CN113321603B - 一种s-取代-缩氨基硫脲结构化合物及其制备方法和应用 - Google Patents
一种s-取代-缩氨基硫脲结构化合物及其制备方法和应用 Download PDFInfo
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Abstract
Description
本申请要求享有申请人2020年2月28日向中国国家知识产权局提交的申请号为202010130869.3,名称为“一种S-取代-缩氨基硫脲结构化合物及其制备方法和应用”的中国发明专利在先申请的优先权权益。上述在先申请的全文以引用的方式结合至本文。
技术领域
本发明属化学技术领域,具体涉及一种S-取代-缩氨基硫脲结构化合物及其制备方法和应用。
背景技术
在现代农业生产中,杀菌剂对保护农作物免受植物病害侵袭,减少病害损失,增加农作物品质具有重要的意义。但随着杀菌剂的广泛使用,耐药问题也越来越突出,农药市场中使用规模较大,时间较长的杀菌剂均出现了不同程度的耐药现象,其对现病原菌的控制作用下降显著。
因此,开发新结构,对现病原菌敏感的杀菌剂对现农业生产具有很大的意义。
发明内容
为改善上述技术问题,本发明提供式I所示的S-取代-缩氨基硫脲结构化合物或其盐,
其中,
R1选自H、C1-C12烷基、卤代C1-C12烷基、C3-C12环烷基、C2-C12烯基、C2-C12炔基、C1-C12烷氧基羰基、C1-C12烷氧基C1-C12烷基、卤代C1-C12烷氧基C1-C12烷基、C1-C12烷硫基C1-C12烷基、卤代C1-C12烷硫基C1-C12烷基、C1-C12烷氧基羰基C1-C12烷基、卤代C1-C12烷氧基羰基C1-C12烷基、C1-C12烷硫基羰基C1-C12烷基、卤代C1-C12烷硫基羰基C1-C12烷基;
每一个R2相同或不同,彼此独立地选自H、卤素、羟基、氨基、硝基、氰基、羧基、C1-C12烷基、卤代C1-C12烷基、C1-C12烷氧基、卤代C1-C12烷氧基、C3-C12环烷基、-O-C3-C12环烷基、C1-C12烷基氨基、卤代C1-C12烷基氨基、二(C1-C12烷基)氨基、-NHC3-C12环烷基、卤代二(C1-C12烷基)氨基、二(C1-C12烷基)氨基羰基、C1-C12烷硫基、-S-C3-C12环烷基、卤代C1-C12烷硫基、C2-C12烯基、C2-C12炔基、C2-C12烯氧基、卤代C2-C12烯氧基、C2-C12炔氧基、卤代C2-C12炔氧基、C1-C12烷基磺酰基、卤代C1-C12烷基磺酰基、C1-C12烷基羰基、-OCOC1-C12烷基、卤代C1-C12烷基羰基、C1-C12烷氧基羰基、卤代C1-C12烷氧基羰基、C1-C12烷氧基C1-C12烷基、卤代C1-C12烷氧基C1-C12烷基、C1-C12烷硫基C1-C12烷基、卤代C1-C12烷硫基C1-C12烷基、C1-C12烷氧基羰基C1-C12烷基、卤代C1-C12烷氧基羰基C1-C12烷基、C1-C12烷硫基羰基C1-C12烷基、卤代C1-C12烷硫基羰基C1-C12烷基、C1-C12烷基羰基氧基、卤代C1-C12烷基羰基氧基、C1-C12烷氧基羰基氧基、卤代C1-C12烷氧基羰基氧基、C1-C12烷基磺酰基氧基、卤代C1-C12烷基磺酰基氧基、C1-C12烷氧基C1-C12烷氧基或卤代C1-C12烷氧基C1-C12烷氧基;
R2取代基的个数可以为1-5,例如1、2、3、4或5个,当存在1-5个R2时,特别是存在2-5个R2时,每个R2取代基相同或不同,彼此独立地选自上文所述的定义。
根据本发明的实施方案,R1选自H、C1-C6烷基、卤代C1-C6烷基、C3-C6环烷基、C2-C6烯基、C2-C6炔基、C1-C6烷氧基羰基、C1-C6烷氧基C1-C6烷基、卤代C1-C6烷氧基C1-C6烷基、C1-C6烷硫基C1-C6烷基、卤代C1-C6烷硫基C1-C6烷基、C1-C6烷氧基羰基C1-C6烷基、卤代C1-C6烷氧基羰基C1-C6烷基、C1-C6烷硫基羰基C1-C6烷基、卤代C1-C6烷硫基羰基C1-C6烷基;
