CN112745260B - 一种含取代苯乙酮结构片段的酰胺类化合物及其制备方法和用途 - Google Patents

一种含取代苯乙酮结构片段的酰胺类化合物及其制备方法和用途 Download PDF

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CN112745260B
CN112745260B CN202011130463.1A CN202011130463A CN112745260B CN 112745260 B CN112745260 B CN 112745260B CN 202011130463 A CN202011130463 A CN 202011130463A CN 112745260 B CN112745260 B CN 112745260B
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CN112745260A (zh
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刘鹏飞
张金波
兰杰
叶艳明
单忠刚
刘玉猛
关爱莹
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Jiangsu Yangnong Chemical Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Abstract

本发明公开了一种含取代苯乙酮结构片段的酰胺类化合物，结构如通式I所示：

Description

一种含取代苯乙酮结构片段的酰胺类化合物及其制备方法和 用途
技术领域
本发明属农用杀菌领域，具体涉及一种新型的含取代苯乙酮结构片段的酰胺类化合物及其制备方法和用途。
背景技术
专利WO2007069777公布了如下通式所示的酰胺类化合物CK1(专利编号I-20)和CK2(专利编号I-84)，作为小麦白粉病、黄瓜白粉病、稻瘟病、芸豆茎腐病和小麦颖枯病等真菌病害的预防和治疗的应用。
Figure BDA0002734956360000011
专利JP 2007210924公布了如下通式所示的酰胺类化合物CK3(专利编号I-6)和CK4(专利编号I-183)，作为小麦白粉病、黄瓜白粉病、稻瘟病、芸豆茎腐病、菜豆菌核病和小麦颖枯病等真菌病害的预防和治疗的应用。
Figure BDA0002734956360000012
但结构如本发明通式I所示的酰胺类化合物作为农用杀菌用途的化合物未见报道。
发明内容
本发明的目的在于提供一种可以控制多种病菌的含取代苯乙酮结构片段的酰胺类化合物，用于农业或其他领域中制备防治病菌的药物的用途。
为实现上述目的，本发明的技术方案如下：
本发明提供一种含取代苯乙酮结构片段的酰胺类类化合物，所述含取代苯乙酮结构片段的酰胺类化合物为如通式I所示化合物，
Figure BDA0002734956360000013
式中：
R1选自氢、卤素、C1-C12烷基、卤代C1-C12烷基、C1-C12烷氧基或卤代C1-C12烷氧基；
R2选自氢、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、C4-C12环烷基烷基或卤代C4-C12环烷基烷基；
R3选自氢、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、C1-C12烷硫基、卤代C1-C12烷硫基、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烷基或卤代C1-C12烷硫基C1-C12烷基；
R4选自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、C1-C12烷硫基、卤代C1-C12烷硫基、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烷基或卤代C1-C12烷硫基C1-C12烷基；
B选自吡啶-3-基、2-二氟甲基吡啶-3-基、1-甲基-3-三氟甲基-5-氟-吡唑-4-基、1-乙基-3-三氟甲基-5-氟-吡唑-4-基、1-甲基-3-三氟甲基-5-甲硫基-吡唑-4-基、1-乙基-3-三氟甲基-5-甲硫基-吡唑-4-基、1-甲基-3-三氟甲基-5-甲砜基-吡唑-4-基、1-乙基-3-三氟甲基-5-甲砜基-吡唑-4-基、1-甲基-3-甲基-吡唑-5-基、1-乙基-3-甲基-吡唑-5-基、1-甲基-5-甲基吡唑-3-基或1-乙基-5-甲基吡唑-3-基、卤素取代的异噻唑基；或被1-2个相同或不同的下述基团取代的吡嗪基、嘧啶基、4位取代的2-羟基噻唑-5-基、5位取代的1-甲基-3-二氟甲基吡唑-4-基、5位取代的1-乙基-3-二氟甲基吡唑-4-基，下述基团为氢、甲基、二氟甲基、三氟甲基、羟基、甲氧基、巯基、甲硫基、甲砜基或卤素；
