WO2015123992A1 - 一种制备分散蓝360的方法 - Google Patents

一种制备分散蓝360的方法 Download PDF

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WO2015123992A1
WO2015123992A1 PCT/CN2014/087534 CN2014087534W WO2015123992A1 WO 2015123992 A1 WO2015123992 A1 WO 2015123992A1 CN 2014087534 W CN2014087534 W CN 2014087534W WO 2015123992 A1 WO2015123992 A1 WO 2015123992A1
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nitrothiazole
reaction
mass ratio
diethylamino
temperature
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PCT/CN2014/087534
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French (fr)
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徐松
刘学峰
郭维成
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江苏道博化工有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/38—Nitrogen atoms
    • C07D277/50—Nitrogen atoms bound to hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
    • C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
    • C09B29/0085—Thiazoles or condensed thiazoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes

Definitions

  • the invention relates to a preparation method of a known disperse dye, and more specifically to a method for synthesizing disperse blue 360, belonging to the field of manufacturing chemical dyeing materials.
  • Disperse Blue 360 chemical name 2-[[4-(diethylamino)-2-methylphenyl]azo]-5-nitrothiazole, which is a novel heterocyclic azo disperse dye, insoluble For whom and ethanol, it is blue in concentrated sulfuric acid.
  • the dye has bright color, high absorption coefficient, high dyeing intensity, excellent improvement rate, good dyeing performance, light fastness and smoke fastness. It is mainly used for dyeing and printing of polyester and blended fabrics, and can also be used for dyeing and printing of polyester and blended fabrics. Dyeing of microfibers. Its molecular formula is C 14 H 17 N 5 O 2 S, and its relative molecular mass is 319.3.
  • the Disperse Blue 360 structure is:
  • Disperse Blue 360 is a relatively new type of dye. It is an environmentally friendly blue dye. There are very few domestic production companies. At present, the demand for domestically dispersed blue 360 must rely on imports.
  • the existing production method at home and abroad is to produce 2-amino-5-nitrothiazole by nitrification using 2-aminothiazole as a raw material, and then diazotization to obtain a diazonium salt, and then N, N-diethyl m-toluidine Coupling to obtain the product, the existing production method synthesis route is as follows:
  • the method has the following shortcomings. Firstly, the synthesis of 2-amino-5-nitrothiazole is difficult, the yield is low, and the cost is high. Domestic and foreign manufacturers have been looking for alternatives; secondly, heterocyclic compound 2 is used. -Diazotization coupling reaction of amino-5-nitrothiazole, the route has many side reactions, the reaction is difficult, the cycle is long, the yield is low, the purity of the obtained product is not high; the third is the diazotization coupling reaction at low temperature Under the control, the temperature control is strict, a large amount of chilled brine is needed, and the reaction conditions are harsh, especially in the summer, the refrigeration performance of the refrigeration unit is a strict test; the fourth is that the diazotization coupling reaction produces a large amount of acidic waste water.
  • Disperse Blue 360 has excellent performance, and the application of the product is continuously developed, with good application potential and development prospects. Therefore, it has important practical significance to develop a disperse blue 360 synthesis process suitable for large-scale clean production.
  • the technical solution for achieving the object of the present invention is: using 2-bromothiazole as a raw material, the target product is obtained by four unit reaction processes of nitrification, deuteration, amination and oxidation, and the specific route is based on 2-bromothiazole as a raw material.
  • the nitration reaction occurs under the action of a mixture of concentrated nitric acid and concentrated sulfuric acid to form 2-bromo-5-nitrothiazole, and the obtained 2-bromo-5-nitrothiazole is treated with 2-methyltetrahydrofuran as a solvent under the action of hydrazine hydrate.
