JPS5939705A - Manufacture of fluorinated phosgene - Google Patents
Manufacture of fluorinated phosgeneInfo
- Publication number
- JPS5939705A JPS5939705A JP57150051A JP15005182A JPS5939705A JP S5939705 A JPS5939705 A JP S5939705A JP 57150051 A JP57150051 A JP 57150051A JP 15005182 A JP15005182 A JP 15005182A JP S5939705 A JPS5939705 A JP S5939705A
- Authority
- JP
- Japan
- Prior art keywords
- phosgene
- fluorinated
- fluoride
- acetonitrile
- manufacture
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 本発明はフッ化ホスゲンの新規製造法に関する。[Detailed description of the invention] The present invention relates to a new method for producing fluorinated phosgene.
さらに詳細には、トリクロロメチルクロロホーメート（
以下ＴＣＰと略記する）をアルカリ金属フッ化物でフッ
素化するフッ化ホスゲンの製造法に関する。More specifically, trichloromethyl chloroformate (
The present invention relates to a method for producing fluorinated phosgene by fluorinating TCP (hereinafter abbreviated as TCP) with an alkali metal fluoride.
フッ化ホスゲンは、染料、農薬等の特に最近は医薬中間
体合成原料として欠くことのできない有用な化合物であ
る。Fluorinated phosgene is an indispensable and useful compound as a raw material for the synthesis of pharmaceutical intermediates, such as dyes and agricultural chemicals.
従来、フッ化ホスゲンの製造法としては、ホスゲンとフ
ッ化水素酸とを鉄製オートクレーブ中で、活性炭の存在
下に１４０〜１５０℃で反応する方法がＢｅ１ｌｓｔｅ
ｌｎｓ Ｅｌ ５ ｐ−２２に、また、***特許第１５
９．９５６号公報明細書属は８０Ｆ、とホスゲンとを４
：１の割合で鉄製チューブの反応器を用いて、無水塩化
第二鉄触媒の存在下、４００℃で反応する方法が開示さ
れている。これらの方法はいずれも′１１１ｉ温反応で
あり、未反応のホスゲンとフッ化ホスゲンとの分離精製
を必須とし、高純度のフッ化ホスゲンを得ることが困難
である。またフッ化水素酸を用いる場合は、装置材質の
選択が困難であり到底工業化のできる方法ではない。Conventionally, a method for producing phosgene fluoride is a method in which phosgene and hydrofluoric acid are reacted in an iron autoclave at 140 to 150°C in the presence of activated carbon.
lns El 5 p-22, and West German Patent No. 15
9.956 publication specifies that 80F and phosgene are 4
A method is disclosed in which the reaction is carried out at 400° C. in the presence of an anhydrous ferric chloride catalyst using an iron tube reactor at a ratio of 1:1. All of these methods are '111i temperature reactions, require separation and purification of unreacted phosgene and fluorinated phosgene, and are difficult to obtain highly pure fluorinated phosgene. Furthermore, when using hydrofluoric acid, it is difficult to select the material for the equipment, and this is not a method that can be industrialized at all.
また、特開昭５４−．１５８３９６号公報明細書には、
アセトニトリル中フッ化水素酸とトリエチルアミンとの
混合物にホスゲンを導入して反応する方法が記載されて
いる。この方法では、低温で反応するため装置材質の腐
蝕の問題点は改善されているが、多量のトリエチルアミ
ンを使用するため工業的にはトリエチルアミンの回収、
再使用を考慮しなければならない等、決して工業的に有
利な方法とは云えない。In addition, Japanese Patent Publication No. 1983-1999. In the specification of 158396 publication,
A method is described in which phosgene is introduced into a mixture of hydrofluoric acid and triethylamine in acetonitrile. This method solves the problem of corrosion of the equipment material because it reacts at low temperatures, but because it uses a large amount of triethylamine, it is difficult to recover triethylamine industrially.
This cannot be said to be an industrially advantageous method, as reuse must be considered.
本発明者等は、このような問題を克服すべく鋭意検討の
結果、ＴＣＰとアルカリ金属フッ化物から極め【容易に
、精製工程を必要とせずして高純度のフッ化ホスゲンが
得られることを見い出し本発明を確立するに至った。As a result of intensive studies to overcome these problems, the present inventors have discovered that highly pure fluorinated phosgene can be easily obtained from TCP and alkali metal fluoride without the need for a purification process. Heading This invention has been established.
