【作者】 游奎一；

【导师】 尹笃林；

【作者基本信息】 湖南师范大学 ， 有机化学， 2005， 硕士

【摘要】 a-蒎烯、β-蒎烯、苧烯、柠檬醛等是几种重要的单萜类化合物,主要存在于马尾松松节油、山苍子油、柠檬油、马鞭草油等精油中。利用它们可以合成马鞭草烯酮、桃金娘烯醛、桃金娘烯醇、香芹醇、香芹酮、香叶酸等一些香料和医药中间体。本文对这四种单萜化合物的光敏氧化反应进行了研究,并对其光敏氧化反应机理进行了探讨。重点考察了反应时间,溶剂,敏化剂,催化剂,温度等对这四种单萜化合物光敏氧化反应的影响规律,并从分子结构考虑,运用密度泛涵理论(DFT),对其反应机理和产物的选择性上进行了解释,得到了合理的结果。 1.a-蒎烯的光敏氧化反应 在a-蒎烯的光敏氧化反应中发现,随着时间的延长,a-蒎烯的转化率逐渐升高。当以虎红为敏化剂,甲醇作溶剂,用2,6-二甲基吡啶和乙酐作复合催化剂时,在303K反应38小时后,原料的转化率高达97.67%,主产物马鞭草烯酮的选择性高达41.89%。当选用DMF为溶剂,且不加催化剂的条件下,在温度为303K反应时,原料的转化率高达98.50%,主产物马鞭草烯酮的选择性高达51.00%。 2.β-蒎烯的光敏氧化反应 在β-蒎烯的光敏氧化反应中,在用虎红作敏化剂,甲醇作溶剂,2,6-二甲基吡啶和乙酐作复合催化剂的条件下,在303K反应47小时后,原料的转化率高达92.45%,主产物桃金娘烯醛的选择性高达73.92%。当选用DMF为溶剂,且不加催化剂,在温度为303K反应时,原料的转化率高达98.80%,主产物桃金娘烯醛的选择性高达85.16%。 3.苧烯的光敏氧化反应 在苧烯的光敏氧化反应中,当以虎红为敏化剂,甲醇作溶剂,用2,6-二甲基吡啶和乙酐作复合催化剂时,在295K反应70小时后,原料的转化率为32.67%,主产物2,8-对孟二烯-1-醇的选择性仅为更多还原

【Abstract】 Alpha-pinene, beta-pinene, limonene and citral are the best important monoterpeniods, which exist in turpentine oil, litsea cubeba oil, lemongrass oil and so on. The verbenone, myrtenal, myrtenol, carveol and carvone can be producted from monoterpenes. In this paper, the photosensitized oxidation and mechanism of the four monoterpenes were studied and the effects of photosensitizer, solvent, catalyst, and temperature were investigated. The reaction mechanism and selectivity of product were interpreted according to density function theory (DFT) from the molecular figuration. The excellent conclusions were obtained.1. The photosensitized oxidation of alpha-pineneIn the photosensitized oxidation of alpha-pinene, the conversion of alpha-pinene is gradually increased with time. The conversion of material is 97.67%; the selectivity of main product verbenone is 41.89% when the reaction, which RB was used as photosensitizer, methyl alcohol as solvent and 2, 6-lutidine and acetic anhydride as composite catalysts was carried for 38h at 303K. While the conversion is 98.50% and the selectivity of verbenone is up to 51.00% in DMF.2. The photosensitized oxidation of beta-pineneThe conversion of beta-pinene is 92.45%; the selectivity of myrtenal is 73.92% when the reaction which RB was used as sensitizer, methyl alcohol as solvent and 2,6-lutidine and acetic anhydride as composite catalysts, was carried for 47 hours at the temperature 303K. The conversion is 98.80% and the myrtenal selectivity is 85.16% in DMF.3. The photosensitized oxidation of limoneneIn the photosensitized oxidation of limonene, the conversion of limonene is 32.67% and the selectivity of main product更多还原