每一个R2相同或不同,彼此独立地选自H、卤素、羟基、氨基、硝基、氰基、羧基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C3-C6环烷基、-O-C3-C6环烷基、C1-C6烷基氨基、卤代C1-C6烷基氨基、二(C1-C6烷基)氨基、-NHC3-C6环烷基、卤代二(C1-C6烷基)氨基、二(C1-C6烷基)氨基羰基、C1-C6烷硫基、-S-C3-C6环烷基、卤代C1-C6烷硫基、C2-C6烯基、C2-C6炔基、C2-C6烯氧基、卤代C2-C6烯氧基、C2-C6炔氧基、卤代C2-C6炔氧基、C1-C6烷基磺酰基、卤代C1-C6烷基磺酰基、C1-C6烷基羰基、-OCOC1-C6烷基、卤代C1-C6烷基羰基、C1-C6烷氧基羰基、卤代C1-C6烷氧基羰基、C1-C6烷氧基C1-C6烷基、卤代C1-C6烷氧基C1-C6烷基、C1-C6烷硫基C1-C6烷基、卤代C1-C6烷硫基C1-C6烷基、C1-C6烷氧基羰基C1-C6烷基、卤代C1-C6烷氧基羰基C1-C6烷基、C1-C6烷硫基羰基C1-C6烷基、卤代C1-C6烷硫基羰基C1-C6烷基、C1-C6烷基羰基氧基、卤代C1-C6烷基羰基氧基、C1-C6烷氧基羰基氧基、卤代C1-C6烷氧基羰基氧基、C1-C6烷基磺酰基氧基、卤代C1-C6烷基磺酰基氧基、C1-C6烷氧基C1-C6烷氧基或卤代C1-C6烷氧基C1-C6烷氧基;
R2取代基的个数可以为1-4,当存在1-4个R2时,特别是存在2-4个R2时,每个R2取代基相同或不同,彼此独立地选自上文所述的定义。
根据本发明的实施方案,R1选自H、C1-C3烷基、卤代C1-C3烷基、C3-C6环烷基、C2-C4烯基、C2-C4炔基、C1-C3烷氧基羰基、C1-C3烷氧基C1-C3烷基、卤代C1-C3烷氧基C1-C3烷基、C1-C3烷硫基C1-C3烷基、卤代C1-C3烷硫基C1-C3烷基、C1-C3烷氧基羰基C1-C3烷基、卤代C1-C3烷氧基羰基C1-C3烷基、C1-C3烷硫基羰基C1-C3烷基、卤代C1-C3烷硫基羰基C1-C3烷基;
每一个R2相同或不同,彼此独立地选自H、卤素、羟基、氨基、硝基、氰基、羧基、C1-C3烷基、卤代C1-C3烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C3-C6环烷基、-O-C3-C4环烷基、C1-C3烷基氨基、卤代C1-C3烷基氨基、二(C1-C3烷基)氨基、-NHC3-C4环烷基、卤代二(C1-C3烷基)氨基、二(C1-C3烷基)氨基羰基、C1-C3烷硫基、-S-C3-C4环烷基、卤代C1-C3烷硫基、C2-C4烯基、C2-C4炔基、C2-C4烯氧基、卤代C2-C4烯氧基、C2-C4炔氧基、卤代C2-C4炔氧基、C1-C3烷基磺酰基、卤代C1-C3烷基磺酰基、C1-C3烷基羰基、-OCOC1-C3烷基、卤代C1-C3烷基羰基、C1-C3烷氧基羰基、卤代C1-C3烷氧基羰基、C1-C3烷氧基C1-C3烷基、卤代C1-C3烷氧基C1-C3烷基、C1-C3烷硫基C1-C3烷基、卤代C1-C3烷硫基C1-C3烷基、C1-C3烷氧基羰基C1-C3烷基、卤代C1-C3烷氧基羰基C1-C3烷基、C1-C3烷硫基羰基C1-C3烷基、卤代C1-C3烷硫基羰基C1-C3烷基、C1-C3烷基羰基氧基、卤代C1-C3烷基羰基氧基、C1-C3烷氧基羰基氧基、卤代C1-C3烷氧基羰基氧基、C1-C3烷基磺酰基氧基、卤代C1-C3烷基磺酰基氧基、C1-C3烷氧基C1-C3烷氧基或卤代C1-C3烷氧基C1-C3烷氧基;
R2取代基的个数可以为1、2、3或4个,当存在1-4个R2时,特别是存在2-4个R2时,每个R2取代基相同或不同,彼此独立地选自上文所述的定义。
根据本发明的实施方案,R1选自H、C1-C3烷基;
R2选自H、卤素、羟基、氨基、硝基、氰基、羧基、C1-C3烷基、卤代C1-C3烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C3-C6环烷基、-O-C3-C4环烷基、C1-C3烷基氨基、卤代C1-C3烷基氨基、二(C1-C3烷基)氨基、-NHC3-C4环烷基、卤代二(C1-C3烷基)氨基、二(C1-C3烷基)氨基羰基、C1-C3烷氧基羰基、卤代C1-C3烷氧基羰基、C1-C3烷基羰基氧基、卤代C1-C3烷基羰基氧基,-S-C3-C4环烷基、-COOC1-C3烷基、-OCOC1-C3烷基。
根据本发明优选的实施方案,R1选自H、甲基;
每一个R2相同或不同,彼此独立地选自H、氟、氯、溴、羟基、硝基、氰基、甲基、三氟甲基、甲氧基、三氟甲氧基、二甲氨基、甲氧基羰基、甲基羰基氧基。
根据本发明优选的实施方案,R1选自H、甲基;
每一个R2相同或不同,彼此独立地选自H、2-硝基、3-硝基、4-硝基、2-甲基、3-甲基、4-甲基、2-甲氧基、3-甲氧基、4-甲氧基、2-氟、3-氟、4-氟、2-氯、3-氯、4-氯、2-三氟甲基、3-三氟甲基、4-三氟甲基、2-三氟甲氧基、3-三氟甲氧基、4-三氟甲氧基、4氯-2-氟、3,4-二甲基、2,4-二氟、3,4,5-三氟、2-氟-5-三氟甲基、2,4,6-三氟、2,4,5-三氟、2,3,4-三氟、3,4-二氟、3-三氟甲基-4-氟、4-羟基、2,4-二羟基、3,4-二甲氧基、4-氟-3-氰基、2,4-二甲氧基、3-羟基、3-羟基-4-甲氧基、3,4-二甲氧基、3-甲基-4-氟。
