【作者】 周颖；

【导师】 来虎钦；

【作者基本信息】 浙江工业大学 ， 农药学， 2006， 硕士

【摘要】 调环酸钙是一种新型的环己稀酮类植物生长调节剂，可以减轻倒伏，它具有低残留、抗逆性等特点，具有广泛的应用前景和较高的研究价值。重点研究了调环酸钙及其中间体的合成。合成出中间体丙酮基丁二酸酯、3，5-二氧代环己烷羧酸乙酯、3-丙酰氧基-5-氧代环己烯羧酸乙酯-3-烯、3，5-二氧代-4-丙酰基环己烷羧酸乙酯及目标产物调环酸钙，并对其结构进行了表征。通过查阅大量的文献，对调环酸钙的不同合成路线进行了比较，重点研究了以顺丁烯二酸二乙酯为起始原料，经Michael加成、Claisen缩合、酰化、重排和碱水解反应后得到目标产物调环酸钙的合成方法，并得出较佳的合成工艺条件。在制备3，5-二氧代环己烷羧酸乙酯的过程中，对文献已报道的方法进行了改进。采用以甲苯作为溶剂，用少量乙醇作为引发剂与金属钠反应制备的乙醇钠作为催化剂，由此得到产品，这样更有利于Michael加成反应的进行，提高了收率。改进后的合成工艺反应条件温和，操作安全，收率高，适合工业化生产。由上述制备得到的95％调环酸钙原药开发了20％调环酸钙环保型新剂型WDG产品，并得出了较佳配方。更多还原

【Abstract】 Prohexadione-Ca, a new type of the plant-growth regulator, could lodge resistant and had the characters: controlling plant growth, having less residual and stress resistant.In this dissertation, the preparation of prohexadione-Ca and its intermediates had been presented and discussed carefully. The intermediates of ethyl acetonylsuccinate, ethyl 3,5-dioxocyclohexane carboxylate, ethyl 3-propionyloxy-5-oxo-3-cyclohexenecarboxylate, ethyl 3,5-dioxo-4-acetylcyclohexane-carboxylate and prohexadione-Ca were synthesized and the structures of these compounds were determined.Different synthetical methods of prohexadione-Ca, reported previously, had been compared. Its preparation from diethyl succinate was achieved via Michael addition reaction, Claisen condensation, acylation, rearrangement, alkali-hydrolysis. The optimal technical process had been obtained.In the preparation of ethyl 3,5-dioxocyclohexane -carboxylate, a comparative method was presented. The sodium ethylate prepared from a catalytic amount of alcohol with excess metallic sodium was used as the catalyst, and ethyl acetonylsuccinate were synthesized in toluene. Michael addition reaction proceeded more smoothly under this condition, thus the yield was improved effectively. The improved method included the followed advantages: mild reaction condition, simple and safe operation, high yield, more suitable for industrial scale.The new environmental-friendly pesticide formulation of 20% prohexadione-Ca water dispersible granule (WDG) had been studied.更多还原