Synthesis and Biological Activities of Myricetin Derivatives Containing Quinoxaline†

doi:10.7503/cjcu20180828

Abstract

Abstract:

According to the active substructure combination theory, a series of novel myricetin derivatives containing quinoxaline moieties was synthesized by introducing the quinoxaline blocks into the structures of myricetins. The antibacterial activities of the target compounds were evaluated via turbidimeter test in vitro. The preliminary bioassay results indicated that all of the title compounds exhibited certain antibacterial activities in vitro against Xanthomonas axonopodis pv. Citri(X. citri) and Xanthomonas oryzae pv. Oryzae(X. oryzae). The compounds were also tested to evaluate the half maximal effective concentration(EC₅₀) of phytopathogenic bacteria. The results showed that all the X. citri EC₅₀ of the target compounds were superior to those of the control drugs of bismerthiazol and thiodiazole copper(54.85 and 61.13 μg/mL, respectively). Compound 4o(EC₅₀=11.17 μg/mL) exhibited the best activity. All of the X. oryzae EC₅₀ of the target compounds were superior to the control drugs of bismerthiazol and thiodiazole copper(148.20 and 175.47 μg/mL, respectively). Compound 4f(EC₅₀=34.49 μg/mL) exhibited the best activity. The in vivo efficacies against tobacco mosaic virus(TMV) of the target compounds were tested through half-leaf method. The results of bioassay showed that the target compounds exhibited certain anti-TMV activities at the concentration of 500 mg/L.

Key words: Myricetin, Quinoxaline, Antibacterial activity, Anti-TMV activity

CLC Number:

O625.42

TrendMD:

LI Pu,CHEN Ying,XIA Rongjiao,GUO Tao,ZHANG Min,JIANG Shichun,ANG Xu,HE Ming,XUE Wei. Synthesis and Biological Activities of Myricetin Derivatives Containing Quinoxaline^†[J]. Chem. J. Chinese Universities, 2019, 40(5): 909.

Figures/Tables 7

References 23

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Compd.	Appearance	Yield(%)	m. p./℃	HRMS(calcd. ), m/z[M+H]⁺
1	Yellow solid	48.8	228—230(227—229^[20])
2a	White solid	83.4	138—140(141—142^[20])
2b	White solid	71.2	152—153(154—156^[20])
2c	White solid	65.5	149—151
2d	White solid	58.1	150—152
4a	White solid	45.3	79—81	575.20241(575.20215)
4b	Yellow solid	63.2	98—100	589.21806(589.21686)
4c	Yellow solid	48.7	164—166	609.16343(609.16229)
4d	Yellow solid	52.2	113—115	613.17927(613.17822)
4e	Yellow solid	47.6	58—60	589.21806(589.21747)
4f	Yellow solid	49.4	103—105	603.23371(603.23242)
4g	Yellow solid	57.3	124—126	623.17908(623.17780)
4h	Yellow solid	54.5	84—86	605.21297(605.21216)
4i	Yellow solid	41.7	152—154	603.23371(603.23236)
4j	Yellow solid	51.6	89—91	617.24936(617.24792)
4k	Yellow solid	60.3	131—133	659.17668(659.17493)
4l	Yellow solid	56.0	88—90	605.21297(605.21216)
4m	White solid	44.1	96—98	655.20524(655.20654)
4n	White solid	53.2	127—129	631.26501(631.26349)
4o	Yellow solid	57.4	83—85	651.21038(651.21038)
4p	White solid	48.6	76—78	633.24427(633.24274)

Compd.	Appearance	Yield(%)	m. p./℃	HRMS(calcd. ), m/z[M+H]⁺
1	Yellow solid	48.8	228—230(227—229^[20])
2a	White solid	83.4	138—140(141—142^[20])
2b	White solid	71.2	152—153(154—156^[20])
2c	White solid	65.5	149—151
2d	White solid	58.1	150—152
4a	White solid	45.3	79—81	575.20241(575.20215)
4b	Yellow solid	63.2	98—100	589.21806(589.21686)
4c	Yellow solid	48.7	164—166	609.16343(609.16229)
4d	Yellow solid	52.2	113—115	613.17927(613.17822)
4e	Yellow solid	47.6	58—60	589.21806(589.21747)
4f	Yellow solid	49.4	103—105	603.23371(603.23242)
4g	Yellow solid	57.3	124—126	623.17908(623.17780)
4h	Yellow solid	54.5	84—86	605.21297(605.21216)
4i	Yellow solid	41.7	152—154	603.23371(603.23236)
4j	Yellow solid	51.6	89—91	617.24936(617.24792)
4k	Yellow solid	60.3	131—133	659.17668(659.17493)
4l	Yellow solid	56.0	88—90	605.21297(605.21216)
4m	White solid	44.1	96—98	655.20524(655.20654)
4n	White solid	53.2	127—129	631.26501(631.26349)
4o	Yellow solid	57.4	83—85	651.21038(651.21038)
4p	White solid	48.6	76—78	633.24427(633.24274)

Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
2c	7.37(s, 2H), 6.81(s, 1H), 6.48(s, 1H), 3.94(t, J=5.6 Hz, 2H), 3.90(s, 3H), 3.88(s, 6H), 3.85(s, 3H), 3.77(s, 3H), 3.48(t, J=6.7 Hz, 2H), 1.89—1.72(m, 2H), 1.71—1.62(m, 2H), 1.51—1.40(m, 2H)
2d	7.37(s, 2H), 6.84(s, 1H), 6.49(s, 1H), 3.95(t, J=6.0 Hz, 2H), 3.90(s, 3H), 3.87(s, 6H), 3.85(s, 3H), 3.76(s, 3H), 3.58(t, J=6.6 Hz, 2H), 1.67—1.64(m, 2H), 1.58—1.47(m, 2H), 1.43—1.35(m, 2H), 1.29—1.23(m, 2H)
4a	8.53(s, 1H), 8.00(d, J=9.2 Hz, 1H), 7.82(d, J=8.6 Hz, 1H), 7.76(t, J=7.6 Hz, 1H), 7.64(t, J=6.8 Hz, 1H), 7.39(s, 1H), 7.38(s, 1H), 6.83(s, 1H), 6.49(s, 1H), 4.54(t, J=6.6 Hz, 2H), 4.16(t, J=6.1 Hz, 2H), 3.90(s, 3H), 3.85(s, 6H), 3.84(s, 3H), 3.70(s, 3H), 2.28—2.07(m, 2H)	172.6, 164.2, 160.7, 158.6, 157.4, 153.2, 152.2, 140.3, 140.2, 140.1, 139.9, 138.8, 130.9, 129.1, 127.3, 127.2, 126.0, 108.9, 106.2, 96.4, 93.6, 69.0, 63.9, 60.6, 56.6, 56.5, 29.6
4b	7.88(d, J=8.2 Hz, 1H), 7.74(t, J=7.7 Hz, 1H), 7.65(d, J=6.8 Hz, 1H), 7.57(t, J=6.8 Hz, 1H), 7.39(s, 1H), 7.36(s, 1H), 6.83(s, 1H), 6.46(s, 1H), 4.53(t, J=6.4 Hz, 2H), 4.09(t, J=6.2 Hz, 2H), 3.91(s, 3H), 3.85(s, 6H), 3.84(s, 3H), 3.70(s, 3H), 2.43(s, 3H), 2.27—2.06(m, 2H)	172.6, 164.2, 160.7, 158.6, 156.2, 154.6, 153.1, 152.1, 148.3, 140.4, 139.6, 138.4, 129.5, 128.2, 126.9, 126.0, 123.7, 108.9, 106.2, 96.3, 93.4, 69.9, 68.9, 63.7, 60.5, 56.4, 29.6, 20.4
Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
4c	8.57(s, 1H), 8.07(s, 1H), 7.81(d, J=12.0 Hz, 1H), 7.67(d, J=11.3 Hz, 1H), 7.38(s, 1H), 7.36(s, 1H), 6.81(s, 1H), 6.48(s, 1H), 4.53(t, J=6.5 Hz, 2H), 4.07(t, J=6.2 Hz, 2H), 3.89(s, 3H), 3.85(s, 6H), 3.84(s, 3H), 3.70(s, 3H), 2.24—2.00(m, 2H)	172.6, 164.2, 160.8, 160.7, 158.6, 157.7, 154.4, 153.2, 153.1, 152.1, 141.5, 140.3, 140.2, 139.8, 139.1, 138.9, 134.1, 131.2, 129.1, 128.0, 126.0, 108.9, 106.2, 96.4, 93.5, 68.9, 64.2, 60.6, 60.6, 56.5, 29.5
4d	7.69(d, J=10.0 Hz, 1H), 7.43(d, J=9.8 Hz, 1H), 7.40(s, 1H), 7.39(s, 1H), 7.25(t, J=6.6 Hz, 1H), 7.06(t, J=7.1 Hz, 1H), 6.86(s, 1H), 6.50(s, 1H), 4.27(t, J=6.8 Hz, 2H), 4.09(t, J=5.9 Hz, 2H), 3.91(s, 3H), 3.85(s, 3H), 3.83(s, 6H), 3.73(s, 3H), 2.07—2.00(m, 2H)	172.6, 166.8, 164.3, 160.7, 158.7, 153.2, 152.1, 140.4, 140.2, 139.8, 133.5, 132.1, 129.6, 129.2, 126.3, 126.0, 108.9, 106.1, 96.4, 93.9, 93.5, 73.8, 65.4, 60.6, 56.5, 56.3, 29.5
4e	8.54(s, 1H), 7.99(d, J=7.0 Hz, 1H), 7.81(d, J=8.3 Hz, 1H), 7.74(t, J=6.9 Hz, 1H), 7.62(t, J=6.8 Hz, 1H), 7.37(s, 2H), 6.81(s, 1H), 6.47(s, 1H), 4.45(t, J=6.3 Hz, 2H), 4.01(t, J=6.1 Hz, 2H), 3.90(s, 3H), 3.86(s, 6H), 3.84(s, 3H), 3.73(s, 3H), 1.95—1.89(m, 2H), 1.88—1.82(m, 2H)	172.7, 164.2, 160.8, 158.6, 157.5, 153.2, 152.1, 140.4, 140.3, 140.1, 139.9, 138.8, 130.8, 129.1, 127.3, 127.2, 126.1, 108.9, 106.3, 96.4, 93.6, 71.7, 66.3, 60.6, 56.6, 56.5, 26.7, 25.4
