JP2001322955A - Method for producing 2-bromo-3,3,3-trifluoropropene - Google Patents
Method for producing 2-bromo-3,3,3-trifluoropropeneInfo
- Publication number
- JP2001322955A JP2001322955A JP2000143022A JP2000143022A JP2001322955A JP 2001322955 A JP2001322955 A JP 2001322955A JP 2000143022 A JP2000143022 A JP 2000143022A JP 2000143022 A JP2000143022 A JP 2000143022A JP 2001322955 A JP2001322955 A JP 2001322955A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- trifluoropropene
- bromo
- dibromo
- trifluoropropane
- 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
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
【０００１】[0001]
【発明の属する技術分野】本発明は、医薬品及び農薬な
どの各種含フッ素化合物の中間原料として有用な物質で
ある２−ブロモ−３，３，３−トリフルオロプロペンの
製造方法に関するものである。The present invention relates to a method for producing 2-bromo-3,3,3-trifluoropropene, a substance useful as an intermediate material for various fluorine-containing compounds such as pharmaceuticals and agricultural chemicals.
【０００２】[0002]
【従来の技術】これまでに提案されている２−ブロモ−
３，３，３−トリフルオロプロペンの製法としては、下
記及びの方法などが知られている。 粒状の水酸化カリウムと、１，２−ジブロモ−３，
３，３−トリフルオロプロパンとを反応させる方法（J.
Org. Chem., 33, 280, 1968.)。 エタノール溶液中、水酸化カリウムと１，２−ジブロ
モ−３，３，３−トリフルオロプロパンとを反応させる
方法（J. Chem. Soc., 3483-90, 1952）。しかしなが
ら、これらの方法は、少量を取り扱う際には問題は少な
いものの、取り扱い量が増加すると、操作あるいは設備
の面で多くの問題が生じ、工業的に好ましい製法ではな
いのが現状である。2. Description of the Prior Art 2-bromo-
As a method for producing 3,3,3-trifluoropropene, the following methods and the like are known. Granular potassium hydroxide, 1,2-dibromo-3,
Method for reacting with 3,3-trifluoropropane (J.
Org. Chem., 33, 280, 1968.). A method of reacting potassium hydroxide with 1,2-dibromo-3,3,3-trifluoropropane in an ethanol solution (J. Chem. Soc., 3483-90, 1952). However, these methods have few problems when handling a small amount, but when the handling amount increases, many problems arise in terms of operation or equipment, and at present, they are not industrially preferable production methods.
【０００３】即ち、上記の方法では、粒状の水酸化カ
リウムを用いた固−液系反応であるため、接触効率の悪
い不均一な反応であり、また反応をコントロールするこ
とが難しく、原料の１，２−ジブロモ−３，３，３−ト
リフルオロプロパンに対し過剰量の水酸化カリウムを使
用することと、反応時間に１２時間以上を要するという
問題がある。また、反応中に粒状の水酸化カリウムが反
応器や撹拌バネなどに付着するため、その付着分がロス
し、さらには副生した臭化カリウムなどの塩も固形物と
して付着するため、撹拌器の故障を起こすことがあり、
工業上好ましい製法ではない。That is, the above-mentioned method is a solid-liquid reaction using granular potassium hydroxide, which is a heterogeneous reaction having poor contact efficiency, and it is difficult to control the reaction. There is a problem that an excessive amount of potassium hydroxide is used with respect to 2,2-dibromo-3,3,3-trifluoropropane and that the reaction time requires 12 hours or more. In addition, during the reaction, granular potassium hydroxide adheres to the reactor and the stirring spring, so that the adhered amount is lost, and furthermore, salts such as by-produced potassium bromide also adhere as solids. May cause a malfunction.
This is not an industrially preferable production method.
