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CAS号[6408-24-8]生产工艺 - C.I.酸性黄106(C.I. 18670)

【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：

Amine

Hydrazine

Acetoacetic ester

Cr2O3

Product

233

30

87

51

890 Type

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

 



文章作者：陈忠源