CN117447430A - 一类香豆素衍生物及其制备和在防治植物病虫害方面的应用 - Google Patents
一类香豆素衍生物及其制备和在防治植物病虫害方面的应用 Download PDFInfo
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- CN117447430A CN117447430A CN202311549968.5A CN202311549968A CN117447430A CN 117447430 A CN117447430 A CN 117447430A CN 202311549968 A CN202311549968 A CN 202311549968A CN 117447430 A CN117447430 A CN 117447430A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
Landscapes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Insects & Arthropods (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
本发明涉及一类香豆素衍生物及其制备和在防治植物病虫害方面的应用，本发明首次发现香豆素衍生物I‑1~I‑12,Ⅱ‑1~Ⅱ‑2,Ⅲ‑1~Ⅲ‑3能很好地抑制烟草花叶病毒(TMV)和黄瓜枯萎，花生褐斑，苹果轮纹，小麦纹枯，玉米小斑，西瓜炭疽，水稻恶苗，番茄早疫，小麦赤霉，水稻稻瘟，辣椒疫霉，油菜菌核，黄瓜灰霉，水稻纹枯14种植物病菌，同时对粘虫，棉铃虫，玉米螟，草地贪菜蛾和蚊幼虫五种植物害虫有一定的杀灭作用。
Description
技术领域
本发明涉及一类香豆素衍生物及其制备和在防治植物病虫害方面的应用，属于农业防护技术领域。
背景技术
天然产物具有结构及作用位点独特、对环境友好等优点，对农药先导分子的发现和探索具有重要意义。香豆素是一类很有前途的天然生物活性杂环化合物，具有独特的物理和化学性质。含有香豆素框架的化合物具有广泛的药理学、生物学和生理学活性，这使得它们在医学、食品工业和农业中的应用非常重要。在常用杀菌剂中引入香豆母核可提高杀菌活性，如将香豆素引入传统的甲氧基丙烯酸酯杀菌剂结构中获得的杀菌剂丁香菌酯对黄瓜霜霉病和苹果树腐病具有优异的防治效果。因此，设计合成含有香豆素母核的衍生物成为一种开发新型农药的热点。
发明内容
在系统总结已有文献的基础上，本发明提供一类香豆素衍生物及其制备方法和在防治植物病虫害中的应用。
本发明的香豆素类化合物具体为I-1~I-12,Ⅱ-1~Ⅱ-2, Ⅲ-1~Ⅲ-3。R1, R2, R3为I-1~I-12结构所示官能团，R4为Ⅱ-1~Ⅱ-2结构所示官能团，R5为Ⅲ-1~Ⅲ-3结构所示官能团。
上述化学结构式I-1~I-12, Ⅱ-1~Ⅱ-2,Ⅲ-1~Ⅲ-3的合成方法如下：
化合物I-1~I-7按照方程式一所示的方法制备：首先以1,2二氯乙烷做溶剂，碳酸钾做碱，加入反应底物1或2，缓慢滴加相应的溴代物，加热回流反应12小时，生成产物I-1,I-2,I-4~I-7；6,7二羟基香豆素1在N,N二甲基甲酰胺做溶剂，碳酸钠做碱条件下，与碘甲烷反应得化合物3，化合物3再以1,2二氯乙烷为溶剂，碳酸钾为碱，与溴癸烷回流反应12小时得到I-3。R1为I-1, I-2, I-4，I-5结构所示基团，R2为I-6~I-7结构所示基团。
方程式一
化合物I-8~I-12, Ⅱ-1~Ⅱ-2,Ⅲ-1~Ⅲ-3按照方程式二所示的方法制备：首先以二氯甲烷做溶剂，吡啶做碱，加入相应的反应底物1,2,4,5，在搅拌条件下加入相应的酰氯化合物和催化剂4-二甲氨基吡啶室温反应8小时生成I-8~I-12, Ⅱ-1~Ⅱ-2,Ⅲ-1~Ⅲ-3。R1, R2, R3为I-8~I-11, Ⅱ-1~Ⅱ-2,Ⅲ-1~Ⅲ-3结构所示基团。
