CN105837491B - 一种新型羧酰胺衍生物杀菌剂及其制备方法和用途 - Google Patents

一种新型羧酰胺衍生物杀菌剂及其制备方法和用途 Download PDF

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CN105837491B
CN105837491B CN201610259242.1A CN201610259242A CN105837491B CN 105837491 B CN105837491 B CN 105837491B CN 201610259242 A CN201610259242 A CN 201610259242A CN 105837491 B CN105837491 B CN 105837491B
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alkyl
het
mixed liquor
carboxamide derivative
novel carboxamide
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CN105837491A (zh
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唐剑峰
潘光民
刘杰
张�杰
额尔敦巴特尔
吴建挺
乔思佳
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SHANDONG UNITED PESTICIDE INDUSTRY Co Ltd
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SHANDONG UNITED PESTICIDE INDUSTRY Co Ltd
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Abstract

本发明公开了一种新型羧酰胺衍生物杀菌剂，其结构通式如下所示：

Description

一种新型羧酰胺衍生物杀菌剂及其制备方法和用途
技术领域
本发明涉及农化与医药技术领域，具体涉及一种新型羧酰胺衍生物杀菌剂及其制备方法和用途。
技术背景
自萎锈灵和氧化萎锈灵标志着内吸性杀菌剂在农业领域应用防治植物病害方面的一大突破，由传统保护性杀菌剂转入内吸性杀菌剂的突破，由于目前的杀菌剂已经产生了较大的抗药性，长期使用对环境污染较大，对人畜的毒性较高，因此研究一种对环境友好，人畜无毒，高效，广谱，低残留和抵抗性的杀菌剂是目前农药领域亟待解决的问题。
发明内容
为解决上述问题，本发明的目的是提供一种新型羧酰胺衍生物杀菌剂及其制备方法和用途。
本发明为实现上述目的，通过以下技术方案实现：
一种新型羧酰胺衍生物杀菌剂，其结构通式I如下所示：
其中R1、R2分别为氢、卤素、氰基、C1-C6的烷基或C1-C6的烷氧基；
-Het表示含有一个、两个或三个相同或不同杂原子的五、六或七元非稠合杂环，-Het通过碳原子连接且至少在邻位上被取代。
优选的，R1、R2分别为氢、溴、氯、氟、氰基、C1-C3-烷基，C1-C3-烷氧基。
优选的，R1、R2分别为氢、溴、氯、氟。
优选的，R1、R2分别为溴。
优选的，-Het为
进一步优选的，Het为
本发明还包括新型羧酰胺衍生物杀菌剂的制备方法，包括以下步骤：
①将和有机溶剂加入反应釜中，在搅拌下升温至回流，滴加氯化亚砜，得到混合液，将混合液继续回流1小时，减压蒸馏除去有机溶剂和氯化亚砜，得到备用；所述的有机溶剂为二氯甲烷和二氯乙烷按照3:1的体积比混合所得；所述有机溶剂和氯化亚砜的质量体积比为1g：5～8ml：1～3ml；-Het表示含有一个、两个或三个相同或不同杂原子的五、六或七元非稠合杂环，-Het通过碳原子连接且至少在邻位上被取代；
②向步骤①所得的中加入N,N-二甲基乙酰胺，搅拌15～20分钟，滴加得到混合液a，控制混合液a的温度在20～30℃搅拌反应8～10小时，反应结束向混合液a中滴加蒸馏水，得到混合液b，混合液b的温度为20～25℃；所述N,N-二甲基乙酰胺、蒸馏水和步骤①的有机溶剂的体积比为1:4～5:3～4；R1、R2分别为氢、卤素、氰基、C1-C6的烷基或C1-C6的烷氧基；
③向步骤②所得混合液b中滴加碳酸钠溶液，调节混合液b的pH至8～9，然后减压抽滤，得到滤饼，将所得滤饼用蒸馏水洗涤，真空干燥得到
