CAS号 [101-12-2] 生产工艺。   3,3’-二氨基苯甲酰苯胺

CAS名：Benzamide, 3-amino-N-(3-aminophenyl)-

用途：染料中间体。LookChem网登录生产与经营单位9家。

BIOS 1153, 301-303.（=胶卷PB 85687）。 3.3’-Diaminobenzanilide (Leverkusen).  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。

Stage 1:  3,3’-Dinitrobenzanilide. (m-Nitrobenzoyl-m-nitroaniline). 

Plant:  1000 l.  enamelled pan.    Wooden nutsche.

Process: 操作步骤：The enamelled pan is charged with 50 kg. of m-nitroaniline (≈25 kg. NaNO2), 600 l. water, and 43.5 kg. of milk of lime.  The suspension is heated to 60 - 620 and at this temperature 75 kg. of molten m-nitrobenzoyl chloride are run in during 2.5 hours.  The mixture is stirred 1 hour at 600 and then stirred and allowed to cool overnight.

Test:  A sample acidified and estimated with NaNO2 should contain not more than 10% of unchanged m-nitroaniline.

(By addition of 10% further acid chloride the conversion can be increased to 94%).

50 l. of hydrochloric acid are added and the mixture is stirred for 1 hour at 600.  It is filtered at this temperature and the product washed with water until neutral.

Stage 2:  3,3’-Diaminobenzanilide.

Plant:  1000 l. iron reducer with reflux condenser.   Iron filter press.   1000 l. vessel, jacketed, for distillation of alcohol.

Process: 操作步骤： The reducer is charged with 160 l. of water, 75 kg. of iron borings and 4 l. of acetic acid.  178 kg. of 3,3’-dinitrobenzanilide are added at 800 during 2 hours.  The temperature rises to the boil and boiling is continued for 3 hours.  A further 10 kg. of iron and 2 l. of acetic acid are added if necessary to maintain soluble iron.

The mixture is cooled to 700 and 180 l. of alcohol then added.  Agitation at 700 is continued overnight.

Test:  A sample filtered and drowned out into water should give a clear solution in hydrochloric acid.

6 kg. of soda ash and 10 kg. of magnesium oxide are added to make batch alkaline, followed by a further 180 l. of alcohol.  The mixture is boiled and filtered through the press.  The iron oxide residue is washed with 300 l. of alcohol.

The alcohol is distilled off from the combined filtrates to a temperature of 95 - 970 and the oily residue then treated with 200 l. of cold water to form fine pellets.  The product is filtered and washed.  The filtrate contains the equivalent of 4 g. NaNO2 per 1 l.

Yield average = 76% theory.

Notes:  This was only a small manufacture and only 3 batches on this scale have been made.  The results were as follows:

Batch No. / Wt. of product / Strength as kg. NaNO2 per 100 kg. product. / Equivqlent yield in kg.
NaNO2

The iron sludge contained the equivalent of 7.3, 2.0 and 3.2 kg. NaNO2 per batch respectively.   The lower yield and high content in the sludge in Batch 1 was due to the use of magnesium oxide only.  Adjusting for this the average yield for the three batches was 76% theory.

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. 97-8.  3,3’-二氨基苯甲酰苯胺，译自BIOS。

    （一）缩合：在1000 L搪瓷锅中加入50 kg 间硝基苯胺（相当于25 kg NaNO2）,600 L水和43.5 kg石灰乳。悬浮体加热到60 – 62℃，在此温度于2.5小时内流入75 kg 熔融的间硝基苯甲酰氯，混合物在60℃搅拌1小时，搅拌并冷却过夜。

检验：取样酸化，用亚硝酸钠溶液滴定，未转化见硝基苯胺含量不多于10%。（若再加入10% 酰氯，转化率增加到94%）。

加入50 L盐酸，混合物在60℃搅拌1小时，在60℃过滤，水洗至中性。得3,3’-二硝基苯甲酰苯胺。

（二）还原：在1000 L铁还原锅中加入160 L水，75 kg 铁屑和4 L醋酸。在80℃于2小时内加入178 kg 3,3’-二硝基苯甲酰苯胺，加热至沸，继续沸腾3小时。为了保持溶解铁的需要，可以再加入10 kg 铁和2 L醋酸。

混合物冷却到70℃，加入180 L乙醇，在70℃继续搅拌过夜。

检验： 取样过滤，投入水中，得到清晰的盐酸溶液。

加入6 kg 碳酸钠和10 kg 氧化镁，使反应物呈碱性，随后再加入180 L乙醇，混合物煮沸，压滤，氧化铁残渣用300 L乙醇洗涤。

滤液和洗涤液合并，蒸馏出乙醇，温度达95 – 97℃。油状残留物用200 L冷水处理，产品过滤并洗涤。每升滤液含相当于4 g 亚硝酸钠的产品。平均收率76%。

何岩彬 主编《染料品种大全》。沈阳出版社 出版。2018年。P. 1851-2038. （染料中间体及可合成的染料），未见列入。

按分子式，可列入P. 1970.  【可合成的染料】C.I. 直接橙73。

陈忠源 2020年12月24日星期四。