CAS号 [51-66-1] 生产工艺  对乙酰氨基苯甲醚

CAS名: Acetamide, N-(4-methoxyphenyl)-, 参考文献: Beil. 13, 461, E¹, 160, E², 243, E³, 1056, E⁴, 1092.

用途:染料，如C.I.冰染重氮组分1，C.I.分散蓝79. 医药，如Antipyretic, Antineuralgic 等

生产工艺文献:以下是本人以前所整理的资料。

BIOS 986, 14-17. (=胶卷PB 77764) No. 3  Acet-p-anisidide distilled specification No. 1851-0 (1-Methoxy-4-acetylaminobenzene)

I. G. Offenbach)    英国人译自德文。抄录如下。

反应式:本人有加注。译者未说明译自哪个德文原件，为什么，不知道。
 

Materials charged:

a.Theory 2600 kg + 1268.3 kg = 3488 kg + 380.5 kg  water

b.Actual 2600 kg + 1700 kg  à 3453 kg + 400 kg acetic acid at 100% (recovery). The acetic acid is 134.1% of theory.

Yield:3470 kg. crude at 99.5% strength = 3453 kg. pure = 132.8 pts/100 pts. P-anisidine = 99% of theory.

1. Mixing pan  （acetylation pan）cast-iron pan double tile-lined, contents 5100 litres (1122 gall.). Heating coil of V₄A steel, cover plated with V₄A, having a manhole, and thermometer pocket connections of V₄A. Ascending pipe (vapour pipe) of V₄A, 2 siphon pipe connections of V₄A to column. Aluminium sucking-in pipe for anisidine and acetic acid. Gate type stirrer (Lit: Lattice) of V₄A, 25 r.p.m.

2.5 Iron cooling pans.

3.Auxiliary apparatus.

(a) V₄A column, 30 cm.dia. x 4.7 m. high filled with Raschig rings. (b) V₄A dephlegmator, 0.63 sq. c. cooling surface. 3 cooling water outlets at different heights. (c) Coil cooler (condenser) of V₄A 2 sq. m. cooling surface. (d) Measuring vessel of V₄A, capacity 750 litres, with bottom outlet. (e) Storage vessel for recovered material.    (f) Catch receiver with horizontal connection to the vacuum pump, filled with caustic soda solution. (g) 2 Intermediate receivers (i.e. catch vessels) filled with stones. (h) 1 catch vessel provided with a duster filter bag.    (i) 1 vacuum pump. (j) 1 disintegrator. (k) Compressed air connection between dephlegmator and condenser.

Process: Raw Materials: 2600 kg. p-anisidine = anisidine fused Spec. No. 2305.0

1700 kg. acetic acid technically pure Spec. No. 1309.1 or enough of this acid to make up 1700 kg. total acetic acid with the recovery from the previous batch.

For the first batch, 1700 kg. acetic acid are sucked into the mixing pan. For subsequent batches, the recovery from the last batch is used along with enough fresh acetic acid to make a total of 1700 kg. acetic acid at 100%. To the acetic acid 2600 kg. p-anisidine previously melted up in containers is sucked in.

Distillation:

Next, the batch is boiled 2 hr. under reflux and then using the dephlegmator, dilute acetic acid is gradually distilled to the storage vessels, (3e), the cooling water being taken off the top of the dephlegmator.

The temperature is then reduced from 120⁰ to 116⁰C. So as to rice again slowly 8 hr. after the beginning of the distillation. The acetic acid content of the aqueous distillate, which is 4% at first, increases steadily in the course of the distillation. When it rises to 35%, i.e. about 175⁰C. internal temperature. The distillate is collected in the measuring vessel (3d) as the recovered acid for use in the next batch. The first fraction of distillate, about 450 litres, contains about 50 kg. acetic acid as 100 and is discarded.

Distillation is continued until internal temperature is 198⁰C. and afterwards at about 180⁰C. the cooling water is taken out from the middle, and later the lowest outlet of the dephlegmator. The water is turned off for the last part of this stage. Distillation takes about 36 hr.

Vacuum distillation:

After releasing the heating steam, the pan is gradually evaculated, the internal temperature falling from 198-175⁰C. The vacuum should be 72-73 cm. of mercury (i.e. 30-40 mm.hg. abs.).

When distillation, at first, very rapid, slows down, steam is turned on again, and the charge is distilled out of the pan until the temperature is 202⁰C. When this temperature is reached the vacuum is released and the steam shut off. Vacuum distillation takes about 6 hr. The product is blown without preliminary cooling to the cooling pans; and after cooling it is broken out of them and ground in the disintergrator.  The finished product shall not contain more than 0.2% unchanged p-anisidine. And shall be of 99-99.5% purity.   