根据本发明优选的实施方案,R1选自H;
每一个R2相同或不同,彼此独立地选自H、2-硝基、3-硝基、4-硝基、2-甲基、3-甲基、4-甲基、2-甲氧基、3-甲氧基、4-甲氧基、2-氟、3-氟、4-氟、2-氯、3-氯、4-氯、2-三氟甲基、3-三氟甲基、4-三氟甲基、2-三氟甲氧基、3-三氟甲氧基、4-三氟甲氧基、2,4-二氟、3,4,5-三氟、2-氟-5-三氟甲基、2,4,6三氟、2,4,5-三氟、2,3,4-三氟、3,4-二氟、3-三氟甲基-4-氟、4-羟基、2,4-二羟基、3,4-二甲氧基、4-氟-3-氰基、2,4-二甲氧基、3-羟基、3-羟基-4-甲氧基、3,4-二甲氧基;
根据本发明优选的实施方案,R1选自甲基;
每一个R2相同或不同,彼此独立地选自H、4-硝基、3-甲基、3-三氟甲基、4氯-2-氟、3,4-二甲基、2,4-二氟、4-羟基、2,4-二羟基、2-氯、3-甲基-4-氟、4-甲基、3-氯、2-氟、4-甲基、4-氯。
根据本发明优选的实施方案,R1选自H;
R2选自4-氯。
根据本发明的实施方案,本发明还提供式II所示的S-取代-缩氨基硫脲结构化合物及其盐,
其中,R1、R2彼此独立地具有本说明书上下文所述的定义;
n选自1、2、3、4或5。
根据本发明的实施方案,式I或式II所示的S-取代-缩氨基硫脲结构化合物的盐选自其农药学上可接受的盐,例如选自盐酸盐、硫酸盐、氢溴酸盐、甲磺酸盐、枸橼酸盐、草酸盐、丁二酸盐、马来酸盐、柠檬酸盐、乙酸盐、乳酸盐、磷酸盐、氢碘酸盐、硝酸盐、酒石酸盐、对甲苯磺酸盐等。
根据本发明优选的实施方案,R1选自如下基团:
表1:
每一个R2相同或不同,彼此独立地选自如下基团:
表2:
作为实例,式I或式II所示的S-取代-缩氨基硫脲化合物选自如下化合物,
表3:
表4:
表5:
以及
表6:
化合物编号 | R<sup>1</sup> | R<sup>2</sup> |
A1 | H | 3-CF<sub>3</sub>,5-F |
A2 | H | 2-NO<sub>2</sub>,4-F |
A3 | H | 2,6-F,4-OCH<sub>3</sub> |
A4 | H | 3-NO<sub>2</sub>,4-Cl |
A5 | H | 3-CF<sub>3</sub>,4-F |
A6 | H | 2-F,5-CF<sub>3</sub> |
A7 | H | 3-CN,4-F |
A8 | H | 2-F,3-CF<sub>3</sub> |
当本发明的上下文在描述多个取代位置上的取代基且仅使用一种取代基时,其表示上述多个取代位置上的取代基均为该一种取代基。例如,2,3-F表示2,3-位的两个取代基均为F;又如,2,3,4-F表示2,3,4-位的三个取代基均为F。
本发明还提供一种农药组合物,例如杀菌剂、抗菌剂或抑菌剂,所述农药组合物包含式I或式II所示的S-取代-缩氨基硫脲结构化合物或其盐。
根据本发明的实施方案,所述农药组合物,例如杀菌剂、抗菌剂或抑菌剂还包含农业上可接受的助剂,以及任选地具备农业生产相关的其他功能的药剂。
根据本发明的实施方案,所述杀菌剂中还可以包括除式I或式II所示的S-取代-缩氨基硫脲结构化合物或其盐外的具有杀菌活性的其他活性成分。
本发明还提供式I或式II所示的S-取代-缩氨基硫脲结构化合物或其盐作为活性组分在用于制备杀菌剂、抗菌剂或抑菌剂中的应用。
本发明还提供一种杀菌、抗菌或抑菌方法,包括将式I或式II所示的S-取代-缩氨基硫脲结构化合物或其盐施用于土壤或农作物。
根据本发明的实施方案,所述活性组分的重量百分含量为0.1-99%。
本发明所述杀菌剂、抗菌剂或抑菌剂可用于防治包括但不限于下列病害:卵菌纲病害,如霜霉病(黄瓜霜霉病、油菜霜霉病、大豆霜霉病、甜菜霜霉病、甘蔗霜霉病、烟草霜霉病、豌豆霜霉病、丝瓜霜霉病、冬瓜霜霉病、甜瓜霜霉病、白菜类霜霉病、菠菜霜霉病、萝卜霜霉病、葡萄霜霉病、葱霜霉病),白锈菌(油菜白锈病、白菜类白锈病),猝倒病(油菜猝倒病、烟草猝倒病、番茄猝倒病、辣椒猝倒病、茄子猝倒病、黄瓜猝倒病、棉苗猝倒病),绵腐病(辣椒绵腐病、丝瓜绵腐病、冬瓜绵腐病),疫病(蚕豆疫病、黄瓜疫病、南瓜疫病、冬瓜疫病、西瓜疫病、甜瓜疫病、辣椒疫病、韭菜疫病、大蒜疫病、棉花疫病),晚疫病(马铃薯晚疫病、番茄晚疫病)等;半知菌病害,如枯萎病(甘薯枯萎病、棉花枯萎病、芝麻枯萎病、蓖麻枯萎病、番茄枯萎病、菜豆枯萎病、黄瓜枯萎病、丝瓜枯萎病、南瓜枯萎病、冬瓜枯萎病、西瓜枯萎病、甜瓜枯萎病、辣椒枯萎病、蚕豆枯萎病、油菜枯萎病、大豆枯萎病),根腐病(辣椒根腐病、茄子根腐病、菜豆根腐病、黄瓜根腐病、苦瓜根腐病、棉黑根腐病、蚕豆根腐病),立枯病(棉苗立枯病、芝麻立枯病、辣椒立枯病、黄瓜立枯病、白菜立枯病),炭疽病(高粱炭疽病、棉