CAS号 [99-60-5] 生产工艺 2-氯-4-硝基苯甲酸

CAS名: Benzoic acid, 2-chloro-4-nitro- 历史参考文献: Beil. 9, 404; E², 276; E³, 1766; E⁴, 1229.

用途: 医药（如：Rivanol [6402-23-9]），有机合成。反应类别:  甲基氧化。

生产工艺参考文献: 按本人手头资料整理如下。

FIAT 1313,I, 110-113. （=胶卷 PB 85172）61.  2-Chloro-4-nitrobenzoic acid for Rivanol. (I.G. Hoechst) 美国人译自德文。抄录如下。

反应式:  本人有加注。译者未说明资料来源。本人暂未找到德文原件（因为收录PB胶卷号不多）。
 

Materials used per ton:  2-Chloro-4-nitrotoluol 1.33 tons.  Sodium bichromate 3.96 tons.

 Monohydrate 6.88 tons. Soda  1.00 tons.

By product: Amt. per ton of main product. Chromic lye containing  5.5-6% Cr₂O₃  1.4 ton of Cr₂O₃.

Service requirements per ton of product:  Electricity 2.4 kwh. Steam 41 tons. Water  5 cbm.  Compressed air  30 cbm.

Procedure:

In the oxidation kettle, 220 kg of 2-chloro-4-nitrotoluol are added 550 kg monohydrate and 60 kg of water. Half of this may consist of recovered moist chlornitrotoluol. The water content has to be calculated with respect to the quantity needed. To this, the chromic acid solution, produced from 317 kg of sodium-dichromate, 158 kg of water and 194 kg of sulfuric acid 78%, is added during 4-5 hours.

Temperature 78-83⁰C. Stir for 2 hours, dilute with 1000 kg water and filter at 20-25⁰C. on the suction filter. Rinse vessel with 500 liters water. Dissolve the raw filtered product in the vessel in 1100 liters of water and about 80 kg of soda at 90⁰C. Test: Alkaline to Delta or Tumeric Paper. Cool down to 20⁰C. and filter through the iron filter press and oil (3 to 4 kg of by-products are the oil which is thrown away) separator to the clarification vessel. The unoxidized chlornitrotoluol remaining in the filterpress is used again for the next charge.

The filtrate is stirred in the clarification vessel with 10 kg of activated charcoal and 10 kg of kieselguhr (diatomaceous earth) for 4 hours, at ordinary temperatures, filtered through the filter press to the precipitation vessel and there precipitated with about 1000 kg of hydrochloric acid. The precipitated chlornitrobenzoic acid is filtered on the suction filter. Well pressed and covered twice with 20 kg of ice water and dried in the air rotation board at 60-70⁰C.

Control:  The content of the recovered moist chlornitrotoluol is determined as follows: A sample in g. corresponding to the quantity in kg is made acid to Congo with the addition of ice and sulfuric acid and is left standing over night. Then it is filtered, and the residue dissolved in methylenchloride, and the methylenchloride is distilled.

The total quantity of chlornitrotoluol in kg corresponding to the weight of the residue in kg.

Quality:  2-Chloro-4-nitrotoluol has a freezing point of 60-61⁰C., the chlornitrobenzoic acid slightly yellowish, fine needles melting at 134-136⁰C. The entirely clear acid crystallized from chlorobenzene melts at 144⁰C. and dissolves almost colorless in alkali.

Note:  About 100 kg of 100% basis unoxidized material is in the iron filter press, 600 x 900, or about 150 to 200 kg of wet product. The cake on the first suction filter is only 10 to 15 cm. deep. A filter this large is unnecessary. On the last suction filter, two batches are combined. The cake depth is 20 to 25 cm. and it weighs about 300 kg wet. The raw filtered product solution with soda is made alkaline to Delta paper or Tumeric paper. The by-product oil, 3 to 4 kg from the oil separator is discarded.

