TW202028187A - 吡啶基苯基胺基喹啉及類似物 - Google Patents
吡啶基苯基胺基喹啉及類似物 Download PDFInfo
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- TW202028187A TW202028187A TW108137518A TW108137518A TW202028187A TW 202028187 A TW202028187 A TW 202028187A TW 108137518 A TW108137518 A TW 108137518A TW 108137518 A TW108137518 A TW 108137518A TW 202028187 A TW202028187 A TW 202028187A
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Classifications
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- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
-
- A—HUMAN NECESSITIES
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Abstract
本發明係關於殺真菌活性化合物,更具體言之,係關於吡啶基苯基胺基喹啉及其類似物、用於其製備之方法及中間體及其作為殺真菌活性化合物,特別是呈殺真菌劑組合物形式的用途。本發明亦係關於使用此等化合物或包含其之組合物控制植物之植物病原性真菌的方法。
Description
本發明係關於殺真菌活性化合物,更具體言之,係關於吡啶基苯基胺基喹啉及其類似物、用於其製備之方法及中間體及其作為殺真菌活性化合物,特別是呈殺真菌劑組合物形式的用途。本發明亦係關於用於使用此等化合物或包含其之組合物控制植物之植物病原性真菌的方法。
WO 2011/081174及WO 2012/161071揭示適用作殺真菌劑之含氮雜環化合物。
WO 2013/058256揭示適用作殺真菌劑之其他含氮雜環化合物。
然而,由於例如在活性範圍、毒性、選擇率、施用量、殘餘物之形成及有利製造方面,對殺真菌劑活性化合物之生態及經濟需要不斷增加,且由於問題亦可與抗性相關,持續需要發展新穎殺真菌化合物及組合物,其在至少一些此等態樣中比起已知化合物及組合物具有優勢。
因此,本發明提供如下文所描述之吡啶基苯基胺基喹啉及其類似物,其可用作殺微生物劑,較佳用作殺真菌劑。活性成分
本發明提供式(I)化合物
其中
• A為苯基或包含1、2或3個獨立地選自由N、O及S組成之清單之雜原子的5或6員不飽和雜環基環,其中該環A分別連接至基團B及基團L之兩個連接點為相鄰碳原子(指示為●);
• B為部分飽和或不飽和6員雜環基環,其包含1、2、3或4個在由N、O及S組成之該清單中獨立選擇之雜原子;
• Q1
為CY1
或N,其中:
Y1
係選自由以下組成之群:氫原子、鹵素原子、C1
-C8
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷基、C2-
C8
烯基、包含至多9個可相同或不同之鹵素原子的C2
-C8
鹵代烯基、C2
-C8
炔基、包含至多9個可相同或不同之鹵素原子的C2
-C8
鹵代炔基、C3
-C7
環烷基、C4
-C7
環烯基、羥基、C1
-C8
烷氧基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷氧基、甲醯基、胺基、C1
-C8
烷胺基、二-C1
-C8
烷胺基、硫基、C1
-C8
烷基硫基、C1
-C8
烷基亞磺醯基、C1
-C8
烷基磺醯基、C1
-C6
三烷基矽烷基、氰基及硝基,
其中該C3
-C7
環烷基及C4
-C7
環烯基可經一或多個Ya
取代基取代;
• Y2
、Y3
、Y4
及Y5
係獨立地選自由以下組成之群:氫原子、鹵素原子、C1
-C8
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷基、C2-
C8
烯基、包含至多9個可相同或不同之鹵素原子的C2
-C8
鹵代烯基、C2
-C8
炔基、包含至多9個可相同或不同之鹵素原子的C2
-C8
鹵代炔基、C3
-C7
環烷基、C4
-C7
環烯基、羥基、C1
-C8
烷氧基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷氧基、甲醯基、胺基、C1
-C8
烷胺基、二C1
-C8
烷胺基、硫基、C1
-C8
烷基硫基、C1
-C8
烷基亞磺醯基、C1
-C8
烷基磺醯基、C1
-C6
三烷基矽烷基、氰基及硝基,
其中該C3
-C7
環烷基及C4
-C7
環烯基可經一或多個Ya
取代基取代;
• Z係獨立地選自由以下組成之群:氫原子、鹵素原子、羥基、C1
-C8
烷基、C2
-C8
烯基、C2
-C8
炔基、包含至多9個可相同或不同之鹵素原子的C2
-C8
鹵代炔基、C1
-C8
烷氧基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷基、包含至多9個可相同或不同之鹵素原子的C2
-C8
鹵代烯基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷氧基、C3
-C7
環烷基、C4
-C7
環烯基、甲醯基、C1
-C8
烷胺基、二C1
-C8
烷胺基、硫基、C1
-C8
烷基硫基、C1
-C8
烷基亞磺醯基、C1
-C8
烷基磺醯基、C1
-C6
三烷基矽烷基、氰基及硝基,
其中該C3
-C7
環烷基及C4
-C7
環烯基可經一或多個Za
取代基取代;
• m為0、1、2、3或4;
• n為0、1、2、3或4;
• L為CR1
R2
或NR3
,其中
R1
及R2
係獨立地選自由以下組成之群:氫原子、鹵素原子、C1
-C8
烷氧基、C1
-C8
烷基;
R3
係選自由以下組成之群:氫原子、C1
-C8
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷基、C2
-C8
烯基、包含至多9個可相同或不同之鹵素原子的C2
-C8
鹵代烯基、C3
-C8
炔基、包含至多9個可相同或不同之鹵素原子的C3
-C8
鹵代炔基、C3
-C7
環烷基、包含至多9個可相同或不同之鹵素原子的C3
-C7
-鹵代環烷基、C3
-C7
環烷基-C1
-C8
烷基、C1
-C8
烷基羰基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷基羰基、C1
-C8
-烷氧羰基、包含至多9個可相同或不同之鹵素原子的C1
-C8
-鹵代烷氧羰基、C1
-C8
烷基磺醯基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷基磺醯基、芳基-C1
-C8
烷基及苯磺醯基,
其中該C3
-C7
環烷基、C3
-C7
環烷基-C1
-C8
烷基、芳基-C1
-C8
烷基及苯磺醯基可經一或多個R3a
取代基取代;
• W係獨立地選自由以下組成之群:鹵素原子、羥基、C1
-C8
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷基、C1
-C8
烷氧基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷氧基、C1
-C8
羥基烷基、C1
-C8
烷氧基-C1
-C8
烷基、C2
-C8
烯基、包含至多9個可相同或不同之鹵素原子的C2
-C8
鹵代烯基、C2
-C8
炔基、包含至多9個可相同或不同之鹵素原子的C2
-C8
鹵代炔基、C3
-C7
環烷基、C4
-C8
環烯基、芳基、芳基-C1
-C8
烷基、雜環基、雜環基-C1
-C8
烷基、芳氧基、雜芳氧基、芳硫基、芳亞磺醯基、芳磺醯基、雜芳硫基、雜芳亞磺醯基、雜芳磺醯基、芳胺基、雜芳胺基、芳氧基-C1
-C8
烷基、雜芳氧基-C1
-C8
烷基、芳硫基-C1
-C8
烷基、芳亞磺醯基-C1
-C8
烷基、芳磺醯基-C1
-C8
烷基、雜芳硫基-C1
-C8
烷基、雜芳亞磺醯基-C1
-C8
烷基、雜芳磺醯基-C1
-C8
烷基、芳胺基-C1
-C8
烷基、雜芳胺基-C1
-C8
烷基、芳基-C1
-C8
烷氧基、雜芳基-C1
-C8
烷氧基、芳基-C1
-C8
烷基硫基、芳基-C1
-C8
烷基亞磺醯基、芳基-C1
-C8
烷基磺醯基、雜芳基-C1
-C8
烷基硫基、雜芳基-C1
-C8
烷基亞磺醯基、雜芳基-C1
-C8
烷基磺醯基、芳基-C1
-C8
烷基胺基、雜芳基-C1
-C8
烷基胺基、甲醯基、C1
-C8
烷基羰基、(羥亞胺基)C1
-C8
烷基、(C1
-C8
-烷氧亞胺基)C1
-C8
烷基、羧基、C1
-C8
烷氧基羰基、胺甲醯基、C1
-C8
烷基胺甲醯基、二-C1
-C8
烷基胺甲醯基、胺基、C1
-C8
烷基胺基、二-C1
-C8
烷基胺基、硫基、C1
-C8
烷基硫基、C1
-C8
烷基亞磺醯基、C1
-C8
烷基磺醯基、C1
-C6
三烷基矽烷基、三(C1
-C8
烷基)矽氧基、三(C1
-C8
烷基)矽氧基-C1
-C8
烷基、氧基、氰基及硝基,
其中該C3
-C7
環烷基、C4
-C8
環烯基、雜環基、芳基及該芳基-C1
-C8
烷基、雜環基-C1
-C8
烷基、芳氧基、雜芳氧基、芳基硫基、芳基亞磺醯基、芳基磺醯基、雜芳基硫基、雜芳基亞磺醯基、雜芳基磺醯基、芳基胺基、雜芳基胺基、芳氧基-C1
-C8
烷基、雜芳氧基-C1
-C8
烷基、芳基硫基-C1
-C8
烷基、芳基亞磺醯基-C1
-C8
烷基、芳基磺醯基-C1
-C8
烷基、雜芳基硫基-C1
-C8
烷基、雜芳基亞磺醯基-C1
-C8
烷基、雜芳基磺醯基-C1
-C8
烷基、芳基胺基-C1
-C8
烷基、雜芳基胺基-C1
-C8
烷基、芳基-C1
-C8
烷氧基、雜芳基-C1
-C8
烷氧基、芳基-C1
-C8
烷基硫基、芳基-C1
-C8
烷基亞磺醯基、芳基-C1
-C8
烷基磺醯基、雜芳基-C1
-C8
烷基硫基、雜芳基-C1
-C8
烷基亞磺醯基、雜芳基-C1
-C8
烷基磺醯基、芳基-C1
-C8
烷基胺基、雜芳基-C1
-C8
烷基胺基基團之該芳基、雜環基及雜芳基部分可經一或多個Wa
取代基取代;
• X係獨立地選自由以下組成之群:鹵素原子、羥基、C1
-C8
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷基、C1
-C8
烷氧基、包含至多9個可相同或不同之鹵素原子的C1
-C8
鹵代烷氧基、C2
-C8
烯基、包含至多9個可相同或不同之鹵素原子的C2
-C8
鹵代烯基、C2
-C8
炔基、包含至多9個可相同或不同之鹵素原子的C2
-C8
鹵代炔基、C3
-C7
環烷基、C4
-C7
環烯基、甲醯基、胺基、C1
-C8
烷基胺基、二-C1
-C8
烷基胺基、硫基、C1
-C8
烷基硫基、C1
-C8
烷基亞磺醯基、C1
-C8
烷基磺醯基、C1
-C6
-三烷基矽氧基、氰基、硝基及C1
-C8
羥基烷基,
其中該C3
-C7
環烷基及C4
-C7
環烯基可經一或多個Xa
取代基取代;
Za
、R3a
、Wa
、Xa
及Ya
係獨立地選自由以下組成之群:鹵素原子、硝基、羥基、氰基、羧基、胺基、硫基、五氟-λ6
-硫基、甲醯基、胺甲醯基、胺基甲酸酯、C1
-C8
烷基、C3
-C7
環烷基、具有1至5個鹵素原子的C1
-C8
鹵代烷基、具有1至5個鹵素原子的C3
-C8
-鹵代環烷基、C2
-C8
烯基、C2
-C8
炔基、C1
-C8
烷基胺基、二-C1
-C8
烷基胺基、C1
-C8
烷氧基、具有1至5個鹵素原子的C1
-C8
鹵代烷氧基、C1
-C8
烷基硫基、具有1至5個鹵素原子的C1
-C8
鹵代烷基硫基、C1
-C8
烷基羰基、具有1至5個鹵素原子的C1
-C8
鹵代烷基羰基、C1
-C8
烷基胺甲醯基、二-C1
-C8
烷基胺甲醯基、C1
-C8
烷氧基羰基、具有1至5個鹵素原子的C1
-C8
鹵代烷氧基羰基、C1
-C8
烷基羰氧基、具有1至5個鹵素原子的C1
-C8
鹵代烷基羰氧基、C1
-C8
烷基羰基胺基、具有1至5個鹵素原子的C1
-C8
鹵代烷基羰基胺基、C1
-C8
烷基硫基、具有1至5個鹵素原子的C1
-C8
鹵代烷基硫基、C1
-C8
烷基亞磺醯基、具有1至5個鹵素原子的C1
-C8
鹵代烷基亞磺醯基、C1
-C8
烷基磺醯基及具有1至5個鹵素原子的C1
-C8
-鹵代烷基-磺醯基;
以及其鹽、N-氧化物、金屬錯合物、類金屬錯合物及光活性異構體或幾何異構體;
其限制條件為式(I)化合物不為:
2-{2-[(6,7-二甲基-3-側氧基-3,4-二氫喹喏啉-2-基)甲基]苯基}-3,5-二側氧基-2,3,4,5-四氫-1,2,4-三嗪-6-甲腈[713527-70-9],及
3,5-二側氧基-2-{2-[(3-側氧基-3,4-二氫喹喏啉-2-基)甲基]苯基}-2,3,4,5-四氫-1,2,4-三嗪-6-甲腈[426815-75-0]。
如本文所用,表述「一或多個取代基」係指基於可用鍵結位點之數目,在一個至可能之最多個取代基的範圍內之多個取代基,其限制條件為滿足穩定性及化學可行性之條件。
如本文中所用,鹵素意謂氟、氯、溴或碘;甲醯基意謂-CH(=O);羧基意謂-C(=O)OH;羰基意謂-C(=O)-;胺甲醯基意謂-C(=O)NH2
;N-羥胺甲醯基意謂-C(=O)NHOH;SO表示亞碸基;SO2
表示碸基;雜原子意謂硫、氮或氧;亞甲基意謂自由基-CH2
-;芳基意謂除非以不同方式提供,否則藉由移除一個氫而衍生自芳族烴之有機基團(諸如苯基或萘基);雜環基意謂不飽和、飽和或部分飽和的5至7員環,較佳為5至6員環,其包含1至4個在由N、O及S組成之清單中獨立選擇之雜原子。如本文中所用之術語「雜環基」涵蓋雜芳基。
如本文所用,舉例而言表述「5員至6員環」中之術語「員」指定構成環之骨架原子之數目。
如本文所使用,含有此等術語之烷基、烯基及炔基以及部分,可為直鏈或分支鏈。
當胺基或任何其他含胺基基團之胺基部分經兩個可相同或不同之取代基取代時,該等兩個取代基與其所連接之氮原子一起可形成雜環基,較佳地5至7員雜環基,其可經取代或可包括其他雜原子,例如嗎啉基或哌啶基。
視化合物中之不對稱中心數而定,本發明化合物中之任一者可以一或多種光學或對掌性異構體形式存在。因此,本發明同樣係關於其所有光學異構體及外消旋或非外消旋混合物(術語「非外消旋」表示不同比例之對映異構體之混合物)且係關於呈各種比例之所有可能立體異構體的混合物。非對映異構體及/或光學異構體可根據一般熟習此項技術者本身已知之方法來分離。
視化合物中之雙鍵數而定,本發明化合物中之任一者亦可以一或多種幾何異構體形式存在。因此,本發明同樣係關於所有幾何異構體且係關於呈各種比例之所有可能的混合物。幾何異構體可根據一般技術者本身已知之通用方法分離。
視鏈或環之取代基之相對位置(同側/反側或順式/反式)而定,本發明化合物中之任一者亦可以一或多種幾何異構體形式存在。因此,本發明同樣係關於所有同側/反側(或順式/反式)異構體及呈所有比例之所有可能同側/反側(或順式/反式)混合物。同側/反側(或順式/反式)異構體可根據一般技術者本身已知之通用方法分離。
當本發明化合物可以互變異構形式形式存在時,即使當不明確地提及此時,本發明亦涵蓋此類化合物之任何互變異構形式。
式(I)化合物在本文中稱為「活性成分」。
在上式(I)中,A較佳選自由以下組成之群:苯基、噻吩基、吡啶基及嘧啶基,A更佳選自由以下組成之群:A-G1、A-G2、A-G3、A-G4、A-G5、A-G6及A-G7:
其中「*」指示連接至L且「#」指示連接至B。
在一些實施例中,A為苯基,A較佳選自由以下組成之群:A-G1、A-G2、A-G3、A-G4及A-G5。在一些實施例中,A為A-G1、A-G2或A-G3。在一些其他實施例中,A為A-G2或A-G3。
在上式(I)中,B可為部分飽和或不飽和6員雜環基環,其包含1、2或3個選自氮原子或氧原子之雜原子(例如吡啶基、嘧啶基、吡嗪基、噠嗪基、二氫哌喃基、二氫吡啶基),B較佳選自由二氫哌喃基、二氫吡啶基、吡啶基及嘧啶基組成之群。
在上式(I)中,B較佳地為包含1、2或3個氮原子之部分飽和或不飽和6員雜環基環,更佳地B選自由以下組成之群:吡啶基(例如吡啶-2-基、吡啶-3-基、吡啶-4-基)、嘧啶基(嘧啶-2-基、嘧啶-4-基、嘧啶-5-基)、吡嗪基(例如,吡嗪-2-基、吡嗪-3-基)、噠嗪基(例如噠嗪-3-基及噠嗪-4-基)、二氫哌喃基(例如3,4-二氫-2H-哌喃-6-基)及二氫吡啶基(例如5,6-二氫吡啶-2-基),在一些實施例中,B為吡啶基基團或嘧啶基基團。
在上式(I)中,Z可較佳地選自由以下組成之群:氫原子、鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C1
-C6
烷氧基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基及氰基。更佳地,Z為氫原子、鹵素原子(例如氯)、或包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基(二氟甲基),甚至更佳地,Z為氫原子或C1
-C6
烷基(例如甲基)。
在上式(I)中,X較佳獨立地選自由以下組成之群:鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、羥基、C1
-C6
烷氧基及包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基,X更佳為鹵素原子(例如氯、氟)、C1
-C6
烷基(例如甲基)、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基(三氟甲基)或包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基(例如三氟甲氧基),甚至更佳地當存在時X為鹵素原子(例如氟)。
在上式(I)中,n較佳為0、1或2,更佳為0或1。
在上式(I)中,n較佳為0、1或2,更佳為0或1,其中X較佳選自由以下組成之群:鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、羥基、C1
-C6
烷氧基及包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基,X更佳為鹵素原子(例如氯、氟)、C1
-C6
烷基(例如甲基)、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基(三氟甲基)或包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基(例如三氟甲氧基),甚至更佳地當存在時X為鹵素原子(例如氟)。
在上式(I)中,Q1
較佳為CY1
或N,其中Y1
選自由以下組成之群:氫原子、鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C3
-C7
環烷基、羥基、C1
-C6
烷氧基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基、C1
-C6
烷氧基羰基、甲醯基及氰基,其中該C3
-C7
環烷基可經一或多個Ya
取代基取代,較佳地Y1
選自由以下組成之群:氫、鹵素(例如氯)及C1
-C6
烷基(例如甲基),更佳地Y1
為氫原子。
在一些實施例中,在上式(I)中,Q1
為CY1
,其中Y1
為氫原子。
在上式(I)中,Y2
、Y3
、Y4
及Y5
較佳獨立地選自由以下組成之群:氫原子、鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C3
-C7
環烷基、羥基、C1
-C6
烷氧基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基、C1
-C6
烷基羰基、甲醯基及氰基,其中該C3
-C7
環烷基可經一或多個Ya
取代基取代,更佳地Y2
、Y3
、Y4
及Y5
獨立地選自由以下組成之群:氫原子、鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基(例如三氟甲基),或氰基,甚至更佳地,Y2
、Y3
、Y4
及Y5
獨立地為氫原子或鹵素原子(例如氟)。
在上式(I)中,W較佳獨立地選自由以下組成之群:鹵素原子(例如氯、溴)、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C1
-C6
烷氧基(例如甲氧基)、C1
-C6
羥基烷基、C1
-C6
烷基硫基、C2
-C6
烯基、C1
-C6
烷氧基羰基、C3
-C7
環烷基(例如環丙基)、芳基、芳基-C1
-C6
烷基(其中該芳基可經一或多個鹵素原子取代)、雜環基、羧基、參(C1
-C6
烷基)矽氧基-C1
-C6
烷基、雜芳基-C1
-C6
烷基、C1
-C6
烷氧基-C1
-C6
烷基、側氧基及氰基。
在一些實施例中,W獨立地選自由以下組成之群:鹵素原子(例如氯、溴)、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C1
-C6
烷氧基(例如甲氧基)、C1
-C6
烷基硫基、C3
-C7
環烷基(例如環丙基)、側氧基及氰基。
在一些實施例中,W為鹵素原子或C1
-C6
烷氧基。
在上式(I)中,m較佳為0、1、2或3,更佳地,m為0、1或2,甚至更佳地m為0或1。
在上式(I)中,m較佳為0、1、2或3,更佳地,m為0或1,且W獨立地選自由以下組成之群:鹵素原子(例如氯、溴)、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C1
-C6
烷氧基(例如甲氧基)、C1
-C6
羥基烷基、C1
-C6
烷基硫基、C2
-C6
烯基、C1
-C6
-烷氧羰基、C3
-C7
環烷基(例如環丙基)、芳基、芳基-C1
-C6
烷基(其中該芳基可經一或多個鹵素原子取代)、雜環基、羧基、參(C1
-C6
烷基)矽氧基-C1
-C6
烷基、雜芳基-C1
-C6
烷基、C1
-C6
