C.I. 酸性红87 (C.I. 45380) 生产工艺  CAS号 [17372-87-1]

CAS 名:  Spiro[isobenzofuran-1-[3H],9^’-[9H]-xanthen-3-one, 2’,4’,5’,7’-tetrabromo-3’,6’-dihydro-, disodium salt.

发明者: Caro  1871年。参考文献: Beil. 19, 2228. E¹,724, E², 254, E⁴, 2917.

生产工艺文献: Colour Index.  BIOS 959, 6.  FIAT 764 – Eosin.

BIOS 959, 28-31. (=胶卷 PB 63858)  Eosine G Konz. (I.G. Ludwigshafen – 1943年12月9日)  英国人译自德文。摘录如下。

反应式: 本人有加注，译者未说明译自哪个PB报告原件，实际是摘译自PB 70135, 1078-1087.
  

反应分子式: 略。理论投得量: 略。实际投得量:  略。 生产周期: 略。工艺工程单耗: 略。 生产设备: 略。

Process Description:  操作步骤:  抄录原文，仅供学习外文参考。同时抄录日文摘译文。

Two kettle charged comprise one batch. The charge for each kettle is 150 kg. F.W. Fluorescein, 131.25 kg. liquid bromine, 35 kg. sodium chlorate, 80 kg. caustic soda 50⁰Be’, 30 kg. soda.

The fluorescein is in the form of alcohol wet, zinc chloride – containing Fluorescein. The content of a batch is estimated by thoroughly mixing with a shovel and boiling 1/1000 of the batch weight in 6 l. water and 50 c.c. hydrochloric acid 20⁰Be’ for 15 min. in an enamel dish over a free flame, filtering hot, washing with 2 x 3 l. hot water and drying at 100⁰C. The weight in g = kg. weight of Fw. Fluorescein. For estimation how many kg. damp fluorescein are equivalent to 150 kg. dry Fluorescein for a batch of Eosine G konz. reckon  kg. damp x 150 / kg. dry.

An amount of alcohol wet Fluorescein corresponding to 150 kg. Fw Fluorescein with alcohol 400 kg. (85-87 vol%) (150 kg. fresh and 250 kg. regen.这是指回收) and 25 kg. hydrochloric acid 20⁰Be’ are stirred in a lead-lined vessel (1). Then during about 1 hr. add 131.25 kg. liquid bromine (35 bottles) so that the temperature does not exceed 45⁰C. At this temperature run in a solution of 35 kg. sodium chlorate in 70 l. water at 45-50⁰C. during about 1¹/₂ hr. Hold for a further ¹/₂ hr. at 70-72⁰C, cool to under 30⁰C (2 hr.) and filter on（5）.Wash the Eosine acid first with 20 kg. 94% alcohol and then with 100 l. cold water. Then stir up twice with 300 l. cold water an the nutsche, suck off and wash again with 100 l. cold water.

Test: Stir ¹/₂ l. water, filter and wash with ¹/₂ l. water. Distil the filtrate twaddell the first 100 c.c. The alcohol content shall be not more than 3%. The alcohol free Eosine from two brominations (= 300 kg. Fw. Fluorescein) is stirred in pan(6) with 3 cm. depth water and 150-160 kg. caustic soda 50⁰Be’.

Test 1: For sufficient caustic soda: If too much soda is required for the completion of solution losses occur at times through too strong frothing.

Test 2: For excess caustic soda: If excess caustic soda is present it must be removed by the addition of Eosine acid or, if none is available, hydrochloric acid.

The test is carried out by shaking 20-25 c.c. of the batch from pan(6) with one litre hot water. Undissolved Eosine acid must be present and must settle out on the bottom of the test vessel.

Such the think mass into the still(8) and distill with 5 ats steam Kristall to an alcohol content of the distillate of 5% - the mass becomes too thick with further distillation. One obtains about 200 l. aqueous alcohol with about 15% alcohol content = about 30 kg. alcohol 94%.

Run through a hair sieve to the pan(6) and dissolve there boiling with about 30 kg. soda dry. Agitate and evaporate to a thick crystalline mass (6 hr.) and dry in (9) during 48 hr.

Yield:  300 kg. Fluorescein  -  612 kg. Fw. Eosine G konz. = 204% v. Fluoresein.   Purity =95%= 581 kg. pure color =93% theory.

