C.I. 冰染重氮组分42 (C.I. 37150) CAS号[97-35-8]

CAS名:Benzenediazonium,5-[(diethylamino)sulfonyl]-2-methoxy-,发明者: Neelmeier, Lamberz 1931年。

用途:C.I. 酸性红187。C.I. 溶剂红99。C.I. 颜料红5。

生产工艺文献:原版Colour Index. BIOS 1149, 28-32. FIAT 764 – Echtrot ITR Base. Echtrotsalz ITR.

BIOS 1149, 23，28-31. (=胶卷PB 80376)  Fast Red ITR Base. O-Anisidine-4-sulphondiethylamine (Leverkusen) 英国人译自德文。

反应式: 本人有加注。译者未说明译自哪个德文原件。（Leverkusen = Bayer公司）
 

Acetyl-o-anisidine-4-sulphonylchloride: [3746-67-6]

Outline: Acet-o-anisidine is heated with chlorosulphonic acid, the product drowned into ice water and the sulphonchloride filtered.

Plant:1 Cast iron vessel of 2000 l. capacity with iron propeller agitator (65-70 r.p.m.),heated with gas and with a water jacket.

1 Measure vessel for chlorosulphonic acid. 1 Wood vat of 10000 l. capacity.

1 C.I. tiled blow-egg of 8000 l. capacity. 2 Presses clothed with nitrated filter cloth.

Charge: Acet-o-anisidide  425 kg. 100% (=180 kg. NaNO₂). Chlorosulphonic acid 1800 kg. Ice 5800 kg.

Process:

The iron sulphonator is charged with 1800 kg. chlorosulphonic acid and the acet-o-anisidide charged in slowly with water cooling so that the temperature does not rise above 30⁰. When all has been charged the batch is held at 35-40⁰ for 10 hours. It is tthen blown into a vat containing 1000 l. water and 1000 kg. ice; further ice charged during the addition so that the temperature does not rise above 15⁰. Total requirements of ice 5800 kg. When all has been charged the precipitated sulphonchloride is filtered in a press, freed from as much mother liquor as possible, and washed almost free with cold water. Yield = 84-86% theory.

日文译文。 细田豊《理论制造染料化学》1957年。P. 654. 译自PB 77764. アセチル-o-アニシシ^”ン-4-スルホニルクロリト

    クロルスルホン酸1.8 tにアセトアニシシ^”ン100% 425 kgを30⁰以下て^”加え, 35-40⁰に1 h保温，水1 t +冰5.8 tに15⁰以下て^”排出，滤洗する。收率 84-86%. 

中文译文。张澍声《精细化工中间体工业生产技术》1996年。P. 141. 译自BIOS 1149, 28.（一）氯磺化。抄录如下。

在200 L铸铁磺化釜内加入1800 kg氯磺酸，在水冷却下缓缓加入425 kg 100% 乙酰基邻氨基苯甲醚（相当于180 kg NaNO₂）,

使温度不超过30⁰C,当所有物料加完后，反应物在35-40⁰C保持10小时，然后压人预先放有1000 L水和 1000 kg冰的10000L

木槽中，在加料过程中还要加冰，使温度不超过15⁰C,总计需要5800 kg冰。当全部加完后，在压滤机上过滤沉淀的磺酰氯，用冷水洗涤。收率84-86%。从日文译文和中文译文比较，译者不同，翻译内容也就有不同！这是本人抄录的目的！ 

FIAT 1313, I, 18-19. (=胶卷PB 85172)   N-Acetyl-4-methoxymetanilyl Chloride  (I.G. Leverkusen)   “Acetorthosinparachlorid” 

这是美国人译自德文生产工艺，未说明资料来源。   (Leverkusen = Bayer公司)   [3746-67-6] 抄录如下。

Apparatus: 设备:

To apparatus under 3-carboxybenzenesulfone chloride（抄注，CAS号[17243-13-9]）,add 2 wood presses with nitrated filter cloth in place of the nutsch.

Materials:  投料量:      

1 – 425 kg. acetorthoanisidine (acetorthsin 这是德文) 2 – 1800 kg. chlorsulfonic acid. 3 – 5800 kg. ice.

Procedure: 操作步骤:

Charge cast iron kettle with (2) and slowly shovel in (1), keeping temperature below 30⁰C. Then stir 10 hours at 35-40⁰C. Drown into 1000 l. water and 1000 kg. ice, adding further ice to keep temperature below 15⁰C. Run to blow case and blow into press. Wash with cold water to remove as much free acid as possible. Yield: 84-86% of theory.

