CN108017607A - 一类新型n-取代胺基香豆素及其除草与杀菌用途 - Google Patents

一类新型n-取代胺基香豆素及其除草与杀菌用途 Download PDF

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CN108017607A
CN108017607A CN201711303401.4A CN201711303401A CN108017607A CN 108017607 A CN108017607 A CN 108017607A CN 201711303401 A CN201711303401 A CN 201711303401A CN 108017607 A CN108017607 A CN 108017607A
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魏艳
郝双红
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Abstract

本发明（名称为：一类新型N‑取代胺基香豆素及其除草与杀菌用途）涉及25种N‑取代氨基香豆素衍生物及其制备方法，以及在抑菌、除草方面的用途。25种N‑取代氨基香豆素衍生物，通过6‑氨基香豆素与间氟苯甲醛缩合并用NaBH4还原得中间体，再将其与不用酰氯在三乙胺存在下缩合得系列目标化合物。这些化合物可作为除草剂防治杂草马唐及反枝苋，也可作为杀菌剂防治番茄灰霉病菌及苹果腐烂病菌。

Description

一类新型N-取代胺基香豆素及其除草与杀菌用途
技术领域
本发明涉及一类新型N-取代胺基香豆素类化合物及其除草与杀菌用途，具体的涉及农用除草剂及杀菌剂领域。
背景技术
香豆素类化合物具有广谱生物活性和广泛用途。该类化合物的农药活性涉及杀虫、杀螨、杀鼠、除草及杀菌作用。酰基芳胺类化合物也具有广泛生物活性，如杀菌剂甲霜灵、萎锈灵，除草剂乙草胺、氟吡草胺等。该专利基于活性亚结构拼接思想，以香豆素为骨架，在其6-位引入氨基，然后在氨基上接上间氟苄基，最后将氨基用不同酰基酰化，合成了一类新型N-取代胺基香豆素类化合物，并评价了该类化合物的除草活性及抑菌活性。
发明内容
本发明的目的在于提供一类新型N-取代胺基香豆素类化合物及其制备方法，它可应用于农业上以防治田间杂草及农作物病害。
本发明的技术方案如下：
本发明提供的新型N-取代胺基香豆素类化合物，其结构通式如下：
R选自：烷基、卤代烷基、烯基、取代芳基；
新型N-取代胺基香豆素类化合物合成反应式：
c d e
e1: R=; e2: R=; e3: R=; e4: R=; e5: R=; e6: R=; e7:R=; e8: R=; e9: R=; e10: R=; e11: R=; e12: R=; e13:R=; e14: R=; e15: R=; e16: R=; e17: R=; e18: R=; e19: R=; e20: R=; e21: R=; e22: R=; e23: R=; e24: R=; e25: R=.
目标化合物参考文献方法合成。6-氨基香豆素c首先与间氟苯甲醛缩合得西弗碱，再用NaBH4还原得中间体d，其与不用酰氯在三乙胺存在下缩合得系列目标化合物e。目标化合物e1- e25的Mp、ESI-MS及1H NMR数据列于表1。
表1. 目标化合物的Mp、MS及1H NMR数据
化合物 Mp /℃ ESI-MS [M+1]+ 1H NMR(500 MHz, CDCl3): δ
e1 wax 324.20 4.98 (2H, s), 5.62(1H, d,J=10.0Hz),6.00(1H, t),6.48 (2H, q, ), 6.98 (3H,m), 7.14(1H,s),7.19(1H,d,J=8.5Hz),7.25 (1H, m),7.32(1H, d, J=9.0Hz),7.61(1H, d, J=9.5Hz).
e2 123-124 338.20 1.01(3H,s), 4.97(2H,s), 5.04(1H,s), 6.44(1H, d, J=9.5 Hz), 6.94-6.99(3H, m), 7.09(1H, d, J=2.0 Hz), 7.16(1H,dd,J=2.0Hz,J=8.5Hz), 7.23-7.27(2H, m), 7.59(1H, d, J=9.5 Hz).
e3 60-63 368.30 0.81(3H, t), 1.06(3H, d,J=7Hz), 1.18(2H, m), 1.72 (2H, m), 2.29 (1H, dd,J=6.5Hz,J=12.5Hz), 4.88 (2H, dd,J=14.5Hz,J=25.5Hz), 6.47 (1H, d, J=9.5Hz), 6.93 (3H, m), 7.08(1H,s),7.12(1H,dd,J=1.5Hz,J=9.0Hz), 7.24 (1H,dd,J=8.0Hz,J=14.5Hz), 7.31(1H, d, J=8.5Hz),7.61(1H, d, J=9.5Hz).
e4 67-68 352.20 1.71(3H,s), 2.18(3H,s), 4.94 (2H, s), 5.44(1H,s), 6.45 (1H, d, J=9.0Hz), 6.94-6.98 (3H, m), 7.15-7.28(4H, m), 7.62 (1H, d, J=9.0 Hz).
