CN118221636A - 一类取代二氢异喹啉衍生物、其制备方法及应用 - Google Patents
一类取代二氢异喹啉衍生物、其制备方法及应用 Download PDFInfo
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- CN118221636A CN118221636A CN202211633493.3A CN202211633493A CN118221636A CN 118221636 A CN118221636 A CN 118221636A CN 202211633493 A CN202211633493 A CN 202211633493A CN 118221636 A CN118221636 A CN 118221636A
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- substituted
- alkyl
- substituted alkyl
- hydrogen
- alkylthio
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 44
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 43
- 125000000304 alkynyl group Chemical group 0.000 claims description 30
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 14
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
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Abstract
本发明公开了一类如下式通式(A)所示的取代二氢异喹啉类衍生物:
Description
技术领域
本发明属于农用杀菌剂领域,特别涉及一类取代二氢异喹啉衍生物、其制备方法及应用。
技术背景
由于现有农药品种的长期的使用,导致了病害对现有农药品种产生了抗性,因此要求不断发现具有新的具有不同作用机理的新农药品种。同时随着现有杀菌剂用量过多,给环境带来了更的压力,故要求发现更高效低用量的新农药品种。
专利CN1910172A公开了如下所示(Ia)、(Ib)、(Ic)和(Id)取代氢化异喹啉联喹啉类化合物
专利WO2017090664公开了如下所示:
上述专利虽然公开了取代氢化异喹啉类衍生物,但并没有公开本发明取代二氢异喹啉联吡唑类衍生物,不同的连接结构,使得化合物表现出不同的生物活性。
发明内容
为了解决上述技术问题,本发明提出了一类取代二氢异喹啉衍生物,如下式(A)所示:
其中:
R选自氢、C1-C10烷基、C3-C10环烷基、C1-C10烯基、C1-C10炔基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基、C1-C10烷基砜基或C1-C10烷基亚砜基、C1-C10芳基取代烷基,或被氢、卤素、C1-C10烷基、C3-C10环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烯基、C1-C10炔基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基、腈基、硝基、C1-C10烷基砜基或C1-C10烷基亚砜基中的至少一种取代基取代的苯基、五元杂芳基或六元杂芳基;
R1、R2独立选自氢、C1-C5烷基、C3-C5环烷基、C1-C10烯基、C1-C10炔基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基;
R3、R4独立选自氢、卤素;
R5、R6、R7和R8独立选自氢、卤素、C1-C10烷基、C3-C10环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烯基、C1-C10炔基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基、腈基、硝基、C1-C10烷基砜基或C1-C10烷基亚砜基。
优选,R选自氢、C1-C5烷基、C3-C5环烷基、C1-C5烯基、C1-C5炔基、C1-C5卤代烷基、C1-C5烷氧取代烷基、C1-C5烷硫取代烷基、C1-C5氰基取代烷基、C1-C5烷基砜基或C1-C5烷基亚砜基、C1-C5芳基取代烷基,或被氢、卤素、C1-C5烷基、C3-C5环烷基、C1-C5烷氧基、C1-C5卤代烷氧基、C1-C5烯基、C1-C5炔基、C1-C5烷硫基、C1-C5卤代烷硫基、C1-C5卤代烷基、C1-C5烷氧取代烷基、C1-C5烷硫取代烷基、C1-C5氰基取代烷基、腈基、硝基、C1-C5烷基砜基或C1-C5烷基亚砜基中的至少一种取代基取代的苯基、五元杂芳基或六元杂芳基;
R1、R2独立选自氢、C1-C5烷基、C3-C5环烷基、C1-C5烯基、C1-C5炔基、C1-C5卤代烷基、C1-C5烷氧取代烷基、C1-C5烷硫取代烷基、C1-C5氰基取代烷基;
R3、R4独立选自氢、卤素;
R5、R6、R7和R8独立选自氢、卤素、C1-C5烷基、C3-C5环烷基、C1-C5烷氧基、C1-C5卤代烷氧基、C1-C5烯基、C1-C5炔基、C1-C5烷硫基、C1-C5卤代烷硫基、C1-C5卤代烷基、C1-C5烷氧取代烷基、C1-C5烷硫取代烷基、C1-C5氰基取代烷基、腈基、硝基、C1-C5烷基砜基或C1-C5烷基亚砜基。
进一步优选,R选自氢、C1-C3烷基、C3-C5环烷基、C1-C3烯基、C1-C3炔基、C1-C3卤代烷基、C1-C3烷氧取代烷基、C1-C3烷硫取代烷基、C1-C3氰基取代烷基、C1-C3烷基砜基或C1-C3烷基亚砜基、C1-C3芳基取代烷基,或被氢、卤素、C1-C3烷基、C3-C3环烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烯基、C1-C3炔基、C1-C3烷硫基、C1-C3卤代烷硫基、C1-C3卤代烷基、C1-C3烷氧取代烷基、C1-C3烷硫取代烷基、C1-C3氰基取代烷基、腈基、硝基、C1-C3烷基砜基或C1-C3烷基亚砜基中的至少一种取代基取代的苯基、五元或六元杂芳基;
R1、R2独立选自氢、C1-C3烷基、C3-C5环烷基、C1-C3烯基、C1-C3炔基、C1-C3卤代烷基、C1-C3烷氧取代烷基、C1-C3烷硫取代烷基、C1-C3氰基取代烷基;
R3、R4独立选自氢、卤素;
R5、R6、R7和R8独立选自氢、卤素、C1-C3烷基、C3-C5环烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烯基、C1-C3炔基、C1-C3烷硫基、C1-C3卤代烷硫基、C1-C3卤代烷基、C1-C3烷氧取代烷基、C1-C3烷硫取代烷基、C1-C3氰基取代烷基、腈基、硝基、C1-C3烷基砜基或C1-C3烷基亚砜基。
更进一步优选,R选自氢、甲基、乙基、叔丁基、环丙基、丙烯基、三氟甲基、二氟甲基、一氟甲基、甲基乙氧基、甲基甲氧基、甲基乙硫基,或被氢、氟、氯、溴、甲基、乙基、三氟甲基、三氟甲氧基、二氟甲基、二氟甲氧基、甲氧基、乙氧基、甲硫基、硝基、腈基至少一种取代基取代的苯基、五元杂芳基或六元杂芳基;
R1、R2独立选自氢、C1-C3烷基、C3-C5环烷基、C1-C3烯基、C1-C3炔基、C1-C3卤代烷基、C1-C3烷氧取代烷基、C1-C3烷硫取代烷基、C1-C3氰基取代烷基;
R3、R4独立选自氢、氟;
R5、R6、R7和R8独立选氢、氟、氯、溴、甲基、乙基、三氟甲基、三氟甲氧基、二氟甲基、二氟甲氧基、甲氧基、乙氧基、甲硫基、硝基、腈基。
最为优选地,所述取代二氢异喹啉衍生物选自下述结构中的至少一种:
本发明通式(A)中部分化合物可以用下表说明具体化合物,但这些具体化合物并不限定本发明
其中:R6、R8为氢
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部分化合物的核磁数据如下:
1215:1H NMR(CDCl3,400MHz)δ:8.20(s,1H,Py-H),7.92(s,1H,Py-H),7.63(d,J=7.2Hz,2H,Ph-H),7.56(d,J=8.0Hz,1H,Ph-H),7.39(t,J=7.2Hz,1H,Ph-H),7.29(t,J=7.6Hz,2H,Ph-H),7.21(d,J=7.2Hz,1H,Ph-H),6.96(d,J=7.2Hz,1H,Ph-H),3.83(s,3H,-OCH3),2.76(s,2H,-CH2),1.24(s,6H,-CH3).13C NMR(CDCl3,100MHz)δ:158.4,157.1,140.9,137.5,133.6,133.3,130.8,128.4,128.2,127.5,126.9,126.8,123.0,120.9,114.5,55.6,54.0,38.8,27.7.