花炭疽病、红麻炭疽病、黄麻炭疽病、亚麻炭疽病、烟草炭疽病、桑炭疽病、辣椒炭疽病、茄子炭疽病、菜豆炭疽病、黄瓜炭疽病、苦瓜炭疽病、西葫芦炭疽病、冬瓜炭疽病、西瓜炭疽病、甜瓜炭疽病、荔枝炭疽病、红小豆炭疽),黄萎病(棉花黄萎病、向日葵黄萎病、番茄黄萎病、辣椒黄萎病、茄子黄萎病),黑星病(西葫芦黑星病、冬瓜黑星病、甜瓜黑星病),灰霉病(棉铃灰霉病、红麻灰霉病、番茄灰霉病、辣椒灰霉病、菜豆灰霉病、芹菜灰霉病、菠菜灰霉病、猕猴桃灰霉病),褐斑病(棉花褐斑病、黄麻褐斑病、甜菜褐斑病、花生褐斑病、辣椒褐斑病、冬瓜褐斑病、大豆褐斑病、向日葵褐斑病、豌豆褐斑病、蚕豆褐斑病),黑斑病(亚麻假黑斑病、油菜黑斑病、芝麻黑斑病、向日葵黑斑病、蓖麻黑斑病、番茄黑斑病、辣椒黑斑病、茄子黑斑病、菜豆黑斑病、黄瓜黑斑病、芹菜黑斑病、胡萝卜黑腐病、胡萝卜黑斑病、苹果黑斑病、花生黑斑病),斑枯病(番茄斑枯病、辣椒斑枯病、芹菜斑枯病),早疫病(番茄早疫病、辣椒早疫病、茄子早疫病、马铃薯早疫病、芹菜早疫病),轮纹病(大豆轮纹病、芝麻轮纹病、菜豆轮纹病、苹果轮纹),叶枯病(芝麻叶枯病、向日葵叶枯病、西瓜叶枯病、甜瓜叶枯病),茎基腐病(番茄茎基腐病、菜豆茎基腐病),及其他(玉米圆斑病、红麻腰折病、稻瘟病、栗黑鞘病、甘蔗眼斑病、棉铃曲霉病、花生冠腐病、大豆茎枯病、大豆黑点病、甜瓜大斑病、花生网斑病、茶赤叶斑病、辣椒白星病、冬瓜叶斑病、芹菜黑腐病、菠菜心腐病、红麻叶霉病、红麻斑点病、黄麻茎斑病、大豆紫斑病、芝麻叶斑病、蓖麻灰斑病、茶褐色叶斑病、茄子褐色圆星病、菜豆红斑病、苦瓜白斑病、西瓜斑点病、黄麻枯腐病、向日葵根茎腐病、菜豆炭腐病、大豆靶点病、茄子棒孢叶斑病、黄瓜靶斑病、番茄叶霉病、茄子叶霉病、蚕豆赤斑病等)等;担子菌病害,如锈病(小麦条锈病、小麦杆锈病、小麦叶锈病、花生锈病、向日葵锈病、甘蔗锈病、韭菜锈病、葱锈病、栗锈病、大豆锈病),黑穗病(玉米丝黑穗病、玉米黑粉病、高粱丝黑穗病、高粱散黑穗病、高粱坚黑穗病、高梁柱黑粉病、栗粒黑穗病、甘蔗黑穗病、菜豆锈病)及其他(如小麦纹枯病、水稻纹枯病等)等;子囊菌病害,如白粉病(小麦白粉病、油菜白粉病、芝麻白粉病、向日葵白粉病、甜菜白粉病、茄子白粉病、豌豆白粉病、丝瓜白粉病、南瓜白粉病、西葫芦白粉病、冬瓜白粉病、甜瓜白粉病、葡萄白粉病、蚕豆白粉病),菌核病(亚麻菌核病、油菜菌核病、大豆菌核病、花生菌核病、烟草菌核病、辣椒菌核病、茄子菌核病、菜豆菌核病、豌豆菌核病、黄瓜菌核病、苦瓜菌核病、冬瓜菌核病、西瓜菌核病、芹菜菌核病),黑星病(苹果黑星病、梨黑星病),小麦赤霉等。
本发明还提供式I所示S-取代-缩氨基硫脲结构化合物的制备方法,包括如下步骤:
1)式A所示化合物与氨基硫脲反应得到式B所示化合物;
2)步骤1)所得式B所示化合物与式C所示化合物反应得到式I所示化合物;
其中,X选自溴或氯;
R1、R2具有如上所述定义。
根据本发明的实施方案,步骤1)中,式A所示化合物在酸性条件下与氨基硫脲反应得到中间体B。
根据本发明的实施方案,步骤1)中,调节酸性条件使用的酸可选自如盐酸、硫酸、硝酸、磷酸、三氟乙酸、乙酸、甲磺酸、苯甲磺酸、对甲苯磺酸等,但优选的是浓盐酸。
根据本发明的实施方案,步骤1)中,所述反应在适宜的溶剂中进行,适宜的溶剂可选自如四氢呋喃、1,4-二氧六环、乙腈、甲苯、二甲苯、苯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲亚砜、丙酮或丁酮、甲基异丁基酮、甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇等,优选无水乙醇。
根据本发明的实施方案,步骤1)中,反应温度可为0℃至溶剂沸点温度,例如可以为40~100℃,如40~80℃。
根据本发明的实施方案,步骤1)中,反应时间为0.5~30小时,例如3~10小时。
根据本发明的实施方案,步骤2)中,式B所示化合物在酸性条件下与式C所示化合物反应得到式I所示化合物。
根据本发明的实施方案,步骤2)中,调节酸性条件使用的酸可选自如盐酸、硫酸、硝酸、磷酸、三氟乙酸、乙酸、甲磺酸、苯甲磺酸、对甲苯磺酸等,优选浓盐酸。
根据本发明的实施方案,步骤2)中,所述反应在适宜的溶剂中进行,适宜的溶剂可选自如四氢呋喃、1,4-二氧六环、乙腈、甲苯、二甲苯、苯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲亚砜、丙酮或丁酮、甲基异丁基酮、甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇等,优选无水乙醇。
根据本发明的实施方案,步骤2)中,所述反应温度为0℃至溶剂沸点温度,例如可以为40~100℃,如40~80℃。
