CN103524417B - 一组3-甲基-4-甲酰吡唑化合物 - Google Patents

一组3-甲基-4-甲酰吡唑化合物 Download PDF

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CN103524417B
CN103524417B CN201310526290.9A CN201310526290A CN103524417B CN 103524417 B CN103524417 B CN 103524417B CN 201310526290 A CN201310526290 A CN 201310526290A CN 103524417 B CN103524417 B CN 103524417B
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孙家隆
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Qingdao Agricultural University
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Abstract

本发明提供了一组3-甲基-4-甲酰吡唑化合物，该化合物通式为

Description

一组3-甲基-4-甲酰吡唑化合物
技术领域
本发明属于农药领域，技术方案涉及一组3-甲基-4-甲酰吡唑化合物，具体涉及一组3-甲基-4-甲酰吡唑衍生物及其制备方法和以其作为活性成分的杀菌剂应用。
背景技术
吡唑类化合物往往具有高的生物活性，已经有多种该类化合物作为农药被广泛应用。例如日本农药株式会社开发的唑螨酯用作高效广谱的快速杀螨剂、日本三井化学公司开发的吡噻菌胺已成为优良的农用杀菌剂。我们对吡唑类化合物结构进行了深入的研究分析，以1，3-二甲基-4-吡唑甲酰氯为母体，分别与不同的亲核试剂反应，合成了系列3-甲基-4-甲酰吡唑化合物，并测定了其杀菌活性。
发明内容
本发明的目的是提供一组3-三氟甲基-4-甲酰吡唑化合物，结构式如式I所示：
其中，X为NH、O或S，R基团选自苯基衍生物、萘基衍生物或杂环基衍生物。
具体的，式I所示化合物为表1中的任意一种。
表1本发明提供的3-甲基-4-甲酰吡唑化合物
本发明的再一个目的是提供所述化合物的制备方法，如下所示：
反应方程式：
包括以下步骤：在低温(0±5℃)下将1，3-甲基-4-吡唑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RXH选自表2中与化合物编号相对应的任意一种。
表2制备本发明3-三氟甲基-4-甲酰吡唑化合物所需RXH
具体的，所述1，3-二甲基-4-吡唑甲酰氯、RXH和K2CO3的摩尔质量比为1：1：1。
具体的，所述惰性溶剂为丙酮、乙腈、氯仿或甲苯。
本发明的第三个目的是提供所述3-甲基-4-甲酰吡唑化合物作为农用杀菌剂应用。
本发明的有益效果是：本发明的3-甲基-4-甲酰吡唑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3-甲基-4-甲酰吡唑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3-甲基-4-甲酰吡唑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Q110907的制备
在装有温度计和电磁搅拌子的100毫升的三口瓶中加入0.01摩尔无水K2CO3粉末、0.01摩尔2-硝基苯胺、30毫升丙酮，低温(0～5℃)下缓慢滴加0.01摩尔1，3-二甲基-4-吡唑甲酰氯溶于20毫升丙酮所配成的溶液，滴加完毕，于室温继续搅拌反应10小时。减压过滤反应混合物，将所得滤液减压脱溶，制得化合物Q110907粗品，用乙腈对化合物Q110907粗品重结晶，制得白色片状晶体化合物Q110907，收率42.9％。
实施例2～12表1中其他11种化合物的制备
具体操作如表3。
表3实施例2～12具体操作
实施例13实施例1-12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1-18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1-12所制备的3-三氟甲基-4-甲酰吡唑化合物物理化学性质及收率
表5实施例1-12所制备的3-三氟甲基-4-甲酰吡唑化合物1H-NMR数据
表6实施例1-12所制备的3-三氟甲基-4甲酰吡唑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
Q110907 IR(KBr)v：3360，1676，1610，1581，1498，1336，1270
Q110920 IR(KBr) v：3361，1674，1644，1449，1287，1233，1047
Q111011 IR(KBr)v：1668，1519，1303，1195，1137，1029
Q111012 IR(KBr)v：3265，3211，1698，1614，1503，1403，1142，1063
Q111013 IR(KBr)v：3091，2925，1656，1544，1469，1365，1208，1083
Q111017 IR(KBr)v：3103，1676，1544，1477，1382，1266，1228，1137
Q111101 IR(KBr)v：3116，1727，1619，1561，1441，1382，1138，1038，881，756，715
Q111121 IR(KBr)v：3381，3124，2929，1680，1548，1415，13116 -->
Q111210 IR(KBr) v：3435，1631，1557，1432，1411，1333，1084，1005，852，760
Q111228 IR(KBr)v：3120，1743，1622，1548，1232，1050
Q120102 IR(KBr)v：3136，2925，2174，1676，1556，1477，1386，1241，1174，1008
Q120624 IR(KBr)v：3129，2971，2934，1673，1544，1420，1316，1241，1179
由表5和表6可见，实施例1-12所制备的3-三氟甲基-4-甲酰吡唑化合物的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14实施例1-12所制备的3-三氟甲基-4-甲酰吡唑化合物对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1-39所制备的3-甲基-4-甲酰吡唑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，嘧菌酯为对照农药。
表7实施例1-12所制备的3-甲基-4-甲酰吡唑化合物杀菌活性
从表7中数据看出，实施例1-12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。

Claims (8)

1.一组3-甲基-4-甲酰吡唑化合物，结构式如式I所示：
其中，XR基团选自苯基衍生物或杂环基衍生物，所述化合物选自下表中的任意一种：
。
2.权利要求1所述化合物的制备方法，包括以下步骤：在温度0±5℃下将1，3-甲基-4-吡唑甲酰氯的丙酮或乙腈或氯仿或甲苯溶液滴加入RXH和K2CO3的丙酮或乙腈或氯仿或甲苯溶液中，滴加完毕后，升至温度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，所述RXH选自下表中与化合物编号相对应的任意一种：
3.根据权利要求2所述的制备方法，其特征在于：所述1-甲基-3-甲基-4-吡唑甲酰氯、RXH和K2CO3的摩尔质量比为1∶1∶1。
4.权利要求1所述的3-甲基-4-甲酰吡唑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3-甲基-4-甲酰吡唑化合物在抑制病原菌生长或杀灭病原菌中的应用；其中所述病原菌引起的疾病不包括人体或动物体的疾病。
6.权利要求1所述的3-甲基-4-甲酰吡唑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；其中所述病原菌引起的疾病不包括人体或动物体的疾病。
7.一种农用组合物，其包含0.1～99.9重量％的权利要求1中所述的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：作为农用杀菌剂中的应用。
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CN109156471B (zh) * 2018-08-29 2020-12-15 浙江工业大学 一种1,3-二甲基-1h-吡唑-4-酰胺衍生物在制备除草剂中的应用
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