JPH02142741A - Production of fluoroalcohol - Google Patents
Production of fluoroalcoholInfo
- Publication number
- JPH02142741A JPH02142741A JP63298818A JP29881888A JPH02142741A JP H02142741 A JPH02142741 A JP H02142741A JP 63298818 A JP63298818 A JP 63298818A JP 29881888 A JP29881888 A JP 29881888A JP H02142741 A JPH02142741 A JP H02142741A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- iodide
- compound
- water
- expressed
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 betaine compound Chemical class 0.000 claims abstract description 13
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 13
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960003237 betaine Drugs 0.000 claims abstract description 9
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical class C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000005871 repellent Substances 0.000 abstract description 2
- 230000002940 repellent Effects 0.000 abstract description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- XVKJSLBVVRCOIT-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-10-iododecane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCI XVKJSLBVVRCOIT-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- MAUMSNABMVEOGP-UHFFFAOYSA-N (methyl-$l^{2}-azanyl)methane Chemical compound C[N]C MAUMSNABMVEOGP-UHFFFAOYSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
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。[Detailed description of the invention] (Industrial application field) The present invention relates to a method for producing fluoroalcohols.
（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 repellents, surfactants, mold 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５Ｌ−３９１３５号）、■ツ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Ｎ ｏ、２
３１８６７７）、０重金属イオン触媒の存在ｆ、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ノア
ルキルサル７エートや塩素化物が多量に副生じ、■の方
法ではツメチルアミン、ギ酸の副生があり、回収−１４
問題となる。又、末端が二重結合の化合物が多量にば１
ｊ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ＩＩ Ｉに耐え得る材質の選択が困難である。Conventionally, as a method for producing fluoroalcohols, a fluoroalkyl iodide or bromide is used as a starting material, and this is brought into contact with (1) oleum or chlorosulfuric acid to produce a sulfuric acid ester,
Next, a method of hydrolyzing (Japanese Patent Publication No. 19085-1985,
(Japanese Patent Publication No. 5L-39135), ■ Method of contacting with trimethylformamide and water (Japanese Patent Publication No. 52-8807),
■pH2 in an aqueous solution of non-oxidizing oxygen acid or hydrogen iodide
Hydrolysis method under the following conditions (German Publication No. 2
318677), the presence of a heavy metal ion catalyst f, and a method of contacting with water in an organic solvent (Japanese Patent Application Laid-Open No. 63-22040). However, in the method (■), fuming sulfuric acid and chlorosulfuric acid are highly corrosive, and large amounts of noalkyl sulfate and chlorinated substances, which are difficult to hydrolyze, are produced as by-products, and in the method (■), trimethylamine and formic acid are produced as by-products.
It becomes a problem. Also, if there are a large amount of compounds with double bonds at the ends, 1
There are problems such as getting pregnant. Furthermore, the method (■) is a high temperature, high pressure reaction of 200°C or higher under strongly acidic conditions with a pH of 2 or lower.
It is difficult to select a material that can withstand the generated III.
又、■の方法では、重金属を使用［るためその毒性、公
害の発生、回収の問題等を有している。Furthermore, since the method (2) uses heavy metals, there are problems with their 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、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) An object of the present invention is to provide a method for producing fluoroalcohol that is safe and has a high yield, without using dangerous chemicals, heavy metals, etc.
（課題を解決するための手段）
本発明は一般式
％式％］）
（！７ｒは炭素数２〜１：（のフルオロアルキル！１（
オーしくけフルオロアルキレン基、−１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
％式％
（１りＩ及び＋１は１．記に同し）で表わされるフルオ
ロアルコール
の製造法に係る。(Means for Solving the Problems) The present invention is based on the general formula % formula %]) (!7r has 2 to 1 carbon atoms: (fluoroalkyl!1(
In the presence of an organic solvent, an iodide represented by the following fluoroalkylene group, -1 is 1 when Rf is a fluoroalkyl group, and 2 when Rf is a fluoroalkylene group,
The present invention relates to a method for producing a fluoroalcohol represented by the general formula % (where 1 and +1 are the same as in 1.) by bringing it into contact with a betaine compound and water.
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
製法にー〕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工稈及び次いでアルカリ水溶液の存でｆ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 previously filed a patent application for a method for producing fluoroalcohol, which involves contacting iodide, a starting material similar to that of the present invention, with a betaine compound to obtain an intermediate, and then hydrolyzing the intermediate. (Patent application 1986-161500
However, this method consists of two steps: the first step to obtain the intermediate in the absence of water, and the second step of hydrolysis under f in the presence of an alkaline aqueous solution. This is different from an invention that consists of one step.
