Synthesis Of Intermediates For Reactive Dyes With High Degree Of Fixation

In recent years, study on reactive dyes with high degree of fixation slowly becomes one of the hot research topics. At present, as the most commonly used kind of reactive dyes, a lot of vinyl sulfone reactive dyes were found with low degree of fixation in application, in the background of mature technology of dyeing and finishing process, the development of new reactive dye intermediates and molecular structures with high degree of fixation is necessary, and is also a pioneering research area. By the increasing of degree of fixation, we can save dyestuff, also reduce pollution, which follows the trend of environment protection and low carbon foot print in dye industry.In this paper, a lot of literature focus on the research about the development and application of reactive dyes and intermediates were introduced and summarized; furthermore, some new ways of synthesizing of a new vinyl sulfone intermediate were designed and realized.The structures of the synthesized compounds were characterized by1H NMR,13C NMR, MS and IR spectra. The optimal conditions for the synthesis were explored. The dissertation mainly contains the following aspects:1. Synthesis of compound5as terminal product by route1. The reaction between p-nitrobenzoic acid and thionyl chloride under reflux in toluene afforded the acyl chloride product in95.0%yield, which was used directly to react with the thioether product1synthesized from β-mercaptoethanol and2-chloroethylamine hydrochloride (or2-bromoethylamine hydrobromide) in toluene at0℃. Acid amide product2was obtained as main product in95.0%yield. Product3, which has both acid amide and ester structure, was obtained as main product if the reaction was conducted at25℃. Sulfone compound4was obtained in92.0%yield by oxidation of the thioether2with hydrogen peroxide in water/toluene at85℃. Amine product5was obtained from reduction of the nitro group in product4in water/ethanol with hydrochloric acid and Fe at60℃for5h in53.6%yield.2. Route2. The acyl chloride product was obtained as route1. Halohydrocarbon product6with acidamide group was obtained from the reaction between the acyl chloride and2-bromoethylamine hydrobromide. Product2was obtained from reaction between product6and β-mercaptoethanol with sodium hydroxide as deacid reagent at60℃for5h in10%yield. Product4and5were obtained as route1.3. Route3. The reaction between p-acetylamino benzoic acid and thionyl chloride under reflux in toluene afforded the acyl chloride product, which was used directly to react with the thioether product1synthesized as route1. Acidamide product7and sulfone product8were obtained by the same method as product2and4. Product5was obtained by hydrolyzing of product8with sodium hydroxide at60℃for5h in40%field.4. Route4. Halohydrocarbon product9was obtained from reaction between p-acetylamino benzoic acid and thionyl chloride in the same way as route2. Acidamide product7and sulfone product8were obtained as route3. Product5was obtained by hydrolyzing of product8as route3.5. Compound10,11,12, and13were obtained in this paper.