CN103554052B - 一组苯甲酰化合物 - Google Patents

一组苯甲酰化合物 Download PDF

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CN103554052B
CN103554052B CN201310528456.0A CN201310528456A CN103554052B CN 103554052 B CN103554052 B CN 103554052B CN 201310528456 A CN201310528456 A CN 201310528456A CN 103554052 B CN103554052 B CN 103554052B
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孙家隆
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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
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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 to ring carbon atoms
    • C07D277/18—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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero 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
    • A01N47/40—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
    • C07D261/12—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical

Abstract

本发明提供了一组苯甲酰化合物，该化合物通式为其中，Y为F或CH3；X为NH、O或S；R为苯衍生物或其他杂环衍生物；本发明公开了这些化合物的结构以及对农业病害的防治效果，同时公开了这些化合物作为杀菌剂的应用。

Description

一组苯甲酰化合物
(一)技术领域
本发明属于农药领域，技术方案涉及一组苯甲酰化合物，具体涉及邻位取代的苯甲酰衍生物及其制备方法和作为杀菌剂应用。
(二)背景技术
邻位取代的苯甲酰衍生物往往是有效的杀菌剂，如灭锈胺、邻酰胺、水杨菌胺等。我们对该类化合物进行了深入的研究分析，认为它们仍有较好的开发前景。为此，我们根据生物等派等农药分子结构设计原理，设计并合成了一组邻位取代的苯甲酰衍生物，生物测定结果表明，新化合物有较好的抑菌、杀菌活性，具有一定的推广应用价值。新化合物合成过程中产生的“三废”较少，并且易于处理，利于产业化而服务“三农”。
(三)发明内容
本发明的目的是提供一组苯甲酰化合物及其合成方法。
本发明的另一个目的是提供苯甲酰化合物为农业杀菌剂应用。
本发明提供的苯甲酰化合物化学结构式通式如式I所示：
其中，Y为F或CH3；X为NH、O或S；R为苯衍生物或其他杂环衍生物。
具体的，式I所标示的化合物见表1。
表1本发明合成的苯甲酰化合物
本发明提供的苯甲酰化合物的合成方法如下：
反应方程式：
具体操作步骤：在低温(0+5℃)下将邻位取代的苯甲酰氯的惰性溶剂溶液滴加入RXH和K2CO3的惰性溶剂溶液中，滴加完毕后，升至室温(25±5℃)反应，反应完毕后抽滤、去除反应溶剂，经重结晶纯化后即得所述化合物。
具体的，所述苯甲酰氯和RXH选自表2中与化合物编号对应的任意一组。
表2制备本发明苯甲酰化合物所需苯甲酰氯和RXH
具体的，制备化合物Q120525时，所述苯甲酰氯为2-甲基苯甲酰氯、RXH为2,5-二巯基-3，4-噻二唑，而且2-甲基苯甲酰氯、2,5-二巯基-3,4-噻二唑、K2CO3的摩尔质量比为2：1：2；制备表1中其他化合物时，所述苯甲酰氯、RXH和K2CO3的摩尔质量比为1：1：1。
具体的，所述惰性溶剂为乙腈、氯仿或甲苯。
本发明的另一个目的是提供所述苯甲酰化合物为农用杀菌剂用途。
本发明的有益效果是：本发明的苯甲酰化合物可用于防治农业病害，部分化合物具有抑制病原菌生长的活性，并可取得很好的效果。
本发明提供的苯甲酰化合物用于防治农业病害是本发明的重要特征之一。
本发明所述新化合物制备过程中产生的“三废”较少，易于处理，作为杀菌剂农药生产时比较环保。
具体实施方式
本发明通过特定制备和生物活性测定实施例具体的说明苯甲酰化合物的制备和生物活性，所述实施例仅用于具体的说明本发明而非限制本发明。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1化合物D120222的制备
100mL的三口瓶中加入乙腈30毫升和1，3-噻唑啉-2-亚氨基氰胺0.01摩尔，再加入碳酸钾0.01摩尔，室温(25+5℃)搅拌五分钟，固体大本分溶解，控温在0+5℃下滴加0.01摩尔2-氟苯甲酰氯与20毫升乙腈的混合物，然后在室温25+5℃温度下反应5小时，反应结束后减压过滤反应混合物，将所得滤液减压脱溶，制得化合物D120222粗品，用甲苯对化合物D120222粗品重结晶，制得白色小颗粒带亮的晶体D120222，收率60.9％。
实施例2～6表1中其他5种化合物的制备
具体操作如表3。
表3实施例2～6具体操作
实施例7实施例1-6所制备化合物的理化参数测定和化学结构鉴定
测定实施例1-6所制备化合物的熔点、1H-NMR和IR，其化学结构式和理化参数见表4、表5和表6。
表4实施例1-6所制备的苯甲酰化合物物理化学性质及收率
表5实施例1-6所制备的苯甲酰化合物1H-NMR数据
表6实施例1-6所制备的苯甲酰化合物红外光谱数据
编号 红外光谱(特征吸收峰)数据(IR)/cm-1
D120222 IR(KBr)：max=2176(CN),1695(C=O)
D110929 IR(KBr)：max=3426(NH),1599(C=O)
D111229 IR(KBr)：max=2934(CH3),1237(C-O-C),1772(C=O),1071(C-F)
D120102 IR(KBr)：max=2975(CH3),1691(C=O)
D120209 IR(KBr)：max=1657(C=O),1125(C-F),1439(C=N)
Q120525 IR(KBr)v：2917,2925,1694,1565,1457,1374,1283,1188
由表5和表6可见，实施例1-6所制备的苯甲酰化合物的1H-NMR显示与其结构相应的化学位移、H的数目与其结构吻合，IR出现相应的骨架吸收峰。
实施例8实施例1～6所制备的苯甲酰化合物对7种常见代表性病害病原的抑菌活性测定
(1)PDA培养基制备：将200g马铃薯去皮切块，加1000mL蒸馏水，煮沸10-20min。用纱布过滤，补加蒸馏水至1000mL。加入20g葡萄糖和17g琼脂，加热融化，分装，高压蒸汽灭菌2h，备用。
(2)病原真菌的培养：用接种针挑取少量病原菌菌丝于PDA培养基上，置于25℃恒温培养箱中培养2-4天，菌丝长好后待用。
(3)测定方法：采用菌丝生长速率法(一定时间内菌落直径的大小)测定化合物的抑菌活性。在离心管中准确称取5mg供试目标化合物，先用适量丙酮溶解，再加入计算量的含有1％吐温20乳化剂的水溶液，稀释成1000mg/L的药液。取1mL药液加入9mL培养基中摇匀，配制成100mg/L的含药培养基，均匀倒入培养皿。同时添加不含共试目标化合物、含有相同量的丙酮及吐温20乳化剂培养基的培养皿做空白对照。用灭菌的打孔器(直径4mm)在生长良好，无污染，长势均匀菌落边缘打取菌饼，在无菌条件下接入含药培养基中心(每个培养皿接种一个菌饼)，盖上皿盖，皿盖朝下，每处理重复3次。将培养基置于25℃恒温培养箱中培养，待对照培养皿中菌落直径扩展到4-5cm后用十字交叉法测量各处理菌饼扩展直径，求平均值，与空白对照比较计算相对抑菌率。
(4)抑菌率的计算：
菌落增长直径(mm)=菌落测量直径(mm)-菌饼直径(mm)
相对抑制率(％)=[对照菌落增长直径(mm)-含药培养基上菌落增长直径(mm)]/对照菌落增长直径(mm)×100
按照上述方法，测定实施例1-6所制备的苯甲酰化合物对七种常见代表性病害病原的抑菌效果，测定结果见表7(表中数据为各化合物在100mg/L时对病原菌生长的抑制百分率)。
其中，其中，设嘧菌酯为对照农药。
表7实施例1-6所制备的苯甲酰化合物杀菌活性
从表7中数据看出，实施例1-6所制备化合物在100mg/L浓度下，对所选七种病原菌大多数具有不同程度的抑菌活性，其中D111229对梨黑斑病菌和苹果腐烂病菌的抑菌率分别达到88.30％和94.32％、D120209对番茄早疫病菌的抑菌率达到91.45％，抑菌率高于对照农药嘧菌酯。