4f	7.87(d, J=8.1 Hz, 1H), 7.70(t, J=8.9 Hz, 1H), 7.60(d, J=7.0 Hz, 1H), 7.44(s, 1H), 7.41(s, 1H), 7.31(t, J=7.6 Hz, 1H), 6.66(s, 1H), 6.40(s, 1H), 4.52(t, J=6.2 Hz, 2H), 4.13(t, J=6.2 Hz, 2H), 3.91(s, 3H), 3.89(s, 6H), 3.86(s, 3H), 3.79(s, 3H), 2.45(s, 3H), 2.08—2.01(m, 2H), 1.96—1.91(m, 2H)	173.7, 165.3, 159.9, 157.5, 154.5, 153.1, 153.1, 149.4, 141.4, 139.8, 134.0, 133.9, 130.8, 129.9, 129.3, 127.9, 124.2, 110.3, 107.2, 96.8, 94.0, 72.3, 67.3, 61.1, 56.8, 56.8, 28.1, 26.6, 20.9
4g	8.43(s, 1H), 7.98(s, 1H), 7.79(d, J=10.3 Hz, 1H), 7.70(d, J=9.5 Hz, 1H), 7.37(s, 1H), 7.34(s, 1H), 6.82(s, 1H), 6.49(s, 1H), 4.44(t, J=6.4 Hz, 2H), 4.01(t, J=6.4 Hz, 2H), 3.90(s, 3H), 3.86(s, 6H), 3.82(s, 3H), 3.71(s, 3H), 2.05—1.86(m, 2H), 1.85—1.75(m, 2H)	172.7, 164.2, 160.7, 158.6, 154.4, 153.1, 152.1, 141.6, 139.8, 134.0, 131.7, 131.2, 127.9, 127.7, 117.3, 108.9, 106.2, 106.1, 96.4, 93.6, 71.5, 66.6, 60.6, 56.5, 56.5, 27.4, 26.7
4h	7.61(d, J=9.5 Hz, 1H), 7.47(d, J=10.1 Hz, 1H), 7.38(s, 1H), 7.36(s, 1H), 7.30(t, J=7.2 Hz, 1H), 7.21(t, J=6.8 Hz, 1H), 6.81(s, 1H), 6.46(s, 1H), 4.36(t, J=6.4 Hz, 2H), 4.00(t, J=6.9 Hz, 2H), 3.89(s, 3H), 3.83(s, 6H), 3.81(s, 3H), 3.72(s, 3H), 2.01—1.83(m, 2H), 1.79—1.64(m, 2H)	172.7, 164.2, 160.8, 158.6, 153.9, 153.3, 153.2, 153.1, 152.1, 140.3, 139.9, 126.8, 126.1, 126.0, 124.3, 115.9, 108.9, 106.2, 96.4, 93.6, 71.6, 60.6, 60.5, 56.5, 56.4, 27.5, 26.7
4i	8.20(s, 1H), 8.00(d, J=8.1 Hz, 1H), 7.82(d, J=7.3 Hz, 1H), 7.74(t, J=6.9 Hz, 1H), 7.63(t, J=6.5 Hz, 1H), 7.40(s, 1H), 7.37(s, 1H), 6.83(s, 1H), 6.50(s, 1H), 4.40(t, J=6.5 Hz, 2H), 3.97(t, J=6.4 Hz, 2H), 3.90(s, 3H), 3.86(s, 6H), 3.85(s, 3H), 3.73(s, 3H), 1.86—1.74(m, 2H), 1.72—1.58(m, 2H), 1.57—1.43(m, 2H)	172.7, 164.2, 160.8, 158.6, 154.6, 153.2, 150.6, 140.3, 140.0, 131.6, 130.8, 130.3, 129.1, 127.3, 126.1, 123.8, 115.2, 109.0, 106.3, 96.4, 93.6, 72.0, 66.6, 60.7, 56.6, 56.5, 29.8, 28.3, 23.3
4j	7.89(d, J=7.3 Hz, 1H), 7.77(t, J=7.5 Hz, 1H), 7.63(d, J=8.3 Hz, 1H), 7.54(t, J=7.7 Hz, 1H), 7.39(s, 1H), 7.37(s, 1H), 6.80(s, 1H), 6.46(s, 1H), 4.39(t, J=6.3 Hz, 2H), 3.96(t, J=6.4 Hz, 2H), 3.90(s, 3H), 3.88(s, 6H), 3.85(s, 3H), 3.75(s, 3H), 2.43(s, 3H), 1.91—1.75(m, 2H), 1.74—1.64(m, 2H), 1.57—1.46(m, 2H)	172.6, 164.1, 160.7, 158.6, 156.3, 154.5, 153.1, 151.8, 148.3, 140.5, 139.8, 139.7, 138.4, 130.1, 129.4, 128.2, 126.9, 123.6, 108.9, 106.2, 106.1, 96.3, 93.5, 71.9, 66.6, 60.6, 56.5, 56.5, 29.8, 28.31, 23.3, 20.4
4k	8.26(s, 1H), 8.06(s, 1H), 7.80(d, J=9.6 Hz, 1H), 7.70(d, J=9.7 Hz, 1H), 7.38(s, 1H), 7.37(s, 1H), 6.83(s, 1H), 6.49(s, 1H), 4.40(t, J=6.4 Hz, 2H), 3.97(t, J=6.4 Hz, 2H), 3.90(s, 3H), 3.86(s, 6H), 3.84(s, 3H), 3.73(s, 3H), 1.94—1.73(m, 2H), 1.72—1.62(m, 2H), 1.59—1.44(m, 2H)	172.7, 164.2, 160.7, 158.6, 157.8, 153.1, 152.1, 141.6, 140.4, 139.8, 139.0, 138.9, 132.0, 131.2, 129.1, 128.0, 126.1, 108.9, 106.2, 96.4, 93.6, 71.9, 66.9, 65.5, 60.6, 56.5, 29.8, 28.2, 22.6