2015:1H NMR(CDCl3,400MHz)δ:9.03(s,1H,Ar-H),8.56(d,J=8.4Hz,1H,Ar-H),8.34(s,1H,Py-H),8.08(d,J=8.4Hz,1H,Ph-H),8.00(s,1H,Py-H),7.51(d,J=7.8Hz,1H,Ph-H),7.42(t,J=7.2Hz,2H,Ar-H),7.30(t,J=7.2Hz,1H,Ph-H),7.24(t,J=7.8Hz,1H,Ar-H),2.77(s,1H,-CH2),1.25(s,6H,-CH3).
101:1H NMR(CDCl3,400MHz)δ:8.11(s,1H,Py-H),7.82(s,1H,Py-H),7.53(d,J=7.6Hz,1H,Ph-H),7.39(t,J=8.0Hz,3H,Ph-H),7.22-7.30(m,2H,Ph-H),2.77(s,2H,-CH2),2.17(s,6H,-CH3),1.25(s,6H,-CH3).13C NMR(CDCl3,100MHz)δ:156.7,141.3,137.7,137.2,131.4,130.8,128.5,128.3,127.4(d,2JC-F=20.3Hz,-CF),126.7,126.6,125.6,125.5,122.3,119.1(q,JC-F=257.9Hz,-CF3),54.0,38.8,27.6,18.0.HRMS(ESI)for C25H23F7N3 m/z:Calculated,498.1775,Found,498.1780[M+H]+.
303:1H NMR(CDCl3,400MHz)δ:7.90(s,1H,Py-H),7.75(s,1H,Py-H),7.52(d,J=7.6Hz,1H,Ph-H),7.36(t,J=7.2Hz,1H,Ph-H),7.27(t,J=7.6Hz,1H,Ph-H),7.18(d,J=6.8Hz,1H,Ph-H),2.73(s,2H,-CH2),1.61(s,9H,-CH3),1.21(s,6H,-CH3).13C NMR(CDCl3,100MHz)δ:157.7,139.2,137.6,130.6,128.4,128.3,127.2,126.7,126.6,120.5,58.7,53.7,38.9,29.8,27.7.
103:1H NMR(CDCl3,400 MHz)δ:8.32(s,1H,Py-H),8.02(s,1H,Py-H),7.90(t,J=8.0 Hz,1H,Ph-H),7.54(d,J=7.6 Hz,1H,Ph-H),7.39(t,J=7.2 Hz,1H,Ph-H),7.21-7.31(m,5H,Ph-H),2.77(s,2H,-CH2),1.25(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:156.9,153.6(d,JC-F=249.1Hz,Ar-F),141.2,137.5,131.5,131.4,130.8,128.4,128.1,128.0,126.8,125.0,124.4,123.3,117.0,116.8,54.0,38.8,27.7.HRMS(ESI)for C20H19FN3 m/z:Calculated,320.1558,Found,320.1563[M+H]+.
2121:1H NMR(CDCl3,400 MHz)δ:8.13(s,1H,Py-H),7.84(s,1H,Py-H),7.53(d,J=7.6Hz,1H,Ph-H),7.49(s,2H,Ph-H),7.39(t,J=7.6 Hz,1H,Ph-H),7.28(t,J=7.6 Hz,1H,Ph-H),7.21(d,J=7.2 Hz,1H,Ph-H),2.77(s,2H,-CH2),1.24(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:156.5,141.9,137.6,136.0,135.0,134.9,132.4,130.8,128.8,128.5,128.3,126.8,126.7,122.7,54.1,38.8,27.6.HRMS(ESI)for C20H17Cl3N3 m/z:Calculated,404.0483,Found,404.0485[M+H]+.
405:1H NMR(CDCl3,400 MHz)δ:8.74(s,1H,Py-H),8.09(s,1H,Py-H),7.88(q,J=4.4 Hz,1H,Ph-H),7.52(d,J=7.6 Hz,2H,Ph-H),7.41(t,J=7.2 Hz,1H,Ph-H),7.31(t,J=7.6 Hz,1H,Ph-H),7.18-7.25(m,2H,Ph-H),2.77(s,2H,-CH2),1.25(s,6H,-CH3).13C NMR(CDCl3,100MHz)δ:160.2(d,JC-F=244.1 Hz,Ar-F),159.5,156.1,147.4,143.7,137.4,131.1,128.6,127.9,127.7,127.0,126.5,126.5,124.9,123.4,115.1(d,2JC-F=24.3 Hz,Ar-F),108.1(d,2JC-F=26.9 Hz,Ar-F),54.3,38.6,27.6.HRMS(ESI)for C21H18FN4S m/z:Calculated,377.1231,Found,377.1236[M+H]+.
