JPS63284138A - Production of 1-bromo-2-fluoroethane - Google Patents
Production of 1-bromo-2-fluoroethaneInfo
- Publication number
- JPS63284138A JPS63284138A JP62117122A JP11712287A JPS63284138A JP S63284138 A JPS63284138 A JP S63284138A JP 62117122 A JP62117122 A JP 62117122A JP 11712287 A JP11712287 A JP 11712287A JP S63284138 A JPS63284138 A JP S63284138A
- Authority
- JP
- Japan
- Prior art keywords
- fluoroethane
- dibromoethane
- bromo
- hydrogen fluoride
- reaction
- 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
- JTLAIKFGRHDNQM-UHFFFAOYSA-N 1-bromo-2-fluoroethane Chemical compound FCCBr JTLAIKFGRHDNQM-UHFFFAOYSA-N 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 13
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims abstract description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 10
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 10
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003682 fluorination reaction Methods 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 abstract description 11
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 abstract description 6
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003880 polar aprotic solvent Substances 0.000 abstract 2
- 238000007269 dehydrobromination reaction Methods 0.000 abstract 1
- 230000000855 fungicidal effect Effects 0.000 abstract 1
- 239000000417 fungicide Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 3
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 2
- CBSIEJGODQIOKA-UHFFFAOYSA-N 2-bromoethyl benzenesulfonate Chemical compound BrCCOS(=O)(=O)C1=CC=CC=C1 CBSIEJGODQIOKA-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- VBTQNRFWXBXZQR-UHFFFAOYSA-N n-bromoacetamide Chemical compound CC(=O)NBr VBTQNRFWXBXZQR-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JUIKUQOUMZUFQT-UHFFFAOYSA-N 2-bromoacetamide Chemical compound NC(=O)CBr JUIKUQOUMZUFQT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は医薬および農薬等の中間体として有用す１−ブ
ロモ−２−フルオロエタンの製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing 1-bromo-2-fluoroethane, which is useful as an intermediate for pharmaceuticals, agricultural chemicals, and the like.
［従来の技術］
従来、１−ブロモ−２−フルオロエタンの合成法として
いくつかの方法が知られている。例えば、Ｊ、Ｏｒｇ、
Ｃｈｅｍ、、 １４．１０５（１９４９）には１．２−
ジブロモエタンをエチレングリコール溶媒中でＫＦを用
いてフッ素化する方法が、またＺｈｕｒ。[Prior Art] Several methods have been known to synthesize 1-bromo-2-fluoroethane. For example, J,Org,
Chem, 14.105 (1949) has 1.2-
A method for fluorinating dibromoethane using KF in ethylene glycol solvent is also described by Zhur.
０ｂｓｈｃｈｅｉ Ｋｈｉｍ、、 １９．９２（＋９４
９）には２−ブロモエチルフェニルスルホネート（Ｐｈ
ＳＯ３−Ｃ１）２Ｃ１）！Ｂｒ）を同様にＫＦを用いて
フッ素化する方法が記載されている。さらに、Ｊ、Ｃｈ
ｅｍ、Ｓｏｃ、、 ７７３（１９４９）ではエチレンク
ロロヒドリンからＫＦを用いて２−フルオロエタノール
を合成しさらにホスホラストリブロマイド（ＰＢｒｉ）
と反応させる方法、またＣａｎ、 Ｊ、 Ｃｈｅｍｌ、
４３．１６８９（＋９６５）にはフッ化水素およびＮ
−ブロモアセトアミド （Ｃ１ｌｓＣＯＮＩＩＢｒ）を
用いてエチレンにＢｒＦを付加させることにより１−ブ
ロモ−２−フルオロエタンを製造する方法が示されてい
る。0bshchei Khim,, 19.92 (+94
9) contains 2-bromoethyl phenyl sulfonate (Ph
SO3-C1)2C1)! A method for fluorinating Br) using KF is also described. Furthermore, J, Ch.
Em, Soc., 773 (1949) synthesized 2-fluoroethanol from ethylene chlorohydrin using KF and further synthesized phosphorus tribromide (PBri).
