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WO2011069444A1 - Anti-plant virus agent of ferulic acid and derivatives thereof - Google Patents

Anti-plant virus agent of ferulic acid and derivatives thereof Download PDF

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Publication number
WO2011069444A1
WO2011069444A1 PCT/CN2010/079539 CN2010079539W WO2011069444A1 WO 2011069444 A1 WO2011069444 A1 WO 2011069444A1 CN 2010079539 W CN2010079539 W CN 2010079539W WO 2011069444 A1 WO2011069444 A1 WO 2011069444A1
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carbon
virus
ferulic acid
och
plant virus
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French (fr)
Chinese (zh)
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汪清民
王开亮
王兹稳
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Nankai University
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Nankai University
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    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
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    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/24—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 two or more hetero atoms
    • A01N43/32—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 two or more hetero atoms six-membered rings
    • A—HUMAN NECESSITIES
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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    • A—HUMAN NECESSITIES
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
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    • 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
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
    • C07C57/42—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the rings
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    • C07C59/40—Unsaturated compounds
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    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings

Definitions

  • the invention relates to a novel anti-plant virus agent and application thereof, in particular to ferulic acid and its derivative as anti-plant virus agent, ferulic acid and its derivative and anti-plant virus active ingredient interaction composition as anti-vegetation Plant viral agents, and their use in the control of plant viral diseases, are in the field of pesticide technology.
  • Ferulic acid chemical name 4-hydroxy-3- Methoxybenzoic acid
  • F is a ubiquitous phenolic acid that crosslinks with polysaccharides and lignin in plant cell walls to form part of the cell wall. It is Awei, Angelica, and Chuan.
  • One of the active ingredients of traditional Chinese medicines such as medlar and cohosh has been widely used in medicine, health care products, cosmetic raw materials and food additives because of its strong antioxidant activity and antiseptic effect.
  • ferulic acid and its derivatives also have excellent antipyretic and analgesic, antithrombotic, hypolipidemic, antibacterial, anti-inflammatory, anti-cancer, anti-mutation, immune function enhancement and enhancement.
  • Biological activity such as human sperm motility and motility has extremely low toxicity and almost no side effects.
  • the anti-plant virus agents that have been found are mainly (Table 1): benzothiadiazole (BTH), thiazolamide (TDL), 4-methyl- 1, 2, 3-thiadiazole-5-carboxylic acid (TDLA), DL- ⁇ -aminobutyric acid (BABA), ribavirin, nymidine, phenanthroline alkaloids antoine, lian Triazole compounds XY-13 and XY-30, virus A (active components are morpholinium dihydrochloride and copper acetate), salicylic acid, polyhydroxy bis naphthaldehyde, amino oligosaccharide (chitin oligosaccharide, scientific name -1-1, 4-oligoglucosamine).
  • the present invention aims to provide a new class of high-efficiency, low-toxic anti-plant virus agents and their anti-plant virus applications.
  • the present invention finds for the first time that natural ferulic acid and its derivatives have high activity against plant viruses.
  • the active ingredient of the anti-plant virus agent of the present invention is ferulic acid and a derivative thereof, and the compound having the structure of the formula ( I ):
  • R 1 , R 2 and R 3 each represent hydrogen, hydroxy, 1 - 6 carkolkoxy, halogen atom, formyl group, carboxyl group, 1 - 4 carbon alkylcarbonyl group, 1 - 4 carbon alkylcarbonyloxy group , 1 - 4 carboalkoxycarbonyloxy or nitro; or R 1 and R 2 , R 2 and R 3 represent OCH 2 O , OCH 2 CH 2 O, respectively; R 4 represents hydrogen, hydroxy, ONa, OK, ONH 4 , glucosyl, alkoxy, hydrocarbon amine, dihydrocarbylamino, 1 - 6 carbon hydrocarbyl, ( 3 - 6 ) hexenyl, ( 3 - 6 ) haloalkenyl, ( 3 - 6 ) Carboalkynyl, 1 - 4 carbohaloalkyl, 1 - 4 carbon alkoxyalkyl, 1 - 4 carbon alkylthioalkyl, phenyl
  • R 1 , R 2 and R 3 represent H, OH and OCH 3 , respectively.
  • R 2 and R 3 represent OCH 2 O , OCH 2 CH 2 O , respectively;
  • R 4 represents OH , OCH 3 , OCH 2 CH 3 ,
  • CH 2 CH CH 2 , NEt 2 , p-Cl-C 6 H 4 NH , ONa, OK, ONH 4 , or glucosyl.
  • the compound of the formula ( I ) of the invention has excellent anti-plant virus activity, and can well inhibit tobacco mosaic virus, capsivirus, tomato virus, sweet potato virus, potato virus and melon virus, and corn dwarf mosaic virus, etc. It can effectively control viral diseases of tobacco, pepper, tomato, melon, food, vegetables, beans and other crops, especially suitable for controlling tobacco mosaic disease.
  • the partial compound of the formula ( I ) of the present invention inhibits tobacco mosaic virus at a concentration of 500 ug/mL as high as 80% or more, and inhibits the activity of tobacco mosaic virus over the commercial varieties of virus A, ribavirin, DADHT and DHT. (The inhibition rate is only 50% at 500 ug/mL).
  • the compound of the formula ( I ) of the present invention can be used as a plant virus inhibitor as it is, or it can be used together with an agriculturally acceptable carrier, and can also be combined with other anti-plant virus agents such as benzothiadiazole (BTH) and thiaform bacteria.
  • BTH benzothiadiazole
  • TDL 4-methyl-1 , 2 , 3-thiadiazole-5-carboxylic acid
  • BABA DL- ⁇ -aminobutyric acid
  • ribavirin nymidine, phenanthrene
  • the ferulic acid and its derivative anti-plant virus agent of the invention have great advantages over the existing virus inhibitors: simple chemical structure, significant anti-plant virus activity, and inhibition to various plant viruses; toxicity Very low, environmentally compatible, safe for non-target organisms.
  • Example 1 Chemical structural formula and physical constant of ferulic acid and its derivatives, see Table 2:
  • vanillin (10 g, 0.065 mol) and malonic acid (7.5 g) were added in sequence. , 0.07 mol ), toluene (15 mL), pyridine and aniline were reacted at 85-95 ° C for 2 hours.
  • the aqueous layer was separated, the pH was adjusted with concentrated hydrochloric acid, and a large amount of solid was precipitated, filtered, washed with water, and dried to give pale yellow needle crystals of trans ferulic acid ( 11.6 g, 92% ), mp 172-173 °C.
  • Example 5 Taking Tobacco mosaic virus (TMV) activity as an example, the procedure for measuring the activity of ferulic acid and its derivatives against tobacco mosaic virus is as follows:
  • Half-leaf necrosis screening method take fresh with typical TMV The three-year-old tobacco leaves with virus symptoms were added with phosphate buffer solution (0.01M, pH 7.2), ground in a mortar, inoculated on the emery leaves of the emery, and quickly rinsed with water. Vaccination 1.5-2 After the hour, the inoculated leaves were cut into two equal half leaves along the main vein, half of the leaves were treated with the DMF solution of the sample to be tested, and the other half was immersed in clear water for comparison. After the hour, the number of dead leaves was counted and the lesion inhibition rate was calculated.
  • phosphate buffer solution (0.01M, pH 7.2
  • Screening method for in vivo protection select the same 5-6 Leaf leaf heart leaf tobacco, gently apply a certain concentration of the sample and the control sample in the left half of the leaf with a brush, and apply the solvent to the right half of the leaf as a control. After 24 hours, the juice is rubbed and inoculated with the virus to treat the leaves, and each treatment 3 Strain ( Total 9 The leaf blade was repeated 3 times. After 72 hours, the number of leaves and leaves of the heart leaf was investigated, and the inhibition rate of the lesion was calculated.
  • Screening method for in vivo passivation select 5-6 leaf stage heart leaf smoke with consistent growth, and separate certain concentrations of samples and control samples with virus juice 1:1 (V/V) mixed passivation for 0.5 h, rubbed inoculated in the left half of the leaves, and virus juice and solvent 1:1 (V/V) mixed friction inoculated in the right half of the leaves, 3 plants per treatment (9 pieces in total) blade ), repeated 3 times, 72 hours later, the number of heart leaf smoke spots was investigated, and the lesion inhibition rate was calculated.
  • V/V virus juice 1:1
  • V/V virus juice and solvent 1:1
  • Screening method for in vivo treatment selection of the same 5-6 Leaf leaf heart leaf tobacco was first inoculated with the virus juice in the treated leaves. After a certain period of time, a certain concentration of the sample and the control sample were applied to the left half of the leaf, and the right half of the leaf was used as the control. Each treatment was 3 (9 in total) Blade Repeated 3 times. After 72 hours, the number of dead leaves of heart leaf was investigated, and the inhibition rate of lesions was calculated.
  • Inhibition rate (%) [(control plaque number - number of treated plaques) / number of control plaques] ⁇ 100%
  • Table 3 and Table 4 are some of the compounds against Tobacco mosaic virus (TMV). ) Activity test results:
  • Compound Concentration ( ⁇ g/mL) Inhibition rate (%) Compound Concentration ( ⁇ g/mL) Inhibition rate (%) 1 500 90.2 11 500 >50 2 500 >50 12 500 >50 3 500 93.6 17 500 >50 5 500 >50 18 500 >50 6 500 >50 26 500 >50 7 500 >50 28 500 >50 9 500 >50 30 500 >50