Acetyl-o-anisidine-4-sulphondiethylamide:  [68540-88-5]

Outline: Acetyl-o-anisidine-4-sulphonylchloride is reacted with diethylamine.

Materials: Acetyl-o-anisidine-4-sulphonylchloride 100% 610 kg. (=160 kg. NaNO₂). Diethylamine 100% 180 kg. 
Caustic liquor 50% 170 kg. 100% 

Plant: 1 Tiled C.I. vessel of 7000 l. capacity with propeller agitator and reflux condenser. Heated with direct steam.

1 Iron, rubber-lined, nutsche of 3000 l. capacity. 1 Iron, tiled, blow-egg of 8000 l. capacity.

Process:

The tiled vessel is charged with 800 l. of water, and 180 kg. of 100% diethylamine run in with slow stirring. It warms up slightly and is cooled back to 18-20⁰. At this temperature the addition of the first half of the sulphonchloride is begun (total batch = 1600 kg. moist paste = 160 kg. NaNO₂). With rapid agitation it can be charged quickly as fast as condensation occurs. The temperature rises to 30⁰, cooling being applied if necessary. Then with slow agitation and cooling, a further 180 kg. 100% diethylamine is run in. With quick agitation the second half of the sulphonchloride is charged as described above. The reaction must always be definitely alkaline to Brilliant Yellow paper. If at the end of the reaction, the alkalinity is only slight, then a shovel-full of soda ash can be added to liberate free diethylamine from the hydrochloride salt which has been formed. The condensation takes 5 hours to complete. During the whole process no gaseous diethylamine must escape from the vessel.

The condensation is stirred for a further 3 hours, hydrochloric acid is added to convert any free diethylamine to the hydrochloride, and the batch filtered and washed from the vessel with 200-300 l. water. The filtrate is blown back from the blow-egg to the condensation vessel and a sample is made alkaline in the laboratory and steam distilled. The diethylamine in the distillate is estimated and steam distilled. The diethylamine in the distillate is estimated and the quantity of caustic required to set free all the diethylamine in the liquor is calculated (ca. 220 l.). This solution can then be used as the first half of the diethylamine required for the next batch, the process being operated as described above for a first batch.

The liquor from the second batch is not used for a third batch as the capacity of the vessel is not sufficient (some 4000 l. liquor). It is, instead, recovered as described below:

After testing in the laboratory the required quantity of caustic liquor (some 300 l.) is charged in, and the diethylamine is distilled off. At 77⁰ inner temperature, diethylamine begins to run from the condenser. Heating is continued to the boil, some 1500-1800 kg. distillate being collected. The recovered diethylamine is estimated by titration with N.H₂SO_4.

Approx. 180 kg. diethylamine 100% is recovered, and this is used as the first charge for a subsequent batch.

Yield of acetyl-o-anisidine-4-sulphondiethylamide = 97% theory. 

日文译文。 细田豊《理论制造染料化学》1957年。P. 654. 译自PB 77764. アセトアニシシ”ン-4-スルホンシ”エチルアマイト^”

    タイル张反应机に水800 lとシ^”エチルアミン180 kgを入れ，18-20⁰て^”,スルホニルクロリト^”305 kg(ヘ⁰-スト1.6 t)を加えれは^”反应して30⁰に上る.冷してシ^”エチルアミン180 kgおよひ^”クロリト^”を追する。反应はにフリリアントエロ-纸にアルカリ性を呈するようにし，もしアルカリ性か^”非常に微弱になつたらNa₂CO₃の少量を加える。8 h搅拌後盐酸を加えてシ^”エチルアミンを盐酸盐として滤過，水200-300 lて^”洗い，滤洗液にNaOH液を加えてシ^”エチルアミン(约180 kg) に遊离し次回の反应に用いる。2回目の滤液はNaOH液を加えてシ^”エチルアミンを蒸馏回收する（约180 kg）,收率97%。 