Can, J. Cheml,
43.1689 (+965) contains hydrogen fluoride and N
- A method for producing 1-bromo-2-fluoroethane by adding BrF to ethylene using bromoacetamide (C1lsCONIIBr) is shown.
［発明の解決しようとする問題点１
前述の１．２−ジブロモエタンをエチレングリコ−、ル
溶媒中でＫＦを用いてフッ素化する方法は脱１）Ｂｒに
よって毒性の極めて高いビニルブロマイドが主として生
成され、目的とする１−ブロ干−２−フルオロエタンの
生成は少なく、収率としては２４％であるに過ぎない。[Problem to be solved by the invention 1 The above-mentioned method of fluorinating 1,2-dibromoethane using KF in an ethylene glycol solvent produces mainly extremely highly toxic vinyl bromide due to removal 1) Br. However, the production of the desired 1-bro-2-fluoroethane is small, with a yield of only 24%.
このようなオレフィンの生成を抑制する手段として、フ
ッ化水素および酸化第一銅を用いて、ジエチルエーテル
あるいはテトラヒドロフランなどのエーテル類の存在下
フッ素化反応させる方法が特開昭６１−６５８２８号公
報に開示され、千ノへロゲノ有機化合物のフッ素化に有
用であるとされている。As a means of suppressing the formation of such olefins, a method of conducting a fluorination reaction using hydrogen fluoride and cuprous oxide in the presence of ethers such as diethyl ether or tetrahydrofuran is disclosed in JP-A-61-65828. and is said to be useful for the fluorination of organic compounds.
しかしながら、溶媒としてはジエチルエーテル、テトラ
ヒドロフランなど引火点の低いエーテル類を使用するこ
とが必要であり、危険性が高く、また、かかる溶媒は水
に易溶性を有することから、溶媒回収などの点で工業化
に際して多くの問題点を有している。However, it is necessary to use ethers with low flash points such as diethyl ether and tetrahydrofuran as solvents, which is highly dangerous, and since such solvents are easily soluble in water, it is difficult to recover the solvent. There are many problems with industrialization.
また、前述の２−ブロモエチルフェニルスルホネートを
ＫＦによってフッ素化する方法では、原料の入手に難点
があり、しかも製造工程が長くなり、１−ブロモ−２−
フルオロエタンの収率も３５％が限度であって、工業的
には好ましくない方法である。In addition, the method of fluorinating 2-bromoethyl phenyl sulfonate with KF has problems in obtaining raw materials and requires a long manufacturing process.
The yield of fluoroethane is also limited to 35%, making it an unfavorable method industrially.
さらに、エチレンクロルヒドリンから得られる２−フル
オロエタノールにホスホラストリブロマイドを反応させ
る方法では、中間生成物としての２−フルオロエタノー
ルを毒性が極めて高く、しかも１−ブロモ−２−フルオ
ロエタンの収率は出発原料としてのエチレンクロロヒド
リンに対し２４％であって極めて低い。そして、フッ化
水素およびＮ−ブロモアセトアミドを用いてエチレンに
ＢｒＦを付加させる方法においては反応温度を一４０℃
〜−２０℃と低温にすることが必要であって、温度制御
に困難を伴ない、それにも拘わらす１−ブロモ−２−フ
ルオロエタンの収率は２３％が限度である。しかも臭素
化剤としてのＮ−ブロモアセトアミドは高価であって工
業的の使用という点では極めて不利であり、かつ入手が
困難であるという問題点がある。Furthermore, in the method of reacting 2-fluoroethanol obtained from ethylene chlorohydrin with phosphorus tribromide, 2-fluoroethanol as an intermediate product is extremely toxic, and the yield of 1-bromo-2-fluoroethane is low. is 24% based on ethylene chlorohydrin as a starting material, which is extremely low. In the method of adding BrF to ethylene using hydrogen fluoride and N-bromoacetamide, the reaction temperature is -40°C.
It is necessary to maintain the temperature at a low temperature of -20 DEG C., making it difficult to control the temperature.Despite this, the yield of 1-bromo-2-fluoroethane is limited to 23%. Moreover, N-bromoacetamide as a brominating agent is expensive, extremely disadvantageous in industrial use, and difficult to obtain.