本发明含取代苯乙酮结构片段的酰胺类化合物中，较为优选的化合物包括：所示通式I中，
R1选自氢、卤素或C1-C8烷基；
R2选自氢、C1-C8烷基、C3-C8环烷基或卤代C1-C8烷基；
R3选自氢、C1-C8烷基或卤代C1-C8烷基；
R4选自C1-C8烷基或卤代C1-C8烷基；
B选自下述B1-B30中任意一个；
Figure BDA0002734956360000021
本发明含取代苯乙酮结构片段的酰胺类化合物中，进一步优选的化合物包括：所示通式I中，
R1选自氢、卤素或C1-C4烷基；
R2选自氢、C1-C4烷基、C3-C6环烷基或卤代C1-C4烷基；
R3选自氢、C1-C4烷基或卤代C1-C4烷基；
R4选自C1-C4烷基或卤代C1-C4烷基；
B选自下述B1-B30中任意一个；
Figure BDA0002734956360000031
本发明含取代苯乙酮结构片段的酰胺类化合物中，再进一步优选的化合物包括：所示通式I中：
R1选自氢、氟、氯、甲基、乙基或异丙基；
R2选自氢、异丙基、正丙基、2-丁基、2-戊基、环丙基、环戊基、环己基、三氟甲基或2,2,2,-三氟乙基；
R3选自氢、甲基、乙基或三氟甲基；
R4选自甲基、乙基或三氟甲基；
B选自B1、B2、B11、B24、B25、B26或B27；
Figure BDA0002734956360000032
本发明含取代苯乙酮结构片段的酰胺类化合物中，更进一步优选的化合物包括：通式I中，
R1选自氢、氯或甲基；
R2选自异丙基、2-丁基、2-戊基、环丙基或环戊基；
R3选自氢或甲基；
R4选自甲基或乙基；
B选自B2、B11、B24、B25或B26；
Figure BDA0002734956360000041
上面给出的通式I化合物的定义中，汇集所用术语一般定义如下：
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：取代或未取代的环状烷基，例如环丙基、环戊基或环己基。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。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：烷基-O-烷基-，例如CH3OCH2-。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ClCH2CH2OCH2-、CF3CH2OCH2-等。烷氧基羰基烷基：烷氧基羰基-烷基-，例如CH3OCOCH2-。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：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。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。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。卤代烯基：直链或支链烯类，在这些烯基上的氢原子可部分或全部被卤原子所取代。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。烯基硫基：直链或支链烯类，经硫原子键连接到结构上。如CH2＝CHCH2S-。烯氧基羰基：如CH2＝CHCH2OCO-等。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。卤代炔基：直链或支链炔类，在这些炔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。环烷基烷基：具有取代或未取代的环状烷基的烷基链，如环丙基甲基、环己基甲基等。卤素取代的异噻唑基：被一至两个卤素取代的异噻唑基，卤素可以相同或不同，如3,4-二氯-异噻唑-5-基、3,5-二溴-异噻唑-4-基。
上文列出的一般或优选的基团定义或说明还可以按照需要彼此组合，即包括各个范围和优选范围之内的组合。定义既适用于终产物，也相应的适用于前体和中间体。此外，某些定义可能不适用。
本发明化合物按照以下方法制备，反应式如下，式中各基团除另有说明外定义同前：
通式化合物I-1的制备可采用如下方法：
Figure BDA0002734956360000051
或参考文献Bioorganic&Medicinal Chemistry Letters,13(3),475-478；2003、WO2014184235等按照如下方法制备：
Figure BDA0002734956360000052
