有机化学 ›› 2020, Vol. 40 ›› Issue (7): 2127-2134.DOI: 10.6023/cjoc202003001 上一篇    下一篇

研究简报

N-取代苯甲酰基-N'-4,7-二甲氧基-[1,2,4]三唑并[1,5-c]嘧啶(硫)脲的设计、合成及生物活性研究

魏凯伦a, 石瑞静a, 姜林a,b, 苗成霞a,b, 李映a,b   

  1. a 山东农业大学化学与材料科学学院 山东泰安 271018;
    b 山东省食品安全分析与检测工程技术研究中心 山东泰安 271018
  • 收稿日期:2020-03-01 修回日期:2020-04-20 发布日期:2020-05-08
  • 通讯作者: 李映 E-mail:ly8049@sdau.edu.cn
  • 基金资助:
    国家自然科学基金(No.21702127)及山东省高等学校青创人才引育计划资助项目.

Design, Synthesis and Biological Activities Evaluation of N-(Substitutedbenzoyl)-N'-4,7-dimethoxy-[1,2,4]-triazolo[1,5-c]pyrimidine (Thio)ureas

Wei Kailuna, Shi Ruijinga, Jiang Lina,b, Miao Chengxiaa,b, Li Yinga,b   

  1. a College of Chemistry and Material Science, Shandong Agricultural University, Tai'an, Shandong 271018;
    b Food Safety Analysis and Test Engineering Technology Research Center of Shandong Province, Tai'an, Shandong 271018
  • Received:2020-03-01 Revised:2020-04-20 Published:2020-05-08
  • Supported by:
    Project supported by the National Natural Science Foundation of China (No. 21702127) and the Incubation Program of Youth Innovation in Shandong Province.

α-甲氧基乙酸甲酯、甲酸乙酯和取代苯甲酸为起始原料,经过环化、Dimroth重排和亲核加成等反应,合成了一系列结构新颖的N-取代苯甲酰基-N'-4,7-二甲氧基-[1,2,4]三唑并[1,5-c]嘧啶(硫)脲类化合物11a11q.目标化合物的结构通过IR、1H NMR、13C NMR和元素分析进行了确认.初步生物活性测试结果表明,在50 mg·L-1下,大部分化合物具有一定的杀菌活性,其中N-(2-氯苯甲酰基)-N'-4,7-二甲氧基-[1,2,4]三唑并[1,5-c]嘧啶硫脲(11m)对黄瓜灰霉菌的抑制率为67.25%.化合物均对2~3龄库蚊幼虫表现一定的昆虫生长调节活性,7个化合物的校正未羽化率高于70%,其中N-(4-甲基苯甲酰基)-N'-4,7-二甲氧基-[1,2,4]三唑并[1,5-c]嘧啶硫脲(11l)的校正未化蛹率和校正未羽化率均达100%,与对照药剂5%(质量分数)吡丙醚乳液相当.构效关系研究表明,苯环上吸电子基团的引入有利于杀菌活性的提高,而给电子基团的引入则有利于昆虫生长调节活性的提高.苯甲酰基脲类化合物11a11i的杀菌活性普遍优于苯甲酰基硫脲类化合物11j11q,而苯甲酰基硫脲类化合物则表现出更好的昆虫生长调节活性.

关键词: 几丁质, 苯甲酰基(硫)脲, 三唑并嘧啶, 杀菌活性, 昆虫生长调节活性

A series of novel N-(substitutedbenzoyl)-N'-4,7-dimethoxy-[1,2,4]triazolo[1,5-c]pyrimidine (thio)ureas (11a~11q) were synthesized from α-methoxyl methyl acetate, ethyl formate and substituted benzoic acids by cyclization, Dimroth rearrangement and nucleophilic addition reactions. The structures of products were confirmed by IR, 1H NMR, 13C NMR and elemental analysis. The preliminary bioassay showed that most of the compounds displayed positive fungicidal activity at 50 mg·L-1. Among them, N-(2-chlorobenzoyl)-N'-4,7-dimethoxy-[1,2,4]triazolo[1,5-c]pyrimidinethiourea (11m) exhibited an inhibition rate of 67.25% against B. cinerea. All compounds showed certain insect growth regulation activities against 2~3 instar culex larvae, in which seven compounds exhibited revised uneclosion rate higher than 70%. N-(4-methylbenzoyl)-N'-4,7-dimethoxy-[1,2,4]triazolo[1,5-c]pyrimidinethiourea (11l) showed excellent insecticidal activity, which was equivalent to the control 5% (mass fraction) pyriproxyfen. The preliminary structure-activity relationship analysis showed that compounds with electron-withdrawing group on the phenyl ring showed higher fungicidal activities, while compounds with electron-donating group exhibited higher insect growth regulation activities. Benzoylureas displayed higher fungicidal activities and benzoylthioureas exhibited good insect growth regulation activities.

Key words: chitin, benzoyl (thio) urea, triazolopyrimidine, fungicidal activity, insect growth regulation activity