CN109593088A - 氮杂双环衍生物及其制备和应用 - Google Patents

氮杂双环衍生物及其制备和应用 Download PDF

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CN109593088A
CN109593088A CN201811610407.0A CN201811610407A CN109593088A CN 109593088 A CN109593088 A CN 109593088A CN 201811610407 A CN201811610407 A CN 201811610407A CN 109593088 A CN109593088 A CN 109593088A
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CN109593088B (zh
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宋恭华
李晖
王佳毅
胡俊杰
王铭铭
杨天骄
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Abstract

本发明公开了一种氮杂双环衍生物及其制备和应用，本发明的氮杂双环衍生物具有式I所示的结构，其中各取代基的定义如说明书和权利要求书所述。本发明的化合物对线虫具有优异的杀灭作用。

Description

氮杂双环衍生物及其制备和应用
技术领域
本发明属于农药领域。具体地，本发明涉及一种氮杂双环衍生物及其制备和应用，具体地，是作为杀线虫剂的应用。
背景技术
线虫导致包括粮食和经济作物的农产品的重大损失，并且对抗具有杀线虫活性的化合物。
许多线虫已经成功演化为动植物的寄生虫，在农业，畜牧业造成了巨大的经济损失，据保守估计，植物寄生线虫在世界范围内每年对农林业造成的经济损失达1000亿美元。目前只有少数化学药剂可有效防治线虫的危害。例如：溴甲烷，1,3-二氯丙烯，有机磷和氨基甲酸酯类杀线虫剂。但这些商品化的杀线虫剂都是高毒化合物，对环境造成严重的破坏。
5-HT3受体主要为门控阳离子通道，2000年Ranganathan,R.等克隆出秀丽隐杆线虫 (Caenorhabditis elegans)体内具有通过门控氯离子通道来调节线虫行为功能的5-羟色胺受体 (5-HT3Ce)。该门控阴离子通道，控制线虫的摄食行为，有着不同于所哺乳动物5-HT受体的新药理学特征，5-HT3Ce对人5-HT3受体的专一配体无响应，相反，它对三环类哺乳动物 5-HT2受体配体米安舍林(Mianserin)和美赛西平(Methiothepin)有响应。这个结果说明秀丽隐杆线虫中存在着一类与人5-HT3A和5-HT3B截然不同的5-羟色胺能门控离子通道。专利 WO01/61000报道了从线虫中克隆的与哺乳动物5-HT3受体同源性较高的受体蛋白单元，该受体蛋白与线虫的咽泵有着关联。哺乳动物5-HT3受体的选择性配体MDL 72222对该泵收缩频率有着生物学影响。同时，测试结果发现MDL 72222展现出对线虫、棉铃虫(Hemiptera armigera)和蚜虫(Myzus persicae)的存活和生长控制的活性。然而，本领域在这方面的研究还不是很多。
发明内容
本发明的目的是提供一类结构新颖的氮杂双环的衍生物。
本发明的另一目的是提供上述化合物的制法和用途，尤其是在杀线虫领域中的应用，从而起到保护植物的作用。
本发明的第一方面，提供一种氮杂双环衍生物或其农药学上可接受的盐，所述氮杂双环衍生物具有式I所示的结构：
式中，R1为取代的或未取代的C5～C10芳基-C1～C15烷基、氢、或取代的或未取代的 C1～C15烷基；所述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基；
Y为S；Z为C或N；
当Z为N时，R2不存在，R3为取代的或未取代的C1～C15烷基、取代的或未取代的 C5～C10芳基、或取代的或未取代的4-8元杂芳基；当Z为C时，R3为氢，R2为取代的或未取代的C1～C15烷基、取代的或未取代的C5～C10芳基、或取代的或未取代的4-8元杂芳基，上述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基；
X为O、S或NH时，为X为亚砜基(-SO-)、砜基(-SO2-)时，为
各n1独立为2或3；各n2独立为2或3。
在另一优选例中，所述的氮杂双环衍生物具有以下结构：
X1为亚砜基(-SO-)、砜基(-SO2-)；
X2为O、S或NH；
R1定义同前，优选为C6～C10芳基-C1～C2烷基、氢、或C1～C4烷基；
当Z为N时，R2不存在，R3为取代的或未取代的C6～C10芳基或取代的或未取代的 4-8元杂芳基；当Z为C时，R3为氢，R2为取代的或未取代的C6～C10芳基或取代的或未取代的4-8元杂芳基，上述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6 烷氧基羰基。
在另一优选例中，所述的氮杂双环衍生物选自下组：
R1、R2和R3的定义如前所述。
在另一优选例中，R1为取代的或未取代的C1～C6烷基、取代的或未取代的C5～C10芳基、取代的或未取代的C5～C10芳基-C1～C6烷基。在另一优选例中，R1为C6～C10芳基 -C1～C2烷基、氢、或取代的或未取代的C1～C4烷基。所述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、卤代C1～C4烷基、C1～C4烷氧基、羧基或C1～C6烷氧基羰基。
在另一优选例中，R1为甲基、苄基。
在另一优选例中，当Z为N时，R2不存在，R3为取代的或未取代的C6～C10芳基，上述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、 C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基。
在另一优选例中，当Z为C时，R3为氢，R2为取代的或未取代的C6～C10芳基，上述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、 C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基。
在另一优选例中，R2为取代的或未取代的苯基、取代的或未取代的吡啶基、取代的或未取代的异丙基、取代的或未取代的呋喃基。在另一优选例中，R2、R3为甲基、取代的或未取代的苯基、取代的或未取代的呋喃基、取代的或未取代的噻吩基、取代的或未取代的吡啶基。在另一优选例中，R3为取代的或未取代的苯基、取代的或未取代的吡啶基、取代的或未取代的异丙基、取代的或未取代的萘基、取代的或未取代的呋喃基、取代的或未取代的苯基-异噁唑基、取代的或未取代的吡啶-异噁唑基、取代的或未取代的呋喃-异噁唑基、取代的或未取代的噻吩-异噁唑基、取代的或未取代的甲基-异噁唑基、取代的或未取代的乙基-异噁唑基。所述取代的是指被选自下组的一个或多个取代基所取代：氟原子、氯原子、溴原子、硝基、甲基、甲氧基、三氟甲基。
上述取代是指被选自下组的一个或多个(优选1个、2个、3个或4个)取代基所取代：氰基、甲基、甲氧基、碘、溴、氯、氟、硝基、乙酰基、三氟甲基、苯基。
在另一优选例中，所述的氮杂双环衍生物为选自下组的任一化合物：A1-1～A1-20、 A2-1～A2-20、B1-1～B1-19、B2-1～B2-42、B3-1～B3-23。
本发明的第二方面，提供一种农药组合物，包含：
(a)第一方面所述氮杂双环衍生物或其农药学上可接受的盐；和
(b)农药学上可接受的载体。
在另一优选例中，所述组合物还含有其它活性物质，所述其它活性物质选自：杀虫剂、饵剂、杀菌剂、杀螨剂、杀线虫剂、杀真菌剂或生长控制剂。
本发明的第三方面，提供一种氮杂双环衍生物或其农药学上可接受的盐的用途，用于杀线虫或者用于制备杀线虫组合物，其中所述氮杂双环衍生物具有式I所示的结构：
式中，R1为取代的或未取代的C5～C10芳基-C1～C15烷基、氢、或取代的或未取代的 C1～C15烷基；所述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基；
Y为S；Z为C或N；
当Z为N时，R2不存在，R3为取代的或未取代的C1～C15烷基、取代的或未取代的 C5～C10芳基、或取代的或未取代的4-8元杂芳基；当Z为C时，R3为氢，R2为取代的或未取代的C1～C15烷基、取代的或未取代的C5～C10芳基、或取代的或未取代的4-8元杂芳基，上述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基；
X为O、S、NH、亚砜基(-SO-)或砜基(-SO2-)；
为n1为2或3；n2为2或3。
在另一优选例中，所述线虫为松材线虫。
在另一优选例中，所述氮杂双环衍生物具有下式：
式A和式B中各取代基的定义同前；
对于式C，n3为2；
X3为O、S或是NH；Y为S；
Z为C或N；
当Z为N时，R2不存在；当Z为C时，R3为氢；
R4为氢、取代的或未取代的C1～C15烷基；
其中，所述R4中，所述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6 烷氧基羰基；
R2、R3为取代的或未取代的C1～C15烷基、取代的或未取代的C5～C10芳基、或取代的或未取代的4-8元杂芳基；
其中，所述R2中，所述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6 烷氧基羰基；
在另一优选例中，所述氮杂双环衍生物选自下组：
式中R1、R2、R3定义同前；
R4为氢、取代的或未取代的C1～C15烷基；所述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6 烷氧基、羧基或C1～C6烷氧基羰基。
在另一优选例中，R4为甲基；
R2、R3为甲基、取代的或未取代的苯基、取代的或未取代的呋喃基、取代的或未取代的噻吩基、取代的或未取代的吡啶基；
其中，所述取代的是指被选自下组的一个或多个取代基所取代：氟原子、氯原子、溴原子、硝基、甲基、甲氧基、三氟甲基。
在另一优选例中，所述的氮杂双环衍生物为选自下组的任一化合物：A1-1～A1-20、A2-1～A2-20、B1-1～B1-19、B2-1～B2-42、B3-1～B3-23、C1-1～C1-22、C2-1～C2-23、C3-1～C3-20、 C4-1～C4-29。
本发明的第四方面，提供一种氮杂双环衍生物的制备方法，
所述方法(a)包括步骤：
(1)在惰性溶剂中，将化合物a1和a2进行反应，得到化合物C3。
(2)在惰性溶剂中，将化合物C3和氧化剂反应，得到化合物A1。
(3)在惰性溶剂中，将化合物A1和氧化剂反应，得到化合物A2。
或所述方法(b)包括步骤：
在惰性溶剂中，将化合物b1和b2进行反应，得到化合物C4。
或所述方法(c)包括步骤：
在惰性溶剂中，将化合物c1和c2进行反应，得到化合物B1。
或所述方法(d)包括步骤：
在惰性溶剂中，将化合物d1和d2进行反应，得到化合物B2。
或所述方法(e)包括步骤：
在惰性溶剂中，将化合物e1和e2进行反应，得到化合物B3。
或所述方法(f)包括步骤：
在惰性溶剂中，将化合物f1和f2进行反应，得到化合物C1。
或所述方法(g)包括步骤：
在惰性溶剂中，将化合物g1和g2进行反应，得到化合物C2。
本发明的第五方面，提供一种杀线虫和/或预防线虫方法，所述方法包括将第一方面所述氮杂双环衍生物或其农药学上可接受的盐或第二方面所述组合物施加于遭受或可能遭受虫害的植物体或其周围的土壤或环境中。
在另一优选例中，所述线虫为松材线虫。
在另一优选例中，所述氮杂双环衍生物或其农药学上可接受的盐或所述农药组合物的施用浓度为0.05-200ppm；较佳地，为0.1-100ppm；更佳地，为0.5-50ppm。
应理解，在本发明范围内中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
具体实施方式
本发明人经过广泛而深入的研究，首次合成了一类结构新颖的氮杂双环类衍生物，这类化合物具有优异的杀线虫活性，有助于线虫五羟色胺受体的进一步研究。在此基础上，发明人完成了本发明。
术语
术语“C1～C15烷基”指具有1-15个碳原子的直链或支链的烷基，例如甲基、乙基、丙基、异丙基、1-丁基、2-丁基、戊基、己基、庚基、辛基、壬基、癸基或类似基团。可优选为C1～C6烷基或C1～C3烷基。
术语“C1～C15烷氧基”指具有1-15个碳原子的直链或支链的烷氧基，例如甲氧基、乙氧基、丙氧基、异丙氧基、1-丁氧基、2-丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基或类似基团。可优选为C1～C6烷氧基或C1～C3烷氧基。
术语“C5～C10芳基”指具有5-10个碳原子的具有芳香性的基团，例如苯基、萘基或类似基团。
术语“4-8元杂芳基”指环原子数为4-8、具有一个或多个选自氮、氧和硫的杂原子的芳香基，例如吡啶基、苯并吡啶基、吡咯基、苯并吡咯基、苯并噻吩基、噻吩基、苯并呋喃基、呋喃基、噻唑基、苯并噻唑基、吲哚基、吡嗪基，嘧啶基，哒嗪基、喹啉基、吖啶基或类似基团。
术语“卤素”为氟、氯、溴、碘。所述“卤代”为氟代、氯代、溴代、碘代。
制备方法
下面更具体地描述本发明化合物的制备方法，但这些具体方法不对本发明构成任何限制。本发明化合物还可以任选将在本说明书中描述的或本领域已知的各种合成方法组合起来而方便的制得，这样的组合可由本发明所属领域的技术人员容易的进行。
通常，在制备流程中，各反应通常在惰性溶剂中，在室温至回流温度(如20℃～160℃，优选50℃～120℃)下进行。反应时间通常为1小时-10小时，较佳地为2-4小时。
一优选例中，以化合物(A1)为例，说明本发明化合物的制备方法。所述方法(a)包括步骤：在惰性溶剂(如二氯甲烷、四氢呋喃、N,N-二甲酰胺、二氧六环、二氯乙烷、氯仿等)中，将化合物a1和a2进行反应，从而得到化合物(C3)；在惰性溶剂(如二氯甲烷、四氢呋喃、N,N-二甲酰胺、二氧六环、二氯乙烷、氯仿等)中，将化合物C3和氧化剂(如双氧水、间氯过氧苯甲酸、氧气、高锰酸钾等)进行反应，从而得到化合物(A1)；在惰性溶剂(如二氯甲烷、四氢呋喃、N,N-二甲酰胺、二氧六环、二氯乙烷、氯仿等)中，将化合物A1和氧化剂(如双氧水、间氯过氧苯甲酸、氧气、高锰酸钾等)进行反应，从而得到化合物(A2)；
式中，R1、R2、R3和R4定义同前
一优选例中，以化合物(A2)为例，说明本发明化合物的制备方法。所述方法(b)包括步骤：在惰性溶剂(如二氯甲烷、四氢呋喃、N,N-二甲酰胺、二氧六环、二氯乙烷、氯仿等)中，将化合物A1和氧化剂(如双氧水、间氯过氧苯甲酸、氧气、高锰酸钾等)进行反应，从而得到化合物(A2)；
式中，R1、R2定义同前。
一优选例中，以化合物(B1)为例，说明本发明化合物的制备方法。所述方法(c)包括步骤：在惰性溶剂(如二氯甲烷、四氢呋喃、N,N-二甲酰胺、二氧六环、二氯乙烷、氯仿等)中，将化合物c1和c2进行反应，从而得到化合物(B1)；
式中，R1、R2定义同前
一优选例中，以化合物(B2)为例，说明本发明化合物的制备方法。所述方法(d)包括步骤：在惰性溶剂(如二氯甲烷、四氢呋喃、N,N-二甲酰胺、二氧六环、二氯乙烷、氯仿等)中，将化合物d1和d2进行反应，从而得到化合物(B2)；
式中，R1、R3定义同前
一优选例中，以化合物(B3)为例，说明本发明化合物的制备方法。所述方法(e)包括步骤：在惰性溶剂(如二氯甲烷、四氢呋喃、N,N-二甲酰胺、二氧六环、二氯乙烷、氯仿等)中，将化合物e1和e2进行反应，从而得到化合物(B3)；
式中，R1、R3定义同前
一优选例中，以化合物(C1)为例，说明本发明化合物的制备方法。所述方法(f)包括步骤：在惰性溶剂(如二氯甲烷、四氢呋喃、N,N-二甲酰胺、二氧六环、二氯乙烷、氯仿等)中，将化合物f1和f2进行反应，从而得到化合物(C1)；
式中，R1、R2和R4定义同前
一优选例中，以化合物(C2)为例，说明本发明化合物的制备方法。所述方法(g)包括步骤：在惰性溶剂(如二氯甲烷、四氢呋喃、N,N-二甲酰胺、二氧六环、二氯乙烷、氯仿等)中，将化合物g1和g2进行反应，从而得到化合物(C2)；
式中，R1、R2和R4定义同前
一优选例中，以化合物(C4)为例，说明本发明化合物的制备方法。所述方法(h)包括步骤：在惰性溶剂(如二氯甲烷、四氢呋喃、N,N-二甲酰胺、二氧六环、二氯乙烷、氯仿等)中，将化合物h1和h2进行反应，从而得到化合物(C4)；
式中，R1、R3和R4定义同前
一优选例中，化合物a1按照如下方法制得：
(1)以化合物a1-1为起始原料，在惰性溶剂(如二氯甲烷、四氢呋喃、N,N-二甲酰胺、二氧六环、二氯乙烷、氯仿等)中，在碱性条件(如NaOAc、氢氧化钠、碳酸钾、碳酸钠、三乙胺、氢氧化钾等)下，碘甲烷，反应得化合物a1-2。
(2)化合物a1-2加入氨气，在惰性溶剂(乙醇、甲醇、异丙醇、水、乙腈等)中回流得到化合物a1。
一优选例中，化合物c1按照如下方法制得：
(1)化合物c1-1为起始原料，在惰性溶剂(如甲醇、乙腈、DMF、异丙醇、乙醇等) 中，在碱性条件(如碳酸钾、氢氧化钠、碳酸钠、三乙胺、氢氧化钾等)下与将多聚甲醛反应，得到化合物c1-2。
(2)在惰性溶剂(如乙腈、甲醇、异丙醇、乙醇、DMF等)中，将化合物c1-2和环戊酮反应，得到化合物c1-3。
(3)在惰性溶剂(如乙腈、甲醇、异丙醇、乙醇、DMF等)中，将化合物c1-3和还原剂(三乙酰氧基硼氢化钠、醋酸硼氢化钠、硼氢化钠、三氟化硼乙醚溶液等)反应，得到化合物c1。
农药组合物
术语“本发明的活性物质”或“本发明的活性化合物”是指本发明化合物或其农药学上可接受的盐。
所述农药学上可接受的盐可以包括无机盐、有机酸盐、碱性氨基酸或酸性氨基酸的盐。本发明中无机酸盐包括例如：盐酸、氢硼酸、硝酸、硫酸或磷酸。本发明中有机酸包括例如：乳酸、甲酸、乙酸(即醋酸)、三氟乙酸、延胡索酸、草酸、马来酸、柠檬酸、琥珀酸、苹果酸、甲磺酸、苯磺酸、或对甲苯磺酸。酸性氨基酸包括例如：甘氨酸、天冬氨酸、或谷氨酸。
本发明的活性物质能用作控制和消灭广泛的农林植物害虫、贮藏谷类的害虫、危害动物健康的害虫以及公共卫生害虫等。在本说明书中，“杀虫剂”是具有防治上述提到的所有害虫的作用的物质的统称。
本发明化合物尤其对线虫有特效。
可将本发明的活性物质以常规的方法制备成杀虫剂组合物。这些活性化合物可做成常规的制剂，例如溶液剂，乳剂，混悬剂，粉剂，泡沫剂，糊剂，颗粒剂，气雾剂等制剂。
这些制剂可用已知的方法生产，例如，将活性化合物与扩充剂混合，这些扩充剂就是液体的或液化气的或固体的稀释剂或载体，并可任意选用表面活性剂即乳化剂和/或分散剂和/或泡沫形成剂。例如在用水作扩充剂时，有机溶剂也可用作助剂。
用液体溶剂作稀释剂或载体时，基本上是合适的，如：芳香烃类，例如二甲苯，甲苯或烷基萘；氯化的芳香或氯化的脂肪烃类，例如氯苯，氯乙烯或二氯甲烷；脂肪烃类，例如环己烷或石蜡，例如矿物油馏分；醇类，例如乙醇或乙二醇以及它们的醚和脂类；酮类，例如丙酮，甲乙酮，甲基异丁基酮或环已酮；或不常用的极性溶剂，例如二甲基甲酰胺和二甲基亚砜，以及水。
就液化气的稀释剂或载体说，指的是在常温常压下将成为气体的液体，例如气溶胶推进剂，如卤化的烃类以及丁烷，丙烷，氮气和二氧化碳。
固体载体可用磨碎的天然的矿物质，例如高岭土，粘土，滑石，石英，活性白土，蒙脱土，或硅藻土，和磨碎的合成的矿物质，例如高度分散的硅酸，氧化铝和硅酸盐。供颗粒用的固体载体是碾碎的和分级的天然告石，例如方解石，大理石，浮石，海泡石和白云石，以及无机和有机粗粉合成的颗粒，和有机材料例如锯木屑，椰子壳，玉米棒子和烟草梗的颗粒等。
非离子的和阴离子的乳化列可用作乳化剂和/或泡沫形成剂。例如聚氧乙烯-脂肪酸酯类，聚氧乙烯-脂肪醇醚类，例如烷芳基聚乙二醇醚类，烷基磺酸酯类，烷基硫酸酯类，芳基磺酸酯类以及白蛋白水解产物。分散剂包括，例如木质素亚硫酸盐废液和甲基纤维素。