中间体II和III在碱性条件下于适宜的溶剂中反应得到通式I化合物。
适宜的碱可选自如氢氧化钾、氢氧化钠、碳酸钠、碳酸钾、碳酸氢钠、三乙胺、吡啶、甲醇钠、乙醇钠、氢化钠、叔丁醇钾或叔丁醇钠等。
反应在适宜的溶剂中进行，适宜的溶剂可选自如二氯甲烷、三氯甲烷、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、丙酮或丁酮等。
反应温度可在低温至溶剂沸点温度之间，通常为-10℃～100℃。
反应时间为30分钟至20小时，通常1-10小时。
中间体II部分有市售，也可以按公知方法制备，例如参照文献WO2016142918A1、WO2011061205A1、EP 569912、WO2015197530A2、Org.Process Res.Dev.2017，21，3，448-450、描述的方法制备。
中间体Ⅲ是制备本发明通式I化合物的关键中间体，按以下方法制备：
Figure BDA0002734956360000053
中间体M1与溴化铜在适宜的温度下，以乙酸乙酯作溶剂反应30分钟至10小时，通常1-4小时，制得中间体M2，此步骤操作方法参照：中国药物化学杂志,12(6),340-343；2002；M2与叠氮化钠在二甲亚砜中，适宜的温度下反应30分钟至10小时，制得M3，此步骤操作方法参照：张树康.琥珀酸脱氢酶抑制剂类杀菌剂Isofetamid的合成工艺研究[D].武汉:武汉工程大学,2016.和WO2006016708A1；最后经三苯基氧磷或锌粉与氯化铵溶液还原制得Ⅲ，此步骤操作方法参照WO2007069777A2和高等学校化学学报,25(5),866-869；2004。
虽然本发明的通式I化合物与现有技术中公开的某些化合物也属于酰胺类化合物，但结构特征仍存在差异。并且由于这些结构上的差异而使得本发明的化合物具有更好的杀菌活性。
通式I化合物对农业或其他领域中的多种病菌显示出优异的活性。因此，本发明的技术方案还包括通式I化合物在农业或其他领域中用作制备杀菌剂的用途。
下面提及的病害的例子仅用来说明本发明，但绝不限定本发明。
通式I化合物可用于防治下列病害：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)，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)，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)等。
由于其积极的特性，上述化合物可有利地用于保护农业和园艺业重要的作物、家畜和种畜，以及人类常去的环境免于病菌的伤害。
为获得理想效果，化合物的用量因各种因素而改变，例如所用化合物、预保护的作物、有害生物的类型、感染程度、气候条件、施药方法、采用的剂型。
每公顷10克－5公斤的化合物剂量能提供充分的防治。
本发明还包括以通式I所示化合物作为活性组分的杀菌组合物。该杀菌组合物中活性组分的重量百分含量在0.5-99％之间。该杀菌组合物中还包括农业、林业、卫生上可接受的载体。
本发明的技术方案还包括防治病菌的方法：将本发明的杀菌组合物施于所述的病菌或其生长介质上。通常选择的较为适宜有效量为每公顷10克到1000克，优选有效量为每公顷20克到500克。
对于某些应用，例如在农业上可在本发明的杀菌组合物中加入一种或多种其它的杀菌剂、杀虫杀螨剂、除草剂、植物生长调节剂或肥料等，由此可产生附加的优点和效果。
应明确的是，在本发明的权利要求所限定的范围内，可进行各种变换和改动。
具体实施方式
以下具体实施例用来进一步说明本发明，但本发明绝非仅限于这些例子(除另有注明外，所用原料均有市售)。
合成实施例
实施例1：中间体α-氨基-4-异丙氧基-2-甲基苯异丁酮的制备
1)α-溴-4-异丙氧基-2-甲基苯异丁酮的制备
Figure BDA0002734956360000071
取30g(0.136mol)4-异丙氧基-2-甲基苯异丁酮与50g(0.224mol)溴化铜放入盛有250ml乙酸乙酯的三口瓶中，升温至70℃反应5～18小时。HPLC监测反应完毕后，将反应液降温至室温，过滤并用乙酸乙酯洗涤滤饼，碳酸氢钠溶液洗涤，干燥后柱层析得浅黄色油液35g，收率85.9％。
2)α-叠氮-4-异丙氧基-2-甲基苯异丁酮的制备
Figure BDA0002734956360000072
取35g(0.117mol)α-溴-4-异丙氧基-2-甲基苯异丁酮于500ml三口瓶中，100ml二甲亚砜作溶剂，升温至50℃，分批次加入15.21g(0.234mol)叠氮化钠，反应4-6小时。HPLC监测反应完毕后，冷却后将反应液倒入水中，乙酸乙酯萃取三次，盐水洗涤，干燥后柱层析得浅黄色油液25g，收率81.8％。