     The loss of spirit after recovery is 150 kg. 94% = 20% v.E.

Remarks: 按德文是操作要点，有的我用了黑体字。

    1.  The temperature given in the above process must be adhered to exactly since small temperature differences affect the shade and the purity of the dyestuff. On the addition of the sodium chlorate the temperature should rise to 70-72⁰C. Temperature under 70⁰C give too yellow shades, temperature over 70⁰C give too blue shades and at the same time a turbidity (of solution).

2.  The lead-lining of the bromination kettle must not be broken since the presence of iron lowers the purity of the colour and the sodium salt gives darker solutions in water.

3.  In dissolving the colour with caustic soda and soda, an excess must be avoided because otherwise the dyestuff decomposes.

4.  Solubility: 1 g. colour in 100 c.c. of water must give a clear solution.

日文摘译文。细田豊，《理论制造染料化学》 1957年。P. 787-8. フルオレツセイン⁴⁾, エオシ G⁵⁾ 抄录如下。

4） PB 70135.   5） BIOS 989.  两者均未写出页号。  下面第一步含C.I.酸性黄73的合成。第二步是C.I.酸性红87.

（1）Fluorescein: 熔 融  4 m³水蒸汽二重釜にレソ^”ルシン440 kgを入れ，半は^”熔して搅拌しなか^”ら無水フタル酸310kgを加え110⁰に热してから104-105⁰に下け^”, ZnCl₂ 270 kgを加え加热を止めて搅拌すれは^”7-10 m後最高に达しそれから下りかかるようになつてなお10 m搅拌後搅拌机を引きあけ^”卷扬机につけた锚を下し熔融物を固まらせ，つきに160⁰に热して塊を釜から離し，翌日碎いて5 mmの筛にかける。 940-950 kg.

精 制  粗フルオレツセイン（ZnCl₂复盐）を76-775アルコ-ル1.7 tに70⁰て^”加え80⁰に1/2 h保温後30⁰に冷して滤過し，94%アルコ-ル100 kgす^”つ3回洗い，多少のZnCl₂を含んた^”ままフ^”ロム化に移る。612 kg (97%纯度)，收率92%。

（2） Eosine G:  上记フルオレツセイン150 kgを含むヘ⁰-ストを85-87 V%アルコ-ル400 kg,盐酸 25 kgと铅张釜に入れ，Br₂ 132 kgを45⁰以下て^”1 hに加え，NaClO₃ 35 kg + 水 70 l.を45-50⁰て^”1¹/₂ hに加える。70-72⁰に¹/₂ h後30⁰以下に冷し滤過，94%アルコ-ル20 kg て^”洗い，水洗の後ヘ⁰-ストを水とNaOH 50⁰Be’约80 kgて^”Na盐にし，Na₂CO₃ 15 kgを加えて浓缩亁燥する。306 kg (纯度95%)，收率93%。以上抄录，供参考。

PB 70135, 1078-1087.  Eosin G.  这是德文生产工艺原件。 1943年12月9日。共10页。未抄录。

PB 82021, 3070-3073. 830347 Rot = Fettloest fuer Lippenstifte 它是酸式C.I. 酸性红87，配成溶剂红43. 未抄录。

这是唇膏的生产工艺。

PB 82021, 3139-3137 Eosin S 未抄录。

有关参考文献：

Kosmetsche Farbemittel / Colours for cosmetics 1984. C –Rot 30 (共3页，有IR 图)

Coloring of Foods, Drugs and Cosmetics. 1999. P. 229-31. 有层析配方。用途等。

Rev. Chim (Bucharest)  - CA: 93:96775. Su. 810492.  CA: 94: 193979.

酸性红87不同成盐体：

分子式     C.I. No.    CAS号     EC号        备注  

C₂₀H₈Br₄O₅      15086-94-9    239-138-3

-----“ --------.2Na    45380    17372-87-1    241-409-6     酸性红87

-----“ --------.2K      6373-06-4

-----“ --------. Rosin  45380:2    溶剂红43

-----“ --------.x Al       16508-80-8    240-569-4

-----“ --------.2/3 Al  45380:3   15876-39-8   240-005-7   颜料红90:1

-----“ --------. Pb  45380:1   1326-05-2   215-415-4    颜料红90

以上仅供参考。

陈忠源    2016年12月20日      于 无锡   明辉国际。