507:1H NMR(CDCl3,400 MHz)δ:8.41(s,1H,Py-H),8.33(d,J=8.0 Hz,2H,Ph-H),8.02(s,1H,Py-H),7.92(d,J=8.4 Hz,2H,Ph-H),7.49(d,J=7.6 Hz,1H,Ph-H),7.41(t,J=7.2 Hz,1H,Ph-H),7.30(t,J=7.6Hz,1H,Ph-H),7.23(d,J=8.4 Hz,1H,Ph-H),2.78(s,2H,-CH2),1.25(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:156.6,145.6,144.1,142.9,137.4,131.2,128.6,127.8,127.7,126.9,126.6,125.4,125.0,118.7,54.3,38.7,27.6.
1:1H NMR(CDCl3,400 MHz)δ:8.38(s,1H,Py-H),7.98(s,1H,Py-H),7.75(d,J=8.4Hz,2H,Ph-H),7.57(d,J=7.8 Hz,1H,Ph-H),7.47(t,J=7.2 Hz,2H,Ph-H),7.42(t,J=7.2Hz,1H,Ph-H),7.32(t,J=7.2 Hz,2H,Ph-H),7.24(d,J=7.2 Hz,1H,Ph-H),2.80(s,2H,-CH2),1.28(s,6H,-CH3).
609:1H NMR(CDCl3,400 MHz)δ:8.78(s,1H,Py-H),8.10(s,1H,Py-H),7.89(d,J=8.4 Hz,1H,Ph-H),7.84(d,J=8.0 Hz,1H,Ph-H),7.54(d,J=7.6 Hz,1H,Ph-H),7.48(t,J=7.2 Hz,1H,Ph-H),7.36-7.43(m,2H,Ph-H),7.32(t,J=8.0 Hz,1H,Ph-H),7.24-7.25(m,1H,Ph-H),2.78(s,2H,-CH2),1.26(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:160.1,156.2,150.9,143.7,137.4,133.2 131.1,128.5,128.1,127.7,127.0,126.7,126.5,125.0,124.8,122.5,121.7,54.3,38.7,27.6.HRMS(ESI)for C21H19N4S m/z:Calculated,359.1325,Found,359.1330[M+H]+.
611:1H NMR(CDCl3,400 MHz)δ:8.61(s,1H,Py-H),8.40(s,1H,Py-H),8.13(t,J=8.0 Hz,2H,Ph-H),8.00(s,1H,Ph-H),7.64(t,J=7.6 Hz,1H,Ph-H),7.51(d,J=7.6 Hz,1H,Ph-H),7.40(t,J=7.2 Hz,1H,Ph-H),7.32(d,J=7.6 Hz,1H,Ph-H),7.21(d,J=7.2Hz,1H,Ph-H),2.77(s,2H,-CH2),1.25(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:156.6,148.9,142.3,140.6,137.4,131.1,130.5,128.6,127.8,127.5,126.9,126.7,124.5,124.4,121.1,113.8,54.2,38.7,27.6.HRMS(ESI)for C20H19N4O2 m/z:Calculated,347.1503,Found,347.1508[M+H]+.
613:1H NMR(CDCl3,400 MHz)δ:8.28(s,1H,Py-H),7.96(s,1H,Py-H),7.56(t,J=8.0 Hz,2H,Ph-H),7.51(d,J=8.0 Hz,1H,Ph-H),7.40(t,J=8.8 Hz,1H,Ph-H),7.33(t,J=7.6 Hz,1H,Ph-H),7.30(t,J=7.6 Hz,1H,Ph-H),7.22(d,J=7.6 Hz,1H,Ph-H),7.11(d,J=7.6 Hz,1H,Ph-H),2.77(s,2H,-CH2),2.42(s,3H,-CH3),1.25(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:157.2,141.2,139.8,139.6,137.5,130.9,129.3,128.4,128.1,127.6,127.6,126.9,126.8,123.2,120.0,116.3,54.0,38.8,27.7,21.5.HRMS(ESI)for C21H22N3m/z:Calculated,316.1808,Found,316.1814[M+H]+.
2118:1H NMR(CDCl3,400 MHz)δ:8.85(s,1H,Py-H),8.03(s,1H,Py-H),7.47(d,J=7.6Hz,1H,Ph-H),7.38(t,J=7.2 Hz,1H,Ph-H),7.28(t,J=7.6 Hz,1H,Ph-H),7.21(d,J=6.8 Hz,1H,Ph-H),5.95(s,1H,Py-H),4.04(s,6H,-OCH3),2.76(s,2H,-CH2),1.24(s,6H,-CH3).13CNMR(CDCl3,100 MHz)δ:172.3,156.8,154.4,143.7,137.4,133.3,130.9,129.8,128.4,128.0,126.8,126.8,123.6,87.7,54.6,54.2,38.7,27.6.HRMS(ESI)for C20H22N5O2m/z:Calculated,364.1768,Found,364.1773[M+H]+.
2116:1H NMR(CDCl3,400 MHz)δ:8.79(s,1H,Py-H),8.62(d,J=4.8 Hz,2H,Py-H),8.05(s,1H,Py-H),7.43(d,J=7.6 Hz,1H,Ph-H),7.26(t,J=7.6 Hz,1H,Ph-H),7.17(t,J=7.6 Hz,1H,Ph-H),7.08-7.12(m,2H,Ph-H,Py-H),2.66(s,2H,-CH2),1.14(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:158.9,156.5,155.8,143.9,137.4,130.9,129.4,128.4,127.9,126.9,126.6,124.1,118.9,54.2,38.7,27.6.HRMS(ESI)for C18H18N5 m/z:Calculated,304.1577,Found,304.1562[M+H]+.
1418:1H NMR(CDCl3,400 MHz)δ:8.21(s,1H,Py-H),8.07(s,1H,Py-H),7.80(d,J=6.4Hz,1H,Ph-H),7.55-7.68(m,4H,Ph-H),7.38(d,J=8.4 Hz,1H,Ph-H),1.37(s,6H,-CH3).13CNMR(CDCl3,100 MHz)δ:155.6,141.4,136.4,134.6,132.1,131.8,131.3,131.0,130.5,128.8,128.4,128.2,127.9,127.0,124.0,121.7,120.1(t,JC-F=245.0 Hz,Ar-F),59.5,23.4.HRMS(ESI)for C20H16Cl2F2N3 m/z:Calculated,406.0684,Found,406.0689[M+H]+.
