【CAS名】Chromate(6), tris[3-[[[3-[(4,5-dihydro-3-methyl-5-oxo-1H-pyrazol-4-yl)azo]phenyl]sulfonyl]amino]-2-hydroxy-5-sulfobenzoato(3-)-, hexasodium.

【CAS号】[6408-24-8]

【酸式CAS号】[10127-20-5]

【产品结构式】略

【分子式/分子量】C₅₁H₃₉CrN₁₅Na₆O₂₇S₆ = 1676.23

【用途】织物染色和皮革着色等

资料I：BIOS 1548 (=胶卷PB 85593), The manufacture of Azo andLake Dyestuffs at Hoechst,Ludwigshafen andLeverkuusen.

【Date of Investigation】September and October: 1946, 这应该是二手资料，因为它译自德文生产工艺资料，此书本人有收藏。

BIOS 1548, 15-17. Palatine Fast Yellow 6GEN (Ludwigshafen) =C.I. Acid Yellow 106。资料抄录如下(其中CAS号为本人所加)：

Chromium complex of the azo compound

(m-Aminobenzenesulphonyl)-o-amino-p-sulphosalicylic acid [6201-85-0] --> 3-methyl-5-pyrazolone [108-26-9]

【产品结构式】略

(m-Aminobenzenesulphonyl)-o-amino-p-sulphosalicylic acid [6201-85-0] is diazotized and coupled alkaline solution with a solution of 3-methyl-5-pyrazolone [108-26-9] made by condensation of acetoacetic ester [141-97-9] and hyudrazine sulphate [10034-93-2]. The azo compound is isolated, chromium formate and the chroming evaporated.

【反应方程式(含参与反应化合物的分子量)】略

【Works charges and yield】如下：

Pure dyestuff content of type = 39%, Yield = 86% theory

【Time per batch】3 days.

【Plant 1】For Coupling

【Plant 2】For Chroming

【设备】略(不再抄录)

【Method】Scale 0.6kg/mol

1.     Coupling

233kg at 100% (m-Amiobenzenesulphonyl)-o-amino-p-sulphosalicylic acid [6201—85-0] (Strength normally 75%) is dissolved alkaline in 1,800L cold water with 100kg 50% caustic soda and is then precipitated with 600L dilute HCl (M= 200). 800kg ice and water are then added to adjust to a volume of 4,200L and a temperature of 12°C. Diazotise with 180L 23% sodium nitrite solution added over 30 minutes. Volume = 4,400L; Temperature = 17°C. Stir 2 hours and then dissolve diazo by adding 345kg sodium acette crystals. Temperature 14°C. The day before the above diazotization, a solution of 3-methyl-5-pyrazolone [108-26-9] is prepared as follows:

82kg (at 100% ca. M. 130) Hydrazine sulphate [1003493-2] is dissolved in 300L water and 100kg 50% caustic soda. Heat to 50°C. and add over 3 hours 87kg (100% M 130) acetoacetic ester [141-97-9]. Maintain a temperature of 50°C. for 3 hours and then stir, cooling overnight. The pyrazolone is then dissolved by adding 50kg, caustic soda and the solution adjusted with ice and water to a volume of 1,500L and a temperature of 15°C. The diazo solution is run in over 0.5 hr. Coupling is complete when all the diazo has been mixed, as shown by testing with alkaline if-acid solution. Volume = 6,000L; Temperature = 18-20°C.Stir 2 hours, add 600kg salt and stir overnight. Next morning dilute with 2,000L water and then filter. Filtration takes 5 hours. The motherLiquors are yellow but contain no true dyestuff. Paste weight = 1200kg.

2.     Chroming and Drying

The press paste is charged into a hot filtered solution of 51kg chromium oxide (100% extra dry) and 102kg 100% formic acid tech in 200L water. Heat to 90°C. and maintain this temperature for 0.5 hour. Transfer to Haveg trays and dry, in thinLayers, in air at 80°C. Yield = 508kg at 57 = 100 = 534kg Palatine Fast Yellow 6GEN conc. (60 = 100) = 890kg Palatine Fast Yellow 6GEN. At 39% pure dyestuff content this corresponds to 346kg pure dyestuff and a yield of 86% theory.

【Note】Trials of drying in vacuo at 100°C. resulted inLower yields then drying in air at 80°C.