④向步骤③所得中加入二氯乙烷和三乙胺，降温至0～10℃后向其中滴加全氯甲硫醇，滴加结束后升温至20～30℃反应8～10小时，得到反应液，向反应液中加入蒸馏水，搅拌20～30分钟，静置后分液，得到有机层，将所得有机层减压蒸馏除去溶剂，加入乙酸乙酯重结晶，抽滤，干燥，得到新型羧酰胺衍生物杀菌剂；所述的二氯乙烷、三乙胺、蒸馏水和乙酸乙酯的质量体积比为3～4g：20～30ml：1ml：10～15ml：10～15ml；所述的和全氯甲硫醇的摩尔比为1：1～2。
本发明还包括新型羧酰胺衍生物杀菌剂的用途为用于防治农业菌类病害。
本发明相比现有技术具有以下优点：
本发明的新型羧酰胺衍生物杀菌剂在低浓度下具有优异的活性，良好的植物耐受性和环境安全性，能够抑制或破坏多种植物或土壤中出现的治病真菌和细菌；本发明的新型羧酰胺衍生物杀菌剂的制备方法采用的原料经济易得，制备方法产率高，合成工艺成本低，具有良好的杀菌活性和杀菌谱。
具体实施方式
本发明的目的是提供一种新型羧酰胺衍生物杀菌剂及其制备方法和用途，通过以下技术方案实现：
一种新型羧酰胺衍生物杀菌剂，其结构通式I如下所示：
其中R1、R2分别为氢、卤素、氰基、C1-C6的烷基或C1-C6的烷氧基；
-Het表示含有一个、两个或三个相同或不同杂原子的五、六或七元非稠合杂环，-Het通过碳原子连接且至少在邻位上被取代。
依据本发明，通式((I)的化合物的Het可以是五元杂环。其中Het是五元杂环的本发明化合物的具体例子包括：
Het表示通式(Het-1)的杂环
式中：
-R3和R4相同或不同，可以是氢原子、卤素原子、氨基、硝基、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
-R5可以是卤素原子、硝基、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
Het表示通式(Het-2)的杂环
式中：
-R6可以是氢原子、卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
-R7和R8可相同或不同，可以是氢原子、卤素原子、氨基、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
前提是R6和R8不都是氢原子。
Het表示通式(Het-3)的杂环
式中：
-R9可以是卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
-R10可以是氢原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
Het表示通式(Het-4)的杂环
式中：
-R11和R12可以相同或不同，可以是氢原子、卤素原子、氨基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C1-C4-烷硫基、C1-C4-烷基磺酰基、任选被卤素原子或C1-C4-烷基取代的苯基，或任选被卤素原子或C1-C4-烷基取代的吡啶基；
-R13可以是卤素原子、氰基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基或具有1到5个卤素原子的C1-C4-卤代烷氧基。
Het表示通式(Het-5)的杂环
式中：
-R14和R15可以相同或不同，可以是氢原子、卤素原子、C1-C4-烷基、C1-C4-烷氧基、具有1到5个卤素原子的C1-C4-卤代烷基；
-R16可以是氢原子、卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
前提是R15和R16不都是氢原子。
Het表示通式(Het-6)的杂环
式中：
-R17可以是氢原子、卤素原子、氰基、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
-R18和R20可相同或不同，可以是氢原子、卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
-R19可以是氢原子、氰基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C1-C4-烷氧基-C1-C4-烷基、羟基-C1-C4-烷基、C1-C4-烷基磺酰基、二(C1-C4-烷基)氨基磺酰基、C1-C6-烷基羰基、任选被卤素原子或C1-C4-烷基取代的苯基磺酰基，或任选被卤素原子或C1-C4烷基取代的苯甲酰基；
前提是R17和R20不都是氢原子。
Het表示通式(Het-7)的杂环
式中：
-R21可以是氢原子、氰基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C1-C4-烷氧基-C1-C4-烷基、羟基-C1-C4-烷基、C1-C4-烷基磺酰基、二(C1-C4-烷基)氨基磺酰基、C1-C6-烷基羰基、任选被卤素原子或C1-C4-烷基取代的苯基磺酰基，或任选被卤素原子或C1-C4-烷基取代的苯甲酰基；
