CN103517900A - 杀真菌剂肟基-四唑衍生物 - Google Patents
杀真菌剂肟基-四唑衍生物 Download PDFInfo
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Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom 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
- A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- 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
-
- 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
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Abstract
本发明涉及式(I)的肟基-四唑衍生物,它们的制备方法,以及它们作为杀真菌活性剂的用途,特别是以杀真菌组合物的形式,以及用这些化合物或组合物来控制植物病原真菌(特别是植物中的植物病原真菌)的方法:
Description
说明
本发明涉及肟基(hydroximoyl)-四唑衍生物,它们的制备方法,以及它们作为杀真菌活性剂的用途,特别是以杀真菌组合物的形式,以及用这些化合物或组合物来控制植物病原真菌(特别是植物中的植物病原真菌)的方法。
欧洲专利申请第1426371号、国际专利申请WO2009020191和WO2010000841中揭示了某些具有以下化学结构的四唑基肟衍生物:
式中,A表示四唑基,Het表示特定吡啶基或特定噻唑基。
在日本专利申请第2004-131392号中,揭示了具有下式化学结构的某些四唑基肟衍生物:
式中Q可选自15种不同杂环基的列表。
在日本专利申请第2004-131416号中,揭示了具有下式化学结构的某些四唑基肟衍生物:
式中Q可选自吡啶基或噻唑基。
这三篇文献中揭示的化合物不能提供与本发明的化合物相当的用途。
在农业领域中人们一直高度关注新农药化合物的应用,以避免或防控对活性成份有耐药性的菌株的产生。同样人们高度关注使用比已知化合物活性更高的新颖化合物,目标在于降低所使用的活性化合物的量,与此同时维持至少与已知化合物相当的效力。本发明人现已发现一类具有上述效果或优点的新化合物。
因此,本发明提供了式(I)的四唑肟衍生物,及其盐、N-氧化物、金属配合物、类金属配合物、或(E)和(Z)异构体,以及它们的混合物:
式中:
·X表示氢原子、卤素原子、取代或未取代的C1-C8-烷基、取代或未取代的C1-C8-烷氧基、氰基、甲磺酰基、硝基、三氟甲基或芳基;
·A表示式(A1)或(A2)的四唑基:
式中,Y表示取代或未取代的C1-C8-烷基;以及
·Het表示式(Het1)的吡啶基或式(Het2)的噻唑基;
式中:
o R表示氢原子或卤素原子;以及
o Q表示取代或未取代的(C3-C8-环烷基)-(C1-C3-烷氧基)-C1-C6-烷基、取代或未取代的(C3-C8-环烷基)-(C1-C3-烷氧基)-C1-C6-烷氧基、取代或未取代的(C3-C8-环烷氧基)-C1-C3-烷氧基、取代或未取代的杂环基-(C1-C3-烷氧基)-C1-C6-烷基、取代或未取代的C3-C6-环烷硫基-C1-C6-烷基、取代或未取代的芳基-(C1-C3-烷硫基)-C1-C6-烷基、取代或未取代的杂环基-环丙基。
本发明的任何化合物可依据该化合物中立体单元(根据IUPAC规则定义)的数目而以一种或多种立体异构体的形式存在。因而本发明同样地涉及所有立体异构体以及所有可能的立体异构体按所有比例的混合物。这些立体异构体可以根据本领域技术人员所熟知的方法进行分离。
需要注意的是,式(I)的四唑基肟衍生物中存在的肟部分的立体结构包括(E)或(Z)异构体,这些立体异构体形成本发明的一部分。
依据本发明,以下通用术语一般按以下含义使用:
·卤素是指氟、氯、溴或碘;
·杂原子可以是氮、氧或硫;
·除非另有说明,否则,根据本发明取代的基团或取代基可被一个或多个下列基团或原子取代:卤原子、硝基、羟基、氰基、氨基、次磺酰基(sulphenylgroup)、五氟-λ6-次磺酰基、甲酰基、取代或未取代的甲醛O-(C1-C8-烷基)肟、甲酰氧基、甲酰氨基、氨基甲酰基、N-羟基氨基甲酰基、甲酰氨基、(羟基亚氨基)-C1-C6-烷基、C1-C8-烷基、三(C1-C8-烷基)甲硅烷基-C1-C8-烷基、C1-C8-环烷基、三(C1-C8-烷基)甲硅烷基-C1-C8-环烷基、含有1-5个卤素原子的C1-C8-卤代烷基、含有1-5个卤素原子的C1-C8-卤代环烷基、C2-C8-烯基、C2-C8-炔基、C2-C8-烯氧基、C2-C8-炔氧基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、C1-C8-烷氧基、含有1-5个卤素原子的C1-C8-卤代烷氧基、C1-C8-烷基次磺酰基、含有1-5个卤素原子的C1-C8-卤代烷基次磺酰基、C2-C8-烯氧基、含有1-5个卤素原子的C2-C8-卤代烯氧基、C3-C8-炔氧基、含有1-5个卤素原子的C3-C8-卤代炔氧基、C1-C8-烷基羰基、含有1-5个卤素原子的C1-C8-卤代烷基羰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、N-C1-C8-烷氧基氨基甲酰基、C1-C8-烷氧基氨基甲酰基、N-C1-C8-烷基-C1-C8-烷氧基氨基甲酰基、C1-C8-烷氧基羰基、含有1-5个卤素原子的C1-C8-卤代烷氧基羰基、C1-C8-烷基羰氧基、含有1-5个卤素原子的C1-C8-卤代烷基羰氧基、C1-C8-烷基羰基氨基、含有1-5个卤素原子的C1-C8-卤代烷基羰基氨基、取代或未取代的C1-C8-烷氧基羰基氨基、取代或未取代的含有1-5个卤素原子的C1-C8-卤代烷氧基羰基氨基、C1-C8-烷基氨基羰氧基、二-C1-C8-烷基氨基羰氧基、C1-C8-烷氧基羰氧基、C1-C8-烷基次磺酰基、含有1-5个卤素原子的C1-C8-卤代烷基次磺酰基、C1-C8-烷基亚磺酰基(sulphinyl)、含有1-5个卤素原子的C1-C8-卤代烷基亚磺酰基、C1-C8-烷基磺酰基(sulphonyl)、含有1-5个卤素原子的C1-C8-卤代烷基磺酰基、C1-C8-烷基氨基氨磺酰基、二-C1-C8-烷基氨基氨磺酰基、(C1-C6-烷氧基亚氨基)-C1-C6-烷基、(C1-C6-烯氧基亚氨基)-C1-C6-烷基、(C1-C6-炔氧基亚氨基)-C1-C6-烷基、(苄氧基亚氨基)-C1-C6-烷基、C1-C8-烷氧基烷基、含有1-5个卤素原子的C1-C8-卤代烷氧基烷基、苄氧基、苄基次磺酰基、苄基氨基、苯氧基、苯基次磺酰基、或苯基氨基;
·术语“芳基”是指苯基或萘基;
·术语“杂环基”是指最多包含4个选自N、O、S的杂原子的、稠合或非稠合的、饱和或不饱和的4-,5-,6-,7-,8-,9-,10-,11-或12-元环。
本发明较好的式(I)的化合物是其中X的取代位置并没有具体限制的化合物。
本发明式(I)的化合物是其中X表示氢原子、卤素原子、取代或未取代的C1-C8-烷基、取代或未取代的C1-C8-烷氧基、氰基、甲磺酰基、硝基、三氟甲基或芳基的化合物。
在这些卤素原子中,氯原子或氟原子是优选的。
代表X的所述取代或未取代C1-C8-烷基优选为含有1-4个碳原子的烷基,其具体的例子包括:甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、和叔丁基。在这些烷基基团中,甲基或叔丁基是更好的。
对于X,所述烷氧基优选为取代或未取代的含有1-3个碳原子的C1-C8-烷氧基,其具体的例子包括:甲氧基、乙氧基、丙氧基和异丙氧基。在这些烷氧基中,甲氧基或乙氧基是更好的。
本发明式(I)的化合物更好为其中X表示氢原子的化合物。
本发明式(I)的化合物为其中Y表示取代或未取代的C1-C8-烷基的化合物。在这些烷基中,优选含1-3个碳原子的烷基,例如甲基、乙基、正丙基或异丙基。在这些烷基中,甲基或乙基是更好的。
本发明式(I)的化合物是其中式(Het1)或(Het2)的吡啶基中的R表示氢原子或卤素原子(例如氯原子、溴原子、碘原子或氟原子)的化合物。其中,氢原子或氯原子是更好的。
本发明式(I)的其它优选化合物是这些化合物,其中Q表示取代或未取代的(C3-C6-环烷基)-(C1-C2-烷氧基)-C1-C2-烷基、取代或未取代的(C3-C6-环烷基)-(C1-C2-烷氧基)-C1-C2-烷氧基、取代或未取代的(C3-C6-环烷氧基)-C2-C3-烷氧基、取代或未取代的杂环基-(C1-C2-烷氧基)-C1-C2-烷基。
本发明式(I)的更优选化合物是这些化合物,其中Q表示取代或未取代的(C3-C6-环烷基)-甲氧基甲基、取代或未取代的(C3-C6-环烷基)-甲氧基-乙氧基、取代或未取代的(C3-C6-环烷氧基)-C2-C3-烷氧基、取代或未取代的杂环基-甲氧基-甲基。
关于本发明式(I)的化合物的取代基的上述较好方案可以以各种方式进行组合。这些优选特征的组合由此提供了本发明化合物的亚类。本发明较好的化合物的这些亚类的例子可具有以下组合特征:
-X的优选特征与A1、A2、Y、Het1、Het2、R和Q中的一个或多个的优选特征;
-A1的优选特征与X、A2、Y、Het1、Het2、R和Q中的一个或多个的优选特征;
-A2的优选特征与X、A1、Y、Het1、Het2、R和Q中的一个或多个的优选特征;
-Y的优选特征与X、A2、A1、Het1、Het2、R和Q中的一个或多个的优选特征;
-Het1的优选特征与X、A1、A2、Y、Het2、R和Q中的一个或多个的优选特征;
-Het2的优选特征与X、A1、A2、Y、Het1、R和Q中的一个或多个的优选特征;
-R的优选特征与X、A1、A2、Y、Het1、Het2和Q中的一个或多个的优选特征;
-Q的优选特征与X、A1、A2、Y、Het1、Het2和R中的一个或多个的优选特征。
在这些依据本发明的化合物的取代基的优选特征的组合中,所述优选特征还可选自各X、A1、A2、Y、Het1、Het2、R和Q的更优选特征,从而形成依据本发明的化合物的最优选子类。
本发明还涉及制备式(I)化合物的方法。因此,根据本发明的另一方面,提供了一种制备如本文所定义的式(I)化合物的方法P1,如以下反应流程所示:
方法P1
其中,A、X、Z、Q和Het如本文所定义,LG表示离去基团。合适的离去基团可选自卤素原子或其它常规离核基团(例如三氟甲磺酸根、甲磺酸根、或甲苯磺酸根)。
对于本发明式(Ia)的化合物,方法P1可根据已知方法通过进一步步骤(包括该基团的额外修饰,特别是通过酰化反应或烷氧基羰基化反应进行修饰)来完成,以得到本发明式(Ib)的化合物。在这种情况下,提供了本发明的方法P2,所述方法P2可通过以下反应流程进行说明:
方法P2
其中,A、X、Q和Het如本文所定义,LG’表示离去基团。合适的离去基团可选自下组:卤原子或其它常规离核基团(如醇盐(alcoolate)、氢氧根或氰根),Het’表示式Het’1的吡啶基或噻唑基Het’2:
其中R如文中所定义。
对于式(Ia)的化合物,实施方法P2之前将需要一个去保护步骤以得到氨基。氨基保护基团及其相关的断裂方法是本领域普通技术人员已知的。
根据本发明,方法P1和P2可(如果合适)在溶剂存在以及(如果合适)在碱存在的条件下实施。
根据本发明,方法P1和P2可(如果合适)在催化剂存在的条件下实施。合适的催化剂可选自4-二甲基-氨基吡啶、1-羟基-苯并三唑或二甲基甲酰胺。
在LG’表示羟基的情况下,本发明的方法P2可在缩合剂存在的条件下实施。合适的缩合剂可选自下组:酰卤形成剂,例如光气、三溴化磷、三氯化磷、五氯化磷、氧化三氯化磷或亚硫酰氯;酐形成剂,例如氯甲酸乙酯、氯甲酸甲酯、氯甲酸异丙酯、氯甲酸异丁酯或甲磺酰氯;碳二亚胺,例如N,N'-二环已基碳二亚胺(DCC);或其它常规缩合剂,例如五氧化二磷、多磷酸、N,N'-羰基-二咪唑、2-乙氧基-N-乙氧基羰基-1,2-二氢喹啉(EEDQ)、三苯基膦/四氯甲烷、水合氯化4-(4,6-二甲氧基[1.3.5]三嗪-2-基)-4-甲基吗啉鎓或溴-三吡咯烷基(tripyrrolidino)-鏻-六氟磷酸盐。
用于实施本发明的方法P1和P2的合适的溶剂是常用的惰性有机溶剂。优选使用可任选卤代的脂族、脂环族或芳族烃类,例如石油醚、己烷、庚烷、环己烷、甲基环己烷、苯、甲苯、二甲苯或萘烷;氯苯、二氯苯、二氯甲烷、氯仿、四氯化碳、二氯乙烷或三氯乙烷;醚类,例如乙醚、二异丙醚、甲基叔丁基醚、甲基叔戊基醚、二噁烷、四氢呋喃、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷或茴香醚;腈类,例如乙腈、丙腈、正丁腈或异丁腈或苄腈;酰胺类,例如N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基甲酰苯胺、N-甲基吡咯烷酮、或六甲基磷酰三胺;酯类,例如乙酸甲酯或乙酸乙酯;亚砜类,例如二甲亚砜;或砜类,例如环丁砜。
用于实施本发明的方法P1和P2的合适的碱是常用于此类反应的无机碱和有机碱。优选使用碱土金属、碱金属氢化物,碱金属氢氧化物或碱金属醇盐,例如氢氧化钠、氢化钠、氢氧化钙、氢氧化钾、叔丁醇钾或其它氢氧化铵;碱金属碳酸盐,例如碳酸钠、碳酸钾、碳酸氢钾、碳酸氢钠、碳酸铯;碱金属或碱土金属乙酸盐,例如乙酸钠、乙酸钾、乙酸钙;以及叔胺类,例如三甲胺、三乙胺、二异丙基乙胺、三丁胺、N,N-二甲基苯胺、吡啶、N-甲基哌啶、N,N-二甲基氨基吡啶、1,4-二氮杂双环[2.2.2]辛烷(DABCO)、1,5-二氮杂双环[4.3.0]壬-5-烯(DBN)或1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)。
当实施本发明的方法P1和P2时,反应温度可在相对宽的范围内独立地变化。
通常本发明的方法P1在温度-20℃至160℃的条件下实施。
本发明的方法P1和P2通常在大气压力下独立地实施。然而,也可在升压或减压的条件下操作。
当进行本发明方法P1时,对于每摩尔的式(II)的肟基四唑,通常使用1摩尔或过量的式Het-CH2-LG的衍生物和1-3摩尔的碱。还可以其它比例使用反应组分。
按照常用方法来实施后处理(Work-up)。通常,用水对反应混合物进行处理,并分离出有机相,干燥后在减压条件下浓缩。如果合适,通过惯常方法如色谱法或重结晶法除去残留的残余物中任何可能仍存在的杂质。
本发明的化合物可按照上述方法进行制备。但应理解,本领域技术人员基于其一般知识以及可获得的出版物,能够根据所需合成的本发明的各种具体化合物对本发明方法进行相应调整。
如本文所述,当A表示式A1的取代基时,可通过(例如)使羟胺与相应的酮反应来制备用作原料的式(II)的化合物,例如,可根据R.Raap(Can.J.Chem.1971,49,2139)所述的方法通过将四唑基锂物质加入式或的酯或其任意的合适合成等价物等中来进行制备,所述合成等价物例如:
如本文所述,当A表示式A2的取代基时,可根据J.Plenkiewicz等人(Bull.Soc.Chim.Belg.1987,96,675)所述的方法由式的肟和5-取代的四唑来制备用作原料的式(II)的化合物。
在另一方面,本发明还涉及含有有效且非植物毒性量的通式(I)的活性化合物的杀真菌剂组合物。
术语“有效及非植物毒性量”是指本发明组合物的一定量,所述量足以控制或者破坏存在或易于出现在农作物上的真菌,而该剂量并不会使所述农作物产生任何可以观察到的植物毒性症状。该量根据以下因素可在很宽的范围内变化:要控制的真菌、作物的类型、气候条件和包含在本发明的杀真菌组合物中的化合物。这个量可以通过系统性田间试验来确定,这是在本领域技术人员能力范围之内的。
因此,本发明提供了一种杀真菌剂组合物,该组合物包含:有效量的如本文所定义的通式(I)化合物作为活性成分、以及农业上可接受的担体(support)、载体或填料(filler)。
根据本发明,术语“担体”表示一种天然的或合成的有机或无机化合物,其与式(I)的活性化合物组合或者联合以使得活性化合物更易于施用于植物,尤其是至植物的部分。因此,此担体通常是惰性的,并且应该是农业上可接受的。担体可为固体或液体。合适的担体的例子包括粘土、天然或合成的硅酸盐、二氧化硅、树脂、蜡、固体肥料、水、醇类(特别是丁醇)、有机溶剂、矿物油和植物油及其衍生物。也可以使用此类担体的混合物。
本发明的组合物还可以包含其它组分。具体地,所述组合物还可包含表面活性剂。所述表面活性剂可为离子型或非离子型的乳化剂、分散剂或润湿剂、或这些表面活性剂的混合物。例如,可包括聚丙烯酸盐、木素磺酸盐、酚磺酸盐或萘磺酸盐、环氧乙烷与脂肪醇或与脂肪酸或与脂肪胺的缩聚物、取代的酚(特别是烷基酚或芳基酚)、磺基琥珀酸酯的盐、牛磺酸衍生物(特别是牛磺酸烷基酯)、聚氧乙基化醇或酚的磷酸酯、多元醇的脂肪酸酯、以及包含硫酸根、磺酸根或磷酸根官能团的上述化合物的衍生物。通常,当活性化合物和/或惰性担体是不溶于水的且所施用的媒介试剂是水时,必需存在至少一种表面活性剂。较佳地,以组合物的重量计,表面活性剂的含量为5-40重量%。
任选地,还可包括其它组分,例如,保护性胶体、粘合剂、增稠剂、触变剂、渗透剂、稳定剂、螯合剂。更一般而言,可将所述活性化合物与符合常用配制技术的任何固体或液体添加剂进行组合。
通常,本发明的组合物可包含0.05-99重量%的活性化合物,优选为10-70重量%。
本发明的组合物可以以各种形式使用并且可用于各种制剂,例如气雾分散剂、胶囊悬浮剂(capsule suspension)、冷雾浓缩剂、可撒粉剂、可乳化的浓缩剂、水包油乳液、油包水乳液、包胶粒剂、细颗粒剂、用于种子处理的可流动浓缩剂、气体(压力下)制剂、气体发生剂、颗粒剂、热雾浓缩剂、大粒剂、微粒剂、油可分散性粉剂、油混溶性可流动浓缩剂、油混溶性液体、糊剂、植物小棒、用于干种处理的粉剂、农药包衣的种子、可溶性浓缩剂、可溶性粉剂、用于种子处理的溶液、悬浮浓缩剂(可流动的浓缩剂)、超低容量(ULV)液体、超低容量(ULV)悬浮剂、水可分散粒剂或片剂、用于浆液处理的水可分散粉剂、水溶性粒剂或片剂、用于种子处理的水溶性粉剂、以及可润湿性粉剂。这些组合物不仅包括将要用合适的设备(例如喷雾器或撒粉设备)施用至经处理的植物或种子上的组合物,而且包括在施用于农作物之前必须进行稀释的浓缩的市售组合物。
制剂可通过原本已知的方式进行制备,例如通过将活性成分与至少一种以下常规物质混合来制备:增容剂、表面活性剂、溶剂或稀释剂、佐剂、乳化剂、分散剂和/或粘结剂或固定剂、湿润剂、防水剂、(如果合适的话)干燥剂和紫外稳定剂,以及(如果合适的话)染料和颜料、消泡剂、防腐剂、无机和有机增稠剂、粘合剂、赤霉素以及其它加工助剂和水。根据待制备的制剂类型,需要其它加工步骤,例如湿法研磨、干法研磨和制粒。
本发明的活性成分可以以本身的形式存在,或者以其(市售)制剂形式以及由这些制剂所制备的用途形式存在,所述制剂是本发明活性成分与以下其它(已知)活性成分的混合物的形式:例如杀虫剂、引诱剂、止繁殖剂、杀细菌剂、杀螨剂、杀线虫剂、杀真菌剂、生长调节剂、除草剂、肥料、安全剂和/或化学信息素。
本发明的化合物还可与一种或多种以下物质混合:杀虫剂、引诱剂、止繁殖剂、杀细菌剂、杀螨剂、杀线虫剂、杀真菌剂、生长调节剂、除草剂、肥料、安全剂、化学信息素或有生物活性的其它化合物。如此获得的混合物通常具有广谱的活性。与其它杀真菌剂化合物的混合物特别有益。
包含式(I)化合物与杀细菌剂化合物的混合物的本发明组合物也是特别有益的。合适的可进行混合的杀细菌剂的例子可选自下组:溴硝醇、双氯酚、三氯甲基吡啶、二甲基二硫代氨基甲酸镍、春雷霉素、辛噻酮、呋喃羧酸、土霉素、噻菌灵、链霉素、叶枯酞、硫酸铜和其它铜制剂。
本发明的另一个目的是,提供一种控制植物、作物或种子的植物病原真菌的方法,其特征在于,将农业上有效且基本上非植物毒性量的本发明的杀虫剂组合物以种子处理、叶部施加、茎部施加、浸透或滴灌施加(化学施加)的方式施用于以下部分:种子、植物或植物果实,或已种植或打算种植植物的土壤或惰性基质(例如无机基质,如砂、石棉、玻璃棉;膨胀矿物质,例如珍珠岩、蛭石、沸石或膨胀粘土)、浮石、火成碎屑物质或材料、合成的有机基质(例如聚氨酯)、有机基质(例如泥炭、堆肥、树木废产物(例如椰壳、木纤维或木屑、树皮))或液体基质(例如浮动水培系统、营养液膜技术、气栽体系)。
术语“施用于待处理的植物”应理解为是指出于本发明的目的,可通过如下的各种处理方法施用作为本发明主题的农药组合物:
·向所述植物的地上部分喷涂包含所述组合物之一的液体;
·在所述植物周围喷粉、向土壤中结合入颗粒或粉末、喷雾、以及当所述植物是树木的情况下进行注射或涂抹;
·借助包含所述组合物之一的植物保护混合物,对所述植物的种子进行涂覆或膜涂覆。
本发明的方法可为治愈、预防或根除的方法。
在该方法中,所用组合物可预先通过将两种或更多种本发明的活性化合物混合来制备。
根据此方法的一种替代性方式,也可同时、连续或分开施用化合物(A)和(B),以产生各包含两种或三种活性成分(A)或(B)中之一的不同组合物相结合(A)/(B)效果。
本发明处理方法中通常施用的活性化合物的剂量通常且适宜为:
·对于叶部处理:0.1-10,000g/ha,较好为10-1,000g/ha,更好为50-300g/ha;在浸透或滴灌施用的情况下,所述剂量甚至可减少,尤其是当使用惰性基质(例如石棉或珍珠岩)时;
·对于种子处理:2-200克/100公斤种子,较好为3-150克/100公斤种子;
·对于土壤处理:0.1-10,000g/ha,较好为1-5,000g/ha。
本文所示的剂量是作为本发明方法的说明性示例给出。本领域技术人员知道如何根据待处理植物或农作物的性质调节施用剂量。
在具体条件下,例如根据待处理或控制的植物致病真菌的性质,较低剂量可提供足够的保护。某些气候条件、抗性或其它因素(例如植物致病真菌的性质或(例如)具有该真菌的植物的感染程度)可需要更高剂量的组合活性成分。最佳剂量通常取决于各种因素,例如待处理的植物致病真菌的类型,受感染植物的类型或发展程度,植被密度或者施用方法。
用本发明的农药组合物或组合处理的作物是例如但不限于,例如葡萄树,也可为谷物、蔬菜、苜蓿、大豆、市售花园作物、草皮、树木或园艺植物。
本发明的处理方法还可用于处理繁殖材料(如块茎或根茎等),以及种子、幼苗或移植幼苗以及植物或移植植物。该处理方法也可用于处理根。本发明的处理方法也可用于处理植物的地上部分,例如有关植物的树干、茎或梗、叶、花和果实。
在可以或能够用本发明的方法予以保护的植物当中,可以一提的有棉花、亚麻、藤本植物、水果或蔬菜作物,如蔷薇科(Rosaceae sp.)(例如,仁果类水果,如苹果和梨,还有核果,诸如杏、扁桃(almond)和桃子)、茶蔗子科(Ribesioidaesp.),胡桃科(Juglandaceae sp.),桦木科(Betulaceae sp.),漆树科(Anacardiaceaesp.),山毛榉科(Fagaceae sp.),桑科(Moraceae sp.),木犀科(Oleaceae sp.),猕猴桃科(Actinidaceae sp.),樟科(Lauraceae sp.),芭蕉科(Musaceae sp.)(例如香蕉树和粉芭蕉(plantins)),茜草科(Rubiaceae sp.),山茶科(Theaceae sp.),梧桐科(Sterculiceae sp.),芸香科(Rutaceae sp.)(例如柠檬、橙子和葡萄柚);茄科(Solanaceae sp.)(例如西红柿),百合科(Liliaceae sp.),紫菀科(Asteraceae sp.)(例如莴苣),伞形科(Umbelliferae sp.),十字花科(Cruciferae sp.),藜科(Chenopodiaceae sp.),葫芦科(Cucurbitaceae sp.),蝶形花科(Papilionaceaesp.)(例如豌豆),蔷薇科(Rosaceae sp.)(例如草莓);主要作物,如禾本科(Graminae sp.)(例如玉米、菌苔或谷物如小麦、稻、大麦和黑小麦),紫菀科(Asteraceae sp.)(例如向日葵),十字花科植物(例如油菜),豆科(Fabacae sp.)(例如花生),蝶形花科(Papilionaceae sp.)(例如大豆),茄科(Solanaceae sp.)(例如马铃薯),藜科(Chenopodiaceae sp.)(例如甜菜根);园艺作物和林业作物;以及这些作物的遗传改进的同系物。
本发明的组合物还可以用于处理用本发明的化合物或者本发明的农用化学组合物对遗传修饰的生物体。所谓遗传修饰的植物是其基因组已被稳定地整合入编码相关蛋白质的异源基因的植物。术语“编码相关的蛋白质的异源基因”主要是指赋予转化植物新的农学性质的基因,或者改善修饰植物的农学性质的基因。
本发明的组合物还可用于治疗易于在木材上或木材内部生长的真菌疾病。术语“木材”是指所有类型的木材物种、以及打算用于建筑的这种木材的所有类型的加工产品,例如实木、高密度木材、层压木材和胶合板。本发明处理木材的方法主要在于接触一种或多种本发明化合物或本发明组合物;这包括例如直接施用、喷涂、浸渍、注射或任意其它适合的方法。
在通过本发明方法可控制的植物或作物的疾病中,可提及:
白粉病,例如:
白粉病(Blumeria diseases),由例如小麦白粉菌(Blumeria graminis)引起;
叉丝单囊壳属病(Podosphaera diseases),由例如白叉丝单囊壳(Podosphaera leuco-tricha)引起;
单丝壳属病(Sphaerotheca diseases),由例如苍耳单丝壳(Sphaerotheca fuliginea)引起的;
钩丝壳属病(Uncinula diseases),例如由葡萄钓丝壳(Uncinula necator)引起;
锈病,例如:
胶锈菌属病(Gymnosporangium diseases),由例如赛宾锈菌(Gymnosporangiumsabinae)引起;
驼孢锈病(Hemileia diseases),由例如咖啡驼孢锈菌(Hemileia vastatrix)引起;
层锈菌属病(Phakopsora diseases),由例如豆薯层锈菌(Phakopsora pachyrhizi)或山马蝗层锈菌(Phakopsora meibomiae)引起;
柄锈菌属病(Puccinia diseases),例如由隐匿柄锈菌(Puccinia recondite)引起;
单胞锈菌属病(Uromyces diseases),由例如疣顶单胞锈菌(Uromycesappendiculatus)引起;
卵菌病(Oomycete diseases),例如:
盘梗霉属病(Bremia diseases),由例如苣盘梗霉(Bremia lactucae)引起;
霜霉属病(Peronospora diseases),由例如豌豆霜霉(Peronospora pisi)或芸苔霜霉(P.brassicae)引起;
疫霉属病(Phytophthora diseases),由例如致病疫霉(Phytophthora infestans)引起;
单轴霉属病(Plasmopara diseases),由例如葡萄生单轴霉(Plasmopara viticola)引起;
假霜霉属病(Pseudoperonospora diseases),由例如葎草霜霉(Pseudoperonosporahumuli)或黄瓜霜霉(Pseudoperonospora cubensis)引起的;
腐霉属病(Pythium diseases),由例如终极腐霉(Pythium ultimum)引起;
叶斑病、叶疱和叶枯病,例如:
支链孢属病(Alternaria diseases),例如由茄链格孢(Alternaria solani)引起;
尾孢霉属病(Cercospora diseases),由例如甜菜生尾孢(Cercospora beticola)引起;
金孢子菌属病(Cladiosporum diseases),例如由瓜枝孢(Cladiosporium cucumerinum)引起;
旋孢腔菌病(Cochliobolus diseases),例如由禾旋孢腔菌(Cochliobolus sativus)引起;
刺盘孢属病(Colletotrichum diseases),由例如豆刺盘孢(Colletotrichumlindemuthianum)引起;
油橄榄孔雀斑病病(Cycloconium diseases),由例如油橄榄孔雀斑菌(Cycloconiumoleaginum)引起;
腐皮壳菌层病(Diaporthe diseases),由例如柑桔间座壳(Diaporthe citri)引起;
痂囊腔菌属病(Elsinoe diseases),由例如柑桔痂囊腔菌(Elsinoe fawcettii)引起;
长孢属病(Gloeosporium diseases),由例如悦色盘长孢(Gloeosporium laeticolor)引起;
小丛壳属病(Glomerella diseases),由例如围小丛壳(Glomerella cingulata)引起;
球座菌属病(Guignardia diseases),由例如葡萄球座菌(Guignardia bidwellii)引起;
小球腔菌属病(Leptosphaeria diseases),由例如十字花科小球腔菌(Leptosphaeriamaculans)、颖枯小球腔菌(Leptosphaeria nodorum)引起;
稻瘟病(Magnaporthe diseases),由例如稻瘟菌(Magnaporthe grisea)引起;
球腔菌属病(Mycosphaerella diseases),由例如禾生球腔菌(Mycosphaerellagraminicola)、落花生球腔菌(Mycosphaerella arachidicola)、香蕉黑条叶斑菌(Mycosphaerella fijiensis)引起的;
壳针孢属病(Phaeosphaeria diseases),由例如颖枯壳针孢(Phaeosphaerianodorum)引起;
核腔菌属病(Pyrenophora diseases),例如由圆核腔菌(Pyrenophora teres)引起;
柱隔孢属病(Ramularia diseases),由例如辛加柱隔孢(Ramularia collo-cygni)引起;
喙孢属病(Rhynchosporium diseases),由例如黑麦喙孢(Rhynchosporium secalis)引起;
壳针孢属病(Septoria diseases),由例如芹菜小壳针孢(Septoria apii)或番茄壳针孢(Septoria lycopersici)引起;
核瑚菌病(Typhula diseases),由例如肉色核瑚菌(Typhula incarnata)引起;
黑星菌属病(Venturia diseases),例如由苹果黑星菌(Venturia inaequalis)引起;
根病和茎病,例如:
伏革菌病(Corticium diseases),由例如禾伏革菌(Corticium graminearum)引起;
镰孢菌(霉)属病(Fusarium diseases),由例如尖镰孢(Fusarium oxysporum)引起;
鲟形属病(Gaeumannomyces diseases),由例如禾顶囊壳(Gaeumannomycesgraminis)引起;
丝核菌属病(Rhizoctonia diseases),由例如立枯丝核菌(Rhizoctonia solani)引起;
塔普斯(Tapesia diseases),由例如塔普斯梭状芽胞杆菌(Tapesia acuformis)引起;
根串珠霉属病(Thielaviopsis diseases),由例如根串珠霉(Thielaviopsis basicola)引起;
耳穗和圆锥花序病,例如:
链格孢属病(Alternaria diseases),由例如链格孢(Alternaria spp.)引起;
曲霉病(Aspergillus diseases),由例如黄曲霉(Aspergillus flavus)引起;
