【CAS名】Methanaminium, N-[4-[[4-dimethylamino]phenyl][4-(methylamino)phenyl]methylene]-2,5-cyclohexadien-1-ylidene]-N-methyl-, Chloride (1:1). Beil. 13, 755.

【用途】织物染色，医药“紫药水”，用于C.I. 颜料紫3；C.I. 溶剂紫8等

FIAT 1313, II, 314-317(=胶卷PB 85172), Methyl Violet N Blue (ludwigshafen).

【结构式】略

全文抄录如下：

Methyl Violet was normally made by the old and well known dry melt procedure in amounts as high as 400 tons per year. It was made only at Ludwigshafen. A large amount of experimental plant work on a fluid melt process had been done but the process had not been adopted because a vessel with satisfactory corrosion resistance and heat transfer could not be found. Enamelled cast iron was best but it did not last well enough. One process found for such a fluid melt was as follows; To a mixture of 1,000L water, 30kg. sodium chloride, 236kg. copper sulfate (equivalent to 59kg copper) in a 5 cbm. Enameled kettle fitted with baffles and a plate agitator add 20°C 400kg dimethyl aniline [121-69-7]. 24 kg cresylic acid DAB4 [106-44-5].  Agitate 30 minutes at 20°C at 50 r.p.m.. Then increase agitator speed to 100 r.p.m. and blow air in. Add salt in portions of 10kg every hour to a total of 222kg. Pass air in as follows:

12 cbm per hour for first 4 hours; 17 cbm per hour for next 16 hours; 23 cbm per hour for last 4 hours. Complete the oxidation in 24 hours, gradually raising temperature to 80°C. The charge was then worked up by the usual basification with sodium hydroxide, treatment with sodium sulfide and extraction. The fluid melt was of interest to I.G. because it would avoid the disagreeable manual handling of the dry melt although the plant chemist pointed out that much of that handling could be avoided by rearrangement of the plant and provision of mechanical devices. As far as could be ascertained, no significant study of oxidation agents other than air had been made by I. G. Likewise nothing concerning continuous processing beyond the rotary vacuum filter already mentioned was found. Process details on the dry melt had been obtained previously by other investigators and are not repeated. The melt was made in shallow cast iron pans (2.05 meters in diameter, 0.6 meter deep) fitted with multi-plow agitators traveling at 15 r.p.m. The charge used was 630-680kg salt (sodium chloride), 58kg copper sulfate, 23kg xylenol, and 100kg dimethyl aniline.  The time for the melt was about 24 hours, starting at a bath temperature of 20°C and raising to 45°C. Actual temperature of the melt was not measured but was about 65-70°C at the finish. Power consumption of the agitator and appearance of the melt were then used as controls, through the melt should not be continued to complete disappearance of dimethyl aniline. Salt quality, especially particle size and surface, is of prime importance. About 60% retained on 80 mesh is proper salt size. The xylenol should be completely alkali soluble. The melts were basified with sodium hydroxide in horizontal steel tanks fitted with spiral agitators and then treated with sodium sulfide. After washing by decantation, the basified mass extracted with dilute sulfuric acid in lead lined equipment, the insoluble copper containing residue filtered off, and the color precipitated as the hydrochloride by the addition of salt to the filtered solution. This crude color was again dissolved in water, the solution screened, and the color salted out once more. Tarry color so obtained was melted and run off into jacketed open kettles where water layers were further separated and discarded or cold water washes were carefully made to reduce salt content for special types.

Methyl Violet was preferably dried on atmospheric double drum dryers. Generally it was necessary to shade with New Fuchsine in the Standardization. The yield was 104kg crude color from 100kg dimethyl aniline, which was stated to be 84.3% of the theoretical since the crude was 91.5% pure. Dimethyl aniline recovered from Michler’S Ketone and Crystal Violet was used for Methyl Violet manufacture at an assigned purity of 99.7% for accounting purposes. The copper containing residue was roasted in shallow ovens and the ash treated with sulfuric acid to recover copper sulfate crystals for reuse. Since the residue tended to be pyrophoric, it was necessary only to initiate the roasting with a gas flame, after which it proceeded spontaneously.

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

PB 25626, 1425-1438, Directions for producing “Methylviolett N blau” (liquid method), Sep 1930-Oct 1937, Price: $1.00.

Detailed directions for the production, by oxidation of dimethyl aniline and phenol are given. One of the four pages is almost illegible. An earlier description (of 1930), is added, using cresol instead of phenol. Also described is the process (1932) for “Methylenviolet 3 RA extra” using diethylaniline and aniline, In German.

PB 70135, Directions for producing various dyes, 1929-1945, 861页, Price: Microfilm $6.00, Photostat $86.50.

PB 70135, 1013 – 1061. Methylviolett N blau (Methyl violet N blue). Sep 1938, Price: $5.00.

PB 70135, Methyl violet base (Methyl violet base), 1938, Price: $1.50.

Colour Index Second Edition, 1956, Volume 3, P.3356, 42535 C.I. Basic Violet 1 (Bluish violet)

42535:1, C.I. Solvent Violet 8 (Bluish bluish violet); 42535:2, C.I. Pigment Violet 3 (Bright bluish violet); 42535:3, C.I. Pigment Violet 27.

【Chemical name】Methyl Violet

A mixture of the hydrochloride of the more highly methylated pararosaniline, containing principally the N-tetra-, penta-, and hexamethl derivatives, obtained by oxidation of N,N-dimethylaniline with cupric chloride, or by the action of air on an intimate mixture of N,N-dimethylaniline, phenol, sodium chloride, and copper sulfate.  The free base is C.I. 42535:1 (C.I. Solvent Violet 8)

Phosphotungstomolybdic acid lake = C.I. Pigment Violet 3.