【０００４】上記の方法では、比較的高価で可燃性の
エタノールを溶媒に使用するため、経済面安全面での問
題がある。また、１，２−ジブロモ−３，３，３−トリ
フルオロプロパンを−５℃程度にまで冷却して反応させ
る都合上、特別な冷却設備を必要とする。さらに、反応
終了後の精製工程には蒸留工程の前処理として、副生す
る臭化カリウム及びエタノールを除去するための水洗工
程も必要となり、そしてエタノールを含む廃液が出ると
いった問題がある。これらの理由により、この方法も工
業的に好ましい製法ではない。以上のように、２−ブロ
モ−３，３，３−トリフルオロプロペンの実用的な工業
的合成方法については、満足のいく方法が見当たらない
のが実状である。[0004] In the above method, since relatively expensive and flammable ethanol is used as a solvent, there is a problem in terms of economy and safety. In addition, a special cooling facility is required because 1,2-dibromo-3,3,3-trifluoropropane is cooled to about −5 ° C. to cause a reaction. Further, in the purification step after the completion of the reaction, a water washing step for removing by-product potassium bromide and ethanol is required as a pretreatment of the distillation step, and there is a problem that a waste liquid containing ethanol is generated. For these reasons, this method is also not an industrially preferred production method. As described above, no satisfactory method has been found for a practical industrial synthesis method of 2-bromo-3,3,3-trifluoropropene.
【０００５】[0005]
【発明が解決しようとする課題】従って、本発明の目的
は、上記及びの従来方法の問題点を解決し、２−ブ
ロモ−３，３，３−トリフルオロプロペンを工業的規模
で安全かつ簡便に製造し得る方法を提供することにあ
る。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems of the conventional methods and to provide 2-bromo-3,3,3-trifluoropropene on an industrial scale, which is safe and convenient. To provide a method that can be manufactured.
【０００６】[0006]
【課題を解決するための手段】本発明は、１，２−ジブ
ロモ−３，３，３−トリフルオロプロパンとアルカリ金
属水酸化物とを水を溶媒として３０〜１３０℃で反応さ
せることを特徴とする２−ブロモ−３，３，３−トリフ
ルオロプロペンの製造方法を提供することにより、上記
目的を達成したものである。The present invention is characterized in that 1,2-dibromo-3,3,3-trifluoropropane and an alkali metal hydroxide are reacted at 30 to 130 ° C. using water as a solvent. The above object has been achieved by providing a method for producing 2-bromo-3,3,3-trifluoropropene.
【０００７】[0007]
【発明の実施の形態】以下、本発明の２−ブロモ−３，
３，３−トリフルオロプロペンの製造方法について詳述
する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, 2-bromo-3,
The method for producing 3,3-trifluoropropene will be described in detail.
【０００８】本発明の２−ブロモ−３，３，３−トリフ
ルオロプロペンの製造方法は、具体的には、アルカリ金
属水酸化物の水溶液を３０〜１３０℃に加熱し撹拌しな
がら、該水溶液に１，２−ジブロモ−３，３，３−トリ
フルオロプロパンを滴下して反応させつつ蒸留精製する
ことにより、２−ブロモ−３，３，３−トリフルオロプ
ロペンを得る方法により実施するのが好ましい。本発明
の方法における反応式は、次のように示される。 CF3CHBrCH2Br ＋ MOH → CF3CBr＝CH2 ＋ MBr ＋ H2
O （式中、Ｍはアルカリ金属を表わす。）The method for producing 2-bromo-3,3,3-trifluoropropene according to the present invention is, specifically, a method of heating an aqueous solution of an alkali metal hydroxide to 30 to 130 ° C. while stirring the aqueous solution. This is carried out by a method in which 1,2-dibromo-3,3,3-trifluoropropane is added dropwise to the mixture, and the mixture is purified by distillation while reacting to obtain 2-bromo-3,3,3-trifluoropropene. preferable. The reaction formula in the method of the present invention is shown as follows. CF 3 CHBr CH 2 Br + MOH → CF 3 CBr = CH 2 + MBr + H 2
O (wherein, M represents an alkali metal)
【０００９】本発明の反応に使用するアルカリ金属水酸
化物としては、水酸化ナトリウムまたは水酸化カリウム
が使用可能である。本発明の方法は、反応に使用するア
ルカリ金属水酸化物の水溶液濃度が、飽和溶解度以下の
濃度範囲で行うことができるが、高濃度では粘性が高く
なるため撹拌が困難であり、低濃度では反応時間が長い
上に廃液が多くなるため、上記アルカリ金属水酸化物の
水溶液濃度は、５〜３０重量％が好ましい。As the alkali metal hydroxide used in the reaction of the present invention, sodium hydroxide or potassium hydroxide can be used. The method of the present invention can be carried out in the concentration range of the aqueous solution of the alkali metal hydroxide used in the reaction, the concentration range being equal to or lower than the saturation solubility. Since the reaction time is long and the amount of waste liquid increases, the concentration of the aqueous solution of the alkali metal hydroxide is preferably 5 to 30% by weight.
