CN115211436B - 一种农用增效杀菌剂及其应用 - Google Patents
一种农用增效杀菌剂及其应用 Download PDFInfo
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- CN115211436B CN115211436B CN202210777791.3A CN202210777791A CN115211436B CN 115211436 B CN115211436 B CN 115211436B CN 202210777791 A CN202210777791 A CN 202210777791A CN 115211436 B CN115211436 B CN 115211436B
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- China
- Prior art keywords
- camphor
- thiosemicarbazone
- agricultural
- camphor thiosemicarbazone
- fungicide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003899 bactericide agent Substances 0.000 title abstract 4
- HFTWOMIQZXSECJ-UHFFFAOYSA-N [(4,7,7-trimethyl-3-bicyclo[2.2.1]heptanylidene)amino]thiourea Chemical compound C1CC2(C)C(=NNC(N)=S)CC1C2(C)C HFTWOMIQZXSECJ-UHFFFAOYSA-N 0.000 claims abstract description 112
- -1 feniostrobin Substances 0.000 claims abstract description 45
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- QGHREAKMXXNCOA-UHFFFAOYSA-N thiophanate-methyl Chemical compound COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC QGHREAKMXXNCOA-UHFFFAOYSA-N 0.000 claims abstract description 14
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical group CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 claims abstract description 14
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- SRVJKTDHMYAMHA-WUXMJOGZSA-N thioacetazone Chemical compound CC(=O)NC1=CC=C(\C=N\NC(N)=S)C=C1 SRVJKTDHMYAMHA-WUXMJOGZSA-N 0.000 claims description 6
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BSDQITJYKQHXQR-UHFFFAOYSA-N methyl prop-2-eneperoxoate Chemical compound COOC(=O)C=C BSDQITJYKQHXQR-UHFFFAOYSA-N 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- 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
- A01N47/08—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 one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
-
- 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
- A01N37/44—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
- A01N37/50—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 the nitrogen atom being doubly bound to the carbon skeleton
