C.I. 冰染重氮组分29（C.I. 37140）生产工艺。  CAS号 [5339-62-8]

色基CAS名：Benzenamine, 5-(ethylsulfonyl)-2-methoxy-     历史参考文献：Beil. 待检索。

发明者：Modersohn,Schleifenbaum 1934年。《Colour Index》，生产工艺参考文献：BIOS 1149, 40-43; FIAT 764 – Echtrot GTR Baase.

BIOS 1149, 42-43.（=胶卷PB 80376）。 4-Ethanesulphonyl-o-anisidine = Fast Red GTR Base. (Le.) 英国人译自德文，无资料来源。

反应式：本人有加注，原料和重氮体暂未找到其CAS号。德文原未抄录！
 
Outline:  概要：4-Ethanesulphonylacet-o-anisidine is hydrolyses with acid. 

Plant: 设备：

1 Tiled C.I. vat, 10000 l. capacity;   1 Tiled C.I. blow-egg 8000 l. capacity;   1 Press for residue;   1 Tiled C.I. vat, 10000 l. capacity:

1 Iron,rubber-covered, nutsche, 3000 l. capacity;   1 Tiled blow-egg 8000 l. capacity.

Materials:  投料量：

4-Ethanesulphonylacet-o-anisidine   632 kg. 100% (=170 kg. nitrite);  Hydrochloric acid  400 l.;  Monohydrate   110 kg;

Caustic liquor as 100% NaOH   300 kg;   Sodium acetate anhyd.  25 kg.

Process:  操作步骤：

The vat is charged with 2000 l of water, 400 l of hydrochloric acid and 110 kg of monohydrate, and heated to 60℃ with direct steam.  The 4-ethanesylphonylacet-o-anisidine is charged in, the batch heated to the boil and held for 3 hours.

Test: A sample on cooling must show no oily drops and must remain in solution.  The contents of the charge must be estimated by diazotization.

When fully hydrolysed, 35 kg of carbon are added, and the batch is cooled to 600 with agitation.  The batch is settled overnight and then dropped the next morning to the blow-egg and blown through the press which is washed to a total volume of 4500 l.  Caustic liquor is added in a thin stream until Congo paper is only coloured a faint blue, the remainder of the mineral acidity then being removed with sodium acetate.  Approx. 360 l of 50% caustic liquor are required.

It is dropped to the nutsche, washed with 400 – 500 l cold water and pulled as dry as possible.  The product dried and ground and standardized to 90% with salt for sales as Fast Red GTR Base.   Yield = 88% theory.   Quality: C. Pt. 102 – 1030.

FIAT 1313, I, 45-46.（=胶卷 PB 85172）。 (3-Amino-4-methoxyphenyl)-ethylsulfone. (Leverkusen).  美国人译自德文，无资料来源。

Apparatus:  设备：

2 – 10,000 l. cast iron tile lined vat;  2 – 8,000 l. tile lined blow case;  1 – filter press for residue;   1 – rubber coated iron nutsch of 3,000 l. capacity.

Charge: 投料量：

632 kg 2-acetylamino-1-methoxy benzol-4-ethyl sulfone 100% = 170 kg Nitrite*;  400 l. hydrochloric acid;  110 kg H2SO4 monohydrate; 

300 kg caustic soda 100%;  25 kg sodium acetate anhydrous;  35 kg carboraffin (purifying carbon).

*Nitrite equivalent, e. g. 170 + 69 X 257 (Mol. Wt.) = 632.  *Nitrite = 亚钠量。

Process:  操作步骤：（Jan. 1, 1940）= 1940年1月1日生产工艺。

2000 l. water, 400 l. hydrochloric acid and 110 kg of H2SO4 monohydrate are charged to a 10,000 l. vat.  This is heated with direct steam to 60℃ and 632 kg of 2-acetylamino-1-methyl-benzol-4-ethyl sulfone 100% (170 kg sodium nitrite equivalent) are added.  The charge is heated to the boil and held at the boil for 3 hours.  A test sample upon cooling should not become oily but must remain in solution.

