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CN103554098A - 一组2-氯-3-吡啶甲酰化合物 - Google Patents

一组2-氯-3-吡啶甲酰化合物 Download PDF

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CN103554098A
CN103554098A CN201310526297.0A CN201310526297A CN103554098A CN 103554098 A CN103554098 A CN 103554098A CN 201310526297 A CN201310526297 A CN 201310526297A CN 103554098 A CN103554098 A CN 103554098A
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CN103554098B (zh
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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2-氯-3-吡啶甲酰化合物，该化合物通式为

Description

一组2-氯-3-吡啶甲酰化合物
技术领域
本发涉及一组吡啶甲酰类化合物，具体涉及一组2-氯-3-吡啶甲酰衍生物及其制备方法和其作为杀菌剂活性成分的应用。
背景技术
酰胺类化合物在农用杀菌剂中占有重要地位，如甲霜灵、高效甲霜灵、烯酰吗啉、氟吗啉、啶酰菌胺等。我们对吡啶酰胺类化合物结构进行了深入的研究，根据生物等排原则，以2-氯-3-吡啶甲酰氯为母体，合成了系列2-氯-3-吡啶甲酰化合物。新化合物作为杀菌剂生产时比较环保，利于产业化而服务“三农”。
发明内容
本发明的目的是提供一组2-氯-3-吡啶甲酰化合物，结构式如式I所示：
Figure BSA0000096922580000011
其中，X选自NH、S或O；R基团选自苯基衍生物、萘基衍生物或其他杂环基衍生物。
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2-氯-3-吡啶甲酰化合物
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：
Figure BSA0000096922580000021
包括以下步骤：在冰水浴(0±2℃)温度下，将2-氯-3-吡啶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(20±5℃)下反应，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对应编号中的任意一种。
表2本发明RXH对应化合物及结构
Figure BSA0000096922580000022
具体的，制备化合物G130328时，所述2-氯-3-吡啶甲酰氯、RXH和K2CO3的摩尔质量比为2∶1∶2，制备表1中其他编号化合物时，所述2-氯-3-吡啶甲酰氯、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。
本发明的第三个目的是提供所述2-氯-3-吡啶甲酰化合物作为农用杀菌剂的应用。
本发明的第四个目的是提供所述2-氯-3-吡啶甲酰化合物作为抑制病原菌生长或杀灭病原菌中的应用。
本发明的第五个目的是提供一种农用组合物作为农用杀菌剂中的应用，该农用组合物包含0.1～99.9重量％本发明所述2-氯-3-吡啶甲酰化合物以及农药学上可接受的载体和/或赋形剂。
本发明的有益效果是：本发明的2-氯-3-吡啶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2-氯-3-吡啶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2-氯-3-吡啶甲酰化合物的合成和生物活性，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1N-(5-三氟甲基-3,4-噻二唑-2-基)-2-氯-3-吡啶甲酰胺(G1301041)的制备
反应方程式：
Figure BSA0000096922580000031
具体操作：将0.01摩尔2-氨基-5-三氟甲基-3，4-噻二唑和0.01摩尔K2CO3加入100ml单口烧瓶中，加入30ml甲苯，搅拌，在冰水浴(0±2℃)温度下滴入含有0.01摩尔2-氯烟酰氯的30ml甲苯溶液，将反应温度升至室温(20±5℃)并继续搅拌反应10小时，停止反应并过滤，滤液旋转蒸发、减压脱溶得到固体物质，该固体物质用乙醇重结晶得到纯品目标物G1301041。
实施例2(5-甲基异噁唑-3-基)-2-氯-3-吡啶甲酸酯(G130225)的制备
反应方程式：
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为5-甲基-3-羟基异噁唑。
实施例3N-(2-咪唑硫酮)基-2-氯-3-吡啶甲酰胺(G1303132)的制备
反应方程式：
Figure BSA0000096922580000033
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为2-咪唑硫酮。
实施例4N-(噻唑烷2-硫酮)基-2-氯-3-吡啶甲酰胺(G130319)的制备
反应方程式：
Figure BSA0000096922580000041
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3,4-噻二唑替换为噻唑烷2-硫酮，将K2CO3替换为三乙胺，反应时间调整为8小时。
实施例5N-苯基-N-(4,6-二甲基嘧啶-2-基)-2-氯-3-吡啶甲酰胺(G130321)的制备
反应方程式：
Figure BSA0000096922580000042
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为苯基-(4,6-二甲基嘧啶-2-基)胺；将K2CO3替换为三乙胺；将反应溶剂甲苯替换为乙腈；将反应时间调整为96小时；重结晶溶剂为乙腈。
实施例6(4,6-二甲基嘧啶-2-基)-2-氯-3-吡啶甲酸酯(G130916)的制备
反应方程式：
Figure BSA0000096922580000043
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为2,5-二巯基-3，4-噻二唑；将反应溶剂甲苯替换为乙腈。
实施例7S-(5-巯基-3,4-噻二唑-2-基)-2-氯-3-吡啶硫代甲酸酯(G130325)的制备
反应方程式：
Figure BSA0000096922580000044
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为2,5-二巯基-3，4-噻二唑；将反应溶剂甲苯替换为乙腈。
实施例8二(2-氯-3-吡啶硫代甲酸)S-(3,4-噻二唑-2,5-二基)酯(G130328)的制备
反应方程式：
Figure BSA0000096922580000051
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为2,5-二巯基-3，4-噻二唑，并且2-氯-3-吡啶甲酰氯、2,5-二巯基-3,4-噻二唑和K2CO3的摩尔质量比为2∶1∶2；将反应溶剂甲苯替换为乙腈。实施例9(4-甲基香豆素-7-基)-2-氯-3-吡啶甲酰胺(G130405)的制备
