JPH0127051B2 - - Google Patents
Info
- Publication number
- JPH0127051B2 JPH0127051B2 JP59186851A JP18685184A JPH0127051B2 JP H0127051 B2 JPH0127051 B2 JP H0127051B2 JP 59186851 A JP59186851 A JP 59186851A JP 18685184 A JP18685184 A JP 18685184A JP H0127051 B2 JPH0127051 B2 JP H0127051B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- mmol
- reaction
- general formula
- hydrogen fluoride
- 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- -1 halogeno organic compound Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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)
Description
〔産業上の利用分野〕
本発明は、フルオロ有機化合物の製法に関す
る。
〔従来の技術〕
従来、陰イオン交換樹脂、相間移動触媒、クラ
ウンエーテル等を利用して、ハロゲン交換反応で
フルオロ有機化合物を合成する方法はよく知られ
ている。例えば、それらはシンセシス
（Synthesis）1976年472頁、同誌1974年428頁、ジ
ヤーナル・オブ・アメリカン・ケミカルソサエテ
イー（Ｊ・Am・Chem・Soc）1976年2250頁等に
記載されている。しかしながら上記公知の方法は
反応温度が高く、反応時間も長いので当該反応を
行うと、フツ素置換体のほかにオレフインが数十
％も副生し、フツ素置換体の収率は低い。
〔発明の目的〕
本発明の目的は、反応条件が温和でオレフイン
の副生がほとんどない収率のよいフルオロ有機化
合物の製法を提供することである。
〔発明の構成〕
本発明の要旨は一般式：
Ｒ−Ｘ
（式中、Ｒは鎖状または環状のアルキル基、Ｘ
は塩素原子または臭素原子を示す。）
で表されるハロゲノ有機化合物とフツ素化水素と
を(a)酸化銅（Ｉ）および(b)テトラヒドロフランま
たはジエチルエーテルの存在下反応させることか
らなる一般式：
Ｒ−Ｆ
（式中、Ｒは前記と同じ。）
で表されるフルオロ有機化合物の製法である。本
発明の製法で原料のハロゲン有機化合物は、一個
の塩素、臭素または沃素が前記一価の有機基に含
有される一個の炭素に共有結合してなる化合物
で、該炭素は本発明の反応に影響がない限り置換
基を有していてもよく、また複数個あつてもよ
い。
このハロゲノ有機化合物の例としては、
[Industrial Field of Application] The present invention relates to a method for producing fluoroorganic compounds. [Prior Art] Conventionally, methods for synthesizing fluoroorganic compounds by halogen exchange reaction using anion exchange resins, phase transfer catalysts, crown ethers, etc. are well known. For example, they are described in Synthesis, 1976, p. 472, the same magazine, 1974, p. 428, Journal of American Chemical Society (J.Am.Chem.Soc), 1976, p. 2250, etc. However, in the above-mentioned known method, the reaction temperature is high and the reaction time is long, so when the reaction is carried out, tens of percent of olefins are produced as by-products in addition to the fluorine-substituted product, and the yield of the fluorine-substituted product is low. [Object of the Invention] An object of the present invention is to provide a method for producing a fluoroorganic compound with mild reaction conditions and with almost no olefin by-product and a good yield. [Structure of the Invention] The gist of the present invention is the general formula: R-X (wherein, R is a chain or cyclic alkyl group,
represents a chlorine atom or a bromine atom. ) A general formula consisting of reacting a halogeno-organic compound represented by the formula with hydrogen fluoride in the presence of (a) copper(I) oxide and (b) tetrahydrofuran or diethyl ether: R-F (wherein R is the same as above.) This is a method for producing a fluoroorganic compound represented by: The halogenated organic compound used as a raw material in the production method of the present invention is a compound in which one chlorine, bromine, or iodine is covalently bonded to one carbon contained in the monovalent organic group, and this carbon is used in the reaction of the present invention. It may have a substituent as long as it has no effect, and it may have a plurality of substituents. Examples of this halogeno organic compound are:
【式】【formula】
【式】【formula】
【式】【formula】
次に本発明の実施例と比較例を示す。
実施例 １〜８
酸化銅（Ｉ）1.0ｇ（7mmol）を25mlのフツ素
樹脂製の容器にとり、これにフツ化水素３ml
（150mmol）および第１表に示すエーテル類から
なる溶液を０℃に冷却しながら加えた。
上記得られた混合物を第１表に示す温度に保ち
ながら、これに第１表に示すハロゲン有機化合物
（5mmol）の四塩化炭素（３ml）溶液を滴下し
た。
反応終了後、有機層を炭酸水素ナトリウム水溶