2018:1H NMR(CDCl3,400 MHz)δ:9.05(s,1H,Py-H),8.57(d,J=4.4 Hz,1H,Py-H),8.35(s,1H,Py-H),8.10-8.13(m,2H,Py-H),8.04(s,1H,Py-H),7.73-7.80(m,2H,Ph-H),7.67(t,J=7.2 Hz,1H,Ph-H),7.44(q,J=4.8 Hz,1H,Ph-H),1.53(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:155.5,148.1,142.0,140.7,136.2,131.9,131.3,131.0,127.8(t,JC-F=245.2 Hz,Ar-F),127.0,126.7,124.1,124.0,123.0,120.0,117.6,59.5,21.6.HRMS(ESI)for C19H17F2N4 m/z:Calculated,339.1416,Found,339.1421[M+H]+.
102:1H NMR(CDCl3,400 MHz)δ:8.15(s,1H,Py-H),7.88(s,1H,Py-H),7.81(d,J=7.6Hz,1H,Ph-H),7.58-7.68(m,3H,Ph-H),7.40(s,2H,Ph-H),2.18(s,6H,-CH3),1.37(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:155.4,141.1,137.2,131.7,131.6,131.4,130.9,128.0,127.6(t,2JC-F=19.8 Hz,-CF),126.8,125.7,124.1,121.3,120.1(t,JC-F=185.0Hz,Ar-F),118.9(q,JC-F=283.3 Hz,-CF3),59.4,21.7,18.0.
304:1H NMR(CDCl3,400 MHz)δ:7.92(s,1H,Py-H),7.80(s,1H,Py-H),7.76(d,J=7.2 Hz,1H,Ph-H),7.64(d,J=7.2 Hz,1H,Ph-H),7.53-7.61(m,2H,Ph-H),1.62(s,9H,-CH3),1.33(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:156.5,139.1,131.5,131.3(t,2JC-F=25.1 Hz,Ar-F),130.8,128.2(t,3JC-F=4.5 Hz,Ar-F),127.4,126.9,123.8(t,3JC-F=5.4Hz,Ar-F),122.7,119.5(t,JC-F=194.5 Hz,Ar-F),58.9,29.7,23.4,21.7.HRMS(ESI)forC18H22F2N3 m/z:Calculated,318.1776,Found,318.1777[M+H]+.
106:1H NMR(CDCl3,400 MHz)δ:8.35(s,1H,Py-H),8.06(s,1H,Py-H),7.91(t,J=7.6 Hz,1H,Ph-H),7.81(d,J=7.6 Hz,1H,Ph-H),7.57-7.69(m,3H,Ph-H),7.22-7.34(m,3H,Ph-H),1.37(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:155.7,153.5(d,JC-F=248.1 Hz,Ar-F),141.0,131.8,131.6,131.5,131.3,131.0,128.4,128.3,128.0,127.1,125.1,124.5,124.0,122.1,120.1(t,JC-F=245.1 Hz,Ar-F),117.7,117.0,116.8,59.5,23.4,21.6.HRMS(ESI)for C20H17F3N3 m/z:Calculated,356.1369,Found,356.1374[M+H]+.
2122:1H NMR(CDCl3,400 MHz)δ:8.13(s,1H,Py-H),7.84(s,1H,Py-H),7.53(d,J=7.6Hz,1H,Ph-H),7.49(s,2H,Ph-H),7.39(t,J=7.6 Hz,1H,Ph-H),7.28(t,J=7.6Hz,1H,Ph-H),7.21(d,J=7.2 Hz,1H,Ph-H),2.77(s,2H,-CH2),1.24(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:155.2,141.8,136.3,135.0,134.8,132.6,131.8,131.4,131.0,128.8,128.0,126.9,121.7,120.1(t,JC-F=244.7 Hz,Ar-F),59.5,21.6.HRMS(ESI)for C20H15Cl3F2N3 m/z:Calculated,440.0294,Found,440.0296[M+H]+.
406:1H NMR(CDCl3,400 MHz)δ:8.79(s,1H,Py-H),8.13(s,1H,Py-H),7.82(d,J=7.6 Hz,2H,Ph-H),7.59-7.67(m,3H,Ph-H),7.54(d,J=9.2 Hz,1H,Ph-H),7.22(t,J=8.8Hz,1H,Ph-H),1.38(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:160.2(d,JC-F=244.5 Hz,Ar-F),154.9,147.3,143.5,134.2,132.0,131.1,128.0,127.5,126.7,124.2,123.7,123.5(d,3JC-F=9.2 Hz,Ar-F),120.0(t,JC-F=244.9 Hz,Ar-F),115.2(d,2JC-F=24.4 Hz,Ar-F),108.2(d,2JC-F=27.0 Hz,Ar-F),59.7,21.5.HRMS(ESI)for C21H16F3N4S m/z:Calculated,413.1042,Found,413.1047[M+H]+.
508:1H NMR(CDCl3,400 MHz)δ:8.44(s,1H,Py-H),8.3(d,J=8.8 Hz,2H,Ph-H),8.08(s,1H,Py-H),7.94(d,J=8.8 Hz,2H,Ph-H),7.83(d,J=7.2 Hz,1H,Ph-H),7.59-7.67(m,3H,Ph-H),1.38(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:155.4,145.8,143.9,142.6,132.1,131.3,131.1,127.8,126.8,125.4,124.2,123.8,120.0(t,JC-F=245.2 Hz,Ar-F),118.9,110.0,59.9,21.6.HRMS(ESI)for C20H17F2N4O2 m/z:Calculated,383.1314,Found,383.1319[M+H]+.
4:1H NMR(CDCl3,400 MHz)δ:8.27(s,1H,Py-H),7.97(s,1H,Py-H),7.72(d,J=6.8Hz,1H,Ph-H),7.65(d,J=8.0 Hz,2H,Ph-H),7.61(d,J=6.8 Hz,1H,Ph-H),7.46-7.52(m,2H,Ph-H),7.32(t,J=7.6 Hz,2H,Ph-H),7.18(t,J=7.2 Hz,1H,Ph-H),1.34(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:155.7,139.6,131.8,131.2(t,2JC-F=25.0 Hz,Ar-F),131.0,129.5,127.0,127.6,127.1,126.9,123.9,122.2,121.44,120.2(t,JC-F=245.1 Hz,Ar-F),119.2,59.4,21.7.HRMS(ESI)for C20H18F2N3 m/z:Calculated,338.1463,Found,338.1468[M+H]+.