  • the reaction produces 2-mercapto-5-nitrothiazole, the resulting 2-mercapto-5-nitrothiazole and 3-methyl-4-chloro-N,N-diethylaniline in the acid-binding agent 2-[[4-(Diethylamino)-2-methylphenyl] hydrazide]-5-nitrothiazole is formed by the action of amine, catalyst cuprous bromide and solvent butanol, and the prepared 2-[ [4-(Diethylamino)-2-methylphenyl] hydrazide]-5-nitrothiazole under the action of an oxidizing agent to produce the target product 2-[[4-(diethylamino)-2-methyl Phenyl phenyl] azo]-5-nitrothiazole.
  • the synthetic route adopted by the present invention is as follows:
  • Nitrification reaction 2-bromothiophene, concentrated sulfuric acid and concentrated nitric acid are put into the reactor, stirred and heated to a certain temperature for reaction. After the reaction is finished, the temperature is lowered, and the cooled reaction solution is added to soft water, filtered, and dried to obtain a solid product.
  • 2-bromo-5-nitrothiazole 2-bromo-5-nitrothiazole
  • Oxidation reaction 2-[[4-(diethylamino)-2-methylphenyl] hydrazin]-5-nitrothiazole, solvent DMSO, catalyst NH 4 VO 3 , CuCl 2 and H 2 SO 4 is put into the reactor, stirred and heated to a certain temperature, and the oxidizing agent sodium perborate is slowly added. After the end of the feeding, the temperature is further increased, and the reaction is kept at a certain temperature. After the reaction is completed, methanol is added dropwise, filtered, and dried to obtain the target product dispersion blue 360.
  • the mass ratio of 2-bromothiophene to concentrated sulfuric acid described in step 1 is 1: (2-4), the mass ratio of 2-bromothiophene to concentrated nitric acid is 1: (2-4), and the reaction temperature is 45-55. At °C, the reaction time is 2 hours or more, and the temperature of the reaction liquid after the temperature reduction is 20 ° C or lower.
  • the mass ratio of 2-bromo-5-nitrothiazole to hydrazine hydrate described in the step 2 is 1: (0.28-0.4), and the mass ratio of 2-bromo-5-nitrothiazole to 2-methyltetrahydrofuran is 1. : (20-40), the mass ratio of 2-bromo-5-nitrothiazole to methanol is 1: (30-40), the reaction temperature is 30-35 ° C, and the reaction time is 1 h or more.
  • the mass ratio of 2-[[4-(diethylamino)-2-methylphenyl] hydrazin]-5-nitrothiazole to DMSO in step 4 is 1: (10-20), 2- The mass ratio of [[4-(diethylamino)-2-methylphenyl] hydrazin]-5-nitrothiazole to NH 4 VO 3 is 1: (0.025-0.05), 2-[[4- The mass ratio of (diethylamino)-2-methylphenyl] hydrazino]-5-nitrothiazole to CuCl 2 is 1: (0.2-0.25), 2-[[4-(diethylamino) The mass ratio of -2-methylphenyl] hydrazin]-5-nitrothiazole to H 2 SO 4 is 1: (0.5-1), 2-[[4-(diethylamino)-2-methyl The mass ratio of phenyl] hydrazine]-5-nitrothiazole to sodium perborate is 1: (1.5-2), 2-[[4-(dieth
  • the new synthetic route is relatively clean and clean, avoiding the formation of a large amount of acidic wastewater in the diazo coupling reaction, and has a competitive advantage in the discharge of the three wastes.
  • the oximation reaction uses 2-methyltetrahydrofuran instead of tetrahydrofuran as the reaction solvent, which improves the yield of the reaction and reduces the energy consumption for solvent recovery.
  • the amination reaction selects the appropriate acid binding agent, catalyst, molar ratio and reaction temperature, and the air in the reaction system is replaced by nitrogen gas, thereby avoiding the occurrence of side reaction double substitution and improving the purity of the product.
