CN113004148A - 一种白藜芦醇衍生物及其制备方法和应用 - Google Patents

一种白藜芦醇衍生物及其制备方法和应用 Download PDF

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CN113004148A
CN113004148A CN202110239422.4A CN202110239422A CN113004148A CN 113004148 A CN113004148 A CN 113004148A CN 202110239422 A CN202110239422 A CN 202110239422A CN 113004148 A CN113004148 A CN 113004148A
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resveratrol
resveratrol derivative
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acyl chloride
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CN113004148B (zh
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于秀玲
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Linyi University
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Abstract

本发明属于农药技术领域，具体涉及一种白藜芦醇衍生物及其制备方法和应用。本发明提供了一种白藜芦醇衍生物，其结构式如式Ⅰ或式Ⅱ所示，其中，R1和R2为杂环基、取代杂环基、芳基、取代芳基、支链烃基或环烷基。

Description

一种白藜芦醇衍生物及其制备方法和应用
技术领域
本发明属于农药技术领域，具体涉及一种白藜芦醇衍生物及其制备方法和应用。
背景技术
植物病毒种类繁多，分布十分广泛，植物病毒病有“植物癌症”之称，在农业生产中病毒病是仅次于真菌的第二大类植物病害。绝大部分经济作物都因受到植物病毒的危害不同程度的减产或品质下降。植物病毒在植物细胞中绝对寄生，其复制所需的物质、能量、场所完全由寄主细胞提供，对寄主植物细胞具有高度依赖性。由于植物没有动物那样完整的免疫***，因而植物病毒病的防治一直是植物病害防治中的一大难题。
烟草花叶病毒(Tobacco Mosaic Virus,TMV)是一种感染性强、危害极大的植物病毒。寄主范围非常广泛，除危害烟草外，还能侵染番茄、茄子、马铃薯、辣椒、龙葵等茄科植物，此外还能侵染葫芦科、蓼科、十字花科、豆科、黎科、菊科等30个科的300多种植物。对于如何防治烟草花叶病毒的侵害一直是科学家们关注的热点。
Figure BDA0002961587500000011
目前有效而令人满意的植物病毒抑制剂还不多，治疗性药剂更少，所报道的药剂在田间实际应用时其防效大多在60％以下。病毒唑(ribavirin)，被广泛的用于防治TMV造成的病害，但是该药物在500μg/mL浓度下对TMV的抑制率不到50％。宁南霉素(ningnanmycin)仅有预防效果，治疗效果差。NK-007还处于产业化开发阶段。到目前为止，一旦植物感染烟草花叶病毒，仍没有一种化学农药能够彻底将其治愈。因此，开发更加实用高效的植物病毒抑制剂仍是一项非常艰巨的任务。
天然活性物质具有结构和生物活性的多样性、独特性和新颖性，一向是新药创制的重要来源。目前人们已经在野生植物资源中发现了很多具有杀虫、杀菌、抗病毒和除草作用的天然活性物质，开发利用这些野生植物资源，合成植物源杀虫剂、杀菌剂、抗病毒剂和除草剂等生物农药具有较大的发展潜力和经济价值。天然来源的农药成为农药研究开发的热点。这些农药天然活性物质是良好的先导化合物，根据所研究的天然产物的性质及其不足有针对性地、个性化的修饰和改造，量体裁衣式地弥补和完善活性或成药性的不足是摆在当今农药化学工作者面前最为重要的科研课题。
白藜芦醇(Resveratrol)，化学名称为3,4′,5-三羟基-1,2-二苯乙烯(亦称芪三酚)，是含有芪类结构的非黄酮类天然多酚化合物。
Figure BDA0002961587500000021
白藜芦醇是许多植物受到真菌、病毒感染、紫外照射或病理状况下产生的一种植物抗毒素，可以提高植物抵抗病原体的能力，对植物起保护作用。但白藜芦醇的成药性差，不能直接作为药物开发。
发明内容
有鉴于此，本发明提供了一种白藜芦醇衍生物。本发明通过对白藜芦醇进行改性引入其它基团提高了白藜芦醇衍生物的成药性。本发明提供的白藜芦醇衍生物中部分对烟草花叶病毒具有较好的抑制效果，部分具有较好的杀虫效果。
为了解决上述技术问题，本发明提供了一种白藜芦醇衍生物，其结构式如式Ⅰ或式Ⅱ所示:
Figure BDA0002961587500000022
其中，R1和R2为杂环基、取代杂环基、芳基、取代芳基、支链烃基或环烷基。
优选的，所述R1包括
Figure BDA0002961587500000023
优选的，所述R1包括
Figure BDA0002961587500000024
R'包括H3CO-、F-、Cl-、Br-、O2N-、CH3-、(CH3)3C-或F3CO-。
优选的，所述R1包括CH3-CH2-、CH3-CH2-CH2-或
Figure BDA0002961587500000025
优选的，所述R2包括
Figure BDA0002961587500000031
优选的，所述R2包括
Figure BDA0002961587500000032
R”包括F-、Cl-、Br-、O2N-、CH3-或(CH3)3C-。
优选的，所述R2包括CH3-CH2-、CH2＝CH-、
Figure BDA0002961587500000033
本发明还提供了上述技术方案所述白藜芦醇衍生物的制备方法，包括以下步骤：
将白藜芦醇、二氯甲烷、三乙胺和酰氯基化合物混合，进行酯化反应，得到所述白藜芦醇衍生物，所述酰氯基化合物包括酰氯或磺酰氯，当所述酰氯基化合物为磺酰氯时，得到式I所示结构的白藜芦醇衍生物，当所述酰氯基化合物为酰氯时，得到式II所示结构的白藜芦醇衍生物；
所述酰氯包括杂环基取代酰氯、取代杂环基取代酰氯、芳基取代酰氯、取代芳基取代酰氯、支链烃基取代酰氯或环烷基取代酰氯；
所述磺酰氯包括杂环取代磺酰氯、取代杂环取代磺酰氯、芳基取代磺酰氯、取代芳基取代磺酰氯、支链烃基取代磺酰氯或环烷基取代磺酰氯。
本发明还提供了上述技术方案所述白藜芦醇衍生物或上述技术方案所述制备方法制备得到的白藜芦醇衍生物在植物病虫害防治中的应用。
优选的，当R1为
Figure BDA0002961587500000034
CH3-CH2-或
Figure BDA0002961587500000035
时，所述应用为式Ⅰ所示结构的白藜芦醇衍生物在抑制烟草花叶病毒中的应用；
当R2为
Figure BDA0002961587500000036
CH2＝CH-、CH3-CH2-、
Figure BDA0002961587500000037
时，所述应用为式Ⅱ所示结构的白藜芦醇衍生物在抑制烟草花叶病毒中的应用。
优选的，当R1为
Figure BDA0002961587500000038
CH3-CH2-CH2-或
Figure BDA0002961587500000039
时，所述应用为式Ⅰ所示结构的白藜芦醇衍生物在植物杀虫中的应用；
当R2为
Figure BDA0002961587500000041
CH3-CH2-、CH2＝CH-、
Figure BDA0002961587500000042
时，所述应用为式Ⅱ所示结构的白藜芦醇衍生物在植物杀虫中的应用。
优选的，所述应用为在植物抗菌中的应用。
本发明提供了一种白藜芦醇衍生物，其结构式如式Ⅰ或式Ⅱ所示:
