CAS号 [128-93-8] 生产工艺 1-溴-4-甲氨基蒽醌

CAS名:  9,10-Anthracenedione, 1-bromo-4-methylamino-参考文献:  Beil. 14, 185. E¹, 447. E³, 424. E⁴, 443.

用途: C.I. 分散蓝3；24.  C.I. 酸性蓝27.  C.I. 溶剂蓝11；63；102.  C.I. 碱性蓝22 等。

生产工艺文献:

BIOS 1484, 19. (=胶卷 PB 86139) 1-Methylamino-4-bromoanthraquinone (Leverkusen)  英国人摘译自德文。抄录如下。

反应式: 本人有加注。
 

   溴化氢回收利用： 2 HBr + Cl₂ à 2 HCl + Br₂

   除余溴： 2 NaHSO₃ + Br₂ à 2 NaBr + SO₂ + H₂SO₄ 

Method:

In an iron vessel of 1000 l. capacity 250 kg. 1-methylaminoanthraquinone is dissolved in 1250 kg. 96% sulphuric acid and when dissolved the solution is blown to a tile-lined vessel containing 8000 l. water. The paste is filtered off, washed and the cake transferred to a 10,000 l. tile-lined vessel containing 1000 l. water, 900 kg. ice and 75 kg. 30% hydrochloric acid. Another 600 kg. ice is added and the suspension stirred.

A mixture of 114 kg. bromine in 500 kg. 30% hydrochloric acid is diluted to 1600 l. with water in a tiled vessel and added to the suspension of the 1-methylaminoanthraquinone at 10⁰C.

30 kg. Chlorine is added and the mixture stirred ¹/₂ hour. If there is no free halogen 10 kg. bromine in 50 kg. 30% hydrochloric acid is added. Bisulphite is then added, the mixture heated to 80⁰C., filtered, washed neutral and dried at 70⁰C.       Yield = 328 kg.

日文译文。 细田豊 《理论制造染料化学》 1957年。 P. 570. 

中文译文。 张澍声 《精细化工中间体工业生产技术》1996年。P. 237.  其中，10⁰C。误写成0⁰C。

FIAT 1313,II, 222. (=胶卷PB 85172) 1-Methylamino-4-bromoanthraquinone. 美国人摘译自德文。抄录如下。

Add 250 kg. 1-methylaminoanthraquione to 1250 kg. 96% sulfuric acid. When all is dissolved, drown in 8000 l. water. Filter in press but do not wash or blow.

Add cake to 1000 l. water, 900 kg. ice, and 75 kg. 30% hydrochloric acid. Add further 600 kg. ice and agitate until uniform. Then below 10⁰C, add solution of 114 kg. bromine dissolved in 500 kg. 30% hydrochloric acid and diluted to 1600 l. with water.  Add 30 kg. Chlorine. After stirring further ¹/₂ hour there should still be unreacted halogen. If not add 10 kg. bromine dissolved in 50 kg. hydrochloric acid.

Destroy excess halogen by adding a few liters of sodium bisulfate solution. Heat to 80⁰C. Filter in press and wash neutral. Dry at 70⁰C.  Yield is 328 kg. dry.

PB 25624, 1287-1291 (共5页)    4-Brom-1-methylaminoanthrachinon.  德文生产工艺规程原件。未抄录。

   本生产工艺规程，很详细，BIOS 和 FIAT 是摘译文，但未说明译自它，二者译法略有差别。 

专利动态:  主要是溶剂选择

FR. 1431211. 混合溶剂。GB. 1239778. 硝基苯. Su. 901580. 二氯甲烷.

 Su. 1330129. 甲醇.  CN. 1296999.  二氯甲烷。

陈忠源    2016年10月19日       于 无锡   明辉国际。