Synthesis and Fungicidal Activities of Biaryl Methanone O-Benzyl Oximes†

doi:10.7503/cjcu20150508

Abstract

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

CLC Number:

O625.43

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2015, 36(12): 2415.

Figures/Tables 6

References 19

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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