【CAS名】Methanaminium, N-[4-[[4-(dimethylamino)phenyl](3,6-disulfo-1-naphthalenyl)methylene]-2,5-cyclohexadien-1-ylidene]-N-, -methyl-, inner salt, sodium salt.

【CAS号】[6434-86-2]

【分子量】C₂₇H₂₅N₂NaO₆S₂ = 560.62

【色号CAS号】[12768-78-4]

【用途】织物染色，化妆品着色，激光染料等

BIOS 1433(=胶卷PB 81029), The Manufacture of Triphenylmethane Dyestuffs at Hoechst, Ludwigshafen and Leverkusen, 1946

BIOS 1433, 49, Naphthalene Green V, (Process Hoechsr dated Sept. 1938) (其中化合物的CAS号为本人所加!)

【Oxidation】合成“四乙基米氏醇”，CAS号[134-91-8]，(已在2021年7月4日上层，不再抄录)

【Addition Compound: 加成化合物】Meanwhile, a solution of 428kg. Naphthalene-2,7-disulphonic acid [92-41-1] 100% M.W.288 in the form of its disodium salt [1655-35-2] (theory – 15%) is dissolved in 2000 litres water into this soln is run the above hydrol [134-91-8], followed by a second bach prepared similarly.  The mixture is stirred 24-36 hrs, at room temp, filtered, washed neutral with cold water, and dried at 70 – 80°C.【Yield】About 680 kg (grey-green powder). A second charge of the hydrol-naphthalene-2,7-disupho addition compound is prepared from 400 kg. G Base [1935-91-1] in the same manner.

【Condensation: 缩合】The montejus is charged with 3200kg. Monohydrate, and 800 kg. Oleum 20% heated to 60°C and the intermediate prepared from 800 kg. G Base [1935-91-1] (about 1360kg) added quickly, whereby the temp rises to about 85°C. There should be no evolution of HCl and SO₂ as in the old process. The melt is then heated to 100°C and stirred at this temp for 7-8 hours, until a test sample of a few drops, diluted with water, neutralized with sodium acetate, and the precipitate redissolved with acetic acid, no longer becomes blue when heated. The soln, is run into two precipitation vessels, each charged with 4000 litres water at 60°C whereby the temperature rises to about 95°C. By this hot dilution the leuco acid is produced in a coarse crystalline form which filters well. The two precipitations are then each diluted to 8000 litres, allowed to cool with stirring to normal temp. filtered on two tile filters and washed neutral. Before filtering the batch, the filtrate from a test sample should be diluted and allowed to stand overnight to see if anymore separation occurs. Both filter-cakes are now stirred with 5000 litres water and dissolved with about 200kg soda, finally adjusted the pH to 7.9-8.1 with about 25 litres Ammonia 25%. This leuco salt soln. is blown into a storage vessel and estimated by a moisture test. The yield from 800kg G Base is about 1100-1160kg Leuco acid. M.W.596 = 71.5-75.4% of theory.

【Oxidation to Dyestuff: 染料的氧化】Three oxidation tests are made, for each 100 pts. Leuco acid 100%, using the same amount of oxalic acid and sulphuric acid with 17, 17.5 and 18 pts. Bichromate in each case. Comparative dyeings are made on wool, and compared for shade and strength. 1000 litres leuco soln containing 200kg Leuco acid M.W.596 are run via a measuring vessel from the storage tank to the oxidation vessel, diluted to 3000 litres, and cooled by means of circulating through a lead coil to 10°C. About 35kg (according to the best oxidation test) of sodium bichromate 100% as soln are run in, followed quickly by a mixture of-45kg Oxalic acid crystals in 100 litres water; 42kg Sulphuric acid and about 20kg Ice. The colour is stirred at 10-20°C for one hour, then, after addition of 3kg. Kieselghur and 24kg 25% Ammonia, filtered through a screening press. The soln from two such oxidations is heated to 40°C, salted with 1800-1900 kg Sulphate to 22°Be’, stirred for 2 hours, filtered and dried at 90-100°C. The yield from 200kg Leuco acid M.W.596 is 221kg of F ware at 23=100, i.e. 960kg Naphthalene Green V type.