Figure BDA0002961587500000043
其中，R1和R2为杂环基、取代杂环基、芳基、取代芳基、支链烃基或环烷基。在本发明中，当R1为
Figure BDA0002961587500000044
CH3-CH2-或
Figure BDA0002961587500000045
时，式Ⅰ所示结构的白藜芦醇衍生物对烟草花叶病毒具有较好的抑制效果；当花叶病毒的浓度为500μg/mL时，所述白藜芦醇衍生物对花叶病毒的活体钝化抑制率为34.5～61.9％。当R2为
Figure BDA0002961587500000046
CH2＝CH-、CH3-CH2-、
Figure BDA0002961587500000047
时，式Ⅱ所示结构的白藜芦醇衍生物对烟草花叶病毒具有较好的抑制效果；所述白藜芦醇衍生物对花叶病毒的活体钝化抑制率为49.8～57.2％。在本发明中，当R1为
Figure BDA0002961587500000048
CH3-CH2-CH2-或
Figure BDA0002961587500000049
时，式Ⅰ所示结构的白藜芦醇衍生物具有良好的植物杀虫性；当R2为
Figure BDA0002961587500000051
CH3-CH2-、CH2＝CH-、
Figure BDA0002961587500000052
时，式Ⅱ所示结构的白藜芦醇衍生物具有良好的植物杀虫性。
具体实施方式
本发明提供了一种白藜芦醇衍生物，其结构式如式Ⅰ或式Ⅱ所示:
Figure BDA0002961587500000053
其中，R1和R2为杂环基、取代杂环基、芳基、取代芳基、支链烃基或环烷基。
在本发明中，当R1为杂环基时，所述杂环基优选包括
Figure BDA0002961587500000054
所述白藜芦醇衍生物优选具有式I-1所示结构：
Figure BDA0002961587500000055
当R1为取代芳基时，所述取代芳基的结构式优选包括
Figure BDA0002961587500000056
R'优选包括H3CO-、F-、Cl-、Br-、O2N-、CH3-、(CH3)3C-或F3CO-；所述取代芳基的结构式更优选为
Figure BDA0002961587500000057
Figure BDA0002961587500000058
所述白藜芦醇衍生物优选具有式I-2～I-10所示结构的化合物：
Figure BDA0002961587500000061
当R1为支链烃基或环烷基时，所述支链烃基优选包括CH3-CH2-或CH3-CH2-CH2-，所述白藜芦醇衍生物优选具有式I-11或I-12所示结构：
Figure BDA0002961587500000062
所述环烷基优选包括
Figure BDA0002961587500000063
所述白藜芦醇衍生物优选具有式I-13所示结构的化合物：
Figure BDA0002961587500000071
在本发明中，当R2为杂环基时，所述杂环基优选包括
Figure BDA0002961587500000072
更优选为
Figure BDA0002961587500000073
所述白藜芦醇衍生物优选具有式Ⅱ-1～Ⅱ-4所示结构：
Figure BDA0002961587500000074
当R2为取代芳基时，所述取代芳基的结构式优选包括
Figure BDA0002961587500000075
R”优选包括F-、Cl-、Br-、O2N-、CH3-或(CH3)3C-；所述取代芳基的结构式更优选为
Figure BDA0002961587500000076
所述白藜芦醇衍生物优选具有式Ⅱ-5～Ⅱ-14所示结构：
Figure BDA0002961587500000081
当R2为支链烃基或环烷基时，所述支链烃基优选包括CH3-CH2-或CH2＝CH-；所述白藜芦醇衍生物优选具有式Ⅱ-15～Ⅱ-16所示结构：
Figure BDA0002961587500000082
所述环烷基优选包括
Figure BDA0002961587500000083
所述白藜芦醇衍生物优选具有式Ⅱ-17～Ⅱ-18所示结构：
Figure BDA0002961587500000084
本发明还提供了上述技术方案所述白藜芦醇衍生物的制备方法，包括以下步骤：
将白藜芦醇、二氯甲烷、三乙胺和酰氯基化合物混合，进行酯化反应，得到所述白藜芦醇衍生物，所述酰氯基化合物包括酰氯或磺酰氯，当所述酰氯基化合物为磺酰氯时，得到式I所示结构的白藜芦醇衍生物，当所述酰氯基化合物为酰氯时，得到式II所示结构的白藜芦醇衍生物；
所述酰氯包括杂环基取代酰氯、取代杂环基取代酰氯、芳基取代酰氯、取代芳基取代酰氯、支链烃基取代酰氯或环烷基取代酰氯；
所述磺酰氯包括杂环取代磺酰氯、取代杂环取代磺酰氯、芳基取代磺酰氯、取代芳基取代磺酰氯、支链烃基取代磺酰氯或环烷基取代磺酰氯。
本发明将白藜芦醇、二氯甲烷、三乙胺和酰氯基化合物混合，进行酯化反应，得到所述白藜芦醇衍生物，所述酰氯基化合物包括酰氯或磺酰氯，当所述酰氯基化合物为磺酰氯时，得到式I所示结构的白藜芦醇衍生物，当所述酰氯基化合物为酰氯时，得到式II所示结构的白藜芦醇衍生物。在本发明中，所述混合优选包括以下步骤：
将白藜芦醇和二氯甲烷进行第一混合，得到白藜芦醇溶液；
将所述白藜芦醇溶液和三乙胺进行第二混合，得到混合溶液；
将酰氯或磺酰氯滴加至所述混合溶液中。
本发明将白藜芦醇和二氯甲烷进行第一混合，得到白藜芦醇溶液。在本发明中，所述二氯甲烷作为溶剂，所述二氯甲烷优选为无水二氯甲烷。本发明对所述二氯甲烷的用量无特殊限定，只要能够是白藜芦醇完全溶解即可。本发明对所述第一混合无特殊限定，只要能够混合均匀即可。
得到白藜芦醇溶液后，本发明将所述白藜芦醇溶液和三乙胺进行第二混合，得到混合溶液。在本发明中，所述三乙胺作为缚酸剂能够促进酯化反应的进行。在本发明中，所述白藜芦醇的和三乙胺的摩尔比优选为1:4～5。本发明对所述第二混合无特殊限定，只要能够混合均匀即可。
得到混合溶液后，本发明将酰氯或磺酰氯滴加至所述混合溶液中。在本发明中，所述白藜芦醇和酰氯的摩尔比优选为1:4～5。在本发明中，所述白藜芦醇和磺酰氯的摩尔比优选为1:4～5。在本发明中，所述滴加优选在搅拌的条件下进行，本发明对所述搅拌的转速无特殊限定，只要能够使滴加的酰氯或磺酰氯与白藜芦醇充分混合即可。在本发明中，所述滴加优选在冰水浴中进行，避免酯化反应太迅速。在本发明中，所述滴加的速率优选为28～32滴/min，更优选为30滴/min。本发明对所述滴加的时间无特殊限定，只要能够滴加完即可。
在本发明中，所述酯化反应的温度优选为室温，更优选25～30℃。本发明优选利用TLC检测酯化反应是否完成。
在本发明中，所述磺酰氯包括杂环基取代磺酰氯、取代杂环基取代磺酰氯、芳基取代磺酰氯、取代芳基取代磺酰氯、支链烃基取代磺酰氯或环烷基取代磺酰氯，优选为杂环取代磺酰氯、芳基取代磺酰氯、取代芳基取代磺酰氯、支链烃基取代磺酰氯或环烷基取代磺酰氯。在本发明中，所述杂环基取代磺酰氯优选包括
Figure BDA0002961587500000101
所述取代芳基取代磺酰氯优选包括
Figure BDA0002961587500000102
Figure BDA0002961587500000103
Figure BDA0002961587500000104
所述支链烃基取代磺酰氯优选包括
Figure BDA0002961587500000105
Figure BDA0002961587500000106
所述环烷基取代磺酰氯优选包括
Figure BDA0002961587500000107
在本发明中，所述酰氯包括杂环取代酰氯、取代杂环取代酰氯、芳基取代酰氯、取代芳基取代酰氯、支链烃基取代酰氯或环烷基取代酰氯，优选为杂环取代酰氯、芳基取代酰氯、取代芳基取代酰氯、支链烃基取代酰氯或环烷基取代酰氯。在本发明中，所述杂环取代酰氯优选包括
Figure BDA0002961587500000108
所述取代芳基取代酰氯优选包括
Figure BDA0002961587500000111
