二芳基肟苄醚类化合物的合成及杀菌活性

doi:10.7503/cjcu20150508

摘要/Abstract

摘要：

以吡啶芳酮为原料, 合成了11个含二芳基肟醚结构单元的甲氧丙烯酸酯类化合物, 通过氢核磁共振谱(¹H NMR)、碳核磁共振谱(¹³C NMR)和高分辨质谱(HRMS)等方法对其结构进行了确证. 离体杀菌活性测定结果表明, 该类化合物对供试的7种植物病原菌普遍表现出较高的抑制活性, 其中化合物5d和5g的活性与对照药剂嘧菌酯和肟菌酯相当. 进一步活体盆栽验证实验结果表明, 在400 mg/L浓度下, 部分化合物表现出很好的防治效果, 如化合物5h对小麦白粉病和黄瓜炭疽病的防治效果达100%. 另外, 该类化合物对稻梨孢的孢子萌发具有强烈的抑制作用, 在25 mg/L浓度下, 绝大多数化合物的抑制率达到100%, 但对灰葡萄孢的孢子萌发普遍无效. 研究结果显示该类化合物具有进一步开发的价值.

关键词: 甲氧丙烯酸酯, 吡啶苯基肟, 苄基醚, 杀菌活性

Abstract:

To discover new strobilurin analogs with high pesticidal activity, 11 novel methoxy acrylates bearing biaryl methanone oxime ether moieties were synthesized from aroyl pyridines, and characterized by ¹H and ¹³C NMR and HRMS. In vitro fungicidal evaluation indicated that all of the target compounds exhibited excellent activities against tested seven phytopathogenic fungi, and compounds 5d and 5g displayed comparable overall activities to azoxystrobin and trifloxystrobin. Some of the target compounds also exhibited excellent in vivo control effects at 400 mg/L, for example, compound 5h could 100% control wheat powdery mildew and cucumber anthracnose. Furthermore, at 25 mg/L, these compounds, including control agents, completely inhibited spores germination of rice blast, but no effect at all for cucumber gray mold. These results suggested that this class of compounds might deserve to be developed as new potential agricultural fungicides.

Key words: Methoxy acrylate, Pyridinyl phenyl metnanone oxime, Benzyl ether, Fungicidal activity

中图分类号:

O625.43

TrendMD:

李秀云, 万川, 杜士杰, 李红, 袁会珠, 蒋家珍, 肖玉梅, 覃兆海. 二芳基肟苄醚类化合物的合成及杀菌活性. 高等学校化学学报, 2015, 36(12): 2415.

LI Xiuyun, WAN Chuan, DU Shijie, LI Hong, YUAN Huizhu, JIANG Jiazhen, XIAO Yumei, QIN Zhaohai. Synthesis and Fungicidal Activities of Biaryl Methanone O-Benzyl Oximes^†. Chem. J. Chinese Universities, 2015, 36(12): 2415.

图/表 6

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Compd.	Appearance	Yield(%)	m.p./℃	¹H NMR(300 MHz, CDCl₃, δ)
4c	White solid	89	165—166	3.79, 3.81(m, 3H), 6.85(dd, J=8.9, 5.9 Hz, 2H), 7.15(d, J=8.9 Hz, 1H),
				7.35(dd, J=13.5, 7.5 Hz, 4H), 8.72(d, J=6.0 Hz, 2H), 10.04(s, 1H)
4d	White solid	87	191—193	2.34—2.44(m, 3H), 7.14—7.49(m, 5H), 8.60(d, J=3.0 Hz, 1H), 8.76
				(d, J=6.0 Hz, 1H), 10.62(s, 1H)
4e	White solid	89	178—179	1.23(s, 3H), 1.26(s, 3H), 2.86—3.00(m, 1H), 7.21(d, J=8.5 Hz, 2H),
				7.29—7.49(m, 5H), 8.75(d, J=5.8 Hz, 2H)
4i	White solid	84	179—180	2.40(s, 3H), 7.11—7.46(m, 6H), 8.36(d, J=5.1 Hz, 1H), 8.52(d, J=
				3.0 Hz, 1H), 9.42(s, 1H)
4j	White solid	79	187—188	1.34(s, 9H), 7.30—7.41(m, 4H), 7.51(d, J=8.5 Hz, 1H), 8.37(d, J=
				5.1 Hz, 1H), 8.52(d, J=6.0 Hz, 1H), 8.73(s, 1H)

