取代噻吩双酰胺类化合物的设计、 合成及生物活性

doi:10.7503/cjcu20160145

摘要/Abstract

摘要：

利用中间体衍生化方法, 将噻吩环引入到双酰胺类化合物中, 合成了一系列取代噻吩双酰胺类化合物1~3; 目标化合物的结构经核磁共振波谱、红外光谱及元素分析确认. 生物活性测试结果表明, 化合物1在600 mg/L剂量下对小菜蛾具有良好的杀虫效果, 致死率均为100%, 其中化合物1a和1e在20 mg/L剂量下对小菜蛾的致死率仍达到60%以上; 改变双酰胺结构中的吡唑环得到化合物2和3, 其杀虫活性消失, 说明该类化合物中吡唑环结构对杀虫活性具有关键作用.

关键词: 双酰胺类化合物, 噻吩, 杀虫活性

Abstract:

To discover novel diamide derivatives with high insecticidal activity, a series of new substituted diamide derivatives(1—3) containing thiophene ring was synthesized by introducing thiophene ring to diamide derivatives utilizing intermediate derivatization methods(IDM). The compounds were identified by ¹H NMR, IR and elemental analysis. Preliminary bioassays indicated that compound 1 exhibited excellent insecticidal activities against Plutella xylostella and showed 100% mortality at 600 mg/L. Compounds 1a and 1e showed above 60% mortality at 20 mg/L. Compounds 2 and 3 attained by changing the pyrazole ring in diamide derivatives have no insecticidal activity, which illustrated that pyrazole ring in diamide derivatives is very important.

Key words: Diamide derivative, Thiophene, Insecticidal activity

中图分类号:

O626

TrendMD:

李林, 李淼, 柴宝山, 杨吉春, 宋玉泉, 刘长令. 取代噻吩双酰胺类化合物的设计、合成及生物活性. 高等学校化学学报, 2016, 37(9): 1649.

LI Lin, LI Miao, CHAI Baoshan, YANG Jichun, SONG Yuquan, LIU Changling. Design, Synthesis and Biological Activity of Novel Substituted Diamides Derivatives Containing Thiophene Ring. Chem. J. Chinese Universities, 2016, 37(9): 1649.

图/表 5

Fig.1 Known diamide pesticides

Scheme 1 Synthetic routes of compounds 1—3 Reagents and conditions: a. S, NHEt2, CH3CN, 50 ℃, 1—5 h; b. NaOH, CH3CH2OH/H2O, reflux, 2 h; c. CH3SO2Cl, pyridine, CH3CN, 2 h; d. R1R2NH, CH3CN, 1—6 h.