Figure BDA0002961587500000112
所述支链烃基取代酰氯优选包括
Figure BDA0002961587500000113
所述环烷基取代酰氯优选包括
Figure BDA0002961587500000114
Figure BDA0002961587500000115
当酯化反应完成后，本发明还优选包括：
将酯化反应产物和水混合后进行分液，得到第一有机相和第一水相；
利用二氯甲烷对所述第一水相萃取两次，两次萃取得到的有机相合并得到第二有机相；
将所述第一有机相和第二有机相合并后，依次进行洗涤、干燥、抽滤和重结晶，得到所述白藜芦醇衍生物。
本发明对所述分液、萃取均无特殊限定，采用本领域技术人员熟知的方式即可。在本发明中，所述洗涤用溶剂优选为饱和食盐水；所述干燥用干燥剂优选为无水硫酸钠。本发明对所述抽滤无特殊限定，采用本领域技术人员熟知的方式即可。在本发明中，所述重结晶用溶剂优选为乙酸乙酯和石油醚的混合物；所述乙酸乙酯和石油醚的体积比优选为1:20～80，更优选为1:50。
本发明还提供了上述技术方案所述白藜芦醇衍生物或上述技术方案所述制备方法制备得到的白藜芦醇衍生物在植物病虫害防治中的应用。在本发明中，所述应用包括在抑制烟草花叶病毒中的应用、在植物抗菌中的应用或在植物杀虫中的应用。
在本发明中，当R1为
Figure BDA0002961587500000121
CH3-CH2-或
Figure BDA0002961587500000122
时，所述应用为式Ⅰ所示结构的白藜芦醇衍生物在抑制烟草花叶病毒中的应用；当R2为
Figure BDA0002961587500000123
Figure BDA0002961587500000124
CH2＝CH-、CH3-CH2-、
Figure BDA0002961587500000125
时，所述应用为式Ⅱ所示结构的白藜芦醇衍生物在抑制烟草花叶病毒中的应用。
在本发明中，当R1为
Figure BDA0002961587500000126
CH3-CH2-CH2-或
Figure BDA0002961587500000127
时，结所述应用为式Ⅰ所示结构的白藜芦醇衍生物在植物杀虫中的应用；当R2为
Figure BDA0002961587500000128
Figure BDA0002961587500000129
CH3-CH2-、CH2＝CH-、
Figure BDA00029615875000001210
时，所述应用为式Ⅱ所示结构的白藜芦醇衍生物在植物杀虫中的应用。在本发明中，所述杀虫的害虫优选包括东方粘虫、棉铃虫、玉米螟或蚊幼虫。
在本发明中，所述抗菌的菌种优选为真菌，所述真菌优选包括番茄早疫、小麦赤霉、马铃薯晚疫、辣椒疫霉、油菜菌核、黄瓜灰霉、水稻纹枯、黄瓜枯萎、花生褐斑、苹果轮纹、水稻恶苗、玉米小斑、西瓜炭疽或小麦纹枯。
在本发明中，所述应用前优选包括：将白藜芦醇衍生物和溶剂进行混合，得到白藜芦醇衍生物溶液。在本发明中，所述溶剂优选包括N，N-二甲基甲酰胺和吐温溶液。在本发明中，所述混合优选包括以下步骤：
将白藜芦醇和N，N-二甲基甲酰胺进行第三混合，得到白藜芦醇衍生物母液；
将所述白藜芦醇衍生物母液和质量浓度为1‰的吐温-80的水溶液进行第四混合，得到所述白藜芦醇衍生物溶液。
本发明对所述第三混合和第四混合无特殊限定，只要能够混合均匀即可。
在本发明中，当应用为在抑制烟草花叶病毒中的应用时，所述白藜芦醇衍生物溶液的浓度优选为100～500μg/mL；当应用为在植物抗菌中的应用时，所述白藜芦醇衍生物溶液的浓度为50μg/mL；当应用为在植物杀虫中的应用时，所述白藜芦醇衍生物溶液的浓度优选为100～600μg/mL。
本发明通过白藜芦醇进行改性，引入酰基或磺酰基，提高了白藜芦醇的稳定性，且白藜芦醇衍生物对烟草花叶病毒表现出很好的抗病毒活性，还表现出良好的杀菌活性和杀虫活性。
为了进一步说明本发明，下面结合实施例对本发明提供的技术方案进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1
将0.1g白藜芦醇(0.438mmol)和20mL二氯甲烷(含水率为0％)混合，得到白藜芦醇溶液；
将所述白藜芦醇溶液和0.22g三乙胺(2.19mmol)混合，得到混合溶液；
将所述混合溶液置于冰水浴中搅拌，将0.31g苯甲酰氯(2.19mmol)按照30滴/min的滴加速率滴加至混合溶液中，在室温条件下进行酯化反应；将酯化反应的产物和水混合进行分液，得到第一有机相和第一水相；利用二氯甲烷对第一水相进行萃取两次，两次萃取得到的有机相合并得到第二有机相；将第一有机相和第二有机相混合后，利用饱和食盐水洗涤两次；将洗涤后的产物利用无水硫酸钠进行干燥后，抽滤，得到滤渣；将滤渣与乙酸乙酯和石油醚的混合物(乙酸乙酯和石油醚的体积比为1：50)混合，进行重结晶，得到0.23g
Figure BDA0002961587500000131
(收率为96％，熔点为170～172℃)。
将得到的白藜芦醇衍生物进行高分辨质谱检测，得到1H NMR(400MHz,CDCl3)δ8.22(m,6H),7.71–7.61(m,3H),7.60–7.48(m,8H),7.36–7.30(m,2H),7.15(m,5H)；13C NMR(100MHz,CDCl3)δ165.13,164.86,151.70,150.73,139.75,134.56,133.83,133.70,130.27,130.23,129.80,129.45,129.25,128.68,128.63,127.78,127.27,122.09,117.24,114.82；HRMS(ESI)(m/z):calcd for C35H24O6[M+NH4]+558.1911,found 558.1911。
实施例2～19
按照实施例1的方法制备白藜芦醇衍生物，具体的酰氯结构及其用量参照表1。
表1制备白藜芦醇衍生物时酰氯的结构及其用量
Figure BDA0002961587500000141
Figure BDA0002961587500000151
对实施例2～19制备得到的白藜芦醇衍生物进行高分辨质谱检测得到结果如下。
实施例21H NMR(400MHz,CDCl3)δ8.28–8.20(m,6H),7.56(d,J＝8.0Hz,2H),7.31(d,J＝2.0Hz,2H),7.25–7.17(m,8H),7.15–7.04(m,3H)；13C NMR(100MHz,CDCl3)δ164.45(d,J＝119Hz,1C),164.14,151.56,150.62,139.80,134.59,132.89(d,J＝9Hz,1C),132.90,132.80,129.87,127.80,127.24,125.47,122.05,117.24,116.05,115.97,115.83,115.74,114.72；HRMS(ESI)(m/z):calcd for C35H21F3O6[M+NH4]+612.1628,found612.1630。
实施例31H NMR(400MHz,CDCl3)δ8.14–8.07(m,6H),7.55(d,J＝8.4Hz,2H),7.36–7.28(m,8H),7.24–7.02(m,5H),2.46(s,9H)；13C NMR(100MHz,CDCl3)δ165.16,164.89,151.76,150.79,144.64,144.50,139.66,134.50,130.29,130.26,129.73,129.38,129.32,127.72,127.30,126.72,126.54,122.10,117.16,114.86,21.80；HRMS(ESI)(m/z):calcdfor C38H30O6[M+NH4]+600.2381,found 600.2379。