枝孢病(Cladosporium diseases),由例如枝孢(Cladosporium spp.)引起;
麦角菌属病(Claviceps diseases),由例如麦角菌(Claviceps purpurea)引起;
镰孢菌(霉)属病(Fusarium diseases),由例如大刀镰孢(Fusarium culmorum)引起;
赤霉病(Gibberella diseases),由例如玉蜀黍赤霉(Gibberella zeae)引起;
水稻云形病(Monographella diseases),由例如水稻云形菌(Monographella nivalis)引起;
黑穗病和腥黑穗病,例如:
轴黑粉菌属病(Sphacelotheca diseases),由例如丝轴黑粉菌(Sphacelothecareilinana)引起;
腥黑粉菌属病(Tilletia diseases),由例如小麦网腥黑粉菌(Tilletia caries)引起;
条黑粉菌属病(Urocystis diseases),由例如隐条黑粉菌(Urocystis occulta)引起;
黑粉菌属病(Ustilago diseases),由例如裸黑粉菌(Ustilago nuda)引起;
果实腐烂和霉菌病,例如:
曲霉病(Aspergillus diseases),由例如黄曲霉(Aspergillus flavus)引起;
葡萄孢菌属病(Botrytis diseases),由例如葡萄孢菌(Botrytis cinerea)引起的;
青霉病(Penicillium diseases),由例如甘薯青霉(Penicillium expansum)引起;
核盘菌属病(Sclerotinia diseases),由例如核盘菌(Sclerotinia sclerotiorum)引起;
轮枝孢属病(Verticilium diseases),由例如黑白轮枝孢(Verticillium alboatrum)引起;
种子和土壤中的腐烂、发霉、枯萎、腐败以及猝倒病:
链格孢病(Alternaria diseases),由例如芥链格孢(Alternaria brassicicola)引起;
丝囊霉属病(Aphanomyces diseases),由例如豌豆丝囊霉(Aphanomyceseuteiches)引起;
壳二孢属病(Ascochyta diseases),由例如晶状体二胞菌(Ascochyta lentis)引起;
曲霉病(Aspergillus diseases),由例如黄曲霉(Aspergillus flavus)引起;
枝孢病(Cladosporium diseases),由例如多主枝孢(Cladosporium herbarum)引起;
旋孢腔菌病(Cochliobolus diseases),例如由禾旋孢腔菌(Cochliobolus sativus)(Conidiaform:Drechslera,Bipolaris Syn:Helminthosporium)引起;
刺盘孢病(Colletotrichum diseases),由例如粒状体刺盘孢(Colletotrichumcoccodes)引起;
镰孢菌(霉)属病(Fusarium diseases),由例如大刀镰孢(Fusarium culmorum)引起;
赤霉病(Gibberella diseases),由例如玉蜀黍赤霉(Gibberella zeae)引起;
壳球孢病(Macrophomina diseases),由例如豆类壳球孢(Macrophominaphaseolina)引起;
水稻云形病(Monographella diseases),由例如水稻云形菌(Monographellanivalis)引起;
青霉病(Penicillium diseases),由例如甘薯青霉(Penicillium expansum)引起;
茎点霉病(Phoma diseases),由例如黑胫茎点霉(Phoma lingam)引起;
拟茎点霉病(Phomopsis diseases),由例如大豆茎点霉(Phomopsis sojae)引起;
疫霉属病(Phytophthora diseases),由例如恶疫霉(Phytophthora cactorum)引起;
核腔菌病(Pyrenophora diseases),由例如麦类核腔菌(Pyrenophora graminea)引起;
梨孢属病(Pyricularia diseases),由例如稻梨孢(Pyricularia oryzae)引起的;
腐霉属病(Pythium diseases),由例如终极腐霉(Pythium ultimum)引起;
丝核菌属病(Rhizoctonia diseases),由例如立枯丝核菌(Rhizoctonia solani)引起;
根霉病(Rhizopus diseases),由例如米根霉(Rhizopus oryzae)引起;
小核菌病(Sclerotium diseases),由例如齐整小核菌(Sclerotium rolfsii)引起的;
壳针孢病(Septoria diseases),例如由颖枯壳针孢(Septoria nodorum)引起;
核瑚菌病(Typhula diseases),由例如肉色核瑚菌(Typhula incarnata)引起;
轮枝孢病(Verticillium diseases),由例如大丽花轮枝孢(Verticillium dahliae)引起;
溃疡、开裂及梢枯病,例如:
丛赤壳属病(Nectria diseases),由例如干癌丛赤壳菌(Nectria galligena)引起;
枯萎病,例如:
链核盘菌属病(Monilinia diseases),由例如核果链核盘菌(Monilinia laxa)引起;
叶泡或卷叶病,例如:
外囊菌属病(Taphrina diseases),由例如畸形外囊菌(Taphrina deformans)引起;
木植物衰退病,例如:
依科病(Esca diseases),由例如根霉格孢菌(Phaeomoniella clamydospora)引起;
葡萄顶枯病(Eutypa dyeback),由例如葡萄藤猝倒病菌(Eutypa lata)引起;
荷兰榆树病(Dutch elm disease),由例如角果属螨(Ceratocystsc ulmi)引起;
花和种子的疾病,例如:
葡萄孢菌属病(Botrytis diseases),由例如葡萄孢菌(Botrytis cinerea)引起的;
根茎类疾病,例如:
丝核菌属病(Rhizoctonia diseases),由例如立枯丝核菌(Rhizoctonia solani)引起;
长蠕孢菌属病(Helminthosporium diseases),由例如立枯长蠕孢(Helminthosporiumsolani)引起。
本发明的化合物还可用于制备用于治疗性或预防性地处理人或动物真菌疾病的组合物,所述人或动物真菌疾病是例如霉菌病(mycose)、皮肤病、癣菌病及念珠菌病、或由曲霉属(Aspergillus spp.)(例如烟曲霉(Aspergillusfumigatus))引起的疾病。
本发明的处理方法可用于处理经遗传改进的有机体(GMOs),例如植物或种子。经遗传改进的植物(或转基因植物)是其中异源基因已经稳定地整合入基因组中的植物。术语“异源基因”主要是指如下基因,其在植物外部提供或组装并且当被引入细胞核、叶绿体或线粒体基因组中时,通过表达相关的蛋白质或多肽或通过下调植物中存在的其它基因或者使得所述其它基因沉默(使用例如反义技术、共抑制技术或RNA干扰-RNAi-技术)来赋予经转化的植物新的或改进的农艺性质或其它性质。位于基因组中的异源基因也称作转基因。植物基因组中由特定位置定义的转基因称作转化或转基因事件。
根据植物物种或植物品种、其位置和生长条件(土壤、气候、生长期、营养),本发明的处理还可产生超叠加(“协同”)效果。因此,例如,减少施用比率和/或拓宽活性范围和/或增加根据本发明可使用的活性化合物和组合物的活性、植物生长更好、对高温或低温的耐受性增加、对干旱或对水或土壤含盐量的耐受性提高、开花性能提高、收获更容易、成熟加速、收获产量更高、果实更大、植物高度更高、叶子颜色更绿、开花更早、收获的产物的品质更高和/或营养价值更高、果实中的糖浓度更高、收获的产物的储存稳定性和/或加工性能更好,上述都是可能的,其超过实际预期的效果。
在某些施用比率下,本发明的活性化合物组合还可在植物中具有强化效果。因此,其还可适用于调动植物防御系统抵抗不希望的植物致病真菌和/或微生物和/或病毒的攻击。这可能(如果合适)是本发明组合增强活性(例如抵抗真菌)的原因之一。在本文中,强化植物(抗性诱导)物质应理解为是指具有以下性质的物质或物质的组合:其能刺激植物的防御系统,从而当随后接种不希望的植物致病真菌和/或微生物和/或病毒时,经处理的植物对这些不希望的植物致病真菌和/或微生物和/或病毒显示出很大程度的抗性。在本文中,不希望的植物致病真菌和/或微生物和/或病毒应理解为是指植物致病真菌、细菌和病毒。因此,本发明的物质可用于保护植物,使其在经过处理后的一段时间内能抵抗上述病原体的攻击。在使用活性化合物处理植物后,实现保护的这段时间通常为1-10天,较好为1-7天。
本发明较好的待处理的植物和植物品种包括具有赋予这些植物特别有利的有用特征的遗传材料(无论通过育种和/或生物技术方式获得)的所有植物。
本发明较好的待处理的植物和植物品种还可抵抗一种或多种生物胁迫,即所述植物对如下的动物和微生物有害物显示出较好的防御,例如线虫、昆虫、螨虫、植物病原真菌、细菌、病毒和/或类病毒。
本发明的待处理的植物和植物品种还可为抵抗一种或多种非生物胁迫的植物。非生物胁迫条件可包括,例如,干旱、冷温暴露、热暴露、渗透胁迫、水淹、土壤盐度增加、矿物质暴露增加、臭氧暴露、强光暴露、限制性供应氮营养素、限制性供应磷营养素、避阴。
本发明的待处理的植物和植物品种还可为其特征在于产量有所增加的植物。所述植物的产量有所增加的原因可为,例如,改进植物生理学、生长和发育(例如用水效率、保水效率)、改进氮使用、增强碳同化、改进光合作用、提高发芽效率和加速成熟。产量还可受改进的植物结构(在胁迫和非胁迫条件下)影响,包括但不限于,提早开花、对杂交种子生产的开花控制,幼苗活力、植物大小、节间数量及距离、根生长、种子大小、果实大小、豆荚大小、豆荚或穗数量、每穗或豆荚的种子数量、种子质量、提高种子填充、减少种子分散、减少豆荚开裂和耐倒伏性。其它产量特性包括种子组成,例如碳水化合物含量、蛋白质含量、油含量及组成、营养价值、减少抗营养化合物、改进加工性和更好的储存稳定性。
本发明可处理的植物是如下的杂交植物,其已经表达出杂种优势或杂交活力的特征,从而通常得到更高产量、活力、健康和对生物和非生物胁迫的抗性。这些植物通常通过近交雄性不育亲本(雌性亲本)与另一近交雄性可育亲本(雄性亲本)杂交获得。杂交种子通常从雄性不育植物收获并出售给种植者。雄性不育植物有时可(例如在玉米中)通过去除雄性产生,即机械去除雄性生殖器官(或雄花),但更通常地,雄性不育是由植物基因组中的遗传决定簇产生。在这种情况下,以及特别是当种子是从杂交植物收获的所需产物时,其通常用于确保杂交植物中的雄性能育性得以完全恢复。这可通过确保雄性亲本具有合适的能育性恢复基因来实现,所述能育性恢复基因能够恢复包含造成雄性不育的遗传决定簇的杂交植物中的雄性能育性。雄性不育的遗传决定簇可位于细胞质中。例如,芸苔属物种(WO1992/005251、WO1995/009910、WO1998/27806、WO2005/002324、WO2006/021972和US6,229,072)中描述了细胞质的雄性不育(CMS)的例子。然而,雄性不育的遗传决定簇也可位于细胞核基因组中。雄性不育植物也可由植物生物技术方法(例如基因工程)获得。WO1989/10396中描述了获得雄性不育植物的特别有用的方法,其中,例如核糖核酸酶(例如芽孢杆菌RNA酶)选择性在雄蕊的绒毡层细胞中表达。然后能育性可通过在绒毡层细胞中表达核糖核酸酶抑制剂(例如芽胞杆菌RNA酶抑制剂)来得到恢复(例如WO1991/002069))。
本发明可处理的植物或植物品种(由植物生物技术方法获得,例如通过基因工程获得)是除草剂耐受植物,即对一种或多种给定的除草剂具有耐受性的植物。这些植物可通过遗传转化,或通过选择包含赋予该除草剂耐受性的突变的植物获得。
耐除草剂植物是例如耐草甘膦植物,即对除草剂草甘膦或其盐具有耐受性的植物。可通过不同的方法使植物对草甘膦具有耐受性。例如,耐草甘膦植物可通过转化具有编码5-烯醇丙酮酰莽草酸-3-磷酸合酶(EPSPS)的基因的植物来获得。这些EPSPS基因的例子是鼠伤寒沙门菌(Salmonella typhimurium)的AroA基因(突变CT7)(Comai等,科学(Science)(1983),221,370-371)、农杆菌(Agrobacterium sp.)的CP4基因(Barry等,Curr.Topics Plant Physiol.(1992),7,139-145)、编码牵牛花EPSPS的基因(Shah等,科学(Science)(1986),233,478-481)、编码番茄EPSPS的基因(Gasser et al.,J.Biol.Chem.(1988),263,4280-4289)、或编码牛筋草(Eleusine)EPSPS的基因(WO2001/66704)。还可为突变的EPSPS,如例如EP-A0837944、WO2000/066746、WO2000/066747或WO2002/026995中所述。耐草甘膦植物还可通过表达编码草甘膦氧化还原酶的基因来获得,如US5,776,760和US5,463,175中所述。耐草甘膦植物还可通过表达编码草甘膦乙酰基转移酶的基因来获得,如例如WO2002/036782、WO2003/092360、WO2005/012515和WO2007/024782中所述。耐草甘膦植物还可通过选择包含天然产生的上述基因突变体的植物来获得,如例如WO2001/024615或WO2003/013226中所述。
其它耐除草剂植物是例如对抑制酶谷氨酰胺合成酶的除草剂(例如双丙氨磷、草胺膦或草丁膦)有耐受性的植物。这些植物可通过表达解除所述除草剂的毒性或抵抗抑制的突变谷氨酰胺合成酶来获得。一种此类有效的解毒酶是一种编码草胺膦乙酰基转移酶的酶(例如链霉菌属(Streptomyces)物种的bar或pat蛋白)。例如,US5,561,236、US5,648,477、US5,646,024、US5,273,894、US5,637,489、US5,276,268、US5,739,082、US5,908,810和US7,112,665中描述了表达外源草胺膦乙酰基转移酶乙酰基转移酶的植物。
其它耐除草剂植物还是对抑制羟基苯基丙酮酸双氧化酶(HPPD)的除草剂具有耐受性的植物。羟基苯基丙酮酸双氧化酶是催化将对-羟基苯丙酮酸(HPP)转化成尿黑酸盐的反应的酶。耐HPPD-抑制剂的植物可使用编码天然产生的抗HPPD酶的基因,或编码突变HPPD酶的基因来转化,如WO1996/038567、WO1999/024585和WO1999/024586中所述。耐HPPD抑制剂还可通过用编码某些能够形成尿黑酸盐的酶的基因转化植物来获得,尽管HPPD抑制剂可抑制天然HPPD酶。WO1999/034008和WO2002/36787中描述了此类植物和基因。植物对耐HPPD抑制剂的耐受性还可通过使用编码酶预苯酸盐脱氢酶的基因(除了使用编码耐HPPD酶的基因外)转化植物来改进,如WO2004/024928中所述。
其它除草剂抗性植物是对乙酰乳酸合酶(ALS)抑制剂具有耐受性的植物。已知ALS抑制剂包括,例如磺酰脲、咪唑并啉酮、三唑并嘧啶、嘧啶氧基(硫基)苯甲酸酯/盐、和/或磺酰基氨基羰基三唑啉酮除草剂。已知ALS酶(也称作乙酰羟基酸合酶,AHAS)中不同突变会赋予对不同除草剂和除草剂基团的耐受性,如例如Tranel和Wright,Weed Science(2002),50,700-712,以及US5,605,011、US5,378,824、US5,141,870和US5,013,659中所述。耐磺酰脲植物和耐咪唑并啉酮植物的生产如US5,605,011、US5,013,659、US5,141,870、US5,767,361、US5,731,180、US5,304,732、US4,761,373、US5,331,107、US5,928,937和US5,378,824、以及国际公开WO1996/033270中所述。其它耐咪唑并啉酮的植物还如例如WO2004/040012、WO2004/106529、WO2005/020673、WO2005/093093、WO2006/007373、WO2006/015376、WO2006/024351和WO2006/060634中所述。其它耐磺酰脲和耐咪唑并啉酮的植物还如(例如)WO2007/024782中所述。
其它耐咪唑并啉酮和/或磺酰脲的植物可通过诱导突变、在存在除草剂的情况下选择细胞培养物、或突变育种来获得,如(例如)US5,084,082(对于大豆)、WO1997/41218(对于水稻)、US5,773,702和WO1999/057965(对于甜菜)、US5,198,599(对于莴苣)、或WO2001/065922(对于向日葵)中所述。
本发明还可处理的植物或植物品种(由植物生物技术方法获得,例如基因工程)是昆虫抗性转基因植物,即抵抗某些目标昆虫的攻击的植物。这些植物可通过遗传转化,或通过选择包含赋予该昆虫抗性的突变的植物来获得。
本文中所用的“昆虫抗性转基因植物”包括任意含有至少一种转基因的植物,所述转基因包括选自下组编码的编码序列:
1)来自苏云金芽孢杆菌(Bacillus thuringiensis)的杀虫晶体蛋白或其杀虫蛋白,例如Crickmore等人,Microbiology and Molecular Biology Reviews(1998),62,807-813,由Crickmore等人(2005)在苏云金芽孢杆菌毒素命名法中更新,网址为http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/)中所列的杀虫晶体蛋白,或其杀虫部分,例如Cry蛋白类Cry1Ab、Cry1Ac、Cry1F、Cry2Ab、Cry3Aa、或Cry3Bb的蛋白或其杀虫部分;或
2)在存在来自苏云金芽孢杆菌(Bacillus thuringiensis)的第二其它晶体蛋白或其部分的情况下,具有杀虫性的来自苏云金芽孢杆菌(Bacillus thuringiensis)的晶体蛋白或其部分,例如由Cry34和Cry35晶体蛋白组成的二元毒素(Moellenbeck等人,自然生物技术(Nat.Biotechnol.)(2001),19,668-72;Schnepf等人,Applied Environm.Microbiol.(2006),71,1765-1774);或
3)包含来自苏云金芽孢杆菌(Bacillus thuringiensis)的不同杀虫晶体蛋白部分的杂交杀虫蛋白,例如上述1)的蛋白的杂交体或上述2)的蛋白的杂交体,例如由玉米事件MON98034产生的Cry1A.105蛋白(WO2007/027777);或
4)上述1)至3)中的任意一种蛋白,其中一些(较好为1-10)氨基酸被另一种氨基酸代替以获得对目标昆虫物种的更高杀虫活性,和/或扩展受影响的目标昆虫物种的范围,和/或由于在克隆或转化过程中在编码DNA中引入的变化,例如玉米事件MON863或MON88017中的Cry3Bb1蛋白,或玉米事件MIR604中的Cry3A蛋白;
5)来自苏云金芽孢杆菌或蜡样芽胞杆菌(Bacillus cereus)的杀虫分泌蛋白,或其杀虫部分,例如在http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html中所列的营养期杀虫(VIP)蛋白,例如来自VIP3Aa蛋白类的蛋白;或
6)来自苏云金芽孢杆菌或蜡样芽孢杆菌的分泌蛋白,该蛋白在来自苏云金芽孢杆菌或蜡样芽孢杆菌的第二分泌蛋白存在下具有杀虫性,例如由VIP1A和VIP2A蛋白组成的二元毒素(WO1994/21795);或
7)包含来自苏云金芽孢杆菌或蜡样芽胞杆菌的不同分泌蛋白部分的杂交杀虫蛋白,例如上述1)中蛋白的杂交体或上述2)中蛋白的杂交体;或
8)上述1)至3)中的任意一种蛋白,其中一些(较好为1-10)氨基酸被另一种氨基酸代替以获得对目标昆虫物种的更高杀虫活性,和/或扩展受影响的目标昆虫物种的范围,和/或由于在克隆或转化过程中在编码DNA中引入的变化(同时仍编码杀虫蛋白),例如玉米事件COT102中的VIP3Aa蛋白。
当然,本文中所用的昆虫抗性转基因植物,还包括包含编码上述1-8类中任一种蛋白的基因的组合的任意植物。在一种实施方式中,昆虫抗性植物包含一种以上编码上述1-8类中的任一种蛋白的转基因,从而在使用针对不同目标昆虫物种的不同蛋白时扩展受影响的目标昆虫物种的范围,或通过使用对相同目标昆虫物种具有杀虫性但具有不同作用模式(例如在昆虫中结合不同的受体结合位点)的不同蛋白来延迟植物的昆虫抗性发展。
本发明还可处理的植物或植物品种(由植物生物技术方法获得,例如基因工程)可耐受非生物胁迫。这些植物可通过遗传转化,或通过选择包含赋予该胁迫抗性的突变的植物来获得。特别有用的胁迫耐受性植物包括:
a.包含能够减少植物细胞或植物中多聚(ADP-核糖)聚合酶(PARP)基因的表达和/或活性的转基因的植物,如WO2000/004173或WO2006/045633或PCT/EP07/004142中所述。
b.包含可增强能够减少植物或植物细胞中的PARG编码基因的表达和/或活性的转基因的胁迫耐受性的植物,如(例如)WO2004/090140中所述。
c.包含可增强烟酰胺腺嘌呤二核苷酸补救合成途径的植物功能化酶的转基因编码的胁迫耐受性的植物,所述植物功能化酶包括烟酰胺酶、烟酸磷酸核糖基转移酶、烟酸单核苷酸腺嘌呤转移酶、烟酰胺腺嘌呤二核苷酸合成酶或烟碱酰胺磷酸核糖基转移酶,如(例如)WO2006/032469或WO2006/133827或PCT/EP07/002433中所述。
本发明还可处理的植物或植物品种(由植物生物技术方法获得,例如基因工程)显示出改变了所收获的产品的数量、品质和/或储存稳定性,和/或改变了所收获的产品的具体成分的性质,例如:
1)合成改性的淀粉的转基因植物,其物理化学性质、尤其是直链淀粉含量或直链淀粉/支链淀粉比、支化程度、平均链长、侧链分布、粘度行为、胶凝强度、淀粉颗粒尺寸和/或淀粉颗粒形貌,与野生型植物细胞或植物中的合成淀粉相比有所改变,从而其更适合于具体的应用。所述合成改性淀粉的转基因植物在以下文献中公开:例如EP0571427、WO1995/004826、EP0719338、WO1996/15248、WO1996/19581、WO1996/27674、WO1997/11188、WO1997/26362、WO1997/32985、WO1997/42328、WO1997/44472、WO1997/45545、WO1998/27212、WO1998/40503、WO99/58688、WO1999/58690、WO1999/58654、WO2000/008184、WO2000/008185、WO2000/008175、WO2000/28052、WO2000/77229、WO2001/12782、WO2001/12826、WO2002/101059、WO2003/071860、WO2004/056999、WO2005/030942、WO2005/030941、WO2005/095632、WO2005/095617、WO2005/095619、WO2005/095618、WO2005/123927、WO2006/018319、WO2006/103107、WO2006/108702、WO2007/009823、WO2000/22140、WO2006/063862、WO2006/072603、WO2002/034923、EP06090134.5、EP06090228.5、EP06090227.7、EP07090007.1、EP07090009.7、WO2001/14569、WO2002/79410、WO2003/33540、WO2004/078983、WO2001/19975、WO1995/26407、WO1996/34968、WO1998/20145、WO1999/12950、WO1999/66050、WO1999/53072、US6,734,341、WO2000/11192、WO1998/22604、WO1998/32326、WO2001/98509、WO2001/98509、WO2005/002359、US5,824,790、US6,013,861、WO1994/004693、WO1994/009144、WO1994/11520、WO1995/35026、WO1997/20936。
2)合成非淀粉碳水化合物聚合物的转基因植物,或与未经过遗传修饰的野生型植物相比具有改变的性质的合成非淀粉碳水化合物聚合物的转基因植物。例子是产生多聚果糖(尤其是菊糖和果聚糖类型)的植物(EP0663956、WO1996/001904、WO1996/021023、WO1998/039460、及WO1999/024593中所揭示);产生α-1,4-葡聚糖的植物(如WO1995/031553、US2002/031826、US6,284,479、US5,712,107、WO1997/047806、WO1997/047807、WO1997/047808及WO2000/014249中所揭示);产生α-1,6-支化α-1,4-葡聚糖的植物(如WO2000/73422中所揭示);产生阿塔娜(alternan)的植物(如WO2000/047727、EP06077301.7、US5,908,975和EP0728213中所揭示);
3)产生透明质酸的转基因植物,如例如WO2006/032538、WO2007/039314、WO2007/039315、WO2007/039316、JP2006/304779、及WO2005/012529中所揭示。
本发明还可处理的植物或植物品种(由植物生物技术方法获得,例如基因工程)是具有改变的纤维特性的植物,例如棉花植物。这些植物可通过遗传转化,或通过选择包含赋予该改变的纤维特性的突变的植物来获得,包括:
a)包含改变形式的纤维素合酶基因的植物,例如棉花植物,如WO1998/000549中所述
b)包含改变形式的rsw2或rsw3同源核酸的植物,例如棉花植物,如WO2004/053219中所述
c)具有增加蔗糖磷酸合酶的表达的植物,例如棉花植物,如WO2001/017333中所述
d)具有增加蔗糖合酶的表达的植物,例如棉花植物,如WO02/45485中所述
e)其中基于纤维细胞的胞间连丝(plasmodesmatal)门控的时间被改变(例如通过下调纤维选择性β1,3-葡聚糖酶)的植物,例如棉花植物,如WO2005/017157中所述
f)具有改变的纤维反应性(例如通过表达包含nodC的N-乙酰基葡糖胺转化酶基因和壳聚糖合成酶(chitinsynthase)基因)的植物,例如棉花植物,如WO2006/136351中所述。
本发明还可处理的植物或植物品种(由植物生物技术方法获得,例如基因工程)是具有改变的油分布(oil profile)性质的植物,例如油菜或相关芸苔属植物。这些植物可通过遗传转化,或通过选择包含赋予该改变的油特性的突变的植物来获得,包括:
a)产生具有高油酸含量的油的植物,例如油菜植物,如例如US5,969,169、US5,840,946或US6,323,392或US6,063,947中所述。
b)产生具有低亚油酸含量的油的植物,例如油菜植物,如US6.270828、US6,169,190或US5,965,755中所述
c)产生具有低水平饱和脂肪酸的油的植物,例如油菜植物,如例如US5,434,283中所述。
本发明可处理的特别有用的转基因植物是包含一种或多种编码一种或多种毒素的基因的植物,例如以如下商品名出售的下列植物:(例如玉米、棉花、大豆)、(例如玉米)、(例如玉米)、(例如玉米)、(例如玉米)、(棉花)、(棉花)、 (棉花)、(例如玉米)、和(马铃薯)。可提及的耐除草剂植物的例子是玉米变种、棉花变种和大豆变种,其以下列商品名出售:(耐草甘膦,例如玉米、棉花、大豆),(耐草胺膦,例如油菜),(耐咪唑并啉酮)and(耐磺酰脲,例如玉米)。可提及的除草剂抗性植物(以常用方式育种以获得耐除草剂的植物)包括以名称出售的变种(例如玉米)。
本发明可处理的特别有用的转基因植物是包含转化事件,或转化事件的组合的植物,其示于例如来自各个国家或地区管理机构的数据库中(参见例如http://gmoinfo.jrc.it/gmp_browse.aspx和http://www.agbios.com/dbase.php)。