【００１０】また、本発明の方法は、反応に使用するア
ルカリ金属水酸化物の使用量が、１，２−ジブロモ−
３，３，３−トリフルオロプロパンに対して１．０当量
以上で行うことが可能であるが、１．２当量を超えて使
用しても、未反応のアルカリ金属水酸化物が増加するだ
けで、その使用量に見合う収率の向上ないしは反応時間
の短縮といった効果が得られない。従って、上記アルカ
リ金属水酸化物の使用量は、１，２−ジブロモ−３，
３，３−トリフルオロプロパンに対して１．０〜１．２
当量が好ましい。In the method of the present invention, the amount of the alkali metal hydroxide used in the reaction is 1,2-dibromo-
The reaction can be carried out in an amount of 1.0 equivalent or more with respect to 3,3,3-trifluoropropane. However, if the amount exceeds 1.2 equivalents, the amount of unreacted alkali metal hydroxide increases only. Therefore, the effect of improving the yield or shortening the reaction time corresponding to the amount used cannot be obtained. Therefore, the amount of the alkali metal hydroxide used is 1,2-dibromo-3,
1.0 to 1.2 based on 3,3-trifluoropropane
Equivalents are preferred.
【００１１】反応は、３０〜１３０℃の温度範囲で行う
ことが可能であるが、低温では反応時間が長く、高温で
は反応が激しいため、４０〜９０℃の温度範囲で行うこ
とが好ましい。また、本反応の好ましい態様は液−液の
二層系反応であるが、攪拌速度は適宜実施し得る。ま
た、１，２−ジブロモ−３，３，３−トリフルオロプロ
パン（またはアルカリ水溶液）の滴下は、定量ポンプま
たは滴下漏斗等を使用し、時間当り５００ｇ〜３．０ｋ
ｇの範囲の滴下速度で行うことが好ましい。滴下速度が
遅ければ反応時間が長くなり、滴下速度が速ければ生成
した２−ブロモ−３，３，３−トリフルオロプロペンの
蒸気圧により反応器内圧が上昇する。また、生成物の蒸
留精製は、１，２−ジブロモ−３，３，３−トリフルオ
ロプロパンの滴下を行いながら、蒸留塔上部温度が３３
〜３４℃を維持するように、留出量を制御することによ
り、純度９９．０％以上の２−ブロモ−３，３，３−ト
リフルオロプロペンを得ることが可能である。The reaction can be carried out in a temperature range of 30 to 130 ° C., but it is preferable to carry out the reaction in a temperature range of 40 to 90 ° C. because the reaction time is long at a low temperature and the reaction is violent at a high temperature. Further, a preferred embodiment of the present reaction is a liquid-liquid two-layer reaction, but the stirring speed can be appropriately carried out. In addition, the dropping of 1,2-dibromo-3,3,3-trifluoropropane (or an aqueous alkali solution) is performed using a metering pump or a dropping funnel, etc., at 500 g to 3.0 k per hour.
It is preferable to carry out at a dropping speed in the range of g. If the dropping rate is slow, the reaction time will be long, and if the dropping rate is fast, the internal pressure of the reactor will increase due to the vapor pressure of the generated 2-bromo-3,3,3-trifluoropropene. In addition, the distillation purification of the product is performed while dropping 1,2-dibromo-3,3,3-trifluoropropane while maintaining the upper temperature of the distillation column at 33.
It is possible to obtain 2-bromo-3,3,3-trifluoropropene having a purity of 99.0% or more by controlling the amount of distillation so as to maintain the temperature at -34 ° C.