610:1H NMR(CDCl3,400 MHz)δ:8.84(s,1H,Py-H),8.14(s,1H,Py-H),7.82-7.91(m,3H,Ph-H),7.62-7.69(m,3H,Ph-H),7.49(t,J=8.0 Hz,1H,Ph-H),7.39(t,J=8.0 Hz,1H,Ph-H),7.24-7.25(m,1H,Ph-H),1.38(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:159.8,154.9,150.8,143.4,133.2(t,JC-F=190.6 Hz,Ar-F),132.0,131.3,131.1,128.2,127.6,126.8,125.2,124.1,123.6,122.5,121.7,119.9,117.6,59.7,21.6.HRMS(ESI)forC21H16F2N4S m/z:Calculated,395.1137,Found,395.1151[M+H]+.
612:1H NMR(CDCl3,400 MHz)δ:8.61(s,1H,Py-H),8.43(s,1H,Py-H),8.14(t,J=8.8 Hz,2H,Ph-H),8.05(s,1H,Ph-H),7.81(d,J=6.0 Hz,1H,Ph-H),7.59-7.67(m,4H,Ph-H),1.37(s,6H,-CH3).13C NMR(CDCl3,100 MHz)δ:155.4,148.9,142.1,140.4,132.0,131.3,131.1,130.6,127.6,126.9,124.6,124.1,123.4,121.5,121.4,120.0(t,JC-F=240.1 Hz,Ar-F),113.9,59.6,23.4.HRMS(ESI)for C20H17F2N4O2 m/z:Calculated,383.1314,Found,383.1320[M+H]+.
614:1H NMR(CDCl3,400 MHz)δ:8.31(s,1H,Py-H),8.01(s,1H,Py-H),7.81(d,J=6.8 Hz,1H,Ph-H),7.68(d,J=8.4 Hz,1H,Ph-H),7.57-7.66(m,4H,Ph-H),7.51(d,J=8.0Hz,1H,Ph-H),7.34(t,J=7.6Hz,1H,Ph-H),7.12(d,J=7.6Hz,1H,Ph-H),2.42(s,6H,-CH3),1.38(s,6H,-CH3).13C NMR(CDCl3,100MHz)δ:151.1,136.3,134.9,134.8,127.0,126.6(t,2JC-F=25.1Hz,Ar-F),126.2,124.6,123.3,123.0,122.9,122.4,119.2,117.4,115.4(t,JC-F=245.1Hz,Ar-F),115.3,111.7,54.7,16.9,16.7.HRMS(ESI)for C21H20F2N3 m/z:Calculated,352.1620,Found,352.1663[M+H]+.
2119:1H NMR(CDCl3,400MHz)δ:8.85(s,1H,Py-H),8.07(d,J=7.6Hz,1H,Ph-H),8.05(s,1H,Py-H),7.73(t,J=8.0Hz,1H,Ph-H),7.66(d,J=7.2Hz,1H,Ph-H),7.62(t,J=8.0Hz,1H,Ph-H),5.94(s,1H,Py-H),4.01(s,6H,-OCH3),1.50(s,6H,-CH3).13C NMR(CDCl3,100MHz)δ:172.3,155.5,154.3,143.3,131.8,131.4(t,2JC-F=25.2Hz,Ar-F),131.0,129.9,127.0,124.0,122.5,120.0,117.6(t,JC-F=255.2Hz,Ar-F),87.8,59.6,54.6,21.5.HRMS(ESI)for C20H20F2N5O2 m/z:Calculated,400.1580,Found,400.1585[M+H]+.
2117:1H NMR(CDCl3,400MHz)δ:8.91(s,1H,Py-H),8.72(d,J=4.8Hz,2H,Py-H),8.15(s,1H,Py-H),7.77(d,J=7.6Hz,1H,Ph-H),7.63(t,J=7.6Hz,2H,Ph-H),7.57-7.61(m,2H,Ph-H,Py-H),7.21(t,J=4.8Hz,1H,Ph-H),1.34(s,6H,-CH3).13C NMR(CDCl3,100MHz)δ:158.9,155.6,155.3,143.6,131.8,131.2(t,2JC-F=25.2Hz,Ar-F),131.0,129.6,127.8,126.8,124.0,122.9,120.1(t,JC-F=245.1Hz,Ar-F),119.1,59.5,21.6.HRMS(ESI)for C18H16F2N5 m/z:Calculated,340.1368,Found,340.1374[M+H]+.
本发明还提供上述取代二氢异喹啉衍生物制备方法,所述制备方法包括以下步骤:
式中:
R选自氢、C1-C10烷基、C3-C10环烷基、C1-C10烯基、C1-C10炔基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基、C1-C10烷基砜基或C1-C10烷基亚砜基、C1-C10芳基取代烷基,或被氢、卤素、C1-C10烷基、C3-C10环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烯基、C1-C10炔基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基、腈基、硝基、C1-C10烷基砜基或C1-C10烷基亚砜基中的至少一种取代基取代的苯基、五元杂芳基或六元杂芳基;
R1、R2独立选自氢、C1-C5烷基、C3-C5环烷基、C1-C10烯基、C1-C10炔基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基;