抄注: 译文中，有一些是德文写法和德文原文，如Chlornitro-, kieselguhr 等。

张澍声  编译。《精细化工中间体工业生产技术》 1996年。 P. 165-167.  2-氯-4-硝基苯甲酸。译自FIAT 1313,I, 112. 抄录如下。

在3000 L氧化锅中加入220 kg 2-氯-4-硝基甲苯，550 kg 硫酸一水合物和60 kg水，2-氯-4-硝基甲苯的一半可以采用含水滤饼，含水量可根据质量要求计算。另将317 kg重铬酸钠，158 kg水和194 kg 78% 硫酸制成铬酸溶液，于4-5小时内加入。温度78-83⁰C，搅拌2小时，用1000 kg水稀释，在20-25⁰C抽滤，用500 L水洗涤氧化锅。滤饼在90⁰C溶解于1100 L水和约80 kg碳酸钠中，经检验应该对硝氮黄试纸为碱性。冷却到20⁰C，过滤，滤液于滤清槽中分离去3-4 kg油，为副产物，弃去。未氧化2-氯-4-硝基甲苯留在压滤机中，在下次反应中复用。

滤液中加入10 kg活性炭和10 kg硅藻土，在常温下处理4小时，过滤。滤液和加1000 kg盐酸沉淀，沉淀出的2-氯-4-硝基苯甲酸抽滤，用冰水洗涤两次，在60-70⁰C滚筒干燥。

2-氯-4-硝基苯甲酸为微黄色细针状结晶，熔点134-136⁰C，在氯苯中结晶熔点144⁰C,可溶于碱为无色。

国内生产工艺:  用高锰酸钾氧化法（下面应该是《上海医药工艺汇编》的内部资料）。

徐克勋  主编。 《有机化工原料及中间体便览》（修订版）。1988年。 P. 535.  2-氯-4-硝基苯甲酸。抄录如下。

制法; 由对硝基甲苯氯化，氧化而得。

将对硝基甲苯在铁丝和·碘片存在下，于58-62⁰C氯化，得2-氯-4-硝基甲苯；再将25倍1-2%氢氧化钠液加入2-氯-4-硝基甲苯中，加热至沸腾，于激烈搅拌下，缓缓加入高锰酸钾，保持温度在100±1⁰C，加完后，继续搅拌，回流30分钟，放冷，分去二氧化锰。滤液用盐酸调至pH =1-2, 沉淀用冰水洗涤，过滤后。于80⁰C干燥而得成品。

抄注:  本书的最大特点是没有资料来源！ 

陆险峰  主编。 中国化工产品目录 – 精细化工原料及中间体分册。 2004版。P. 542.  2-氯-4-硝基苯甲酸。 抄录如下。

生产方法: 由对硝基甲苯经氯化，氧化而得。

将对硝基甲苯投入干燥的反应器中，加热熔融后，加热铁丝和碘片，于58-62⁰C，通入等摩尔量氯气，经热水洗涤，碳酸钠中和后，倒入冰水中，搅拌析出结晶，过滤去水阴干得2-氯-4-硝基甲苯（抄注：[121-86-8]）。再将25倍1-2%氢氧化钠液加入2-氯-4-硝基甲苯中，加热至沸腾，于激烈搅拌下，缓缓加入高锰酸钾，保持温度在100±1⁰C，加完后，继续搅拌，回流30 min，放冷，分去二氧化锰，滤液用盐酸调至pH为1-2，沉淀用冰水洗涤，过滤后，于80⁰C干燥而得产品。

氯化操作也可以在三氯化铁存在下进行，仍然在58-62⁰C通氯。氯化，氧化的总收率约为70%。

抄注:  本书的最大特点是没有资料来源！

加注: 

为什么要抄录上述中文？请读者评述！本人只希望少一些抄来抄去，多化时间开发一些已进口而没有被大家所知道的，应该是有用的技术资料。

陈忠源  2017年8月24日                             于 无锡   明辉国际。