【００１２】尚、上記の実施形態では、３０〜１３０℃
に加熱し撹拌しているアルカリ金属水酸化物の水溶液に
１，２−ジブロモ−３，３，３−トリフルオロプロパン
を滴下して反応させているが、本発明の方法は、３０〜
１３０℃に加熱し撹拌している１，２−ジブロモ−３，
３，３−トリフルオロプロパンにアルカリ金属水酸化物
の水溶液を滴下して反応させてもよい。また、アルカリ
金属水酸化物の水溶液と１，２−ジブロモ−３，３，３
−トリフルオロプロパンとの全量を反応器内に投入し、
３０〜１３０℃に加熱し撹拌して反応させてもよい。In the above embodiment, the temperature is 30 to 130 ° C.
1,2-dibromo-3,3,3-trifluoropropane is added dropwise to and reacted with an aqueous solution of an alkali metal hydroxide which is heated and stirred.
1,2-dibromo-3, heated to 130 ° C. and stirred
An aqueous solution of an alkali metal hydroxide may be added dropwise to 3,3-trifluoropropane for reaction. Further, an aqueous solution of an alkali metal hydroxide and 1,2-dibromo-3,3,3,3
Charging the whole amount with trifluoropropane into the reactor,
The reaction may be carried out by heating to 30 to 130 ° C. and stirring.
【００１３】[0013]
【実施例】以下に、本発明の実施例を比較例と共に挙げ
るが、本発明はこれらの実施例に制限されるものではな
い。EXAMPLES Examples of the present invention will be described below together with comparative examples, but the present invention is not limited to these examples.
【００１４】〔実施例１〕還流器を付した蒸留塔を取り
付けた１Ｌ容のフラスコに２０重量％水酸化ナトリウム
水溶液１２０ｇ（０．６０ｍｏｌ）を入れ、８０℃に加
熱撹拌し、これに１，２−ジブロモ−３，３，３−トリ
フルオロプロパン１２８ｇ（０．５０ｍｏｌ）を１時間
かけて滴下しながら、生成物の蒸留を行った。蒸留は蒸
留塔上部温度を３３〜３４℃に維持し、留出量を制御し
ながら行い、目的の２−ブロモ−３，３，３−トリフル
オロプロペン８６ｇ（収率９８％）を得た。得られた物
質の物性値は以下の通りであった。1 Ｈ−ＮＭＲ（ＣＤＣｌ3)：δ６．０１〜６．０６
（ｍ，１Ｈ）、δ６．４８〜６．５２（ｍ，１Ｈ）19 Ｆ−ＮＭＲ（ＣＤＣｌ3)：δ−６８．９（ｓ） また、反応終了時、反応液水層部に沈降物は見られなか
った。Example 1 120 g (0.60 mol) of a 20% by weight aqueous sodium hydroxide solution was placed in a 1 L flask equipped with a distillation column equipped with a reflux condenser, and heated and stirred at 80 ° C. The product was distilled while 128 g (0.50 mol) of 2-dibromo-3,3,3-trifluoropropane was added dropwise over 1 hour. Distillation was performed while maintaining the upper temperature of the distillation column at 33 to 34 ° C. and controlling the amount of distillation, to obtain 86 g (yield 98%) of the desired 2-bromo-3,3,3-trifluoropropene. The physical properties of the obtained substance were as follows. 1 H-NMR (CDCl 3 ): δ 6.01 to 6.06
(M, 1H), δ 6.48 to 6.52 (m, 1H) 19 F-NMR (CDCl 3 ): δ-68.9 (s) Also, at the end of the reaction, sediment in the aqueous layer of the reaction solution I couldn't see it.
【００１５】〔実施例２〕１，２−ジブロモ−３，３，
３−トリフルオロプロパン１２８ｇ（０．５０ｍｏｌ）
及び２０重量％水酸化ナトリウム水溶液１２０ｇ（０．
６０ｍｏｌ）を１Ｌ容のフラスコに秤り取り、８０℃で
加熱撹拌を６時間行った。反応終了後、生成物を蒸留す
ることにより、目的の２−ブロモ−３，３，３−トリフ
ルオロプロペン８５ｇ（収率９７％）を得た。また、反
応終了時、反応液水層部に沈降物は見られなかった。Example 2 1,2-dibromo-3,3,3
128 g (0.50 mol) of 3-trifluoropropane
And 120 g of a 20% by weight aqueous sodium hydroxide solution (0.
