CAS号 [101495-54-9] 生产工艺    5-氯-4-硝基-2-甲基苯腈

CAS名: Benzonitrile, 5-chloro-2-methyl-4-nitro- 历史参考文献: 未检索。

用途: 冰染重氮组分。有机合成。  发明者: Laska, Zitscher, Heil 1936年。    反应类别: 重氮化，Sandmeyer 反应。

BIOS 1149, 32-33. （=胶卷PB 80376）。 4-Chloro-5-nitro-o-tolunitrile. (Mainkur).  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（译文无生产工艺年份！）。
 
Materials:  4-Chloro-5-nitro-o-toluidine (MW. 186.5) 339 kg. = 1.82 kg. mol.   Hydrochloric acid 200Be’   680 l.   Sodium nitrite   142 kg. = 2.06 kg. mol.      Copper (as sodium cuprochloride)   51 kg. = 0.81 kg. mol.   Sodium cyanide   231 kg. = 4.71 kg. mol.     Chalk    110 kg. 

Procedure:   (a) Diazotisation:

The 4-chloro-5-nitro-o-toluidine is milled in a ball-mil with 1200 l. water for 4 hours.  It is then run into 500 l. of water, 480 l. of hydrochloric acid and 200 – 500 kg. of ice.  Diazotisation is effected by running in a solution of 142 kg. sodium nitrite in water.  Temperature 15 – 20℃.

(b) Preparation of sodium cuprocyanide.

The sodium cuprocyanide solution is made up by treating sodium cuprochloride solution (see Note) containing an equivalent of 51 kg. copper with 153 kg. of sodium cyanide,  This solution is run into one made from 1000 kg. of ice, 110 kg. of chalk and 700 l. of water.  Temperature 30℃.

(c) Sandmeyer reaction.

Maintaining the temperature at 30℃, the diazo solution is added in 4 equal portions with addition of sodium cyanide between each:

1/4 of the diazo solution, 26 kg. sodium cyanide as solution;  1/4 of the diazo solution, 26 kg. sodium cyanide as solution;  1/4 of the diazo solution, 26 kg. sodium cyanide solution,  1/4 of the diazo solution.  Total sodium cyanide = 78 kg.

The product is then filtered (press) and washed.  The filtrates are treated with sodium tetra sulphide to convert excess cyanide into sulphocyanide, which is then run to drain.  The crude product contains chalk which has to be removed.

(d) Purification.  The crude product is pasted with 3000 l. of water, 1000 kg. ice and 200 l. hydrochloric acid.  Temperature 5℃.  It is filtered and washed.   Yield = 900 kg. paste. = 350 kg. dry product. = 268 kg. 100% （M.W. 196.5）= 75.0% theory.

Estimation:   The product is estimated by hydrolysis with caustic and titration of the liberated ammonia.  Specification: M. Pt.  115 – 117℃.

Note:  Sodium cuprochloride solution.     For all cyano-reaction and chloro Sandemeyer reactions, sodium cuprochloride made up as follows is used.

Waste copper solutions from pyrites (obtained from Rio-Tinto, Spain) from sulphuric acid manufacture, or from copper recovered from cuprammonium silk manufacture, are precipitated with iron.  This recovered copper is dissolved in hydrochloric acid, sodium chloride and a little sodium chlorate.  This solution is estimated by titration with potassium permanganate and the content of copper calculated.  Before use this is neutralized with caustic soda.

张澍声 《精细化工中间体工业生产技术》 1996年。 P. 20. 5-氯-4-硝基-2-甲基苯腈。 译自BIOS 1149, 31.

（一）重氮化:  339 kg 4-氯-5-硝基-2-氨基甲苯（1.82 kg. mol）在球磨机中与1200 L水研磨4小时，然后流入500 L水，480 L 31% 盐酸和200 – 500 kg冰中。将142 kg 亚硝酸钠（2.06 kg. mol）溶于水中，于15-20℃ 加入进行重氮化。

（二）氰亚铜酸钠的制备:  将含有51 kg铜和153 kg1氰化钠的氯亚铜酸钠（Na[CuCl2]）溶液流入1000 kg冰，110 kg 碳酸钙和700 L水中，在30℃处理，得到氢亚铜酸钠（Na3[Cu(CN)4]）溶液。

（三）Sandmeyer 反应:  保持温度在30℃，将重氮液分为四分加入到上述氰亚铜酸钠溶液中，每加入一份重氮液，加入26 kg氰化钠（配成溶液），第4次只加入重氮液，氰化钠三次共加入78 kg。

产品过滤并洗涤，滤液用四硫化钠处理，使过量的氰化物转变为硫氰酸盐，然后流入下水道。粗产品中含有碳酸钙，必须除去。

（四）精制:  粗品用3000 L水，1000 kg冰和200 L盐酸打浆，温度5℃。过滤并洗涤。得到900 kg滤饼，相当于350 kg干产品或268 kg 100% 产品。收率75%。

学习与思考：早期历史文献，但是大的CAS号，无三废处理（Run to drain = 放入下水道！），我想了解一下是可以的吧！

陈忠源 2018年3月19日。