实施例41H NMR(400MHz,CDCl3)δ8.14–8.11(m,4H),8.07(d,J＝8.4Hz,2H),7.55–7.47(m,9H),7.30(d,J＝2.0Hz,2H),7.21(d,J＝8.4Hz,2H),7.13–7.04(m,2H)；13C NMR(100MHz,CDCl3)δ164.24,163.96,161.30,151.51,150.58,141.42,140.43,140.26,139.83,134.61,131.89,131.60,129.89,129.38,129.08,129.00,127.81,122.00,117.23,114.62；HRMS(ESI)(m/z):calcd for C35H21Cl3O6[M+NH4]+660.0742,found 660.0731。
实施例51H NMR(400MHz,CDCl3)δ8.08–8.05(m,4H),7.99(d,J＝8.0Hz,2H),7.68–7.65(m,6H),7.55(d,J＝8.4Hz,2H),7.31(d,J＝2.0Hz,2H),7.22(d,J＝8.4Hz,2H),7.17–7.03(m,3H)；13C NMR(100MHz,CDCl3)δ164.43,164.13,161.46,151.48,150.55,139.84,134.61,132.41,132.10,132.01,131.95,131.70,129.90,129.18,128.08,127.82,127.20,122.01,117.25,114.63；HRMS(ESI)(m/z):calcd for C35H21Br3O6[M+NH4]+793.9206,found793.9171。
实施例61H NMR(400MHz,CDCl3)δ8.42–8.27(m,12H),7.59(d,J＝8.4Hz,2H),7.38(d,J＝2.0Hz,2H),7.27(d,J＝8.0Hz,2H),7.23–7.06(m,3H)；13C NMR(100MHz,CDCl3)δ162.97,151.28,151.09,150.39,140.11,134.79,134.46,131.40,131.37,130.95,130.20,128.86,127.97,127.15,123.89,123.80,123.72,121.91,117.40,114.37；HRMS(ESI)(m/z):calcd for C35H21N3O12[M-OH]-658.1092,found 657.9651。
实施例71H NMR(400MHz,CDCl3)δ8.21–8.15(m,3H),7.57(d,J＝8.4Hz,2H),7.52–7.47(m,3H),7.36–7.31(m,8H),7.22(d,J＝8.4Hz,2H),7.15–7.05(m,3H),2.70(s,6H),2.68(s,3H)；13C NMR(100MHz,CDCl3)δ165.74,165.38,151.70,150.68,141.57,141.43,139.72,134.54,132.96,132.83,132.06,132.01,131.30,131.21,129.75,128.18,127.75,127.29,126.02,125.96,122.19,117.26,114.98,22.07,22.00；HRMS(ESI)(m/z):calcdfor C38H30O6[M+NH4]+600.2381,found 600.2379。
实施例81H NMR(400MHz,CDCl3)δ8.04–8.00(m,6H),7.56(d,J＝8.4Hz,2H),7.47–7.38(m,6H),7.32(d,J＝2.0Hz,2H),7.23(t,J＝8.0Hz,2H),7.18–7.04(m,3H),2.46(s,6H),2.45(s,3H)；13C NMR(100MHz,CDCl3)δ165.27,164.98,151.77,150.80,139.72,138.51,138.46,134.56,134.44,130.77,130.72,129.78,129.41,129.23,128.55,128.50,127.75,127.42,127.37,127.32,122.08,117.17,114.80,21.32；HRMS(ESI)(m/z):calcdfor C38H30O6[M+NH4]+600.2381,found 600.2379。
实施例91H NMR(400MHz,CDCl3)δ7.59(d,J＝8.4Hz,2H),7.33(d,J＝1.6Hz,2H),7.27–7.24(m,2H),7.17–7.06(m,3H),6.95–6.91(m,6H),2.48(s,12H),2.46(s,6H),2.33(s,6H),2.32(s,3H)；13C NMR(100MHz,CDCl3)δ168.31,167.88,151.62,150.56,140.27,140.09,139.80,135.93,135.69,134.62,129.85,129.51,128.79,128.70,127.86,127.33,121.95,117.04,114.26,21.23,20.24,20.07；HRMS(ESI)(m/z):calcd for C44H42O6[M+NH4]+684.3320,found 684.3316。
实施例101H NMR(400MHz,CDCl3)δ8.16–8.12(m,6H),7.57–7.52(m,8H),7.30(d,J＝2.0Hz,2H),7.21(d,J＝8.6Hz,2H),7.14–7.02(m,3H),1.38(s,18H),1.37(s,9H)；13C NMR(100MHz,CDCl3)δ165.11,164.86,157.62,157.49,151.78,150.80,139.66,134.51,130.18,130.14,129.74,127.74,127.30,126.66,126.47,125.67,125.61,122.12,117.19,114.87,35.25,31.14；HRMS(ESI)(m/z):calcd for C47H48O6[M+NH4]+726.3789,found726.4049。
实施例111H NMR(400MHz,CDCl3)δ7.47(d,J＝8.4Hz,2H),7.13–6.91(m,6H),6.83(t,J＝2.0Hz,1H),1.89–1.79(m,3H),1.22–1.14(m,6H),1.07–0.99(m,6H)；13C NMR(100MHz,CDCl3)δ173.44,173.11,151.40,150.52,139.42,134.36,129.55,127.59,127.19,121.92,116.82,114.50,13.04,9.40,9.35；HRMS(ESI)(m/z):calcd for C26H24O6[M+NH4]+450.1911,found 450.1914。
实施例121H NMR(400MHz,CDCl3)δ7.47(d,J＝8.4Hz,2H),7.08(.m,J＝1.6Hz,3H),7.04(d,J＝5.12Hz,2H),7.00–6.91(m,1H),6.82–6.72(m,1H),2.60–2.50(m,3H),2.12–2.02(m,6H),1.87–1.78(m,6H),1.71–1.68(m,2H),1.65–1.55(m,6H),1.43–1.24(m,10H)；13C NMR(100MHz,CDCl3)δ174.47,174.11,151.56,150.65,139.44,134.34,129.55,127.58,127.20,121.88,116.73,114.42,43.22,28.94,25.72,25.36；HRMS(ESI)(m/z):calcd forC35H42O6[M+NH4]+576.3320,found 576.3323。