60 mol) was weighed into a 1 L flask, and heated and stirred at 80 ° C. for 6 hours. After completion of the reaction, the product was distilled to obtain 85 g of the desired 2-bromo-3,3,3-trifluoropropene (yield 97%). At the end of the reaction, no sediment was observed in the aqueous layer of the reaction solution.
【００１６】〔実施例３〕還流器を付した蒸留塔を取り
付けた２Ｌ容のフラスコに５重量％水酸化ナトリウム水
溶液４８０ｇ（０．６０ｍｏｌ）を入れ、４０℃に加熱
撹拌し、これに１，２−ジブロモ−３，３，３−トリフ
ルオロプロパン１２８ｇ（０．５０ｍｏｌ）を１時間か
けて滴下しながら、生成物の蒸留を行った。蒸留は蒸留
塔上部温度を３３〜３４℃に維持し、留出量を制御しな
がら行い、目的の２−ブロモ−３，３，３−トリフルオ
ロプロペン８５ｇ（収率９７％）を得た。また、反応終
了時、反応液水層部に沈降物は見られなかった。Example 3 A 480 g (0.60 mol) of a 5% by weight aqueous sodium hydroxide solution was placed in a 2 L flask equipped with a distillation column equipped with a reflux condenser, and heated and stirred at 40 ° C. The product was distilled while 128 g (0.50 mol) of 2-dibromo-3,3,3-trifluoropropane was added dropwise over 1 hour. Distillation was performed while maintaining the upper temperature of the distillation column at 33 to 34 ° C. and controlling the amount of distillate to obtain 85 g of the desired 2-bromo-3,3,3-trifluoropropene (yield 97%). At the end of the reaction, no sediment was observed in the aqueous layer of the reaction solution.
【００１７】〔実施例４〕還流器を付した蒸留塔を取り
付けた４０Ｌ容のフラスコに２０重量％水酸化カリウム
水溶液１６．８ｋｇ（６０ｍｏｌ）を入れ、９０℃に加
熱撹拌し、これに１，２−ジブロモ−３，３，３−トリ
フルオロプロパン１２．８ｋｇ（５０ｍｏｌ）を６時間
かけて滴下しながら、生成物の蒸留を行った。蒸留は蒸
留塔上部温度を３３〜３４℃に維持し、留出量を制御し
ながら行い、目的の２−ブロモ−３，３，３−トリフル
オロプロペン８．０ｋｇ（収率９２％）を得た。また、
反応終了時、反応液水層部に沈降物は見られなかった。Example 4 16.8 kg (60 mol) of a 20% by weight aqueous solution of potassium hydroxide was placed in a 40 L flask equipped with a distillation column equipped with a reflux condenser, and heated and stirred at 90 ° C. The product was distilled while 12.8 kg (50 mol) of 2-dibromo-3,3,3-trifluoropropane was added dropwise over 6 hours. Distillation is performed while maintaining the upper temperature of the distillation column at 33 to 34 ° C. and controlling the amount of distillate to obtain 8.0 kg of the desired 2-bromo-3,3,3-trifluoropropene (yield 92%). Was. Also,
At the end of the reaction, no sediment was observed in the aqueous layer of the reaction solution.
【００１８】〔実施例５〕還流器を付した蒸留塔を取り
付けた４０Ｌ容のフラスコに２０重量％水酸化ナトリウ
ム水溶液２２．０ｋｇ（１１０ｍｏｌ）を入れ、８０℃
に加熱撹拌し、これに１，２−ジブロモ−３，３，３−
トリフルオロプロパン２５．６ｋｇ（１００ｍｏｌ）を
８時間かけて滴下しながら、生成物の蒸留を行った。蒸
留は蒸留塔上部温度を３３〜３４℃に維持し、留出量を
制御しながら行い、目的の２−ブロモ−３，３，３−ト
リフルオロプロペン１７．１ｋｇ（収率９８％）を得
た。また、反応終了時、反応液水層部に沈降物は見られ
なかった。Example 5 A 20% by weight aqueous sodium hydroxide solution (22.0 kg, 110 mol) was placed in a 40 L flask equipped with a distillation column equipped with a reflux condenser.
