以吲哚啉季铵盐为原料,分别采用两步法和固相法合成了3种水溶性不对称吲哚方酸菁染料.两步法为将不同N-烷基取代的2,3,3-三甲基-3H-吲哚-5-磺酸季铵盐与方酸反应,再与另一种吲哚啉季铵盐反应制备不对称菁染料.固相法是用对氨基苯甲酸做桥连物,将方酸化学键连到高分子固相载体聚乙二醇上,然后与吲哚啉季铵盐杂环母核缩合制得带有固相高分子载体的半菁,再与另一吲哚啉季铵盐杂环母核反应切掉载体,合成不对称菁染料.产品用C-18反相柱进行分离提纯,通过核磁共振氢谱和质谱对产品结构进行了表征,测试了产品的光谱性能.比较而言,固相法合成不对称染料效果更好,产率接近传统两步法的二倍,是一种更适合的合成水溶性不对称吲哚方酸菁染料的方法.
N-Alkyl-2,3,3-trimethyl-3H-indoleninium-5-sulfonates as the initial raw material,the water-soluble asymmetrical squarylium indocyanine dyes were synthesized by two-step synthesis method and solid-phase synthesis method,respectively.In two-step synthesis method,a series of squarylium hemicyanine dyes were synthesized by condensation of squaric acid with various N-alkyl-2,3,3-trimethyl-3H-indoleninium-5-sulfonates,then the water-soluble asymmetrical squarylium indocyanine dyes were synthesized by condensation of squarylium hemicyanine dyes with another N-alkyl-2,3,3-trimethyl-3H-indoleninium-5-sulfonate.Solid-phase synthesis method mainly includes three steps.Firstly,squaric acid was linked to the solid-phase polymer support PEG with chemical bond using p-aminobenzoic acid as bridge.And then,squarylium hemicyanine dyes with solid-phase polymer support were synthesized by reaction of squaric acid linked solid-phase polymer support and N-alkyl-2,3,3-trimethyl-3H-indoleninium-5-sulfonates.Lastly,the water-soluble asymmetrical squarylium indocyanine dyes were gotten by condensation of squarylium hemicyanine dyes linked solid-phase polymer support with different indoleniniums and cuting off the solid-phase support from squarylium hemicyanine dyes.These raw dyes were purified by C-18 reverse phase column chromatograph.Their structures were confirmed by 1H NMR and MS.The spectral properties of the title products were checked.In the process of synthesizing of water-soluble asymmetrical squarylium indocyanine,it is found that the yields of the title products by solid-phase synthesis method are 2 times of those of traditional two-step method.Solid-phase synthesis method is more suitable to synthesize water-soluble asymmetrial squarylium indocyanine dyes.