-R22、R23和R24可相同或不同，可以是氢原子、卤素原子、氰基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基或C1-C4-烷基羰基；
前提是R21和R24不都是氢原子。
Het表示通式(Het-8)的杂环
式中：
-R25可以是氢原子或C1-C4-烷基；
-R26可以是卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
Het表示通式(Het-9)的杂环
式中：
-R27可以是氢原子或C1-C4-烷基；
-R28可以是卤素原子、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基或任选被卤素原子或C1-C4-烷基取代的苯基。
Het表示通式(Het-10)的杂环
式中：
-R29可以是氢原子、卤素原子、氨基、氰基、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基，或任选被卤素原子或C1-C4-烷基取代的苯基；
-R30可以是卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
Het表示通式(Het-11)的杂环
式中：
-R31可以是氢原子、卤素原子、氨基、氰基、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
-R32可以是卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
Het表示通式(Het-12)的杂环
式中：
-R33可以是卤素原子、氰基、硝基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C3-C6-环烷基、C1-C4-烷氧基、具有1-到5个卤素原子的C1-C4-卤代烷氧基、C1-C4-烷硫基、具有1到5个卤素原子的C1-C4-卤代烷硫基、氨基羰基或氨基羰基-C1-C4-烷基；
-R34可以是氢原子、卤素原子、氰基、硝基、C1-C4-烷基、C1-C4-烷氧基或C1-C4-烷硫基；
-R35可以是氢原子、苯基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、羟基-C1-C4-烷基、C2-C6-烯基、C3-C6-环烷基、C1-C4-烷硫基-C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷硫基-C1-C4-烷基、C1-C4-烷氧基-C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷氧基-C1-C4-烷基。
Het表示通式(Het-13)的杂环
式中：
-R36可以是氢原子、卤素原子、氰基、硝基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C3-C6-环烷基、C1-C4-烷氧基、具有1-到5个卤素原子的C1-C4-卤代烷氧基、C1-C4-烷硫基、具有1到5个卤素原子的C1-C4-卤代烷硫基、氨基羰基或氨基羰基-C1-C4-烷基；
-R37可以是氢原子、卤素原子、氰基、C1-C4-烷基、C1-C4-烷氧基、具有1到5个卤素原子的C1-C4-卤代烷氧基或C1-C4-烷硫基；
-R38可以是氢原子、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、羟基-C1-C4-烷基、C2-C6-烯基、C3-C6-环烷基、C1-C4-烷硫基-C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷硫基-C1-C4-烷基、C1-C4-烷氧基-C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷氧基-C1-C4-烷基或任选被卤素原子、C1-C4-烷基、C1-C4-烷氧基烷基或硝基取代的苯基；
前提是R36和R37不都是氢原子。
Het表示通式(Het-14)的杂环
式中：
-R39可以是氢原子、卤素原子、氰基、硝基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C3-C6-环烷基、C1-C4-烷氧基、具有1-到5个卤素原子的C1-C4-卤代烷氧基、C1-C4-烷硫基、具有1到5个卤素原子的C1-C4-卤代烷硫基、氨基羰基或氨基羰基-C1-C4-烷基；