3)α-氨基-4-异丙氧基-2-甲基苯异丁酮的制备
Figure BDA0002734956360000073
取25g(95.67mmol)α-叠氮-4-异丙氧基-2-甲基苯异丁酮于500ml三口瓶中，用450ml四氢呋喃作溶剂，加入50ml水，0～15℃，加入12.51g(0.191mol)锌粉，滴加加入7g(0.131mol)氯化铵饱和溶液，反应4～16小时。TLC监测反应完毕后。过滤，饱和盐水洗涤两次，干燥后柱层析得浅黄色油液17g，久置可析出白色固体或无色晶体，收率75.51％。
实施例2：化合物I-2的制备
Figure BDA0002734956360000074
将0.235g(1mmol)α-氨基-4-异丙氧基-2-甲基苯异丁酮加入20ml二氯甲烷中，冰浴下滴加加入0.230g(1.2mmol，1.2eqiv)2-二氟甲基烟酰氯。滴加加入0.121g(1.2mmol，1.2eqiv)三乙胺，自然升至室温反应2-6小时，TLC监测反应完毕后，脱溶后残余物柱层析,洗脱剂为乙酸乙酯与石油醚(沸程60-90℃)，体积比为0:100至20:80梯度洗脱得黄色固体0.251g，收率64.3％。
按照上述记载的通式I化合物的制备方法，以及合成实例中给出的具体过程，仅将原料物质进行替换即可获得通式I所示的其他化合物(参见表1)。
表1部分通式I化合物的结构和物理性质
Figure BDA0002734956360000081
Figure BDA0002734956360000091
Figure BDA0002734956360000101
Figure BDA0002734956360000111
Figure BDA0002734956360000121
本发明的其他化合物可以参照以上实施例制备。
部分化合物的物性数据及核磁数据(1HNMR，600MHz，内标TMS，ppm)如下：
化合物I-1：1H NMR(600MHz,CDCl3)δ8.14(s,1H),7.42(d,J＝8.6Hz,1H),6.77(d,J＝2.4Hz,1H),6.67(dd,J＝8.6,2.5Hz,1H),4.59(hept,J＝6.1Hz,1H),2.33(s,3H),1.82(s,6H),1.34(d,J＝6.1Hz,6H).
化合物I-2：1H NMR(600MHz,CDCl3)δ8.70(d,J＝4.0Hz,1H),7.67(d,J＝7.6Hz,1H),7.47(d,J＝8.6Hz,1H),7.40(dd,J＝7.6,4.9Hz,1H),6.97(s,1H),6.79(d,J＝1.7Hz,1H),6.75(t,J＝54.5Hz,1H),6.65(dd,J＝8.6,2.1Hz,1H),4.73–4.47(m,1H),2.38(s,3H),1.78(s,6H),1.34(d,J＝6.0Hz,6H).
化合物I-3：1H NMR(600MHz,CDCl3)δ8.96(d,J＝1.8Hz,1H),8.71(dd,J＝4.8,1.5Hz,1H),8.04(dt,J＝7.9,1.9Hz,1H),7.48(d,J＝8.6Hz,1H),7.38–7.31(m,2H),6.76(d,J＝2.4Hz,1H),6.65(dd,J＝8.6,2.5Hz,1H),4.57(hept,J＝6.1Hz,1H),2.36(s,3H),1.81(s,6H),1.33(d,J＝6.1Hz,6H).
化合物I-5：1H NMR(600MHz,CDCl3)δ8.86(d,J＝2.3Hz,1H),8.79(s,1H),8.68(d,J＝2.2Hz,1H),7.75(t,J＝54.2Hz,1H),7.46(d,J＝8.6Hz,1H),6.75(d,J＝2.3Hz,1H),6.59(dd,J＝8.6,2.5Hz,1H),4.59–4.52(m,1H),2.38(s,3H),1.80(s,6H),1.31(d,J＝6.1Hz,6H).
化合物I-11：1H NMR(600MHz,CDCl3)δ7.43(d,J＝8.6Hz,1H),7.02(s,1H),6.75(d,J＝2.2Hz,1H),6.64(dd,J＝8.6,2.4Hz,1H),4.66–4.48(m,1H),3.81(s,3H),2.33(s,3H),1.76(s,6H),1.33(d,J＝6.1Hz,6H)
化合物I-15：1H NMR(600MHz,CDCl3)δ7.67(s,1H),7.44(d,J＝8.6Hz,1H),6.77(s,1H),6.75(d,J＝2.3Hz,1H),6.64(dd,J＝8.6,2.4Hz,1H),4.57(hept,J＝6.0Hz,1H),3.82(s,3H),2.44(s,3H),2.33(s,3H),1.76(s,6H),1.33(d,J＝6.1Hz,6H).
化合物I-16：1H NMR(600MHz,CDCl3)δ7.44(d,J＝8.6Hz,1H),6.91(s,1H),6.75(d,J＝2.3Hz,1H),6.62(dd,J＝8.6,2.4Hz,1H),6.28(s,1H),4.56(hept,J＝6.0Hz,1H),4.34(q,J＝7.2Hz,2H),2.36(s,3H),2.26(s,3H),1.76(s,6H),1.33(d,J＝6.1Hz,6H),1.28(t,J＝7.2Hz,3H).
化合物I-17：1H NMR(600MHz,CDCl3)δ7.54(d,J＝8.6Hz,1H),7.50(s,1H),6.72(d,J＝2.4Hz,1H),6.59(dd,J＝8.6,2.5Hz,1H),6.43(s,1H),4.55(hept,J＝6.1Hz,1H),3.78(s,3H),2.39(s,3H),2.25(s,3H),1.73(s,6H),1.31(d,J＝6.1Hz,6H).
化合物I-18：1H NMR(600MHz,CDCl3)δ7.55(d,J＝8.6Hz,1H),7.51(s,1H),6.72(d,J＝2.1,1H),6.59(dd,J＝8.6,2.0Hz,1H),6.42(s,1H),4.55(hept,J＝5.9Hz,1H),4.07(q,J＝7.3Hz,2H),2.39(s,3H),2.26(s,3H),1.73(s,6H),1.42(t,J＝7.3Hz,3H),1.31(d,J＝6.0Hz,6H).
化合物I-19：1H NMR(600MHz,CDCl3)δ7.42(d,J＝8.6Hz,1H),7.06(s,1H),6.77(d,J＝2.4Hz,1H),6.67(dd,J＝8.6,2.5Hz,1H),4.58(hept,J＝6.0Hz,1H),2.61(s,3H),2.33(s,3H),1.78(s,6H),1.34(d,J＝6.1Hz,6H).
化合物I-21：1H NMR(600MHz,CDCl3)δ7.54(s,1H),7.50(d,J＝8.6Hz,1H),6.78(t,J＝53.7Hz,1H),6.75(d,J＝2.3Hz,1H),6.65(dd,J＝8.5,2.3Hz,1H),4.57(hept,J＝6.1Hz,1H),4.22(s,3H),3.39(s,3H),2.35(s,4H),1.73(s,6H),1.33(d,J＝6.1Hz,6H).
化合物I-22：1H NMR(600MHz,CDCl3)δ8.19(s,1H),7.47(d,J＝8.6Hz,1H),7.13(t,J＝54.2Hz,1H),6.74(d,J＝2.3Hz,1H),6.61(dd,J＝8.6,2.5Hz,1H),4.56(hept,J＝6.0Hz,1H),4.02(s,3H),2.41(s,3H),2.36(s,3H),1.76(s,6H),1.32(d,J＝6.1Hz,6H).MS:[M+1]+found 440.0,Cal 440.18；[M+Na]+found 461.9,Cal 462.16。
化合物I-24：1H NMR(600MHz,CDCl3)δ7.46(d,J＝8.6Hz,1H),6.99(t,J＝54.0Hz,1H),6.75(d,J＝2.3Hz,1H),6.63(dd,J＝8.6,2.4Hz,1H),4.60–4.53(m,1H),3.89(s,3H),2.35(s,3H),1.76(s,6H),1.33(d,J＝6.1Hz,6H).
化合物I-25：1H NMR(600MHz,CDCl3)δ7.45(d,J＝8.6Hz,1H),7.02(s,1H),6.95(t,J＝53.9Hz,1H),6.74(d,J＝2.2Hz,1H),6.63(dd,J＝8.6,2.4Hz,1H),4.60–4.54(m,1H),3.80(s,3H),2.34(s,3H),1.74(s,6H),1.33(d,J＝6.0Hz,6H).