实施例131H NMR(400MHz,CDCl3)δ7.93–7.86(m,3H),7.62–7.57(m,6H),7.53(d,J＝8.6Hz,2H),7.46–7.38(m,10H),7.25(d,J＝2.3Hz,2H),7.18(d,J＝8.6Hz,2H),7.15–6.98(m,3H),6.67–6.61(m,3H)；13C NMR(100MHz,CDCl3)δ165.36,165.04,151.52,150.57,147.07,146.80,139.62,134.51,134.16,134.11,130.86,130.79,129.70,129.06,128.98,128.41,128.36,127.73,127.30,121.98,117.19,117.01,114.58；HRMS(ESI)(m/z):calcdfor C41H30O6[M+NH4]+636.2381,found 636.2383。
实施例141H NMR(400MHz,CDCl3)δ7.48(d,J＝8.4Hz,2H),7.11(d,J＝2.0Hz,2H),7.10–7.07(m,2H),7.05–6.92(m,2H),6.82(t,J＝2.0Hz,1H),2.63–2.56(m,6H),1.27(t,J＝7.6Hz,9H)；13C NMR(100MHz,CDCl3)δ172.92,172.57,151.41,150.52,139.50,134.39,129.60,127.63,127.20,121.89,116.82,114.41,27.78,9.08,9.05；HRMS(ESI)(m/z):calcd for C23H24O6[M+NH4]+414.1911,found 414.1910。
实施例151H NMR(400MHz,CDCl3)δ7.48(d,J＝8.5Hz,2H),7.13–7.11(m,2H),7.10–7.07(m,2H),7.05–6.93(m,2H),6.84–6.81(m,1H),2.31(s,9H)；13C NMR(100MHz,CDCl3)δ169.45,169.04,151.32,150.44,139.55,134.48,129.67,127.68,127.20,121.91,116.93,114.42,21.14；HRMS(ESI)(m/z):calcd for C23H18O6[M-H2O]+372.0997,found372.1443。
实施例161H NMR(400MHz,CDCl3)δ9.45–9.39(m,3H),8.92–8.85(m,3H),8.51–8.44(m,3H),7.58(d,J＝8.4Hz,1H),7.54–7.47(m,4H),7.37(d,J＝1.6Hz,1H),7.25–7.20(m,2H),7.17–7.14(m,1H),7.12–6.92(m,3H)；13C NMR(100MHz,CDCl3)δ163.79,163.49,154.18,151.36,151.26,137.77,134.74,130.08,127.91,127.76,127.19,125.33,123.65,123.60,121.96,121.85,117.37；HRMS(ESI)(m/z):calcd for C32H21N3O6[M+H]+544.1503,found 544.1505。
实施例171H NMR(400MHz,CDCl3)δ8.34–8.29(m,3H),7.69–7.65(m,3H),7.53(d,J＝8.6Hz,2H),7.40–7.36(m,3H),7.29(d,J＝2.0Hz,2H),7.20(d,J＝8.6Hz,2H),7.16–7.01(m,3H)；13C NMR(100MHz,CDCl3)δ160.96,160.65,151.42,150.47,139.70,134.54,134.35,134.17,132.78,132.56,129.77,128.24,127.76,127.26,126.55,126.45,122.06,117.19,114.74；HRMS(ESI)(m/z):calcd for C29H18O6S3[M+NH4]+576.0604,found 576.0605。
实施例181H NMR(400MHz,CDCl3)δ8.03–7.96(m,3H),7.71–7.65(m,3H),7.54(d,J＝8.3Hz,2H),7.34–7.29(m,2H),7.23(d,J＝8.4Hz,2H),7.20–7.16(m,3H),7.13–7.01(m,3H)；13C NMR(100MHz,CDCl3)δ160.50,160.19,151.27,150.37,139.70,134.99,134.81,134.61,133.88,133.64,132.78,132.52,129.84,128.15,128.09,127.76,127.25,122.01,117.22,114.62；HRMS(ESI)(m/z):calcd for C29H18O6S3[M+NH4]+576.0604,found576.0605。
实施例191H NMR(400MHz,CDCl3)δ7.73–7.66(m,3H),7.53(d,J＝7.9Hz,2H),7.43–7.37(m,3H),7.32–7.28(m,2H),7.22(d,J＝8.1Hz,2H),7.15–6.98(m,3H),6.64–6.56(m,3H)；13C NMR(100MHz,CDCl3)δ156.83,156.46,150.92,149.99,147.46,147.27,143.89,143.68,139.76,134.65,129.88,127.81,127.23,121.95,119.87,119.63,117.21,114.48,112.32,112.26；HRMS(ESI)(m/z):calcd for C29H18O9[M+NH4]+528.1289,found 528.1291。
根据实施例1～19的质谱数据可知实施例1～19制备得到的是白藜芦醇的衍生物。
实施例20
将0.3g白藜芦醇(1.3mmol)和25mL二氯甲烷(含水率为0％)混合，得到第一溶液；
将所述第一溶液和0.506g三乙胺(5.2mmol)混合，得到第二溶液；
将第二溶液置于冰水浴中搅拌，将1.075g对甲氧基苯磺酰氯(5.2mmol)按照30滴/min的滴加速率滴加至第二溶液中，在室温条件下进行酯化反应；将酯化反应的产物和水混合进行分液，得到第一有机相；利用二氯甲烷对分液得到的水相进行萃取两次，两次萃取得到的有机相合并得到第二有机相；将第一有机相和第二有机相混合后，利用饱和食盐水洗涤两次；将洗涤后的产物利用无水硫酸钠进行干燥后，抽滤，得到滤渣；将滤渣与乙酸乙酯和石油醚的混合物(乙酸乙酯和石油醚的体积比为1：50)混合，进行重结晶，得到0.77g
Figure BDA0002961587500000191
(收率为86％，熔点为154～156℃)。
实施例21～36
按照实施例20的方法制备白藜芦醇衍生物，具体的磺酰氯结构及其用量参照表2。
表2制备白藜芦醇衍生物时磺酰氯的结构及其用量
Figure BDA0002961587500000201
Figure BDA0002961587500000211
对实施例20～36制备得到的白藜芦醇衍生物进行高分辨质谱检测得到结果如下。
实施例201H NMR(400MHz,CDCl3)δ7.80–7.68(m,6H),7.36(d,J＝8.4Hz,2H),7.05(s,2H),7.03–6.94(m,8H),6.83(d,J＝4.7Hz,2H),6.46(s,1H),3.89(s,9H)；13C NMR(100MHz,CDCl3)δ164.40,164.19,150.05,149.46,139.79,135.10,130.79,130.76,127.86,126.91,126.52,126.04,122.93,119.03,115.75,114.57,114.38,55.84；HRMS(ESI)(m/z):calcd for C35H30O12S3[M+NH4]+756.1238,found 756.1242。