4l	7.70(d, J=10.7 Hz, 1H), 7.51(d, J=9.6 Hz, 1H), 7.39(s, 1H), 7.37(s, 1H), 7.22(t, J=10.4 Hz, 1H), 7.05(t, J=9.2 Hz, 1H), 6.85(s, 1H), 6.50(s, 1H), 4.23(t, J=9.5 Hz, 2H), 3.97(t, J=9.1 Hz, 2H), 3.90(s, 3H), 3.85(s, 6H), 3.82(s, 3H), 3.72(s, 3H), 1.91—1.74(m, 2H), 1.72—1.65(m, 2H), 1.54—1.46(m, 2H)	172.7, 164.2, 160.8, 158.6, 154.0, 153.2, 153.2, 153.1, 152.1, 140.3, 139.9, 126.8, 126.1, 126.0, 124.3, 115.9, 108.9, 106.2, 96.4, 93.6, 71.6, 60.6, 60.5, 56.5, 56.4, 27.5, 26.7
Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
4m	7.66(s, 1H), 7.49(d, J=8.7 Hz, 1H), 7.44(d, J=8.0 Hz, 1H), 7.42(s, 1H), 7.42(s, 1H), 7.30(t, J=10.7 Hz, 1H), 7.21(t, J=11.4 Hz, 1H), 6.67(s, 1H), 6.41(s, 1H), 4.22(t, J=5.4 Hz, 2H), 4.01(t, J=5.1 Hz, 2H), 3.91(s, 3H), 3.90(s, 6H), 3.87(s, 3H), 3.79(s, 3H), 1.81—1.78(m, 2H), 1.72—1.68(m, 2H), 1.52—1.49(m, 2H), 1.46—1.42(m, 2H)	173.9, 165.3, 162.2, 159.9, 155.1, 154.4, 153.1, 151.4, 141.8, 141.4, 132.5, 132.2, 128.6, 128.1, 127.5, 127.4, 125.1, 107.3, 107.3, 96.8, 94.0, 73.0, 73.0, 61.1, 57.1, 56.7, 27.9, 27.6, 26.9
4n	7.74(d, J=9.2 Hz, 1H), 7.63(d, J=8.2 Hz, 1H), 7.49(t, J=6.9 Hz, 1H), 7.41(t, J=8.3 Hz, 1H), 7.32(s, 1H), 7.32(s, 1H), 6.58(s, 1H), 6.32(s, 1H), 4.35(t, J=6.5 Hz, 2H), 3.94(t, J=6.5 Hz, 2H), 3.78(s, 3H), 3.78(s, 6H), 3.77(s, 3H), 3.67(s, 3H), 2.44(s, 3H), 1.97—1.92(m, 2H), 1.92—1.87(m, 2H), 1.49—1.42(m, 2H), 1.41—1.33(m, 2H)	173.7, 165.3, 162.3, 160.0, 157.6, 154.5, 153.0, 149.4, 141.9, 141.4, 141.1, 139.8, 130.0, 129.3, 127.9, 127.5, 127.4, 110.4, 107.4, 96.8, 94.0, 73.0, 67.5, 61.1, 57.0, 56.8, 27.0, 27.0, 26.9, 20.9
4o	8.61(s, 1H), 8.05(s, 1H), 7.83(d, J=8.9 Hz, 1H), 7.74(d, J=7.4 Hz, 1H), 7.38(s, 1H), 7.37(s, 1H), 6.83(s, 1H), 6.49(s, 1H), 4.40(t, J=6.6 Hz, 2H), 3.95(t, J=6.7 Hz, 2H), 3.90(s, 3H), 3.86(s, 3H), 3.85(s, 6H), 3.74(s, 3H), 1.80—1.67(m, 2H), 1.66—1.59(m, 2H), 1.49—1.41(m, 2H), 1.40—1.31(m, 2H)	172.7, 164.2, 160.8, 158.6, 157.8, 153.1, 152.0, 141.7, 140.4, 139.9, 139.0, 138.9, 131.2, 131.1, 129.1, 127.9, 126.1, 108.9, 106.3, 96.4, 93.6, 72.0, 66.8, 60.6, 56.5, 56.5, 30.0, 28.5, 25.7
4p	7.84(d, J=7.9 Hz, 1H), 7.66(d, J=7.1 Hz, 1H), 7.60(t, J=6.4 Hz, 1H), 7.39(t, J=7.0 Hz, 1H), 7.40(s, 2H), 7.36(s, 1H), 6.70(s, 1H), 6.44(s, 1H), 4.32(t, J=6.6 Hz, 2H), 4.04(t, J=6.3 Hz, 2H), 3.94(s, 3H), 3.93(s, 3H), 3.92(s, 6H), 3.82(s, 3H), 1.97—1.82(m, 2H), 1.73—1.63(m, 2H), 1.49—1.37(m, 2H), 1.31—1.11(m, 2H)	173.8, 165.3, 162.2, 159.9, 154.5, 153.0, 151.4, 141.8, 141.4, 134.7, 132.3, 131.5, 130.1, 128.4, 127.5, 124.4, 110.4, 107.3, 96.8, 94.0, 72.9, 67.5, 61.1, 57.1, 56.7, 28.3, 27.6, 26.8

Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
2c	7.37(s, 2H), 6.81(s, 1H), 6.48(s, 1H), 3.94(t, J=5.6 Hz, 2H), 3.90(s, 3H), 3.88(s, 6H), 3.85(s, 3H), 3.77(s, 3H), 3.48(t, J=6.7 Hz, 2H), 1.89—1.72(m, 2H), 1.71—1.62(m, 2H), 1.51—1.40(m, 2H)
2d	7.37(s, 2H), 6.84(s, 1H), 6.49(s, 1H), 3.95(t, J=6.0 Hz, 2H), 3.90(s, 3H), 3.87(s, 6H), 3.85(s, 3H), 3.76(s, 3H), 3.58(t, J=6.6 Hz, 2H), 1.67—1.64(m, 2H), 1.58—1.47(m, 2H), 1.43—1.35(m, 2H), 1.29—1.23(m, 2H)
4a	8.53(s, 1H), 8.00(d, J=9.2 Hz, 1H), 7.82(d, J=8.6 Hz, 1H), 7.76(t, J=7.6 Hz, 1H), 7.64(t, J=6.8 Hz, 1H), 7.39(s, 1H), 7.38(s, 1H), 6.83(s, 1H), 6.49(s, 1H), 4.54(t, J=6.6 Hz, 2H), 4.16(t, J=6.1 Hz, 2H), 3.90(s, 3H), 3.85(s, 6H), 3.84(s, 3H), 3.70(s, 3H), 2.28—2.07(m, 2H)	172.6, 164.2, 160.7, 158.6, 157.4, 153.2, 152.2, 140.3, 140.2, 140.1, 139.9, 138.8, 130.9, 129.1, 127.3, 127.2, 126.0, 108.9, 106.2, 96.4, 93.6, 69.0, 63.9, 60.6, 56.6, 56.5, 29.6
4b	7.88(d, J=8.2 Hz, 1H), 7.74(t, J=7.7 Hz, 1H), 7.65(d, J=6.8 Hz, 1H), 7.57(t, J=6.8 Hz, 1H), 7.39(s, 1H), 7.36(s, 1H), 6.83(s, 1H), 6.46(s, 1H), 4.53(t, J=6.4 Hz, 2H), 4.09(t, J=6.2 Hz, 2H), 3.91(s, 3H), 3.85(s, 6H), 3.84(s, 3H), 3.70(s, 3H), 2.43(s, 3H), 2.27—2.06(m, 2H)	172.6, 164.2, 160.7, 158.6, 156.2, 154.6, 153.1, 152.1, 148.3, 140.4, 139.6, 138.4, 129.5, 128.2, 126.9, 126.0, 123.7, 108.9, 106.2, 96.3, 93.4, 69.9, 68.9, 63.7, 60.5, 56.4, 29.6, 20.4
Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
4c	8.57(s, 1H), 8.07(s, 1H), 7.81(d, J=12.0 Hz, 1H), 7.67(d, J=11.3 Hz, 1H), 7.38(s, 1H), 7.36(s, 1H), 6.81(s, 1H), 6.48(s, 1H), 4.53(t, J=6.5 Hz, 2H), 4.07(t, J=6.2 Hz, 2H), 3.89(s, 3H), 3.85(s, 6H), 3.84(s, 3H), 3.70(s, 3H), 2.24—2.00(m, 2H)	172.6, 164.2, 160.8, 160.7, 158.6, 157.7, 154.4, 153.2, 153.1, 152.1, 141.5, 140.3, 140.2, 139.8, 139.1, 138.9, 134.1, 131.2, 129.1, 128.0, 126.0, 108.9, 106.2, 96.4, 93.5, 68.9, 64.2, 60.6, 60.6, 56.5, 29.5
4d	7.69(d, J=10.0 Hz, 1H), 7.43(d, J=9.8 Hz, 1H), 7.40(s, 1H), 7.39(s, 1H), 7.25(t, J=6.6 Hz, 1H), 7.06(t, J=7.1 Hz, 1H), 6.86(s, 1H), 6.50(s, 1H), 4.27(t, J=6.8 Hz, 2H), 4.09(t, J=5.9 Hz, 2H), 3.91(s, 3H), 3.85(s, 3H), 3.83(s, 6H), 3.73(s, 3H), 2.07—2.00(m, 2H)	172.6, 166.8, 164.3, 160.7, 158.7, 153.2, 152.1, 140.4, 140.2, 139.8, 133.5, 132.1, 129.6, 129.2, 126.3, 126.0, 108.9, 106.1, 96.4, 93.9, 93.5, 73.8, 65.4, 60.6, 56.5, 56.3, 29.5
4e	8.54(s, 1H), 7.99(d, J=7.0 Hz, 1H), 7.81(d, J=8.3 Hz, 1H), 7.74(t, J=6.9 Hz, 1H), 7.62(t, J=6.8 Hz, 1H), 7.37(s, 2H), 6.81(s, 1H), 6.47(s, 1H), 4.45(t, J=6.3 Hz, 2H), 4.01(t, J=6.1 Hz, 2H), 3.90(s, 3H), 3.86(s, 6H), 3.84(s, 3H), 3.73(s, 3H), 1.95—1.89(m, 2H), 1.88—1.82(m, 2H)	172.7, 164.2, 160.8, 158.6, 157.5, 153.2, 152.1, 140.4, 140.3, 140.1, 139.9, 138.8, 130.8, 129.1, 127.3, 127.2, 126.1, 108.9, 106.3, 96.4, 93.6, 71.7, 66.3, 60.6, 56.6, 56.5, 26.7, 25.4