  • the suitable oxidant sodium perborate and the composite catalyst NH 4 VO 3 /CuCl 2 /H 2 SO 4 were screened for ruthenium oxidation, which solved the problem that the oxidation conversion rate of oxidant was not high with hydrogen peroxide as the azo dye.
  • the synthesis provides a new preparation method.
  • a method for preparing disperse blue 360 the steps of which are as follows
  • Nitrification reaction (synthesis of 2-bromo-5-nitrothiazole): Put concentrated sulfuric acid and concentrated nitric acid into the reactor, reduce the temperature to 15 ° C, add 2-bromothiazole, stir the temperature to 45-55 ° C, keep the reaction for 2 h.
  • the mass ratio of 2-bromothiophene to concentrated sulfuric acid is 1: (2-4), and the mass ratio of 2-bromothiophene to concentrated nitric acid is 1: (2-4); after the reaction is finished, the temperature is lowered to 20 ° C, at 20 The reaction solution was added to soft water below ° C, filtered, and the filter cake was washed with water to neutrality and dried to give a solid product, 2-bromo-5-nitrothiazole.
  • the mass ratio is 1: (20-40), the mass ratio of 2-bromo-5-nitrothiazole to methanol is 1: (30-40); after adding methanol, filtering, the filter cake is washed with methanol, below 55 ° C Drying in vacuo gave the solid product 2-mercapto-5-nitrothiazole.
  • Amination reaction (synthesis of 2-[[4-(diethylamino)-2-methylphenyl] hydrazide]-5-nitrothiazole): 2-mercapto-5-nitrothiazole , 3-methyl-4-chloro-N,N-diethylaniline, triethylamine, cuprous bromide, butanol were put into the reactor, the reactor was replaced with nitrogen, the reactor was sealed, and the temperature was raised to 60-64.
  • the temperature ratio of 2-mercapto-5-nitrothiazole to 3-methyl-4-chloro-N,N-diethylaniline was 1:2 (1.3-1.38), 2- The mass ratio of mercapto-5-nitrothiazole to triethylamine is 1: (2-3), and the mass ratio of 2-mercapto-5-nitrothiazole to cuprous bromide is 1: (0.025-0.1) , the mass ratio of 2-mercapto-5-nitrothiazole to methyl ethyl ketone is 1: (5-10); after the reaction is completed, it is cooled to normal temperature, filtered, and the filter cake is washed with a small amount of methanol, and dried to obtain a solid product 2-[[4 -(Diethylamino)-2-methylphenyl] hydrazin]-5-nitrothiazole.