このように従来の公知技術はいずれも高収率で１．しか
も低コストを不可欠とする工業的な製造方法とするには
遠く及ばないものである。In this way, all conventional known techniques have a high yield of 1. Moreover, it is far from being an industrial manufacturing method that requires low cost.
［問題点を解決するための手段］
本発明は、前述の如く、従来技術が有していた。高い毒
性と危険性をもち、しかも高価な原料の使用と、低収率
といった問題点を解決すべくなされたものであり、安価
で工業的に入手容易な原料を用いて１−ブロモ−２−フ
ルオロエタンを高収率で、かつ低コストで製造し得る製
造方法の提供を目的とするものである。[Means for Solving the Problems] As described above, the present invention has the prior art. This method was developed to solve the problems of using highly toxic and dangerous raw materials, as well as the use of expensive raw materials and low yields. 1-Bromo-2- The object of the present invention is to provide a manufacturing method that can produce fluoroethane in high yield and at low cost.
即ち、本発明は１．２−ジブロモエタンとフッ化水素と
を酸化第一銅および非プロトン性極性溶媒の存在下、フ
ッ素化反応させることを特徴とする１−ブロモ−２−フ
ルオロエタンの製造方法を提供するものである。That is, the present invention relates to the production of 1-bromo-2-fluoroethane, which is characterized by subjecting 1,2-dibromoethane and hydrogen fluoride to a fluorination reaction in the presence of cuprous oxide and an aprotic polar solvent. The present invention provides a method.
本発明において、原料としての１．２−ジブロモエタン
は、エチレンに臭素を付加させるか、アセチレンに臭化
水素を付加させることにより製造され、殺線虫剤として
広く使用されているものであり、安価で容易に入手し得
る。In the present invention, 1,2-dibromoethane as a raw material is produced by adding bromine to ethylene or adding hydrogen bromide to acetylene, and is widely used as a nematocide. Cheap and easily available.
本発明での非プロトン性極性溶媒はジメチルスルホキシ
ド、スルホラン、Ｎ−メチル−２−ピロリドン、ジメチ
ルホルムアミド、ジメチルスルホン、アセトニトリル、
ヘキサメチルホスホルトリアミド、ベンゾニトリルなど
が用いられるが、通常はスルホランまたはジメチルスル
ホキシドが使用される。これらはエーテル類に比して取
り扱いや回収の点で工業的に好ましい。The aprotic polar solvent used in the present invention is dimethylsulfoxide, sulfolane, N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfone, acetonitrile,
Hexamethylphosphortriamide, benzonitrile, etc. are used, but sulfolane or dimethyl sulfoxide is usually used. These are industrially preferable compared to ethers in terms of handling and recovery.
本発明にまけるフッ素化反応の際のフッ化水素と酸化第
一銅および非プロトン性極性溶媒の使用量としての割合
は、通常モル比で１．２−ジブロモエタン１に対して、
それぞれ１〜５０．０．５〜５および５〜１００であり
、好ましくは １〜３０、０．５〜１ 、５〜ｌＯであ
る。The ratio of hydrogen fluoride, cuprous oxide, and aprotic polar solvent used in the fluorination reaction of the present invention is usually 1:1 to 1.2-dibromoethane in molar ratio.
They are respectively 1-50, 0.5-5 and 5-100, preferably 1-30, 0.5-1, and 5-1O.
フッ素化反応における反応温度は通常０〜２００℃、好
ましくは １００〜１５０℃で、反応時間は通常３０分
〜ｌＯ時間、好ましくは １〜６時間である。反応時の
反応圧力は常圧あるいは自然発生圧力下である。The reaction temperature in the fluorination reaction is usually 0 to 200°C, preferably 100 to 150°C, and the reaction time is usually 30 minutes to 10 hours, preferably 1 to 6 hours. The reaction pressure during the reaction is normal pressure or naturally occurring pressure.
本、発明のフッ素化反応は、通常１．２−ジブロモエタ
ンと酸化第一銅および非プロトン性極性溶媒を反応容器
にとり、これにフッ化水素を冷却しながら添加し、所定
温度に設定した後、所定時間反応させることにより行な
うことができる。In the fluorination reaction of the present invention, 1,2-dibromoethane, cuprous oxide, and an aprotic polar solvent are usually placed in a reaction vessel, hydrogen fluoride is added thereto while cooling, and the temperature is set at a predetermined temperature. This can be carried out by reacting for a predetermined period of time.
