新型β-萘酚类Betti碱及其环化衍生物的合成和杀虫活性研究
收稿日期: 2024-11-14
修回日期: 2024-12-02
网络出版日期: 2024-12-12
基金资助
国家自然科学基金(22077070); 国家自然科学基金(21772103)
Studies on the Synthesis and Insecticidal Activities of Novel β-Naphthol Betti Bases and Their Cyclized Derivatives
Received date: 2024-11-14
Revised date: 2024-12-02
Online published: 2024-12-12
Supported by
National Natural Science Foundation of China(22077070); National Natural Science Foundation of China(21772103)
基于骨架跃迁分子设计策略, 通过三组分“一锅”的Betti反应, 合成了8个新的β-萘酚类Betti碱Ia~Ih, 再进行成环反应合成14个新型二氢萘并噁嗪(硫)酮类衍生物IIa~IIn. 生物活性测试结果表明, 部分化合物在200 mg•L－1对小菜蛾和东方粘虫致死率分别达80%~100%和40%~100%. 整体而言, Betti碱1-((3-溴-1-(3-氯吡啶-2-基)-1H-吡唑- 5-基)(异丁基氨基)甲基)萘-2-酚(Ia)和1-(((4-氟苯基)氨基)(2-苯基-2H-1,2,3-三唑-4-基)甲基)萘-2-酚(If)及成环衍生物1-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-2-异丁基-1,2-二氢-3H-萘并[1,2-e][1,3]噁嗪-3-酮(IIa)、1-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-2-异丁基-1,2-二氢-3H-萘并[1,2-e][1,3]噁嗪-3-硫酮(IIc)和1-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-2-(4-氟苯基)-1,2-二氢-3H-萘并[1,2-e][1,3]噁嗪-3-硫酮(IIk)杀虫活性优良, 值得进一步研究. 对化合物构效关系进行了分析. 本研究结果对基于酚类衍生物的新型农药分子设计具有一定的参考价值和借鉴意义.
黄昊秦 , 杨娜 , 熊丽霞 , 王宝雷 . 新型β-萘酚类Betti碱及其环化衍生物的合成和杀虫活性研究[J]. 有机化学, 2025 , 45(4) : 1386 -1394 . DOI: 10.6023/cjoc202408040
Based on the strategy of scaffold hopping molecular design, eight novel β-naphthol Betti bases Ia~Ih were synthesized through a one-pot Betti reaction of β-naphthol, heterocyclic aldehydes, and different types of amines. Fourteen novel dihydronaphthoxazine (thio) ketone derivatives IIa~IIn were further obtained via the cyclization of the synthesized Betti bases. The bioassay results showed that some of the compounds exhibited good insecticidal activity at 200 mg•L－1 with lethality rates of 80%~100% and 40%~100% against Plutella xylostella L. and Mythimna separata Walker, respectively. Overall, the Betti bases 1-((3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)(isobutylamino)methyl)naphthalen-2-ol (Ia) and 1- (((4-fluorophenyl)amino)(2-phenyl-2H-1,2,3-triazol-4-yl)methyl)naphthalen-2-ol (If), and the cyclized derivatives 1-(3-bromo- 1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)-2-isobutyl-1,2-dihydro-3H-naphtho[1,2-e][1,3]oxazin-3-one (IIa), 1-(3-bromo-1-(3- chloro-pyridin-2-yl)-1H-pyrazol-5-yl)-2-isobutyl-1,2-dihydro-3H-naphtho[1,2-e][1,3]oxazine-3-thione (IIc) and 1-(3-bromo- 1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)-2-(4-fluorophenyl)-1,2-dihydro-3H-naphtho[1,2-e][1,3]oxazine-3-thione (IIk) possess favorable insecticidal potentials and deserve further investigation. The structure-activity relationship of the compounds was analyzed and discussed in detail. The results of this study provide useful reference and guidance for the molecular design of new pesticides based on phenolic derivatives.
Key words： naphthol derivatives; Betti base; scaffold hopping; synthesis; insecticidal activity
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