在制剂中可以用粘合剂，例如羧甲基纤维素和以粉末，颗粒或乳液形式的天然和合成的多聚物，例如阿拉伯胶，聚乙烯基醇和聚乙烯醋酸酯。
可以用着色剂例如无机染料，如氧化铁，氧化钻和普鲁士蓝；有机染料，如有机染料，如偶氯染料或金属钛菁染料；和用痕量营养剂，如铁，猛，硼，铜，钴，铝和锌的盐等。
这些制剂通常含有占所述杀虫剂组合物0.001-99.99重量％，优选0.01-99.9重量％，更优选0.05-90重量％的本发明的活性化合物。从商品制剂制成使用剂型中的活性化合物的浓度可在广阔的范围内变动。使用剂型中的活性化合物的浓度可从0.0000001-100％(g/v)，最好在0.0001与1％(g/v)之间。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数按重量计算。
实施例1：中间体a1的合成
(1)将0.157g(1mmol)托品硫醇，60％钠氢0.06(1.5mmol)溶于10mL无水THF中室温搅拌1h。加入0.15g(2mmol)二硫化碳温搅拌3h。加入0.284g(2mmol)碘甲烷室温搅拌12h。反应结束后，减压除去有机溶剂得化合物3。
(2)将上一步得到的化合物3溶于10mL乙醇中，加入2mL氨水，回流反应5h。反应结束后除去溶剂，得到粗产物用柱层析分离，得到中间体a1 0.11g，反应总产率51％。
实施例2：中间体b1的合成
(1)将0.139(1mmol)托品醇、0.308g(2mmol)对甲苯磺酰甲基异腈、0.148g(2mmol)叔丁醇和0.224g(3mmol)叔丁醇钾溶于15mL无水THF中室温搅拌12h。反应结束后，减压除去有机溶剂得化合物2。
(2)将上一步得到的化合物2溶于1mL硫化氢水溶液，加入9mL吡啶，55℃反应24h。反应结束后除去溶剂，得到粗产物用柱层析分离，得到中间体b1 0.127g，反应总产率69％。
实施例3：中间体c1的合成
(1)在100mL圆底烧瓶中，分别加入4.32g(40mmol)苄胺，3g(100mmol)多聚甲醛和9.92g(160mmol)乙二醇，60mL环己烷，油浴加热回流过夜。反应结束后，用去离子水、饱和食盐水各10mL洗涤2次，无水MgSO4除水，减压除去溶剂得化合物 1。
(2)在100mL圆底烧瓶中加入1.68g(20mmol)环戊酮和30mL的甲醇，置于冰浴中冷却至0℃。加入6.48g(60mmol)三甲基氯硅烷和0.3g(0.3mmol)浓硫酸，搅拌15min。然后，缓慢滴加溶于10mL甲醇中的化合物1，GC跟踪反应，2小时后反应基本结束。用30％的NaOH溶液中和反应液，调pH至12或以上，用乙酸乙酯(3*10mL) 萃取，合并有机相浓缩得化合物2。
(3)将化合物2溶于10mL 3N的稀盐酸中，油浴加热至110℃反应2h。用30％的 NaOH溶液中和反应液，调pH至12，用乙酸乙酯(3*10mL)萃取，无水硫酸镁干燥，浓缩有机相后，通过柱层析得c1 3.5g，总产率70％。
实施例4：中间体f1的合成
(1)将0.140g(1mmol)托品氨，60％钠氢0.06(1.5mmol)溶于10mL无水THF中室温搅拌1h。加入0.15g(2mmol)二硫化碳温搅拌3h。加入0.284g(2mmol)碘甲烷室温搅拌12h。反应结束后，减压除去有机溶剂得化合物3。
(2)将上一步得到的化合物3溶于10mL乙醇中，加入2mL氨水，回流反应5h。反应结束后除去溶剂，得到粗产物用柱层析分离，得到中间体f1 0.131g，反应总产率66％。
实施例5：中间体g1的合成
(1)将0.141g(1mmol)托品氨，60％钠氢0.06(1.5mmol)溶于10mL无水THF中室温搅拌1h。加入0.15g(2mmol)二硫化碳温搅拌3h。加入0.284g(2mmol)碘甲烷室温搅拌12h。反应结束后，减压除去有机溶剂得化合物3。
(2)将上一步得到的化合物3溶于10mL乙醇中，加入2mL氨水，回流反应5h。反应结束后除去溶剂，得到粗产物用柱层析分离，得到中间体f1 0.094g，反应总产率47％。
实施例6：氮杂双环噻唑硫醚类化合物合成C3-1
将0.216g(1mmol)中间体a1、0.199g(1mmol)溴代苯乙酮溶于15mL无水乙醇中，回流反应3h，TLC点板跟踪。反应结束后除去溶剂，得到粗产物用柱层析分离，得到化合物C3-1，收率78％。1H NMR(400MHz,CDCl3)δ7.76(d,J＝5.5Hz,1H),7.41–7.19(m,4H),4.07– 3.89(m,1H),3.48(s,2H),2.47(s,3H),2.29–2.03(m,6H),1.81(d,J＝10.5Hz,2H).13C NMR(101MHz,CDCl3)δ161.53,154.34,132.96,127.76,127.26,125.16,112.17,61.17,37.46,37.07,34.98,24.63.
实施例7：氮杂双环噻唑亚砜类化合物合成A1-1
将0.316g(1mmol)化合物C3-1、0.051g(1.5mmol)双氧水溶于15mL醋酸中，室温反应12h，TLC点板跟踪。反应结束后除去溶剂，得到粗产物用柱层析分离，得到化合物A1-1，收率82％。1H NMR(400MHz,DMSO)δ8.53(s,1H),7.98(d,J＝7.3Hz,2H),7.51–7.39(m, 3H),3.47–3.35(m,1H),3.22(d,J＝18.0Hz,2H),2.16(s,3H),2.05–1.73(m,6H),1.61(t,J ＝9.2Hz,1H),1.44(t,J＝9.0Hz,1H).13C NMR(101MHz,DMSO)δ174.00,156.48,133.27,128.92,128.65,126.12,118.87,59.44,55.32,38.22,28.73,26.12,25.67.
实施例8：氮杂双环噻唑砜类化合物合成A2-1
将0.332g(1mmol)化合物A1-1、0.068g(2mmol)双氧水溶于15mL醋酸中，室温反应12h，TLC点板跟踪。反应结束后除去溶剂，得到粗产物用柱层析分离，得到化合物A2-1，收率82％。1H NMR(400MHz,DMSO)δ8.79(s,1H),8.03(d,J＝7.1Hz,2H),7.57–7.43(m, 3H),4.31–4.21(m,1H),3.73(s,2H),3.13(s,3H),2.50–2.32(m,4H),2.22–2.11(m,2H), 1.79(d,J＝7.5Hz,2H).13C NMR(101MHz,DMSO)δ161.63,155.83,131.40,128.07,127.92,125.26,121.70,70.09,50.03,46.20,27.01,24.28.
实施例9：氮杂双环噻唑醚类化合物合成B1-1
将0.705g(0.5mmol)中间体c1，加入5mL无水THF、0.1g(2.5mmol)60％NaH 常温搅拌0.5h后，再加入0.119g(0.5mmol)2-溴-4-苯基噻唑，油浴70℃反应5h左右， TLC跟踪，反应结束，冷却至室温，缓慢滴加甲醇除去多余的NaH，减压除溶后，通过柱层析得化合物B1-1，产率64％。1H NMR(400MHz,CDCl3)：δ7.79–7.67(m,2H),7.49–7.08 (m,8H),6.83(s,1H),4.98(t,J＝4.7Hz,1H),3.54(s,2H),2.63(d,J＝10.1Hz,2H),2.48(d,J ＝10.7Hz,4H),1.91(d,J＝7.1Hz,2H),1.81–1.67(m,2H)；13C NMR(100MHz,CDCl3)：δ 173.49,148.12,139.71,133.50,133.18,128.75,128.70,128.17,127.17,126.75,104.82,82.11, 62.15,52.66,36.35,24.69。
实施例10：氮杂双环噻二唑醚类化合物合成B2-1
将0.705g(0.5mmol)中间体d1，加入5mL无水THF、0.1g(2.5mmol)60％NaH 常温搅拌0.5h后，再加入2-氯-5-苯基-1,3,4-噻二唑，油浴70℃反应5h左右，TLC跟踪，反应结束，冷却至室温，缓慢滴加甲醇除去多余的NaH，减压除溶后，通过柱层析得化合物B2-1，产率73％。1HNMR(400MHz,CDCl3)：δ7.82(dt,J＝9.5,3.4Hz,2H),7.50-7.40(m, 3H),7.38-7.19(m,5H),5.09(t,J＝4.5Hz,1H),3.54(s,2H),2.60(d,J＝9.8Hz,2H),2.51(d,J ＝8.1Hz,4H),2.02-1.83(m,2H),1.72(m,J＝27.8,23.4Hz,2H)；13C NMR(100MHz,CDCl3)：δ174.37,162.30,139.51,130.88,130.57，129.04,128.69,128.18,127.07,126.80,83.48,62.13,52.54,36.26,24.52。
实施例11：氮杂双环噻二唑醚类化合物合成B3-1
将0.705g(0.5mmol)中间体e1，加入5mL无水THF、0.1g(2.5mmol)60％NaH 常温搅拌0.5h后，再加入2-氯-5-苯基-1,3,4-噻二唑，油浴70℃反应8h左右，TLC跟踪，反应结束，冷却至室温，缓慢滴加甲醇除去多余的NaH，减压除溶后，通过柱层析得化合物B3-1，产率52％。1H NMR(400MHz,CDCl3)δ7.83-7.80(m,2H),7.43-7.42(m,3H),5.07 (d,J＝3.7Hz,1H),2.96(d,J＝10.6Hz,1H),2.70(d,J＝10.6Hz,1H),2.63-2.48(m,2H),2.38 (d,J＝11.8Hz,1H),2.29(s,2H),2.16(s,3H),1.95(dd,J＝12.8,5.3Hz,2H),1.88-1.73(m, 1H),1.63(dd,J＝13.8,6.1Hz,1H),1.46(m,1H)；13C NMR(100MHz,CDCl3)δ174.21, 161.99,130.86,130.83,130.52,130.4,129.00,127.00,84.59,60.89,55.05,45.85,33.33,32.67,31.22,24.9,20.80
实施例12：氮杂双环噻唑亚胺类化合物合成C1-1
将0.199g(1mmol)中间体f1、0.199g(1mmol)溴代苯乙酮溶于15mL无水乙醇中，回流反应3h，TLC点板跟踪。反应结束后除去溶剂，得到粗产物用柱层析分离，得到化合物 C1-1，收率89％。1H NMR(400MHz,MeOD)δ7.77(d,J＝7.3Hz,2H),7.37(t,J＝7.6Hz,2H), 7.28(t,J＝7.3Hz,1H),6.67(s,1H),4.37–4.24(m,1H),3.87(s,2H),2.76(s,3H),2.43–2.21(m,6H),2.16(d,J＝8.7Hz,2H).13C NMR(101MHz,MeOD)δ172.55,151.74,132.45,127.90,126.26,124.47,113.90,64.00,39.82,37.96,33.43,25.94.
实施例13：氮杂双环噻唑醚类合物合成C2-1
将0.200g(1mmol)中间体g1、0.199g(1mmol)溴代苯乙酮溶于15mL无水乙醇中，回流反应3h，TLC点板跟踪。反应结束后除去溶剂，得到粗产物用柱层析分离，得到化合物C2-1，收率91％。1H NMR(400MHz,CDCl3)δ7.77(d,J＝7.3Hz,2H),7.38(t,J＝7.5Hz,2H),7.29(t,J＝7.3Hz,1H),6.89(s,1H),5.43(t,J＝4.4Hz,1H),3.79(s,2H),3.04(d,J＝15.9Hz,2H), 2.77(s,3H),2.46–2.23(m,6H).13C NMR(101MHz,CDCl3)δ171.98,149.18,134.11,128.62, 128.00,125.75,104.86,72.34,61.91,38.82,33.89,24.55.
实施例14：氮杂双环噻二唑醚类合物合成C4-1
将0.141g(1mmol)中间体h1，加入5mL无水THF、0.1g(2.5mmol)60％NaH常温搅拌0.5h后，再加入2-氯-5-苯基-1,3,4-噻二唑，油浴50℃反应2h左右，TLC跟踪，反应结束，冷却至室温，缓慢滴加甲醇除去多余的NaH，减压除溶后，通过柱层析得化合物C4-1，产率66％。1H NMR(400M Hz,CDCl3)δ：7.71-7.62(m,2H),7.52-7.43(m,3H),4.70 (tt,J＝8.5,2.2Hz,1H),3.51(s,2H),2.96-2.78(m,2H),2.55(s,3H),2.26-2.15(m,6H)；13C NMR(101MHz,CDCl3)δ：169.2,149.2,130.8,129.1,125.8,60.4,47.3,39.2,33.9,25.4。
按照上述实施例1～14所示方法，采用不同的起始原料制备如下化合物
1H NMR(400MHz,MeOD)δ7.68(d,J＝8.0Hz,2H),7.24(s,1H),7.20(d,J＝7.9Hz,2H),4.04–3.95(m,1H),3.41(s,2H),2.45(s,3H),2.37(s,3H),2.22–2.05(m,6H),1.81(d,J＝8.2Hz,2H).13C NMR(101MHz,MeOD)δ69.83,150.87,135.19,134.12,129.59,128.54,102.66,64.01,45.96,39.06,37.06,30.77,25.98.
1H NMR(400MHz,MeOD)δ8.21(s,1H),7.98(dd,J＝8.9,5.3Hz,2H),7.18(t,J＝8.8Hz,2H),3.70–3.47(m,3H),2.46(s,3H),2.32–2.11(m,4H),2.04(d,J＝13.3Hz,1H),1.86(t, J＝9.6Hz,1H),1.71(t,J＝9.5Hz,1H),1.45(d,J＝13.4Hz,1H).13C NMR(101MHz,MeOD)δ173.65,164.50(d,J＝247.2Hz),158.18,131.34,131.31,129.60(d,J＝8.3Hz),119.28,116.81(d,J＝22.0Hz),62.40,55.86,38.98,30.48,26.59.
1H NMR(400MHz,CDCl3)δ7.78–7.69(m,3H),7.33(d,J＝8.6Hz,2H),3.39(d,J＝15.6Hz,2H),3.34–3.23(m,1H),2.35(s,3H),2.32–2.15(m,2H),2.06(d,J＝8.1Hz,2H),1.76(d,J＝13.0Hz,1H),1.56(dd,J＝41.4,10.3Hz,2H),1.30(d,J＝13.2Hz,1H).1H NMR(400MHz,CDCl3)δ7.75,7.72,7.71,7.34,7.32,3.41,3.37,3.33,3.32,3.30,3.29,3.27,3.26, 3.24,2.35,2.30,2.27,2.24,2.21,2.17,2.07,2.05,1.78,1.75,1.62,1.60,1.52,1.49,1.32,1.28.
1H NMR(400MHz,MeOD)δ7.89(d,J＝8.6Hz,2H),7.71(s,1H),7.39(d,J＝8.6Hz,2H),3.78(s,2H),3.67–3.55(m,1H),2.66(s,3H),2.37–2.14(m,6H),2.05(d,J＝8.1Hz,2H).13C NMR(101MHz,MeOD)δ174.66,154.95,134.83,134.55,129.90,128.88,114.39,64.18,39.67,37.85,33.29,25.80.
1H NMR(400MHz,MeOD&CDCl3)δ7.79(s,1H),7.72(d,J＝6.7Hz,2H),6.86(d,J＝8.7Hz,2H),3.72(s,3H),3.55(d,J＝20.2Hz,2H),3.48–3.37(m,1H),2.41(s,3H),2.26–2.04(m,4H),1.95(d,J＝8.9Hz,1H),1.80–1.72(m,1H),1.66–1.58(m,1H),1.38(d,J＝12.4Hz,1H).13C NMR(101MHz,MeOD&CDCl3)δ173.02,161.69,159.34,129.08,127.58,117.53,115.54,62.69,56.32,55.67,39.08,30.37,26.75.
1H NMR(400MHz,MeOD)δ8.11(d,J＝8.2Hz,2H),7.92(s,1H),7.69(d,J＝8.4Hz,2H),3.91(s,2H),3.71–3.63(m,1H),2.76(s,3H),2.44–2.35(m,4H),2.23(d,J＝10.1,2H),2.12(d,J＝8.8Hz,2H).13C NMR(101MHz,MeOD)δ171.50,146.82,136.43,128.59(q,J＝32.3Hz),125.02,124.59(d,J＝7.5),123.16(q,J＝271.9Hz),105.98,72.08,60.73,38.59, 33.47,23.97.
1H NMR(400MHz,MeOD)δ8.06(d,J＝8.2Hz,2H),7.81(d,J＝8.2Hz,2H),7.63(s,1H),5.42(t,J＝4.6Hz,1H),3.77(s,2H),2.79(s,3H),2.55(d,J＝16.1Hz,2H),2.40–2.27(m, 6H).13C NMR(101MHz,MeOD)δ174.40,148.41,148.26,141.66,127.61,125.00,111.03,74.69,62.87,39.30,35.49,25.52.
1H NMR(400MHz,CDCl3)δ7.80(d,J＝7.8Hz,1H),7.35(d,J＝7.0Hz,1H),7.29–7.13(m,2H),5.31(t,J＝4.6Hz,1H),3.69(s,2H),2.90(d,J＝16.0Hz,2H),2.65(s,3H),2.37 –2.26(m,4H),2.23–2.18(dd,2H).13C NMR(101MHz,CDCl3)δ170.09,144.75,131.65,130.55,130.38,129.55,127.84,125.96,109.53,71.72,60.81,38.40,33.32,23.93.
1H NMR(400MHz,CDCl3)δ7.65(d,J＝7.9Hz,1H),7.58–7.49(m,2H),7.43–7.38(m,1H),6.82(s,1H),5.16(t,J＝4.4Hz,1H),3.80(s,2H),2.94(d,J＝15.7Hz,2H),2.73(s,3H), 2.38–2.24(m,6H).13C NMR(101MHz,CDCl3)δ174.41,154.23,147.77,134.10,131.06,128.99,122.33,120.31,118.07,58.99,58.85,55.21,36.92,27.64,25.40.
1H NMR(400MHz,CDCl3)δ8.12(dd,J＝7.6,1.7Hz,1H),7.40(s,1H),7.08(t,J＝7.6Hz,1H),6.82(t,J＝7.1Hz,1H),6.72(d,J＝8.2Hz,1H),5.35(t,J＝4.5Hz,1H),3.84(s,3H), 3.03(d,J＝15.8Hz,2H),2.73(s,3H),2.42–2.20(m,6H).13C NMR(101MHz,CDCl3)δ169.24,155.87,144.11,128.97,127.79,121.67,119.79,110.02,108.94,70.57,61.39,54.45, 38.35,32.90,23.79.
1H NMR(400MHz,MeOD)δ8.34(s,1H),8.15(t,J＝1.7Hz,1H),7.93(d,J＝7.3Hz,1H),7.53(d,J＝7.0Hz,1H),7.38(t,J＝7.9Hz,1H),3.85(d,J＝30.1Hz,2H),3.68(m,1H),2.65(s,3H),2.41–2.17(m,5H),2.03(t,J＝9.8Hz,1H),1.86(t,J＝9.8Hz,1H),1.58(d,J＝14.0Hz,1H).13C NMR(101MHz,MeOD)δ173.73,157.55,136.90,132.82,131.86,130.41,126.21,123.99,120.90,63.37,54.72,38.83,30.36,25.92.
1H NMR(400MHz,CDCl3)δ7.74(s,1H),7.58(d,J＝7.1Hz,1H),7.32(t,J＝7.2Hz,1H),7.15(d,J＝7.5Hz,1H),6.88(s,1H),5.43(t,J＝4.2Hz,1H),3.81(s,2H),3.10(d,J＝15.8Hz,2H),2.75(s,3H),2.44–2.20(m,9H).13C NMR(101MHz,CDCl3)δ170.75,148.50,137.36,133.00,127.90,127.55,125.57,121.85,103.78,70.77,61.43,38.36,32.97,23.80, 20.49.
1H NMR(400MHz,CDCl3)δ7.72(s,1H),7.58(d,J＝7.1Hz,1H),7.26–7.18(m,3H),4.10–3.92(m,1H),3.54(s,2H),2.53(s,3H),2.31(t,J＝13.0Hz,2H),2.25–2.15(m,2H),2.09(d,J＝12.2Hz,2H),1.87(d,J＝8.5Hz,2H).13C NMR(101MHz,CDCl3)δ163.07, 153.83,135.65,134.70,130.06,128.18,126.37,124.18,114.13,62.33,38.50,37.96,35.88,25.59.
1H NMR(400MHz,MeOD)δ8.54(t,J＝1.9Hz,1H),8.14–8.00(m,2H),7.52(t,J＝8.0Hz,1H),7.15(s,1H),5.36(t,J＝4.8Hz,1H),3.82(s,2H),2.82–2.61(m,5H),2.45–2.22(m,6H).13C NMR(101MHz,MeOD)δ171.92,147.80,146.00,135.09,130.83,128.92,121.62,119.71,106.98,71.71,61.15,33.35,28.78,23.66.
1H NMR(400MHz,CDCl3)δ7.91(d,J＝7.3Hz,1H),7.51(s,1H),7.27(t,J＝7.6Hz,1H),6.92–6.71(m,2H),4.00–3.87(m,1H),3.72(s,3H),3.57(s,2H),2.53(s,3H),2.39–2.06(m,6H),1.83(d,J＝8.6Hz,2H).13C NMR(101MHz,CDCl3)δ159.79,156.52,150.86,129.53,129.04,122.35,120.64,117.62,111.11,62.55,55.35,38.19,37.16,35.37,25.16.
1H NMR(400MHz,MeOD)δ8.21(s,1H),7.71(t,J＝8.3Hz,2H),7.46(t,J＝7.6Hz,1H),7.36–7.30(m,1H),3.78–3.58(m,3H),2.56(s,3H),2.41–2.09(m,5H),1.93(t,J＝9.8Hz,1H),1.77(t,J＝9.6Hz,1H),1.49(d,J＝13.8Hz,1H).13C NMR(101MHz,MeOD)δ 161.00,154.55,137.37,132.85,128.10,127.70,125.87,122.31,112.23,61.52,37.07,36.44,34.31,24.37,20.54.
1H NMR(400MHz,MeOD)δ7.82(d,J＝6.9Hz,1H),7.69(s,1H),7.50–7.38(m,3H),4.22(s,2H),3.70–3.58(m,1H),2.72(m,3H),2.40–2.29(m,7H),2.25–2.17(m,2H),2.08(d,J＝8.8Hz,2H).13C NMR(101MHz,MeOD)δ173.21,156.48,137.53,135.89,131.96,130.92,129.47,127.04,117.09,64.56,39.56,37.50,32.93,25.63,21.40.
1H NMR(400MHz,MeOD)δ7.81(d,J＝2.2Hz,1H),7.52(dd,J＝8.1,2.2Hz,1H),7.42(s,1H),7.30(d,J＝8.4Hz,1H),4.23–4.14(m,1H),3.71(s,2H),2.60(s,3H),2.32–2.17(m,6H),1.96(d,J＝8.9Hz,2H).13C NMR(101MHz,MeOD)δ164.13,154.34,135.28,134.15,133.33,132.12,129.39,126.74,116.66,64.50,39.59,38.48,37.26,26.26.
1H NMR(400MHz,CDCl3)δ7.73(d,J＝1.9Hz,2H),7.43(s,1H),7.20(t,J＝1.9Hz,1H),4.18–4.06(m,1H),3.69(s,2H),2.62(s,3H),2.44(t,J＝12.3Hz,2H),2.34–2.24(m,2H),2.18–2.09(m,2H),1.93(d,J＝8.8Hz,2H).13C NMR(101MHz,CDCl3)δ162.32, 151.40,135.57,134.33,126.94,123.56,114.28,61.67,37.40,36.48,34.53,24.32.
1H NMR(400MHz,CDCl3)δ7.79–7.68(m,3H),7.18(d,J＝7.9Hz,2H),3.78–3.63(m,1H), 3.44(s,2H),2.44–2.24(m,8H),2.10(d,J＝9.3Hz,2H),1.81(d,J＝12.1Hz,2H),1.61(d,J＝ 8.5Hz,2H).13C NMR(101MHz,CDCl3)δ161.85,157.60,138.36,129.09,128.64,125.59, 118.07,58.75,54.13,36.77,26.97,25.11,20.32.
1H NMR(400MHz,MeOD)δ7.86–7.80(m,2H),7.63(s,1H),7.25(t,J＝8.7Hz,2H),3.88(s,2H),3.62–3.52(m,1H),2.58(s,3H),2.33–2.08(m,6H),1.99(d,J＝8.1Hz,2H).13CNMR(101MHz,MeOD)δ175.05,163.06(d,J＝235.0Hz),157.15,134.35,129.34(d,J＝8.2Hz),116.50(d,J＝21.9Hz),113.48,63.85,39.81,38.09,33.52,25.99.
1H NMR(400MHz,CDCl3)δ7.89–7.84(m,3H),7.43(d,J＝8.6Hz,2H),3.76–3.66(m,1H),3.43(s,2H),2.36(s,3H),2.30(t,J＝12.9Hz,2H),2.16–2.10(m,2H),1.87(d,J＝11.3, 2H),1.64(d,J＝8.4Hz,2H).13C NMR(101MHz,CDCl3)δ163.48,157.30,135.28,131.30, 129.19,127.98,119.96,59.66,55.47,37.99,28.37,26.15.
1H NMR(400MHz,CDCl3)δ7.89(d,J＝8.6Hz,2H),7.71(s,1H),7.39(d,J＝8.6Hz,2H),3.78(s,2H),3.67–3.55(m,1H),2.66(s,3H),2.37–2.14(m,6H),2.05(d,J＝8.1Hz,2H).13C NMR(101MHz,CDCl3)δ174.66,154.95,134.83,134.55,129.90,128.88,114.39,64.18,39.67,37.85,33.29,25.80.
1H NMR(400MHz,CDCl3)δ7.86(d,J＝8.9Hz,2H),7.71(s,1H),6.97(d,J＝8.9Hz,2H),3.86(s,3H),3.77–3.66(m,1H),3.30(s,2H),2.29(s,3H),2.20–2.14(m,2H),2.09–2.03(m,2H),1.77(d,J＝11.5Hz,2H),1.56(d,J＝8.2Hz,2H).13C NMR(101MHz,CDCl3)δ163.34,160.45,158.29,128.06,125.73,117.79,114.31,59.53,55.76,55.40,38.40,28.43,26.45.
1H NMR(400MHz,MeOD)δ8.19(d,J＝8.0Hz,2H),7.96(s,1H),7.75(d,J＝8.0Hz,2H),4.10(s,2H),3.81–3.72(m,1H),2.76(s,3H),2.44–2.35(m,4H),2.23(d,J＝10.1,2H),2.12(d,J＝8.8Hz,2H).13C NMR(101MHz,MeOD)δ174.38,154.42,139.32,130.62(q,J＝32.3Hz),127.86,124.19(q,J＝3.8Hz),121.78(q,J＝256.3Hz),116.45,64.52,39.66,37.49, 33.09,25.68.
1H NMR(400MHz,CDCl3)δ8.27(d,J＝9.0Hz,2H),8.10(d,J＝9.0Hz,2H),7.84(s,1H),3.80(s,2H),3.70–3.55(m,1H),2.68(s,3H),2.43–2.35(m,4H),2.22(d,J＝16.6Hz,2H),2.08(d,J＝8.8Hz,2H).13C NMR(101MHz,CDCl3)δ175.21,153.91,148.52,141.73,128.27,125.39,117.71,64.02,40.21,37.90,33.68,26.31.
1H NMR(400MHz,CDCl3)δ7.97(s,1H),7.72(d,J＝7.1Hz,1H),7.65(s,1H),7.32–7.13(m,2H),3.44–3.31(m,3H),2.35(s,3H),2.18–1.87(m,6H),1.77(d,J＝8.5Hz,2H).13CNMR(101MHz,CDCl3)δ175.87,154.45,137.76,135.76,131.38,128.95,127.38,125.57,114.91,63.31,40.05,38.45,33.90,26.31.
1H NMR(400MHz,CDCl3)δ8.52(t,J＝7.3Hz,2H),8.13–8.04(m,2H),7.75(s, 1H),7.62(t,J＝7.9Hz,1H),3.67–3.58(m,3H),2.49(s,3H),2.29–2.18(m,2H),2.13–2.01 (m,4H),1.89(d,J＝8.7Hz,2H).13C NMR(101MHz,CDCl3)δ174.41,154.23,147.77,134.10,131.06,128.99,122.33,120.31,118.07,58.99,55.21,36.92,27.64,25.40.
1H NMR(400MHz,MeOD)δ8.30(s,1H),7.54–7.50(m,2H),7.35(t,J＝8.2Hz,1H),6.97–6.93(m,1H),3.93–3.77(m,4H),3.41(s,2H),2.31(s,3H),2.23–2.05(m,4H),1.89(d,J＝13.9Hz,2H),1.68(d,J＝8.5Hz,2H).13C NMR(101MHz,MeOD)δ164.50,161.68, 159.34,135.60,131.25,122.69,120.09,115.86,113.35,61.64,56.06,56.02,39.25,30.35,26.51.
1H NMR(400MHz,CDCl3)δ7.82(s,1H),7.68(d,J＝7.7Hz,1H),7.60(s,1H),7.32–7.13(m,2H),3.44–3.31(m,3H),2.35(s,3H),2.18–1.87(m,6H),1.77(d,J＝8.5Hz,2H).13CNMR(101MHz,CDCl3)δ175.87,154.45,137.76,135.76,131.38,128.95,127.38,125.57,114.91,63.31,40.05,38.45,33.90,26.31.
1H NMR(400MHz,CDCl3)δ7.50(d,J＝6.9Hz,1H),7.39(s,1H),7.30–7.18(m,3H),3.88(s,2H),3.70–3.58(m,1H),2.72(m,3H),2.40–2.29(m,7H),2.25–2.17(m,2H),2.08(d,J＝8.8Hz,2H).13C NMR(101MHz,CDCl3)δ173.21,156.48,137.53,135.89,131.96,130.92,129.47,127.04,117.09,64.56,39.56,37.50,32.93,25.63,21.40.
1H NMR(400MHz,MeOD)δ7.84(dd,J＝7.5,1.9Hz,1H),7.79(s,1H),7.48(d,J＝7.5, 1H),7.41–7.29(m,2H),3.81(s,2H),3.71–3.57(m,1H),2.67(s,3H),2.37–2.25(m,4H), 2.19(d,J＝13.2Hz,2H),2.06(d,J＝8.6Hz,2H).13C NMR(101MHz,MeOD)δ173.59,152.62,134.57,133.21,132.76,131.53,130.60,128.23,118.99,64.23,39.69,37.75,33.14, 25.81.
1H NMR(400MHz,DMSO)δ8.65(s,1H),8.01(d,J＝8.0Hz,1H),7.90(d,J＝8.8Hz,1H),7.83(t,J＝8.1Hz,1H),7.73(t,J＝8.4Hz,1H),3.77–3.68(m,1H),3.21(s,2H),2.15(s, 3H),2.00–1.81(m,4H),1.65–1.55(m,4H).13C NMR(101MHz,DMSO)δ163.66,152.23,148.63,132.98,131.24,130.54,126.40,126.16,124.28,59.08,54.87,54.79,38.49,28.13, 25.53.
1H NMR(400MHz,MeOD)δ8.12(dd,J＝7.7,1.7Hz,1H),7.88(s,1H),7.34–7.28(m,1H),7.09(d,J＝7.9Hz,1H),7.01(t,J＝7.5Hz,1H),3.93(s,5H),3.71–3.62(m,1H),2.77(s, 3H),2.41–2.25(m,6H),2.16(d,J＝8.7Hz,2H).13C NMR(101MHz,MeOD)δ171.48,158.40,152.11,130.93,130.24,124.25,121.62,117.63,112.46,64.72,55.95,39.28,37.55, 32.74,25.44.
1H NMR(400MHz,CDCl3)δ7.91(t,J＝1.8Hz,1H),7.67–7.62(m,1H),7.44(s,1H),7.16–7.03(m,1H),6.90(t,J＝7.9Hz,1H),3.74(s,2H),3.64–3.52(m,1H),2.63(s,3H),2.31–2.22(m,4H),2.17–2.11(m,2H),2.01(d,J＝8.8Hz,2H).13C NMR(101MHz,CDCl3) δ174.86,154.36,137.92,131.98,131.70,130.34,126.01,123.87,115.17,64.06,39.77,37.90, 33.36,25.89.
1H NMR(400MHz,CDCl3)δ7.62(s,1H),7.48(d,J＝7.6Hz,1H),7.27–7.13(m,3H),3.74–3.61(m,1H),3.30(s,2H),2.36(s,3H),2.30–2.12(m,5H),2.01(d,J＝4.4Hz,2H),1.71(d,J＝15.4Hz,2H),1.51(d,J＝8.3Hz,2H).13C NMR(101MHz,CDCl3)δ161.47, 157.56,135.25,131.78,130.08,128.97,128.10,125.13,122.21,58.73,54.22,37.23,27.28,25.14,20.04.
1H NMR(400MHz,CDCl3)δ7.89(s,1H),7.70–7.55(m,2H),7.31(d,J＝8.0Hz,1H),3.71(s,2H),3.54–3.47(m,1H),2.58(s,3H),2.34–2.06(m,6H),1.98(d,J＝8.5Hz,2H).13CNMR(101MHz,CDCl3)δ174.64,153.74,135.93,133.93,132.89,131.94,129.37,126.83,115.43,64.18,39.83,37.78,33.37,25.97.
1H NMR(400MHz,CDCl3)δ7.84–7.79(m,3H),7.34(t,J＝1.9Hz,1H),3.84(s,2H),3.58–3.48(m,1H),2.60(s,3H),2.27–2.16(m,4H),2.14–2.07(m,2H),1.99(d,J＝8.8Hz,2H).13C NMR(101MHz,CDCl3)δ174.77,153.05,138.85,136.53,128.53,125.73,116.48,64.30,39.64,37.73,33.19,25.72.
1H NMR(400MHz,CDCl3)：δ7.68(m,2H),7.38-7.26(m,4H),7.25-7.13(m,3H),6.78(s, 1H),4.99(t,J＝4.3Hz,1H),3.54(s,2H),2.64(m,2H),2.48(m,4H),2.35(s,3H),1.91(m,2H), 1.80-1.68(m,2H)；13C NMR(100MHz,CDCl3)δ173.27,149.38,137.61,132.07,129.30, 128.74,128.18,126.76,125.84,103.60,81.94,62.18,52.71,36.38,24.73,21.32
1H NMR(400MHz,CDCl3)：δ7.81-7.72(m,2H),7.39-7.26(m,4H),7.22(dd,J＝8.1,6.1 Hz,1H),7.10-6.99(m,2H),6.76(s,1H),4.97(t,J＝4.7Hz,1H),3.54(s,2H),2.63(m,J＝10.0 Hz,2H),2.55-2.40(m,4H),1.98-1.83(m,2H),1.82-1.68(m,2H)；13C NMR(100MHz,CDCl3)：δ173.49,δ162.52(d,J＝247.0Hz),148.29,139.73,131.00(d,J＝3.2Hz),127.63(d,J ＝8.1Hz),126.76,115.49(m,J＝21.6Hz).δ103.97,82.06,62.17,52.68,36.37,24.71.
1H NMR(400MHz,CDCl3)：δ7.79-7.66(m,2H),7.43-7.27(m,6H),7.23(dd,J＝12.1, 5.1Hz,1H),6.84(s,1H),4.98(t,J＝4.7Hz,1H),3.54(s,2H),2.63(d,J＝10.0Hz,2H), 2.55-2.39(m,4H),1.92(q,J＝5.3Hz,2H),1.82-1.65(m,2H)；13C NMR(100MHz,CDCl3)：δ173.49,148.12,133.49,133.18,128.74,128.68,128.15,127.16,126.73,104.80,82.10,62.14, 52.66,36.34,24.68.
1H NMR(400MHz,CDCl3)：δ7.79-7.66(m,2H),7.43-7.27(m,6H),7.23(dd,J＝12.1, 5.1Hz,1H),6.84(s,1H),4.98(t,J＝4.7Hz,1H),3.54(s,2H),2.63(d,J＝10.0Hz,2H), 2.55-2.39(m,4H),1.92(q,J＝5.3Hz,2H),1.82-1.65(m,2H)；13C NMR(100MHz,CDCl3)：δ173.49,148.12,133.49,133.18,128.74,128.68,128.15,127.16,126.73,104.80,82.10,62.14, 52.66,36.34,24.68.
1H NMR(400MHz,CDCl3)：δ7.90(d,J＝8.1Hz,2H),7.62(d,J＝8.2Hz,2H),7.39-7.27 (m,4H),7.26-7.20(m,1H),6.97(s,1H),5.00(t,J＝4.7Hz,1H),3.55(s,2H),2.63(d,J＝10.1 Hz,2H),2.50(d,J＝10.8Hz,4H),1.92(d,J＝7.2Hz,2H),1.84-1.69(m,2H).；13CNMR(100 MHz,CDCl3)：δ173.60,147.83,139.67,δ129.52(q,J＝65.1,32.5Hz),128.16,128.69,126.75, 126.04,125.58(q,J＝3.8Hz),δ123.65(q,J＝271.8Hz),δ106.48,82.22,62.14,52.65,36.34, 24.67.
1H NMR(400MHz,CDCl3)：δ8.23(d,J＝8.9Hz,2H),7.95(d,J＝8.9Hz,2H),7.32(dt, J＝14.8,7.4Hz,4H),7.24(dd,J＝12.0,4.9Hz,1H),7.09(s,1H),5.02(t,J＝4.7Hz,1H),3.55 (s,2H),2.63(d,J＝10.3Hz,2H),2.56-2.40(m,4H),1.94(d,J＝7.2Hz,2H),1.84-1.69(m,2H)； 13C NMR(100MHz,CDCl3)：δ173.77,153.36,147.01,140.43,138.86,128.69,128.17,126.85, 126.36,124.09,108.47,82.41,62.12,52.61,36.33,24.65.
1H NMR(400MHz,CDCl3)：δ7.89(d,J＝2.0Hz,1H),7.60(dd,J＝8.4,2.0Hz,1H),7.46-7.40(m,1H),7.38-7.27(m,4H),7.23(dd,J＝12.0,4.9Hz,1H),6.88(s,1H),4.99(t,J＝4.7Hz,1H),3.55(s,2H),2.62(d,J＝10.5Hz,2H),2.49(dd,J＝16.2,5.2Hz,4H),1.98-1.86(m, 2H),1.82-1.68(m,2H)；13C NMR(100MHz,CDCl3)：δ173.62,146.90,139.66,134.62, 132.75,131.50,130.50,128.68,128.16,127.78,126.75,124.97,105.83,82.22,62.13,52.64, 36.34,24.67.
1H NMR(400MHz,CDCl3)：δ7.89-7.73(m,2H),7.39(t,J＝7.5Hz,2H),7.30(t,J＝7.3 Hz,1H),6.89(s,1H),5.02(t,J＝4.9Hz,1H),2.80(s,4H),2.58(d,J＝1.6Hz,2H),2.47(s,3H), 2.08(q,J＝5.0Hz,2H),1.95-1.76(m,2H)；13C NMR(100MHz,CDCl3)：δ172.79,149.32, 134.46,128.63,127.96,125.86,104.76,80.38,54.70,45.48,35.77,23.84.
1H NMR(400MHz,CDCl3)：δ7.69(d,J＝8.1Hz,2H),7.18(d,J＝8.0Hz,2H),6.80(s,1H),4.98(t,J＝4.9Hz,1H),2.75-2.61(m,4H),2.53(s,2H),2.37(s,6H),2.36(s,2H),2.02-1.91(m,2H),1.87-1.76(m,2H)；13C NMR(100MHz,CDCl3)：δ172.93,149.37,137.70,131.89,129.29,125.79,103.76,80.80,54.88,45.61,35.95,24.21,21.28.
1H NMR(400MHz,CDCl3)：δ7.80-7.66(m,2H),7.41-7.31(m,2H),6.85(s,1H),4.97(t, J＝4.8Hz,1H),2.60(m,4H),2.50(s,2H),2.34(s,3H),1.97-1.86(m,2H),1.81(m,2H)；13C NMR(100MHz,CDCl3)：δ173.28,148.11,133.54,133.08,128.75,127.14,104.93,81.21, 54.95,45.67,36.04,24.38.
1H NMR(400MHz,CDCl3)：δ7.67(d,J＝8.5Hz,2H),7.49(d,J＝8.5Hz,2H),6.87(s,1H),4.98(t,J＝4.8Hz,1H),2.71-2.58(m,4H),2.51(s,2H),2.36(s,3H),2.01-1.89(m,2H), 1.87-1.74(m,2H)；13C NMR(100MHz,CDCl3)：δ173.22,148.14,133.48,131.70,127.44, 121.76,105.10,81.10,54.89,45.64,35.98,24.28.
1H NMR(400MHz,CDCl3)：δ7.84-7.59(m,2H),7.05-6.89(m,2H),6.71(s,1H),4.89(t, J＝4.8Hz,1H),2.52(m,4H),2.44-2.39(m,2H),2.24(s,3H),1.86-1.77(m,2H),1.78-1.70(m, 2H)；13C NMR(100MHz,CDCl3)：δ172.27,147.23,13C NMR(100MHz,CDCl3)δ172.27, 161.47(d,J＝247.1Hz),147.23,129.86(d,J＝3.2Hz),126.55(d,J＝8.1Hz),114.44(d,J＝ 21.7Hz).103.00(d,J＝1.4Hz),80.20,53.94,44.65,35.04,23.40.
1H NMR(400MHz,CDCl3)：δ8.24(d,J＝8.5Hz,2H),7.95(d,J＝8.5Hz,2H),7.13(s,1H),5.04(t,J＝4.7Hz,1H),2.74(s,4H),2.56(s,2H),2.43(s,3H),2.04(d,J＝7.7Hz,2H),1.93-1.77(m,2H)；13C NMR(100MHz,CDCl3)：δ173.40,147.02,140.25,126.36,124.10,108.74,81.13,54.78,45.58,35.87,24.07.
1H NMR(400MHz,CDCl3)：δ7.91(d,J＝8.1Hz,2H),7.63(d,J＝8.2Hz,2H),6.99(s,1H),5.00(t,J＝4.8Hz,1H),2.68-2.56(m,4H),2.52(d,J＝1.6Hz,2H),2.34(s,3H),1.99-1.87 (m,2H),1.87-1.76(m,2H)；13C NMR(100MHz,CDCl3)：δ173.41,147.83,δ137.77,129.56 (q,J＝32.4Hz),126.03,125.58(q,J＝3.8Hz).δ121.51(q,J＝271.8Hz).106.60,81.34,54.94, 45.66,36.04,24.37
1H NMR(400MHz,CDCl3)：δ8.31(d,J＝2.2Hz,1H),8.02(dd,J＝8.8,2.3Hz,1H),7.41(s,1H),7.15(d,J＝8.8Hz,1H),4.59(t,J＝4.7Hz,1H),2.71(d,J＝10.9Hz,2H),2.61-2.51(m,2H),2.37(d,J＝11.8Hz,5H),1.97(d,J＝7.6Hz,2H),1.86-1.71(m,2H)；13CNMR(100MHz,CDCl3)：δ153.12,151.12,140.23,136.50,131.47,126.05,123.31,116.26,115.57,78.37,54.61,45.53,36.12,24.43.
1H NMR(400MHz,CDCl3)：δ7.89(d,J＝2.0Hz,1H),7.60(dd,J＝8.4,2.0Hz,1H),7.42(d,J＝8.4Hz,1H),6.89(s,1H),4.98(t,J＝4.8Hz,1H),2.69-2.54(m,4H),2.50(s,2H), 2.34(s,3H),2.00-1.73(m,4H)；13C NMR(100MHz,CDCl3)：δ173.42,146.88,134.52,132.74,131.53,130.50,27.74,124.95,105.95,81.35,54.94,45.67,36.05,24.38.
1H NMR(400MHz,CDCl3)：δ7.80(t,J＝1.7Hz,1H),7.66(dt,J＝7.6,1.5Hz,1H),7.27 (tt,J＝4.6,3.3Hz,2H),6.89(s,1H),4.99(t,J＝4.8Hz,1H),2.57(dt,J＝11.0,6.9Hz,4H), 2.49(s,2H),2.31(s,3H),1.95-1.74(m,4H)；13C NMR(101MHz,CDCl3)：δ173.34,147.84, 136.34,134.59,129.83,127.78,126.04,123.88,105.61,81.35,54.99,45.69,36.10,24.46.
1H NMR(400MHz,CDCl3)：δ7.86(dd,J＝7.8,1.8Hz,1H),7.43(dd,J＝7.9,1.2Hz,1H),7.30(td,J＝7.6,1.3Hz,1H),7.25(s,1H),7.22(dd,J＝7.5,1.8Hz,1H),4.98(t,J＝4.9Hz, 1H),2.94-2.60(m,4H),2.54(d,J＝1.9Hz,2H),2.41(s,3H),2.01(q,J＝5.4Hz,2H),1.91-1.73 (m,2H)；13C NMR(101MHz,CDCl3)：δ171.95,145.68,133.05,131.74,131.33,130.56, 128.73,126.86,110.38,80.66,54.79,45.58,35.86,24.06.
1H NMR(400MHz,CDCl3)：δ7.89-7.75(m,2H),7.32(dd,J＝19.5,7.2Hz,4H),7.27-7.20(m,1H),7.14(t,J＝8.1Hz,2H),5.08(t,1H),3.54(s,2H),2.59(dd,J＝10.0Hz,2H), 2.51(dd,J＝8.5Hz,4H),1.92(dd,J＝7.0Hz,2H),1.76(m,2H)；13C NMR(100MHz,CDCl3)：δ174.32,δ164.06(d,J＝251.4Hz),161.07,139.48,128.97(d,J＝8.5Hz),128.67,128.18, 127.16(d,J＝3.3Hz),126.81,116.23(d,J＝22.2Hz),83.57,62.12,52.52,36.25,24.50。
1H NMR(400MHz,CDCl3)：δ7.76(d,J＝8.5Hz,2H),7.42(d,J＝8.5Hz,2H),7.37-7.20 (m,5H),5.09(t,J＝4.5Hz,1H),3.54(s,2H),2.55(dd,J＝29.9,9.5Hz,6H),1.92(m,J＝7.2 Hz,2H),1.82-1.68(m,2H)；13C NMR(100MHz,CDCl3)：δ174.50,161.11,139.46,132.27, 129.78,128.67,128.39,128.18,126.81,124.88,83.69,62.12,52.51,36.25,24.49。
1H NMR(400MHz,CDCl3)：δ7.75-7.65(m,2H),7.63-7.54(m,2H),7.32(dt,J＝14.8, 7.3Hz,4H),7.23(t,J＝7.0Hz,1H),5.09(t,J＝4.7Hz,1H),3.54(s,2H),2.69-2.40(m,6H), 1.97-1.86(m,2H),1.80-1.68(m,2H)；13C NMR(100MHz,CDCl3)：δ174.50,161.11,139.46, 132.27,129.78,128.67,128.39,128.18,126.81,124.88,83.69,62.12,52.51,36.25,24.49。
1H NMR(400MHz,CDCl3)：δ7.76(d,J＝8.8Hz,2H),7.33(dd,J＝13.3,7.1Hz,5H),6.95(d,J＝8.8Hz,2H),5.06(t,J＝4.5Hz,1H),3.84(s,3H),3.54(s,2H),2.59(d,J＝9.8Hz, 2H),2.50(d,J＝8.6Hz,4H),1.89(dd,J＝14.6Hz,2H),1.75(dd,J＝17.9,12.8Hz,2H)；13C NMR(100MHz,CDCl3)：δ173.80,162.09,161.47,139.53,128.61(m,J＝14.7Hz),128.17, 126.79,123.60,114.41,83.31,62.14,55.44,52.55,36.26,24.53。
1H NMR(400MHz,CDCl3)：δ7.95(d,J＝8.2Hz,2H),7.71(d,J＝8.3Hz,2H),7.38-7.19 (m,5H),5.12(t,J＝4.5Hz,1H),3.55(s,2H),2.59(d,J＝9.8Hz,2H),2.52(d,J＝8.9Hz,4H), 2.00-1.85(m,2H),1.80-1.69(m,2H)；13C NMR(100MHz,CDCl3)：δ174.94,160.59, 139.43,134.07(2C),132.20(q,J＝36.3Hz)128.19,127.28,126.83,126.07(q,J＝4.0Hz),123.93(q, J＝273.7Hz)83.91,62.12,52.51,36.27,24.49。
1H NMR(400MHz,CDCl3)：δ7.94(d,J＝7.7Hz,2H),7.74(d,J＝7.7Hz,2H),7.40-7.19 (m,5H),5.12(s,1H),3.55(s,2H),2.55(dd,J＝24.4,9.9Hz,6H),1.93(dd,J＝7.1Hz,2H), 1.76(m,2H)；13C NMR(100MHz,CDCl3)：δ175.21,160.08,139.37,134.81,132.83,128.66, 128.19,127.42,126.84,118.15,113.91,84.10,62.10,52.48,36.26,29.71,24.46。
1H NMR(400MHz,CDCl3)：δ7.71(d,J＝8.2Hz,2H),7.32(dt,J＝14.8,7.3Hz,4H),7.24(d,J＝8.3Hz,3H),5.07(s,1H),3.54(s,2H),2.59(d,J＝9.7Hz,2H),2.50(d,J＝8.3Hz, 4H),2.39(s,3H),1.96-1.84(m,2H),1.79-1.68(m,2H)；13C NMR(100MHz,CDCl3)：δ174.09,162.44,140.91,139.53,129.71,128.68,128.18,126.97,126.80,83.37,62.14,52.55, 36.26,24.53,21.49。
1H NMR(400MHz,CDCl3)：δ7.83(t,J＝1.7Hz,1H),7.68(dt,J＝7.4,1.5Hz,1H),7.43-7.26(m,6H),7.26-7.18(m,1H),5.09(t,J＝4.7Hz,1H),3.54(s,2H),2.59(d,J＝9.8Hz, 2H),2.54-2.45(m,4H),1.91(q,J＝5.4Hz,2H),1.73(dd,J＝10.8,6.5Hz,2H)；13CNMR(100 MHz,CDCl3)：δ174.64,160.70,139.45,135.10,132.48,130.53,130.32,128.69,128.20,126.88 (m,J＝9.1Hz),125.19,83.76,62.13,52.52,36.27,24.51。
1H NMR(400MHz,CDCl3)：δ7.47-7.42(m,1H),7.38-7.26(m,6H),7.24-7.19(m,1H), 7.02-6.94(m,1H),5.08(t,J＝4.6Hz,1H),3.85(s,3H),3.54(s,2H),2.59(d,J＝9.7Hz,2H), 2.55-2.45(m,4H),1.91(q,J＝5.3Hz,2H),1.79-1.68(m,2H)；13C NMR(100MHz,CDCl3)：δ174.39,162.17,159.98,139.50,132.05,130.08,128.69,128.19,126.81,119.81,116.88, 111.50,83.51,62.14,55.45,52.54,36.27,24.53。
1H NMR(400MHz,CDCl3)：δ8.27-8.12(m,1H),7.55-7.43(m,1H),7.44-7.26(m,6H), 7.27-7.17(m,1H),5.11(t,J＝4.5Hz,1H),3.55(s,2H),2.56(dd,J＝37.5,9.0Hz,6H), 2.01-1.83(m,2H),1.83-1.62(m,2H)；13C NMR(100MHz,CDCl3)：δ176.17,157.54,139.53, 131.92,131.15,130.50,129.62,128.69,128.18,127.29,126.80,83.44,62.14,52.56,36.31, 24.54。
1H NMR(400MHz,CDCl3)：δ8.34(dd,J＝7.9,1.5Hz,1H),7.44-7.37(m,1H),7.37-7.19 (m,5H),7.07(t,J＝7.6Hz,1H),6.99(d,J＝8.3Hz,1H),5.08(t,J＝4.4Hz,1H),3.96(s,3H), 3.54(s,2H),2.61(d,J＝9.6Hz,2H),2.50(d,J＝8.0Hz,4H),1.95-1.84(dd,2H),1.80-1.68(dd, 2H)；13C NMR(100MHz,CDCl3)：δ176.24,156.02,155.35,139.63,131.42,128.68,128.17, 127.73,126.77,121.30,119.85,111.34,82.72,62.18,55.71,52.61,36.31,24.59。
1H NMR(400MHz,CDCl3)：δ7.70(d,J＝1.8Hz,2H),7.42(t,J＝1.8Hz,1H),7.38-7.19 (m,5H),5.10(t,J＝4.7Hz,1H),3.55(s,2H),2.58(d,J＝10.1Hz,2H),2.52(d,J＝10.8Hz, 4H),1.92(dd,J＝7.3Hz,2H),1.80-1.69(dd,2H)；13C NMR(100MHz,CDCl3)：δ174.90, 159.29,139.38,135.78,133.46,130.28,128.69,128.20,126.85,125.26,84.02,62.11,52.48, 36.26,24.47。
1H NMR(400MHz,CDCl3)：δ8.17(d,J＝8.6Hz,1H),7.51(d,J＝2.0Hz,1H),7.41-7.19 (m,6H),5.11(t,J＝4.5Hz,1H),3.54(s,2H),2.60(d,J＝9.9Hz,2H),2.52(d,J＝9.0Hz,4H), 2.01-1.84(m,2H),1.83-1.64(m,2H)；13C NMR(100MHz,CDCl3)：δ176.25,156.54,139.48, 136.65,132.40,131.23,130.21,128.67,128.21,127.81,126.81,83.61,62.13,52.54,36.30, 26.93,24.52。
1H NMR(400MHz,CDCl3)：δ7.93(d,J＝2.0Hz,1H),7.65(dd,J＝8.4,2.1Hz,1H),7.52(d,J＝8.4Hz,1H),7.39-7.27(m,4H),7.26-7.20(m,1H),5.10(t,J＝4.7Hz,1H),3.55(s, 2H),2.55(dd,J＝27.3,10.0Hz,6H),1.92(d,J＝7.2Hz,2H),1.81-1.66(m,2H).；13CNMR (100MHz,CDCl3)：δ174.74,159.69,139.42,134.71,133.48,131.05,130.67,128.67,128.58, 128.18,126.82,125.99,83.92,62.11,52.50,36.25,24.48。
1H NMR(400MHz,CDCl3)：δ7.93–7.74(m,2H),7.55–7.35(m,3H),5.07(t,J＝4.4Hz, 1H),2.54(m,6H),2.30(s,3H),1.94–1.69(m,4H).13C NMR(101MHz,CDCl3)：δ174.28, 162.34,130.83,130.58,129.03,127.05,82.85,54.93,45.69,36.06,24.40。
1H NMR(400MHz,CDCl3)：δ7.90-7.73(m,2H),7.20-7.05(m,2H),5.06(t,J＝4.5Hz, 1H),2.53(s,6H),2.29(s,3H),1.93-1.69(m,4H)；13C NMR(100MHz,CDCl3)：δ174.24, 164.04(d,J＝251.5Hz),161.10,128.03(d,J＝185.5,6.0Hz),127.11(d,J＝3.4Hz),116.21(d, J＝22.2Hz),82.96,54.91,45.67,36.06,24.39。
H NMR(4000MHz,CDCl3)：δ7.76(d,J＝8.5Hz,2H),7.42(d,J＝8.5Hz,2H),5.07(t,J＝ 4.4Hz,1H),2.52(s,6H),2.29(s,3H),1.91-1.70(m,4H).13C NMR(100MHz,CDCl3)：δ174.39,161.05,136.57,129.30,128.17,83.06,54.91,45.68,36.06,24.40。
1H NMR(400MHz,CDCl3)：δ7.70(d,J＝8.5Hz,2H),7.58(d,J＝8.5Hz,2H),5.07(t,J ＝4.5Hz,1H),2.53(s,6H),2.29(s,3H),1.96-1.70(m,4H)；13C NMR(100MHz,CDCl3)：δ174.40,161.13,132.26,129.73,128.36,124.88,83.08,54.91,45.68,36.06,24.40。
1H NMR(400MHz,CDCl3)：δ7.75(d,J＝8.7Hz,2H),6.94(d,J＝8.7Hz,2H),5.03(t,J ＝4.0Hz,1H),3.84(s,3H),2.52(s,6H),2.28(s,3H),1.81(m,4H)；13C NMR(100MHz,CDCl3)：δ173.66,162.08,161.44,128.47,123.50,114.37,82.67,55.38,54.92,45.67,36.04, 24.41。
1H NMR(400MHz,CDCl3)：δ7.96(d,J＝8.1Hz,2H),7.72(d,J＝8.2Hz,2H),5.10(t,J ＝4.4Hz,1H),2.54(s,6H),2.30(s,3H),1.92-1.74(m,4H)；13C NMR(100MHz,CDCl3)：δ174.87,160.64,134.03,132.22(q,J＝32.8Hz),127.26,126.06(q,J＝3.8Hz),δ123.71(q,J＝ 272.5Hz).83.30,54.91,45.67,36.08,24.38。
1H NMR(400MHz,CDCl3)：δ7.95(d,J＝8.2Hz,2H),7.75(d,J＝8.1Hz,2H),5.10(t,J ＝4.1Hz,1H),2.53(s,6H),2.29(s,3H),1.96-1.70(m,4H)；13C NMR(100MHz,CDCl3)：δ175.13,160.10,134.75,132.82,127.40,118.11,113.89,83.50,54.87,45.65,36.07,24.37。
1H NMR(400MHz,CDCl3)：δ7.71(d,J＝8.2Hz,2H),7.24(d,J＝7.9Hz,2H),5.05(t,J ＝4.4Hz,1H),2.53(s,6H),2.39(s,3H),2.29(s,3H),1.93-1.70(m,4H)；13C NMR(100MHz, CDCl3)：δ174.00,162.46,140.91,129.70,128.13,126.95,82.76,54.95,45.70,36.07,24.43, 21.46。
1H NMR(400MHz,CDCl3)：δ7.75(d,J＝8.3Hz,2H),7.30(d,J＝8.2Hz,2H),5.06(t,J ＝4.4Hz,1H),2.95(dt,J＝13.8,6.9Hz,1H),2.54(s,6H),2.29(s,3H),1.91-1.72(m,4H),1.27 (d,J＝6.9Hz,6H)；13C NMR(100MHz,CDCl3)：δ174.03,162.44,151.80,128.46,127.11(m, J＝1.3Hz),82.76,54.96,45.71,36.08,34.09,24.43,23.78。
1H NMR(400MHz,CDCl3)：δ8.32(d,J＝7.8Hz,2H),8.02(d,J＝7.7Hz,2H),5.12(t,J ＝4.8Hz,1H),2.54(m,6H),2.30(s,3H),1.97-1.70(m,4H)；13C NMR(100MHz,CDCl3)：δ175.34,159.70,148.76,136.44,127.68,124.38,83.58,54.87,45.65,36.07,24.34。
1H NMR(400MHz,CDCl3)：δ7.71(d,J＝8.7Hz,2H),6.93(d,J＝8.7Hz,2H),5.04(t,J ＝4.8Hz,1H),3.50(s,1H),2.70-2.44(m,6H),2.32(s,3H),1.95-1.71(m,4H)；13C NMR(100 MHz,CDCl3)δ173.68,162.57,158.60,128.81,123.02,116.18,82.62,54.83,45.65,35.99, 24.20。
1H NMR(400MHz,CDCl3)：δ7.74-7.55(m,2H),7.33(t,J＝7.6Hz,1H),7.26(d,J＝8.2 Hz,1H).,5.06(t,J＝4.4Hz,1H),2.65-2.49(m,6H),2.39(s,3H),2.31(s,3H),1.95-1.71(m, 4H)；13C NMR(100MHz,CDCl3)：δ174.12,162.62,138.87,131.43,130.69,128.92,127.57, 124.31,82.64,54.88,45.67,36.00,24.29,21.35。
1H NMR(400MHz,CDCl3)：δ7.45(m,1H),7.38–7.30(m,2H),7.05–6.91(m,1H),5.06(t,J＝4.3Hz,1H),3.86(s,3H),2.53(s,6H),2.29(s,3H),1.93-1.70(m,4H)；13C NMR(100MHz,CDCl3)：δ174.31,162.21,159.96,132.01,130.06,119.79,116.88,111.47,82.90,55.43, 54.94,45.70,36.06,24.41。
1H NMR(400MHz,CDCl3)：δ7.83(t,J＝1.7Hz,1H),7.69(dd,J＝7.3,1.4Hz,1H),7.47–7.35(m,2H),5.11(t,J＝4.9Hz,1H),2.80(t,J＝12.7Hz,4H),2.61(s,2H),2.49(s,3H), 2.22-2.02(m,2H),1.94-1.78(m,2H)；13C NMR(100MHz,CDCl3)：δ174.15,161.11,135.10, 132.20,130.69,130.36,126.88,125.20,82.14,54.49,45.48,35.66,23.66。
1H NMR(400MHz,CDCl3)：δ8.63(s,1H),8.39-8.11(m,2H),7.68(t,J＝8.0Hz,1H),5.13(t,J＝4.9Hz,1H),2.70(m,4H),2.59(m,2H),2.41(s,3H),2.02(m,2H),1.84(m,2H)；13C NMR(100MHz,CDCl3)：δ174.75,159.87,148.59,132.42,132.30,130.26,125.01,121.87, 82.95,54.66,45.56,35.85,23.97。
1H NMR(400MHz,CDCl3)：δ8.34(dd,J＝7.9,1.6Hz,1H),7.47–7.38(m,1H),7.08(t,J ＝7.6Hz,1H),7.00(d,J＝8.4Hz,1H),5.07(t,J＝4.8Hz,1H),3.97(s,3H),2.57(m,6H),2.33 (s,3H),2.01-1.69(m,4H)；13C NMR(100MHz,CDCl3)：δ176.03,156.13,155.31,131.47, 127.67,121.27,119.70,111.31,81.83,55.68,54.87,45.66,35.98,24.27。
1H NMR(400MHz,CDCl3)：δ8.28–8.13(m,1H),7.53-7.45(m,1H),7.43–7.34(m,2H), 5.09(t,J＝4.4Hz,1H),2.63-2.47(m,6H),2.30(s,3H),1.94-1.71(m,4H)；13C NMR(100 MHz,CDCl3)：δ176.09,157.57,131.90,131.15,130.48(m,J＝6.8Hz),129.58,127.28,82.83, 54.95,45.70,36.11,24.43。
1H NMR(400MHz,CDCl3)：δ7.98(dd,J＝8.0,0.9Hz,1H),7.78–7.61(m,3H),5.10(t,J ＝4.8Hz,1H),2.65-2.45(m,6H),2.32(s,3H),1.98-1.64(m,4H)；13C NMR(100MHz,CDCl3)：δ175.99,156.48,148.49,132.88,132.12,131.17,125.08,124.71,83.30,54.90,45.66, 36.05,24.32。
1H NMR(400MHz,CDCl3)：δ7.63(d,J＝1.7Hz,2H),7.36(d,J＝0.9Hz,1H),5.02(t,J ＝4.8Hz,1H),2.68-2.41(m,6H),2.29(s,3H),1.90(m,J＝7.6Hz,2H),1.80-1.67(m,2H)；13C NMR(100MHz,CDCl3)：δ174.65,159.49,135.79,133.32,130.35,125.24,82.99,54.71,45.59, 35.90,24.06。
1H NMR(400MHz,CDCl3)：δ8.31(d,J＝1.9Hz,1H),8.00(dd,J＝8.4,2.0Hz,1H),7.66(d,J＝8.4Hz,1H),5.10(t,J＝4.7Hz,1H),2.64-2.49(m,6H),2.32(s,3H),1.96-1.73(m, 4H)；13C NMR(100MHz,CDCl3)：δ176.65,155.30,146.85,137.87,131.64,131.05,125.53, 125.11,83.39,54.88,45.65,36.09,24.36。
1H NMR(400MHz,CDCl3)：δ9.11(d,J＝2.7Hz,1H),8.23(dd,J＝8.8,2.7Hz,1H),7.70(d,J＝8.8Hz,1H),5.14(t,J＝4.5Hz,1H),2.56(s,6H),2.31(s,3H),1.95-1.86(m,2H), 1.85-1.75(m,2H)；13C NMR(100MHz,CDCl3)：δ176.65,155.30,146.85,137.87,131.64, 131.05,125.53,125.11,83.39,54.88,45.65,36.09,24.36。
1H NMR(400MHz,CDCl3)：δ8.17(d,J＝8.6Hz,1H),7.52(d,J＝2.0Hz,1H),7.39(dd, J＝8.6,2.0Hz,1H),5.12(t,J＝4.9Hz,1H),2.92-2.66(m,4H),2.61(s,2H),2.46(s,3H), 1.93-1.76(m,2H),1.93-1.76(m,2H)；13C NMR(100MHz,CDCl3)：δ175.78,156.94,136.84, 132.39,131.20,130.22,127.99,127.87,82.06,54.54,45.50,35.73,23.72。
1H NMR(400MHz,CDCl3)：δ7.97-7.80(m,1H),7.73-7.56(m,1H),7.06(t,J＝6.5Hz, 1H),5.11(t,J＝4.8Hz,1H),2.68-2.45(m,6H),2.31(s,3H),2.0-1.70(m,4H)；13CNMR(100 MHz,CDCl3)：δ176.07,δ161.73(d,J＝248.6Hz),157.79,135.27(d,J＝8.0Hz),133.22(d,J＝ 8.4Hz),118.76(d,J＝22.8Hz),118.06(d,J＝25.3Hz),115.89(d,J＝3.3Hz),83.01,54.90, 45.67,36.08,24.36。
1H NMR(400MHz,CDCl3)：δ7.93(d,J＝1.3Hz,1H),7.65(dd,J＝8.3,1.4Hz,1H),7.52(d,J＝8.4Hz,1H),5.08(t,J＝4.3Hz,1H),2.65-2.45(m,6H),2.30(s,3H),1.95-1.82(m, 2H),1.82-1.71(m,2H)；13C NMR(100MHz,CDCl3)：δ174.63,159.71,134.69,133.45,131.03,130.61,128.52,125.97,83.27,54.87,45.66,36.05,24.35。
1H NMR(400MHz,CDCl3)：δ8.41(d,J＝2.2Hz,1H),8.07(dd,J＝8.8,2.2Hz,1H),7.21(s,1H),7.19(d,J＝3.9Hz,1H),5.01(t,J＝4.8Hz,1H),2.66-2.38(m,6H),2.26(s,3H), 1.96-1.62(m,4H)；13C NMR(100MHz,CDCl3)：δ174.32,159.61,156.73,135.20,133.61, 123.71,123.42,121.30,83.11,54.81,45.65,35.98,24.19。
1H NMR(400MHz,CDCl3)：δ6.98(d,J＝2.2Hz,2H),6.53(t,J＝2.1Hz,1H),5.05(t,J ＝4.8Hz,1H),3.84(s,6H),2.57(t,J＝12.0Hz,6H),2.32(s,3H),2.03-1.69(m,4H)；13CNMR (100MHz,CDCl3)：δ174.06,162.14,153.57,140.20,126.14,104.30,82.90,56.31,54.91, 45.67,36.03,24.36。
1H NMR(400MHz,CDCl3)：δ6.98(s,2H),4.97(t,J＝4.3Hz,1H),3.85(s,6H),3.82(s, 3H),2.55-2.40(m,6H),2.22(s,3H),1.97–1.70(m,4H)；13C NMR(100MHz,CDCl3)：δ174.06,162.14,153.57,140.20,126.14,104.30,82.90,60.97,56.31,54.91,45.67,36.03,24.36。
1H NMR(400MHz,CDCl3)δ7.71(d,J＝8.1Hz,2H),7.24(d,J＝8.3Hz,2H),5.07(s,1H),2.97(d,J＝10.9Hz,1H),2.64-2.46(m,2H),2.39(s,5H),2.29(s,2H),2.18(s,3H),1.97 (dd,J＝13.0,6.5Hz,2H),1.87-1.75(m,1H),1.65-1.59(m,1H),1.52-1.39(m,1H).；13C NMR (100MHz,CDCl3)δ173.98,162.18,140.89,140.83,129.69,129.68,128.19,126.94,84.49, 60.93,55.05,45.87,33.35,32.69,31.19,24.94,21.45,20.80。
1H NMR(400MHz,CDCl3)δ7.74(t,J＝7.73Hz,2H),7.06(t,J＝8.6Hz,2H),5.00(t,J ＝5.0Hz,1H),2.89(d,J＝10.7Hz,2H),2.47(m,1H),2.31(d,J＝11.8Hz,2H),2.21(s,2H), 2.10(s,3H),1.99-1.76(m,2H),1.56(m,2H),1.4(m,1H)；13C NMR(100MHz,CDCl3)δ174.25(s),164.02(d,J＝251.3Hz),160.82,128.94(d,J＝8.6Hz),127.20(d,J＝3.4Hz),116.19(d,J＝22.1Hz),84.82,60.93,45.83,32.71,24.95,20.81。
1H NMR(400MHz,CDCl3)δ7.76(d,J＝8.4Hz,2H),7.42(d,J＝8.5Hz,2H),5.08(t,J＝3.7Hz,1H),2.97(d,J＝10.6Hz,1H),2.71(d,J＝9.9Hz,1H),2.55(dt,J＝13.0,6.5Hz,2H), 2.38(d,J＝11.8Hz,1H),2.29(s,2H),2.17(s,3H),1.96(dd,J＝13.0,6.5Hz,2H),1.82(dd,J＝ 16.3,11.4Hz,1H),1.64(dd,J＝13.7,6.1Hz,1H),1.47(dd,J＝13.1,6.5Hz,1H)；13C NMR (100MHz,CDCl3)δ174.40,160.76,136.51,129.39,129.29,128.17,84.95,60.92,55.15,45.82, 33.44,32.71,31.36,24.96,20.81。
1H NMR(400MHz,CDCl3)δ7.69(d,J＝8.6Hz,2H),7.58(d,J＝8.6Hz,2H),5.09(s,1H),2.97(s,2H),2.55(dd,J＝12.8,6.2Hz,1H),2.39(d,J＝8.3Hz,2H),2.29(s,2H),2.19(s, 3H),2.04-1.90(m,2H),1.64(dd,J＝13.2,5.5Hz,2H),1.56-1.42(m,1H)；13C NMR(100MHz, CDCl3)δ174.39,160.86,132.24,129.79,128.36,124.81,84.88,60.88,45.88,32.67,24.92, 20.78。
1H NMR(400MHz,CDCl3)δ8.24(d,J＝8.9Hz,2H),7.94(d,J＝9.0Hz,2H),5.07(t,J＝3.7Hz,1H),2.91(d,J＝10.7Hz,2H),2.49(dt,J＝13.0,6.4Hz,1H),2.32(d,J＝11.8Hz,2H),2.23(s,2H),2.11(s,3H),1.98-1.84(m,2H),1.58(dd,J＝13.8,6.1Hz,2H),1.41(dt,J＝ 12.8,6.3Hz,1H)；13C NMR(100MHz,CDCl3)δ175.36,159.37,148.72,136.53,127.66,124.36,85.64,60.89,45.79,32.74,24.94,20.78。
1H NMR(400MHz,CDCl3)δ7.87(d,J＝8.5Hz,2H),7.67(d,J＝8.5Hz,2H),5.05(s,1H),2.92(d,J＝10.6Hz,2H),2.55-2.39(m,1H),2.33(d,J＝10.9Hz,2H),2.22(s,2H),2.12(s, 3H),1.95-1.83(m,2H),1.58(dd,J＝13.7,5.9Hz,2H),1.41(m,1H)；13C NMR(100MHz,CDCl3)δ174.14,162.29,138.84,131.34,128.91,127.56,124.29,84.30,60.86,45.96,32.63, 24.86,21.37。
1H NMR(400MHz,CDCl3)δ7.74(dd,J＝5.2,3.1Hz,2H),6.93(dd,J＝5.2,2.8Hz,2H), 5.04(s,1H),3.82(s,3H),2.96(d,J＝10.7Hz,1H),2.71(s,1H),2.55(dd,J＝11.5,6.3Hz,2H), 2.37(d,J＝10.8Hz,1H),2.28(s,2H),2.18(d,J＝16.2Hz,3H),1.95(d,J＝10.7Hz,2H),1.80 (s,1H),1.62(d,J＝12.9Hz,1H),1.55-1.37(m,1H).；13C NMR(100MHz,CDCl3)δ173.54, 161.75,161.34,128.39,123.46,114.32,84.24,60.81,55.33,45.84,32.58,24.85,20.74。
1H NMR(400MHz,CDCl3)δ7.91(s,1H),7.69(dt,J＝7.3,1.5Hz,1H),7.40(m,2H),5.10(s,1H),2.99(s,2H),2.56(dd,J＝12.6,6.4Hz,1H),2.42(s,2H),2.30(s,2H),2.20(s,3H), 2.06-1.90(m,2H),1.65(dd,J＝13.4,5.5Hz,2H),1.55-1.43(m,1H).；13C NMR(100MHz, CDCl3)δ174.51,160.49,135.07,132.49,130.48,130.29,126.89,125.17,60.83,45.91,32.64, 29.70,24.85,20.69。
1H NMR(400MHz,CDCl3)δ8.62(s,1H),8.40–8.24(m,1H),8.19(d,J＝7.7Hz,1H),7.67(t,J＝8.0Hz,1H),5.11(d,J＝3.4Hz,1H),2.98(d,J＝10.9Hz,1H),2.71(d,J＝10.5Hz, 1H),2.55(d,J＝7.1Hz,2H),2.40(d,J＝11.5Hz,1H),2.30(s,2H),2.18(s,3H),1.97(d,J＝ 4.8Hz,2H),1.83(t,J＝13.4Hz,1H),1.65(dd,J＝13.5,5.8Hz,1H),1.47(dt,J＝14.5,6.9Hz, 1H).；13C NMR(100MHz,CDCl3)δ174.45,160.21,133.33,132.65,130.50,129.65,125.58, 123.04,84.91,60.84,45.86,32.63,24.90,20.77。
1H NMR(400MHz,CDCl3)δ8.62(s,1H),8.40-8.24(m,1H),8.19(d,J＝7.7Hz,1H),7.67(t,J＝8.0Hz,1H),5.11(d,J＝3.4Hz,1H),2.98(d,J＝10.9Hz,1H),2.71(d,J＝10.5Hz, 1H),2.55(d,J＝7.1Hz,2H),2.40(d,J＝11.5Hz,1H),2.30(s,2H),2.18(s,3H),1.97(d,J＝ 4.8Hz,2H),1.83(t,J＝13.4Hz,1H),1.65(dd,J＝13.5,5.8Hz,1H),1.47(dt,J＝14.5,6.9Hz, 1H)；13C NMR(100MHz,CDCl3)δ173.89,158.29,147.54,131.43,131.37,129.17,123.81, 120.74,84.43,59.83,54.03,44.77,32.38,31.67,30.27,23.89,19.74。
1H NMR(400MHz,CDCl3)δ8.62(s,1H),8.40-8.24(m,1H),8.19(d,J＝7.7Hz,1H),7.67(t,J＝8.0Hz,1H),5.11(d,J＝3.4Hz,1H),2.98(d,J＝10.9Hz,1H),2.71(d,J＝10.5Hz, 1H),2.55(d,J＝7.1Hz,2H),2.40(d,J＝11.5Hz,1H),2.30(s,2H),2.18(s,3H),1.97(d,J＝ 4.8Hz,2H),1.83(t,J＝13.4Hz,1H),1.65(dd,J＝13.5,5.8Hz,1H),1.47(dt,J＝14.5,6.9Hz, 1H).；13C NMR(100MHz,CDCl3)δ174.46,162.85(d,J＝247.4Hz),160.55,132.80(d,J＝ 8.3Hz),130.66(d,J＝8.3Hz),122.85(d,J＝1.5Hz),117.39(d,J＝21.3Hz),113.64(d,J＝ 23.8Hz),84.91,60.87,45.81,32.65,24.91,20.79。
1H NMR(400MHz,CDCl3)δ8.26(t,J＝7.0Hz,1H),7.50-7.34(m,1H),7.26(t,J＝7.5 Hz,1H),7.21-7.10(m,1H),5.10(s,1H),2.97(d,J＝10.9Hz,2H),2.63-2.46(m,1H),2.39(d,J ＝11.1Hz,2H),2.29(s,2H),2.17(s,3H),1.98(t,J＝13.2Hz,2H),1.63(dd,J＝13.3,5.4Hz, 2H),1.48(dd,J＝12.3,6.0Hz,1H).；13C NMR(100MHz,CDCl3)δ175.97(d,J＝6.2Hz), 158.98(d,J＝251.0Hz),154.03(d,J＝7.4Hz),131.80(d,J＝8.6Hz),128.08(d,J＝2.1Hz), 124.74(d,J＝3.3Hz),118.81(d,J＝11.7Hz),115.99(d,J＝21.7Hz),84.46,60.86,45.84, 32.66,24.89,20.75。
1H NMR(400MHz,CDCl3)δ8.25-8.11(m,1H),7.54-7.44(m,1H),7.38(dd,J＝6.0,3.5 Hz,2H),5.10(d,J＝3.7Hz,1H),2.97(d,J＝10.5Hz,1H),2.70(d,J＝10.4Hz,1H),2.56(dd,J ＝13.0,6.4Hz,2H),2.39(d,J＝11.8Hz,1H),2.30(s,2H),2.17(s,3H),1.97(dd,J＝12.5,5.1 Hz,2H),1.83(dd,J＝16.2,11.4Hz,1H),1.64(dd,J＝13.8,6.1Hz,1H),1.47(dd,J＝13.1,6.5 Hz,1H)；13C NMR(100MHz,CDCl3)δ176.08,157.41,131.91,131.16,130.49,130.45,129.62, 127.31,84.54,60.93,55.02,45.92,33.37,32.70,31.19,24.94,20.80。
1H NMR(400MHz,CDCl3)δ8.04(dd,J＝7.9,1.6Hz,1H),7.68(dd,J＝8.0,1.0Hz,1H), 7.42(t,J＝7.6Hz,1H),7.35-7.21(m,1H),5.11(d,J＝3.4Hz,1H),2.97(d,J＝10.9Hz,1H), 2.69(s,1H),2.55(m,2H),2.37(t,J＝14.5Hz,1H),2.30(s,2H),2.18(s,3H),2.09-1.87(m, 2H),1.92-1.74(m,1H),1.64(dd,J＝13.8,6.1Hz,1H),1.47(dt,J＝21.4,7.4Hz,1H).；13C NMR(100MHz,CDCl3)δ175.82,158.75,133.84,131.67,131.39,131.29,127.75,121.85, 84.58,60.91,45.89,32.72,24.93,20.78。
1H NMR(400MHz,CDCl3)δ7.96(dd,J＝8.0,1.0Hz,1H),7.86-7.50(m,3H),5.12(t,J ＝3.6Hz,1H),2.97(d,J＝11.0Hz,1H),2.56(m,2H),2.39(d,J＝11.6Hz,1H),2.30(s,2H), 2.24-2.11(m,3H),2.08-1.91(m,2H),1.82(t,J＝13.9Hz,1H),1.65(dd,J＝13.8,6.1Hz,2H), 1.48(dt,J＝12.7,6.3Hz,1H)；13C NMR(100MHz,CDCl3)δ175.97,156.16,148.52,132.81, 132.07,131.09,125.09,124.67,85.19,60.87,45.85,32.70,24.91,20.73。
1H NMR(400MHz,CDCl3)δ8.62(s,1H),8.40-8.24(m,1H),8.19(d,J＝7.7Hz,1H),7.67(t,J＝8.0Hz,1H),5.11(d,J＝3.4Hz,1H),2.98(d,J＝10.9Hz,1H),2.71(d,J＝10.5Hz, 1H),2.55(d,J＝7.1Hz,2H),2.40(d,J＝11.5Hz,1H),2.30(s,2H),2.18(s,3H),1.97(d,J＝ 4.8Hz,2H),1.83(t,J＝13.4Hz,1H),1.65(dd,J＝13.5,5.8Hz,1H),1.47(dt,J＝14.5,6.9Hz, 1H)；13C NMR(100MHz,CDCl3)δ175.93,155.60,155.18,131.30,127.38,121.07,119.64, 111.24,83.53,60.88,55.52,45.82,32.63,24.92,20.83。
1H NMR(400MHz,CDCl3)δ7.70(d,J＝1.9Hz,2H),7.42(s,1H),5.11(s,1H),2.99(d, J＝11.1Hz,2H),2.56(tt,J＝13.2,6.7Hz,1H),2.40(d,J＝11.3Hz,2H),2.29(s,2H),2.19(s, 3H),2.02-1.87(m,2H),1.65(dd,J＝13.7,6.0Hz,2H),1.54-1.44(m,1H)；13C NMR(100MHz, CDCl3)δ174.81,159.04,135.75,133.49,130.22,125.22,85.30,60.86,45.84,32.69,24.90, 20.73。
1H NMR(400MHz,CDCl3)δ6.98(d,J＝2.2Hz,2H),6.53(s,1H),5.07(d,J＝3.1Hz,1H),3.84(s,6H),2.96(d,J＝11.0Hz,1H),2.53(dd,J＝12.9,6.4Hz,2H),2.38(d,J＝11.5Hz, 1H),2.29(s,2H),2.17(s,3H),1.96(dd,J＝12.3,5.8Hz,2H),1.81(t,J＝13.6Hz,1H),1.63 (dd,J＝13.7,6.0Hz,2H),1.47(dd,J＝13.2,6.2Hz,1H).；13C NMR(100MHz,CDCl3)δ 174.24,161.89,161.01,132.47,104.92,102.66,84.70,60.91,55.51,45.84,32.66,24.94,20.83。
1H NMR(400MHz,CDCl3)δ7.06(s,2H),5.07(s,1H),3.92(s,6H),3.90(s,3H),2.97(d, J＝10.9Hz,2H),2.60-2.47(m,1H),2.38(d,J＝11.1Hz,2H),2.29(s,2H),2.18(s,3H),2.02-1.91(m,2H),1.64(dd,J＝13.5,5.9Hz,2H),1.51-1.42(m,1H).；13C NMR(100MHz,CDCl3)δ174.05,161.84,153.57,140.13,126.23,104.27,84.73,60.98,60.87,56.31,45.87, 32.65,24.90,20.76。
1H NMR(4000MHz,CDCl3)δ8.47(d,J＝2.0Hz,1H),8.14(dd,J＝8.8,2.2Hz,1H),7.42-7.11(m,1H),5.09(d,J＝2.9Hz,1H),2.98(d,J＝10.2Hz,1H),2.76(d,J＝11.3Hz,1H), 2.65-2.44(m,2H),2.39(d,J＝11.9Hz,1H),2.29(s,2H),2.20(d,J＝13.2Hz,3H),1.98(dd,J ＝13.0,6.4Hz,2H),1.89-1.72(m,1H),1.71-1.58(m,1H),1.48(dt,J＝13.4,6.0Hz,1H).；13C NMR(100MHz,CDCl3)δ174.44,159.12,156.34,135.27,133.53,123.79,123.57,121.07, 85.27,60.89,45.83,32.71,24.93,20.77。
1H NMR(400MHz,CDCl3)δ9.12(d,J＝2.7Hz,1H),8.23(dd,J＝8.8,2.7Hz,1H),7.69 (d,J＝8.8Hz,1H),5.16(s,1H),2.99(d,J＝11.0Hz,1H),2.56(dd,J＝12.8,6.3Hz,2H), 2.47-2.33(m,1H),2.31(s,2H),2.19(s,3H),2.07-1.87(m,2H),1.84(s,1H),1.66(dd,J＝13.5, 5.8Hz,2H),1.48(dd,J＝12.3,6.1Hz,1H)；13C NMR(100MHz,CDCl3)δ176.65,155.05, 146.88,137.90,131.62,131.16,125.55,125.04,85.26,60.86,45.86,32.72,24.91,20.73。
1H NMR(400MHz,CDCl3)δ7.86(dd,J＝9.5,3.1Hz,1H),7.64(dd,J＝8.9,5.2Hz,1H), 7.05(ddd,J＝8.8,7.4,3.1Hz,1H),5.12(s,1H),2.98(d,J＝11.2Hz,1H),2.56(dt,J＝19.6,6.5 Hz,2H),2.40(d,J＝11.5Hz,1H),2.27(d,J＝21.0Hz,2H),2.18(s,3H),1.98(dd,J＝12.9,6.6 Hz,2H),1.83(t,J＝13.6Hz,1H),1.65(dd,J＝13.7,6.0Hz,2H),1.49(dt,J＝12.4,6.2Hz,1H)； 13C NMR(100MHz,CDCl3)δ176.02,161.70(d,J＝248.5Hz),157.55,135.27(d,J＝8.0Hz), 133.25(d,J＝8.3Hz),118.71(d,J＝22.7Hz),118.01(d,J＝25.3Hz),115.91(d,J＝3.3Hz), 84.56,60.79,45.97,32.64,24.81,20.65。
1H NMR(400MHz,DMSO)δ7.95(d,J＝8.1Hz,2H),7.49(s,1H),7.32(d,J＝7.9Hz,2H),4.14–4.08(m,1H),3.41(s,2H),2.40(s,3H),2.31(s,3H),2.22–2.05(m,6H),1.81(d,J＝8.2Hz,2H).13C NMR(101MHz,DMSO)δ166.93,158.53,149.51,127.74,126.86,113.77,98.85,61.50,55.05,44.62,34.66,24.81.
1H NMR(400MHz,DMSO)δ8.08(d,J＝8.2Hz,2H),7.74(d,J＝8.3Hz,2H),7.36(s,1H),4.20–4.09(m,1H),3.99(s,2H),2.73(s,3H),2.36–2.23(m,2H),2.12–1.93(m,2H).13CNMR(101MHz,DMSO)δ162.78,162.71(d,J＝247.8Hz),154.42,130.32,130.29,127.93(d, J＝8.2Hz),115.69(d,J＝21.7Hz),112.78,62.22,38.47,38.03,35.97,25.65.
1H NMR(400MHz,MeOD)δ7.77(d,J＝8.4Hz,2H),7.35(d,J＝8.4Hz,2H),6.85(s,1H),4.18(m,1H),3.69(s,2H),2.35–2.19(m,4H),2.04(d,J＝8.7Hz,2H),1.84(t,J＝12.3Hz,2H).13C NMR(101MHz,DMSO)δ166.95,148.41,133.59,131.61,128.43,127.29,102.16,62.76,43.90,38.20,35.13,24.00.
1H NMR(400MHz,DMSO)δ7.81(d,J＝8.4Hz,2H),7.57(d,J＝8.4Hz,2H),7.17(s,1H),4.15–4.07(m,1H),3.97(s,2H),2.70(s,3H),2.33–2.24(m,4H),2.12–1.88(m,4H).13CNMR(101MHz,DMSO)δ166.94,148.42,133.91,131.34,127.62,120.20,102.27,62.74,43.90,38.19,35.10,24.00.
1H NMR(400MHz,DMSO)δ7.78(d,J＝8.6Hz,2H),7.01–6.86(m,3H),4.14–4.05(m,1H),3.96(s,2H),3.77(s,3H),2.70(s,3H),2.33–2.24(s,4H),2.09–1.88(m,4H).13C NMR(101MHz,DMSO)δ166.76,158.58,149.45,127.63,126.91,113.79,99.12,62.76,55.08,43.90, 38.19,35.16,23.99.
1H NMR(400MHz,MeOD)δ7.98(d,J＝8.1Hz,2H),7.64(d,J＝8.1Hz,2H),7.03(s,1H), 4.28–4.20(m,1H),3.77(s,2H),2.69(s,3H),2.38–2.24(m,4H),2.08(d,J＝8.6Hz,2H), 1.91(t,J＝12.7Hz,2H).13C NMR(101MHz,DMSO)δ167.21,148.15,138.46,127.23(q,J＝ 31.7Hz),126.06,125.37(d,J＝3.7Hz),124.35(q,J＝271.9Hz),104.02,61.69,44.46,37.52, 34.44,24.62.
1H NMR(400MHz,MeOD&CDCl3)δ8.12(d,J＝8.5Hz,2H),7.92(d,J＝8.5Hz,2H),7.04(s,1H),4.28–4.20(m,1H),3.88(s,2H),2.73(s,3H),2.42–2.24(m,4H),2.12(d,J＝8.9 Hz,2H),1.96(t,J＝12.8Hz,2H).13C NMR(101MHz,MeOD&CDCl3)δ165.01,154.40,148.63,141.20,128.10,125.33,119.02,64.07,39.66,39.03,37.91,26.33.
1H NMR(400MHz,MeOD)δ7.72(d,J＝7.4Hz,1H),7.45(d,J＝7.6Hz,1H),7.38–7.26(m, 2H),6.87(s,1H),4.28–4.21(m,1H),3.91(s,2H),2.79(s,3H),2.37–2.31(m,4H),2.17(d,J ＝8.5Hz,2H),1.96(t,J＝12.9Hz,2H).13C NMR(101MHz,MeOD)δ168.87,148.67,135.40, 133.45,132.51,131.31,130.11,127.98,107.16,64.79,45.25,38.79,36.61,25.40.
1H NMR(400MHz,DMSO)δ8.64(s,1H),8.31(d,J＝8.0Hz,1H),8.12(d,J＝9.0Hz,1H),7.98(d,J＝6.7Hz,1H),7.69(t,J＝8.0Hz,1H),7.45(s,1H),4.18–4.08(m,1H),3.98(s, 2H),2.74(s,3H),2.36–2.22(s,4H),2.07–1.94(m,4H).13C NMR(101MHz,DMSO)δ167.25,148.18,147.28,136.17,131.75,130.11,121.77,119.80,104.20,62.61,44.02,42.41, 34.97,24.06.
1H NMR(400MHz,CDCl3)δ7.28(d,J＝7.4Hz,2H),7.19(t,J＝7.9Hz,1H),6.75(d,J＝8.6 Hz,1H),6.59(s,1H),4.19–4.09(m,1H),3.76(m,5H),2.68(s,3H),2.35(t,J＝12.0Hz,2H), 2.28–2.17(m,4H),1.98(d,J＝8.9Hz,2H).13C NMR(101MHz,CDCl3)δ162.53,153.67, 135.48,134.56,130.12,128.15,126.19,124.19,114.46,63.05,38.33,36.94,35.28,24.99.
1H NMR(400MHz,MeOD)δ7.89(t,J＝1.8Hz,1H),7.64(d,J＝7.9Hz,1H),7.33(d,J＝8.0Hz,1H),7.29(s,1H),7.17(t,J＝7.9Hz,1H),3.99–3.89(m,1H),3.58(s,2H),2.54(s,3H),2.30–2.16(m,4H),2.12–2.03(m,2H),1.83(d,J＝8.7Hz,2H).13C NMR(101MHz, MeOD)δ162.95,153.53,135.81,131.02,130.35,129.17,124.63,122.82,114.30,62.45,38.61,37.90,35.95,25.42.
1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.9Hz,1H),7.20–7.16(m,1H),7.02(d,J＝7.6Hz,1H),6.58(s,1H),4.15–4.05(m,1H),3.67(s,2H),2.61(s,3H),2.32–2.15(m,9H),1.97(d,J＝8.7Hz,2H).13C NMR(101MHz,CDCl3)δ161.00,154.55,137.37,132.85,128.10,127.70,125.87,122.31,112.23,61.52,37.07,36.44,34.31,24.37,20.54.
1H NMR(400MHz,MeOD&CDCl3)δ7.66(s,1H),7.52(d,J＝7.6Hz,1H),7.19–7.12(m,2H),6.56(s,1H),4.20–4.10(m,1H),3.88(s,2H),2.78(s,3H),2.39(t,J＝12.3Hz,2H),2.29 –2.18(m,4H),2.01(d,J＝8.8Hz,2H).13C NMR(101MHz,MeOD&CDCl3)δ169.53,150.53,138.35,135.51,131.14,128.42,127.03,125.35,103.81,65.14,45.23,39.35,37.14,25.50.
1H NMR(400MHz,DMSO)δ7.90(d,J＝6.6Hz,1H),7.84(d,J＝7.8Hz,1H),7.72(d,J＝8.0Hz,1H),7.64(t,J＝7.6Hz,1H),7.51(t,J＝7.7Hz,1H),7.17(s,1H),3.99–3.89(m,1H), 3.83(s,2H),2.62(s,3H),2.26–2.06(m,4H),2.01–1.89(m,4H).13C NMR(101MHz,DMSO) δ166.63,148.88,145.00,131.51,129.08,128.52,127.25,123.25,105.32,62.05,44.12,37.49, 34.17,24.10.
1H NMR(400MHz,MeOD)δ7.99(d,J＝6.8Hz,1H),7.25(t,J＝7.7Hz,1H),7.10(s,1H), 7.07–6.95(m,2H),4.35–4.20(m,1H),3.96–3.88(m,5H),2.80(s,3H),2.47–2.29(m,4H), 2.17(d,J＝8.7Hz,2H),1.96(t,J＝12.7Hz,2H).13C NMR(101MHz,MeOD)δ167.68,158.47,147.64,130.86,129.56,124.87,121.56,112.31,106.77,65.15,55.92,45.14,39.30, 37.20,25.42.
1H NMR(400MHz,MeOD)δ7.62(dd,J＝19.9,7.8Hz,2H),7.37(t,J＝7.5Hz,1H),7.23(t,J ＝7.7Hz,1H),6.76(s,1H),4.32–4.15(m,1H),3.93(s,2H),2.80(s,3H),2.38–2.29(m,4H), 2.16(d,J＝8.7Hz,2H),2.01(t,J＝12.7Hz,2H).13C NMR(101MHz,MeOD)δ169.02, 150.28,137.69,134.58,132.70,130.56,128.58,123.32,106.85,64.91,45.19,38.93,36.69, 25.36.
1H NMR(400MHz,MeOD)δ7.42(d,J＝7.1Hz,1H),7.24–7.16(m,3H),6.43(s,1H),4.26–4.18(m,1H),3.93(s,2H),2.80(s,3H),2.46–2.26(m,7H),2.16(d,J＝8.6Hz,2H),2.06(t,J＝12.3Hz,2H).13C NMR(101MHz,MeOD)δ161.55,155.82,136.02,134.12,130.95,129.65,128.26,125.94,116.20,62.03,38.54,38.16,36.17,25.68,21.29.
1H NMR(400MHz,DMSO)δ8.09(s,1H),7.98(d,J＝6.6Hz,1H),7.87(d,J＝8.5Hz,1H), 7.65(d,J＝8.4Hz,1H),7.33(s,1H),4.19–4.08(m,1H),3.94(s,2H),2.72(s,3H),2.37–2.19 (m,4H),2.16–1.98(m,4H).13C NMR(101MHz,DMSO)δ167.09,147.06,135.29,131.24, 130.63,129.33,127.08,125.66,103.63,62.14,44.04,37.31,34.18,24.32.
1H NMR(400MHz,MeOD)δ7.88(d,J＝1.9Hz,2H),7.46(t,J＝1.9Hz,1H),7.41(s,1H), 4.17–4.07(m,1H),3.94(s,2H),2.72(s,3H),2.43–2.20(m,4H),2.10–1.98(m,4H).13CNMR(101MHz,MeOD)δ162.32,151.40,135.57,134.33,126.94,123.56,114.28,61.67,37.40, 36.48,34.53,24.32.
1H NMR(400MHz,MeOD)δ8.50(d,J＝6.3Hz,2H),7.84(d,J＝4.7Hz,2H),7.28(s,1H), 4.37–4.28(m,1H),3.96(s,2H),2.82(s,3H),2.44–2.36(m,4H),2.20(d,J＝8.8Hz,2H), 1.99(t,J＝12.9Hz,2H).13C NMR(101MHz,MeOD)δ169.62,150.34,149.06,144.38,121.88, 107.59,64.85,45.29,36.59,30.74,25.54.
1H NMR(400MHz,MeOD)δ6.12(s,1H),4.20–4.12(m,1H),3.95(s,2H),2.82(s,3H),2.38 –2.33(m,2H),2.30–2.14(m,7H),1.99(t,J＝12.2Hz,2H).13C NMR(101MHz,MeOD)δ170.04,148.71,148.57,101.90,64.90,45.08,38.93,36.70,25.27,17.24.
1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.1Hz,2H),7.06(d,J＝8.0Hz,2H),6.71(s,1H), 5.28(t,J＝4.5Hz,1H),3.58(s,2H),2.82(d,J＝15.9Hz,2H),2.59(s,3H),2.26–2.10(m, 9H).13C NMR(101MHz,CDCl3)δ172.00,149.13,137.68,131.46,129.21,125.60,103.90, 72.69,61.50,38.90,34.08,24.63,21.16.
1H NMR(400MHz,MeOD)δ7.84(dd,J＝8.2,5.7Hz,2H),7.14–7.08(m,3H),5.32(t,J＝ 4.5Hz,1H),3.75(s,2H),2.71(s,3H),2.49(d,J＝16.2Hz,2H),2.41–2.26(m,6H).13CNMR (101MHz,MeOD)δ172.55,162.42(d,J＝245.8Hz),148.01,130.80,130.77,127.31(d,J＝ 8.1Hz),114.82(d,J＝21.9Hz),104.67,72.80,61.33,37.73,33.96,23.97.
