JPH082815B2 - Fluoro alcohol manufacturing method - Google Patents
Fluoro alcohol manufacturing methodInfo
- Publication number
- JPH082815B2 JPH082815B2 JP63298818A JP29881888A JPH082815B2 JP H082815 B2 JPH082815 B2 JP H082815B2 JP 63298818 A JP63298818 A JP 63298818A JP 29881888 A JP29881888 A JP 29881888A JP H082815 B2 JPH082815 B2 JP H082815B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- represented
- compound
- iodide
- group
- 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
Links
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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造法に関する。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、これを発煙
硫酸又はクロロ硫酸と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、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 brought into contact with fuming sulfuric acid or chlorosulfuric acid to produce a sulfuric acid ester, and then hydrolyzed (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, with the method, fuming sulfuric acid and chlorosulfuric acid are highly corrosive, and a large amount of dialkyl sulphate and chlorinated compounds, which are difficult to hydrolyze, are by-produced. Becomes Further, there is a problem that a compound having a double bond at the end is produced as a large amount. Further method is pH2
It is difficult to select a material that can withstand the generated HI under the conditions of high acidity and high temperature of 200 ° C or higher under the following conditions.
In addition, since the method (1) uses heavy metal, it has problems of toxicity, generation of 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、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造法を提
供することにある。(Problems to be solved by the invention) The object of the present invention is to use no dangerous chemicals, heavy metals, etc.
It is to provide a method for producing a fluoroalcohol that is safe and has a high yield.
（課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、有機溶媒の存在下に、ベタイン化合物及び
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造法に
係る。(Means for Solving the Problems) 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, iodide represented by 2) is brought into contact with a betaine compound and water in the presence of an organic solvent to give a compound represented by the general formula Rf (CH 2 CH 2 OH) n (Rf and n are as described above). Same as above).
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、次いで該
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
工程の２工程からなるものであり、本発明の１工程から
なるものとは相違するものである。The 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 intermediate. 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.
This is a two-step process, and is different from the one-step process 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、ジヤーナル・オブ・ザ・ケミカル・ソサエテイー 1
950年 3041頁、サ・ジヤーナル・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 fluoroalkylene group having 2 to 13 carbon atoms, n is 1 when Rf is a fluoroalkyl group, or 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 produced by the Journal of the Chemical Society 1
950, 3041 pages, Sa Journal of Organic
Chemistry 23: 1166 (1958).
本発明で使用されるベタイン化合物の好適な例は一般
式 R1R2R3N CH2CO2 （R1,R2,R3は炭素数１〜24のアルキル基）で表わされる
化合物であり、例えば、 （CH3）3N CH2CO2 、 （C2H5）3N CH2CO2 、 C8H17（CH3）2N CH2CO2 、 C12H25（CH3）2N CH2CO2 、 C18H37（CH3）2N CH2CO2 等を挙げることができる。これら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 compounds used in the present invention are generally
Expression R1R2R3N CH2CO2 (R1, R2, R3Is represented by an alkyl group having 1 to 24 carbon atoms)
A compound, such as (CH3)3N CH2CO2 , (C2HFive)3N CH2CO2 , C8H17(CH3)2N CH2CO2 , C12Htwenty five(CH3)2N CH2CO2 , C18H37(CH3)2N CH2CO2 Etc. can be mentioned. Process for producing these betaine compounds
Are described in, for example, U.S. Pat.
There is.
本発明において用いられる有機溶媒は水と相溶しやす
く、原料ヨウ化物と水の混和を助けるものが良く、例え
ばメタノール、エタノール、プロパノールなどのアルコ
ール類、アセトン、アセトニトリル、エチレングリコー
ル、グリセリン、グライム、セロソルブ、プロピオン
酸、フエノール、クレゾール、スルホラン、Ｎ−メチル
ピロリドン、γ−ブチロラクトン等を挙げることができ
る。The organic solvent used in the present invention is easily compatible with water, and it is preferable to use a material that aids the mixing of the raw material iodide and water, for example, alcohols such as methanol, ethanol, propanol, acetone, acetonitrile, ethylene glycol, glycerin, glyme, Examples thereof include cellosolve, propionic acid, phenol, cresol, sulfolane, N-methylpyrrolidone and γ-butyrolactone.
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、ｎが２のとき２当量）に対して、
ベタイン化合物を通常１〜20当量、好ましくは1.2〜５
当量使用する。又、原料ヨウ化物１当量に対して水を通
常１〜200当量（水１モルは１当量）、好ましくは２〜1
40当量使用する。有機溶媒は体積比で水１部に対して0.
1〜10部、好ましくは１〜５部使用するのが良い。反応
温度は、通常80〜200℃、反応速度、加熱の容易さの点
で好ましくは120〜160℃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。In the present invention, 1 equivalent of raw material iodide (1 mol of iodide is
(1 equivalent when n is 1, 2 equivalents when n is 2)
The betaine compound is usually 1 to 20 equivalents, preferably 1.2 to 5
Use equivalent amount. Water is usually 1 to 200 equivalents (1 mole of water is 1 equivalent), preferably 2-1 to 1 equivalent of raw material iodide.
Use 40 equivalents. The volume of organic solvent is 0.
It is preferable to use 1 to 10 parts, preferably 1 to 5 parts. The reaction temperature is usually 80 to 200 ° C, and preferably 120 to 160 ° C in view of reaction rate and ease of heating. Reaction time is usually 1-10
The time is sufficient, and the time is preferably 2 to 6 hours.
