Synthesis and Biological Activities of Novel 5-(Pyridine-3-yl)-1,2,4-triazole Mannich Bases and Bis-Mannich Bases Containing Piperazine Moiety†

doi:10.7503/cjcu20160042

Abstract

Abstract:

According to the drug design principle of active groups combination, a series of 5-(pyridine-3-yl)-1,2,4-triazole Mannich bases and bis-Mannich bases containing piperazine and fluorine moieties was designed and synthesized through the Mannich reaction of 1,2,4-triazole thiol intermediate. All the structures of new title compounds were characterized by ¹H NMR, ¹³C NMR and elemental analysis. The bioassay results showed that several compounds exhibited herbicidal activities against Brassica campestris in certain extent; compounds 2a, 2d and 2f possessed significant antifungal activities against P. piricola and were comparable with the control fungicide, triadimefon, at the concentration of 50 mg/L. Also, compounds 2a, 2b, 2d and 2i showed favorable in vitro ketol-acid reductoisomerase(KARI) inhibitory activities with inhibition rate of 51.7%—88.7% at 180 mg/L.

Key words: Pyridine, 1,2,4-Triazole Mannich base, Piperazine, Biological activity

CLC Number:

O626.32

TrendMD:

ZHANG Yan, WANG Baolei, ZHAN Yizhou, ZHANG Liyuan, LI Yonghong, LI Zhengming. Synthesis and Biological Activities of Novel 5-(Pyridine-3-yl)-1,2,4-triazole Mannich Bases and Bis-Mannich Bases Containing Piperazine Moiety^†[J]. Chem. J. Chinese Universities, 2016, 37(6): 1100.

Figures/Tables 6

References 36

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Compd.	Apperance	m.p./℃	Yield(%)	Elemental analysis(%, calcd.)
Compd.	Apperance	m.p./℃	Yield(%)	C	H	N
1a	White solid	246—247	90	55.97(56.18)	3.52(3.37)	23.15(23.40)
1b	White solid	261—262	94	51.60(51.57)	2.75(2.89)	19.98(20.05)
2a	White solid	118—119	83	59.85(59.82)	4.89(4.83)	18.60(18.78)
2b	White solid	137—138	86	56.47(56.12)	4.26(4.35)	17.62(17.78)
2c	White solid	134—135	91	63.67(63.41)	4.78(5.11)	20.91(20.70)
2d	White solid	190—191	81	59.26(59.62)	5.20(5.20)	24.62(25.03)
2e	White solid	147—148	74	60.73(60.74)	4.89(4.89)	23.39(23.61)
2f	White solid	125—127	99	56.84(56.69)	4.61(4.41)	17.23(17.14)
2g	White solid	136—138	89	53.38(53.47)	3.92(3.99)	16.23(16.17)
2h	White solid	130—131	83	59.51(59.64)	4.80(4.62)	18.49(18.73)
2i	White solid	128—130	99	55.51(55.65)	4.80(4.48)	23.73(23.36)
2j	White solid	125—126	66	56.18(56.41)	4.70(4.73)	22.56(22.77)
2k	White solid	151—152	90	56.95(57.24)	4.45(4.42)	21.22(21.36)
3a	White solid	235—236	58	57.60(57.61)	4.21(4.27)	24.05(23.71)
3b	White solid	224—226	99	53.33(53.46)	3.81(3.74)	20.90(20.78)

Compd.	Apperance	m.p./℃	Yield(%)	Elemental analysis(%, calcd.)
Compd.	Apperance	m.p./℃	Yield(%)	C	H	N
1a	White solid	246—247	90	55.97(56.18)	3.52(3.37)	23.15(23.40)
1b	White solid	261—262	94	51.60(51.57)	2.75(2.89)	19.98(20.05)
2a	White solid	118—119	83	59.85(59.82)	4.89(4.83)	18.60(18.78)
2b	White solid	137—138	86	56.47(56.12)	4.26(4.35)	17.62(17.78)
2c	White solid	134—135	91	63.67(63.41)	4.78(5.11)	20.91(20.70)
2d	White solid	190—191	81	59.26(59.62)	5.20(5.20)	24.62(25.03)
2e	White solid	147—148	74	60.73(60.74)	4.89(4.89)	23.39(23.61)
2f	White solid	125—127	99	56.84(56.69)	4.61(4.41)	17.23(17.14)
2g	White solid	136—138	89	53.38(53.47)	3.92(3.99)	16.23(16.17)
2h	White solid	130—131	83	59.51(59.64)	4.80(4.62)	18.49(18.73)
2i	White solid	128—130	99	55.51(55.65)	4.80(4.48)	23.73(23.36)
2j	White solid	125—126	66	56.18(56.41)	4.70(4.73)	22.56(22.77)
2k	White solid	151—152	90	56.95(57.24)	4.45(4.42)	21.22(21.36)
3a	White solid	235—236	58	57.60(57.61)	4.21(4.27)	24.05(23.71)
3b	White solid	224—226	99	53.33(53.46)	3.81(3.74)	20.90(20.78)

Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
1a^a	14.42(s, 1H, SH), 9.81(s, 1H, N=CH), 9.04(s, 1H, Pyridine-H), 8.74(d, J=4.5 Hz, 1H, Pyridine-H ), 8.28(d, J=7.8 Hz, 1H, Pyridine-H), 8.01—7.95(m, 2H, Ph—H), 7.63—7.58(m, 1H, Pyridine-H), 7.42(t, J=8.5 Hz, 2H, Ph—H)	165.7, 163.6(C=S), 162.5, 151.3(CH=N), 148.7, 146.8(Triazole-C), 135.9, 131.40(d, J=9.0 Hz, F—Ph—C), 128.6, 123.8 , 122.0, 116.5
1b^a	14.47(s, 1H, SH), 10.09(s, 1H, N=CH), 9.05(s, 1H, Pyridine-H), 8.75(d, J=4.5 Hz, 1H, Pyridine-H), 8.27(d, J=7.9 Hz, 1H, Pyridine-H), 8.12(d, J=8.0 Hz, 2H, Ph—H), 7.94(d, J=8.0 Hz, 2H, Ph—H), 7.60(dd, J=7.9, 4.5 Hz, 1H, Pyridine-H)	163.9(C=S), 162.6(s), 151.0(CH=N), 148.5, 147.0(Triazole-C), 136.7, 135.9, 132.3(d, J=33.3 Hz, CF₃—Ph—C), 129.5, 126.3, 124.1, 123.9(q, J=273.7 Hz, CF₃), 122.2
2a^b	10.23(s, 1H, N=CH), 9.21(s, 1H, Pyridine-H), 8.74(s, 1H, Pyridine-H), 8.26(s, 1H, Pyridine-H), 7.89—7.85(m, 2H, Ph—H), 7.46—7.42(s, 1H, Pyridine-H), 7.27—7.16(m, 6H, Ph—H), 5.26(s, 2H, CH₂), 3.45(s, 2H, CH₂), 2.98—2.91(m, 4H, Piperazine-CH₂), 2.65—2.25(m, 4H, Piperazine-CH₂)	165.5, 164.0(C=S), 162.3, 151.4(CH=N), 149.5, 146.0(Triazole-C), 136.6, 135.9, 132.8, 131.2(d, J=9.0 Hz, F—Ph—C), 130.4, 128.5, 128.4, 123.3, 122.0, 116.1, 69.6, 62.3, 53.0, 50.5
2b^b	10.25(s, 1H, N=CH), 9.22(s, 1H, Pyridine-H), 8.74(d, J=4.7 Hz, 1H, Pyridine-H), 8.27(d, J=8.0 Hz, 1H, Pyridine-H), 7.90—7.86(m, 2H, Ph—H), 7.44(dd, J=8.0, 4.7 Hz, 1H, Pyridine-H), 7.38—7.32(m, 2H, Ph—H), 7.20—7.16(m, 3H, Ph—H), 5.28(s, 2H, CH₂), 3.56(s, 2H, CH₂), 2.98—2.90(m, 4H, Piperazine-CH₂), 2.61—2.48(m, 4H, Piperazine-CH₂)	165.5, 164.1(C=S), 162.3, 151.4(CH=N), 149.5, 146.0(Triazole-C), 135.9, 134.8, 134.5, 133.1, 131.4, 131.2(d, J=9.0 Hz, F—Ph—C), 129.2, 128.5, 126.9, 123.3, 122.1, 116.5, 69.7, 58.7, 53.1, 50.6
2c^b	10.24(s, 1H, N=CH), 9.21(s, 1H, Pyridine-H), 8.74(d, J=3.8 Hz, 1H, Pyridine-H), 8.27(d, J=8.0 Hz, 1H, Pyridine-H), 7.91—7.85(m, 2H, Ph—H), 7.44(dd, J=8.0, 3.8 Hz, 1H, Pyridine-H), 7.28—7.23(m, 2H, Ph—H), 7.18(t, J=8.5 Hz, 2H, Ph—H), 6.91(d, J=8.1 Hz, 2H, Ph—H), 6.86(t, J=7.2 Hz, 1H, Ph—H), 5.34(s, 2H, CH₂), 3.24—3.20(m, 4H, Piperazine-CH₂), 3.10—3.04(m, 4H, Piperazine-CH₂)	165.6, 165.1(C=S), 162.4, 151.5(CH=N), 151.3, 149.5, 146.1(Triazole-C), 136.0, 131.2(d, J=9.0 Hz, F—Ph—C), 129.2, 128.5, 123.4, 122.0, 120.0, 116.5, 116.4, 69.6, 50.6, 49.6
