JPH02157238A - Production of fluoroalcohol - Google Patents
Production of fluoroalcoholInfo
- Publication number
- JPH02157238A JPH02157238A JP63310753A JP31075388A JPH02157238A JP H02157238 A JPH02157238 A JP H02157238A JP 63310753 A JP63310753 A JP 63310753A JP 31075388 A JP31075388 A JP 31075388A JP H02157238 A JPH02157238 A JP H02157238A
- Authority
- JP
- Japan
- Prior art keywords
- water
- iodide
- fluoroalcohol
- contact
- general formula
- 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.)
- Pending
Links
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 nitride salt Chemical class 0.000 claims abstract description 14
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 229960003237 betaine Drugs 0.000 claims abstract description 7
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000002940 repellent Effects 0.000 abstract description 2
- 239000005871 repellent Substances 0.000 abstract description 2
- 208000012839 conversion disease Diseases 0.000 abstract 1
- 150000002826 nitrites Chemical class 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 10
- 235000010288 sodium nitrite Nutrition 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000002994 raw material Substances 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 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
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001577 simple distillation Methods 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 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
- 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 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
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 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
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000605 extraction Methods 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
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000003 magnesium salts 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 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
- 238000001953 recrystallisation Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (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方法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a method for producing fluoroalcohols.
（従来の技術）
（Ｒｆ及びＩ＋は上記に同じ）で表わされるヨウ化物を
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) A fluoroalcohol containing an iodide represented by (Rf and I+ are the same as above) 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
キルヨウ化物又はシュウ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４０−１９０８
５号、特公昭５８−３９１３５号）、■ツメチルホルム
アミド及び水と接触させる方法（Ｖｆ公昭５２−８８０
７号）、■非酸化性の酸素酸又はヨツ化水素の水溶液中
でｐＨ２以下の条件で加水分解する方法（ドイツ公開Ｎ
ｏ、 ２３１８６７７）、０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６３−２
２０４０号）ａ！？が知られている。Conventionally, the method for producing fluoroalcohols uses fluoroalkyl iodide or oxalide as a starting material, and
A method of producing a sulfuric acid ester by contacting it with fuming sulfuric acid or chlorosulfuric acid, and then hydrolyzing it (Japanese Patent Publication No. 40-1908)
No. 5, Special Publication No. 58-39135), ■ Method of contacting with methylformamide and water (Vf Publication No. 52-880
7), ■ A method of hydrolysis in an aqueous solution of non-oxidizing oxygen acid or hydrogen iodide under conditions of pH 2 or less (German Publication No.
o, 2318677), a method of contacting with water in an organic solvent in the presence of a heavy metal ion catalyst (JP-A-63-2
No. 2040) a! ? It has been known.
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ェートや
塩素化物が多量に副生し、■の方法ではツメチルアミン
、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
上の商温、高圧反応で、発生するＨ Ｉ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。However, in the method (■), fuming sulfuric acid and chlorosulfuric acid are highly corrosive, and large amounts of dialkyl 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, which poses problems in terms of recovery. becomes. Further, there is a problem that a large amount of compounds having double bonds at the ends are produced as by-products. Furthermore, in method (2), it is difficult to select a material that can withstand the H I generated under strongly acidic conditions of pH 2 or less, commercial temperature of 200° C. or more, and high pressure reaction. In addition, method (2) uses heavy metals, which causes 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、重金属等を使用゛しない、
安全なフルオロアルコールの新規な９１遣方法を提供し
、好ましい実施！！！様では、この目的に加えて、収率
の良いフルオロアルコールの製造方法を提供することに
ある。(Problem to be solved by the invention) The purpose of the present invention is to avoid using dangerous chemicals, heavy metals, etc.
Providing a new and preferred method for dispensing fluoroalcohols that is safe! ! ! In addition to this purpose, it is also an object of the present invention to provide a method for producing fluoroalcohols with good yield.
（課題を解決するための手段）
本発明は一般式
％式％）
（Ｒｒ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
されるヨウ化物を亜硝酸塩及び水と接触させることによ
り一般式
％式％）
（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方
法に係る。(Means for Solving the Problems) The present invention has the general formula % (Rr is a fluoroalkyl group or a fluoroalkylene group having 2 to 13 carbon atoms, n is 1 when Rf is a fluoroalkyl group, and a fluoroalkylene group) In the case of 2), a method for producing a fluoroalcohol comprising contacting the iodide represented by 2) with nitrite and water to obtain a fluoroalcohol represented by the general formula %) (Rf and n are the same as above) Pertains to.
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申開体を得、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ｔ
ｊＳ１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 method for producing a fluoroalcohol, which involves contacting iodide, a starting material similar to that of the present invention, with a betaine compound to obtain an open compound, and then hydrolyzing the intermediate. (Gan Sho 62-161500)
However, this method allows the intermediate to be obtained in the absence of water.