-R40可以是氢原子、卤素原子、氰基、C1-C4-烷基、C1-C4-烷氧基、C1-C4-烷硫基或具有1到5个卤素原子的C1-C4-卤代烷基；
-R41可以是氢原子、苯基、苄基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、羟基-C1-C4-烷基、C2-C6-烯基、C3-C6-环烷基、C1-C4-烷硫基-C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷硫基-C1-C4-烷基、C1-C4-烷氧基-C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷氧基-C1-C4-烷基；
前提是R40和R41不都是氢原子。
Het表示通式(Het-15)的杂环
式中：
-R42可以是氢原子、卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
-R43可以是卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
Het表示通式(Het-16)的杂环
式中：
-R44和R45可以相同或不同，可以是氢原子、卤素原子、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、任选被卤素原子或C1-C4-烷基取代的苯基，或任选被卤素原子或C1-C4-烷基取代的杂环基；
前提是R44和R45不都是氢原子。
Het表示通式(Het-17)的杂环
式中：
-R46可以是卤素原子、C1-C4烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
-R47可以是卤素原子、C1-C4烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
Het表示通式(Het-18)的杂环
式中：
-R48可以是卤素原子、C1-C4烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
Het表示通式(Het-19)的杂环
式中：
-R49可以是卤素原子、C1-C4烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
-R50可以是氢原子、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基或任选被卤素原子或C1-C4-烷基取代的苯基。
Het表示通式(Het-20)的杂环
式中：
-R51可以是卤素原子、C1-C4烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
依据本发明，通式(I)的化合物的“Het”可以是六元杂环。其中Het为六元杂环的本发明化合物的具体例子包括：
Het表示通式(Het-21)的杂环
式中：
-R52可以是卤素原子、羟基、氰基、C1-C4烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C1-C4-烷氧基、C1-C4-烷硫基、具有1到5个卤素原子的C1-C4-卤代烷硫基或具有1到5个卤素原子的C1-C4-卤代烷氧基；
-R53，R54和R55可相同或不同，可以是氢原子、卤素原子、氰基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C1-C4-烷氧基、C1-C4-烷硫基、具有1到5个卤素原子的C1-C4-卤代烷氧基、C1-C4-烷基亚磺酰基或C1-C4-烷基磺酰基。
Het表示通式(Het-22)的杂环
式中：
-R56可以是氢原子、卤素原子、羟基、氰基、C1-C4烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C1-C4-烷氧基、C1-C5-烷硫基、C2-C5-烯硫基、。。具有1到5个卤素原子的C1-C4-卤代烷硫基、具有1到5个卤素原子的C1-C4-卤代烷氧基、任选被卤素原子或C1-C4-烷基取代的苯氧基，或任选被卤素原子或C1-C4-烷基取代的苯硫基；
-R57，R58和R59可相同或不同，可以是氢原子、卤素原子、氰基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C1-C4-烷氧基、C1-C4-烷硫基、具有1到5个卤素原子的C1-C4-卤代烷氧基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基或任选被卤素原子或C1-C4烷基取代的N-吗啉，或任选被卤素原子或C1-C4-烷基取代的噻吩基；