2d^b	10.24(s, 1H, N=CH), 9.20(s, 1H, Pyridine-H), 8.73(d, J=4.5 Hz, 1H, Pyridine-H), 8.25(d, J=7.9 Hz, 1H, Pyridine-H), 7.91—7.84(m, 2H, Ph—H), 7.43(dd, J=7.9, 4.5 Hz, 1H, Pyridine-H), 7.18(t, J=8.4 Hz, 2H, Ph—H), 6.23(s, 1H, Pyrimidin-H), 5.34(s, 2H, CH₂), 3.95—3.87(m, 4H, Piperazine-CH₂), 2.97—2.90(m, 4H, Piperazine-CH₂), 2.25(s, 6H, CH₃)	167.1(C=S), 165.5, 164.1, 162.3, 161.6, 151.4(CH=N), 149.5, 146.0(Triazole-C), 135.9, 131.2(d, J=9.0 Hz, F—Ph—C), 128.5, 123.3, 122.0, 116.5, 108.9, 69.9, 50.7, 43.6, 24.1
2e^b	10.23(s, 1H, N=CH), 9.20(s, 1H, Pyridine-H), 8.73(s, 1H, Pyridine-H), 8.26(d, J=6.3 Hz, 1H, Pyridine-H), 8.16(s, 1H, Pyridine-H), 7.87(d, J=7.1 Hz, 2H, Ph—H), 7.50—7.37(m, 2H, Pyridine-H), 7.19(d, J=7.1 Hz, 2H, Ph—H), 6.68—6.50(m, 2H, Pyridine-H), 5.34(s, 2H, CH₂), 3.68—3.52(s, 4H, Piperazine-CH₂), 3.10—2.93(s, 4H, Piperazine-CH₂)	165.5, 164.0(C=S), 162.4, 159.3, 151.5(CH=N), 149.5, 148.0, 146.1(Triazole-C), 137.5, 136.0, 131.2(d, J=9.0 Hz, F—Ph—C), 128.5, 123.4, 122.0, 116.5, 113.3, 107.1, 69.7, 50.4, 45.2
2f^b	10.58(s, 1H, N=CH), 9.19(d, J=1.6 Hz, 1H, Pyridine-H), 8.75(d, J=4.8 Hz, 1H, Pyridine-H), 8.24(dd, J=8.0, 1.6 Hz, 1H, Pyridine-H), 7.97(d, J=8.1 Hz, 2H, Ph—H), 7.75(d, J=8.1 Hz, 2H, Ph—H), 7.45(dd, J=8.0, 4.8 Hz, 1H, Pyridine-H), 7.26—7.18(m, 4H, Ph—H), 5.28(s, 2H, CH₂), 3.45(s, 2H, CH₂), 2.96—2.88(m, 4H, Piperazine-CH₂), 2.53—2.43(m, 4H, Piperazine-CH₂)	164.0(C=S), 160.5, 151.6(CH=N), 149.6, 146.2(Triazole-C), 136.6, 136.1, 135.7, 133.9(d, J=33.0 Hz, CF₃—Ph—C), 132.8, 130.4, 129.1, 128.4, 126.1, 123.6(q, J=272.7 Hz, CF₃), 123.4, 121.9, 69.6, 62.3, 53.0, 50.5
2g^b	10.58(s, 1H, N=CH), 9.19(d, J=1.6 Hz, 1H, Pyridine-H), 8.76(d, J=5.0 Hz, 1H, Pyridine-H), 8.26(dd, J=8.0 Hz, 1.6 Hz, 1H, Pyridine-H), 7.97(d, J=8.1 Hz, 2H, Ph—H), 7.75(d, J=8.1 Hz, 2H, Ph—H), 7.46(dd, J=8.0, 5.0 Hz, 1H, Pyridine-H), 7.35(m, 2H, Ph—H), 7.17(dd, J=8.2, 1.8 Hz, 1H, Ph—H), 5.26(s, 2H, CH₂), 3.56(s, 2H, CH₂), 2.97—2.92(m, 4H, Piperazine-CH₂), 2.85—2.30(m, 4H, Piperazine-CH₂)	164.0(C=S), 160.5, 151.6(CH=N), 149.6, 146.2(Triazole-C), 136.1, 135.7, 135.1, 134.9, 134.5, 134.0(d, J=32.3 Hz, CF₃—Ph—C), 133.1, 131.4, 129.1, 126.9, 126.1, 123.6(q, J=275.7 Hz, CF₃), 123.4, 121.9, 69.6, 58.7, 53.1, 50.6
2h^b	10.59(s, 1H, N=CH), 9.20(d, J=1.4 Hz, 1H, Pyridine-H), 8.76(d, J=4.4 Hz, 1H, Pyridine-H), 8.25(d, J=8.3, 1.4 Hz, 1H, Pyridine-H), 7.97(d, J=8.0 Hz, 2H, Ph—H), 7.75(d, J=8.0 Hz, 2H, Ph—H), 7.46(dd, J=8.3, 4.4 Hz, 1H, Pyridine-H) , 7.25(d, J=9.5 Hz, 2H, Ph—H), 6.92(d, J=7.9 Hz, 2H, Ph—H), 6.86(t, J=7.1 Hz, 1H, Ph—H), 5.34(s, 2H, CH₂), 3.26—3.18(m, 4H, Piperazine-CH₂), 3.11—2.98(m, 4H, Piperazine-CH₂)	164.1(C=S), 160.6, 151.6(CH=N), 151.3, 149.6, 146.3(Triazole-C), 136.1, 135.7, 134.0(d, J=32.3 Hz, CF₃—Ph—C), 129.2, 129.1, 126.1, 123.6(q, J=273.7 Hz, CF₃), 123.4, 121.9, 120.1, 116.5, 69.6, 50.6, 49.5