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

Anti-plant virus agent of ferulic acid, its derivatives, and the use thereof are provided. The structure of the ferulic acid is showed as formula (I). As a new anti-plant virus agent, the ferulic acid and its derivatives can well inhibit tobacco mosaic virus, pepper virus, tomato virus, sweet potato virus, potato virus, melon virus and maize dwarf mosaic virus and so on, and can effectively control viral diseases of many kinds of crops like tobacco, pepper, tomato, melon, foodstuff, vegetable, bean, etc., especially tobacco mosaic disease.

Description

阿魏酸及其衍生物抗植物病毒剂 Ferulic acid and its derivatives against plant virus agents

技术领域 Technical field

本发明涉及一类新型抗植物病毒剂及其应用，具体涉及阿魏酸及其衍生物作为抗植物病毒剂，阿魏酸及其衍生物与具有抗植物病毒活性成分的互作组合物作为抗植物病毒剂，以及它们在防治植物病毒病上的应用，属农药技术领域。 The invention relates to a novel anti-plant virus agent and application thereof, in particular to ferulic acid and its derivative as anti-plant virus agent, ferulic acid and its derivative and anti-plant virus active ingredient interaction composition as anti-vegetation Plant viral agents, and their use in the control of plant viral diseases, are in the field of pesticide technology.

背景技术 Background technique

阿魏酸（ ferulic acid (FA) ，化学名称为 4- 羟基 -3- 甲氧基苯丙烯酸）是普遍存在的一种酚酸，在植物细胞壁中与多糖和木质素交联构成细胞壁的的一部分，是阿魏、当归、川 芎、升麻等中药的有效成分之一，因其具有较强的抗氧化活性和防腐作用而已经被广泛应用于医药、保健品、化妆品原料和食品添加剂方面。近年来对其药理药效方面的广泛深入研究发现阿魏酸及其衍生物还具有很好的解热镇痛、抗血栓、降血脂、抗菌消炎、防癌、抗突变、增强免疫功能以及增强人体精子活力和运动性等生物活性，其毒性极低，几乎无副作用。 Ferulic acid (FA), chemical name 4-hydroxy-3- Methoxybenzoic acid) is a ubiquitous phenolic acid that crosslinks with polysaccharides and lignin in plant cell walls to form part of the cell wall. It is Awei, Angelica, and Chuan. One of the active ingredients of traditional Chinese medicines such as medlar and cohosh has been widely used in medicine, health care products, cosmetic raw materials and food additives because of its strong antioxidant activity and antiseptic effect. In recent years, extensive and in-depth research on its pharmacological effects has found that ferulic acid and its derivatives also have excellent antipyretic and analgesic, antithrombotic, hypolipidemic, antibacterial, anti-inflammatory, anti-cancer, anti-mutation, immune function enhancement and enhancement. Biological activity such as human sperm motility and motility has extremely low toxicity and almost no side effects.

目前，除了阿魏酸可作为食品、粮食防腐剂在农业上的相关应用以外，有关阿魏酸及其衍生物在农业上用于抗植物病毒病活性的研究实属空白。迄今尚未见以阿魏酸及其衍生物作为植物病毒抑制剂的相关报道，也未见阿魏酸及其衍生物抗植物病毒活性的相关研究报道。 At present, in addition to the application of ferulic acid as a food and food preservative in agriculture, research on the use of ferulic acid and its derivatives in agriculture for antiviral disease activity is a blank. So far, there have been no reports on the use of ferulic acid and its derivatives as plant virus inhibitors, and no reports on the anti-plant virus activity of ferulic acid and its derivatives have been reported.

