两种磺酰胺类染料中间体的合成与表征

Synthesis and Characterization of Two Sulfonamide Dye Intermediates

合成了两种磺酰胺类染料中间体N (4 氨基苯磺酰基) N′ (3 氨基 4 甲氧基苯磺酰基) 1,4 苯二胺(Ⅴ)和N (4 氨基苯磺酰基) N′ (4 氨基 3 甲基苯磺酰基) 1,4 苯二胺(Ⅸ)。合成步骤如下:(1)乙酰苯胺和氯磺酸反应所得的对乙酰氨基苯磺酰氯与对苯二胺一步胺化得4 氨基 4′ 乙酰氨基苯磺酰苯胺(Ⅰ);(2)邻氨基苯甲醚和邻甲苯胺的氨基保护后与氯磺酸反应得3 乙酰氨基 4 甲氧基 苯磺酰氯(Ⅲ)和3 甲基 4 乙酰氨基 苯磺酰氯(Ⅶ);(3)Ⅰ分别与Ⅲ、Ⅶ在NaOH溶液中进行第二步胺化,所得缩合物水解得产品Ⅴ、Ⅸ。产品均经红外、质谱、核磁、元素分析表征确定了结构。第二步胺化反应优化条件均为:n(Ⅰ)∶n(Ⅲ或Ⅶ)=1∶1 5,反应温度70℃,反应时间4 5h,溶剂为w(NaOH)=3%,n(NaOH)∶n(Ⅰ)=3∶1的溶液,产率分别为91 66%、93 22%。

Two sulfonamide dye intermediates N-(4-aminobenzenesulfonyl)-N′-(3-amino-4-methoxybenzenesulfonyl)-1,4-phenylenediamine (Ⅴ) and N-(4-aminobenzenesulfonyl)-N′-(4-amino-3-methylbenzenesulfonyl)-1,4-phenylenediamine (Ⅸ) were synthesized by the following steps.(1)4-Amino-4′-acetaminobenzenesulfonanilide (Ⅰ) was prepared by reaction of 4-acetaminobenzenesulfonyl chloride with p-phenylenediamine.(2)3-Acetylamino-4-methoxybenzenesulfonyl chloride (Ⅲ) and 3-methyl-4-acetylamino-benzenesulfonyl chloride(Ⅶ) were respectively prepared from o-methoxyaniline and o-methylaniline by protecting the amino groups and then reacting with chlorosulfonic acid.(3)Ⅰ reacted respectively with Ⅲ and Ⅶ in NaOH solution,and their condensation products were changed into the final products Ⅴ and Ⅸ by hydrolysis.The products were characterized by IR,MS,~1HNMR and EA.The optimum conditions for the reaction of Ⅰ with Ⅲ or Ⅶ were determined:n(Ⅰ)∶n(Ⅲ or Ⅶ)=1∶1.5,3% NaOH as solvent n(NaOH)∶KG-*2n(Ⅰ)= 3∶1,reacting at 70 ℃ for 4.5 h.The yields were respectively 91.66% and 93.22%.