CAS号 [94-02-0] 生产工艺。   苯甲酰乙酸乙酯。

CAS名: Acetic acid, benzoyl-, ethyl ester.     历史参考文献：Beil. 10. 674; E1, 320; E2, 467; E3, 2991.

用途：酸性红143。 酸性红143:1。 颜料红263。 医药。 LookChem网登录生产与经营单位105家。

BIOS 1149, 115-116. （=胶卷PB 80376）。 Benzoylacetic ester.  (for Naphtol 50313). (Höchst).  英国人译自德文（无资料来源）。

反应式: 本人有加注，未抄录德文原件。

Benzoylchloride is condensed with acetoacetic ester and the resulting compound hydrolysed with ammonia.  An abstract from the original I.G. process. 

Plant:  1.  Iron condensation vessel, 7 cu.m., coil and iron stirrer.    2.  Iron separator.  5 cu.m.     3.  Iron agitated vessel,  2.5 cu.m., coil.

       4.  Clarifting press.    5.  Rubber-lined precipitating vessel,  2.5 cu.m.,  rubber-covered anchor stirrer.  Jacketed.

Process:

The reaction pan (1) is charged with 1000 l. of water, 500 l. of naphtha C, 130 l. of 33% caustic liquor (= 180 kg.), 390 kg. of acetoacetic ester (= 3.0 kg. mol.) and 500 kg. of ice.  The remperature should be 5-8℃.

To the mixture is run in simultaneously 422 kg. of benzoyl chloride (= 3.0 kg. mol.) and 540 l. of 33% caustic liquor at such a rate that the temperature does not rise above 150 during the addition of the first half and rises finally to more than 200.  The reaction mixture is stirred for a further hour and than heated to 35℃.

The batch is now blown to item (2) and allowed to settle.  After 11/2 hours, the lower aqueous solution is run into (3), stirred with 10 kh. Kieselguhr and screened through (4) into (5).  Here 160 kg. of ammonium chloride are added and the mixture stirred overnight at room temperature.  80-100 kg. of common salt are now added to give a Sp. Gr. Of 1.13.  The benzoylacetic ester separates out slowly as an oil and is removed via the separating vessel.

Yield = 415 kg. = 72% theory.

The naphtha remaining in item (2) is run to (3) and distilled with steam.  After separating, the moist recovered naphtha can be used again.

Recovery = 475 l. = 95% theory.

Qyality Tests:  Benzoyl chloride:  Sp.Gr.  1.211; B.Pt.  1980.  M.Pt.  -10.    Acetoacetic ester:  commercial product.    Naphtha C:  B.Pt. 130-1900.

             Sp.Gr.  0.88.    Benzoylacetic ester  Sp.Gr.  1.118/200.  B.Pt. 149℃./ 12 mm.     Strength is estimated by alkali hydrolysis.

Raw Materials usages per ton (1000 kg.): 每吨原料单耗：略。

张澍声 《精细化工中间体工业生产技术》1996年。 P. 29.  苯甲酰乙酸乙酯。 译自BIOS 1149, 115.

在7000 L缩合锅中加入1000 L水，500 L石脑油，130 L 33% 氢氧化钠溶液，390 kg 乙酰乙酸乙酯 (3.0 kg – mol) 和500 kg冰，温度应为5-8℃。

向混合物中同时流入422 kg 苯甲酰氯(3.0 kg – mol) 和540 L 33% 氢氧化钠溶液，其流速的控制是，在加入前一半小时温度不超过15℃，最终达到20℃以上。反应混合物应呈明显碱性，加完后再搅拌1小时，然后加热到35℃。

物料压送到5000 L分离器中，静置1.5小时，放出下层水溶液，加入10 kg硅藻土，压滤。滤液加入160 kg氯化铵，室温下搅拌过夜。加入80-100 kg 食盐，使比重为1.13. 苯甲酰乙酸乙酯以油状物分离出来，得到415 kg产品，收率72%。

石脑油水蒸汽蒸馏回收，可以复用。回收475 L，回收率95%。 苯甲酰乙酸乙酯比重1.118（20℃），沸点149℃/ 12 mm。

PB 73377, 2394-2396.  Benzoylacetic ester.  未抄录。

学习与思考：

本中间体原来是用于Naphtol 50313的生产，其结构式需査PB 74741品种卡片。用于酸性红143:1是后来开发的，LookChem网登录生产与经营单位有5家。用于颜料红263，有3家。这应该是创新！

陈忠源  2019年4月。