JPH082814B2 - Fluoro alcohol manufacturing method - Google Patents
Fluoro alcohol manufacturing methodInfo
- Publication number
- JPH082814B2 JPH082814B2 JP63297000A JP29700088A JPH082814B2 JP H082814 B2 JPH082814 B2 JP H082814B2 JP 63297000 A JP63297000 A JP 63297000A JP 29700088 A JP29700088 A JP 29700088A JP H082814 B2 JPH082814 B2 JP H082814B2
- Authority
- JP
- Japan
- Prior art keywords
- betaine
- type surfactant
- water
- represented
- compound
- 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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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- 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） 本発明はフルオロアルコールの製法に関する。TECHNICAL FIELD The present invention relates to a method for producing fluoroalcohol.
（従来の技術） フルオロアルコールは、撥水撥油剤、界面活性剤、離型
剤等の中間体として有用な化合物である。(Prior Art) Fluoroalcohol is a compound useful as an intermediate for water- and oil-repellent agents, surfactants, release agents and the like.
従来、フルオロアルコールの製法として、フルオロア
ルキル沃化物又は臭化物を出発物質とし、これと発煙
硫酸又はクロロ硫酸を接触させて硫酸エステルを製造
し、次いで加水分解する方法（特公昭40−19085号、特
公昭58−39135号）、ジメチルホルムアミド及び水と
接触させる方法（特公昭52−8807号）、非酸化性の酸
素酸又はヨウ化水素の水溶液中でpH2以下の条件で加水
分解する方法（ドイツ公開No.2318677）、重金属イオ
ン触媒の存在下、有機溶剤中、水と接触させる方法（特
開昭63−22040号）等が知られている。しかし、の方
法では発煙硫酸やクロロ硫酸は腐食性が強く、しかも加
水分解困難なジアルキルサルフエートや塩素化物が多量
に副生し、の方法では有機溶剤を使用するので危険で
あり、ジメチルアミン、ギ酸の副生があり、回収上問題
となる。又、末端が二重結合の化合物が多量に副生する
等の問題がある。更にの方法はpH2以下の強酸性下の
条件で、200℃以上の高温、高圧反応で、発生するHIに
耐え得る材質の選択が困難である。又、の方法では有
機溶剤を使用するので危険であり、重金属を使用するた
めその毒性、公害の発生、回収の問題等を有している。Conventionally, as a method for producing a fluoroalcohol, a method in which a fluoroalkyl iodide or bromide is used as a starting material, and this is contacted with fuming sulfuric acid or chlorosulfuric acid to produce a sulfuric acid ester, and then hydrolysis is performed (Japanese Patent Publication No. 40-19085, JP-B-58-39135), a method of contacting with dimethylformamide and water (JP-B-52-8807), and a method of hydrolyzing in an aqueous solution of non-oxidizing oxygen acid or hydrogen iodide at a pH of 2 or less (German publication) No. 2318677), a method of contacting with water in an organic solvent in the presence of a heavy metal ion catalyst (JP-A-63-22040) and the like are known. However, fuming sulfuric acid and chlorosulfuric acid are highly corrosive by the method of, and a large amount of dialkyl sulfate and chlorinated compound, which are difficult to hydrolyze, are by-produced, and by the method of using an organic solvent, dimethylamine, There is a by-product of formic acid, which poses a problem in recovery. Further, there is a problem that a compound having a double bond at the end is produced as a large amount. Further, it is difficult to select a material that can withstand the HI generated at a high temperature of 200 ° C. or higher under a high acidic condition of pH 2 or less. In addition, the method (1) is dangerous because it uses an organic solvent, and since it uses a heavy metal, it has problems such as toxicity, pollution, and recovery.
（発明が解決しようとする課題） 本発明の目的は危険な薬品、有機溶剤、重金属等を使
用しない、安全で且つ収率の良いフルオロアルコールの
製法を提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to provide a safe and high-yield production method of fluoroalcohol which does not use dangerous chemicals, organic solvents, heavy metals and the like.