方程式二
本发明的香豆素衍生物I-1~I-12, Ⅱ-1~Ⅱ-2,Ⅲ-1~Ⅲ-3表现出很好的抗植物病毒和病菌活性，能很好地抑制烟草花叶病毒(TMV)和黄瓜枯萎，花生褐斑，苹果轮纹，小麦纹枯，玉米小斑，西瓜炭疽，水稻恶苗，番茄早疫，小麦赤霉，水稻稻瘟，辣椒疫霉，油菜菌核，黄瓜灰霉，水稻纹枯14种植物病菌，该类化合物同样表现出一定的杀虫活性。
具体实施方式
下述的实施例和生测试验结果可用来进一步说明本发明，但不意味着限制本发明。
实施例1：化合物I-1~I-7的合成
向100 mL单口瓶中加入反应底物1或2 (1.0 equiv)，DCE (50 mL),再加入碳酸钾(2.0 equiv)，搅拌10 min,缓慢滴加溴代物(2.0 equiv)，加热回流反应过夜。TLC监测反应结束后脱溶，二氯甲烷萃取，饱和食盐水洗涤有机相，无水硫酸钠干燥，抽滤，减压脱溶，柱层析得产物：
I-1黄色晶体，收率60%，熔点77−80 ºC。1H NMR (400 MHz, CDCl3)δ7.60 (d,J=9.4 Hz, 1H), 6.98 (s, 1H), 6.81 (s, 1H), 6.28 (d,J= 9.4 Hz, 1H), 5.80 (s,1H), 4.44 (dd,J= 11.8, 5.9 Hz, 1H), 1.78 (m, 2H), 1.39 (d,J= 6.0 Hz, 3H),1.01 (t,J= 7.4 Hz, 3H).13C NMR (100 MHz, CDCl3)δ161.6, 149.2, 148.5, 143.5,143.4, 113.6, 112.0, 111.0, 100.8, 28.9, 19.1, 9.7. HRMS C13H15O4 +[M+H]+ calcd.235.0965, found 235.0962.
I-2 橘黄色晶体，收率58%，熔点48−50 ºC。1H NMR (400 MHz, CDCl3)δ7.58 (d,J=9.4 Hz, 1H), 6.94 (d,J= 3.5 Hz, 1H), 6.82 (s, 1H), 6.25 (d,J= 9.5 Hz, 1H),4.35 (dd,J= 12.0, 6.0 Hz, 1H), 4.19 (dd,J= 11.2, 5.2 Hz, 1H), 1.86 – 1.61 (m,5H), 1.29 (t,J= 6.2 Hz, 3H), 1.25 (s, 2H), 1.01 (t,J= 7.4 Hz, 6H). 13C NMR(100 MHz, CDCl3)δ161.6, 153.3, 150.2, 145.4, 143.5, 114.1, 112.9, 111.3,102.6, 82.1, 81.0, 32.8, 32.7, 24.1, 23.8. HRMS C14H15O4 +[M+H]+cald. 247.0965,found 247.0961.
I-3 黄色晶体，收率37%，熔点64−65 ºC。1H NMR (400 MHz, CDCl3)δ7.61 (d,J=9.6 Hz, 1H), 6.85 (d,J= 8.5 Hz, 2H), 6.28 (d,J= 9.4 Hz, 1H), 4.02 (t,J= 6.8Hz, 2H), 3.93 (s, 2H), 1.91 – 1.82 (m, 2H), 1.47 (ddd,J= 12.2, 7.4, 5.3 Hz,3H), 1.27 (s, 12H), 0.88 (t,J= 6.4 Hz, 3H).13C NMR (100 MHz, CDCl3)δ161.5,153.3, 150.0, 145.8, 143.4, 113.4, 111.4, 109.5, 100.0, 69.7, 56.3, 31.9,29.6, 29.4, 29.3, 29.1, 25.9, 22.7, 14.1. HRMS C20H29O4 + [M+H]+calcd. 333.2060,found 333.2056.