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、重金属を使用せず、安全
である。又、本発明の方法では出発物質の転化率、目的
物の選択率が良い。(Effect of the Invention) The production method of the present invention is safe without using dangerous chemicals or heavy metals. Further, in the method of the present invention, the conversion of the starting material and the selectivity of the target substance 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）、（CH3）3N
CH2COO 14.1g（120mmol）、イソプロパノール（IPA）
50g及び水20g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−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97％、選択率93％でCF3（CF2）7CH2CH
2OHが得られた。Example 1 CF3(CF2)7CH2CH2I 57.4g (100mmol), (CH3)3N
CH2COO 14.1g (120mmol), isopropanol (IPA)
Charge 50g and 20g of water into a 200ml autoclave, 150 ℃
The mixture was heated and stirred for 6 hours. After cooling the reaction mixture to room temperature, water
And that of trichlorotrifluoroethane (R-113)
After extracting with 100 ml of each, the oil layer is subjected to gas chromatography.
analyzed. CF with 97% conversion and 93% selectivity3(CF2)7CH2CH
2OH was obtained.
実施例２ ICH2CH2（CF2）6CH2CH2I 61.0g（100mmol）、（CH3）3N
CH2COO 28.1g（240mmol）、IPA60g及び水30gを200m
l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), (CH3)3N
CH2COO 28.1g (240mmol), IPA 60g and water 30g 200m
I put it in an autoclave of l and heat it with stirring at 150 ℃ for 6 hours.
Was. After cooling the reaction mixture to room temperature, that of water and that of R-113
After extracting with 100 ml of each, the oil layer is subjected to gas chromatography.
analyzed.
ICH2CH2（CF2）6CH2CH2Iの転化率は95％で、HOCH2CH2
（CF2）6CH2CH2OHの選択率は87％であつた。CH2＝CH（C
F2）6CH2CH2OHが10％副生していた。The conversion rate of ICH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 I is 95%, and HOCH 2 CH 2
The selectivity of (CF 2 ) 6 CH 2 CH 2 OH was 87%. CH 2 = CH (C
10% of F 2 ) 6 CH 2 CH 2 OH was by-produced.
実施例３ CF3（CF2）7CH2CH2I 57.4g（100mmol）、（CH3）3N
CH2COO 11.7g（100mmol）、IPA40g、水15g及びベタイ
ン型界面活性剤としてC12H25（CH3）2N CH2COO 5.4g
（20mmol）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95％でCF
3（CF2）7CH2CH2OHが得られた。Example 3 CF3(CF2)7CH2CH2I 57.4g (100mmol), (CH3)3N
CH2COO 11.7 g (100 mmol), IPA 40 g, water 15 g and beta
C as a surfactant12Htwenty five(CH3)2N CH2COO 5.4g
(20mmol) was charged into a 200ml autoclave, and at 150 ℃
The mixture was heated and stirred for 6 hours. After cooling the reaction mixture to room temperature,
After extraction with 100 ml of R-113 and R-113 respectively, the oil layer was gas chromatographed.
It was analyzed by Tografie. CF with conversion of 99% and selectivity of 95%
3(CF2)7CH2CH2OH was obtained.
実施例４〜７ 有機溶媒としてイソプロパノールの代りに第１表に記
載した溶媒を用いる以外は実施例１と同様の操作を行つ
た。CF3（CF2）7CH2CH2Iの転化率及びCF3（CF2）7CH2CH
2OHの選択率を第１表に示す。Examples 4 to 7 The same operations as in Example 1 were carried out except that the solvent shown in Table 1 was used instead of isopropanol as the organic solvent. CF 3 (CF 2 ) 7 CH 2 CH 2 I conversion and CF 3 (CF 2 ) 7 CH 2 CH
Table 1 shows the selectivity of 2 OH.
比較例１ 実施例１のベタイン化合物を使用しない以外は実施例
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 When the same operation as in Example 1 was performed except that the betaine compound of Example 1 was not used, the conversion rate of CF 3 (CF 2 ) 7 CH 2 CH 2 I was 0%.
Claims (2)
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、有機溶媒の存在下に、ベタイン化合物及び
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造法。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. By contacting the iodide represented by 2) with a betaine compound and water in the presence of an organic solvent, the fluoro represented by the general formula Rf (CH 2 CH 2 OH) n (Rf and n are the same as above). A process for producing fluoroalcohol, which comprises obtaining alcohol.
化合物である請求項１記載の製造法。2. A betaine compound having the general formula R1R2R3N CH2CO2 (R1, R2, R3Is represented by an alkyl group having 1 to 24 carbon atoms)
The method according to claim 1, which is a compound.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63298818A JPH082815B2 (en) | 1988-11-25 | 1988-11-25 | 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 |
|---|---|---|---|
| JP63298818A JPH082815B2 (en) | 1988-11-25 | 1988-11-25 | Fluoro alcohol manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02142741A JPH02142741A (en) | 1990-05-31 |
| JPH082815B2 true JPH082815B2 (en) | 1996-01-17 |
Family
ID=17864616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63298818A Expired - Lifetime JPH082815B2 (en) | 1988-11-24 | 1988-11-25 | Fluoro alcohol manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082815B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE358659T1 (en) | 2001-07-02 | 2007-04-15 | Tosoh F Tech Inc | METHOD FOR PRODUCING FLUORINATED ALCOHOLS |
-
1988
- 1988-11-25 JP JP63298818A patent/JPH082815B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02142741A (en) | 1990-05-31 |
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