（問題を解決するための手段） 本発明は一般式 Rf（CH2CH2I）ｎ （Rfは炭素数２〜13のフルオロアルキル基若しくはフル
オロアルキレン基、ｎはRfがフルオロアルキル基のとき
は１、フルオロアルキレン基のときは２）で表わされる
ヨウ化物を、ベタイン型界面活性剤及び水と接触させる
ことにより一般式 Rf（CH2CH2OH）ｎ （Rf及びｎは上記に同じ）で表わされるフルオロアルコ
ールを得ることからなるフルオロアルコールの製法に係
る。(Means for Solving the Problem) The present invention provides a compound represented by the general formula Rf (CH 2 CH 2 I) n (Rf is a fluoroalkyl group or fluoroalkylene group having 2 to 13 carbon atoms, and n is Rf is a fluoroalkyl group. In the case of a fluoroalkylene group, an iodide represented by 2) is brought into contact with a betaine-type surfactant and water to give a compound of the general formula Rf (CH 2 CH 2 OH) n (Rf and n are the same as above). A process for producing a fluoroalcohol, which comprises obtaining the fluoroalcohol represented.
本発明では、ベタイン型界面活性剤の一部分又は大部
分をその他のベタイン化合物で置き換えることができ
る。In the present invention, a part or most of the betaine-type surfactant can be replaced with another betaine compound.
本出願人は先に本発明と同様の出発原料であるヨウ化
物をベタイン化合物と接触させて中間体を得、次いで核
中間体を加水分解することからなるフルオロアルコール
の製法について特許出願（特願昭62−161500号）してい
るが、この方法は水の非存在下で中間体を得る第１工程
及び次いでアルカリ水溶液の存在下で加水分解する第２
工程からなる２段反応であり、本発明の１工程からなる
１段反応とは相違するものである。The present applicant has previously filed a patent application for a process for producing a fluoroalcohol, which comprises contacting an iodide, which is a starting material similar to that of the present invention, with a betaine compound to obtain an intermediate, and then hydrolyzing the nuclear intermediate (patent application No. 62-161500), but this method comprises a first step for obtaining an intermediate in the absence of water and a second step for hydrolysis in the presence of an aqueous alkaline solution.
It is a two-step reaction consisting of steps, which is different from the one-step reaction consisting of one step of the present invention.
本発明において出発原料は 一般式 Rf（CH2CH2I）ｎ （Rfは炭素水２〜13のフルオロアルキル基若しくはフル
オロアルキレン基、ｎはRfがフルオロアルキル基のとき
は１、フルオロアルキレン基のときは２）で表わされる
ヨウ化物であり、具体例としては、CF3（CF2）7CH2CH
2I、CF3（CF2）9CH2CH2I、（CF3）2CF（CF2）4CH2CH
2I、ICH2CH2（CF2CF2）2CH2CH2I、ICH2CH2（CF2CF2）3C
H2CH2I等を挙げることができる。これら化合物の製法
は、ジャーナル・オブ・ザ・ケミカル・ソサエテイー
1950年 3041頁、ザ・ジャーナル・オブ・オーガニツク
・ケミストリー 23巻 1166頁 （1958年）等に記載さ
れている。In the present invention, the starting material is represented by the general formula Rf (CH 2 CH 2 I) n (Rf is a fluoroalkyl group or a fluoroalkylene group of carbon water 2 to 13, n is 1 when Rf is a fluoroalkyl group, a fluoroalkylene group When it is an iodide represented by 2), and as a specific example, CF 3 (CF 2 ) 7 CH 2 CH
2 I, CF 3 (CF 2 ) 9 CH 2 CH 2 I, (CF 3 ) 2 CF (CF 2 ) 4 CH 2 CH
2 I, ICH 2 CH 2 (CF 2 CF 2 ) 2 CH 2 CH 2 I, ICH 2 CH 2 (CF 2 CF 2 ) 3 C
H 2 CH 2 I and the like can be mentioned. These compounds are manufactured by Journal of the Chemical Society
1950, 3041; The Journal of Organic Chemistry, Vol. 23, 1166 (1958).