(Test: the free amine content of the batch is determined by diazotization of an aliquot taken from the charge.).  When the charge has been completely hydrolyzed, 35 kg of clarifying carbon is added and the charge stirred until has cooled to 60℃.  Agitation is stopped and the charge permitted to stand overnight..  The next morning the charge is drawn into the blow case, filtered thru a press to free it of carbon and the filtrate run to a 10,000 l. vat.  The press is washed with water and the washings run to the vat until the total volume of solution is about 4500 l.  A thin stream of caustic soda solution is then run in until only a faintly blue coloration is obtained on Congo Red paper, the last traces of acidity being removed with sodium acetate.  About 360 l. of 50% caustic soda liquor are required.

The material is filtered on the nutsch, washed with 400 to 500 l. of cold water and sucked well dry, then dried and ground, and standardized with sodium chloride to give Echtrot GTR Base of 90% purity.  Yield; 88% of theory.

张澍声《精细化工中间体工业生产技术》。《染料工业》编辑部 出版。1996年。P.97. （3-氨基-4-甲氧基）苯基乙基砜。译文。

在10000 L锅中加入2000 L水，400 L盐酸和110 kg 硫酸一水合物，用直接蒸汽加热至60℃，加入632 kg 100% 2-乙酰氨基-1-甲氧基苯基-4-乙基砜（相当于170 kg 亚钠），加热至沸，保持沸腾3小时。取样检验：冷却后不应是显示油状，必须保持溶解。当物料全部水解后，加入35 kg活性炭，搅拌冷却到60℃，停止搅拌，放置过夜，压滤去除活性炭，滤液流入10000 L锅中，压滤机水洗，洗水也流入锅中，至总溶液体积约4500 L。

将碳酸钠溶液以细流加入，直至刚果红试纸呈微蓝色，最后痕量的酸度加醋酸钠除去，约需360 L 50% 氢氧化钠溶液。抽滤，400 – 500 L冷水洗涤，干燥并研磨，用食盐标准化，得纯度90% 的坚牢红GTR色基。收率88%。熔点102 – 103℃。

PB 70422, 2074-2076.  Fast red Sal GTR.  By Prosiegel. = 稳定重氮盐。 1937年6月23日德文生产工艺，未抄录。

PB 82232, 254-257. “Echtrot GTR”= 2-Amino-1-methoxybenzene-4-ethylsulfone. 1940年德文生产工艺，2美元。未抄录。

国内研究动态：

穆振义（大连工学院）。 《猩红LG及红GTR色基的试制》。[J] 有机化学工业技术报导。1959, 11, 50-52. 摘录。

三。 合成方法的讨论：

我们合成是参考了BIOS 1149 的资料，认为这个资料还是可靠的，但是在资料中未提到产品分析及鉴定。（抄注：研究者不知道有PB报告！）。

I.  猩红LG 色基：本人已在2020年5月7日上网。

II。 红GTR 色基：

1. 乙基化：根据BIOS 的办法，没遇到什么困难。  2. 水解：和LG色基的水解基本相同。

结论：BIOS 的实验方法还是可靠的，我们的总产率比BIOS提高了5 – 7%。

肖 刚  杨新玮 等主编 《世界染料品种 – 2005年》。全国染料工业信息中心 出版。P. 233.  C.I. 冰染重氮组分29.

生产工艺“参考文献”。 BIOS 1149, 40-43; FIAT 764 – Echtrot GTR Base; Echtrotsalz GTR.

何岩彬 主编 《染料品种大全》。沈阳出版社 出版。2018年。P. 400.  C.I. 冰染重氮组分29.

生产工艺“参考文献”PB 70422, 2074-6 (1937); PB 82233, 254-5 (1945).

 BIOS 1149, 40-43.; FIAT 764 – Echtrot GTR Base; Echtrotsalz GTR.  有机化学工业技术报导，1959,(11): 50-52.

本人为什么要这样利用剩余的有限时间，抄录这类历史文献资料？已无需再说！

陈忠源 2020年6月12日星期五。