本発明において出発原料は−・般式
％式％）
（Ｉｌｆは炭素数２〜１：）のフルオロアルキル基若し
くはフルオロアルキレン７Ａ、ＩＩはＩＩＦ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、具体例としテｌｉ、
ＣＦＪ（ＣＦ’２ン，（ｌＩ２ｃＩＩ２１，ＣＦ。In the present invention, the starting material is a fluoroalkyl group or fluoroalkylene of the general formula %) (Ilf is a carbon number of 2 to 1: 7A, II is 1 when IIF is a fluoroalkyl group, and 1 when it is a fluoroalkylene group) is an iodide represented by 2), and specific examples are teri,
CFJ(CF'2n, (lI2cII21, CF.
（Ｃ Ｆ ２）、Ｃ ＩＩ 、Ｃ ＩＩ 」、（Ｃ Ｆ
．）、Ｃ Ｉ’ （Ｃ ＦＬＣｌ（２ＣＨ２１．ＩＣ１
１２Ｃ１１２（ＣＦ，ＣＦ，ＬＣＩＩ。(C F 2), C II, C II'', (C F
．． ), C I' (C FLCl(2CH21.IC1
12C112 (CF, CF, LCII.
ＣＨ２Ｉ，ＩＣＨ．、Ｃｌｌ，（ＣＦ，ＣＦ．）、ＣＩ
Ｉ，ＣＩＩ−■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
ィー１９５０年３０４１頁、ザ・ノ゛ヤーナル・オブ・
オーガニック・ケミストリー ２３巻 １１６６真 （
１９５８年）等に記載されている。CH2I, ICH. , Cll, (CF, CF.), C.I.
I, CII-■, etc. can be mentioned. Methods for producing these compounds are described in Journal of the Chemical Society, 1950, p. 3041, The Journal of the Chemical Society, 1950, p.
Organic Chemistry Volume 23 1166 True (
(1958) and others.
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
％式％（）
（Ｒ’， Ｒ２， Ｔ＜’は炭素数１へ２４のアルキル
基）で表わされる化合物であり、例えば、
（ＣＨ３）３Ｎ＠ＣＨ２ＣＯ２０
（ Ｃ ２ Ｈ ｓ ） ］ Ｎ ｅＣ Ｈ ２ Ｃ
Ｏ ２ ｅＣ ａ Ｈ ｌ ７ （ Ｃ Ｈ ３ ）
２ Ｎ ｅＣ Ｉ−１ ２ Ｃ ０ ２ ｅＣ 、２Ｈ
２，（Ｃ Ｈ ３）２Ｎ ｅ Ｃ ＩＩ 、Ｃ ０２
ｅＣＩ８１１．（ＣＩｌｌ）２ＮｅＣｌｌ，Ｃ（’）、
０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筒２，８００，５０２号明細書等に
記載されている。A preferred example of the betaine compound used in the present invention is a compound represented by the general formula % () (R', R2, T<' is an alkyl group having 1 to 24 carbon atoms), for example, (CH3 )3N@CH2CO20 (C 2 H s ) ] N eC H 2 C
O 2 eC a H 7 (C H 3 )
2 N eC I-1 2 C 0 2 eC , 2H
2, (C H 3)2N e C II , C 02
eCI811. (CIll)2NeCll,C('),
0 etc. can be mentioned. Methods for producing these betaine compounds are described, for example, in US Pat. No. 2,800,502.
本発明において用いられる有機溶媒は水と相溶じやすく
、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／−ル、エタノール、プロパツ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、
フェノール、クレゾール、スルホラン、Ｎ−メチルピロ
リドン、γー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 preferably one that is easily compatible with water and helps mix the raw material iodide with water, such as alcohols such as methanol, ethanol, propatool, acetone, acetonitrile, ethylene glycol, glycerin, grime, cellosolve, propionic acid,
Examples include 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、１
１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当量に月して水
を通常１〜２００当量（水１モルは２当量）、好ましく
は２〜１４０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’Ｃ、反応速
度、加熱の容易さの点で好ましくは１２０〜＋ ６ ０
’Ｃ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 mole of iodide is 1
1 equivalent when 1 is 1, 2 equivalents when n is 2),
Usually 1 to 20 equivalents of betaine compound, preferably 1.2 equivalents
~5 equivalents are used. Further, water is usually used in an amount of 1 to 200 equivalents (1 mole of water is 2 equivalents), preferably 2 to 140 equivalents per equivalent of raw material iodide. The organic solvent is preferably used in a volume ratio of 0.1 to 10 parts, preferably 1 to 5 parts, per 1 part of water. The reaction temperature is usually 80 to 200'C, preferably 120 to +60'C in terms of reaction rate and ease of heating.