  • Oxidation reaction (synthesis of disperse blue 360): 2-[[4-(diethylamino)-2-methylphenyl] hydrazin]-5-nitrothiazole, solvent DMSO, catalyst NH 4 VO 3 /CuCl 2 /H 2 SO 4 was put into the reactor, stirred and heated to 80-85 ° C, and the oxidizing agent sodium perborate was added for about 1 hour.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thiazole And Isothizaole Compounds (AREA)

Abstract

本发明公开了一种制备分散蓝360的方法。以2-溴噻唑为原料，经硝化、肼化、胺化、氧化四个单元反应过程得到目标产物，其具体途径是以2-溴噻唑为原料，在浓硝酸和浓硫酸的混合物的作用下发生硝化反应，生成2-溴-5-硝基噻唑，所得2-溴-5-硝基噻唑用2-甲基四氢呋喃作溶剂，在水合肼作用下进行反应，生成2-肼基-5-硝基噻唑，生成的2-肼基-5-硝基噻唑与3-甲基-4-氯-N,N-二乙基苯胺在三乙胺、溴化亚铜、丁醇的作用下生成2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑，制备的2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑在氧化剂的作用下生成目标产物。本发明以过硼酸钠和复合催化剂进行肼氧化，解决了采用双氧水做氧化剂肼氧化转化率不高的难题，为该偶氮染料的合成提供了一条新的制备方法。

Description

一种制备分散蓝360的方法 技术领域
本发明涉及一种已知分散染料的制备方法，确切地说是一种分散蓝360的合成方法，属于化工染化料的制造领域。
背景技术
分散蓝360，化学名为2-[[4-(二乙基氨基)-2-甲基苯基]偶氮]-5-硝基噻唑，它是一种新型杂环偶氮分散染料，不溶于谁和乙醇，在浓硫酸中为蓝色。该染料色光鲜艳，吸光系数大，染色强度高，有优异的提升率，拔染性能和耐晒牢度及烟熏牢度较好，主要用于涤纶及混纺织物的染色和印花，也可用于超细纤维的染色。其分子式为C14H17N5O2S，相对分子质量为319.3。分散蓝360结构式为：
Figure PCTCN2014087534-appb-000001
分散蓝360是较新的染料品种，是环保蓝色染料，国内生产企业寥寥无几，目前国内分散蓝360的需求必须依赖进口。国内外现有的生产方法是以2-氨基噻唑为原料经过硝化生产2-氨基-5-硝基噻唑，然后重氮化制得重氮盐，再与N、N-二乙基间甲苯胺偶合得到产品，现有的生产方法合成路线如下：
Figure PCTCN2014087534-appb-000002
该方法存在以下几个方面的不足，首先2-氨基-5-硝基噻唑的合成难度较大，收率较低，成本较高，国内外厂家一直寻找其替代品；其次采用杂环化合物2-氨基-5-硝基噻唑进行的重氮化偶合反应，该路线副反应多，反应难度较大、周期长、收率低，所得产品纯度不高；第三该重氮化偶合反应在低温下进行，对温度的控制要求严格，需要大量的冷冻盐水，反应条件比较苛刻，尤其在夏天对冷冻机组的制冷性能是个严格的考验；第四该重氮化偶合反应产生酸性废水量大， 杂质复杂，治理难度大，对环境压力较大。分散蓝360具有优良的性能，产品的应用不断被开发，具有较好的应用潜力及发展前景。因此，开发出适合规模化清洁生产的分散蓝360合成工艺具有很重要的现实意义。
发明内容
本发明的目的在于提供一种分散蓝360的合成方法。