Table 1 Yields, melting points, elemental analysis and IR data of compounds 1—3

Compd.	Yield (%)	m.p./℃	Elemental analysis(%, calcd.)			IR, $ν ˙$ /cm^-1
Compd.	Yield (%)	m.p./℃	C	H	N	IR, $ν ˙$ /cm^-1
1a	23	221—222	42.38 (43.56)	3.44 (3.23)	15.03 (14.94)	3460(m, N—H), 2980, 2960(m, C—H), 1620(s, C=O), 1565, 1455(m, aromatic rings), 1450, 1360(m, C—H), 1320(s, C—O), 830, 750, 720(m, Ph-H)
1b	29	238—239	45.65 (44.78)	3.50 (3.55)	14.34 (14.51)	3440(m, N—H), 2970, 2940(m, C—H), 1610(s, C=O), 1555, 1440(m, aromatic rings), 1440, 1370(m, C—H), 1310(s, C—O), 810, 770, 730(m, Ph-H)
1c	21	224—225	46.524 (45.9)	3.73 (3.86)	14.02 (14.10)	3450(m, N—H), 2980(m, C—H), 1620(s, C=O), 1560, 1440(m, aromatic rings), 1450, 1370(m, C—H), 1330(s, C—O), 820, 760, 700(m, Ph-H)
1d	25	238—239	45.43 (46.12)	3.58 (3.46)	14.27 (14.15)	3440(m, N—H), 2950(m, C—H), 1600(s, C=O), 1555, 1435(m, aromatic rings), 1450, 1360(m, C—H), 1320(s, C—O), 800, 770, 720(m, Ph-H)
1e	32	217—218	47.36 (48.12)	3.55 (3.56)	16.63 (16.51)	3460(m, N—H), 2975, 2960(m, C—H), 1620(s, C=O), 1560, 1450(m, aromatic rings), 1470, 1370(m, C—H), 1330(s, C—O), 830, 760, 690(m, Ph-H)
1f	58	235—236	49.28 (49.32)	3.89 (3.91)	15.99 (15.98)	3440(m, N—H), 2970(m, C—H), 1610(s, C=O), 1565, 1455(m, aromatic rings), 1460, 1350(m, C—H), 1310(s, C—O), 820, 750, 710(m, Ph-H)
1g	41	217—218	51.78 (50.45)	4.16 (4.23)	15.38 (15.48)	3430(m, N—H), 2980, 2960(m, C—H), 1630(s, C=O), 1570, 1460(m, aromatic rings), 1470, 1365(m, C—H), 1320(s, C—O), 820, 770, 730(m, Ph-H)
1h	50	257—258	51.11 (50.01)	3.82 (3.99)	14.50 (14.58)	3420(m, N—H), 2980, 2960(m, C—H), 1600(s, C=O), 1550, 1440(m, aromatic rings), 1440, 1370(m, C—H), 1300(s, C—O), 800, 760, 740(m, Ph-H)
2a	25	170—171	57.84 (56.64)	4.67 (4.75)	13.86 (13.91)	3420(m, N—H), 2980, 2960(m, C—H), 1600(s, C=O), 1550, 1440(m, aromatic rings), 1440, 1370(m, C—H), 1300(s, C—O), 800, 760, 740(m, Ph-H)
2b	38	175—176	56.90 (57.62)	5.21 (5.08)	13.52 (13.44)	3440(m, N—H), 2980, 2950(m, C—H), 1620(s, C=O), 1530(m, aromatic rings), 1420, 1350(m, C—H), 1330(s, C—O), 820, 780, 720(m, Ph-H)
2c	30	234—235	57.46 (58.53)	5.44 (5.38)	13.15 (13.00)	3430(m, N—H), 2960(m, C—H), 1610(s, C=O), 1540(m, aromatic rings), 1440, 1370(m, C—H), 1300(s, C—O), 800, 760, 740(m, Ph-H)
2d	40	245—246	57.69 (58.80)	5.02 (4.94)	13.13 (13.06)	3450(m, N—H), 2980(s, C—H), 1620(s, C=O), 1520(s, aromatic rings), 1450, 1390(m, C—H), 1220, 1200(s, C—O), 840, 760(s, Ph-H)
3a	52	127—128	54.63 (53.93)	4.18 (4.24)	7.78 (7.86)	3440(m, N—H), 2970(m, C—H), 1670(s, C=O), 1620, 1560, 1510(s, aromatic rings), 1400, 1310(m, C—H), 1130(s, C—F), 780, 710(m, Ph-H)
3b	50	185—186	56.87 (55.13)	4.57 (4.63)	7.42 (7.56)	3430(m, N—H), 2950(m, C—H), 1660(s, C=O), 1610, 1550, 1500(s, aromatic rings), 1410, 1320(m, C—H), 1120(s, C—F), 820, 790, 700(m, Ph-H)
3c	52	147—148	55.30 (56.24)	5.07 (4.98)	7.35 (7.29)	3440(m, N—H), 2960(m, C—H), 1670(s, C=O), 1600, 1550(s, aromatic rings), 1420, 1320(m, C—H), 1110(s, C—F), 760, 700(m, Ph-H)
3d	58	151—152	56.58 (56.54)	4.49 (4.48)	7.34 (7.33)	3420(m, N—H), 2970(m, C—H), 1650(s, C=O), 1620, 1540(s, aromatic rings), 1430, 1320(m, C—H), 1130(s, C—F), 830, 780, 720(m, Ph-H)
3e	33	187—188	55.90 (55.33)	4.71 (4.64)	6.68 (6.79)	3430(m, N—H), 2950(m, C—H), 1660(s, C=O), 1630, 1580, 1520(s, aromatic rings), 1410, 1300(m, C—H), 1120(s, C—F), 800, 770, 710(m, Ph-H)