细田豊《理论制造染料化学》，技报當出版，1957年，P.782-783，ナフタリン グリ-ン V. 译自 BIOS 1433。 (反应式：略)

1. Tetraethyldiaminobenzhydrol [134-91-8]，已上传，不再抄录

2. 【附加化合物】ナフタリン-2,7-ジスルホン酸 [92-41-1] 428kgをNa盐 [1655-35-2]として水2tに溶し，これに前记ヒドロ-ル液2回分を加え，室温で24-36 h搅拌候附加化合物を滤過し水洗，70-80°Cで乾燥する680kg

3. 【缩合】H₂SO₄ 3.2t + SO₃ 20% 0.8 tを60°Cに热し，メタンベ-ス800kg分の附加化合物1360kgを急に加えれば约85°Cに上る。100°Cで7-8h搅拌後60°Cの水8tに排出，16m³にうすめリウコ酸の沉淀を常温で滤過，水洗し，ケ-クを水5t + Na₂CO₃ 200kgに溶し，25% NH₃约25Lを加えてpHを7.9-8.1にリウコ酸(M.W.596)を定量する。1100-1160kg，收率71.5-75.4%。

4. 【酸化】リウコ酸200kgを含む溶液1m³にうすめ，10°Cで重クロム酸ソ-ダ约35kgを溶液で加え(修酸结晶45kg+水100L)+(硫酸42kg+冰20kg)を急に加える。10-20°Cで1h搅拌後硅藻土3kgと25% NH₃ 24kgを加えて滤過する。滤液を40°C でNa₂SO₄ 900-950kgを加えて22°Be’とし2h搅拌後滤過，乾燥する, 221kg = 960kg标准。

PB 25626, Methods for production of dyestuffs, 1932-1939, 1107页, Price: Microfilm $6.00; Enlargement print: $111.00.

PB 25626, 1452-1461. Supplement to the directions for the process for “Naphthalingrün V” concentrated, Sep 1928-Sep 1937. Price: Microfilm $1.00, Photostat $1.00. The first item in this folder describes improved methods for two steps of the process. Earlier description of the production of “Naphthalingrün”leuco salt, and of its oxidation of “Naphthalingrün V”, follow. Directions for the production of “Wallgrün BS” ods. And “S” and their leuco acids are added. In German.

PB 74067, Dyes and Textile auxiliaries production methods, and fire fighting agents etc, 851页, 这是手工抄录本，无Price。

PB 74067, 136-138, Naphthalene Green V, 无Price, 上海染料研究所有从“中国科学院图书馆”复印的复印本。

PB 74067, 168-170, Naphthalene Green highly conc. F. 无price.

Colour Index Second Edition, 1956年出版, Volume 3, P.3376, C.I.44025, C.I.Acid Green 16 (Green),

【结构式】略

Condense 4,4’-bis(dimethylamino)benzhydrol* with 2,7-naphthalenedisulfonic acid in 15% sulfuric acid, oxidize with lead peroxide and convert into the sodium salt. *Yellower hues are obtained with 4,4’-bis(diethylamino)benzhydrol.

【Discoverer】Hermann 1899

【生产工艺参考文献】BIOS 1433, 49, FIAT 764-Naphtalingruen V.

И. М. Коган ХимияКрасителей, 1956, P.273, Кислотный Зеленый Ж.

【结构式】略

Который получается путем конденсаци театраэтилди-аминобезгидрола с 2,7-нафталиндисульфокислотой в слабом оле-уме при 100-102°C последующим окислением продукта конденсации.

沈剑渊译《苏联有机染料技术条件汇编》，化学工业出版社出版，1959年，P.189-190。

黄光酸性绿(Кислотный Зеленый Ж)，化工部技术条件(Т.У.МХП) No.2125-49, (具体文件资料，不再抄录)

【加注】国内活性染料生产厂，准备编写“活性染料产品标准”，可以参考“ГОСТ”中的“АктивыеКрасите-ли”。上海图书馆有进口，本人手头只有1984年的一本目录 ‘Органические Синтетические Красители, Каталог, 1984’.

Mitsuo Maeda, Laser Dyes, Academic Press, INC 出版, 1984, P.106, Table 13, Laser Characteristics of Triarylmethane Dyes.

其中#M 127, 【结构式】略, Naphthalene Green, Solvent (Glycerin); Wavelength (tuning) 756 (nm); Excitation (Ruby).