由于植物病毒病种类繁多（常见种类 2000 余种），防治极为困难，素有 ' 植物癌症 ' 之称，其危害仅次于真菌病害，给农业生产已造成极大损失。据统计，全世界每年农作物因此造成的经济损失达 200 亿美元，其中仅烟草花叶病毒（ Tobacco mosaic virus, TMV ）每年造成的经济损失超过 1 亿美元（ Bos L. 100 years of virology: from vitalism via molecular biology to genetic engineering. Trends in microbiology, 2000, 8(2): 82-87 ）。抗植物病毒药剂的需求和开发一直受到很大关注，已发现的抗植物病毒药剂主要有（表 1 ）：苯并噻二唑（ BTH ）、噻酰菌胺（ TDL ）、 4- 甲基 -1 ， 2 ， 3- 噻二唑 -5- 甲酸（ TDLA ）、 DL-β- 氨基丁酸（ BABA ）、病毒唑、宁南霉素、菲并吲哚里西啶生物碱安托芬、联三唑类化合物 XY-13 和 XY-30 、病毒 A （ 有效成分为盐酸吗啉双胍和醋酸铜） 、水杨酸、多羟基双萘醛、氨基寡糖素（几丁寡糖，学名为 β-1 ， 4- 寡聚葡萄糖胺）。而现有的这些抗植物病毒剂中实用化品种并不多，而且防治效果差，一般低于 60% ，质量控制较为困难，长期使用都存在一定的环境风险。因此，开发以天然植物活性物质为有效成分的高效、低毒的绿色抗植物病毒农药新品种意义非常重大。Due to the wide variety of plant virus diseases (more than 2,000 common types), it is extremely difficult to control, and it is known as 'plant cancer'. Its harm is second only to fungal diseases, causing great losses to agricultural production. According to statistics, the annual economic losses caused by crops in the world amount to 20 billion US dollars, of which only Tobacco mosaic virus (TMV) causes economic losses of more than 100 million US dollars per year (Bos L. 100 years of virology: from vitalism Via molecular biology to genetic engineering. Trends in microbiology , 2000, 8(2): 82-87). The demand for and development of anti-plant virus agents has been receiving great attention. The anti-plant virus agents that have been found are mainly (Table 1): benzothiadiazole (BTH), thiazolamide (TDL), 4-methyl- 1, 2, 3-thiadiazole-5-carboxylic acid (TDLA), DL-β-aminobutyric acid (BABA), ribavirin, nymidine, phenanthroline alkaloids antoine, lian Triazole compounds XY-13 and XY-30, virus A (active components are morpholinium dihydrochloride and copper acetate), salicylic acid, polyhydroxy bis naphthaldehyde, amino oligosaccharide (chitin oligosaccharide, scientific name -1-1, 4-oligoglucosamine). However, there are not many practical varieties of these anti-plant virus agents, and the control effect is poor, generally less than 60%. Quality control is difficult, and there are certain environmental risks in long-term use. Therefore, the development of new varieties of high-efficiency, low-toxic green anti-plant virus pesticides with natural plant active substances as active ingredients is of great significance.

表 1. 部分具有抗病毒活性化合物的化学结构 名称（代号） 苯并噻二唑（ BTH ） 噻酰菌胺（ TDL ） 4- 甲基 -1 ， 2 ， 3- 噻二唑 -5- 甲酸（ TDLA ） β- 氨基丁酸（ BABA ） 化学结构

Figure PCTCN2010079539-appb-C000001
Figure PCTCN2010079539-appb-C000002
Figure PCTCN2010079539-appb-C000003
Figure PCTCN2010079539-appb-C000004
 名称（代号） 宁南霉素 安托芬 XY-13 化学结构
Figure PCTCN2010079539-appb-C000005
Figure PCTCN2010079539-appb-C000006
Figure PCTCN2010079539-appb-C000007
 名称（代号） 病毒唑 XY-30 水杨酸 化学结构
Figure PCTCN2010079539-appb-C000008
Figure PCTCN2010079539-appb-C000009
Figure PCTCN2010079539-appb-C000010
 名称（代号） 多羟基双萘醛 化学结构
Figure PCTCN2010079539-appb-C000011
 Table 1. Chemical structures of some compounds with antiviral activity Name (code) Benzothiadiazole (BTH) Thiabendamide ( TDL ) 4-methyl-1 , 2 , 3-thiadiazole-5-carboxylic acid ( TDLA ) --aminobutyric acid (BABA) Chemical structure
Figure PCTCN2010079539-appb-C000001
Figure PCTCN2010079539-appb-C000002
Figure PCTCN2010079539-appb-C000003
Figure PCTCN2010079539-appb-C000004
 Name (code) Ningnanmycin Antoine XY-13 Chemical structure
Figure PCTCN2010079539-appb-C000005
Figure PCTCN2010079539-appb-C000006
Figure PCTCN2010079539-appb-C000007
 Name (code) Ribavirin XY-30 Salicylic acid Chemical structure
Figure PCTCN2010079539-appb-C000008
Figure PCTCN2010079539-appb-C000009
Figure PCTCN2010079539-appb-C000010
 Name (code) Polyhydroxy bis naphthaldehyde Chemical structure
Figure PCTCN2010079539-appb-C000011

发明内容 Summary of the invention

本发明目的在于提供一类新型、高效、低毒的抗植物病毒剂及其抗植物病毒应用。本发明首次发现天然阿魏酸及其衍生物具有高效抗植物病毒活性。 The present invention aims to provide a new class of high-efficiency, low-toxic anti-plant virus agents and their anti-plant virus applications. The present invention finds for the first time that natural ferulic acid and its derivatives have high activity against plant viruses.

本发明抗植物病毒剂有效成分为阿魏酸及其衍生物，其结构通式为（ I ）所示结构的化合物：The active ingredient of the anti-plant virus agent of the present invention is ferulic acid and a derivative thereof, and the compound having the structure of the formula ( I ):

