CAS号 [90-04-0] 生产工艺       邻氨基苯甲醚

CAS名: Benzenamine, 2-methoxy-参考文献: Beil. 13, 358; E1, 108; E2, 165; E3, 754; E4, 806.

用途: 冰染重氮组分13。 冰染偶合组分20, 45。 酸性黄66。 酸性红4, 5, 26:1, 56, 107, 264。 酸性紫12。 碱性红76。

直接黄44, 49, 132, 142。 直接橙70。 直接红14, 24, 26, 55, 64, 72, 123。 直接紫63。 直接蓝183。 分散橙29。

溶剂黄20, 72。 溶剂红1。 颜料黄194。 颜料红67。 医药和香兰素等。

生产工艺文献:  按手头资料整理如下：

BIOS 986, 51. （=胶卷PB 77764）  No. 16.  o-Anisidine. (I.G. Griesheim).  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。德文原件未抄录。

Up to 70 tons a month of o-anisidine have been made. There were 8 reducers, each taking a 4 ton charge of nitro compound, used as required for various reduction processes. This reduction, with many similar ones, is done in a series of reducers originally designed for aniline. They are of the usual type and tiled-lined with a heavy stirrer of 5% Silicon iron with renewable blades, with ample vapour pipe and condenser, and take 4000 kg. of nitrobody per charge. The reducer covers are convex downwards. The iron borings are delivered to a separate shed, picked up by a magnet, dropped through a screen to remove large pieces of metal, into a Kellorgang Mill, and thence to a sieve to pass the fines and return the coarse material to the mill. The fine material is delivered an overhead hopper, from which are filled a number of weighing cans travelling on an overhead rail over a weighing machine to the reduction building. These can of about 3 cu.ft. capacity have conical bottoms with a simple discharge valve through which the iron can be run into the funnel with wide stop cock on the lid of the reducer. The powdered iron itself acts as a seal against loss of vapour until the weighing can is empty.

The reducer is charged with 2000 lit. boiling water, 15 kg. formic acid, 1500 kg. ground iron, 100 kg. nitro anisole C.Pt. 10℃. 1000 kg. more nitroanisole is added slowly, then 15 kg. formic acid and 1500 kg. iron, then 3000 kg. more nitroanisole slowly and 1000 kg. more iron.

The finished batch is allowed to settle, the oil layer sucked off through an adjustable stand pipe, and the residue steamed for removal of anisidine, the distillate going through a separator. This separator and all liquor lines, being made for general service on various products, were steam heated. Crude anisidine oil is allowed to settle, any sludge being deposited should not be returned to the reducer. Filtration of the oil is considered unnecessary. The collected settled oil is distilled in vacuum through a small column and successive batches mixed to ensure uniformity. No high degree of fractionation is needed because the nitroanisole used is of high quality.

132 of o-nitroanisole yield 100 of o-anisidine of C.Pt. 6.6℃. The iron sludge is delivered to draining grounds having a liquor-tight wooden fence round them. The liquor drains out through the earth into a collecting channel outside the fence, and goes to waste. The sludge when somewhat dried is filled off into tip wagons for return to the Ruhr iron furaces.

细田豊  《理论制造染料化学》 1957年。 P. 481.  译自PB 77764.   o-Anisidine.  抄录如下。

水2 t，铁粉1.5 kg, 義酸15 kgを煮沸し，ニトロアニソ”-ル1100 kgを徐加し，義酸15 kgと铁粉1.5 tを追加，ニトロ3 tと铁粉1 tを追加する。还原终れは”静置して上澄液をぬき，これは小さなカラムて”减压蒸馏し，铁の残渣からは水汽蒸馏て”アニシシ”ンを追出す。3100 kg (cp 6.60).

张澍声  编译。 《精细化工中间体及产品生产工艺》 2006年。 P. 417.   译自BIOS 986, 50.  邻氨基苯甲醚。  抄录如下。

还原锅为衬砖铁锅，重型搅拌器用5%硅铁制成，桨叶可以更换，还原锅盖向下凸出。铁屑在分离棚中用磁铁拾起，再经过筛，以除去大块金属。再经研磨机研磨，筛出细粉，粗粒子仍回到研磨机中。

还原锅中加入2000 L沸水，15 kg甲酸，1500 kg铁粉和100 kg熔点为10℃的邻硝基苯甲醚，开始启动反应。再缓缓加入1000 kg 邻硝基苯甲醚，15 kg甲酸和1500 kg铁粉。再缓缓加入3000 kg邻硝基苯甲醚和1000 kg铁粉。

反应结束后，静置。通过可调节的立式管抽吸出油层，残余物通直接蒸汽蒸馏出邻氨基苯甲醚，馏出物经过一分离器。粗品油层静置，沉降分离任何铁泥。油不需进行过滤，收集的静置油经一短塔真空蒸馏，并将几批混合，以求均匀。

132 kg邻硝基苯甲醚得到100 kg熔点6.6℃的邻氨基苯甲醚。

 PB 70189, 6636.  o-Anisidine. 产品分析方法。Nr. 252.  未抄录。

 PB 74239, 133-134.    o-Anisidine.  1940年 德文生产工艺原件。 未抄录。

 上海市有机化学工业公司。 《染料生产工艺汇编》  1976年。 P. 42.    邻氨基苯甲醚。抄录如下。

还原反应:  在还原锅中加入23%的硫化钠4150升，搅拌，加热至106℃，在沸腾状态下，在2小时内加入邻硝基苯甲醚1170公斤。加完后升温驱走空气，然后加压回流3小时，压强为0.5-0.6公斤/厘米2表压，温度为118-120℃。取样测定，重氮值≥98%为合格。合格后冷却搅拌2小时。在50-60℃静置2小时，分去废水。经真空蒸馏得重氮值≥99%，凝固点≥4.5℃的浅棕色透明的邻氨基苯甲醚。  抄注: 这是内部资料，但已有人抄录，以正式出版物出版！

陈忠源   2017年11月9日