I-4 淡黄色油状物，收率48%。1H NMR (400 MHz, CDCl3)δ7.58 (d,J= 9.4 Hz,1H), 6.94 (d,J= 3.5 Hz, 1H), 6.82 (s, 1H), 6.25 (d,J= 9.5 Hz, 1H), 4.35 (dd,J= 12.0, 6.0 Hz, 1H), 4.19 (dd,J= 11.2, 5.2 Hz, 1H), 1.85 – 1.73 (m, 2H), 1.70– 1.62 (m, 2H), 1.28 (dd,J= 13.3, 7.1 Hz, 6H), 1.01 (t,J= 7.4 Hz, 6H).13C NMR(100 MHz, CDCl3)δ161.6, 153.8, 150.6, 145.5, 143.4, 116.2, 115.8, 113.0,111.5, 78.6, 29.3, 29.2, 29.0, 29.0, 19.2, 19.0, 9.8, 9.7, 9.7. HRMS C17H23O4 +[M+H]+calcd. 291.1591, found 291.1586.
I-5 淡黄色晶体，收率60%，熔点88−90 ºC。1H NMR (400 MHz, CDCl3)δ7.58 (d,J=9.4 Hz, 1H), 6.94 (d,J= 3.5 Hz, 1H), 6.82 (s, 1H), 6.25 (d,J= 9.5 Hz, 1H),4.35 (dd,J= 12.0, 6.0 Hz, 1H), 4.19 (dd,J= 11.2, 5.2 Hz, 1H), 1.86–1.61 (m,5H), 1.28 (dd,J= 13.3, 7.1 Hz, 5H), 1.01 (t,J= 7.4 Hz, 6H).13C NMR (100 MHz,CDCl3)δ161.6, 153.3, 150.2, 145.4, 143.5, 114.1, 112.9, 111.3, 102.6, 82.1,81.0, 32.8, 32.7, 24.1, 23.8. HRMS C19H23O4 +[M+H]+cald. 315.1591, found315.1585.
I-6 淡黄色晶体，收率83%，熔点74−75 ºC。1HNMR (400 MHz, CDCl3)δ7.62 (d,J=9.4 Hz, 1H), 7.26 (s, 1H), 7.18 (s, 1H), 6.76 (s, 1H), 6.22 (d,J= 9.4 Hz,1H), 5.46 (s, 1H), 5.28 (t,J= 7.4 Hz, 1H), 4.59 (d,J= 6.4 Hz, 2H), 3.31 (d,J=7.3 Hz, 2H), 1.81 (s, 3H), 1.77 (s, 5H), 1.70 (s, 2H), 1.61 (s, 1H).13C NMR(100 MHz, CDCl3)δ161.7, 159.9, 154.4, 143.7, 138.6, 133.5, 127.8, 127.4,121.5, 119.0, 112.6, 111.8, 99.5, 65.6, 28.0, 25.9, 25.8, 18.4, 17.8. HRMSC18H23O3 +[M+H]+cald. 287.1642, found 287.1643.