根据本发明的实施方案,步骤2)中,所述反应时间为0.5小时~30小时,例如2~5小时。
有益效果
本发明式I或式II所示的S-取代-缩氨基硫脲化合物对农业常见病原菌具备出色的防治效果,且在离体与活体测试上优于现阳性药物嘧菌酯,具备替代或补充现市场现有杀菌剂、抗菌剂或抑菌剂的潜力。
术语与定义
除非另有定义,否则本文所有科技术语具有的含义与所属领域技术人员通常理解的含义相同。
“C1-C12”表示具有1、2、3、4、5、6、7、8、9、10、11或12个碳原子。“C3-C12”表示具有3、4、5、6、7、8、9、10、11或12个碳原子。“C2-C12”表示具有2、3、4、5、6、7、8、9、10、11或12个碳原子。同理,“C1-C6”、“C3-C6”表示具有对应个数的碳原子。
卤素:指氟、氯、溴或碘。
烷基:直链或支链烷基,例如甲基、乙基、丙基、异丙基、正丁基或叔丁基。
环烷基:取代或未取代的含杂原子的环状烷基,例如环丙基、环戊基或环己基。其取代基如甲基、卤素等。
杂环烷基:取代或未取代的含有1个或多个N、O、S杂原子的环状烷基,例如四氢呋喃基、环戊哌啶基。其取代基如甲基、卤素等。
卤代烷基:直链或支链烷基,在这些烷基上的氢原子可部分或全部被卤原子所取代,例如,氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基等。
烷氧基:直链或支链烷基,经氧原子键连接到结构上。
卤代烷氧基:直链或支链烷氧基,在这些烷氧基上的氢原子可部分或全部被卤原子所取代。例如,氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、氯氟甲氧基、三氟乙氧基等。
烷氧基烷基:烷氧基经烷基连接到结构上。如-CH2OCH3,-CH2OCH2CH3。
卤代烷氧基烷基:烷氧基烷基的烷基上的氢原子可部分或全部被卤原子所取代。如-CH2OCH2CH2Cl。
烷硫基:直链或支链烷基,经硫原子键连接到结构上。
卤代烷硫基:直链或支链烷硫基,在这些烷基上的氢原子可部分或全部被卤原子所取代。例如,氯甲硫基、二氯甲硫基、三氯甲硫基、氟甲硫基、二氟甲硫基、三氟甲硫基、氯氟甲硫基等。
烯基:直链或支链烯类,例如乙烯基、1-丙烯基、2-丙烯基和不同的丁烯基、戊烯基和己烯基异构体。烯基还包括多烯类,如1,2-丙二烯基和2,4-己二烯基。
炔基:直链或支链炔类,例如乙炔基、1-丙炔基、2-丙炔基和不同的丁炔基、戊炔基和己炔基异构体。炔基还包括由多个三键组成的基团,如2,5-己二炔基。
烯氧基:直链或支链烯类,经氧原子键连接到结构上。
卤代烯氧基:直链或支链烯氧基,在这些烯氧基上的氢原子可部分或全部被卤原子所取代。
炔氧基:直链或支链炔类,经氧原子键连接到结构上。
卤代炔氧基:直链或支链炔氧基,在这些炔氧基上的氢原子可部分或全部被卤原子所取代。
烷基羰基:直链或支链烷基经羰基(-CO-)连接到结构上,如乙酰基。
卤代烷基羰基:直链或支链烷基羰基,其烷基上的氢原子可部分或全部被卤原子所取代,如三氟乙酰基。
烷氧基羰基:烷氧基经羰基连接到结构上。如-COOCH3,-COOCH2CH3。
卤代烷氧基羰基:烷氧基羰基的烷基上的氢原子可部分或全部被卤原子所取代,如-COOCH2CF3,-COOCH2CH2Cl等。
烷基磺酰基:直链或支链烷基经磺酰基(-SO2-)连接到结构上,如甲基磺酰基。
卤代烷基磺酰基:直链或支链烷基磺酰基,其烷基上的氢原子可部分或全部被卤原子所取代。
烷基磺酰基氧基:烷基-SO2-O-。
卤代烷基磺酰基氧基:烷基磺酰基氧基的烷基上的氢原子可部分或全部被卤原子所取代,例如CF3-SO2-O。
烷氧基羰基烷基:烷氧基羰基-烷基-,例如CH3OCOCH2-。
卤代烷氧基羰基烷基:烷氧基羰基烷基的烷基上的氢原子可部分或全部被卤原子所取代,例如CF3CH2OCOCH2-。
烷氧基羰基氧基:烷氧基羰基-氧基-,例如CH3OCOO-。
卤代烷氧基羰基氧基:烷氧基羰基氧基的烷基上的氢原子可部分或全部被卤原子所取代,例如CF3OCOO-。
烷硫基羰基烷基:烷硫基羰基-烷基-,例如CH3SCOCH2-。
卤代烷硫基羰基烷基:烷硫基羰基烷基的烷基上的氢原子可部分或全部被卤原子所取代,例如CF3CH2SCOCH2-。
烷氧基烷氧基:如CH3OCH2O-等。
卤代烷氧基烷氧基:烷氧基上的氢原子可部分或全部被卤原子所取代,例如CF3OCH2O-。
烷硫基烷基:烷基-S-烷基-,例如CH3SCH2-。
卤代烷硫基烷基:烷硫基烷基的烷基上的氢原子可部分或全部被卤原子所取代,如ClCH2CH2SCH2-、CF3CH2SCH2-等。
附图说明
图1为化合物3-19的核磁氢谱1H NMR谱图。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明,以下实施例中使用的原料和试剂均为市售商品,或者可以通过已知方法制备。