烷氧基-C1
-C6
烷基、側氧基及氰基。
在上式(I)中,R1
較佳為氫原子或鹵素原子,更佳地,R1
為氫原子。
在上式(I)中,R2
較佳為氫原子或鹵素原子,更佳地,R2
為氫原子。
在上式(I)中,R3
較佳為氫原子或經取代或未經取代之C1
-C6
烷基,較佳地,R3
為氫原子或甲基,甚至更佳地,R3
為氫原子。
在一些實施例中,根據本發明之化合物為式(I)化合物,其中Y2
及Y3
為氫原子且Y4
及Y5
為鹵素原子。
在一些實施例中,根據本發明之化合物為式(I)化合物,其中Y2
、Y3
及Y4
為氫原子且Y5
為鹵素原子。
以上Q1
、Y1
、Y2
、Y3
、Y4
、Y5
、R1
、R2
、R3
、Z、L、A、B、X、W、n及m之指定定義(例如寬泛定義以及較佳、更佳、甚至更佳的定義)可以各種方式組合以提供根據本發明之化合物的子類。
在一些實施例(在本文中與實施例(a)相關)中,根據本發明之化合物為式(I)化合物,其中:
其中
A選自由苯基、噻吩基、吡啶基及嘧啶基組成之群,較佳A為苯基;
B為部分飽和或不飽和6員雜環基環,其包含1、2或3個選自氮原子或氧原子之雜原子,較佳B選自由以下組成之群:二氫哌喃基、二氫吡啶基、吡啶基及嘧啶基;
Q1
為CY1
或N,其中Y1
選自由以下組成之群:氫原子、鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C3
-C7
環烷基、羥基、C1
-C6
烷氧基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基、C1
-C6
-烷氧羰基、甲醯基及氰基,其中該C3
-C7
環烷基可經一或多個Ya
取代基取代,較佳Y1
選自由以下組成之群:氫、鹵素(例如氯)及C1
-C6
烷基(例如甲基),更佳Y1
為氫原子,更佳Q1
為CY1
,其中Y1
為氫原子;
Y2
、Y3
、Y4
及Y5
獨立地選自由以下組成之群:氫原子、鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C3
-C7
環烷基、羥基、C1
-C6
烷氧基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基、C1
-C6
烷基羰基、甲醯基及氰基,其中該C3
-C7
環烷基可經一或多個Ya
取代基取代,較佳Y2
、Y3
、Y4
及Y5
獨立地選自由以下組成之群:氫原子、鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基(例如三氟甲基),或氰基,甚至更佳地,Y2
、Y3
、Y4
及Y5
獨立地為氫原子或鹵素原子(例如氟);
Z選自由以下組成之群:氫原子、鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C1
-C6
烷氧基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基及氰基,更佳地,Z為氫原子、鹵素原子(例如氯)、C1
-C6
烷基(例如甲基)或包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基(例如二氟甲基),更佳地Z為氫原子或C1
-C6
烷基(例如甲基);
m為0、1、2或3,較佳m為0、1或2,更佳m為0或1;
n為0、1或2,較佳為0或1;
L為CR1
R2
或NR3
,其中R1
及R2
獨立地為氫原子或鹵素原子,較佳地,R1
及R2
均為氫原子,R3
為氫原子或經取代或未經取代之C1
-C6
烷基,較佳地,R3
為氫原子或甲基,更佳地,R3
為氫原子;
W獨立地選自由以下組成之群:鹵素原子(例如氯、溴)、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基(例如甲氧基)、C1
-C6
羥基烷基、C1
-C6
烷基硫基、C2
-C6
烯基、C1
-C6
烷氧基羰基、C3 -
C7
環烷基(例如環丙基)、芳基、芳基-C1
-C6
烷基(其中該芳基可經一或多個鹵素原子取代)、雜環基、羧基、三(C1
-C6
烷基)矽氧基-C1
-C6
烷基、雜芳基-C1
-C6
烷基、C1
-C6
烷氧基-C1
-C6
烷基、側氧基及氰基,較佳地,W選自由以下組成之群:鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C1
-C6
烷氧基、C1
-C6
羥基烷基、C2
-C6
烯基、C1
-C6
烷氧基羰基、C3
-C7
環烷基、芳基、芳基-C1
-C6
烷基(其中該芳基可經一或多個鹵素原子取代)、雜環基、羧基、三(C1
-C6
烷基)矽氧基-C1
-C6
烷基、雜芳基-C1
-C6
烷基及C1
-C6
烷氧基-C1
-C6
烷基;
X獨立地選自由以下組成之群:鹵素原子、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、羥基、C1
-C6
烷氧基及包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基,較佳地X為鹵素原子(例如氯、氟)、C1
-C6
烷基(例如甲基)、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基(三氟甲基)或包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷氧基(例如三氟甲氧基),更佳地X為鹵素原子(例如氟)。
在一些實施例(在本文中與實施例(b)相關)中,根據本發明之化合物為式(I)化合物,其中:
其中
A選自由苯基、噻吩基、吡啶基及嘧啶基組成之群,較佳A為苯基;
B為部分飽和或不飽和6員雜環基環,其包含1、2或3個選自氮原子或氧原子之雜原子,較佳B選自由以下組成之群:二氫哌喃基、二氫吡啶基、吡啶基及嘧啶基;
Q1
為N或CY1
,其中Y1
為氫原子;
Y2
、Y3
、Y4
及Y5
獨立地為氫原子或鹵素原子;
Z為氫原子或C1
-C6
烷基;
m為0、1或2;
n為0或1;
L為CR1
R2
,其中R1
及R2
為氫原子或L為NR3
,其中R3
為氫原子;
W獨立地選自由以下組成之群:鹵素原子(例如氯、溴)、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C1
-C6
烷氧基(例如甲氧基)、C1
-C6
羥基烷基、C1
-C6
烷基硫基、C2
-C6
烯基、C1
-C6
烷氧基羰基、C3
-C7
環烷基(例如環丙基)、芳基、芳基-C1
-C6
烷基(其中該芳基可經一或多個鹵素原子取代)、雜環基、羧基、三(C1
-C6
烷基)矽氧基-C1
-C6
烷基、雜芳基-C1
-C6
烷基、C1
-C6
烷氧基-C1
-C6
烷基、側氧基及氰基,更佳地,W獨立地選自由以下組成之群:鹵素原子(例如氯、溴)、C1
-C6
烷基、包含至多9個可相同或不同之鹵素原子的C1
-C6
鹵代烷基、C1
-C6
烷氧基(例如甲氧基)、C1
-C6
烷基硫基、C3
-C7
環烷基(例如環丙基)、側氧基及氰基;
X為鹵素原子。
在根據實施例(a)或(b)之一些實施例中,根據本發明之化合物為式(I)化合物,其中A選自由以下組成之群:A-G1、A-G2、A-G3、A-G4、A-G5、A-G6及A-G7,較佳A-G1、A-G2、A-G3、A-G4及A-G5。
其中「*」指示連接至L且「#」指示連接至B。
在根據實施例(a)或(b)之一些實施例中,根據本發明之化合物為式(I)化合物,其中A為A-G1、A-G2或A-G3。
在根據實施例(a)或(b)之一些實施例中,根據本發明之化合物為式(I)化合物,其中L為NR3
,其中R3
為氫原子。
在根據實施例(a)或(b)之一些實施例中,根據本發明之化合物為式(I)化合物,其中Y2
及Y3
為氫原子且Y4
及Y5
為鹵素原子。
在根據實施例(a)或(b)之一些實施例中,根據本發明之化合物為式(I)化合物,其中Y2
、Y3
及Y4
為氫原子且Y5
為鹵素原子。
用於製備活性成分之方法
本發明亦關於用於製備式(I)化合物之方法。除非另外指示,否則自由基A、B、Q1
、Y1
、Y2
、Y3
、Y4
、Y5
、Z、L、m、n、W及X具有上文針對式(I)化合物給出之含義。此等定義不僅應用於式(I)之最終產物,但同樣應用於所有中間體。
如本文所定義之式(I)化合物可藉由方法P1製備,該方法包含使式(II)化合物與式(III)化合物反應之步驟:
方法P1:
Hal表示Cl、Br、I,較佳Br或I;
Ra
及Rb
獨立地為H或C1
-C8
烷基,或Ra
及Rb
基團可連同其分別所連接之氧原子形成5員或6員環;較佳地,Ra
及Rb
均為H,或Ra
及Rb
連同其分別所連接之氧原子形成四甲基乙二醇莰基。
根據已知方法,方法P1可在過渡金屬催化劑(諸如鈀)存在下且適當時在膦配位體或N-雜環碳烯配位體存在下、適當時在鹼存在下且適當時在溶劑存在下進行。
根據已知方法(Patai's Chemistry of Functional Groups - Amino, Nitroso, Nitro and Related Groups - 1996),式(II)之鹵代芳基衍生物可藉由使式(IV)之苯胺或其鹽中的一者重氮化而製備。
根據已知方法(Journal of Heterocyclic Chemistry (2008),45
, 1199 and Synthetic Communications (1999),29
, 1393),式(II)之鹵代芳基衍生物亦可藉由芳族親核取代而製備。
根據已知方法(Patai's Chemistry of Functional Groups - Amino, Nitroso, Nitro and Related Groups - 1996),式(IV)之苯胺可藉由減少式(V)之硝基或其鹽中的一者而製備。
式(III)之硼酸或硼酸酯衍生物為商業上可獲得的,或可藉由已知方法製備。
方法P1可在諸如金屬鹽或錯合物之催化劑存在下進行。出於此目的,適合之金屬衍生物為過渡金屬催化劑,諸如鈀。出於此目的,適合之金屬鹽或錯合物為例如:氯化鈀、乙酸鈀、肆(三苯基膦)鈀(0)、雙(二苯亞甲基丙酮)鈀(0)、參(二苯亞甲基丙酮)二鈀(0)、雙(三苯基膦)二氯化鈀(II)、[1,1'-雙(二苯膦基)二茂鐵]二氯化鈀(II)、雙(苯烯丙基)二氯化二鈀(II)、雙(烯丙基)-二氯化二鈀(II)或[1,1'-雙(二-第三丁基膦基)二茂鐵]二氯化鈀(II)。
亦可藉由單獨添加至鈀鹽與配位體或鹽之反應來在反應混合物中產生鈀錯合物,諸如三乙基膦、三-第三丁基膦、三第三丁基鏻四氟硼酸鹽、三環己基膦、2-(二環己基膦)聯苯、2-(二-第三丁基膦)聯苯、2-(二環己基膦)-2'-(N,N-二甲胺基)二苯基、2-(第三丁基膦)-2'-(N,N-二甲胺基)聯苯、2-二-第三丁基膦-2',4',6'-三異丙基聯苯2-二環己基膦基-2',4',6'-三異丙基聯苯、2-二環己基膦基-2,6'-二甲氧基聯苯、2-二環己基膦基-2',6'-二異丙氧基聯苯、三苯基膦、參-(鄰甲苯基)膦、3-(二苯膦基)苯磺酸鈉、參-2-(甲氧基-苯基)膦、2,2'-雙(二苯膦基)-1,1'-聯萘、1,4-雙(二苯膦基)丁烷、1,2-雙(二苯膦基)乙烷、1,4-雙(二環己基膦)丁烷、1,2-雙(二環己基膦)-乙烷、2-(二環己基膦)-2'-(N,N-二甲胺基)-聯苯、1,1'-雙(二苯膦基)-二茂鐵、(R)-(-)-1-[(S)-2-二苯基-膦基)二茂鐵基]乙基二環己基膦、參-(2,4-第三丁基-苯基)亞磷酸鹽、二(1-金剛烷基)-2-嗎啉基苯基膦或1,3-雙(2,4,6-三甲基苯基)咪唑鎓氯化物。
亦宜從商業目錄(諸如Strem Chemicals之「Metal Catalysts for Organic Synthesis」)或Strem Chemicals之「Phosphorous Ligands and Compounds」)選擇適當的催化劑及/或配體。
用於進行方法P1之合適的鹼可為此類反應習用之無機鹼及有機鹼。較佳使用鹼土金屬或鹼金屬氫氧化物,諸如氫氧化鈉、氫氧化鈣、氫氧化鉀或其他氫氧化銨衍生物;鹼土金屬、鹼金屬或氟化銨,諸如氟化鉀、氟化銫或氟化四丁基銨;鹼土金屬或鹼金屬碳酸鹽,諸如碳酸鈉、碳酸鉀、碳酸氫鉀、碳酸氫鈉或碳酸銫;鹼金屬或鹼土金屬乙酸鹽,諸如乙酸鈉、乙酸鋰、乙酸鉀或乙酸鈣;鹼金屬或鹼土金屬磷酸鹽,諸如鹼性磷酸三鉀;鹼金屬醇化物,諸如第三丁醇鉀或第三丁醇鈉;三級胺,諸如三甲胺、三乙胺、三丁胺、N,N-二甲基苯胺、N,N-二環己基甲胺、N,N-二異丙基乙胺、N-甲基哌啶、N,N-二甲胺基吡啶、二氮雜二環辛烷(DABCO)、二氮雜二環壬烯(DBN)或二氮雜雙環十一烯(DBU);亦及芳族鹼,諸如吡啶、甲基吡啶、二甲基吡啶或三甲基吡啶。
用於進行方法P1之合適的溶劑可為習用惰性有機溶劑。較佳使用視情況選用之鹵化、脂族、脂環或芳族烴,諸如石油醚、戊烷、己烷、庚烷、環己烷、甲基環己烷、苯、甲苯、二甲苯或十氫萘;氯苯、二氯苯、二氯甲烷、三氯甲烷、四氯化碳、二氯乙烷或三氯乙烷;醚,諸如乙醚、二異丙基醚、甲基第三丁基醚、甲基第三戊基醚、二噁烷、四氫呋喃、2-甲基四氫呋喃、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷或苯甲醚;腈,諸如乙腈、丙腈、正丁腈或異丁腈或苯甲腈;醯胺,諸如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基甲醯苯胺、N-甲基吡咯啶酮或六甲基磷醯三胺;脲,諸如1,3-二甲基-3,4,5,6-四氫-2(1H)-嘧啶酮;酯,諸如乙酸甲酯或乙酸乙酯;亞碸,諸如二甲亞碸;或碸,諸如環丁碸;及其混合物。
亦可有利的為利用諸如水或醇之共溶劑進行方法P1,該醇諸如甲醇、乙醇、丙醇、異丙醇或第三
丁醇。
方法P1可在諸如氬氣氣或氮氣氛圍之惰性氛圍中進行。當進行方法P1時,每莫耳式(II)化合物可採用1莫耳或過量之式(III)化合物及1至5莫耳鹼及0.01至20莫耳百分數之鈀錯合物。亦有可能以其他比率採用反應組分。藉由已知方法逐漸完成。
如本文所定義之式(I)化合物可藉由方法P2製備,該方法包含使式(VI)化合物與式(VII)化合物反應之步驟:
方法P2:
T表示硼衍生物,諸如,硼酸、硼酸酯或三氟硼酸鉀衍生物;
U表示氯、溴、碘、甲磺醯基、甲苯磺醯基或三氟甲磺醯基;較佳為溴或碘。
根據已知方法,方法P2可在過渡金屬催化劑(諸如鈀)存在下且適當時在膦配位體或N-雜環碳烯配位體存在下、適當時在鹼存在下且適當時在溶劑存在下進行。
根據已知方法,式(VI)之硼酸或硼酸酯衍生物可在過渡金屬催化劑(諸如鈀)存在下且適當時在膦配位體或N-雜環碳烯配位體存在下、適當時在鹼存在下且適當時在溶劑存在下使用諸如雙(頻哪醇根基)二硼之試劑由鹵代芳基衍生物(III)來製備。
用於進行方法P2及用於合成式(VI)之中間體之適合催化劑、鹼及溶劑可如與方法P1結合揭示。
方法P2可在諸如氬氣氣或氮氣氛圍之惰性氛圍中進行。當進行方法P2時,每莫耳式(VI)化合物可採用1莫耳或過量之式(VII)化合物及1至5莫耳鹼及0.01至20莫耳百分數之鈀錯合物。亦有可能以其他比率採用反應組分。藉由已知方法逐漸完成。
或者,式(VI)之硼酸或硼酸酯衍生物可使用適當有機金屬試劑(諸如正丁基鋰)及含適當硼衍生物(諸如硼酸三甲酯)之適當的有機溶劑(諸如醚,較佳為四氫呋喃或二乙醚)藉由鹵素金屬交換由鹵代芳基衍生物(III)來製備。
式(VII)之鹵化物衍生物為商業上可獲得的,且可藉由熟習此項技術者已知之方法製備。
如本文所定義之式(Ia)化合物,亦即式(I)化合物,其中L為NH,可藉由方法P3製備,該方法包含使式(VIII)化合物與式(IX)化合物反應之步驟:
方法P3:
Hal表示Cl、Br、I,較佳Br或I。
根據已知方法,方法P3可在過渡金屬催化劑(諸如鈀)且適當時在膦配位體或N-雜環碳烯配位體存在下、適當時在鹼存在下且適當時在溶劑存在下存在下進行。
式(VIII)之胺及式(IX)之鹵代芳基為商業上可獲得的,或可根據熟習此項技術者已知之方法製備。
用於進行方法P3之適合催化劑、鹼及溶劑可如與方法P1結合揭示。
方法P3可在諸如氬氣氣或氮氣氛圍之惰性氛圍中進行。當進行方法P3時,每莫耳式(IX)化合物可採用1莫耳或過量之式(VIII)化合物及1至5莫耳鹼以及0.01至20莫耳百分數之鈀錯合物。亦有可能以其他比率採用反應組分。藉由已知方法逐漸完成。
根據已知方法,方法P4可在過渡金屬催化劑(諸如鈀)存在下且適當時在膦配位體或N-雜環碳烯配位體存在下、適當時在鹼存在下且適當時在溶劑存在下進行。
式(X)之鹵代芳基及式(XI)之胺為商業上可獲得的,或可根據熟習此項技術者已知之方法製備。
用於進行方法P4之適合催化劑、鹼及溶劑可如與方法P1結合揭示。
方法P4可在諸如氬氣氣或氮氣氛圍之惰性氛圍中進行。當進行方法P4時,每莫耳式(XI)化合物可採用1莫耳或過量之式(X)化合物及1至5莫耳鹼及0.01至20莫耳百分數之鈀錯合物。亦有可能以其他比率採用反應組分。藉由已知方法逐漸完成。
如本文所定義之式(Ib)化合物(亦即式(I)化合物,其中L為CH2
)可藉由方法P5製備,該方法P5包含使式(XII)化合物與式(XIII)化合物反應之步驟:
方法P5:
Hal表示Cl、Br、I,較佳Cl或Br;
Ra
及Rb
獨立地為H或C1
-C8
烷基,或Ra
及Rb
基團可連同其分別所連接之氧原子形成5員或6員環;較佳地,Ra
及Rb
均為H,或Ra
及Rb
連同其分別所連接之氧原子形成四甲基乙二醇莰基。
根據已知方法,方法P5可在過渡金屬催化劑(諸如鈀)存在下且適當時在膦配位體或N-雜環碳烯配位體存在下、適當時在鹼存在下且適當時在溶劑存在下進行。
式(XII)之硼衍生物為商業上可獲得的,或可根據熟習此項技術者已知之方法製備。
用於進行方法P5之適合催化劑、鹼及溶劑可如與方法P1結合揭示。
方法P5可在諸如氬氣氣或氮氣氛圍之惰性氛圍中進行。當進行方法P5時,每莫耳式(XIII)化合物可採用1莫耳或過量之式(XII)化合物及1至5莫耳鹼以及0.01至20莫耳百分數之鈀錯合物。亦有可能以其他比率採用反應組分。藉由已知方法逐漸完成。
或者,如本文所定義之式(Ib)化合物可藉由方法P6製備,該方法包含使式(XV)化合物與式(XVI)化合物反應之步驟:
方法P6:
Hal表示Cl、Br、I,較佳Br或I;
Ra
及Rb
獨立地為H或C1
-C8
烷基,或Ra
及Rb
基團可連同其分別所連接之氧原子形成5員或6員環;較佳地,Ra
及Rb
均為H,或Ra
及Rb
連同其分別所連接之氧原子形成四甲基乙二醇莰基。
根據已知方法,方法P6可在過渡金屬催化劑(諸如鈀)存在下且適當時在膦配位體或N-雜環碳烯配位體存在下、適當時在鹼存在下且適當時在溶劑存在下進行。
式(XV)之鹵化物及式(XVI)之硼衍生物為可商購的或可根據熟習此項技術者已知之方法製備。
用於進行方法P6之適合催化劑、鹼及溶劑可如與方法P1結合揭示。
方法P6可在諸如氬氣氣或氮氣氛圍之惰性氛圍中進行。當進行方法P6時,每莫耳式(XVI)化合物可採用1莫耳或過量之式(XV)化合物及1至5莫耳鹼及0.01至20莫耳百分數之鈀錯合物。亦有可能以其他比率採用反應組分。藉由已知方法逐漸完成。
根據方法P1、P2、P3或P4製備之式(Ia)化合物可用於製備式(Id)化合物。式(Ia)化合物通常用鹼(諸如氫化鈉及烷基鹵化物,較佳為碘烷基,諸如碘甲烷)處理。反應通常在極性非質子溶劑(諸如二甲基甲醯胺)中進行。
當進行方法P7時,每莫耳烷基鹵化物化合物可採用1莫耳或過量之式(Ia)化合物及1至5莫耳鹼。亦有可能以其他比率採用反應組分。藉由已知方法逐漸完成。
方法P1、P2、P3、P4、P5、P6及P7通常在常壓下進行。亦有可能在加壓或減壓下操作。
當進行方法P1、P2、P3、P4、P5、P6及P7時,反應溫度可在相對較寬之範圍內變化。一般而言,此等方法係在-78℃至200℃、較佳為-78℃至150℃之溫度下進行。控制該等方法之溫度的方式為使用微波技術。
一般而言,反應混合物係在減壓下濃縮。剩餘之殘基可藉由諸如層析或結晶之已知方法自仍可存在之任何雜質中釋放。
藉由慣用方法逐漸完成。一般而言,用水處理反應混合物,且分離出有機相且在乾燥後於減壓下濃縮。適當時,則剩餘的殘餘物可藉由諸如層析、結晶或蒸餾之習用方法自仍可存在之任何雜質釋放。
式(I)化合物可根據上文所描述之製備之通用方法來製備。然而應理解,基於其常識及可用之公開案,習此相關技藝之人士將能夠根據所需合成的每一化合物之特殊性來調整該等方法。
組合物及調配物
本發明進一步係關於一種組合物,詳言之用於控制非所需微生物之組合物。可將組合物施加至微生物及/或其生境中。
組合物通常包含至少一種式(I)化合物及至少一種農業上適合之助劑,例如載劑及/或界面活性劑。
載劑為固體或液體、天然或合成的、有機或無機物質,其一般係惰性的。該載劑一般改良化合物至例如植物、植物部分或種子之施加。適合之固體載劑
之實例包括但不限於:銨鹽;天然石粉,諸如高嶺土、黏土、滑石、白堊、石英、綠坡縷石(attapulgite)、蒙脫石或矽藻土;及合成石粉,諸如經細微粉碎二氧化矽、氧化鋁及矽酸鹽。通常適用於製備顆粒之固體載劑之實例包括(但不限於):碾碎且分級之天然岩石,諸如方解石、大理石、浮石、海泡石及白雲石;合成的無機及有機粉末顆粒;及有機材料(諸如紙張、鋸屑、椰子殼、玉米穗軸及菸草梗)之顆粒。適合液體載劑
之實例包括但不限於水、有機溶劑及其組合。適合溶劑之實例包括極性及非極性有機化學液體,例如來自芳族及非芳族烴之類別(諸如環己烷、石蠟、烷基苯、二甲苯、甲苯烷基萘、氯化芳族物或氯化脂族烴(諸如氯苯、氯乙烯或二氯甲烷))、醇及多元醇(其可視情況亦經取代、醚化及/或酯化,諸如丁醇或二醇)、酮(諸如丙酮、甲基乙基酮、甲基異丁基酮或環己酮)、酯(包括脂肪及油)及(聚)醚、未經取代及經取代之胺、醯胺(諸如二甲基甲醯胺)、內醯胺(諸如N烷基吡咯啶酮)及內酯、碸及亞碸(諸如二甲亞碸)。載劑亦可為液化氣態填充劑(亦即在標準溫度下及在標準壓力下為氣態的液體),例如,氣溶膠推進劑,諸如,鹵代烴、丁烷、丙烷、氮氣及二氧化碳。載劑之量的範圍以組合物之重量計通常為1至99.99%、較佳地5至99.9%、更佳地10至99.5 %及最佳地20至99%。