实现本发明目的的技术解决方案为：以2-溴噻唑为原料，经硝化、肼化、胺化、氧化四个单元反应过程得到目标产物，其具体途径是以2-溴噻唑为原料，在浓硝酸和浓硫酸的混合物的作用下发生硝化反应，生成2-溴-5-硝基噻唑，所得2-溴-5-硝基噻唑用2-甲基四氢呋喃作溶剂，在水合肼作用下进行反应，生成2-肼基-5-硝基噻唑，生成的2-肼基-5-硝基噻唑与3-甲基-4-氯-N,N-二乙基苯胺在缚酸剂三乙胺、催化剂溴化亚铜、溶剂丁醇的作用下生成2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑，制备的2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑在氧化剂的作用下生成目标产物2-[[4-(二乙基氨基)-2-甲基苯基]偶氮]-5-硝基噻唑。
本发明采用的合成路线如下：
Figure PCTCN2014087534-appb-000003
Figure PCTCN2014087534-appb-000004
具体反应步骤如下：
1、硝化反应：将2-溴噻吩、浓硫酸、浓硝酸投入反应器中，搅拌升温至一定温度反应，反应结束后降温，将降温后的反应液加到软水中，过滤，干燥得到固体产物2-溴-5-硝基噻唑；
2、肼化反应：将2-溴-5-硝基噻唑、水合肼、2-甲基四氢呋喃投入反应器中，搅拌保温至一定温度反应，反应结束后加入适量甲醇，过滤，真空干燥出固体产物2-肼基-5-硝基噻唑；
3、胺化反应：将2-肼基-5-硝基噻唑、3-甲基-4-氯-N,N-二乙基苯胺、三乙胺、溴化亚铜、丁醇投入反应器，氮气置换反应器，密闭反应器，搅拌升温至一定温度反应，反应结束后降至常温，过滤，干燥得到固体产物2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑；
4、氧化反应：将2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑、溶剂DMSO、催化剂NH4VO3、CuCl2和H2SO4投入反应器，搅拌升温至一定温度，缓慢加入氧化剂过硼酸钠，加料结束后继续升温，在一定温度下保温反应，反应结束后滴加甲醇，过滤，干燥得到目标产物分散蓝360。
步骤1中所述的2-溴噻吩与浓硫酸的质量比为1：(2-4)，2-溴噻吩与浓硝酸的质量比为1：(2-4)，反应温度为45-55℃，反应时间为2h以上，降温后的反应液的温度为20℃以下。
步骤2中所述的2-溴-5-硝基噻唑与水合肼的质量比为1：(0.28-0.4)，2-溴-5-硝基噻唑与2-甲基四氢呋喃的质量比为1：(20-40)，2-溴-5-硝基噻唑与甲醇的质量比为1：(30-40)，反应温度为30-35℃，反应时间为1h以上。
步骤3中所述的2-肼基-5-硝基噻唑与3-甲基-4-氯-N,N-二乙基苯胺的质量比 为1：(1.3-1.38)，2-肼基-5-硝基噻唑与三乙胺的质量比为1：(2-3)，2-肼基-5-硝基噻唑与溴化亚铜的质量比为1：(0.025-0.1)，2-肼基-5-硝基噻唑与丁酮的质量比为1：(5-10)，反应温度为60-64℃，反应时间为2-2.5h。
步骤4所述的2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与DMSO的质量比为1：(10-20)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与NH4VO3的质量比为1：(0.025-0.05)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与CuCl2的质量比为1：(0.2-0.25)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与H2SO4的质量比为1：(0.5-1)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与过硼酸钠的质量比为1：(1.5-2)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与甲醇的质量比为1：(30-60)，反应温度为120-125℃，反应时间为4h以上。
本发明与现有技术相比，具有显著的有点：
1、开发了一条新的合成路线，以2-溴噻唑为原料，经硝化、肼化、胺化、氧化四个单元反应过程得到目标产物，每一环节都有明显优势，成本大幅度降低，具有较好的发展前景。
2、新的合成路线与现有的重氮化偶合路线相比，反应系统相对清洁干净，避免了重氮偶合反应大量的酸性废水的生成，在三废排放量上具有竞争优势。
3、肼化反应采用2-甲基四氢呋喃替换四氢呋喃做反应溶剂，提高了该反应的收率，降低了溶剂回收的能耗。