本発明の製造方法によって得られるｌ−ブロモ−２−フ
ルオロエタンは、医薬、農薬などの中間体として有用で
あり、例えば、下記のスキームに示すように合成抗菌剤
６，８−ジフルオロ−１，４−ジヒドロ−１−フルオロ
エチル−７−（４−メチル−１−ピペラジル）−４−オ
キソ゛−３−キノリンカルボン酸合成の際のフルオロエ
チル化剤として用いることができる。l-Bromo-2-fluoroethane obtained by the production method of the present invention is useful as an intermediate for medicines, agricultural chemicals, etc. For example, as shown in the scheme below, the synthetic antibacterial agent 6,8-difluoro-1, It can be used as a fluoroethylating agent in the synthesis of 4-dihydro-1-fluoroethyl-7-(4-methyl-1-piperazyl)-4-oxo-3-quinolinecarboxylic acid.
以下に本発明を具体的に実施例によって説明する。The present invention will be specifically explained below using examples.
［実施例］
実施例１
２００ｍ℃ハステロイＣ製オートクレーブに１．２ジブ
ロモエタン１８．９ｇ（０，１ｍｏｌ）と酸化第一銅７
．２ｇ （０，０５ｍｏｌ）、これに溶媒としてスルホ
ランを７０ｇ仕込み、減圧、冷却後フッ化水素６０、５
ｇ（３ｍａｌｌ を添加した。その後、反応器内の温度
を１００℃に上げ激しく攪拌しながら６時間反応させた
。冷却後過剰のＨＦを脱気して常圧にもどし、冷水６０
ｇを加えてから反応液を約３００ｃｃの氷水に投入した
。油層を塩化メチレンで抽出し、中和、水洗後ガスクロ
で分析したところ、原料の反応率は６９．７％、１−ブ
ロモ−２−フルオロエタンの選択率は９３．５％であり
、ビニルブロマイドへの選択率は５．７％であった。[Example] Example 1 18.9 g (0.1 mol) of 1.2 dibromoethane and 7 cuprous oxides were placed in a Hastelloy C autoclave at 200 m°C.
．． 2 g (0.05 mol), 70 g of sulfolane as a solvent was added thereto, and after cooling and reducing the pressure, hydrogen fluoride 60.5
After that, the temperature inside the reactor was raised to 100°C and the reaction was carried out for 6 hours while stirring vigorously. After cooling, excess HF was degassed and the pressure returned to normal pressure.
After adding 1.5 g of the reaction mixture, the reaction solution was poured into about 300 cc of ice water. The oil layer was extracted with methylene chloride, neutralized, washed with water, and then analyzed by gas chromatography. The reaction rate of the raw materials was 69.7%, the selectivity of 1-bromo-2-fluoroethane was 93.5%, and the conversion of vinyl bromide to vinyl bromide was 69.7%. The selectivity to was 5.7%.
実施例２
実施例１における酸化第一銅を Ｉ ４．４ｇ （０，
１ｍｏｌ）とした他は同様に反応させた。その結果。Example 2 The cuprous oxide in Example 1 was 4.4 g (0,
The reaction was carried out in the same manner except that the amount was changed to 1 mol). the result.
原料の反応率は９６．２％、１−ブロモ−２−フルオロ
エタンの選択率は９９，１％であった。この際ビニルブ
ロマイドの生成はほとんど認められなかった。The reaction rate of the raw materials was 96.2%, and the selectivity of 1-bromo-2-fluoroethane was 99.1%. At this time, almost no vinyl bromide was observed.
実施例３
実施例１に、おけるフッ化水素を２０ｇ （１ｍｏｌ）
とした他は同様に反応させた。その結果、原料の反応
率は４３．３％、１−ブロモ−２−フルオロエタンの選
択率は９３％であった。Example 3 20g (1 mol) of hydrogen fluoride in Example 1
Other than that, the reaction was carried out in the same manner. As a result, the reaction rate of the raw materials was 43.3%, and the selectivity of 1-bromo-2-fluoroethane was 93%.