e5 102-105 360.18 0.86(3H,s), 4.19(1H,s),4.78(1H,d,J=14.0Hz), 5.00(1H,d,J=14.0Hz), 6.47(1H, d, J=9.5 Hz), 6.93-6.96 (3H, m), 7.23-7.27 (3H, m), 7.33(1H,d,J=8.0Hz),7.62(1H, d, J=9.5 Hz).
e6 wax 374.18 0.92(3H, t, J=7.5Hz, J=7.5Hz), 1.93(1H, dd, J=5.0Hz, J=14.5Hz), 2.12(1H,dd, J=5.0Hz, J=14.5Hz), 3.92 (1H, t, J=7.5Hz, J=7.5Hz), 4.85 (1H, d,J=14.5Hz),4.95 (1H, d,J=14.5Hz),6.48 (1H, d, J=9.5 Hz), 6.97 (3H, m), 7.21(2H, m),7.34(1H, d, J=8.5Hz),7.62(1H, d, J=8.5Hz).
e7 88-90 401.18 1.78(1H, d, J=7.0Hz), 4.16 (1H, q, J=7.0, Hz,J=13.0Hz), 4.78 (1H, d,J=14.5Hz),4.98 (1H, d,J=14.5Hz),6.48 (1H, d, J=9.5 Hz), 6.94 (3H, m), 7.25(2H, m),7.33(1H, d, J=8.5Hz),7.62(1H, d, J=9.5Hz).
e8 oil 446.10 0.88(3H, s),1.26, (4H,s), 1.97(1H, m), 2.18 (1H, m), 3.95 (1H, t, J=7.5Hz, J=7.5Hz), 4.82(1H, d,J=14.5Hz), 4.97 (1H, d,J=14.5Hz), 6.49 (1H,d, J=9.5 Hz), 6.94-7.00 (3H, m), 7.27 (2H, m),7.34(1H, d, J=8.5Hz),7.62(1H, d, J=8.5Hz).
e9 128-131 388.21 2.26 (3H, s), 5.11 (2H, s),6.38 (1H, d, J=9.5 Hz), 6.95 (1H, m)，7.00(3H,d, J=7.5 Hz), 7.04 (2H, d, J=7.5Hz),7.08(1H, dd,J=2.5 Hz,J=9.0 Hz ),7.13 (1H, d, J=9.0 Hz), 7.22 (1H, s),7.23 (1H, s)7.27 (1H, s), 7.47(1H,d, J=9.5 Hz).
e10 97-99 402.20 1.15(3H, s), 2.56 (2H, s), 5.12 (2H, s),6.38 (1H, d, J=8.5 Hz), 6.96(1H, m), 7.03(4H, m), 7.10(1H, m), 7.13 (1H, dd, J=8.0 Hz,J=22.0 Hz),7.25 (4H, s), 7.47(1H, d, J=8.5Hz).
e11 110-112 390.20 2.04(2H, s), 3.42(2H, t, J1=5.0Hz, J2=5.0Hz), 4.30(2H, s), 4.87(2H,s),6.42(1H, d,J=10.0Hz), 6.95-7.01(3H, m), 7.29(4H, m), 7.62(1H,d, J=10.0Hz).
e12 131-135 404.20 3.70(3H, s), 5.13(2H, s), 6.46(1H, d,J=9.5Hz), 6.79 (2H, d, J=8.5 Hz),7.05 (2H, dd,J=8.0Hz,J=15Hz), 7.14(2H,d,J=8.0Hz), 7.26(1H,d,J=8.5Hz),7.32(4H, m),7.55(1H, d, J=9.5Hz).
（续表1）
具体实施方式
实例1 除草活性评价
先将目标化合物用丙酮溶解配制成3000 mg/L的母液，取上述母液1 mL加入到30 mL0.5%的琼脂溶液中，充分混匀，得100 mg/L带毒培养基，然后将其分匀倒入3个10 mL小烧杯中。取1 mL丙酮加入培养基中做空白对照（CK)，每处理重复3次。
把催芽露白的马唐和反枝苋种子分别接到培养基上培养，每个小杯接种10粒，将接种后的小杯放入培养箱（28 ℃，相对湿度90%，L/D=12h:12h）中培养，当空白对照根长到合适长度时测量种子根、茎长度。按照下式计算根茎生长抑制率：
抑制率/ % = [对照根（茎）长-处理根（茎）长]/ 对照根（茎）长×100
化合物e1-e25的除草活性数据列于表2中。
表2. 目标化合物的除草活性评价数据（抑制率，%，100 mg/L）
实例2 抑菌活性测定
待测化合物加丙酮溶解，配制成合适浓度的药液。无菌条件下，分别移取1 mL加入到100 mL 60 ℃左右灭菌的PDA培养基中， 混匀后，快速倒入灭菌的培养皿中，凝固后将供试菌菌饼移接至培养基上。每个处理重复三次，以含等量丙酮的灭菌培养基作对照。置于27℃恒温培养箱中培养， 待对照组菌落长至培养皿直径的3/4时，采用十字交叉法测量菌落直径，以其平均值作为菌落大小，并计算抑制率。目标化合物除草活性数据列于表3中。
表3. 目标化合物的抑菌活性评价数据（抑制率，%，100 mg/L）