Table 1 Yields, melting points, elemental analysis and IR data of compounds 1—3

Compd.	Yield (%)	m.p./℃	Elemental analysis(%, calcd.)			IR, $ν ˙$ /cm^-1
Compd.	Yield (%)	m.p./℃	C	H	N	IR, $ν ˙$ /cm^-1
1a	23	221—222	42.38 (43.56)	3.44 (3.23)	15.03 (14.94)	3460(m, N—H), 2980, 2960(m, C—H), 1620(s, C=O), 1565, 1455(m, aromatic rings), 1450, 1360(m, C—H), 1320(s, C—O), 830, 750, 720(m, Ph-H)
1b	29	238—239	45.65 (44.78)	3.50 (3.55)	14.34 (14.51)	3440(m, N—H), 2970, 2940(m, C—H), 1610(s, C=O), 1555, 1440(m, aromatic rings), 1440, 1370(m, C—H), 1310(s, C—O), 810, 770, 730(m, Ph-H)
1c	21	224—225	46.524 (45.9)	3.73 (3.86)	14.02 (14.10)	3450(m, N—H), 2980(m, C—H), 1620(s, C=O), 1560, 1440(m, aromatic rings), 1450, 1370(m, C—H), 1330(s, C—O), 820, 760, 700(m, Ph-H)
1d	25	238—239	45.43 (46.12)	3.58 (3.46)	14.27 (14.15)	3440(m, N—H), 2950(m, C—H), 1600(s, C=O), 1555, 1435(m, aromatic rings), 1450, 1360(m, C—H), 1320(s, C—O), 800, 770, 720(m, Ph-H)
1e	32	217—218	47.36 (48.12)	3.55 (3.56)	16.63 (16.51)	3460(m, N—H), 2975, 2960(m, C—H), 1620(s, C=O), 1560, 1450(m, aromatic rings), 1470, 1370(m, C—H), 1330(s, C—O), 830, 760, 690(m, Ph-H)
1f	58	235—236	49.28 (49.32)	3.89 (3.91)	15.99 (15.98)	3440(m, N—H), 2970(m, C—H), 1610(s, C=O), 1565, 1455(m, aromatic rings), 1460, 1350(m, C—H), 1310(s, C—O), 820, 750, 710(m, Ph-H)
1g	41	217—218	51.78 (50.45)	4.16 (4.23)	15.38 (15.48)	3430(m, N—H), 2980, 2960(m, C—H), 1630(s, C=O), 1570, 1460(m, aromatic rings), 1470, 1365(m, C—H), 1320(s, C—O), 820, 770, 730(m, Ph-H)
1h	50	257—258	51.11 (50.01)	3.82 (3.99)	14.50 (14.58)	3420(m, N—H), 2980, 2960(m, C—H), 1600(s, C=O), 1550, 1440(m, aromatic rings), 1440, 1370(m, C—H), 1300(s, C—O), 800, 760, 740(m, Ph-H)
2a	25	170—171	57.84 (56.64)	4.67 (4.75)	13.86 (13.91)	3420(m, N—H), 2980, 2960(m, C—H), 1600(s, C=O), 1550, 1440(m, aromatic rings), 1440, 1370(m, C—H), 1300(s, C—O), 800, 760, 740(m, Ph-H)
2b	38	175—176	56.90 (57.62)	5.21 (5.08)	13.52 (13.44)	3440(m, N—H), 2980, 2950(m, C—H), 1620(s, C=O), 1530(m, aromatic rings), 1420, 1350(m, C—H), 1330(s, C—O), 820, 780, 720(m, Ph-H)
2c	30	234—235	57.46 (58.53)	5.44 (5.38)	13.15 (13.00)	3430(m, N—H), 2960(m, C—H), 1610(s, C=O), 1540(m, aromatic rings), 1440, 1370(m, C—H), 1300(s, C—O), 800, 760, 740(m, Ph-H)
2d	40	245—246	57.69 (58.80)	5.02 (4.94)	13.13 (13.06)	3450(m, N—H), 2980(s, C—H), 1620(s, C=O), 1520(s, aromatic rings), 1450, 1390(m, C—H), 1220, 1200(s, C—O), 840, 760(s, Ph-H)
3a	52	127—128	54.63 (53.93)	4.18 (4.24)	7.78 (7.86)	3440(m, N—H), 2970(m, C—H), 1670(s, C=O), 1620, 1560, 1510(s, aromatic rings), 1400, 1310(m, C—H), 1130(s, C—F), 780, 710(m, Ph-H)
3b	50	185—186	56.87 (55.13)	4.57 (4.63)	7.42 (7.56)	3430(m, N—H), 2950(m, C—H), 1660(s, C=O), 1610, 1550, 1500(s, aromatic rings), 1410, 1320(m, C—H), 1120(s, C—F), 820, 790, 700(m, Ph-H)
3c	52	147—148	55.30 (56.24)	5.07 (4.98)	7.35 (7.29)	3440(m, N—H), 2960(m, C—H), 1670(s, C=O), 1600, 1550(s, aromatic rings), 1420, 1320(m, C—H), 1110(s, C—F), 760, 700(m, Ph-H)
3d	58	151—152	56.58 (56.54)	4.49 (4.48)	7.34 (7.33)	3420(m, N—H), 2970(m, C—H), 1650(s, C=O), 1620, 1540(s, aromatic rings), 1430, 1320(m, C—H), 1130(s, C—F), 830, 780, 720(m, Ph-H)
3e	33	187—188	55.90 (55.33)	4.71 (4.64)	6.68 (6.79)	3430(m, N—H), 2950(m, C—H), 1660(s, C=O), 1630, 1580, 1520(s, aromatic rings), 1410, 1300(m, C—H), 1120(s, C—F), 800, 770, 710(m, Ph-H)