Compd.	Appearance	Yield(%)	m.p./℃	¹H NMR(300 MHz, CDCl₃, δ)
4c	White solid	89	165—166	3.79, 3.81(m, 3H), 6.85(dd, J=8.9, 5.9 Hz, 2H), 7.15(d, J=8.9 Hz, 1H),
				7.35(dd, J=13.5, 7.5 Hz, 4H), 8.72(d, J=6.0 Hz, 2H), 10.04(s, 1H)
4d	White solid	87	191—193	2.34—2.44(m, 3H), 7.14—7.49(m, 5H), 8.60(d, J=3.0 Hz, 1H), 8.76
				(d, J=6.0 Hz, 1H), 10.62(s, 1H)
4e	White solid	89	178—179	1.23(s, 3H), 1.26(s, 3H), 2.86—3.00(m, 1H), 7.21(d, J=8.5 Hz, 2H),
				7.29—7.49(m, 5H), 8.75(d, J=5.8 Hz, 2H)
4i	White solid	84	179—180	2.40(s, 3H), 7.11—7.46(m, 6H), 8.36(d, J=5.1 Hz, 1H), 8.52(d, J=
				3.0 Hz, 1H), 9.42(s, 1H)
4j	White solid	79	187—188	1.34(s, 9H), 7.30—7.41(m, 4H), 7.51(d, J=8.5 Hz, 1H), 8.37(d, J=
				5.1 Hz, 1H), 8.52(d, J=6.0 Hz, 1H), 8.73(s, 1H)

Compd.	m.p./℃	Yield(%)	HRMS(calcd.), m/z(M+H)⁺	Compd.	m.p./℃	Yield(%)	HRMS(calcd.), m/z(M+H)⁺
5a	85—87	78	404.1605(404.1605)	5g	103—104	70	472.0907(472.0825)
5b	—^*	75	418.1710(418.1761)	5h	—^*	75	460.2232(460.2231)
5c	—^*	65	434.1710(434.1710)	5i	84—85	71	452.1374(452.1372)
5d	88—90	72	452.1374(452.1372)	5j	—^*	74	494.1844(494.1841)
5e	—^*	80	446.2078(446.2074)	5k	—^*	67	514.1528(514.1528)
5f	104—106	68	482.0710(482.0710)

Compd.	m.p./℃	Yield(%)	HRMS(calcd.), m/z(M+H)⁺	Compd.	m.p./℃	Yield(%)	HRMS(calcd.), m/z(M+H)⁺
5a	85—87	78	404.1605(404.1605)	5g	103—104	70	472.0907(472.0825)
5b	—^*	75	418.1710(418.1761)	5h	—^*	75	460.2232(460.2231)
5c	—^*	65	434.1710(434.1710)	5i	84—85	71	452.1374(452.1372)
5d	88—90	72	452.1374(452.1372)	5j	—^*	74	494.1844(494.1841)
5e	—^*	80	446.2078(446.2074)	5k	—^*	67	514.1528(514.1528)
5f	104—106	68	482.0710(482.0710)