すなわち、本発明はアセトニトリル中でＴＣＰとアルカ
リ金属フッ化物とを反応させることを特徴とするフッ化
ホスゲンの製造法である。That is, the present invention is a method for producing phosgene fluoride, which is characterized by reacting TCP and an alkali metal fluoride in acetonitrile.
本発明方法は、アセトニトリルとアルカリ金属フッ化物
との混合系ＫＴＣＦを添加し、加温下に反応させると生
成したフッ化ホスゲンは、反応系内からガス体として得
られる。このフッ化ホスゲンはそのまま直ちに次の反応
に用いるか、ボンベに充填し必要な時に用いることもで
きる。In the method of the present invention, when KTCF, a mixed system of acetonitrile and an alkali metal fluoride, is added and reacted under heating, the generated phosgene fluoride is obtained as a gas from within the reaction system. This fluorinated phosgene can be used as it is for the next reaction immediately, or it can be filled into a cylinder and used when necessary.
本発明では反応溶媒としてアセトニトリルが好ましい。In the present invention, acetonitrile is preferred as the reaction solvent.
その他の、例えばジメチルスルホアミドではＴＣＰの分
解によりホスゲンを生成しフッ化ホスゲンは得られない
。その使用量は特に限定されないが、アルカリ金属フッ
化物を添加した時攪拌が良好に行なわれるに必要な量を
使用すればよい。通常はアルカリ金属フッ化物忙対して
２〜本発明の出発原料でＴＣＰは、工業的にメタノール
のホスゲン化でメチルクロロホーメートを経てさらに塩
素化により製造されており、容易に入手できる。Other methods, such as dimethylsulfamide, produce phosgene by decomposition of TCP, and fluorinated phosgene cannot be obtained. The amount used is not particularly limited, but it may be used in an amount necessary to ensure good stirring when the alkali metal fluoride is added. TCP, which is usually an alkali metal fluoride as a starting material for the present invention, is industrially produced by phosgenation of methanol, methyl chloroformate, and further chlorination, and is easily available.
フッ素化剤として使用するアルカリ金属フッ化物として
は、フッ化ナトリウム、フッ化カリウム、フッ化リチウ
ム等があげられるが、高純度、高収率でフッ化ホスゲン
を得るためＫはスプレードライ品のフッ化カリウムを用
いることが好ましい。Alkali metal fluorides used as fluorinating agents include sodium fluoride, potassium fluoride, lithium fluoride, etc., but in order to obtain fluorinated phosgene with high purity and high yield, K is used as a spray-dried fluoride. Preferably, potassium oxide is used.
アルカリ金属フッ化物の使用量はＴＣＦＫ対して４．０
〜１２．０倍モル、好ましくは４．２〜６．０倍モル比
である。The amount of alkali metal fluoride used is 4.0 compared to TCFK.
The molar ratio is 12.0 times to 12.0 times, preferably 4.2 to 6.0 times.
反応温度は、アセトニトリルの沸点以下で行われるが、
好ましくは５０〜８０℃である。The reaction temperature is below the boiling point of acetonitrile,
Preferably it is 50 to 80°C.
ＴＣＰの添加は通常５０℃以下で全景を添加し、その後
昇温し還流下に反応させるが、反応系を５０〜８０℃に
保ってＴＣＰを添加して反応させることもできる。Generally, TCP is added in its entirety at 50° C. or lower, and then the temperature is raised and the reaction is carried out under reflux, but it is also possible to maintain the reaction system at 50 to 80° C. and add TCP to carry out the reaction.
上記のよう忙、本発明法によれば極めて容易、かつ高純
度、高収率でフッ化ホスゲンを製造できる。As described above, according to the method of the present invention, fluorinated phosgene can be produced extremely easily and with high purity and high yield.
以下、実施例をあげて本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail by giving examples.