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
- A01P3/00—Fungicides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C337/06—Compounds containing any of the groups, e.g. thiosemicarbazides
- C07C337/08—Compounds containing any of the groups, e.g. thiosemicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. thiosemicarbazones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
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Abstract
本发明属于农药樟脑缩氨基硫脲技术领域，具体涉及一种农用增效杀菌剂，所述农用增效杀菌剂为樟脑缩氨基硫脲或由樟脑缩氨基硫脲和市售杀菌剂组成，所述樟脑缩氨基硫脲与市售杀菌剂之间摩尔比为1‑55∶55‑99，所述杀菌剂为三环唑、己唑醇、苯醚甲环唑、醚菌脂、嘧菌酯和甲基硫菌灵中的一种。本发明高效制备樟脑缩氨基硫脲，并将其用作增效杀菌剂，或与市售杀菌剂组合使用，提高了现有市售抗菌剂的使用效果，减少农药用量；并测试了本发明农用增效杀菌剂对植物真菌病害的体外抗菌活性，研究结果表明，樟脑缩氨基硫脲对植物真菌病害(尤其水稻纹枯病菌)体现出一定的抗菌活性，具有作为新型农药前体化合物或增效剂的性质。
Description
技术领域
本发明属于农药樟脑缩氨基硫脲技术领域，具体涉及一种农用增效杀菌剂及其应用。
背景技术
防治植物病害的方法主要有农业防治、生物防治和化学防治。其中化学防治是使用化学药剂防治植物病害的方法，具有高效、速效、使用方便、经济效益高等优点，目前是防治植物病害最主要的方法。广泛用于防治植物病害的抗菌剂种类(代表性抗菌剂)包括：无机类(代森锰锌)、抗生素类(井冈霉素)、微生物类(拮抗细菌枯草芽孢杆菌和蜡质芽孢杆菌)、有机磷类(稻瘟净、异稻瘟净)、甾醇生物合成抑制剂类(十三吗啉、三唑酮)、苯并咪唑类(多菌灵、苯菌灵、青菌灵等)、三唑类(己唑醇、丙环唑、苯醚甲环唑等)、甲氧基丙烯酸酯类(吡唑醚菌酯)和琥珀酸脱氢酶抑制剂类(噻呋酰胺)等。
然而，由于近几十年来，新型抗菌剂的研发速度有限，井冈霉素、丙环唑、吡唑醚菌酯、噻氟酰胺等主流抗菌剂已经因为长时间使用，导致植物病害对它们形成不同程度的抗性。例如：井冈霉素是最成功的生物源抗菌剂之一，已累计使用超过50年。目前发现井冈霉素的作用机理包括：抑制病菌海藻糖酶活性，使海藻糖不能分解为葡萄糖；抑制肌醇的生物合成来影响磷脂的产生；抑制病菌纤维素降解酶和多聚半乳糖醛酸酶，从而降低病菌致病力。丙环唑属于三唑类抗菌剂，是一种甾醇甲基化抑制剂，主要干扰真菌类固醇生物合成，抑制麦角甾醇的合成；吡唑醚菌酯是一种新型广谱甲氧基丙烯酸酯类抗菌剂，通过抑制线粒体呼吸作用，最终导致细胞死亡，具有保护、治疗、叶片渗透传导作用；噻呋酰胺是琥珀酸脱氢酶抑制剂，抑制病菌三羧酸循环中琥珀酸脱氢酶，导致菌体死亡，这3种抗菌剂均已累计使用达30年或更久。研究表明，由于长期重复使用，加之在使用中存在用药不科学等原因，植物病害已逐渐对井冈霉素、丙环唑、吡唑醚菌酯、噻呋酰胺等抗菌剂产生不同程度的抗药性。如果没有新型替代抗菌剂或抗菌增效剂的出现，病菌抗药性的将进一步升高，直接导致植物病害防治效果下降，对于作物的种植安全和经济产出将形成巨大威胁。因此，进一步地开发作用机理独特的新型替代抗菌剂或抗菌增效剂迫在眉睫。
发明内容
本发明目的在于克服现有技术不足，针对市售抗菌剂因长期使用，导致植物病害产生抗性和防治效果下降的问题，提供一种农用增效杀菌剂，用于解决现有市售抗菌剂使用效果下降和抗性提升的问题，延长现有市售抗菌剂的使用寿命。
为达到上述目的，本发明采用的技术方案如下：
一种农用增效杀菌剂，所述农用增效杀菌剂为樟脑缩氨基硫脲或由樟脑缩氨基硫脲和市售杀菌剂组成。
优选地，所述樟脑缩氨基硫脲与市售杀菌剂之间的摩尔比为1-50∶50-99，所述杀菌剂为三环唑、己唑醇、苯醚甲环唑、醚菌脂、嘧菌酯和甲基硫菌灵中的一种。
本发明的目的还在于克服现有技术中樟脑缩氨基硫脲制备工艺存在的不足，提供一种反应成本低，操作条件温和，能源消耗低，对环境友好，原料转化率高、成品产率高的樟脑缩氨基硫脲的制备方法。
所述樟脑缩氨基硫脲的制备方法，包括如下步骤：以樟脑、氨基硫脲为原料进行反应得到粗产品，再经重结晶得到樟脑缩氨基硫脲成品。