And stirred with 1,2-dibromo-3,3,3-
The product was distilled while 25.6 kg (100 mol) of trifluoropropane was added dropwise over 8 hours. Distillation is performed while maintaining the upper temperature of the distillation column at 33 to 34 ° C. and controlling the amount of distillate to obtain 17.1 kg of the desired 2-bromo-3,3,3-trifluoropropene (98% yield). Was. At the end of the reaction, no sediment was observed in the aqueous layer of the reaction solution.
【００１９】〔実施例６〕還流器を付した蒸留塔を取り
付けた４０Ｌ容のフラスコに１，２−ジブロモ−３，
３，３−トリフルオロプロパン２５．６ｋｇ（１００ｍ
ｏｌ）を入れ、８０℃に加熱撹拌し、これに２０重量％
水酸化ナトリウム水溶液２２．０ｋｇ（１１０ｍｏｌ）
を８時間かけて滴下しながら、生成物の蒸留を行った。
蒸留は蒸留塔上部温度を３３〜３４℃に維持し、留出量
を制御しながら行い、目的の２−ブロモ−３，３，３−
トリフルオロプロペン１７．０ｋｇ（収率９７％）を得
た。また、反応終了時、反応液水層部に沈降物は見られ
なかった。Example 6 1,2-dibromo-3,4-dibromo-3 was added to a 40-liter flask equipped with a distillation column equipped with a reflux condenser.
25.6 kg of 3,3-trifluoropropane (100 m
ol), stirred at 80 ° C., and added 20% by weight
Sodium hydroxide aqueous solution 22.0kg (110mol)
Was added dropwise over 8 hours to distill the product.
Distillation was performed while maintaining the upper temperature of the distillation column at 33 to 34 ° C. and controlling the amount of distillate, to obtain the desired 2-bromo-3,3,3-
17.0 kg (97% yield) of trifluoropropene were obtained. At the end of the reaction, no sediment was observed in the aqueous layer of the reaction solution.
【００２０】〔比較例１〕１，２−ジブロモ−３，３，
３−トリフルオロプロパン１２８ｇ（０．５０ｍｏｌ）
及び２０重量％水酸化ナトリウム水溶液１２０ｇ（０．
６０ｍｏｌ）を反応器に秤り取り、２５℃で加熱撹拌を
２４時間行った。反応終了後、生成物を蒸留することに
より、２−ブロモ−３，３，３−トリフルオロプロペン
３ｇ（収率３％）を得た。尚、転化率は４％であった。
また、反応終了時、反応液水層部に沈降物は見られなか
った。Comparative Example 1 1,2-Dibromo-3,3
128 g (0.50 mol) of 3-trifluoropropane
And 120 g of a 20% by weight aqueous sodium hydroxide solution (0.
60 mol) was weighed into a reactor, and heated and stirred at 25 ° C. for 24 hours. After completion of the reaction, the product was distilled to obtain 3 g of 2-bromo-3,3,3-trifluoropropene (yield 3%). Incidentally, the conversion was 4%.
At the end of the reaction, no sediment was observed in the aqueous layer of the reaction solution.
【００２１】〔比較例２〕２Ｌ容のフラスコに、粒状の
水酸化カリウム５１４ｇ（７．８ｍｏｌ）を反応器に秤
り取り、氷浴下撹拌しながらゆっくりと１，２−ジブロ
モ−３，３，３−トリフルオロプロパン５１２ｇ（２．
０ｍｏｌ）を滴下した。滴下終了後、氷浴からウォータ
ーバスに取り替え、７０℃に加熱撹拌しながら反応させ
た。ところが、反応が始まると器内圧が大幅に上昇し
た。そこで、還流器を付した蒸留塔を取り付け、生成物
の留出を行いながら、反応を続行した。１２時間加熱撹
拌後、留出液として、２−ブロモ−３，３，３−トリフ
ルオロプロペン３２２ｇ（収率９２％）を得た。反応が
始まり１時間しない内に、水酸化カリウムの粒は反応器
に付着し、撹拌しても動かなくなり、反応終了時には、
未反応の水酸化カリウムと副生した臭化カリウムが反応
器下部を中心に付着していた。Comparative Example 2 Granular potassium hydroxide (514 g, 7.8 mol) was weighed and placed in a 2 L flask and stirred slowly in an ice bath while stirring 1,2-dibromo-3,3. 512 g of 2,3-trifluoropropane (2.