实施例1化合物3-19的制备
将(E)-2-(2-(溴甲基)苯基)-3-甲氧基丙烯酸甲酯2.8g(10mmol)、氨基硫脲0.9g(10mmol)、25毫升无水乙醇以及三滴浓盐酸投入到100mL三口瓶中,升温至80℃,并维持5小时。薄层色谱(TLC)跟踪反应进度物料转化完全后,冷却,有黄色固体析出。过滤干燥,得黄色固体(E)-2-(2-((((E)-氨基甲酰肼基)硫基)甲基)苯基)-3-甲氧基丙烯酸甲酯1.6g。
将(E)-2-(2-((((E)-氨基甲酰肼基)硫基)甲基)苯基)-3-甲氧基丙烯酸甲酯1.6g(5.3mmol)、4-氯苯甲醛0.85g(6mmol)、25毫升无水乙醇以及三滴浓盐酸投入到100mL三口瓶中,升温至80℃,并维持3小时。薄层色谱(TLC)跟踪反应进度物料转化完全后,冷却,柱层析纯化,得淡黄色固体0.62g。
化合物3-19:
1H NMR(600MHz,DMSO-d6)δ9.83(s,2H),8.60(s,1H),8.00(d,J=8.4Hz,2H),7.70(s,1H),7.57(d,J=8.1Hz,3H),7.35–7.30(m,2H),7.12–7.07(m,1H),4.55(s,2H),3.87(s,3H),3.63(s,3H).
参考上述方法,制备得到如下化合物:
化合物3-6
1H NMR(400MHz,DMSO-d6)δ9.84(s,2H),8.75(s,1H),8.42(dd,J=15.5,8.5Hz,1H),7.70(s,1H),7.58–7.54(m,1H),7.46–7.39(m,1H),7.36–7.25(m,3H),7.12–7.08(m,1H),4.53(s,2H),3.87(s,3H),3.63(s,3H).
化合物3-9
1H NMR(400MHz,DMSO-d6)δ9.91(s,2H),8.57(s,1H),8.31–8.24(m,1H),7.77–7.72(m,1H),7.70(s,1H),7.61–7.53(m,2H),7.36–7.28(m,2H),7.12–7.07(m,1H),4.56(s,2H),3.87(s,3H),3.63(s,3H).
化合物3-11
1H NMR(400MHz,DMSO-d6)δ9.98(s,2H),8.85(s,1H),8.26(dd,J=13.8,6.7Hz,1H),7.70(s,1H),7.58-7.57(m,1H),7.49(dd,J=17.0,8.4Hz,1H),7.34-7.29(m,2H),7.11-7.08(m,1H),4.59(s,2H),3.87(s,3H),3.63(s,3H).
化合物3-14
1H NMR(400MHz,DMSO-d6)δ9.88(s,2H),8.70(s,1H),8.53-8.51(m,1H),7.79–7.71(m,1H),7.70(s,1H),7.59–7.55(m,1H),7.37–7.27(m,2H),7.12–7.07(m,1H),4.54(s,2H),3.87(s,3H),3.63(s,3H).
化合物3-15
1H NMR(400MHz,DMSO-d6)δ9.70(s,2H),8.81(s,1H),7.70(s,1H),7.58-7.53(m,1H),7.41(t,J=9.2Hz,2H),7.35-7.30(m,2H),7.12-7.08(m,1H),4.55(s,2H),3.87(s,3H),3.63(s,3H).
化合物3-16
1H NMR(400MHz,DMSO-d6)δ9.89(s,2H),8.45(s,1H),8.09–8.04(m,2H),7.70(s,1H),7.58–7.55(m,1H),7.36–7.29(m,2H),7.12–7.08(m,1H),4.53(s,2H),3.87(s,3H),3.63(s,3H).
化合物3-17
1H NMR(400MHz,DMSO-d6)δ9.91(s,2H),9.02(s,1H),8.42(d,J=7.9Hz,1H),7.70(s,1H),7.59-7.52(m,3H),7.46(t,J=7.1Hz,1H),7.36–7.30(m,2H),7.15–7.07(m,1H),4.56(s,2H),3.87(s,3H),3.63(s,3H).
化合物3-79
1H NMR(400MHz,DMSO-d6)δ9.67(s,2H),8.57(s,1H),7.90(d,J=8.6Hz,2H),7.70(s,1H),7.59–7.55(m,1H),7.36–7.30(m,2H),7.11–7.08(m,1H),7.05(d,J=8.7Hz,2H),4.55(s,2H),3.87(s,3H),3.83(s,3H),3.63(s,3H).