化合物I-26：1H NMR(600MHz,CDCl3)δ7.77(s,1H),7.55(d,J＝8.6Hz,1H),7.05(s,1H),6.84(t,J＝54.2Hz,1H),6.72(d,J＝2.4Hz,1H),6.59(dd,J＝8.6,2.5Hz,1H),4.55(hept,J＝6.0Hz,1H),3.86(s,3H),2.39(s,3H),1.72(s,6H),1.31(d,J＝6.1Hz,6H).
化合物I-27：1H NMR(600MHz,CDCl3)δ10.72(s,1H),7.70(s,1H),7.25(d,J＝8.8Hz,1H),6.75(d,J＝2.0Hz,1H),6.68(dd,J＝8.6,2.3Hz,1H),6.41(t,J＝54.2Hz,1H),4.62–4.51(m,1H),3.46(s,3H),2.28(s,3H),1.71(s,6H),1.33(d,J＝6.0Hz,6H).
化合物I-162：1H NMR(600MHz,CDCl3)δ7.85(s,1H),7.27(d,J＝8.9Hz,2H),6.99(t,J＝54.2Hz,1H),6.96(d,J＝8.7Hz,2H),4.92(p,J＝6.6Hz,1H),4.61-4.55(m,1H),3.94(s,3H),1.36(dd,J＝6.0,1.1Hz,6H),1.29(d,J＝6.7Hz,6H).
生物活性测定实施例
本发明化合物对农业领域中的多种病菌表现出较好的活性。
实施例3：杀菌活性测定
用本发明化合物样品对植物的多种真菌病害进行了活体保护效果试验。杀菌活性测定结果见以下各实施例。
(1)活体保护活性测定
测定方法如下：采用活体盆栽测定方法，即将待测上述获得通式I化合物样品用少量溶剂(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。
部分化合物的活体保护活性测试结果如下：
对黄瓜霜霉病的活体保护活性：
在400ppm剂量下，化合物I-1、I-5、I-19、I-23、I-25等对黄瓜霜霉病防效在80％以上，而化合物CK1，CK2，CK3，CK4对黄瓜霜霉病防效均为0；
对小麦白粉病的活体保护活性：
在100ppm剂量下，化合物I-2、I-25等对小麦白粉病防效在90％以上，而化合物CK1，CK2，CK3，CK4在400ppm剂量下，对小麦白粉病防效分别为85％、85％、85％、75％；
对玉米锈病的活体保护活性：
在400ppm剂量下，化合物I-25、I-26、I-27等对玉米锈病防效在80％以上，而化合物CK1，CK2，CK3，CK4对玉米锈病防效均为0；
对黄瓜炭疽病的活体保护活性：
在400ppm剂量下，化合物I-1、I-26对黄瓜炭疽病防效分别为60％、40％，而化合物CK1，CK2，CK3，CK4对黄瓜炭疽病防效均为0；
对黄瓜灰霉病的活体保护活性：
在200ppm剂量下，化合物I-11对黄瓜灰霉病防效在80％以上，而化合物CK1，CK2，CK3，CK4对黄瓜灰霉病防效分别为0，0，60％，25％；
对番茄灰霉病的活体保护活性：
在100ppm剂量下，化合物I-5、I-15、I-19、I-24、I-25对番茄瓜灰霉病防效在80％以上，而化合物CK2，CK3，CK4对番茄灰霉病防效分别为20％，35％，0。
按照以上方法，选取部分本发明化合物与已知化合物CK1(自制，专利WO2007069777中编号为I-20)、CK2(自制，专利WO2007069777中编号为I-84)、CK3(自制，专利JP2007210924中编号为I-6)、CK4(自制，专利JP 2007210924中编号为I-183)进行了防治黄瓜霜霉病活性的平行测定。试验结果见表2。
上述获得化合物CK1～CK4的1H NMR(600MHz,CDCl3)数据及物化数据如下：
CK1：1H NMR(600MHz,CDCl3)δ8.73(d,J＝3.9Hz,1H),7.55(d,J＝7.5Hz,1H),7.48(dd,J＝7.4,4.9Hz,1H),7.45(d,J＝8.5Hz,1H),6.84(s,1H),6.79(s,1H),6.68(dd,J＝1.4Hz,J＝8.3Hz,1H),4.64–4.57(m,1H),2.36(s,3H),1.80(s,6H),1.35(d,J＝6.0Hz,6H).白色固体，m.p.88.6℃。