Figure PCTCN2010079539-appb-C000012
Figure PCTCN2010079539-appb-C000012

式中， R1 ， R2 ， R3 分别代表氢、羟基、 1 － 6 碳烷氧基、卤素原子、甲酰基、羧基、 1 － 4 碳烷基羰基、 1 － 4 碳烷基羰氧基、 1 － 4 碳烷氧基羰氧基或硝基；或者 R1 和 R2 ， R2 和 R3 分别代表 OCH2O ， OCH2CH2O ； R4 代表氢、羟基、 ONa 、 OK 、 ONH4 、葡萄糖基、烃氧基、烃胺基、二烃胺基、 1 － 6 碳烃基、（ 3 － 6 ）碳烯基、（ 3 － 6 ）卤代碳烯基、（ 3 － 6 ）碳炔基、 1 － 4 碳卤代烷基、 1 － 4 碳烷氧烷基、 1 － 4 碳烷硫烷基、苯基、萘基、色满、 2 ， 3 －二氢－ 1 ， 4 －苯并二噁嗪、 4H-1 ， 3 －苯并二噁嗪、 2 ， 3 －二氢－苯并呋喃、苯并呋喃、苯并噻唑、 1 ， 3 －苯并噁唑、 1 ， 2 －苯并异噁唑或苯并咪唑，各基团是未取代的，或是被一个或一个以上下述基团取代：卤素、 1 － 4 碳烷基、 1 － 4 碳烷氧基、 1 － 4 碳卤代烷基、 1 － 4 碳卤代烷氧基、 1 － 4 碳烷氧烷基、 1 － 4 碳烷硫基、 1 － 4 碳烷基亚磺酰基、 1 － 4 碳烷基磺酰基、硝基、氰基、羟基、羧基、 1 － 4 碳烷基羰基、 1 － 4 碳烷氧基羰基或亚胺基。双键的构型为反式、或顺式、或顺反混合。 Wherein R 1 , R 2 and R 3 each represent hydrogen, hydroxy, 1 - 6 carkolkoxy, halogen atom, formyl group, carboxyl group, 1 - 4 carbon alkylcarbonyl group, 1 - 4 carbon alkylcarbonyloxy group , 1 - 4 carboalkoxycarbonyloxy or nitro; or R 1 and R 2 , R 2 and R 3 represent OCH 2 O , OCH 2 CH 2 O, respectively; R 4 represents hydrogen, hydroxy, ONa, OK, ONH 4 , glucosyl, alkoxy, hydrocarbon amine, dihydrocarbylamino, 1 - 6 carbon hydrocarbyl, ( 3 - 6 ) hexenyl, ( 3 - 6 ) haloalkenyl, ( 3 - 6 ) Carboalkynyl, 1 - 4 carbohaloalkyl, 1 - 4 carbon alkoxyalkyl, 1 - 4 carbon alkylthioalkyl, phenyl, naphthyl, chroman, 2,3-dihydro-1, 4-benzene Dioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole, 1 , 3 -benzoxazole, 1 , 2 -benzene And isoxazolyl or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 carbon alkyl, 1 - 4 carbon alkoxy, 1 - 4 Carbohaloalkyl, 1 - 4 carbohalide Alkenyloxy, 1 - 4 carbon alkoxyalkyl, 1 - 4 carbon alkylthio, 1 - 4 carbon alkylsulfinyl, 1 - 4 carbon alkylsulfonyl, nitro, cyano, hydroxy, carboxy , 1 - 4 carbon alkylcarbonyl, 1 - 4 carbon alkoxycarbonyl or imino group. The configuration of the double bond is trans, or cis, or cis-mix.

本发明所述的阿魏酸及其衍生物中 R1 ， R2 ， R3 分别代表 H ， OH ， OCH3 ，In the ferulic acid and its derivatives of the present invention, R 1 , R 2 and R 3 represent H, OH and OCH 3 , respectively.

OCH2CH3 ， OCOCH3 ， F ， Cl ， Br ， CHO ， CO2H 或 NO2 ；或者 R1 和 R2 ， OCH 2 CH 3 , OCOCH 3 , F , Cl , Br , CHO , CO 2 H or NO 2 ; or R 1 and R 2 ,

R2 和 R3 分别代表 OCH2O ， OCH2CH2O ； R4 代表 OH ， OCH3 ， OCH2CH3 ， R 2 and R 3 represent OCH 2 O , OCH 2 CH 2 O , respectively; R 4 represents OH , OCH 3 , OCH 2 CH 3 ,

CH2CH=CH2 ， NEt2 ， p-Cl-C6H4NH ， ONa, OK, ONH4 ，或葡萄糖基。CH 2 CH=CH 2 , NEt 2 , p-Cl-C 6 H 4 NH , ONa, OK, ONH 4 , or glucosyl.

本发明通式（ I ）的化合物具有优异的抗植物病毒活性，能很好地抑制烟草花叶病毒、辣椒病毒、番茄病毒、甘薯病毒、马铃薯病毒和瓜类病毒及玉米矮花叶病毒等，可有效防治烟草、辣椒、番茄、瓜菜、粮食、蔬菜、豆类等多种作物的病毒病，尤其适合于防治烟草花叶病。The compound of the formula ( I ) of the invention has excellent anti-plant virus activity, and can well inhibit tobacco mosaic virus, capsivirus, tomato virus, sweet potato virus, potato virus and melon virus, and corn dwarf mosaic virus, etc. It can effectively control viral diseases of tobacco, pepper, tomato, melon, food, vegetables, beans and other crops, especially suitable for controlling tobacco mosaic disease.

本发明通式（ I ）的部分化合物在 500 ug/mL 的浓度对烟草花叶病毒的抑制率高达 80% 以上，超过商品化品种病毒 A 、病毒唑、 DADHT 和 DHT 抑制烟草花叶病毒的活性（在 500 ug/mL 抑制率都只有 50 ％）。The partial compound of the formula ( I ) of the present invention inhibits tobacco mosaic virus at a concentration of 500 ug/mL as high as 80% or more, and inhibits the activity of tobacco mosaic virus over the commercial varieties of virus A, ribavirin, DADHT and DHT. (The inhibition rate is only 50% at 500 ug/mL).

本发明通式（ I ）的化合物作为植物病毒抑制剂可以直接使用，也可以加上农业上接受的载体使用，也可以和其他抗植物病毒剂如苯并噻二唑（ BTH ）、噻酰菌胺（ TDL ）、 4- 甲基 -1 ， 2 ， 3- 噻二唑 -5- 甲酸（ TDLA ）、 DL-β- 氨基丁酸（ BABA ）、病毒唑、宁南霉素、菲并吲哚里西啶生物碱安托芬、联三唑类化合物 XY-13 和 XY-30 、病毒 A 、水杨酸、多羟基双萘醛、氨基寡糖素形成互作组合物使用，这些组合物有的表现增效作用，有的表现相加作用。The compound of the formula ( I ) of the present invention can be used as a plant virus inhibitor as it is, or it can be used together with an agriculturally acceptable carrier, and can also be combined with other anti-plant virus agents such as benzothiadiazole (BTH) and thiaform bacteria. Amine ( TDL ), 4-methyl-1 , 2 , 3-thiadiazole-5-carboxylic acid (TDLA), DL-β-aminobutyric acid (BABA), ribavirin, nymidine, phenanthrene The use of the rixidine alkaloids antofen, the triazole compounds XY-13 and XY-30, the virus A, the salicylic acid, the polyhydroxysinaphthaldehyde, and the amino oligosaccharide to form an interaction composition, these compositions have Performance synergy, and some performance additive effects.