4、胺化反应选用了合适的缚酸剂、催化剂、摩尔比及反应温度，通过氮气置换出反应体系中的空气，避免了副反应双取代的发生，提高了产物的纯度。
5、筛选出了适宜的氧化剂过硼酸钠和复合催化剂NH4VO3/CuCl2/H2SO4进行肼氧化，解决了采用双氧水做氧化剂肼氧化转化率不高的难题，为该偶氮染料的合成提供了一条新的制备方法。
具体实施方式
以下集合实施例对本发明作进一步描述，但不局限于此。
实施例所用的原料，除另有说明外，均为适合染料及中间体使用的市售工业品；
一种制备分散蓝360的方法，其步骤如下，
1、硝化反应(2-溴-5-硝基噻唑的合成)：将浓硫酸、浓硝酸投入反应器中，降温至15℃，加入2-溴噻唑，搅拌升温至45-55℃保温反应2h以上，2-溴噻吩与浓硫酸的质量比为1：(2-4)，2-溴噻吩与浓硝酸的质量比为1：(2-4)；反应结束后降温至20℃，于20℃以下将反应液加到软水中，过滤，水洗涤滤饼至中性，干燥，得到固体产物2-溴-5-硝基噻唑。
2、肼化反应(2-肼基-5-硝基噻唑的合成)：将2-溴-5-硝基噻唑、水合肼、2-甲基四氢呋喃投入反应器中，搅拌保温至30-35℃反应1h以上，反应结束后加入甲醇，2-溴-5-硝基噻唑与水合肼的质量比为1：(0.28-0.4)，2-溴-5-硝基噻唑与2-甲基四氢呋喃的质量比为1：(20-40)，2-溴-5-硝基噻唑与甲醇的质量比为1：(30-40)；加甲醇结束，过滤，滤饼用甲醇洗涤，55℃以下真空干燥，得到固体产物2-肼基-5-硝基噻唑。
3、胺化反应(2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑的合成)：将2-肼基-5-硝基噻唑、3-甲基-4-氯-N,N-二乙基苯胺、三乙胺、溴化亚铜、丁醇投入反应器，用氮气置换反应器，密闭反应器，搅拌升温至60-64℃保温2-2.5h反应，2-肼基-5-硝基噻唑与3-甲基-4-氯-N,N-二乙基苯胺的质量比为1：(1.3-1.38)，2-肼基-5-硝基噻唑与三乙胺的质量比为1：(2-3)，2-肼基-5-硝基噻唑与溴化亚铜的质量比为1：(0.025-0.1)，2-肼基-5-硝基噻唑与丁酮的质量比为1：(5-10)；反应结束后降至常温，过滤，少量甲醇洗涤滤饼，干燥得到固体产物2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑。
4、氧化反应(分散蓝360的合成)：将2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑、溶剂DMSO、催化剂NH4VO3/CuCl2/H2SO4投入反应器，搅拌升温至80-85℃，1小时左右加入氧化剂过硼酸钠，加料结束后继续升温至120-125℃保温反应4小时以上，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与DMSO的质量比为1：(10-20)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与NH4VO3的质量比为1：(0.025-0.05)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与CuCl2的质量比为1：(0.2-0.25)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与H2SO4的质量比为1：(0.5-1)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与过硼酸钠的质量比为1：(1.5-2)；反应结束后滴加甲醇离析，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与甲醇的质量比为1： (30-60)，过滤，少量水洗涤滤饼，干燥，得到目标产物分散蓝360。
实施例1
步骤1、2-溴-5-硝基噻唑的合成
在带有机械搅拌、温度计的250ml四口瓶中加入浓硫酸50g、浓硝酸50g，降温至15℃，再加入2-溴噻唑25g，搅拌升温至45℃保温反应2.5h；反应结束后降温至20℃，将反应液加到软水中，温度控制在20℃以下，过滤，水洗涤滤饼至中性，干燥，得到固体产物2-溴-5-硝基噻唑31.5g，含量97.5％，收率96.0％。
实施例2
步骤1、2-溴-5-硝基噻唑的合成
在带有机械搅拌、温度计的250ml四口瓶中加入浓硫酸75g、浓硝酸75g，降温至15℃，再加入2-溴噻唑25g，搅拌升温至48℃保温反应2h；反应结束后降温至20℃，将反应液加到软水中，温度控制在20℃以下，过滤，水洗涤滤饼至中性，干燥，得到固体产物2-溴-5-硝基噻唑32.0g，含量97.0％，收率97％。
