8-羧乙基⊿^(9)六氢香豆素的合成及其反应

Reaction and Synthesis of 8-Carboxyethyl⊿^(9) Hexahydrocoumarin

环己酮与丙烯腈在氮氧化钾的乙二醇饱和溶液催化下合成了2,6-二(氰乙基)环己酮1,1水解得2,6-二(羧乙基)环己酮2经固体硫酸铁水合物催化加热合成了8-羧乙基⊿^(9)六氢香豆素3.2与乙醇、丙醇、丁醇、戊醇在硫酸铁水合物催化下反应得相应的二元酸酯4、5、6及7。化合物3的环由水解、醇解及氨解开环分别得2、6、7及8-羧乙基⊿^(9)八氢-2-氧代喹啉8.3与溴加成,脱溴化氢得8-羧乙基-5,6,7,8-四氢香立素9,9与顺丁烯二酸酐共热得化合物10。用^(13)C NMR谱分析结果肯定了1、2的结构,纠正了文献上的错误。

2,6-Di(β-cyanoethyl)cyclohexanone 1 was prepared by treating cyclohexa-none with acrylonitrile in the presence of KOH/ethyleneglycol,then 1 was converted to 2,6-di(carboxyelhyl)cyclohexanone 2 by refluxing with dil HCl.When 2 was heated in xylene with ferric sulfate 8-carboxyethyl⊿^(9) hexahydrocoumarin 3 was formed.2 reacted with alcohols(ethanol,propanol,butanol,pentanol)by the action of hydrated ferric sulfate as catalyst,the esters 4,5,6 and 7 were obtained,respectively.3 could easily be hydrolyzed,alcoholyzed and ammonolyzed to give 2,6,7 and 8.3 reacted with bromine and then heated,hydrobromied was quickly liberated from the addition product thus 9 was formed.When a xylene solution of 9 and maleic anhydride was refluxed for 11h the adduct 10 was obtained.