为了能够进一步保证反应迅速且产物得率高，在小分子醇溶剂存在条件下，分别加入樟脑、氨基硫脲、催化剂，持续搅拌混合均匀，然后调控反应体系至适宜温度后，反应适宜时间，得到樟脑缩氨基硫脲粗品，再经重结晶后，得到樟脑缩氨基硫脲成品。
优选地，所述樟脑与氨基硫脲之间的摩尔比为1∶0.5-2。
优选地，所述小分子醇溶剂选自甲醇、乙醇、异丙醇中的一种，进一步优选为异丙醇，其中，所述樟脑与小分子醇溶剂之间的摩尔体积比为1moL∶2L。
优选地，所述催化剂为无机酸的溶液或小分子有机酸的溶液，所述无机酸为盐酸或硫酸，所述小分子有机酸选自甲酸、乙酸、柠檬酸中的一种，所述催化剂的浓度为5％wt-15％wt，所述樟脑与小分子醇溶剂之间的摩尔体积比为1moL∶0.1L。
优选地，所述适宜温度为10℃-35℃，所述适宜时间为2h-6h。
优选地，重结晶中使用的溶剂选自乙醇、乙醇水溶液、乙醇石油醚混合溶液中的一种。
基于一个总的发明构思，本发明的另一个目的在于保护上述农用增效杀菌剂在防治植物真菌病害方面的应用。
与现有技术相比，本发明高效制备樟脑缩氨基硫脲，并将其用作增效杀菌剂，或与市售杀菌剂组合使用，提高了现有市售抗菌剂的使用效果，减少农药用量；并测试了本发明中的农用增效杀菌剂对植物真菌病害的体外抗菌活性，研究结果表明，樟脑缩氨基硫脲对植物真菌病害(尤其水稻纹枯病菌)体现出一定的抗菌活性，具有作为新型农药前体化合物或增效剂的性质。
附图说明
图1本发明合成樟脑缩氨基硫脲的路线图；
图2本发明合成的樟脑缩氨基硫脲的氢谱表征图；
图3本发明合成的樟脑缩氨基硫脲的碳谱表征图；
图4本发明合成的樟脑缩氨基硫脲的红外表征图；
图5本发明合成的樟脑缩氨基硫脲的核磁表征图；
图6ZNSN含量变化对ZNSN/己唑醇复配物抗菌活性的影响；
图7ZNSN含量变化对ZNSN/三环唑复配物抗菌活性的影响；
图8ZNSN含量变化对ZNSN/苯醚甲环唑复配物抗菌活性的影响；
图9ZNSN含量变化对ZNSN/醚菌脂复配物抗菌活性的影响；
图10ZNSN含量变化对ZNSN/嘧菌酯复配物抗菌活性的影响；
图11ZNSN含量变化对ZNSN/甲基硫菌灵复配物抗菌活性的影响。
具体实施方式
为使本发明的目的、技术方案和优点更加明白清楚，结合具体实施方式，对本发明做进一步描述，但是本发明并不限于这些实施例。需要说明的是，在不相冲突的前提下，以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。在本发明中，所采用的设备和原料等均可从市场购得或本领域常用的。下述实施例中的方法，如没有特别说明，均为本领域的常规方法。
本文中所用的术语“包含”、“包括”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或者优选值与任何范围下限或优选值的任意一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1至5”时，所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。当数值范围在本文中被描述时，除非另外地说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。
下面对本发明的具体实施例做详细说明。
实施例
本实施例中的樟脑缩氨基硫脲的制备方法，包括如下步骤：
在配有磁力搅拌器的50mL圆底烧瓶中分别加入1.522g(10mmol)樟脑、0.910g(10mmol)氨基硫脲、20mLIPA(异丙醇)、1mL 10％HCl，在室温25℃条件下搅拌反应4h，通过TLC检测反应进度，展开剂为石油醚和乙酸乙酯(V石油醚/V乙酸乙酯＝4.5∶1)；
反应完全后，抽滤得固体粉末，乙醇重结晶提纯，再次抽滤，用石油醚冲洗滤饼2-3次后干燥得纯品。
具体合成路线如图1所示，采用1H NMR、13C NMR、FT-IR、HRMS对所得化合物的结构进行表征。
樟脑缩氨基硫脲结构表征数据如下：白色针状晶体，产率：93.24％；m.p.196-200℃；FT-IR v(cm-1):3423,3250,3163(N-H),1739,1664(C＝N),1304(C＝S)；1H NMR(400MHz,DMSO)δ9.82(s,1H),8.04(s,1H),7.41(s,1H),3.35(s,1H),2.02(d,J＝18.0Hz,1H),1.92(t,J＝4.3Hz,1H),1.78(ddd,J＝11.9,8.0,3.8Hz,1H),1.72–1.66(m,1H),1.30–1.25(m,1H),1.20–1.15(m,1H),0.95(s,2H),0.88(s,2H),0.69(s,2H).13C NMR(101MHz,DMSO-d6)δ178.57,166.64,52.87,47.99,43.80,35.00,32.82,27.20,19.69,18.95,11.61.HRMS:m/z225.1378[M+H]+.