液で中和し、生成物をガスクロマトグラフイーで
分析した。結果を第１表に示す。
比較例１および２
フツ素樹脂容器にフツ化水素３ml（150mmol）
およびテトラヒドロフラン３mlからなる溶液を入
れ、これに実施例６および７で使用したと同じハ
ロゲノ有機化合物（5mmol）を溶解させた３ml
の四塩化炭素溶液をそれぞれ50および20℃で滴下
し、該温度でそれぞれ２および１時間反応させた
が原料を回収したのみで目的物は全く得られなか
つた。
比較例 ３
フツ素樹脂容器に酸化銅（Ｉ）ｇ（7mmol）
をとり、これにフツ化水素３ml（150mmol）を
０℃で加えた。得られた混合物に実施例７で使用
したのと同じハロゲノ有機化合物（5mmol）を
溶解させた３mlの四塩化炭素溶液を加え20℃で１
時間反応させたところ、式：
Next, examples of the present invention and comparative examples will be shown. Examples 1 to 8 1.0 g (7 mmol) of copper (I) oxide was placed in a 25 ml fluororesin container, and 3 ml of hydrogen fluoride was added to it.
(150 mmol) and a solution consisting of the ethers shown in Table 1 were added while cooling to 0°C. While maintaining the mixture obtained above at the temperature shown in Table 1, a solution of the halogen organic compound (5 mmol) shown in Table 1 in carbon tetrachloride (3 ml) was added dropwise thereto. After the reaction was completed, the organic layer was neutralized with an aqueous sodium hydrogen carbonate solution, and the product was analyzed by gas chromatography. The results are shown in Table 1. Comparative Examples 1 and 2 3 ml (150 mmol) of hydrogen fluoride in a fluororesin container
and 3 ml of tetrahydrofuran, and 3 ml of the same halogeno organic compound (5 mmol) used in Examples 6 and 7 was dissolved therein.
Carbon tetrachloride solutions were added dropwise at 50 and 20°C, respectively, and the reaction was allowed to proceed at these temperatures for 2 and 1 hours, respectively, but only the raw materials were recovered and no target product was obtained. Comparative example 3 Copper (I) oxide g (7 mmol) in a fluororesin container
was taken, and 3 ml (150 mmol) of hydrogen fluoride was added thereto at 0°C. To the resulting mixture was added 3 ml of carbon tetrachloride solution in which the same halogeno organic compound (5 mmol) used in Example 7 was dissolved, and the mixture was heated at 20°C for 1 hour.
After a time reaction, the formula:
【式】で表わ
されるオレフインおよびその重合体が90％の収率
で得られたのみであつた。The olefin represented by the formula and its polymer were obtained in a yield of only 90%.
Claims (1)
は塩素原子または臭素原子を示す。） で表されるハロゲノ有機化合物とフツ化水素とを
(a)酸化銅（Ｉ）および(b)テトラヒドロフランまた
はジエチルエーテルの存在下反応させることから
なる一般式： Ｒ−Ｆ （式中、Ｒは前記と同じ。） で表されるフルオロ有機化合物の製法。[Claims] 1 General formula: R-X (wherein, R is a chain or cyclic alkyl group,
represents a chlorine atom or a bromine atom. ) and hydrogen fluoride.
A method for producing a fluoroorganic compound represented by the general formula: R-F (wherein R is the same as above), which comprises reacting in the presence of (a) copper (I) oxide and (b) tetrahydrofuran or diethyl ether. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59186851A JPS6165828A (en) | 1984-09-06 | 1984-09-06 | Method for producing fluoroorganic compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59186851A JPS6165828A (en) | 1984-09-06 | 1984-09-06 | Method for producing fluoroorganic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6165828A JPS6165828A (en) | 1986-04-04 |
| JPH0127051B2 true JPH0127051B2 (en) | 1989-05-26 |
Family
ID=16195755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59186851A Granted JPS6165828A (en) | 1984-09-06 | 1984-09-06 | Method for producing fluoroorganic compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6165828A (en) |
-
1984
- 1984-09-06 JP JP59186851A patent/JPS6165828A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6165828A (en) | 1986-04-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |