CN110357861A - 一种吡唑喹唑啉二酮类化合物及其应用和一种农药除草剂 - Google Patents

一种吡唑喹唑啉二酮类化合物及其应用和一种农药除草剂 Download PDF

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CN110357861A
CN110357861A CN201910290134.4A CN201910290134A CN110357861A CN 110357861 A CN110357861 A CN 110357861A CN 201910290134 A CN201910290134 A CN 201910290134A CN 110357861 A CN110357861 A CN 110357861A
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杨光富
曲仁渝
严耀超
南甲戌
王现全
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Shandong Cynda Chemical Co Ltd
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Abstract

本发明涉及农药除草剂领域，公开了一种吡唑喹唑啉二酮类化合物及其应用和一种农药除草剂，该化合物具有式(I)所示的结构。本发明提供的吡唑喹唑啉二酮类化合物具有优异的作物安全性和优异的除草效果。

Description

一种吡唑喹唑啉二酮类化合物及其应用和一种农药除草剂
技术领域
本发明涉及农药领域，具体涉及一种吡唑喹唑啉二酮类化合物及其应用、一种农药除草剂。
背景技术
杂草抗药性的爆发性增长已经成为现代农业可持续发展所面临的一个关键挑战，而创制新型超高效除草剂是解决这一挑战的根本途径。
截至目前，我国正式报道的抗性杂草种类超过40种，是世界上抗性杂草危害最为严重的五个国家之一。特别是在我国几类重要的农作物田中，杂草抗药性的问题已经呈现出愈演愈烈的趋势。
例如，水稻田中的稗草、马唐、狗尾草、千金子等杂草对目前市面上的主要稻田除草剂均产生了严重的抗药性；小麦田中的播娘蒿、荠菜、看麦娘、日本看麦娘、雀麦、节节麦、野燕麦等主要杂草的抗性种群也已经发展成为优势杂草，导致部分省市区域的稻田或麦田除草剂用量不断加大，不仅增加了防治成本，而且导致药害事件频发、农药残留超标。
因此，为了实现“减量增效、绿色发展”的发展要求，创制出作用机制新颖的超高效除草剂以替代传统除草剂，是防治抗性杂草、实现减量增效和绿色发展的根本途径。
靶向对羟苯基丙酮酸双加氧酶(HPPD)的除草剂因其高效、低毒、环境友好以及抗性风险低等特点被广泛使用。
截止目前，靶向HPPD所开发成功的除草剂多达数十种，以结构分类大致可以归为三大类：
1、以硝磺草酮(Mesotrione)为代表的三酮类；
2、以苯唑草酮(Topramezone)为代表的吡唑类；
3、以异噁氯草酮(Isoxachlortole)为代表的异噁唑类。
经过农药市场销售额调查，HPPD抑制类除草剂进入市场时间与AHAS-、PPO-以及ACCase-抑制类除草剂相比起步虽晚，但不妨碍其中的“明星分子”对市场的迅速占领，特别是由先正达公司研发的三酮类除草剂-硝磺草酮(又名：甲基磺草酮)，连续多年占领除草剂销售额前五。在抗性杂草多发的玉米田中，硝磺草酮已经逐渐代替了其他类型的除草剂，成为使用最广和最为有效的玉米田除草剂。
然而，硝磺草酮仍然存在着一些自身不足，例如其对其它的一些大宗作物如水稻、小麦等安全性较差，同时硝磺草酮对多种禾本科杂草(如普发性杂草狗尾草和金狗尾草等)防效较差，也有文献报道使用硝磺草酮后杂草易出现返青现象等。
我国农业生产实际中还没有兼备广谱性和超高效除草活性且能够用于水稻田的HPPD除草剂，尤其是还没有对抗性稗草、千金子等多种难防除的恶性杂草具有优异防效的除草剂。
因此，为满足我国农业生产中的现实需求，创制出对水稻安全的新型超高效HPPD除草剂具有十分重要的意义。
另外，WO2017/140612A1公开了一类喹唑啉二酮-6-羰基衍生物作为HPPD抑制剂。然而，该现有技术中记载的化合物对水稻、小麦等作物并没有表现出足够的安全性，使得它们不能直接用于水稻田进行杂草的防治。
发明内容
本发明的目的是为了克服现有技术存在的前述缺陷，提供一类新的、具有高的安全性的能够用于防除作物(特别是水稻田)中的杂草的吡唑喹唑啉二酮类化合物以实现优异的除草效果。
为了实现前述发明目的，本发明的第一方面提供了一种吡唑喹唑啉二酮类化合物，该化合物具有式(I)所示的结构，
其中，在式(I)中，
X选自C1-12的烷基、由1-6个选自卤素的原子取代的C1-12的烷基、由C1-3的烷氧基取代的C2-12的烷基、C2-12的烯基、C2-12的炔基、含有选自O、N、S中的至少一种杂原子的C2-12的环烷基、由含有选自O、N、S中的至少一种杂原子的C2-6的环烷基取代的C3-12的烷基；
Y选自H、C1-6的烷基；
Z为H或式(I-1)所示的基团，其中，在式(I-1)中，R1和R2相同或不同，各自独立地选自C1-6的烷基。
以下对本发明的术语进行解释。
“C1-12的烷基”表示碳原子总数为1-12的烷基，包括直链烷基、支链烷基或者环烷基，例如可以为碳原子总数为1、2、3、4、5、6、7、8、9、10、11或12的直链烷基、支链烷基或者环烷基，例如可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、环丙基、甲基环丙基、乙基环丙基、环丁基、甲基环丁基、乙基环丁基、环戊基、甲基环戊基、乙基环戊基、环己基、甲基环己基、乙基环己基等。
“由1-6个选自卤素的原子取代的C1-12的烷基”表示碳原子总数为1-12的烷基，包括直链烷基、支链烷基和环烷基，并且该C1-12的烷基中的1-6个H由选自卤素的卤原子取代，例如该C1-12的烷基中的1、2、3、4、5或6个H由选自氟、氯、溴、碘中的任意一个或者多个卤原子取代，例如可以为三氟甲基、二氟甲基、一氟甲基、一氟乙基、二氟乙基、三氟乙基、一氟丙基、二氟丙基、三氟丙基等。
“由C1-3的烷氧基取代的C2-12的烷基”表示碳原子总数为2-12的基团，且该基团的结构式可以表示为-R1OR2，其中，R1和R2中的碳原子数之和为2-12，且R1直接与本发明的式(I)所示结构的化合物的母核结构连接。
“C2-12的烯基”表示碳原子总数为2-12的烃基，且该烃基中至少有一个烯键。
“C2-12的炔基”表示碳原子总数为2-12的烃基，且该烃基中至少有一个炔键。
“含有选自O、N、S中的至少一种杂原子的C2-12的环烷基”表示碳原子总数为2-12的环烷基，且形成环的原子中含有选自O、N、S中的至少一种杂原子，并且形成环的各个原子上可以含有烷基取代基，该烷基取代基中含有的碳原子数包括在前述碳原子总数范围内。例如可以为三元环、四元环、五元环、六元环、七元环、八元环、九元环、十元环、十一元环或十二元环，并且，环烷基中的H可以任意地被取代基取代或者未取代，若被取代，其中的取代基各自独立地选自烷基、卤素、羟基、硝基和巯基中的至少一种。
“由含有选自O、N、S中的至少一种杂原子的C2-6的环烷基取代的C3-12的烷基”表示碳原子总数为3-12的基团，且该基团中含有至少一个包括选自O、N、S中的至少一种杂原子的C2-6的环烷基，该环烷基中的碳原子数包括在前述碳原子总数范围内。
根据一种优选的具体实施方式，在式(I)中，
X选自C1-8的烷基、由1-6个选自卤素的原子取代的C1-8的烷基、由C1-3的烷氧基取代的C2-8的烷基、C2-8的烯基、C2-8的炔基、含有至少一个O原子的C2-8的环烷基、由含有至少一个O原子的C2-6的环烷基取代的C3-8的烷基；
Y选自H、C1-4的烷基；
Z为H或式(I-1)所示的基团，其中，在式(I-1)中，R1和R2相同或不同，各自独立地选自C1-4的烷基。
优选情况下，在式(I)中，Z为H。
根据一种特别优选的具体实施方式，在式(I)中，
X选自C1-12的烷基、由1-6个选自卤素的原子取代的C1-12的烷基、由C1-3的烷氧基取代的C2-12的烷基、C2-12的烯基、C2-12的炔基、含有选自O、N、S中的至少一种杂原子的C2-12的环烷基、由含有选自O、N、S中的至少一种杂原子的C2-6的环烷基取代的C3-12的烷基；
Y选自H、C1-6的烷基；
Z为H。
根据另一种特别优选的具体实施方式，在式(I)中，
X选自C1-8的烷基、由1-6个选自卤素的原子取代的C1-8的烷基、由C1-3的烷氧基取代的C2-8的烷基、C2-8的烯基、C2-8的炔基、含有至少一个O原子的C2-8的环烷基、由含有至少一个O原子的C2-6的环烷基取代的C3-8的烷基；
Y选自H、C1-4的烷基；
Z为H。
根据还有一种特别优选的具体实施方式，在式(I)中，
X选自C1-12的烷基、由1-6个选自卤素的原子取代的C1-12的烷基、由C1-3的烷氧基取代的C2-12的烷基、C2-12的烯基、C2-12的炔基、含有选自O、N、S中的至少一种杂原子的C2-12的环烷基、由含有选自O、N、S中的至少一种杂原子的C2-6的环烷基取代的C3-12的烷基；
Y选自H、C1-6的烷基；
Z为式(I-1)所示的基团，且在式(I-1)中，R1和R2相同或不同，各自独立地选自C1-3的烷基。
根据还有一种特别优选的具体实施方式，在式(I)中，
X选自C1-8的烷基、由1-6个选自卤素的原子取代的C1-8的烷基、由C1-3的烷氧基取代的C2-8的烷基、C2-8的烯基、C2-8的炔基、含有至少一个O原子的C2-6的环烷基、由含有至少一个O原子的C2-6的环烷基取代的C3-8的烷基；
Y选自H、C1-4的烷基；
Z为式(I-1)所示的基团，且在式(I-1)中，R1和R2相同或不同，各自独立地选自C1-3的烷基。
特别优选情况下，本发明所述的吡唑喹唑啉二酮类化合物选自权利要求5中所列举的具体化合物中的至少一种。
本发明提供的吡唑喹唑啉二酮类化合物具有优异的作物安全性和优异的除草效果。
特别优选地，本发明提供的引入了烷基取代的氨基甲酸片段的吡唑喹唑啉二酮类化合物不仅对稻田杂草效果有效，而且明显比现有技术的化合物对水稻的安全性更高。
本发明对合成式(I)所示的吡唑喹唑啉二酮类化合物的方法没有特别的限定，本领域技术人员根据本发明提供的化合物结构结合化学领域内的合成方法能够获得合适的制备式(I)所示的吡唑喹唑啉二酮类化合物的方法，本发明在此不再一一赘述。
例如，本发明的式(I)所示的吡唑喹唑啉二酮类化合物可以根据如下合成路线合成：
上述合成路线中的起始原料例如可以利用CN104557739A中所描述的方法制备。
在上述合成路线中，在酯化反应中，产物的合成方法例如可以为：将原料溶于溶剂中，加草酰氯，低温下搅拌反应。待反应完毕，脱干溶剂，剩余固体用溶剂溶解备用。低温下，将吡唑酮溶于溶剂中，并加入三乙胺，搅拌后，将用溶剂溶解的酰氯溶液滴加到反应体系中，TLC监测反应。待反应完毕，向反应体系中加入饱和NaHCO3溶液，萃取合并有机层，干燥浓缩进行柱层析得到产物。
在上述合成路线中，在重排反应中，产物的合成方法例如可以为：将原料、乙腈加入到烧瓶中，搅拌，加入Et3N和丙酮氰醇。TLC监测反应，待反应完成后，向反应体系中加入HCl溶液，继续搅拌，析出固体抽滤。
本发明的第二方面提供第一方面所述的吡唑喹唑啉二酮类化合物在防治杂草中的应用。
优选地，所述杂草选自阔叶杂草、禾本科杂草和莎草科杂草中的至少一种。
进一步优选地，所述杂草包括狗尾草、稗草、千金子、马唐、节节麦、苋菜、灰菜、苘麻、雀麦、野燕麦、看麦娘、日本看麦娘、黑麦草、饭包草、决明草、牵牛花、苍耳、莎草、大巢菜、反枝苋、假酸浆、鳢肠、马齿苋、刺苋、鬼针草、双穗雀稗、稻李氏禾、水竹叶、野慈姑、泽泻、雨久花、鸭跖草、鸭舌草、萤蔺、异型莎草等中的至少一种。
优选地，在本发明中，所述阔叶杂草包括苋菜、灰菜、苘麻、饭包草、决明草、牵牛、苍耳、反枝苋、假酸浆、鳢肠、马齿苋、刺苋、水竹叶、野慈姑、泽泻、雨久花、鸭跖草、鸭舌草和莎草中的至少一种。所述莎草包括萤蔺、异型莎草等。
优选地，在本发明中，所述禾本科杂草包括狗尾草、稗草、千金子、马唐、节节麦、雀麦、野燕麦、看麦娘、日本看麦娘、黑麦草、莎草、大巢菜、鬼针草、双穗雀稗、稻李氏禾中的至少一种。
本发明的第三方面提供第一方面所述的吡唑喹唑啉二酮类化合物作为农药除草剂的应用。
本发明的第四方面提供一种农药除草剂，该农药除草剂由活性成分和辅料组成，所述活性成分包括前述第一方面中所述的吡唑喹唑啉二酮类化合物中的至少一种。
优选地，在所述农药除草剂中，所述活性成分的含量为1～99.9999重量％。
根据一种优选的具体实施方式，所述活性成分中进一步包括安全剂。所述安全剂可以为本领域内常规使用的各种类型的安全剂。
例如，所述安全剂可以为吡唑解草酯、解毒喹、双苯噁唑酸、环丙磺酰胺、萘二甲酸酐、氯草烯安、R-28725、苯叉酰胺、解草酮、解草胺腈、解草唑、解草啶、BAS-145138、呋喃解草唑、喹啉衍生物、2,4-D、新型解毒剂T和赤霉素中的至少一种。
优选情况下，所述农药除草剂的剂型选自乳油、悬浮剂、可湿性粉剂、粉剂、粒剂、水剂、毒饵、母液和母粉中的至少一种。
所述悬浮剂例如可以包括干悬浮剂、可分散油悬浮剂和水乳剂。
本发明的所述农药除草剂中的辅料包括但不限于表面活性剂、保护胶体、粘合剂、增稠剂、触变剂、渗透剂、螯合剂、染料、着色剂和聚合物等，例如还可以为充当载体的其它常规助剂。
本文中的载体表示一种或多种有机物、无机物、天然产物或合成的物质。它们有助于活性成分的施用，该载体一般是惰性的且必须是农业上可以接受的，特别是可以被处理植物所接受的。载体可以是固体的，如：陶土、天然或合成的硅酸盐、二氧化硅、树脂、蜡、固体肥料等；或者是液体的，如：水，醇类、酮类、石油馏分、芳烃或蜡烃、氯代烃、液化气等。
本发明所述表面活性剂的成分包括乳化剂，分散剂或润湿剂，它们可以是离子型的或非离子型的。可提及的实例是：聚丙烯酸盐、木质素磺酸盐、苯酚磺酸或萘磺酸盐、环氧乙烷与脂肪族醇或与脂肪族酸或与脂肪族胺与取代的苯酚(特别是烷基苯酚或芳基苯酚)的聚合物、磺酸琥珀酸盐、牛磺酸衍生物及醇的磷酸酯或多羟基乙基化的苯酚磷酸酯、烷基磺酸酯盐、烷基芳基磺酸盐、烷基硫酸盐、月桂基醚硫酸盐、脂肪醇硫酸盐、以及硫酸化十六-十七-十八烷醇以及硫酸化脂肪醇乙二醇醚，此外还有萘或萘磺酸与苯酚和甲醛的缩合物、聚氧乙烯辛基苯甲醚、乙氧基化异辛基醚、辛基酚或壬基酚、烷基苯基聚乙二醇醚、三丁基苯基聚乙二醇醚、三硬酯基苯基聚乙二醇醚、烷基芳基聚醚醇、醇和脂肪醇/氧化乙烯缩合物、乙氧基化蓖麻油、聚氧乙烯烷基醚、乙氧基化聚氧丙烯、月桂醇聚乙二醇醚缩醛、山梨醇酯、木素亚硫酸盐废液、以及蛋白质、变性蛋白、多糖、疏水改性淀粉、聚乙烯醇、聚羧酸盐、聚氧烷基化物、聚乙烯胺、聚乙烯吡咯烷酮以及共聚物。
本发明对制备所述农药除草剂的方法没有特别的限制，本领域技术人员可以采用农药领域内常规的制备方法进行制备以形成相应的试剂。
本发明所述的农药除草剂包括但不限于通过例如喷雾的方法用于农作物。
本发明提供的吡唑喹唑啉二酮类化合物及含有该吡唑喹唑啉二酮类化合物的农药除草剂具有HPPD类除草剂的全部优点，并且具有环境友好，后茬作物安全、用量低、时效性好、杀草谱广、安全性高等优点。
特别地，本发明提供的吡唑喹唑啉二酮类化合物对玉米、小麦和水稻表现出了优良的作物安全性。
本发明提供的吡唑喹唑啉二酮类化合物对阔叶杂草、禾本科杂草和莎草科杂草均具有很高的除草活性，尤其是对水稻田内杂草的防效显著，例如对水稻田中的禾本科杂草(稗草、千金子、双穗雀稗、狗尾草、马唐、稻李氏禾等)；阔叶杂草(水竹叶、野慈姑、泽泻、雨久花、鸭跖草、鸭舌草等)；莎草(萤蔺、异型莎草等)。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
以下提供本发明的部分具体化合物的制备方法，本领域技术人员不应理解为对本发明的限制。在没有特别说明的情况下，使用的各种原料均来自商购。
化合物1的合成：
将1g的中间体a加入到50mL单颈瓶中，加入18mL干燥的THF，室温下缓慢滴加1.8g的SOCl2，滴加完毕后75℃回流反应约1.5h，TLC跟踪反应进程，反应结束后脱干溶剂。加入20mL干燥的CHCl3，0.7g的2,5-二甲基-2,4-二氢-3H-吡唑-3-酮，0.61g的Et3N，反应约0.5h，TLC跟踪至酰氯消失。反应完毕后用20mL水洗一次，每次用10mL的1摩尔/升的HCl洗2次，每次用10mL的饱和NaHCO3洗2次，无水Na2SO4干燥，过柱得中间体b。
将0.7g式化合物b加入到50mL两颈瓶中，加入28mL无水乙腈，N2保护下加入0.38g的Et3N，0.018g(10％当量)的丙酮氰醇。室温下反应8h，TLC跟踪至反应原料消失。反应完毕后脱干乙腈，加入约30mL的CHCl3。每次用10mL的1摩尔/升的盐酸洗三次，饱和氯化钠每次10mL洗3次，有机层用无水硫酸钠干燥。减压脱去溶剂得浅黄色油状物，所得油状物用10mL甲醇重结晶，得到化合物1。
化合物2的合成：
将10mmol的中间体a加入到50mL单颈瓶中，加入18mL干燥的THF，室温下缓慢滴加15mmol的SOCl2，滴加完毕后75℃回流反应约1.5h，TLC跟踪反应进程，反应结束后脱干溶剂。加入20mL干燥的CHCl3，15mmol的5-环丙基-2-甲基-2,4-二氢-3H-吡唑-3-酮，15mmol的Et3N，反应约0.5h，TLC跟踪至酰氯消失。反应完毕后用20mL水洗一次，每次用10mL的1摩尔/升的HCl洗2次，每次用10mL的饱和NaHCO3洗2次，无水Na2SO4干燥，过柱，得中间体c。
将5mmol中间体c加入到50mL两颈瓶中，加入28mL无水乙腈，N2保护下加入10mmol的Et3N，0.05mmol(10％当量)的丙酮氰醇。室温下反应8h，TLC跟踪至反应原料消失。反应完毕后脱干乙腈，加入约30mL的CHCl3。每次用10mL的1摩尔/升的盐酸洗三次，饱和氯化钠每次10mL洗3次，有机层用无水硫酸钠干燥。减压脱去溶剂得浅黄色油状物，所得油状物用10mL甲醇重结晶，得到化合物2。
化合物5合成：
在冰浴下，将1mmol化合物1溶于干燥的二氯甲烷中，加入Et3N(1.5mmol)，并缓慢向反应体系中加入N,N-二甲基氨基甲酰氯(1.5mmol)溶液，室温反应。当反应完成后，向反应体系中加入饱和碳酸氢钠溶液(15ml)，二氯甲烷萃取(10mL×3)，合并有机相，减压蒸馏，拌样柱层析分离提纯得到化合物5。
采用前述相似的方法合成本发明的其他化合物，部分化合物的表征数据如下：
化合物1收率:62％.1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.18(d,J＝8.8Hz,1H),3.65(s,3H),3.64(s,3H),3.47(s,3H),2.78(s,3H),1.71(s,3H).
化合物2收率:73％.1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.8Hz,1H),7.14(d,J＝8.8Hz,1H),3.69(s,3H),3.58(s,3H),3.47(s,3H),2.78(s,3H),0.98–0.90(m,1H),0.83–0.75(m,2H),0.55–0.45(m,2H).
化合物3收率:66％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,1H),7.21(s,1H),7.17(d,J＝8.8Hz,1H),3.65(s,3H),3.64(s,3H),3.47(s,3H),2.78(s,3H).
化合物4收率:89％.,1H NMR(400MHz,CDCl3)δ7.49(d,J＝7.6Hz,1H),7.10(d,J＝7.6Hz,1H),3.62(s,3H),3.60(s,3H),3.46(s,3H),3.23(s,6H),2.74(s,3H),2.16(s,3H).
化合物5收率:78％.1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.07(d,J＝8.8Hz,1H),3.61(s,3H),3.60(s,3H),3.46(s,3H),3.19(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.76(s,3H),2.18(s,3H),1.08(t,J＝7.2Hz,3H),1.05–1.01(t,J＝7.2Hz,3H).
化合物6收率:70％.1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.8Hz,1H),7.10(d,J＝8.8Hz,1H),3.61(s,3H),3.59(s,3H),3.46(s,3H),3.19(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.76(s,3H),1.08(t,J＝7.2Hz,3H),1.05–1.01(t,J＝7.2Hz,3H),0.98–0.90(m,1H),0.83–0.75(m,2H),0.55–0.45(m,2H).
化合物7收率:65％.,1H NMR(400MHz,CDCl3)δ7.55(d,J＝7.6Hz,1H),7.08(d,J＝7.6Hz,1H),3.62(s,3H),3.60(s,3H),3.45(s,3H),3.23(s,3H),3.07(q,J＝8.4Hz,2H),2.76(s,3H),2.18(s,3H),1.17(t,J＝7.2Hz,3H).
化合物8收率:70％.,1H NMR(400MHz,CDCl3)δ7.53(d,J＝7.6Hz,1H),7.07(d,J＝7.6Hz,1H),3.61(s,3H),3.59(s,3H),3.46(s,3H),3.29–3.21(m,5H),2.76(s,3H),2.18(s,3H),1.75–1.61(m,2H),0.87(t,J＝7.6Hz,3H).
化合物9收率:69％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,1H),7.16(d,J＝8.8Hz,1H),4.12(q,J＝6.8Hz,2H),3.63(s,3H),3.62(s,3H),2.77(s,3H),1.70(s,3H),1.28(t,J＝7.2Hz,3H).
化合物10收率:63％.1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),4.12(q,J＝6.8Hz,2H),3.61(s,3H),3.59(s,3H),2.82(s,3H),1.28(t,J＝6.8Hz,3H),0.98–0.90(m,1H),0.83–0.75(m,2H),0.55–0.45(m,2H).
化合物11收率:66％.1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.8Hz,1H),7.20(s,1H),7.16(d,J＝8.8Hz,1H),4.12(q,J＝6.8Hz,2H),3.63(s,3H),3.60(s,3H),2.78(s,3H),1.27(t,J＝7.2Hz,3H).
化合物12收率:65％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.08(d,J＝8.8Hz,1H),4.12(q,J＝7.2Hz,2H),3.62(s,3H),3.60(s,3H),3.23(s,6H),2.34(s,3H),1.98(s,3H),1.18(t,J＝7.6Hz,3H).
化合物13收率:68％.1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.8Hz,1H),7.08(d,J＝8.8Hz,1H),4.12(q,J＝7.2Hz,2H),3.61(s,3H),3.59(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),2.21(s,3H),1.27(t,J＝7.2Hz,3H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H).
化合物14收率:74％.1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.8Hz,1H),7.09(d,J＝8.8Hz,1H),4.11(q,J＝7.2Hz,2H),3.61(s,3H),3.59(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.82(s,3H),1.27(t,J＝7.2Hz,3H),1.08(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H),0.98–0.90(m,1H),0.83–0.75(m,2H),0.55–0.45(m,2H).
化合物15收率:73％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.10(d,J＝8.8Hz,1H),4.12(q,J＝7.2Hz,2H),3.61(s,3H),3.58(s,3H),3.23(s,3H),3.15(q,J＝12.8Hz,2H),2.75(s,3H),2.21(s,3H),1.14–0.97(m,6H).
化合物16收率:78％.,1H NMR(400MHz,CDCl3)δ7.51(d,J＝8.8Hz,1H),7.08(d,J＝8.8Hz,1H),4.10(q,J＝6.8Hz,2H),3.62(s,3H),3.56(s,3H),3.24(s,3H),3.20–2.88(m,2H),2.74(s,3H),2.22(s,3H),1.75–1.61(m,2H),1.18(t,J＝7.6Hz,3H),1.01(t,J＝7.2Hz,3H).
化合物17收率:72％.1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.8Hz,1H),7.16(d,J＝8.8Hz,1H),4.05–3.99(m,2H),3.64(s,3H),3.62(s,3H),2.77(s,3H),1.75–1.69(m,5H),0.99(t,J＝7.4Hz,3H).
化合物18收率:64％.1H NMR(400MHz,CDCl3)δ7.58(d,J＝8.8Hz,1H),7.17(d,J＝8.8Hz,1H),4.05–3.99(m,2H),3.64(s,3H),3.62(s,3H),2.84(s,3H),1.77–1.66(m,2H),1.05–0.94(m,4H),0.88–0.80(m,2H),0.58–0.50(m,2H).
化合物19收率:77％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,1H),7.20(s,1H),7.17(d,J＝8.8Hz,1H),4.05–3.99(m,2H),3.64(s,3H),3.62(s,3H),2.80(s,3H),1.77–1.66(m,2H),1.00(t,J＝7.2Hz,3H).
化合物20收率:69％.,1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.8Hz,1H),7.09(d,J＝8.8Hz,1H),4.05–3.97(m,2H),3.62(s,3H),3.59(s,3H),3.23(s,6H),2.74(s,3H),2.21(s,3H),1.75–1.66(m,2H),0.99(t,J＝7.2Hz,3H).
化合物21收率:79％.1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.8Hz,1H),7.08(d,J＝8.8Hz,1H),4.05–3.97(m,2H),3.61(s,3H),3.59(s,3H),3.18(q,J＝7.1Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),2.22(s,3H),1.75–1.64(m,2H),1.08(t,J＝7.2Hz,3H),1.03–0.95(m,6H).
化合物22收率:83％.1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.8Hz,1H),7.06(d,J＝8.8Hz,1H),4.05–3.97(m,2H),3.61(s,3H),3.59(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),1.75–1.64(m,2H),1.08(t,J＝7.2Hz,3H),1.03–0.90(m,7H),0.83–0.75(m,2H),0.55–0.45(m,2H).
化合物23收率:73％.,1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.8Hz,1H),7.08(d,J＝8.8Hz,1H),4.05–3.98(m,2H),3.61(s,3H),3.58(s,3H),3.23(s,3H),3.07(q,J＝7.6Hz,2H),2.74(s,3H),2.21(s,3H),1.75–1.64(m,2H),1.16(t,J＝7.2Hz,3H),0.99(t,J＝7.2Hz,3H).
化合物24收率:76％.,1H NMR(400MHz,CDCl3)δ7.46(d,J＝9.2Hz,1H),7.09(d,J＝9.2Hz,1H),4.05–3.97(m,2H),3.62(s,3H),3.59(s,3H),3.26–3.19(m,4H),3.04(t,J＝7.6Hz,1H),2.75(s,3H),2.20(s,3H),1.74–1.62(m,4H),0.91–0.80(m,6H).
化合物25收率:69％.1H NMR(400MHz,CDCl3)δ7.43(d,J＝8.8Hz,1H),7.13(d,J＝8.8Hz,1H),5.35–5.24(m,1H),3.64(s,3H),3.58(s,3H),2.75(s,3H),1.71(s,3H),1.52(d,J＝6.8Hz,6H).
化合物26收率:89％.1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.8Hz,1H),7.11(d,J＝8.8Hz,1H),5.33–5.23(m,1H),3.60(s,3H),3.57(s,3H),2.79(s,3H),1.52(d,J＝6.8Hz,6H),1.00–0.92(m,1H),0.83–0.76(m,2H),0.56–0.47(m,2H).
化合物27收率:79％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,1H),7.21(s,1H),7.12(d,J＝8.8Hz,1H),5.33–5.23(m,1H),3.60(s,3H),3.57(s,3H),2.79(s,3H),1.52(d,J＝6.8Hz,6H).
化合物28收率:79％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝9.6Hz,1H),7.03(d,J＝9.6Hz,1H),5.35–5.22(m,1H),3.61(s,3H),3.54(s,3H),3.23(s,6H),2.72(s,3H),2.22(s,3H),1.52(d,J＝12.0Hz,6H).
化合物29收率:87％.1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.04(d,J＝8.8Hz,1H),5.35–5.22(m,1H),3.61(s,3H),3.55(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.73(s,3H),2.23(s,3H),1.51(d,J＝6.8Hz,6H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H).
化合物30收率:73％.1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.8Hz,1H),7.03(d,J＝8.8Hz,1H),5.33–5.22(m,1H),3.61(s,3H),3.57(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.72(s,3H),1.51(d,J＝6.8Hz,6H),1.08(t,J＝7.2Hz,3H),1.03–0.92(m,4H),0.83–0.76(m,2H),0.56–0.47(m,2H).
化合物31收率:80％.,1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.4Hz,1H),7.04(d,J＝8.4Hz,1H),5.35–5.22(m,1H),3.62(s,3H),3.57(s,3H),3.23(s,3H),3.07(q,J＝7.6Hz,2H),2.73(s,3H),2.21(s,3H),1.51(d,J＝6.8Hz,6H),1.17(t,J＝7.2Hz,3H).
化合物32收率:77％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝9.2Hz,1H),7.03(d,J＝9.2Hz,1H),5.35–5.22(m,1H),3.63(s,3H),3.57(s,3H),3.27–3.19(m,4H),3.01(t,J＝9.6Hz,1H),2.75(s,3H),2.23(s,3H),1.74–1.62(m,2H),1.51(d,J＝7.2Hz,6H),0.90(t,J＝7.2Hz,3H).
化合物33收率:65％.1H NMR(400MHz,CDCl3)δ7.44(d,J＝8.8Hz,1H),7.13(d,J＝8.8Hz,1H),5.11–5.00(m,1H),3.64(s,3H),3.59(s,3H),2.75(s,3H),2.17–2.03(m,1H),1.97–1.84(m,1H),1.72(s,3H),1.50(d,J＝6.8Hz,3H),0.88(t,J＝7.6Hz,3H).
化合物34收率:77％.1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.4Hz,1H),7.12(d,J＝8.4Hz,1H),5.11–5.00(m,1H),3.60(s,3H),3.58(s,3H),2.80(s,3H),2.16–2.04(m,1H),1.97–1.84(m,1H),1.50(d,J＝6.8Hz,3H),1.01–0.94(m,1H),0.88(t,J＝7.2Hz,3H),0.83–0.77(m,2H),0.58–0.48(m,2H).
化合物35收率:72％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.4Hz,1H),7.19(s,1H),7.12(d,J＝8.4Hz,1H),5.11–5.00(m,1H),3.61(s,3H),3.58(s,3H),2.80(s,3H),2.16–2.04(m,1H),1.97–1.84(m,1H),1.51(d,J＝6.8Hz,3H),0.89(t,J＝7.2Hz,3H).
化合物36收率:80％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.03(d,J＝8.8Hz,1H),5.10–5.00(m,1H),3.60(s,3H),3.56(s,3H),3.23(s,6H),2.72(s,3H),2.23(s,3H),2.17–1.81(m,2H),1.47(d,J＝6.8Hz,3H),0.87(t,J＝7.2Hz,3H).
化合物37收率:74％.1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.4Hz,1H),7.04(d,J＝8.4Hz,1H),5.10–4.99(m,1H),3.60(s,3H),3.55(s,3H),3.16(q,J＝7.2Hz,2H),3.01(q,J＝7.2Hz,2H),2.72(s,3H),2.25(s,3H),2.17–2.03(m,1H),1.94–1.81(m,1H),1.48(d,J＝7.2Hz,3H),1.05(t,J＝7.2Hz,3H),1.00(t,J＝7.2Hz,3H),0.86(t,J＝7.2Hz,3H).
化合物38收率:79％.1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.4Hz,1H),7.07(d,J＝8.4Hz,1H),5.10–4.98(m,1H),3.60(s,3H),3.55(s,3H),3.16(q,J＝7.2Hz,2H),3.01(q,J＝7.2Hz,2H),2.70(s,3H),2.16–1.81(m,2H),1.48(d,J＝7.2Hz,3H),1.05(t,J＝7.2Hz,3H),1.01–0.94(m,4H),0.86(t,J＝7.2Hz,3H),0.83–0.77(m,2H),0.58–0.48(m,2H).
化合物39收率:70％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.03(d,J＝8.8Hz,1H),5.10–5.00(m,1H),3.61(s,3H),3.55(s,3H),3.23(s,3H),3.07(q,J＝7.2Hz,2H),2.74(s,3H),2.25(s,3H),2.17–2.03(m,1H),1.94–1.81(m,1H),1.48(d,J＝7.2Hz,3H),1.17(t,J＝6.8Hz,3H),0.86(t,J＝7.2Hz,3H).
化合物40收率:85％.,1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.4Hz,1H),7.04(d,J＝8.4Hz,1H),5.10–4.99(m,1H),3.61(s,3H),3.54(s,3H),3.29–3.17(m,4H),3.04(t,J＝7.2Hz,1H),2.74(s,3H),2.23(s,3H),2.17–1.61(m,4H),1.48(d,J＝7.2Hz,3H),0.87(t,J＝7.2Hz,6H).
化合物41收率:86％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,1H),7.16(d,J＝8.8Hz,1H),4.05(t,J＝7.2Hz 2H),3.64(s,3H),3.62(s,3H),2.77(s,3H),1.71(s,3H),1.69–1.62(m,2H),1.46–1.36(m,2H),0.96(t,J＝7.2Hz,3H).
化合物42收率:87％.1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),4.08–4.02(m,2H),3.61(s,3H),3.59(s,3H),2.82(s,3H),1.71–1.61(m,2H),1.46–1.35(m,2H),0.96(t,J＝5.6Hz,3H),0.94–0.91(m,1H),0.83–0.76(m,2H),0.55–0.46(m,2H).
化合物43收率:72％.1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.8Hz,1H),7.19(s,1H),7.15(d,J＝8.8Hz,1H),4.08–4.03(m,2H),3.61(s,3H),3.59(s,3H),2.82(s,3H),1.71–1.61(m,2H),1.46–1.36(m,2H),0.96(t,J＝5.7Hz,3H).
化合物44收率:71％.,1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.8Hz,1H),7.07(d,J＝8.8Hz,1H),4.05(t,J＝7.2Hz,2H),3.61(s,3H),3.59(s,3H),3.23(s,6H),2.74(s,3H),2.21(s,3H),1.69–1.60(m,2H),1.46–1.35(m,2H),0.96(t,J＝7.2Hz,3H).
化合物45收率:77％.1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.4Hz,1H),7.08(d,J＝8.4Hz,1H),4.05(t,J＝7.2Hz,2H),3.62(s,3H),3.59(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),2.22(s,3H),1.69–1.60(m,2H),1.46–1.35(m,2H),1.08(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H),0.96(t,J＝7.2Hz,3H).
化合物46收率:75％.1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.4Hz,1H),7.08(d,J＝8.4Hz,1H),4.05(t,J＝7.2Hz,2H),3.60(s,3H),3.57(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),1.69–1.60(m,2H),1.46–1.35(m,2H),1.08(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H),0.99–0.91(m,4H),0.83–0.76(m,2H),0.55–0.46(m,2H).
化合物47收率:65％.,1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.8Hz,1H),7.07(d,J＝8.8Hz,1H),4.08–4.02(m,2H),3.62(s,3H),3.59(s,3H),3.23(s,3H),3.07(q,J＝7.2Hz,2H),2.75(s,3H),2.21(s,3H),1.68–1.59(m,2H),1.46–1.35(m,2H),1.17(t,J＝7.2Hz,3H),0.96(t,J＝12.8Hz,3H).
化合物48收率:83％.,1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.8Hz,1H),7.08(d,J＝8.8Hz,1H),4.05(t,J＝7.2Hz,2H),3.62(s,3H),3.59(s,3H),3.26–3.01(m,5H),2.74(s,3H),2.22(s,3H),1.68–1.53(m,4H),1.46–1.35(m,2H),0.96(t,J＝6.8Hz,3H),0.88(t,J＝7.2Hz,3H).
化合物49收率:86％.1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.8Hz,1H),7.18(d,J＝8.8Hz,1H),4.77(t,J＝5.2Hz,1H),4.66(t,J＝5.2Hz,1H),4.49(t,J＝5.2Hz,1H),4.43(t,J＝5.2Hz,1H),3.64(s,3H),3.63(s,3H),2.77(s,3H),1.71(s,3H).
化合物50收率:74％.1H NMR(400MHz,CDCl3)δ7.58(d,J＝8.8Hz,1H),7.17(d,J＝8.8Hz,1H),4.77(t,J＝5.2Hz,1H),4.66(t,J＝5.2Hz,1H),4.49(t,J＝5.2Hz,1H),4.43(t,J＝5.2Hz,1H),3.63(s,3H),3.60(s,3H),2.82(s,3H),0.99–0.90(m,1H),0.85–0.74(m,2H),0.56–0.47(m,2H).
化合物51收率:67％.1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.8Hz,1H),7.20(s,1H),7.16(d,J＝8.8Hz,1H),4.77(t,J＝5.2Hz,1H),4.66(t,J＝5.2Hz,1H),4.49(t,J＝5.2Hz,1H),4.43(t,J＝5.2Hz,1H),3.63(s,3H),3.60(s,3H),2.80(s,3H).
化合物52收率:83％.,1H NMR(400MHz,CDCl3)δ7.51(d,J＝8.8Hz,1H),7.11(d,J＝8.8Hz,1H),4.80–4.62(m,2H),4.52–4.41(m,2H),3.61(s,3H),3.59(s,3H),3.23(s,6H),2.74(s,3H),2.21(s,3H).
化合物53收率:78％.1H NMR(400MHz,CDCl3)δ7.52(d,J＝8.8Hz,1H),7.11(d,J＝8.8Hz,1H),4.76(t,J＝5.2Hz,1H),4.64(t,J＝5.2Hz,1H),4.49(t,J＝5.2Hz,1H),4.43(t,J＝5.2Hz,1H),3.61(s,3H),3.60(s,3H),3.17(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),2.23(s,3H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H).
化合物54收率:76％.1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.8Hz,1H),7.13(d,J＝8.8Hz,1H),4.76(t,J＝5.2Hz,1H),4.64(t,J＝5.2Hz,1H),4.49(t,J＝5.2Hz,1H),4.43(t,J＝5.2Hz,1H),3.61(s,3H),3.60(s,3H),3.17(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H),0.99–0.90(m,1H),0.85–0.74(m,2H),0.56–0.47(m,2H).
化合物55收率:71％.,1H NMR(400MHz,CDCl3)δ7.52(d,J＝9.2Hz,1H),7.11(d,J＝9.2Hz,1H),4.80–4.62(m,2H),4.52–4.40(m,2H),3.62(s,3H),3.60(s,3H),3.22(s,3H),3.06(q,J＝7.2Hz,2H),2.75(s,3H),2.23(s,3H),1.17(t,J＝7.2Hz,3H).
化合物56收率:82％.,1H NMR(400MHz,CDCl3)δ7.52(d,J＝8.8Hz,1H),7.11(d,J＝8.8Hz,1H),5.36–5.18(m,1H),5.12–4.84(m,2H),4.03–3.86(m,4H),3.60(s,3H),3.28–3.19(m,4H),3.04(t,J＝7.2Hz,1H),2.75(s,3H),2.23(s,3H),1.67–1.48(m,2H),0.87(t,J＝7.2Hz,3H).
化合物57收率:79％.1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.20(d,J＝8.8Hz,1H),6.13(td,J＝56.7,28.4Hz,1H),4.49(td,J＝13.2,4.6Hz,2H),3.61(s,3H),3.60(s,3H),2.76(s,3H),1.70(s,3H).
化合物58收率:57％.1H NMR(400MHz,CDCl3)δ7.61(d,J＝8.8Hz,1H),7.18(d,J＝8.8Hz,1H),6.32–6.00(m,1H),4.56–4.42(m,2H),3.63(s,3H),3.60(s,3H),2.81(s,3H),0.97–0.89(m,1H),0.84–0.78(m,2H),0.55–0.48(m,2H).
化合物59收率:75％.1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.8Hz,1H),7.20(s,1H),7.16(d,J＝8.8Hz,1H),6.32–6.00(m,1H),4.56–4.42(m,2H),3.63(s,3H),3.60(s,3H),2.81(s,3H).
化合物60收率:82％.,1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.8Hz,1H),7.12(d,J＝8.8Hz,1H),6.32–6.00(m,1H),4.56–4.42(m,2H),3.61(s,3H),3.59(s,3H),3.23(s,6H),2.74(s,3H),2.22(s,3H).
化合物61收率:69％.1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.8Hz,1H),7.12(d,J＝8.8Hz,1H),6.15(tt,J＝56.8,4.8Hz,1H),4.50(td,J＝13.2,4.8Hz,2H),3.62(s,3H),3.61(s,3H),3.18(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.74(s,3H),2.22(s,3H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H).
化合物62收率:86％.1H NMR(400MHz,CDCl3)δ7.58(d,J＝8.8Hz,1H),7.17(d,J＝8.8Hz,1H),6.32–6.00(m,1H),4.56–4.42(m,2H),3.62(s,3H),3.60(s,3H),3.18(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.75(s,3H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H),0.97–0.89(m,1H),0.84–0.78(m,2H),0.55–0.48(m,2H).
化合物63收率:68％.,1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.8Hz,1H),7.11(d,J＝8.8Hz,1H),6.15(tt,J＝56.8,4.8Hz,1H),4.50(td,J＝13.2,4.8Hz,2H),3.62(s,3H),3.61(s,3H),3.23(s,3H),3.07(q,J＝7.2Hz,2H),2.74(s,3H),2.23(s,3H),1.17(t,J＝7.2Hz,3H).
化合物64收率:81％.,1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.8Hz,1H),7.12(d,J＝8.8Hz,1H),6.32–5.99(m,1H),4.56–4.42(m,2H),3.62(s,3H),3.60(s,3H),3.31–3.14(m,4H),3.04(t,J＝7.2Hz,1H),2.75(s,3H),2.22(s,3H),1.67–1.44(m,2H),0.88(t,J＝7.2Hz,3H).
化合物65收率:76％.1H NMR(400MHz,CDCl3)δ7.51(d,J＝8.8Hz,1H),7.21(d,J＝8.8Hz,1H),4.82(q,J＝8.4Hz,2H),3.65(s,3H),3.64(s,3H),2.76(s,3H),1.71(s,3H).
化合物66收率:78％.1H NMR(400MHz,CDCl3)δ7.62(d,J＝8.8Hz,1H),7.19(d,J＝8.8Hz,1H),4.82(q,J＝8.4Hz,2H),3.64(s,3H),3.60(s,3H),2.81(s,3H),0.97–0.89(m,1H),0.83–0.77(m,2H),0.55–0.49(m,2H).
化合物67收率:82％.1H NMR(400MHz,CDCl3)δ7.51(d,J＝8.8Hz,1H),7.21(s,1H)7.22(d,J＝8.8Hz,1H),4.82(q,J＝8.4Hz,2H),3.64(s,3H),3.60(s,3H),2.82(s,3H).
化合物68收率:84％.,1H NMR(400MHz,CDCl3)δ7.55(d,J＝9.2Hz,1H),7.12(d,J＝9.2Hz,1H),4.82(q,J＝8.4Hz,2H),3.62(s,3H),3.60(s,3H),3.23(s,6H),2.74(s,3H),2.24(s,3H).
化合物69收率:80％.1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.8Hz,1H),7.13(d,J＝8.8Hz,1H),4.83(q,J＝8.4Hz,2H),3.62(s,3H),3.61(s,3H),3.16(q,J＝7.2Hz,2H),3.00(q,J＝7.2Hz,2H),2.75(s,3H),2.27(s,3H),1.06(t,J＝7.2Hz,3H),0.99(t,J＝7.2Hz,3H).
化合物70收率:84％.1H NMR(400MHz,CDCl3)δ7.58(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),4.85(q,J＝8.4Hz,2H),3.64(s,3H),3.60(s,3H),3.16(q,J＝7.2Hz,2H),3.01(q,J＝7.2Hz,2H),2.76(s,3H),1.06(t,J＝7.2Hz,3H),1.02–0.89(m,4H),0.83–0.77(m,2H),0.55–0.49(m,2H).
化合物71收率:81％.,1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.4Hz,1H),7.14(d,J＝8.4Hz,1H),4.83(q,J＝8.4Hz,2H),3.62(s,3H),3.61(s,3H),3.23(s,3H),3.07(q,J＝7.6Hz,2H),2.75(s,3H),2.26(s,3H),1.17(t,J＝7.2Hz,3H).
化合物72收率:73％.,1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.8Hz,1H),7.13(d,J＝8.8Hz,1H),4.84(q,J＝8.4Hz,2H),3.63(s,3H),3.61(s,3H),3.30(t,J＝8.4Hz,1H),3.23(s,3H),3.08(t,J＝8.4Hz,1H),2.74(s,3H),2.27(s,3H),1.68–1.47(m,2H),0.87(t,J＝7.2Hz,3H).
化合物73收率:76％.1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.17(d,J＝8.8Hz,1H),4.62(t,J＝6.0Hz,1H),4.51(t,J＝6.0Hz,1H),4.23(t,J＝7.2Hz,2H),3.63(s,3H),3.63(s,3H),2.77(s,3H),2.20–2.05(m,2H),1.70(s,3H).
化合物74收率:68％.1H NMR(400MHz,CDCl3)δ7.57(d,J＝8.8Hz,1H),7.16(d,J＝8.8Hz,1H),4.62(t,J＝6.0Hz,1H),4.50(t,J＝6.0Hz,1H),4.23(t,J＝7.2Hz,2H),3.62(s,3H),3.59(s,3H),2.82(s,3H),2.20–2.04(m,2H),0.98–0.89(m,1H),0.82–0.76(m,2H),0.55–0.46(m,2H).
化合物75收率:69％.1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.8Hz,1H),7.21(s,1H)7.16(d,J＝8.8Hz,1H),4.62(t,J＝6.0Hz,1H),4.50(t,J＝6.0Hz,1H),4.23(t,J＝7.2Hz,2H),3.62(s,3H),3.60(s,3H),2.82(s,3H),2.20–2.04(m,2H).
化合物76收率:71％.,1H NMR(400MHz,CDCl3)δ7.51(d,J＝9.2Hz,1H),7.10(d,J＝9.2Hz,1H),4.62(t,J＝6.0Hz,1H),4.50(t,J＝6.0Hz,1H),4.23(t,J＝7.2Hz,2H),3.61(s,3H),3.59(s,3H),3.23(s,6H),2.74(s,3H),2.22–2.05(m,5H).
化合物77收率:68％.1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.09(d,J＝8.8Hz,1H),4.62(t,J＝6.0Hz,1H),4.50(t,J＝6.0Hz,1H),4.23(t,J＝7.2Hz,2H),3.62(s,3H),3.59(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),2.22(s,3H),2.18–2.04(m,2H),1.08(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H).
化合物78收率:75％.1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.8Hz,1H),7.11(d,J＝8.8Hz,1H),4.62(t,J＝6.0Hz,1H),4.49(t,J＝6.0Hz,1H),4.24(t,J＝7.2Hz,2H),3.64(s,3H),3.59(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),2.18–2.04(m,2H),1.08(t,J＝7.2Hz,3H),1.03–0.89(m,4H),0.82–0.76(m,2H),0.55–0.46(m,2H).
化合物79收率:63％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.10(d,J＝8.8Hz,1H),4.62(t,J＝6.4Hz,1H),4.50(t,J＝6.4Hz,1H),4.23(t,J＝7.2Hz,2H),3.61(s,3H),3.59(s,3H),3.23(s,3H),3.07(q,J＝7.2Hz,2H),2.75(s,3H),2.21(s,3H),2.18–2.04(m,2H),1.17(t,J＝7.2Hz,3H).
化合物80收率:69％.,1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.4Hz,1H),7.08(d,J＝8.4Hz,1H),4.62(t,J＝6.0Hz,1H),4.50(t,J＝6.0Hz,1H),4.23(t,J＝7.2Hz,2H),3.62(s,3H),3.59(s,3H),3.31–3.06(m,5H),2.74(s,3H),2.21(s,3H),2.18–2.04(m,2H),1.67–1.33(m,2H),0.87(t,J＝7.2Hz,3H).
化合物81收率:78％.1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.18(d,J＝8.8Hz,1H),4.39–4.28(m,2H),3.63(s,3H),3.61(s,3H),2.75(s,3H),2.60–2.46(m,2H),1.69(s,3H).
化合物82收率:70％.1H NMR(400MHz,CDCl3)δ7.52(d,J＝8.8Hz,1H),7.16(d,J＝8.8Hz,1H),4.41–4.30(m,2H),3.62(s,3H),3.61(s,3H),2.75(s,3H),2.64–2.49(m,2H),1.01–0.91(m,1H),0.83–0.77(m,2H),0.55–0.46(m,2H).
化合物83收率:65％.1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.8Hz,1H),7.20(s,1H),7.17(d,J＝8.8Hz,1H),4.39–4.28(m,2H),3.63(s,3H),3.61(s,3H),2.75(s,3H),2.60–2.46(m,2H).
化合物84收率:73％.,1H NMR(400MHz,CDCl3)δ7.52(d,J＝8.8Hz,1H),7.10(d,J＝8.8Hz,1H),4.38–4.31(m,2H),3.62(s,3H),3.60(s,3H),3.23(s,6H),2.74(s,3H),2.62–2.48(m,2H),2.21(s,3H).
化合物85收率:68％.1H NMR(400MHz,CDCl3)δ7.52(d,J＝8.8Hz,1H),7.10(d,J＝8.8Hz,1H),4.38–4.31(m,2H),3.61(s,3H),3.60(s,3H),3.19(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.75(s,3H),2.62–2.47(m,2H),2.20(s,3H),1.08(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H).
化合物86收率:69％.1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.8Hz,1H),7.13(d,J＝8.8Hz,1H),4.38–4.31(m,2H),3.61(s,3H),3.60(s,3H),3.20(q,J＝7.2Hz,2H),3.05(q,J＝7.2Hz,2H),2.75(s,3H),2.62–2.47(m,2H),1.08(t,J＝7.2Hz,3H),1.02–0.89(m,4H),0.83–0.77(m,2H),0.55–0.46(m,2H).
化合物87收率:73％.,1H NMR(400MHz,CDCl3)δ7.52(d,J＝9.2Hz,1H),7.10(d,J＝9.2Hz,1H),4.38–4.31(m,2H),3.62(s,3H),3.60(s,3H),3.23(s,3H),3.07(q,J＝7.2Hz,2H),2.74(s,3H),2.62–2.47(m,2H),2.22(s,3H),1.17(t,J＝7.6Hz,3H).
化合物88收率:78％.,1H NMR(400MHz,CDCl3)δ7.52(d,J＝8.8Hz,1H),7.10(d,J＝9.2Hz,1H),4.38–4.30(m,2H),3.61(s,3H),3.59(s,3H),3.30–3.15(m,4H),3.04(t,J＝7.2Hz,1H),2.75(s,3H),2.62–2.47(m,2H),2.20(s,3H),1.64–1.46(m,2H),0.87(t,J＝7.2Hz,3H).
化合物89收率:83％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.4Hz,1H),7.16(d,J＝8.4Hz,1H),4.31(t,J＝5.2Hz,2H),3.68(t,J＝5.2Hz,2H),3.63(s,3H),3.62(s,3H),3.37(s,3H),2.76(s,3H),1.70(s,3H).
化合物90收率:84％.1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),4.33(t,J＝5.6Hz,2H),3.69(t,J＝5.6Hz,2H),3.61(s,3H),3.59(s,3H),3.37(s,3H),2.82(s,3H),0.99–0.89(m,1H),0.83–0.75(m,2H),0.56–0.47(m,2H).
化合物91收率:73％.1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.8Hz,1H),7.20(s,1H),7.17(d,J＝8.8Hz,1H),4.33(t,J＝5.6Hz,2H),3.69(t,J＝5.6Hz,2H),3.61(s,3H),3.59(s,3H),3.37(s,3H),2.76(s,3H).
化合物92收率:78％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝9.2Hz,1H),7.09(d,J＝9.2Hz,1H),4.33(t,J＝5.6Hz,2H),3.67(t,J＝5.6Hz,2H),3.62(s,3H),3.60(s,3H),3.36(s,3H),3.23(s,6H),2.75(s,3H),2.22(s,3H).
化合物93收率:59％.1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.08(d,J＝8.8Hz,1H),4.33(t,J＝5.6Hz,2H),3.67(t,J＝5.6Hz,2H),3.62(s,3H),3.59(s,3H),3.36(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),2.23(s,3H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H).
化合物94收率:70％.1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.8Hz,1H),7.04(d,J＝8.8Hz,1H),4.34(t,J＝5.6Hz,2H),3.67(t,J＝5.6Hz,2H),3.64(s,3H),3.58(s,3H),3.36(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.74(s,3H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H),0.99–0.89(m,1H),0.83–0.75(m,2H),0.56–0.47(m,2H).
化合物95收率:81％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝7.6Hz,1H),7.07(d,J＝7.6Hz,1H),4.33(t,J＝5.6Hz,2H),3.67(t,J＝5.6Hz,2H),3.61(s,3H),3.59(s,3H),3.36(s,3H),3.23(s,3H),3.07(q,J＝7.2Hz,2H),2.74(s,3H),2.22(s,3H),1.17(t,J＝7.2Hz,3H).
化合物96收率:73％.,1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.8Hz,1H),7.06(d,J＝8.8Hz,1H),4.34(t,J＝5.6Hz,2H),3.67(t,J＝5.6Hz,2H),3.62(s,3H),3.59(s,3H),3.36(s,3H),3.30–3.15(m,4H),3.05(t,J＝7.2Hz,1H),2.75(s,3H),2.23(s,3H),1.70–1.43(m,2H),0.87(t,J＝7.2Hz,3H).
化合物97收率:80％.1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.8Hz,1H),7.17(d,J＝8.8Hz,1H),6.01–5.89(m,1H),5.31(d,J＝17.2Hz,1H),5.21(d,J＝10.4Hz,1H),4.68(d,J＝5.6Hz,2H),3.63(s,3H),3.62(s,3H),2.77(s,3H),1.70(s,3H).
化合物98收率:79％.1H NMR(400MHz,CDCl3)δ7.57(d,J＝8.8Hz,1H),7.16(d,J＝8.8Hz,1H),6.02–5.89(m,1H),5.31(d,J＝17.2Hz,1H),5.22(d,J＝10.4Hz,1H),4.68(d,J＝5.6Hz,2H),3.62(s,3H),3.60(s,3H),2.82(s,3H),0.98–0.91(m,1H),0.85–0.76(m,2H),0.56–0.43(m,2H).
化合物99收率:80％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,1H),7.20(s,1H),7.16(d,J＝8.8Hz,1H),6.02–5.90(m,1H),5.31(d,J＝17.2Hz,1H),5.22(d,J＝10.4Hz,1H),4.68(d,J＝5.6Hz,2H),3.62(s,3H),3.60(s,3H),2.78(s,3H).
化合物100收率:81％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.4Hz,1H),7.09(d,J＝8.4Hz,1H),6.00–5.88(m,1H),5.32–5.18(m,2H),4.68(d,J＝5.8Hz,2H),3.63(s,3H),3.59(s,3H),3.23(s,6H),2.74(s,3H),2.21(s,3H).
化合物101收率:78％.1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.09(d,J＝8.8Hz,1H),5.99–5.87(m,1H),5.28(d,J＝17.2Hz,1H),5.20(d,J＝10.4Hz,1H),4.68(d,J＝5.8Hz,2H),3.62(s,3H),3.60(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),2.21(s,3H),1.07(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H).
化合物102收率:90％.1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.8Hz,1H),7.08(d,J＝8.8Hz,1H),6.00–5.87(m,1H),5.30(d,J＝17.2Hz,1H),5.22(d,J＝10.4Hz,1H),4.68(d,J＝5.8Hz,2H),3.64(s,3H),3.59(s,3H),3.18(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),1.07(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H),0.98–0.91(m,1H),0.85–0.76(m,2H),0.56–0.43(m,2H).
化合物103收率:66％.,1H NMR(400MHz,CDCl3)δ7.51(d,J＝9.2Hz,1H),7.10(d,J＝9.2Hz,1H),6.00–5.88(m,1H),5.28(d,J＝17.2Hz,1H),5.20(d,J＝10.4Hz,1H),4.68(d,J＝6.0Hz,2H),3.62(s,3H),3.59(s,3H),3.23(s,3H),3.07(q,J＝7.6Hz,2H),2.74(s,3H),2.20(s,3H),1.17(t,J＝7.6Hz,3H).
化合物104收率:67％.,1H NMR(400MHz,CDCl3)δ7.52(d,J＝8.4Hz,1H),7.10(d,J＝8.4Hz,1H),6.01–5.88(m,1H),5.32–5.24(m,1H),5.24–5.18(m,1H),4.68(d,J＝6.0Hz,2H),3.62(s,3H),3.60(s,3H),3.23(s,3H),3.14(t,J＝7.2Hz,1H),3.01(t,J＝7.2Hz,1H),2.75(s,3H),2.21(s,3H),1.69–1.41(m,2H),0.87(t,J＝7.2Hz,3H).
化合物105收率:79％.1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.8Hz,1H),7.19(d,J＝8.8Hz,1H),4.84(d,J＝2.0Hz,2H),3.65(s,3H),3.63(s,3H),2.78(s,3H),2.19(t,J＝2.4Hz,1H),1.70(s,3H).
化合物106收率:68％.1H NMR(400MHz,CDCl3)δ7.58(d,J＝8.4Hz,1H),7.17(d,J＝8.4Hz,1H),4.84(d,J＝2.0Hz,2H),3.64(s,3H),3.59(s,3H),2.83(s,3H),2.19(t,J＝2.4Hz,1H),1.00–0.87(m,1H),0.83–0.72(m,2H),0.55–0.44(m,2H).
化合物107收率:80％.1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.4Hz,1H),7.21(s,1H),7.18(d,J＝8.4Hz,1H),4.84(d,J＝2.0Hz,2H),3.64(s,3H),3.59(s,3H),2.83(s,3H),2.19(t,J＝2.3Hz,1H).
化合物108收率:87％.,1H NMR(400MHz,CDCl3)δ7.52(d,J＝8.8Hz,1H),7.11(d,J＝8.8Hz,1H),4.84(d,J＝2.4Hz,2H),3.62(s,3H),3.60(s,3H),3.23(s,6H),2.75(s,3H),2.20(s,3H),2.19(t,J＝2.4Hz,1H).
化合物109收率:77％.1H NMR(400MHz,CDCl3)δ7.52(d,J＝8.8Hz,1H),7.11(d,J＝8.8Hz,1H),4.84(d,J＝2.4Hz,2H),3.62(s,3H),3.61(s,3H),3.18(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.77(s,3H),2.21(s,3H),2.19(t,J＝2.4Hz,1H),1.08(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H).
化合物110收率:69％.1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.8Hz,1H),7.13(d,J＝8.8Hz,1H),4.84(d,J＝2.4Hz,2H),3.63(s,3H),3.61(s,3H),3.18(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.75(s,3H),2.19(t,J＝2.4Hz,1H),1.08(t,J＝7.2Hz,3H),1.01–0.87(m,4H),0.83–0.72(m,2H),0.55–0.44(m,2H).
化合物111收率:77％.,1H NMR(400MHz,CDCl3)δ7.52(d,J＝9.2Hz,1H),7.10(d,J＝9.2Hz,1H),4.84(d,J＝2.4Hz,2H),3.62(s,3H),3.60(s,3H),3.23(s,3H),3.12–3.01(m,2H),2.75(s,3H),2.21(s,3H),2.19(t,J＝2.4Hz,1H),1.17(t,J＝7.6Hz,3H).
化合物112收率:69％.,1H NMR(400MHz,CDCl3)δ7.52(d,J＝8.8Hz,1H),7.10(d,J＝8.8Hz,1H),4.84(d,J＝2.4Hz,2H),3.62(s,3H),3.59(s,3H),3.24–3.16(m,4H),3.08(t,J＝6.0Hz,1H),2.74(s,3H),2.21(s,3H),2.19(t,J＝2.4Hz,1H),1.66–1.49(m,2H),0.87(t,J＝7.6Hz,3H).
化合物113收率:75％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),5.36–5.24(m,1H),4.66(d,J＝6.8Hz,2H),3.63(s,3H),3.61(s,3H),2.78(s,3H),1.85(s,3H),1.75–1.67(m,6H).
化合物114收率:70％.1H NMR(400MHz,CDCl3)δ7.57(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),5.39–5.27(m,1H),4.67(d,J＝6.8Hz,2H),3.65(s,3H),3.59(s,3H),2.78(s,3H),1.79(s,3H),1.66(s,3H),1.01–0.88(m,1H),0.83–0.72(m,2H),0.55–0.44(m,2H).
化合物115收率:74％.1H NMR(400MHz,CDCl3)δ7.44(d,J＝8.8Hz,1H),7.21(s,1H),7.15(d,J＝8.8Hz,1H),5.36–5.24(m,1H),4.66(d,J＝6.8Hz,2H),3.64(s,3H),3.61(s,3H),2.78(s,3H),1.79(s,3H),1.66(s,3H).
化合物116收率:72％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝9.2Hz,1H),7.06(d,J＝9.2Hz,1H),5.26(t,J＝6.8Hz,1H),4.66(d,J＝6.8Hz,2H),3.62(s,3H),3.60(s,3H),3.23(s,6H),2.75(s,3H),2.21(s,3H),1.86(s,3H),1.71(s,3H).
化合物117收率:73％.1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.8Hz,1H),7.07(d,J＝8.8Hz,1H),5.26(t,J＝6.8Hz,1H),4.66(d,J＝6.8Hz,2H),3.61(s,3H),3.59(s,3H),3.17(q,J＝7.2Hz,2H),3.02(q,J＝7.2Hz,2H),2.76(s,3H),2.22(s,3H),1.85(s,3H),1.71(s,3H),1.07(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H).
化合物118收率:65％.1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.8Hz,1H),7.08(d,J＝8.8Hz,1H),5.26(t,J＝6.8Hz,1H),4.67(d,J＝6.8Hz,2H),3.62(s,3H),3.59(s,3H),3.17(q,J＝7.2Hz,2H),3.02(q,J＝7.2Hz,2H),2.75(s,3H),1.85(s,3H),1.71(s,3H),1.07(t,J＝7.2Hz,3H),1.03–0.87(m,4H),0.83–0.72(m,2H),0.55–0.44(m,2H).
化合物119收率:65％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.2Hz,1H),7.06(d,J＝8.2Hz,1H),5.28–5.24(m,1H),4.66(d,J＝6.8Hz,2H)3.61(s,3H),3.59(s,3H),3.23(s,3H),3.07(q,J＝7.2Hz,2H),2.75(s,3H),2.22(s,3H),1.85(s,3H),1.71(s,3H),1.17(t,J＝7.2Hz,3H).
化合物120收率:80％.,1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.8Hz,1H),7.07(d,J＝8.8Hz,1H),5.26(t,J＝6.8Hz,1H),4.66(d,J＝6.8Hz,2H),3.61(s,3H),3.59(s,3H),3.27–3.20(m,4H),3.04(t,J＝6.0Hz,1H),2.76(s,3H),2.23(s,3H),1.85(s,3H),1.71(s,3H),1.65–1.49(m,2H),0.87(t,J＝7.2Hz,3H).
化合物121收率:70％.1H NMR(400MHz,CDCl3)δ7.42(d,J＝8.8Hz,1H),7.12(d,J＝8.8Hz,1H),3.65–3.59(m,4H),3.53(s,3H),2.69(s,3H),1.87(s,3H),1.19–1.10(m,2H),0.78–0.68(m,2H).
化合物122收率:76％.1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.6Hz,1H),7.12(d,J＝8.6Hz,1H),3.66–3.53(m,7H),2.79(s,3H),1.24–1.17(m,2H),0.98–0.91(m,1H),0.82–0.76(m,4H),0.53–0.48(m,2H).
化合物123收率:69％.1H NMR(400MHz,CDCl3)δ7.43(d,J＝8.8Hz,1H),7.22(s,1H),7.12(d,J＝8.8Hz,1H),3.66–3.53(m,7H),2.79(s,3H),1.20–1.11(m,2H),0.78–0.68(m,2H).
化合物124收率:85％.,1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,1H),7.05(d,J＝8.8Hz,1H),3.60(s,3H),3.57(s,3H),2.82–2.74(m,4H),2.70(s,3H),2.68(s,3H),2.19(s,3H),1.29–1.14(m,2H),0.81–0.71(m,2H).
化合物125收率:64％.1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.05(d,J＝8.8Hz,1H),3.65–3.59(m,4H),3.57(s,3H),3.18(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.72(s,3H),2.20(s,3H),1.23–1.17(m,2H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H),0.78–0.71(m,2H).
化合物126收率:72％.1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.8Hz,1H),7.06(d,J＝8.8Hz,1H),3.65–3.59(m,7H),3.18(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.74(s,3H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H),1.24–1.17(m,2H),0.98–0.91(m,1H),0.82–0.76(m,4H),0.53–0.48(m,2H).
化合物127收率:86％.,1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.4Hz,1H),7.05(d,J＝8.4Hz,1H),3.60(s,3H),3.56(s,3H),3.10(dq,J＝36.9,7.1Hz,2H),2.86–2.74(m,2H),2.71(m,3H),2.65(s,2H),2.23(s,2H),2.15(s,1H),1.19(m,2H),1.03(dt,J＝34.9,7.1Hz,3H),0.81–0.66(m,2H).
化合物128收率:88％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.4Hz,1H),7.05(d,J＝8.4Hz,1H),3.65–3.59(m,7H),3.27–3.20(m,4H),3.06(t,J＝6.0Hz,1H),2.73(s,3H),2.20(s,3H),1.65–1.49(m,2H),1.23–1.17(m,2H),0.87(t,J＝7.2Hz,3H).0.78–0.71(m,2H).
化合物129收率:66％.1H NMR(400MHz,CDCl3)δ7.43(d,J＝8.8Hz,1H),7.12(d,J＝8.8Hz,1H),5.32–5.20(m,1H),3.63(s,3H),3.58(s,3H),2.91–2.80(m,2H),2.73(s,3H),2.39–2.30(m,2H),1.96–1.73(m,2H),1.70(s,3H).
化合物130收率:60％.1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.8Hz,1H),7.11(d,J＝8.8Hz,1H),5.29–5.18(m,1H),3.59(s,3H),3.57(s,3H),2.92–2.81(m,2H),2.78(s,3H),2.41–2.29(m,2H),1.95–1.69(m,2H),0.99–0.89(m,1H),0.82–0.74(m,2H),0.54–0.46(m,2H).
化合物131收率:86％.,1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.4Hz,1H),7.03(d,J＝8.4Hz,1H),5.27–5.17(m,1H),3.61(s,3H),3.55(s,3H),3.23(s,6H),2.90–2.77(m,2H),2.72(s,3H),2.41–2.29(m,2H),2.21(s,3H),1.94–1.73(m,2H),
化合物132收率:84％.1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.04(d,J＝8.8Hz,1H),5.27–5.17(m,1H),3.61(s,3H),3.55(s,3H),3.18(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.90–2.77(m,2H),2.72(s,3H),2.41–2.29(m,2H),2.21(s,3H),1.94–1.73(m,2H),1.08(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H).
化合物133收率:73％.1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.8Hz,1H),7.06(d,J＝8.8Hz,1H),5.25–5.15(m,1H),3.63(s,3H),3.57(s,3H),3.18(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.90–2.77(m,2H),2.72(s,3H),2.41–2.29(m,2H),1.94–1.73(m,2H),1.08(t,J＝7.2Hz,3H),1.03–0.89(m,4H),0.82–0.74(m,2H),0.54–0.46(m,2H).
化合物134收率:85％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.4Hz,1H),7.04(d,J＝8.4Hz,1H),5.27–5.17(m,1H),3.62(s,3H),3.55(s,3H),3.23(s,3H),3.07(q,J＝7.6Hz,2H),2.90–2.77(m,2H),2.73(s,3H),2.41–2.29(m,2H),2.21(s,3H),1.94–1.73(m,2H),1.17(t,J＝7.6Hz,3H).
化合物135收率:75％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.4Hz,1H),7.04(d,J＝8.4Hz,1H),5.27–5.17(m,1H),3.62(s,3H),3.55(s,3H),3.22(s,3H),3.19(t,J＝7.6Hz,1H),2.98(t,J＝7.6Hz,1H),2.90–2.77(m,2H),2.73(s,3H),2.41–2.29(m,2H),2.21(s,3H),1.94–1.73(m,2H),1.65–1.48(m,2H),0.87(t,J＝7.2Hz,3H).
化合物136收率:70％.1H NMR(400MHz,CDCl3)δ7.43(d,J＝8.8Hz,1H),7.13(d,J＝8.8Hz,1H),5.48–5.38(m,1H),3.63(s,3H),3.59(s,3H),2.76(s,3H),2.21–2.11(m,2H),2.05–1.95(m,2H),1.93–1.83(m,2H),1.71(s,3H),1.68–1.58(m,2H).
化合物137收率:74％.1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.8Hz,1H),7.11(d,J＝8.8Hz,1H),5.48–5.37(m,1H),3.60(s,3H),3.59(s,3H),2.80(s,3H),2.23–2.11(m,2H),2.06–1.96(m,2H),1.93–1.83(m,2H),1.67–1.58(m,2H),1.00–0.92(m,1H),0.81–0.75(m,2H),0.54–0.47(m,2H).
化合物138收率:71％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.4Hz,1H),7.06(d,J＝8.4Hz,1H),5.46–5.36(m,1H),3.62(s,3H),3.56(s,3H),3.22(s,6H),2.73(s,3H),2.22(s,3H),2.18–2.09(m,2H),2.04–1.95(m,2H),1.92–1.82(m,2H),1.67–1.57(m,2H),
化合物139收率:73％.1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.05(d,J＝8.8Hz,1H),5.46–5.36(m,1H),3.62(s,3H),3.56(s,3H),3.18(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.73(s,3H),2.22(s,3H),2.18–2.09(m,2H),2.04–1.95(m,2H),1.92–1.82(m,2H),1.67–1.57(m,2H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H).
化合物140收率:77％.1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.8Hz,1H),7.07(d,J＝8.8Hz,1H),5.46–5.36(m,1H),3.62(s,3H),3.56(s,3H),3.18(q,J＝7.2Hz,2H),3.04(q,J＝7.2Hz,2H),2.73(s,3H),2.18–2.09(m,2H),2.04–1.82(m,4H),1.67–1.57(m,2H),1.08(t,J＝7.2Hz,3H),1.03–0.92(m,4H),0.81–0.75(m,2H),0.54–0.47(m,2H).
化合物141收率:69％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.05(d,J＝8.8Hz,1H),5.46–5.36(m,1H),3.62(s,3H),3.56(s,3H),3.21(s,3H),3.05(q,J＝7.6Hz,2H),2.73(s,3H),2.22(s,3H),2.18–2.09(m,2H),2.04–1.95(m,2H),1.92–1.82(m,2H),1.67–1.57(m,2H),1.17(t,J＝7.6Hz,3H).
化合物142收率:73％.,1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.06(d,J＝8.8Hz,1H),5.46–5.36(m,1H),3.62(s,3H),3.58(s,3H),3.29–3.16(m,4H),3.03(t,J＝7.6Hz,1H),2.75(s,3H),2.22(s,3H),2.18–2.09(m,2H),2.04–1.95(m,2H),1.92–1.82(m,2H),1.67–1.48(m,4H),0.87(t,J＝7.2Hz,3H).
化合物143收率:72％.1H NMR(400MHz,CDCl3)δ7.43(d,J＝8.8Hz,1H),7.12(d,J＝8.8Hz,1H),4.93–4.84(m,1H),3.64(s,3H),3.58(s,3H),2.75(s,3H),2.53–2.40(m,2H),1.91–1.82(m,2H),1.71(s,3H),1.70–1.64(m,3H),1.46–1.25(m,3H).
化合物144收率:74％.1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.8Hz,1H),7.11(d,J＝8.8Hz,1H),4.94–4.83(m,1H),3.59(s,3H),3.57(s,3H),2.80(s,3H),2.53–2.41(m,2H),1.90–1.82(m,2H),1.72–1.64(m,3H),1.45–1.23(m,3H),1.00–0.92(m,1H),0.82–0.76(m,2H),0.55–0.48(m,2H).
化合物145收率:72％.1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.4Hz,1H),7.04(d,J＝8.4Hz,1H),4.94–4.81(m,1H),3.62(s,3H),3.55(s,3H),3.17(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.72(s,3H),2.53–2.40(m,2H),2.23(s,3H),1.90–1.81(m,2H),1.72–1.61(m,3H),1.46–1.25(m,3H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H).
化合物146收率:80％.1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.8Hz,1H),7.17(d,J＝8.8Hz,1H),3.97(d,J＝7.2Hz,2H),3.63(s,3H),3.62(s,3H),2.77(s,3H),1.71(s,3H),1.36–1.27(m,1H),0.52–0.46(m,2H),0.46–0.40(m,2H).
化合物147收率:73％.1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),3.97(d,J＝7.2Hz,2H),3.62(s,3H),3.60(s,3H),2.82(s,3H),1.39–1.26(m,1H),1.00–0.91(m,1H),0.83–0.77(m,2H),0.54–0.43(m,6H).
化合物148收率:82％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝9.2Hz,1H),7.10(d,J＝9.2Hz,1H),3.97(d,J＝7.2Hz,2H),3.62(s,3H),3.59(s,3H),3.23(s,6H),2.75(s,3H),2.23(s,3H),1.36–1.24(m,1H),0.50–0.42(m,4H).
化合物149收率:77％.1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.0Hz,1H),7.09(d,J＝8.0Hz,1H),3.97(d,J＝7.2Hz,2H),3.62(s,3H),3.60(s,3H),3.17(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),2.24(s,3H),1.36–1.24(m,1H),1.08(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H),0.49–0.42(m,4H).
化合物150收率:65％.1H NMR(400MHz,CDCl3)δ7.57(d,J＝8.8Hz,1H),7.07(d,J＝8.8Hz,1H),3.97(d,J＝7.2Hz,2H),3.62(s,3H),3.59(s,3H),3.17(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.82(s,3H),1.39–1.26(m,1H),1.08(t,J＝7.2Hz,3H),1.02–0.91(m,4H),0.83–0.77(m,2H),0.54–0.42(m,6H).
化合物151收率:63％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.10(d,J＝8.8Hz,1H),3.98(d,J＝7.2Hz,2H),3.62(s,3H),3.60(s,3H),3.23(s,3H),3.07(q,J＝7.6Hz,2H),2.74(s,3H),2.24(s,3H),1.36–1.24(m,1H),1.17(t,J＝7.6Hz,3H),0.52–0.42(m,4H).
化合物152收率:78％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝9.2Hz,1H),7.09(d,J＝9.2Hz,1H),3.98(d,J＝7.2Hz,2H),3.62(s,3H),3.60(s,3H),3.29–3.15(m,4H),3.07(t,J＝7.6Hz,1H),2.75(s,3H),2.23(s,3H),1.68–1.48(m,2H),1.36–1.24(m,1H),0.87(t,J＝7.2Hz,3H),0.50–0.42(m,4H).
化合物153收率:69％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),4.13(d,J＝7.2Hz,2H),3.63(s,3H),3.61(s,3H),2.76(s,3H),2.06–1.80(m,7H),1.71(s,3H).
化合物154收率:67％.1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.8Hz,1H),7.14(d,J＝8.8Hz,1H),4.13(d,J＝7.2Hz,2H),3.60(s,6H),2.81(s,3H),2.08–1.77(m,7H),0.99–0.91(m,1H),0.85–0.75(m,2H),0.59–0.47(m,2H).
化合物155收率:68％.1H NMR(400MHz,CDCl3)δ7.48(d,J＝7.8Hz,1H),7.07(d,J＝7.8Hz,1H),4.13(d,J＝7.2Hz,2H),3.61(s,3H),3.57(s,3H),3.16(q,J＝7.2Hz,2H),3.01(q,J＝7.2Hz,2H),2.79–2.70(m,4H),2.23(s,3H),2.05–1.93(m,2H),1.83–1.85(m,4H),1.06(t,J＝6.8Hz,3H),1.00(t,J＝7.0Hz,3H).
化合物156收率:74％.1H NMR(400MHz,CDCl3)δ7.49(d,J＝7.8Hz,1H),7.04(d,J＝7.8Hz,1H),4.13(d,J＝7.2Hz,2H),3.61(s,3H),3.57(s,3H),3.16(q,J＝7.2Hz,2H),3.01(q,J＝7.2Hz,2H),2.79–2.70(m,4H),,2.05–1.93(m,2H),1.83–1.85(m,4H),1.06(t,J＝6.8Hz,3H),1.00(t,J＝7.0Hz,3H),1.00–0.92(m,1H),0.82–0.76(m,2H),0.55–0.48(m,2H).
化合物157收率:69％.1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.8Hz,1H),7.17(d,J＝8.8Hz,1H),4.06(d,J＝7.6Hz,2H),3.64(s,3H),3.62(s,3H),2.77(s,3H),2.45–2.32(m,1H),1.75–1.63(m,7H),1.57–1.47(m,2H),1.40–1.29(m,2H).
化合物158收率:82％.1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),4.05(d,J＝7.6Hz,2H),3.61(s,3H),3.60(s,3H),2.82(s,3H),2.47–2.33(m,1H),1.78–1.64(m,4H),1.57–1.46(m,2H),1.39–1.28(m,2H),0.99–0.91(m,1H),0.86–0.76(m,2H),0.58–0.47(m,2H).
化合物159收率:73％.,1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.4Hz,1H),7.07(d,J＝8.4Hz,1H),4.05(d,J＝7.6Hz,2H),3.62(s,3H),3.59(s,3H),3.23(s,6H),2.75(s,3H),2.44–2.32(m,1H),2.24(s,3H),1.75–1.63(m,4H),1.57–1.45(m,2H),1.44–1.26(m,2H),
化合物160收率:67％.1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.8Hz,1H),7.08(d,J＝8.8Hz,1H),4.05(d,J＝7.6Hz,2H),3.62(s,3H),3.59(s,3H),3.17(q,J＝7.2Hz,2H),3.01(q,J＝7.2Hz,2H),2.75(s,3H),2.44–2.32(m,1H),2.24(s,3H),1.75–1.62(m,4H),1.57–1.45(m,2H),1.44–1.26(m,2H),1.06(t,J＝7.2Hz,3H),1.01(t,J＝7.2Hz,3H).
化合物161收率:69％.1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.8Hz,1H),7.07(d,J＝8.8Hz,1H),4.06(d,J＝7.6Hz,2H),3.62(s,3H),3.57(s,3H),3.17(q,J＝7.2Hz,2H),3.03(q,J＝7.2Hz,2H),2.75(s,3H),2.44–2.32(m,1H),1.75–1.62(m,4H),1.57–1.45(m,2H),1.44–1.26(m,2H),1.06(t,J＝7.2Hz,3H),1.02–0.91(m,4H),0.86–0.76(m,2H),0.58–0.47(m,2H).
化合物162收率:81％.,1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.8Hz,1H),7.08(d,J＝8.8Hz,1H),4.05(d,J＝7.6Hz,2H),3.61(s,3H),3.59(s,3H),3.23(s,3H),3.07(q,J＝7.6Hz,2H),2.74(s,3H),2.44–2.32(m,1H),2.23(s,3H),1.75–1.62(m,4H),1.57–1.45(m,2H),1.44–1.26(m,2H),1.17(t,J＝7.2Hz,3H).
化合物163收率:69％.,1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.4Hz,1H),7.07(d,J＝8.4Hz,1H),4.05(d,J＝7.6Hz,2H),3.62(s,3H),3.59(s,3H),3.28–3.19(m,4H),3.11–2.98(m,1H),2.75(s,3H),2.44–2.32(m,1H),2.22(s,3H),1.75–1.45(m,8H),1.44–1.26(m,2H),0.87(t,J＝6.8Hz,3H).
化合物164收率:70％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,1H),7.16(d,J＝8.8Hz,1H),3.94(d,J＝7.4Hz,2H),3.64(s,3H),3.62(s,3H),2.77(s,3H),1.90–1.79(m,1H),1.73–1.62(m,8H),1.23–1.03(m,5H).
化合物165收率:73％.1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),3.94(d,J＝7.2Hz,2H),3.61(s,3H),3.60(s,3H),2.82(s,3H),1.89–1.78(m,1H),1.75–1.61(m,5H),1.25–1.15(m,3H),1.13–1.02(m,2H),1.01–0.91(m,1H),0.84–0.78(m,2H),0.55–0.48(m,2H).
化合物166收率:74％.1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.4Hz,1H),7.07(d,J＝8.4Hz,1H),3.93(d,J＝7.2Hz,2H),3.61(s,3H),3.58(s,3H),3.16(q,J＝7.2Hz,2H),3.00(q,J＝7.2Hz,2H),2.75(s,3H),2.24(s,3H),1.89–1.79(m,1H),1.75–1.68(m,2H),1.67–1.58(m,3H),1.27–1.11(m,4H),1.08–1.04(m,4H),1.00(t,J＝7.2Hz,3H).
化合物167收率:66％.1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),5.79–5.69(m,1H),4.30(q,J＝7.6Hz,1H),4.06–3.92(m,3H),3.64(s,3H),3.61(s,3H),2.75(s,3H),2.42–2.32(m,1H),2.25–2.15(m,1H),1.70(s,3H).
化合物168收率:69％.1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.8Hz,1H),7.14(d,J＝8.8Hz,1H),5.79–5.68(m,1H),4.30(q,J＝7.6Hz,1H),4.05–3.95(m,3H),3.60(s,3H),3.59(s,3H),2.80(s,3H),2.41–2.32(m,1H),2.25–2.14(m,1H),0.98–0.90(m,1H),0.84–0.75(m,2H),0.52–0.47(m,2H).
化合物169收率:67％.1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.07(d,J＝8.8Hz,1H),5.78–5.68(m,1H),4.30(q,J＝7.6Hz,1H),4.06–3.93(m,3H),3.62(s,3H),3.58(s,3H),3.21(q,J＝7.2Hz,2H),3.08(q,J＝7.2Hz,2H),2.73(s,3H),2.39–2.30(m,1H),2.25–2.18(m,1H),2.17(s,3H),1.10(t,J＝7.2Hz,3H),1.03(t,J＝7.2Hz,3H).
化合物170收率:66％.1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.8Hz,1H),7.07(d,J＝8.8Hz,1H),5.78–5.68(m,1H),4.30(q,J＝7.6Hz,1H),4.06–3.93(m,3H),3.62(s,3H),3.58(s,3H),3.21(q,J＝7.2Hz,2H),3.08(q,J＝7.2Hz,2H),2.73(s,3H),2.39–2.30(m,1H),2.25–2.18(m,1H),1.10(t,J＝7.2Hz,3H),1.03(t,J＝7.2Hz,3H),0.98–0.90(m,1H),0.84–0.75(m,2H),0.52–0.47(m,2H).
化合物171收率:69％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,1H),7.14(d,J＝8.8Hz,1H),5.20–5.10(m,1H),4.12–4.05(m,2H),3.64(s,3H),3.59(s,3H),3.54–3.48(m,2H),2.92–2.80(m,2H),2.74(s,3H),1.71(s,3H),1.64–1.55(m,2H).
化合物172收率:76％.1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.8Hz,1H),7.12(d,J＝8.8Hz,1H),5.20–5.09(m,1H),4.13–4.04(m,2H),3.59(s,3H),3.58(s,3H),3.54–3.47(m,2H),2.91–2.82(m,2H),2.79(s,3H),1.64–1.53(m,2H),1.00–0.90(m,1H),0.83–0.76(m,2H),0.55–0.46(m,2H).
化合物173收率:82％.,1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.4Hz,1H),7.06(d,J＝8.4Hz,1H),5.20–5.08(m,1H),4.14–4.04(m,2H),3.62(s,3H),3.56(s,3H),3.52(t,J＝11.6Hz,2H),3.23(s,6H),2.92–2.79(m,2H),2.74(s,3H),2.19(s,3H),1.59–1.52(m,2H).
化合物174收率:73％.1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.4Hz,1H),7.06(d,J＝8.4Hz,1H),5.20–5.08(m,1H),4.14–4.04(m,2H),3.62(s,3H),3.56(s,3H),3.51(t,J＝11.6Hz,2H),3.19(q,J＝7.2Hz,2H),3.07(q,J＝7.2Hz,2H),2.92–2.79(m,2H),2.72(s,3H),2.19(s,3H),1.59–1.52(m,2H),1.09(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H).
化合物175收率:69％.1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.4Hz,1H),7.05(d,J＝8.4Hz,1H),5.20–5.08(m,1H),4.14–4.04(m,2H),3.62(s,3H),3.56(s,3H),3.51(t,J＝11.6Hz,2H),3.19(q,J＝7.2Hz,2H),3.07(q,J＝7.2Hz,2H),2.92–2.79(m,2H),2.72(s,3H),1.59–1.52(m,2H),1.09(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H),1.00–0.90(m,1H),0.83–0.76(m,2H),0.55–0.46(m,2H).
化合物176收率:89％.,1H NMR(400MHz,CDCl3)δ7.48(d,J＝9.2Hz,1H),7.06(d,J＝9.2Hz,1H),5.20–5.08(m,1H),4.14–4.04(m,2H),3.62(s,3H),3.56(s,3H),3.51(t,J＝11.6Hz,2H),3.23(s,3H),3.07(q,J＝7.6Hz,2H),2.92–2.79(m,2H),2.72(s,3H),2.19(s,3H),1.59–1.52(m,2H),1.17(t,J＝7.2Hz,3H).
化合物177收率:89％.,1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.4Hz,1H),7.06(d,J＝8.4Hz,1H),5.20–5.08(m,1H),4.14–4.04(m,2H),3.62(s,3H),3.56(s,3H),3.51(t,J＝11.6Hz,2H),3.29–3.21(m,4H),3.11–2.98(m,1H),2.92–2.79(m,2H),2.74(s,3H),2.20(s,3H),1.59–1.52(m,2H),1.68–1.48(m,2H),0.87(t,J＝7.2Hz,3H).
化合物178收率:68％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.4Hz,1H),7.15(d,J＝8.4Hz,1H),4.35(d,J＝7.2Hz,2H),4.05–3.88(m,2H),3.81–3.71(m,1H),3.63(s,3H),3.61(s,3H),2.76(s,3H),2.12–1.96(m,2H),1.94–1.59(m,5H).
化合物179收率:64％.1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.8Hz,1H),7.13(d,J＝8.8Hz,1H),4.42–4.31(m,2H),4.00–3.90(m,2H),3.78–3.70(m,1H),3.60(s,3H),3.59(s,3H),2.81(s,3H),2.12–1.96(m,2H),1.94–1.83(m,1H),1.74–1.63(m,1H),0.97–0.88(m,1H),0.85–0.75(m,2H),0.58–0.48(m,2H).
化合物180收率:69％.1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.4Hz,1H),7.15(d,J＝8.4Hz,1H),4.35(d,J＝7.2Hz,2H),4.05–3.88(m,2H),3.81–3.71(m,1H),3.63(s,3H),3.61(s,3H),3.19(q,J＝7.2Hz,2H),3.07(q,J＝7.2Hz,2H),2.76(s,3H),2.19(s,3H),2.12–1.96(m,2H),1.94–1.59(m,2H),1.09(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H).
化合物181收率:75％.1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.4Hz,1H),7.12(d,J＝8.4Hz,1H),4.35(d,J＝7.2Hz,2H),4.05–3.88(m,2H),3.81–3.71(m,1H),3.63(s,3H),3.61(s,3H),3.19(q,J＝7.2Hz,2H),3.07(q,J＝7.2Hz,2H),2.76(s,3H),2.12–1.96(m,2H),1.94–1.59(m,2H),1.09(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H),0.97–0.88(m,1H),0.85–0.75(m,2H),0.58–0.48(m,2H).
化合物182收率:69％.1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.18(d,J＝8.8Hz,1H),4.22–4.15(m,1H),4.12–4.05(m,1H),3.98–3.91(m,1H),3.87–3.74(m,2H),3.66–3.59(m,7H),2.80–2.72(m,4H),2.06–1.96(m,1H),1.82–1.74(m,1H),1.71(s,3H).
化合物183收率:70％.1H NMR(400MHz,CDCl3)δ7.58(d,J＝8.8Hz,1H),7.16(d,J＝8.8Hz,1H),4.22–4.15(m,1H),4.12–4.05(m,1H),3.98–3.91(m,1H),3.86–3.74(m,2H),3.63–3.58(m,7H),2.81(s,3H),2.79–2.72(m,1H),2.09–1.95(m,1H),1.84–1.71(m,1H),1.01–0.90(m,1H),0.84–0.75(m,2H),0.56–0.46(m,2H).
化合物184收率:86％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝9.2Hz,1H),7.10(d,J＝9.2Hz,1H),4.22–4.15(m,1H),4.12–4.04(m,1H),3.98–3.90(m,1H),3.84–3.74(m,2H),3.64–3.57(m,7H),3.23(s,6H),2.78–2.71(m,4H),2.21(s,3H),2.04–1.92(m,1H),1.80–1.68(m,1H),
化合物185收率:80％.1H NMR(400MHz,CDCl3)δ7.51(d,J＝8.8Hz,1H),7.09(d,J＝8.8Hz,1H),4.22–4.15(m,1H),4.12–4.04(m,1H),3.98–3.90(m,1H),3.84–3.74(m,2H),3.64–3.57(m,7H),3.19(q,J＝7.2Hz,2H),3.06(q,J＝7.2Hz,2H),2.78–2.71(m,4H),2.20(s,3H),2.04–1.92(m,1H),1.80–1.68(m,1H),1.08(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H).
化合物186收率:69％.1H NMR(400MHz,CDCl3)δ7.57(d,J＝8.8Hz,1H),7.06(d,J＝8.8Hz,1H),4.22–4.15(m,1H),4.12–4.04(m,1H),3.98–3.90(m,1H),3.84–3.74(m,2H),3.64–3.57(m,7H),3.19(q,J＝7.2Hz,2H),3.06(q,J＝7.2Hz,2H),2.78–2.71(m,4H),2.04–1.92(m,1H),1.80–1.68(m,1H),1.08(t,J＝7.2Hz,3H),1.03–0.90(m,4H),0.84–0.75(m,2H),0.56–0.46(m,2H).
化合物187收率:77％.,1H NMR(400MHz,CDCl3)δ7.51(d,J＝9.2Hz,1H),7.09(d,J＝9.2Hz,1H),4.22–4.04(m,2H),3.98–3.90(m,1H),3.84–3.74(m,2H),3.64–3.57(m,7H),3.23(s,3H),3.07(q,J＝7.2Hz,2H),2.78–2.71(m,4H),2.20(s,3H),2.04–1.92(m,1H),1.80–1.68(m,1H),1.17(t,J＝7.2Hz,3H).
化合物188收率:79％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.4Hz,1H),7.09(d,J＝8.4Hz,1H),4.22–4.04(m,2H),3.98–3.90(m,1H),3.84–3.74(m,2H),3.64–3.57(m,7H),3.29–3.18(m,4H),3.11–2.98(m,1H),2.78–2.71(m,4H),2.20(s,3H),2.04–1.92(m,1H),1.80–1.50(m,3H),0.87(t,J＝7.2Hz,3H).
化合物189收率:74％.1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.8Hz,1H),7.17(d,J＝8.8Hz,1H),4.00(d,J＝7.2Hz,2H),3.99–3.93(m,2H),3.64(s,3H),3.62(s,3H),3.39–3.31(m,2H),2.77(s,3H),2.15–2.05(m,1H),1.71(s,3H),1.62–1.55(m,2H),1.54–1.45(m,2H).
化合物190收率:69％.1H NMR(400MHz,CDCl3)δ7.57(d,J＝8.8Hz,1H),7.15(d,J＝8.8Hz,1H),4.00(d,J＝7.2Hz,2H),3.98–3.92(m,2H),3.61(s,3H),3.59(s,3H),3.38–3.30(m,2H),2.81(s,3H),2.15–2.04(m,1H),1.62–1.55(m,2H),1.54–1.45(m,2H),0.99–0.91(m,1H),0.82–0.76(m,2H),0.53–0.46(m,2H).
化合物191收率:77％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝9.2Hz,1H),7.09(d,J＝9.2Hz,1H),4.06–3.98(m,2H),3.98–3.91(m,2H),3.62(s,3H),3.59(s,3H),3.38–3.29(m,2H),3.23(s,6H),2.75(s,3H),2.19(s,3H),2.11–2.01(m,1H),1.59–1.41(m,4H),
化合物192收率:66％.1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.09(d,J＝8.8Hz,1H),4.06–3.98(m,2H),3.98–3.91(m,2H),3.62(s,3H),3.59(s,3H),3.38–3.29(m,2H),3.19(q,J＝7.2Hz,2H),3.06(q,J＝7.2Hz,2H),2.75(s,3H),2.19(s,3H),2.11–2.01(m,1H),1.59–1.41(m,4H),1.08(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H).
化合物193收率:69％.1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.8Hz,1H),7.03(d,J＝8.8Hz,1H),4.06–3.98(m,2H),3.98–3.91(m,2H),3.62(s,3H),3.59(s,3H),3.38–3.29(m,2H),3.19(q,J＝7.2Hz,2H),3.06(q,J＝7.2Hz,2H),2.75(s,3H),2.11–2.01(m,1H),1.59–1.41(m,4H),1.08(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H),0.99–0.91(m,1H),0.82–0.76(m,2H),0.53–0.46(m,2H).
化合物194收率:88％.,1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.8Hz,1H),7.09(d,J＝8.8Hz,1H),4.06–3.99(m,2H),3.98–3.91(m,2H),3.62(s,3H),3.59(s,3H),3.38–3.29(m,2H),3.23(s,3H),3.07(q,J＝7.2Hz,2H),2.75(s,3H),2.20(s,3H),2.12–2.02(m,1H),1.59–1.41(m,4H),1.17(t,J＝12.8Hz,3H).
化合物195收率:81％.,1H NMR(400MHz,CDCl3)δ7.49(d,J＝8.8Hz,1H),7.08d,J＝8.8Hz,1H),4.06–3.99(m,2H),3.98–3.91(m,2H),3.62(s,3H),3.59(s,3H),3.38–3.17(m,6H),3.11–2.98(m,1H),2.75(s,3H),2.20(s,3H),2.12–2.02(m,1H),1.65–1.41(m,6H),0.87(t,J＝7.2Hz,3H).
本发明还提供如下3个对比化合物：
化合物D1收率:65％.1H NMR(600MHz,CDCl3)δ7.54(d,J＝8.4Hz,1H),7.37(dt,J＝3.2,1.4Hz,2H),7.36–7.32(m,2H),7.17(d,J＝7.2Hz,1H),3.68(s,3H),3.66(s,3H),2.76(s,3H),2.18(s,3H),1.79(s,3H).
化合物D2收率:92％.1HNMR(600MHz,CDCl3)δ7.88(d,J＝7.8Hz,2H),7.63(dd,J＝8.4,8.4Hz,1H),7.54–7.45(m,3H),7.36–7.31(m,3H),7.20–7.12(m,2H),3.77(s,3H),3.63(s,3H),2.68(s,3H),2.16(s,3H),1.80(s,3H).
化合物D3收率89％，1HNMR(600MHz,CDCl3)δ7.86(d,J＝7.0Hz,2H),7.61(t,J＝7.8Hz,1H),7.52–7.45(m,3H),7.36–7.31(m,3H),7.17(d,J＝8.4Hz,1H),7.14(d,J＝6.0Hz,1H),5.83(s,2H),3.84(s,3H),3.62(s,3H),2.69(s,3H),2.15(s,3H),1.80(s,3H).
测试例
初筛试验(盆栽法)：供试靶标为如表2-表6中所示。
苗后茎叶喷雾：取内径7cm纸杯，装复合土(菜园土：育苗基质，1：2，v/v)至3/4处，直接播种杂草，覆土0.2cm，待长至4-5叶期备用。本发明的化合物和前述对比化合物D1、D2、D3均按照12克/亩的剂量在自动喷雾塔施药后，待作物叶面药液晾干后移入温室培养(25度-28度，湿度70％)，30天后调查结果。
生长抑制率评价方法为目测法，具体根据表1所示的情况进行评级，测试结果如表2-表6中所示。
表1
(％) 评价(抑制、畸形、白化等) 生长抑制率级别
0-5 对杂草或作物生长无影响，无药效症状。 0
5-29 对杂草或作物生长有轻微影响，无明显药效症状 1
30-49 对杂草或作物生长有抑制，无明显药效症状。 2
50-69 对杂草或作物长有影响，有明显药效症状。 3
70-89 杂草或作物受到严重生长抑制。 4
80-100 杂草或作物死亡。 5
表2
表3：部分化合物对玉米的安全性评价
表4：部分化合物对小麦的安全性评价
表5：部分化合物对籼稻的安全性评价
表6：部分化合物对粳稻的安全性评价
由上述结果可知，本发明的化合物在除草测试实验中，对常见的禾本科和阔叶杂草均表现出良好的除草活性，特别对稗草和狗尾草具有很好的防治效果，与对照药剂D1、D2、D3具有相当的除草活性。
同时，本发明的化合物对玉米、小麦安全，进一步地，本发明中连接了氨基甲酸酯片段后的化合物对两种水稻(籼稻和粳稻)也非常安全，作物安全性明显优于对照化合物，能够用于水稻田防除稗草等恶性杂草。
并且，对照药剂D1、D2和D3对测试籼稻和粳稻不具有安全性，几乎完全抑制，不能用于水稻田进行杂草防治。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (10)

1.一种吡唑喹唑啉二酮类化合物，该化合物具有式(I)所示的结构，
其中，在式(I)中，
X选自C1-12的烷基、由1-6个选自卤素的原子取代的C1-12的烷基、由C1-3的烷氧基取代的C2-12的烷基、C2-12的烯基、C2-12的炔基、含有选自O、N、S中的至少一种杂原子的C2-12的环烷基、由含有选自O、N、S中的至少一种杂原子的C2-6的环烷基取代的C3-12的烷基；
Y选自H、C1-6的烷基；
Z为H或式(I-1)所示的基团，其中，在式(I-1)中，R1和R2相同或不同，各自独立地选自C1-6的烷基。
2.根据权利要求1所述的化合物，其中，在式(I)中，
X选自C1-8的烷基、由1-6个选自卤素的原子取代的C1-8的烷基、由C1-3的烷氧基取代的C2-8的烷基、C2-8的烯基、C2-8的炔基、含有至少一个O原子的C2-8的环烷基、由含有至少一个O原子的C2-6的环烷基取代的C3-8的烷基；
Y选自H、C1-4的烷基；
Z为H或式(I-1)所示的基团，其中，在式(I-1)中，R1和R2相同或不同，各自独立地选自C1-4的烷基。
3.根据权利要求1或2所述的化合物，其中，在式(I)中，Z为H。
4.根据权利要求1或2所述的化合物，其中，在式(I)中，Z为式(I-1)所示的基团，且在式(I-1)中，R1和R2相同或不同，各自独立地选自C1-3的烷基。
5.根据权利要求1所述的化合物，其中，所述吡唑喹唑啉二酮类化合物选自以下化合物中的至少一种：
6.权利要求1-5中任意一项所述的吡唑喹唑啉二酮类化合物在防治杂草中的应用；
优选地，所述杂草选自阔叶杂草、禾本科杂草和莎草科杂草中的至少一种。
7.权利要求1-5中任意一项所述的吡唑喹唑啉二酮类化合物作为农药除草剂的应用。
8.一种农药除草剂，该农药除草剂由活性成分和辅料组成，所述活性成分包括权利要求1-5中任意一项所述的吡唑喹唑啉二酮类化合物中的至少一种。
9.根据权利要求8所述的农药除草剂，其中，所述活性成分的含量为1～99.9999重量％。
10.根据权利要求8或9所述的农药除草剂，其中，所述农药除草剂的剂型选自乳油、悬浮剂、可湿性粉剂、粉剂、粒剂、水剂、毒饵、母液和母粉中的至少一种。
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WO2017140612A1 (de) * 2016-02-18 2017-08-24 Bayer Cropscience Aktiengesellschaft Chinazolindion-6-carbonylderivate und ihre verwendung als herbizide
CN106146414A (zh) * 2016-07-07 2016-11-23 浙江大学 喹唑啉二酮类衍生物及其制备方法和用途
CN110357862A (zh) * 2018-04-11 2019-10-22 山东先达农化股份有限公司 含喹唑啉二酮片段的吡唑类衍生物及其应用和一种农药除草剂
CN110357859A (zh) * 2018-04-11 2019-10-22 山东先达农化股份有限公司 一种含不饱和基的喹唑啉二酮类化合物及其应用和一种农药除草剂

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