本発明で使用されるベタイン型界面活性剤の好適な例
は一般式 R1R2R3N CH2CO2 （R1,R2は炭素数１〜５のアルキル基、R3は炭素数６〜2
4、好ましくは８〜20のアルキル基）で表わされる化合
物であり、例えば C8H17（CH3）2N CH2CO2 、 C12H25（CH3）2N CH2CO2 、 C18H37（CH3）2N CH2CO2 等を挙げることができる。又、本発明では必要に応じ上
記ベタイン型界面活性剤の一部分ないし大部分を一般式 R1R2R4N CH2CO2 （R1,R2及びR4は炭素数１〜５のアルキル基）で表わさ
れるベタイン化合物で置き換えることができる。これら
ベタイン型界面活性剤及びその他のベタイン化合物の製
法は例えば米国特許第2,800,502号明細書等に記載され
ている。 Suitable examples of betaine-type surfactants used in the present invention
Is the general formula R1R2R3N CH2CO2 (R1, R2Is an alkyl group having 1 to 5 carbon atoms, R3Has 6 to 2 carbon atoms
4, preferably 8 to 20 alkyl groups)
Object, for example C8H17(CH3)2N CH2CO2 , C12Htwenty five(CH3)2N CH2CO2 , C18H37(CH3)2N CH2CO2 Etc. can be mentioned. In addition, according to the present invention, if necessary
A part or most of the betaine-type surfactant is represented by the general formula R1R2RFourN CH2CO2 (R1, R2And RFourIs an alkyl group having 1 to 5 carbon atoms)
Can be replaced by a betaine compound. these
Preparation of betaine type surfactants and other betaine compounds
The method is described in, for example, U.S. Pat.No. 2,800,502.
ing.
本発明では原料ヨウ化物１当量（ヨウ化物１モルは、
ｎが１のとき１当量、２のとき２当量）に対して、ベタ
イン型界面活性剤を通常１〜20当量、好ましくは1.2〜
５当量使用し、ベタイン型界面活性剤以外のベタイン化
合物で置き換えるときは、ベタイン型界面活性剤は0.2
当量以上とするのが良い。又、原料ヨウ化物１当量に対
して水を通常１〜200当量（水の１モルは１当量）、好
ましくは２〜140当量使用する。反応温度は、通常80〜2
00℃、反応速度、加熱の容易さの点で好ましくは120〜1
60℃である。反応時間は通常１〜10時間程度で十分であ
り、好ましくは２〜６時間程度である。本発明ではベタ
イン型界面活性剤と接触させるため、有機溶剤を使用す
る必要がない。In the present invention, 1 equivalent of raw material iodide (1 mol of iodide is
When n is 1, it is 1 equivalent, and when it is 2, it is 2 equivalents), and the betaine surfactant is usually 1 to 20 equivalents, preferably 1.2 to
When using 5 equivalents and replacing with a betaine compound other than the betaine-type surfactant, the betaine-type surfactant is 0.2
It is better to use more than the equivalent. Water is usually used in an amount of 1 to 200 equivalents (1 mol of water is 1 equivalent), preferably 2 to 140 equivalents, relative to 1 equivalent of the raw material iodide. Reaction temperature is usually 80-2
00 ℃, reaction rate, in terms of ease of heating preferably 120 ~ 1
60 ° C. The reaction time is usually about 1 to 10 hours, and preferably about 2 to 6 hours. In the present invention, it is not necessary to use an organic solvent because it is brought into contact with the betaine type surfactant.
本発明の目的物は通常公知の手段で分離、精製され、
例えば抽出、蒸留、再結晶、ガスクロマトグラフイー、
カラムクロマトグラフイー等の手段を用い得る。The object of the present invention is usually separated and purified by a known means,
For example, extraction, distillation, recrystallization, gas chromatography,
Means such as column chromatography can be used.
（発明の効果） 本発明の製法は危険な薬品、有機溶剤、重金属を使用
しない、従って安全で、有機溶剤の回収工程がない。
又、本発明の方法では出発原料の転化率、目的物の選択
率が良い。(Effects of the Invention) The production method of the present invention does not use dangerous chemicals, organic solvents, and heavy metals, and thus is safe and does not have an organic solvent recovery step.
Further, in the method of the present invention, the conversion of the starting material and the selectivity of the target product are good.
（実 施 例） 以下に実施例を挙げて説明する。(Examples) Examples will be described below.