R5、R6、R7和R8独立选自氢、卤素、C1-C10烷基、C3-C10环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烯基、C1-C10炔基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基、腈基、硝基、C1-C10烷基砜基或C1-C10烷基亚砜基。
本发明还提供上述任一所述的取代二氢异喹啉衍生物的应用,所述取代二氢异喹啉衍生物用于农用杀菌,特别适用用于防治作物灰霉病、稻瘟病等病害中的一种、两种或三种以上组合。当用于配制农用化学杀菌剂时,本发明所述具取代二氢异喹啉衍生物在杀菌剂中的质量百分含量为1~99%,可以被配制成各种剂型:如乳油、油悬浮剂、水悬浮剂、微乳剂、水乳剂、可湿性粉剂、可溶性粉剂、颗粒剂、水分散粒剂或胶囊剂。载体至少包括两种,其中至少一种是表面活性剂。载体可以是固体或液体。合适的固体载体包括天然的或合成的粘土和硅酸盐,例如天然硅石和硅藻土;硅酸镁例如滑石;硅酸铝镁例如高岭石、高岭土、蒙脱土和云母;白碳黑、碳酸钙、轻质碳酸钙;硫酸钙;石灰石;硫酸钠;胺盐如硫酸铵、六甲撑二胺。液体载体包括水和有机溶剂,当用水做溶剂或稀释剂时,有机溶剂也能用做辅助剂或防冻添加剂。合适的有机溶剂包括芳烃例如苯、二甲苯、甲苯等;氯代烃,例如氯代苯、氯乙烯、三氯甲烷、二氯甲烷等;脂肪烃,例如石油馏分、环己烷、轻质矿物油;醇类,例如异丙醇、丁醇、乙二醇、丙三醇和环己醇等;以及它们的醚和酯;还有酮类,例如丙酮、环己酮以及二甲基甲酰胺和N-甲基-吡咯烷酮。
表面活性剂可以是乳化剂、分散剂或湿润剂;可以是离子型的或非离子型的。非离子型乳化剂例如聚氧乙烯脂肪酸脂、聚氧乙烯脂肪醇醚、聚氧乙烯脂肪氨,以及市售的乳化剂:农乳2201B、农乳0203B、农乳100#、农乳500#、农乳600#、农乳600-2#、农乳1601、农乳2201、农乳NP-10、农乳NP-15、农乳507#、农乳OX-635、农乳OX-622、农乳OX-653、农乳OX-667、宁乳36#。分散剂包括木质素磺酸钠、拉开粉、木质素磺酸钙、甲基萘磺酸甲醛缩合物等。湿润剂为:月桂醇硫酸钠、十二烷基苯磺酸钠、烷基萘磺酸钠等。
这些制剂可由通用的方法制备。例如,将活性物质与液体溶剂和/或固体载体混合,同时加入表面活性剂如乳化剂、分散剂、稳定剂、湿润剂,还可以加入其它助剂如:粘合剂、消泡剂、氧化剂等。
相比与现有技术,本发明提供的通式(I)所示的取代二氢异喹啉衍生物,具有以下优点:
本发明的含取代二氢异喹啉衍生物杀菌活性高,在25ppm浓度下防治葡萄、黄瓜灰霉病效果大于80%,在25ppm浓度下防治水稻稻瘟病效果大于90%。
具体实施方式
下面结合具体实施例来对本发明进行进一步说明,但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到,本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。
(一)化合物制备:
实施例1:中间体B的合成
在0℃下将含有化合物2-甲基-1-苯基丙烷-2-醇(120.20g,0.80mol)和乙腈(33.01g,0.80mol)的溶液滴加到浓硫酸(400mL)中。滴加结束后,在室温下进行搅拌6h。反应完成后倒入3000mL冰水中,氨水中和后用乙酸乙酯(3×200mL)萃取,无水氯化钙干燥1h后过滤得到滤液,旋蒸除去乙酸乙酯得到黑色液体中间体B,收率为73.6%。1H NMR(CDCl3,400MHz)δ:7.46(d,J=7.6Hz,1H,Ph-H),7.32(t,J=6.8Hz,1H,Ph-H),7.26(t,J=7.6Hz,1H,Ph-H),7.12(d,J=7.2Hz,1H,Ph-H),2.67(s,2H,-CH2),2.36(s,3H,-CH3),1.18(s,3H,-CH3).
实施例2:中间体C的合成
将含DMF(38.00g)的二甲苯溶液(450mL)冷却至4℃,于10℃以下滴加草酰氯(68.00g,0.52mol)。滴加完成后在室温下搅拌30分钟,然后滴加含有中间体B(30.01g,0.20mol)的二甲苯(60mL)溶液。在80℃进行2h搅拌。反应结束后冷却至室温加入水(300mL),充分进行搅拌,然后分离二甲苯层和水层,得到含有中间体C的水层。
实施例3:中间体D的合成
往含有中间体C的水层滴加30%氢氧化钠溶液(100mL)至pH=9,在95℃下进行2h反应。在冷却至8℃后,于20℃以下滴加浓盐酸(60mL)。进行1h搅拌后过滤,乙酸乙酯(3×150mL)萃取滤液。无水硫酸镁充分干燥后过滤,旋蒸除去乙酸乙酯。柱色谱分离(洗脱剂为乙酸乙酯和石油醚)得到橙红色固体中间体D,收率为75.6%。1H NMR(CDCl3,400MHz)δ:9.77(s,2H,-CHO),7.62(d,J=7.6Hz,1H,Ph-H),7.53(t,J=6.8Hz,1H,Ph-H),7.36(t,J=7.6Hz,1H,Ph-H),7.25(d,J=7.2Hz,1H,Ph-H),2.89(s,2H,-CH2),1.30(s,3H,-CH3).13CNMR(CDCl3,100MHz)δ:190.0,164.4,137.1,133.3,131.5,129.0,126.8,124.3,108.2,50.8,41.1,26.7.
实施例4:化合物G的合成
将中间体D(5.70g,26mmol)加入圆底烧瓶中,加入冰乙酸(35mL)搅拌溶解,再加入化合物2,4,6-三氯苯基肼(6.44g,26mmol),在100℃下加热搅拌8h。反应结束后加入水(100mL),用氨水中和后乙酸乙酯(3×50mL)萃取,无水硫酸镁充分干燥有机相后过滤,旋蒸除去乙酸乙酯。柱色谱分离(洗脱剂为乙酸乙酯和石油醚)得到化合物G,收率为75.5%。其它化合物合成方法相同,合成一系列目标化合物G。1H NMR(CDCl3,400MHz)δ:8.13(s,1H,Py-H),7.84(s,1H,Py-H),7.53(d,J=7.6Hz,1H,Ph-H),7.49(s,2H,Ph-H),7.39(t,J=7.6Hz,1H,Ph-H),7.28(t,J=7.6Hz,1H,Ph-H),7.21(d,J=7.2Hz,1H,Ph-H),2.77(s,2H,-CH2),1.24(s,6H,-CH3).