反应方程式：
Figure BSA0000096922580000052
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为4-甲基-7-羟基香豆素。
实施例10N-(4-环丙烷基-6-甲基嘧啶-2-基)-2-氯-3-吡啶甲酰胺(G1304101)的制备
反应方程式：
Figure BSA0000096922580000053
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为4-环丙烷基-6-甲基-2-氨基嘧啶。
实施例11N-(5-巯基-3,4-噻二唑-2-基)-2-氯-3-吡啶甲酰胺(G1309232)的制备
反应方程式：
Figure BSA0000096922580000054
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为5-巯基-2-氨基-3，4-噻二唑。
实施例12N-[5-(吡啶-4-基)-3,4-噻二唑-2-基]-2-氯-3-吡啶甲酰胺(G130925)的制备
反应方程式：
Figure BSA0000096922580000061
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为5-(吡啶-4-基)-2-氨基-3，4-噻二唑；将反应溶剂甲苯替换为乙腈；重结晶溶剂为N,N-二甲基甲酰胺。
实施例13N-[5-(吡啶-3-基)-3,4-噻二唑-2-基]-2-氯-3-吡啶甲酰胺(G1303282)的制备
反应方程式：
Figure BSA0000096922580000062
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为5-(吡啶-3-基)-2-氨基-3，4-噻二唑；将反应溶剂甲苯替换为乙腈；重结晶溶剂为N,N-二甲基甲酰胺。
实施例14S-(4,6-二甲基嘧啶-2-基)-2-氯-3-吡啶硫代甲酸酯(G1304162)的制备
反应方程式：
Figure BSA0000096922580000063
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为2-巯基-4,6-二甲基嘧啶；将反应溶剂甲苯替换为氯仿。
实施例15N-(2-亚氨基氰基噻唑烷)基-2-氯-3-吡啶甲酰胺(G130928)的制备
反应方程式：
Figure BSA0000096922580000064
具体操作：同实施例1，不同之处有：将反应物3-甲基苯胺2-氨基-5-三氟甲基-3，4-噻二唑替换为2-亚氨基氰基噻唑烷；将反应溶剂甲苯替换为乙腈。
实施例16实施例1-15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1-15所制备化合物的收率、熔点、1H-NMR和IR，并确认其性状。施例1-15所制备化合物的化学结构式和理化参数见表3、表4和表5。
表3实施例1-15所制备的2-氯-3-吡啶甲酰化合物物理化学性质及收率
Figure BSA0000096922580000071
Figure BSA0000096922580000081
表4实施例1-15所制备的2-氯-3-吡啶甲酰化合物核磁共振氢谱数据
表5实施例1-15所制备的2-氯-3-吡啶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(KBr)v/cm-1
G1301041 3148,2917,1689,1606,1582,1544,1490,1407,1320,1150,1042,897,744
G130225 3137,3050,1723,1631，1577,1445,1403,1382,1291，1076,964
G1303132 2952,2930,1673,1635,1594,1561,1432,1403,1337,1134,1088,715,607
G130319 3137,3050,1723,1631，1577,1445,1403,1382,1291，1076,964,905,818
G130321 3033,1673,1586,1536,1490,1407,1370,1295,1217,1158,1096,1059,1005,860,727
G130325 2971,2921,1635,1565,1407,1125,623
G130328 1718，1611，1499,1403,1378,1266,1071,852,769
G1303282 1685,1586,1428,1399,1316,1059,876,756
G130405 3079,3058,1752,1735,1623,1573,1407,1266,1134,1067,1038,893,847,756,615
G1304101 3203,3124,2983,1660,1594,1540,1499,1445,1333,1167,1063,1022,964,818,744,677,557
G1304162 3029,2913，1627,1561,1436,1337,1237,1221，1188,976,852,711
G130916 3056,1801,1723,1626,1577,1553,1432,1403,1337,1262,1196,1146,1063,980,818
G1309232 3133,2929,1689,1569,1557,1528,1399,1312，1258,1134，1059,1038,893
G130925 1685,1586,1428,1399,1316,1059,876,756
G130928 2187，1681，1573,1441，1374,1403,1308,1250,1175,752
由表4和表5可见，实施例1-15所制备的2-氯-3-吡啶甲酰化合物的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17实施例1-15所制备的2-氯-3-吡啶甲酰化合物对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1-15所制备的2-氯-3-吡啶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6(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6实施例1-15所制备的2-氯-3-吡啶甲酰化合物杀菌活性
Figure BSA0000096922580000101
从表6中数据看出，实施例1-15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G1301041和G1304101对番茄早疫病菌的抑菌率分别达到91.10％和92.45％，G1301041、G130225和G1304101对西瓜枯萎病菌的抑菌率分别达到85.32％、87.45％和77.68％，G1301041、G130225、G130321和G1304101对黄瓜灰霉病菌的抑菌率分别达到72.25％、74.30％、88.52％和70.10％，G1304101对苹果腐烂病菌的抑菌率达到98.00％，G1304101对立枯丝核菌的抑菌率达到77.13％，抑菌率高于对照农药嘧菌酯。