前提是R56和R59不都是氢原子。
Het表示通式(Het-23)的杂环
式中：
-R60，R61，R62和R63可相同或不同，可以是氢原子、卤素原子、羟基、氰基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C1-C4-烷氧基、C1-C4-烷硫基、具有1到5个卤素原子的C1-C4-卤代烷硫基、具有1到5个卤素原子的C1-C4-卤代烷氧基、C1-C4-烷基亚磺酰基或C1-C4-烷基磺酰基；
前提是R60和R63不都是氢原子。
Het表示通式(Het-24)的杂环
式中：
-R64可以是卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
-R65可以是氢原子、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C1-C6-烷氧基羰基、任选被1到3个卤素原子取代的苄基、任被选1到3个卤素原子或取代的苄氧基羰基或杂环基。
Het表示通式(Het-25)的杂环
式中：
-R66可以是卤素原子、羟基、氰基、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基、C1-C4-烷氧基、C1-C4-烷硫基、具有1到5个卤素原子的C1-C4-卤代烷硫基或具有1到5个卤素原子的C1-C4-卤代烷氧基；
-R67可以是氢原子、C1-C4-烷基、具有1到5个卤素原子的C1-C4-卤代烷基或苄基。
Het表示通式(Het-26)的杂环
式中：
-X1可以是硫原子、-SO-、-SO2-或-CH2-；
-R68可以是C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基；
-R69和R70可相同或不同，可以是氢原子或C1-C4-烷基。
Het表示通式(Het-27)的杂环
式中：
-R71可以是C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
Het表示通式(Het-28)的杂环
式中：
-R72可以是C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
Het表示通式(Het-29)的杂环
式中：
-R73可以是卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
依据本发明，通式(I)的化合物的“Het”可以是苯环。其中Het为苯环的本发明化合物的具体例子包括：
Het表示通式(Het-30)的苯环
-R74、R75、R76、R77、R78可以是氢原子、卤素原子、C1-C4-烷基或具有1到5个卤素原子的C1-C4-卤代烷基。
优选的，R1、R2分别为氢、溴、氯、氟、氰基、C1-C3-烷基，C1-C3-烷氧基。
优选的，R1、R2分别为氢、溴、氯、氟。
优选的，R1、R2分别为溴。
优选的，-Het为
进一步优选的，Het为
本发明还包括新型羧酰胺衍生物杀菌剂的制备方法，包括以下步骤：
①将和有机溶剂加入反应釜中，在搅拌下升温至回流，滴加氯化亚砜，得到混合液，将混合液继续回流1小时，减压蒸馏除去有机溶剂和氯化亚砜，得到备用；所述的有机溶剂为二氯甲烷和二氯乙烷按照3:1的体积比混合所得；所述有机溶剂和氯化亚砜的质量体积比为1g：5～8ml：1～3ml；-Het表示含有一个、两个或三个相同或不同杂原子的五、六或七元非稠合杂环，-Het通过碳原子连接且至少在邻位上被取代；
②向步骤①所得的中加入N,N-二甲基乙酰胺，搅拌15～20分钟，滴加得到混合液a，控制混合液a的温度在20～30℃搅拌反应8～10小时，反应结束向混合液a中滴加蒸馏水，得到混合液b，混合液b的温度为20～25℃；所述N,N-二甲基乙酰胺、蒸馏水和步骤①的有机溶剂的体积比为1:4～5:3～4；R1、R2分别为氢、卤素、氰基、C1-C6的烷基或C1-C6的烷氧基；
③向步骤②所得混合液b中滴加碳酸钠溶液，调节混合液b的pH至8～9，然后减压抽滤，得到滤饼，将所得滤饼用蒸馏水洗涤，真空干燥得到
④向步骤③所得中加入二氯乙烷和三乙胺，降温至0～10℃后向其中滴加全氯甲硫醇，滴加结束后升温至20～30℃反应8～10小时，得到反应液，向反应液中加入蒸馏水，搅拌20～30分钟，静置后分液，得到有机层，将所得有机层减压蒸馏除去溶剂，加入乙酸乙酯重结晶，抽滤，干燥，得到新型羧酰胺衍生物杀菌剂；所述的二氯乙烷、三乙胺、蒸馏水和乙酸乙酯的质量体积比为3～4g：20～30ml：1ml：10～15ml：10～15ml；所述的和全氯甲硫醇的摩尔比为1：1～2。
