CAS号 [100727-93-3] 生产工艺    3-硝基-4-甲氧基二苯砜

CAS名: Benzene, 1-methoxy-2-nitro-4-(phenylsulfonyl)-   历史参考文献: Beil. 未检索。 

用途: 有机颜料（C.I. 12450）。聚丙烯的Crona treatment 用 （见CA. 112:36642.）。    反应类别: -Cl à -OCH3 。

BIOS 1153, 106-107. （=胶卷PB 85687）。 3-Nitro-4-methoxydiphenyl sulphone. 英国人译自德文（无资料来源）。

反应式: 本人有加注。生产厂是Leverkusen = Bayer，暂未找到德文原件。

Plant:  10000 l. agitated vessel (6300 l. working volume).
Process:

1000 kg. of 4-chloro-3-nitrodiphenyl sulphone (≈ 230-234 kg. NaNO2 ) are dissolved in 3500 l. of methanol by heating to the boil. During 3 hours, with maintenance of reflux conditions, there is run in from a measure vessel a methanolic solution of caustic soda made up from 156 kg. 100% caustic soda flake and 1500 l. methanol (=115% theory usage).  No air is necessary as oxidizing agent but the reaction must not be allowed to become too violet.  The B. Pt. of the mixture is 65-700.

After completion of the caustic addition it is boiled until the chlorine content of a sample is constant (ca. 5 hours).  If the process is continued for too long a period decomposition occurs and the quality of the product suffers.

When reaction is complete, the batch is blown at 55-600 into an agitated vessel containing 2500 l. of cold water to granulate the product.  After cooling it is filtered in a box nutsche and washed with cold water until the washings are colourless.

The aqueous methanol solution (prior to washing) is run off and the methanol recovered by distillation.  The aqueous residue from this distillation contains a further proportion of the product which is of lower quality and separates in a tarry form.  The liquor contains 4-5% of the charge.

Yield  of 3-nitro-4-methoxydiphenyl sulphone (main fraction) = 90-91% theory..  Quality: M. Pt. ≮101-102℃.

Notes:  1.  If the sample taken for testing the completion of reaction shows a poor conversion the isolation conditions are charged.  Instead of blowing into water the methanol solution is stirred until cold and filtered directly.  The precipitated salt is then washed out of the product with water.  This method of isolation causes a drop in yield and it is only used in exceptional cases.

2.  A very thorough boiling out of the apparatus with water and methanol between each batch is necessary for successful operation of the process.

张澍声 《精细化工中间体工业生产技术》 1996年。 P. 144,  3-硝基-4-甲氧基二苯砜。 译自BIOS 1153, 105.

在10000 L 搅拌釜（工作体积6300 L）中，加入1000 kg 4-氯-3-硝基二苯砜（相当于230-234kg NaNO2）和3500 L 甲醇，加热煮沸。于3小时内在回流条件下从计量槽中流入甲醇苛性钠溶液（由156 kg 100% 片状氢氧化钠和1500 L甲醇制成，为理论量的115%）。不需要空气作氧化剂，但反应不可变得过于强烈，混合物的沸点为65-70℃.

在完成苛性钠加料后，再沸腾5小时，直至样品的氯含量为恒定。如果工艺继续太长时间，会发生分解，产品质量受到损害。反应完毕时反应物在55-60℃压入含2500 L冷水的釜中，使产品成粒状。冷却后过滤，洗涤至洗水未无色。

洗涤前的甲醇水溶液收集后，经蒸馏回流甲醇。该蒸馏的馏余物还有一定比例的产品，其质量较低，以焦油状分出，其中含4-5%物料。3-硝基-4-甲氧基二苯砜的熔点为104℃，软化点101-102℃. 实际产品熔点不小于101-102℃。 按主馏份计，3-硝基-4-甲氧基二苯砜的收率90-91%。

致读者：

上网已2年多了，本人一直说：美国出版了PB报告，而美国化学文摘至今未见对该资料有任何摘录，本文CAS号[100727-93-3]只是其中一例。读者不要以为这些资料已是老掉牙的资料，开辟新用途也是创新！

2年多了，无人相信（No body, No technician believe !），Why ? I don’t know ? 以前说过了，不再多说。

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陈忠源 2018年2月18日（年初三）