This method is comprised of two steps: a step S1 and a second step of hydrolysis in the presence of an aqueous alkaline solution, and is different from the one step method of the present invention.
本発明において出発物質１よ一般式
％式％）
（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、ＣＦ 、（Ｃ
Ｆ２）７ＣＨ２ＣＨ２１、ＣＦ３（ＣＦ ２）ＩＣＨ
２ＣＨ２Ｉ 、 （ＣＦ 、＞２ＣＦ （ＣＦ
２ＬＣＨ□ＣＨ２Ｉ、 ＩＣＨ２ＣＨ□（ＣＦ
２ＣＦ 、）２Ｃト］ ２ＣＨ２Ｉ、Ｉ Ｃ）（
、ＣＨ２（ＣＦ２ＣＦ２）３ＣＨ，ＣＨ３Ｉ等を挙げる
ことがでさる。これらの化合物の製法は、ジャーナル・
オブ・ザ・ケミカル・ソサエティー１９５０年３０４１
頁、ザ・ツヤ−ナル・オブ・オーガニック・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, starting material 1 (general formula % formula %) (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) It is an iodide represented by CF, (C
F2)7CH2CH21, CF3(CF2)ICH
2CH2I, (CF, >2CF (CF
2LCH□CH2I, ICH2CH□(CF
2CF,)2Ct] 2CH2I,I C)(
, CH2(CF2CF2)3CH, CH3I and the like. The methods for making these compounds are described in the journal
of the chemical society 1950 3041
Page, The Natural of Organic Chemistry, Vol. 23, p. 1166 (1958).
本発明で用いられる亜硝酸塩としては例えば亜硝酸のナ
トリウム塩、カリウム塩等のアルカリ金属塩又はカルシ
ウム塩、マグネシウム塩等のアルカリ土類金属塩を挙げ
ることができる。Examples of the nitrite used in the present invention include alkali metal salts of nitrous acid such as sodium salts and potassium salts, and alkaline earth metal salts such as calcium salts and magnesium salts.
本発明では原料ヨウ化物１当量に対して、亜硝酸塩を１
〜２０当量、好ましくは１．２〜５当量使月１する。又
、原料ヨウ化物１当量に対して水を１〜２００当量、好
ましくは２〜１４０当量使用する。In the present invention, 1 equivalent of nitrite is added to 1 equivalent of raw material iodide.
~20 equivalents, preferably 1.2 to 5 equivalents per month. Further, 1 to 200 equivalents, preferably 2 to 140 equivalents of water are used per 1 equivalent of raw material iodide.
本発明の反応は有ぺ溶媒の存在下に行うことが好ましい
、用いられる育成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、例工ばメタノール、
エタ／−ル、１−７０パ／−ル、２−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、７エ／−ル、クレゾール、スルホフン、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 reaction of the present invention is preferably carried out in the presence of a solvent. The growth solvent used is preferably one that is easily compatible with water and helps mix the raw material iodide with water, such as methanol,
Alcohols such as ethanol, 1-70 p/l, 2-propanol, acetone, acetonitrile, ethylene glycol, glycerin, glyme, cellosolve, propionic acid, 7 p/l, cresol, sulfophane, N-
Examples include methylpyrrolidone and γ-butyrolactone.
有機？８媒は体積比で水１部に対して０．１〜１０部、
好まし４は１〜５部使用するのが良い。Organic? 8 medium is 0.1 to 10 parts by volume per 1 part of water,
It is preferable to use 1 to 5 parts of 4.
本発明の反応を有機溶媒の不存在下に行う場合は、亜硝
酸塩及び水と共にベタイン型界面活性剤と出発物質のヨ
ウ化物を接触させるのが好ましい。When the reaction of the present invention is carried out in the absence of an organic solvent, it is preferable to contact the betaine type surfactant and the starting iodide together with nitrite and water.
使用されるベタイン型界面活性剤の好適な例は一般式
％式％
（Ｒ’、Ｒ２は炭素数１〜５のアルキル基、Ｒ３は炭素
数６〜２４、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、
ＣｓＨ１７（Ｃｌ（３）２Ｎ ８Ｃ８２ＣＯ２ｅＣ１２
Ｈ２Ｓ（ＣＩ−１，）２ Ｎ ＠ ＣＨ２ＣＯ□”ｃ
、、ｓ、ｔ（ｃｒイ 、）２ Ｎ Φ Ｃ８２Ｃｏ
２θ等を挙げることがでさる。A suitable example of the betaine type surfactant used is the general formula % (R', R2 is an alkyl group having 1 to 5 carbon atoms, R3 is an alkyl group having 6 to 24 carbon atoms, preferably 8 to 20 carbon atoms). For example, CsH17(Cl(3)2N 8C82CO2eC12
H2S(CI-1,)2 N @ CH2CO□”c
,,s,t(cr i ,)2 N Φ C82Co
2θ etc. can be mentioned.