本发明新型羧酰胺衍生物杀菌剂的制备原理为：
包括通式(Ⅱ)的化合物与通式(Ⅲ)的羧酸衍生物在催化剂存在下反应，且如果L2是羟基，则还在缩合剂存在下反应，生成通式(Ⅳ)：
其中通式(Ⅱ)：
式中，R1和R2如以上权利要求中任一项所定义；
其中通式(Ⅲ)：
式中：
-Het如以上权利要求中任一项所定义；
-L2是离去基团，选自卤素原子、羟基、-OR6、-OCOR6，R6为C1-C6烷基、C1-C6卤代烷基、苄基、4-甲氧基苄基、五氟苯基或通式为
的基团。
通式(Ⅳ)与全氯甲硫醇反应生成产物通式(I)。
以类似的方式，使用类似的方法可以制备得到表1一种新型羧酰胺衍生物杀菌剂，如通式(I)所示：
本发明还包括新型羧酰胺衍生物杀菌剂的用途为用于防治农业菌类病害。
实施例1
制备表1中序号13的化合物包括下述步骤：
1)制备2-甲基-4-三氟甲基-5-(2＇，6＇-二溴-4＇-三氟甲氧基苯胺羰基)噻唑100ml烧瓶加入2-甲基-4-三氟甲基-5-噻唑甲酸4.2g(0.02mol)，分别加入二氯甲烷24ml、二氯乙烷8ml，搅拌，加热升温至回流，回流状态下滴加氯化亚砜4ml，回流至溶液变澄清，再继续回流1小时，脱溶剂至釜温达60℃，再减压蒸馏残留的氯化亚砜和二氯乙烷，釜温不大于45℃，真空度大于0.09MPa。
釜残中加入N，N-二甲基乙酰胺12ml，搅拌15分钟。分批加入2,6-二溴-4-三氟甲氧基苯胺6.7g(0.02mol)。常温搅拌过夜，冰水降温，滴加水48ml，控制釜温25℃以下。滴加碳酸钠溶液调pH为8-9。减压抽滤，水洗滤饼，干燥得样品9.2g，收率86.2％。
2)化合物13的合成
500ml烧瓶中加入2-甲基-4-三氟甲基-5-(2＇，6＇-二溴-4＇-三氟甲氧基苯胺羰基)噻唑13.2g(0.025mol)，二氯乙烷100g，三乙胺3.6g，降温至10℃下滴加全氯甲硫醇7.2g(0.039mol)，升温至室温搅拌过夜，加水30g搅拌30min，静置分层，有机层负压脱干溶剂，加乙酸乙酯10ml重结晶，抽滤得到样品，干燥后重12.9g，收率75.8％。
经分析：m/z:677.71(100.0％)，675.71(88.2％)，673.71(29.4％)，679.71(28.3％)，679.70(27.0％)，678.71(17.0％)，676.71(15.4％)，681.70(14.7％)，680.71(8.7％)，674.72(4.5％)，682.71(2.0％)，683.70(2.0％)，677.72(1.2％)。
元素分析:C，24.83；H，0.74；Br，23.59；Cl，15.71；F，16.82；N，4.13；O，4.72；S，9.46。
实施例2
制备表1中序号21的化合物包括下述步骤：
1)制备N-(2,6-二溴-4-(三氟甲氧基)苯基)-2-(三氟甲基)苯甲酰胺
100ml烧瓶加入邻三氟甲基苯甲酸3.8g(0.02mol)，分别加入二氯甲烷24ml、二氯乙烷8ml，搅拌，加热升温至回流，回流状态下滴加氯化亚砜4ml，回流至溶液变澄清，再继续回流1小时，脱溶剂至釜温达60℃，再减压蒸馏残留的氯化亚砜和二氯乙烷，釜温不大于45℃，真空度大于0.09MPa。
釜残中加入N，N-二甲基乙酰胺12ml，搅拌15分钟。分批加入2,6-二溴-4-三氟甲氧基苯胺6.7g(0.02mol)。常温搅拌过夜，冰水降温，滴加水48ml，控制釜温25℃以下。滴加碳酸钠溶液调pH为8-9。减压抽滤，水洗滤饼，干燥得样品8.7g，收率85.0％。
2)化合物21的合成
500ml烧瓶中加入N-(2,6-二溴-4-(三氟甲氧基)苯基)-2-(三氟甲基)苯甲酰胺12.6g(0.025mol)，二氯乙烷100g，三乙胺3.6g，降温至10℃下滴加全氯甲硫醇6.9g(0.037mol)，升温至室温搅拌过夜，加水30g搅拌30min，静置分层，有机层负压脱干溶剂，加乙酸乙酯10ml重结晶，抽滤得到样品，干燥后重12.7g，收率76.8％。
经分析：m/z:656.74(100.0％),654.74(90.7％),658.74(52.1％),652.75(30.8％),657.74(18.5％),655.75(15.6％),660.74(9.6％),659.74(9.5％),653.75(5.4％),660.73(4.1％),661.74(2.3％),656.75(1.8％),658.75(1.6％),662.73(1.5％),655.74(1.3％)
元素分析:C,29.27；H,0.92；Br,24.34；Cl,16.20；F,17.36；N,2.14；O,4.86；S,4.88
实施例3