实施例5:中间体H的合成
将化合物G(0.51g,1.2mmol)加入到圆底烧瓶中,用四氯化碳(30mL)作溶剂,加入溴代丁二酰亚胺(0.43g,2.4mmol)和偶氮二异丁腈(0.10g,0.6mmol),加热搅拌回流反应4h,TLC检测反应完全。反应完成后过滤不溶物,旋蒸除去四氯化碳,得到粗品中间体H,收率为80.1%。其它中间体H的合成方法相同。
实施例6:化合物2106的合成
将中间体H(0.54g,1.0mmol)加入到圆底烧瓶中,加入三乙胺三氟化氢盐(8mL),在95℃下加热搅拌8h。反应结束后加入50mL水,用氨水中和后乙酸乙酯(3×10mL)萃取,用无水硫酸镁充分干燥有机相后过滤,旋蒸除去乙酸乙酯,板层析分离得到产物2106。1H NMR(CDCl3,400MHz)δ:8.13(s,1H,Py-H),7.84(s,1H,Py-H),7.53(d,J=7.6Hz,1H,Ph-H),7.49(s,2H,Ph-H),7.39(t,J=7.6Hz,1H,Ph-H),7.28(t,J=7.6Hz,1H,Ph-H),7.21(d,J=7.2Hz,1H,Ph-H),2.77(s,2H,-CH2),1.24(s,6H,-CH3).13C NMR(CDCl3,100MHz)δ:155.2,141.8,136.3,135.0,134.8,132.6,131.8,131.4,131.0,128.8,128.0,126.9,121.7,120.1(t,JC-F=244.7Hz,Ar-F),59.5,21.6.HRMS(ESI)for C20H15Cl3F2N3 m/z:Calculated,440.0294,Found,440.0296[M+H]+.
(二)制剂配制
以下实施例按照质量配比配制。
实施例7:30%水分散粒剂
将化合物4、萘磺酸盐甲醛缩合物、萘磺酸盐、白炭黑和高岭土进行混合粉碎,再加水捏合后,加入装有一定规格筛网的造粒机中进行造粒。然后再经干燥、筛分(按筛网范围)即得颗粒状产品。
实施例8:30%水悬浮剂
将上述所有成分(除0.1%黄原胶外)在剪切机中进行预混合,再加入砂磨机中砂磨至所需的粒径,过滤后得到悬浮母液,加入配置好的0.1%黄原胶水溶液剪切混合均匀即可。
实施例9:30%乳油
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将化合物305、亚磷酸和乙氧基化甘油三酸酯加入甲苯中,加热搅拌得到透明的溶液。
实施例10:60%可湿性粉剂
将化合物2015、十二烷基萘磺酸钠、木质素磺酸钠及硅澡土混合在一起,在粉碎机中粉碎,直到混合物粒径达到标准。
(三)生物活性测试
实施例11:稻瘟病预防试验
选择二叶一心期长势一致盆栽水稻苗,待测化合物用少量N,N-二甲基甲酰胺溶解,然后用含0.1%吐温80的水稀释成所要测试的浓度,将配制好的药剂用喷枪均匀的喷施在供试水稻苗,药剂喷雾处理后自然晾干,24h后在已长满孢子的培养皿中,加入无菌水,轻轻刮取表面孢子,用2-4层纱布过滤,制成浓度为20-30万个/ml的孢子悬浮液。用接种喷雾器(压力0.1Mpa),在水稻苗上均匀喷雾接种,3组重复试验。接种后的试材移到人工气候室(温度保持28℃、相对湿度100%)培养24h,然后保持湿度80-90%诱导发病,每天观察稻苗生长状况,一周后视空白对照发病情况进行分级调查,按病指计算防效%。
水稻稻瘟病调查方法
0级:无病斑;
1级:叶片病斑数少于5个,长度小于1cm;
3级:叶片病斑数6~10个,部分病斑长度大于1cm;
5级:叶片病斑数11~25个,部分病斑连成片,占叶面积10~25%;
7级:叶片病斑数26个以上,病斑连成片,占叶面积26~50%;
9级:病斑连成片,占叶面积50%以上。
病情指数=∑(各级病叶数×相对级数值)×100/(总叶数×9);
防治效果(%)=(对照病情指数-处理病情指数)×100/对照病情指数。
在100ppm下化合物1,4,103,106,203,206,305,308,407,406,410,509,512,615,618,610,715,718,815,818,915,918,1015,1018,1115,1118,1215,1218,1515,1518,1815,1818,1715,1718,1918,2018,2117,2119对水稻稻瘟病预防效果优于90%。在25ppm下化合物4,106,206,308,410,1518,1718,2018对水稻稻瘟病预防效果优于85%。
实施例12:黄瓜灰霉病预防试验
选择2~3叶期长势一致盆栽黄瓜苗,待测化合物用少量N,N-二甲基甲酰胺溶解,然后用含0.1%吐温80的水稀释成所要测试的浓度,将配制好的药剂用喷枪均匀的喷施在供试水稻苗,药剂喷雾处理后自然晾干,24h后在已长满孢子的培养皿中,加入无菌水,轻轻刮取表面孢子,用2-4层纱布过滤,制成浓度为20-30万个/ml的孢子悬浮液。用接种喷雾器(压力0.1Mpa),在黄瓜苗上均匀喷雾接种,3组重复试验。接种后的试材移到人工气候室(温度保持28℃、相对湿度100%)培养24h,然后保持湿度80-90%诱导发病,每天观察稻黄瓜苗生长状况,一周后视空白对照发病情况进行分级调查,按病指计算防效%。
黄瓜灰霉病调查方法
0级:无病斑;
1级:叶片病斑数少于5个,长度小于1cm;
3级:叶片病斑数6~10个,部分病斑长度大于1cm;
5级:叶片病斑数11~25个,部分病斑连成片,占叶面积10~25%;
7级:叶片病斑数26个以上,病斑连成片,占叶面积26~50%;
9级:病斑连成片,占叶面积50%以上。
病情指数=∑(各级病叶数×相对级数值)×100/(总叶数×9);
防治效果(%)=(对照病情指数-处理病情指数)×100/对照病情指数。
在50ppm下化合物1,4,103,106,203,206,305,308,407,406,410,509,512,615,618,610,715,718,815,818,915,918,1015,1018,1115,1118,1215,1218,1515,1518,1815,1818,1918,1715,1718,1918,2018,2117,2119对黄瓜灰霉病预防效果优于90%。在25ppm下化合物4,106,206,308,410,1518,1718,2018对黄瓜灰霉病预防效果优于85%。
Claims (10)
1.一类取代二氢异喹啉衍生物,如下通式(A)所示:
其中:
R选自氢、C1-C10烷基、C3-C10环烷基、C1-C10烯基、C1-C10炔基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基、C1-C10烷基砜基或C1-C10烷基亚砜基、C1-C10芳基取代烷基,或被氢、卤素、C1-C10烷基、C3-C10环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烯基、C1-C10炔基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基、腈基、硝基、C1-C10烷基砜基或C1-C10烷基亚砜基中的至少一种取代基取代的苯基、五元杂芳基或六元杂芳基;
R1、R2独立选自氢、C1-C5烷基、C3-C5环烷基、C1-C10烯基、C1-C10炔基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基;
R3、R4独立选自氢、卤素;
R5、R6、R7和R8独立选自氢、卤素、C1-C10烷基、C3-C10环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烯基、C1-C10炔基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10卤代烷基、C1-C10烷氧取代烷基、C1-C10烷硫取代烷基、C1-C10氰基取代烷基、腈基、硝基、C1-C10烷基砜基或C1-C10烷基亚砜基。
2.根据权利要求1所述的取代二氢异喹啉衍生物,其特征在于:
R选自氢、C1-C5烷基、C3-C5环烷基、C1-C5烯基、C1-C5炔基、C1-C5卤代烷基、C1-C5烷氧取代烷基、C1-C5烷硫取代烷基、C1-C5氰基取代烷基、C1-C5烷基砜基或C1-C5烷基亚砜基、C1-C5芳基取代烷基,或被氢、卤素、C1-C5烷基、C3-C5环烷基、C1-C5烷氧基、C1-C5卤代烷氧基、C1-C5烯基、C1-C5炔基、C1-C5烷硫基、C1-C5卤代烷硫基、C1-C5卤代烷基、C1-C5烷氧取代烷基、C1-C5烷硫取代烷基、C1-C5氰基取代烷基、腈基、硝基、C1-C5烷基砜基或C1-C5烷基亚砜基中的至少一种取代基取代的苯基、五元杂芳基或六元杂芳基;
R1、R2独立选自氢、C1-C5烷基、C3-C5环烷基、C1-C5烯基、C1-C5炔基、C1-C5卤代烷基、C1-C5烷氧取代烷基、C1-C5烷硫取代烷基、C1-C5氰基取代烷基;
R3、R4独立选自氢、卤素;
R5、R6、R7和R8独立选自氢、卤素、C1-C5烷基、C3-C5环烷基、C1-C5烷氧基、C1-C5卤代烷氧基、C1-C5烯基、C1-C5炔基、C1-C5烷硫基、C1-C5卤代烷硫基、C1-C5卤代烷基、C1-C5烷氧取代烷基、C1-C5烷硫取代烷基、C1-C5氰基取代烷基、腈基、硝基、C1-C5烷基砜基或C1-C5烷基亚砜基。
3.根据权利要求2所述的取代二氢异喹啉衍生物,其特征在于:
R选自氢、C1-C5烷基、C3-C5环烷基、C1-C5烯基、C1-C5炔基、C1-C5卤代烷基、C1-C5烷氧取代烷基、C1-C5烷硫取代烷基、C1-C5氰基取代烷基、C1-C5烷基砜基或C1-C5烷基亚砜基、C1-C5芳基取代烷基,或被氢、卤素、C1-C5烷基、C3-C5环烷基、C1-C5烷氧基、C1-C5卤代烷氧基、C1-C5烯基、C1-C5炔基、C1-C5烷硫基、C1-C5卤代烷硫基、C1-C5卤代烷基、C1-C5烷氧取代烷基、C1-C5烷硫取代烷基、C1-C5氰基取代烷基、腈基、硝基、C1-C5烷基砜基或C1-C5烷基亚砜基中的至少一种取代基取代的苯基、五元杂芳基或六元杂芳基;
R1、R2独立选自氢、C1-C3烷基、C3-C5环烷基、C1-C3烯基、C1-C3炔基、C1-C3卤代烷基、C1-C3烷氧取代烷基、C1-C3烷硫取代烷基、C1-C3氰基取代烷基;
R3、R4独立选自氢、卤素;
R5、R6、R7和R8独立选自氢、卤素、C1-C3烷基、C3-C5环烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烯基、C1-C3炔基、C1-C3烷硫基、C1-C3卤代烷硫基、C1-C3卤代烷基、C1-C3烷氧取代烷基、C1-C3烷硫取代烷基、C1-C3氰基取代烷基、腈基、硝基、C1-C3烷基砜基或C1-C3烷基亚砜基。
4.根据权利要求3所述的取代二氢异喹啉衍生物,其特征在于:
R选自氢、甲基、乙基、叔丁基、环丙基、丙烯基、三氟甲基、二氟甲基、一氟甲基、甲基乙氧基、甲基甲氧基、甲基乙硫基,或被氢、氟、氯、溴、甲基、乙基、三氟甲基、三氟甲氧基、二氟甲基、二氟甲氧基、甲氧基、乙氧基、甲硫基、硝基、腈基至少一种取代基取代的苯基、五元杂芳基或六元杂芳基;
R1、R2独立选自氢、C1-C3烷基、C3-C5环烷基、C1-C3烯基、C1-C3炔基、C1-C3卤代烷基、C1-C3烷氧取代烷基、C1-C3烷硫取代烷基、C1-C3氰基取代烷基;
R3、R4独立选自氢、氟;
R5、R6、R7和R8独立选氢、氟、氯、溴、甲基、乙基、三氟甲基、三氟甲氧基、二氟甲基、二氟甲氧基、甲氧基、乙氧基、甲硫基、硝基、腈基。
5.根据权利要求4所述的取代二氢异喹啉衍生物,其特征在于:所述取代二氢异喹啉衍生物选自下述结构中的至少一种:
6.权利要求1-5任一所述取代二氢异喹啉衍生物制备方法,其特征在于:所示制备方法包括以下步骤:
式中:R、R1、R2、R5、R6、R7、R8同权利要求1-4所述。
7.权利要求1-5任一所述的含取代二氢异喹啉衍生物的应用,其特征在于:所述含取代二氢异喹啉衍生物用于农用杀菌。
8.根据权利要求7所述的含取代二氢异喹啉衍生物的应用,其特征在于:所述含取代二氢异喹啉衍生物用于防治作物灰霉病、稻瘟病、早疫病、叶斑病。
9.根据权利要求8所述的含取代二氢异喹啉衍生物的应用,其特征在于:所述含取代二氢异喹啉衍生物用于防治葡萄灰霉病、黄瓜灰霉病、水稻稻瘟病。
10.一种农用化学杀菌剂,其特征在于:所述农用化学杀菌剂中含有1~99%质量百分含量的权利要求1-5任一所述的含取代二氢异喹啉衍生物,其余为农业上可接受的载体。
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