JPH0147403B2 - - Google Patents
Info
- Publication number
- JPH0147403B2 JPH0147403B2 JP57150051A JP15005182A JPH0147403B2 JP H0147403 B2 JPH0147403 B2 JP H0147403B2 JP 57150051 A JP57150051 A JP 57150051A JP 15005182 A JP15005182 A JP 15005182A JP H0147403 B2 JPH0147403 B2 JP H0147403B2
- Authority
- JP
- Japan
- Prior art keywords
- phosgene
- fluoride
- tcf
- reaction
- alkali metal
- 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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 9
- QLBWPQUBNGIDMY-UHFFFAOYSA-N carbonyl dichloride;hydrofluoride Chemical compound F.ClC(Cl)=O QLBWPQUBNGIDMY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 claims description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical class ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 235000003270 potassium fluoride Nutrition 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Description
【発明の詳細な説明】
本発明はフツ化ホスゲンの新規製造法に関す
る。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TCFと略記する）をアルカリ金
属フツ化物でフツ素化するフツ化ホスゲンの製造
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing phosgene fluoride. More specifically, the present invention relates to a method for producing fluorinated phosgene by fluorinating trichloromethyl chloroformate (hereinafter abbreviated as TCF) with an alkali metal fluoride.
フツ化ホスゲンは、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。 Phosgene fluoride is an indispensable and useful compound as a raw material for the synthesis of pharmaceutical intermediates, such as dyes and agricultural chemicals.
従来、フツ化ホスゲンの製造法としては、ホス
ゲンとフツ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Beilsteins Ｅ３p.22に、また、西独特許第
139936号公報明細書にはSOF2とホスゲンとを
４：１の割合で鉄製チユ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
高温反応であり、未反応のホスゲンとフツ化ホス
ゲンとの分離精製を必須とし、高純度のフツ化ホ
スゲンを得ることが困難である。またフツ化水素
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, the method for producing phosgene fluoride involves reacting phosgene and hydrofluoric acid in an iron autoclave at 140 to 150°C in the presence of activated carbon, as described in Beilsteins E 3 p. 22 and in a West German patent. No.
139936, SOF 2 and phosgene were mixed in a ratio of 4:1 using an iron tube reactor,
A method is disclosed in which the reaction is carried out at 400° C. in the presence of an anhydrous ferric chloride catalyst. All of these methods involve high-temperature reactions and require separation and purification of unreacted phosgene and fluorinated phosgene, making it difficult to obtain highly purified 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
セトニトリル中フツ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。 Further, JP-A-54-158396 describes a method in which phosgene is introduced into a mixture of hydrofluoric acid and triethylamine in acetonitrile for reaction. This method solves the problem of corrosion of the equipment material because it reacts at low temperatures, but since it uses a large amount of triethylamine, recovery and reuse of triethylamine must be considered, so it is never suitable for industrial use. This cannot be said to be an advantageous method.
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、TCFとアルカリ金属フツ化物か
ら極めて容易に、精製工程を必要とせずして高純
度のフツ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つた。 As a result of intensive studies to overcome these problems, the present inventors discovered that highly purified phosgene fluoride can be obtained extremely easily from TCF and an alkali metal fluoride without the need for a purification process. The present invention has now been established.
すなわち、本発明はアセトニトリル中でTCF
とアルカリ金属フツ化物とを反応させることを特
徴とするフツ化ホスゲンの製造法である。 That is, the present invention provides TCF in acetonitrile.
This is a method for producing phosgene fluoride, which is characterized by reacting phosgene with an alkali metal fluoride.
本発明方法は、アセトニトリルとアルカリ金属
フツ化物との混合系にTCFを添加し、加温下に
反応させると生成したフツ化ホスゲンは、反応系
内からガス体として得られる。このフツ化ホスゲ
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, TCF is added to a mixed system of acetonitrile and an alkali metal fluoride, and when the mixture is 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 needed.
本発明では反応溶媒としてアセトニトリルが好
ましい。その他の、例えばジメチルスルホキシド
ではTCFの分解によりホスゲンを生成しフツ化
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、アルカリ金属フツ化物を添加した時撹
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ツ化物に対して２〜10
重量倍が用いられる。 In the present invention, acetonitrile is preferred as the reaction solvent. Other methods, such as dimethyl sulfoxide, produce phosgene by decomposition of TCF, 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. Usually 2-10 for alkali metal fluoride
Weight times are used.
