CAS号 [328-99-4] 生产工艺。  间三氟甲基苯甲酰氟

CAS名：Benzoylfluoride, 3-(trifluoromethyl)-    历史参考文献：Beil. 9. 待检索。

用途：有机合成。C.I. 还原蓝30。  LookChem网登录生产与经营单位18家。  反应类别：氟取代氯。

BIOS 985, 397-398.（=胶卷PB 77764）。 m-Trifluoromethylbenzoyl fluoride. 英国人译自德文（无资料来源）。

反应式：本人有加注。德文原件未抄录。

Handling of Hydrofluoric acid: See Chlorobenzotrifuorides (No. 34). 

Apparatus:  same as for m- and p-chlorobenzotrifluoride, which is a steel, nickel-plated still (1 cbm. capacity) fitted with a nickel-plated steel column.

Charge:

The autoclave (1) is charged with 350 kg. m-trichloromethylbenzoyl chloride and 150 kg. anhydrous hydrofluoric acid blown in from (2) via (3).

Steam is introduced into the jacket for a short time until at about 30℃. a pressure of 22 atmospheres is reached.  Temperature and pressure then rise of their own accord.  The HF vapor is condensed in the refluxing coil, and returns beneath the surface of the reaction mixture.  When 30 atmospheres pressure show on the gauge, the hydrogen chloride evolved is allowed to escape through a needle valve at such a rate that the reaction takes 8 – 10 hours.  The gas is measured by a flowmeter and manometer arrangement, and is taken away by an Igelit injector to be dissolved in water.  Between 50 and 80℃. a sharp increase in pressure sets in which can be controlled only by careful attention to the heating.  As the pressure starts to fall, more vigorous heating can be applied.  When eventually, in spite of increase of temperature, the pressure begins to fall, the heating is shut off until the pressure falls to zero.  Then, with condenser cooling-water shut off, excess HF is driven off by heating again up to 90℃.  The last traces of HF are removed by cooling to ordinary temperature and blowing air through.

After sampling, the contents of the autoclave are blown into the nickel-plated still (4) and fractionated under a moderate vacuum (steam-ejector). First and last runnings are rejected.   Yield about 125 kg.

Laboratory Tests:  The hydrofluoric acid should be of the highest possible strength (98%).  Sample from autoclave: 70% should distil between 100-180℃.  m-Trifluoromethylbenzoylfluoride should contain not more than 2% chloride.  B.P. 120-128℃. under 540 mm.

Output per year – 2 tone.

张澍声 《精细化工中间体工业生产技术》1996年。 P. 20.  间三氟甲基苯甲酰氟。  译自BIOS 986, 397.

在高压釜中加入350 kg 间三氯甲基苯酰氯和150 kg 无水氢氟酸。稍微加热至30℃，压力达到22巴。温度和压力自动上升，氢氟酸蒸汽在回流冷凝器中凝缩，流回到反应混合物表面的下层。当表压达到30巴时，释出的氯化氢通过针形阀逸出，其逸出速度要使反应进行8-10小时。气体的测量用流量计和压力计。在50-80℃间压力急剧增加，只好仔细注意加热来控制。当压力开始下降时，可以更强烈加热。最后尽管提高温度，压力仍在下降，则停止加热，再加热赶出过量的氟化氢，直至90℃。 最后痕量的氟化氢是先冷却至常温，再吹空气赶出。

反应物在蒸汽喷射泵抽真空下进行精馏，初馏份和尾馏份排放。得到125 kg 间三氟甲基苯甲酰氟。

产品氯含量不大于2%，沸程120-128℃ （540 mmHg）.

PB 70063, 45-48.  Analysis of trifluoromethyl-m-benzoyl fluoride. 1942年5月。 未抄录。

PB 70190, 7865-8.  间三氟甲基苯甲酰氟 分析标准。650号。 未抄录。

PB 70361.  Reports on the preparation of intermediates and inorganic chemicals. Machine shop pamphlets. 1929-1946年。 6美元。

PB 70361, 7080.  m-Trifluoromethylbenzoylfluoride. By Eokelmann.  1941年1月10日德文生产工艺。 1.5美元。本人未抄录。

加注：以上德文资料，国内有进口，当然在今天来说，已经是过时了。德文原件应该与英国人的译文会有差别。BIOS 的译文有人翻译，我想利用一下也应该是可以的，可惜本人未抄录。

国内染料专业出版物。

何岩彬 主编 《染料品种大全》沈阳出版社出版。 P. 1895.  3-(三氟甲基)苯甲酰氟。

以上资料抄录文作为补充（因为书中未列合成工艺文献）。

陈忠源 2019年5月13日星期一。