Claims (10)

1.一组2-氯-3-吡啶甲酰化合物，结构式如式I所示： 
Figure FSA0000096922570000011
其中，X选自NH、S或O；R基团选自苯基衍生物、萘基衍生物或其他杂环基衍生物。 
2.根据权利要求1所述的2-氯-3-吡啶甲酰化合物，其特征在于：具有式I结构，其中所述化合物选自下表中的任意一种。 
Figure FSA0000096922570000012
。
3.权利要求1或2所述化合物的制备方法，包括以下步骤：在冰水浴(0±2℃)温度下，将2-氯-3-吡啶甲酰氯的惰性溶剂(乙腈或氯仿或甲苯)溶液滴加入RXH和K2CO3的惰性溶剂(乙腈或氯仿或甲苯)溶液中，滴加完毕后，升至室温(20±5℃)下反应，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。 
4.根据权利要求3所述的制备方法，其特征在于：所述RXH选自下表中与编号对应的化学结构式的任意一种。 
Figure FSA0000096922570000021
。
5.根据权利要求3或4所述的制备方法，其特征在于：制备权利要求2之化合物G130328时，所述2-氯-3-吡啶甲酰氯、RXH和K2CO3的摩尔质量比为2∶1∶2；制备权利要求2之其他化合物时，所述2-氯-3-吡啶甲酰氯、RXH和K2CO3的摩尔质量比为1∶1∶1。 
6.权利要求1或2所述的2-氯-3-吡啶甲酰化合物在防治农作物农业病害中的应用。 
7.权利要求1或2所述的2-氯-3-吡啶甲酰化合物在抑制病原菌生长或杀灭病原菌中的应用。 
8.权利要求1或2所述的2-氯-3-吡啶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。 
9.一种农用组合物，其包含0.1～99.9重量％的权利要求1和权利要求2中任一项所述的化合物以及农药学上可接受的载体和/或赋形剂。 
10.根据权利要求9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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