【Discoverer】Lauth 1861

【生产工艺参考文献】FIAT 1313, 2, 314. FIAT 764 - Methylviolettbase.

上海市有机化学工业公司《染料生产工艺汇编》，1976年，P. 555-556，碱性紫6BN。

【结构式/反应式】略

【氧化与缩合】在锅中加盐252公斤和 无水硫酸铜粉末11.8公斤，搅匀，加苯酚[108-95-2]6.5公斤。搅拌10分钟，加入N,N-二甲基苯胺[121-69-7] 36公斤。在40-68°C保温4.5-5小时。

【检验终点】1. 反应物发绿色闪光；2. 冷却变硬变脆；3. 仅有苯酚味，无刺鼻味。终点到达后，冷却，切碎。

【转位】在桶中加入172.5公斤30% 液碱，2100升水及4批上述物料。1小时升温至50°C，第二小时升温至60°C，第三小时升温至70°C，第四小时升温至80°C，第五小时升温至95°C，在95°C保温15分钟。加水4.7 – 6吨，冷至60 – 70°C，加入74公斤硫化钠溶液(含52% 硫化钠24公斤)，搅拌1小时，以硝酸铅试纸检验硫化钠微过量。终点到达后，过夜，过滤，洗涤至洗液使酚酞试纸呈微红。

分离：将上述滤饼稀释于120升水中，加入65% 硫酸40公斤，4小时加热至沸。(第一小时升温至40°C，用石蕊试纸显微红色。 第二小时升温至60°C，第三小时升温至90°C，第四小时升温至沸。)沸腾15分钟，过滤，滤渣加水600升，加热至沸。过滤，将滤液及洗液合并，加盐540公斤盐析。次日，将析出染料取出，于65°C真空烘干，标准化后得成品140公斤。

Kosmetische Fäbemittel / Colours for Cosmetics, Verlag Chemie, 1984, C-ext, Violett 5, Colour Index 42535, Basic Violet 1.

【学名】/【分子式】/【分子式】/【结构式】/【毒性数据】/【红外曲线图】略。

(俄)A.B. Eльцова，《染料及中间体实验室合成方法》，1985年，§4.1 碱性紫K (Основной Фиолетовый К)。

【反应式】略

C.I. 碱性紫1 合成方法：(本人译文，供参考)

【预先准备】(a) 4.8克硫酸铜结晶粉；(b)0.57克三氯化铁和4.5克氯化钠于25毫升0.4% 盐酸中配成溶液；(c) 25毫升20% 氢氧化钠溶液；(d)8毫升20% 硫酸溶液。

将装有搅拌，温度计和回流冷凝器的250毫升三口烧瓶，置于电加热水浴中，加入10毫升二甲基苯胺 [121-69-7] 和5克对甲基苯酚 [106-49-0]，搅拌下加入4.8克硫酸铜5水物细粉，5克氯化钠和45毫升热水(约60°C)，物料加热至60 – 65°C，搅拌保温反应6 – 7小时，放置过夜。反应完毕，物料应有金属光泽，然后加25毫升20% 氢氧化钠溶液至反应物中，再加水100毫升，稀释液搅拌成均匀的悬浮液，加热至57 – 60°C，随后加撤去水浴，停搅拌，放置约1小时，此时碱性染料成树脂状浮于液体表面，冷却至升温，通过过滤器虹吸出下面的水层，滤液弃去，留在烧杯内的物料中，加入150毫升水，搅拌后用同一个过滤器过滤，滤饼用100毫升水(每次25毫升)洗涤到中性或弱碱性(pH 7 - 8)。将装有搅拌，温度计和滴液漏斗的300毫升烧杯置于电炉上，固定在卡圈内，将碱性染料滤饼放入烧杯内，加100毫升水进行搅拌，然后滴加8毫升20% 硫酸，物料加热到75°C，趁热过滤，滤液置于同一个烧杯内，加入三氯化铁和氯化钠的盐酸溶液，染料成树脂状浮出液面，用玻璃取下，置于培养皿中，于50-60°C干燥。得量在3.8到9.5克之间波动(约13-32%)，薄层展开(醋酸：水)，Rf 0.65。

【乙醇中吸收曲线图】略

Coloring of Foods, Drugs and Cosmetics, Axel Mixa, 1999, P.214. C.I. 42535, C.I. Basic Violet 1. 摘录:

【Chromatography】DC = TLC. Cellulose.

【Carrier】Tert. Butanol 40ml + Methylethylketone 25ml + Water 25ml

【Absorption maximum】584nm (own assay: 584nm).

【Main applications】Food: stamp color for food products.

【认证国家】7家

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.277，C.I. 碱性紫 1 (C.I. basic Violet 1)

【C.I. 42525】错了

【化学结构式】错了

【制法】译自《Colour Index》，中文译文，不再抄录。

【参考文献】FIAT 1313,2,314；FIAT 764 – Methylviolettbase. 抄自Colour Index

何岩彬主编《染料品种大全》，沈阳出版社出版，2018年，P.459，C.I. 碱性紫1 (C.I. 42535)

【制法】译自Colour Index

【参考文献】增加了本人免费提供的部分资料目录

陈荣圻(上海纺织职工大学)《有机色素在非传统着色领域的应用》，[J] 染料与染色, 2021, 2, 17-34。摘录：

【在生物医学上的应用】早期作为药品的染料，本文主要介绍家庭药箱中的外用消炎药，其中提到C.I. 碱性紫1，资料全文不再抄录。

陈忠源 2021年10月，国庆节假日