有机化学 ›› 2019, Vol. 39 ›› Issue (8): 2287-2294.DOI: 10.6023/cjoc201903023 上一篇    下一篇

所属专题: 陈茹玉先生诞辰100周年

研究论文

新型1,3,4-噻二唑并[3,2-a]嘧啶酮类介离子衍生物的合成及其生物活性

何文静, 刘登曰, 甘秀海, 张建, 刘峥军, 易崇粉, 宋宝安   

  1. 贵州大学绿色农药与农业生物工程国家重点实验室培育基地/教育部绿色农药与生物工程重点实验室/精细化工研究开发中心 贵阳 55002
  • 收稿日期:2019-03-13 修回日期:2019-04-05 出版日期:2019-08-25 发布日期:2019-04-16
  • 通讯作者: 宋宝安 E-mail:songbaoan22@yahoo.com
  • 基金资助:

    国家重点研发计划(No.2018YFD0200100)资助项目.

Synthesis and Biological Activity of Novel 1,3,4-Thiadiazolo[3,2-a]pyrimidinone Mesoionic Derivatives

He Wenjing, Liu Denyue, Gan Xiuhai, Zhang Jian, Liu Zhengjun, Yi Chongfen, Song Bao'an   

  1. State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agriculture Bioengineering, Ministry of Education, Center for Research and Development of Fine Chemicals, Guizhou University, Guiyang 550025
  • Received:2019-03-13 Revised:2019-04-05 Online:2019-08-25 Published:2019-04-16
  • Contact: 10.6023/cjoc201903023 E-mail:songbaoan22@yahoo.com
  • Supported by:

    Project supported by the National Key Research and Development Program of China (No. 2018YFD0200100).

以三氟苯嘧啶为先导化合物,设计并合成了一系列结构新颖的1,3,4-噻二唑并[3,2-a]嘧啶酮类介离子衍生物.利用1H NMR,13C NMR,19F NMR和HRMS对其进行结构表征.初步生物活性表明,多数化合物在100 μg/mL浓度下表现出一定的杀虫活性,其中2-((4-溴苄基)硫基)-8-((2-氯噻唑-5-基)甲基)-5-氧代-6-(3-(三氟甲基)苯基)-5H-[1,3,4]噻二唑并[3,2-a]嘧啶-8-鎓-7-盐(8b)和2-(((2-氯噻唑-5-基)甲基)硫基)-8-((2-氯噻唑-5-基)甲基)-5-氧代-6-(3-(三氟甲基)苯基)-5H-[1,3,4]噻二唑并[3,2-a]嘧啶-8-鎓-7-盐(8d)对白背飞虱(white-backed planthopper,WBPH)的致死率均为70%;此外,部分化合物在浓度为50 μg/mL时对水稻白叶枯病菌(Xanthomonas oryzae pv. oryzaeXoo),水稻细菌性条斑病菌(Xanthomonas oryzae pv. oryzicolaXoc)和柑橘溃疡病菌(Xanthomonas citri pv. citriXcc)表现出较好的抑抗菌性,其中2-((2-(三氟甲基)苄基)硫基)-8-((2-氯噻唑-5-基)甲基)-5-氧代-6-(3-(三氟甲基)苯基)-5H-[1,3,4]噻二唑并[3,2-a]嘧啶-8- 鎓-7-盐(8h)对水稻白叶枯病菌和水稻细菌性条斑病菌的抑制率分别为70.91%和53.34%,均优于对照药剂三氟苯嘧啶(42.85%和51.22%)、噻菌铜(47.76%和23.25%)和叶枯唑(66.97%和17.24%);2-((3-(三氟甲基)苄基)硫基)-8-((2-氯噻唑-5-基)甲基)-5-氧代-6-(3-(三氟甲基)苯基)-5H-[1,3,4]噻二唑并[3,2-a]嘧啶-8-鎓-7-盐(8e)对柑橘溃疡病菌的抑制率为68.97%,优于噻菌铜(35.85%)和叶枯唑(37.53%).

关键词: 介离子, 1,3,4-噻二唑并[3,2-a]嘧啶酮, 杀虫活性, 抑菌活性

A series of 1,3,4-thiadiazolo[3,2-a]pyrimidinone mesoionic derivatives were designed and synthesized with triflumezopyrim as the leading compound, and their structures were characterized by 1H NMR, 13C NMR, 19F NMR and HRMS. The preliminary biological activities indicated that the target compounds showed certain insecticidal activities at 100 μg/mL, of which the lethality rates of 2-((4-chlorobenzyl)thio)-8-((2-chlorothiazol-5-yl)methyl)-5-oxo-6-(3-(trifluoromethyl)phen-yl)-5H-[1,3,4]-thiadiazolo[3,2-a]pyrimidin-8-ium-7-olate (8b) and 2-(((2-chlorothiazol-5-yl)methyl)thio)-8-((2-chlorothiazol-5-yl)methyl)-5-oxo-6-(3-(trifluoromethyl)phenyl)-5H-[1,3,4]thiadiazolo-[3,2-a]pyrimidin-8-ium-7-olate (8d) against white-backed planthopper (WBPH) were 70%. Some compounds showed good antibacterial activities against Xanthomonas oryzae pv. oryzae (Xoo), Xanthomonas oryzae pv. oryzicola (Xoc) and Xanthomonas citri pv. citri (Xcc) at 50 μg/mL, and the inhi-bitory rates of 2-((2-(trifluoromethyl)benzyl)thio)-8-((2-chlorothiazol-5-yl)methyl)-5-oxo-6-(3-(trifluoromethyl)phenyl)-5H-[1,3,4]thiadiazolo[3,2-a]pyrimidin-8-ium-7-olate (8h) to Xoo and Xoc were 70.91% and 53.34%, respectively, which were better than thiodiazole copper (47.76% and 23.25%) and bismerthiazol (66.97% and 17.24%). The inhibition rate of 2-((3-(tri-fluoromethyl)benzyl)thio)-8-((2-chlorothiazol-5-yl)methyl)-5-oxo-6-(3-(trifluoromethyl)phenyl)-5H-[1,3,4]thiadiazolo[3,2-a]-pyrimidin-8-ium-7-olate (8e) to Xcc was 68.97%, which was better than thiediazole copper (35.85%) and bismerthiazol (37.53%)

Key words: mesoionic, 1,3,4-thiadiazolo[3,2-a]pyrimidinone, insecticidal activity, antibacterial activity