界面活性劑可為離子(陽離子或陰離子)或非離子界面活性劑,諸如離子或非離性乳化劑、泡沫形成物、分散劑、濕潤劑及其任何混合物。適合之界面活性劑之實例包括(但不限於):聚丙烯酸之鹽、木質磺酸之鹽、酚磺酸或萘磺酸之鹽、乙烯及/或環氧丙烷與脂肪醇、脂肪酸或脂肪胺之聚縮合物(聚氧乙烯脂肪酸酯、聚氧乙烯脂肪醇醚,例如烷芳基聚二醇醚)、經取代酚(較佳烷基酚或芳基酚)、磺化丁二酸酯之鹽、牛磺酸衍生物(較佳牛磺酸烷酯)、聚乙氧基化醇或酚之磷酸酯、多元醇之脂肪酯及含有硫酸酯、磺酸酯及磷酸酯之化合物之衍生物(例如烷基磺酸酯、硫酸烷酯、芳基磺酸酯)、蛋白質水解產物、木質亞硫酸鹽廢液及甲基纖維素。界面活性劑通常在式(I)化合物及/或載劑不溶於水且用水進行施加時使用。隨後,界面活性劑之量通常在組合物之5至40重量%範圍內。
適合之助劑之其他實例包括:拒水劑;乾燥劑;黏合劑(黏著劑、增黏劑、固定劑,諸如羧甲基纖維素;呈粉末、顆粒或膠乳形式之天然及合成聚合物,諸如阿拉伯膠、聚乙烯醇及聚乙酸乙烯酯;諸如腦磷脂及卵磷脂之天然磷脂及合成磷脂;聚乙烯吡咯啶酮;及泰勒纖維素(tylose));增稠劑;穩定劑(例如,低溫穩定劑、防腐劑、抗氧化劑、光穩定劑或改良化學及/或物理穩定性之其他試劑);染料或顏料(諸如無機顏料,例如鐵氧化物、氧化鈦及普魯士藍;有機染料,例如茜素、偶氮基及金屬酞菁染料);消泡劑(例如,聚矽氧消泡劑及硬脂酸鎂);防腐劑(例如,二氯酚及苯甲醇半縮甲醛);二次增稠劑(纖維素衍生物、丙烯酸衍生物、三仙膠、經改質黏土及細微粉碎二氧化矽);黏著劑;赤黴素及處理助劑;礦物及植物油;香料;蠟;營養素(包括微量營養素,諸如鐵、錳、硼、銅、鈷、鉬及鋅之鹽);保護性膠體;搖溶性物質;滲透劑;掩蔽劑及錯合物形成劑。
助劑之選擇與式(I)化合物之預期應用模式及/或其物理特性有關。此外,助劑可經選擇以向組合物或自其製備之使用形式賦予特定特性(工業、物理及/或生物特性)。助劑之選擇可允許針對特定需求定製組合物。
組合物可呈任何習用形式,諸如溶液(例如水溶液)、乳液、可濕潤粉末、水基及油基懸浮液、粉末、粉塵、糊狀物、可溶性粉末、可溶性顆粒、用於散佈之顆粒、懸乳劑濃縮物、浸漬有式(I)化合物之天然或合成產物、肥料以及聚合物質之微膠囊。式(I)化合物可以懸浮、乳化或溶解形式存在。
可將組合物作為備用調配物提供至終端使用者,亦即組合物可藉由適合裝置(諸如噴灑或撒粉裝置)直接施加至植物或種子。或者,可將呈濃縮物形式之組合物提供至終端使用者,其在使用之前必須經稀釋,較佳地用水稀釋。
組合物可以習知方式製備,例如藉由使式(I)化合物與諸如本文上文所揭示之一或多種適合助劑混合來製備。
組合物一般含有0.01至99 wt%、0.05至98 wt%、較佳地0.1至95 wt%、更佳地0.5至90 wt%、最佳地1至80 wt%之式(I)化合物。組合物可能包含兩種或多於兩種式(I)化合物。在此情況下,概述之範圍係指本發明之化合物之總量。
混合物/組合
式(I)化合物及包含其之組合物可與如殺真菌劑、殺細菌劑、殺蟎劑、殺線蟲劑、殺昆蟲劑、除草劑、肥料、生長調節劑、安全劑或訊息化合物之其他活性成份混合。此可使得活性範圍變寬或防止出現耐藥性。已知殺真菌劑、殺蟲劑、殺蟎劑、殺線蟲劑及殺菌劑之實例揭示於Pesticide Manual,第17版中。
可與式(I)化合物及組合物混合之尤佳殺真菌劑的實例為:
1)麥角固醇生物合成之抑制劑,例如(1.001)環克座(cyproconazole)、(1.002)待克利(difenoconazole)、(1.003)依普座(epoxiconazole)、(1.004)環醯菌胺(fenhexamid)、(1.005)苯鏽啶(fenpropidin)、(1.006)芬普福(fenpropimorph)、(1.007)胺苯吡菌酮(fenpyrazamine)、(1.008)氟喹唑(fluquinconazole)、(1.009)護汰芬(flutriafol)、(1.010)依滅列(imazalil)、(1.011)依滅列硫酸鹽(imazalil sulfate)、(1.012)種菌唑(ipconazole)、(1.013)滅特座(metconazole)、(1.014)邁克尼(myclobutanil)、(1.015)巴克素(paclobutrazol)、(1.016)撲克拉(prochloraz)、(1.017)普克利(propiconazole)、(1.018)丙硫菌唑(prothioconazole)、(1.019)啶菌噁唑(Pyrisoxazole)、(1.020)螺環菌胺(spiroxamine)、(1.021)得克利(tebuconazole)、(1.022)四克利(tetraconazole)、(1.023)三泰隆(triadimenol)、(1.024)三得芬(tridemorph)、(1.025)滅菌唑(triticonazole)、(1.026) (1R,2S,5S)-5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基) 環戊醇、(1.027) (1S,2R,5R)-5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基) 環戊醇、(1.028) (2R)-2-(1-氯環丙基)-4-[(1R)-2,2-二氯環丙基]-1-(1H-1,2,4-三唑-1-基) 丁-2-醇、(1.029) (2R)-2-(1-氯環丙基)-4-[(1S)-2,2-二氯環丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.030) (2R)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.031) (2S)-2-(1-氯環丙基)-4-[(1R)-2,2-二氯環丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.032) (2S)-2-(1-氯環丙基)-4-[(1S)-2,2-二氯環丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.033) (2S)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.034) (R)-[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.035) (S)-[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.036) [3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.037) 1-({(2R,4S)-2-[2-氯-4-(4-氯苯氧基)苯基]-4-甲基-1,3-二氧環戊-2-基}甲基)-1H-1,2,4-三唑、(1.038) 1-({(2S,4S)-2-[2-氯-4-(4-氯苯氧基)苯基]-4-甲基-1,3-二氧環戊-2-基}甲基)-1H-1,2,4-三唑、(1.039) 1-{[3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫代氰酸鹽、(1.040) 1-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫代氰酸鹽、(1.041) 1-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫代氰酸鹽、(1.042) 2-[(2R,4R,5R)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.043) 2-[(2R,4R,5S)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.044) 2-[(2R,4S,5R)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.045) 2-[(2R,4S,5S)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.046) 2-[(2S,4R,5R)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.047) 2-[(2S,4R,5S)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.048) 2-[(2S,4S,5R)-1-(2,4-二氯苯基)-5-羥基-2,6,6-二甲基庚-4-基]-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.049) 2-[(2S,4S,5S)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.050) 2-[1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.051) 2-[2-氯-4-(2,4-二氯苯氧基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.052) 2-[2-氯-4-(4-氯苯氧基) 苯基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.053) 2-[4-(4-氯苯氧基)-2-(三氟甲基) 苯基]-1-(1H-1,2,4-三唑-1-基) 丁-2-醇、(1.054) 2-[4-(4-氯苯氧基)-2-(三氟甲基) 苯基]-1-(1H-1,2,4-三唑-1-基)戊-2-醇、(1.055) Mefentrifluconazole、(1.056) 2-{[3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.057) 2-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.058) 2-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-2,4-二氫-3H-1,2,4-三唑-3-硫酮、(1.059) 5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基)環戊醇、(1.060) 5-(烯丙硫基)-1-{[3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-三唑、(1.061) 5-(烯丙硫基)-1-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-三唑、(1.062) 5-(烯丙硫基)-1-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-三唑、(1.063) N'-(2,5-二甲基-4-{[3-(1,1,2,2-四氟乙氧基) 苯基]硫基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(1.064) N'-(2,5-二甲基-4-{[3-(2,2,2-三氟乙氧基)苯基]硫基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(1.065) N'-(2,5-二甲基-4-{[3-(2,2,3,3-四氟丙氧基)苯基]硫基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(1.066) N'-(2,5-二甲基-4-{[3-(五氟乙氧基)苯基]硫基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(1.067) N'-(2,5-二甲基-4-{3-[(1,1,2,2-四氟乙基)硫基]苯氧基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(1.068) N'-(2,5-二甲基-4-{3-[(2,2,2-三氟乙基)硫基]苯氧基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(1.069) N'-(2,5-二甲基-4-{3-[(2,2,3,3-四氟丙基)硫基]苯氧基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(1.070) N'-(2,5-二甲基-4-{3-[(五氟乙基)硫基]苯氧基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(1.071) N'-(2,5-二甲基-4-苯氧基苯基)-N-乙基-N-甲基亞胺基甲醯胺、(1.072) N'-(4-{[3-(二氟甲氧基)苯基]硫基}-2,5-二甲基苯基)-N-乙基-N-甲基亞胺基甲醯胺、(1.073) N'-(4-{3-[(二氟甲基)硫基]苯氧基}-2,5-二甲基苯基)-N-乙基-N-甲基亞胺基甲醯胺、(1.074) N'-[5-溴-6-(2,3-二氫-1H-茚-2-基氧基)-2-甲基吡啶-3-基]-N-乙基-N-甲基亞胺基甲醯胺、(1.075) N'-{4-[(4,5-二氯-1,3-噻唑-2-基)氧基]-2,5-二甲基苯基}-N-乙基-N-甲基亞胺基甲醯胺、(1.076) N'-{5-溴-6-[(1R)-1-(3,5-二氟苯基) 乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亞胺基甲醯胺、(1.077) N'-{5-溴-6-[(1S)-1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亞胺基甲醯胺、(1.078) N'-{5-溴-6-[(順-4-異丙基環己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亞胺基甲醯胺、(1.079) N'-{5-溴-6-[(反-4-異丙基環己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亞胺基甲醯胺、(1.080) N'-{5-溴-6-[1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亞胺基甲醯胺、(1.081) 依芬三扶康唑(Ipfentrifluconazole)。
2) 錯合物I或II之呼吸性鏈之抑制劑,例如:(2.001)苯丙烯氟菌唑、(2.002)必殺吩、(2.003)白可列、(2.004)萎鏽靈、(2.005)氟吡菌醯胺、(2.006)福多寧、(2.007)氟唑菌醯胺、(2.008)福拉比、(2.009)艾索非他米、(2.010)異吡瑞沙(反側-差向異構的對映異構體1R,4S,9S)、(2.011)異吡瑞沙(反側-差向異構的對映異構體1S,4R,9R)、(2.012)異吡瑞沙(反側-差向異構的外消旋體1RS,4SR,9SR)、(2.013)異吡瑞沙(同側-差向異構的外消旋體1RS,4SR,9RS與反側-差向異構的外消旋體1RS,4SR,9SR之混合物)、(2.014)異吡瑞沙(同側-差向異構之對映異構體1R,4S,9R)、(2.015)異吡瑞沙(同側-差向異構之對映異構體1S,4R,9S)、(2.016)異吡瑞沙(同側-差向異構之外消旋體1RS,4SR,9RS)、(2.017)噴福芬(penflufen)、(2.018)吡噻菌胺(penthiopyrad)、(2.019)吡二氟甲多芬(pydiflumetofen)、(2.020)吡瑞氟密得(pyraziflumid)、(2.021)氟唑環菌胺(sedaxane)、(2.022) 1,3-二甲基-N-(1,1,3-三甲基-2,3-二氫-1H-茚-4-基)-1H-吡唑-4-甲醯胺、(2.023) 1,3-二甲基-N-[(3R)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2.024) 1,3-二甲基-N-[(3S)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2.025) 1-甲基-3-(三氟甲基)-N-[2'-(三氟甲基)聯苯-2-基]-1H-吡唑-4-甲醯胺、(2.026) 2-氟-6-(三氟甲基)-N-(1,1,3-三甲基-2,3-二氫-1H-茚-4-基)苯甲醯胺、(2.027) 3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氫-1H-茚-4-基)-1H-吡唑-4-甲醯胺、(2.028) 3-(二氟甲基)-1-甲基-N-[(3R)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2.029) 3-(二氟甲基)-1-甲基-N-[(3S)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2.030) 氟茚唑菌胺(Fluindapyr)、(2.031) 3-(二氟甲基)-N-[(3R)-7-氟-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1-甲基-1H-吡唑-4-甲醯胺、(2.032) 3-(二氟甲基)-N-[(3S)-7-氟-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1-甲基-1H-吡唑-4-甲醯胺、(2.033) 5,8-二氟-N-[2-(2-氟-4-{[4-(三氟甲基)吡啶-2-基]氧基}苯基)乙基]喹唑啉-4-胺、(2.034) N-(2-環戊基-5-氟苄基)-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.035) N-(2-第三-丁基-5-甲基苄基)-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.036) N-(2-第三-丁基苄基)-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.037) N-(5-氯-2-乙基苄基)-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.038) isoflucypram、(2.039) N-[(1R,4S)-9-(二氯亞甲基)-1,2,3,4-四氫-1,4-甲橋萘-5-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲醯胺、(2.040) N-[(1S,4R)-9-(二氯亞甲基)-1,2,3,4-四氫-1,4-甲橋萘-5-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲醯胺、(2.041) N-[1-(2,4-二氯苯基)-1-甲氧烷萘-2-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲醯胺、(2.042) N-[2-氯-6-(三氟甲基)苄基]-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.043) N-[3-氯-2-氟-6-(三氟甲基)苄基]-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.044) N-[5-氯-2-(三氟甲基)苄基]-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.045) N-環丙基-3-(二氟甲基)-5-氟-1-甲基-N-[5-甲基-2-(三氟甲基)苄基]-1H-吡唑-4-甲醯胺、(2.046) N-環丙基-3-(二氟甲基)-5-氟-N-(2-氟-6-異丙基苄基)-1-甲基-1H-吡唑-4-甲醯胺、(2.047) N-環丙基-3-(二氟甲基)-5-氟-N-(2-異丙基-5-甲基苄基)-1-甲基-1H-吡唑-4-甲醯胺、(2.048) N-環丙基-3-(二氟甲基)-5-氟-N-(2-異丙基苄基)-1-甲基-1H-吡唑-4-硫代碳醯胺、(2.049) N-環丙基-3-(二氟甲基)-5-氟-N-(2-異丙基苄基)-1-甲基-1H-吡唑-4-甲醯胺、(2.050) N-環丙基-3-(二氟甲基)-5-氟-N-(5-氟-2-異丙基苄基)-1-甲基-1H-吡唑-4-甲醯胺、(2.051) N-環丙基-3-(二氟甲基)-N-(2-乙基-4,5-di甲基苄基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.052) N-環丙基-3-(二氟甲基)-N-(2-乙基-5-氟苄基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.053) N-環丙基-3-(二氟甲基)-N-(2-乙基-5-甲基苄基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.054) N-環丙基-N-(2-環丙基-5-氟苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.055) N-環丙基-N-(2-環丙基-5-甲基苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.056) N-環丙基-N-(2-環丙基苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(2.057) 食蚜蠅(pyrapropoyne)。