制备表1中序号1的化合物包括下述步骤：
①将1.25g和6ml二氯甲烷、2ml二氯乙烷加入反应釜中，在搅拌下升温至回流，滴加2.5ml氯化亚砜，得到混合液，将混合液继续回流1小时，减压蒸馏除去有机溶剂和氯化亚砜，得到备用；
②向步骤①所得的中加入2mlN,N-二甲基乙酰胺，搅拌15～20分钟，滴加得到混合液a，控制混合液a的温度在25℃搅拌反应9小时，反应结束向混合液a中滴加10ml蒸馏水，得到混合液b，控制混合液b的温度在为22℃；
③向步骤②所得混合液b中滴加碳酸钠溶液，调节混合液b的pH至8～9，然后减压抽滤，得到滤饼，将所得滤饼用蒸馏水洗涤，真空干燥得到
④向步骤③所得2g中加入14ml二氯乙烷和0.5ml三乙胺，降温至0～10℃后向其中滴加1.4g全氯甲硫醇，滴加结束后升温至20～30℃反应8～10小时，得到反应液，向反应液中加入6ml蒸馏水，搅拌20～30分钟，静置后分液，得到有机层，将所得有机层减压蒸馏除去溶剂，加入5ml乙酸乙酯重结晶，抽滤，干燥，得到新型羧酰胺衍生物杀菌剂
以类似的方式，使用类似的方法可以制备得到表1中的新型羧酰胺衍生物杀菌剂化合物。
实施例4
针对叶锈病(小麦褐霉病)的作用
用置于喷雾室中配制好的本发明的化合物(0.02％活性成分)处理1星期大的小麦植株cv.Arina，施用一天后，通过在试验植株上喷孢子悬浮液(105夏孢子/ml)对小麦植株进行接种，在20℃，95％的相对湿度下，接种两天后，在20℃，60％的相对湿度的温室中保存8天，评定接种10天后的发病率，在该实验中表1中的化合物1～41均显示出优良的活性，尤其是化合物1、4、8、13、21和34的感染率＜10％，显示出强杀菌效力。
针对苹果黑星病的作用
用置于喷雾室中配制好的本发明的化合物(0.02％活性成分)处理4星期大的苹果秧苗cv.Mclntosh。施用一天后，通过在试验植株上喷孢子悬浮液(4×105分生孢子/ml)对苹果植株进行接种。在21℃，95％的相对湿度下培育4天后，植株置于21℃，60％的相对湿度的温室中保存4天，在21℃，95％的相对湿度下另外培育4天后，评定发病率。
在该实验中，表1～41的化合物表现出优良的活性，尤其是化合物2，9，13，21和37的的感染率＜10％，显示出强杀菌效力。

Claims (7)

1.一种新型羧酰胺衍生物杀菌剂，其特征在于：其结构通式I如下所示：
其中R1、R2分别为氢、卤素、氰基、C1-C6的烷基或C1-C6的烷氧基；
-Het为
2.根据权利要求1所述的一种新型羧酰胺衍生物杀菌剂，其特征在于：R1、R2分别为氢、溴、氯、氟、氰基、C1-C3-烷基，C1-C3-烷氧基。
3.根据权利要求1所述的一种新型羧酰胺衍生物杀菌剂，其特征在于：R1、R2分别为氢、溴、氯、氟。
4.根据权利要求1所述的一种新型羧酰胺衍生物杀菌剂，其特征在于：R1、R2分别为溴。
5.根据权利要求1所述的一种新型羧酰胺衍生物杀菌剂，其特征在于：-Het为
6.权利要求1所述的新型羧酰胺衍生物杀菌剂的制备方法，其特征在于：包括以下步骤：
①将和有机溶剂加入反应釜中，在搅拌下升温至回流，滴加氯化亚砜，得到混合液，将混合液继续回流1小时，减压蒸馏除去有机溶剂和氯化亚砜，得到备用；所述的有机溶剂为二氯甲烷和二氯乙烷按照3:1的体积比混合所得；所述有机溶剂和氯化亚砜的质量体积比为1g：5～8ml：1～3ml；
其中-Het为
②向步骤①所得的中加入N,N-二甲基乙酰胺，搅拌15～20分钟，滴加得到混合液a，控制混合液a的温度在20～30℃搅拌反应8～10小时，反应结束向混合液a中滴加蒸馏水，得到混合液b，混合液b的温度为20～25℃；所述N,N-二甲基乙酰胺、蒸馏水和步骤①的有机溶剂的体积比为1:4～5:3～4；R1、R2分别为氢、卤素、氰基、C1-C6的烷基或C1-C6的烷氧基；
③向步骤②所得混合液b中滴加碳酸钠溶液，调节混合液b的pH至8～9，然后减压抽滤，得到滤饼，将所得滤饼用蒸馏水洗涤，真空干燥得到
④向步骤③所得中加入二氯乙烷和三乙胺，降温至0～10℃后向其中滴加全氯甲硫醇，滴加结束后升温至20～30℃反应8～10小时，得到反应液，向反应液中加入蒸馏水，搅拌20～30分钟，静置后分液，得到有机层，将所得有机层减压蒸馏除去溶剂，加入乙酸乙酯重结晶，抽滤，干燥，得到新型羧酰胺衍生物杀菌剂；所述的二氯乙烷、三乙胺、蒸馏水和乙酸乙酯的质量体积比为3～4g：20～30ml：1ml：10～15ml：10～15ml；所述的和全氯甲硫醇的摩尔比为1：1～2。
7.权利要求1所述的新型羧酰胺衍生物杀菌剂的用途，其特征在于：用于防治农业菌类病害。
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