摘要
为了探索二氢杨梅素半合成杨梅素作用机理,依据文献中提出的最佳反应条件,并进行重复验证,同时利用高效液相色谱对反应过程进行痕迹跟踪.实验结果表明:二氢杨梅素在最佳反应条件下搅拌反应,杨梅素的生成率为11.2%,与文献值基本符合.然而,液相色谱并没检测到文献中提出的查尔酮结构中间体和环氧烷结构中间体.另外,分别探讨了氢氧化钠用量与生成查尔酮结构中间体和杨梅素生成率之间的关系.实验结果表明:二氢杨梅素在1%的氢氧化钠水溶液(5.5 mL)、恒温水浴35℃搅拌20 h,反应过程通过液相色谱跟踪,并未检测到对应的查尔酮结构中间体生成,却检测到杨梅素成分的生成痕迹;随着反应时间的延长,杨梅素生成率逐渐升高,可达65.1%.最后,利用电子顺磁共振波谱仪(EPR)对二氢杨梅素在碱性环境中释放超氧阴离子的行为进行观察.结果表明:二氢杨梅素溶于弱碱性(pH值为8～9)的甲醇(φ=50%)溶液中,且有氧条件下,加入自旋电子捕获剂DMPO(5,5-二甲基-1-吡咯啉-N-氧化物)后,可观察到DMPO捕捉超氧阴离子形成的加合物特征峰,且随着时间的延长,其特征峰的强度也增强.综上所述,实验证实了文献中提出的二氢杨梅素半合成杨梅素作用机理的不合理性,并合理地提出了基于超氧阴离子催化二氢杨梅素脱氢合成杨梅素的作用机理.
In order to investigate rational mechanism of myricetin derived from dihydromyricetin in appropriate alkaline solution, all of data originated from references were carried out to be verified via applying high performance liquid chromatography(HPLC) to keep the trace of the whole reacting process, under the optimal conditions, which was done by the reference. The results demonstrated that the yield(11.2%) of myricetin transformed from dihydromyricetin is agreeable to that of the reference documented. However, the intermediates of correspoding chalcone and epoxyalkane were not detected by HPLC. In addition, the trial explored respectively the factor of sodium hydrate on generation of the intermediate of chalcone and product of myricetin in yield, the results demonstrated that the intermediate of corresponding chalcone is not able to be detected by HPLC,when dihydroyricetin proceeds to be stirring for 20 h at 35 ℃, in the presence of 1% sodium hydrate aquaous solution(5.5 mL). In contrast, the formation of myricetin is able to detect. And as reacting time prolonged, it performed to be ascending in yield of myricetin. The yield was allowed to be up to 65.1%. Finally, experiment investigated on superoxide anion generated from dihdromyricetin in alkaline surroundings, via EPR technology. The results demonstrated that typic signals of adduct of superoxide anion are being on, when dihydromyricetin was dissolved in air-saturated alkaline solution(50% in methanol), with adding spin trapping reagent of DMPO(5,5-dimethyl-1-pyrroline-N-oxide). Simultaneously, as reacting time prolonged, the intensity of typic signals of adduct of superoxide anion is ungraded. Consequently, relying on above data, it proposed that a plausible mechanism is involved with generation of superoxide anion from dihydromyricetin in air-saturated alkaline surroundings, is rather than that of proposed by the reference.
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