CAS号 [882-36-0] 生产工艺        N-苄基乙酰乙酰胺

CAS名: Butanamide, 3-oxo-N-(phenylmethyl)-      历史参考文献: Beil. 12. E2, 559; E3, 2298.

用途: 有机合成。   生产工艺参考文献: 按本人手头资料整理如下。

BIOS 1153, 312-313.（=胶卷PB 85687）。 Acetoacetbenzylamide. (Hoechst).  英国人译自德文（未说明资料来源）。   抄录如下。

反应式: 本人有加注。暂未找到德文原件。

Plant:  设备:  以下抄录不再分项。

 1.  1 Jacketed vessel, aluminium, 1 cu.m. capacity, with agitator。  2.  1 Storage vessel for xylene, C.I., 10 cu.m。  3.  1 Measure vessel for xylene, aluminium, 0.75 cu.m。  4.  1 Measure vessel for acetoacetic ester, aluminium, 0.2 cu.m。  5.  1 Dissolving vessel for base, with coil and stirrer. aluminium, 0.8 cu.m。  6.  1 Cooling vessel with stirrer, aluminium 1 cu.m。  7.  1 Cooling vessel with stirrer, aluminium, 2 cu.m。  8.  1 Centrifuge, capacity 150 kg。  9.  1 Column with condensaer etc. aluminium。   10.  1 Drying chamber.

Process:

(1) is charged with 400 l. of xylene from (2) through (3), and a solution of 1 kg. of triethanolamine in 3 l. of ethanol is then added, 20-30 l. of this solution is distilled to remove water, and 103 kg. of acetoacetic ester are then added.  The mixture us refluxed (200 l. per hour) and a solution of 50 kg. of benzylamine in 100 l. of xylene is blown in from (5) during 45 min. (1-1.5 atm. nitrogen used for blowing).  With a reflux ratio of 3:1 throughout the addition, 150 l. of solvent are removed.  Boiling is continued for 15 min, and the outflow of the distillate then throttled to cause an accumulation of alcohol at the top of the column.  This is then released and the temperature at the head gradually rises to 1370.  The hot solution is then immediately discharged into (6) and cooled to 400 with vigorous agitation.  The partly crystalline mass is then transferred to (7) where it is cooled further to 5-70.  The crystals are centrifuged in (8), washed with 60 l. of xylene, and dried in (10) at 70-800.

Concentration of the xylene to half-volume gives a further 4-5 kg. of product.  After purification with sulphuric acid the xylene is re-used.      Yield = 65 kg. at 100% (estimated with NaNO2). = 73% theory on benzylamine.

Specifications:  Acetoacetic ester.  Acidity ≯ 0.3% calc. as acetic acid.  Benzylamine  B.Pt. 1850. Sp. Gr. 0.981 at 200.

Acetoacetbenzylamide  M.P. 102-105℃.

Services (per tone of product):  Electricity  1800 kw-hr.  Steam  30 tones,   Water  2500 cu.m.   Brine. Calc. as ice.  1.5 tones.

张澍声  《精细化工中间体工业生产技术》 1996年。 P. 147.   乙酰乙酰苄胺。 译自BIOS 1153, 312.            抄录如下。

在1000 L铝釜中加入400 L二甲苯和 1 kg 三乙醇胺在乙醇中的溶液。20-30 L该溶液进行蒸馏以除去水分，然后加入103 kg 乙酰乙酸乙酯。混合物回流（200 L/hr），于45分钟内用1-1.5巴氮压入50公斤苄胺在100 L二甲苯的溶液。在整个加料过程中回流比为3:1，除去150 L溶剂。继续沸腾15分钟，蒸馏物的流出进行节流，引起醇在塔顶的积聚。然后又放开节流阀，塔顶温度缓缓上升到137℃。热溶液立即放至冷却槽，剧烈搅拌下冷却至40℃，部分结晶的反应液又转移到另一冷却槽中，进一步冷却到5-7℃。结晶离心过滤，用60 L二甲苯洗涤，在70-80℃干燥。

二甲苯浓缩液到一半体积，又得到4-5 kg产品。二甲苯用硫酸精制后可以复用。

得到65 kg 100% 产品，以苄胺计收率73%。乙酰乙酸乙酯酸度不大于0.3%（以醋酸计）。苄胺沸点185℃，比重（20℃）0.981。乙酸乙酰苄胺熔点102-105℃.

加注:  本人抄录目的是希望通过它了解产品的历史，同时可作为外文学习参考！一位Unnecessary Old man !

陈忠源 2018年1月25日。