実施例１
１２０部のアセトニトリルと３５部のスプレー）゛ライ
品のフッ化カリウム（森田化学製）とを室温で混合し、
この中にかきまぜ下５０℃以下を保って２０部のＴＣＰ
を１時間を要し滴下した。さらに約１時間で５０℃まで
昇温し、５０〜８０℃で５時間反応させた。反応中発生
するガスをＩＲ分析した結果、純品のフッ化ホスゲンで
あることを確認した。ガスの全発生量はａａｓｏ禦ｅ＜
２ｓ℃）であった。Example 1 120 parts of acetonitrile and 35 parts of spray) dried potassium fluoride (manufactured by Morita Chemical) were mixed at room temperature,
Add 20 parts of TCP to this while stirring and keeping the temperature below 50℃.
was added dropwise over a period of 1 hour. The temperature was further increased to 50°C in about 1 hour, and the reaction was continued at 50 to 80°C for 5 hours. IR analysis of the gas generated during the reaction confirmed that it was pure fluorinated phosgene. The total amount of gas generated is aaso=e<
2s°C).
実施例２
スプレードライ品のフッ化カリウムの代りに約１００メ
ツシユに粉砕したフッ化ナトリウムを使用した他は実施
例１と同様に反応した。その結果発生ガスをＩＲ分析し
た結果、純品のフッ化ホスゲンを得た。全発生ガス量は
６４６０−であった。Example 2 The reaction was carried out in the same manner as in Example 1, except that sodium fluoride pulverized into about 100 meshes was used in place of the spray-dried potassium fluoride. As a result of the IR analysis of the generated gas, pure fluorinated phosgene was obtained. The total amount of gas generated was 6460-.
保土谷化学工業株式会社
手 続 補 正 書（自発）
昭和５８年 ７月 ４ＩＪ
特許庁長官殿
１、事件の表示
昭和５７年特８′［顕部 １５００５１ 号２、発明
の名称
フン化ホスゲンの製造法
３、補正をする者
事件との関係 特許出願人
郵便番号 １０５
住 所 東京都港区虎）門−丁目４番２号名
称 （５３１）保土谷化学］二業株式会社代表者
取締役社長 藤 岡 腎 −自重 話
５０４−８７２３
５、ｌ１ｔｉ正の内容
（１）第３頁第１５行目の「ジメヂルスルホアミ１１」
を「ジメヂルスルホキシ１゛」に訂正する。Hodogaya Chemical Industry Co., Ltd. Procedural Amendment (Voluntary) July 1981 4IJ Director General of the Patent Office 1, Indication of the Case 1988 Special Patent No. 8' [Akenbe 150051 No. 2, Title of Invention: Manufacture of phosgene fluoride Law 3, Relationship with the case of the person making the amendment Patent applicant Postal code: 105 Address: 4-2 Toramon-chome, Minato-ku, Tokyo
Name (531) Hodogaya Chemical] Nigyo Co., Ltd. Representative Director and President Ren Fujioka - Story
504-8723 5, l1tiCorrect content (1) "Dimedyl sulfoamide 11" on page 3, line 15
is corrected to "dimethyl sulfoxy 1".
保土谷化学工業株式会社Hodogaya Chemical Industry Co., Ltd.
Claims (1)
とアルカリ金属フッ化物とを反応させることを特徴とす
るフッ化ホスゲンの製造法。A method for producing phosgene fluoride, which comprises reacting tricumylomethyl chloroformate and an alkali metal fluoride in acetonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57150051A JPS5939705A (en) | 1982-08-31 | 1982-08-31 | Manufacture of fluorinated phosgene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57150051A JPS5939705A (en) | 1982-08-31 | 1982-08-31 | Manufacture of fluorinated phosgene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5939705A true JPS5939705A (en) | 1984-03-05 |
| JPH0147403B2 JPH0147403B2 (en) | 1989-10-13 |
Family
ID=15488424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57150051A Granted JPS5939705A (en) | 1982-08-31 | 1982-08-31 | Manufacture of fluorinated phosgene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5939705A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002098792A1 (en) * | 2001-06-05 | 2002-12-12 | Daikin Industries, Ltd. | Method of separating acid |
| WO2004092067A1 (en) * | 2003-02-17 | 2004-10-28 | Daikin Industries, Ltd. | Method for producing carbonyl difluoride |
-
1982
- 1982-08-31 JP JP57150051A patent/JPS5939705A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002098792A1 (en) * | 2001-06-05 | 2002-12-12 | Daikin Industries, Ltd. | Method of separating acid |
| US7423174B2 (en) | 2001-06-05 | 2008-09-09 | Daikin Industries, Ltd. | Method of separating acid |
| WO2004092067A1 (en) * | 2003-02-17 | 2004-10-28 | Daikin Industries, Ltd. | Method for producing carbonyl difluoride |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0147403B2 (en) | 1989-10-13 |
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