ベタイン型界面活性剤を使用する場合は、重量比で原料
ヨウ化物１００ｆｆｌに対して１〜２００部、好ましく
は、５〜１００部使用するのが良い１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°Ｃである６反応時闇は通常１〜１
０時間程時間子分であり、好ましくは２〜６時間程度で
ある。When using a betaine type surfactant, it is recommended to use 1 to 200 parts, preferably 5 to 100 parts by weight, per 100 ffl of raw material iodide.1 The reaction temperature is usually 80 to 200°C; In terms of speed and ease of heating, the temperature is preferably 120 to 160°C.6 The temperature during the reaction is usually 1 to 1.
The duration is about 0 hours, 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、ガスクロマトグラフィー、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, gas chromatography, column chromatography, and the like.
（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、本発明の好ましい実施態様では出発原料の転
化率、目的物の選択率が良い。(Effects of the Invention) The manufacturing method of the present invention does not use dangerous chemicals or heavy metals and is safe. Further, in a preferred embodiment of the present invention, the conversion rate 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。(Example) Examples will be described below.
実施例Ｉ
ＣＦ ｓ（ＣＦ ２）ｔ ＣＨ２ＣＨ２１２２，９６ｇ
（４０ｍｓｏｌ ）、亜硝酸ナトリウム４．１４ｇ（６
０ｍｓｏｌ ）、水１８ｇ（１ｍｏｌ）及びアセトニト
リル５０−１を２００１のオートクレーブに仕込み、１
５０℃で６時間加熱撹拌した。反応混合物を室温に冷却
後、７セトニ） ＩＪルを単蒸留で除いた後、油層をガ
スクロマトグラフィーで分析した。転化率９９％以上、
選択率９２％でＣＦ 、（ＣＦ ２）、ＣＦ（２ＣＨ２
０Ｈが得られた。Example I CFs(CF2)t CH2CH2122, 96g
(40msol), sodium nitrite 4.14g (6
0 msol), 18 g (1 mol) of water, and 50-1 acetonitrile were placed in a 2001 autoclave.
The mixture was heated and stirred at 50°C for 6 hours. After the reaction mixture was cooled to room temperature, 7 cetonyl IJ was removed by simple distillation, and the oil layer was analyzed by gas chromatography. Conversion rate of 99% or more,
CF, (CF2), CF(2CH2) with a selectivity of 92%
0H was obtained.
実施例２
Ｉ Ｃ１−１２ＣＩ（２（ＣＦ２）−ＣＨ２ＣＨ２Ｉ
２８．４ｇ（４０１ｆｉ＋ｍｏｌ）、亜硝酸ナトリウ
ム８．２８Ｈ（１２０ｗｓｏｌ）、水３６ビ（２＋＾ｏ
１）及びアセトニトリル１００輸１を２００鴎１のオー
トクレーブに仕込み、１５０’Ｃで６時間加熱撹拌した
。反応７１６合物を室温に冷却後、アセトニトリルを単
蒸留で除いた後、油層をガスクロマトグラフィーで分析
した。Example 2 I C1-12CI(2(CF2)-CH2CH2I
28.4g (401fi+mol), sodium nitrite 8.28H (120wsol), water 36bis(2+^o
1) and 100 parts of acetonitrile were placed in a 200 part autoclave and heated and stirred at 150'C for 6 hours. After cooling the reaction compound 716 to room temperature, acetonitrile was removed by simple distillation, and the oil layer was analyzed by gas chromatography.
Ｉ ＣＨ２ＣＨ２（ＣＦ２）−ＣＨ２Ｃｌ１Ｉの転化率
は９９％以上で、Ｉ（ＯＣＨ２Ｃ１１２（ＣＦ２）、Ｃ
ｌ−１２ＣＨ２０ｔｌの選択率は９０％であった。The conversion rate of I CH2CH2(CF2)-CH2Cl1I was more than 99%, and the conversion rate of I(OCH2C112(CF2), C
The selectivity of 1-12CH20tl was 90%.
実施例３〜７
アセトニトリルの代りに第１表に示す溶媒を使用した以
外は実施例１と同様に反応を行った。Examples 3 to 7 Reactions were carried out in the same manner as in Example 1, except that the solvents shown in Table 1 were used instead of acetonitrile.
ＣＦ、（ＣＦ２）、ＣＨ２Ｃｌ１．Ｉの転化率及びＣＦ
、（ＣＦ２）、ＣＨ２ＣＨ２０Ｈの選択率を第１表に示
す。CF, (CF2), CH2Cl1. Conversion rate of I and CF
, (CF2) and CH2CH20H are shown in Table 1.