实施例211HNMR(400MHz,CDCl3)δ7.60(d,2H),7.33(d,J＝1.9Hz,2H),7.24(s,2H),7.19–7.06(m,3H),6.97–6.91(m,6H),2.57–2.39(m,18H),2.37–2.27(m,9H)；13C NMR(100MHz,CDCl3)δ168.34,167.90,151.60,150.54,140.28,140.10,139.80,135.93,135.69,134.62,129.85,129.49,128.80,128.70,127.86,127.31,121.95,117.06,114.27,21.25,20.26,20.08；HRMS(ESI)(m/z):calcd for C41H42O9S3[M-C7H6]+684.1527,found684.3310。
实施例221HNMR(400MHz,CDCl3)δ7.86(dt,J＝6.5,4.5Hz,6H),7.39(d,J＝8.6Hz,2H),7.29–7.19(m,7H),7.09(d,J＝2.1Hz,2H),7.00(d,J＝8.6Hz,2H),6.87(q,J＝16.3Hz,2H),6.55–6.49(m,1H)；13C NMR(100MHz,CDCl3)δ166.25(d,J＝258Hz,1C),166.10(d,J＝256Hz,1C),149.82,149.29,140.16,135.24,131.42(d,J＝10.0Hz,1C),131.39(d,J＝10.0Hz,1C),131.23(d,J＝4.0Hz,1C),130.88(d,J＝4.0Hz,1C),130.50,128.06,126.83,122.81,119.13,117.00,116.78,116.56,115.53；HRMS(ESI)(m/z):calcd for C32H21F3O9S3[M+NH4]+720.0638,found 720.0641。
实施例231HNMR(400MHz,CDCl3)δ7.80–7.73(m,6H),7.58–7.48(m,6H),7.40(d,J＝7.9Hz,2H),7.09(s,2H),7.00(d,J＝7.8Hz,2H),6.94–6.80(m,2H),6.52(d,J＝1.2Hz,1H)；13C NMR(100MHz,CDCl3)δ149.80,149.28,141.55,141.20,140.20,135.26,133.70,133.35,130.57,129.93,129.86,129.81,129.62,128.11,126.84,122.79,119.12,115.46；HRMS(ESI)(m/z):calcd for C32H21Cl3O9S3[M+NH4]+769.9722,found769.9718。
实施例241H NMR(400MHz,CDCl3)δ7.74–7.66(m,12H),7.41(d,J＝8.6Hz,2H),7.08(d,J＝2.0Hz,2H),7.00(d,J＝8.6Hz,2H),6.92–6.81(m,2H),6.53(t,J＝1.9Hz,1H)；13CNMR(100MHz,CDCl3)δ149.81,149.29,140.23,135.28,134.29,133.95,132.82,132.61,130.59,130.16,129.95,129.87,128.14,126.86,122.78,119.10,115.44；HRMS(ESI)(m/z):calcd for C32H21Br3O9S3[M+NH4]+903.8195,found 903.8180。
实施例251H NMR(400MHz,CDCl3)δ8.51–8.44(m,6H),8.19–8.11(m,6H),7.57(d,J＝8.7Hz,2H),7.37(d,J＝2.1Hz,2H),7.26–7.14(m,2H),7.11(d,J＝8.7Hz,2H),6.75(t,J＝2.1Hz,1H)；13C NMR(100MHz,CDCl3)δ151.20,151.07,149.03,148.54,148.38,140.70,139.37,138.81,135.77,130.58,130.08,130.05,128.51,126.92,125.10,125.01,122.49,119.45；HRMS(ESI)(m/z):calcd for C32H21N3O15S3[M+NH4]+801.0473,found 801.0438。
实施例261HNMR(400MHz,CDCl3)δ7.76–7.65(m,6H),7.40–7.30(m,8H),7.05(d,J＝1.6Hz,2H),6.98(d,J＝8.5Hz,2H),6.90–6.76(m,2H),6.47(s,1H),2.46(s,9H)；13C NMR(100MHz,CDCl3)δ150.01,149.43,145.92,145.55,139.81,135.14,132.27,131.86,130.22,129.99,129.84,128.54,128.47,127.87,126.91,122.86,118.99,115.65,21.81,21.77；HRMS(ESI)(m/z):calcd for C35H30O9S3[M+NH4]+708.1390,found708.1397。
实施例271HNMR(400MHz,CDCl3)δ8.14(dd,J＝8.5,2.7Hz,5H),7.59–7.46(m,8H),7.30(d,J＝1.8Hz,2H),7.21(dd,J＝19.9,11.4Hz,3H),7.08(dd,J＝21.3,14.1Hz,3H),1.40–1.36(m,24H),1.35(s,3H)；13C NMR(100MHz,CDCl3)δ165.12,164.87,157.63,157.51,151.80,150.82,139.68,134.52,130.19,130.14,129.75,127.74,127.32,126.68,126.49,125.67,125.62,125.50,122.12,117.19,114.87,35.26,31.14；HRMS(ESI)(m/z):calcdfor C44H48O9S3[M-C7H6]+726.1996,found 726.3790。
实施例281HNMR(400MHz,CDCl3)δ7.70–7.58(m,6H),7.53–7.38(m,6H),7.36(d,J＝8.6Hz,2H),7.04(d,J＝2.0Hz,2H),6.99(d,J＝8.6Hz,2H),6.89–6.78(m,2H),6.52(t,J＝2.0Hz,1H),2.44(s,9H)；13C NMR(100MHz,CDCl3)δ149.95,149.39,139.87,139.82,139.63,135.43,135.17,134.78,130.23,129.18,129.04,128.73,128.71,127.88,126.88,125.66,125.58,122.85,119.05,115.68,21.34；HRMS(ESI)(m/z):calcd for C35H30O9S3[M+NH4]+708.1390,found 708.1397。
实施例291HNMR(400MHz,CDCl3)δ7.87–7.80(m,6H),7.74–7.66(m,3H),7.59–7.53(m,6H),7.35(d,J＝8.6Hz,2H),7.04(d,J＝2.0Hz,2H),6.98(d,J＝8.6Hz,2H),6.88–6.76(m,2H),6.49(t,J＝2.0Hz,1H)；13C NMR(100MHz,CDCl3)δ149.93,149.37,139.91,135.29,135.18,134.90,134.65,134.38,130.30,129.40,129.24,128.51,128.46,127.93,126.84,122.83,119.05,115.62；HRMS(ESI)(m/z):calcd for C32H24O9S3[M+NH4]+666.0921,found666.0918。
