杂环类甲型铜络合物的合成

Synthesis of heterocyclic copper complex formazan

以2-氨基-4-磺酸基苯甲酸为原料,经过重氮化、还原并与糠醛缩合,生成2-羧基-5-磺酸基苯肼糠醛腙.该中间产物与3-乙酰氨基-5-氨基-4-羟基苯磺酸的重氮盐反应,生成甲化合物,再经铜离子络合,水解,得到最终产品N-(2-羧基-5-磺酸基苯基)-2-N’-(5-磺酸基-2-羟基-3-氨基苯基)-C-呋喃基甲铜络合物.经优化得到了重氮化和还原的最佳工艺条件:n(2-氨基-4-磺基苯甲酸)∶n(盐酸)∶n(氯化亚锡)=1∶2∶2;重氮化反应温度为10℃;氯化亚锡溶于盐酸滴加;还原反应温度为10℃.中间产物结构经1H NMR和MS表征确认,收率大于70%.甲铜络合物收率大于90%,经紫外分析λmax=632.5 nm,表明中心碳原子上引入杂环呋喃后,最大吸收波长将发生红移,为开发深色系列甲铜络合物染料提供了思路.

N- （2-carboxyl-5-sulfophenyl）-N ＇- （ 5-sulfo-2-hydroxyl-3-aminophenyl）-C-furylformazan copper complex was prepared from 2-amino-4-sulfobenzoic acid by diazotization, reduction, condensation with furfural, complexation and hydrolysis. The influences of diazotization and reduction reactions such as temperature, molar ratio and feeding mode were investigated. The optimum reaction conditions were as follows： the molar ratio of 2-amino-4-sulfobenzoic acid, hydrochloric acid and stannous chloride was 1 ： 2 ： 2, the temperature of reduction and condensation was 10 ℃, stannous chloride was dissolved in hydrochloric acid and then dropped into the reaction solution. The yield of 2-（2-（furan-2-ylmethyleme）hydrazingl）-4-sulfobenzoic acid was more than 70% and the structure was confirmed by ^1H NMR and MS. The HPLC purity of the final product is above 90%, λmax = 632. 5 nm. This shows that the maximum absorbed wavelength was red shifted when the central carbon atom was combined with heterocyclic ring, and would open new avenues to explore dark formazan reactive dye.