1H NMR(400MHz,CDCl3)δ7.71(d,J＝8.5Hz,2H),7.35(d,J＝8.5Hz,2H),6.89(s,1H), 5.45(t,J＝4.5Hz,1H),3.84(s,2H),3.15(s,2H),2.81(s,3H),2.52–2.25(m,6H).13CNMR (101MHz,CDCl3)δ172.11,148.13,133.70,132.61,128.78,127.07,105.24,72.41,62.19, 39.12,34.11,24.55.
1H NMR(400MHz,MeOD&CDCl3)δ7.58(d,J＝8.6Hz,2H),7.41(d,J＝8.6Hz,2H),6.91(s,1H),5.30(t,J＝4.7Hz,1H),3.86(s,2H),2.76–2.71(m,5H),2.43–2.25(m,6H).13C NMR(101MHz,MeOD&CDCl3)δ171.38,147.22,132.29,130.78,126.56,120.95,105.03,71.11,61.38,38.19,33.29,23.61.
1H NMR(400MHz,CDCl3)δ7.62(d,J＝8.7Hz,2H),6.82(d,J＝8.7Hz,2H),6.66(s,1H), 5.34(s,1H),3.82(s,2H),3.74(s,3H),2.99(d,J＝15.3Hz,2H),2.75(s,3H),2.35–2.22(m, 6H).13C NMR(101MHz,CDCl3)δ170.89,158.50,148.07,131.47,126.15,113.00,101.99, 71.01,61.19,54.37,32.94,28.66,23.67.
1H NMR(400MHz,CDCl3)δ7.81(d,J＝7.8Hz,2H),7.55(d,J＝7.8Hz,2H),6.93(s,1H), 5.35(s,1H),3.69(s,2H),2.88(d,J＝15.7Hz,2H),2.65(s,3H),2.36–2.16(m,6H).13CNMR (101MHz,CDCl3)δ171.50,146.82,136.43,128.59(q,J＝32.3Hz),125.02,124.59(d,J＝7.5), 123.16(q,J＝271.9Hz),105.98,72.08,60.73,38.59,33.47,23.97.
1H NMR(400MHz,MeOD)δ8.23(d,J＝8.7Hz,2H),8.06(d,J＝8.7Hz,2H),7.53(s,1H), 5.38(t,J＝4.6Hz,1H),3.78(s,2H),2.73(s,3H),2.53(d,J＝16.4Hz,2H),2.45–2.27(m, 6H).13C NMR(101MHz,MeOD)δ174.40,148.41,148.26,141.66,127.61,125.00,111.03,74.69,62.87,39.30,35.49,25.52.
1H NMR(400MHz,CDCl3)δ7.70(t,J＝1.8Hz,1H),7.59(dt,J＝7.6,1.4Hz,1H),7.31–7.14 (m,2H),6.83(s,1H),5.31(t,J＝4.8Hz,1H),3.54(s,2H),2.76(d,J＝15.8Hz,2H),2.56(s, 3H),2.31–2.08(m,6H).13C NMR(101MHz,CDCl3)δ171.52,146.97,134.97,133.64,128.90, 126.95,124.93,122.89,104.68,72.59,60.30,38.45,33.66,24.05.
1H NMR(400MHz,MeOD&CDCl3)δ8.54(t,J＝1.9Hz,1H),8.14–8.00(m,2H),7.52(t,J＝8.0Hz,1H),7.15(s,1H),5.36(t,J＝4.8Hz,1H),3.82(s,2H),2.82–2.61(m,5H),2.45–2.22(m,6H).13C NMR(101MHz,MeOD&CDCl3)δ171.92,147.80,146.00,135.09,130.83,128.92,121.62,119.71,106.98,71.71,61.15,33.35,28.78,23.66.
1H NMR(400MHz,CDCl3)δ8.00(dd,J＝7.8,1.7Hz,1H),7.30(s,1H),7.18(t,J＝7.8Hz, 1H),6.94(t,J＝7.1Hz,1H),6.87(d,J＝8.2Hz,1H),5.35(t,J＝4.5Hz,1H),3.84(s,3H),3.03 (d,J＝15.8Hz,2H),2.73(s,3H),2.42–2.20(m,6H).13C NMR(101MHz,CDCl3)δ169.24, 155.87,144.11,128.97,127.79,121.67,119.79,110.02,108.94,70.57,61.39,54.45,38.35, 32.90,23.79.
1H NMR(400MHz,CDCl3)δ7.54(s,1H),7.48(d,J＝7.8Hz,1H),7.20(t,J＝7.3Hz,1H), 7.05(d,J＝7.5Hz,1H),6.80(s,1H),5.39(t,J＝4.6Hz,1H),3.86(s,2H),3.10(d,J＝15.8Hz, 2H),2.75(s,3H),2.44–2.20(m,9H).13C NMR(101MHz,CDCl3)δ170.75,148.50,137.36, 133.00,127.90,127.55,125.57,121.85,103.78,70.77,61.43,38.36,32.97,23.80,20.49.
1H NMR(400MHz,CDCl3)δ7.54(s,1H),7.48(d,J＝7.8Hz,1H),7.20(t,J＝7.3Hz,1H), 7.05(d,J＝7.5Hz,1H),6.80(s,1H),5.39(t,J＝4.6Hz,1H),3.86(s,2H),3.10(d,J＝15.8Hz, 2H),2.75(s,3H),2.44–2.20(m,9H).13C NMR(101MHz,CDCl3)δ170.75,148.50,137.36, 133.00,127.90,127.55,125.57,121.85,103.78,70.77,61.43,38.36,32.97,23.80,20.49.
1H NMR(400MHz,CDCl3)δ7.80(d,J＝7.8Hz,1H),7.35(d,J＝7.0Hz,1H),7.29–7.13(m, 2H),5.31(t,J＝4.6Hz,1H),3.69(s,2H),2.90(d,J＝16.0Hz,2H),2.65(s,3H),2.37–2.26(m, 4H),2.23–2.18(dd,2H).13C NMR(101MHz,CDCl3)δ170.09,144.75,131.65,130.55,130.38, 129.55,127.84,125.96,109.53,71.72,60.81,38.40,33.32,23.93.
1H NMR(400MHz,CDCl3)δ7.65(d,J＝7.9Hz,1H),7.58–7.49(m,2H),7.43–7.38(m,1H), 6.82(s,1H),5.16(t,J＝4.4Hz,1H),3.80(s,2H),2.94(d,J＝15.7Hz,2H),2.73(s,3H),2.38– 2.24(m,6H).13C NMR(101MHz,CDCl3)δ170.88,148.14,143.91,131.02,129.26,128.02, 127.39,122.92,108.22,71.71,60.93,32.42,28.67,23.87.
1H NMR(400MHz,CDCl3)δ8.00(dd,J＝7.8,1.7Hz,1H),7.30(s,1H),7.18(t,J＝7.8Hz, 1H),6.94(t,J＝7.1Hz,1H),6.87(d,J＝8.2Hz,1H),5.35(t,J＝4.5Hz,1H),3.84(s,3H),3.03 (d,J＝15.8Hz,2H),2.73(s,3H),2.42–2.20(m,6H).13C NMR(101MHz,CDCl3)δ169.24, 155.87,144.11,128.97,127.79,121.67,119.79,110.02,108.94,70.57,61.39,54.45,38.35, 32.90,23.79.
1H NMR(400MHz,CDCl3)δ7.64(d,J＝7.7Hz,1H),7.56(d,J＝8.0Hz,1H),7.28(t,J＝7.1 Hz,1H),7.15–7.07(m,2H),5.33(t,J＝4.3Hz,1H),3.89(s,2H),3.11(s,2H),2.77(s,3H), 2.40–2.28(m,6H).13C NMR(101MHz,CDCl3)δ169.97,146.29,133.82,132.82,130.61, 128.31,126.51,120.31,109.36,70.91,61.73,33.27,28.66,23.77.
1H NMR(400MHz,CDCl3)δ7.53–7.40(m,1H),7.19–7.12(m,3H),6.60(s,1H),5.30(t,J＝4.7Hz,1H),3.77(s,2H),2.96(d,J＝16.1Hz,2H),2.69(s,3H),2.42–2.21(m,9H).13CNMR (101MHz,CDCl3)δ170.15,148.91,134.98,133.27,129.97,128.47,127.13,124.91,107.13, 71.16,61.05,38.33,33.06,23.92,20.39.
1H NMR(400MHz,CDCl3)δ7.78(s,1H),7.51(d,J＝8.4Hz,1H),7.35(d,J＝8.4Hz,1H), 6.86(s,1H),5.33(s,1H),3.76(s,2H),2.91(d,J＝16.2Hz,2H),2.71(s,3H),2.27(dt,J＝10.3, 8.6Hz,6H).13C NMR(101MHz,CDCl3)δ171.39,145.88,133.15,131.74,130.66,129.56, 126.65,123.95,105.45,71.68,60.91,37.72,33.04,23.54.
1H NMR(400MHz,CDCl3)δ7.57(s,2H),7.20(s,1H),6.86(s,1H),5.33(t,J＝4.6Hz,1H), 3.60(s,2H),2.88(d,J＝15.9Hz,2H),2.62(s,3H),2.33–2.13(m,6H).13C NMR(101MHz, CDCl3)δ174.08,147.80,138.54,136.58,128.84,125.49,108.95,74.37,62.98,39.88,35.69, 30.94,25.85.
1H NMR(400MHz,CDCl3)δ7.32(s,1H),6.75(s,1H),6.56(d,J＝3.0Hz,1H),6.37(d,J＝ 3.3Hz,1H),5.31(s,1H),3.84(s,2H),2.97(d,J＝13.2Hz,2H),2.75(s,3H),2.42–2.18(m, 6H).13C NMR(101MHz,CDCl3)δ171.44,148.98,141.14,140.07,110.49,106.15,103.19, 71.40,61.11,38.30,33.04,23.74.
1H NMR(400MHz,MeOD)δ8.54(d,J＝6.3Hz,2H),7.86(d,J＝6.3Hz,2H),7.66(s,1H), 5.42(s,1H),3.99(s,2H),2.88(s,3H),2.65–2.32(m,8H).13C NMR(101MHz,MeOD)δ174.27,150.57,147.45,143.68,121.72,112.27,73.86,63.57,35.70,30.69,25.20.
1H NMR(400MHz,MeOD)δ6.48(d,J＝1.1Hz,1H),5.15(t,J＝4.7Hz,1H),3.91(s,2H), 2.82(s,3H),2.55–2.49(m,2H),2.43–2.29(m,6H),2.23(d,J＝1.1Hz,3H).13C NMR(101 MHz,MeOD)δ173.93,148.21,106.92,73.47,63.36,39.14,35.24,30.77,25.18,17.53.
1H NMR(400MHz,CDCl3)δ7.75(d,J＝8.1Hz,2H),7.29(s,1H),7.22(d,J＝7.9Hz,2H), 4.04–3.95(m,1H),3.41(s,2H),2.45(s,3H),2.37(s,3H),2.22–2.05(m,6H),1.81(d,J＝8.2 Hz,2H).13C NMR(101MHz,CDCl3)δ162.58,155.51,138.11,131.38,129.44,126.11,112.29, 61.80,38.77,38.71,36.50,25.95,21.29.
1H NMR(400MHz,CDCl3)δ7.86–7.79(m,2H),7.31(s,1H),7.10(t,J＝8.7Hz,2H),4.11– 3.99(m,1H),3.59(s,2H),2.58(s,3H),2.42–2.12(m,6H),1.92(d,J＝8.5Hz,2H).13CNMR (101MHz,CDCl3)δ162.78,162.71(d,J＝247.8Hz),154.42,130.32,130.29,127.93(d,J＝8.2 Hz),115.69(d,J＝21.7Hz),112.78,62.22,38.47,38.03,35.97,25.65.
1H NMR(400MHz,MeOD)δ7.69(d,J＝8.5Hz,2H),7.46(s,1H),7.26(d,J＝8.5Hz,2H), 3.99–3.90(m,1H),3.65(s,2H),2.55(s,3H),2.29–2.07(m,6H),1.90(d,J＝8.8Hz,2H).13C NMR(101MHz,MeOD)δ163.75,155.65,135.27,133.87,130.20,128.87,115.91,64.43,39.59, 38.63,37.51,26.21.
1H NMR(400MHz,CDCl3)δ7.66(d,J＝8.5Hz,2H),7.46(d,J＝8.5Hz,2H),7.28(s,1H), 4.00–3.84(m,1H),3.29(s,2H),2.34(s,3H),2.11–1.97(m,6H),1.71(d,J＝8.2Hz,2H).13C NMR(101MHz,CDCl3)δ163.50,154.23,133.00,131.87,127.76,122.17,113.38,61.72,39.08, 38.98,36.83,26.05,18.47.
1H NMR(400MHz,CDCl3)δ7.80(d,J＝8.8Hz,2H),7.22(s,1H),6.94(d,J＝8.8Hz,2H), 4.03–3.90(m,1H),3.84(s,3H),3.34(s,2H),2.39(s,3H),2.18–2.03(m,6H),1.77(d,J＝8.2 Hz,2H).13C NMR(101MHz,CDCl3)δ162.67,159.65,155.26,127.52,127.09,114.10,111.26, 61.57,55.34,39.17,38.86,36.82,26.12.
1H NMR(400MHz,CDCl3)δ7.97(d,J＝8.2Hz,2H),7.67(d,J＝8.2Hz,2H),7.48(s,1H), 4.08–4.00(m,1H),3.41(s,2H),2.45(s,3H),2.24–2.05(m,6H),1.82(d,J＝8.2Hz,2H).13C NMR(101MHz,CDCl3)δ163.89,153.81,137.24,129.92(q,J＝32.5Hz),125.75(q,J＝3.7 Hz),126.37,124.13(q,J＝272.0Hz),114.75,61.83,38.94,36.78,25.99.
1H NMR(400MHz,MeOD&CDCl3)δ8.18(d,J＝9.0Hz,2H),8.00(d,J＝9.0Hz,2H),7.85(s,1H),4.09–3.96(m,1H),3.55(s,2H),2.48(s,3H),2.25–2.14(m,4H),2.06–1.98(m,2H),1.90(d,J＝8.7Hz,2H).13C NMR(101MHz,MeOD)δ165.01,154.40,148.63,141.20,128.10,125.33,119.02,64.07,39.66,39.03,37.91,26.33.
1H NMR(400MHz,CDCl3)δ7.78(s,1H),7.64(d,J＝7.5Hz,1H),7.36–7.18(m,3H),4.10– 3.92(m,1H),3.54(s,2H),2.53(s,3H),2.31(t,J＝13.0Hz,2H),2.25–2.15(m,2H),2.09(d,J ＝12.2Hz,2H),1.87(d,J＝8.5Hz,2H).13C NMR(101MHz,CDCl3)δ163.07,153.83,135.65, 134.70,130.06,128.18,126.37,124.18,114.13,62.33,38.50,37.96,35.88,25.59.
1H NMR(400MHz,MeOD&CDCl3)δ8.62(t,J＝1.9Hz,1H),8.13–8.02(m,2H),7.60(s,1H),7.52(t,J＝8.0Hz,1H),4.17–3.96(m,1H),3.59(s,2H),2.52(s,3H),2.30–2.13(m,6H), 1.95(d,J＝8.8Hz,2H).13C NMR(101MHz,MeOD&CDCl3)δ162.78,151.74,147.72,134.62,130.91,129.03,121.77,120.16,114.83,61.89,37.62,36.76,35.31,24.30.
1H NMR(400MHz,CDCl3)δ7.71(s,1H),7.59(d,J＝7.6Hz,1H),7.36–7.14(m,3H),4.05– 3.95(m,1H),3.82(s,2H),2.71(s,3H),2.47(t,J＝13.1Hz,2H),2.38–2.27(m,2H),2.23– 2.11(m,2H),1.94(d,J＝8.8Hz,2H).13C NMR(101MHz,CDCl3)δ162.53,153.67,135.48, 134.56,130.12,128.15,126.19,124.19,114.46,63.05,38.33,36.94,35.28,24.99.
1H NMR(400MHz,CDCl3)δ7.89(t,J＝1.8Hz,1H),7.64(d,J＝7.9Hz,1H),7.33(d,J＝8.0 Hz,1H),7.29(s,1H),7.17(t,J＝7.9Hz,1H),3.99–3.89(m,1H),3.58(s,2H),2.54(s,3H), 2.30–2.16(m,4H),2.12–2.03(m,2H),1.83(d,J＝8.7Hz,2H).13C NMR(101MHz,CDCl3) δ162.95,153.53,135.81,131.02,130.35,129.17,124.63,122.82,114.30,62.45,38.61,37.90, 35.95,25.42.
1H NMR(400MHz,CDCl3)δ7.61–7.53(m,2H),7.27(s,1H),7.22(t,J＝7.6Hz,1H),7.07(d, J＝7.6Hz,1H),4.05–3.94(m,1H),3.63(s,2H),2.59(s,3H),2.42(t,J＝12.3Hz,2H),2.32(s, 3H),2.28–2.22(m,2H),2.15–2.08(m,2H),1.90(d,J＝8.7Hz,2H).13C NMR(101MHz, CDCl3)δ161.00,154.55,137.37,132.85,128.10,127.70,125.87,122.31,112.23,61.52,37.07, 36.44,34.31,24.37,20.54.
1H NMR(400MHz,CDCl3)δ7.73(d,J＝7.6Hz,1H),7.57(s,1H),7.41–7.35(m,1H),7.30–7.17(m,WH),4.10–3.97(m,1H),3.76(s,2H),2.69(s,3H),2.57(t,J＝13.1Hz,2H),2.23(d,J＝51.3,4H),1.96(d,J＝11.0Hz,2H).13C NMR(101MHz,CDCl3)δ161.05,151.95,132.66,131.90,131.21,130.55,129.27,126.98,118.43,62.85,37.90,36.87,34.85,25.08.
1H NMR(400MHz,MeOD)δ7.70–7.65(m,3H),7.58(t,J＝7.6Hz,1H),7.47(t,J＝7.7Hz, 1H),4.04–3.91(m,1H),3.68(s,2H),2.58(s,3H),2.22–2.14(m,4H),2.08–1.89(m,4H).13C NMR(101MHz,MeOD)δ164.32,152.22,150.69,133.47,131.48,130.57,129.02,125.08, 118.98,64.79,39.17,38.13,37.42,25.33.
1H NMR(400MHz,CDCl3)δ8.04(d,J＝7.7Hz,1H),7.71(s,1H),7.17(t,J＝7.6Hz,1H), 6.97–6.81(m,2H),4.00–3.87(m,1H),3.78(s,3H),3.57(s,2H),2.53(s,3H),2.39–2.06(m, 6H),1.83(d,J＝8.6Hz,2H).13C NMR(101MHz,CDCl3)δ159.79,156.52,150.86,129.53, 129.04,122.35,120.64,117.62,111.11,62.55,55.35,38.19,37.16,35.37,25.16.
1H NMR(400MHz,CDCl3)δ7.95(t,J＝1.7Hz,1H),7.68(d,J＝7.8Hz,1H),7.36(d,J＝8.0 Hz,1H),7.30(s,1H),7.19(t,J＝7.9Hz,1H),4.04–3.83(m,1H),3.31(s,2H),2.35(s,3H), 2.12–1.96(m,6H),1.73(d,J＝8.3Hz,2H).13C NMR(101MHz,CDCl3)δ163.51,153.67, 135.96,131.03,130.29,129.30,124.64,122.89,113.99,61.75,58.07,39.02,38.92,36.71,25.98.