中文译文。张澍声 《精细化工中间体工业生产技术》 1996年。P, 141-142.（二）缩合:  [68540-88-5] 抄录如下。

在7000 L铸铁衬砖缩合釜中，加入800 L水和180 kg 100% 乙二胺，冷却到18-20⁰C. 在此温度开始加入一半的磺酰氯（总量为1600 kg 湿滤饼，相当于160 kg NaNO₂）。在快速搅拌下加料可以象缩合发生的那样快，温度上升到30⁰C，必要时应进行冷却。然后在缓慢搅拌和冷却下再加入180 kg 100%二乙胺，在快速搅拌下加入另一半的磺酰氯，反应必须一直是对亮黄试纸为碱性。如果在反应末期碱性仅是很微弱的，可以加入一满铲的碳酸钠，使从已经形成的盐酸盐中释出游离的二乙胺。缩合进行5小时即告完成，在整个反应过程中必须没有气态二乙胺从反应器中逸出。

缩合后再搅拌3小时，加入盐酸转变任何游离的二乙胺为盐酸盐，将反应物过滤，用200-300 L水对缩合釜中进行洗涤。滤液再压回缩合釜中。取样在实验室中转为碱性并水蒸汽蒸馏，蒸馏物中的二乙胺进行测定，计算出游离液体中全部二乙胺所需的氢氧化钠数量，约220 L，溶液能够用作下次反应所需的前一半的二乙胺。

第二次反应的液体并不用于第三次反应，因为反应器的容积不够（约4000 L液体），而是采用下述方法来回收。

在实验室中检验出所需氢氧化钠溶液数量，约300 L,将其加入后，蒸馏出二乙胺。在内温77⁰C时，二乙胺开始从冷凝器流出，继续加热至沸，收集1500-1800 kg蒸馏物。回收的二乙胺用1N H₂SO₄ 滴定。约可回收180 kg 100% 二乙胺，在下次反应中用作前一半加料。

乙酰基邻氨基苯甲醚-4-N,N-二乙基磺酰胺收率97%。  

o-Anisidine-4-sulphondiethylamide (Fast Red ITR Base): [97-35-8]

Outline: Acetyl-o-anisidine-4-sulphondiethylamide is hydrolysed with acid, clarified with carbon and the base precipitated with caustic liquor.

Plant:  略！

Materials:  Acetyl-o-anisidine-4-sulphondiethylamide 780 kg. = 180 kg. NaNO₂. Monohydrate 110 kg.

Hydrochloric acid 500 kg. Caustic liquor as 100%  360 kg. Carboraffin    30 kg.

Process: 操作步骤:

The vat is charged with 3200 l. of water, 460 l. of hydrochloric acid and 110 kg. of monohydrate, to give 8% acid. Whilst heating with

direct steam, the acetyl-o-anisidine-4-sulphondiethylamide is charged in. After ¹/₂ hour at the boil the original oil is largely in solution

and after 1 hour from the completion of charging, the hydrolysis is complete.

Test: A sample is made alkaline, the nitrite is value taken, and the m.p. determined.  30 kg. Carboraffin are added, the batch

Cooled to 35-40⁰, screened in the press, and the filtrate blown to second vat. Then caustic liquor, 580 l. at 50%, is run in to give only faint

acidity (acid to litmus). Further alkali must not be added as otherwise the product becomes coloured with precipitated iron hydroxide.

The product is precipitated as monoolinic crystals.

Test: Nitrite estimation is carried out on both solid and filtrate.   The precipitated product is dropped to the nutsch, well washed

with water and pilled as dry as possible. Yield = 97% theory.

    The product is dried and standardized to 90% with salt and put on the market as Fast Red ITR Base.  

日文译文。细田豊 《理论制造染料化学》1957年。P. 654. O-アニシシ^”ン-4-スルホンシ^”エチルアマイト(フアスト. レツトITR

ヘ-ス)  译自PB 77764.  抄录：  コム张釜て^”水3.2 t, 盐酸460 l, 硫酸110 kgを生蒸气て^”热し，前记アセチル化物100% 780kg