本发明可处理的特别有用的转基因植物是包含转化事件,或转化事件的组合的植物,其示于例如来自各个国家或地区管理机构的数据库中,包括事件1143-14A(棉花,昆虫控制,未保藏,参见WO2006/128569);事件1143-51B(棉花,昆虫控制,未保藏,参见WO2006/128570);事件1445(棉花,耐除草剂,未保藏,参见US-A2002-120964或WO02/034946);事件17053(水稻,耐除草剂,保藏号为PTA-9843,参见WO2010/117737);事件17314(水稻,耐除草剂,保藏号为PTA-9844,参见WO2010/117735);事件281-24-236(棉花,昆虫控制-耐除草剂,保藏号为PTA-6233,参见WO2005/103266或US-A2005-216969);事件3006-210-23(棉花,昆虫控制-耐除草剂,保藏号为PTA-6233,参见US-A2007-143876或WO2005/103266);事件3272(玉米,品质特征,保藏号为PTA-9972,参见WO2006/098952或US-A2006-230473);事件40416(玉米,昆虫控制-耐除草剂,保藏号为ATCC PTA-11508,参见WO2011/075593);事件43A47(玉米,昆虫控制-耐除草剂,保藏号为ATCC PTA-11509,参见WO2011/075595);事件5307(玉米,昆虫控制,保藏号为ATCC PTA-9561,参见WO2010/077816);事件ASR-368(常绿草,耐除草剂,保藏号为ATCCPTA-4816,参见US-A2006-162007或WO2004/053062);事件B16(玉米,耐除草剂,未保藏,参见US-A2003-126634);事件BPS-CV127-9(大豆,耐除草剂,保藏号为NCIMB No.41603,参见WO2010/080829);事件CE43-67B(棉花,昆虫控制,保藏号为DSM ACC2724,参见US-A2009-217423或WO2006/128573);事件CE44-69D(棉花,昆虫控制,未保藏,参见US-A2010-0024077);事件CE44-69D(棉花,昆虫控制,未保藏,参见WO2006/128571);事件CE46-02A(棉花,昆虫控制,未保藏,参见WO2006/128572);事件COT102(棉花,昆虫控制,未保藏,参见US-A2006-130175或WO2004/039986);事件COT202(棉花,昆虫控制,未保藏,参见US-A2007-067868或WO2005/054479);事件COT203(棉花,昆虫控制,未保藏,参见WO2005/054480);事件DAS40278(玉米,耐除草剂,保藏号为ATCC PTA-10244,参见WO2011/022469);事件DAS-59122-7(玉米,昆虫控制-耐除草剂,保藏号为ATCC PTA11384,参见US-A2006-070139);事件DAS-59132(玉米,昆虫控制-耐除草剂,未保藏,参见WO2009/100188);事件DAS68416(大豆,耐除草剂,保藏号为ATCCPTA-10442,参见WO2011/066384或WO2011/066360);事件DP-098140-6(玉米,耐除草剂,保藏号为ATCC PTA-8296,参见US-A2009-137395或WO2008/112019);事件DP-305423-1(大豆,品质特征,未保藏,参见US-A2008-312082或WO2008/054747);事件DP-32138-1(玉米,杂交体系,保藏号为ATCC PTA-9158,参见US-A2009-0210970或WO2009/103049);事件DP-356043-5(大豆,耐除草剂,保藏号为ATCC PTA-8287,参见US-A2010-0184079或WO2008/002872);事件EE-1(茄子,昆虫控制,未保藏,参见WO2007/091277);事件FI117(玉米,耐除草剂,保藏号为ATCC209031,参见US-A2006-059581或WO98/044140);事件GA21(玉米,耐除草剂,保藏号为ATCC209033,参见US-A2005-086719或WO98/044140);事件GG25(玉米,耐除草剂,保藏号为ATCC209032,参见US-A2005-188434或WO98/044140);事件GHB119(棉花,昆虫控制-耐除草剂,保藏号为ATCC PTA-8398,参见WO2008/151780);事件GHB614(棉花,耐除草剂,保藏号为ATCC PTA-6878,参见US-A2010-050282或WO2007/017186);事件GJ11(玉米,耐除草剂,保藏号为ATCC209030,参见US-A2005-188434或WO98/044140);事件GMRZ13(甜菜,抗病毒性,保藏号为NCIMB-41601,参见WO2010/076212);事件H7-1(甜菜,耐除草剂,保藏号为NCIMB41158或NCIMB41159,参见US-A2004-172669或WO2004/074492);事件JOPLIN1(小麦,耐病性,未保藏,参见US-A2008-064032);事件LL27(大豆,耐除草剂,保藏号为NCIMB41658,参见WO2006/108674或US-A2008-320616);事件LL55(大豆,耐除草剂,保藏号为NCIMB41660,参见WO2006/108675或US-A2008-196127);事件LLcotton25(棉花,耐除草剂,保藏号为ATCC PTA-3343,参见WO03/013224或US-A2003-097687);事件LLRICE06(水稻,耐除草剂,保藏号为ATCC-23352,参见US6,468,747或WO00/026345);事件LLRICE601(水稻,耐除草剂,保藏号为ATCC PTA-2600,参见US-A2008-2289060或WO00/026356);事件LY038(玉米,品质特征,保藏号为ATCC PTA-5623,参见US-A2007-028322或WO2005/061720);事件MIR162(玉米,昆虫控制,保藏号为PTA-8166,参见US-A2009-300784或WO2007/142840);事件MIR604(玉米,昆虫控制,未保藏,参见US-A2008-167456或WO2005/103301);事件MON15985(棉花,昆虫控制,保藏号为ATCC PTA-2516,参见US-A2004-250317或WO02/100163);事件MON810(玉米,昆虫控制,未保藏,参见US-A2002-102582);事件MON863(玉米,昆虫控制,保藏号为ATCCPTA-2605,参见WO2004/011601或US-A2006-095986);事件MON87427(玉米,授粉控制,保藏号为ATCC PTA-7899,参见WO2011/062904);事件MON87460(玉米,胁迫耐受性,保藏号为ATCC PTA-8910,参见WO2009/111263或US-A2011-0138504);事件MON87701(大豆,昆虫控制,保藏号为ATCC PTA-8194,参见US-A2009-130071或WO2009/064652);事件MON87705(大豆,品质特征-耐除草剂,保藏号为ATCC PTA-9241,参见US-A2010-0080887或WO2010/037016);事件MON87708(大豆,耐除草剂,保藏号为ATCC PTA9670,参见WO2011/034704);事件MON87754(大豆,品质特征,保藏号为ATCC PTA-9385,参见WO2010/024976);事件MON87769(大豆,品质特征,保藏号为ATCC PTA-8911,参见US-A2011-0067141或WO2009/102873);事件MON88017(玉米,昆虫控制-耐除草剂,保藏号为ATCCPTA-5582,参见US-A2008-028482或WO2005/059103);事件MON88913(棉花,耐除草剂,保藏号为ATCC PTA-4854,参见WO2004/072235或US-A2006-059590);事件MON89034(玉米,昆虫控制,保藏号为ATCC PTA-7455,参见WO2007/140256或US-A2008-260932);事件MON89788(大豆,耐除草剂,保藏号为ATCC PTA-6708,参见US-A2006-282915或WO2006/130436);事件MS11(油菜,授粉控制-耐除草剂,保藏号为ATCC PTA-850或PTA-2485,参见WO01/031042);事件MS8(油菜,授粉控制-耐除草剂,保藏号为ATCCPTA-730,参见WO01/041558或US-A2003-188347);事件NK603(玉米,耐除草剂,保藏号为ATCC PTA-2478,参见US-A2007-292854);事件PE-7(水稻,昆虫控制,未保藏,参见WO2008/114282);事件RF3(油菜,授粉控制-耐除草剂,保藏号为ATCC PTA-730,参见WO01/041558或US-A2003-188347);事件RT73(油菜,耐除草剂,未保藏,参见WO02/036831或US-A2008-070260);事件T227-1(甜菜,耐除草剂,未保藏,参见WO02/44407或US-A2009-265817);事件T25(玉米,耐除草剂,未保藏,参见US-A2001-029014或WO01/051654);事件T304-40(棉花,昆虫控制-耐除草剂,保藏号为ATCCPTA-8171,参见US-A2010-077501或WO2008/122406);事件T342-142(棉花,昆虫控制,未保藏,参见WO2006/128568);事件TC1507(玉米,昆虫控制-耐除草剂,未保藏,参见US-A2005-039226或WO2004/099447);事件VIP1034(玉米,昆虫控制-耐除草剂,保藏号为ATCC PTA-3925.,参见WO03/052073),事件32316(玉米,昆虫控制-耐除草剂,保藏号为PTA-11507,参见WO2011/084632),事件4114(玉米,昆虫控制-耐除草剂,保藏号为PTA-11506,参见WO2011/084621)。
本发明还涉及如本文所定义的组合物,该组合物包含至少一种选自下组的其它活性成分:杀虫剂、引诱剂、止繁殖剂、杀细菌剂、杀螨剂、杀线虫剂、杀真菌剂、生长调节剂、除草剂、肥料、安全剂和化学信息素。
本发明还涉及一种控制植物病原有害真菌的方法,其特征在于,将本文所定义的活性化合物组合施用于植物病原有害真菌和/或其栖息地。
本发明还涉及一种制造用于控制植物病原有害真菌的组合物的方法,其特征在于,将如本文所定义的活性化合物组合与增容剂(extender)和/或表面活性剂混合。
本发明还涉及如本文所定义的活性化合物组合用于控制植物病原有害真菌的用途。
本发明还涉及如本文所定义的活性化合物组合作为植物生长调节剂的用途。
本发明还涉及如本文所定义的活性化合物组合用于处理转基因植物的用途。
本发明还涉及如本文所定义的活性化合物组合用于处理种子和转基因植物的种子的用途。
现将参照下列化合物实施例的表1以及下列制备或功效实施例对本发明的各个方面予以说明。
下表1以非限制性的方式对本发明化合物的实施例予以说明。
在表1中,使用下列缩写用于本发明一般结构(I)的指定要求的要素“Het”和“A”:
表1
logP值是依据EEC指令79/831附录V.A8(EEC Directive79/831AnnexV.A8)由HPLC(高效液相色谱)在反相柱上用下列方法测定的:
LC-MS的测定在是在以下条件下完成的:在pH=2.7的条件下用0.1%甲酸的水溶液并使用乙腈(包含0.1%甲酸)作为洗脱剂,线性梯度为10%乙腈至95%乙腈。
使用logP值已知的非支链烷2-酮(包含3-16个碳原子)进行校准(logP值是采用两个相邻烷酮之间的线性内插法由保留时间确定的)。使用200纳米至400纳米的紫外光谱,在色谱信号最大值处确定λmax值。
在表1中,M+H(或M H)是指在质谱中所观察到的分子离子峰,分别加上或减去1a.m.u(原子质量单位),M(ApcI+)是指在质谱中通过正大气压化学电离所发现的分子离子峰。
NMR峰列表
所选实施例的1H-NMR数据以1H-NMR-峰列表的形式列出。对于各信号峰列出的δ值,单位是ppm,信号强度在圆括号内。 δ值(信号强度)对之间以分号隔开。
因此,示例性峰列表具有如下的形式:
δ1(强度1);δ2(强度2);........;δi(强度i);......;δn(强度n)
实施例1,溶剂:DMSO,光谱仪:400.13MHz
9.9255(2.36);8.0461(1.36);8.0255(1.68);7.8715(1.37);7.8521(2.03);7.8321(1.17);7.5406(0.64);7.5287(1.46);7.5171(1.32);7.5073(1.02);7.4971(0.38);7.4838(0.41);7.4648(10.77);7.4539(7.80);7.1358(1.95);7.1175(1.85);5.3390(0.49);5.3236(6.98);4.1215(8.81);4.1063(0.83);4.0525(16.00);3.3722(5.01);3.3549(5.10);3.3310(7.19);2.5152(8.14);2.5111(15.77);2.5066(20.74);2.5021(15.10);2.4981(7.27);1.0803(0.55);1.0782(0.55);1.0726(0.52);1.0688(0.47);1.0606(0.94);1.0525(0.53);1.0486(0.58);1.0431(0.56);1.0408(0.56);1.0286(0.37);0.5156(0.75);0.5049(2.20);0.5006(2.33);0.4959(1.15);0.4904(1.15);0.4848(2.27);0.4805(2.12);0.4704(0.81);0.2342(0.86);0.2237(2.55);0.2202(2.58);0.2119(2.30);0.2082(2.56);0.1972(0.62)
实施例3,溶剂:CDCl3,光谱仪:250.13MHz
9.0451(0.70);8.1574(1.52);8.1223(1.91);7.8704(1.63);7.8356(1.30);7.5559(1.00);7.5502(1.35);7.5433(0.70);7.5326(0.51);7.5239(1.89);7.5168(1.68);7.4439(0.83);7.4336(0.29);7.4238(0.76);7.4172(1.12);7.4100(0.78);7.4005(1.89);7.3948(0.75);7.3771(0.72);7.3714(1.53);7.3512(0.29);7.3438(0.56);7.3362(0.33);7.2622(18.54);5.4282(5.64);4.0714(12.50);4.0549(0.45);4.0275(1.31);4.0003(1.35);3.9732(0.40);3.5031(0.49);3.4751(0.52);3.4617(1.01);3.4338(1.07);3.3882(1.05);3.3602(1.07);3.3467(0.54);3.3187(0.55);2.0474(0.55);1.5626(8.59);1.4796(4.92);1.4524(4.80);1.2605(0.54);1.1315(0.27);1.1036(0.47);1.0716(0.31);0.5993(0.33);0.5808(0.96);0.5760(1.23);0.5578(0.52);0.5488(1.12);0.5441(0.95);0.5267(0.43);0.2618(0.46);0.2437(1.34);0.2245(1.18);0.2207(1.23);0.2019(0.32);0.0694(0.32);0.0128(0.54);-0.0002(17.55);-0.0135(0.66)
实施例4,溶剂:CDCl3,光谱仪:400.13MHz
8.8107(1.00);8.1867(1.61);8.1661(1.74);7.7344(1.10);7.7148(1.80);7.6949(1.05);7.5203(2.27);7.5076(0.77);7.5024(3.11);7.4987(2.43);7.4658(0.45);7.4538(0.38);7.4474(1.49);7.4419(0.45);7.4325(0.83);7.4292(1.22);7.3958(2.40);7.3801(1.68);7.3766(2.80);7.3628(0.44);7.3589(0.99);7.2637(7.67);7.0469(1.74);7.0282(1.63);5.2936(7.49);4.0670(9.50);4.0008(16.00);3.5891(4.47);3.5719(4.61);3.4886(0.58);3.4711(0.60);3.0257(0.45);2.9931(0.46);2.6950(0.62);2.6762(0.84);2.6575(0.67);2.1565(0.40);2.1500(0.37);2.1453(0.72);2.1364(0.87);2.1297(0.67);2.1251(0.93);2.1161(0.88);2.1110(0.76);2.1074(0.69);2.1044(0.75);2.0972(0.46);2.0906(0.35);2.0848(0.40);2.0467(0.45);1.9860(0.48);1.9791(0.54);1.9585(1.11);1.9391(0.70);1.9302(0.47);1.9188(0.82);1.9094(0.47);1.9074(0.46);1.8981(0.51);1.8364(0.48);1.8179(1.01);1.7985(0.90);1.7927(1.12);1.7700(0.81);1.6012(7.35);1.2778(0.44);1.2605(1.11);1.2271(0.66);1.2096(1.20);1.1920(0.61);0.8983(0.50);0.8817(1.39);0.8640(0.60);0.0704(0.50);-0.0002(6.55)
实施例5,溶剂:CDCl3,光谱仪:400.13MHz
8.7579(0.92);8.1188(1.44);8.0983(1.56);7.6650(1.01);7.6453(1.63);7.6255(0.97);7.4545(1.59);7.4518(2.06);7.4479(1.10);7.4393(0.74);7.4340(2.98);7.4302(2.23);7.3957(0.43);7.3838(0.36);7.3775(1.40);7.3717(0.42);7.3625(0.80);7.3591(1.16);7.3556(0.56);7.3259(2.18);7.3224(0.93);7.3104(1.55);7.3068(2.59);7.2930(0.42);7.2891(0.95);7.2859(0.54);7.1932(1.63);6.9778(1.55);6.9593(1.46);5.2271(6.89);4.0043(9.05);3.9332(16.00);3.4359(0.40);3.4183(1.41);3.4125(4.39);3.4007(1.45);3.3947(4.49);3.3833(0.43);2.2165(0.67);2.1976(0.91);2.1788(0.71);1.7670(0.59);1.7538(0.63);1.7503(0.67);1.7475(0.68);1.7346(0.89);1.7247(0.48);1.7220(0.49);1.7194(0.50);1.7150(0.50);1.5842(0.37);1.5787(0.38);1.5656(0.94);1.5592(0.79);1.5483(1.76);1.5408(1.11);1.5290(11.47);1.5154(0.94);1.5066(0.72);1.4958(0.42);1.2377(0.69);1.2241(0.74);1.2188(0.78);1.2109(0.65);1.2064(0.82);1.1990(0.59);1.1896(0.75);1.1717(0.32);1.1569(1.24);1.1394(2.39);1.1218(1.17);-0.0002(0.40)
实施例6,溶剂:CDCl3,光谱仪:400.13MHz
8.7983(1.42);8.1880(1.92);8.1673(2.10);7.7338(1.25);7.7141(2.12);7.6943(1.23);7.5219(2.69);7.5039(3.45);7.5004(3.02);7.4645(0.55);7.4525(0.46);7.4461(1.72);7.4280(1.45);7.3951(2.72);7.3757(3.29);7.3580(1.19);7.2651(3.39);7.0485(2.08);7.0298(1.98);5.3005(8.46);4.0556(9.82);4.0046(16.00);3.5052(0.33);3.4876(0.91);3.4701(0.94);3.4526(0.36);3.4023(4.65);3.3860(4.84);1.8242(1.40);1.7892(1.98);1.7848(1.98);1.7677(1.09);1.7428(1.62);1.7198(1.21);1.7112(1.12);1.7023(1.20);1.6935(1.19);1.6750(0.74);1.6663(0.44);1.6578(0.33);1.6445(3.81);1.3386(0.52);1.3072(1.62);1.2837(1.80);1.2759(2.54);1.2653(2.96);1.2450(1.43);1.2342(1.15);1.2262(1.53);1.2083(2.39);1.1980(0.69);1.1909(1.16);1.1814(0.39);1.1742(0.63);1.1669(0.39);1.0471(0.59);1.0396(0.67);1.0157(1.34);1.0093(1.42);0.9859(1.16);0.9798(1.29);0.9560(0.46);0.8978(1.13);0.8814(2.79);0.8638(1.30);-0.0002(2.39)
实施例7,溶剂:CDCl3,光谱仪:400.13MHz
8.8710(1.13);8.1864(1.54);8.1659(1.67);7.7295(1.05);7.7099(1.71);7.6900(1.01);7.5260(2.16);7.5135(0.74);7.5082(3.06);7.5045(2.31);7.4675(0.44);7.4556(0.35);7.4492(1.44);7.4435(0.42);7.4342(0.81);7.4309(1.21);7.4275(0.59);7.3978(2.28);7.3823(1.59);7.3787(2.71);7.3649(0.42);7.3610(0.97);7.3579(0.58);7.2634(1.86);7.0372(1.63);7.0186(1.53);5.2989(7.06);4.0041(16.00);3.9577(0.51);3.9407(1.71);3.9238(1.73);3.9068(0.51);3.5064(0.85);3.4888(2.58);3.4713(2.61);3.4538(0.87);3.4085(0.47);3.3923(0.60);3.3857(1.56);3.3691(2.08);3.3504(1.58);3.3443(0.57);3.3277(0.50);1.8538(0.44);1.8497(0.44);1.8225(0.88);1.8183(0.93);1.7803(0.93);1.7728(0.98);1.7645(0.75);1.7389(0.90);1.7311(0.96);1.7233(0.85);1.7156(0.74);1.7058(0.58);1.6939(0.67);1.6859(0.87);1.6777(0.88);1.6697(0.60);1.6615(0.39);1.6495(0.32);1.5866(6.11);1.4630(6.45);1.4460(6.35);1.4326(0.39);1.3152(0.40);1.3071(0.81);1.2992(0.75);1.2915(0.40);1.2835(0.59);1.2754(1.06);1.2678(1.02);1.2607(0.66);1.2535(0.56);1.2439(0.64);1.2369(0.60);1.2277(3.27);1.2196(0.53);1.2102(5.61);1.1926(2.96);1.1660(0.49);1.0298(0.80);1.0215(0.60);0.9997(0.98);0.9921(0.58);0.9771(0.51);0.9699(0.67);0.0080(0.37);-0.0002(8.88);-0.0084(0.32)
实施例8,溶剂:CDCl3,光谱仪:400.13MHz
8.9110(1.03);8.1862(1.50);8.1656(1.64);7.7283(1.04);7.7087(1.66);7.6888(0.99);7.5260(2.10);7.5222(1.09);7.5134(0.73);7.5082(3.00);7.5044(2.23);7.4663(0.43);7.4543(0.34);7.4480(1.42);7.4423(0.41);7.4330(0.79);7.4297(1.17);7.4262(0.56);7.3968(2.20);7.3934(0.93);7.3813(1.55);7.3777(2.64);7.3639(0.42);7.3600(0.96);7.3569(0.55);7.2634(1.29);7.0365(1.59);7.0179(1.51);5.2958(6.96);4.0017(16.00);3.9818(0.53);3.9648(1.73);3.9478(1.74);3.9309(0.52);3.5086(0.83);3.4883(1.54);3.4864(1.60);3.4706(1.34);3.4686(1.53);3.4313(1.38);3.4135(1.48);3.4089(0.92);3.3910(0.80);2.2644(0.67);2.2456(0.91);2.2268(0.72);1.8391(0.43);1.8242(0.70);1.8090(0.56);1.8044(0.57);1.7905(0.49);1.6442(0.36);1.6293(0.84);1.6251(0.82);1.6110(1.57);1.6079(1.64);1.5981(3.88);1.5921(1.54);1.5770(0.84);1.5702(0.68);1.5563(0.36);1.4709(6.48);1.4540(6.39);1.4325(0.39);1.3043(0.69);1.2985(0.54);1.2862(0.85);1.2737(0.86);1.2658(0.76);1.2558(0.92);1.2272(0.99);1.2097(1.82);1.1921(0.90);-0.0002(5.87)
实施例9,溶剂:CDCl3,光谱仪:250.13MHz
9.0315(1.19);8.3001(0.94);8.2858(0.91);8.2640(1.03);8.2498(0.93);7.5335(1.59);7.5294(1.70);7.5034(2.85);7.4964(2.12);7.4718(2.02);7.4383(1.75);7.4171(1.12);7.4116(1.28);7.3943(2.27);7.3650(1.88);7.3376(0.57);7.3302(0.34);7.2785(1.17);5.3757(3.85);5.3681(3.63);4.1907(0.74);4.0554(0.51);4.0181(12.50);4.0014(1.61);3.9743(0.50);3.5210(0.63);3.4932(0.72);3.4796(1.18);3.4520(1.18);3.3884(1.17);3.3602(1.21);3.3470(0.74);3.3187(0.66);2.0431(0.85);1.8496(0.25);1.4827(5.40);1.4555(5.29);1.2860(0.35);1.2615(0.75);1.2578(0.83);1.2289(0.27);1.1581(0.39);1.1458(0.37);1.1398(0.33);1.1269(0.62);1.1129(0.36);1.1072(0.38);1.0987(0.45);0.8797(0.37);0.6320(0.35);0.6270(0.34);0.6117(1.73);0.6077(1.76);0.5941(0.78);0.5800(1.76);0.5613(0.51);0.2862(0.63);0.2674(2.07);0.2484(1.94);0.2278(0.50);0.0032(0.33);-0.0002(0.51)
实施例10,溶剂:CDCl3,光谱仪:400.13MHz
8.8428(1.30);8.2078(1.82);8.1871(1.95);7.7554(1.21);7.7358(1.99);7.7159(1.14);7.5406(2.47);7.5226(3.40);7.5188(2.67);7.4870(0.48);7.4749(0.41);7.4687(1.61);7.4505(1.27);7.4173(2.54);7.3979(2.99);7.3801(1.03);7.2831(1.64);7.0659(1.95);7.0472(1.83);5.3176(8.08);4.1334(0.59);4.0786(9.53);4.0206(16.00);3.6659(2.36);3.6489(4.80);3.6319(2.37);3.5085(0.58);3.4910(0.58);1.7712(1.19);1.7451(2.49);1.7202(1.09);1.7113(1.39);1.7062(1.42);1.6666(0.59);1.6272(1.17);1.6140(8.27);1.5933(3.28);1.5763(1.21);1.4754(0.35);1.4666(0.44);1.4579(0.51);1.4515(0.72);1.4402(0.48);1.4314(0.41);1.4221(0.36);1.3278(0.38);1.2956(1.06);1.2882(0.93);1.2803(0.97);1.2728(1.44);1.2645(1.42);1.2472(0.94);1.2418(0.84);1.2297(1.88);1.2122(0.76);1.1982(0.67);1.1667(0.52);1.0229(0.51);1.0164(0.58);0.9863(1.27);0.9578(1.05);0.9339(0.36);0.9224(0.33);0.9014(0.41)
实施例11,溶剂:CDCl3,光谱仪:400.13MHz
8.8318(1.18);8.1899(1.75);8.1692(1.90);7.7360(1.16);7.7163(1.93);7.6965(1.12);7.5206(2.42);7.5026(3.32);7.4990(2.64);7.4667(0.46);7.4547(0.38);7.4483(1.57);7.4301(1.25);7.3969(2.48);7.3776(2.95);7.3599(1.01);7.2633(6.66);7.0472(1.89);7.0285(1.78);5.2958(7.94);4.1134(0.41);4.0663(9.50);3.9991(16.00);3.6288(2.33);3.6117(4.76);3.5945(2.41);3.4888(0.84);3.4712(0.85);1.9178(0.49);1.8993(0.81);1.8813(0.75);1.8629(0.47);1.8473(0.65);1.8366(0.77);1.8321(0.72);1.8238(0.95);1.8187(0.80);1.8053(0.90);1.7962(0.75);1.7783(0.39);1.7360(1.24);1.7189(3.35);1.7016(2.95);1.6842(0.99);1.6554(0.63);1.6468(0.81);1.6374(1.16);1.6348(1.19);1.6248(0.88);1.6186(0.94);1.6102(0.73);1.5935(5.61);1.5841(0.88);1.5610(0.97);1.5504(1.02);1.5433(1.09);1.5319(0.83);1.5252(0.66);1.5133(0.36);1.4324(0.33);1.2273(0.92);1.2098(1.79);1.1922(0.92);1.1818(0.37);1.1637(0.84);1.1494(0.79);1.1443(0.99);1.1339(0.93);1.1139(0.74);-0.0002(3.44)
实施例12,溶剂:CDCl3,光谱仪:400.13MHz
8.8934(1.43);8.1864(1.95);8.1658(2.09);7.7294(1.27);7.7098(2.09);7.6899(1.17);7.5239(2.76);7.5059(3.59);7.5024(3.16);7.4664(0.56);7.4480(1.74);7.4299(1.45);7.3970(2.85);7.3777(3.37);7.3599(1.18);7.2649(4.13);7.0367(2.06);7.0180(1.94);5.3222(0.36);5.2916(8.49);4.1306(0.36);4.1232(0.65);4.1129(0.35);4.0139(1.42);3.9993(16.00);3.9748(0.65);3.9579(1.87);3.9409(1.89);3.9239(0.61);3.6123(0.86);3.5950(1.06);3.5888(1.65);3.5717(1.61);3.5342(1.60);3.5170(1.71);3.5108(1.06);3.4935(0.92);2.6757(0.76);2.6571(1.03);2.6384(0.81);2.6200(0.37);2.1522(0.44);2.1432(0.78);2.1334(1.03);2.1238(1.26);2.1134(1.32);2.1043(1.20);2.0934(0.91);2.0847(0.64);2.0470(1.40);1.9931(0.40);1.9722(0.56);1.9656(0.80);1.9450(1.20);1.9245(0.90);1.9170(0.64);1.9054(0.97);1.8949(0.67);1.8844(0.69);1.8788(0.47);1.8741(0.45);1.8571(0.39);1.8397(0.66);1.8295(0.67);1.8223(0.90);1.8084(1.36);1.7889(1.28);1.7804(1.36);1.7603(0.99);1.6252(3.36);1.4687(7.19);1.4517(7.14);1.2781(0.45);1.2601(0.96);1.2424(0.44)