实施例301HNMR(400MHz,CDCl3)δ7.84–7.76(m,3H),7.75–7.66(m,3H),7.40(d,J＝8.6Hz,2H),7.35–7.27(m,6H),7.18(d,J＝1.9Hz,2H),7.12(d,J＝8.6Hz,2H),6.94–6.80(m,2H),6.75(s,1H)；13C NMR(100MHz,CDCl3)δ160.64,158.09(d,J＝10.0Hz,1C),149.66,149.11,140.19,137.23(d,J＝8.0Hz,1C),136.92(d,J＝8.0Hz,1C),135.37,131.46,131.38,130.44,128.11,126.88,124.61(d,J＝4.0Hz,1C),124.74(d,J＝4.0Hz,1C),123.14,123.01,122.52,118.98,117.63(d,J＝2.0Hz,1C),117.50(d,J＝2.0Hz,1C),115.11；HRMS(ESI)(m/z):calcd for C32H21F3O9S3[M+NH4]+720.0638,found720.0640。
实施例311HNMR(400MHz,CDCl3)δ7.93–7.88(m,6H),7.41–7.35(m,8H),7.10(d,J＝1.6Hz,2H),7.01(d,J＝8.4Hz,2H),6.93–6.81(m,2H),6.57(s,1H)；13C NMR(100MHz,CDCl3)δ153.62,153.41,149.72,149.23,140.24,135.29,133.38,133.01,130.80,130.77,130.53,130.35,128.08,126.80,122.76,121.01,120.79,119.16,118.86,115.57；HRMS(ESI)(m/z):calcd for C35H21O12F9S3[M+NH4]+918.0390,found 918.0387。
实施例321H NMR(400MHz,CDCl3)δ7.52–7.40(m,17H),7.12(d,J＝8.6Hz,2H),7.08(d,J＝2.0Hz,2H),6.98–6.83(m,2H),6.71(t,J＝2.0Hz,1H),4.54(s,6H)；13C NMR(100MHz,CDCl3)δ149.63,149.01,140.23,135.25,130.96,130.90,130.38,129.54,129.40,129.15,129.07,128.13,127.11,126.89,126.85,122.46,118.63,115.13,57.23,56.95；HRMS(ESI)(m/z):calcd for C35H30O9S3[M+NH4]+708.1390,found 708.1394。
实施例331HNMR(400MHz,CDCl3)δ7.53(d,J＝8.7Hz,2H),7.37(d,J＝2.1Hz,2H),7.30–7.27(m,2H),7.12–7.09(m,1H),7.04–6.86(m,2H),3.39–3.28(m,6H),1.61–1.53(m,9H)；13C NMR(100MHz,CDCl3)δ149.57,140.53,135.30,130.56,128.30,128.09,126.94,122.47,118.70,115.15,45.61,45.23,8.29；HRMS(ESI)(m/z):calcd for C20H24O9S3[M+NH4]+522.0921,found 522.0911。
实施例341HNMR(400MHz,CDCl3)δ7.54(d,J＝7.0Hz,2H),7.37(s,2H),7.30–7.24(m,2H),7.18–6.96(m,3H),3.34–3.23(m,6H),2.12–1.98(m,6H),1.20–1.10(m,9H)；13C NMR(100MHz,CDCl3)δ149.57,148.96,140.50,135.29,130.55,128.29,126.98,122.49,118.71,115.19,52.57,52.27,17.37,12.89,12.86；HRMS(ESI)(m/z):calcd for C23H30O9S3[M+NH4]+564.1390,found 564.1390。
实施例351HNMR(400MHz,CDCl3)δ7.53(d,J＝8.6Hz,2H),7.40(d,J＝1.9Hz,2H),7.32(d,J＝8.6Hz,2H),7.20–7.17(m,1H),7.15–6.98(m,2H),2.69–2.60(m,3H),1.33–1.27(m,6H),1.22–1.13(m,6H)；13C NMR(100MHz,CDCl3)δ150.08,149.50,140.32,135.28,130.51,128.16,126.98,122.76,118.99,115.80,28.01,27.87,6.45,6.30；HRMS(ESI)(m/z):calcd for C23H24O9S3[M+NH4]+558.0921,found 558.0918。
实施例361HNMR(400MHz,CDCl3)δ7.77(d,J＝5.0Hz,2H),7.74(d,J＝5.0Hz,1H),7.65–7.59(m,3H),7.41(d,J＝8.6Hz,2H),7.17–7.11(m,5H),7.05(d,J＝8.6Hz,2H),6.95–6.82(m,2H),6.58(s,1H)；13C NMR(100MHz,CDCl3)δ150.01,149.46,140.05,135.84,135.57,135.39,135.17,134.73,134.58,134.02,130.45,128.01,127.86,127.62,126.93,122.73,119.21,115.45；HRMS(ESI)(m/z):calcd for C26H18O9S6[M+NH4]+683.9613,found683.9613。
根据实施例20～36的质谱数据可知实施例20～36制备得到的是白藜芦醇的衍生物。
按照如下方法检测实施例9、10、14、15、17、19、21、24、29、33、35制备得到的白藜芦醇衍生物对烟草花叶病毒的抑制作用：
按照Leberman的聚乙二醇沉淀法提纯TMV植物病毒，所提取的病毒为乳白色沉淀，根据A260吸收，可计算出病毒的质量浓度C(mg/mL)＝A260/3.1。
白藜芦醇衍生物溶液的配制：
将白藜芦醇衍生物溶解于DMF中，制备得到质量浓度为1×105μg/mL的白藜芦醇衍生物母液，再用质量浓度为1‰的吐温-80的水溶液对白藜芦醇衍生物母液进行稀释，得到质量浓度分别为500μg/mL和100μg/mL的白藜芦醇衍生物溶液。
对比溶液的配制：
将白藜芦醇溶解于DMF中，制备得到质量浓度为1×105μg/mL的白藜芦醇母液，再用质量浓度为1‰的吐温-80的水溶液对白藜芦醇母液进行稀释，得到质量浓度分别为500μg/mL或100μg/mL的白藜芦醇溶液；
将药剂病毒唑直接兑水稀释，得到浓度为500μg/mL或100μg/mL的病毒唑溶液。
对TMV侵染的活体保护作用：
选长势均匀一致的3～5叶期珊西烟，全株喷雾施药(只要喷洒均匀即可)，每组测试重复测试3遍取平均值；同时设质量百分比浓度为1‰吐温-80水溶液对照；24h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10μg/mL，接种后用流水冲洗。3天后记录病斑数，计算防效，其结果列于表3中。
对TMV侵染的活体治疗作用：
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10μg/mL，接种后用流水冲洗；叶面收干后，全株喷雾施药(只要喷洒均匀即可)，每组测试重复3次取平均值；并设质量百分比浓度为1‰吐温-80水溶液对照；3天后记录病斑数，计算防效，其结果列于表3。
对TMV侵染的活体钝化作用
选长势均匀一致的3～5叶期珊西烟，将药剂溶液与等体积的病毒汁液混合钝化30min后，摩擦接种，病毒浓度20μg/mL，接种后即用流水冲洗，每组测试重复3次取平均值；设质量百分比浓度为1‰吐温-80水溶液对照；3天后数病斑数，计算结果，其结果列于表3中。