3) 錯合物III處之呼吸鏈之抑制劑,例如(3.001)辛唑嘧菌胺(ametoctradin)、(3.002)吲唑磺菌胺(amisulbrom)、(3.003)亞托敏(azoxystrobin)、(3.004)甲香菌酯(coumethoxystrobin)、(3.005)丁香菌酯(coumoxystrobin)、(3.006)賽座滅(cyazofamid)、(3.007)地莫菌胺(dimoxystrobin)、(3.008)亞烷基嘧菌酯(enoxastrobin)、(3.009)凡殺同(famoxadone)、(3.010)咪唑菌酮(fenamidone)、(3.011)氟菌蟎酯(flufenoxystrobin)、(3.012)氟嘧菌酯(fluoxastrobin)、(3.013)克收欣(kresoxim-methyl)、(3.014)苯氧菌胺(metominostrobin)、(3.015)肟醚菌胺(orysastrobin)、(3.016)啶氧菌酯(picoxystrobin)、(3.017)百克敏(pyraclostrobin)、(3.018)唑胺菌酯(pyrametostrobin)、(3.019)唑菌酯(pyraoxystrobin)、(3.020)三氟敏(trifloxystrobin)、(3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-氟-2-苯基乙烯基]氧基}苯基)亞乙基]胺基}氧基)甲基]苯基}-2-(甲氧基亞胺基)-N-甲基乙醯胺、(3.022) (2E,3Z)-5-{[1-(4-氯苯基)-1H-吡唑-3-基]氧基}-2-(甲氧基亞胺基)-N,3-二戊甲基-3-烯醯胺、(3.023) (2R)-2-{2-[(2,5-二甲基苯氧基)甲基]苯基}-2-甲氧基-N-甲基乙醯胺、(3.024) (2S)-2-{2-[(2,5-二甲基苯氧基)甲基]苯基}-2-甲氧基-N-甲基乙醯胺、(3.025) (3S,6S,7R,8R)-8-苄基-3-[({3-[(異丁醯基氧基)甲氧基]-4-甲氧基吡啶-2-基}羰基)胺基]-6-甲基-4,9-二氧-1,5-二氧-7-基 2-甲基丙酸、(3.026) mandestrobin、(3.027) N-(3-乙基-3,5,5-三甲基環己基)-3-甲醯胺基-2-羥基苄醯胺、(3.028) (2E,3Z)-5-{[1-(4-氯-2-氟苯基)-1H-吡唑-3-基]氧基}-2-(甲氧基亞胺基)-N,3-二戊甲基-3-烯醯胺、(3.029) 甲基 {5-[3-(2,4-二甲基苯基)-1H-吡唑-1-基]-2-甲基苄基}胺基甲酸酯、(3.030) 氟氰蟲醯胺(metyltetraprole)、(3.031) florylpicoxamid。
4) 有絲分裂及細胞分裂之抑制劑,例如(4.001)貝芬替(carbendazim)、(4.002)乙黴威(diethofencarb)、(4.003)噻唑菌胺(ethaboxam)、(4.004)氟吡菌胺(fluopicolide)、(4.005)賓克隆(pencycuron)、(4.006)噻苯達唑(thiabendazole)、(4.007)托布津-甲酯(thiophanate-methyl)、(4.008)座賽胺(zoxamide)、(4.009) 3-氯-4-(2,6-二氟苯基)-6-甲基-5-苯基噠嗪、(4.010) 3-氯-5-(4-氯苯基)-4-(2,6-二氟苯基)-6-甲基噠嗪、(4.011) 3-氯-5-(6-氯吡啶-3-基)-6-甲基-4-(2,4,6-三氟苯基)噠嗪、(4.012) 4-(2-溴-4-氟苯基)-N-(2,6-二氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.013) 4-(2-溴-4-氟苯基)-N-(2-溴-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.014) 4-(2-溴-4-氟苯基)-N-(2-溴苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.015) 4-(2-溴-4-氟苯基)-N-(2-氯-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.016) 4-(2-溴-4-氟苯基)-N-(2-氯苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.017) 4-(2-溴-4-氟苯基)-N-(2-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.018) 4-(2-氯-4-氟苯基)-N-(2,6-二氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.019) 4-(2-氯-4-氟苯基)-N-(2-氯-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.020) 4-(2-氯-4-氟苯基)-N-(2-氯苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.021) 4-(2-氯-4-氟苯基)-N-(2-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.022) 4-(4-氯苯基)-5-(2,6-二氟苯基)-3,6-二甲基噠嗪、(4.023) N-(2-溴-6-氟苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.024) N-(2-溴苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.025) N-(4-氯-2,6-二氟苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺。
5)能夠具有多位點作用之化合物,例如(5.001)紫紅混合物、(5.002)四氯丹、(5.003)蓋普丹(captan)、(5.004)四氯異苯腈、(5.005)氫氧化銅、(5.006)環烷酸銅、(5.007)銅氧化物、(5.008)鹼性氯氧化銅、(5.009)硫酸銅(2+)、(5.010)腈硫醌、(5.011)多寧(dodine)、(5.012)福爾培(folpet)、(5.013)鋅錳乃浦(mancozeb)、(5.014)錳乃浦(maneb)、(5.015)免得爛(metiram)、(5.016)免得爛鋅、(5.017)咢辛-銅、(5.018)甲基鋅乃浦、(5.019)包括鈣聚硫化物之硫及硫製劑、(5.020)得恩地(thiram)、(5.021)鋅乃浦(zineb)、(5.022)益穗(ziram)、(5.023)6-乙基-5,7-二側氧基-6,7-二氫-5H-吡咯并[3',4':5,6][1,4]二噻𠯤并[2,3-c][1,2]噻唑-3-甲腈。
6) 能夠引發宿主防護之化合物,例如:(6.001)活化酯-S-甲基、(6.002)異噻菌胺(isotianil)、(6.003)撲殺熱(probenazole)、(6.004)汰敵寧(tiadinil)。
7) 胺基酸及/或蛋白質生物合成之抑制劑,例如(7.001)嘧菌環胺(cyprodinil)、(7.002)春日黴素(kasugamycin)、(7.003)水合春日黴素鹽酸鹽、(7.004)土黴素(oxytetracycline)、(7.005)嘧黴胺(pyrimethanil)、(7.006) 3-(5-氟-3,3,4,4-四甲基-3,4-二氫異喹啉-1-基)喹啉。
8) ATP產生之抑制劑,例如(8.001)矽硫芬。
9) 細胞壁合成之抑制劑,例如:(9.001)苯噻菌胺、(9.002)達滅芬、(9.003)氟嗎啉、(9.004)纈黴威、(9.005)雙炔醯菌胺、(9.006)丁吡嗎啉、(9.007)威利芬那雷特、(9.008)(2E)-3-(4-第三丁基苯基)-3-(2-氯吡啶-4-基)-1-(嗎啉-4-基)丙-2-烯-1-酮、(9.009)(2Z)-3-(4-第三丁基苯基)-3-(2-氯吡啶-4-基)-1-(嗎啉-4-基)丙-2-烯-1-酮。
10) 脂質及膜合成之抑制劑,例如:(10.001)霜黴威(propamocarb)、(10.002)霜黴威鹽酸鹽、(10.003)甲基脫克松(tolclofos-methyl)。
11) 黑色素生物合成之抑制劑,例如:(11.001)三賽唑(tricyclazole)、(11.002) {3-甲基-1-[(4-甲基苯甲醯基)胺基]丁-2-基}胺基甲酸2,2,2-三氟乙酯。
12) 核酸合成之抑制劑,例如:(12.001)本達樂(benalaxyl)、(12.002)本達樂-M (精苯霜靈(kiralaxyl))、(12.003)滅達樂(metalaxyl)、(12.004)滅達樂-M (右滅達樂(mefenoxam))。
13) 信號轉導之抑制劑,例如:(13.001)護汰寧(fludioxonil)、(13.002)依普同(iprodione)、(13.003)撲滅寧(procymidone)、(13.004)丙氧喹啉(proquinazid)、(13.005)快諾芬(quinoxyfen)、(13.006)免克寧(vinclozolin)。
14) 能夠充當解偶聯劑之化合物,例如:(14.001)扶吉胺(fluazinam)、(14.002)敵蟎普(meptyldinocap)。
15) 其他化合物,例如(15.001)脫落酸、(15.002)苯噻硫氰(benthiazole)、(15.003)吡托沙嗪(bethoxazin)、(15.004)卡巴西黴素(capsimycin)、(15.005)香芹酮(carvone)、(15.006)蟎離丹(chinomethionat)、(15.007)硫雜靈(cufraneb)、(15.008)環氟菌胺(cyflufenamid)、(15.009)克絕(cymoxanil)、(15.010)環丙磺醯胺、(15.011)氟替尼(flutianil)、(15.012)福賽得鋁(fosetyl-aluminium)、(15.013)福賽得鈣、(15.014)福賽得鈉、(15.015)異硫氰酸甲酯、(15.016) 滅芬農、(15.017) 滅粉黴素、(15.018) 遊黴素、(15.019) 鎳二甲基二硫基胺基甲酸酯、(15.020) 異丙消、(15.021) 奧沙莫卡(oxamocarb)、(15.022) 奧沙派林(oxathiapiprolin)、(15.023) 奧施康定(oxyfenthiin)、(15.024) 五氯酚及鹽、(15.025) 亞磷酸及其鹽、(15.026) 福賽得三乙膦酸酯(propamocarb-fosetylate)、(15.027) 氯芬酮(pyriofenone) (氯芬酮(chlazafenone))、(15.028) 特布弗克(tebufloquin)、(15.029) 克枯爛(tecloftalam)、(15.030) 托尼發尼(tolnifanide)、(15.031) 1-(4-{4-[(5R)-5-(2,6-二氟苯基)-4,5-二氫-1,2-噁唑-3-基]-1,3-噻唑-2-基}哌啶-1-基)-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮、(15.032) 1-(4-{4-[(5S)-5-(2,6-二氟苯基)-4,5-二氫-1,2-噁唑-3-基]-1,3-噻唑-2-基}哌啶-1-基)-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮、(15.033) 2-(6-苄基吡啶-2-基)喹唑啉、(15.034) dipymetitrone、
(15.035) 2-[3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(15.036) 2-[3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-氯-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(15.037) 2-[3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-氟-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(15.038) 2-[6-(3-氟-4-甲氧基苯基)-5-甲基吡啶-2-基]喹唑啉、(15.039) 2-{(5R)-3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}-3-氯苯基甲磺酸酯、(15.040) 2-{(5S)-3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}-3-氯苯基甲磺酸酯、(15.041) Ipflufenoquin、(15.042) 2-{2-氟-6-[(8-氟-2-甲基喹啉-3-基)氧基]苯基}丙-2-醇、(15.043) 2-{3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}-3-氯苯基甲磺酸酯、(15.044) 2-{3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}苯基甲磺酸酯、(15.045) 2-苯基酚及鹽、(15.046) 3-(4,4,5-三氟-3,3-二甲基-3,4-二氫異喹啉-1-基)喹啉、(15.047) quinofumelin、(15.048) 4-胺基-5-氟嘧啶-2-醇(互變異構體:4-胺基-5-氟嘧啶-2(1H)-酮)、(15.049) 4-氧代-4-[(2-苯基乙基)胺基]丁酸、(15.050) 5-胺基-1,3,4-噻二唑-2-硫醇、(15.051) 5-氯-N'-苯基-N'-(丙-2-炔-1-基)噻吩-2-磺醯肼、(15.052) 5-氟-2-[(4-氟苄基)氧基]嘧啶-4-胺、(15.053) 5-氟-2-[(4-甲基苄基)氧基]嘧啶-4-胺、(15.054) 9-氟-2,2-二甲基-5-(喹啉-3-基)-2,3-二氫-1,4-苯并噁西平、(15.055) 丁基-3-炔-1-基 {6-[({[(Z)-(1-甲基-1H-四唑基-5-基)(苯基)亞甲基]胺基}氧基)甲基]吡啶-2-基}胺基甲酸酯、(15.056) 乙基(2Z)-3-胺基-2-氰基-3-苯基丙烯酸酯、(15.057) 吩嗪-1-羧酸、(15.058) 丙基 3,4,5-三羥基苯甲酸酯、(15.059) 喹啉-8-醇、(15.060) 喹啉-8-醇硫酸 (2:1)、(15.061) 第三-丁基 {6-[({[(1-甲基-1H-四唑基-5-基)(苯基)亞甲基]胺基}氧基)甲基]吡啶-2-基}胺基甲酸酯、(15.062) 5-氟-4-亞胺基-3-甲基-1-[(4-甲基苯基)碸基]-3,4-二氫嘧啶-2(1H)-酮、(15.063) 胺基比芬諾(pyrifen)。
如本文上文中所描述之類別(1)至(15)之所有提及的混合搭配物,可以游離化合物形式及/或(若其官能基致能此)其農業上可接受之鹽形式存在。
式(I)化合物及組合物亦可與一或多種生物控制劑組合。
可與式(I)化合物及包含其之組合物組合的生物控制劑之實例為:
(A) 選自由以下組成之群的抗細菌劑:
(A1)細菌,諸如(A1.1)枯草桿菌(Bacillus subtilis
),詳言之,菌株QST713/AQ713 (可以SERENADE OPTI或SERENADE ASO之形式自美國Bayer CropScience LP獲得,具有NRRL寄存編號B21661且描述於美國專利第6,060,051號中);(A1.2) 解澱粉芽孢桿菌(Bacillus amyloliquefaciens
),詳言之,菌株D747 (可以Double Nickel™形式自美國Certis獲得,具有寄存編號FERM BP-8234且揭示於美國專利第7,094,592號中);(A1.3)短小芽孢桿菌(Bacillus pumilus
),詳言之,菌株BU F-33 (具有NRRL寄存編號50185);(A1.4)枯草芽孢桿菌類解澱粉芽孢桿菌(Bacillus subtilis var. amyloliquefaciens
)菌株FZB24(可以Taegro®
形式自美國Novozymes獲得);(A1.5)類芽孢桿菌屬(Paenibacillus sp.)菌株,其具有寄存編號NRRL B-50972或寄存編號NRRL B-67129且描述於國際專利公開案第WO 2016/154297號中;且
(A2)真菌,諸如(A2.1)出芽短梗黴菌(Aureobasidium pullulans
),詳言之,菌株DSM14940之芽生孢子;(A2.2)菌株DSM 14941之出芽短梗黴菌(Aureobasidium pullulans
)芽生孢子;(A2.3)出芽短梗黴菌(Aureobasidium pullulans
),詳言之,菌株DSM14940及DSM14941之芽生孢子的混合物;
(B)選自由以下組成之群的殺真菌劑:
(B1)細菌,諸如(B1.1)枯草桿菌(Bacillus subtilis
),詳言之,菌株QST713/AQ713 (可以SERENADE OPTI或SERENADE ASO之形式自美國Bayer CropScience LP獲得,具有NRRL寄存編號B21661且描述於美國專利第6,060,051號中);(B1.2)短小芽孢桿菌(Bacillus pumilus
),詳言之,菌株QST2808 (可以SONATA®
之形式自美國Bayer CropScience LP獲得,具有寄存編號NRRL B-30087且描述於美國專利第6,245,551號中);(B1.3)短小芽孢桿菌(Bacillus pumilus
),詳言之,菌株GB34 (可以Yield Shield®
之形式自Bayer AG, DE獲得);(B1.4)短小芽孢桿菌(Bacillus pumilus
),詳言之,菌株BU F-33 (具有NRRL寄存編號50185);(B1.5)解澱粉芽孢桿菌(Bacillus amyloliquefaciens
),詳言之,菌株D747 (可以Double Nickel™形式自美國Certis獲得,具有寄存編號FERM BP-8234且揭示於美國專利第7,094,592號中);(B1.6)枯草桿菌(Bacillus subtilis
) Y1336 (可以BIOBAC®
WP之形式自臺灣Bion-Tech獲得,其在臺灣以寄存編號4764、5454、5096及5277註冊為生物殺真菌劑);(B1.7)解澱粉芽孢桿菌(Bacillus amyloliquefaciens
)菌株MBI 600 (可以SUBTILEX之形式自BASF SE獲得);(B1.8)枯草桿菌(Bacillus subtilis
)菌株GB03 (可以Kodiak®
之形式自Bayer AG, DE獲得);(B1.9) 枯草桿菌變種解澱粉芽孢桿菌(Bacillus subtilis var. amyloliquefaciens
)菌株FZB24 (可以殺真菌劑TAEGRO®
或TAEGRO®
ECO (EPA寄存編號70127-5)之形式自Novozymes Biologicals Inc., Salem, Virginia或Syngenta Crop Protection, LLC, Greensboro, North Carolina獲得;(B1.10)蕈狀桿菌(Bacillus mycoides
)分株J(可以BmJ TGAI或WG之形式自美國Certis獲得);(B1.11)地衣芽孢桿菌(Bacillus licheniformis
),詳言之,菌株SB3086 (可以EcoGuard TM生物殺真菌劑及Green Releaf之形式自Novozymes獲得);(B1.12)類芽孢桿菌屬(Paenibacillus sp.)菌株,其具有寄存編號NRRL B-50972或寄存編號NRRL B-67129且描述於國際專利公開案第WO 2016/154297號中。
在一些實施例中,生物控制劑為產生豐原素(fengycin)或大側柏素(plipastatin)類化合物、伊枯草菌素(iturin)類化合物及/或表面活性素類化合物的枯草桿菌或解澱粉芽孢桿菌菌株。對於先前技術,參見以下評論文章:Ongena, M.等人, 「Bacillus Lipopeptides: Versatile Weapons for Plant Disease Biocontrol,」 Trends in Microbiology,第16卷,第3期,2008年3月,第115-125頁。能夠產生脂肽之芽孢桿菌菌株(包括枯草芽孢桿菌(Bacillus subtilis
)) QST713 (可以SERENADE OPTI或SERENADE ASO形式自美國Bayer CropScience LP獲得,其具有NRRL寄存編號B21661且描述於美國專利第6,060,051號中)、解澱粉芽孢桿菌(Bacillus amyloliquefaciens
)菌株D747 (可以Double Nickel™形式自美國Certis獲得,具有寄存編號FERM BP-8234且揭示於美國專利第7,094,592號中);枯草芽孢桿菌MBI600(可以SUBTILEX®
形式自美國EPA Reg.第71840-8號Becker Underwood獲得);枯草桿菌(Bacillus subtilis
) Y1336 (可以BIOBAC®
WP之形式自臺灣Bion-Tech獲得,其在臺灣以寄存編號4764、5454、5096及5277註冊為生物殺真菌劑);解澱粉芽孢桿菌,尤其菌株FZB42(可以RHIZOVITAL®
形式自ABiTEP, DE獲得);枯草桿菌變種解澱粉芽孢桿菌(Bacillus subtilis var. amyloliquefaciens
)菌株FZB24 (可以殺真菌劑TAEGRO®
或TAEGRO®
ECO (EPA寄存編號70127-5)之形式自Novozymes Biologicals Inc., Salem, Virginia或Syngenta Crop Protection, LLC, Greensboro, North Carolina獲得;及
(B2)真菌,例如:(B2.1)盾殼黴(Coniothyrium minitans
),詳言之,菌株CON/M/91-8 (寄存編號DSM-9660;例如來自Bayer之 Contans®
);(B2.2)核果梅奇酵母(Metschnikowia fructicola),詳言之,NRRL Y-30752 (例如Shemer®
);(B2.3)赫色小球殼孢菌(Microsphaeropsis ochracea) (例如來自Prophyta之Microx®
);(B2.5) 木黴菌屬(Trichoderma spp.
