2-甲氧基吴茱萸次碱合成工艺改进

以吲哚为起始原料,与丙烯酸发生Michael加成反应制得吲哚丙酸,然后通过酰化、叠氮化、Curtius重排、环合反应得到咔啉,最后与2-氨基-4-甲氧基苯甲酸在脱水剂作用下环合制成2-甲氧基吴茱萸次碱。     

Insecticidal compounds from Evodia rutaecarpa against Drosophila melanogaster

In the course of screening for novel naturally occurring insecticides from Chinese crude drugs, the MeOH extract of the fruits of Evodia rutaecarpa Benth was found to give insecticidal activity against larvae of Drosophila melanogaster Meigen. Three alkaloids, evodiamine ( 1 ), rutaecarpine ( 2 ) and rhetsinine ( 3 ), were isolated by bioassay‐guided fractionation of the extract. Insecticidal activity against larvae of D melanogaster was demonstrated; compounds 1 and 2 gave LC₅₀ values of 0.30 and 0.28 µmol ml^?1 diet respectively. Acute toxicity against adults of D melanogaster was also found; compound 2 had the most potent activity, with an LD₅₀ value of 3.58 µg per adult. However, compound 3 had only weak activity in this study. Therefore compounds 1 and 2 were identified as insecticidal compounds from the fruits of E rutaecarpa. Compound 3 was obtained by the photoxidation of evodiamine. Investigation of the structure–activity relationship indicated the importance of the indoloquinazoline unit at the C‐14 position. © 2002 Society of Chemical Industry     

吴茱萸次碱衍生物的合成及抑菌活性

以吴茱萸次碱为原料,通过硫代反应以54.5%~87.6%的收率合成了硫代吴茱萸次碱及其5种N-取代衍生物(Ⅱ、Ⅳa~e),采用HRMS、FTIR、1HNMR和13CNMR对产物进行了结构表征;分析了质量浓度为10 mg/L的样品对9种植物病原菌的抑菌活性。结果表明:合成的6种化合物(Ⅱ、Ⅳa~e)对植物病原真菌几乎没有抑制作用,化合物Ⅳa、Ⅳb及Ⅳd对细菌[水稻白叶枯病菌,Xanthomonas oryzae pv.oryzae(Ishiyama)]具有较明显的抑菌活性,其中N-苄基硫代吴茱萸次碱(Ⅳb)和N-(4-甲基苄基)-硫代吴茱萸次碱(Ⅳd)的抑制率分别为81.84%和59.95%。通过细胞毒活性实验发现合成的化合物(Ⅱ、Ⅳa~e)对人体正常细胞(人肺成纤维细胞,HFL1)几乎没有毒性(IC5080μmol/L)。     

模拟移动床色谱分离吴茱萸碱和吴茱萸次碱

以C18为固定相、甲醇/水=70/30（体积比）为流动相,利用三区带模拟移动床分离了两种生物碱,吴茱萸碱和吴茱萸次碱。通过前沿分析法测定了两种生物碱的吸附等温线,在实验浓度范围内符合线性吸附等温线,吴茱萸碱和吴茱萸次碱的亨利系数分别为3.11和5.25。利用经验公式估算了轴向扩散系数和有效传质系数。分别利用三角形理论和基于模型的优化方法对三区带模拟移动床的操作条件进行设计,在优化的条件下,最大进料流量为0.55 ml?min^-1,两种产品纯度均大于99%。通过异步切换策略,在不增加设备投资及保证产品纯度大于99%的前提下,将进料流量提高至0.62 ml?min^-1。