实施例3
步骤1、2-溴-5-硝基噻唑的合成
在带有机械搅拌、温度计的500ml四口瓶中加入浓硫酸100g、浓硝酸100g，降温至15℃，再加入2-溴噻唑25g，搅拌升温至55℃保温反应2h；反应结束后降温至20℃，将反应液加到软水中，温度控制在20℃以下，过滤，水洗涤滤饼至中性，干燥，得到固体产物2-溴-5-硝基噻唑31.2g，含量98.0％，收率95.5％。
实施例4
步骤2、2-肼基-5-硝基噻唑的合成
在带有机械搅拌、温度计的1000ml四口瓶中加入2-溴-5-硝基噻唑10g、水合肼4g、2-甲基四氢呋喃200g，搅拌保温至30℃反应2h，反应结束后加入300g甲醇，过滤，滤饼用甲醇洗涤，55℃真空干燥12h，得到固体产物2-肼基-5-硝基噻唑7.12g，含量99.0％，收率94.3％。
实施例5
步骤2、2-肼基-5-硝基噻唑的合成
在带有机械搅拌、温度计的1000ml四口瓶中加入2-溴-5-硝基噻唑10g、水合肼2.8g、2-甲基四氢呋喃300g，搅拌保温至32℃反应1h，反应结束后加入350g 甲醇，过滤，滤饼用甲醇洗涤，50℃真空干燥12h，得到固体产物2-肼基-5-硝基噻唑7.16g，含量99.1％，收率95.0％。
实施例6
步骤2、2-肼基-5-硝基噻唑的合成
在带有机械搅拌、温度计的2000ml四口瓶中加入2-溴-5-硝基噻唑10g、水合肼3.5g、2-甲基四氢呋喃400g，搅拌保温至35℃反应1h，反应结束后加入400g甲醇，过滤，滤饼用甲醇洗涤，50℃真空干燥12h，得到固体产物2-肼基-5-硝基噻唑7.13g，含量99.5％，收率95.0％。
实施例7
步骤3、2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑的合成
在带有机械搅拌、温度计的100ml四口瓶中加入2-肼基-5-硝基噻唑10g、3-甲基-4-氯-N,N-二乙基苯胺13g、三乙胺30g、溴化亚铜0.25g、丁醇50g，用氮气置换反应体系，密闭反应器，搅拌升温至64℃保温2h反应，；反应结束后降至室温，过滤，少量甲醇洗涤滤饼，干燥得到固体产物2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑20.1g，含量95.2％，收率93.3％。
实施例8
步骤3、2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑的合成
在带有机械搅拌、温度计的250ml四口瓶中加入2-肼基-5-硝基噻唑10g、3-甲基-4-氯-N,N-二乙基苯胺13.8g、三乙胺20g、溴化亚铜1g、丁醇80g，用氮气置换反应体系，密闭反应器，搅拌升温至60℃保温2.5h反应；反应结束后降至常温，过滤，少量甲醇洗涤滤饼，干燥得到固体产物2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑20.5g，含量95.5％，收率95.5％。
实施例9
步骤3、2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑的合成
在带有机械搅拌、温度计的250ml四口瓶中加入2-肼基-5-硝基噻唑10g、3-甲基-4-氯-N,N-二乙基苯胺13.5g、三乙胺25g、溴化亚铜0.5g、丁醇100g，用氮气置换反应体系，密闭反应器，搅拌升温至63℃保温2.5h反应；反应结束后降至常温，过滤，少量甲醇洗涤滤饼，干燥得到固体产物2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑20.9g，含量94.8％，收率96.6％。
实施例10
步骤4、分散蓝360的合成
在带有机械搅拌、温度计的1000ml四口瓶中加入2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑10g、DMSO100g、NH4VO30.5g、CuCl22g、H2SO45g，搅拌升温至80℃，在1小时内缓慢加入过硼酸钠15g，加料结束后继续升温至120℃保温反应5h；反应结束后滴加300g甲醇离析，过滤，少量水洗涤滤饼，干燥，得到目标产物9g分散蓝360，含量99.1％，收率89.7％。
实施例11
步骤4、分散蓝360的合成
