CAS号[91-40-7] 生产工艺  二苯胺-2-羧酸

CAS名: Benzoic acid, 2-(phenylamino)- 历史参考文献: Beil. 14, 327; E¹, 533; E², 213; E³, 898; E⁴, 1019.

用途: 硫化蓝2。医药，有机合成。反应类别: 脱氯化氢缩合。

生产工艺参考文献: 按本人手头资料整理如下：

BIOS 986, 185-187.（=胶卷 PB 77764）Diphenylamine-2-carboxylic acid (Diphenylsaeure) I.G. Mainkur. 英国人译自德文。如下。

反应式: 本人有加注，译者未说明资料来源。（未抄录相对应的德文原件。）

Materials usage per batch:  343 kg. o-Chlorobenzoic acid M.W. 156.5.   570 kg.  Aniline. 310 kg. Caustic potash. 1.1 kg. Copper

114 kg. Soda. 110 kg. Hydrochloric acid I plus 110 kg. water. 450 kg. Hydrochloric acid II. 1,000 kg. Salt.

Services Consumptions (1935 basis):  Per Batch   Per 100 kg. of product.

Steam   11.9 tones   2.9 tones

Electricity   267 kw.H.   65 K.W.H.

Air   1,506 cu. m.  367 cu. m.

Process hours   48   11.7

The expenses per batch were 502.62 RM, and the expenses per 100 kg. were 122.59 RM.

Plant Description: 生产设备:  共11项。以下略，

Process Description: 操作步骤:  括号内数字为设备号。

With agitation charge 570 kg. aniline, 310 kg. caustic potash and 1.1 kg. copper to (1) and heat to 150⁰C. During 6-7 hours add 343 kg. o-chlorbenzoic acid with agitation by means of funnel so that the temperature does not exceed 117-118⁰C.; with recovered aniline the reaction is more sluggish and a little steam should be used. Heat to 125⁰C. hold for 4 hours at this temperature, cool to 100⁰C. fill the vessel with hot water and blow into the still (2), diluted to 4,000 l. and add 114 kg. soda, drive off the excess aniline with direct and indirect steam (24 hours). The initial temperature of distillation is 112-115⁰C., the final temperature of the distillation being 122⁰C. The completion of the distillation is determined in the laboratory by the estimation of the aniline content of a filtered sample of the batch. The aniline water from the distillate is treated with 1,000 kg. of salt and the separated aniline blown to the bulk.

At the end of the distillation there is about 3,000 l. of slurry in the still. Add cold water and ice to give a volume of 5,000 l. and a temperature of 40⁰C with agitation. Neutralise very carefully with a mixture of 111 kg. hydrochloric acid and 111 l. of water until there is only very weak reaction on Betagelb. Fill the vessel with water and screen at 35-40⁰C. through (8) to the precipitation vessel (9). Wash the screening pres at first from the stil and then directly from the water main. Test on Betagelb. Dilute in the precipitation vessel to 12,000 l. with water and precipitate very carefully with 450 kg. hydrochloric acid during 2-3 hours, the final reaction being acid to Methyl Orange and the end point checked in the laboratory. Filter in two halves on (11). Wash acid free.

The product precipitates in white flakes and is sparingly soluble in water. M.P. 182-183⁰C.

Yield: About 1,200 kg. of paste = 460 kg. dry = 432 kg. 100% = 92.8% th.

380 kg. aniline is recovered and 46 kg. is present in the aniline water. Theoretical yield requirement is 203 kg.

Rema:

    (1) At the conclusion of the condensation period a sample is boiled in a test tube in hot water and conc. Hydrochloric acid added. Boil again and filter. The filtered mass remains quite clear. If crystals of o-chlorbenzoic acid separate the condensation is not complete.

(2) The product is estimated by dissolving 3.195 g.=0.05 mol. In 150 c.c. acetic acid by heating to 60⁰C. for a short time. Cool to room temperature and make the following additions in succession.

15 c.c. hydrochloric acid dilute 1:1.   24 c.c. N/2 nitrite.   10 c.c. hydrochloric acid dilute.   600 c.c. water and titrate with N/1 nitrite to a 10 min, end-point on starch iodide paper.

张澍声  编译。 《精细化工中间体工业生产技术》1996年。 P. 7. 二苯胺-2-羧酸。译自BIOS 986, 185. 抄录如下。

在搅拌下将570 kg苯胺，310 kg苛性钾和1.1 kg铜加到1250 L搪瓷釜中，加热到150⁰C。于6-7小时内在搅拌下加入343 kg邻氯苯甲酸，要使温度不超过117-118⁰C,如果用回收苯胺，则反应液更稠厚，要通一些蒸汽。加热到125⁰C,在此温度保持4小时。冷却到100⁰C,将釜内用热水充满，并压入到5500 L苯胺蒸馏锅中，稀释到4000 L，并加入114 kg碳酸钠，水蒸汽蒸馏赶出过量苯胺。蒸馏的最初温度为112-115⁰C,最终温度为122⁰C.蒸馏的完成在实验室中测定过量样品的苯胺含量。蒸馏的苯胺水用100 kg盐处理，收集分离出的苯胺。

在蒸馏末期在锅内仍有300 L浆状物，加冷水和冰并进行搅拌，使体积达5000 L,温度为40⁰C。仔细用111 kg盐酸和111 L水的混合物中和，直至对硝氮黄试纸呈极弱的酸性反应。加水使充满反应器，在36-40⁰C过滤，水洗压滤机。洗水与滤液合并，用硝氮黄试纸检验，然后加水稀释至12000 L,于2-3小时内用450 kg盐酸仔细沉淀，最后应对甲基橙呈酸性，过滤，水洗至不含酸。

产品二苯胺-2-羧酸为白色片状物，熔点182-183⁰C.  得到1200 kg滤饼，相当于460 kg干品，收率为92.8%。

回收380 kg苯胺，有46 kg存在于苯胺水中，理论需要量是203 kg。

PB 25624, 1047. Phenylanthranilic acid. 德文生产工艺。未抄录。

PB 74181, 2363-2367. Phenylanthranilic acid. 德文生产工艺，1938年。未抄录。

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陈忠源   2017年8月8日       于 无锡   明辉国际。