),包括深綠木黴菌(Trichoderma atroviride
),菌株SC1,描述於國際申請案第PCT/IT2008/000196號中);(B2.6)哈茨木黴(Trichoderma harzianum rifai
)菌株KRL-AG2 (亦被稱為菌柱T-22, /ATCC 208479,例如來自美國BioWorks之PLANTSHIELD T-22G, Rootshield®
及TurfShield);(B2.14)粉紅膠黴菌(Gliocladium roseum
),來自W.F. Stoneman Company LLC之菌株321U;(B2.35)黃色籃狀菌(Talaromyces flavus
),菌株V117b;(B2.36)棘孢木黴(Trichoderma asperellum
),來自Isagro之菌株ICC 012;(B2.37) 棘孢木黴,菌株SKT-1 (例如,來自Kumiai Chemical Industry之ECO-HOPE®);(B2.38)深綠木黴菌(Trichoderma atroviride
),菌株CNCM I-1237 (例如來自法國Agrauxine之Esquive®
WP);(B2.39)深綠木黴菌,菌株NMI編號V08/002387;(B2.40)深綠木黴菌,菌株NMI編號V08/002388;(B2.41)深綠木黴菌,菌株NMI編號V08/002389;(B2.42)深綠木黴菌,菌株NMI編號V08/002390;(B2.43)深綠木黴菌,菌株LC52 (例如,Agrimm Technologies Limited之Tenet);(B2.44)深綠木黴菌,菌株ATCC 20476 (IMI 206040);(B2.45)深綠木黴菌,菌株T11 (IMI352941/ CECT20498);(B2.46)Trichoderma harmatum ;
(B2.47)哈茨木黴;(B2.48)哈茨木黴T39
(例如來自美國Makhteshim之trichodex®
);(B2.49)哈茨木黴,詳言之,菌株KD (例如來自Biological Control Products, SA之Trichoplus (由Becker Underwood獲得));(B2.50)哈茨木黴,菌株ITEM 908 (例如來自Koppert之Trianum-P);(B2.51)哈茨木黴,菌株TH35 (例如由Mycontrol獲得之Root-Pro);(B2.52) 綠木黴菌屬(Trichoderma
)(亦被稱為黏綠膠黴菌(Gliocladium virens)
),詳言之菌株GL-21 (例如美國Certis之SoilGard 12G);(B2.53)綠木黴菌,菌株TV1(例如Koppert之Trianum-P);(B2.54) 白粉寄生孢(Ampelomyces quisqualis
),詳言之菌株AQ 10 (例如IntrachemBio Italia之AQ10®
);(B2.56)出芽短梗黴菌(Aureobasidium pullulans
),詳言之菌株DSM 14940之芽生孢子;(B2.57)出芽短梗黴菌(Aureobasidium pullulans
),詳言之菌株DSM14941之芽生孢子;(B2.58)出芽短梗黴菌,詳言之菌株DSM14940及DSM 14941之芽生孢子的混合物(例如瑞士bio-ferm之Botector®
);(B2.64)枝狀分枝孢子菌屬(Cladosporium cladosporioides
),菌株H39 (Stichting Dienst Landbouwkundig Onderzoek);(B2.69) 鏈抱黏帚菌(Gliocladium catenulatum
) (同義詞:鏈狀粉紅黏帚黴(Clonostachys rosea f . catenulate
)菌株J1446 (例如,AgBio Inc.之Prestop®
以及例如Kemira Agro Oy之Primastop®
);(B2.70) 臘蚧輪刺孢菌(Lecanicillium lecanii
) (以前被稱為蠟蚧輪枝菌(Verticillium lecanii
),菌株KV01之分生孢子(例如,Koppert/Arysta之Vertalec®
);(B2.71)蠕青黴菌;(B2.72)異常畢赤酵母,菌株WRL-076 (NRRL Y-30842);(B2.75)深綠木黴菌,菌株SKT-1 (FERM P-16510);(B2.76)深綠木黴菌,菌株SKT-2 (FERM P-16511);(B2.77)深綠木黴菌,菌株SKT-3 (FERM P-17021);(B2.78)綠木黴菌(以前被稱為綠色木黴(T. viride)
), 菌株ICC080 (IMI CC 392151 CABI, 例如AGROBIOSOL DE MEXICO, S.A. DE C.V.之BioDerma);(B2.79)哈茨木黴,菌株DB 103 (例如Dagutat Biolab之T-Gro 7456);(B2.80)綠木多孢黴菌,菌株IMI 206039 (例如BINAB Bio-Innovation AB, Sweden之Binab TF WP);(B2.81)綠木黴菌(例如Ceplac, Brazil之tricovab);(B2.83) 奧德曼細基格孢(Ulocladium oudemansii
),詳言之菌株HRU3 (例如,紐西蘭Botry-Zen Ltd之Botry-Zen®
);(B2.84)黑白輪枝菌(Verticillium albo-atrum
)(以前稱為大麗輪枝菌(V. dahliae
)),菌株WCS850 (CBS 276.92;例如Tree Care Innovations之Dutch Trig);(B2.86)厚垣輪枝孢菌(Verticillium chlamydosporium)
;(B2.87)棘孢木黴菌株ICC 012及綠木黴菌菌株ICC 080之混合物(如例如來自美國Bayer CropScience LP之BIO-TAMTM
已知之產品)。
可與式(I)化合物及包含其之組合物組合之生物控制劑之其他實例為:
選自由以下組成之群的細菌:蠟狀芽孢桿菌,特別是蠟狀芽孢桿菌菌株CNCM I-1562)及強固芽胞桿菌,菌株I-1582(寄存編號CNCM I-1582)、枯草芽孢桿菌菌株OST 30002(寄存編號NRRL B50421)、蘇雲金芽胞桿菌(尤其蘇力菌亞門菌(血清型H14)),菌株AM65-52(寄存編號ATCC 1276)、蘇雲金芽胞桿菌aizawai
, 尤其菌株ABTS-1857 (SD-1372)、蘇雲金芽胞桿菌kurstaki
菌株HD-1、蘇雲金芽胞桿菌tenebrionis
菌株NB 176 (SD-5428)、穿刺芽孢桿菌(Pasteuria penetrans)
, 穿刺芽孢桿菌菌屬(美國免除農藥巴斯德菌屬(Rotylenchulus reniformis nematode))-PR3 (寄存編號ATCC SD-5834)、細黃鏈黴菌(Streptomyces microflavus)
菌株AQ6121 (= QRD 31.013, NRRL B-50550), 及鮮黃鏈黴 (Streptomyces galbus)
菌株AQ 6047 (寄存編號NRRL 30232);
選自由以下組成之群的真菌及酵母:白殭菌(Beauveria bassiana
),特別是菌株ATCC 74040、輪枝菌屬(Lecanicillium spp
.),特別是菌株HRO LEC 12、黑殭菌屬(Metarhizium anisopliae
),特別是菌株F52(DSM3884或ATCC 90448)、玫菸色擬青黴(Paecilomyces fumosoroseus
)(目前:Isaria fumosorosea),特別是菌株IFPC 200613、或菌株Apopka 97(Accesion 第ATCC 20874號)、及淡紫擬青黴(Paecilomyces lilacinus
),特別是P . lilacinus
菌株251(AGAL 89/030550);
選自由以下組成之群的病毒:茶姬捲葉蛾(Adoxophyes orana
)(夏季水果捲葉蛾)顆粒體病毒(granulosis virus;GV);蘋果蠹蛾(Cydia pomonella
)(蘋果捲葉蛾)顆粒體病毒(GV);番茄夜蛾(Helicoverpa armigera
)(棉鈴蟲)核多角體病毒(NPV);甜菜菜蛾(Spodoptera exigua
)(甜菜夜蛾) mNPV;草地黏蟲(Spodoptera frugiperda
)(秋夜蛾) mNPV;及灰翅夜蛾(Spodoptera littoralis
)(非洲棉葉蟲) NPV。
可以「接種劑」形式添加至植物或植物部分或植物器官且由於其特定特性而有助於植物生長及植物健康的細菌及真菌。實例為:農桿菌屬(Agrobacterium spp .
)、莖瘤固氮根瘤菌(Azorhizobium caulinodans
)、固氮螺旋菌屬(Azospirillum spp .
)、固氮菌屬(Azotobacter spp .
)、慢生根瘤菌屬(Bradyrhizobium spp .
)、伯克霍爾德菌屬(Burkholderia spp .
)(尤其洋蔥伯克霍爾德氏菌(以前稱為洋蔥假單胞菌))、巨孢囊黴屬(Gigaspora spp .
)或單孢球囊黴(Gigaspora monosporum
)、叢枝菌根菌屬(Glomus spp .
)、蠟蘑菌屬(Laccaria spp .
)、布氏乳桿菌(Lactobacillus buchneri
)、類球囊黴屬(Paraglomus spp .
)、彩色豆馬勃(Pisolithus tinctorus
)、假單胞菌屬(Pseudomonas spp .
)、根瘤菌屬(Rhizobium spp .
)(尤其三葉草根瘤菌)、麥蕈屬(Rhizopogon spp .
)、硬皮馬勃屬(Scleroderma spp .
)、兔蕈屬(Suillus spp .
)及鏈黴菌屬(Streptomyces spp .
)。
可用作生物控制劑的包括蛋白質及次級代謝物的植物萃取物及由微生物形成的產物,諸如蒜(Allium sativum
)、中亞苦蒿(Artemisia absinthium
)、印楝素(azadirachtin
)、Biokeeper WP、黑決明(Cassia nigricans
)、苦皮藤(Celastrus angulatus
)、藜屬土荊芥(Chenopodium anthelminticum
)、甲殼素、Armour-Zen、歐洲鱗毛蕨(Dryopteris filix - mas
)、問荊(Equisetum arvense
)、Fortune Aza、薄荷油(Fungastop
)、Heads Up (藜麥(Chenopodium quinoa
)皂素萃取物)、除蟲菊/除蟲菊精(Pyrethrum / Pyrethrins
)、蘇林南苦木(Quassia amara
)、櫟屬(Quercus
)、皂皮樹屬(Quillaja
)、Regalia、「Requiem ™殺昆蟲劑」、魚藤酮、魚尼丁/理阿諾鹼(ryania
/ryanodine)、聚合草(Symphytum officinale
)、菊蒿(Tanacetum vulgare
)、瑞香草酚、Triact 70、TriCon、旱金蓮(Tropaeulum majus
)、異株蕁麻(Urtica dioica
)、藜蘆鹼(Veratrin)、槲寄生(Viscum album
)、十字花科(Brassicaceae
)萃取物,尤其油菜粉或芥末粉。
分別可與式(I)化合物及包含其之組合物混合的殺昆蟲劑、殺蟎劑及殺線蟲劑之實例為:
(1) 乙醯膽鹼酯酶(AChE)抑制劑,諸如胺基甲酸酯類,例如棉靈威(alanycarb)、得滅克(aldicarb)、惡蟲威(bendiocarb)、免扶克(benfuracarb)、丁酮威(butocarboxim)、丁酮碸威(butoxycarboxim)、加保利(carbaryl)、加保扶(carbofuran)、丁基加保扶(carbosulfan)、殺蟲丹(ethiofencarb)、仲丁威(fenobucarb)、複滅蟎(formetanate)、呋線威(furathiocarb)、葉蟬散(isoprocarb)、滅賜克(methiocarb)、納乃得(methomyl)、速滅威(metolcarb)、歐殺滅(oxamyl)、比加普(pirimicarb)、安丹(propoxur)、硫敵克(thiodicarb)、久效威(thiofanox)、唑蚜威(triazamate)、混滅威(trimethacarb)、XMC及滅殺威(xylylcarb);或有機磷酸酯,例如歐殺松(acephate)、亞滅松(azamethiphos)、乙基谷速松(azinphos-ethyl)、甲基谷速松(azinphos-methyl)、硫線磷(cadusafos)、氯氧磷(chlorethoxyfos)、克芬松(chlorfenvinphos)、氯甲磷(chlormephos)、甲基陶斯松(chlorpyrifos-methyl)、蠅毒磷(coumaphos)、殺螟腈(cyanophos)、甲基硫代內吸磷(demeton-S-methyl)、大利松(diazinon)、二氯松(dichlorvos)/DDVP、雙特松(dicrotophos)、大滅松(dimethoate)、甲基毒蟲畏(dimethylvinphos)、二硫松(disulfoton)、EPN、愛殺松(ethion)、普伏松(ethoprophos)、伐滅磷(famphur)、芬滅松(fenamiphos)、撲滅松(fenitrothion)、芬殺松(fenthion)、噻唑磷(fosthiazate)、庚烯磷(heptenophos)、新菸磷(imicyafos)、異柳磷(isofenphos)、O-(甲氧基胺基硫基-磷醯基)水楊酸異丙酯、加福松(isoxathion)、馬拉硫磷(malathion)、滅蚜磷(mecarbam)、達馬松(methamidophos)、滅大松(methidathion)、美文松(mevinphos)、亞素靈(monocrotophos)、二溴磷(naled)、氧樂果(omethoate)、甲基滅多松(oxydemeton-methyl)、甲基巴拉松(parathion-methyl)、賽達松(phenthoate)、福瑞松(phorate)、裕必松(phosalone)、益滅松(phosmet)、福賜米松(phosphamidon)、巴賽松(phoxim)、甲基亞特松(pirimiphos-methyl)、布飛松(profenofos)、巴胺磷(propetamphos)、普硫松(prothiofos)、吡唑硫磷(pyraclofos)、噠嗪硫磷(pyridaphenthion)、喹惡磷(quinalphos)、治螟磷(sulfotep)、丁基嘧啶磷(tebupirimfos)、雙硫磷(temephos)、託福松(terbufos)、樂本松(tetrachlorvinphos)、甲基乙拌磷(thiometon)、三落松(triazophos)、三氯松(triclorfon)及蚜滅多(vamidothion)。
(2) GABA閘控氯離子通道阻斷劑,諸如環戊二烯-有機氯類,例如氯丹(chlordane)及安殺番(endosulfan)或苯基吡唑(非潑羅(fiproles)),例如乙蟲清(ethiprole)及費普尼(fipronil)。
(3) 鈉通道調節劑,諸如擬除蟲菊酯類,例如阿納寧(acrinathrin)、丙烯除蟲菊酯(allethrin)、d-順式反式丙烯菊酯、d-反式丙烯菊酯、畢芬寧(bifenthrin)、生物丙烯菊酯、S-環戊烯基生物丙烯菊酯異構體、苄呋菊脂(bioresmethrin)、乙氰菊脂(cycloprothrin)、賽扶寧(cyfluthrin)、β-賽扶寧、賽洛寧(cyhalothrin)、λ-賽洛寧、γ-賽洛寧、賽滅寧(cypermethrin)、α-賽滅寧、β-賽滅寧、θ-賽滅寧、ξ-賽滅寧、賽酚寧[(1R)-反式異構體]、第滅寧(deltamethrin)、烯炔菊酯[(EZ)-(1R)-異構體]、益化利(esfenvalerate)、依芬寧(etofenprox)、芬普寧(fenpropathrin)、芬化利(fenvalerate)、護賽寧(flucythrinate)、氟氯苯菊酯(flumethrin)、τ-福化利(tau-fluvalinate)、苄蟎醚(halfenprox)、依普寧(imiprothrin)、噻嗯菊酯(kadethrin)、甲氧苄氟菊酯(momfluorothrin)、百滅寧(permethrin)、苯醚菊酯[(1R)-反式異構體]、普亞列寧(prallethrin)、除蟲菊精(除蟲菊)、苄呋菊脂(resmethrin)、矽護芬(silafluofen)、七氟菊酯(tefluthrin)、治滅寧(tetramethrin)、治滅寧[(1R)-異構體]、泰滅寧(tralomethrin)及拜富寧(transfluthrin)或DDT或甲氧滴滴涕(methoxychlor)。
(4) 菸鹼乙醯膽鹼受體(nAChR)競爭性調節劑,諸如新菸鹼類似物類,例如啶蟲脒(acetamiprid)、可尼丁(clothianidin)、呋蟲胺(dinotefuran)、吡蟲啉(imidacloprid)、烯啶蟲胺(nitenpyram)、噻蟲啉(thiacloprid)及噻蟲嗪(thiamethoxam)或菸鹼或氟啶蟲胺腈(sulfoxaflor)或氟吡呋喃酮(flupyradifurone)。