Table 2 1H NMR data of compounds 1—3*

Compd.	¹H NMR(300 MHz), δ
1a	13.14(s, 1H, NH), 8.49(dd, J=1.5, 4.5 Hz, 1H, pyridin-6-H), 7.89(dd, J=1.5, 1.8 Hz, 1H, pyridin-4-H), 7.42(dd, J=4.5, 8.4 Hz, 1H, pyridin-5-H), 6.98(s, 1H, pyrazole-H), 6.11(s, 1H, NH), 3.03(d, J=3.0 Hz, 3H, CH₃), 2.30(s, 3H, thiophene-5-CH₃), 2.25(s, 3H, thiophene-4-CH₃)
1b	11.97(s, 1H, NH), 8.52(dd, J=1.5, 4.8 Hz, 1H, pyridin-6-H), 8.23(dd, J=1.5, 4.8 Hz, 1H, pyridin-4-H), 7.66(dd, J=4.8, 8.4 Hz, 1H, pyridin-5-H), 7.34(s, 1H, pyrazole), 2.87(s, 3H, CH₃), 2.79(s, 3H, CH₃), 2.21(s, 3H, thiophene-5-CH₃), 1.91(s, 3H, thiophene-4-CH₃)
1c	13.11(s, 1H, NH), 8.49(dd, J=1.8, 5.1 Hz, 1H, pyridin-6-H), 7.89(dd, J=1.8, 5.1 Hz, 1H, pyridin-4-H), 7.42(dd, J=5.1, 8.1 Hz, 1H, pyridin-5-H), 6.98(s, 1H, pyrazole-H), 5.89(br, 1H, NH), 4.28(m, 1H, CH), 2.27(s, 3H, thiophene-5-CH₃), 2.23(s, 3H, thiophene-4-CH₃), 1.28(d, J=5.1 Hz, 6H, 2CH₃)
1d	11.91(s, 1H, NH), 8.54(dd, J=1.2, 4.8 Hz, 1H, pyridin-6-H), 8.25(dd, J=1.5, 4.5 Hz, 1H, pyridin-4-H), 7.68(dd, J=4.8, 8.1 Hz, 1H, pyridin-5-H), 7.29(s, 1H, pyrazole), 6.98(s, 1H, NH), 2.81(m, 1H, CH), 2.10(s, 3H, thiophene-5-CH₃), 2.06(s, 3H, thiophene-4-CH₃), 0.70(m, 2H, CH₂), 0.55(m, 2H, CH₂)
1e	13.14(s, 1H, NH), 8.49(dd, J=1.5, 5.1 Hz, 1H, pyridin-6-H), 7.89(dd, J=1.2, 5.1 Hz, 1H, pyridin-4-H), 7.42(dd, J=4.8, 8.7 Hz, 1H, pyridin-5-H), 6.98(s, 1H, pyrazole-H), 6.11(s, 1H, NH), 3.03(d, J=3.3 Hz, 3H, CH₃), 2.30(s, 3H, thiophene-5-CH₃), 2.25(s, 3H, thiophene-4-CH₃)
1f	10.45(s, 1H, NH), 8.50(dd, J=1.8, 4.5 Hz, 1H, pyridin-6-H), 7.89(dd, J=1.8, 4.8 Hz,1H, pyridin-4-H), 7.42(dd, J=4.5, 8.4 Hz, 1H, pyridin-5-H), 6.99(s, 1H, pyrazole-H), 3.03(s, 6H, 2CH₃), 2.23(s, 3H, thiophene-5-CH₃), 2.03(s, 3H, thiophene-4-CH₃)
1g	13.11(s, 1H, NH), 8.49(dd, J=1.2, 5.1 Hz, 1H, pyridin-6-H), 7.89(dd, J=1.5, 5.1 Hz, 1H, pyridin-4-H), 7.42(dd, J=5.1, 8.7 Hz, 1H, pyridin-5-H), 6.98(s, 1H, pyrazole-H), 5.89(br, 1H, NH), 4.28(m, 1H, CH), 2.27(s, 3H, thiophene-5-CH₃), 2.23(s, 3H, thiophene-4-CH₃), 1.28(d, J=6.9 Hz, 6H, 2CH₃)
1h	10.43(s, 1H, NH), 8.49(dd, J=1.5, 4.8 Hz, 1H, pyridin-6-H), 7.91(dd, J=1.2, 4.8 Hz, 1H, pyridin-4-H), 7.43(dd, J=4.8, 8.4 Hz, 1H, pyridin-5-H), 6.96(s, 1H, pyrazole-H), 3.71(m, 4H, morpholine-2,6-2CH₂), 3.54(m, 4H, morpholine-3,5-2CH₂), 2.22(s, 3H, thiophene-5-CH₃), 2.04(s, 3H, thiophene-4-CH₃)
2a	8.33(s, 1H, pyrazole-H), 7.70(s, 1H, NH), 7.65(d, J=6.6 Hz, 2H, Ph-2,6-2H), 7.47(d, J=6.6 Hz, 2H, Ph-3,5-2H), 3.93(s, 3H, pyrazole-CH₃), 2.93(s, 3H, CH₃), 2.23(s, 3H, thiophene-5-CH₃), 1.92(s, 3H, thiophene-4-CH₃)
2b	8.23(s, 1H, pyrazole-H), 7.71(s, 1H, NH), 7.68(d, J=6.9 Hz, 2H, Ph-2,6-2H), 7.47(d, J=6.9 Hz, 2H, Ph-3,5-2H), 3.93(s, 3H, pyrazole-CH₃), 2.83(s, 6H, 2CH₃), 2.23(s, 3H, thiophene-5-CH₃), 1.92(s, 3H, thiophene-4-CH₃)
2c	12.01(s, 1H, NH), 8.31(s, 1H, pyrazole-H), 7.68(d, J=6.3 Hz, 2H, Ph-2,6-2H), 7.47(d, J=6.3 Hz, 2H, Ph-3,5-2H), 3.96(m, 1H, CH), 3.95(s, 3H, pyrazole-CH₃), 2.23(s, 3H, thiophene-5-CH₃), 2.15(s, 3H, thiophene-4-CH₃), 1.13(s, 3H, CH₃), 1.11(s, 3H, CH₃)
2d	8.29(s, 1H, pyrazole-H), 7.71(s, 1H, NH), 7.66(d, J=6.6 Hz, 2H, Ph-2,6-2H), 7.43(d, J=6.6 Hz, 2H, Ph-3,5-2H), 3.93(s, 3H, pyrazole-CH₃), 2.32(m, 1H, CH), 2.23(s, 3H, thiophene-5-CH₃), 1.92(s, 3H, thiophene-4-CH₃), 0.83(m, 4H, 2CH₂)
3a	12.40(s, 1H, NH), 7.77—7.58(m, 4H, Ph), 6.05(s, 1H, NH), 2.95(d, J=3.0 Hz, 3H, CH₃), 2.32(s, 6H, thiophene-2CH₃)
3b	9.19(s, 1H, NH), 7.75—7.59(m, 4H, Ph), 3.02(s, 6H, 2CH₃), 2.32(s, 3H, thiophene-5-CH₃), 2.06(s, 3H, thiophene-4-CH₃)
3c	12.31(s, 1H, NH), 7.76—7.58(m, 4H, Ph), 5.85(br, 1H, NH), 4.19(m, 1H, CH), 2.31(s, 6H, thiophene-2CH₃), 1.24(d, J=5.1 Hz, 6H, 2CH₃)
3d	12.39(s, 1H, NH), 7.77—7.58(m, 4H, Ph), 6.19(s, 1H, NH), 2.80(m, 1H, CH), 2.31(s, 3H, thiophene-5-CH₃), 2.26(s, 3H, thiophene-4-CH₃), 0.85(m, 4H, 2CH₂)
3e	9.26(s, 1H, NH), 7.76—7.64(m, 4H, Ph), 3.78—3.46(m, 8H, morpholine), 2.31(s, 3H, thiophene-5-CH₃), 2.07(s, 3H, thiophene-4-CH₃)