实施例14,溶剂:DMSO,光谱仪:399.95MHz
12.0426(1.86);7.9520(0.66);7.5370(0.53);7.5331(0.42);7.5267(0.59);7.5228(0.92);7.5188(0.73);7.5166(0.73);7.5138(0.76);7.5102(0.77);7.5075(0.93);7.5014(0.99);7.4842(1.15);7.4794(1.15);7.4704(11.59);7.4624(3.74);7.4575(2.57);7.4558(2.59);7.4364(0.40);7.2713(3.77);5.2850(6.32);4.1796(0.50);4.1629(1.76);4.1461(1.68);4.1296(0.49);3.9942(16.00);3.2988(134.00);3.2750(4.53);3.2518(4.62);3.2347(4.55);2.8903(5.36);2.7318(4.39);2.6736(0.35);2.6691(0.43);2.5390(0.83);2.5087(25.03);2.5044(44.53);2.4999(56.51);2.4955(39.10);2.4912(18.70);2.3268(0.37);1.3125(6.38);1.2958(6.27);1.0243(0.44);1.0214(0.46);1.0163(0.44);1.0125(0.39);1.0043(0.77);0.9963(0.39);0.9923(0.47);0.9873(0.46);0.9843(0.45);0.4627(0.84);0.4581(1.40);0.4534(1.01);0.4494(1.07);0.4442(1.51);0.4380(1.40);0.4330(0.97);0.4295(0.95);0.4259(1.19);0.4215(0.80);0.1832(0.49);0.1715(2.30);0.1674(2.16);0.1597(2.11);0.1555(2.14);0.1445(0.38);0.0079(0.78);-0.0002(13.43);-0.0084(0.56)
实施例15,溶剂:CDCl3,光谱仪:400.13MHz
9.5808(1.10);7.5361(2.26);7.5232(0.81);7.5183(3.09);7.5145(2.31);7.4650(0.48);7.4621(0.32);7.4534(0.36);7.4467(1.48);7.4410(0.44);7.4319(0.84);7.4286(1.24);7.4253(0.63);7.3988(2.34);7.3833(1.60);7.3796(2.77);7.3659(0.44);7.3620(0.99);7.3589(0.58);7.2638(8.20);6.9516(3.18);5.2816(7.28);4.1547(9.35);3.9540(16.00);3.5843(4.47);3.5670(4.62);3.5062(0.43);3.4887(1.28);3.4711(1.30);3.4536(0.44);2.6641(0.61);2.6455(0.83);2.6267(0.66);2.1494(0.37);2.1430(0.38);2.1387(0.69);2.1293(0.84);2.1229(0.70);2.1181(0.88);2.1135(0.74);2.1088(0.90);2.1035(0.77);2.0969(0.78);2.0900(0.47);2.0833(0.36);2.0782(0.41);2.0468(0.43);1.9913(0.49);1.9848(0.55);1.9636(1.07);1.9415(0.73);1.9293(0.47);1.9190(0.72);1.9067(0.47);1.8969(0.46);1.8915(0.33);1.8085(0.42);1.7886(1.09);1.7692(0.98);1.7633(1.09);1.7406(0.78);1.6053(6.91);1.2777(0.39);1.2606(0.97);1.2271(1.38);1.2096(2.66);1.1921(1.32);0.8984(0.44);0.8818(1.24);0.8641(0.53);-0.0002(6.97)
实施例16,溶剂:CDCl3,光谱仪:400.13MHz
9.5273(1.54);7.4670(2.81);7.4487(3.44);7.3952(0.54);7.3766(1.69);7.3589(1.43);7.3294(2.84);7.3100(3.19);7.2923(1.07);7.1940(1.39);6.8833(3.94);5.2139(8.66);4.0920(9.76);3.8879(16.00);3.4360(0.80);3.4185(2.36);3.4063(5.18);3.4013(2.97);3.3885(5.14);2.2002(0.39);2.1814(0.91);2.1625(1.24);2.1437(0.96);2.1249(0.41);1.7646(0.38);1.7516(0.91);1.7354(1.09);1.7203(1.22);1.7060(0.78);1.6897(0.43);1.5774(0.58);1.5572(1.69);1.5440(11.62);1.5283(2.90);1.5133(1.28);1.4936(0.50);1.2218(0.47);1.2058(1.08);1.1874(1.40);1.1753(1.26);1.1570(3.16);1.1394(4.71);1.1219(2.24);-0.0002(0.73)
实施例17,溶剂:CDCl3,光谱仪:400.13MHz
9.5651(1.17);7.5363(2.23);7.5235(0.78);7.5185(3.08);7.5147(2.30);7.4649(0.49);7.4618(0.32);7.4532(0.37);7.4466(1.49);7.4409(0.45);7.4318(0.84);7.4284(1.26);7.4250(0.64);7.3988(2.34);7.3833(1.57);7.3796(2.76);7.3659(0.44);7.3620(0.98);7.3589(0.59);7.2630(8.74);6.9519(3.14);5.2868(7.18);4.1426(9.00);3.9555(16.00);3.3936(4.20);3.3773(4.31);1.7949(1.00);1.7715(2.00);1.7675(2.01);1.7470(0.93);1.7378(1.14);1.7318(1.15);1.7119(0.52);1.7032(0.60);1.6916(0.77);1.6831(0.70);1.6755(0.65);1.6669(0.61);1.6586(0.45);1.6503(0.34);1.6471(0.34);1.6385(0.35);1.5937(6.19);1.3301(0.33);1.2979(0.84);1.2740(1.05);1.2664(1.49);1.2426(0.64);1.2359(0.79);1.2270(0.72);1.2057(0.36);1.1986(0.57);1.1918(0.44);1.1676(0.48);1.0219(0.42);1.0146(0.48);0.9913(0.87);0.9840(1.10);0.9610(0.83);0.9553(0.84);0.8817(0.65);0.0700(0.78);-0.0002(7.11)
实施例18,溶剂:CDCl3,光谱仪:400.13MHz
9.6297(1.44);7.5390(2.50);7.5210(3.27);7.5173(2.45);7.4655(0.53);7.4537(0.42);7.4469(1.60);7.4414(0.49);7.4289(1.33);7.3996(2.57);7.3803(2.98);7.3627(1.02);7.2635(1.97);6.9497(3.46);5.2849(7.86);4.0727(0.55);4.0558(1.81);4.0388(1.84);4.0218(0.56);3.9693(16.00);3.5064(0.46);3.4889(1.36);3.4714(1.36);3.4538(0.47);3.4278(0.89);3.4113(1.02);3.4054(1.44);3.3889(1.39);3.3305(1.39);3.3144(1.47);3.3081(0.99);3.2919(0.90);1.8065(1.11);1.7732(2.16);1.7310(1.29);1.6875(0.74);1.6795(0.65);1.6671(0.46);1.6586(0.53);1.6504(0.58);1.6420(0.48);1.6339(0.43);1.6220(0.39);1.5878(6.77);1.4751(6.95);1.4581(6.83);1.3253(0.37);1.3026(1.06);1.2941(1.02);1.2788(1.05);1.2633(2.13);1.2399(0.88);1.2277(2.02);1.2102(3.02);1.2012(0.53);1.1927(2.01);1.1629(0.50);1.0238(0.36);1.0151(0.34);1.0008(0.68);0.9927(0.78);0.9760(0.89);0.9638(0.71);0.9530(0.60);0.9472(0.68);0.8982(0.56);0.8817(1.40);0.8640(0.64);-0.0002(9.17)
实施例19,溶剂:CDCl3,光谱仪:400.13MHz
9.6694(1.17);7.5397(2.23);7.5270(0.77);7.5219(3.06);7.5181(2.24);7.4644(0.49);7.4527(0.37);7.4459(1.45);7.4402(0.43);7.4312(0.83);7.4278(1.25);7.4244(0.63);7.3986(2.31);7.3833(1.56);7.3795(2.70);7.3659(0.43);7.3620(0.97);7.3587(0.56);7.2637(1.43);6.9483(3.01);5.2813(6.96);4.1884(0.40);4.0967(0.51);4.0797(1.73);4.0627(1.76);4.0457(0.54);3.9692(16.00);3.5262(0.91);3.5041(1.56);3.4885(1.90);3.4861(1.60);3.4711(1.57);3.4536(0.53);3.4066(1.37);3.3890(1.47);3.3843(1.08);3.3667(0.95);2.2362(0.70);2.2174(0.97);2.1986(0.75);2.1798(0.33);1.8466(0.34);1.8318(0.49);1.8282(0.49);1.8153(0.80);1.8014(0.64);1.7964(0.67);1.7885(0.49);1.7832(0.62);1.6227(1.10);1.6060(3.64);1.5956(2.02);1.5822(0.99);1.5753(0.75);1.5618(0.36);1.4838(6.65);1.4668(6.58);1.4324(0.41);1.2819(0.59);1.2629(1.15);1.2527(0.93);1.2438(0.80);1.2272(2.04);1.2097(3.49);1.1922(1.70);1.1812(0.73);1.1653(0.71);0.8817(0.40);0.0702(1.23);-0.0002(6.62)
实施例20,溶剂:CDCl3,光谱仪:400.13MHz
9.5382(1.39);7.5148(0.35);7.4662(2.50);7.4482(3.24);7.4446(2.54);7.3983(0.95);7.3944(1.02);7.3835(0.68);7.3768(1.67);7.3713(0.57);7.3586(1.35);7.3292(2.55);7.3100(3.00);7.2923(1.04);7.1930(1.54);6.8824(3.59);6.8637(0.53);5.2354(1.24);5.2156(7.83);4.1018(2.50);4.0736(9.64);3.8802(16.00);3.5668(2.31);3.5498(4.70);3.5327(2.33);1.6517(2.50);1.6240(2.86);1.5720(0.66);1.5414(5.97);1.5061(1.03);1.4891(3.00);1.4809(0.81);1.4721(3.25);1.4640(0.75);1.4551(1.22);1.3612(0.42);1.3454(0.36);1.3376(0.45);1.3288(0.50);1.3200(0.58);1.3111(0.50);1.3020(0.46);1.2929(0.41);1.2220(0.39);1.1905(1.25);1.1666(1.10);1.1570(1.39);1.1384(1.19);1.1256(1.24);1.1094(0.54);1.1000(0.71);1.0941(0.77);1.0692(0.52);0.9107(0.65);0.8812(1.44);0.8548(1.16);0.8276(0.43)
实施例21,溶剂:CDCl3,光谱仪:400.13MHz
9.6211(1.14);7.5369(2.39);7.5241(0.85);7.5191(3.15);7.5153(2.46);7.4692(0.51);7.4658(0.64);7.4543(0.49);7.4475(1.58);7.4420(0.54);7.4327(0.88);7.4294(1.31);7.3999(2.47);7.3843(1.63);7.3807(2.88);7.3670(0.46);7.3631(1.01);7.2639(6.67);6.9531(3.40);5.3050(0.51);5.2850(7.50);4.1728(1.04);4.1530(9.29);3.9502(16.00);3.6222(2.26);3.6051(4.60);3.5880(2.32);3.5063(0.78);3.4888(2.32);3.4712(2.35);3.4537(0.80);1.8874(0.49);1.8690(0.81);1.8511(0.76);1.8319(0.81);1.8225(0.69);1.8157(0.93);1.8115(0.78);1.8028(0.98);1.7977(0.83);1.7885(0.88);1.7838(0.90);1.7753(0.78);1.7574(0.41);1.7047(1.27);1.6876(3.29);1.6787(0.77);1.6704(3.10);1.6608(0.71);1.6530(1.55);1.6434(1.05);1.6305(1.55);1.6150(2.46);1.5933(0.71);1.5796(0.80);1.5651(0.61);1.5560(0.97);1.5459(1.05);1.5388(1.09);1.5279(0.86);1.5206(0.68);1.5090(0.39);1.2551(0.35);1.2272(2.48);1.2097(4.84);1.1921(2.43);1.1667(0.39);1.1495(0.86);1.1302(1.04);1.1198(0.95);1.1000(0.78);-0.0002(3.97)
实施例22,溶剂:CDCl3,光谱仪:400.13MHz
9.6575(1.20);7.5384(2.44);7.5206(3.17);7.5169(2.49);7.4646(0.71);7.4527(0.50);7.4461(1.53);7.4406(0.52);7.4312(0.88);7.4280(1.32);7.3984(2.51);7.3828(1.67);7.3793(2.88);7.3656(0.46);7.3617(1.01);7.2639(6.62);6.9481(3.36);5.3021(0.51);5.2773(7.50);4.1860(1.02);4.1309(0.63);4.1130(0.65);4.0950(0.34);4.0911(0.57);4.0740(1.78);4.0570(1.81);4.0400(0.55);3.9646(16.00);3.6357(0.94);3.6181(1.07);3.6123(1.44);3.5947(1.37);3.5069(1.40);3.4898(1.50);3.4836(1.09);3.4664(1.02);2.6508(0.66);2.6320(0.89);2.6135(0.71);2.1519(0.38);2.1428(0.64);2.1329(0.89);2.1232(0.99);2.1147(1.07);2.1041(0.94);2.0951(0.89);2.0843(0.53);2.0472(2.77);2.0065(0.38);1.9857(0.48);1.9788(0.76);1.9644(0.40);1.9579(1.06);1.9366(0.90);1.9229(0.51);1.9131(0.75);1.9008(0.58);1.8902(0.52);1.8843(0.41);1.8807(0.33);1.7942(0.39);1.7836(0.65);1.7750(0.98);1.7648(0.86);1.7549(1.17);1.7469(0.80);1.7352(0.70);1.7263(0.48);1.6047(3.50);1.4826(7.10);1.4656(7.03);1.2782(0.77);1.2603(1.58);1.2425(0.77)
实施例23,溶剂:DMSO,光谱仪:400.13MHz
9.9255(3.55);8.0585(2.43);8.0379(2.97);7.8842(2.40);7.8648(3.67);7.8447(2.03);7.6123(1.18);7.5988(1.04);7.5940(3.27);7.5893(1.13);7.5784(1.52);7.5755(2.41);7.5186(3.67);7.4986(6.48);7.4845(1.33);7.4800(3.43);7.4062(6.56);7.3877(4.92);7.3841(3.47);7.1396(3.73);7.1210(3.54);5.3228(13.46);4.3065(0.38);4.2889(0.37);4.1224(16.00);4.1019(0.40);3.3709(9.43);3.3535(9.77);3.3356(9.01);2.8943(0.36);2.5458(0.77);2.5245(32.77);2.5157(15.80);2.5113(29.94);2.5069(39.32);2.5024(28.08);2.4981(12.97);2.4525(0.64);1.2963(0.47);1.2786(0.93);1.2608(0.47);1.0947(0.37);1.0870(0.48);1.0826(0.37);1.0770(0.92);1.0750(0.93);1.0694(0.88);1.0656(0.76);1.0574(1.58);1.0492(0.76);1.0453(0.93);1.0397(0.93);1.0376(0.96);1.0320(0.35);1.0254(0.52);1.0200(0.39);0.5129(1.43);0.5022(4.19);0.4979(4.25);0.4930(1.94);0.4876(2.09);0.4821(4.24);0.4778(3.85);0.4676(1.53);0.2321(1.65);0.2216(4.74);0.2181(4.66);0.2098(4.21);0.2061(4.68);0.1952(1.21)
实施例25,溶剂:CDCl3,光谱仪:400.13MHz
8.8201(0.98);8.1962(1.60);8.1755(1.73);7.7404(1.10);7.7208(1.77);7.7009(1.05);7.5150(0.50);7.5112(0.33);7.5034(0.40);7.4975(1.19);7.4920(0.52);7.4845(0.56);7.4800(0.99);7.4760(0.59);7.4245(1.11);7.4041(2.82);7.3858(2.99);7.3796(3.30);7.3764(3.77);7.3639(0.50);7.3588(1.27);7.3545(0.83);7.2640(7.99);7.0317(1.72);7.0130(1.62);5.2741(7.45);4.0667(9.52);3.5876(4.46);3.5705(4.64);3.4887(0.76);3.4712(0.77);3.0261(0.33);2.9935(0.33);2.6934(0.60);2.6747(0.83);2.6560(0.65);2.5206(16.00);2.1535(0.39);2.1471(0.34);2.1423(0.72);2.1334(0.86);2.1268(0.66);2.1222(0.92);2.1131(0.87);2.1081(0.77);2.1043(0.70);2.1015(0.77);2.0943(0.47);2.0876(0.36);2.0819(0.41);2.0469(0.75);1.9823(0.48);1.9753(0.53);1.9550(1.13);1.9356(0.65);1.9272(0.50);1.9159(0.79);1.9065(0.47);1.8949(0.52);1.8894(0.32);1.8844(0.34);1.8347(0.46);1.8163(0.97);1.7970(0.88);1.7910(1.12);1.7878(1.00);1.7786(0.32);1.7684(0.82);1.6037(6.89);1.2602(0.60);1.2272(0.81);1.2097(1.57);1.1921(0.80);0.0705(1.32);-0.0002(6.82);-0.0083(0.33)
实施例26,溶剂:CDCl3,光谱仪:400.13MHz
8.7662(1.23);8.1277(1.81);8.1070(1.98);7.6705(1.19);7.6509(1.99);7.6310(1.14);7.4444(0.52);7.4270(1.30);7.4140(0.59);7.4096(1.02);7.4057(0.64);7.3541(1.20);7.3338(3.15);7.3155(3.64);7.3105(3.83);7.3073(4.17);7.2898(1.31);7.2855(0.85);7.1934(1.35);6.9620(1.96);6.9433(1.85);5.2075(8.18);4.0038(9.72);3.4177(0.75);3.4109(4.80);3.4004(0.87);3.3930(4.93);3.3836(0.35);2.4526(16.00);2.2335(0.34);2.2147(0.83);2.1958(1.13);2.1770(0.88);2.1582(0.38);1.7648(0.76);1.7461(0.89);1.7327(1.12);1.7196(0.66);1.7132(0.62);1.7024(0.38);1.5815(0.47);1.5756(0.48);1.5629(1.19);1.5453(2.34);1.5359(9.95);1.5121(1.15);1.5038(0.90);1.4924(0.51);1.2537(0.32);1.2353(0.86);1.2170(1.01);1.2039(1.01);1.1861(0.87);1.1706(0.32);1.1567(0.60);1.1392(1.08);1.1216(0.54);-0.0002(0.64)
实施例27,溶剂:CDCl3,光谱仪:400.13MHz
8.8069(0.99);8.1977(1.51);8.1770(1.64);7.7401(1.06);7.7204(1.69);7.7005(1.01);7.5146(0.48);7.5033(0.39);7.4973(1.11);7.4915(0.47);7.4845(0.54);7.4798(0.96);7.4756(0.56);7.4247(1.04);7.4204(0.57);7.4087(1.05);7.4043(2.74);7.3920(0.61);7.3861(3.33);7.3816(3.25);7.3780(3.70);7.3658(0.47);7.3606(1.14);7.3561(0.73);7.2638(6.58);7.0322(1.62);7.0136(1.53);5.2817(7.07);4.0558(9.11);3.5057(0.43);3.4881(1.32);3.4706(1.34);3.4531(0.45);3.4013(4.06);3.3849(4.22);2.5227(16.00);1.8297(0.81);1.8245(0.90);1.7882(1.27);1.7823(1.21);1.7737(0.85);1.7650(0.66);1.7488(0.84);1.7401(1.09);1.7302(0.92);1.7209(0.80);1.7174(0.80);1.7098(0.77);1.7013(0.85);1.6929(0.78);1.6893(0.76);1.6856(0.76);1.6820(0.68);1.6734(0.51);1.6073(5.28);1.3360(0.37);1.3130(0.65);1.3054(0.99);1.2817(0.98);1.2740(1.44);1.2666(1.18);1.2564(1.27);1.2425(0.88);1.2324(0.79);1.2265(1.85);1.2090(3.11);1.2043(0.82);1.1960(0.54);1.1915(1.54);1.1729(0.51);1.0453(0.44);1.0380(0.46);1.0142(0.95);1.0072(0.99);0.9847(0.83);0.9777(0.90);0.8816(0.62);0.8639(0.33);0.0707(0.36);-0.0002(5.23)
实施例28,溶剂:CDCl3,光谱仪:400.13MHz
8.8785(1.35);8.1953(1.81);8.1746(1.95);7.7356(1.18);7.7159(1.93);7.6960(1.12);7.5164(0.53);7.5126(0.37);7.4992(1.25);7.4866(0.58);7.4819(1.01);7.4777(0.62);7.4266(1.20);7.4062(3.14);7.3881(4.15);7.3849(4.02);7.3810(4.15);7.3637(1.21);7.3592(0.76);7.2639(1.40);7.0217(1.91);7.0030(1.80);5.2797(7.88);3.9563(0.54);3.9393(1.78);3.9224(1.80);3.9054(0.55);3.4055(0.49);3.3892(0.65);3.3828(1.79);3.3670(3.39);3.3509(1.78);3.3449(0.62);3.3280(0.50);2.5545(0.35);2.5225(16.00);1.8529(0.55);1.8173(1.14);1.7777(1.09);1.7700(1.15);1.7617(0.93);1.7366(1.10);1.7293(1.17);1.7208(1.02);1.7132(0.92);1.7047(0.78);1.6919(0.78);1.6848(0.97);1.6767(1.06);1.6688(0.77);1.6603(0.50);1.6482(0.38);1.5979(5.11);1.4625(6.85);1.4456(6.74);1.4328(0.77);1.3124(0.49);1.3044(0.95);1.2967(0.88);1.2808(0.67);1.2728(1.22);1.2653(1.18);1.2583(0.78);1.2496(0.51);1.2414(0.71);1.2345(0.67);1.2273(0.80);1.2182(0.45);1.2101(0.62);1.2027(0.44);1.1949(0.79);1.1880(0.49);1.1646(0.55);1.0505(0.32);1.0281(0.93);1.0201(0.70);0.9981(1.16);0.9907(0.69);0.9754(0.60);0.9681(0.79);0.0077(0.35);-0.0002(6.50)
实施例29,溶剂:CDCl3,光谱仪:400.13MHz
8.9189(1.06);8.1948(1.51);8.1743(1.64);7.7343(1.04);7.7147(1.66);7.6948(1.02);7.5151(0.49);7.5111(0.34);7.5042(0.41);7.4980(1.09);7.4921(0.54);7.4855(0.59);7.4807(1.00);7.4763(0.63);7.4258(1.03);7.4214(0.65);7.4099(1.02);7.4053(2.72);7.3934(0.76);7.3872(3.66);7.3844(3.62);7.3803(3.93);7.3685(0.64);7.3630(1.23);7.3585(0.84);7.2640(1.28);7.0208(1.59);7.0023(1.52);5.2762(6.89);3.9804(0.50);3.9634(1.72);3.9464(1.76);3.9295(0.57);3.5056(1.09);3.4884(1.93);3.4828(1.59);3.4711(1.41);3.4651(1.54);3.4536(0.53);3.4313(1.43);3.4136(1.53);3.4090(1.00);3.3911(0.86);2.5210(16.00);2.5116(0.65);2.2627(0.68);2.2439(0.93);2.2251(0.75);2.2064(0.34);1.8544(0.35);1.8370(0.48);1.8220(0.76);1.8071(0.62);1.8024(0.65);1.7906(0.57);1.7759(0.34);1.7713(0.33);1.6411(0.43);1.6265(0.92);1.6209(0.97);1.6067(4.02);1.5884(1.64);1.5738(1.02);1.5667(0.88);1.5532(0.50);1.5407(0.32);1.4704(6.49);1.4534(6.49);1.4416(0.45);1.4325(0.59);1.3020(0.75);1.2957(0.62);1.2842(0.95);1.2716(0.97);1.2605(0.89);1.2543(0.98);1.2358(0.39);1.2273(1.49);1.2098(2.66);1.1922(1.34);1.1835(0.55);1.1676(0.50);0.0715(0.38);-0.0002(5.84);-0.0084(0.32)