试验例
1.本试验所需的水稻纹枯病菌(Rhizoctonia solani)是由江西农业大学国家林草局木本香料(华东)工程技术研究中心提供和培养。
2.实验步骤
2.1培养基制备
称取适量马铃薯葡萄糖琼脂培养基(PDA)，将所取PDA和去离子蒸馏水混合煮至30min，至煮沸，取出加入到大号量筒定容(根据液体体积选取合适量筒)，再倒入100mL量筒最终定容至60mL，然后倒入锥形瓶，用带芯封口膜、橡皮筋进行封口。最后将锥形瓶和后续实验要用到的移液枪头放入立式压力蒸汽灭菌锅灭菌。
2.2含药平板制备
准备一定规格的离心管和计算出所需的药品，药品在万分之一天平称取后装入离心管中，再将提前准备好的移液枪、封口膜和打孔器以及离心管放入无菌室中的无菌超净工作台，做好戴手套和口罩等一系列安全规范操作后，开始准备培养皿(分别在培养皿上标注日期、所接菌种、复配物的名称以及其比例浓度)。然后打开紫外灯灭菌30min，离开无菌室，记录数据并定期观察灭菌锅是否气压过高，如若过高，则打开放气阀，保证实验安全。30min后，无菌室灭菌完毕，与此同时灭菌锅亦完成培养基和相关器械的灭菌，取出带PDA的锥形瓶和移液枪回到灭菌室重新做好安全规范操作，并开始下一步实验。以第一梯度为1000μmol/L为例，用移液枪吸取400μL溶解剂(溶解剂选用的是无毒、常用且价格低廉的95％无水乙醇)，注入离心管中，充分震荡摇匀，使其完全溶解，之后吸取200μL的溶剂注入含培养基的60mL锥形瓶中，摇匀混合备用，此锥形瓶为1000μmol/L复配物浓度梯度，然后吸取200μL溶解剂注入离心管中，震荡摇匀，吸取200μL溶剂注入含培养基的60mL锥形瓶中，此锥形瓶为500μmol/L复配物浓度梯度，以此列推。将含培养基的60mL锥形瓶均匀的倒入培养皿中，待冷却后准备接菌。在含药平板制备的过程中，空白对照组也要加入同等剂量的的溶解剂，避免实验误差。
2.3接菌和培养
将60 mL培养基均分倒入3个培养皿当中，待培养基凝固后(大概30min，待培养液由深黄变至浅黄即可)使用5mm打孔器(使用前先灭菌烧红)打孔(垂直落下)，使用接种针(使用前先用酒精灯灭菌烧红)将5mm菌饼接至培养皿中心位置，接菌完成后使用封口膜封口，做好标记。将接菌后的培养皿含培养基的一面朝上置于28℃培养箱中培养，最后打扫实验卫生并排除一系列安全隐患。
2.4数据测量和计算
待空白对照组(CK)菌落长满整个培养皿三分之二时即可测量数据，使用十字交叉法量取菌落的直径，求其平均值，减去菌落的直径(0.5cm)，可得单个菌落的直径。然后对测量所得的数据进行计算得到抑菌率，计算公式如下：
利用SPSS软件进行按照步骤和要求计算得到EC50、毒力回归方程以及相关系数R2。复配物的理论EC50(假设复配物两个组分之间无协同抗菌效果时的EC50值)，计算方法如下，以5％ZNSN和95％三环唑的复配物为例(摩尔含量)，理论EC50值等于5％乘以ZNSN阳性对照的EC50值加上95％乘以三环唑阳性对照的EC50值。
3.结果与讨论
