CAS号 [6548-34-1] 生产工艺。  4-氨基-4’-氯二苯胺-2-磺酸

CAS名：4-Amino-4’-chlorodiphenylamine-2-sulfonic acid    历史参考文献：Beil. 待检索。

用途：C.I. 直接蓝190.  LookChem网登录生产与经营单位2家。 反应类别：缩合，还原。

FIAT 1313, I, 90-92.（=胶卷PB 85172）。 4’-Chloro-4-aminodiphenylamine-2-sulfonic acid. 美国人译自德文，无资料来源。

“Chlorphenylparaminsäure”. 这是德文化学名。生产厂 Hoechst。 反应式：为本人所加注（其中硝基体暂未找到CAS号）。

Plant capacity: 设备生产能力： 2 tons. 

Equipment: 设备：

    (1)  2 cast steel bombs, 1000 l. each, gas heated.  Test pressure 100 atm. gauge pressure.；(2)  1 brick-lined reduction apparatus, working capacity 5.2 cu. m.; (3)  1 clarifying press for iron sludge capable of being washed out, 21 chambers, 80 X 80, covered with grey cotton and bearskin filter cloth.; (4)  1 brick-lined precipitation vessel, working capacity 5.8 cu. m.; (5)  1 press for product, 21 chambers 80 X 80, covered with grey cotton filter cloth.; (6)  1 storage vessel for hydrochloric acid and 1 measuring vessel.

Materials used per ton: 每吨原料用量；

“p-Nitrochlorsäure”(p-nitrochlorobenzene-o-sulfonic acid)  950 kg.;  p-Chloraniline   520 kg.;  Magnesia   100 kg.;  Acetic acid   80 kg.;

Iron turnings, sieved   1500 kg.;   Soda   100 kg.

Service requirements per ton of product:  每吨公用工程单耗：

Electricity   1700 kwh.;  Steam   15 tons.;   Water   250 cu. m.;   Gas   1250 cu. m.;  Compressed air   4000 cu. m.

Procedure:  操作步骤：

Into a 1000 l. cast steel bomb are charged 480 l. of water, 95 kg of“p-Nitrochlorsäure”100% molecular weight 237.5 in the form of a 40-45% wet paste.  51 kg. of p-chloraniline 100%, molecular weight 127.5, 10 kg. of magnesia containing about 84% of MgO.  The batch is well stirred and then heated to 170℃.; a temperature of 170 – 175℃. is kept for 18 hours.  The pressure in the bomb is 7 to 8 atm. gauge pressure.  The contents of the bomb are then cooled to below 100℃., emptied and acidified with acetic acid until the reaction of the liquid is slightly acid to litmus.  Two batches of the condensation liquor, in which the“Nitrosäure”is nearly completely separated, are introduced into the reduction apparatus and, while constantly boiling, reduced with about 300 kg. of sieved iron turnings stirred with water and cauterized with a small quantity of acetic acid.  Water is added to avoid too high concentration of the reduction mixture.  The reduction of the“Nitrosäure”is finished when a test drop on filter paper shows that the liquid is colorless and the test with Mohr’s salt is quite satisfactory.  When the reduction is finished, the batch is made slightly alkaline with 20 kg. of soda, filtered boiling hot from the iron sludge through the clarifying press and the sludge is washed with boiling water until it no longer contains any product.  From the clear mother liquor, combined with the wash water, the“Chlorparaminsäure”is separated by addition of about 200 kg. of crude hydrochloric acid 20% as a light bluish voluminous precipitate.  The mixture is stirred until cold, the product is filtered through a filter press and blown as dry as possible with air.  The product from the press analyzes 30 – 35%, molecular weight 298.5.

Yield: from 190 kg. of“p-Nitrochlorsäure”= 200 kg. of“Chlorparaminsäure”100%, molecular weight 298.5 = 83.8% of theoretical.

Controls: 生产控制：

Constant control of the temperature in the bomb.  Testing for the end of the reduction of the“Nitrosäure”by decolorizing the reduction liquor and with Mohr’s salt.  Testing of the iron sludge for completeness of washing.  Determination of the content of“Chlorparaminsäure”by titration with n/1 nitrite solution.

Quality: 原料及产品质量控制：

“p-Nitrochlorsäure”, moist product, manufactured in own plant, content 42 – 45% , molecular weight 237.5.;  p-Chloraniline from Griesheim, about 96%, M. P. at 70℃.  magnesia, should be as free from carbonate as possible and contain about 84% of MgO. ;  Hydrochloric acid crude 20%; commercial quality. ;  Sieved iron tuenings must be free from coarse particles.:  The finished product is a light bluish, voluminous, finely crystalline paste with a content of 30 – 35% molecular weight 298.5.

张澍声 《精细化工中间体工业生产技术》。《染料工业》编辑部 出版。1996年。P. 37.  4’-氯-4-氨基二苯胺-2-磺酸。译文。

在1000 L铸钢高压容器（试验压力100巴）中，加入480 L水，95 kg 100% 对硝基氯苯邻磺酸（为40 – 45% 滤饼），51 kg 对氯苯胺和10 kg 氧化镁（约含84% MgO）。混合物很好搅拌，并加热到170℃，在170 – 175℃保持18小时，压力7 – 8巴。然后将温度降至100℃以下，用醋酸酸化至反应液对石蕊试纸为微酸性。将两锅的缩合液合并，分离出其中的4’-氯-4-硝基二苯胺-2-磺酸，送往还原锅中。还原锅中有300 kg 铁粉，少量醋酸和稀释用的水，并经常保持沸腾状态。当取样滴在滤纸上为无色，并且莫尔盐（抄注：CAS号[1185-57-5]）试验满意时，还原即告完成。反应物用20 kg 碳酸钠使呈碱性，沸腾过滤分出铁泥，铁泥再用沸水洗涤至不含4’-氯-4-氨基二苯胺-2-磺酸。将清晰的母液与洗水合并，加入约200 kg粗盐酸，则4’-氯-4-氨基二苯胺-2-磺酸以微蓝色疏松沉淀分离出来。混合物搅拌至冷，产品过滤，并用空气尽可能吹干，滤饼中产品含量30 – 35%。

由190 kg 4’-氯-4-硝基二苯胺-2-磺酸得到200 kg 100%  4’-氯-4-氨基二苯胺-2-磺酸，收率83.8% 。

缩合生成的4’-氯-4-硝基二苯胺-2-磺酸湿产品含量42 – 45%。

【抄注】莫尔盐是 Ferrous ammonium sulfate = [1185-57-5]。

PB 73377, 2468 – 2470.  “Chlorparaminsäure”= 4’-Chloro-4-aminodiphenylamine-2-sulfonic acid. 未抄录。

国内化工产品 出版物。暂未见到有报导。

何岩彬 主编 《染料品种大全》。沈阳出版社 出版。 2018年。 P. 1954-1955.  4-氨基-4’-氯二苯胺-2-磺酸。

可合成的染料：C.I. 直接蓝190.

陈忠源 2020年5月6日星期三。