Table 2 1H NMR data of compounds 1—3*

Compd.	¹H NMR(300 MHz), δ
1a	13.14(s, 1H, NH), 8.49(dd, J=1.5, 4.5 Hz, 1H, pyridin-6-H), 7.89(dd, J=1.5, 1.8 Hz, 1H, pyridin-4-H), 7.42(dd, J=4.5, 8.4 Hz, 1H, pyridin-5-H), 6.98(s, 1H, pyrazole-H), 6.11(s, 1H, NH), 3.03(d, J=3.0 Hz, 3H, CH₃), 2.30(s, 3H, thiophene-5-CH₃), 2.25(s, 3H, thiophene-4-CH₃)
1b	11.97(s, 1H, NH), 8.52(dd, J=1.5, 4.8 Hz, 1H, pyridin-6-H), 8.23(dd, J=1.5, 4.8 Hz, 1H, pyridin-4-H), 7.66(dd, J=4.8, 8.4 Hz, 1H, pyridin-5-H), 7.34(s, 1H, pyrazole), 2.87(s, 3H, CH₃), 2.79(s, 3H, CH₃), 2.21(s, 3H, thiophene-5-CH₃), 1.91(s, 3H, thiophene-4-CH₃)
1c	13.11(s, 1H, NH), 8.49(dd, J=1.8, 5.1 Hz, 1H, pyridin-6-H), 7.89(dd, J=1.8, 5.1 Hz, 1H, pyridin-4-H), 7.42(dd, J=5.1, 8.1 Hz, 1H, pyridin-5-H), 6.98(s, 1H, pyrazole-H), 5.89(br, 1H, NH), 4.28(m, 1H, CH), 2.27(s, 3H, thiophene-5-CH₃), 2.23(s, 3H, thiophene-4-CH₃), 1.28(d, J=5.1 Hz, 6H, 2CH₃)
1d	11.91(s, 1H, NH), 8.54(dd, J=1.2, 4.8 Hz, 1H, pyridin-6-H), 8.25(dd, J=1.5, 4.5 Hz, 1H, pyridin-4-H), 7.68(dd, J=4.8, 8.1 Hz, 1H, pyridin-5-H), 7.29(s, 1H, pyrazole), 6.98(s, 1H, NH), 2.81(m, 1H, CH), 2.10(s, 3H, thiophene-5-CH₃), 2.06(s, 3H, thiophene-4-CH₃), 0.70(m, 2H, CH₂), 0.55(m, 2H, CH₂)
1e	13.14(s, 1H, NH), 8.49(dd, J=1.5, 5.1 Hz, 1H, pyridin-6-H), 7.89(dd, J=1.2, 5.1 Hz, 1H, pyridin-4-H), 7.42(dd, J=4.8, 8.7 Hz, 1H, pyridin-5-H), 6.98(s, 1H, pyrazole-H), 6.11(s, 1H, NH), 3.03(d, J=3.3 Hz, 3H, CH₃), 2.30(s, 3H, thiophene-5-CH₃), 2.25(s, 3H, thiophene-4-CH₃)
1f	10.45(s, 1H, NH), 8.50(dd, J=1.8, 4.5 Hz, 1H, pyridin-6-H), 7.89(dd, J=1.8, 4.8 Hz,1H, pyridin-4-H), 7.42(dd, J=4.5, 8.4 Hz, 1H, pyridin-5-H), 6.99(s, 1H, pyrazole-H), 3.03(s, 6H, 2CH₃), 2.23(s, 3H, thiophene-5-CH₃), 2.03(s, 3H, thiophene-4-CH₃)
1g	13.11(s, 1H, NH), 8.49(dd, J=1.2, 5.1 Hz, 1H, pyridin-6-H), 7.89(dd, J=1.5, 5.1 Hz, 1H, pyridin-4-H), 7.42(dd, J=5.1, 8.7 Hz, 1H, pyridin-5-H), 6.98(s, 1H, pyrazole-H), 5.89(br, 1H, NH), 4.28(m, 1H, CH), 2.27(s, 3H, thiophene-5-CH₃), 2.23(s, 3H, thiophene-4-CH₃), 1.28(d, J=6.9 Hz, 6H, 2CH₃)
