CN111039896B - 一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途 - Google Patents

一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途 Download PDF

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CN111039896B
CN111039896B CN202010003268.6A CN202010003268A CN111039896B CN 111039896 B CN111039896 B CN 111039896B CN 202010003268 A CN202010003268 A CN 202010003268A CN 111039896 B CN111039896 B CN 111039896B
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benzothiazole
acyl
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acyl thiourea
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郝双红
王传平
姚晓芳
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Qingdao Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82—Nitrogen atoms
    • 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<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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Abstract

本发明（名称为：一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途）涉及9种苯并噻唑酰基硫脲类化合物及其制备方法，以及在抑菌方面的用途。9种苯并噻唑酰基硫脲类化合物，通过硫氰酸胺先与不同酰氯缩合得中间体酰基硫氰酸酯，再与2‑氨基苯并噻唑衍生物发生加成反应得系列目标化合物。这些化合物可作为杀菌剂防治番茄灰霉病菌及苹果腐烂病菌。

Description

一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途
技术领域
本发明涉及一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途，具体的涉及农用杀菌剂领域。
背景技术
苯并噻唑类化合物在农业、医药以及工业等各个领域都被广泛应用。该化合物及其衍生物在农药领域也有多样生物活性，如杀虫、抑菌及除草作用等。酰基硫脲类化合物在农药、医药领域也具有广泛生物活性。该专利基于活性亚结构拼接思想，以苯并噻唑为先导，同时引入酰基硫脲基活性基团，设计合成了一类新型苯并噻唑酰基硫脲类化合物，并筛选了该类化合物的杀菌活性。
发明内容
本发明的目的在于提供一类苯并噻唑酰基硫脲类化合物及制备方法，它可应用于农业上以防治致病菌。
本发明的技术方案如下：
本发明提供的苯并噻唑酰基硫脲类化合物，其结构通式如下：
Figure 761730DEST_PATH_IMAGE001
Ⅰ
R1选自：6-甲氧基、6-硝基、5-硝基、4-硝基；
R2选自：环己基、环丙基、2-氯吡啶-5-基、3-硝基苯基、3-三氟甲基苯基、萘-2-基；
该苯并噻唑酰基硫脲类化合物合成反应式：
Figure 288658DEST_PATH_IMAGE002
Ⅱ Ⅲ
Figure 239034DEST_PATH_IMAGE003
Figure 634243DEST_PATH_IMAGE004
Ⅰ
式中R1及R2定义如上；
通式化合物制备方法：在适当溶剂中，适当温度下，加入适当催化剂，Ⅱ、Ⅲ和
Figure 183036DEST_PATH_IMAGE003
发生缩合，反应一定时间后，处理即得目的产物Ⅰ。
适当溶剂可选自苯、甲苯、二甲苯、二氯甲烷、三氯甲烷、二氯乙烷等；
适当温度指20℃至溶剂的沸点温度；
适当催化剂指无水碳酸钾、无水碳酸钠、三乙胺等；
反应时间为2小时至30小时。
本发明的化合物对番茄灰霉病菌及苹果腐烂病菌有一定抑制作用，同时对大肠杆菌有一定的抑制作用。
具体实施方式
实例1 化合物Ⅰ-1的制备
Figure 5499DEST_PATH_IMAGE005
Figure 944636DEST_PATH_IMAGE006
将91.2 mg（1.2 mmol）硫氰酸钾，175.3 mg（1.2 mmol）环己酰氯，6 mL甲苯，加入到25 mL反应管中，再滴加1滴三乙胺，60-70 ℃搅拌，反应1 h，加入180.4 mg（1 mmol）6-甲氧基-2-氨基苯并噻唑，4 mL甲苯，TLC跟踪反应。反应完毕，抽滤，浓缩得黄色固体，通过柱层析[流动相为V（石油醚）：V（乙酸乙酯）= 4：1]分离获得。
化合物Ⅰ-2~Ⅰ-9按照与Ⅰ-1相似的方法合成，合成化合物MS及1H NMR数据列于表1。
表1 目标化合物MS及1H NMR数据
Figure 143536DEST_PATH_IMAGE007
Figure 920737DEST_PATH_IMAGE008
Figure 914101DEST_PATH_IMAGE009
实例2 抑菌活性初筛
称取5 mg化合物，加入2 mL丙酮（10%DMSO溶液），溶解配制成2500 mg/L浓度的药液；取1 mL 2500 mg/L的溶液，加入1 mL丙酮（10%DMSO溶液），溶匀配制成1250 mg/L浓度的药液，同法依次配置625、312.5、156.3、78.1、39.1、19.5 mg/L等8个浓度的药液。
用96孔板，每孔加180μL菌液，加20μL药液，设置三组平行，20μL丙酮（10%DMSO溶液）加入180μL菌液中做对照。封口，放置摇床培养12 h（苹果腐烂菌28 ℃，番茄灰霉菌25℃），肉眼观察菌液浑浊情况。菌液未浑浊的药液浓度为最低抑制浓度（MIC）。
化合物Ⅰ-1~Ⅰ-9的抑菌活性数据列于表2中。
表2 目标化合物抑菌活性初筛
Figure 340534DEST_PATH_IMAGE010
实例3 抑菌活性复筛
称取15 mg 化合物溶于15 mL丙酮（10%DMSO），配置成1000 mg/L浓度的药液，通过二倍稀释法配置500 mg/L、250 mg/L浓度的药液。取3 mL不同浓度的药液分别加入到27 mL熔融的马铃薯琼脂培养基中，然后趁热倒入培养皿，冷却形成带毒平板培养基，分别接种苹果腐烂病菌和番茄灰霉病菌，对照用等量丙酮（10%DMSO），每个处理（不同浓度药液及对照）每个菌种设置三个重复。放置适宜温度下（苹果腐烂菌28 ℃，番茄灰霉菌25 ℃）培养，十字交叉法量取菌落直径，求取平均值。按照下式得到不同浓度药液的抑菌率。
抑菌率公式：
抑菌率 =（对照菌落直径 - 处理菌落直径）/对照直径 * 100%
表3 目标化合物抑菌活性复筛
Figure 77546DEST_PATH_IMAGE011

Claims (2)

1.一种苯并噻唑酰基硫脲类化合物，其特征在于，所述苯并噻唑酰基硫脲类化合物结构如通式所示：
Figure 738674DEST_PATH_IMAGE001
R1选自：6-甲氧基、6-硝基、5-硝基、4-硝基；
R2选自：环己基、环丙基、2-氯-吡啶-5-基、3-三氟甲基苯基、萘-2-基。
2.权利要求1所述化合物在防治植物病害方面的用途，其特征在于，所述的植物病害选自苹果腐烂病菌、番茄灰霉病菌。
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