实施例30,溶剂:CDCl3,光谱仪:400.13MHz
8.7599(1.26);8.1262(1.77);8.1055(1.92);7.6708(1.17);7.6511(1.94);7.6312(1.12);7.4450(0.53);7.4417(0.37);7.4275(1.31);7.4145(0.58);7.4101(1.02);7.4063(0.63);7.3544(1.23);7.3340(3.11);7.3158(3.19);7.3092(3.55);7.3062(4.03);7.2886(1.33);7.2844(0.87);7.1924(1.57);6.9593(1.91);6.9406(1.79);5.2071(7.94);3.9875(9.47);3.5739(2.28);3.5568(4.65);3.5398(2.30);3.4175(0.67);3.3999(0.68);2.4491(16.00);1.6797(1.13);1.6525(2.38);1.6278(1.06);1.6183(1.37);1.6139(1.41);1.5752(0.57);1.5293(6.97);1.5177(3.04);1.5006(3.21);1.4837(1.19);1.3836(0.33);1.3751(0.42);1.3661(0.49);1.3607(0.67);1.3485(0.46);1.3395(0.40);1.3305(0.36);1.2361(0.37);1.2043(1.01);1.1973(0.87);1.1892(0.94);1.1815(1.41);1.1726(1.37);1.1561(1.00);1.1503(0.79);1.1386(2.00);1.1211(0.85);1.1124(0.58);1.1054(0.64);1.0979(0.54);1.0747(0.52);1.0676(0.33);0.9298(0.48);0.9231(0.55);0.8927(1.23);0.8646(1.01);0.8405(0.35);0.8284(0.35);0.8101(0.34)
实施例31,溶剂:CDCl3,光谱仪:400.13MHz
8.8402(1.25);8.1996(1.81);8.1790(1.97);7.7424(1.18);7.7228(1.98);7.7029(1.12);7.5159(0.53);7.4985(1.34);7.4852(0.60);7.4809(1.04);7.4254(1.25);7.4051(3.20);7.3868(3.27);7.3799(3.79);7.3772(4.11);7.3596(1.35);7.3555(0.88);7.2637(6.36);7.0320(1.95);7.0134(1.84);5.2765(8.10);4.0663(9.56);3.6279(2.30);3.6107(4.70);3.5936(2.39);2.5190(16.00);1.9170(0.59);1.8985(0.84);1.8805(0.78);1.8622(0.48);1.8459(0.67);1.8351(0.81);1.8222(0.99);1.8035(0.95);1.7945(0.79);1.7771(0.42);1.7346(1.27);1.7175(3.44);1.7003(3.07);1.6828(1.10);1.6727(0.33);1.6543(0.67);1.6454(0.85);1.6333(1.26);1.6236(0.99);1.6172(1.09);1.5995(4.80);1.5825(0.88);1.5682(0.63);1.5597(1.03);1.5491(1.05);1.5418(1.14);1.5310(0.89);1.5238(0.69);1.5121(0.39);1.2557(0.38);1.1800(0.39);1.1618(0.94);1.1423(1.10);1.1319(1.06);1.1121(0.87);1.0932(0.34);0.0713(0.34);-0.0002(3.38)
实施例32,溶剂:CDCl3,光谱仪:400.13MHz
8.9239(1.03);8.2009(1.86);8.1801(1.99);7.7399(1.20);7.7202(2.00);7.7003(1.12);7.5157(0.59);7.4983(1.42);7.4853(0.68);7.4810(1.11);7.4254(1.35);7.4051(3.46);7.3868(4.13);7.3824(4.36);7.3791(4.65);7.3616(1.39);7.3575(0.93);7.2636(1.22);7.0237(2.01);7.0050(1.88);5.2755(8.21);3.9741(0.58);3.9571(1.83);3.9401(1.84);3.9232(0.58);3.6088(0.83);3.5916(0.98);3.5853(1.63);3.5682(1.61);3.5352(1.55);3.5180(1.65);3.5118(0.98);3.4945(0.84);3.1275(0.34);3.0261(0.45);2.9935(0.46);2.9588(0.84);2.8856(0.71);2.6759(0.76);2.6573(0.99);2.6386(0.79);2.6203(0.36);2.5280(1.08);2.5178(16.00);2.1493(0.44);2.1404(0.76);2.1304(1.00);2.1206(1.22);2.1104(1.26);2.1015(1.15);2.0906(0.84);2.0817(0.61);1.9887(0.40);1.9675(0.55);1.9612(0.79);1.9406(1.20);1.9197(0.86);1.9138(0.62);1.9016(0.91);1.8912(0.63);1.8809(0.66);1.8752(0.46);1.8705(0.44);1.8537(0.39);1.8400(0.45);1.8271(0.68);1.8228(0.76);1.8064(1.33);1.7870(1.23);1.7781(1.31);1.7582(0.97);1.5978(0.38);1.4682(7.19);1.4512(7.08);1.3718(0.33);-0.0002(7.21)
实施例34,溶剂:DMSO,光谱仪:399.95MHz
12.0681(1.63);7.9522(0.59);7.6061(0.56);7.6031(0.39);7.5931(0.51);7.5879(1.54);7.5826(0.59);7.5725(0.80);7.5693(1.25);7.5662(0.76);7.5190(1.78);7.4991(3.21);7.4853(0.75);7.4808(1.69);7.4094(3.14);7.3913(2.41);7.3877(1.75);7.2993(3.88);5.2802(6.24);4.1827(0.45);4.1657(1.62);4.1490(1.66);4.1322(0.48);3.2973(98.53);3.2735(4.27);3.2506(4.48);3.2335(4.46);2.8903(4.86);2.7318(3.84);2.6691(0.40);2.5391(0.67);2.5087(23.05);2.5044(42.78);2.4999(55.92);2.4955(39.88);2.4912(19.99);2.4627(16.00);2.3265(0.40);1.3110(6.19);1.2943(6.14);1.0226(0.41);1.0199(0.45);1.0148(0.43);1.0108(0.39);1.0027(0.73);0.9945(0.38);0.9907(0.45);0.9854(0.45);0.9827(0.46);0.4606(0.83);0.4567(1.29);0.4520(0.95);0.4474(0.97);0.4420(1.50);0.4366(1.38);0.4315(0.89);0.4275(0.89);0.4222(1.17);0.1818(0.46);0.1702(2.13);0.1661(2.05);0.1583(2.01);0.1541(2.07);0.1429(0.38);0.0080(0.97);-0.0002(19.17);-0.0084(0.92)
实施例35,溶剂:CDCl3,光谱仪:400.13MHz
9.5894(1.12);7.5134(0.49);7.5094(0.33);7.5025(0.41);7.4964(1.15);7.4905(0.52);7.4839(0.56);7.4790(0.98);7.4747(0.60);7.4267(1.09);7.4064(2.92);7.3875(4.14);7.3817(3.96);7.3697(0.49);7.3644(1.12);7.3599(0.69);7.2641(8.31);6.9508(3.18);5.2644(7.29);4.1545(9.30);3.5824(4.45);3.5651(4.59);3.5063(0.49);3.4888(1.44);3.4712(1.46);3.4537(0.49);2.6629(0.63);2.6440(0.85);2.6253(0.67);2.4761(16.00);2.1476(0.39);2.1368(0.73);2.1276(0.87);2.1211(0.72);2.1163(0.90);2.1117(0.76);2.1069(0.92);2.1017(0.78);2.0950(0.80);2.0881(0.47);2.0814(0.36);2.0763(0.42);2.0469(0.50);1.9878(0.51);1.9813(0.57);1.9601(1.12);1.9471(0.33);1.9381(0.79);1.9265(0.53);1.9164(0.82);1.9038(0.49);1.8941(0.47);1.8883(0.33);1.8080(0.45);1.7873(1.12);1.7678(1.01);1.7622(1.12);1.7392(0.80);1.6091(7.50);1.2779(0.41);1.2605(1.04);1.2272(1.55);1.2097(2.97);1.1922(1.48);0.8983(0.41);0.8818(1.10);0.8641(0.47);0.0702(1.07);0.0078(0.33);-0.0002(7.06)
实施例36,溶剂:CDCl3,光谱仪:400.13MHz
9.5339(1.17);7.4438(0.48);7.4398(0.33);7.4328(0.40);7.4267(1.15);7.4208(0.53);7.4143(0.55);7.4094(0.98);7.4051(0.60);7.3574(1.06);7.3370(2.92);7.3175(4.24);7.3125(4.05);7.3005(0.50);7.2952(1.12);7.2907(0.71);7.1940(1.70);6.8830(3.21);5.1972(7.28);4.0919(9.14);3.4363(0.87);3.4187(2.70);3.4048(4.89);3.4014(3.59);3.3870(4.80);2.4100(16.00);2.1803(0.75);2.1614(1.03);2.1426(0.81);2.1237(0.36);1.7513(0.68);1.7349(0.81);1.7194(0.98);1.7063(0.59);1.7001(0.56);1.6891(0.33);1.5753(0.36);1.5556(1.19);1.5386(11.47);1.5259(2.29);1.5208(1.70);1.5109(0.98);1.5026(0.78);1.4917(0.40);1.2205(0.35);1.2045(0.85);1.1910(1.13);1.1857(1.10);1.1733(1.00);1.1662(0.67);1.1572(3.42);1.1397(5.70);1.1222(2.74);0.8114(0.35);-0.0002(0.59)
实施例37,溶剂:CDCl3,光谱仪:400.13MHz
9.5729(0.96);7.5131(0.47);7.5024(0.39);7.4961(1.01);7.4900(0.51);7.4838(0.57);7.4788(0.96);7.4744(0.62);7.4269(0.95);7.4222(0.59);7.4111(0.97);7.4065(2.57);7.3946(0.70);7.3871(3.85);7.3821(3.72);7.3704(0.58);7.3649(1.13);7.3603(0.75);7.2638(8.17);6.9520(2.57);5.2700(6.00);5.2693(5.90);4.1424(8.30);3.5060(0.63);3.4884(1.90);3.4709(1.94);3.4534(0.68);3.3917(3.74);3.3754(3.88);2.4777(16.00);1.8015(0.76);1.7969(0.85);1.7938(0.85);1.7696(1.73);1.7440(0.86);1.7355(1.03);1.7289(1.02);1.7019(0.58);1.6934(0.67);1.6898(0.71);1.6860(0.70);1.6819(0.68);1.6738(0.64);1.6654(0.60);1.6571(0.44);1.6487(0.36);1.6455(0.35);1.6369(0.36);1.6057(5.14);1.3273(0.32);1.3029(0.66);1.2954(0.85);1.2881(0.75);1.2717(1.23);1.2642(1.88);1.2410(0.74);1.2334(0.86);1.2267(2.63);1.2092(4.21);1.2038(0.60);1.1916(2.34);1.1651(0.49);1.0201(0.37);1.0129(0.43);0.9894(0.73);0.9820(0.93);0.9595(0.71);0.9532(0.75);0.8986(0.49);0.8817(1.41);0.8641(0.60);0.0701(0.49);-0.0002(6.66);-0.0085(0.33)
实施例38,溶剂:CDCl3,光谱仪:400.13MHz
9.6346(1.56);7.5136(0.53);7.4965(1.29);7.4842(0.60);7.4793(1.05);7.4752(0.65);7.4274(1.23);7.4070(3.38);7.3884(5.89);7.3835(4.48);7.3664(1.17);7.3618(0.70);7.2635(2.00);6.9497(3.64);5.2679(8.09);4.0718(0.56);4.0547(1.81);4.0377(1.83);4.0208(0.55);3.4246(0.88);3.4080(1.05);3.4022(1.47);3.3857(1.42);3.3296(1.41);3.3135(1.50);3.3074(0.99);3.2911(0.90);2.4902(16.00);1.8056(1.19);1.7719(2.27);1.7280(1.33);1.6855(0.81);1.6570(0.54);1.6487(0.60);1.6405(0.50);1.6326(0.46);1.6205(0.42);1.5879(7.31);1.4739(6.92);1.4569(6.81);1.3227(0.33);1.2991(0.94);1.2915(0.91);1.2754(0.74);1.2672(1.32);1.2604(1.32);1.2441(0.52);1.2363(0.79);1.2285(0.79);1.2194(0.75);1.2124(0.58);1.1915(0.74);1.1594(0.52);1.1524(0.33);1.0221(0.34);1.0122(0.36);0.9983(0.73);0.9907(0.79);0.9734(0.93);0.9617(0.76);0.9504(0.64);0.9448(0.71);0.0076(0.51);-0.0002(9.39)
实施例39,溶剂:CDCl3,光谱仪:400.13MHz
9.6729(1.32);7.5125(0.49);7.5082(0.33);7.5018(0.43);7.4956(1.15);7.4896(0.52);7.4836(0.55);7.4785(0.98);7.4740(0.60);7.4269(1.07);7.4064(3.06);7.3883(6.18);7.3837(4.21);7.3719(0.49);7.3667(1.04);7.3619(0.60);7.2647(1.12);6.9485(3.30);5.2646(7.54);4.0959(0.54);4.0789(1.77);4.0619(1.82);4.0449(0.57);3.5227(0.94);3.5045(1.34);3.5004(1.53);3.4887(1.15);3.4822(1.46);3.4712(1.07);3.4537(0.36);3.4058(1.38);3.3883(1.51);3.3836(1.08);3.3660(0.96);2.4899(16.00);2.2341(0.76);2.2153(1.04);2.1964(0.81);2.1777(0.36);1.8447(0.38);1.8297(0.54);1.8137(0.88);1.8001(0.72);1.7949(0.72);1.7818(0.67);1.7691(0.34);1.7641(0.32);1.6237(3.27);1.6085(2.03);1.5916(2.10);1.5781(1.03);1.5712(0.81);1.5579(0.38);1.4827(6.76);1.4657(6.67);1.4325(0.33);1.2794(0.66);1.2605(1.33);1.2499(0.96);1.2418(0.89);1.2275(1.75);1.2098(2.57);1.1922(1.20);1.1831(0.55);1.1672(0.50);0.8817(0.38);0.0707(1.33);-0.0002(5.17)
实施例40,溶剂:CDCl3,光谱仪:400.13MHz
9.5491(1.15);7.4443(0.49);7.4402(0.34);7.4334(0.43);7.4272(1.14);7.4213(0.56);7.4148(0.61);7.4099(1.03);7.4056(0.66);7.3580(1.08);7.3421(1.18);7.3375(2.85);7.3193(3.86);7.3168(3.88);7.3126(4.01);7.3007(0.69);7.2953(1.28);7.2908(0.86);7.1940(1.54);6.8824(3.05);5.1990(6.76);4.0742(8.67);3.5655(2.07);3.5485(4.29);3.5315(2.17);3.4364(0.51);3.4188(1.52);3.4013(1.55);3.3838(0.55);2.4036(16.00);1.6494(1.86);1.6227(2.27);1.5719(0.63);1.5456(3.97);1.5051(0.99);1.4881(2.69);1.4711(2.95);1.4541(1.16);1.3619(0.42);1.3372(0.38);1.3287(0.42);1.3202(0.49);1.3110(0.43);1.3018(0.41);1.2926(0.38);1.2218(0.38);1.2143(0.32);1.1905(1.28);1.1715(0.73);1.1660(1.04);1.1572(2.56);1.1396(3.60);1.1221(2.45);1.1131(0.81);1.0972(1.05);1.0680(0.51);1.0609(0.35);0.9141(0.43);0.9086(0.51);0.8789(1.12);0.8532(0.93);0.8263(0.47);0.8113(0.48);-0.0002(0.69)
实施例41,溶剂:CDCl3,光谱仪:400.13MHz
9.6220(1.25);7.5144(0.49);7.5104(0.33);7.5034(0.42);7.4973(1.20);7.4915(0.52);7.4848(0.56);7.4800(0.99);7.4757(0.60);7.4279(1.13);7.4075(3.07);7.3884(4.41);7.3829(4.10);7.3707(0.50);7.3656(1.15);7.3611(0.71);7.2645(5.54);6.9527(3.42);5.2685(7.62);4.1527(9.18);3.6206(2.23);3.6035(4.58);3.5864(2.31);2.4729(16.00);1.8872(0.47);1.8687(0.78);1.8509(0.73);1.8312(0.71);1.8210(0.62);1.8143(0.86);1.8097(0.70);1.8014(0.92);1.7963(0.75);1.7869(0.84);1.7822(0.84);1.7737(0.72);1.7622(0.37);1.7561(0.37);1.7031(1.26);1.6860(3.29);1.6689(3.07);1.6513(1.45);1.6405(0.98);1.6221(2.26);1.6052(0.81);1.5909(0.54);1.5773(0.73);1.5629(0.56);1.5543(0.91);1.5439(0.99);1.5368(1.03);1.5259(0.81);1.5188(0.63);1.5068(0.36);1.2557(0.35);1.2098(0.47);1.1641(0.37);1.1473(0.84);1.1331(0.82);1.1282(0.98);1.1176(0.93);1.0980(0.74);1.0784(0.32);-0.0002(2.87)
实施例42,溶剂:CDCl3,光谱仪:400.13MHz
9.6557(1.02);7.5130(0.47);7.5091(0.36);7.5021(0.42);7.4960(1.04);7.4899(0.55);7.4838(0.54);7.4788(0.92);7.4744(0.62);7.4268(1.01);7.4063(2.65);7.3874(4.51);7.3826(3.75);7.3709(0.55);7.3654(1.03);7.3608(0.68);7.2625(17.72);6.9473(2.72);5.2603(6.32);4.1492(0.35);4.1314(1.00);4.1135(1.03);4.0956(0.41);4.0896(0.51);4.0726(1.54);4.0556(1.56);4.0384(0.48);3.6324(0.80);3.6149(0.91);3.6091(1.22);3.5915(1.17);3.5049(1.14);3.4879(1.23);3.4816(0.93);3.4645(0.84);2.6483(0.63);2.6300(0.76);2.6109(0.61);2.4853(13.85);2.1486(0.33);2.1402(0.55);2.1301(0.74);2.1203(0.83);2.1123(0.92);2.1026(0.82);2.0923(0.71);2.0817(0.47);2.0477(4.45);2.0018(0.33);1.9807(0.46);1.9739(0.66);1.9598(0.35);1.9531(0.95);1.9318(0.82);1.9187(0.48);1.9090(0.67);1.8966(0.52);1.8867(0.47);1.7924(0.37);1.7811(0.56);1.7731(0.85);1.7628(0.73);1.7528(0.99);1.7446(0.68);1.7330(0.61);1.7238(0.45);1.5689(16.00);1.4813(5.89);1.4643(5.86);1.2785(1.23);1.2607(2.44);1.2428(1.24);-0.0002(0.49)
实施例45,溶剂:DMSO,光谱仪:399.95MHz
12.0033(1.19);7.9519(0.41);7.5363(0.46);7.5319(0.36);7.5279(0.48);7.5258(0.49);7.5220(0.80);7.5179(0.63);7.5160(0.66);7.5131(0.65);7.5094(0.64);7.5065(0.79);7.5005(0.86);7.4946(0.33);7.4837(0.99);7.4793(0.97);7.4697(9.89);7.4619(3.21);7.4568(2.17);7.4549(2.22);7.4357(0.35);7.2593(3.73);5.2796(5.48);4.1517(7.71);3.9850(14.16);3.5209(2.06);3.5042(4.26);3.4875(2.08);3.2977(94.19);3.2739(3.68);2.8902(3.38);2.7318(2.80);2.7306(2.57);2.6688(0.35);2.5388(0.64);2.5086(20.80);2.5042(37.22);2.4997(47.42);2.4953(32.75);2.4909(15.66);2.3265(0.33);1.7159(0.32);1.6992(0.67);1.6823(0.87);1.6656(0.74);1.6488(0.41);1.4614(1.16);1.4446(3.29);1.4277(3.02);1.4108(0.95);0.8832(16.00);0.8665(15.24);0.0079(0.67);-0.0002(12.17);-0.0085(0.49)
实施例46,溶剂:DMSO,光谱仪:399.95MHz
12.0265(1.76);7.9519(0.35);7.6053(0.51);7.6022(0.35);7.5922(0.47);7.5871(1.42);7.5819(0.52);7.5716(0.71);7.5685(1.12);7.5655(0.65);7.5184(1.61);7.4984(2.90);7.4846(0.64);7.4801(1.53);7.4092(2.81);7.3957(0.77);7.3910(2.17);7.3874(1.54);7.2878(2.99);5.2749(5.75);4.1528(7.52);3.5200(2.10);3.5032(4.34);3.4865(2.15);3.2961(50.61);2.8903(2.80);2.7317(2.25);2.6689(0.36);2.5390(0.67);2.5220(1.87);2.5086(20.01);2.5043(36.52);2.4999(47.14);2.4955(33.11);2.4911(16.13);2.4551(14.24);1.7155(0.34);1.6986(0.69);1.6818(0.90);1.6650(0.77);1.6483(0.42);1.4601(1.18);1.4434(3.35);1.4265(3.09);1.4095(0.98);0.8823(16.00);0.8656(15.22);0.0079(1.03);-0.0002(18.83);-0.0084(0.82)
实施例48,溶剂:DMSO,光谱仪:400.13MHz
10.1243(2.25);8.0612(1.14);8.0405(1.42);7.8745(1.31);7.8550(1.85);7.8349(1.11);7.5382(0.62);7.5283(1.22);7.5175(1.30);7.5071(0.89);7.4967(0.34);7.4854(0.45);7.4822(0.40);7.4729(1.03);7.4629(8.77);7.4520(7.64);7.4124(0.41);7.4065(0.76);7.3914(7.62);7.3862(3.70);7.3752(3.50);7.3699(0.72);7.3607(0.57);7.3555(0.88);7.3366(0.74);7.3309(0.97);7.3235(0.77);7.3149(0.89);7.3052(0.38);7.2998(0.36);7.1362(1.81);7.1178(1.72);5.3178(6.39);4.6087(8.52);4.1901(7.76);4.0943(0.34);4.0643(0.59);4.0408(0.56);4.0301(16.00);3.3450(63.03);2.5288(0.73);2.5156(7.47);2.5112(15.11);2.5067(20.16);2.5021(14.19);2.4977(6.33);1.9930(0.68);1.2792(0.54);1.2614(0.36);1.2484(0.40);1.1778(0.37);0.8607(0.55)
实施例50,溶剂:DMSO,光谱仪:400.13MHz
12.1482(2.27);7.5509(0.48);7.5441(0.76);7.5397(0.46);7.5355(0.58);7.5297(1.03);7.5242(0.81);7.5208(0.76);7.5168(0.80);7.5141(0.99);7.5082(1.13);7.5022(0.69);7.4914(1.25);7.4773(11.98);7.4696(3.67);7.4627(2.61);7.4433(0.41);7.4032(0.45);7.3974(0.83);7.3826(8.40);7.3771(4.03);7.3668(3.83);7.3612(0.73);7.3521(0.63);7.3468(1.09);7.3280(0.79);7.3220(1.05);7.3149(0.90);7.3060(1.23);7.2967(0.57);7.2852(3.98);5.3450(0.37);5.2902(6.33);4.5913(9.08);4.2511(8.70);4.1672(1.11);4.0421(0.90);4.0243(1.01);4.0047(1.84);3.9985(16.00);3.9874(0.36);3.3367(19.47);2.5290(0.77);2.5157(7.91);2.5113(16.01);2.5068(21.42);2.5023(15.23);2.4978(6.93);1.9937(3.76);1.2751(0.32);1.2623(0.36);1.2496(0.88);1.1964(1.02);1.1786(1.99);1.1608(0.98);0.8787(0.37);0.8619(1.13);0.8443(0.44)