实施例1的樟脑缩氨基硫脲、6种市售抗菌剂、以及樟脑缩氨基硫脲和市售抗菌剂的复配物的抗菌活性数据列于下表1。在表1中，A代表己唑醇，B代表三环唑，C代表苯醚甲环唑，D代表醚菌酯，E代表嘧菌酯，F代表甲基硫菌灵，ZNSN代表樟脑缩氨基硫脲。A1表示ZNSN/己唑醇复配物中含有5％(摩尔含量)的ZNSN；A2表示ZNSN/己唑醇复配物中含有10％(摩尔含量)的ZNSN，A3表示ZNSN/己唑醇复配物中含有15％(摩尔含量)的ZNSN，之后的复配物以此类推。
表1樟脑缩氨基硫脲与农药复配的抗菌活性数据
注：A代表己唑醇，B代表三环唑，C代表苯醚甲环唑，D代表醚菌酯，E代表嘧菌酯，F代表甲基硫菌灵，A1的意思是占比5％的ZNSN和95％的己唑醇的复配物，A2中ZNSN占比10％，一直到A5中ZNSN占比25％，之后的复配物以此类推。“-”表示无测试数据。
3.1樟脑缩氨基硫脲与己唑醇协同抗菌分析
由表1可知，樟脑缩氨基硫脲/己唑醇复配物(A1-A5)对水稻纹枯病菌的EC50值在0.07μmol/L-0.11μmol/L之间，体现出高效的抗菌活性，且它们的EC50值均低于樟脑缩氨基硫脲和己唑醇的EC50值，表明樟脑缩氨基硫脲/己唑醇复配物相比樟脑缩氨基硫脲和己唑醇而言，对水稻纹枯病菌具有更强的抗菌活性，也证明樟脑缩氨基硫脲和己唑醇之间存在良好的协同抗菌作用。ZNSN含量变化对ZNSN/己唑醇复配物抗菌活性的影响见图6。由图6可知，樟脑缩氨基硫脲/己唑醇复配物的实验EC50值均低于樟脑缩氨基硫脲/己唑醇复配物按照组分比例计算获得的理论EC50值(即樟脑缩氨基硫脲和己唑醇无协同作用时的EC50算数值)，这进一步表明，樟脑缩氨基硫脲和己唑醇之间存在协同抗菌作用。樟脑缩氨基硫脲/己唑醇复配物A2体现出最强的抗菌活性，其EC50值为0.07μmol/L，表明当樟脑缩氨基硫脲的摩尔含量为10％，樟脑缩氨基硫脲/己唑醇复配物中的两种组分之间可以形成最强的协同抗菌作用。
3.2樟脑缩氨基硫脲与三环唑协同抗菌分析
由表1可知，樟脑缩氨基硫脲/三环唑复配物B1-B5对水稻纹枯病菌的EC50值在40.87μmol/L-93.11μmol/L之间，体现出一定的抗菌活性，且它们的EC50值均低于三环唑的EC50值。脑缩氨基硫脲/三环唑复配物B4-B5相比樟脑缩氨基硫脲，对水稻纹枯病菌具有更强的抗菌活性，它们的EC50值均低于樟脑缩氨基硫脲的EC50值，表明樟脑缩氨基硫脲/三环唑复配物B4-B5相比樟脑缩氨基硫脲而言，对水稻纹枯病菌具有更强的抗菌活性。上述结果证明樟脑缩氨基硫脲和三环唑之间存在良好的协同抗菌作用。ZNSN含量变化对ZNSN/三环唑复配物抗菌活性的影响见图7。由图7可知，樟脑缩氨基硫脲/三环唑复配物的实验EC50值均低于其理论EC50值，这进一步表明，樟脑缩氨基硫脲和三环唑之间存在协同抗菌作用。樟脑缩氨基硫脲/三环唑复配物B5体现出最低的EC50值(40.87μmol/L)，表明当樟脑缩氨基硫脲的摩尔含量为25％，樟脑缩氨基硫脲/三环唑复配物中的两种组分之间可以形成最强的协同抗菌作用。
3.3樟脑缩氨基硫脲与苯醚甲环唑协同抗菌分析
