Huang Jia-Xing, Jia Yue-Mei, Liang Xiao-Mei, Zhu Wei-Juan, Zhang Jian-Jun, Dong Yan-Hong, Yuan Hui-Zu, Qi Shu-Hua, Wu Jin-Ping, Chen Fu-Heng, Wang Dao-Quan
Key Laboratory of Pesticide Chemistry and Application Technology, Department of Applied Chemistry, China Agricultural University, Beijing, People's Republic of China.
J Agric Food Chem. 2007 Dec 26;55(26):10857-63. doi: 10.1021/jf072733+. Epub 2007 Dec 4.
Three series of novel macrolactams and macrolactones--12-alkoxyimino-tetradecanlactam, 12-alkoxyiminopentadecanlactam, and 12-alkoxyiminodecanlactone derivatives (7A, 7B, and 7C)--were synthesized from corresponding 12-oxomacrolactams and 12-oxomacrolactone. Their structures were confirmed by 1H NMR and elemental analysis. The Z and E isomers of 7A and 7B were separated, and their configurations were determined by 1H NMR. These compounds showed fair to excellent fungicidal activities against Rhizoctonia solani Kühn. It is interesting that the Z and E isomers of most of the compounds have quite different fungicidal activities. The fact that the compounds have a gradual increase of fungicidal activity in the order of 7A, 7C, and 7B indicated that the macrocyclic derivatives with a hydrogen-bonding acceptor (=N-O-) and a hydrogen-bonding donor (-CONH-) on the ring, and a three methylenes distance (CH2CH2CH2) between these two functional groups, exhibited the best fungicidal activity. The bioassay also showed that 7B not only has good fungicidal activity but also may have a broad spectrum of fungicidal activities.
合成了三个系列的新型大环内酰胺和大环内酯——12-烷氧基亚氨基十四烷内酰胺、12-烷氧基亚氨基十五烷内酰胺和12-烷氧基亚氨基癸内酯衍生物（7A、7B和7C），它们由相应的12-氧代大环内酰胺和12-氧代大环内酯合成。通过1H NMR和元素分析确认了它们的结构。分离出了7A和7B的Z型和E型异构体，并通过1H NMR确定了它们的构型。这些化合物对立枯丝核菌表现出良好到优异的杀菌活性。有趣的是，大多数化合物的Z型和E型异构体具有相当不同的杀菌活性。化合物的杀菌活性按7A、7C和7B的顺序逐渐增加，这一事实表明，在环上具有氢键受体（=N-O-）和氢键供体（-CONH-）且这两个官能团之间相隔三个亚甲基距离（CH2CH2CH2）的大环衍生物表现出最佳的杀菌活性。生物测定还表明，7B不仅具有良好的杀菌活性，而且可能具有广谱的杀菌活性。