2i^b	10.57(s, 1H, N=CH), 9.19(s, 1H, Pyridine-H), 8.75(d, J=4.0 Hz, 1H, Pyridine-H), 8.24(d, J=7.8 Hz, 1H, Pyridine-H), 8.13(d, J=4.8 Hz, 1H, Pyrimidin-H), 7.96(d, J=7.8 Hz, 2H, Ph—H), 7.74(d, J=7.9 Hz, 2H, Ph—H), 7.47—7.42(m, 1H, Pyridine-H), 6.34(d, J=4.8 Hz, 1H, Pyrimidin-H), 5.34(s, 2H, CH₂), 3.92—3.86(m, 4H, Piperazine-CH₂), 2.99—2.93(m, 4H, Piperazine-CH₂), 2.30(s, 3H, CH₃)	167.7(C=S), 164.0, 161.5, 160.6, 157.2, 151.5(CH=N), 149.6, 146.2(Triazole-C), 136.2, 135.9, 133.9(d, J=33.3 Hz, CF₃—Ph—C) 129.1, 126.1, 123.6(q, J=274.7 Hz, CF₃), 123.4, 121.9, 109.5, 69.8, 50.6, 43.6, 24.3
2j^b	10.57(s, 1H, N=CH), 9.18(d, J=1.5 Hz, 1H, Pyridine-H), 8.74(dd, J=4.9, 1.5 Hz, 1H, Pyridine-H), 8.23(d, J=8.0 Hz, 1H, Pyridine-H), 7.96(d, J=8.1 Hz, 2H, Ph—H), 7.74(d, J=8.1 Hz, 2H, Ph—H), 7.44(dd, J=8.0, 4.9 Hz, 1H, Pyridine-H), 6.23(s, 1H, Pyrimidin-H), 5.34(s, 2H, CH₂), 3.92—3.88(m, 4H, Piperazine-CH₂), 2.97—2.93(m, 4H, Piperazine-CH₂), 2.26(s, 6H, CH₃)	167.1(C=S), 164.0, 161.6, 160.6, 151.5(CH=N), 149.6, 146.2(Triazole-C), 136.1, 135.7, 133.9(q, J=32.3 Hz, CF₃—Ph—C), 129.1, 126.1, 123.6(q, J=273.7 Hz, CF₃), 123.4, 121.9, 109.0, 69.9, 50.7, 43.5, 24.1
2k^b	10.58(s, 1H, N=CH), 9.19(s, 1H, Pyridine-H), 8.75(d, J=4.4 Hz, 1H, Pyridine-H), 8.24(d, J=7.5 Hz, 1H, Pyridine-H), 8.16(d, J=3.4 Hz, 1H, Pyridine-H), 7.97(d, J=7.8 Hz, 2H, Ph—H), 7.74(d, J=7.8 Hz, 2H, Ph—H), 7.45(dd, J=10.5, 5.9 Hz, 2H, Pyridine-H), 6.61(dd, J=13.4, 7.4 Hz, 2H, Pyridine-H), 5.34(s, 2H, CH₂), 3.62—3.53(m, 4H, Piperazine-CH₂), 3.05—2.96(m, 4H, Piperazine-CH₂)	164.1(C=S), 160.6, 159.3, 151.6(CH=N), 149.6, 148.0, 146.3(Triazole-C), 133.9(d, J=33.3 Hz, CF₃—Ph—C), 137.5, 136.1, 135.7, 129.1, 126.1, 123.6(q, J=273.7 Hz, CF₃), 123.4, 121.9, 113.4, 107.1, 69.7, 50.4, 45.23
3a^b	10.23(s, 2H, N=CH), 9.20(s, 2H, Pyridine-H), 8.74(d, J=3.6 Hz, 2H, Pyridine-H), 8.25(d, J=7.2 Hz, 2H, Pyridine-H), 7.87(t, J=8.2 Hz, 4H, Ph—H), 7.46—7.41(m, 2H, Pyridine-H), 7.18(t, J=8.2 Hz, 4H, Ph—H), 5.24(s, 4H, CH₂), 2.96(s, 8H, Piperazine-CH₂)	165.5, 164.0(C=S), 160.6, 151.4(CH=N), 149.5, 146.0(Triazole-C), 136.1, 131.2(d, J=9.0 Hz, F—Ph—C), 128.5, 123.3, 122.0, 116.5, 69.9, 50.6
3b^b	10.57(s, 2H, N=CH), 9.18(s, 2H, Pyridine-H), 8.75(s, 2H, Pyridine-H), 8.24(s, 2H, Pyridine-H), 7.96(d, J=7.2 Hz, 4H, Ph—H), 7.74(d, J=7.2 Hz, 4H, Ph—H), 7.45(s, 2H, Pyridine-H), 5.24(s, 4H, CH₂), 2.96(s, 8H, Piperazine-CH₂)	163.9(C=S), 160.5, 151.6(CH=N), 149.6, 146.3(Triazole-C), 136.1, 135.6, 133.9(d, J=33.3 Hz, CF₃—Ph—C), 129.1, 126.1, 123.6(q, J=273.7 Hz, CF₃), 123.4, 121.8, 69.6, 50.5

Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
1a^a	14.42(s, 1H, SH), 9.81(s, 1H, N=CH), 9.04(s, 1H, Pyridine-H), 8.74(d, J=4.5 Hz, 1H, Pyridine-H ), 8.28(d, J=7.8 Hz, 1H, Pyridine-H), 8.01—7.95(m, 2H, Ph—H), 7.63—7.58(m, 1H, Pyridine-H), 7.42(t, J=8.5 Hz, 2H, Ph—H)	165.7, 163.6(C=S), 162.5, 151.3(CH=N), 148.7, 146.8(Triazole-C), 135.9, 131.40(d, J=9.0 Hz, F—Ph—C), 128.6, 123.8 , 122.0, 116.5
1b^a	14.47(s, 1H, SH), 10.09(s, 1H, N=CH), 9.05(s, 1H, Pyridine-H), 8.75(d, J=4.5 Hz, 1H, Pyridine-H), 8.27(d, J=7.9 Hz, 1H, Pyridine-H), 8.12(d, J=8.0 Hz, 2H, Ph—H), 7.94(d, J=8.0 Hz, 2H, Ph—H), 7.60(dd, J=7.9, 4.5 Hz, 1H, Pyridine-H)	163.9(C=S), 162.6(s), 151.0(CH=N), 148.5, 147.0(Triazole-C), 136.7, 135.9, 132.3(d, J=33.3 Hz, CF₃—Ph—C), 129.5, 126.3, 124.1, 123.9(q, J=273.7 Hz, CF₃), 122.2
2a^b	10.23(s, 1H, N=CH), 9.21(s, 1H, Pyridine-H), 8.74(s, 1H, Pyridine-H), 8.26(s, 1H, Pyridine-H), 7.89—7.85(m, 2H, Ph—H), 7.46—7.42(s, 1H, Pyridine-H), 7.27—7.16(m, 6H, Ph—H), 5.26(s, 2H, CH₂), 3.45(s, 2H, CH₂), 2.98—2.91(m, 4H, Piperazine-CH₂), 2.65—2.25(m, 4H, Piperazine-CH₂)	165.5, 164.0(C=S), 162.3, 151.4(CH=N), 149.5, 146.0(Triazole-C), 136.6, 135.9, 132.8, 131.2(d, J=9.0 Hz, F—Ph—C), 130.4, 128.5, 128.4, 123.3, 122.0, 116.1, 69.6, 62.3, 53.0, 50.5
2b^b	10.25(s, 1H, N=CH), 9.22(s, 1H, Pyridine-H), 8.74(d, J=4.7 Hz, 1H, Pyridine-H), 8.27(d, J=8.0 Hz, 1H, Pyridine-H), 7.90—7.86(m, 2H, Ph—H), 7.44(dd, J=8.0, 4.7 Hz, 1H, Pyridine-H), 7.38—7.32(m, 2H, Ph—H), 7.20—7.16(m, 3H, Ph—H), 5.28(s, 2H, CH₂), 3.56(s, 2H, CH₂), 2.98—2.90(m, 4H, Piperazine-CH₂), 2.61—2.48(m, 4H, Piperazine-CH₂)	165.5, 164.1(C=S), 162.3, 151.4(CH=N), 149.5, 146.0(Triazole-C), 135.9, 134.8, 134.5, 133.1, 131.4, 131.2(d, J=9.0 Hz, F—Ph—C), 129.2, 128.5, 126.9, 123.3, 122.1, 116.5, 69.7, 58.7, 53.1, 50.6