'C. A reaction time of about 1 to 10 hours is usually sufficient, and preferably about 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、〃スクロマトグラフイー、カ
ラムクロマトグラフィー等の手段を用い得る。The object of the present invention is usually separated and purified by known means, such as extraction, distillation, recrystallization, chromatography, and column chromatography.
（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。(Effects of the Invention) The manufacturing method of the present invention does not use dangerous chemicals or heavy metals and is safe. Furthermore, the method of the present invention has good conversion rates of starting materials and selectivity of target products.
（実 施 例） 以下に実施例を挙げて説明する。(Example) Examples will be described below.
実施例Ｉ
ＣＦ ３（ＣＦ ２）７ＣＨ２ＣＨ２Ｉ ５７．４ｇ（
１００＋ａ＋ｎｏｌ）、（ＣＨ３）３Ｎｅ ＣＨ２Ｃｏ
ｏθ１４．１ｌｌ（１２０＋１１１１１０１ ）、イン
プロパツール（ＩＰＡ）５０ｇ及び水２０ｇを２００１
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１００＋ｎ
ｌで抽出後、油層を〃スクロマトグラフイーで分析した
。転化率９７％、選択率９３％でＣＦ ３（ＣＦ ２Ｌ
ＣＨ２ＣＨ２０Ｈが得られた。Example I 57.4 g of CF3(CF2)7CH2CH2I (
100+a+nol), (CH3)3Ne CH2Co
oθ14.1ll (120+1111101), 50g of Improper Tool (IPA) and 20g of water in 2001
The mixture was placed in an autoclave and heated and stirred at 150°C for 6 hours. After cooling the reaction mixture to room temperature, 100+n each of water and trichlorotrifluoroethane (R-113) were added.
After extraction with l, the oil layer was analyzed by chromatography. CF 3 (CF 2L) with a conversion rate of 97% and a selectivity of 93%.
CH2CH20H was obtained.
実施例２
Ｉ ＣＨ２Ｃｌ−（２（ＣＦ２）６ＣＨ２ＣＨ，、Ｉ
６１．Ｏｆ＋（＋００＋ａ＋ｎｏｌ）、（ＣＩ−１３）
３ＮΦＣＨ２ＣＯＯθ ２８．１ｇ（２４０＋ｕｎｏｌ
）、ＩＰＡ６０ｇ及び水３０ｇを２００１のオートクレ
ーブに仕込み、１５０℃で６時間加熱撹件した。反応混
合物を室温に冷却後、水及びＲ−１１３のそれぞれ１０
０１で抽出後、油層を〃スクロマトグラフイーで分析し
た。Example 2 I CH2Cl-(2(CF2)6CH2CH,,I
61. Of+(+00+a+nol), (CI-13)
3NΦCH2COOθ 28.1g (240+unol
), 60 g of IPA, and 30 g of water were placed in a 2001 autoclave, and heated and stirred at 150° C. for 6 hours. After cooling the reaction mixture to room temperature, 10% each of water and R-113 were added.
After extraction with 01, the oil layer was analyzed by chromatography.
ＩＣ１（２ＣＨ２（ＣＦ２）６ＣＨ２ＣＨ２Ｉの転化率
は９５％で、ＨＯＣＨ２ＣＩ−１２（ＣＦ２）、ＣＨ２
ＣＨ，、ＯＨの選択率は８７％であった。ＣＨ２＝ＣＨ
（ＣＦ２）、ＣＨ２ＣＨ２０Ｈが１０％副生じていた。The conversion rate of IC1(2CH2(CF2)6CH2CH2I is 95%, HOCH2CI-12(CF2), CH2
The selectivity of CH,,OH was 87%. CH2=CH
(CF2) and CH2CH20H were produced by 10%.