Claims (3)

1.所述N-取代氨基香豆素衍生物结构如通式所示：
R选自乙烯基、甲基乙烯基、1-甲基丁基、2-甲基丙烯基、1-氯乙基、1-氯丙基、1-溴乙基、1-溴戊基、4-甲基苯基、4-乙基苯基、3-氯丙氧基、4-甲氧苯基、苯氧基、3-溴苯基、萘-1-基、萘-2-基、噻吩-2-基、噻吩-2-甲基、噻吩-3-基、呋喃-2-基、吡啶-4-基、2-氯吡啶-5-基、2-氯吡啶-3-基、3-氟吡啶-5-基、4-叔丁基苯基。
2.权利要求1所述化合物在防治植物病害方面的用途，所述的植物病害包括番茄灰霉病菌、苹果腐烂病菌。
3.权利要求1所述化合物在防治杂草方面的用途，所述的杂草包括单子叶植物马唐及双子叶植物反枝苋。
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102775373A (zh) * 2012-08-10 2012-11-14 青岛农业大学 一种n-取代氨基香豆素类化合物及其制备与应用
CN104592183A (zh) * 2015-01-15 2015-05-06 青岛农业大学 N-酰基-n-间氟苄基-8-氨基香豆素类化合物及其制备与除草用途

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CN104592183A (zh) * 2015-01-15 2015-05-06 青岛农业大学 N-酰基-n-间氟苄基-8-氨基香豆素类化合物及其制备与除草用途

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