0 mol) was added dropwise. After completion of the dropping, the ice bath was replaced with a water bath, and the reaction was carried out while heating and stirring at 70 ° C. However, when the reaction started, the internal pressure increased significantly. Therefore, a distillation column equipped with a reflux condenser was attached, and the reaction was continued while distilling the product. After heating and stirring for 12 hours, 322 g (yield 92%) of 2-bromo-3,3,3-trifluoropropene was obtained as a distillate. Within one hour after the reaction has begun, the potassium hydroxide particles adhere to the reactor and become immobile even with stirring.
Unreacted potassium hydroxide and by-product potassium bromide were attached to the lower portion of the reactor.
【００２２】〔比較例３〕２Ｌ容のフラスコに、１，２
−ジブロモ−３，３，３−トリフルオロプロパン５１２
ｇ（２．０ｍｏｌ）を秤り取り、−５℃に冷却撹拌しな
がらゆっくりと氷冷した水酸化カリウム１４５ｇ（２．
２ｍｏｌ）のエタノール（３００ｍＬ）溶液を滴下し
た。滴下終了後、１時間攪拌した後、反応混合液を、希
塩酸（５００ｍＬ）を用いて酸洗浄及び水（５００ｍ
Ｌ）を用いて水洗を行い、エタノール及び副生する臭化
カリウムを分液、除去した。さらに、蒸留することによ
り２−ブロモ−３，３，３−トリフルオロプロペン３０
４ｇ（収率８７％）を得た。Comparative Example 3 Into a 2 L flask were placed 1,2
-Dibromo-3,3,3-trifluoropropane 512
g (2.0 mol), 145 g of potassium hydroxide (2.
2 mol) in ethanol (300 mL) was added dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour, and the reaction mixture was washed with dilute hydrochloric acid (500 mL) and washed with water (500 ml).
Washing with water was performed using L) to separate and remove ethanol and by-product potassium bromide. Further, by distillation, 2-bromo-3,3,3-trifluoropropene 30
4 g (87% yield) were obtained.
【００２３】[0023]
【発明の効果】本発明の方法によれば、２−ブロモ−
３，３，３−トリフルオロプロペンを工業的規模で安全
かつ簡便に製造することができる。According to the method of the present invention, 2-bromo-
3,3,3-trifluoropropene can be produced safely and easily on an industrial scale.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4H006 AA02 AC13 AD11 BA02 BA29 BB31 BC10 BD20 BD21 4H039 CA29 CG20 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA02 AC13 AD11 BA02 BA29 BB31 BC10 BD20 BD21 4H039 CA29 CG20
Claims (5)
ルオロプロパンとアルカリ金属水酸化物とを水を溶媒と
して３０〜１３０℃で反応させることを特徴とする２−
ブロモ−３，３，３−トリフルオロプロペンの製造方
法。1. The method according to claim 1, wherein 1,2-dibromo-3,3,3-trifluoropropane is reacted with an alkali metal hydroxide at 30 to 130 ° C. using water as a solvent.
A method for producing bromo-3,3,3-trifluoropropene.
１３０℃に加熱し撹拌しながら、該水溶液に１，２−ジ
ブロモ−３，３，３−トリフルオロプロパンを滴下して
反応させつつ蒸留精製することにより、２−ブロモ−
３，３，３−トリフルオロプロペンを得ることを特徴と
する２−ブロモ−３，３，３−トリフルオロプロペンの
製造方法。2. An aqueous solution of an alkali metal hydroxide having a concentration of 30 to
1,2-Dibromo-3,3,3-trifluoropropane was added dropwise to the aqueous solution while heating and stirring at 130 ° C., and the mixture was purified by distillation while reacting.
A process for producing 2-bromo-3,3,3-trifluoropropene, which comprises obtaining 3,3,3-trifluoropropene.