(5) 菸鹼乙醯膽鹼受體(nAChR)異位調節劑,諸如賜諾殺類(spinosyn),例如斯平托蘭(spinetoram)及賜諾殺(spinosad)。
(6) 麩胺酸閘控氯離子通道(GluCl)異位調節劑,諸如阿維菌素類(avermectin)/米爾倍黴素類(milbemycin),例如阿巴汀(abamectin)、因滅汀苯甲酸酯(emamectin benzoate)、林皮沒丁(lepimectin)及密滅汀(milbemectin)。
(7) 青少年激素模擬物,諸如青少年激素類似物,例如烯蟲乙酯(hydroprene)、烯蟲炔酯(kinoprene)及美賜平(methoprene)或芬諾克(fenoxycarb)或百利普芬(pyriproxyfen)。
(8) 各種非特異性(多位點)抑制劑,諸如烷基鹵化物,例如溴化甲烷及其他烷基鹵化物;或氯化苦或磺醯氟或硼砂或牙垢催吐劑或異氰酸甲酯產生劑,例如必速滅(diazomet)及威百畝(metam)。
(9) 弦音器官(Chordotonal Organs)之調節劑,諸如派滅淨(pymetrozine)或氟啶蟲醯胺(flonicamid)。
(10) 蟎生長抑制劑,諸如克芬蟎(clofentezine)、合賽多(hexythiazox)及氟蟎嗪(diflovidazin)或依殺蟎(etoxazole)。
(11) 昆蟲腸膜之微生物瓦解劑,諸如蘇力菌以色列亞種、枯草芽孢桿菌、蘇力菌亞莎華亞種、蘇力菌庫斯塔克亞種、蘇力菌擬步行甲亞種亞種及B.t.植物蛋白:Cry1Ab、Cry1Ac、Cry1Fa、Cry1A.105、Cry2Ab、Vip3A、mCry3A、Cry3Ab、Cry3Bb、Cry34Ab1/35Ab1。
(12) 粒線體ATP合成酶之抑制劑,諸如ATP瓦解劑,諸如汰芬諾克(diafenthiuron)或有機錫化合物,例如三唑錫(azocyclotin)、錫蟎丹(cyhexatin)及芬布錫(fenbutatin oxide)或毆蟎多(propargite)或四氯殺蟎碸(tetradifon)。
(13) 經由破壞質子梯度氧化磷酸化之去偶合劑,諸如克凡派(chlorfenapyr)、DNOC及氟蟲胺(sulfluramid)。
(14) 菸鹼乙醯膽鹼受體通道阻斷劑,諸如殺蟲磺(bensultap)、培丹鹽酸鹽(cartap hydrochloride)、硫賜安(thiocylam)及殺蟲雙鈉(thiosultap-sodium)。
(15) 甲殼素生物合成之抑制劑,0型,諸如雙三氟蟲脲(bistrifluron)、克福隆(chlorfluazuron)、二福隆(diflubenzuron)、氟環脲(flucycloxuron)、氟芬隆(flufenoxuron)、六伏隆(hexaflumuron)、祿芬隆(lufenuron)、諾伐隆(novaluron)、多氟脲(noviflumuron)、得福隆(teflubenzuron)及三福隆(triflumuron)。
(16) 甲殼素生物合成之抑制劑,1型,例如布芬淨(buprofezin)。
(17) 脫皮干擾劑(特別是用於雙翅目,亦即雙翅目昆蟲),諸如賽滅淨(cyromazine)。
(18) 蛻皮激素受體促效劑,諸如環蟲醯肼(chromafenozide)、合芬隆(halofenozide)、滅芬諾(methoxyfenozide)及得芬諾(tebufenozide)。
(19) 章魚胺受體促效劑,諸如三亞蟎(amitraz)。
(20) 粒線體複合物III電子傳輸抑制劑,諸如伏蟻腙(hydramethylnone)或亞醌蟎(acequinocyl)或嘧蟎酯(fluacrypyrim)。
(21) 粒線體複合物I電子傳輸抑制劑,諸如來自METI殺蟎劑之群,例如芬殺蟎(fenazaquin)、芬普蟎(fenpyroximate)、嘧蟎醚(pyrimidifen)、比達本(pyridaben)、得芬瑞(tebufenpyrad)及脫芬瑞(tolfenpyrad)或魚藤酮(rotenone)(魚藤(Derris))。
(22) 電壓依賴性鈉通道阻斷劑,諸如因得克(indoxacarb)或氰氟蟲胺(metaflumizone)。
(23) 乙醯CoA羧化酶之抑制劑,諸如特窗酸(tetronic acid)及特特拉姆酸(tetramic acid)衍生物,例如賜派芬(spirodiclofen)、螺甲蟎酯(spiromesifen)及螺蟲乙酯(spirotetramat)。
(24) 粒線體錯合物IV電子傳輸抑制劑,諸如膦,例如磷化鋁、磷化鈣、膦及磷化鋅;或氰化物,例如氰化鈣、氰化鉀及氰化鈉。
(25) 粒線體複合物II電子傳輸抑制劑,諸如β-開托利(beta-ketonitrile)衍生物,例如腈吡蟎酯(cyenopyrafen)及丁氟蟎酯(cyflumetofen),及甲苯胺類,諸如吡氟蟎酯(pyflubumide)。
(28) 理阿諾鹼受體調節劑,諸如二醯胺類,例如氯蟲苯甲醯胺(chlorantraniliprole)、氰強尼普羅(cyantraniliprole)及氟蟲雙醯胺(flubendiamide),
其他活性化合物,諸如雙丙環蟲酯(Afidopyropen)、阿福拉納(Afoxolaner)、印楝素(Azadirachtin)、苯氯噻(Benclothiaz)、苯蟎特(Benzoximate)、畢芬載(Bifenazate)、溴蟲氟苯雙醯胺(Broflanilide)、溴蟎酯(Bromopropylate)、蟎離丹(Chinomethionat)、右旋反式氯丙炔菊酯(Chloroprallethrin)、冰晶石(Cryolite)、右旋反式氯丙炔菊酯(Cyclaniliprole)、環氧蟲啶(Cycloxaprid)、氯氟氰蟲醯胺(Cyhalodiamide)、二氯加士(Dicloromezotiaz)、開樂散(Dicofol)、ε-甲氧苄氟菊酯(epsilon-Metofluthrin)、ε-單氟菊酯(ε-Momfluthrin)、孚蟎喹(Flometoquin)、三氟咪啶醯胺(Fluazaindolizine)、氟噻蟲碸(Fluensulfone)、氟芬內林(Flufenerim)、氟菌蟎酯(Flufenoxystrobin)、丁蟲腈(Flufiprole)、福薩豐(Fluhexafon)、氟吡菌醯胺(Fluopyram)、弗拉拉納(Fluralaner)、氣釀醯胺(Fluxametamide)、呋喃蟲醯肼(Fufenozide)、戊吡蟲胍(Guadipyr)、右旋七氟甲醚菊酯(Heptafluthrin)、氯噻啉(Imidaclothiz)、依普同(Iprodione)、κ-畢芬寧(kappa-Bifenthrin)、κ-七氟菊酯(kappa-Tefluthrin)、洛替拉納(Lotilaner)、氯氟醚菊酯(Meperfluthrin)、哌蟲啶(Paichongding)、啶蟲丙醚(Pyridalyl)、哌氟喹腙(Pyrifluquinazon)、嘧蟎胺(Pyriminostrobin)、螺蝴雙醋(Spirobudiclofen)、四氟醚菊酯(Tetramethylfluthrin)、氟氰蟲醯胺(Tetraniliprole)、四氯蟲醯胺(Tetrachlorantraniliprole)、泰格藍喏(Tigolaner)、硫噁唑芬(Tioxazafen)、硫氟肟醚(Thiofluoximate)、三氟苯嘧啶(Triflumezopyrim)及碘甲烷(iodomethane);其他基於強固芽胞桿菌(Bacillus firmus
)之製劑(I-1582, BioNeem, Votivo),亦及以下混合物:1-{2-氟-4-甲基-5-[(2,2,2-三氟乙基)亞碸基]苯基}-3-(三氟甲基)-1H-1,2,4-三唑-5-胺 (由WO2006/043635已知) (CAS 885026-50-6)、{1'-[(2E)-3-(4-氯苯基)丙-2-烯-1-基]-5-氟螺[吲哚-3,4'-哌啶]-1(2H)-基}(2-氯吡啶-4-基)乙酮 (由WO2003/106457已知) (CAS 637360-23-7)、2-氯-N-[2-{1-[(2E)-3-(4-氯苯基)丙-2-烯-1-基]哌啶-4-基}-4-(三氟甲基)苯基]異菸醯胺(由WO2006/003494已知) (CAS 872999-66-1)、3-(4-氯-2,6-二甲基苯基)-4-羥基-8-甲氧基-1,8-二氮螺[4.5]癸-3-烯-2-酮(由WO 2010052161已知) (CAS 1225292-17-0)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-2-側氧基-1,8-二氮螺[4.5]癸-3-烯-4-基乙基碳酸(由EP2647626已知) (CAS 1440516-42-6)、4-(丁基-2-炔-1-基氧基)-6-(3,5-二甲基哌啶-1-基)-5-氟嘧啶 (由WO2004/099160已知) (CAS 792914-58-0)、PF1364 (由JP2010/018586已知) (CAS 1204776-60-2)、N-[(2E)-1-[(6-氯吡啶-3-基)甲基]吡啶-2(1H)-亞基]-2,2,2-三氟乙醯胺 (由WO2012/029672已知) (CAS 1363400-41-2)、(3E)-3-[1-[(6-氯-3-吡啶基)甲基]-2-亞吡啶基]-1,1,1-三氟-丙烷-2-酮 (由WO2013/144213已知) (CAS 1461743-15-6)、N-[3-(苄基苯甲醯基)-4-氯苯基]-1-甲基-3-(五氟乙基)-4-(三氟甲基)-1H-吡唑-5-甲醯胺 (由WO2010/051926已知) (CAS 1226889-14-0)、5-溴-4-氯-N-[4-氯-2-甲基-6-(甲基苯甲醯基)苯基]-2-(3-氯-2-吡啶基)吡唑-3-甲醯胺 (由CN103232431已知) (CAS 1449220-44-3)、4-[5-(3,5-二氯苯基)-4,5-二氫-5-(三氟甲基)-3-異噁唑基]-2-甲基-N-(順-1-氧-3-硫化丙烯)-苄醯胺、4-[5-(3,5-二氯苯基)-4,5-二氫-5-(三氟甲基)-3-異噁唑基]-2-甲基-N-(反-1-氧-3-硫化丙烯)-苄醯胺及4-[(5S)-5-(3,5-二氯苯基)-4,5-二氫-5-(三氟甲基)-3-異噁唑基]-2-甲基-N-(反-1-氧-3-硫化丙烯)苄醯胺 (由WO 2013/050317 A1已知) (CAS 1332628-83-7)、N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亞碸基]-丙烷醯胺、(+)-N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亞碸基]-丙烷醯胺及(-)-N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亞碸基]-丙烷醯胺 (由WO 2013/162715 A2、WO 2013/162716 A2、US 2014/0213448 A1已知) (CAS 1477923-37-7)、5-[[(2E)-3-氯-2-丙烯-1-基]胺基]-1-[2,6-二氯-4-(三氟甲基)苯基]-4-[(三氟甲基)亞碸基]-1H-吡唑-3-甲腈(由CN 101337937 A已知) (CAS 1105672-77-2)、3-溴-N-[4-氯-2-甲基-6-[(甲基胺基)硫酮基甲基]苯基]-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲醯胺、(Liudaibenjiaxuanan、由CN 103109816 A已知) (CAS 1232543-85-9);N-[4-氯-2-[[(1,1-二甲基乙基)胺基]羰基]-6-甲基苯基]-1-(3-氯-2-吡啶基)-3-(氟甲氧基)-1H-吡唑-5-甲醯胺 由WO 2012/034403 A1已知) (CAS 1268277-22-0)、N-[2-(5-胺基-1,3,4-噻二唑-2-基)-4-氯-6-甲基苯基]-3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲醯胺 (由WO 2011/085575 A1已知) (CAS 1233882-22-8)、4-[3-[2,6-二氯-4-[(3,3-二氯-2-丙烯-1-基)氧基]苯氧基]丙氧基]-2-甲氧基-6-(三氟甲基)-嘧啶 (由CN 101337940 A已知) (CAS 1108184-52-6);(2E)-及2(Z)-2-[2-(4-氰基苯基)-1-[3-(三氟甲基)苯基]亞乙基]-N-[4-(二氟甲氧基)苯基]-肼甲醯胺 (由CN 101715774 A已知) (CAS 1232543-85-9);3-(2,2-二氯乙烯基)-2,2-二甲基-4-(1H-苯并唑-2-基)苯基-環丙烷羧酸酯(由CN 103524422 A)已知 (CAS 1542271-46-4);(4aS)-7-氯-2,5-二氫-2-[[(甲氧基羰基)[4-[(三氟甲基)硫基]苯基]胺基]羰基]-茚 [1,2-e][1,3,4]氧雜二嗪-4a(3H)-羧酸甲酯(由CN 102391261 A已知) (CAS 1370358-69-2);6-癸氧-3-O-乙基-2,4-二-O-甲基-、1-[N-[4-[1-[4-(1,1,2,2,2-五氟乙氧基)苯基]-1H-1,2,4-三唑-3-基]苯基]胺基甲酸酯]-α-L-甘露糖(由US 2014/0275503 A1已知) (CAS 1181213-14-8);8-(2-環丙基甲氧基-4-三氟甲基-苯氧基)-3-(6-三氟甲基-噠嗪-3-基)-3-氮雜-二環[3.2.1 ]辛烷 (CAS 1253850-56-4)、(8-逆)-8-(2-環丙基甲氧基-4-三氟甲基-苯氧基)-3-(6-三氟甲基-噠嗪-3-基)-3-氮雜-二環[3.2.1 ]辛烷 (CAS 933798-27-7)、(8-同)-8-(2-環丙基甲氧基-4-三氟甲基-苯氧基)-3-(6-三氟甲基-噠嗪-3-基)-3-氮雜-二環[3.2.1 ]辛烷 (由WO 2007040280 A1、WO 2007040282 A1已知) (CAS 934001-66-8)、N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)硫基]-丙烷醯胺 (由WO 2015/058021 A1、WO 2015/058028 A1已知) (CAS 1477919-27-9)及N-[4-(胺基硫酮基甲基)-2-甲基-6-[(甲基胺基)羰基]苯基]-3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲醯胺 (由CN 103265527 A已知) (CAS 1452877-50-7)、5-(1,3-二噁-2-基)-4-[[4-(三氟甲基)苯基]甲氧基]-嘧啶 (由WO 2013/115391 A1已知) (CAS 1449021-97-9)、3-(4-氯-2,6-二甲基苯基)-4-羥基-8-甲氧基-1-甲基-1,8-二氮螺[4.5]癸-3-烯-2-酮 (由WO 2010/066780 A1、WO 2011/151146 A1已知) (CAS 1229023-34-0)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-1-甲基-1,8-二氮螺[4.5]癸烷-2,4-二酮 (由WO 2014/187846 A1已知) (CAS 1638765-58-8)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-1-甲基-2-氧-1,8-二氮螺[4.5]癸-3-烯-4-基-乙基碳酸酯 (由WO 2010/066780 A1、WO 2011151146 A1已知) (CAS 1229023-00-0)、N-[1-[(6-氯-3-吡啶基)甲基]-2(1H)-吡啶亞基]-2,2,2-三氟-乙醯胺 (由DE 3639877 A1、WO 2012029672 A1已知) (CAS 1363400-41-2)、[N(E)]-N-[1-[(6-氯-3-吡啶基)甲基]-2(1H)-吡啶亞基]-2,2,2-三氟-乙醯胺、(由WO 2016005276 A1已知) (CAS 1689566-03-7)、[N(Z)]-N-[1-[(6-氯-3-吡啶基)甲基]-2(1H)-吡啶亞基]-2,2,2-三氟-乙醯胺、(CAS 1702305-40-5)、3-內-3-[2-丙氧基4-(三氟甲基)苯氧基]-9-[[5-(三氟甲基)-2-吡啶基]氧基]-9-氮雜二環[3.3.1]壬烷(由WO 2011/105506 A1、WO 2016/133011 A1已知) (CAS 1332838-17-1)。
可與式(I)化合物及包含其之組合物混合的安全劑之實例為:例如解草酮(benoxacor)、(庚基)解毒喹(cloquintocet)、解草胺腈(cyometrinil)、環丙磺醯胺、二氯丙烯胺、(乙基)解草唑(fenchlorazole)、解草啶(fenclorim)、解草安(flurazole)、肟草安(fluxofenim)、呋喃解草唑(furilazole)、雙苯噁唑酸(isoxadifen(-ethyl))、吡唑解草酯(mefenpyr(-diethyl))、萘二甲酸酐、解草腈(oxabetrinil)、2-甲氧基-N-({4-[(甲基胺甲醯基)胺基]苯基}磺醯基)苯甲醯胺(CAS 129531-12-0)、4-(二氯乙醯基)-1-氧雜-4-氮雜螺[4.5]癸烷(CAS 71526-07-3)、2,2,5-三甲基-3-(二氯乙醯基)-1,3-噁唑啶(CAS 52836-31-4)。