I-7 黄色晶体，收率70%，熔点57−59oC。1H NMR (400 MHz, CDCl3)δ7.61 (d,J=9.4 Hz, 1H), 7.17 (s, 1H), 6.76 (s, 1H), 6.21 (d,J= 9.4 Hz, 1H), 5.30 – 5.19(m, 1H), 4.82 (dq,J= 8.0, 2.6 Hz, 1H), 3.27 (d,J= 7.3 Hz, 2H), 2.00 – 1.88(m, 4H), 1.83 – 1.77 (m, 2H), 1.75 (s, 3H), 1.70 (s, 3H), 1.69 – 1.63 (m,2H).13C NMR (100 MHz, CDCl3)δ161.7, 159.1, 154.3, 143.8, 133.2, 128.1, 127.5,121.7, 112.3, 100.2, 80.2, 32.8, 28.2, 25.8, 24.1, 17.8. HRMS C19H23O3 +[M+H]+cald. 299.1642, found 299.1637。
实施例2：香豆素衍生物I-8~I-12, Ⅱ-1~Ⅱ-2,Ⅲ-1~Ⅲ-3的合成
在50 mL小瓶中加入反应底物(1 equiv)、溶剂二氯甲烷(30 mL)、吡啶(2.0equiv)，搅拌条件下加入酰氯化合物(2.0 equiv)和DMAP (0.2 equiv),室温条件下反应3h，TLC监测反应结束后，二氯甲烷萃取，有机相饱和食盐水洗涤，无水硫酸钠干燥，柱层析得产物：
I-8 黄色固体，收率83%，熔点80−82 °C。1H NMR (400 MHz, CDCl3)δ7.67 (d,J=9.5 Hz, 1H), 7.31 (s, 1H), 7.07 (s, 1H), 6.36 (d,J= 9.5 Hz, 1H), 5.95 (s,1H), 5.22 (t,J= 7.2 Hz, 1H), 3.26 (d,J= 7.2 Hz, 2H), 2.24 (s, 3H), 2.02 (s,3H), 1.71 (d,J= 27.6 Hz, 6H).13C NMR (100 MHz, CDCl3)δ164.0, 161.6, 160.8,152.8, 151.6, 143.2, 134.2, 131.0, 128.3, 120.8, 116.7, 115.7, 114.4, 111.2,28.2, 27.8, 25.8, 20.7, 17.9. HRMS C19H21O4 +[M+H]+cald. 313.1434, found313.1430.
I-9 淡黄色晶体，收率53%，熔点43−45 °C。1H NMR (400 MHz, CDCl3)δ7.66 (d,J=9.5 Hz, 1H), 7.31 (s, 1H), 7.05 (s, 1H), 6.36 (d,J= 9.5 Hz, 1H), 5.27 – 5.18(m, 1H), 3.26 (d,J= 7.1 Hz, 2H), 2.50 (s, 2H), 1.73 (d,J= 31.2 Hz, 6H), 1.15(s, 9H). 13C NMR (100 MHz, CDCl3)δ170.0, 160.6, 152.8, 151.5, 143.0, 134.4,130.7, 128.4, 120.7, 116.8, 115.9, 110.9, 47.5, 31.1, 29.6, 28.1, 25.8, 17.9.HRMS C20H25O4 +[M+H]+cald. 329.1747, found 329.1743.
I-10 黄色油状物，收率91%。1H NMR (400 MHz, CDCl3)δ7.67 (d,J= 9.5 Hz,1H), 7.29 (d,J= 10.8 Hz, 1H), 7.01 (s, 1H), 6.36 (d,J= 9.5 Hz, 1H), 5.25 (t,J= 6.9 Hz, 1H), 3.24 (d,J= 7.0 Hz, 2H), 1.73 (d,J= 36.7 Hz, 6H), 1.40 (s, 9H).13C NMR (100 MHz, CDCl3)δ176.3, 160.7, 152.8, 151.8, 143.1, 134.5, 130.8,128.3, 120.6, 116.7, 115.9, 110.7, 39.4, 27.8, 27.1, 27.0, 25.7, 22.5, 17.9.HRMS C19H23O4 +[M+H]+cald. 315.1591, found 315.1587.