請求項１または２記載の製造方法。3. The method according to claim 1, wherein the reaction temperature is in the range of 40 to 90 ° C.
ムまたは水酸化カリウムのいずれかである請求項１また
は２記載の製造方法。4. The method according to claim 1, wherein the alkali metal hydroxide is either sodium hydroxide or potassium hydroxide.
〜３０重量％である請求項１または２記載の製造方法。5. An aqueous solution of an alkali metal hydroxide having a concentration of 5
3. The method according to claim 1, wherein the amount is from 30 to 30% by weight.
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|---|---|---|---|
| JP2000143022A JP2001322955A (en) | 2000-05-16 | 2000-05-16 | Method for producing 2-bromo-3,3,3-trifluoropropene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000143022A JP2001322955A (en) | 2000-05-16 | 2000-05-16 | Method for producing 2-bromo-3,3,3-trifluoropropene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001322955A true JP2001322955A (en) | 2001-11-20 |
| JP2001322955A5 JP2001322955A5 (en) | 2007-04-19 |
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ID=18649894
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000143022A Pending JP2001322955A (en) | 2000-05-16 | 2000-05-16 | Method for producing 2-bromo-3,3,3-trifluoropropene |
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| Country | Link |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011068644A (en) * | 2009-08-31 | 2011-04-07 | Sumitomo Chemical Co Ltd | Process for producing 1,1,3-trichloro-1-propene |
| CN102206134A (en) * | 2011-04-02 | 2011-10-05 | 西安近代化学研究所 | Preparation method of 2-bromine-3,3,3-trifluoropropene |
| WO2014046250A1 (en) * | 2012-09-21 | 2014-03-27 | セントラル硝子株式会社 | Production method for 1,2-dichloro-3,3,3-trifluoropropene |
| US8877988B2 (en) | 2012-12-21 | 2014-11-04 | Honeywell International Inc. | Synthesis of 1-BROM0-3,3,3-trifluoropropene |
| WO2023176434A1 (en) * | 2022-03-16 | 2023-09-21 | 株式会社レゾナック | Method for storing fluoroalkene |
| WO2023176433A1 (en) * | 2022-03-16 | 2023-09-21 | 株式会社レゾナック | Fluoroalkene storage method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5921648A (en) * | 1982-07-29 | 1984-02-03 | Sagami Chem Res Center | Methacrylic acid ester containing fluorine |
-
2000
- 2000-05-16 JP JP2000143022A patent/JP2001322955A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5921648A (en) * | 1982-07-29 | 1984-02-03 | Sagami Chem Res Center | Methacrylic acid ester containing fluorine |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011068644A (en) * | 2009-08-31 | 2011-04-07 | Sumitomo Chemical Co Ltd | Process for producing 1,1,3-trichloro-1-propene |
| CN102206134A (en) * | 2011-04-02 | 2011-10-05 | 西安近代化学研究所 | Preparation method of 2-bromine-3,3,3-trifluoropropene |
| CN102206134B (en) * | 2011-04-02 | 2014-02-05 | 西安近代化学研究所 | Preparation method of 2-bromine-3,3,3-trifluoropropene |
| WO2014046250A1 (en) * | 2012-09-21 | 2014-03-27 | セントラル硝子株式会社 | Production method for 1,2-dichloro-3,3,3-trifluoropropene |
| US9090530B1 (en) | 2012-09-21 | 2015-07-28 | Central Glass Company, Limited | Method for producing 1,2-dichloro-3,3,3-trifluoropropene |
| JPWO2014046250A1 (en) * | 2012-09-21 | 2016-08-18 | セントラル硝子株式会社 | Process for producing 1,2-dichloro-3,3,3-trifluoropropene |
| US8877988B2 (en) | 2012-12-21 | 2014-11-04 | Honeywell International Inc. | Synthesis of 1-BROM0-3,3,3-trifluoropropene |
| WO2023176434A1 (en) * | 2022-03-16 | 2023-09-21 | 株式会社レゾナック | Method for storing fluoroalkene |
| WO2023176433A1 (en) * | 2022-03-16 | 2023-09-21 | 株式会社レゾナック | Fluoroalkene storage method |
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