本发明的阿魏酸及其衍生物抗植物病毒剂较现有使用的病毒抑制剂，具有很大的优势：化学结构简单，抗植物病毒活性显著，且对多种植物病毒具有抑制作用；毒性极低，环境兼容性好，对非靶标生物安全。 The ferulic acid and its derivative anti-plant virus agent of the invention have great advantages over the existing virus inhibitors: simple chemical structure, significant anti-plant virus activity, and inhibition to various plant viruses; toxicity Very low, environmentally compatible, safe for non-target organisms.

具体实施方式 detailed description

以下通过实施例对本发明作进一步的详细说明，但本发明不限于这些实施例。 The invention is further illustrated by the following examples, but the invention is not limited to the examples.

实施例 1 ： 阿魏酸及其衍生物的化学结构式和物理常数，见表 2 ： Example 1: Chemical structural formula and physical constant of ferulic acid and its derivatives, see Table 2:

表 2. 部分阿魏酸及其衍生物的化学结构式和物理常数 Table 2. Chemical structural formulas and physical constants of some ferulic acid and its derivatives

化合物编号 Compound number 化学结构式Chemical Structure 熔点 (°C) Melting point (°C) 1 1

Figure PCTCN2010079539-appb-C000013
Figure PCTCN2010079539-appb-C000013
172-173 172-173 2 2
Figure PCTCN2010079539-appb-C000014
Figure PCTCN2010079539-appb-C000014
 黄色油状物 Yellow oil 3 3
Figure PCTCN2010079539-appb-C000015
Figure PCTCN2010079539-appb-C000015
 194-198 194-198 4 4
Figure PCTCN2010079539-appb-C000016
Figure PCTCN2010079539-appb-C000016
 132-133 132-133 5 5
Figure PCTCN2010079539-appb-C000017
Figure PCTCN2010079539-appb-C000017
 184-185 184-185 6 6
Figure PCTCN2010079539-appb-C000018
Figure PCTCN2010079539-appb-C000018
 240-242 240-242 7 7
Figure PCTCN2010079539-appb-C000019
Figure PCTCN2010079539-appb-C000019
 191-193 191-193 8 8
Figure PCTCN2010079539-appb-C000020
Figure PCTCN2010079539-appb-C000020
 126-128 126-128 9 9
Figure PCTCN2010079539-appb-C000021
Figure PCTCN2010079539-appb-C000021
 186-189 186-189 10 10
Figure PCTCN2010079539-appb-C000022
Figure PCTCN2010079539-appb-C000022
 230-232 230-232 11 11
Figure PCTCN2010079539-appb-C000023
Figure PCTCN2010079539-appb-C000023
 230-232 230-232 12 12
Figure PCTCN2010079539-appb-C000024
Figure PCTCN2010079539-appb-C000024
 154-157 154-157 13 13
Figure PCTCN2010079539-appb-C000025
Figure PCTCN2010079539-appb-C000025
 200-202 200-202 14 14
Figure PCTCN2010079539-appb-C000026
Figure PCTCN2010079539-appb-C000026
 198-200 198-200 15 15
Figure PCTCN2010079539-appb-C000027
Figure PCTCN2010079539-appb-C000027
 211-214 211-214 16 16
Figure PCTCN2010079539-appb-C000028
Figure PCTCN2010079539-appb-C000028
 184-187 184-187 17 17
Figure PCTCN2010079539-appb-C000029
Figure PCTCN2010079539-appb-C000029
 62-63 62-63 18 18
Figure PCTCN2010079539-appb-C000030
Figure PCTCN2010079539-appb-C000030
 75-76 75-76 19 19
Figure PCTCN2010079539-appb-C000031
Figure PCTCN2010079539-appb-C000031
 216-218 216-218 20 20
Figure PCTCN2010079539-appb-C000032
Figure PCTCN2010079539-appb-C000032
 91-92 91-92 21 twenty one
Figure PCTCN2010079539-appb-C000033
Figure PCTCN2010079539-appb-C000033
 192-194 192-194 22 twenty two
Figure PCTCN2010079539-appb-C000034
Figure PCTCN2010079539-appb-C000034
 172-174 172-174 23 twenty three
Figure PCTCN2010079539-appb-C000035
Figure PCTCN2010079539-appb-C000035
 118-119 118-119 24 twenty four
Figure PCTCN2010079539-appb-C000036
Figure PCTCN2010079539-appb-C000036
 133-134 133-134 25 25
Figure PCTCN2010079539-appb-C000037
Figure PCTCN2010079539-appb-C000037
 223-226 223-226 26 26
Figure PCTCN2010079539-appb-C000038
Figure PCTCN2010079539-appb-C000038
 ＞ 300 > 300 27 27
Figure PCTCN2010079539-appb-C000039
Figure PCTCN2010079539-appb-C000039
 ＞ 300 > 300 28 28
Figure PCTCN2010079539-appb-C000040
Figure PCTCN2010079539-appb-C000040
 ＞ 300 > 300 29 29
Figure PCTCN2010079539-appb-C000041
Figure PCTCN2010079539-appb-C000041
 白色固体 White solid 30 30
Figure PCTCN2010079539-appb-C000042
Figure PCTCN2010079539-appb-C000042
 白色固体 White solid 31 31
Figure PCTCN2010079539-appb-C000043
Figure PCTCN2010079539-appb-C000043
 182-184 182-184 32 32
Figure PCTCN2010079539-appb-C000044
Figure PCTCN2010079539-appb-C000044
 白色固体 White solid 33 33
Figure PCTCN2010079539-appb-C000045
Figure PCTCN2010079539-appb-C000045
 199-202 199-202 34 34
Figure PCTCN2010079539-appb-C000046
Figure PCTCN2010079539-appb-C000046
 白色固体 White solid 35 35
Figure PCTCN2010079539-appb-C000047
Figure PCTCN2010079539-appb-C000047
 白色固体 White solid 36 36
Figure PCTCN2010079539-appb-C000048
Figure PCTCN2010079539-appb-C000048
 白色固体 White solid 37 37
Figure PCTCN2010079539-appb-C000049
Figure PCTCN2010079539-appb-C000049
 白色固体 White solid 38 38
Figure PCTCN2010079539-appb-C000050
Figure PCTCN2010079539-appb-C000050
 白色固体 White solid 39 39
Figure PCTCN2010079539-appb-C000051
Figure PCTCN2010079539-appb-C000051
 白色固体 White solid 40 40
Figure PCTCN2010079539-appb-C000052
Figure PCTCN2010079539-appb-C000052
 149-151 149-151 41 41
Figure PCTCN2010079539-appb-C000053
Figure PCTCN2010079539-appb-C000053
 白色固体 White solid 42 42
Figure PCTCN2010079539-appb-C000054
Figure PCTCN2010079539-appb-C000054
 白色固体 White solid 43 43
Figure PCTCN2010079539-appb-C000055
Figure PCTCN2010079539-appb-C000055
 170-172 170-172 44 44
Figure PCTCN2010079539-appb-C000056
Figure PCTCN2010079539-appb-C000056
 135-136 135-136 45 45
Figure PCTCN2010079539-appb-C000057
Figure PCTCN2010079539-appb-C000057
 白色固体 White solid 46 46
Figure PCTCN2010079539-appb-C000058
Figure PCTCN2010079539-appb-C000058
 160-165 160-165 47 47
Figure PCTCN2010079539-appb-C000059
Figure PCTCN2010079539-appb-C000059
 208-210 208-210

