异莰烷基甲酸及其酯类的合成与结构分析

Synthesis and structural analysis of isocamphanyl formic acid and its esters

以莰烯为原料,经Vilsmeier-Haack反应、催化加氢得到异莰烷基甲醛,异莰烷基甲醛经氧化反应得到异莰烷基甲酸。在对甲苯磺酸的催化下,与一系列一元醇(正丙醇、正丁醇、异丁醇、仲丁醇、正戊醇、异戊醇和环己醇)进行酯化反应,合成了未见报道的7种异莰烷基甲酸酯类化合物4a-4g,产率在61~84%之间,采用IR、MS、~1H NMR及^(13)C NMR对产物进行了结构表征。分析了异莰烷基甲酸酯及其反应中间体的合成方法。本研究可为莰烯的精细化学利用提供一定的理论基础。

Isocamphyl formaldehyde was synthesized from camphene by the Vilsmeier-Haack reaction and catalytic hydrogenation.Isocamphanyl formaldehyde was converted into isocamphanyl formic acid through the oxidation with K2Cr2O7-H2SO4. Then,seven novel ester derivatives of isocamphanyl formic acid were synthesized by the esterification reaction of isocamphanyl formic acid and seven monohydric alcohol（ n-propanol,n-butanol,iso-butanol,sec-butanol,n-pentanol,iso-pentanol and cyclohexanol）,under the catalysis by p-toluenesulfonic acid.The yield of these ester derivatives were ranged between 61 - 84%. The structures of these synthesized compounds were characterized by infrared spectroscopy（ IR）,mass spectrometry（ MS）,and nuclear magnetic resonance spectroscopy（^1H NMR,^13C NMR）. Synthetic method of isocamphanyl formic acid,ester derivaitves and other intermediates were discussed.This study provided a theoretical basis to the fine chemistry utilization of camphene.