromethylethanol was obtained by distillation.
本発明の製法によれば、１，１―ビストリフル
オロメチルアルカノールを容易にかつ安価で得る
ことができる。
According to the production method of the present invention, 1,1-bistrifluoromethylalkanol can be obtained easily and at low cost.
Claims (1)
水素、アルカリ金属またはアンモニウムを表わ
す。〕 で示される化合物とペルオキソ硫酸またはペルオ
キソ硫酸塩を反応させて 一般式：RC（CF3）2OH 〔式中、Ｒは前記と同意義。〕 で示される化合物を得ることを特徴とする１，１
―ビストリフルオロメチルアルカノールの製法。 ２ ペルオキソ硫酸が、ペルオキソ一硫酸または
ペルオキソ二硫酸である特許請求の範囲第１項記
載の製法。 ３ ペルオキソ硫酸塩が、ペルオキソニ硫酸カリ
ウム、ペルオキソ二硫酸ナトリウム、ペルオキソ
二硫酸アンモニウムまたはペルオキソ二硫酸バリ
ウムである特許請求の範囲第１項記載の製法。[Claims] 1 General formula: RC(CF 3 ) 2 CO 2 M [In the formula, R represents an alkyl group having 1 to 5 carbon atoms, and M represents hydrogen, an alkali metal or ammonium. ] A compound represented by the following is reacted with peroxosulfuric acid or a peroxosulfate to obtain the general formula: RC(CF 3 ) 2 OH [wherein, R has the same meaning as above. ] 1,1 characterized by obtaining a compound represented by
-Production method of bistrifluoromethylalkanol. 2. The manufacturing method according to claim 1, wherein the peroxosulfuric acid is peroxomonosulfuric acid or peroxodisulfuric acid. 3. The method according to claim 1, wherein the peroxosulfate is potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, or barium peroxodisulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13534685A JPS61291533A (en) | 1985-06-20 | 1985-06-20 | Method for producing 1,1-bistrifluoromethylalkanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13534685A JPS61291533A (en) | 1985-06-20 | 1985-06-20 | Method for producing 1,1-bistrifluoromethylalkanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61291533A JPS61291533A (en) | 1986-12-22 |
| JPS64390B2 true JPS64390B2 (en) | 1989-01-06 |
Family
ID=15149621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13534685A Granted JPS61291533A (en) | 1985-06-20 | 1985-06-20 | Method for producing 1,1-bistrifluoromethylalkanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61291533A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8763991A (en) * | 1990-12-04 | 1992-07-08 | Allied-Signal Inc. | Partially fluorinated alkanols having a tertiary structure |
| US5254755A (en) * | 1990-12-04 | 1993-10-19 | Allied-Signal Inc. | Partially fluorinated alkanols having a tertiary structure |
| JP2015193589A (en) * | 2014-03-26 | 2015-11-05 | セントラル硝子株式会社 | METHOD FOR PRODUCING 1,1,1,3,3,3-HEXAFLUORO-tert-BUTANOL |
-
1985
- 1985-06-20 JP JP13534685A patent/JPS61291533A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61291533A (en) | 1986-12-22 |
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