I-11 淡黄色油状物，收率52%。1H NMR (400 MHz, CDCl3)δ7.65 (d,J= 9.6 Hz,1H), 7.32 (d,J= 7.2 Hz, 2H), 7.28 (d,J= 3.4 Hz, 2H), 7.26 (t,J= 4.1 Hz, 2H),6.95 (s, 1H), 6.37 (d,J= 9.5 Hz, 1H), 5.18 (t,J= 7.2 Hz, 1H), 3.14 (d,J= 7.2Hz, 2H), 3.09 (t,J= 7.6 Hz, 2H), 2.94 (t,J= 7.5 Hz, 2H), 1.76 (s, 3H), 1.66(s, 3H). 13C NMR (100 MHz, CDCl3)δ170.7, 160.6, 152.8, 151.3, 143.0, 139.8,134.4, 130.7, 128.7, 128.4, 126.7, 120.6, 116.9, 116.0, 111.0, 35.8, 30.9,28.0, 25.8, 17.9. HRMS C23H23O4 +[M+H]+cald. 363.1591, found 363.1586.
I-12 白色固体，收率17%，熔点132−141 ℃。1H NMR (400 MHz, CDCl3)δ7.83 (d,J= 7.9 Hz, 1H), 7.54 (d,J= 8.1 Hz, 1H), 7.34 – 7.29 (m, 1H), 7.26 (s, 1H),5.68 (s, 1H), 4.14 (t,J= 6.4 Hz, 1H), 1.94 – 1.84 (m, 2H), 1.62 – 1.50 (m,4H), 1.02 (t,J= 7.4 Hz, 2H). 13C NMR (100 MHz, CDCl3)δ164.7, 163.1, 153.5,132.3, 123.8, 123.1, 116.8, 116.2, 91.2, 81.8, 32.7, 24.1. HRMS C14H15O3 +[M+H]+cald. 231.1016, found 231.1012.
Ⅱ-1 淡黄色油状物，收率21%。1H NMR (400 MHz, CDCl3)δ7.59 (d,J= 9.5 Hz,1H), 7.15 (s, 1H), 6.79 (s, 1H), 6.23 (d,J= 9.5 Hz, 1H), 4.99 (t,J= 5.2 Hz,1H), 3.17 (dd,J= 17.0, 4.7 Hz, 1H), 2.80 (dd,J= 17.0, 5.6 Hz, 1H), 1.37 (s,6H), 1.16 (s, 9H).13C NMR (100 MHz, CDCl3)δ177.7, 161.3, 156.4, 154.2, 143.2,128.5, 115.9, 113.3, 112.8, 104.7, 70.1, 38.9, 27.7, 27.0, 27.0, 25.2, 22.7.HRMS C19H23O5 +[M+H]+cald. 331.1540, found 331.1538.
Ⅱ-2 淡黄色油状物，收率32%。1H NMR (400 MHz, CDCl3)δ7.59 (d,J= 9.5 Hz,1H), 7.16 (s, 1H), 6.78 (s, 1H), 6.23 (d,J= 9.5 Hz, 1H), 5.03 (t,J= 5.0 Hz,1H), 3.20 (dd,J= 17.1, 4.6 Hz, 1H), 2.86 (dd,J= 17.1, 5.1 Hz, 1H), 2.24 (s,1H), 2.21 (d,J= 1.3 Hz, 1H), 1.38 (d,J= 8.1 Hz, 6H), 0.98 (s, 9H).13C NMR (100MHz, CDCl3)δ171.7, 161.3, 156.4, 154.2,149.0, 143.2,136.7, 128.6,124.0,115.8, 113.3, 112.9, 104.7, 70.1, 47.9, 30.8, 29.6, 29.6, 27.8, 25.1, 23.1.HRMS C20H25O5 +[M+H]+cald. 345.1697, found 345.1693.