1h	10.43(s, 1H, NH), 8.49(dd, J=1.5, 4.8 Hz, 1H, pyridin-6-H), 7.91(dd, J=1.2, 4.8 Hz, 1H, pyridin-4-H), 7.43(dd, J=4.8, 8.4 Hz, 1H, pyridin-5-H), 6.96(s, 1H, pyrazole-H), 3.71(m, 4H, morpholine-2,6-2CH₂), 3.54(m, 4H, morpholine-3,5-2CH₂), 2.22(s, 3H, thiophene-5-CH₃), 2.04(s, 3H, thiophene-4-CH₃)
2a	8.33(s, 1H, pyrazole-H), 7.70(s, 1H, NH), 7.65(d, J=6.6 Hz, 2H, Ph-2,6-2H), 7.47(d, J=6.6 Hz, 2H, Ph-3,5-2H), 3.93(s, 3H, pyrazole-CH₃), 2.93(s, 3H, CH₃), 2.23(s, 3H, thiophene-5-CH₃), 1.92(s, 3H, thiophene-4-CH₃)
2b	8.23(s, 1H, pyrazole-H), 7.71(s, 1H, NH), 7.68(d, J=6.9 Hz, 2H, Ph-2,6-2H), 7.47(d, J=6.9 Hz, 2H, Ph-3,5-2H), 3.93(s, 3H, pyrazole-CH₃), 2.83(s, 6H, 2CH₃), 2.23(s, 3H, thiophene-5-CH₃), 1.92(s, 3H, thiophene-4-CH₃)
2c	12.01(s, 1H, NH), 8.31(s, 1H, pyrazole-H), 7.68(d, J=6.3 Hz, 2H, Ph-2,6-2H), 7.47(d, J=6.3 Hz, 2H, Ph-3,5-2H), 3.96(m, 1H, CH), 3.95(s, 3H, pyrazole-CH₃), 2.23(s, 3H, thiophene-5-CH₃), 2.15(s, 3H, thiophene-4-CH₃), 1.13(s, 3H, CH₃), 1.11(s, 3H, CH₃)
2d	8.29(s, 1H, pyrazole-H), 7.71(s, 1H, NH), 7.66(d, J=6.6 Hz, 2H, Ph-2,6-2H), 7.43(d, J=6.6 Hz, 2H, Ph-3,5-2H), 3.93(s, 3H, pyrazole-CH₃), 2.32(m, 1H, CH), 2.23(s, 3H, thiophene-5-CH₃), 1.92(s, 3H, thiophene-4-CH₃), 0.83(m, 4H, 2CH₂)
3a	12.40(s, 1H, NH), 7.77—7.58(m, 4H, Ph), 6.05(s, 1H, NH), 2.95(d, J=3.0 Hz, 3H, CH₃), 2.32(s, 6H, thiophene-2CH₃)
3b	9.19(s, 1H, NH), 7.75—7.59(m, 4H, Ph), 3.02(s, 6H, 2CH₃), 2.32(s, 3H, thiophene-5-CH₃), 2.06(s, 3H, thiophene-4-CH₃)
3c	12.31(s, 1H, NH), 7.76—7.58(m, 4H, Ph), 5.85(br, 1H, NH), 4.19(m, 1H, CH), 2.31(s, 6H, thiophene-2CH₃), 1.24(d, J=5.1 Hz, 6H, 2CH₃)
3d	12.39(s, 1H, NH), 7.77—7.58(m, 4H, Ph), 6.19(s, 1H, NH), 2.80(m, 1H, CH), 2.31(s, 3H, thiophene-5-CH₃), 2.26(s, 3H, thiophene-4-CH₃), 0.85(m, 4H, 2CH₂)
3e	9.26(s, 1H, NH), 7.76—7.64(m, 4H, Ph), 3.78—3.46(m, 8H, morpholine), 2.31(s, 3H, thiophene-5-CH₃), 2.07(s, 3H, thiophene-4-CH₃)

Table 3 Insecticidal activity against Plutella xylostella of the target compounds 1

Compd.	Mortality(%)
Compd.	600 mg/L	20 mg/L
1a	100	70
1b	100	40
1c	100	50
1d	100	30
1e	100	60
1f	100	50
1g	100	50
1h	100	20
Chlomtraniliprole	100	100

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