实施例51,溶剂:DMSO,光谱仪:400.13MHz
10.2125(4.89);8.1122(0.49);8.1026(3.28);8.0915(0.88);8.0820(3.90);7.9016(0.36);7.8920(2.50);7.8821(0.75);7.8726(3.79);7.8525(2.13);7.6131(1.28);7.6102(1.05);7.6043(0.79);7.5948(3.37);7.5900(1.73);7.5791(1.72);7.5763(2.48);7.5279(0.65);7.5185(3.83);7.4985(6.71);7.4843(1.78);7.4800(3.55);7.4049(7.13);7.3867(7.40);7.3827(6.72);7.3725(16.00);7.3674(10.36);7.3566(7.65);7.3514(3.01);7.3457(1.35);7.3418(1.42);7.3368(1.93);7.3174(1.51);7.3119(2.17);7.3047(1.89);7.2959(2.06);7.2870(0.96);7.2809(0.84);7.2748(0.50);7.1582(0.56);7.1486(3.86);7.1302(3.68);5.7786(0.36);5.7728(0.73);5.7635(7.44);5.7591(1.26);5.7520(0.52);5.3342(2.01);5.3251(13.25);4.6007(0.36);4.5913(2.85);4.5782(0.49);4.5715(0.67);4.5620(5.47);4.5136(0.67);4.5042(5.33);4.4927(0.60);4.4841(0.35);4.4749(2.86);4.3134(0.69);4.2958(0.74);4.2723(1.06);4.2559(3.12);4.2393(3.04);4.2229(0.87);3.3408(29.59);2.8938(1.63);2.7353(1.40);2.5161(5.34);2.5117(10.30);2.5028(36.50);2.4917(3.35);2.4510(0.61);1.3781(1.79);1.3688(12.40);1.3523(11.84);1.3286(0.36);1.2986(0.79);1.2808(1.52);1.2766(0.39);1.2671(0.43);1.2630(0.78)
实施例59,溶剂:DMSO,光谱仪:399.95MHz
11.8960(0.64);11.8622(0.75);7.9520(0.94);7.5434(0.33);7.5367(0.57);7.5317(0.45);7.5288(0.52);7.5222(1.01);7.5166(0.88);7.5135(0.80);7.5064(0.98);7.5007(1.11);7.4945(0.53);7.4850(1.25);7.4803(1.13);7.4703(11.66);7.4632(3.73);7.4570(2.62);7.4551(2.75);7.4358(0.51);7.4333(0.36);7.2731(3.03);5.2850(6.82);4.1788(1.03);4.1638(2.20);4.1470(1.18);3.9842(16.00);3.9266(0.47);3.8993(0.81);3.8956(0.79);3.8728(0.41);3.8688(0.42);3.5089(0.48);3.5010(0.65);3.4795(1.04);3.4614(0.76);3.4450(0.61);3.4369(0.61);3.4313(0.61);3.4269(0.54);3.4087(2.50);3.3963(1.49);3.3743(0.84);3.3667(0.91);3.3474(0.83);3.3005(225.76);3.2768(6.76);2.8903(7.89);2.7317(6.25);2.6736(0.40);2.6691(0.52);2.6645(0.40);2.5390(0.85);2.5220(2.50);2.5087(30.08);2.5044(55.61);2.4999(72.39);2.4955(51.24);2.4912(25.23);2.3312(0.41);2.3267(0.51);2.3222(0.39);1.7581(0.53);1.7435(0.69);1.5240(0.59);1.4905(0.80);1.4638(0.32);1.4533(0.49);1.4455(0.38);1.4149(2.13);1.4043(1.93);1.3142(5.89);1.2973(5.92);1.2356(0.44);1.2250(0.33);1.1927(0.36);1.1657(0.37);0.0079(0.74);-0.0002(14.31);-0.0084(0.64)
实施例60,溶剂:DMSO,光谱仪:399.95MHz
11.9489(0.79);11.9157(0.87);7.9520(1.00);7.5438(0.42);7.5371(0.76);7.5323(0.63);7.5291(0.76);7.5226(1.38);7.5169(1.23);7.5139(1.09);7.5095(1.11);7.5067(1.35);7.5011(1.48);7.4940(0.61);7.4852(1.80);7.4806(1.67);7.4707(16.00);7.4633(5.26);7.4575(3.48);7.4555(3.55);7.4403(0.37);7.4364(0.61);7.4335(0.42);7.2796(4.33);5.2874(8.13);4.2298(0.38);4.2128(1.24);4.1961(1.46);4.1811(1.58);4.1644(1.45);4.1474(0.39);4.0246(0.37);4.0072(1.13);3.9943(13.17);3.9892(13.95);3.9808(1.31);3.9732(0.96);3.9628(0.86);3.9574(0.68);3.9468(0.57);3.7853(0.49);3.7731(0.61);3.7688(0.89);3.7648(0.81);3.7560(0.94);3.7527(1.26);3.7485(1.17);3.7364(1.07);3.7321(0.74);3.7199(0.54);3.6454(0.71);3.6421(0.69);3.6253(1.49);3.6080(1.46);3.5913(0.56);3.5882(0.50);3.5054(0.83);3.4956(0.83);3.4798(1.25);3.4700(1.20);3.4632(0.75);3.4529(0.73);3.4373(1.45);3.4270(1.37);3.4045(1.59);3.3970(1.59);3.3892(1.61);3.3796(1.89);3.3714(1.32);3.3633(1.17);3.3543(1.47);3.3022(358.52);3.2785(8.28);2.8904(8.16);2.7319(6.66);2.6736(0.54);2.6691(0.70);2.6646(0.53);2.5391(1.41);2.5221(4.07);2.5089(40.82);2.5045(72.58);2.5001(92.06);2.4957(63.27);2.4913(29.94);2.3315(0.45);2.3269(0.59);2.3220(0.42);1.9032(0.55);1.8975(0.41);1.8877(0.67);1.8843(0.72);1.8797(0.63);1.8746(0.62);1.8703(0.69);1.8653(0.66);1.8584(0.67);1.8538(0.67);1.8489(0.35);1.8407(0.56);1.8366(0.44);1.8110(0.58);1.8021(0.58);1.7955(1.13);1.7905(0.94);1.7845(1.14);1.7797(1.51);1.7748(1.45);1.7637(1.42);1.7595(1.38);1.7461(0.85);1.7433(0.85);1.7310(0.36);1.5812(0.35);1.5733(0.55);1.5641(0.69);1.5512(0.76);1.5431(0.93);1.5343(0.73);1.5258(0.55);1.5228(0.50);1.5137(0.41);1.3214(7.13);1.3045(7.07);1.2366(0.37);0.0079(0.86);-0.0002(14.98);-0.0084(0.58)
实施例62,溶剂:DMSO,光谱仪:399.95MHz
11.9132(1.06);11.8802(1.10);7.9521(0.78);7.6053(0.60);7.6022(0.41);7.5919(0.54);7.5870(1.65);7.5819(0.61);7.5715(0.84);7.5684(1.29);7.5653(0.76);7.5182(1.87);7.4982(3.36);7.4844(0.75);7.4799(1.77);7.4096(3.28);7.3912(2.47);7.3876(1.77);7.3025(2.65);5.2800(6.61);4.1828(0.98);4.1667(1.43);4.1503(1.07);3.9301(0.40);3.9025(0.73);3.8763(0.40);3.8717(0.41);3.5155(0.46);3.5077(0.58);3.4844(1.06);3.4617(0.67);3.4454(0.59);3.4378(0.59);3.4319(0.63);3.4115(2.33);3.4002(1.14);3.3896(0.68);3.3722(0.71);3.3646(0.75);3.3472(0.66);3.2962(71.91);2.8903(6.44);2.7317(5.16);2.6735(0.37);2.6689(0.47);2.6643(0.35);2.5389(0.88);2.5219(2.43);2.5086(27.55);2.5043(50.09);2.4998(64.54);2.4955(45.26);2.4911(22.01);2.4557(16.00);2.3312(0.34);2.3266(0.43);1.7598(0.50);1.7426(0.62);1.5206(0.54);1.4878(0.73);1.4512(0.45);1.4424(0.35);1.4121(1.94);1.4025(1.84);1.3137(5.69);1.2969(5.66);1.2350(0.38);1.1896(0.34);0.0079(1.46);-0.0002(26.73);-0.0084(1.14)实施例63,溶剂:DMSO,光谱仪:399.95MHz
11.9749(1.54);11.9348(1.69);7.9520(1.12);7.6087(0.64);7.6057(1.01);7.6026(0.69);7.5924(0.93);7.5874(2.76);7.5823(1.04);7.5720(1.44);7.5689(2.22);7.5658(1.30);7.5186(3.17);7.5021(3.11);7.4987(5.67);7.4848(1.33);7.4804(3.00);7.4104(5.48);7.3969(1.52);7.3922(4.13);7.3886(2.95);7.3079(4.30);5.2829(9.71);4.2331(0.40);4.2163(1.38);4.1996(1.76);4.1831(1.86);4.1663(1.53);4.1495(0.44);4.0151(0.33);4.0078(0.71);3.9979(0.78);3.9900(0.84);3.9805(0.86);3.9715(0.83);3.9606(0.76);3.9550(0.72);3.9447(0.62);3.9375(0.33);3.7871(0.54);3.7712(1.10);3.7667(0.91);3.7513(1.55);3.7350(1.40);3.7196(0.61);3.6445(0.73);3.6394(0.72);3.6267(1.35);3.6235(1.53);3.6059(1.49);3.5904(0.59);3.5853(0.53);3.5086(0.89);3.4988(0.90);3.4830(1.34);3.4732(1.25);3.4616(0.71);3.4513(0.71);3.4358(1.56);3.4255(1.46);3.4049(1.57);3.3945(1.70);3.3896(1.64);3.3776(1.76);3.3690(1.24);3.3639(0.94);3.3519(1.17);3.2969(174.17);3.2737(5.31);2.8903(9.35);2.7318(7.49);2.7308(7.24);2.6780(0.35);2.6735(0.61);2.6689(0.79);2.6644(0.60);2.6597(0.34);2.5389(1.47);2.5220(4.01);2.5087(44.18);2.5043(80.86);2.4998(104.74);2.4954(73.38);2.4910(35.91);2.4636(15.22);2.4578(16.00);2.3311(0.55);2.3266(0.72);2.3220(0.52);1.9074(0.39);1.9014(0.65);1.8831(0.84);1.8688(0.79);1.8634(0.79);1.8568(0.75);1.8519(0.75);1.8468(0.41);1.8391(0.59);1.8346(0.54);1.8070(0.58);1.7993(0.69);1.7920(1.26);1.7820(1.28);1.7748(1.76);1.7663(1.27);1.7589(1.62);1.7446(0.90);1.7417(0.91);1.7382(0.89);1.7288(0.44);1.5903(0.35);1.5783(0.43);1.5728(0.65);1.5679(0.45);1.5614(0.91);1.5563(0.70);1.5496(0.77);1.5424(0.92);1.5404(0.92);1.5323(0.76);1.5229(0.70);1.5111(0.51);1.3212(7.67);1.3192(7.30);1.3043(7.71);1.2355(0.46);0.0080(2.07);-0.0002(39.61);-0.0085(1.67)
实施例68,溶剂:DMSO,光谱仪:250.13MHz
10.3162(1.67);7.8127(1.34);7.8009(1.48);7.7902(3.27);7.7675(0.28);7.5413(0.65);7.5269(0.55);7.5216(0.59);7.5066(0.84);7.4907(0.74);7.4747(7.44);7.4567(2.90);7.3455(0.42);7.3372(0.68);7.3284(0.34);7.3057(2.51);7.2763(2.10);7.2686(0.59);7.2536(0.53);7.2458(0.96);7.2419(0.70);7.2331(0.82);7.2228(0.41);7.2069(0.58);7.0748(0.76);7.0638(0.76);7.0524(0.69);7.0415(0.71);5.7733(9.11);5.3056(3.62);4.4923(4.28);4.1310(3.68);4.0422(10.18);3.3443(7.19);3.3205(0.52);2.5301(1.13);2.5229(2.39);2.5156(3.28);2.5082(2.30);2.5010(1.03);2.0028(0.36);1.2793(12.50)
实施例69,溶剂:DMSO,光谱仪:399.95MHz
12.2576(1.48);7.9519(1.20);7.5377(0.49);7.5327(0.40);7.5300(0.48);7.5230(0.94);7.5176(0.85);7.5146(0.73);7.5099(0.73);7.5070(0.95);7.5016(1.04);7.4872(1.32);7.4828(1.06);7.4725(10.53);7.4654(3.69);7.4590(2.35);7.4568(2.50);7.4378(0.50);7.4348(0.37);7.4196(1.61);7.4165(1.64);7.4068(1.71);7.4037(1.65);7.2643(4.06);7.0127(1.26);7.0100(1.32);7.0042(1.57);7.0016(1.44);6.9391(1.72);6.9305(1.50);6.9263(1.69);6.9177(1.31);5.2822(6.17);4.1012(6.74);3.9927(16.00);3.9731(0.41);3.3906(7.84);3.3331(0.42);3.2973(120.32);3.2735(5.00);2.8900(10.04);2.7316(8.02);2.7305(7.71);2.6733(0.36);2.6686(0.45);2.6640(0.34);2.5387(0.77);2.5217(2.20);2.5084(26.75);2.5041(49.09);2.4996(63.67);2.4952(44.50);2.4908(21.56);2.3309(0.36);2.3263(0.45);2.3218(0.34);0.0079(1.00);-0.0002(18.96);-0.0084(0.79)
实施例70,溶剂:DMSO,光谱仪:399.95MHz
12.2814(1.54);7.9518(1.04);7.5367(0.50);7.5319(0.39);7.5287(0.49);7.5223(0.91);7.5166(0.77);7.5136(0.72);7.5093(0.70);7.5066(0.90);7.5008(0.98);7.4940(0.34);7.4843(1.10);7.4799(1.02);7.4700(10.98);7.4625(3.66);7.4568(2.43);7.4549(2.52);7.4357(0.45);7.4329(0.32);7.2799(1.02);7.2761(0.58);7.2594(5.97);7.2487(1.12);7.2439(2.94);7.2220(2.69);7.2180(3.69);7.2125(0.92);7.2012(1.74);7.1938(1.04);7.1904(0.99);7.1860(0.58);7.1779(0.62);7.1725(1.38);7.1664(0.38);7.1588(0.34);7.1548(0.49);5.2835(6.10);3.9787(16.00);3.4287(7.31);3.2976(124.11);3.2739(5.03);2.8900(8.94);2.8731(0.49);2.8602(1.22);2.8486(8.93);2.8244(0.32);2.7317(7.17);2.7306(6.62);2.6735(0.38);2.6687(0.47);2.6641(0.34);2.5387(0.77);2.5218(2.24);2.5085(26.88);2.5041(49.18);2.4996(63.50);2.4952(44.11);2.4908(21.29);2.3309(0.35);2.3264(0.46);2.3219(0.34);0.0079(0.89);-0.0002(17.29);-0.0085(0.71)实施例71,溶剂:DMSO,光谱仪:399.95MHz
12.2594(1.54);7.9520(1.20);7.5393(0.52);7.5320(0.51);7.5243(0.98);7.5190(0.81);7.5161(0.76);7.5109(0.75);7.5079(0.93);7.5028(1.07);7.4905(1.32);7.4864(1.24);7.4752(9.22);7.4687(3.55);7.4611(2.22);7.4587(2.25);7.4398(0.51);7.4367(0.33);7.2956(1.04);7.2912(1.47);7.2860(0.80);7.2744(3.80);7.2711(3.39);7.2630(6.27);7.2450(3.19);7.2408(1.22);7.2298(0.84);7.2262(1.23);7.1976(0.74);7.1937(1.10);7.1891(0.60);7.1826(0.54);7.1762(1.13);7.1696(0.34);7.1589(0.41);5.2874(6.02);3.9927(16.00);3.8382(6.12);3.7182(0.42);3.7008(1.46);3.6832(1.47);3.6655(0.43);3.2989(161.61);3.2752(5.28);2.8901(9.87);2.7317(8.17);2.7305(7.51);2.6733(0.37);2.6688(0.48);2.6642(0.36);2.5388(0.93);2.5086(28.63);2.5042(50.62);2.4997(64.04);2.4953(43.93);2.4909(20.81);2.3310(0.33);2.3265(0.42);1.3825(5.82);1.3649(5.67);0.0079(0.82);-0.0002(13.98);-0.0085(0.54)
实施例72,溶剂:DMSO,光谱仪:399.95MHz
12.2473(1.59);7.9522(0.81);7.5372(0.53);7.5326(0.42);7.5290(0.52);7.5228(0.92);7.5170(0.79);7.5140(0.75);7.5100(0.74);7.5071(0.94);7.5013(1.01);7.4853(1.18);7.4809(1.14);7.4711(11.17);7.4634(3.67);7.4580(2.45);7.4561(2.50);7.4369(0.42);7.2552(4.00);5.8081(0.62);5.8012(0.37);5.7903(0.37);5.7833(1.03);5.7656(1.07);5.7587(0.40);5.7480(0.40);5.7408(0.76);5.7229(0.34);5.2809(6.31);5.1754(1.24);5.1712(1.25);5.1329(1.10);5.1288(1.10);5.1104(1.36);5.1082(1.22);5.1060(1.13);5.0855(1.23);5.0833(1.11);5.0811(1.05);3.9901(16.00);3.3460(8.97);3.2996(139.69);3.2758(4.77);3.2625(3.42);3.2447(3.15);2.8902(6.62);2.7318(5.44);2.6735(0.33);2.6690(0.42);2.6645(0.32);2.5389(0.76);2.5087(24.25);2.5043(43.26);2.4999(55.00);2.4955(38.10);2.4911(18.29);2.3266(0.37);0.0079(0.72);-0.0002(12.22);-0.0085(0.50)
实施例74,溶剂:DMSO,光谱仪:400.13MHz
12.3046(2.28);7.5445(0.51);7.5408(0.37);7.5356(0.59);7.5306(0.86);7.5270(0.64);7.5242(0.64);7.5215(0.67);7.5155(0.82);7.5091(0.93);7.4959(0.46);7.4901(1.03);7.4856(0.97);7.4765(12.16);7.4684(3.56);7.4628(2.65);7.4429(0.33);7.2752(3.85);5.2940(6.12);4.3143(0.51);4.2965(0.50);4.0420(0.66);4.0242(0.71);4.0063(0.47);3.9918(16.00);3.7482(0.40);3.7308(1.48);3.7132(1.50);3.6957(0.40);3.3351(10.81);2.8357(0.47);2.8263(0.54);2.5460(0.40);2.5291(1.44);2.5158(14.97);2.5113(30.31);2.5068(40.59);2.5023(28.76);2.4979(13.04);1.9940(2.81);1.9392(0.54);1.8282(0.56);1.8031(0.45);1.6525(0.91);1.6220(0.69);1.5283(0.47);1.5046(0.44);1.3944(5.64);1.3769(5.51);1.2991(0.89);1.2812(1.97);1.2712(1.23);1.2635(1.76);1.2503(3.18);1.2460(3.10);1.2229(2.47);1.2030(0.98);1.1967(1.51);1.1789(1.96);1.1611(0.99);0.8793(0.55);0.8626(1.67);0.8450(0.67)
实施例76,溶剂:CDCl3,光谱仪:250.13MHz
10.0645(0.80);8.0237(0.38);7.5508(1.54);7.5453(1.64);7.5385(0.86);7.5192(2.44);7.5121(1.97);7.4813(0.39);7.4759(0.40);7.4676(0.38);7.4522(1.12);7.4407(0.53);7.4311(1.17);7.4246(1.54);7.4170(1.36);7.4085(2.20);7.3795(1.92);7.3527(0.58);7.3441(0.38);7.2626(12.17);6.9560(2.79);5.3010(3.56);5.2893(5.99);4.1892(0.42);3.9659(12.50);3.4624(7.37);2.9589(2.75);2.8866(2.45);2.7481(0.31);2.7331(0.35);2.7063(0.52);2.6644(0.28);2.3591(0.28);2.1439(0.25);1.9887(0.83);1.9472(1.23);1.9012(0.28);1.7809(1.03);1.7584(1.09);1.6276(0.67);1.5867(8.59);1.5602(1.10);1.4324(1.11);1.3793(0.83);1.3481(1.50);1.3047(1.78);1.2737(1.96);1.2360(0.92);0.0699(7.34);-0.0002(11.88);-0.0132(0.57)
实施例77,溶剂:CDCl3,光谱仪:400.13MHz
10.0029(0.98);7.4678(2.14);7.4640(1.14);7.4554(0.69);7.4502(2.98);7.4464(2.24);7.3974(0.47);7.3857(0.35);7.3791(1.41);7.3733(0.44);7.3643(0.79);7.3608(1.22);7.3574(0.62);7.3310(2.25);7.3156(1.47);7.3119(2.64);7.2983(0.41);7.2943(0.96);7.2910(0.56);7.1940(1.60);6.8890(3.47);5.2158(6.73);3.8965(16.00);3.4190(0.66);3.3963(9.32);3.3841(0.33);3.0600(0.77);3.0425(1.05);3.0253(0.68);1.9706(0.55);1.9672(0.46);1.9568(0.85);1.9448(0.73);1.9393(0.76);1.9266(0.78);1.9095(0.35);1.7073(0.50);1.7027(0.53);1.6944(0.90);1.6857(0.95);1.6762(0.61);1.6702(0.79);1.6637(0.51);1.5511(7.27);1.5329(0.80);1.5267(1.07);1.5159(1.10);1.5041(0.77);1.4981(1.04);1.4850(0.82);1.4829(0.81);1.4780(0.76);1.4672(0.74);1.4631(0.79);1.4503(0.78);1.4334(0.55);1.1573(0.60);1.1398(1.18);1.1223(0.60);-0.0002(2.21)
实施例79,溶剂:CDCl3,光谱仪:250.13MHz
9.1969(0.87);8.1715(1.32);8.1385(1.49);7.7550(0.99);7.7242(1.60);7.6916(0.91);7.5266(0.40);7.5172(0.47);7.5024(0.89);7.4884(0.80);7.4770(0.96);7.4677(0.62);7.4411(0.99);7.4080(3.35);7.3901(4.22);7.3823(5.86);7.3569(0.54);7.2626(10.31);7.0360(1.56);7.0059(1.41);5.3011(3.03);5.2837(6.39);3.3978(7.50);2.7529(0.35);2.7245(0.60);2.7108(0.54);2.6848(0.32);2.5371(12.50);2.5017(0.29);2.0166(0.93);1.9743(1.41);1.7899(0.88);1.7748(1.07);1.7528(1.19);1.6685(0.29);1.6182(0.74);1.5787(7.03);1.5518(1.07);1.4321(0.56);1.3979(0.86);1.3582(1.62);1.3144(1.98);1.2710(1.94);1.2388(1.01);0.0703(2.36);-0.0002(10.30)
实施例80,溶剂:CDCl3,光谱仪:400.13MHz