2c^b	10.24(s, 1H, N=CH), 9.21(s, 1H, Pyridine-H), 8.74(d, J=3.8 Hz, 1H, Pyridine-H), 8.27(d, J=8.0 Hz, 1H, Pyridine-H), 7.91—7.85(m, 2H, Ph—H), 7.44(dd, J=8.0, 3.8 Hz, 1H, Pyridine-H), 7.28—7.23(m, 2H, Ph—H), 7.18(t, J=8.5 Hz, 2H, Ph—H), 6.91(d, J=8.1 Hz, 2H, Ph—H), 6.86(t, J=7.2 Hz, 1H, Ph—H), 5.34(s, 2H, CH₂), 3.24—3.20(m, 4H, Piperazine-CH₂), 3.10—3.04(m, 4H, Piperazine-CH₂)	165.6, 165.1(C=S), 162.4, 151.5(CH=N), 151.3, 149.5, 146.1(Triazole-C), 136.0, 131.2(d, J=9.0 Hz, F—Ph—C), 129.2, 128.5, 123.4, 122.0, 120.0, 116.5, 116.4, 69.6, 50.6, 49.6
2d^b	10.24(s, 1H, N=CH), 9.20(s, 1H, Pyridine-H), 8.73(d, J=4.5 Hz, 1H, Pyridine-H), 8.25(d, J=7.9 Hz, 1H, Pyridine-H), 7.91—7.84(m, 2H, Ph—H), 7.43(dd, J=7.9, 4.5 Hz, 1H, Pyridine-H), 7.18(t, J=8.4 Hz, 2H, Ph—H), 6.23(s, 1H, Pyrimidin-H), 5.34(s, 2H, CH₂), 3.95—3.87(m, 4H, Piperazine-CH₂), 2.97—2.90(m, 4H, Piperazine-CH₂), 2.25(s, 6H, CH₃)	167.1(C=S), 165.5, 164.1, 162.3, 161.6, 151.4(CH=N), 149.5, 146.0(Triazole-C), 135.9, 131.2(d, J=9.0 Hz, F—Ph—C), 128.5, 123.3, 122.0, 116.5, 108.9, 69.9, 50.7, 43.6, 24.1
2e^b	10.23(s, 1H, N=CH), 9.20(s, 1H, Pyridine-H), 8.73(s, 1H, Pyridine-H), 8.26(d, J=6.3 Hz, 1H, Pyridine-H), 8.16(s, 1H, Pyridine-H), 7.87(d, J=7.1 Hz, 2H, Ph—H), 7.50—7.37(m, 2H, Pyridine-H), 7.19(d, J=7.1 Hz, 2H, Ph—H), 6.68—6.50(m, 2H, Pyridine-H), 5.34(s, 2H, CH₂), 3.68—3.52(s, 4H, Piperazine-CH₂), 3.10—2.93(s, 4H, Piperazine-CH₂)	165.5, 164.0(C=S), 162.4, 159.3, 151.5(CH=N), 149.5, 148.0, 146.1(Triazole-C), 137.5, 136.0, 131.2(d, J=9.0 Hz, F—Ph—C), 128.5, 123.4, 122.0, 116.5, 113.3, 107.1, 69.7, 50.4, 45.2
2f^b	10.58(s, 1H, N=CH), 9.19(d, J=1.6 Hz, 1H, Pyridine-H), 8.75(d, J=4.8 Hz, 1H, Pyridine-H), 8.24(dd, J=8.0, 1.6 Hz, 1H, Pyridine-H), 7.97(d, J=8.1 Hz, 2H, Ph—H), 7.75(d, J=8.1 Hz, 2H, Ph—H), 7.45(dd, J=8.0, 4.8 Hz, 1H, Pyridine-H), 7.26—7.18(m, 4H, Ph—H), 5.28(s, 2H, CH₂), 3.45(s, 2H, CH₂), 2.96—2.88(m, 4H, Piperazine-CH₂), 2.53—2.43(m, 4H, Piperazine-CH₂)	164.0(C=S), 160.5, 151.6(CH=N), 149.6, 146.2(Triazole-C), 136.6, 136.1, 135.7, 133.9(d, J=33.0 Hz, CF₃—Ph—C), 132.8, 130.4, 129.1, 128.4, 126.1, 123.6(q, J=272.7 Hz, CF₃), 123.4, 121.9, 69.6, 62.3, 53.0, 50.5
