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| CAS号 [630-88-6] 生产工艺 3’,6’-二氯荧光素 |
CAS号 [630-88-6] 生产工艺 3’,6’-二氯荧光素
CAS名: Spiro[isobenzofuran-1(3H),9’-[9H]xanthen]-3-one, 3’,6’-dichloro- 参考文献: Beil. 19, 147; E2, 173.
用途: 酸性紫9, 30。碱性紫10。
溶剂红246。溶剂紫10。颜料红173。颜料紫1, 1:2。功能染料等。
生产工艺文献: 按手头现有资料整理，抄录如下。
BIOS 986, 156-158. No. 95. Dichlorofluorescein. (I.G.
Ludwigshafen) 英国人译自德文（未说明资料来源）抄录如下。
反应式: 本人有加注。英国人应该是译自PB
25602 的德文原件。
Materials usage per batch: Flurescein 300 kg. Phosphorus oxy chloride 280 kg.
o-Dichlorobenzene（8% loss）36 kg. Caustic soda 400Be’ 400 kg.
Services consumptions: Steam 5 tones. Warm water 20 cu. m. Rhine water 100 cu. m.
Electricity 300 K.W.H. (power). Light 40 K.W.H. Air 30 cu. m. Nitrogen 40 cu. m.
Plant Description:
1. 1.2 cu. m. homogeneously lead-lined kettle
with oil circulatory heating with steam and cooling coils. Thermometer,
anchor-type agitator, closed lead-lined condenser. Vacuum ventilation and
nitrogen connections and blowleg to still.
2. 4.5 cu. m. still, stone-lined lead-covered
with bottom outlet and open steam feed.
3. Wood press with 100 cm. frames – nitrofilter
clothes. 4. Schilde – Trockenschrank. Capacity: 1 batch per day.
Process Description:
Charge 400 kg. o-dichlorobenzene water-free
and with stirring at ordinary temperature add 300 kg. Fluorescein 100%. Suck in
280
Kg. phosphorus oxy chloride by
vacuum. Heat slowly with steam. At 40-450C. the reaction commences. Shut off the steam at this
Temperature. The temperature
rises on its own to 80-900C. at which the main reaction proceeds
with the evolution of hydrochloric acid.
Control the reaction by coil
cooling. After a short time the main
reaction is complete and the temperature falls back slowly. Heat
Carefully to 1350C. –
at 120-1250C. a slight reaction sets in. Hold at 1350C.
for 2 hr. and sample. If the test is O. K. shut off the heating and
blow nitrogen through the batch
to remove the hydrochloric acid. Cool to
50-600C. and suck to the still containing 1,500-2,000 l. cold
water. Wash out the kettle with
about 50 kg. o-dichlorobenzene. Decompose the resulting hydrochloric acid with
300-400 kg. of 400Be’
Caustic soda. Distil the
contents of the still at slight acidity. The o-dichlorobenzene is reused after
purification. Filter, wash, and dry at
1000C. Yield: 300 kg. Fluorescein actual = 100% 309 kg. fluorescein- chloride actual 100% = 92%.
Remarks:
1. o-Dichlorobenzene
must be water-free. 2. The phosphorus oxy chloride for every batch
is tested. If too little or bad quality
Phosphorus oxy chloride is charged, the melt
remains at 100-1050C. and can be processed further by the addition
of more phosphorus
oxy chloride only with
difficulty. 3. The heating-up must be done very carefully
because of the vigorous of the reaction.
Test: Add a kettle sample to water and
distil. Filter wash neutral, and dry. M.P. should be not less than 2500C.
Suspend a sample of the
product in water, and caustic soda and
filter. There shall be no green fluorescence in filtrate.
The fluoresein varies in colour from orange
to deep red. The fluorescein chloride is brownish-yellow and crystalline. M.P.
250-2530C.
张澍声《精细化工中间体及产品生产工艺》2006年。P. 694. 译自BIOS
986, 166.（译者未知有德文原件）抄录如下。
在1200 L均匀衬铅的锅中加入400 kg无水邻二氯苯，在搅拌及常温下加入300 kg 100% 荧光素，真空吸入280 kg磷酰氯
（POCl3），缓缓加热，在40-450C反应开始，在此温度停止加热，温度自身上升到80-900C, 这时反应大量进行，并释出氯化氢，
蛇管冷却控制反应。短时间后反应完成，温度缓缓回落。仔细加热到1350C,在120-1250C发生少量反应。在1350C保持2小时，并取样。
检验: 将样品加入水中并蒸馏，过滤，水洗至中性，干燥，熔点应不低于2500C。 将干产品取样悬浮于水中，加氢氧化钠
并过滤，在滤液中应没有绿色荧光。
合格后，停止加热，用氮气吹除盐酸气，冷却到50-600C,抽吸到含有1500-2000 L冷水的蒸馏釜中，用50 kg邻二氯苯洗锅，
用300-400 kg 35% NaOH分解生成的盐酸。蒸馏釜含微酸性。邻二氯苯精制后可复用。过滤，洗涤，于1000C干燥，得309
kg二
氯荧光素，收率92%。
邻二氯苯必须不含水。磷酰氯必须每锅检验，如果磷酰氯加料量少或质量低劣，物料应保持在100-1050C, 可以加入更多的
磷酰氯进一步处理，但有一定困难。荧光素的颜色从橙色变化至深红色。二氯荧光素是黄棕色结晶，熔点250-2530C.
PB 25602,146-148. Fluoresein Chloride. 二氯荧光素德文生产工艺。未抄录。
本胶卷北京有收藏以外，沈阳院也有收藏，其收藏盒编号为BP 32-42和BP 472-24。美国人介绍如下：
PB 25602. Manufacturing methods of “Basefabrik” and
other manufacturing methods (FIAT Reel C-85)
(f. 1-1430) 1946年 共1430页。（本人已抄下了目录）
本胶卷含苯系，萘系，杂环系等中间体生产工艺。其中部分中间体被英国人和美国人摘译成英文出版，
即BIOS和FIAT，但是他们没有说明译自哪个PB报告。其中已上网的部分中间体，我是在沈阳院工作时，用放大镜抄录下来的，部分已译成中文，部分未译，只是抄录而已。问题是张澍声老先生只是翻译了BIOS和FIAT部分，未利用胶卷部分。
我再说一遍，上述资料均未列入Beilstein手册中，也未被美国化学文摘摘录，不信请你检索一些CA。
今天条件好多了，如果读者认为还有一定参考价值，那么请您，或者请老板化点小钱到北京复制过来，
本人目前还有条件做点工作，请放心，我是免费服务！当然年轻人愿意，我可以免费教您一点德文！
陈忠源 一名资料收集单干户
（不收费！） 2017年5月10日 于 无锡 明辉国际。
文章作者：陈忠源 |