4f	7.87(d, J=8.1 Hz, 1H), 7.70(t, J=8.9 Hz, 1H), 7.60(d, J=7.0 Hz, 1H), 7.44(s, 1H), 7.41(s, 1H), 7.31(t, J=7.6 Hz, 1H), 6.66(s, 1H), 6.40(s, 1H), 4.52(t, J=6.2 Hz, 2H), 4.13(t, J=6.2 Hz, 2H), 3.91(s, 3H), 3.89(s, 6H), 3.86(s, 3H), 3.79(s, 3H), 2.45(s, 3H), 2.08—2.01(m, 2H), 1.96—1.91(m, 2H)	173.7, 165.3, 159.9, 157.5, 154.5, 153.1, 153.1, 149.4, 141.4, 139.8, 134.0, 133.9, 130.8, 129.9, 129.3, 127.9, 124.2, 110.3, 107.2, 96.8, 94.0, 72.3, 67.3, 61.1, 56.8, 56.8, 28.1, 26.6, 20.9
4g	8.43(s, 1H), 7.98(s, 1H), 7.79(d, J=10.3 Hz, 1H), 7.70(d, J=9.5 Hz, 1H), 7.37(s, 1H), 7.34(s, 1H), 6.82(s, 1H), 6.49(s, 1H), 4.44(t, J=6.4 Hz, 2H), 4.01(t, J=6.4 Hz, 2H), 3.90(s, 3H), 3.86(s, 6H), 3.82(s, 3H), 3.71(s, 3H), 2.05—1.86(m, 2H), 1.85—1.75(m, 2H)	172.7, 164.2, 160.7, 158.6, 154.4, 153.1, 152.1, 141.6, 139.8, 134.0, 131.7, 131.2, 127.9, 127.7, 117.3, 108.9, 106.2, 106.1, 96.4, 93.6, 71.5, 66.6, 60.6, 56.5, 56.5, 27.4, 26.7
4h	7.61(d, J=9.5 Hz, 1H), 7.47(d, J=10.1 Hz, 1H), 7.38(s, 1H), 7.36(s, 1H), 7.30(t, J=7.2 Hz, 1H), 7.21(t, J=6.8 Hz, 1H), 6.81(s, 1H), 6.46(s, 1H), 4.36(t, J=6.4 Hz, 2H), 4.00(t, J=6.9 Hz, 2H), 3.89(s, 3H), 3.83(s, 6H), 3.81(s, 3H), 3.72(s, 3H), 2.01—1.83(m, 2H), 1.79—1.64(m, 2H)	172.7, 164.2, 160.8, 158.6, 153.9, 153.3, 153.2, 153.1, 152.1, 140.3, 139.9, 126.8, 126.1, 126.0, 124.3, 115.9, 108.9, 106.2, 96.4, 93.6, 71.6, 60.6, 60.5, 56.5, 56.4, 27.5, 26.7
4i	8.20(s, 1H), 8.00(d, J=8.1 Hz, 1H), 7.82(d, J=7.3 Hz, 1H), 7.74(t, J=6.9 Hz, 1H), 7.63(t, J=6.5 Hz, 1H), 7.40(s, 1H), 7.37(s, 1H), 6.83(s, 1H), 6.50(s, 1H), 4.40(t, J=6.5 Hz, 2H), 3.97(t, J=6.4 Hz, 2H), 3.90(s, 3H), 3.86(s, 6H), 3.85(s, 3H), 3.73(s, 3H), 1.86—1.74(m, 2H), 1.72—1.58(m, 2H), 1.57—1.43(m, 2H)	172.7, 164.2, 160.8, 158.6, 154.6, 153.2, 150.6, 140.3, 140.0, 131.6, 130.8, 130.3, 129.1, 127.3, 126.1, 123.8, 115.2, 109.0, 106.3, 96.4, 93.6, 72.0, 66.6, 60.7, 56.6, 56.5, 29.8, 28.3, 23.3
4j	7.89(d, J=7.3 Hz, 1H), 7.77(t, J=7.5 Hz, 1H), 7.63(d, J=8.3 Hz, 1H), 7.54(t, J=7.7 Hz, 1H), 7.39(s, 1H), 7.37(s, 1H), 6.80(s, 1H), 6.46(s, 1H), 4.39(t, J=6.3 Hz, 2H), 3.96(t, J=6.4 Hz, 2H), 3.90(s, 3H), 3.88(s, 6H), 3.85(s, 3H), 3.75(s, 3H), 2.43(s, 3H), 1.91—1.75(m, 2H), 1.74—1.64(m, 2H), 1.57—1.46(m, 2H)	172.6, 164.1, 160.7, 158.6, 156.3, 154.5, 153.1, 151.8, 148.3, 140.5, 139.8, 139.7, 138.4, 130.1, 129.4, 128.2, 126.9, 123.6, 108.9, 106.2, 106.1, 96.3, 93.5, 71.9, 66.6, 60.6, 56.5, 56.5, 29.8, 28.31, 23.3, 20.4
4k	8.26(s, 1H), 8.06(s, 1H), 7.80(d, J=9.6 Hz, 1H), 7.70(d, J=9.7 Hz, 1H), 7.38(s, 1H), 7.37(s, 1H), 6.83(s, 1H), 6.49(s, 1H), 4.40(t, J=6.4 Hz, 2H), 3.97(t, J=6.4 Hz, 2H), 3.90(s, 3H), 3.86(s, 6H), 3.84(s, 3H), 3.73(s, 3H), 1.94—1.73(m, 2H), 1.72—1.62(m, 2H), 1.59—1.44(m, 2H)	172.7, 164.2, 160.7, 158.6, 157.8, 153.1, 152.1, 141.6, 140.4, 139.8, 139.0, 138.9, 132.0, 131.2, 129.1, 128.0, 126.1, 108.9, 106.2, 96.4, 93.6, 71.9, 66.9, 65.5, 60.6, 56.5, 29.8, 28.2, 22.6