可與式(I)化合物及包含其之組合物混合的殺草劑之實例為:
乙草胺、三氟羧草醚、三氟羧草醚鈉、苯草醚、甲草胺、草毒死、禾草滅、禾草滅鈉、莠滅淨、胺唑草酮、先甲草胺、醯嘧磺隆、4-胺基-3-氯-6-(4-氯-2-氟-3-甲基苯基)-5-氟吡啶-2-羧酸、環丙嘧啶酸、環丙嘧啶酸鉀、甲基環丙嘧啶酸、氯胺吡啶酸、殺草強、胺基磺酸銨、莎稗磷、黃草靈、莠去津、草芬定、四唑嘧磺隆、氟丁醯草胺、草除靈、乙基草除靈、氟草胺、呋草磺、苄嘧磺隆、甲基苄嘧磺隆、地散磷、滅草松、苯并雙環酮、吡草酮、雙環比隆、必芬諾、畢拉草、畢拉草鈉、雙草醚、雙草醚鈉、除草定、溴丁醯草胺、殺草全、溴苯腈、丁酸溴苯腈、-鉀、-庚酸鹽、及-辛酸鹽、羥草酮、丁草胺、氟丙嘧草酯、抑草磷、丁烯草胺、比達甯、丁苯草酮、丁草敵、唑草胺、長殺草、克繁草、乙基克繁草、克爛本、氯溴隆、伐草克、伐草克鈉、燕麥酯、氯甲丹、甲基氯甲丹、氯草敏、氯嘧磺隆、乙基氯嘧磺隆、chlorophthalim、綠麥隆、二甲基敵草索、氯磺隆、吲哚酮草酯、乙基吲哚酮草酯、環庚草醚、醚磺隆、氯醯草膦、克草同、炔草酸、炔丙基炔草酸、可滅蹤、稗草胺、畢克草、氯酯磺草胺、甲基氯酯磺草胺、苄草隆、氰胺、氰草津、環草敵、cyclopyrimorate、環磺隆、環殺草、氰氟草酯、氰氟草酯、環草津、2,4-D、2,4-D-丁氧基乙基、-丁基、-二甲胺、-diolamin、-乙基、-2-乙基己基、-異丁基、-異辛基、-異丙銨、-鉀、-三異丙銨、及-三乙醇胺、2,4-DB、2,4-DB-丁基、-二甲胺、-異辛基、-鉀、及-鈉、殺草隆(daimuron)(殺草隆(dymron))、茅草枯、邁隆、正癸醇、甜菜安、detosyl-吡唑特(DTP)、麥草畏、敵草腈、2-(2,4-二氯苄基)-4,4-二甲基-1,2-噁唑啶-3-酮、2-(2,5-二氯苄基)-4,4-二甲基-1,2-噁唑啶-3-酮、2,4-滴丙酸、2,4-滴丙酸-P、禾草靈、甲基禾草靈、禾草靈-P-甲基、雙氯磺草胺、苯敵快、吡氟草胺、二氟吡隆、二氟吡隆鈉、噁唑隆、哌草丹、二甲草胺、異戊乙淨、二甲噻草胺、二甲噻草胺-P、dimetrasulfuron、敵樂胺、特樂酚、草乃敵、敵草快、敵草快-二溴、氟硫草定、達有龍、DNOC、草多索、EPTC、戊草丹、乙丁烯氟靈、胺苯磺隆、甲基胺苯磺隆、乙嗪草酮、乙呋草黃、氯氟草醚、乙基氯氟草醚、乙氧嘧磺隆、乙氧苯草胺、 F-9600、F-5231,亦即正{2-氯-4-氟-5-[4-(3-氟丙基)-5-側氧基-4,5-二氫-1H-四唑-1-基]苯基}乙磺醯胺、F-7967,亦即3-[7-氯-5-氟基-2-(三氟甲基)-1H-苯并咪唑-4-基]-1-甲基-6-(三氟甲基)嘧啶-2,4(1H,3H)-二酮、噁唑禾草靈、噁唑禾草靈-P、乙基噁唑禾草靈、噁唑禾草靈-P-乙基、異噁苯碸、芬昆諾三酮、四唑醯草胺、氟燕靈、異丙基高效麥草伏、甲基高效麥草伏、嘧啶磺隆、雙氟磺草胺、吡氟禾草靈、吡氟禾草靈-P、丁基吡氟禾草靈、吡氟禾草靈-P-丁基、氟酮磺隆、氟酮磺隆鈉、氟吡磺隆、氟消草、氟噻草胺、氟噠嗪草酯、乙基氟噠嗪草酯、唑嘧磺草胺、氟胺草酯、戊基氟胺草酯、丙炔氟草胺、伏草隆、抑草丁、丁基抑草丁、-二甲胺及-甲基、乙羧氟草醚、乙基乙羧氟草醚、四氟丙酸、氟啶嘧磺隆、氟啶嘧磺隆-甲基-鈉、氟啶草酮、氟咯草酮、氟草定、甲基氟草定、呋草酮、氟噻草酯、甲基氟噻草酯、氟磺胺草醚、氟磺胺草醚鈉、甲醯嘧磺隆、殺木膦、草銨膦(glufosinate)、草銨膦(glufosinate-ammonium)、草銨膦-P-鈉、草銨膦-P-銨、草銨膦-P-鈉、草甘膦、草甘膦-銨、-異丙銨、-二銨、-二甲胺、-鉀、-鈉、及-三甲基硫、H-9201,亦即O-(2,4-二甲基-6-硝苯)O-乙基異丙基硫代磷醯胺酯、氟氯吡啶酯、甲基氟氯吡啶酯、氟硝磺醯胺、氯吡嘧磺隆、甲基氯吡嘧磺隆、吡氟氯禾靈、吡氟氯禾靈-P、乙氧基乙基吡氟氯禾靈、吡氟氯禾靈-P-乙氧基乙基、甲基吡氟氯禾靈、吡氟氯禾靈-P-甲基、六嗪同、HW-02,亦即1-(二甲氧基磷醯基)乙基-(2,4-二氯苯氧基)乙酸、咪草酸、甲基咪草酸、甲氧咪草菸、甲氧咪草菸-銨、甲基咪草菸、甲基咪草菸-銨、依滅草、依滅草-異丙銨、滅草喹、滅草喹-銨、咪草菸、咪草菸-亞胺鎓、唑吡嘧磺隆、茚草酮、茚嗪氟草胺、碘甲磺隆、碘甲磺隆-甲基-鈉、碘苯腈、碘苯腈-辛酸鹽、-鉀及-鈉、艾分卡巴腙、異丙隆、異惡隆、異噁草胺、異噁唑草酮、卡草靈、KUH-043,亦即3-({[5-(二氟甲基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-基]甲基}磺醯基)-5,5-二甲基-4,5-二氫-1,2-噁唑、ketospiradox、乳氟禾草靈、環草定、利谷隆、MCPA、丁氧基乙基MCPA、-二甲胺、-2-乙基己基、-異丙銨、-鉀、及-鈉、MCPB、MCPB-甲基、-乙基、及-鈉、甲氯丙酸、甲氯丙酸-鈉、及-丁氧基乙基、甲氯丙酸-P、甲氯丙酸-P-丁氧基乙基、-二甲胺、-2-乙基己基、及-鉀、苯噻醯草胺、氟磺醯草胺、甲基二磺隆、甲基二磺隆-甲基、甲基磺草酮、甲基苯噻隆、威百畝、噁唑醯草胺、苯嗪草酮、吡草胺、雙醚氯吡嘧磺隆、甲基苯噻隆、甲硫嘧磺隆、methiozolin、異硫氰酸甲酯、溴谷隆、異丙甲草胺、S-異丙甲草胺、磺草唑胺、甲氧隆、賽克津、甲磺隆、甲基甲磺隆、molinat、綠谷隆、單嘧磺隆、單嘧磺隆-酯、MT-5950,亦即N-(3-氯-4-異丙基苯基)-2-甲基戊醯胺、NGGC-011、敵草胺、NC-310,亦即[5-(苯甲氧基)-1-甲基-1H-吡唑-4-基](2,4-二氯苯基)甲酮、草不隆、菸嘧磺隆、壬酸(天竺葵酸)、達草滅、油酸(脂肪酸)、坪草丹、嘧苯胺磺隆、氨磺樂靈、丙炔噁草酮、噁草酮、環氧嘧磺隆、oxaziclomefon、乙氧氟草醚、巴拉割、二氯化巴拉割、克草猛、二甲戊樂靈、平速爛、pentachlorphenol、環戊噁草酮、烯草胺、石油油、甜菜寧、胺氯吡啶酸、氟吡草胺、唑啉草酯、哌草磷、丙草胺、氟嘧磺隆、甲基氟嘧磺隆、氨基丙氟靈、環苯草酮、撲滅通、撲草淨、撲草胺、敵稗、噁草酸、撲滅津、苯胺靈、異丙草胺、丙苯磺隆、丙苯磺隆鈉、丙嘧磺隆、戊炔草胺、苄草丹、氟磺隆、雙唑草腈、吡草醚、乙基吡草醚、磺醯草吡唑、吡唑特(pyrazolynate)(吡唑特(pyrazolate))、吡嘧磺隆、乙基吡嘧磺隆、苄草唑、草醚、異丙基草醚、丙基草醚、嘧啶肟草醚、稗草丹、吡啶達醇、噠草特、環酯草醚、嘧草醚、甲基嘧草醚、嘧啶硫蕃、嘧硫草醚、嘧硫草醚鈉、碸吡草唑、甲氧磺草胺、二氯喹啉酸、喹草酸、莫克草、快伏草、乙基快伏草、快伏草-P、快伏草-P-乙基、喹禾糠酯、碸嘧磺隆、苯嘧磺草胺、西殺草、環草隆、草滅淨、西草淨、SL-261、sulcotrion、甲磺草胺、甲嘧磺隆、甲基甲嘧磺隆、磺醯磺隆、SYN-523、SYP-249,亦即1-乙氧基-3-甲基-1-側氧基丁-3-烯-2-基5-[2-氯-4-(三氟甲基)苯氧基]-2-硝基苯甲酸酯、SYP-300,亦即1-[7-氟基-3-側氧基-4-(丙-2-炔-1-基)-3,4-二氫-2H-1,4-苯并噁嗪-6-基]-3-丙基-2-硫代咪唑啶-4,5-二酮、2,3,6-TBA、TCA(三氯乙酸)、TCA-鈉、得匍隆、特呋喃隆、環磺酮、吡喃草酮、特草定、特草靈、甲氧去草淨、草淨津、去草淨、甲氧噻草胺、噻草定、噻酮磺隆、甲基噻酮磺隆、噻吩磺隆、甲基噻吩磺隆、禾草丹、替艾芬斯、托拉唑胺、苯吡唑草酮、肟草酮、氟酮磺草胺、三-allate、醚苯磺隆、三嗪氟草胺、苯磺隆、甲基苯磺隆、綠草定、草達津、三氟啶磺隆、三氟啶磺隆鈉、三氟草嗪、氟樂靈、氟胺磺隆、甲基氟胺磺隆、三氟甲磺隆、硫酸脲、滅草敵、XDE-848、ZJ-0862,亦即3,4-二氯-正{2-[(4,6-二甲氧基嘧啶-2-基)伸氧基]苄基}苯胺、及以下化合物:
植物生長調節劑之實例為:
活化酯、活化酯-S-甲基、5-胺基乙醯丙酸、嘧啶醇、6-苄基胺基嘌呤、芸苔素內酯(Brassinolid)、兒茶素(catechine)、氯化克美素(chlormequat chloride)、坐果安(cloprop)、環丙酸醯胺(cyclanilide)、3-(環丙-1-烯基)丙酸、丁醯肼(daminozide)、邁隆(dazomet)、正癸醇、敵草克(dikegulac)、敵草克鈉(dikegulac-sodium)、草多索(endothal)、草多索二鉀(endothal-dipotassium)、草多索二鈉及草多索單(N,N-二甲基烷基銨)、益收生長素(ethephon)、氟節胺(flumetralin)、抑草丁(flurenol)、抑草丁丁酯(flurenol-butyl)、調嘧醇(flurprimidol)、氯吡脲(forchlorfenuron)、赤黴酸、依納素(inabenfide)、吲哚-3-乙酸(IAA)、4-吲哚-3-基丁酸、稻瘟靈(isoprothiolane)、撲殺熱、茉莉酸、順丁烯二醯肼、縮節胺(mepiquat chloride)、1-甲基環丙稀、茉莉酸甲酯、2-(1-萘基)乙醯胺、1-萘基乙酸、2-萘氧基乙酸、硝基酚鹽混合物、巴克素(paclobutrazol)、N-(2-苯乙基)-β-丙胺酸、N-苯基鄰胺甲醯苯甲酸、調環酸(prohexadione)、調環酸鈣(prohexadione-calcium)、茉莉酮(prohydrojasmone)、水楊酸、獨腳金內酯(strigolactone)、四氯硝基苯(tecnazene)、噻苯隆(thidiazuron)、三十烷醇(triacontanol)、抗倒酯(trinexapac)、抗倒乙酯(trinexapac-ethyl)、斯脫得(tsitodef)、烯效唑(uniconazole)、烯效唑-P(uniconazole-P)。
方法及用途
式(I)化合物及包含其之組合物具有強殺微生物活性及/或植物防禦調節潛力。其可用於控制非所需微生物,諸如非所需真菌及細菌。如本文下文中更詳細地描述,其可尤其適用於作物保護(其控制引起植物病害之微生物)或尤其適用於保護材料(例如,工業材料、木材、儲存貨物)。更具體言之,式(I)化合物及包含其之組合物可用以保護種子、發芽植物、所冒出苗木、植物、植物部分、果實、收穫物及/或植物生長之土壤免受非所需微生物傷害。
如本文所用,控制(control/controlling)涵蓋不合需要之微生物之保護性、治癒性及根除性處理。非所需微生物可為病原性細菌、病原性病毒、病原性卵菌或病原性真菌,更具體言之可為植物病原性細菌、植物病原性病毒、植物病原性卵菌或植物病原性真菌。如本文下文中所詳細描述,此等植物病原性微生物係廣泛範圍之植物病害之致病原因。
更特別地,式(I)化合物及包含其之組合物可用作殺真菌劑。出於本說明書之目的,術語「殺真菌劑」係指可用於作物保護以供控制非所需真菌(諸如根腫菌(Plasmodiophoromycetes)、壺菌(Chytridiomycetes)、接合菌(Zygomycetes)、子囊菌(Ascomycetes)、擔子菌(Basidiomycetes)及半知菌(Deuteromycetes))及/或控制卵菌(Oomycetes)的化合物或組合物。
式(I)化合物及包含其之組合物亦可用作抗細菌劑。詳言之,其可適用於作物保護,例如用於控制非所需細菌,諸如假單胞菌科、根瘤菌科、黃單胞菌科、腸內菌科、棒狀桿菌科及鏈絲菌科。
式(I)化合物及包含其之組合物亦可用作作物保護中的抗病毒劑。舉例而言,式(I)化合物及包含其之組合物可對植物病毒引起之病害有效,該等植物病毒諸如菸草嵌紋病毒(TMV)、菸草脆裂病毒(tobacco rattle virus)、菸草矮化病毒(TStuV)、菸草捲葉病毒(VLCV)、菸草脈葉藍嵌紋病毒(TVBMV)、菸草壞死性矮縮病毒(TNDV)、菸草條紋病毒(TSV)、馬鈴薯病毒X (PVX)、馬鈴薯病毒Y、馬鈴薯病毒S、馬鈴薯病毒M及馬鈴薯病毒A、馬鈴薯奧古巴嵌紋病毒(potato acuba mosaic virus;PAMV)、馬鈴薯帚頂病毒(PMTV)、馬鈴薯捲葉病毒(PLRV)、苜蓿花葉病毒(AMV)、胡瓜嵌紋病毒(CMV)、胡瓜綠色斑駁花葉病毒(CGMMV)、胡瓜黃化病毒(CuYV)、西瓜嵌紋病毒(WMV)、番茄斑萎病毒(TSWV)、番茄輪點病毒(TomRSV)、甘蔗嵌紋病毒(SCMV)、水稻矮縮病毒、水稻條斑病毒、水稻黑條矮縮病毒、草莓斑紋病毒(SMoV)、草莓鑲脈病毒(SVBV)、草莓輕度黃邊病毒(SMYEV)、草莓連葉病毒(SCrV)、蠶豆萎凋病毒(BBWV)及甜瓜壞死性斑點病毒(MNSV)。
本發明亦係關於一種用於控制非所需微生物,諸如非想要之真菌、卵菌及細菌之方法,該方法包含以下步驟:將至少一種式(I)化合物或至少一種本發明之組合物施加至植物、植物部分、種子、果實或施加至植物生長的土壤。
通常,當式(I)化合物及包含其之組合物用於治癒性或保護性方法以控制植物病原性真菌及/或植物病原性卵菌時,將其有效量及植物可相容量施加至植物、植物部分、果實、種子或施加至植物生長的土壤或基質。可用於培育植物之適合基質包括基於無機物之基質,諸如礦棉,尤其岩棉、珍珠岩、砂或礫石;有機基質,諸如泥炭、松樹皮或鋸屑;及基於石油之基質,諸如聚合泡沫或塑料珠粒。有效量及植物可相容量意謂足以控制或毀壞耕地上存在或易在耕地上出現的真菌,且不會引起該等作物之任何顯著的植物毒性症狀。視待控制之真菌、作物類型、作物生長階段、氣候條件及所用之各別式(I)化合物或組合物而定,此類量可在廣泛圍內變化。此量可藉由熟習此項技術者能力範圍內之系統田間試驗來測定。
植物及植物部分
式(I)化合物及包含其之組合物可施加於任何植物或植物部分。
植物意謂所有植物及植物群體,諸如所需及不合需要之野生植物或作物植物(包括天然產生之作物植物)。作物植物可為藉由習知育種及最佳化方法或藉由生物技術及基因工程方法或此等方法之組合可獲得的植物,包括經基因修飾之植物(GMO或轉殖基因植物)及可受及不受植物育種者權利保護的植物栽培品種。
經基因修飾之植物 ( GMO )
經基因修飾之植物(GMO或轉殖基因植物)為異源基因已穩定整合於基因組中之植物。表現「異源基因」基本上意謂在植物外部且在引入核、葉綠體或粒線體基因組中時提供或組裝的基因。此基因藉由表現相關蛋白質或多肽或藉由下調或抑制植物中存在之其他基因(使用例如反義技術、共抑制技術、RNA干擾-RNAi技術或微RNA-miRNA技術)賦予轉化植物新的或改良的農藝特性或其他特性。位於基因組中之異源基因亦稱為轉基因。由在植物基因組中之特定位置定義之轉殖基因稱為轉化或轉殖基因事件。
植物栽培品種應理解為意謂具有新型特性(「性狀」)且已藉由習知育種、藉由誘變或藉由重組DNA技術獲得的植物。其可為栽培品種、變種、生物型或基因型。
植物部分應理解為意謂地上及地下之植物的所有部分及器官,諸如幼芽、葉片、針葉、莖梗(stalk)、莖稈(stem)、花朵、子實體、果實、種子、根部、塊莖及根莖。植物部分亦包括收穫之物質及無性與有性繁殖物質,例如插條、塊莖、根莖、幼枝及種子。
可根據本文所描述之方法處理之植物包括以下:棉花、亞麻、葡萄藤、果實、蔬菜,諸如薔薇科(Rosaceae sp .
) (例如仁果,諸如蘋果及梨,以及核果,諸如杏、櫻桃、杏仁及桃子,及軟果,諸如草莓)、茶藨子科(Ribesioidae sp .
)、胡桃科(Juglandaceae sp .
)、樺科(Betulaceae sp .
)、漆樹科(Anacardiaceae sp .
)、山毛櫸科(Fagaceae sp .
)、桑科(Moraceae sp .
)、木樨科(Oleaceae sp .
)、獼猴桃科(Actinidaceae sp .
)、樟科(Lauraceae sp .
)、芭蕉科(Musaceae sp .
) (例如香蕉樹及人造林)、茜草科(Rubiaceae sp .
) (例如咖啡)、茶科(Theaceae sp .
)、梧桐科(Sterculiceae sp .
)、芸香科(Rutaceae sp .
) (例如檸檬、橙子及葡萄柚);茄科(Solanaceae sp .
) (例如蕃茄)、百合科(Liliaceae sp .
)、菊科(Asteraceae sp .
) (例如萵苣)、傘形科(Umbelliferae sp .
)、十字花科(Cruciferae sp .
)、藜科(Chenopodiaceae sp .
)、葫蘆科(Cucurbitaceae sp .
) (例如胡瓜)、蔥科(Alliaceae sp .
) (例如韭菜、洋蔥)、蝶形花科(Papilionaceae sp .
) (例如豌豆);主要糧食作物,諸如禾本科(Gramineae sp .
) (例如玉米、草皮、穀類,諸如小麥、粗麥、大米、大麥、燕麥、栗及黑小麥)、菊科(Asteraceae sp .
) (例如葵花)、十字花科(Brassicaceae sp .
) (例如白球甘藍、紅球甘藍、椰菜、花椰菜、孢子甘藍(Brussels sprout)、白菜、球莖甘藍、蘿蔔及油菜、氮芥、辣根及水芹)、豆科(Fabacae sp .
) (例如菜豆、花生)、蝶形花科(Papilionaceae sp .
) (例如大豆)、茄科(Solanaceae sp .
) (例如馬鈴薯)、藜科(Chenopodiaceae sp .
