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在前一阶段工作的基础上,进一步研究了α-蒎烯与三氧化二氮的反应条件,以期提高主要产物——α-蒎烯亚氮氧化物(Ⅰ)——的产率。实验结果表明,可将反应温度自-12℃提高到30℃,但是由于(Ⅰ)不很稳定的原故,因而更高的温度是不利的。既可用氮气也可用压缩空气作为载气。影响(Ⅰ)的产率的主要因素是三氧化二氮的发生速度及浓度(与硝酸的滴加速度,载气的流速,发生器中的反应温度有关),适当熔剂的选择(以乙醚为最佳)以及全部装置,溶剂及三氧化二氮的干燥度。考虑到这些因素后,就可将(Ⅰ)的产率由原来的5—10％增高到47.8％。对于反应后所得的乙醚滤液也进行了初步研究,分离出一种针状结晶,熔点119—20℃,其结构须待测定。也研究了(Ⅰ)的转变为香芹酮的条件。初步结果表明,(Ⅰ)的二氯甲烷熔液于室温及漫射光下放置6—8天后可自动分解为香芹酮,产率达57.9％。
Based on the previous work, the reaction conditions of α-pinene and nitrous oxide were further studied in order to improve the yield of α-pinene nitrous oxide (Ⅰ), the main product. The experimental results show that the reaction temperature can be raised from -12 ° C to 30 ° C, but higher temperatures are unfavorable because (I) is not very stable. Both nitrogen and compressed air can be used as a carrier gas. The main factors influencing the yield of (Ⅰ) are the occurrence rate and concentration of nitrous oxide (related to the dropping rate of nitric acid, the flow rate of carrier gas and the reaction temperature in the generator), the choice of suitable flux Good) and all devices, solvents and nitrogen dioxide dryness. Taking these factors into consideration, the yield of (I) can be increased from the original 5-10% to 47.8%. After the reaction of the resulting ether filtrate was also preliminary study, isolated a needle crystal, melting point 119-20 ℃, its structure to be determined. The conversion of (I) to carvone has also been studied. The preliminary results show that the dichloromethane solution of (Ⅰ) can be decomposed into carvone automatically after 6-8 days at room temperature and diffuse light, with the yield of 57.9%.