【Patent Reference】DRP.633,834.

资料II：PB 25625, Manufacturing methods of preparation of dyestuffs, 1932-1939, 1171, 【Price】Microfilm $6.00; Enlargement print $117.50.

PB 25625, 950-954. Directions for producing “Palatinechtgelb 5 GN” and “6 GEN”, 【Price】Microfilm $1.00. Photostat $1.00.

The intermediate for “Palatinechtgelb 5 GN” is obtained by diazotization of aniline-3-sulfamide [98-18-0] and coupling with 1-(2’-hydroxy-3’-carboxy-5’-sulfophenyl)-3-methyl-5-pyrazolone. For “Palatinechtgelb 6 GEN” m-aminobenzenesulfonyl-o-amino-p-sulfo-salicylic acid is diazotized and coupled with methylpyrazolone. Either intermediate then is chromed by means of chromic oxide and formic acid. In German. (德文资料原件未抄录)

资料III：PB 73561 (这是本人手工抄录的目录)

PB 74561, 321-325, Palatinechtgelb 6 GEN, 1943年5月25日德文生产工艺 (资料原件未抄录)

资料IV：Colour Index Second Edition, 1956, Volume 3, P.3108, C.I. 18670, C.I. Acid Yellow 106 (Greenish yellow).

【A chromium complex 结构式】略

【制法】3-(m-Aminophenylsulfoamido)-5-sulfosalicylic acid --> 3-Methyl-5-pyrazolone; then convert to the chromium complex by heating in aqueous solution at 85°C with chromium formate.

【Discoverers-H】Winkeler and E. Fischer ,1934

【生产工艺参考文献】BIOS 1548, 15; FIAT 764-Palatinechtgelb 6 GEN.

资料V：张兆麟、张玉珍著《染料丛书-金属络合染料》，化学工业出版社出版，1986年，P.114-115。

派拉丁坚老黄6GEN(Palatin Fast Yellow 6 GEN)，译自BIOS 1548,15，抄录如下(其中CAS号为本人所加)：

(间氨基苯磺酰基)-邻氨基-对磺基水杨酸 --> 3-甲基-5-吡唑啉酮偶氮化合物的铬络合物

【结构式】略

【重氮化-偶合】(规模0.6kg/mol)

233kg 100%(间氨基苯磺酰基)邻氨基对磺基水杨酸 [6201-85-0](一般浓度75%)用100kg 50% 苛性钠溶解在1800L冷水中，然后加600L稀盐酸进行沉淀，加800kg 冰和水将体积调到4200L，温度降至12°C，用180L 23% 亚硝酸钠溶液在30分钟以上的时间内进行重氮化，体积4400L，温度17°C，搅拌2小时后加入345kg结晶醋酸钠使重氮化合物溶解，温度为14°C。在重氮化的前一天按着如下方法准备好3-甲基-5-吡唑啉酮[108-26-9]的偶合液：

用100kg 50%苛性钠将82kg (100%) 肼硫酸盐[10034-98-2]溶解在300L水中，升温至50°C并在3小时左右的时间内加入87kg (100%) 乙酸乙酯 [141-97-9]。在50°C下保温3小时，搅拌冷却过夜之后，加50kg 50%苛性钠溶液，将生成的吡唑啉酮溶解，用冰和水稀释到1500L，温度调到15°C。将重氮液在半小时内加到偶合液中。當重氮液加完后，以H酸碱性作为指示剂，检验偶合反应完成。体积6000L温度18-20°C。搅拌两小时后，加600kg食盐，搅拌过夜，次晨，加2000L水稀释，过滤，过滤约需5小时。母液呈黄色，但不含真正的染料，滤饼1200kg。

【铬络合与干燥】

将滤饼加入51kg氧化铬(100%干燥品)和102kg 100% 的工业甲酸溶于200L水的过滤的热溶液中，加热至90°C，保持半小时，转移至干燥盘(Havey tray)中，以薄层状态于80°C下干燥，产率86%。

资料VI：何岩彬主编《染料品种大全》，沈阳出版社出版，2018年，P.33，C.I.酸性黄106 (C.I. 18670)。

资料译自Colour Index，参考文献增补了本人提供的“特种文献号”，但是未提及BIOS 1548的译文。

【国内生产厂商】浙江杭州下沙恒升化工有限公司

陈忠源 2022年2月10日，星期四