CAS号 [98-15-7] 生产工艺。   3-氯三氟甲苯

CAS名：Benzene, 1-chloro-3-(trifluoromethyl)-      历史参考文献：Beil. 5. E3, 692.

用途：冰染重氮组分17。医药及有机合成。 LookChem网登录生产与经营单位72家。  反应类别：氯氟代。

BIOS 986, 75-76. （=胶卷PB 77764）。 m-Chlorobenzotrifluoride. (I.G. Hoechst).  英国人译自德文（无资料来源）。

反应式：本人有加注，暂未找到德文原件（因为本人手头抄录的美国人提供的共享目录不多！）。

Apparatus – see diagram, Appendix 5. 

In vessel (1) charge 350 kg. m-chlorobenzotrichloride (No. 33) and blow in from (2) via (3) 120 kg. anhydrous HF.  Heat with 15 atmospheres pressure steam until the pressure in the autoclave reaches about 25 atmospheres, which occurs normally at 100-110℃.  Shut at this point has been observed, heating is cautiously started again.  Hydrofluoric acid vapor is condensed in the coil and returned beneath the surface of the reaction mixture.  The hydrogen chloride evolved is led off through the gas take-off (needle valve) at such a rate that the reaction takes 8-10 hours.  The hydrogen chloride evolved is measured by means of a flow meter and differential manometer (of glass and lead) and removed by solution in water through an Igelit injector.  When the pressure starts to fall, in spite of rises in temperature, the autoclave is heated more strongly.  Then the heating is shut off and the pressure allowed to fall. As much hydrogen fluoride as possible is next distilled off by heating again to 90℃. under atmospheric pressure with the condenser cooling water shut off.

After sampling the contents of the autoclave are blown over into a soda solution in the steam still (4).  Here it is first boiled under reflux condenser for 1/2 hour by direct steam heating, then distilled off alkaline with steam into a little continuous separator, where it is automatically separated from the condensed water.  The oil is finally passed through a tower packed with calcium chloride to dry it, before running it into drums.  Yield about 250 kg.

The bye-product left as a hard residue in the steam still must be removed whilst it is still hot.

Laboratory tests:

m-Chlorobenzotrichloride should have a setting-point in the neighborhood of 2℃.   Hydrofluoric acid should be of the highest possible strength (98%).

Sample from autoclave at least 90% should distil between 100-150℃.  m-Chlorobenzotrifluoride should have setting-point -51 to -52℃. (solid CO2 used for these low temperatures).  Boiling point 138℃.

Production: Estimated at 6 tons per year – dependant, of course, on the p-isomeric production.

Materials required per ton product:  m-Chlorobenzotrichloride  1450 kg. from “Methylbetrieb” I.G. Hoechst.

                                Anhydrous hydrogen  500 kg. from I.G. Leverkusen or Rütgeswerke, Dohna (Sachsen).   Soda  90 kg.

张澍声 《精细化工中间体·工艺生产技术》 1996年。 P. 74.  间氯苯基三氟甲烷。 译自BIOS 986, 74.

在高压釜中加350 kg间氯苯基三氯甲烷，通入120 kg无水HF，加热至高压釜压力达到25巴，通常在100-110℃产生。停止加热，在这时可以观察到压力激烈升高，此后可以再小心地加热。氢氟酸蒸汽在蛇管中凝缩下来，并返回到反应混合物表明的下部。释出的氯化氢经针形阀导出，导出速度要使反应约需8-10小时。释出的氯化氢经流量计测量，并溶解于水中。压力开始下降时，尽管温度在升高，高压釜还是更强地加热。然后撤去加热，让压力下降。釜加热到90℃以蒸馏出尽可能多的氟化氢（常压）。

将高压釜内容物送入碳酸钠溶液中，首先用直接蒸汽沸腾回流0.5小时，然后有蒸汽蒸出，进入一小的连续分离器，在此自动与凝缩水分离，油层最后通过氯化钙填充塔将其干燥，得产物250 kg。

留在蒸汽内的副产物硬残渣必须在热的时候除去。间氯苯基三氟甲烷凝固点-51 - -52℃，沸点138℃. 每吨产品消耗：间氯苯基三氟甲烷1450 kg，无水氟化氢500 kg; 碳酸钠90 kg。

侯乐山  主编。《中国精细化工产品集 – 原料及中间体 10396种》2006年。 3-氯三氟甲苯。  P. 737. 同见p. 898.

中国化工信息中心  全国精细化工原料及中间体行业协作组  出版。

抄注：该书除分子式；分子量；CAS号；结构式；产品性状；技术指标；用途和生产厂以外，再也没有生产工艺。当然也没有上述本人抄录的资料。为什么？本人无法回答！因为编写者是中国，又是全国！

学习与思考：我想：多点参考文献，总比没有好。

陈忠源  2018年7月28日星期六。