第 １ 表
実施例８
ＣＦ ｓ（ＣＦ ２）７ＣＨ２ＣＨ２Ｉ ２２．９６
ｇ（４０ｗｍｏｌ）、亜硝酸ナトリウム３．３１ｇ（４
８ｍｍｏｌ）、Ｃ，，１−２２，（ＣＨ３）２Ｎ ｅＣ
Ｈ２Ｃ’００ Ｃ２，１７ｇ（８ｍｍｏｌ）及ヒ水１８
、（１論ｏｆ）を２００ｍ ｌ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、下層をガスクロマトグラフィーで分析した。Table 1 Example 8 CF s(CF 2)7CH2CH2I 22.96
g (40 wmol), sodium nitrite 3.31 g (4
8 mmol), C,, 1-22, (CH3)2N eC
H2C'00 C2, 17g (8mmol) and water 18
(1 theory of) was placed in a 200 ml autoclave and heated and stirred at 150°C for 6 hours. After cooling the reaction mixture to room temperature, the lower layer was analyzed by gas chromatography.
転化率９９％、選択率９３％でＣＦ 、（ＣＦ ２）、
ＣＨ２ＣＨ、ＯＨが得られた。CF, (CF2), with a conversion rate of 99% and a selectivity of 93%.
CH2CH,OH was obtained.
比較ｇ４１
実施例１において亜硝酸ナトリウムを使用しない以外は
実施例１と同様の繰作を行ったところ、ＣＦ ＊（ＣＦ
２）？ＣＩ（２ＣＨ２１の転化率は０％であった。Comparison g41 When the same repetition as in Example 1 was performed except that sodium nitrite was not used in Example 1, CF*(CF
2)? The conversion rate of CI (2CH21) was 0%.
比較例２
実施例８において亜硝酸ナトリウムを使用しない以外は
実施例８と同様の操作を行ったところ、ＣＦ、（ＣＦ、
）ｊｃ８２ｃＩ−１２Ｉの忙化率は２２％であり、ＣＦ
、（ＣＦ ２）、ＣＩ＋ ２ＣＩ−１２０１１の選択
率は９２％であった。Comparative Example 2 When the same operation as in Example 8 was performed except that sodium nitrite was not used in Example 8, CF, (CF,
) jc82cI-12I busy rate is 22%, CF
, (CF2), CI+ The selectivity of 2CI-12011 was 92%.
（以 上） 出 願 人 ダイキン工業株式会社(that's all) Sender: Daikin Industries, Ltd.
Claims (5)
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
されるヨウ化物を亜硝酸塩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方
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) A method for producing a 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 an iodide with a nitrite and water.
造方法。(2) The manufacturing method according to claim 1, wherein the contact is carried out in the presence of an organic solvent.
硝酸塩、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（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方
法。(3) By bringing an iodide represented by the general formula Rf(CH_2CH_2I)n (Rf and n are the same as above) into contact with a nitrite, a betaine type surfactant, and water, the general formula Rf(CH_2CH_2OH)n (Rf and A method for producing a fluoroalcohol, which comprises obtaining a fluoroalcohol represented by (n is the same as above).
塩である請求項１〜３のいずれかに記載の製造方法。(4) The manufacturing method according to any one of claims 1 to 3, wherein the nitrite is an alkali metal salt or an alkaline earth metal salt.
１、Ｒ＾２は炭素数１〜５のアルキル基、Ｒ＾３は炭素
数６〜２４のアルキル基）で表わされる化合物である請
求項３記載の製造方法。(5) Betaine type surfactants have the general formula R^1R^2R^3N^■CH_2CO_2^■(R^
4. The manufacturing method according to claim 3, wherein R^2 is an alkyl group having 1 to 5 carbon atoms, and R^3 is an alkyl group having 6 to 24 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63310753A JPH02157238A (en) | 1988-12-07 | 1988-12-07 | Production of fluoroalcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63310753A JPH02157238A (en) | 1988-12-07 | 1988-12-07 | Production of fluoroalcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02157238A true JPH02157238A (en) | 1990-06-18 |
Family
ID=18009069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63310753A Pending JPH02157238A (en) | 1988-12-07 | 1988-12-07 | Production of fluoroalcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02157238A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276415A (en) * | 2011-05-16 | 2011-12-14 | 山东中氟化工科技有限公司 | Method for improving fluorine-containing alkyl alcohol yield |
-
1988
- 1988-12-07 JP JP63310753A patent/JPH02157238A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276415A (en) * | 2011-05-16 | 2011-12-14 | 山东中氟化工科技有限公司 | Method for improving fluorine-containing alkyl alcohol yield |
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