吡啶联噁唑酰胺类化合物的设计、合成及杀菌活性

doi:10.6023/cjoc202007009

摘要/Abstract

以吡啶-2-甲醛为起始原料, 经环合、氧化、取代、水解、氯化和胺解反应, 采用中间体衍生化法合成了13个新型的吡啶联噁唑酰胺类化合物, 其结构经¹H NMR和高分辨质谱表征. 初步的杀菌活性测试结果显示, 在100 mg/L浓度下有7个化合物对黄瓜灰霉病菌(Botrytis cinerea)的抑制率为100%, 其中N-4-氟苯基-2-(吡啶-2-基)-噁唑-4-甲酰胺(7b)对水稻纹枯病菌(Rhizoctonia solani)的抑制率也为100%, 进一步的杀菌活性测试结果表明, 部分目标化合物杀菌活性优于嘧菌酯, 值得进一步研究.

关键词: 噁唑, 酰胺, 吡啶, 杀菌活性

Thirteen novel pyridyl oxazoamide compounds were synthesized using pyridine-2-formaldehyde as the starting material through cyclization, oxidation, substitution, hydrolysis, chlorination and ammonolysis reactions via the disclosed intermediate derivatization method (IDM). The structures of title compounds were characterized by ¹H NMR and HRMS. Preliminary bioassay results indicated that at 100 mg/L, 7 compounds exhibited 100% fungicidal activities against Botrytis cinerea, and N-(4-fluorophenyl)-2-(pyridin-2-yl)oxazole-4-carboxamide (7b) exhibited 100% fungicidal activities against Rhizoctonia solani. Further fungicidal activity test results suggested that some of the target compounds had better fungicidal activity than azoxystrobin, which was worthy of further study.

Key words: oxazole, amide, pyridine, fungicide activity

引用此文

陈澍, 任朝丽, 田晓雨, 张冬林, 杨森,
袁绍顷, 杜晓华, 谭成侠. 吡啶联噁唑酰胺类化合物的设计、合成及杀菌活性[J]. 有机化学, 2021, 41(2): 842-848.

Shu Chen, Chaoli Ren, Xiaoyu Tian, Donglin Zhang, Sen Yang, Shaoqing Yuan, Xiaohua Du, Chengxia Tan. Design, Synthesis and Fungicidal Activities of Pyridyl Oxazoamide Compounds[J]. Chinese Journal of Organic Chemistry, 2021, 41(2): 842-848.

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Entry	Oxidant	Yield/%
1	K₂S₂O₈/H₂SO₄	24
2	H₂O₂/H₂SO₄	12
3	CCl₃Br/DBU	68

Entry	Oxidant	Yield/%
1	K₂S₂O₈/H₂SO₄	24
2	H₂O₂/H₂SO₄	12
3	CCl₃Br/DBU	68

Compd.	R	黄瓜灰霉病菌 (B. cinerea)	水稻纹枯病菌 (R. solani)
7a	2-F	100	90
7b	4-F	100	100
7c	2,4-F₂	100	80
7d	2,6-F₂	100	80
7e	3-Cl	100	90
7f	3,5-Cl₂	85	60
7g	3-Cl-2-CH₃	90	80
7h	3-Br	90	80
7i	3-CF₃	90	80
7j	4-CH₃	100	70
7k	2,4-(CH₃)₂	100	90
7l	4-OC₂H₅	90	80
7m	4-tert-C₄H₉	90	70
嘧菌酯		100	100

Compd.	R	黄瓜灰霉病菌 (B. cinerea)	水稻纹枯病菌 (R. solani)
7a	2-F	100	90
7b	4-F	100	100
7c	2,4-F₂	100	80
7d	2,6-F₂	100	80
7e	3-Cl	100	90
7f	3,5-Cl₂	85	60
7g	3-Cl-2-CH₃	90	80
7h	3-Br	90	80
7i	3-CF₃	90	80
7j	4-CH₃	100	70
7k	2,4-(CH₃)₂	100	90
7l	4-OC₂H₅	90	80
7m	4-tert-C₄H₉	90	70
嘧菌酯		100	100

Compd.	黄瓜灰霉病菌(B. cinerea)			水稻纹枯病菌(R. solani)
Compd.	50 mg?L^–1	25 mg?L^–1	12.5 mg?L^–1	50 mg?L^–1	25 mg?L^–1	12.5 mg?L^–1
7a	45.88	12.36	—	47.06	29.31	17.69
7b	52.06	41.18	30.08	51.77	41.71	31.77
7c	63.83	40.30	29.71	79.12	18.24	16.77
7d	62.06	49.41	32.94	50.00	42.06	20.06
7e	66.47	14.71	—	57.90	18.83	11.77
7f	42.06	14.41	6.77	—	—	—
7g	65.00	44.71	17.36	66.77	36.77	6.18
7h	50.59	11.76	0.88	68.83	8.82	1.47
7i	51.77	27.06	24.12	—	—	—
7j	41.76	7.65	3.83	—	—	—
7k	64.41	28.83	7.06	55.30	34.41	4.41
7l	67.35	38.21	29.71	49.12	25.30	19.12
7m	47.65	30.30	9.71	—	—	—
嘧菌酯	40	20	0	60	20	0