化合物3-94
1H NMR(400MHz,DMSO-d6)δ8.62(s,2H),8.17(d,J=8.3Hz,2H),8.09(s,1H),7.97(d,J=8.3Hz,2H),7.59–7.55(m,1H),7.35–7.29(m,2H),7.10(dd,J=5.4,3.5Hz,1H),4.54(s,2H),3.87(s,3H),3.63(s,3H).
化合物3-101
1H NMR(400MHz,DMSO-d6)δ9.98(s,2H),8.97(s,1H),8.51(d,J=7.6Hz,1H),8.13(d,J=8.1Hz,1H),7.85(t,J=7.5Hz,1H),7.76(t,J=7.7Hz,1H),7.71(s,1H),7.61–7.56(m,1H),7.37-7.30(m,2H),7.13–7.09(m,1H),4.56(s,2H),3.87(s,3H),3.64(s,3H).
化合物3-102
1H NMR(400MHz,DMSO-d6)δ9.92(s,2H),8.85(s,1H),8.66(s,1H),8.38(d,J=7.8Hz,1H),8.33(d,J=9.4Hz,1H),7.79(t,J=8.0Hz,1H),7.71(s,1H),7.59-7.56(m,1H),7.37–7.29(m,2H),7.10(m,1H),4.53(s,2H),3.87(s,3H),3.63(s,3H).
化合物3-103
1H NMR(400MHz,DMSO-d6)δ9.96(s,2H),8.72(s,1H),8.32(d,J=8.2Hz,1H),8.25(d,J=8.7Hz,1H),7.70(s,1H),7.58-7.56(m,1H),7.35–7.29(m,2H),7.12–7.08(m,1H),4.57(s,2H),3.87(s,3H),3.63(s,3H).
化合物3-112
1H NMR(400MHz,DMSO-d6)δ9.79(s,1H),9.57(s,2H),8.45(s,1H),7.77(d,J=8.7Hz,2H),7.70(s,1H),7.57–7.54(m,1H),7.35–7.29(m,2H),7.11–7.08(m,1H),6.89(d,J=8.7Hz,2H),4.51(s,2H),3.86(s,3H),3.63(s,3H).
化合物A1
1H NMR(400MHz,DMSO-d6)δ10.00(s,2H),8.62(d,J=14.6Hz,1H),8.29(d,J=9.4Hz,1H),8.22(s,1H),7.83(d,J=8.2Hz,1H),7.71(s,1H),7.59(d,J=6.0Hz,1H),7.35-7.29(m,J=6.7Hz,2H),7.13-7.07(m,1H),4.56(s,2H),3.87(s,3H),3.63(s,3H).
化合物A2
1H NMR(400MHz,DMSO-d6)δ9.99(s,2H),8.92(s,1H),8.62(dd,J=8.7,5.8Hz,1H),8.08(dd,J=8.6,2.4Hz,1H),7.86–7.75(m,2H),7.70(s,1H),7.61–7.53(m,1H),7.35-7.30(p,J=5.6Hz,2H),7.11-7.09(m,1H),4.55(s,2H),3.87(s,3H),3.63(s,3H).
化合物A3
1H NMR(400MHz,DMSO-d6)δ9.54(s,2H),8.72(s,1H),7.70(s,1H),7.57–7.53(m,1H),7.32(m,5.2Hz,2H),7.12–7.08(m,1H),6.96–6.83(m,2H),4.52(s,2H),3.86(s,6H),3.63(s,3H).
化合物A4
1H NMR(400MHz,DMSO-d6)δ9.92(s,2H),8.75(d,J=1.7Hz,1H),8.60(s,1H),8.25(dd,J=8.4,1.8Hz,1H),7.91(d,J=8.4Hz,1H),7.70(s,1H),7.57(dd,J=6.5,2.5Hz,1H),7.35–7.29(m,2H),7.12–7.08(m,1H),4.54(s,2H),3.87(s,3H),3.63(s,4H).
化合物A5
1H NMR(400MHz,DMSO-d6)δ9.94(s,2H),8.61(s,1H),8.46(d,J=6.7Hz,1H),8.36–8.32(m,1H),7.70(s,1H),7.70–7.65(m,1H),7.60–7.56(m,1H),7.37–7.29(m,2H),7.12–7.08(m,1H),4.55(s,2H),3.87(s,3H),3.63(s,3H).
化合物A6
1H NMR(400MHz,DMSO-d6)δ10.00(s,2H),8.84(s,1H),8.75(d,J=4.8Hz,1H),7.96-7.94(m,1H),7.70(s,1H),7.62-7.57(m,2H),7.36–7.29(m,2H),7.12–7.08(m,1H),4.57(s,2H),3.87(s,3H),3.63(s,3H).
化合物A7
1H NMR(400MHz,DMSO-d6)δ9.92(s,2H),8.69(d,J=6.1Hz,1H),8.59(s,1H),8.37–8.31(m,1H),7.72–7.64(m,2H),7.59-7.56(m,1H),7.35-7.30(m,2H),7.13–7.07(m,1H),4.56(s,2H),3.87(s,3H),3.63(s,3H).
化合物A8
1H NMR(400MHz,DMSO-d6)δ10.02(s,2H),8.94(s,1H),8.74–8.68(m,1H),7.93(t,J=6.8Hz,1H),7.70(s,1H),7.62–7.50(m,2H),7.36–7.28(m,2H),7.12–7.08(m,1H),4.60(s,2H),3.88(s,3H),3.63(s,3H).