1H NMR(400MHz,CDCl3)δ7.47(d,J＝6.7Hz,1H),7.26–7.12(m,3H),7.07(s,1H),4.03–3.88(m,1H),3.42(s,2H),2.44(s,3H),2.38(s,3H),2.24–2.08(m,4H),2.02(d,J＝17.1Hz,2H),1.76(d,J＝8.5Hz,2H).13C NMR(101MHz,CDCl3)δ161.55,155.82,136.02,134.12,130.95,129.65,128.26,125.94,116.20,62.03,38.54,38.16,36.17,25.68,21.29.
1H NMR(400MHz,MeOD)δ7.87(d,J＝2.0Hz,1H),7.59(dd,J＝8.4,2.1Hz,1H),7.48(s,1H),7.39(d,J＝8.4Hz,1H),4.05–3.94(m,1H),3.71(s,2H),2.60(s,3H),2.32–2.17(m,6H),1.96(d,J＝8.9Hz,2H).13C NMR(101MHz,MeOD)δ164.13,154.34,135.28,134.15,133.33,132.12,129.39,126.74,116.66,64.50,39.59,38.48,37.26,26.26.
1H NMR(400MHz,CDCl3)δ7.63(d,J＝1.9Hz,2H),7.37(s,1H),7.21(t,J＝1.9Hz,1H),4.08–3.96(m,1H),3.69(s,2H),2.62(s,3H),2.44(t,J＝12.3Hz,2H),2.34–2.24(m,2H),2.18–2.09(m,2H),1.93(d,J＝8.8Hz,2H).13C NMR(101MHz,CDCl3)δ162.32, 151.40,135.57,134.33,126.94,123.56,114.28,61.67,37.40,36.48,34.53,24.32.
1H NMR(400M Hz,CDCl3)δ：7.69(d,J＝8.0Hz,2H),7.25(d,J＝7.9Hz,2H),5.36(m,1H),3.65(s,2H),2.89-2.80(m,2H),2.66(s,3H),2.39(s,3H),2.37-2.22(m,6H)；13CNMR (101M Hz,CDCl3)δ173.2,162.8,141.2,129.7,129.5,128.5,127.8,127.0,75.6,60.9, 39.0,34.4,25.0,21.4。
1H NMR(400M Hz,CDCl3)δ：7.81(dd,J＝8.6,5.3Hz,2H),7.15(t,J＝8.5Hz,2H),5.41 (m,1H),3.81(s,2H),3.03(d,J＝16.2Hz,2H),2.78(s,3H),2.31-2.43(m,6H)；13CNMR(101 M Hz,CDCl3)δ：173.3,165.4,162.9,161.6,129.1,129.0,126.7(d,J＝3.4Hz),116.4,116.2, 75.1,61.4,38.8,34.0,24.7。
1H NMR(400M Hz,CDCl3)δ：7.81-7.71(m,2H),7.48-7.39(m,2H),5.40(m,1H),3.74 (s,2H),3.01-2.92(m,2H),2.73(s,3H),2.44-2.23(m,6H)；13C NMR(101M Hz,CDCl3)δ：173.5,161.5,136.9,129.4,128.9,128.2,75.5,61.2,38.9,34.2,24.8。
1H NMR(400M Hz,CDCl3)δ：7.69(d,J＝8.5Hz,2H),7.60(d,J＝8.5Hz,2H),5.41(m,1H),3.76(s,2H),3.09-3.00(m,2H),2.74(s,3H),2.44-2.25(m,6H)；13C NMR(101M Hz,CDCl3)δ：173.4,161.7,132.4,131.1,131.0,129.4,128.4,125.3,75.4,61.3,38.7,34.0,24.8。
1H NMR(400M Hz,CDCl3)δ：7.94(d,J＝8.1Hz,2H),7.72(d,J＝8.2Hz,2H),5.41(m, 1H),3.55(s,2H),2.82-2.73(m,2H),2.59(s,3H),2.35-2.17(m,6H)；13C NMR(101MHz, CDCl3)δ：174.2,160.9,133.8,132.4(q,J＝33.3Hz),127.3,126.1,125.0,122.3,116.2,77.2, 60.7,39.4,34.8,25.1。
1H NMR(400M Hz,CDCl3)δ：8.31(d,J＝8.7Hz,2H),8.00(d,J＝8.7Hz,2H),5.37(m, 1H),3.21(s,2H),2.34(s,3H),2.30(m,2H),2.18-1.93(m,6H)；13C NMR(101M Hz,CDCl3) δ：175.3,159.4,148.7,136.4,127.7,124.4,78.9,59.7,40.3,36.1,25.7。
1H NMR(400M Hz,CDCl3)δ：7.94(m,2H),7.76(m,2H),5.41(m,1H),3.52(s,2H),2.78-2.69(m,2H),2.57(s,3H),2.32-2.14(m,6H)；13C NMR(101M Hz,CDCl3)δ：174.6,160.3,134.5,132.9,127.5,118.1,114.1,77.1,60.6,39.6,35.0,25.2。
1H NMR(400M Hz,CDCl3)δ：7.74(m,2H),6.95(m,2H),5.31(m,1H),3.85(s,3H),3.41 (s,2H),2.61-2.51(m,2H),2.49(s,3H),2.29-2.07(m,6H)；13C NMR(101M Hz,CDCl3)δ： 173.3,162.2,161.5,128.5,123.3,114.4,76.5,60.4,55.4,39.7,35.2,25.3。
1H NMR(400M Hz,CDCl3)δ：7.73(m,2H),7.31(m,2H),5.37(m,1H),3.64(s,2H),2.95 (m,1H),2.92-2.83(m,2H),2.36(s,3H),2.43-2.18(m,6H),1.28(s,3H),1.26(s,3H)；13C NMR (101M Hz,CDCl3)δ：173.2,162.8,152.1,128.1,127.2,127.1,75.5,61.1,39.2,34.4,34.1,25.0, 23.7。
1H NMR(400M Hz,CDCl3)δ：7.82(s,1H),7.68(d,J＝7.3Hz,1H),7.44-7.37(m,2H),5.40(m,1H),3.64(s,2H),2.87-2.78(m,2H),2.65(s,3H),2.40-2.18(m,6H)；13C NMR(101M Hz,CDCl3)δ：173.5,161.5,136.9,129.4,128.9,128.2,75.5,61.2,38.9,34.2,24.8。
1H NMR(400M Hz,CDCl3)δ：7.44(s,1H),7.37-7.30(m,2H),7.00(m,1H),5.36(m,1H), 3.87(s,3H),3.51(s,2H),2.77-2.68(m,2H),2.57(s,3H),2.36-2.10(m,6H)；13C NMR(101M Hz,CDCl3)δ：173.6,162.7,138.9,131.5,130.4,128.9,127.5,124.2,76.1,60.7,39.4,34.8,25.1, 21.3。
1H NMR(400M Hz,CDCl3)δ：8.61(t,J＝1.9Hz,1H),8.32(ddd,J＝8.2,2.2,0.9Hz,1H),8.27-8.17(m,1H),7.68(t,J＝8.0Hz,1H),5.42(m,1H),3.55(s,2H),2.67-2.58(m,2H), 2.58(s,3H),2.36-2.16(m,6H)；13C NMR(101M Hz,CDCl3)δ：174.3,160.0,148.6,132.4, 132.2,130.3,125.2,122.0,77.2,60.8,39.3,34.8,25.1。
1H NMR(400M Hz,CDCl3)δ：7.82(s,1H),7.68(d,J＝7.3Hz,1H),7.44-7.37(m,2H),5.40(m,1H),3.64(s,2H),2.89-2.80(m,2H),2.65(s,3H),2.40-2.18(m,6H)；13C NMR(101M Hz,CDCl3)δ：173.8,161.0,135.1,132.1,130.7,130.4,126.9,125.2,76.1,60.7,39.0,34.4,25.0。
1H NMR(400M Hz,CDCl3)δ：8.32(dd,J＝7.9,1.4Hz,1H),7.43(m,1H),7.08(m,1H), 7.01(m,1H),5.35(m,1H),3.98(s,3H),3.52(s,2H),2.75-2.64(m,2H),2.57(s,3H),2.32-2.15 (m,6H)；13C NMR(101M Hz,CDCl3)δ：175.5,156.2,155.3,131.6,127.6,121.3,119.5,111.3, 75.3,60.8,55.7,39.4,34.8,25.1。
1H NMR(400M Hz,CDCl3)δ：8.00(m,2H),7.77-7.66(m,3H),5.44(m,1H),3.77(s,2H), 3.02-2.93(m,2H),2.74(s,3H),2.45-2.28(m,6H)；13C NMR(101M Hz,CDCl3)δ：175.2, 157.0,148.4,133.1,132.1,131.5,124.8,124.7,75.8,61.2,38.9,34.1,24.8。
1H NMR(400M Hz,CDCl3)δ：7.92(d,J＝2.0Hz,1H),7.64(dd,J＝8.4,2.1Hz,1H),7.53 (d,J＝8.4Hz,1H),5.37(m,1H),3.47(s,2H),2.71-2.62(m,2H),2.53(s,3H),2.31-2.10(m, 6H)；13C NMR(101M Hz,CDCl3)δ：174.2,159.9,134.9,133.5,131.1,130.4,128.6,126.0, 77.2,60.5,39.6,35.1,25.2。
1H NMR(400M Hz,CDCl3)δ：8.17(d,J＝8.6Hz,1H),7.51(d,J＝2.1Hz,1H),7.38(dd, J＝8.6,2.1Hz,1H),5.39(m,1H),3.42(s,2H),2.66-2.57(m,2H),2.50(s,3H),2.29-2.11(m, 6H)；13C NMR(101M Hz,CDCl3)δ：175.7,156.6,136.8,132.4,131.2,130.2,128.0,127.9, 76.9,60.4,39.8,35.3,25.3。
1H NMR(400M Hz,CDCl3)δ：7.70(d,J＝1.9Hz,2H),7.44(t,J＝1.8Hz,1H),5.41(m, 1H),3.59(s,2H),2.87-2.78(m,2H),2.62(s,3H),2.37-2.17(m,6H)；13C NMR(101MHz, CDCl3)δ：174.1,159.6,135.8,133.1,130.5,125.3,76.6,60.8,39.3,34.7,25.1。
1H NMR(400M Hz,CDCl3)δ：8.29(d,J＝2.1Hz,1H),7.99(dd,J＝8.4,2.1Hz,1H),7.66(d,J＝8.4Hz,1H),5.37(m,1H),3.30(s,2H),2.50-2.41(m,2H),2.41(s,3H),2.21-1.99(m, 6H)；13C NMR(101M Hz,CDCl3)δ：174.9,158.4,148.2,132.7,130.7,130.7,128.8,123.7, 78.5,60.0,40.1,35.8,25.5。
1H NMR(400M Hz,CDCl3)δ：9.10(d,J＝2.7Hz,1H),8.25(dd,J＝8.8,2.8Hz,1H),7.70(d,J＝8.8Hz,1H),5.46(m,1H),3.61(s,2H),2.90-2.81(m,2H),2.63(s,3H),2.40-2.16(m, 6H)；13C NMR(101M Hz,CDCl3)δ：176.0,155.5,146.9,137.9,131.7,130.8,125.5,125.3, 76.7,60.9,39.4,34.7,25.1。
1H NMR(400M Hz,CDCl3)δ：8.23(d,J＝2.3Hz,1H),8.08(dd,J＝8.8,2.3Hz,1H),7.19 (d,J＝8.9Hz,1H),5.35(m,1H),4.03(s,3H),3.36(s,2H),2.56-2.46(m,2H),2.45(s,3H), 2.22-2.08(m,6H)；13C NMR(101M Hz,CDCl3)δ：174.1,159.5,154.4,139.7,132.1,124.4, 123.4,114.2,77.6,60.2,56.9,39.9,35.5,25.4。
1H NMR(400M Hz,CDCl3和DMSO-d6)δ：8.46(d,J＝2.2Hz,1H),8.13(dd,J＝8.8,2.3 Hz,1H),7.27(s,1H),7.25(s,1H),5.39(m,1H),3.55(s,2H),2.75-2.67(m,2H),2.59(s,3H), 2.35-2.20(m,6H)。
1H NMR(400M Hz,CDCl3)δ：6.97(d,J＝2.3Hz,2H),6.55(t,J＝2.3Hz,1H),5.36(m, 1H),3.84(s,6H),3.48(s,2H),2.71-2.62(m,2H),2.54(s,3H),2.32-2.14(m,6H)；13CNMR (101M Hz,CDCl3)δ：173.8,162.4,161.1,132.2,105.1,102.9,76.4,60.7,55.6,39.6,35.0,25.2。
1H NMR(400M Hz,CDCl3)δ：7.86(dd,J＝9.4,3.1Hz,1H),7.64(dd,J＝8.9,5.2Hz,1H), 7.06(m,1H),5.37(m,1H),3.30(s,2H),2.46(m,2H),2.41(s,3H),2.22-2.04(m,6H)；13C NMR(101M Hz,CDCl3)δ：175.9,163.0,160.5,157.6(d,J＝2.5Hz),135.3(d,J＝8.1Hz), 133.2(d,J＝8.6Hz),118.8(d,J＝23.2Hz),118.1(d,J＝25.8Hz),115.9(d,J＝3.5Hz),77.7, 60.0,40.1,35.7,25.5。
1H NMR(400M Hz,CDCl3)δ：7.04(s,2H),5.38(m,1H),3.92(s,6H),3.90(s,3H),3.66 (s,2H),2.89-2.80(m,2H),2.67(s,3H),2.40-2.23(m,6H)；13C NMR(101M Hz,CDCl3)δ： 174.1,159.6,135.8,133.1,130.5,125.3,76.6,60.8,39.3,34.7,25.1。
1H NMR(400M Hz,CDCl3)δ：7.54(dd,J＝1.7,0.6Hz,1H),7.03(dd,J＝3.5,0.6Hz,1H), 6.55(dd,J＝3.5,1.8Hz,1H),5.33(m,1H),3.40(s,2H),2.60-2.51(m,2H),2.49(s,3H), 2.25-2.08(m,6H)；13C NMR(101M Hz,CDCl3)δ：173.6,152.8,145.5,144.3,112.3,110.3, 77.3,60.3,39.8,35.3,25.3。
1H NMR(400M Hz,CDCl3)δ：7.44(dd,J＝5.1,1.0Hz,1H),7.38(dd,J＝3.7,1.0Hz,1H),7.09(dd,J＝5.0,3.7Hz,1H),5.36(m,1H),3.57(s,2H),2.85-2.76(m,2H),2.61(s,3H), 2.37-2.11(m,6H)；13C NMR(101M Hz,CDCl3)δ：172.9,160.0,156.6,132.9,128.6,128.4, 127.7,76.2,60.8,39.3,34.6,25.1。
1H NMR(400M Hz,CDCl3)δ：8.99(s,1H),8.70(d,J＝3.6Hz,1H),8.20(dt,J＝8.0,1.9 Hz,1H),7.43(dd,J＝7.9,4.9Hz,1H),5.42(m,1H),3.58(s,2H),2.86-2.77(m,2H),2.61(s, 3H),2.37-2.18(m,6H)；13C NMR(101M Hz,CDCl3)δ：174.1,159.2,151.6,148.1,134.0, 126.9,123.9,76.5,60.8,39.4,34.7,25.1。
实施例15：本发明化合物的杀线虫测试。
本发明所选取的松材线虫(Bursaphelenchus xylophilus)购自中科院湖州现代农业中心，用来测试确定本发明化合物的杀松材线虫活性。
具体测试操作过程：
电子分析天平分别准确称取阳性对照药物及目标化合物，并用二甲基亚砜溶解，再用含0.2％曲拉通的水溶液稀释成为一定浓度的母液，其中有机溶剂在水中的含量要小于1％，母液浓度为测试所需最高浓度的2倍量。实际测试时，分别取适量的母液和含0.2％曲拉通的水溶液稀释至所需浓度备用。将配制好的药液加入到96孔板中，每孔50μL，每个药物两次重复。用连续加样器在药物中加入线虫悬浮液50μL(线虫约50条)，加盖后置于22±1℃的观察室中。设CK对照组(空白对照组，死亡率﹤5％)和阿维菌素阳性对照组，72小时检查线虫死亡数，计算三次重复试验中线虫的平均死亡率。
校正死亡率＝(处理组死亡率-CK对照组死亡率)/(1-CK对照组死亡率)×100％
结果见表1。
表1 40ppm下本发明化合物对松材线虫的杀灭活性
从表1的结果可以看出，在40ppm下，化合物具有杀松材线虫活性。
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

1.一种氮杂双环衍生物或其农药学上可接受的盐，所述氮杂双环衍生物具有式I所示的结构：
式中，R1为取代的或未取代的C5～C10芳基-C1～C15烷基、氢、或取代的或未取代的C1～C15烷基；所述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基；
Y为S；Z为C或N；
当Z为N时，R2不存在，R3为取代的或未取代的C1～C15烷基、取代的或未取代的C5～C10芳基、或取代的或未取代的4-8元杂芳基；当Z为C时，R3为氢，R2为取代的或未取代的C1～C15烷基、取代的或未取代的C5～C10芳基、或取代的或未取代的4-8元杂芳基，上述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基；
X为O、S或NH时，为X为亚砜基(-SO-)、砜基(-SO2-)时，为
各n1独立为2或3；各n2独立为2或3。
2.如权利要求1所述的氮杂双环衍生物，其特征在于，R1为C6～C10芳基-C1～C2烷基、氢、或取代的或未取代的C1～C4烷基，所述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、卤代C1～C4烷基、C1～C4烷氧基、羧基或C1～C6烷氧基羰基。
3.如权利要求1所述的氮杂双环衍生物，其特征在于，当Z为N时，R2不存在，R3为取代的或未取代的C6～C10芳基，上述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基；
当Z为C时，R3为氢，R2为取代的或未取代的C6～C10芳基，上述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基。
4.如权利要求1所述的氮杂双环衍生物，其特征在于，所述的氮杂双环衍生物选自下组：
R1、R2和R3的定义如权利要求1所述。
5.如权利要求1所述的氮杂双环衍生物，其特征在于，所述的氮杂双环衍生物为：
6.一种农药组合物，其特征在于，包含：
(a)权利要求1-5任一项所述氮杂双环衍生物或其农药学上可接受的盐；和
(b)农药学上可接受的载体。
7.一种氮杂双环衍生物或其农药学上可接受的盐的用途，其特征在于，用于杀线虫或者用于制备杀线虫组合物，其中所述氮杂双环衍生物具有式I所示的结构：
式中，R1为取代的或未取代的C5～C10芳基-C1～C15烷基、氢、或取代的或未取代的C1～C15烷基；所述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基；
Y为S；Z为C或N；
当Z为N时，R2不存在，R3为取代的或未取代的C1～C15烷基、取代的或未取代的C5～C10芳基、或取代的或未取代的4-8元杂芳基；当Z为C时，R3为氢，R2为取代的或未取代的C1～C15烷基、取代的或未取代的C5～C10芳基、或取代的或未取代的4-8元杂芳基，上述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基；
X为O、S、NH、亚砜基(-SO-)或砜基(-SO2-)；
为n1为2或3；n2为2或3。
8.如权利要求7所述的应用，其特征在于，所述氮杂双环衍生物选自下组：
式中R1、R2、R3定义同前；
R4为氢、取代的或未取代的C1～C15烷基；所述取代的是指被选自下组的一个或多个取代基所取代：卤素、氰基、硝基、羟基、氨基、C1～C6烷基、卤代C1～C6烷基、C1～C6烷氧基、羧基或C1～C6烷氧基羰基。
9.如权利要求7所述的应用，其特征在于，所述氮杂双环衍生物选自下组：
10.一种杀线虫和/或预防线虫方法，其特征在于，所述方法包括将如权利要求1～5任一项所述氮杂双环衍生物或其农药学上可接受的盐或如权利要求6所述组合物施加于遭受或可能遭受虫害的植物体或其周围的土壤或环境中。
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