Ⅲ-1 黄色油状物，收率73%。1H NMR (400 MHz, CDCl3)δ7.58 (d,J= 9.5 Hz,1H), 7.28 (s, 1H), 7.25 (s, 1H), 7.20 (d,J= 7.4 Hz, 1H), 7.18 (s, 1H), 7.13(d,J= 7.3 Hz, 2H), 6.69 (s, 1H), 6.18 (d,J= 9.5 Hz, 1H), 4.99 (dd,J= 9.5, 7.4Hz, 1H), 3.14 (dd,J= 16.1, 9.7 Hz, 1H), 3.02 (dd,J= 16.4, 7.2 Hz, 1H), 2.83(t,J= 7.6 Hz, 2H), 2.53 (dd,J= 11.1, 4.8 Hz, 2H), 1.50 (d,J= 12.5 Hz, 6H).13CNMR (100 MHz, CDCl3)δ172.0, 163.3, 161.4, 155.7, 143.8, 140.3, 128.5, 128.3,126.3, 124.5, 123.3, 112.7, 112.2, 97.8, 88.7, 82.3, 36.8, 31.0, 29.4, 22.0,21.1. HRMS C23H23O5 +[M+H]+cald. 379.1514, found 379.1536.
Ⅲ-2 乳黄色固体，收率27%，熔点130−131 ºC。1H NMR (400 MHz, CDCl3)δ7.60(d,J= 9.5 Hz, 1H), 7.27 (s, 1H), 6.73 (s, 1H), 6.22 (d,J= 9.5 Hz, 1H), 5.09 –4.98 (m, 1H), 3.23 (qd,J= 16.0, 8.6 Hz, 2H), 2.08 (s, 2H), 1.56 (d,J= 8.6 Hz,6H), 0.98 (s, 9H).13C NMR (100 MHz, CDCl3)δ171.6, 163.4, 161.5, 155.8, 143.7,142.2, 142.1, 124.5, 123.2, 112.7, 112.3, 97.9, 88.8, 81.9, 49.2, 30.9, 29.6,22.1, 21.2. HRMS C20H25O5 +[M+H]+cald. 345.1697, found 345.1693.
Ⅲ-3 黄色晶体，收率58%，熔点126−128 ºC。1H NMR (400 MHz, CDCl3)δ7.60 (d,J= 9.5 Hz, 1H), 7.22 (s, 1H), 6.74 (s, 1H), 6.21 (dd,J= 9.5, 2.5 Hz, 1H), 5.56(d,J= 1.2 Hz, 1H), 5.14 (dd,J= 9.3, 8.0 Hz, 1H), 3.34 – 3.15 (m, 2H), 2.10(s, 3H), 1.85 (s, 3H), 1.57 (d,J= 23.2 Hz, 6H).13C NMR (100 MHz, CDCl3)δ165.9,163.4, 161.4, 156.6, 155.8, 143.7, 124.6, 123.3, 116.9, 112.7, 112.2, 97.9,88.9, 81.3, 29.6, 27.4, 22.3, 21.3, 20.1。
实施例3：抗烟草花叶病毒活性的测定，测定程序如下：
1、病毒提纯及浓度测定：