实施例 2 ： 反式阿魏酸（ 1 ）的合成 Example 2: Synthesis of trans-ferulic acid ( 1 )

在 50 mL 圆底烧瓶中，依次加入香兰醛（ 10 g ， 0.065 mol ）、丙二酸（ 7.5 g ， 0.07 mol ）、甲苯（ 15 mL ）、吡啶和苯胺，于 85-95 °C 反应 2 小时。加入 25% 碳酸钾水溶液（ 35 mL ），搅拌。分出水层，用浓盐酸调 pH ，析出大量固体，过滤，用水洗涤，干燥得淡黄色针状结晶反式阿魏酸（ 11.6 g ， 92% ）， mp 172-173 °C 。 In a 50 mL round bottom flask, vanillin (10 g, 0.065 mol) and malonic acid (7.5 g) were added in sequence. , 0.07 mol ), toluene (15 mL), pyridine and aniline were reacted at 85-95 ° C for 2 hours. Add 25% aqueous potassium carbonate solution (35 mL) ), stirring. The aqueous layer was separated, the pH was adjusted with concentrated hydrochloric acid, and a large amount of solid was precipitated, filtered, washed with water, and dried to give pale yellow needle crystals of trans ferulic acid ( 11.6 g, 92% ), mp 172-173 °C.

实施例 3 ： 目标化合物 20 的合成 Example 3: Synthesis of target compound 20

在 100 mL 圆底烧瓶中加入反式阿魏酸 0.5 g ，无水乙醇 30 mL ， 10% Pd-C 催化剂 0.1 g ，室温下由氢气球鼓入氢气 6 小时，过滤除去 Pd-C 催化剂，脱溶得白色固体 0.48 g ，收率 96% ， mp 91-92 °C 。 Add trans ferulic acid 0.5 g, absolute ethanol 30 mL, 10% Pd-C in a 100 mL round bottom flask Catalyst 0.1 g, hydrogen gas was bubbled through a hydrogen balloon at room temperature for 6 hours, Pd-C catalyst was removed by filtration, and desolved to give a white solid 0.48 g, yield 96%, mp 91-92 °C .

实施例 4 ： 目标化合物 25 的合成 Example 4: Synthesis of target compound 25

在 50 mL 圆底烧瓶中加入 8.8 g (E)-3-[(4- 羟基 -3- 甲氧基 -5- 溴 ) 苯基 ] 丙烯酸， 10 mL 乙酸酐， 10 滴无水吡啶，搅拌加热回流 3 小时，冷至室温，析出沉淀，抽滤，滤饼用蒸馏水洗涤，得白色粉末，干燥，用冰醋酸重结晶得 (E)-3-[(4- 乙酰氧基 -3- 甲氧基 -5- 溴 ) 苯基 ] 丙烯酸白色晶体 7.6g ，收率 75.0% ，熔点 208-212 °C 。Add 8.8 g of ( E )-3-[(4-hydroxy-3-methoxy-5-bromo)phenyl]acrylic acid to a 50 mL round bottom flask, 10 mL of acetic anhydride, 10 drops of anhydrous pyridine, stir and heat. After refluxing for 3 hours, cooling to room temperature, precipitation was precipitated, suction filtration, and the filter cake was washed with distilled water to obtain a white powder, which was dried and recrystallized from glacial acetic acid to give ( E )-3-[(4- acetoxy-3- methoxy Base 5-(bromo)phenyl]acrylic acid white crystal 7.6 g, yield 75.0%, melting point 208-212 °C.

在装有尾气吸收装置的 50 mL 圆底烧瓶中加入 3.14 g （ 0.01 mol ） (E)-3-[(4- 乙酰氧基 -3- 甲氧基 -5- 溴 ) 苯基 ] 丙烯酸， 10 mL 无水苯， 3 mL 二氯亚砜，搅拌下加热回流至无气体放出为止，反应完毕，减压除去过量二氯亚砜和溶剂，再将所得酰氯溶于 10 mL 苯用于下一步反应。In a 50 mL round bottom flask equipped with a tail gas absorption unit, 3.14 g (0.01 mol) of ( E )-3-[(4-acetoxy-3-methoxy-5-bromo)phenyl]acrylic acid was added, 10 mL anhydrous benzene, 3 mL of thionyl chloride, heated under reflux with stirring until no gas is released. After the reaction is completed, excess thionyl chloride and solvent are removed under reduced pressure, and the obtained acid chloride is dissolved in 10 mL of benzene for the next reaction. .

在装有滴液漏斗和尾气吸收装置的 150 mL 反应瓶中加入 0.02 mol 对氯苯胺， 15 mL 无水苯，室温搅拌下缓慢滴加上述酰氯溶液，滴毕，反应物继续搅拌 8 小时，有沉淀析出，抽滤得粉末状固体，干燥，经乙醇重结晶得 25 白色针状晶体 3.7 g ，收率 87.1% ，熔点 223-226°C 。Add 0.02 mol of p-chloroaniline and 15 mL of anhydrous benzene to a 150 mL reaction flask equipped with a dropping funnel and a tail gas absorption device. Slowly add the above acid chloride solution while stirring at room temperature. After the dropwise addition, the reaction mixture was stirred for 8 hours. precipitated, suction filtered to give a powdery solid, dried, and recrystallized from ethanol to give 25 as white needle crystals 3.7 g, 87.1% yield, m.p. 223-226 ° C.