在带有机械搅拌、温度计的1000ml四口瓶中加入2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑10g、DMSO200g、NH4VO30.25g、CuCl22.5g、H2SO410g，搅拌升温至83℃，在1小时内缓慢加入过硼酸钠20g，加料结束后继续升温至125℃保温反应4；反应结束后滴加600g甲醇离析，过滤，少量水洗涤滤饼，干燥，得到目标产物9.1g分散蓝360，含量98.9％，收率90.5％。
实施例12
步骤4、分散蓝360的合成
在带有机械搅拌、温度计的1000ml四口瓶中加入2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑10g、DMSO150g、NH4VO30.25g、CuCl22g、H2SO410g，搅拌升温至85℃，在1小时内缓慢加入过硼酸钠18g，加料结束后继续升温至123℃保温反应6h；反应结束后滴加450g甲醇离析，过滤，少量水洗涤滤饼，干燥，得到目标产物9.1g分散蓝360，含量99.3％，收率90.9％。

Claims (5)

  1. 一种制备分散蓝360的方法，其特征在于包括以下步骤：
    步骤1、硝化反应：将2-溴噻吩、浓硫酸、浓硝酸投入反应器中，搅拌升温至一定温度反应，反应结束后降温，将降温后的反应液加到软水中，过滤，干燥得到固体产物2-溴-5-硝基噻唑；
    步骤2、肼化反应：将2-溴-5-硝基噻唑、水合肼、2-甲基四氢呋喃投入反应器中，搅拌保温至一定温度反应，反应结束后加入适量甲醇，过滤，真空干燥出固体产物2-肼基-5-硝基噻唑；
    步骤3、胺化反应：将2-肼基-5-硝基噻唑、3-甲基-4-氯-N,N-二乙基苯胺、三乙胺、溴化亚铜、丁醇投入反应器，氮气置换反应器，密闭反应器，搅拌升温至一定温度反应，反应结束后降至常温，过滤，干燥得到固体产物2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑；
    步骤4、氧化反应：将2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑、溶剂DMSO、催化剂NH4VO3、CuCl2和H2SO4投入反应器，搅拌升温至一定温度，缓慢加入氧化剂过硼酸钠，加料结束后继续升温，在一定温度下保温反应，反应结束后滴加甲醇，过滤，干燥得到目标产物分散蓝360。
  2. 根据权利要求1所述的制备分散蓝360的方法，其特征在于步骤1中所述的2-溴噻吩与浓硫酸的质量比为1：(2-4)，2-溴噻吩与浓硝酸的质量比为1：(2-4)，反应温度为45-55℃，反应时间为2h以上，降温后的反应液的温度为20℃以下。
  3. 根据权利要求1所述的制备分散蓝360的方法，其特征在于步骤2中所述的2-溴-5-硝基噻唑与水合肼的质量比为1：(0.28-0.4)，2-溴-5-硝基噻唑与2-甲基四氢呋喃的质量比为1：(20-40)，2-溴-5-硝基噻唑与甲醇的质量比为1：(30-40)，反应温度为30-35℃，反应时间为1h以上。
  4. 根据权利要求1所述的制备分散蓝360的方法，其特征在于步骤3中所述的2-肼基-5-硝基噻唑与3-甲基-4-氯-N,N-二乙基苯胺的质量比为1：(1.3-1.38)，2-肼基-5-硝基噻唑与三乙胺的质量比为1：(2-3)，2-肼基-5-硝基噻唑与溴化亚铜的质量比为1：(0.025-0.1)，2-肼基-5-硝基噻唑与丁酮的质量比为1：(5-10)，反应温度为60-64℃，反应时间为2-2.5h。
  5. 根据权利要求1所述的制备分散蓝360的方法，其特征在于步骤4所述的 2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与DMSO的质量比为1：(10-20)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与NH4VO3的质量比为1：(0.025-0.05)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与CuCl2的质量比为1：(0.2-0.25)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与H2SO4的质量比为1：(0.5-1)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与过硼酸钠的质量比为1：(1.5-2)，2-[[4-(二乙基氨基)-2-甲基苯基]联氨]-5-硝基噻唑与甲醇的质量比为1：(30-60)，反应温度为120-125℃，反应时间为4h以上。
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