を装入し，1¹/₂ h煮沸して加水分解し，活性炭30 kgを加え35-40⁰て^”滤過，滤液にNaOH 50% 液580 lを加えて微酸性とし，

ヘ^”-スを滤洗，干燥する。收率97%。Fast Red ITR baseは盐て^”うすめ90% 纯度とする。 

中文译文。 张澍声《精细化工中间体工业生产技术》1996年。P. 142. 译自BIOS 1149.（三）水解:  [97-35-8]  抄录如下。

在10000 L橡胶衬里铁反应釜中，加入3200 L水，460 L盐酸（500 kg）和110 kg 硫酸一水合物，得到8%的酸。在通直接蒸

汽加热的同时，加入780 kg 100% 乙酰基邻氨基苯甲醚-4-N,N-二乙基磺酰胺，相当于180 kg NaNO₂ 。煮沸0.5小时后，原来的

油状物大部分溶解，加完料1小时后，水解完成。

加入30 kg活性炭，反应物冷却到35-40⁰C. 压滤，滤液压入第二个10000 L槽中，加入580 L 50% NaOH溶液，至对石蕊试纸

仅呈弱酸性。不能加入再多的碱，否则产品与沉淀的Fe(OH)₃形成颜色。产品以单斜结晶沉淀。抽滤，水洗，尽可能抽干。收率

97%。产品干燥，用盐标准化至90%。

以下未德文生产工艺原件：

PB 25625, 376-379. Echtrotsalz  ITR  1940年2月 1美元。这是稳定重氮盐，美国人介绍如下。未抄录。

2-Anisidine-4-diethylsulfonamide hydrochloride is diazotized and precipitated with zinc chloride. [14263-90-2] In German. 

PB 70422,1914-1920. Acetortho-anisidine-p-chloride. [3746-67-6]1941年11月14日。1.5美元。未抄录。

PB 70422, 1921-1923. 和1937-1939. 2-Acetylamino-1-methoxybenzene-4-sulfonic acid diethylamine.[68540-88-5] 1941年11月14日。 各1.5美元  未抄录。

PB 70422, 1924-1936.（共13页）  2-Amino-1-methpxybenzene-4-sulfodiethylamide. [97-35-8] 1941年11月14日。

1.5美元。以上是德文生产工艺原件。未抄录。

PB 74026, 2374. 2-氨基-1-甲氧基-4-二乙氨基苯磺酰苯胺，C.I.冰染重氮组分42. [97-35-8]. 德文生产工艺摘要。未抄录。

国内研究动态:

杨鸿敏 王双青 胡津昕（天大）提高红色基ITR贝司收率的合成工艺研究。[J]染料工业，1998,5,25-27. 摘录如下。

3. 氯磺化。[3746-67-6]. 在四口瓶中加入计量的氯磺酸，再逐渐加入邻乙酰氨基苯甲醚，而后在25-30⁰C下保温8小时。

反应完毕将反应液倒入冰水中，充分搅拌。析出过程，温度不超过5⁰C, 过滤。滤饼用冰水洗至中性待用。滤后母液待用作水解

反应介质。注：其中CAS号，是本人所加！ 
4.  胺解反应。[68540-88-5].   在四口瓶中加入定量底水，在冰水浴冷却下加入计算量二分之一的二乙胺和二分之一上一步反应滤饼。保持温度不超过30⁰C,而后再加入另一半二乙胺和磺酰氯滤饼。加入适量碱使体系保持碱性，反应在30⁰C下保持5小时。反应完毕冷却过滤，滤饼待用，母液回收二乙胺。 
5. 水解反应。 [97-35-8].   在四口瓶中加入一定量的上述胺解反应滤饼和计算量的氯磺化母液（废酸），补适量的水，升温至沸腾，回流1小时，体系澄清后继续搅拌保持0.5小时。降温至70-80⁰C, 加入适量的活性炭搅拌10分钟，过滤。滤液用氢氧化钠溶液中和到中性，过滤，干燥。得目的产物3-氨基-N,N-二乙基-4-甲氧基苯磺酰胺。
其余，略。
参考文献: 5篇。其中，只引用BIOS 1149，p. 28-31. 不知为什么未引用上述德文原件资料？  

加注: 

本产品为老产品，抄录上述资料的目的是要说明资料的编目很重要，我们在开发新产品或者在老产品的工艺改进上，参考这类文献可以节省时间，并可避免去做一些重复性的和别人已做过的工作。

其次，国内有上述资料，本人也看过，所谓未抄录，是因为能力有限。今天整理上网只是编目而已。大学应该有条件，可能天大没有，所以研究论文中未见引用。

当然新产品，只能是参考它的单元反应，如磺化，消化，还原等等。

为什么说BIOS 是英国人译自德文，FIAT是美国人译自德文？请读者看上面的抄录文，可以看出译文的差别？为什么，不知道！我只能告诉你，最好是看原件。   

陈忠源  2017年2月19日              于 无锡   明辉国际。