【CAS名】Methanaminium, N-[4-[[4-(dimethylamino)phenyl](2-hydroxy-3,6-disulfo-1-naphthalenyl)methylene]-2,5-cyclohexadien-1-yliden]-N-methyl-, inner salt, monosodium salt [3087-16-9]

【酸式：CAS号】[25317-10-6]

【用途】织物染色，也用于皮革，食品，医药和化妆品的着色。

FIAT 1313(=胶卷PB 85172), 1 February 1948, German Dyestuffs and Dyestuff Intermediates, 共3卷

FIAT 1313, 2, 350, Wool Green BS (Leverkusen). (染料结构式：略。其中化合物CAS号为本人所加)

To 2200kg 600Be’ sulfuric acid diluted with 1000kg water in lead lined kettle add below 40°C alternately 375kg 100% Michler’s Hydrol [119-58-4] (Manganese dioxide process) as about 949kg paste and 610kg R-acid [148-75-4] (equivalent to 104.5kg sodium nitrite). Rinse upper part of kettle with 140kg water. When hydrol [119-58-4] has dissolved, heat to 90°C during 5 hours and hold until hydrol has been consumed.  Cool to 55°C and dilute with 6000L water. Cool to 25°C, agitate 24 hours, filter on nutsch and wash acid free. Dissolve the leuco paste in water with 325–330kg sodium carbonate and dilute to 3000kg. To 1500kg of the solution add 600kg 11% manganese dioxide paste at 20–25°C. The solution will warm to 33–34°C. Agitate 6 hours. Filter and wash. Acidify the filtrate with 165kg. 600Be’ surfuric acid and salt out the color at 60–70°C. with 1200kg sodium sulfate. Dry on drum dryer. Dry weight was 780–840 kg, equivalent to 2625kg. Wool Green BS [3087-16-9]. The manganese dioxide-manganess carbonate sludge may be used over again, the recovery from three charges being combined for one charge.

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

PB 25626, 1821-1821A. “Woolgrün B S” Jun 1921, Price: Microfilm $1.00, Photostat  $1.00. Directions for producing this dye from“Hydrol [119-58-4]”and 2-naphthol-3,6-disulfonic acid [148-75-4] are given. In German.

PB 25627. Methods for production of dyestuffs, 1929-1940, 1138页, Price: Microfilm $6.00, Enlargement print $114.00.

PB 25627, 3148-3150, “Wool Green BSNA”, Apr 1930, Price: Microfil $1.00, Photostat $1.00. This dye is produced by condensation of R-salt [148-75-4] and “Hydrol [119-58-4]” and oxidation with manganese dioxide. The process is described. In German.

PB 82232. Production of dyes, 1939-1946, 1078页, Price: Microfilm $7.00, Enlargement print $109.00.

PB 82232, 799, “Woolgrün B S”, n. d, In German, Price: Microfilm $2.00. From R-salt [135-51-3] and hydrol [119-58-4].

Colour Index Second Edition, 1956, Vol. 3, P.3378, C.I. 44090, C.I. Acid Green 50 = C.I. Food Green 4. (结构式：略)

Condense p,p’-(dichloromethylene)bis[N,N-dimethylaniine] with 2-naphthol, sulfonate with oleum, and convert into the sodium salt.

Condense 4,4’-bis(dimethylamino)benzhydrol with 2-naphthol-3,6-disulfonic acid, oxidize the product and convert into the sodium salt.

【Discoverer】Badische Co. 1883.

【生产工艺参考文献】FIAT 1313, 2, 350, FIAT 764 – Wollgruen S。

(日)细田豊 《理论制造染料化学》，技报當出版，1957年，P.781，ウ-ル グリ-ン BS，译自PB 25626。

(1) リウコ酸(隐色酸，其CAS号暂未找到，反应式：略)

60%硫酸1.3tにR酸[148-75-4] 100% 324kgと，テトラメチルジアミノベンゾヒドロ-ル[119-58-4]100% 258kg (ペ-スト6–700kg)を同时に装入し，1hで800に上げ2–3hヒドロ-ル消失えるまで保温，冰600kgを加え，6m³にうすめ1夜搅拌，リウコ酸を滤洗する。ペ-スト800kg=乾燥560kg.

(2) Wool Green BS Extra highly conc [3087-16-9]

400の水2tにNa₂CO₃ 230kgを溶し，MnO₂ 100% 97kgのペ-スト加え，リウコ酸ペ-スト800kgを加え，400で约16h染料浓度の增加しなくなるまでつづける。450でNa₂SO₄ 1.2t，60% 硫酸240kgを加えて染料を树脂状で落し，分けて1000 で减压乾燥する。ペ-スト950kg =乾燥600kg [3087-16-9]，30/100。

Kosmetische Färbemittel / Colours for Cosmrtics, 1984, C-Grün 4, C.I. 44090, C.I. Acid Green 50.

【学名/分子式/分子量/结构式】略

【商品名】Acilangrün BS

【其他数据，含毒性数据】略

【层析】2个斑点

【吸收曲线和红外光谱图】略

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P.14，(十八)酸性羊毛绿[3087-16-9]R酸结构：

于40°C以下，将米氏醇[119-58-4]膏状物与R酸交替地加入稀硫酸中，慢慢加热升温至90°C，缩合反应至无米氏醇为终点。终点后冷却并用水稀释，沉析出隐色体后过滤。滤饼用水打浆稀释，加入MnO₂，于33–34°C搅拌氧化6小时，过滤后水洗，滤液用硫酸酸化，冷却，盐析即得羊毛绿BS。(【抄注】此资料为FIAT 1313, 2, 350的摘译文！)

Coloring of Foods, Drugs and Cosmetics, 1999, P.220-221. C.I. 44090. C.I. Acid Green 50 =C.I. Food Green 4. 摘录：

【Chromatography】DC = TLC: Kieselgel. Carrier: Acetic acid ester 11ml + Pyridine 6ml + Water 4ml.

【Main application】Food - Candies, Cosmetics - Poor light stability in products containing tensides.

【毒性数据】略

何岩彬主编《染料品种大全》，沈阳出版社出版，2018年，P.289, C.I.酸性绿50, P.985, C.I.食品绿4。

陈忠源 2021年9月14日，星期二