実施例３
ＣＦ ３（ＣＦ ２）７ ＣＨ２ＣＨ２Ｉ ５７．４ｇ
（１００ｉｏｍｏｌ ）、（ＣＨｊ＞ｆｆＮ＠Ｃｌ−１
２Ｃ００θ １１．７ｇ（１００ｍｍｏｌ）、ＩＰ Ａ
４０．１水１５ｇ及びベタイン型界面活性剤としてＣ
，２１−１２，（ＣＨ３）２Ｎ＠ Ｃ１１２ＣＯＯθ
５．４ｇ（２０＋ｎｍｏｌ）を２００ｍ１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１０
０１６１で抽出後、油層を〃スクロマトグフフイーで分
析した。転化率９９％、選択率９５％でＣＦ ３（ＣＦ
２）７ＣＩＩ 、ＣＩＩ ２０Ｈが得られた。Example 3 CF3(CF2)7CH2CH2I 57.4g
(100iomol), (CHj>ffN@Cl-1
2C00θ 11.7g (100mmol), IP A
40.1 15 g of water and C as a betaine type surfactant
,21-12,(CH3)2N@C112COOθ
5.4g (20+nmol) was charged into a 200ml autoclave, and heated and stirred at 150°C for 6 hours. After cooling the reaction mixture to room temperature, 10% each of water and R-113 were added.
After extraction with 0161, the oil layer was analyzed using chromatography. CF3 (CF
2) 7CII and CII 20H were obtained.
実施例４〜７
有機溶媒としてイソプロパツールの代りに第１表に記載
した溶媒を用いる以外は実施例１と同様の操作を行った
。ＣＦ ３（ＣＦ ２）７Ｃ８２ＣＩ−（２１の転化率
及びＣＦ ３（ＣＦ ２）、Ｃ１１２ＣＨ２０１１の選
択率を第１表に示す。Examples 4 to 7 The same operations as in Example 1 were performed except that the solvents listed in Table 1 were used instead of isopropanol as the organic solvent. Table 1 shows the conversion rate of CF3(CF2)7C82CI-(21) and the selectivity of CF3(CF2), C112CH2011.
第 １ 表
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
と同様の操作を行ったところ、ＣＦ、（ＣＦ ２ ）７
ＣＨ２ＣＨ２１の転化率は０％であった。Table 1 Comparative Example 1 Example 1 except that the betaine compound of Example 1 is not used.
When the same operation was performed, CF, (CF 2 )7
The conversion rate of CH2CH21 was 0%.
（以 上）
出 願 人 ダイキン工業株式会社
代 理 人 弁理士 １）村 巌
手
続
補
正
書
１、事件の表示
昭和６３年特許願第２９８８１８号
２、発明の名称
フルオロアルコールの製造法
３、補正をする者
事件との関係 特許出願人
（２８５）ダイキン工業株式会社
４、代
埋入
〒５３０大阪府大阪市北区曽根崎１丁目２番８号５、補
正命令の日付
自 発
６、補正の対象
明細書中［発明の詳細な説明］の項
７、補正の内容
（１）明細書中第６頁第１６行(Above) Applicant Daikin Industries, Ltd. Agent Patent Attorney 1) Iwao Mura Procedural Amendment 1, Indication of Case 1988 Patent Application No. 298818 2, Title of Invention Process for Manufacturing Fluoro Alcohol 3, Amendment Patent applicant (285) Daikin Industries, Ltd. 4, Substitute address: 1-2-8-5 Sonezaki, Kita-ku, Osaka, Osaka 530, Date of amendment order: 6, Details subject to amendment Section 7 of [Detailed Description of the Invention], Contents of Amendment (1) Page 6, Line 16 of the Specification
Claims (2)
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（ＣＨ＿２ＣＨ＿２ＯＨ）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) General formula Rf(CH_2CH_2I)n (Rf is a fluoroalkyl group or fluoroalkylene group having 2 to 13 carbon atoms, n is 1 when Rf is a fluoroalkyl group, and 2 when it is a fluoroalkylene group) Production of fluoroalcohol, which comprises obtaining a fluoroalcohol represented by the general formula Rf(CH_2CH_2OH)n (Rf and n are the same as above) by contacting iodide with a betaine compound and water in the presence of an organic solvent. Law.
１、Ｒ＾２、Ｒ＾３は炭素数１〜２４のアルキル基）で
表わされる化合物である請求項１記載の製造法。(2) The betaine compound has the general formula R^1R^2R^3N^■CH_2CO_2^■(R^
2. The method according to claim 1, wherein R^2 and R^3 are alkyl groups having 1 to 24 carbon atoms.
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 true JPH02142741A (en) | 1990-05-31 |
| JPH082815B2 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6894197B2 (en) | 2001-07-02 | 2005-05-17 | Tosoh F-Tech, Inc. | Process for producing fluorinated alcohol |
-
1988
- 1988-11-25 JP JP63298818A patent/JPH082815B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6894197B2 (en) | 2001-07-02 | 2005-05-17 | Tosoh F-Tech, Inc. | Process for producing fluorinated alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH082815B2 (en) | 1996-01-17 |
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