実施例１ CF3（CF2）7CH2CH2I 57.4g（100mmol）、水100g及び
ベタイン型界面活性剤としてC12H25（CH3）2N CH2COO
32.6g（120mmol）を200mlのオートクレーブに仕込
み、150℃で６時間加熱撹拌した。反応混合物を室温に
冷却後、水及びトリクロロトリフルオロエタン（Ｒ−11
3）のそれぞれ100mlで抽出後、油層をガスクロマトグラ
フイーで分析した。転化率99％、選択率96％でCF3（C
F2）7CH2CH2OHが得られた。Example 1 CF3(CF2)7CH2CH2I 57.4g (100mmol), water 100g and
C as a betaine-type surfactant12Htwenty five(CH3)2N CH2COO
Charge 32.6 g (120 mmol) into a 200 ml autoclave
And stirred at 150 ° C. for 6 hours. Bring the reaction mixture to room temperature
After cooling, water and trichlorotrifluoroethane (R-11
After extraction with 100 ml of each of 3), the oil layer was gas chromatographed.
It was analyzed by Hui. CF with 99% conversion and 96% selectivity3(C
F2)7CH2CH2OH was obtained.
実施例２ ICH2CH2（CF2）6CH2CH2I 61.0g（100mmol）、水100g
及びベタイン型界面活性剤としてC12H25（CH3）2N CH2
COO 65.1g（240mmol）を200mlのオートクレーブに仕
込み、150℃で６時間加熱撹拌した。反応混合物を室温
に冷却後、水及びＲ−113のそれぞれ100mlで抽出後、油
層をガスクロマトグラフイーで分析した。Example 2 ICH2CH2(CF2)6CH2CH2I 61.0 g (100 mmol), water 100 g
And C as betaine-type surfactant12Htwenty five(CH3)2N CH2
COO 65.1g (240mmol) was prepared in 200ml autoclave.
The mixture was heated and stirred at 150 ° C. for 6 hours. Reaction mixture at room temperature
After cooling to 100ml, extract with 100ml each of water and R-113,
The layers were analyzed by gas chromatography.
ICH2CH2（CF2）6CH2CH2Iの転化率は99％で、HOCH2CH2
（CF2）6CH2CH2OHの選択率は90％であった。CH2＝CH（C
F2）6CH2CH2OHが８％副生していた。The conversion of ICH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 I is 99%, and HOCH 2 CH 2
The selectivity of (CF 2 ) 6 CH 2 CH 2 OH was 90%. CH 2 = CH (C
8% of F 2 ) 6 CH 2 CH 2 OH was by-produced.
実施例３ CF3（CF2）7CH2CH2I 43.1g（75mmol）、（CH3）3N
CH2COO 8.8g（75mmol）、水60g及びベタイン型界面
活性剤としてC12H25（CH3）2N CH2COO 4.1g（15mmo
l）を200mlのオートクレーブに仕込み、150℃で６時間
加熱撹拌した。反応混合物を室温に冷却後、水及びＲ−
113のそれぞれ100mlで抽出後、油層をガスクロマトグラ
フイーで分析した。転化率99％、選択率97％でCF3（C
F2）7CH2CH2OHが得られた。Example 3 CF3(CF2)7CH2CH2I 43.1 g (75 mmol), (CH3)3N
CH2COO 8.8g (75mmol), 60g of water and betaine type interface
C as activator12Htwenty five(CH3)2N CH2COO 4.1g (15mmo
l) was charged into a 200 ml autoclave and kept at 150 ℃ for 6 hours.
Heated and stirred. After cooling the reaction mixture to room temperature, water and R-
After extracting 113 of each with 100 ml, the oil layer was gas chromatographed.
It was analyzed by Hui. CF with 99% conversion and 97% selectivity3(C
F2)7CH2CH2OH was obtained.
比較例１ 実施例１のベタイン型界面活性剤の代りにアニオン系
界面活性剤であるラウリル硫酸ナトリウム32.8g（120mm
ol）を用いる以外は実施例１と同様の操作を行つたとこ
ろ、CF3（CF2）7CH2CH2Iの転化率は０％であつた。Comparative Example 1 Instead of the betaine-type surfactant of Example 1, 32.8 g (120 mm) of anionic surfactant sodium lauryl sulfate was used.
was performed in the same manner as in Example 1 except that the ol) was used, the conversion of CF 3 (CF 2 ) 7 CH 2 CH 2 I was 0%.