9.0937(0.88);8.1000(1.29);8.0793(1.40);7.6764(1.07);7.6568(1.73);7.6369(1.03);7.4469(0.48);7.4358(0.39);7.4297(1.12);7.4239(0.51);7.4170(0.54);7.4123(0.96);7.4080(0.58);7.3571(1.03);7.3411(1.01);7.3367(2.76);7.3245(0.64);7.3186(3.53);7.3147(3.46);7.3110(3.82);7.2989(0.46);7.2936(1.14);7.2892(0.73);7.1938(1.37);6.9625(1.66);6.9439(1.57);5.2118(7.25);3.3342(8.97);3.0889(0.67);3.0718(0.90);3.0542(0.54);2.4662(16.00);1.9776(0.62);1.9673(0.86);1.9615(0.78);1.9487(0.87);1.9441(0.68);1.9368(0.62);1.9191(0.41);1.6992(0.61);1.6912(0.90);1.6827(1.18);1.6703(0.79);1.6618(0.45);1.5437(1.08);1.5352(1.12);1.5236(1.08);1.5159(1.20);1.5054(1.73);1.4974(1.92);1.4885(1.39);1.4817(0.92);1.4717(0.82);1.4674(0.77);1.4555(0.54);-0.0002(0.93)
实施例81,溶剂:DMSO,光谱仪:399.95MHz
12.2606(1.40);7.9523(0.69);7.6052(0.54);7.5921(0.50);7.5870(1.51);7.5819(0.54);7.5715(0.75);7.5684(1.16);7.5653(0.68);7.5182(1.71);7.4981(3.05);7.4842(0.69);7.4798(1.61);7.4098(2.94);7.3958(0.84);7.3913(2.24);7.3877(1.58);7.2822(3.86);5.2751(5.94);3.3765(7.40);3.2979(105.51);3.2741(4.19);2.8904(5.64);2.7317(4.61);2.6734(0.34);2.6690(0.42);2.6645(0.34);2.6188(2.21);2.6027(1.81);2.5998(2.50);2.5805(2.32);2.5608(0.34);2.5391(0.81);2.5087(23.60);2.5044(42.43);2.5000(54.31);2.4956(37.84);2.4912(18.22);2.4542(14.65);2.3267(0.35);1.6388(0.37);1.6221(0.71);1.6053(0.94);1.5888(0.81);1.5721(0.46);1.4341(1.20);1.4170(1.77);1.3960(1.86);1.3789(0.90);0.8399(16.00);0.8233(15.18);0.0079(0.84);-0.0002(14.63);-0.0085(0.62)
实施例82,溶剂:DMSO,光谱仪:399.95MHz
12.2805(2.02);7.9520(1.17);7.6074(0.58);7.6044(0.40);7.5942(0.50);7.5891(1.59);7.5840(0.59);7.5738(0.80);7.5707(1.25);7.5675(0.75);7.5218(1.78);7.5019(3.24);7.4881(0.72);7.4836(1.69);7.4165(3.20);7.4029(0.87);7.3983(2.42);7.3947(1.74);7.2932(4.45);7.2723(3.63);7.2691(3.14);7.2604(2.52);7.2552(0.77);7.2428(3.19);7.2387(1.24);7.2236(1.27);7.1950(0.70);7.1910(1.10);7.1867(0.60);7.1799(0.51);7.1735(1.15);7.1669(0.34);7.1562(0.41);5.2818(6.18);3.8384(6.78);3.7234(0.42);3.7058(1.45);3.6882(1.45);3.6706(0.42);3.2976(107.69);3.2757(2.69);2.8901(9.72);2.7316(7.76);2.6733(0.37);2.6688(0.48);2.6640(0.38);2.5388(0.90);2.5218(2.47);2.5086(27.51);2.5042(50.31);2.4998(65.03);2.4954(45.71);2.4910(22.29);2.4622(16.00);2.3309(0.33);2.3265(0.44);1.3810(5.86);1.3634(5.75);0.0079(1.52);-0.0002(27.69);-0.0085(1.19)
实施例83,溶剂:DMSO,光谱仪:399.95MHz
12.2689(1.28);7.9518(0.51);7.6091(0.36);7.6059(0.58);7.6029(0.39);7.5928(0.52);7.5877(1.57);7.5826(0.58);7.5723(0.83);7.5692(1.26);7.5661(0.73);7.5194(1.80);7.5028(1.79);7.4995(3.23);7.4856(0.75);7.4812(1.74);7.4112(3.14);7.3979(0.88);7.3931(2.42);7.3895(1.72);7.2833(4.14);5.8073(0.61);5.8003(0.33);5.7895(0.35);5.7824(1.00);5.7647(1.05);5.7578(0.40);5.7470(0.38);5.7399(0.73);5.7221(0.35);5.2756(6.34);5.1741(1.19);5.1700(1.23);5.1316(1.06);5.1277(1.08);5.1082(1.29);5.1061(1.16);5.1039(1.10);5.0833(1.20);5.0812(1.07);5.0790(1.03);3.3472(8.79);3.2976(100.84);3.2738(4.38);3.2619(3.36);3.2440(3.14);2.8902(4.17);2.7317(3.32);2.6691(0.37);2.5390(0.68);2.5087(23.27);2.5044(42.48);2.4999(54.81);2.4955(38.36);2.4911(18.76);2.4585(16.00);2.3266(0.39);0.0078(0.94);-0.0002(17.27);-0.0084(0.71)
实施例84,溶剂:DMSO,光谱仪:399.95MHz
12.2788(1.44);7.9521(1.10);7.6062(0.58);7.6033(0.38);7.5932(0.49);7.5880(1.57);7.5829(0.59);7.5726(0.78);7.5695(1.26);7.5664(0.76);7.5200(1.76);7.5036(1.69);7.5002(3.23);7.4864(0.71);7.4819(1.71);7.4180(2.49);7.4152(4.46);7.4056(2.15);7.4024(2.07);7.3951(2.48);7.3915(1.84);7.2923(4.08);7.0115(1.22);7.0088(1.31);7.0031(1.54);7.0004(1.45);6.9376(1.66);6.9290(1.47);6.9248(1.65);6.9163(1.30);5.2771(6.12);4.1004(6.62);3.3917(7.71);3.2974(115.33);3.2735(4.92);2.8900(9.09);2.7316(7.21);2.7307(7.10);2.6733(0.35);2.6688(0.45);2.6641(0.32);2.5388(0.76);2.5218(2.15);2.5085(25.88);2.5042(47.93);2.4997(62.55);2.4953(44.26);2.4909(21.91);2.4622(16.00);2.4411(0.50);2.3310(0.34);2.3264(0.45);2.3219(0.34);0.0079(1.21);-0.0002(24.71);-0.0084(1.11)
实施例88,溶剂:CDCl3,光谱仪:250.13MHz
9.7752(0.69);7.5216(0.34);7.5142(0.29);7.5073(0.59);7.4951(0.48);7.4824(0.62);7.4725(0.58);7.4521(0.56);7.4417(0.33);7.4187(2.45);7.4159(2.15);7.4057(2.74);7.3954(4.43);7.3719(0.32);7.2624(11.17);7.0973(9.10);6.9433(2.42);5.2652(4.59);3.7767(6.38);3.3444(6.81);2.5010(12.50);2.3805(10.56);2.0478(0.34);1.5957(5.86);1.2601(0.26);0.0700(0.98);0.0129(0.49);-0.0002(10.19);-0.0134(0.26)
实施例89,溶剂:CDCl3,光谱仪:250.13MHz
10.0920(0.66);7.5268(0.33);7.5164(0.42);7.5019(0.76);7.4880(0.74);7.4772(0.87);7.4670(0.62);7.4436(0.89);7.4105(3.05);7.3942(3.61);7.3853(5.60);7.3606(0.49);7.2629(11.17);6.9563(2.77);5.3013(3.45);5.2715(5.95);3.4625(7.43);2.9589(1.29);2.8863(1.06);2.7448(0.31);2.7053(0.47);2.6918(0.43);2.4825(12.50);2.3562(0.32);2.1440(0.28);1.9847(0.84);1.9489(1.26);1.7760(0.94);1.7543(1.02);1.6716(0.41);1.6246(0.74);1.5907(5.25);1.5634(0.92);1.4325(0.75);1.3771(0.90);1.3434(1.49);1.3009(1.67);1.2711(1.87);1.2334(0.84);1.1661(0.38);1.1185(0.40);1.0590(0.36);0.0700(5.52);-0.0002(10.96)
实施例90,溶剂:CDCl3,光谱仪:400.13MHz
10.0079(1.14);7.4462(0.52);7.4421(0.38);7.4354(0.45);7.4292(1.19);7.4234(0.58);7.4169(0.60);7.4120(1.02);7.4076(0.64);7.3599(1.15);7.3394(3.08);7.3204(4.97);7.3154(4.18);7.3035(0.51);7.2983(1.12);7.2937(0.69);7.1945(1.58);6.8905(3.65);5.1998(7.54);3.4365(2.02);3.4190(5.99);3.4013(7.24);3.3975(10.35);3.3839(2.12);3.0586(0.85);3.0411(1.15);3.0240(0.73);2.4140(16.00);1.9693(0.66);1.9555(1.00);1.9437(0.83);1.9381(0.90);1.9253(0.91);1.9081(0.41);1.7097(0.50);1.7004(0.67);1.6923(1.06);1.6839(1.14);1.6738(0.73);1.6686(0.93);1.6620(0.60);1.6544(0.37);1.5560(8.70);1.5426(0.99);1.5303(0.94);1.5240(1.23);1.5132(1.29);1.5013(0.96);1.4963(1.27);1.4827(1.06);1.4666(0.87);1.4624(0.93);1.4494(0.90);1.4320(0.63);1.1573(6.25);1.1397(12.19);1.1222(5.99);-0.0002(1.31)
实施例94,溶剂:CDCl3,光谱仪:250.13MHz
8.3844(0.89);8.1937(0.93);8.1600(1.06);7.7275(0.58);7.6951(1.01);7.6643(0.59);7.5247(1.20);7.4981(1.64);7.4921(1.87);7.4505(0.74);7.4233(0.93);7.4026(1.63);7.3733(1.42);7.3472(0.46);7.2638(8.60);7.2622(9.57);7.0205(1.05);6.9910(0.99);5.2757(4.08);3.9942(7.60);2.8346(4.29);2.7773(1.32);2.5989(0.49);2.5825(0.41);1.9693(0.81);1.9279(1.03);1.7222(0.94);1.6428(0.33);1.5654(0.68);1.3920(12.50);1.3533(0.44);1.2952(4.74);1.2550(2.03);1.2277(2.00);1.1906(1.42);1.1634(0.85);-0.0002(6.95)
实施例95,溶剂:DMSO,光谱仪:250.13MHz
9.9514(0.30);8.0172(0.26);7.4700(1.45);7.4521(0.66);7.3877(0.76);7.3700(1.62);5.3191(0.83);4.0451(2.06);3.9860(1.02);3.3419(12.50);3.3183(0.36);2.5256(0.53);2.5186(1.06);2.5114(1.40);2.5043(1.01);2.4973(0.47);1.4561(0.84);1.4304(0.82)
实施例96,溶剂:DMSO,光谱仪:399.95MHz
10.5584(0.83);10.5441(1.42);8.0666(1.19);8.0459(1.41);7.9531(0.37);7.8300(1.27);7.8106(1.83);7.7905(1.16);7.5467(0.32);7.5346(0.71);7.5248(1.37);7.5141(1.39);7.5036(1.01);7.4934(0.34);7.4825(0.40);7.4795(0.37);7.4601(9.91);7.4492(8.30);7.0967(1.83);7.0785(1.78);5.3264(0.40);5.3112(6.35);4.0954(0.57);4.0437(0.53);4.0309(16.00);3.7427(0.51);3.7261(0.65);3.7107(0.43);3.3992(0.50);3.3913(0.43);3.3838(0.90);3.3765(0.40);3.3684(0.95);3.3370(73.69);3.2594(5.64);3.2363(1.20);3.2178(11.22);3.2040(6.20);3.1956(0.94);3.1830(12.40);3.1364(0.49);2.8907(2.83);2.7318(2.29);2.7308(2.24);2.7039(0.49);2.6967(0.34);2.6860(0.51);2.6800(0.41);2.6676(0.87);2.6617(0.49);2.6497(0.72);2.5397(0.77);2.5258(1.38);2.5207(1.33);2.5120(12.89);2.5076(25.42);2.5030(33.31);2.4985(24.26);2.4941(11.94);2.4770(0.58);2.4618(0.45);2.4413(0.33);1.8056(0.54);1.7877(0.55);1.7707(0.66);1.7542(0.34);1.5348(0.35);1.5279(0.38);1.5231(0.40);1.5157(0.62);1.5078(0.39);1.5032(0.40);1.4963(0.36);1.4784(0.39);1.4635(0.69);1.4486(0.41);1.4436(0.38);1.4286(0.56);1.2326(0.50);1.0924(4.62);1.0771(4.89);1.0688(2.60);1.0621(0.62);1.0535(2.44);-0.0002(4.31)
实施例97,溶剂:DMSO,光谱仪:399.95MHz
10.5575(2.25);8.0875(1.39);8.0668(1.66);7.9529(0.41);7.8383(1.30);7.8187(1.86);7.7987(1.20);7.5387(0.38);7.5358(0.60);7.5253(1.16);7.5177(0.70);7.5143(1.29);7.5040(0.89);7.4808(0.38);7.4778(0.34);7.4723(0.34);7.4580(8.05);7.4471(7.87);7.3146(0.39);7.2959(2.81);7.2899(3.12);7.2817(12.51);7.2733(0.72);7.2689(0.78);7.2536(0.83);7.2474(0.79);7.2441(0.68);7.2415(0.58);7.2355(0.65);7.2321(0.77);7.2279(0.49);7.2214(0.34);7.2184(0.34);7.0985(1.89);7.0802(1.79);5.3266(0.37);5.3121(6.41);4.5086(0.71);4.4780(3.73);4.4662(3.69);4.4357(0.67);4.0874(0.57);4.0151(16.00);3.6529(0.88);3.6306(1.68);3.6088(1.12);3.4195(1.00);3.4057(1.21);3.3964(0.99);3.3827(0.93);3.3392(77.99);3.0561(0.38);3.0387(0.59);3.0215(0.56);3.0044(0.36);2.8902(3.18);2.7308(2.53);2.5254(0.67);2.5204(1.08);2.5119(12.61);2.5075(25.06);2.5030(32.64);2.4984(23.85);2.4940(11.62);1.2345(0.39);1.0588(5.88);1.0415(5.78);-0.0002(5.13)
实施例98,溶剂:DMSO,光谱仪:400.13MHz
10.1708(3.15);7.8213(0.36);7.8002(2.26);7.7928(2.46);7.7862(5.33);7.7719(0.41);7.5385(0.63);7.5267(1.33);7.5149(1.20);7.5049(0.98);7.4742(0.71);7.4639(11.08);7.4530(7.40);7.0502(1.28);7.0435(1.27);7.0362(1.12);7.0295(1.22);5.2849(6.87);4.1460(1.75);4.1298(3.83);4.1136(1.80);4.1047(0.37);4.0598(0.36);4.0440(16.00);4.0244(0.75);3.8641(0.70);3.8563(0.73);3.8500(1.00);3.8435(0.78);3.8359(0.49);3.4325(1.85);3.4169(4.07);3.4014(1.94);3.3386(86.03);3.3163(0.49);2.5111(22.16);2.5067(29.57);2.5024(21.52);1.9932(2.66);1.8390(0.45);1.8232(1.73);1.8073(2.60);1.7914(1.69);1.7755(0.43);1.6695(0.54);1.6572(0.94);1.6474(0.74);1.6418(0.87);1.6311(0.86);1.6206(0.98);1.6148(1.05);1.6060(0.83);1.5991(0.92);1.5896(1.17);1.5797(1.97);1.5749(2.28);1.5700(2.48);1.5473(1.17);1.5431(1.04);1.5323(0.78);1.4850(0.46);1.4696(0.92);1.4568(1.10);1.4458(0.96);1.2501(1.28);1.1965(0.74);1.1787(1.41);1.1609(0.69);0.8785(0.57);0.8619(1.68);0.8443(0.68)
实施例99,溶剂:CDCl3,光谱仪:400.13MHz
8.7162(0.80);8.0706(0.96);8.0500(1.03);7.6401(1.10);7.6205(1.68);7.6006(1.02);7.4492(2.20);7.4366(0.74);7.4314(3.04);7.4276(2.32);7.3920(0.47);7.3800(0.37);7.3736(1.47);7.3681(0.47);7.3585(0.98);7.3549(2.03);7.3516(1.89);7.3497(1.89);7.3320(2.66);7.3214(2.37);7.3058(1.58);7.3022(2.71);7.2843(1.79);7.2807(1.70);7.2758(0.58);7.2630(2.76);7.2590(1.32);7.2445(1.66);7.2291(0.72);7.2256(1.22);7.2221(0.73);7.2144(0.42);7.2079(1.24);7.2003(0.36);7.1903(9.71);6.9451(1.62);6.9264(1.58);5.2275(2.02);5.2144(6.75);4.5449(7.06);4.0009(0.54);3.8523(16.00);3.7790(1.99);3.7649(3.31);3.7505(2.10);2.6396(1.94);2.6253(3.15);2.6111(1.88);1.5249(7.82);1.1846(1.42);-0.0002(0.44)
实施例100,溶剂:CDCl3,光谱仪:400.13MHz
8.1181(0.90);8.0973(0.96);7.9291(1.11);7.7151(1.18);7.6955(1.84);7.6755(1.10);7.5153(2.34);7.4974(3.32);7.4937(2.63);7.4677(0.61);7.4557(0.51);7.4493(1.62);7.4438(0.59);7.4343(0.95);7.4310(1.32);7.3955(2.46);7.3763(2.94);7.3585(1.15);7.3154(1.63);7.3020(1.84);7.2939(2.05);7.2805(1.93);7.2609(13.07);7.0198(2.06);7.0151(2.28);7.0099(0.93);7.0008(2.28);6.9934(3.69);6.9767(0.74);6.9717(1.74);6.9642(0.32);5.2989(1.35);5.2717(7.44);4.1003(0.43);3.9772(16.00);3.7419(6.98);2.8208(1.58);2.8028(3.95);2.7856(2.42);2.6229(2.05);2.6054(3.37);2.5876(1.47);1.5884(10.92);1.2554(2.67);0.8804(0.53);0.8628(0.39);0.8531(0.41);0.8359(0.34)
实施例101,溶剂:CDCl3,光谱仪:400.13MHz
8.1209(0.83);8.1001(0.87);7.9217(0.92);7.7105(1.08);7.6908(1.63);7.6709(0.98);7.5190(1.61);7.5163(2.10);7.5125(1.14);7.5039(0.74);7.4986(3.04);7.4948(2.46);7.4660(0.45);7.4540(0.36);7.4477(1.40);7.4421(0.44);7.4328(0.79);7.4294(1.19);7.4260(0.61);7.3945(2.20);7.3911(1.01);7.3790(1.55);7.3754(2.66);7.3616(0.47);7.3577(1.02);7.3546(0.68);7.3501(0.39);7.3438(0.64);7.3284(6.87);7.3235(3.30);7.3118(3.00);7.3065(0.70);7.2973(0.49);7.2920(0.75);7.2603(11.06);7.2519(0.70);7.2436(0.79);7.2282(0.33);7.0176(1.56);6.9990(1.47);5.2977(1.76);5.2704(6.82);4.0943(0.52);3.9691(16.00);3.7694(8.12);2.8285(1.55);2.8105(3.84);2.7931(2.16);2.5933(1.84);2.5758(3.16);2.5579(1.32);1.5923(5.94);1.2558(0.99)
实施例102,溶剂:CDCl3,光谱仪:250.13MHz
9.8902(0.36);7.5434(1.10);7.5168(1.39);7.5103(1.50);7.4751(0.46);7.4651(0.44);7.4481(0.82);7.4281(0.55);7.4217(0.85);7.4143(0.71);7.4052(1.51);7.3756(1.22);7.3489(0.38);7.3417(0.34);7.2624(9.32);6.9191(1.89);6.8976(0.27);5.2840(0.50);5.2624(3.66);4.1795(0.94);3.9531(7.36);2.8331(4.23);2.7781(1.03);2.6005(0.31);2.5723(0.40);2.5605(0.38);2.0468(0.47);1.9506(0.76);1.9095(0.87);1.7186(0.84);1.6371(0.33);1.5881(0.88);1.3866(12.50);1.2958(3.64);1.2723(1.42);1.2598(1.69);1.2313(2.05);1.2051(1.38);1.1880(1.03);1.1623(0.71);-0.0002(6.57)
实施例103,溶剂:DMSO,光谱仪:399.95MHz
12.1803(1.89);7.9533(0.65);7.5393(0.62);7.5304(0.73);7.5256(1.03);7.5159(0.86);7.5112(0.99);7.5042(1.04);7.4917(0.54);7.4854(1.13);7.4723(13.31);7.4638(4.20);7.4591(3.64);7.4387(0.38);7.2309(3.89);5.2800(6.81);4.0045(0.73);3.9922(15.35);3.7618(0.60);3.7480(0.73);3.7306(0.51);3.3894(0.63);3.3738(1.08);3.3578(1.20);3.3353(56.48);3.2406(5.79);3.2315(1.02);3.1992(16.00);3.1845(1.52);3.1784(11.64);3.1361(0.42);2.8909(4.82);2.7316(4.31);2.6891(0.62);2.6713(0.87);2.6525(1.21);2.6345(1.26);2.5988(0.91);2.5858(0.92);2.5620(0.51);2.5488(0.57);2.5364(0.71);2.5114(14.90);2.5073(27.93);2.5030(35.87);2.4988(26.89);1.8012(0.57);1.7834(0.59);1.7661(0.69);1.7497(0.37);1.5296(0.49);1.5203(0.47);1.5146(0.78);1.5012(0.45);1.4968(0.45);1.4838(0.41);1.4690(0.73);1.4541(0.45);1.4491(0.40);1.4340(0.59);1.2352(0.44);1.0920(4.79);1.0768(4.81);1.0676(2.89);1.0523(2.64);-0.0002(5.26)
实施例104,溶剂:DMSO,光谱仪:399.95MHz
12.2005(2.37);7.9527(0.86);7.5396(0.52);7.5361(0.39);7.5305(0.61);7.5258(0.90);7.5223(0.69);7.5194(0.67);7.5166(0.71);7.5131(0.71);7.5107(0.85);7.5043(0.95);7.4913(0.42);7.4853(0.95);7.4806(0.90);7.4717(12.43);7.4635(3.84);7.4579(2.99);7.4382(0.36);7.3065(0.50);7.3034(0.76);7.2998(0.40);7.2886(1.36);7.2858(2.18);7.2824(1.95);7.2751(0.82);7.2682(4.09);7.2571(4.88);7.2460(5.40);7.2323(0.69);7.2246(1.32);7.2080(0.37);5.2795(6.48);4.4934(0.58);4.4628(3.64);4.4527(3.58);4.4221(0.56);3.9782(16.00);3.6469(0.87);3.6247(1.74);3.6024(1.27);3.4676(1.05);3.4539(1.26);3.4444(1.01);3.4308(0.90);3.3364(68.81);2.9886(0.44);2.9711(0.64);2.9571(0.59);2.9538(0.61);2.9366(0.41);2.8899(6.83);2.7307(5.57);2.5245(0.73);2.5113(13.18);2.5070(26.26);2.5025(34.58);2.4980(25.65);2.4936(12.83);1.2347(0.43);1.0789(6.09);1.0615(5.97);-0.0002(4.92)