潘国光《三芳甲烷系列酸性染料的合成》，[J] 染料工业, 1993, 5, 11-20，其中酸性绿B合成工艺：

1. 【氧化】将200kg四乙氨基二苯甲烷(下称G-色基)配成40% 溶液，与121.92kg 100% 硫酸混合，用冰冷却至-6°C，于氧化锅内制备新生的100% 二氧化锰67.2 kg(理论量增加20%，外观为15-20% 浆糊状)，用冰冷却，于高速搅拌下迅速倒入G色基溶液(30秒内)，加完的温度不超过0-2°C，3分钟后加入78kg 60°Be’硫酸，搅拌10分钟。由于二聚水合物从铜式转变成烯醇结构，从而使溶液从蓝色转变为棕黄色。 新生的二氧化锰最好是通过硫酸锰(制备苯甲醛-2,4-二磺酸的副产物)与高锰酸钾在苏打-碱溶液中反应而得，收率几乎接近理论量。

2. 【加成化合物】预先将100% 428kg 2,7-萘二磺酸钠盐(理论量加15%)溶解于2000L水中，加入以上二聚水化合物，于室温搅拌24-36小时，过滤后用冷水洗至中性，滤饼于70-80°C干燥。约得680kg灰绿色粉末。

3. 【缩合】将3200kg硫酸与800kg 20% 发烟硫酸加到缩合锅内，加热至60°C，快速加入由800kg G色基制得的中间体(约1360kg)，自然升温至85°C，再加热至100°C，保温搅拌7-8小时至终点。终点后倒入两只均盛有4000L 60°C热水的沉析锅中，自然升温至95°C。由于热稀释，析出易过滤得粗晶体。将两锅沉析物分别稀释至8000L，搅拌降温至常温，过滤后洗至中性。将两批滤饼用5000L水搅拌，用约200kg碳酸钠溶解，最后用25L 25%氨调pH至7.9-8.1。将此无色盐溶液放入贮罐，测定水分，800kg G色基约得1100-1160 kg无色酸，收率71.5-75.4%。

4. 【染料的氧化】将1000L无色酸溶液(含200kg无色酸)从贮罐通过计量槽放入氧化锅中，稀释至3000L，冷却至10°C。根据氧化试验最佳结果，加入约35kg 100% 重铬酸钠配成的溶液，立即加入以下组成的混合液：

     46kg草酸+100L水；42kg硫酸；20kg冰

于10-20°C搅拌1小时，然后加3kg硅藻土与24kg 25%氨，通过筛滤器过滤，合并两批氧化滤液，加热至40°C，加1800-1900 kg硫酸钠盐析至22°Be’。搅拌2小时，过滤，滤饼于90-100°C干燥。200kg无色酸可得221kg染料干品，强度435%，拼混后得染料商品。

5. 【参考文献】79篇，上述译文应该是译自BIOS 1433, 49。

丁忠传等主编《染料品种指南》，中国化工信息中心出版，1995年，P.120，C.I.酸性绿16(C.I. 44025)。

【化学结构】/【制法】/【主要文献】全部译自Colour Index未提及上述本人抄录的一些资料！

Axel Mixa, Coloring of Foods, Drugs and Cosmetics, 1999, P.217-218, C.I.44025, C.I.Acid Green 16, 摘录:

【Chromatography】DC Schleicher & Schüll 2043 b MgI;

【Carrier】Acetic acid ester 11ml + Pyridine 5ml + Water 4ml.

【Mian applications】Cosmetics: Shampoo, shower gel; -Liquid soap.

杨新玮、肖刚等主编《世界染料品种-2000年》，沈阳院出版，P.330, C.I.酸性绿16 (C.I.44025)，同上！

肖刚、杨新玮等主编《世界染料品种-2005年》，全国染料工业信息中心出版，P.158，C.I.酸性绿16(C.I. 44025)，同上！

何岩彬主编《染料品种大全》，沈阳出版社出版，2018年，P. 279，C.I.酸性绿16 (C.I.4025)。

【参考文献】增加了本人免费提供的部分资料目录，今天增加了一些以前没有抄录和本人所登记的资料目录

陈忠源 2021年10月14日，星期四