实施例 5 ： 以抗烟草花叶病毒（ Tobacco mosaic virus, TMV ）活性为例，阿魏酸及其衍生物抗烟草花叶病毒活性的测定程序如下： Example 5: Taking Tobacco mosaic virus (TMV) activity as an example, the procedure for measuring the activity of ferulic acid and its derivatives against tobacco mosaic virus is as follows:

离体半叶枯斑法 ( Half-leaf necrosis) 筛选方法 ：取新鲜具有典型 TMV 病毒症状的三生烟叶，加入磷酸缓冲溶液 ( 0.01M ， pH 7.2) ，在研钵中研碎，在撒有金刚砂的珊西烟叶上接种，并用清水快速冲洗。接种 1.5-2 小时后，将接种叶片沿主脉剪成两个相等半叶，一半叶片用待测样品的 DMF 溶液浸叶处理，另一半浸于清水中作对照， 72 小时后，统计半叶枯斑数，计算病斑抑制率。 Half-leaf necrosis screening method: take fresh with typical TMV The three-year-old tobacco leaves with virus symptoms were added with phosphate buffer solution (0.01M, pH 7.2), ground in a mortar, inoculated on the emery leaves of the emery, and quickly rinsed with water. Vaccination 1.5-2 After the hour, the inoculated leaves were cut into two equal half leaves along the main vein, half of the leaves were treated with the DMF solution of the sample to be tested, and the other half was immersed in clear water for comparison. After the hour, the number of dead leaves was counted and the lesion inhibition rate was calculated.

活体保护作用筛选方法：选长势一致的 5-6 叶期心叶烟，用毛笔轻轻在左半叶分别涂施一定浓度的试样和对照样，右半叶片涂施溶媒作对照， 24 小时后，汁液摩擦接种病毒于处理叶片，每处理 3 株 ( 共计 9 片叶片 ) ，重复 3 次， 72h 后调查心叶烟枯斑数，计算病斑抑制率。 Screening method for in vivo protection: select the same 5-6 Leaf leaf heart leaf tobacco, gently apply a certain concentration of the sample and the control sample in the left half of the leaf with a brush, and apply the solvent to the right half of the leaf as a control. After 24 hours, the juice is rubbed and inoculated with the virus to treat the leaves, and each treatment 3 Strain ( Total 9 The leaf blade was repeated 3 times. After 72 hours, the number of leaves and leaves of the heart leaf was investigated, and the inhibition rate of the lesion was calculated.

活体钝化作用筛选方法：选长势一致的 5-6 叶期心叶烟，将一定浓度的试样和对照样分别与病毒汁液 1:1(V/V) 混合钝化 0.5h ，摩擦接种于处理左半叶片，病毒液汁与溶媒 1:1(V/V) 混合摩擦接种于右半叶，每处理 3 株 ( 共计 9 片叶片 ) ，重复 3 次， 72h 后调查心叶烟枯斑数，计算病斑抑制率。 Screening method for in vivo passivation: select 5-6 leaf stage heart leaf smoke with consistent growth, and separate certain concentrations of samples and control samples with virus juice 1:1 (V/V) mixed passivation for 0.5 h, rubbed inoculated in the left half of the leaves, and virus juice and solvent 1:1 (V/V) mixed friction inoculated in the right half of the leaves, 3 plants per treatment (9 pieces in total) blade ), repeated 3 times, 72 hours later, the number of heart leaf smoke spots was investigated, and the lesion inhibition rate was calculated.

活体治疗作用筛选方法：选长势一致的 5-6 叶期心叶烟，先用病毒汁液摩擦接种于处理叶片，一定时间后分别涂施一定浓度的试样和对照样在左半叶，右半叶以溶媒为对照，每处理 3 株 ( 共计 9 片叶片 ) ，重复 3 次， 72h 后调查心叶烟枯斑数，计算病斑抑制率。 Screening method for in vivo treatment: selection of the same 5-6 Leaf leaf heart leaf tobacco was first inoculated with the virus juice in the treated leaves. After a certain period of time, a certain concentration of the sample and the control sample were applied to the left half of the leaf, and the right half of the leaf was used as the control. Each treatment was 3 (9 in total) Blade Repeated 3 times. After 72 hours, the number of dead leaves of heart leaf was investigated, and the inhibition rate of lesions was calculated.

抑制率 (%)=[( 对照枯斑数 - 处理枯斑数 )/ 对照枯斑数 ]×100% Inhibition rate (%) = [(control plaque number - number of treated plaques) / number of control plaques] × 100%

表 3 ，表 4 为部分化合物的抗烟草花叶病毒（ Tobacco mosaic virus, TMV ）活性测试结果： Table 3 and Table 4 are some of the compounds against Tobacco mosaic virus (TMV). ) Activity test results:

表 3. 离体半叶枯斑法测定各试样抗 TMV 活性 Table 3. Determination of anti-TMV activity of each sample by in vitro half-leaf method

化合物 Compound 浓度 (µg/mL) Concentration (μg/mL) 抑制率 (%) Inhibition rate (%) 化合物 Compound 浓度 (µg/mL) Concentration (μg/mL) 抑制率 (%) Inhibition rate (%) 1 1 500 500 90.2 90.2 11 11 500 500 >50 >50 2 2 500 500 >50 >50 12 12 500 500 >50 >50 3 3 500 500 93.6 93.6 17 17 500 500 >50 >50 5 5 500 500 >50 >50 18 18 500 500 >50 >50 6 6 500 500 >50 >50 26 26 500 500 >50 >50 7 7 500 500 >50 >50 28 28 500 500 >50 >50 9 9 500 500 >50 >50 30 30 500 500 >50 >50

表 4. 活体 测试各试样抗 TMV 活性 Table 4. Living body Test each sample against TMV activity

化合物 Compound 浓度 (µg/mL) Concentration (μg/mL) 保护效果(%) Protection effect (%) 治疗效果 (%) treatment effect (%) 钝化效果 (%) Passivation effect (%) 1 1 100 100 70.5 70.5 44.8 44.8 53.3 53.3

Claims (6)