Y/％＝[(C–A)/C]×100，其中：Y为化合物对烟草花叶病毒病斑的抑制率；C为对照组病斑数，单位：个；A为处理组病斑数，单位：个；对照组和处理组的病斑数均取各组3次重复的平均数。
表3白藜芦醇衍生物抑制烟草花叶病毒活性
Figure BDA0002961587500000261
Figure BDA0002961587500000271
由表3的数据结果可知，由实施例9、10、14、15、17、19、21、24、29、33、35制备得到的白藜芦醇衍生物对烟草花叶病毒具有良好的抑制效果。
按照如下方法检测实施例1～36制备得到的白藜芦醇衍生物的杀菌性能：
将植物真菌接到PDA培养基上培养7天，用打孔器在菌落边缘制取直径4cm的菌碟接种到含有50μg/mL和不含药剂的PDA培养基上培养4天，量取菌落直径，与对照组比较计算出药剂的杀菌百分率，其结果列于表4中。其中真菌包括aAverage ofthreereplicates.bF.C,Fusarium oxysporiumf.sp.cucumeris(黄瓜枯萎)；C.H,CercosporaarachidicolaHori(花生褐斑)；P.P,Physalosporapiricola(苹果轮纹)；R.C,Rhizoctoniacerealis(水稻恶苗)；B.M,Bipolaris maydis(玉米小斑)；W.A,Watermelon anthracnose(西瓜炭疽)；F.M,Fusarium moniliforme(小麦纹枯)；A.S,Alternaria solani(番茄早疫)；F.G,Fusariumgraminearum(小麦赤霉)；P.I,Phytophthora infestans(马铃薯晚疫)；P.C,Phytophthora capsici(辣椒疫霉)；S.S,Sclerotinia sclerotiorum(油菜菌核)；R.S,Rhizoctonia solani(水稻纹枯)；B.C,Botrytis cinerea(黄瓜灰霉)。
表4白藜芦醇衍生物的杀菌性能
Figure BDA0002961587500000272
Figure BDA0002961587500000281
Figure BDA0002961587500000291
由表4中的数据可知本发明提供的白藜芦醇衍生物具有一定的杀菌性能。
按照如下方法检测实施例1～3、6～8、10～19、24、25、28、32、36制备得到的白藜芦醇衍生物的杀虫性能：
东方粘虫的活性测试：
浸叶法，配置600μg/mL的白藜芦醇衍生物溶液，把直径约为5～6cm的叶片浸入药液中6s，取出，放在吸水纸上晾干，放在指定的培养皿中，接入10头3龄幼虫，放入27±1℃的养虫室中观察4天后检查结果，其结果列于表5中。
蚊幼虫的活性测试：
以尖音库蚊淡色亚种，室内饲养的正常群体为测试对象。称取测试药品于药瓶中，加适量丙酮，振荡溶解，得到母液。用蒸馏水稀释至所需浓度，选取10头4龄初蚊子幼虫，连同药液一并倒入烧杯中，放入标准处理室内，1天后检查结果；以含有试验溶剂的水溶液为空白对照，其结果列于表5中。
棉铃虫的活性测试：
在南开大学农药工程中心生测平台利用饲料混药法进行测试，移取3mL配置好的溶液加入到约27g的刚配置好的棉铃虫饲料(玉米粉、黄豆粉、蔗糖、琼脂、酵母粉、维生素、防腐剂)中，从而得到稀释十倍的所需浓度。药剂混匀后均匀地倒入干净的24孔板中，晾凉后接入24头3龄棉铃虫，4天后检查结果，其结果列于表5中。
玉米螟的活性测试：
浸叶法，配置成600μg/mL的溶液后，把直径约为5～6cm叶片浸入药液中6s，取出，放在吸水纸上晾干，放在指定的培养皿中，接入10头3龄幼虫，放入27±1℃的养虫室中，观察4天后检查结果，其结果列于表5中。
表5白藜芦醇衍生物的杀虫活性
Figure BDA0002961587500000292
Figure BDA0002961587500000301
由表5中的数据可知，本发明提供的白藜芦醇衍生物具有一定的杀虫性能。
尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，人们还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。

Claims (12)

1.一种白藜芦醇衍生物，其结构式如式Ⅰ或式Ⅱ所示:
Figure FDA0002961587490000011
其中，R1和R2为杂环基、取代杂环基、芳基、取代芳基、支链烃基或环烷基。
2.根据权利要求1所述白藜芦醇衍生物，其特征在于，所述R1包括
Figure FDA0002961587490000012
3.根据权利要求1所述白藜芦醇衍生物，其特征在于，所述R1包括
Figure FDA0002961587490000013
Figure FDA0002961587490000014
R'包括H3CO-、F-、Cl-、Br-、O2N-、CH3-、(CH3)3C-或F3CO-。
4.根据权利要求1所述白藜芦醇衍生物，其特征在于，所述R1包括CH3-CH2-、CH3-CH2-CH2-或
Figure FDA0002961587490000015
5.根据权利要求1所述白藜芦醇衍生物，其特征在于，所述R2包括
Figure FDA0002961587490000016
Figure FDA0002961587490000017
6.根据权利要求1所述白藜芦醇衍生物，其特征在于，所述R2包括
Figure FDA0002961587490000018
Figure FDA0002961587490000019
R”包括F-、Cl-、Br-、O2N-、CH3-或(CH3)3C-。
7.根据权利要求1所述白藜芦醇衍生物，其特征在于，所述R2包括CH3-CH2-、CH2＝CH-、
Figure FDA00029615874900000110
8.权利要求1～7任一项所述白藜芦醇衍生物的制备方法，包括以下步骤：
将白藜芦醇、二氯甲烷、三乙胺和酰氯基化合物混合，进行酯化反应，得到所述白藜芦醇衍生物，所述酰氯基化合物包括酰氯或磺酰氯，当所述酰氯基化合物为磺酰氯时，得到式I所示结构的白藜芦醇衍生物，当所述酰氯基化合物为酰氯时，得到式II所示结构的白藜芦醇衍生物；
所述酰氯包括杂环基取代酰氯、取代杂环基取代酰氯、芳基取代酰氯、取代芳基取代酰氯、支链烃基取代酰氯或环烷基取代酰氯；
所述磺酰氯包括杂环取代磺酰氯、取代杂环取代磺酰氯、芳基取代磺酰氯、取代芳基取代磺酰氯、支链烃基取代磺酰氯或环烷基取代磺酰氯。
9.权利要求1～7任一项所述白藜芦醇衍生物或权利要求8所述制备方法制备得到的白藜芦醇衍生物在植物病虫害防治中的应用。
10.根据权利要求9所述的应用，其特征在于，当R1为
Figure FDA0002961587490000021
CH3-CH2-或
Figure FDA0002961587490000022
时，所述应用为式Ⅰ所示结构的白藜芦醇衍生物在抑制烟草花叶病毒中的应用；
当R2为
Figure FDA0002961587490000023
CH2＝CH-、CH3-CH2-、
Figure FDA0002961587490000024
时，所述应用为式Ⅱ所示结构的白藜芦醇衍生物在抑制烟草花叶病毒中的应用。
11.根据权利要求9所述的应用，其特征在于，当R1为
Figure FDA0002961587490000025
CH3-CH2-CH2-或
Figure FDA0002961587490000026
时，所述应用为式Ⅰ所示结构的白藜芦醇衍生物在植物杀虫中的应用；
当R2为
Figure FDA0002961587490000031
CH3-CH2-、CH2＝CH-、
Figure FDA0002961587490000032
时，所述应用为式Ⅱ所示结构的白藜芦醇衍生物在植物杀虫中的应用。
12.根据权利要求9所述的应用，其特征在于，所述应用为在植物抗菌中的应用。
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