2g^b	10.58(s, 1H, N=CH), 9.19(d, J=1.6 Hz, 1H, Pyridine-H), 8.76(d, J=5.0 Hz, 1H, Pyridine-H), 8.26(dd, J=8.0 Hz, 1.6 Hz, 1H, Pyridine-H), 7.97(d, J=8.1 Hz, 2H, Ph—H), 7.75(d, J=8.1 Hz, 2H, Ph—H), 7.46(dd, J=8.0, 5.0 Hz, 1H, Pyridine-H), 7.35(m, 2H, Ph—H), 7.17(dd, J=8.2, 1.8 Hz, 1H, Ph—H), 5.26(s, 2H, CH₂), 3.56(s, 2H, CH₂), 2.97—2.92(m, 4H, Piperazine-CH₂), 2.85—2.30(m, 4H, Piperazine-CH₂)	164.0(C=S), 160.5, 151.6(CH=N), 149.6, 146.2(Triazole-C), 136.1, 135.7, 135.1, 134.9, 134.5, 134.0(d, J=32.3 Hz, CF₃—Ph—C), 133.1, 131.4, 129.1, 126.9, 126.1, 123.6(q, J=275.7 Hz, CF₃), 123.4, 121.9, 69.6, 58.7, 53.1, 50.6
2h^b	10.59(s, 1H, N=CH), 9.20(d, J=1.4 Hz, 1H, Pyridine-H), 8.76(d, J=4.4 Hz, 1H, Pyridine-H), 8.25(d, J=8.3, 1.4 Hz, 1H, Pyridine-H), 7.97(d, J=8.0 Hz, 2H, Ph—H), 7.75(d, J=8.0 Hz, 2H, Ph—H), 7.46(dd, J=8.3, 4.4 Hz, 1H, Pyridine-H) , 7.25(d, J=9.5 Hz, 2H, Ph—H), 6.92(d, J=7.9 Hz, 2H, Ph—H), 6.86(t, J=7.1 Hz, 1H, Ph—H), 5.34(s, 2H, CH₂), 3.26—3.18(m, 4H, Piperazine-CH₂), 3.11—2.98(m, 4H, Piperazine-CH₂)	164.1(C=S), 160.6, 151.6(CH=N), 151.3, 149.6, 146.3(Triazole-C), 136.1, 135.7, 134.0(d, J=32.3 Hz, CF₃—Ph—C), 129.2, 129.1, 126.1, 123.6(q, J=273.7 Hz, CF₃), 123.4, 121.9, 120.1, 116.5, 69.6, 50.6, 49.5
2i^b	10.57(s, 1H, N=CH), 9.19(s, 1H, Pyridine-H), 8.75(d, J=4.0 Hz, 1H, Pyridine-H), 8.24(d, J=7.8 Hz, 1H, Pyridine-H), 8.13(d, J=4.8 Hz, 1H, Pyrimidin-H), 7.96(d, J=7.8 Hz, 2H, Ph—H), 7.74(d, J=7.9 Hz, 2H, Ph—H), 7.47—7.42(m, 1H, Pyridine-H), 6.34(d, J=4.8 Hz, 1H, Pyrimidin-H), 5.34(s, 2H, CH₂), 3.92—3.86(m, 4H, Piperazine-CH₂), 2.99—2.93(m, 4H, Piperazine-CH₂), 2.30(s, 3H, CH₃)	167.7(C=S), 164.0, 161.5, 160.6, 157.2, 151.5(CH=N), 149.6, 146.2(Triazole-C), 136.2, 135.9, 133.9(d, J=33.3 Hz, CF₃—Ph—C) 129.1, 126.1, 123.6(q, J=274.7 Hz, CF₃), 123.4, 121.9, 109.5, 69.8, 50.6, 43.6, 24.3
2j^b	10.57(s, 1H, N=CH), 9.18(d, J=1.5 Hz, 1H, Pyridine-H), 8.74(dd, J=4.9, 1.5 Hz, 1H, Pyridine-H), 8.23(d, J=8.0 Hz, 1H, Pyridine-H), 7.96(d, J=8.1 Hz, 2H, Ph—H), 7.74(d, J=8.1 Hz, 2H, Ph—H), 7.44(dd, J=8.0, 4.9 Hz, 1H, Pyridine-H), 6.23(s, 1H, Pyrimidin-H), 5.34(s, 2H, CH₂), 3.92—3.88(m, 4H, Piperazine-CH₂), 2.97—2.93(m, 4H, Piperazine-CH₂), 2.26(s, 6H, CH₃)	167.1(C=S), 164.0, 161.6, 160.6, 151.5(CH=N), 149.6, 146.2(Triazole-C), 136.1, 135.7, 133.9(q, J=32.3 Hz, CF₃—Ph—C), 129.1, 126.1, 123.6(q, J=273.7 Hz, CF₃), 123.4, 121.9, 109.0, 69.9, 50.7, 43.5, 24.1