阿魏酸及其衍生物抗植物病毒剂 ，其特征在于，它具有如下通式（ I ）所示结构： Ferulic acid and its derivative anti-plant virus agent, characterized in that it has the structure represented by the following formula (I):
Figure PCTCN2010079539-appb-I000001
式中， R1 ， R2 ， R3 分别代表氢、羟基、 1 － 6 碳烷氧基、卤素原子、甲酰基、羧基、 1 － 4 碳烷基羰基、 1 － 4 碳烷基羰氧基、 1 － 4 碳烷氧基羰氧基或硝基；或者 R1 和 R2 ， R2 和 R3 分别代表 OCH2O ， OCH2CH2O ； R4 代表氢、羟基、 ONa 、 OK 、 ONH4 、葡萄糖基、烃氧基、烃胺基、二烃胺基、 1 － 6 碳烃基、（ 3 － 6 ）碳烯基、（ 3 － 6 ）卤代碳烯基、（ 3 － 6 ）碳炔基、 1 － 4 碳卤代烷基、 1 － 4 碳烷氧烷基、 1 － 4 碳烷硫烷基、苯基、萘基、色满、 2 ， 3 －二氢－ 1 ， 4 －苯并二噁嗪、 4H-1 ， 3 －苯并二噁嗪、 2 ， 3 －二氢－苯并呋喃、苯并呋喃、苯并噻唑、 1 ， 3 －苯并噁唑、 1 ， 2 －苯并异噁唑或苯并咪唑，各基团是未取代的，或是被一个或一个以上下述基团取代：卤素、 1 － 4 碳烷基、 1 － 4 碳烷氧基、 1 － 4 碳卤代烷基、 1 － 4 碳卤代烷氧基、 1 － 4 碳烷氧烷基、 1 － 4 碳烷硫基、 1 － 4 碳烷基亚磺酰基、 1 － 4 碳烷基磺酰基、硝基、氰基、羟基、羧基、 1 － 4 碳烷基羰基、 1 － 4 碳烷氧基羰基或亚胺基。双键的构型为反式、或顺式、或顺反混合。
Figure PCTCN2010079539-appb-I000001
Wherein R 1 , R 2 and R 3 each represent hydrogen, hydroxy, 1 - 6 carkolkoxy, halogen atom, formyl group, carboxyl group, 1 - 4 carbon alkylcarbonyl group, 1 - 4 carbon alkylcarbonyloxy group , 1 - 4 carboalkoxycarbonyloxy or nitro; or R 1 and R 2 , R 2 and R 3 represent OCH 2 O , OCH 2 CH 2 O, respectively; R 4 represents hydrogen, hydroxy, ONa, OK, ONH 4 , glucosyl, alkoxy, hydrocarbon amine, dihydrocarbylamino, 1 - 6 carbon hydrocarbyl, ( 3 - 6 ) hexenyl, ( 3 - 6 ) haloalkenyl, ( 3 - 6 ) Carboalkynyl, 1 - 4 carbohaloalkyl, 1 - 4 carbon alkoxyalkyl, 1 - 4 carbon alkylthioalkyl, phenyl, naphthyl, chroman, 2,3-dihydro-1, 4-benzene Dioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole, 1 , 3 -benzoxazole, 1 , 2 -benzene And isoxazolyl or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 carbon alkyl, 1 - 4 carbon alkoxy, 1 - 4 Carbohaloalkyl, 1 - 4 carbon Alkenyloxy, 1 - 4 carbon alkoxyalkyl, 1 - 4 carbon alkylthio, 1 - 4 carbon alkylsulfinyl, 1 - 4 carbon alkylsulfonyl, nitro, cyano, hydroxy, carboxy , 1 - 4 carbon alkylcarbonyl, 1 - 4 carbon alkoxycarbonyl or imino group. The configuration of the double bond is trans, or cis, or cis-mix. 根据权利要求 1 所述的阿魏酸及其衍生物抗植物病毒剂，其特征在于， R1 ， R2 ， R3 分别代表 H ， OH ， OCH3 ， OCH2CH3 ， OCOCH3 ， F ， Cl ， Br ， CHO ， CO2H 或 NO2 ；或者 R1 和 R2 ， R2 和 R3 分别代表 OCH2O 、 OCH2CH2O ； R4 代表 OH ， OCH3 ， OCH2CH3 ， CH2CH=CH2 ， NEt2 ， p-Cl-C6H4NH ， ONa, OK, ONH4 或葡萄糖基；双键的构型为反式、或顺式、或顺反混合。The ferulic acid and its derivative anti-plant virus agent according to claim 1, wherein R 1 , R 2 and R 3 represent H, OH, OCH 3 , OCH 2 CH 3 , OCOCH 3 , F , respectively. Cl , Br , CHO , CO 2 H or NO 2 ; or R 1 and R 2 , R 2 and R 3 represent OCH 2 O , OCH 2 CH 2 O , respectively; R 4 represents OH , OCH 3 , OCH 2 CH 3 , CH 2 CH=CH 2 , NEt 2 , p-Cl-C 6 H 4 NH , ONa, OK, ONH 4 or glucosyl; the configuration of the double bond is trans, or cis, or cis-mix. 根据权利要求 1 或 2 所述的阿魏酸及其衍生物抗植物病毒剂，其特征在于，优选的通式 I 所示的化合物是反式阿魏酸。The ferulic acid and its derivative anti-plant virus agent according to claim 1 or 2, wherein the preferred compound represented by the formula I is trans-ferulic acid. 一种权利要求 1 所述的阿魏酸及其衍生物抗植物病毒剂的应用，其特征在于，它作为抗植物病毒剂，能很好地抑制烟草花叶病毒、辣椒病毒、番茄病毒、甘薯病毒、马铃薯病毒和瓜类病毒及玉米矮花叶病毒，可有效防治烟草、辣椒、番茄、瓜菜、粮食、蔬菜、豆类作物的病毒病。Claim 1 The use of ferulic acid and its derivative against plant virus agent is characterized in that it is an anti-plant virus agent, which can well inhibit tobacco mosaic virus, capsivirus, tomato virus, sweet potato virus, potato virus and Melon virus and corn dwarf mosaic virus can effectively control viral diseases of tobacco, pepper, tomato, melon, food, vegetables, and bean crops. 根据权利要求 4 所述的阿魏酸及其衍生物抗植物病毒剂的应用，其特征在于，它作为抗植物病毒剂直接使用。According to claim 4 The use of ferulic acid and its derivatives against plant viral agents is characterized in that it is used directly as an anti-plant virus agent. 根据权利要求 4 所述的阿魏酸及其衍生物抗植物病毒剂的应用，其特征在于，它作为抗植物病毒剂和下述抗植物病毒剂苯并噻二唑 BTH 、噻酰菌胺 TDL 、 4- 甲基 -1 ， 2 ， 3- 噻二唑 -5- 甲酸 TDLA 、 DL-β- 氨基丁酸 BABA 、病毒唑、宁南霉素、菲并吲哚里西啶生物碱安托芬、联三唑类化合物 XY-13 和 XY-30 、病毒 A 、水杨酸、多羟基双萘醛或氨基寡糖素形成互作组合物使用。Use of ferulic acid and a derivative thereof against plant virus agent according to claim 4, characterized in that it is used as an anti-plant virus agent and the following anti-plant virus agent benzothiadiazole BTH, thiazide TDL, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid TDLA, DL-β-aminobutyric acid BABA , ribavirin, nymidine, phenanthroline alkaloids antoine, bis-triazoles XY-13 and XY-30, virus A Use of salicylic acid, polyhydroxy bis naphthaldehyde or amino oligosaccharide to form an interactive composition.
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