实施例105,溶剂:DMSO,光谱仪:399.95MHz
12.0017(2.29);7.9528(0.79);7.5369(0.57);7.5281(0.62);7.5238(0.94);7.5164(0.66);7.5137(0.84);7.5094(0.79);7.5023(0.97);7.4903(0.51);7.4811(0.96);7.4764(1.07);7.4686(12.36);7.4594(4.12);7.4557(3.30);7.3642(6.42);7.3535(12.68);7.3426(0.68);7.3070(0.93);7.2959(1.22);7.2853(1.26);7.2781(0.59);7.2704(3.79);5.2745(6.06);4.6077(0.51);4.5918(1.76);4.5757(1.76);4.5596(0.49);4.1561(0.38);4.0837(1.25);4.0452(3.50);4.0124(3.51);3.9841(16.00);3.9740(1.55);3.3446(111.66);3.3170(0.39);2.8904(6.27);2.7316(4.87);2.7307(5.05);2.5253(0.93);2.5121(13.31);2.5077(26.18);2.5031(34.17);2.4985(25.12);2.4941(12.40);1.4187(6.66);1.4026(6.61);1.2344(0.35);-0.0002(5.21)实施例106,溶剂:CDCl3,光谱仪:400.13MHz
9.8310(0.85);7.5378(2.44);7.5198(3.26);7.5160(2.39);7.4586(0.60);7.4469(0.43);7.4404(1.64);7.4347(0.47);7.4254(0.94);7.4222(1.32);7.3929(2.52);7.3736(3.51);7.3618(6.11);7.3547(5.16);7.3496(4.71);7.3344(0.76);7.3285(0.95);7.3233(0.93);7.3161(0.96);7.3056(0.64);7.3016(0.82);7.2929(0.38);7.2609(9.21);6.9099(3.94);5.2981(1.27);5.2640(7.66);4.6316(8.97);4.1467(0.54);3.8814(16.00);3.8199(2.03);3.8061(3.40);3.7919(2.14);2.7591(2.14);2.7451(3.43);2.7311(2.05);2.0445(0.61);1.6166(3.77);1.2555(1.33);1.2411(0.34)
实施例107,溶剂:CDCl3,光谱仪:400.13MHz
9.1984(1.06);7.5185(2.39);7.5059(0.81);7.5007(3.17);7.4970(2.48);7.4581(0.48);7.4549(0.35);7.4461(0.42);7.4397(1.56);7.4342(0.50);7.4248(0.86);7.4215(1.27);7.3881(2.41);7.3725(1.62);7.3689(2.84);7.3552(0.46);7.3513(1.02);7.2963(1.54);7.2913(0.83);7.2829(1.74);7.2747(2.03);7.2611(12.88);7.0123(1.92);7.0073(0.71);6.9958(0.83);6.9907(3.51);6.9742(0.60);6.9691(1.63);6.9197(4.04);5.2989(4.23);5.2440(7.06);3.9387(16.00);3.7281(6.98);2.8114(1.31);2.7938(3.62);2.7771(2.20);2.6650(2.17);2.6483(3.28);2.6300(1.23);1.6484(7.27);1.2551(2.93);0.8802(0.54);0.8621(0.36);0.8528(0.39)
实施例108,溶剂:CDCl3,光谱仪:400.13MHz
9.1237(0.98);7.5249(1.70);7.5223(2.20);7.5186(1.25);7.5099(0.85);7.5046(3.14);7.5008(2.38);7.4601(0.34);7.4568(0.54);7.4535(0.40);7.4449(0.45);7.4385(1.52);7.4327(0.56);7.4236(0.91);7.4202(1.33);7.4167(0.73);7.3880(2.35);7.3846(1.12);7.3726(1.68);7.3689(2.81);7.3552(0.66);7.3512(1.21);7.3480(0.82);7.3194(6.86);7.3084(8.21);7.2896(0.55);7.2865(0.55);7.2783(0.56);7.2684(1.08);7.2602(11.58);7.2477(1.19);7.2375(0.66);7.2255(0.36);6.9143(3.75);5.2979(3.05);5.2467(6.52);3.9347(16.00);3.7588(8.77);2.8203(1.45);2.8024(3.71);2.7855(2.20);2.6199(2.09);2.6028(3.50);2.5851(1.45);1.6334(5.17);1.2555(2.21);1.2256(0.33);0.8803(0.45);0.8531(0.33)
实施例109,溶剂:CDCl3,光谱仪:250.13MHz
8.3504(0.79);8.2010(0.94);8.1677(1.05);7.7334(0.60);7.7013(1.01);7.6701(0.59);7.4970(0.54);7.4844(0.41);7.4739(0.56);7.4659(0.43);7.4346(0.57);7.4019(1.76);7.3757(3.64);7.3491(0.49);7.3408(0.30);7.2628(7.91);7.0067(1.04);6.9767(0.96);5.2543(4.11);2.8303(4.29);2.7800(0.66);2.6208(0.28);2.5940(0.37);2.5819(0.36);2.5495(0.27);2.5159(8.16);2.0467(0.30);1.9668(0.63);1.9272(0.85);1.7220(0.75);1.6422(0.30);1.5709(0.60);1.3893(12.50);1.2977(2.56);1.2546(1.62);1.2270(1.56);1.2084(1.20);1.1891(1.40);1.1753(0.71);1.1635(0.90);-0.0002(5.53)
实施例110,溶剂:CDCl3,光谱仪:400.13MHz
8.7810(1.04);8.1509(1.36);8.1302(1.46);7.7174(1.18);7.6977(1.92);7.6778(1.12);7.5152(0.32);7.5108(0.53);7.5068(0.36);7.4937(1.23);7.4814(0.57);7.4765(0.99);7.4722(0.63);7.4198(2.99);7.3999(5.53);7.3806(5.34);7.3756(4.28);7.3584(2.10);7.3545(1.92);7.3376(3.05);7.3190(1.90);7.3038(1.39);7.2929(0.46);7.2862(1.30);7.2611(8.47);6.9994(1.91);6.9808(1.79);5.2982(0.38);5.2675(7.89);4.6174(7.82);3.8431(2.09);3.8289(3.69);3.8146(2.22);2.7075(2.09);2.6931(3.56);2.6790(2.04);2.4738(16.00);1.6003(7.62);1.2552(1.21)
实施例111,溶剂:CDCl3,光谱仪:400.13MHz
8.1327(0.70);8.1123(0.77);7.8859(0.94);7.7260(1.02);7.7063(1.57);7.6864(0.97);7.5212(0.33);7.5173(0.53);7.5135(0.36);7.5056(0.43);7.4998(1.14);7.4941(0.52);7.4865(0.59);7.4821(1.01);7.4780(0.62);7.4250(1.12);7.4205(0.66);7.4088(1.12);7.4045(2.61);7.3919(0.71);7.3863(2.61);7.3782(2.93);7.3750(3.44);7.3625(0.62);7.3573(1.35);7.3530(0.94);7.3155(1.41);7.3102(0.73);7.3022(1.56);7.2938(1.70);7.2858(0.81);7.2804(1.60);7.2727(0.43);7.2613(11.57);7.0233(0.34);7.0154(2.78);6.9943(4.52);6.9892(0.85);6.9777(0.63);6.9725(1.51);5.2989(3.26);5.2504(6.56);3.7412(5.95);2.8199(1.34);2.8016(3.43);2.7846(2.08);2.6199(1.73);2.6025(2.85);2.5847(1.22);2.4959(16.00);1.5910(10.18);1.2553(1.95);0.8803(0.36)
实施例112,溶剂:CDCl3,光谱仪:400.13MHz
8.1347(0.79);8.1141(0.85);7.8800(0.95);7.7203(1.07);7.7007(1.64);7.6807(1.01);7.5195(0.33);7.5155(0.51);7.5118(0.33);7.5040(0.38);7.4981(1.12);7.4925(0.50);7.4850(0.52);7.4805(0.96);7.4764(0.58);7.4238(1.05);7.4196(0.60);7.4078(1.02);7.4035(2.63);7.3910(0.58);7.3852(2.73);7.3784(3.00);7.3751(3.53);7.3628(0.47);7.3575(1.26);7.3531(0.90);7.3446(0.61);7.3297(7.16);7.3243(3.26);7.3135(2.97);7.3080(0.59);7.2989(0.43);7.2936(0.68);7.2673(0.83);7.2604(10.67);7.2457(0.74);7.0091(1.58);6.9905(1.50);5.2979(0.80);5.2500(6.98);3.7684(8.24);2.8268(1.56);2.8088(3.85);2.7914(2.19);2.5878(1.83);2.5703(3.14);2.5524(1.36);2.4925(16.00);2.4834(0.36);1.5885(5.77);1.2556(1.32)
实施例113,溶剂:CDCl3,光谱仪:250.13MHz
9.6028(0.60);7.5142(0.27);7.4974(0.53);7.4861(0.52);7.4740(0.61);7.4659(0.53);7.4390(0.59);7.4063(2.04);7.3904(2.35);7.3815(4.10);7.3565(0.44);7.2649(7.09);7.2628(7.25);7.2579(4.23);6.9208(2.04);5.2517(4.21);2.8223(4.27);2.7864(0.43);2.5915(0.31);2.5715(0.42);2.5577(0.51);2.4807(7.17);2.4790(7.54);2.0472(0.55);1.9501(0.72);1.9066(0.95);1.7193(0.88);1.6011(1.40);1.3833(12.50);1.3007(1.76);1.2600(1.51);1.2293(1.85);1.2035(1.43);0.0019(4.92);-0.0002(5.09);-0.0051(3.03)
实施例114,溶剂:CDCl3,光谱仪:400.13MHz
9.8328(0.82);7.5072(0.44);7.5023(0.33);7.4981(0.39);7.4945(0.52);7.4912(0.94);7.4844(0.52);7.4806(0.52);7.4746(0.91);7.4694(0.57);7.4227(0.84);7.4178(0.54);7.4071(0.85);7.4021(2.90);7.3874(4.16);7.3843(5.72);7.3725(0.93);7.3666(1.37);7.3592(5.06);7.3520(3.71);7.3469(3.62);7.3459(3.63);7.3391(0.48);7.3321(0.65);7.3280(0.69);7.3256(0.79);7.3214(0.86);7.3145(0.81);7.3100(0.59);7.3039(0.53);7.2996(0.71);7.2614(10.80);6.9098(3.45);5.2988(4.04);5.2517(6.63);4.6324(8.18);4.1307(0.92);4.1128(0.93);3.8100(1.84);3.7962(2.90);3.7820(1.93);2.7556(1.95);2.7413(2.90);2.7275(1.84);2.4410(16.00);2.0449(4.12);1.6106(2.80);1.2768(1.21);1.2589(2.80);1.2411(1.22);-0.0002(0.34)
实施例115,溶剂:CDCl3,光谱仪:400.13MHz
9.2214(1.34);7.4391(0.50);7.4351(0.34);7.4279(0.45);7.4220(1.23);7.4096(0.58);7.4048(1.02);7.4005(0.62);7.3500(1.12);7.3296(3.12);7.3106(4.98);7.3054(4.23);7.2882(1.18);7.2837(0.73);7.2285(1.59);7.2151(1.83);7.2072(2.02);7.1913(10.96);6.9408(1.99);6.9358(0.67);6.9192(3.64);6.9024(0.65);6.8976(1.69);6.8607(4.20);5.2288(0.94);5.1631(7.65);3.6611(7.48);2.7462(1.24);2.7284(3.54);2.7119(2.37);2.6155(2.31);2.5987(3.44);2.5812(1.24);2.4020(16.00);1.5717(9.05);1.1855(2.92);0.8104(0.53);0.7930(0.37);0.7831(0.39);0.7755(0.33)
实施例116,溶剂:CDCl3,光谱仪:400.13MHz
9.1901(1.10);7.5068(0.49);7.5026(0.34);7.4964(0.40);7.4900(1.06);7.4839(0.52);7.4781(0.54);7.4729(0.95);7.4683(0.60);7.4191(0.96);7.4147(0.60);7.4034(0.95);7.3987(2.75);7.3804(5.82);7.3759(4.10);7.3644(0.46);7.3589(1.02);7.3541(0.63);7.3192(6.65);7.3081(6.37);7.2890(0.33);7.2861(0.38);7.2667(0.95);7.2604(10.43);7.2457(0.93);7.2406(0.33);7.2351(0.44);6.9222(3.83);5.2338(6.74);3.7596(8.92);2.8222(1.41);2.8045(3.73);2.7875(2.15);2.6320(2.15);2.6149(3.40);2.5971(1.35);2.4688(16.00);1.6309(4.88);1.2554(2.15);1.2409(0.36);0.8802(0.40)
尖锐信号的强度与图像例的NMR光谱中的信号高度(以厘米计)相关,并显示了信号强度的真实关系。从宽信号可以显示几个峰或信号的中间值以及它们相对于光谱中最密集信号的相对强度。
为了校准1H光谱的化学位移,特别是在DMSO中测得光谱时,我们使用四甲基硅烷和/或所用溶剂的化学位移。因此,在NMR峰列表中,可存在四甲基硅烷峰,但这不是必须的。
1H-NMR峰列表与典型的1H-NMR图像类似,因此其通常包含在典型NMR-解释中所列出的所有峰。
另外,它们还可显示如溶剂、目标化合物的立体异构体(也是本发明的目的)和/或杂质峰的典型1H-NMR图像信号。
为了显示溶剂和/或水的δ范围内的化合物信号,我们的1H-NMR峰列表中显示了常见溶剂峰(例如DMSO在DMSO-D6中的峰和水的峰),并且平均来看通常具有高强度。
平均来看,目标化合物的立体异构体的峰和/或杂质的峰与目标化合物(例如纯度>90%)的峰相比通常具有较低的强度。
此类立体异构体和/或杂质对于特定制备过程来说可能是典型的。因此,它们的峰可以通过“副产物指纹(side-products-fingerprints)”帮助识别我们的制备过程的重现性。
专业人员通过使用已知的方法(MestreC,ACD-模拟,还可使用经验评估预期值)计算目标化合物的峰,并且根据需要任选地使用其它强度过滤器,从而可以分离目标化合物的峰。该分离与在典型1H-NMR解释挑选的相关峰类似。
可在研究公开数据库第564025号的公开发表物“专利申请中的NMR峰列表数据的引用”中找到含峰列表的NMR数据描述的其它细节。
以下实施例以非限制性的方式对依据本发明的通式(I)化合物的制备和药效予以说明。
用途实施例
实施例A
疫霉测试(番茄)/预防性的
溶剂:49重量份的N,N-二甲基甲酰胺
乳化剂:1重量份的烷基芳基聚乙二醇醚
为了获得活性化合物的合适制剂,将1重量份的活性化合物与所述量的溶剂和乳化剂进行混合,并用水将浓缩物稀释至所需的浓度。
为了测试预防活性,使用活性化合物的制剂在所述施用比率下对幼龄植物进行喷涂。在该处理1天后,用致病疫霉的水性孢子悬浮液对上述植物进行接种。将所述植物在约22℃、相对大气湿度为100%的温育箱中保持1天。然后将所述植物放置在约20℃、相对大气湿度为96%的温育箱中。
在接种7天后对测试进行评估。0%表示相当于未处理的对照样的功效,100%的功效表示没有观察到疾病。
在该测试中,本发明下列化合物显示出在500ppm的活性成分的浓度条件下功效为70%甚至更高。
表
疫霉测试(番茄)/预防性的
实施例编号 | 功效% |
3 | 100 |
4 | 97 |
5 | 97 |
6 | 95 |
7 | 100 |
8 | 100 |
9 | 100 |
10 | 95 |
11 | 95 |
12 | 100 |
14 | 100 |
15 | 100 |
16 | 97 |
17 | 100 |
18 | 100 |
19 | 100 |
20 | 100 |
21 | 95 |
22 | 100 |
23 | 95 |
24 | 100 |
25 | 97 |
26 | 97 |
27 | 95 |
28 | 100 |
29 | 100 |
30 | 95 |
31 | 97 |
32 | 100 |
34 | 100 |
35 | 100 |
36 | 97 |
37 | 100 |
38 | 100 |
39 | 100 |
40 | 95 |
41 | 98 |
42 | 100 |
44 | 100 |
45 | 100 |
46 | 100 |
48 | 95 |
50 | 100 |
51 | 95 |
52 | 93 |
54 | 93 |
55 | 100 |
56 | 100 |
57 | 95 |
58 | 100 |
59 | 100 |
60 | 100 |
62 | 98 |
63 | 100 |
66 | 95 |
68 | 100 |
69 | 95 |
70 | 98 |
71 | 100 |
72 | 100 |
73 | 95 |
74 | 100 |
75 | 93 |
76 | 100 |
77 | 95 |
78 | 100 |
79 | 100 |
80 | 100 |
81 | 95 |
82 | 100 |
83 | 88 |
84 | 98 |
85 | 98 |
86 | 93 |
87 | 100 |
88 | 100 |
89 | 100 |
90 | 95 |
92 | 98 |
93 | 98 |
94 | 100 |
95 | 100 |
96 | 100 |
97 | 100 |
98 | 100 |
99 | 90 |
100 | 95 |
101 | 90 |
102 | 100 |
103 | 95 |
104 | 100 |
105 | 95 |
106 | 93 |
107 | 95 |
108 | 90 |
109 | 95 |
110 | 85 |
111 | 90 |
112 | 88 |
113 | 98 |
114 | 93 |
115 | 80 |
116 | 80 |
实施例B
单轴霉测试(葡萄树)/预防性的
溶剂:24.5重量份的丙酮
24.5重量份的二甲基乙酰胺
乳化剂:1重量份的烷基芳基聚乙二醇醚
为了获得活性化合物的合适制剂,将1重量份的活性化合物与所述量的溶剂和乳化剂进行混合,并用水将浓缩物稀释至所需的浓度。
为了测试预防活性,使用活性化合物的制剂在所述施用比率下对幼龄植物进行喷涂。待所述喷涂涂料已干燥后,用葡萄生单轴霉的水性孢子悬浮液对上述植物进行接种,然后将该植物在大约20℃,100%的相对大气湿度的条件下,在培育橱中保持1天。随后将该植物放置于大约21℃,大约90%的相对大气湿度的条件下的温室中4天。然后对该植物喷薄雾,并放置于培育橱中1天。
在接种6天后对测试进行评估。0%表示相当于未处理的对照样的功效,100%的功效表示没有观察到疾病。
在该测试中,本发明下列化合物显示出在10ppm的活性成分的浓度条件下功效为70%甚至更高。
实施例编号 | 功效% |
2 | 95 |
4 | 80 |
9 | 89 |
12 | 84 |
13 | 79 |
14 | 97 |
15 | 100 |
16 | 90 |
17 | 94 |
19 | 91 |
22 | 88 |
24 | 81 |
25 | 80 |
33 | 94 |
34 | 94 |
35 | 91 |
42 | 93 |
45 | 91 |
48 | 96 |
49 | 92 |
50 | 100 |
52 | 91 |
60 | 85 |
65 | 84 |
67 | 78 |
71 | 82 |
74 | 82 |
88 | 84 |
91 | 77 |
96 | 78 |
98 | 81 |
实施例C
腐霉测试(棉花)/种子处理
该测试在温室条件下进行。
将用溶解在N-甲基-2-吡咯烷酮并用水稀释成所需剂量的活性化合物或化合物组合处理过的棉花播种在6*6厘米的盆中,该盆含有4厘米的1:1蒸发田间土壤和砂子的混合物。
用终极腐霉的菌丝体片段温育珍珠岩。在经处理的棉花种子之间散播1毫升经感染的珍珠岩。再用轻质膨胀粘土骨料覆盖种子。在20℃和80%相对湿度条件下在温室中使盆温育7天。
由新生幼苗的计数进行评估。0%表示相当于对照样的功效,100%的药效表示所有幼苗都已形成。
在该测试中,本发明下列化合物显示出在活性成分剂量为50g/dt种子的条件下功效为70%甚至更高。
Claims (15)
1.一种通式(I)的化合物,及其盐、N-氧化物、金属配合物、类金属配合物、或(E)和(Z)异构体,以及它们的混合物:
式中:
·X表示氢原子、卤素原子、取代或未取代的C1-C8-烷基、取代或未取代的C1-C8-烷氧基、氰基、甲磺酰基、硝基、三氟甲基或芳基;
·A表示式(A1)或(A2)的四唑基:
式中,Y表示取代或未取代的C1-C8-烷基;以及
·Het表示式(Het1)的吡啶基或式(Het2)的噻唑基;
式中:
o R表示氢原子或卤素原子;以及
o Q表示取代或未取代的(C3-C8-环烷基)-(C1-C3-烷氧基)-C1-C6-烷基、取代或未取代的(C3-C8-环烷基)-(C1-C3-烷氧基)-C1-C6-烷氧基、取代或未取代的(C3-C8-环烷氧基)-C1-C3-烷氧基、取代或未取代的杂环基-(C1-C3-烷氧基)-C1-C6-烷基、取代或未取代的C3-C6-环烷硫基-C1-C6-烷基、取代或未取代的芳基-(C1-C3-烷硫基)-C1-C6-烷基、取代或未取代的杂环基-环丙基;
o除非另有说明,否则,取代的基团或取代基被一个或多个下列基团或原子取代:卤素原子、硝基、羟基、氰基、氨基、次磺酰基、五氟-λ6-次磺酰基、甲酰基、取代或未取代的甲醛O-(C1-C8-烷基)肟、甲酰氧基、甲酰氨基、氨基甲酰基、N-羟基氨基甲酰基、甲酰氨基、(羟基亚氨基)-C1-C6-烷基、C1-C8-烷基、三(C1-C8-烷基)甲硅烷基-C1-C8-烷基、C1-C8-环烷基、三(C1-C8-烷基)甲硅烷基-C1-C8-环烷基、含有1-5个卤素原子的C1-C8-卤代烷基、含有1-5个卤素原子的C1-C8-卤代环烷基、C2-C8-烯基、C2-C8-炔基、C2-C8-烯氧基、C2-C8-炔氧基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、C1-C8-烷氧基、含有1-5个卤素原子的C1-C8-卤代烷氧基、C1-C8-烷基次磺酰基、含有1-5个卤素原子的C1-C8-卤代烷基次磺酰基、C2-C8-烯氧基、含有1-5个卤素原子的C2-C8-卤代烯氧基、C3-C8-炔氧基、含有1-5个卤素原子的C3-C8-卤代炔氧基、C1-C8-烷基羰基、含有1-5个卤素原子的C1-C8-卤代烷基羰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、N-C1-C8-烷氧基氨基甲酰基、C1-C8-烷氧基氨基甲酰基、N-C1-C8-烷基-C1-C8-烷氧基氨基甲酰基、C1-C8-烷氧基羰基、含有1-5个卤素原子的C1-C8-卤代烷氧基羰基、C1-C8-烷基羰氧基、含有1-5个卤素原子的C1-C8-卤代烷基羰氧基、C1-C8-烷基羰基氨基、含有1-5个卤素原子的C1-C8-卤代烷基羰基氨基、取代或未取代的C1-C8-烷氧基羰基氨基、取代或未取代的含有1-5个卤素原子的C1-C8-卤代烷氧基羰基氨基、C1-C8-烷基氨基羰氧基、二-C1-C8-烷基氨基羰氧基、C1-C8-烷氧基羰氧基、C1-C8-烷基次磺酰基、含有1-5个卤素原子的C1-C8-卤代烷基次磺酰基、C1-C8-烷基亚磺酰基、含有1-5个卤素原子的C1-C8-卤代烷基亚磺酰基、C1-C8-烷基磺酰基、含有1-5个卤素原子的C1-C8-卤代烷基磺酰基、C1-C8-烷基氨基氨磺酰基、二-C1-C8-烷基氨基氨磺酰基、(C1-C6-烷氧基亚氨基)-C1-C6-烷基、(C1-C6-烯氧基亚氨基)-C1-C6-烷基、(C1-C6-炔氧基亚氨基)-C1-C6-烷基、(苄氧基亚氨基)-C1-C6-烷基、C1-C8-烷氧基烷基、含有1-5个卤素原子的C1-C8-卤代烷氧基烷基、苄氧基、苄基次磺酰基、苄基氨基、苯氧基、苯基次磺酰基、或苯基氨基。
2.如权利要求1所述的化合物,其特征在于,X表示氢原子、氯原子、氟原子、甲基、叔丁基、甲氧基、乙氧基、氰基、甲磺酰基、硝基、三氟甲基或芳基。
3.如权利要求1或2所述的化合物,其特征在于,X表示氢原子。
4.如权利要求1-3中任一项所述的化合物,其特征在于,Y表示甲基或乙基。
5.如权利要求1-4中任一项所述的化合物,其特征在于,R表示氢原子或氯原子。
6.如权利要求1-5中任一项所述的化合物,其特征在于,Q表示取代或未取代的(C3-C6-环烷基)-(C1-C2-烷氧基)-C1-C2-烷基、取代或未取代的(C3-C6-环烷基)-(C1-C2-烷氧基)-C1-C2-烷氧基、取代或未取代的(C3-C6-环烷氧基)-C2-C3-烷氧基、取代或未取代的杂环基-(C1-C2-烷氧基)-C1-C2-烷基。
7.如权利要求1-6中任一项所述的化合物,其特征在于,Q表示取代或未取代的(C3-C6-环烷基)-甲氧基甲基、取代或未取代的(C3-C6-环烷基)-甲氧基-乙氧基、取代或未取代的(C3-C6-环烷氧基)-C2-C3-烷氧基、取代或未取代的杂环基-甲氧基-甲基。
8.一种控制植物病原有害真菌的组合物,其特征在于,除了包含至少一种增容剂和/或一种表面活性剂之外,该组合物包含一定量的至少一种如权利要求1-7中任一项所述的式(I)的化合物。
9.如权利要求8所述的杀真菌剂组合物,该组合物包含至少一种选自下组的其它活性成分:杀虫剂、引诱剂、止繁殖剂、杀细菌剂、杀螨剂、杀线虫剂、杀真菌剂、生长调节剂、除草剂、肥料、安全剂和化学信息素。
10.一种控制作物的植物病原真菌的方法,其特征在于,将农业有效且基本上无植物毒性量的如权利要求1至7中任一项所述的化合物或者如权利要求8或9所述的组合物施用到植物生长或者能够生长的土壤,施用到植物叶子和/或植物果实上,或者施用到植物种子上。
11.如权利要求1-7中任一项所述的通式(I)的化合物用于控制植物病原有害真菌的用途。
12.如权利要求1-7中任一项所述的通式(I)的化合物作为植物生长调节剂的用途。
13.控制植物病原有害真菌的组合物的制备方法,其特征在于,将增容剂和/或表面活性剂与如权利要求1-7中任一项所述的通式(I)的衍生物混合。
14.如权利要求1-7中任一项所述的通式(I)的化合物用于处理转基因植物的用途。
15.如权利要求1-7中任一项所述的通式(I)的化合物用于处理种子和转基因植物的种子的用途。
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- 2012-03-30 BR BR112013025871A patent/BR112013025871A2/pt not_active IP Right Cessation
- 2012-03-30 US US14/110,485 patent/US20140051575A1/en not_active Abandoned
- 2012-03-30 EP EP12711180.5A patent/EP2694494A1/en not_active Withdrawn
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CN109071495B (zh) * | 2016-04-13 | 2022-04-19 | 瑞戴格作物保护公司 | 农业化学品 |
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WO2012136581A1 (en) | 2012-10-11 |
US20140051575A1 (en) | 2014-02-20 |
BR112013025871A2 (pt) | 2016-07-26 |
EP2694494A1 (en) | 2014-02-12 |
JP2014512358A (ja) | 2014-05-22 |
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