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机构地区:[1]南开大学元素有机化学研究所,天津300071
出 处:《化学学报》1992年第5期508-514,共7页Acta Chimica Sinica
摘 要:本文以(三苄基锡)氧化物和相应的羧酸反应,合成了20个三苄基锡羧酸酯,由波谱对结构的研究表明,红外光谱的酰基振动频率与羧基上取代基的空间和电子效应密切相关,三苄基锡羧酸酯的结构微小变化,明显地反映了^(119)Sn和^(13)CNMR化学位移的差异,^(119)Sn化学位移与三苄基锡取代的苯甲酸酯的对位取代基Hammett常数(σ)之间存在着良好的线性关系:δ_(119Sn)=15.48σ+14.23,n=7,r=0.995.去烃基化是这一类化合物质谱裂解的特点。Twenty tribenzyltin carboxylates were synthesized by reaction of bis(tribenzyltin) oxide with corresponding carboxylic acids. The IR, ~1H, ^(13)C, ^(119)Sn NMR, MS and elemental analysis were determined. The results are shown that the vibrational frequencies of carboxyl group relate to the bulk and electron effect of the carboxy group. A slight structural change of these compounds can be reflect on the difference of ^(119)Sn, ^(13)C chemical shifts and their coupling constants. There is a relationship between ^(119)Sn chemical shift and Hammett Constan (σ)of the para-substituent of corresponding compounds:δ_(119)=15.48σ+14.23, n=7, r=0.995.The study on MS of some tribenzyltin carboxylates showed that first fragmentation step was elimination of benzyl group.
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