Compd.	¹H NMR(300 MHz, CDCl₃, δ)	¹³C NMR(75 MHz, CDCl₃, δ)
5a	3.70(d, J=2.1 Hz, 3H), 3.98(d, J=0.9 Hz, 3H), 5.11(s, 2H), 7.20—7.13(m, 1H), 7.23(dd, J=4.4, 1.6 Hz, 1H), 7.44—7.30(m, 9H), 8.56(dd, J=4.4, 1.7 Hz, 1H), 8.69(dd, J=4.5, 1.5 Hz, 1H)	52.8, 63.2, 75.1, 122.1, 123.8, 127.6, 128.5, 129.3, 129.8, 131.6, 134.8, 135.8, 141.2, 144.0, 149.3, 149.7, 154.8, 163.7
5b	2.37(d, J=15.0 Hz, 3H), 3.71(d, J=0.5 Hz, 3H), 3.98(d, J=3.1 Hz, 3H), 5.10(s, 2H), 7.13—7.22(m, 5H), 7.26(s, 1H), 7.28—7.42(m, 4H), 8.51(d, J=6.2 Hz, 1H), 8.67(d, J=5.1 Hz, 1H)	21.4, 52.8(s), 63.7(s), 75.0, 127.2—128.1(m), 128.1— 130.0(m), 132.0, 135.9, 139.4, 140.0, 141.3, 149.3, 149.7, 154.9, 163.2
5c	3.69(s, 3H), 3.83(s, 3H), 3.99(s, 3H), 5.12(s, 2H), 6.88—6.97(m, 2H), 7.12—7.20(m, 1H), 7.28—7.48(m, 7H), 8.55(d, J =5.6 Hz, 2H)	52.7, 55.2, 63.7, 75.1, 113.7, 113.8, 122.4, 123.7, 123.8, 127.7, 128.4, 128.8, 129.0, 129.4, 129.7, 131.2, 135.9, 141.4, 144.4, 149.3, 149.8, 154.5, 160.2, 160.9, 163.1
5d	2.32—2.41(m, 3H), 3.70(s, 3H), 3.97(d, J=2.1 Hz, 3H), 5.11(s, 2H), 7.12—7.18(m, 2H), 7.21(dd, J=4.4, 1.6 Hz, 1H), 7.26— 7.47(m, 6H), 8.56(dd, J=4.7, 1.4 Hz, 1H), 8.69(dd, J=4.5, 1.5 Hz, 1H)	20.1, 52.8, 63.7, 75.2, 122.0, 123.8, 126.3, 128.0, 128.1, 128.5, 128.8, 129.1, 129.4, 129.9, 131.5, 133.3, 135.6, 136.3, 140.9, 143.7, 149.2, 149.8, 154.0, 163.1
5e	1.25(d, J=6.9 Hz, 6H), 2.77—3.05(m, 1H), 3.68(d, J=4.7 Hz, 3H), 3.97(s, 3H), 5.11(s, 2H), 7.10—7.52(m, 11H), 8.54(d, J=5.5 Hz, 1H), 8.67(d, J=5.5 Hz, 1H)	23.8, 33.9, 52.7, 63.7, 75.0, 122.2, 123.8, 126.4, 127.7, 128.6, 129.4, 132.4, 135.9, 141.2, 144.2, 149.3, 149.8, 150.1, 150.8, 154.8, 163.1
5f	3.71(d, J=1.7 Hz, 3H), 3.98(d, J=2.7 Hz, 3H), 5.10(s, 2H), 7.22—7.13(m, 3H), 7.31—7.23(m, 3H), 7.59—7.35(m, 5H), 8.57(dd, J=4.5, 1.6 Hz, 1H), 8.68(dd, J=3.0, 1.6 Hz, 1H)	52.8, 63.7, 75.1, 122.1, 123.9, 127.7, 128.1—130.0(m), 131.6, 134.8, 135.8, 141.2, 144.0, 149.3, 149.7, 154.8, 163.2
5g	3.71(d, J=2.6 Hz, 3H), 3.97(d, J=1.6 Hz, 3H), 5.11(s, 2H), 7.11—7.20(m, 3H), 7.25—7.30(m, 1H), 7.38(m, 4H), 7.50(dd, J= 5.2, 2.9 Hz, 1H), 8.57(dd, J=4.5, 1.5 Hz, 1H), 8.70(dd, J=3.0, 1.5 Hz, 1H)	52.8, 63.7, 75.5, 121.7, 123.5, 126.8, 127.9, 128.6, 129.1, 129.4, 130.4, 131.1, 132.8, 133.6, 133.9, 134.8, 135.4, 139.9, 142.8, 149.2, 150.0, 152.7, 163.1
5h	1.29(s, 9H), 3.62(d, J=5.5 Hz, 3H), 3.91(s, 3H), 5.09(s, 2H), 7.09—7.25(m, 3H), 7.26—7.45(m, 7H), 8.57(m, 2H)	31.2, 34.7, 52.7, 63.6, 75.1, 77.0, 122.2, 123.7, 125.2, 127.5, 128.6, 129.3, 129.6, 132.0, 135.9, 141.1, 144.1, 149.3, 149.8, 152.3, 153.0, 154.7, 163.1
5i	2.38(d, J=15.5 Hz, 3H), 3.73(d, J=4.6 Hz, 3H), 3.99(d, J=3.1 Hz, 3H), 5.10(s, 2H), 7.10—7.30(m, 7H), 7.33—7.49(m, 4H), 8.31(d, J=5.2 Hz, 1H), 8.45(d, J=5.1 Hz, 1H)	21.4, 52.8, 63.8, 75.2, 120.9, 122.6, 124.2, 127.4, 127.8, 128.8, 129.2, 129.4, 131.4, 135.7, 139.7, 140.3, 144.3, 147.2, 149.2, 149.6, 151.7, 153.6, 154.0, 163.2
5j	1.31(s, 9H), 3.72(s, 3H), 3.99(s, 3H), 5.09(s, 2H), 7.16(s, 2H), 7.24(dd, J=1.2, 0.7 Hz, 1H), 7.28—7.47(m, 7H), 8.45(dd, J=5.0, 0.6 Hz, 1H)	31.2, 31.2, 31.3, 34.8, 52.8, 63.7, 75.0, 122.2, 123.9, 125.2, 127.3, 127.7, 128.4, 128.7, 128.9, 129.2, 129.3, 129.4, 131.9 , 135.9, 141.5, 149.6, 152.4, 153.2, 154.7, 163.2
5k	3.71(s, 3H), 3.97(s, 3H), 5.19(s, 2H), 7.19(t, J=7.0 Hz, 2H), 7.27—7.52(m, 10H), 7.57(dd, J=7.8, 3.5 Hz, 4H), 8.38(m, 1H)	52.8, 63.7, 75.4, 122.7, 124.3, 127.0, 128.0, 129.0, 129.5, 129.8, 133.1, 135.7, 140.0, 142.7, 144.1, 149.3, 149.9, 151.7, 153.4, 163.1