4l	7.70(d, J=10.7 Hz, 1H), 7.51(d, J=9.6 Hz, 1H), 7.39(s, 1H), 7.37(s, 1H), 7.22(t, J=10.4 Hz, 1H), 7.05(t, J=9.2 Hz, 1H), 6.85(s, 1H), 6.50(s, 1H), 4.23(t, J=9.5 Hz, 2H), 3.97(t, J=9.1 Hz, 2H), 3.90(s, 3H), 3.85(s, 6H), 3.82(s, 3H), 3.72(s, 3H), 1.91—1.74(m, 2H), 1.72—1.65(m, 2H), 1.54—1.46(m, 2H)	172.7, 164.2, 160.8, 158.6, 154.0, 153.2, 153.2, 153.1, 152.1, 140.3, 139.9, 126.8, 126.1, 126.0, 124.3, 115.9, 108.9, 106.2, 96.4, 93.6, 71.6, 60.6, 60.5, 56.5, 56.4, 27.5, 26.7
Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
4m	7.66(s, 1H), 7.49(d, J=8.7 Hz, 1H), 7.44(d, J=8.0 Hz, 1H), 7.42(s, 1H), 7.42(s, 1H), 7.30(t, J=10.7 Hz, 1H), 7.21(t, J=11.4 Hz, 1H), 6.67(s, 1H), 6.41(s, 1H), 4.22(t, J=5.4 Hz, 2H), 4.01(t, J=5.1 Hz, 2H), 3.91(s, 3H), 3.90(s, 6H), 3.87(s, 3H), 3.79(s, 3H), 1.81—1.78(m, 2H), 1.72—1.68(m, 2H), 1.52—1.49(m, 2H), 1.46—1.42(m, 2H)	173.9, 165.3, 162.2, 159.9, 155.1, 154.4, 153.1, 151.4, 141.8, 141.4, 132.5, 132.2, 128.6, 128.1, 127.5, 127.4, 125.1, 107.3, 107.3, 96.8, 94.0, 73.0, 73.0, 61.1, 57.1, 56.7, 27.9, 27.6, 26.9
4n	7.74(d, J=9.2 Hz, 1H), 7.63(d, J=8.2 Hz, 1H), 7.49(t, J=6.9 Hz, 1H), 7.41(t, J=8.3 Hz, 1H), 7.32(s, 1H), 7.32(s, 1H), 6.58(s, 1H), 6.32(s, 1H), 4.35(t, J=6.5 Hz, 2H), 3.94(t, J=6.5 Hz, 2H), 3.78(s, 3H), 3.78(s, 6H), 3.77(s, 3H), 3.67(s, 3H), 2.44(s, 3H), 1.97—1.92(m, 2H), 1.92—1.87(m, 2H), 1.49—1.42(m, 2H), 1.41—1.33(m, 2H)	173.7, 165.3, 162.3, 160.0, 157.6, 154.5, 153.0, 149.4, 141.9, 141.4, 141.1, 139.8, 130.0, 129.3, 127.9, 127.5, 127.4, 110.4, 107.4, 96.8, 94.0, 73.0, 67.5, 61.1, 57.0, 56.8, 27.0, 27.0, 26.9, 20.9
4o	8.61(s, 1H), 8.05(s, 1H), 7.83(d, J=8.9 Hz, 1H), 7.74(d, J=7.4 Hz, 1H), 7.38(s, 1H), 7.37(s, 1H), 6.83(s, 1H), 6.49(s, 1H), 4.40(t, J=6.6 Hz, 2H), 3.95(t, J=6.7 Hz, 2H), 3.90(s, 3H), 3.86(s, 3H), 3.85(s, 6H), 3.74(s, 3H), 1.80—1.67(m, 2H), 1.66—1.59(m, 2H), 1.49—1.41(m, 2H), 1.40—1.31(m, 2H)	172.7, 164.2, 160.8, 158.6, 157.8, 153.1, 152.0, 141.7, 140.4, 139.9, 139.0, 138.9, 131.2, 131.1, 129.1, 127.9, 126.1, 108.9, 106.3, 96.4, 93.6, 72.0, 66.8, 60.6, 56.5, 56.5, 30.0, 28.5, 25.7
4p	7.84(d, J=7.9 Hz, 1H), 7.66(d, J=7.1 Hz, 1H), 7.60(t, J=6.4 Hz, 1H), 7.39(t, J=7.0 Hz, 1H), 7.40(s, 2H), 7.36(s, 1H), 6.70(s, 1H), 6.44(s, 1H), 4.32(t, J=6.6 Hz, 2H), 4.04(t, J=6.3 Hz, 2H), 3.94(s, 3H), 3.93(s, 3H), 3.92(s, 6H), 3.82(s, 3H), 1.97—1.82(m, 2H), 1.73—1.63(m, 2H), 1.49—1.37(m, 2H), 1.31—1.11(m, 2H)	173.8, 165.3, 162.2, 159.9, 154.5, 153.0, 151.4, 141.8, 141.4, 134.7, 132.3, 131.5, 130.1, 128.4, 127.5, 124.4, 110.4, 107.3, 96.8, 94.0, 72.9, 67.5, 61.1, 57.1, 56.7, 28.3, 27.6, 26.8