実施例４
実施例１において溶媒をジメチルスルホキシド７０ｇと
した他は同様にして反応させた。その結果、原料の反応
率は６５％、１−ブロモ−２−フルオロエタンの選択率
は９２％であった。Example 4 The reaction was carried out in the same manner as in Example 1 except that 70 g of dimethyl sulfoxide was used as the solvent. As a result, the reaction rate of the raw materials was 65%, and the selectivity of 1-bromo-2-fluoroethane was 92%.
比較例１
１．２−ジブロモエタン１８．９ｇ （０，１ｍｏｌ）
と酸化第一銅７．２ｇ （０，０５ｍｏｌ）およびフッ
化水素６０、５ｇ （３ｍｏｌ）をテトラヒドロフラン
７０ｇ中で５０℃、３時間反応させたところ、原料の反
応率４２．５％、Ｉ−ブロモ−２−フルオロエタンの選
択率は５６．５％であった。Comparative example 1 1,2-dibromoethane 18.9 g (0.1 mol)
When 7.2 g (0.05 mol) of cuprous oxide and 60.5 g (3 mol) of hydrogen fluoride were reacted in 70 g of tetrahydrofuran at 50°C for 3 hours, the reaction rate of the raw materials was 42.5%, and I-bromo The selectivity of -2-fluoroethane was 56.5%.
比較例２
酸化第一銅とフッ化水素よりあらかじめ調整したフッ素
化剤１０ｇと１．２−ジブロモエタン１８．９ｇをテト
ラヒドロフラン中で３時間還流・させたところ、原料の
反応率３７％、！−ブロモー２−フルオロエタンの選択
率は５２％であった。Comparative Example 2 When 10 g of a fluorinating agent prepared in advance from cuprous oxide and hydrogen fluoride and 18.9 g of 1,2-dibromoethane were refluxed in tetrahydrofuran for 3 hours, the reaction rate of the raw materials was 37%! -Bromo-2-fluoroethane selectivity was 52%.
［発明の効果１
本発明によれば、１−ブロモ−２−フルオロエタンを１
．２−ジブロモエタンから工業的に高収率、かつ低コス
トで得ることができる。すなわち、ジハロゲノ化合物で
ある１、２−ジブロモエタンを選択的にモノフルオロ化
することができ、また、脱ＨＢｒによる毒性の極めて高
いビニルブロマイドの生成をも抑制できるという効果を
有するものである。[Effect of the invention 1 According to the present invention, 1-bromo-2-fluoroethane is
．． It can be obtained industrially from 2-dibromoethane in high yield and at low cost. That is, it has the effect of being able to selectively monofluorinate 1,2-dibromoethane, which is a dihalogeno compound, and also being able to suppress the production of highly toxic vinyl bromide due to HBr removal.
Claims (2)
一銅および非プロトン性極性溶媒の存在下、フッ素化反
応させることを特徴とする１−ブロモ−２−フルオロエ
タンの製造方法。(1) A method for producing 1-bromo-2-fluoroethane, which comprises subjecting 1,2-dibromoethane and hydrogen fluoride to a fluorination reaction in the presence of cuprous oxide and an aprotic polar solvent.
ルスルホキシドである特許請求の範囲第１項記載の製造
方法。(2) The manufacturing method according to claim 1, wherein the aprotic polar solvent is sulfolane or dimethyl sulfoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62117122A JPS63284138A (en) | 1987-05-15 | 1987-05-15 | Production of 1-bromo-2-fluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62117122A JPS63284138A (en) | 1987-05-15 | 1987-05-15 | Production of 1-bromo-2-fluoroethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63284138A true JPS63284138A (en) | 1988-11-21 |
Family
ID=14703976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62117122A Pending JPS63284138A (en) | 1987-05-15 | 1987-05-15 | Production of 1-bromo-2-fluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63284138A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021064908A1 (en) * | 2019-10-02 | 2021-04-08 | 三菱電機株式会社 | Refrigeration cycle device |
-
1987
- 1987-05-15 JP JP62117122A patent/JPS63284138A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021064908A1 (en) * | 2019-10-02 | 2021-04-08 | 三菱電機株式会社 | Refrigeration cycle device |
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