由表1可知，樟脑缩氨基硫脲/苯醚甲环唑复配物C1-C5对水稻纹枯病菌的EC50值在0.03μmol/L-0.27μmol/L之间，体现高效的抗菌活性，樟脑缩氨基硫脲/苯醚甲环唑复配物C3-C5的EC50值低于苯醚甲环唑的EC50值，表明樟脑缩氨基硫脲/苯醚甲环唑复配物C3-C5相比苯醚甲环唑而言，对水稻纹枯病菌具有更强的抗菌活性，且樟脑缩氨基硫脲/苯醚甲环唑复配物C1-C5相比樟脑缩氨基硫脲而言，对水稻纹枯病菌均具有更强的抗菌活性，以上可证明樟脑缩氨基硫脲和苯醚甲环唑之间存在良好的协同抗菌作用。ZNSN含量变化对ZNSN/苯醚甲环唑复配物抗菌活性的影响见图8。由图8可知，樟脑缩氨基硫脲/苯醚甲环唑复配物的实验EC50值均低于其理论EC50值，这进一步表明，樟脑缩氨基硫脲和苯醚甲环唑之间存在协同抗菌作用。在复配物中C1到C2实验EC50值呈上升趋势，C3到C5的EC50值逐渐下降，樟脑缩氨基硫脲/苯醚甲环唑复配物C5体现出最低的EC50值(0.03μmol/L)，表明当樟脑缩氨基硫脲的摩尔含量为25％，樟脑缩氨基硫脲/苯醚甲环唑复配物中的两种组分之间可以形成最强的协同抗菌作用，并且其抗菌活性很强，具有良好的市场化前景。
3.4樟脑缩氨基硫脲与醚菌脂协同抗菌分析
由表1可知，樟脑缩氨基硫脲/醚菌脂复配物D1-D5对水稻纹枯病菌的EC50值在6.21μmol/L-8.65μmol/L之间，体现一定的抗菌活性，樟脑缩氨基硫脲/醚菌脂复配物D1-D5的EC50值均高于于醚菌脂的EC50值，表明樟脑缩氨基硫脲对醚菌脂的抗菌活性增效不显著。ZNSN含量变化对ZNSN/醚菌脂复配物抗菌活性的影响见图9。由图9可知，樟脑缩氨基硫脲/醚菌脂复配物D1-D2实验EC50值高于其理论EC50值，随着ZNSN比例增加，复配物D3-D5实验EC50值低于其理论EC50值，由此可知樟脑缩氨基硫脲对醚菌脂具有抗菌增效作用，但不显著。樟脑缩氨基硫脲/醚菌脂复配物D1体现出最低的EC50值(6.21μmol/L)，表明当樟脑缩氨基硫脲的摩尔含量为5％，樟脑缩氨基硫脲/醚菌脂复配物中的两种组分之间可以形成最强的协同抗菌作用。
3.5樟脑缩氨基硫脲与嘧菌酯协同抗菌分析
由表1可知，樟脑缩氨基硫脲/嘧菌脂复配物E1-E5对水稻纹枯病菌的EC50值在0.19μmol/L-0.39μmol/L之间，体现出高效的抗菌活性，樟脑缩氨基硫脲/嘧菌酯复配物E3-E5的EC50值低于嘧菌酯的EC50值，表明樟脑缩氨基硫脲/嘧菌酯复配物E3-E5相比嘧菌酯而言，对水稻纹枯病菌具有更强的抗菌活性，且樟脑缩氨基硫脲/嘧菌酯复配物E1-E5相比樟脑缩氨基硫脲而言，对水稻纹枯病菌均具有更强的抗菌活性，证明樟脑缩氨基硫脲和嘧菌酯之间存在良好的协同抗菌作用。ZNSN含量变化对ZNSN/嘧菌酯复配物抗菌活性的影响见图10。由图10可知，樟脑缩氨基硫脲/嘧菌酯复配物E1-E5的实验EC50值均低于其理论EC50值，这进一步表明，樟脑缩氨基硫脲和嘧菌酯之间存在协同抗菌作用。樟脑缩氨基硫脲/嘧菌酯复配物E5体现出最低的EC50值(0.19μmol/L)，表明当樟脑缩氨基硫脲的摩尔含量为25％，樟脑缩氨基硫脲/嘧菌酯复配物中的两种组分之间可形成最强的协同抗菌作用。
3.6樟脑缩氨基硫脲与甲基硫菌灵协同抗菌分析
