CAS号 [6331-70-0] 生产工艺 2-乙氧基-5-甲基苯胺

CAS名; Benzenamine, 2-ethoxy-5-methyl- 历史参考文献: Beil. 13. 572.

用途: C.I. 冰染重氮组分45。反应类别: 羟基烷基化，硝基还原。

生产工艺参考文献: 按本人手头资料整理如下：

BIOS 1149, 73-75. （=胶卷PB 80376）3-Amino-p-tolyl ethyl ether (Leverkusen). 英国人译自德文（未说明来源） 抄录如下。

反应式: 本人有加注。本人暂未找到德文原件。
 

Stage 1.  3-Nitro-p-tolylethyl ether:

A cast iron agitated autoclave (capacity 6000 l.) is charged with 2100 l. of ethanol, 1650 kg. of 3-nitro-p-cresol, 432 kg. of 50% caustic soda, 654 kg. of 30% caustic soda and 195 kg. of soda ash. The autoclave is closed and agitated, and 900 kg. of ethylchloride added. With steam at 2 atm. on the jacket the autoclave is heated to 100⁰C. The pressure is now 8-9 atm. The temperature continues to rise to 130⁰C. and the pressure to 9-10 atm. and these conditions are held for 8 hours. After this length of time the reaction mass is cooled to 50⁰C. and tested in the laboratory for completion of reaction.

The ethanol is distilled off with direct steam and purified in the ethanol distillation plant for re-use.

The product, after distilling off the ethanol, is blown into a washer and washed neutral with water. As little water as possible is used on account of the solubility of the product. The washed oil is dried under vacuum.

Yield: 1710 kg. =87.5% theory assuming 100% strength.

Stage 2.  3-Amino-p-tolyl ethyl ether: Outline: 3-Nitro-p-tolyl ethyl ether is reduced in aqueous suspension with iron and distilled.

Plant: 1 Reducer, 2500 l. capacity, with water condenser. 1 Still. 1 Vac. pump. 2 Receivers.

Materials: 3-Nitro-p-tolyl ethyl ether 400 kg. Iron powder 380 kg. Formic acid 90% 7 kg. Caustic soda 10 kg.

Process:

The reducer is charged with 600 l. of water, 380 kg. of iron powder and 7 kg. of 90% formic acid, and heated to 75⁰C with direct and jacket steam. 400 kg. of 3-nitro-p-tolyl ethyl ether are charged in during 8-9 hours with the temperature rising to 85⁰C,; this temperature is then held for a further 2 hours when reaction should be complete.

The reduction is heated to 100⁰C, neutralized with caustic soda, and steam distilled. The oil with some water is transferred to the still and distilled in vacuo. Water with some oil distils at 40-60⁰ during 4 hours, the main product then distilling at 120-135⁰ during 10 hours. The aqueous forerunnings, amounting to 300 l., are charged back to the next reduction.

Yield = 95% theory.  

张澍声 编译。《精细化工中间体工业生产技术》 1996年。P. 27. 3-氨基-4-乙氧基甲苯。译自BIOS 1149, 73. 抄录如下。

（一）3-硝基-4-乙氧基甲苯: 在6000 L铸铁高压釜中加入2100 L乙醇，1650 kg 3-硝基-4-羟基甲苯，432 kg 50% NaOH溶液，654 kg 30% NaOH溶液和195 kg Na₂CO₃. 关闭高压釜，开动搅拌，加入900 kg 氯乙烷。加热至100⁰C，压力为8-9巴；继续升温至130⁰C，压力9-10巴，在此条件下保持8小时。然后冷却到50⁰C，用直接蒸汽蒸馏出乙醇。产品用水洗至中性，考虑到产品的可溶性，要用尽可能少量的水。然后真空干燥。

得到1710 kg 3-硝基-4-乙氧基甲苯，假定为100%，收率87.5%。

（二）3-氨基-4-乙氧基甲苯: 在2500 L 还原锅中加入600 L水，380 kg 铁粉和7 kg 90% 甲酸，加热到75⁰C,于8-9小时内加入400 kg 3-硝基-4-乙氧基甲苯，同时温度升至85⁰C，再在85⁰C保持2小时，还原完成。

还原物加热到100⁰C，用氢氧化钠中和，水蒸汽蒸馏。带少量水的油转移到蒸馏釜中，真空蒸馏，于4小时内在40-60⁰C蒸馏出水和一些油，然后在10小时内于120-135⁰C蒸馏主产品，含水的前馏份300 L回到下次还原中。收率95%。 

上海市有机化学工业公司。《染料生产工艺汇编》 1976年。P. 56-58. 3-氨基-4-乙氧基甲苯。抄录如下。

3. 烷基化反应: 在高压锅内加入2-硝基-4-甲基苯酚153公斤和乙醇300升，搅拌，加入40% 液碱198升，于35-40⁰C保温1小时。压入一氯乙烷115.2公斤，于1小时内升温到100⁰C，压强为8-9公斤/厘米²表压。再于1小时内升温到130⁰C,表压为12公斤/厘米²，保温8小时。冷却到80⁰C，加入水180升，加热蒸出乙醇，当温度升到100⁰C以后停止蒸馏。加入水90公斤，搅拌15分钟。然后压至水洗锅内，加水扩大体积至3000升，搅拌30分钟，静置4小时以上，将下层物料分离至保温贮槽中，废水放掉。

4. 还原反应: 在还原锅内加入二硫化钠101.4公斤（配成20%溶液），加热到95-100⁰C,在此温度下于1.5-2小时内均匀加入烷基化物。加完后保温2小时。再升温到110-120⁰C,表压为1公斤/厘米²以下，保温20小时。取样测定，凝固点大于35⁰C时为合格。合格后，冷却到25⁰C进行放料。物料水洗至中性。

烷基化反应和还原反应两步合并收率为72%。 

拜耳公司 1978年产品规格。Ethylcresidine.（抄录文仅供参考！）抄录如下。

Form supplied: Distilled

Product properties: Light brown, crystalline mass.  The product is sensitive to light.

Technical data: Content (gas chromatography):  min. 98%.   Solidification point (dried): min. 42⁰C.

Uses: Intermediate for dyestuffs. Standard packing:  Rolling channel drum, contents approx. 200 kg.

Storage: Stable for min. 2 years when properly stored in closed standard packing.

Toxicity and hazards: Blood poison ! Contamination of the skin and inhalation of dust and vapours can be hazardous to health.

Staining!Protective gloves and clothing should therefore be worn when handling the product.

加注: 本人所说，暂未找到是指德文胶卷目录和德文资料原件。 

陈忠源  2017年7月26日          于 无锡   明辉国际。