Claims (8)

1.一组苯甲酰化合物，结构式为：
2.权利要求1所述苯甲酰化合物的制备方法：在0±5℃温度下将对应邻位取代的苯甲酰氯的氯仿或乙腈或甲苯溶液滴加入 和K2CO3的氯仿或乙腈或甲苯溶液中，滴加完毕后，升至25±5℃温度反应，反应完毕后抽滤、去除反应溶剂，经重结晶纯化后即得所述化合物。
3.根据权利要求2所述的制备方法，其特征在于：制备时 K2CO3摩尔数之比为1∶1∶1，制备时K2CO3摩尔数之比为1∶1∶1，制备时K2CO3摩尔数之比为1∶1∶1，制备时K2CO3摩尔数之比为1∶1∶1，制备时K2CO3摩尔数之比为1∶1∶1，制备时K2CO3摩尔数之比为2∶1∶2。
4.权利要求1所述的苯甲酰化合物在防治农作物农业病害中的应用。
5.权利要求1所述的苯甲酰化合物在抑制病原菌生长或杀灭病原菌中的应用，其中所述病原菌不包括人体或动物体的病原菌。
6.权利要求1所述的苯甲酰化合物在制备抑制病原菌生长或杀灭病原菌药物中的应用，其中所述病原菌不包括人体或动物体的病原菌。
7.一种农用组合物，其包含0.1～99.9重量％的权利要求1中任一所述化合物以及农药学上可接受的载体和/或赋形剂。
8.根据权利要求7所述的农用组合物的用途，其特征在于：作为农用杀菌剂的应用。
CN201310528456.0A 2013-11-01 2013-11-01 一组苯甲酰化合物 Expired - Fee Related CN103554052B (zh)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101456815A (zh) * 2007-12-13 2009-06-17 中国科学院兰州化学物理研究所 碘代芳烃羰基化合成芳香族羧酸酯方法
CN103242308A (zh) * 2013-05-24 2013-08-14 青岛农业大学 2-氟烟酰衍生物及其制备方法和其应用

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JPS5310975B2 (zh) * 1974-05-18 1978-04-18
JPS5266629A (en) * 1975-11-27 1977-06-02 Hokko Chem Ind Co Ltd Agricultural and horticultural fungicide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101456815A (zh) * 2007-12-13 2009-06-17 中国科学院兰州化学物理研究所 碘代芳烃羰基化合成芳香族羧酸酯方法
CN103242308A (zh) * 2013-05-24 2013-08-14 青岛农业大学 2-氟烟酰衍生物及其制备方法和其应用

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