实施例2离体保护活性测试
采用平皿法(菌丝生长速率法)。首先将待测化合物样品(使用的对照阳性药物为嘧菌酯)用适合的溶剂(溶剂的种类如丙酮、甲醇、DMF等,并且依据其对样品的溶解能力而选择)溶解,配制成所需浓度待测液。在超净工作环境下用移液枪将计量好的待测液加入到融化的PDA(在45-50℃下)(马铃薯葡萄糖培养基)中,迅速摇匀制得相应浓度的含药培养基,趁热倒入到3个培养皿中,冷却后待用。接种直径5mm的菌块,在25±1℃下培养7天(空白对照中菌落充分生长为标准)。测量菌落直径(十字交叉法),抑菌率按照以下公式进行计算:
测试结果显示:化合物3-19对水稻纹枯、苹果轮纹、红小豆炭疽、黄瓜菌核、小麦赤霉和棉花黄萎的EC50值(mg/L)均低于5ppm。而对照阳性药物嘧菌酯对水稻纹枯、苹果轮纹、红小豆炭疽、黄瓜菌核、小麦赤霉和棉花黄萎的EC50值(mg/L)均大于10ppm。
此外,本发明其它化合物对水稻纹枯、苹果轮纹、红小豆炭疽、黄瓜菌核、小麦赤霉和棉花黄萎的EC50值(mg/L)优选低于50ppm,还优选低于20ppm,进一步优选低于5ppm。
在100ppm浓度下,化合物3-6、3-9、3-11、3-12、3-15、3-16、3-17、3-79、3-94、3-101、3-102、3-103、3-112、A1、A2、A3、A4、A5、A6、A7和A8对水稻纹枯、黄瓜菌核和小麦赤霉的抑制率大于90%。对照药剂嘧菌酯抑制率大于90%。
在50ppm浓度下,化合3-6、3-9、3-11、3-12、3-15、3-16、3-17、3-79、3-94、3-102、3-103、3-112、A2、A3、A4、A5、A6和A7对水稻纹枯、黄瓜菌核和小麦赤霉的抑制率大于90%。对照药剂嘧菌酯抑制率大于90%。
在10ppm浓度下,化合物3-6、3-12、3-15、3-79、3-94、A3对水稻纹枯、黄瓜菌核和小麦赤霉的抑制率大于90%。对照药剂嘧菌酯抑制率小于90%。
表7杀菌活性实验结果
实施例3活体保护活性测定:
测定方法如下:采用活体盆栽测定方法,即将待测化合物样品(使用的对照阳性药物为嘧菌酯)用少量溶剂(溶剂的种类如丙酮、甲醇、DMF等,并且依据其对样品的溶解能力而选择,溶剂量与喷液量的体积比等于或小于0.05)溶解,用含有0.1%吐温80的水稀释,配制成所需浓度待测液。在作物喷雾机上,将待测液喷施于病害寄主植物上(寄主植物水稻为在温室内培养的标准盆栽苗),24小时后进行病害接种。依据病害特点,将需要控温保湿培养的病害植物接种后放在人工气候室中培养,待病害完成侵染后,移入温室培养,将不需要保湿培养的病害植物直接在温室内接种并培养。待对照充分发病后(通常为一周时间)进行化合物防病效果评估。
药效计算方法:
在100ppm剂量下,化合物3-19对水稻纹枯病的防治效果在80%以上。而对照阳性药物嘧菌酯的防治效果低于70%。
本发明其他化合物的防治效果在50%以上,优选在70%以上,还优选在80%以上。
由上述活性测试结果可见,通式I所示S-取代-缩氨基硫脲化合物对农业常见病原菌具备出色的防治效果,且在离体与活体测试上优于现阳性药物嘧菌酯,具备替代或补充现市场现有杀菌剂的潜力。
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (11)
2.根据权利要求1所述的化合物或其盐,其特征在于,R2取代基的个数为1、2、3或4个,每一个R2相同或不同,彼此独立地选自卤素、羟基、氨基、硝基、氰基、C1-C3烷基、C1-C3烷氧基。
4.根据权利要求1所述的化合物或其盐,其特征在于,每一个R2相同或不同,彼此独立地选自如下基团:
2-硝基、3-硝基、4-硝基、2-甲基、3-甲基、4-甲基、2-甲氧基、3-甲氧基、4-甲氧基、2-氟、3-氟、4-氟、2-氯、3-氯、4-氯、4氯-2-氟、3,4-二甲基、2,4-二氟、3,4,5-三氟、2,4,6三氟、2,4,5-三氟、2,3,4-三氟、3,4-二氟、4-羟基、2,4-二羟基、3,4-二甲氧基、4-氟-3-氰基、2,4-二甲氧基、3-羟基、3-羟基-4-甲氧基、3,4-二甲氧基、3-甲基-4-氟。
6.一种农药组合物,其特征在于,所述农药组合物包含权利要求1-5任一项的化合物或其盐。
7.根据权利要求6所述的农药组合物,其特征在于,所述农药组合物选自杀菌剂、抗菌剂或抑菌剂。
8.根据权利要求6或7所述的农药组合物,其特征在于,所述农药组合物还包含农业上可接受的助剂,以及任选地具备农业生产相关的其他功能的药剂。
9.权利要求1-5任一项所述的化合物或其盐作为活性组分在用于制备杀菌剂中的应用。
10.根据权利要求9所述的应用,其特征在于,所述活性组分的重量百分含量为0.1-99%。
11.一种杀菌、抗菌或抑菌方法,包括将权利要求1-5任一项所述的化合物或其盐施用于土壤或农作物。
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WO1998050352A1 (en) * | 1997-05-02 | 1998-11-12 | Agrevo Uk Limited | Dithiocarbazonic acid derivatives as pesticides |
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