Compd.	n	R	Inhibition rate^a (%)
			X. citri		X. oryzae
			100 μg/mL	50 μg/mL	100 μg/mL	50 μg/mL
4a	3	H	73.69±5.97	67.82±2.64	40.78±3.60	33.63±5.14
4b	3	3-CH₃	83.52±2.19	68.13±1.20	49.33±2.85	44.71±4.65
4c	3	6-Cl	73.17±7.31	63.18±6.12	50.23±4.81	43.66±8.00
4d	3	3-OH	77.50±2.97	67.71±7.99	52.78±5.55	43.77±5.57
4e	4	H	75.23±9.52	62.10±2.25	55.17±5.65	42.52±5.98
4f	4	3-CH₃	74.61±2.36	65.50±5.74	61.30±4.24	53.27±8.16
4g	4	6-Cl	74.20±9.83	61.79±7.18	47.19±5.92	37.91±6.71
4h	4	3-OH	77.96±1.47	68.07±6.74	53.22±6.21	42.31±2.88
4i	5	H	80.38±6.90	69.88±4.33	47.57±5.99	37.48±2.00
4j	5	3-CH₃	76.67±2.63	66.63±6.14	50.23±5.71	44.80±1.41
4k	5	6-Cl	81.00±8.11	69.41±4.79	36.18±0.32	31.99±6.24
4l	5	3-OH	73.07±4.23	67.35±7.10	49.61±3.08	38.20±8.51
4m	6	H	76.00±7.20	65.55±4.94	54.74±8.50	46.65±7.34
4n	6	3-CH₃	77.45±1.75	67.35±6.36	47.95±7.65	39.92±9.61
4o	6	6-Cl	76.21±5.41	68.13±7.63	29.61±2.46	18.79±4.44
4p	6	3-OH	77.45±3.28	66.37±3.42	33.72±1.93	21.23±6.28
Myricetin			49.38±4.06	40.37±0.41	41.38±5.94	32.32±2.85
Bismerthiazol^b			59.47±7.65	49.49±5.74	47.03±3.06	39.59±6.08
Thiodiazole-copper^b			56.90±1.47	47.94±8.47	43.23±3.01	38.18±6.32