病毒提纯及浓度测定参照南开大学元素所生测室编制烟草花叶病毒SOP规范执行。病毒粗提液经2次聚乙二醇离心处理后，测定浓度，4 °C冷藏备用。
2、化合物溶液配制：
称量后，原药加入DMF溶解，制得1 × 105 µg/mL母液，后用含1‰吐温80水溶液稀释至所需浓度。
3、活体保护作用：
选长势均匀一致的3–5叶期珊西烟，全株喷雾施药，每处理3次重复，并设1‰吐温80水溶液对照。24 h后，叶面撒布金刚砂(500目)，用毛笔蘸取病毒液，在全叶面沿支脉方向轻擦2次，叶片下方用手掌支撑，病毒浓度10 µg/mL，接种后用流水冲洗。3 d后记录病斑数，计算防效。
4、活体治疗作用：
选长势均匀一致的3–5叶期珊西烟，用毛笔全叶接种病毒，病毒浓度为10 µg/mL，接种后用流水冲洗。叶面收干后，全株喷雾施药，每处理3次重复，并设1‰吐温80水溶液对照。3 d后记录病斑数，计算防效。
5、活体钝化作用：
选长势均匀一致的3–5叶期珊西烟，将药剂与等体积的病毒汁液混合钝化30 min后，摩擦接种，病毒浓度20 µg/mL，接种后即用流水冲洗，重复3次，设1‰吐温80水溶液对照。3 d后数病斑数，计算结果。
抑制率(%) = [(对照枯斑数−处理枯斑数)/对照枯斑数] × 100%。
首先在处理剂量500 µg/mL条件下进行所有化合物的抗烟草花叶病毒活体钝化活性测试，相对抑制率大于40%的化合物进一步进行处理剂量500 µg/mL条件下的活体治疗和活性保护活性测试以及处理剂量100 µg/mL条件下的抗烟草花叶病毒活体钝化、活体治疗、活体保护活性测试。阳性对照为商品化抗植物病毒药剂病毒唑。
表1 香豆素衍生物I-1~I-12, Ⅱ-1~Ⅱ-2,Ⅲ-1~Ⅲ-3的抗烟草花叶病毒（TMV）活性测试结果：
从表1数据可见，香豆素类化合物大部分具有良好的抗TMV活性，其中在500 µg/mL情况下，化合物I-1, I-4, I-5, I-7, I-10, I-11, Ⅲ-1和Ⅲ-2的活性都优于病毒唑，具有极大的开发价值。呋喃环香豆素衍生物(Ⅲ-1~Ⅲ-3)抗TMV活性高于吡喃环香豆素衍生物(Ⅱ-1~Ⅱ-2)。
实施例4：抗菌活性测试，测定程序如下：
离体杀菌测试，菌体生长速率测定法(平皿法)：将一定量药剂溶解在适量丙酮内，然后用含有200 µg/mL乳化剂水溶液稀释至所需浓度，然后各吸取1 mL药液注入培养皿内，再分别加入9 mL培养基，摇匀后制成50 µg/mL的含药平板，以添加1 mL灭菌水的平板做空白对照。用直径4 mm的打孔器沿菌丝外缘切取菌盘，移至含药平板上。每处理重复三次。将培养皿放在24±1 ℃恒温培养箱内培养。48小时后调查各处理菌盘扩展直径，求平均值，与空白对照比较计算相对抑菌率；
表2 香豆素衍生物I-1~I-12, Ⅱ-1~Ⅱ-2,Ⅲ-1~Ⅲ-3的抗植物病菌活性测试结果：
从表2可以看出，香豆素衍生物在测试浓度为50 μg/mL的条件下对14种被测试菌都表现出广谱的优异抑制活性。大部分化合物对番茄早疫病菌的抑制率均优于百菌清和多菌灵，Ⅰ-1对番茄早疫的抑制效果为85%，与市售杀菌剂嘧菌胺相当。化合物Ⅰ-8和Ⅲ-2对水稻稻瘟具有较好的抑制活性，其抑菌活性均高于3个商业对照。Ⅰ-9对花生褐斑的抑制率远优于百菌清和多菌灵，活性与嘧菌胺相近。化合物I-2对玉米小斑的抑制活性高于嘧菌胺。大部分化合物对油菜菌核具有良好的抑菌活性，化合物Ⅰ-1和Ⅰ-8的抑菌率均在90%以上。化合物Ⅰ-2对大多数真菌有良好的抑制作用，具有极大的开发价值。
实施例5：杀虫活性测试方法
