摘要
以松节油为起始原料，经四步合成，得到新一类环戊烷衍生物香料的重要中间体——环戊烷羟基酮。环戊烷羟基酮可合成环戊烷衍生物类系列香料，这将为我国松节油的利用开辟一条新的途径。以松节油为起始原料，经四步合成，得到新一类环戊烷衍生物香料的重要中间体——环戊烷羟基酮。环戊烷羟基酮可合成环戊烷衍生物类系列香料，这将为我国松节油的利用开辟一条新的途径。首先以松节油的主要成分α－蒎烯为原料，经水合萜二醇合成α－松油醇。确定了在３０％Ｈ２ＳＯ４溶液中，反应温度２８～３１℃，反应时间２４ｈ，添加乳化剂的量为蒎烯的０．７％时，为水合萜二醇得率（７３．２％）的最佳反应条件。接着在沸腾的０．３％的Ｈ２ＳＯ４溶液中反应５～６ｈ，粗松油醇得率为９５％，α－松油醇含量超过５３％。然后又以高锰酸钾为氧化剂，将α－松油醇氧化为１，２，８－艹孟三醇。本文讨论了水溶液法和相转移催化固－液法、液－液法三种氧化方法的反应机理。并研究了加料顺序、反应物料配比、催化剂种类及用量、反应时间、温度和高锰酸钾浓度等因素对反应的影响。在所采用的催化剂中，以四丁基硫酸氢铵为最佳，艹孟三醇得率达６５％。将相转移催化技术应用于氧化α－松油醇中，尚未见文献报道。水溶液法?
This paper describes the steps of synthesizing cyclopentane hydroxyketone which is a key intermediate for synthesizing a series of perfumery materials of cyclopentane derivatives.This will present a new pathway for utilization of Chinese turpentine.Firstly,αterpineol was synthesized via terpine hydrate from αpinene which is the principal constituent of turpentine.The optimum condition for producing terpine hydrate were:catalyst 30% H2SO4;amount of emulsifying agent 0.7% of turpentine;reaction temperature 28～31℃;reaction time 24 h. The yield of terpine hydrate was 73.2%. Then, terpine hydrate was hydrolyzed in 0.3% H2SO4 solution at 104℃ for 5～6 h.The raw terpineol yield was 95% which contained more than 53% αterpineol.Secondly,1,2,8menthanetriol was synthesized from αterpineol with potassium permanganate as oxidizer.The reaction mechanism of three synthetic methods, namely aqueous permanganate,PTC solidliquid and PTC liquidliquid methods were studied.Effects of factors such as: the order of adding chemicals,molar ratio of reaction materials,amount and kind of catalysts,reaction temperature,reaction time and the concentration of patassium permanganate solution on product yield were studied.Results showed that tetrabutylammonium bisulfate(TBAB) was an ideal solidliquid phase transfer catalyst.The yield was 65% which was the highest of the three procedures studied.The synthetic method of oxidizing αterpineol with PTC was not seen in literature.Aqueous permanganate oxidation of αterpineol yielded triol (56%).The yield was much cleaner and higher than that of similar oxidation described in literature.The optimum conditions were as follows:KMnO4 solution was dropped into αterpineol with the molar ratio 5.5∶3,reaction temperature 0～5℃,reaction time 2 h,concentration of KMnO4 0.1 mol/L.
出处
《林产化学与工业》
EI
CAS
CSCD
北大核心
1997年第4期33-44,共12页
Chemistry and Industry of Forest Products
基金
南京中医药大学科学基金
