CAS号 [133-78-8] 生产工艺    2-甲基-4-氨基苯磺酸

CAS名: Benzenesulfonic acid, 4-amino-2-methyl-          历史参考文献: Beil. 14, 722; E2, 445; E3, 2210; E4, 2774.

用途: 颜料红51,  51:1 等。       反应类别: 磺化。

BIOS 986, 388-391. （=胶卷 PB 77764）.No. 190.  m-Toluidine-6-sulphonic acid. (I.G. Ludeigshafen).  英国人译自德文。

反应式: 本人有加注，译者未说明其资料来源。钙盐未找到CAS号。

(a)  m-Toluidinsäure-6 (3-Toluidin-6-sulfosäure): （间甲苯胺-6-磺酸）  Plant:  设备: (1201) 和 (1206) 略。

Process:  操作步骤: （抄注： 译者所用的品名为德文！）。

Charge 935 kg. sulphuric acid 98% to the sulphonator (1206) from (1201). Run in 70 l. water and then 1,000 kg. m-toluidine with initial cooling.  The temperature rises to 150℃.  The distilled water / m-toluidine mixture condenses in the reflux condenser.  The acid sulphate is transferred to trays 12 of which go to a rack.  One batch gives about 9 racks.  The racks are drawn through the oven during 11/2 – 11/4 hr. counter-counter to the direction of the hot gases from the burners these being conducted from one end of the oven to the other in metal ducting.  The bulk of the hot gas mixture is recirculated, a portion only being bled off to the absorption.

The gases enter the oven at a temperature of 12 M.V. = 2250 (Fe-Konstantin element).  The pressure before the bleed-off valve is 10 mm., and in the circulating tube ± 0 cm. water gauge . On leaving the oven the trays are allowed to cool and then discharge.

Yield per batch:  1,570 kg. m-Toluidinsäure-6 100% estimated by nitrite titration = 90% theory.  The strength shall be not less then 96%.

(b)  m-Toluidinsäure-6 Calcium feucht (Calcium salt of 3-Toluidine-6-sulfosäure)  （间甲苯胺-6磺酸钙盐） Plant:  略。

Process:  操作步骤:

In serial production charge to (307) 4.6 cu.m. filter press wash liquors from (304) and mother liquors or wash liquor from (310) and without stirring add 3,000 kg. m-toluidinesäure-6 100%.  At the same time heat with direct steam to 70℃.  Add 495 kg. ground chalk, and steam so that solution is complete in about 3 hr. and distil off the unsulfonated m-toluidine in further 3 hr.

Test: Distil a 1-litre sample in steam in the laboratory to completion.  The m-toluidine in the distillate should correspond to not more than 10-12 cc. N/1 sodium nitrite.

Then fill (307) with mother liquor or wash-liquor from (301) to volume of 13-14 cu.m. and add at the same time 50-60 kg. recovered sulphuric acid 380

Be’to neutrality.  A sample at 80℃ should have density of 13-140 Be’.  Add 40 kg. Carboraffin.  Pump through press (304) to (305).  Wash out the empty pan immediately with about 300 l. hot water.  Wash the press with hot water to 50 Be’ to the batch, and with about 2 cu.m. hot water to 00 Be’ to (307).  Discard the press residue.  About two-thirds of the batch is pumped to (308) and concentrated to 16-170 Be’.  It is important that the pipes be blown through with steam.  Cool in (308) with both coils and rapid stirring to 18-25℃.  Filter on nutsche (902) via pressure vessel (310).  The mother liquors have a density of 6-70Be’ and contain 9-11% volume of m-toluidinsäure.  They are used in (307) at the initial charging stage or for dilution after the unsulphonated m-toluidine has been distilled off.  Stir the nutsche paste with 500 l. and suck dry.  Save this wash as in the case of the mother liquors.  For the first batch of a compare warm water is used instead of mother liquor and wash liquor.  In this case the adjustment to 13-140 Be’ is carried out by diluting to about 200 cm. instead of to 260-280 cm. as in serial production.

After the last batch of a campaign thr mother liquor and wash liquors to a density of 16-170 Be’ are worked up.  If the liquors are too dark in colour pump to (307) instead of (308) and clarify with Carboraffin through press (304).  The mother liquor from such a mother liquor product has a density of about 110Be’ and contains 11-12% by volume.  These mother liquors are worked up a second and a third time and finally they have a density of 220 Be’.  From seven batches about 600 l. with a content of 24 volume % calc. on M.W. 187 are obtained.  A further working up of this liquor is not desirable.

Yield per batch: 2,940 kg. m-Toluidinsäures calcium about 100% as about 60% nutsche cake estimated by titration with N/1 sodium nitrite =98% theory.

Quality:  The product is soluble in water and crystallizes with 3 mol. water.