本発明の出発原料でTCF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。 TCF, which is the starting material of the present invention, is industrially produced by phosgenation of methanol, methyl chloroformate, and further chlorination, and is easily available.
フツ素化剤として使用するアルカリ金属フツ化
物としては、フツ化ナトリウム、フツ化カリウ
ム、フツ化リチウム等があげられるが、高純度、
高収率でフツ化ホスゲンを得るためにはスプレー
ドライ品のフツ化カリウムを用いることが好まし
い。 Examples of alkali metal fluorides used as fluorinating agents include sodium fluoride, potassium fluoride, and lithium fluoride.
In order to obtain phosgene fluoride in high yield, it is preferable to use spray-dried potassium fluoride.
アルカリ金属フツ化物の使用量はTCFに対し
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 to be used is 4.0 to 12.0 times, preferably 4.2 to 6.0 times, molar ratio to TCF.
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 50 to 80°C.
TCFの添加は通常30℃以下で全量を添加し、
その後昇温し還流下に反応させるが、反応系を50
〜80℃に保つてTCFを添加して反応させること
もできる。 When adding TCF, the entire amount is usually added at 30℃ or below.
After that, the temperature is raised and the reaction is carried out under reflux, but the reaction system is
It is also possible to react by adding TCF while maintaining the temperature at ~80°C.
上記のように、本発明法によれば極めて容易、
かつ高純度、高収率でフツ化ホスゲンを製造でき
る。 As mentioned above, according to the method of the present invention, it is extremely easy to
In addition, fluorinated phosgene can be produced with high purity and high yield.
以下、実施例をあげて本発明を詳細に説明す
る。 Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例 １
120部のアセトニトリルと35部のスプレードラ
イ品のフツ化カリウム（森田化学製）とを室温で
混合し、この中にかきまぜ下30℃以下を保つて20
部のTCF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、
純品のフツ化ホスゲンであることを確認した。ガ
スの全発生量は4450ml（25℃）であつた。Example 1 120 parts of acetonitrile and 35 parts of spray-dried potassium fluoride (manufactured by Morita Chemical Co., Ltd.) were mixed at room temperature, and stirred into the mixture while keeping the temperature below 30°C for 20 minutes.
of TCF was added dropwise over a period of 1 hour. About 1 more
The temperature was raised to 50°C over an hour, and the reaction was carried out at 50 to 80°C for 5 hours. As a result of IR analysis of the gas generated during the reaction,
It was confirmed that it was pure fluorinated phosgene. The total amount of gas evolved was 4450ml (25°C).
実施例 ２
スプレードライ品のフツ化カリウムの代りに約
100メツシユに粉砕したフツ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、純品のフツ化ホスゲ
ンを得た。全発生ガス量は3460mlであつた。Example 2 In place of potassium fluoride in the spray-dried product, approx.
The reaction was carried out in the same manner as in Example 1, except that sodium fluoride pulverized into 100 mesh pieces was used. As a result of IR analysis of the generated gas, pure fluorinated phosgene was obtained. The total amount of gas generated was 3460ml.
Claims (1)
ホーメートとアルカリ金属フツ化物とを反応させ
ることを特徴とするフツ化ホスゲンの製造法。1. A method for producing phosgene fluoride, which comprises reacting trichloromethyl 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 | Method for producing phosgene fluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57150051A JPS5939705A (en) | 1982-08-31 | 1982-08-31 | Method for producing phosgene fluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5939705A JPS5939705A (en) | 1984-03-05 |
| JPH0147403B2 true 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 | Method for producing phosgene fluoride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5939705A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4264689B2 (en) | 2001-06-05 | 2009-05-20 | ダイキン工業株式会社 | Acid separation method |
| JP2004262679A (en) * | 2003-02-17 | 2004-09-24 | Daikin Ind Ltd | Method for producing carbonyl difluoride |
-
1982
- 1982-08-31 JP JP57150051A patent/JPS5939705A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5939705A (en) | 1984-03-05 |
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