由表1可知，樟脑缩氨基硫脲/甲基硫菌灵复配物F1-F5对水稻纹枯病菌的EC50值在10.90μmol/L-18.01μmol/L之间，体现出一定的抗菌活性，且它们的EC50值均低于樟脑缩氨基硫脲和甲基硫菌灵的EC50值，表明樟脑缩氨基硫脲/甲基硫菌灵复配物相比樟脑缩氨基硫脲和甲基硫菌灵而言，对水稻纹枯病菌具有更强的抗菌活性，也证明樟脑缩氨基硫脲和甲基硫菌灵之间存在良好的协同抗菌作用。ZNSN含量变化对ZNSN/甲基硫菌灵复配物抗菌活性的影响见图11。由图11可知，樟脑缩氨基硫脲/甲基硫菌灵复配物F1-F5实验EC50值均低于其理论EC50值，这进一步表明，樟脑缩氨基硫脲和甲基硫菌灵之间存在协同抗菌作用。樟脑缩氨基硫脲/甲基硫菌灵复配物F2体现出最低的EC50值(10.90μmol/L)，表明当樟脑缩氨基硫脲的摩尔含量为10％，樟脑缩氨基硫脲/甲基硫菌灵复配物中的两种组分之间可形成最强的协同抗菌作用。
本试验例以水稻纹枯病菌为受试菌种，采用菌丝生长速率法，研究了樟脑缩氨基硫脲和6种市售抗菌剂之间的协同抗菌活性，发现樟脑缩氨基硫脲分别与己唑醇、三环唑、苯醚甲环唑、嘧菌酯和甲基硫菌灵均存在良好的协同抗菌作用。
上述实施例仅是本发明的较优实施方式，凡是依据本发明的技术实质对以上实施例所做的任何简单修饰、修改及替代变化，均属于本发明技术方案的范围内。
Claims (11)
1.一种农用增效杀菌剂，其特征在于，所述农用增效杀菌剂为由樟脑缩氨基硫脲和己唑醇组成，所述樟脑缩氨基硫脲与己唑醇的摩尔比为5-25∶75-95。
2.一种农用增效杀菌剂，其特征在于，所述农用增效杀菌剂为由樟脑缩氨基硫脲和三环唑组成，所述樟脑缩氨基硫脲与三环唑的摩尔比为20-25∶75-80。
3.一种农用增效杀菌剂，其特征在于，所述农用增效杀菌剂为由樟脑缩氨基硫脲和苯醚甲环唑组成，所述樟脑缩氨基硫脲与苯醚甲环唑的摩尔比为15-25∶75-85。
4.一种农用增效杀菌剂，其特征在于，所述农用增效杀菌剂为由樟脑缩氨基硫脲和嘧菌酯组成，所述樟脑缩氨基硫脲与嘧菌酯的摩尔比为15-25∶75-85。
5.一种农用增效杀菌剂，其特征在于，所述农用增效杀菌剂为樟脑缩氨基硫脲或由樟脑缩氨基硫脲和甲基硫菌灵组成，所述樟脑缩氨基硫脲与甲基硫菌灵的摩尔比为5-25∶75-95。
6.根据权利要求1-5任一项所述的一种农用增效杀菌剂，其特征在于，所述樟脑缩氨基硫脲的制备方法，包括如下步骤：以樟脑、氨基硫脲为原料进行反应得到粗产品，再经重结晶得到樟脑缩氨基硫脲成品。
7.根据权利要求6所述的一种农用增效杀菌剂，其特征在于，在异丙醇存在的条件下，分别加入樟脑、氨基硫脲、催化剂，持续搅拌混合均匀，然后调控反应体系至10℃-35℃温度后，反应2h-6h，得到樟脑缩氨基硫脲粗品，再经重结晶后，得到樟脑缩氨基硫脲成品。
8.根据权利要求6所述的一种农用增效杀菌剂，其特征在于，所述樟脑与氨基硫脲之间的摩尔比为1∶0.5-2。
9.根据权利要求7所述的一种农用增效杀菌剂，其特征在于，所述催化剂为无机酸的溶液或小分子有机酸的溶液，所述无机酸为盐酸或硫酸，所述小分子有机酸选自甲酸、乙酸、柠檬酸中的一种，所述催化剂的浓度为5%wt-15%wt，所述樟脑与异丙醇之间的摩尔体积比为1moL∶0.1L。
10.根据权利要求6所述的一种农用增效杀菌剂，其特征在于，重结晶使用的溶剂选自乙醇、乙醇石油醚混合溶液中的一种。
11.权利要求1-10中任一项所述农用增效杀菌剂在防治植物真菌病害中的应用，所述植物真菌为水稻纹枯病菌。
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