1.杀粘虫(Mythimna separata Walker)、棉铃虫(Helicoverpa armigera) 、草地贪夜蛾(Spodoptera frugiperda)和玉米螟(Ostrinia nubilalis Hubner)的活性测试：各种虫均为室内饲养的正常群体。采用浸叶法，用丙酮溶解原药配制成原液，将玉米叶浸渍于丙酮配制的原液中，待药液干后再接入10头3龄幼虫，主要体现为胃毒、触杀作用，同时观察幼虫取食的现象。三天后检查死亡率。每实验重复二或三次，取平均值。
2. 杀蚊幼虫活性测试：蚊幼虫为尖音库蚊淡色亚种(Culex pipiens pallens)，
且为室内饲养的正常群体。用丙酮溶解原药配制成原液，再用水将原液稀释至一定浓度配置成饲养液。将10头3龄库蚊幼虫放置于饲养液中，三天后检查死亡率。以含有1mL试验溶剂水溶液作为空白对照。每实验重复三次，取平均值。
表3 香豆素衍生物I-1~I-12, Ⅱ-1~Ⅱ-2,Ⅲ-1~Ⅲ-3的杀虫活性测试结果：
从表3可以看出，大部分香豆素衍生物同样表现出一定程度的杀虫活性。在600 μg/mL浓度下，I-8对草地贪菜蛾具有良好的致死活性，致死率为67%，高于苦参碱。
Claims (6)
1.一类香豆素衍生物，具体为I-1~I-12, Ⅱ-1~Ⅱ-2,Ⅲ-1~Ⅲ-3中的一种；图中R1, R2,R3为I-1~I-12结构所示官能团，R4为Ⅱ-1~Ⅱ-2结构所示官能团，R5为Ⅲ-1~Ⅲ-3结构所示官能团；
。
2.权利要求1中I-1~I-12, Ⅱ-1~Ⅱ-2, Ⅲ-1~Ⅲ-3的制备方法：
化合物I-1~I-7按照方程式一所示的方法制备：首先以1,2二氯乙烷做溶剂，碳酸钾做碱，加入反应底物1或2，缓慢滴加相应的溴代物，加热回流反应12小时，生成产物I-1, I-2,I-4~I-7；6,7二羟基香豆素1在N,N二甲基甲酰胺做溶剂，碳酸钠做碱条件下，与碘甲烷反应得化合物3，化合物3再以1,2二氯乙烷为溶剂，碳酸钾为碱，与溴癸烷回流反应12小时得到I-3；R1为I-1, I-2, I-4, I-5结构所示基团，R2为I-6~I-7结构所示基团；
方程式一。
3.化合物I-8~I-12, Ⅱ-1~Ⅱ-2, Ⅲ-1~Ⅲ-3按照方程式二所示的方法制备：首先以二氯甲烷做溶剂，吡啶做碱，加入相应的反应底物1, 2, 4, 5，在搅拌条件下加入相应的酰氯化合物和催化剂4-二甲氨基吡啶室温反应8小时生成I-8~I-12, Ⅱ-1~Ⅱ-2, Ⅲ-1~Ⅲ-3；R1, R2, R3为I-8~I-11, Ⅱ-1~Ⅱ-2, Ⅲ-1~Ⅲ-3结构所示基团；
方程式二。
4.权利要求1所述的香豆素衍生物I-1~I-12, Ⅱ-1~Ⅱ-2, Ⅲ-1~Ⅲ-3在防治烟草花叶病毒病方面的应用。
5.权利要求1所述的香豆素衍生物I-1~I-12, Ⅱ-1~Ⅱ-2, Ⅲ-1~Ⅲ-3在防治植物病菌病方面的应用，其特征在于所述的植物病菌病为黄瓜枯萎病，花生褐斑病，苹果轮纹病，小麦纹枯病，玉米小斑病，西瓜炭疽病，水稻恶苗病，番茄早疫病，小麦赤霉病，水稻稻瘟病，辣椒疫霉病，油菜菌核病，黄瓜灰霉病或水稻纹枯病。
6.权利要求1所述的香豆素衍生物I-1~I-12, Ⅱ-1~Ⅱ-2, Ⅲ-1~Ⅲ-3在防治植物害虫方面的应用，其特征在于所述的植物害虫为粘虫，棉铃虫，玉米螟，草地贪菜蛾和蚊幼虫五种害虫。
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