(c)  m-Toluidinsäure-6 in Lösung, dated 3.9. 45  (3-Toluidin-6-sulfosäure as sodium salt)（间甲苯胺-6-磺酸钠盐）Plant:  略。

Process:  操作步骤 :  这里说明是1945年9月3日的生产工艺。

Charge 3,300 l. hot water to (500).  Add 1,400 kg. m-toluidinsäure calcium feucht tel quell = about 900 kg. m-toluidinsäure calcium feucht.  Boil and add 270 kg. soda, adjust to 5 cu.m. (about 7-80Be’ hot), and filter on (501) via (502) from calcium carbonate.  Wash with hot water to 6.5 cu.m.  The solution is then about 13.6% by volume and has a density cold of 8.50Be’.  Yield per batch = 882 kg. m-toluidinsäure-6 in solution as about 13.6 vol.% of the sodium salt estimated by N/1 sodium nitrite titration = 98% theory..

抄注: 本译文是否忠于译文，不知道？当然，抄录是否有用，也不知道！

张澍声  《精细化工中间体工业生产技术》 1996年。 P. 19.   2-甲基-4-氨基苯磺酸。   译自BIOS 986, 388.

（一）2-甲基-4-氨基苯磺酸： 在3000 L磺化锅中加入935 kg 98% 硫酸，加入70 L水和1000 kg间甲苯胺。升温至150℃，蒸馏出的水/间甲苯胺化合物在回流冷凝器中凝缩。将间甲苯胺硫酸盐装入盘中，12盘装在一导轨架上，每锅约需9导轨架，送入焙烘炉中，用发生炉煤气加热，由空气循环，导轨架在炉内运行90-100分钟，与热气体逆流相遇。气体进入炉内的温度为225℃，压力10 mm。导轨架和盘离炉后冷却，卸料。

得到1570 kg 100% 2-甲基-4-氨基苯磺酸，收率90%。沉淀不低于96%。

（二） 2-甲基-4-氨基苯磺酸钙滤饼： 在15200 L锅中加入4600 L压滤洗水或母液，无搅拌加入3000 kg 100% 2-甲基-4-氨基苯磺酸，同量用直接蒸汽加热到70℃。加入495 kg研磨的碳酸钙，通蒸汽于约3小时内完全溶解，再用3小时蒸馏出未磺化的间甲苯胺。

然后加母液或洗水使体积达13000-14000 L，同时加入50-70 kg回收的硫酸进行中和，在80℃时的比重应为1.100. 加40 kg活性炭，压滤，锅内用300 L热水洗涤，压滤机用热水洗涤，弃去滤渣。

将反应液的2/3送往蒸发器，浓缩至比重1.13，重要的是管路要用蒸汽吹，迅速搅拌冷却到18-25℃。抽滤，母液比重1.046，含9-11% 2-胶卷-4-氨基苯磺酸，它们用于最初加料阶段，或蒸馏出未磺化间甲苯胺后的稀释。将滤饼用500 L水打浆，抽干，该洗水如母液同样利用。对于第一锅只能用温水代替母液和洗水，当然稀释到比重1.13就不会用那么多水。

每锅对的2940 kg 100% 2-甲基-4-氨基苯磺酸钙，为60% 滤饼，收率98%。

（三） 2-甲基-4-氨基苯磺酸钠溶液： 在锅中加入3300 L热水，加入1400 kg 2-甲基-4-氨基苯磺酸湿滤饼，约900 kg 2-甲基-4-氨基苯磺酸钙。煮沸并加入270 kg碳酸钠，调整体积至5000 L，过滤出碳酸钙，热水洗涤至滤液体积为6500 L。得到约13.6% 的溶液，比重1.062，含有882 kg 2-甲基-4-氨基苯磺酸钠。 收率98%。

PB 25602, 859-860.  No. 4107-0.  m-Toluidinsäure-6 100%.  2-甲基-4-氨基苯磺酸。100% 德文生产工艺原件。未抄录。

PB 25602, 861-862.  No. 4107-4.  m-Toluidinsäure-6 Lösung.  2-甲基-4-氨基苯磺酸。 液体。德文生产工艺原件。 未抄录。

PB 25602, 863-866.  No. 4107-1.  m-Toluidinsäure-6 Feucht.  2-甲基-4-氨基苯磺酸。滤饼。德文生产工艺原件。未抄录。

PB 70063, 308-309.  3-Toluidine-6-sulfonic acid.  By Heinze.  1945年9月10日德文生产工艺。  未抄录。

PB 70063, 310-313.  Manufacture of Calcium salt of 3-Toluidine-6-sulfonic acid.  By Heinze.  1945年9月3日德文生产工艺。

PB 70063, 314-315.  Manufacture of sodium 3-Toluidine-6-sulfonate.  By Heinze.  1945年9月3日德文生产工艺。 未抄录。

抄注:  PB 70063. 按美国人介绍，共587页。其中：有含氟中间体，丙烯酸丁酯，甲基丙烯酸甲酯，苯系中间体，萘系中间体和蒽醌类中间体等。收藏单位：中科图书馆，编号：M00706.  上海图书馆，编号F 643.

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