2k^b	10.58(s, 1H, N=CH), 9.19(s, 1H, Pyridine-H), 8.75(d, J=4.4 Hz, 1H, Pyridine-H), 8.24(d, J=7.5 Hz, 1H, Pyridine-H), 8.16(d, J=3.4 Hz, 1H, Pyridine-H), 7.97(d, J=7.8 Hz, 2H, Ph—H), 7.74(d, J=7.8 Hz, 2H, Ph—H), 7.45(dd, J=10.5, 5.9 Hz, 2H, Pyridine-H), 6.61(dd, J=13.4, 7.4 Hz, 2H, Pyridine-H), 5.34(s, 2H, CH₂), 3.62—3.53(m, 4H, Piperazine-CH₂), 3.05—2.96(m, 4H, Piperazine-CH₂)	164.1(C=S), 160.6, 159.3, 151.6(CH=N), 149.6, 148.0, 146.3(Triazole-C), 133.9(d, J=33.3 Hz, CF₃—Ph—C), 137.5, 136.1, 135.7, 129.1, 126.1, 123.6(q, J=273.7 Hz, CF₃), 123.4, 121.9, 113.4, 107.1, 69.7, 50.4, 45.23
3a^b	10.23(s, 2H, N=CH), 9.20(s, 2H, Pyridine-H), 8.74(d, J=3.6 Hz, 2H, Pyridine-H), 8.25(d, J=7.2 Hz, 2H, Pyridine-H), 7.87(t, J=8.2 Hz, 4H, Ph—H), 7.46—7.41(m, 2H, Pyridine-H), 7.18(t, J=8.2 Hz, 4H, Ph—H), 5.24(s, 4H, CH₂), 2.96(s, 8H, Piperazine-CH₂)	165.5, 164.0(C=S), 160.6, 151.4(CH=N), 149.5, 146.0(Triazole-C), 136.1, 131.2(d, J=9.0 Hz, F—Ph—C), 128.5, 123.3, 122.0, 116.5, 69.9, 50.6
3b^b	10.57(s, 2H, N=CH), 9.18(s, 2H, Pyridine-H), 8.75(s, 2H, Pyridine-H), 8.24(s, 2H, Pyridine-H), 7.96(d, J=7.2 Hz, 4H, Ph—H), 7.74(d, J=7.2 Hz, 4H, Ph—H), 7.45(s, 2H, Pyridine-H), 5.24(s, 4H, CH₂), 2.96(s, 8H, Piperazine-CH₂)	163.9(C=S), 160.5, 151.6(CH=N), 149.6, 146.3(Triazole-C), 136.1, 135.6, 133.9(d, J=33.3 Hz, CF₃—Ph—C), 129.1, 126.1, 123.6(q, J=273.7 Hz, CF₃), 123.4, 121.8, 69.6, 50.5

Compd.	Herbicidal activity(%)		Compd.	Herbicidal activity(%)		Compd.	Herbicidal activity(%)
Compd.	Brassica campestris		Echinochloa crusgalli		Brassica campestris	Echinochloa crusgalli	Brassica campestris	Echinochloa crusgalli
2a	16.7	5.0	2f	0	20.0	2k	0	9.0
2b	42.2	5.0	2g	28.1	13.0	3a	10.3	0
2c	0	0	2h	0	5.0	3b	0	0
2d	3.4	0	2i	0	10.0	Chlorsulfuron	80.4	22.9
2e	0	10.0	2j	29.3	13.0	CPD	76.8	7.0