日文译文  细田豊 《理论制造染料化学》 1957年。 P. 655.  アセト-o-アニシシ^”ンとほとんと^”同样にして制する。收率99%。

中文摘译文  张澍声 《精细化工中间体工业生产技术》1996年。P. 78. N-乙酰基对氨基苯甲醚。 译自BIOS 986,13.  抄录如下。

对于第一次反应，醋酸加料量为1700 kg。 在随后的反应中，由前一次反应回收的醋酸和新的醋酸一齐加入，其总量要达到1700 kg 100%醋酸。在5100 L酰化锅中加入1700 kg 100%醋酸后，再加入2600 kg 对氨基苯甲醚，是将其预先熔融后吸入的。将反应物沸腾回流2小时，然后通过分凝器将稀醋酸缓缓蒸馏到贮槽中，冷却水从分凝器顶部流出。

然后温度从120⁰C降底到116⁰C,蒸馏开始8小时后温度再缓缓上升。蒸馏出的醋酸水溶液中的醋酸含量最初为4%，在蒸馏过程中稳步增长。当其增加到35%，即内部温度约175⁰C,馏出物收集在计量槽中，作为下一次反应的回收醋酸。

馏出物的初馏份约450 L,含有约50 kg醋酸，弃去不用。继续蒸馏至内部温度为198⁰C,可以停止分凝器中部得冷凝水（共有上中下三部分冷却水），然后在约180⁰C将下部冷却水停止。蒸馏进行约36小时。

真空蒸馏 – 停止加热，将酰化釜缓缓抽真空，内部温度从198⁰C降至175⁰C,真空度应为30-40 mmHg (绝对)。蒸馏最初是很迅速的，渐趋缓慢，重新加热，物料从釜内蒸馏出来，直至温度达202⁰C.达到此温度后，释去压力，停止加热。真空蒸馏约6小时。

产品放入冷却锅中，冷却后将其击碎，在粉碎机中研磨，最终产品纯度应为99-99.5%，未变化的对氨基苯甲醚不高于0.2%。  

PB 70422,1873-1875. (共3页) P-Acetanisidine. By Wollemann.1943年5月25日。德文生产工艺。1.5美元。未抄录。 

国内研究动态:

天染，天染所。分散藏青2GL 试制总结   [J] 染料工业，1976, 2, 14-15.  对-乙酰氨基苯甲醚的制备。抄录如下。

配方: 对-氨基苯甲醚  100%  24.6公斤； 醋酸  98%  60公斤；  醋酐  100%  22.4公斤。

操作: 将醋酸和对-氨基苯甲醚加入1³ 锅内，在45-50⁰C,搅至物料全溶，然后在夹套中通冰盐水，冷却至5⁰C,慢慢加入醋酐。加料速度控制温度不超过5⁰C. 加完醋酐后，升温到70⁰C, 在70⁰C保持半小时，然后冷却至20⁰C,将反应物加入到内盛30升冰水，代有搅拌的反应釜中。加完反应液后，再搅拌20分钟左右，抽滤，抽干，得浅灰色产品。熔点126-130⁰C.  

朱华 吕积国  陈刚  第六届染料学术报告会论文集 1997年。P. 205. 对乙酰氨基苯甲醚的制备。抄录如下。

    在装有搅拌器，温度计，长分馏柱装置的三口瓶中，加入对氨基苯甲醚及冰醋酸，加热回流反应，蒸出反应产生的水，当反应完成后，减压蒸去过量的冰醋酸，然后冷却到170⁰C放料。经冷却，结晶，粉碎得白色固体，熔点124-125⁰C,纯度＞98%，收率为98.5%。

国外考察报告: [J] 染料工业,1984,1,19. 邻氨基对乙酰氨基苯甲醚的制备 抄录如下。

罗马尼亚方法; 将对氨基苯甲醚加热融化，搅拌，于140⁰C加入醋酐进行酰化，然后于160-165⁰C反应3小时。物料放入10-15⁰C冰水中稀释析出，过滤，于60⁰C烘干，粉碎。

加注: 

抄录文是否有用，请读者思考。我是作为养老的动力在工作，希望能对年轻的技术人员有点用！否则是浪费时间，浪费大家的精力。总之是请大家多提意见，以便今后改进工作，谢谢！ 

陈忠源  2017年2月13日        于 无锡   明辉国际。