比較例２ 実施例１のベタイン型界面活性剤の代りにカチオン系
界面活性剤であるオクタデシルトリメチルアンモニウム
クロライド41.8g（120mmol）を用いる以外は実施例１と
同様の操作を行つたところ、CF3（CF2）7CH2CH2Iの転化
率は０％であつた。Comparative Example 2 The same operation as in Example 1 was carried out except that 41.8 g (120 mmol) of octadecyltrimethylammonium chloride, which is a cationic surfactant, was used in place of the betaine-type surfactant of Example 1, and CF 3 ( The conversion rate of CF 2 ) 7 CH 2 CH 2 I was 0%.
比較例３ 実施例１のベタイン型界面活性剤の代りにノニオン系
界面活性剤である を用い、反応条件を100℃、24時間にした以外は実施例
１と同様の操作を行つたところ、CF3（CF2）7CH2CH2Iの
転化率は０％であつた。Comparative Example 3 The betaine-type surfactant of Example 1 was replaced by a nonionic surfactant. The same operation as in Example 1 was carried out except that the reaction conditions were 100 ° C. and 24 hours, and the conversion of CF 3 (CF 2 ) 7 CH 2 CH 2 I was 0%.
Claims (3)
オロアルキレン基、ｎはRfがフルオロアルキル基のとき
は１、フルオロアルキレン基のときは２）で表わされる
ヨウ化物を、ベタイン型界面活性剤及び水と接触させる
ことにより一般式 Rf（CH2CH2OH）ｎ （Rf及びｎは上記に同じ）で表わされるフルオロアルコ
ールを得ることからなるフルオロアルコールの製法。1. Rf (CH 2 CH 2 I) n (Rf is a fluoroalkyl group or a fluoroalkylene group having 2 to 13 carbon atoms, n is 1 when Rf is a fluoroalkyl group, and n is a fluoroalkylene group. To obtain a fluoroalcohol represented by the general formula Rf (CH 2 CH 2 OH) n (Rf and n are the same as above) by contacting the iodide represented by 2) with a betaine-type surfactant and water. A process for producing fluoroalcohol.
4のアルキル基）で表わされる化合物である請求項１記
載の製法。2. A betaine type surfactant is represented by the general formula R1R2R3N CH2CO2 (R1, R2Is an alkyl group having 1 to 5 carbon atoms, R3Has 6 to 2 carbon atoms
4. A compound represented by the alkyl group 4).
Manufacturing method
分を一般式 R1R2R4N CH2CO2 （R1,R2及びR4は炭素数１〜５のアルキル基）で表わさ
れるベタイン化合物で置き換える請求項１記載の製法。3. A part or most of the betaine-type surfactant.
Minutes to the general formula R1R2RFourN CH2CO2 (R1, R2And RFourIs an alkyl group having 1 to 5 carbon atoms)
The method according to claim 1, wherein the betaine compound is replaced with a betaine compound.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63297000A JPH082814B2 (en) | 1988-11-24 | 1988-11-24 | Fluoro alcohol manufacturing method |
| DE1989608104 DE68908104T2 (en) | 1988-11-24 | 1989-11-23 | Process for the preparation of fluorinated alcohols. |
| EP19890121665 EP0371399B1 (en) | 1988-11-24 | 1989-11-23 | Process for preparing fluoroalcohols |
| US07/770,751 US5264637A (en) | 1988-11-24 | 1991-10-04 | Process for preparing fluoroalcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63297000A JPH082814B2 (en) | 1988-11-24 | 1988-11-24 | Fluoro alcohol manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02142740A JPH02142740A (en) | 1990-05-31 |
| JPH082814B2 true JPH082814B2 (en) | 1996-01-17 |
Family
ID=17840955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63297000A Expired - Lifetime JPH082814B2 (en) | 1988-11-24 | 1988-11-24 | Fluoro alcohol manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082814B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003012578A (en) * | 2001-06-28 | 2003-01-15 | Asahi Glass Co Ltd | Method for reacting organohalogen compound with high- temperature and high-pressure water |
| ATE358659T1 (en) | 2001-07-02 | 2007-04-15 | Tosoh F Tech Inc | METHOD FOR PRODUCING FLUORINATED ALCOHOLS |
-
1988
- 1988-11-24 JP JP63297000A patent/JPH082814B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02142740A (en) | 1990-05-31 |
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