CK2：1H NMR(600MHz,CDCl3)δ8.48–8.31(m,1H),7.79-7.77(m,1H),7.50(d,J＝8.6Hz,1H),7.29–7.25(m,2H),6.77(d,J＝2.3Hz,1H),6.64(dd,J＝8.6,2.4Hz,1H),4.62–4.55(m,1H),2.38(s,3H),1.81(s,6H),1.34(d,J＝6.1Hz,6H).白色固体，m.p.124.3℃。
CK3：1H NMR(600MHz,CDCl3)δ7.81(s,1H),7.48(d,J＝8.6Hz,1H),6.87(s,1H),6.74(d,J＝2.1Hz,1H),6.61(dd,J＝8.6,2.3Hz,1H),4.62–4.50(m,1H),3.92(s,3H),2.36(s,3H),1.73(s,6H),1.32(d,J＝6.0Hz,6H).白色固体，m.p.137.4℃。
CK4：1H NMR(600MHz,CDCl3)δ7.43(d,J＝8.6Hz,1H),7.05(s,1H),6.75(d,J＝2.4Hz,1H),6.64(dd,J＝8.6,2.5Hz,1H),4.57(hept,J＝6.3Hz,1H),3.90(s,3H),2.34(s,3H),1.77(s,6H),1.33(d,J＝6.1Hz,6H).白色固体，m.p.119.0℃。
表2：部分本发明化合物与已知化合物对黄瓜霜霉病防效的比较
Figure BDA0002734956360000141
按照以上方法，选取部分本发明化合物与已知化合物进行了防治小麦白粉病活性的平行测定。试验结果见表3。
表3：部分本发明化合物与已知化合物对小麦白粉病防效的比较
Figure BDA0002734956360000142
Figure BDA0002734956360000151
注：“-”代表未测试。
按照以上方法，选取部分本发明化合物与已知化合物进行了防治玉米锈病活性的平行测定。试验结果见表4。
表4：部分本发明化合物与已知化合物对玉米锈病防效的比较
Figure BDA0002734956360000152
按照以上方法，选取部分本发明化合物与已知化合物进行了防治黄瓜灰霉病活性的平行测定。试验结果见表5。
表5：部分本发明化合物与已知化合物对黄瓜灰霉病防效的比较
Figure BDA0002734956360000153
按照以上方法，选取部分本发明化合物与已知化合物进行了防治番茄灰霉病活性的平行测定。试验结果见表6。
表6：部分本发明化合物与已知化合物对番茄灰霉病防效的比较
Figure BDA0002734956360000154
Figure BDA0002734956360000161
注：“-”代表未测试。

Claims (4)

1.一种含取代苯乙酮结构片段的酰胺类化合物，其特征在于：含取代苯乙酮结构片段的酰胺类化合物为通式I所示化合物；
Figure 360073DEST_PATH_IMAGE001
所述化合物取代基如下表所示：
化合物编号 R<sub>1</sub> R<sub>2</sub> R<sub>3</sub> R<sub>4</sub> B I-11 Me <i>i</i>-Pr Me Me
Figure DEST_PATH_IMAGE002
 I-24 Me <i>i</i>-Pr Me Me
Figure 949318DEST_PATH_IMAGE003
 I-25 Me <i>i</i>-Pr Me Me
Figure DEST_PATH_IMAGE004
 I-26 Me <i>i</i>-Pr Me Me
Figure 666738DEST_PATH_IMAGE005
 I-162 H i-Pr H Me
Figure DEST_PATH_IMAGE006
。
2.一种按照权利要求1所述的通式I化合物在农业或其他领域中用作制备杀菌药物的用途。
3.一种杀菌组合物，含有如权利要求1所述的通式I所示化合物为活性组分和农业、林业或卫生上可接受的载体，组合物中作为活性组分的通式I化合物的重量含量为1-99%。
4.一种控制病害的方法，其特征在于：将权利要求3所述的组合物以每公顷10克到1000克的有效剂量施于需要控制的病害或其生长的介质上。
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