) (例如糖用甜菜、飼用甜菜、紅頭菜、甜菜根);用於園林及森林區域之有用植物及觀賞植物;及此等植物中每一者之遺傳修飾變體。
可藉由上文所揭示之方法處理之植物及植物栽培品種包括抗一或多種生物性逆境的植物及植物栽培品種,亦即,該等植物展示對動物及微生物害蟲之更佳防禦,諸如抵抗線蟲、昆蟲、蟎、植物病原性真菌、細菌、病毒及/或類病毒。
可藉由上文所揭示之方法處理之植物及植物栽培品種包括抗一或多種非生物性逆境的彼等植物。非生物性逆境條件可包括例如乾旱、低溫暴露、熱暴露、滲透壓力、洪水、增加之土壤鹽度、增加之礦物質暴露、臭氧暴露、高光暴露、氮養分之有限可用性、磷養分之有限可用性、避蔭。
可藉由上文所揭示之方法處理之植物及植物栽培品種包括特徵為產量特徵增強之彼等植物。該等植物之產量增加可為例如改良植物生理學、生長及發育(諸如水利用效率、水保持效率、改良氮使用、增強碳同化、改良光合成、增加發芽效率及加快成熟)之結果。產量可另外受改良之植物株型影響(在逆境及非逆境條件下),該改良之植物株型包括(但不限於)早期開花、對雜交種子生產之開花控制、幼苗活力、植物大小、節間數目及距離、根生長、種子大小、果實大小、豆莢大小、豆莢或穗數目、每個豆莢或穗之種子數目、種子質量、增強之種子填充、降低之種子散佈度、降低之豆莢開裂性及抗倒伏性。另外產量性狀包括種子組合物,諸如,碳水化合物含量及例如棉或澱粉之組合物、蛋白質含量、油含量及組成、營養值、反側營養化合物之還原、經改良可加工性及更佳儲存穩定性。
可藉由上文所揭示之方法處理之植物及植物栽培品種包括為雜交植物之植物及植物栽培品種,該等雜交植物已表現大體上引起較高產量、活力、健康及抗生物及非生物逆境之雜種優勢或雜交活力的特徵。
可藉由上文所揭示之方法處理之植物及植物栽培品種(藉由諸如基因工程之植物生物技術方法獲得)包括為除草劑耐受性植物之植物及植物栽培品種,亦即對一或多種給定除草劑耐受的植物。此類植物可藉由遺傳轉化或藉由選擇含有賦予此類除草劑耐受性之突變之植物獲得。
可藉由上文所揭示之方法處理之植物及植物栽培品種(藉由諸如基因工程之植物生物技術方法獲得)包括為昆蟲抗性轉殖基因植物之植物及植物栽培品種,亦即對某些靶標昆蟲之攻擊具有抗性的植物。此類植物可藉由遺傳轉化或藉由選擇含有賦予此類耐昆蟲性之突變之植物獲得。
可藉由上文所揭示之方法處理之植物及植物栽培品種(藉由諸如基因工程之植物生物技術方法獲得)包括為病害抗性轉殖基因植物之植物及植物栽培品種,亦即對某些目標昆蟲之攻擊具有抗性的植物。此類植物可藉由遺傳轉化或藉由選擇含有賦予此類耐昆蟲性之突變之植物獲得。
可藉由上文所揭示之方法處理之植物及植物栽培品種(藉由諸如基因工程之植物生物技術獲得)包括對非生物逆境耐受之植物及植物栽培品種。此類植物可藉由遺傳轉化或藉由選擇含有賦予此類逆境耐受性之突變之植物獲得。
可藉由上文所揭示之方法處理之植物及植物栽培品種(藉由諸如基因工程之生物技術方法獲得)包括展示更改所收穫產物之數量、品質及/或儲存穩定性及/或更改所收穫產物之特定成分之特性的植物及植物栽培品種。
可藉由上文所揭示之方法處理之植物及植物栽培品種(藉由諸如基因工程之植物生物技術方法獲得)包括具有經更改纖維特徵之植物及植物栽培品種(諸如,棉植物)。此類植物可藉由基因轉形或藉由選擇含有賦予此類經更改纖維特徵之突變之植物獲得。
可藉由上文所揭示之方法處理之植物及植物栽培品種(藉由諸如基因工程之植物生物技術方法獲得)包括具有經更改出油概況特徵之植物及植物栽培品種,諸如油菜或相關甘藍型植物。此類植物可藉由基因轉形或藉由選擇含有賦予此類經更改油型態特徵之突變之植物來獲得。
可藉由上文所揭示之方法處理之植物及植物栽培品種(藉由諸如基因工程之植物生物技術方法獲得)包括具有經更改落粒性特徵之植物及植物栽培品種,諸如油菜或相關甘藍型植物。此類植物可藉由基因轉形或藉由選擇含有賦予此類經更改落粒性特徵之突變之植物來獲得,且包括具有延時或經降低落粒性之植物,諸如油菜植物。
可藉由上文所揭示之方法處理之植物及植物栽培品種(藉由諸如基因工程之植物生物技術方法獲得)包括具有經更改轉譯後蛋白修飾模式之植物及植物栽培品種,諸如菸草植物。
病原體
可根據本發明治療之病害之病原體的非限制性實例包括:
由白粉病病原體引起之病害,該等白粉病病原體例如:白粉病菌屬(Blumeria
species),例如禾本科布氏白粉菌(Blumeria graminis
);叉絲單囊殼屬(Podosphaera
species),例如白叉絲單囊殼(Podosphaera leucotricha
);單絲殼屬(Sphaerotheca
species),例如單絲殼白粉菌(Sphaerotheca fuliginea
);鉤絲殼屬(Uncinula
species),例如葡萄白粉病菌(Uncinula necator
);
由銹病病原體引起之病害,該等銹病病原體例如:膠鏽菌屬(Gymnosporangium
species),例如褐色膠鏽菌(Gymnosporangium sabinae
);駝孢鏽菌屬(Hemileia
species),例如咖啡駝孢鏽菌(Hemileia
vastatrix);層鏽菌屬(Phakopsora
species),例如大豆鏽菌(Phakopsora pachyrhizi
)或層鏽層假尾孢菌(Phakopsora meibomiae
);柄鏽菌屬(Puccinia
species),例如麥類葉銹病菌(Puccinia recondita
)、禾柄鏽菌奧德條形柄鏽菌(Puccinia graminis oder Puccinia striiformis);單孢鏽菌屬(Uromyces
species),例如菜豆銹病菌(Uromyces appendiculatus
);
由來自卵菌之群的病原體引起之病害,該等病原體例如:白銹病屬(Albugo
species),例如白鏽菌(Albugo candida
);萵苣露菌病菌屬(Bremia
species),例如萵苣露菌病(Bremia lactucae
);霜黴菌屬(Peronospora
species),例如豌豆霜黴菌(Peronospora pisi
)或芸苔根腫菌(P . brassicae
);疫黴菌屬(Phytophthora
species),例如致病疫黴(Phytophthora infestans
);單軸黴屬(Plasmopara
species),例如葡萄生單軸黴(Plasmopara viticola
);假霜黴屬(Pseudoperonospora
species),例如葎草假霜黴(Pseudoperonospora humuli
)或古巴假霜黴菌(Pseudoperonospora cubensis
);腐黴菌屬(Pythium
species),例如終極腐黴菌(Pythium ultimum
);
由例如以下引起之葉斑病及葉萎病:交鏈孢屬(Alternaria
species),例如立枯交鏈孢(Alternaria solani
);尾孢菌屬(Cercospora
species),例如甜菜尾孢菌(Cercospora beticola
);黑星病菌屬(Cladiosporium
species),例如黃瓜黑星病菌(Cladiosporium cucumerinum
);旋孢腔菌屬(Cochliobolus
species),例如禾旋孢腔菌(Cochliobolus sativus) (分生孢子形式:內臍蠕孢屬(Drechslera
),同義詞:長蠕孢(Helminthosporium
))或宮部旋孢腔菌(Cochliobolus miyabeanus
);刺盤孢屬(Colletotrichum
species),例如菜豆炭疽病菌(Colletotrichum lindemuthanium
);棒孢黴屬(Corynespora
species),例如多主棒孢黴(Corynespora cassiicola
);孔雀斑菌屬(Cycloconium
species),例如油橄欖孔雀斑菌(Cycloconium oleaginum
);黑點病菌屬(Diaporthe species),例如柑橘黑點病菌(Diaporthe citri
);痂囊腔菌屬(Elsinoe
species),例如柑桔痂囊腔菌(Elsinoe fawcettii
);炭疽病菌屬(Gloeosporium
species),例如桃炭疽病菌(Gloeosporium
laeticolor);小叢殼屬(Glomerella
species),例如圍小叢殼菌(Glomerella cingulata
);球座菌屬(Guignardia
species),例如葡萄球座菌(Guignardia bidwelli
);小球腔菌屬(Leptosphaeria
species),例如十字花科小球腔菌(Leptosphaeria maculans
);稻瘟菌屬(Magnaporthe
species),例如稻瘟菌(Magnaporthe grisea
);微結節菌屬(Microdochium
species),例如雪黴枯葉病菌(Microdochium nivale
);球腔菌屬(Mycosphaerella
species),例如禾生球腔菌(Mycosphaerella graminicola
)、落花生球腔菌(Mycosphaerella arachidicola
)或斐濟球腔菌(Mycosphaerella fijiensis
);暗球腔菌屬(Phaeosphaeria
species),例如小麥葉枯病菌(Phaeosphaeria nodorum
);核腔菌屬(Pyrenophora
species),例如大麥網斑病菌(Pyrenophora teres
)或偃麥草核腔菌(Pyrenophora tritici repentis
);柱隔孢屬(Ramularia
species),例如柱隔孢(Ramularia collo-cygni)或白斑柱隔孢;雲紋病菌屬(Rhynchosporium
species),例如大麥雲紋病菌(Rhynchosporium secalis
);殼針孢屬(Septoria
species),例如芹菜小殼針孢(Septoria apii
)或番茄殼針孢(Septoria lycopersici
);殼多孢屬(Stagonospora
species),例如穎枯殼針孢(Stagonospora nodorum
);核瑚菌屬(Typhula
species),例如肉孢核瑚菌(Typhula incarnata
);黑星菌屬(Venturia
species),例如蘋果黑星病菌(Venturia inaequalis
);
由例如以下引起之根部及莖稈病害:伏革菌屬(Corticium
species),例如禾穀鐮孢伏革菌(Corticium graminearum
);鐮菌屬(Fusarium
species),例如尖孢鐮刀菌(Fusarium oxysporum
);頂囊殼屬(Gaeumannomyces
species),例如禾草頂囊殼菌(Gaeumannomyces graminis
);根腫菌屬(Plasmodiophora
species),例如甘藍根腫菌(Plasmodiophora brassicae
);絲核菌屬(Rhizoctonia
species),例如立枯絲核菌(Rhizoctonia solani
);帚枝黴屬(Sarocladium
species),例如稻葉鞘腐敗病菌(Sarocladium oryzae
);小核菌屬(Sclerotium
species),例如稻小核菌(Sclerotium oryzae
);塔普斯菌屬(Tapesia
species),例如塔普斯梭狀芽胞桿菌(Tapesia acuformis
);根串珠黴屬(Thielaviopsis
species),例如菫菜根腐病菌(Thielaviopsis basicola
);
由例如以下引起之穗及圓錐花序病害(包括玉米穗軸):交鏈孢屬(Alternaria
species),例如交鏈孢菌(Alternaria spp .
);麴菌屬(Aspergillus
species),例如黃麴菌(Aspergillus flavus
);分枝孢子菌屬(Cladosporium
species),例如芽枝狀枝孢黴(Cladosporium cladosporioides
);麥角菌屬(Claviceps
species),例如紫黑麥角菌(Claviceps purpurea
);鐮菌屬(Fusarium
species),例如黃色鐮孢菌(Fusarium culmorum
);赤黴菌屬(Gibberella
species),例如玉米赤黴(Gibberella zeae
);小畫線殼屬(Monographella
species),例如雪黴小畫線殼(Monographella nivalis
);殼多孢菌屬(Stagnospora
species),例如穎枯殼針孢(Stagonospora nodorum
);
由黑穗病真菌引起之病害,該等黑穗病真菌例如:蜀黍小黑穗病菌屬(Sphacelotheca
species),例如高粱絲黑粉菌(Sphacelotheca reiliana
);腥黑粉菌屬(Tilletia
species),例如小麥矮腥黑粉菌(Tilletia caries
或Tilletia
controversa);條黑粉菌屬(Urocystis
species),例如隱條黑粉菌(Urocystis occulta
);黑粉菌屬(Ustilago
species),例如麥散黑粉菌(Ustilago nuda
);
由例如以下引起之果腐病:麴菌屬(Aspergillus
species),例如黃麴菌(Aspergillus flavus
);葡萄孢屬(Botrytis
species),例如灰葡萄孢菌(Botrytis cinerea
);鏈核盤菌屬(Monilinia
species),例如拉克撒鏈核盤菌(Monilinia laxa
);青黴菌屬(Penicillium
species),例如擴展青黴(Penicillium expansum
)或產紫青黴(Penicillium purpurogenum
);根黴菌屬(Rhizopus
species),例如匍枝根黴(Rhizopus stolonifer
);核盤菌屬(Sclerotinia
species),例如向日葵核盤菌(Sclerotinia sclerotiorum
);輪枝孢屬(Verticilium
species),例如黃萎輪枝黴(Verticilium alboatrum
);
種子及土壤媒介腐病及萎病以及由例如以下引起之苗木病害:交鏈孢屬,例如甘藍交鏈孢黴(Alternaria brassicicola
);絲囊黴屬(Aphanomyces
species),例如兵豆絲囊黴(Aphanomyces euteiches
);殼二孢屬(Ascochyta
species),例如晶狀殼二孢(Ascochyta lentis
);麴菌屬,例如黃麴菌;分枝孢子菌屬,例如多主枝孢黴(Cladosporium herbarum
);旋孢腔菌屬,例如禾旋孢腔菌(分生孢子形式:內臍蠕孢屬,同義詞:長蠕孢);刺盤孢屬,例如仙人掌炭疽刺盤孢菌(Colletotrichum coccodes
);鐮菌屬,例如黃色鐮孢菌;赤黴菌屬,例如玉米赤黴;殼球孢屬(Macrophomina
species),例如萊豆殼球孢(Macrophomina phaseolina
);微結節菌屬,例如雪黴枯葉病菌;小畫線殼屬,例如雪黴小畫線殼;青黴菌屬,例如擴展青黴;莖點黴屬(Phoma
species),例如黑脛莖點黴(Phoma lingam
);擬莖點黴屬(Phomopsis
species),例如大豆擬莖點黴;疫黴菌屬(Phytophthora
species),例如惡疫黴(Phytophthora cactorum
);核腔菌屬,例如大麥核腔菌;梨孢屬(Pyricularia
species),例如稻梨孢(Pyricularia oryzae
);腐黴菌屬,例如終極腐黴菌;絲核菌屬,例如立枯絲核菌;根黴菌屬,例如酒麴菌;小核菌屬,例如白絹病小核菌(Sclerotium rolfsii
);殼針孢屬,例如穎枯殼針孢;核瑚菌屬,例如內孢核瑚菌;輪枝菌屬,例如大麗花輪枝孢;
由例如以下引起之癌症、蟲癭及叢枝病:叢赤殼屬(Nectria
species),例如,仁果乾癌叢赤殼(Nectria galligena
);
由例如以下引起之萎病:輪枝菌屬,例如長孢輪枝菌(Verticillium longisporum
);鐮菌屬,例如尖孢鐮刀菌;
由例如以下引起之葉片、花及果實之畸形:外擔菌屬(Exobasidium
species),例如,壞損外擔菌(Exobasidium vexans
);外囊菌屬(Taphrina
species),例如,畸形外囊菌(Taphrina deformans
);
由例如以下引起之木本植物之退行性病害:埃斯卡屬(Esca
species),例如,根黴格孢菌(Phaeomoniella
chlamydospora)、褐枝頂孢黴(Phaeoacremonium
aleophilum)或地中海嗜藍孢孔菌(Fomitiporia
mediterranea);靈芝屬(Ganoderma
species),例如,島靈芝(Ganoderma boninense
);
由以下引起之植物塊莖之病害:絲核菌屬(Rhizoctonia
species),例如,立枯絲核菌(Rhizoctonia solani
);長蠕孢屬,例如,立枯長蠕孢菌;
由細菌性病原體引起之病害,該等細菌性病原體例如黃單孢菌屬(Xanthomonas
species),例如野油菜黃單胞菌(Xanthomonas campestris pv . oryzae
);假單胞菌屬,例如甜瓜細菌性葉斑病菌(Pseudomonas syringae pv . lachrymans
);歐文菌屬(Erwinia
species),例如解澱粉歐文菌(Erwinia amylovora
);黃龍病菌屬(Liberibacter
species),例如柑橘黃龍病(Liberibacter asiaticus
);變形菌屬(Xyella
species),例如葉緣焦枯病菌(Xylella fastidiosa
);羅爾斯頓菌屬(Ralstonia
species),例如茄科羅爾斯頓菌(Ralstonia solanacearum
);基氏菌屬(Dickeya
species),例如立枯基氏菌(Dickeya solani
);棍狀桿菌屬,例如密執安棍狀桿菌(Clavibacter michiganensis
);鏈黴菌屬,例如疥鏈黴菌(Streptomyces scabies
)。
大豆病害:
由例如以下引起的葉片、莖稈、豆莢及種子之真菌性病害:交鏈孢屬葉斑病(細極交鏈孢黴;Alternaria spec . atrans tenuissima
),炭疽病(赤葉枯刺盤孢菌變種;Colletotrichum gloeosporoides dematium var . truncatum
),褐斑病(大豆褐紋殼針孢;Septoria glycines
),尾孢菌葉斑病及枯萎病(菊池尾孢菌;Cercospora kikuchii
),笄黴屬葉枯病(漏斗笄黴菌;Choanephora infundibulifera trispora
(同義)),dactuliophora
葉斑病(Dactuliophora
甘胺酸),霜黴病(東北霜黴;Peronospora manshurica
),內臍蠕孢枯萎病(格利思尼內臍蠕孢;Drechslera glycini
),辣椒葉斑病(大豆灰斑病菌),小光腔菌葉斑病(三葉草小光腔菌;Leptosphaerulina trifolii
),葉點黴葉斑病(大豆生葉點黴;Phyllosticta sojaecola
),豆莢及莖稈枯萎病(大豆擬莖點黴),白粉病(白粉病菌;Microsphaera diffusa
),鬚殼孢葉斑病(鬚殼孢甘胺酸),絲核菌氣根、葉及網脈枯萎病(立枯絲核菌;Rhizoctonia solani
),銹病(大豆鏽菌(Phakopsora pachyrhizi
)、層鏽層假尾孢菌(Phakopsora meibomiae
)),瘡斑病(痂圓孢菌甘胺酸),匍柄黴葉枯病(匍柄黴;Stemphylium botryosum
),猝死症(棒形鐮刀菌;Fusarium virguliforme
),靶斑病(多主棒孢黴;Corynespora cassiicola
)。
由例如以下引起之根及莖基部真菌性病害:黑根腐病(野百合尾孢菌(Calonectria crotalariae
))、炭腐病(菜豆立枯病菌(Macrophomina phaseolina
))、鐮菌枯萎病或萎蔫病、根腐病以及豆莢及根頸腐病(尖孢鐮刀菌(Fusarium oxysporum
)、直喙鐮孢(Fusarium orthoceras
)、半裸鐮孢(Fusarium semitectum
)、木賊鐮孢(Fusarium equiseti
))、細圓盤黴根腐病(褐紅壞死病病菌(Mycoleptodiscus terrestris
))、赤殼菌(neocosmospora)(侵菅新赤殼菌(Neocosmospora vasinfecta
))、豆莢及莖稈枯萎病(大豆黑點病菌(Diaporthe phaseolorum
))、莖潰瘍(大豆黑點病菌變種(Diaporthe phaseolorum var . caulivora
))、疫黴菌腐病(大雄疫黴菌(Phytophthora megasperma
))、褐莖腐病(大豆莖褐腐病菌(Phialophora gregata
))、腐黴菌腐病(瓜果腐黴Pythium aphanidermatum
)、畸雌腐黴(Pythium irregulare
)、德巴利腐黴(Pythium debaryanum
)、群結腐黴(Pythium myriotylum
)、終極腐黴(Pythium ultimum
))、絲核菌根腐病(rhizoctonia root rot)、莖腐病及猝倒病(立枯絲核菌(Rhizoctonia solani
))、核盤菌莖腐病(向日葵核盤菌(Sclerotinia sclerotiorum
))、核盤菌白絹病(白絹病核盤菌(Sclerotinia rolfsii
))、根串珠黴根腐病(菫菜根腐病菌(Thielaviopsis basicola
))。
黴菌毒素 另外,式(I)化合物及包含其之組合物可降低所收穫物質及自其製備之食品與飼料中之徵菌毒素含量。黴菌毒素尤其但非排他地包括以下:脫氧雪腐鐮刀菌烯醇(deoxynivalenol) (DON)、雪腐鐮刀菌醇(nivalenol)、15-Ac-DON、3-Ac-DON、T2-毒素及HT2-毒素、伏馬菌素(fumonisins)、玉米赤黴烯酮(zearalenon)、串珠鐮刀菌素(moniliformin)、鐮刀菌素(fusarin)、蛇形菌素(diaceotoxyscirpenol) (DAS)、白僵菌素(beauvericin)、恩鐮孢菌素(enniatin)、福撒羅多育麴菌素(fusaroproliferin)、福撒羅菌素(fusarenol)、赭麯黴素(ochratoxins)、散毒素(patulin)、麥角生物鹼(ergot alkaloid)及黃麴黴毒素(aflatoxins),其可例如藉由以下真菌產生:鐮刀菌屬(Fusarium spec .
),諸如銳頂鐮刀菌(F . acuminatum
)、亞洲鐮刀菌(F . asiaticum
)、燕麥鐮刀菌(F . avenaceum
)、克地鐮刀菌(F . crookwellense
)、黃色鐮刀菌(F . culmorum
)、禾穀鐮刀菌(F . graminearum
) (玉米赤黴菌(Gibberella zeae
))、木賊鐮刀菌(F . equiseti
)、水稻鐮刀菌(F . fujikoroi
)、香蕉鐮刀菌(F . musarum
)、尖鐮孢菌(F . oxysporum
)、串珠鐮刀菌(F . proliferatum
)、梨孢鐮刀菌(F . poae
)、小麥莖基腐病菌假禾穀鐮刀菌(F . pseudograminearum
)、接骨木鐮刀菌(F . sambucinum
)、蕉草鐮刀菌(F . scirpi
)、半裸鐮刀菌(F . semitectum
)、立枯鐮刀菌(F . solani
)、擬枝孢鐮刀菌(F . sporotrichoides
)、穀物鐮刀菌(F . langsethiae
)、膠孢鐮刀菌(F . subglutinans
)、三線鐮刀菌(F . tricinctum
)、輪枝樣鐮刀菌(F . verticillioides
)等,以及藉由以下產生:麴菌屬(Aspergillus spec .
),諸如黃麴菌(A . flavus
)、寄生麴菌(A . parasiticus
)、稻米麴菌(A . nomius
)、赭麯黴(A . ochraceus
)、棒麯黴(A . clavatus
)、土麴菌(A . terreus
)、雜色麯黴(A . versicolor
),青黴菌屬(Penicillium spec .
),諸如疣孢青黴菌(P . verrucosum
)、鮮綠青黴菌(P . viridicatum
)、桔青黴(P . citrinum
)、擴展青黴(P . expansum
)、棒狀青黴(P . claviforme
)、洛克福耳青黴菌(P . roqueforti
),麥角菌屬(Claviceps spec .
),諸如菊麥角菌(C . purpurea
)、紡綞形麥角菌(C . fusiformis
)、雀稗麥角菌(C . paspali
)、非洲麥角菌(C . africana
),葡萄穗黴菌屬(Stachybotrys spec .
)及其他。
物質保護 式(I)化合物及包含其之組合物亦可用於保護物質,尤其用於保護抗植物病原性真菌之攻擊及破壞的工業物質。
另外,式(I)化合物及包含其之組合物可單獨或與其他活性成份組合用作防污組合物。
本上下文中的工業材料應理解為意謂已經製備以用於工業中的非生物物質。舉例而言,欲保護以免受微生物改變或破壞之工業物質可為黏著劑、膠、紙張、牆紙及紙板/卡紙板、紡織物、地毯、皮革、原木、纖維及紙巾、塗料及塑膠製品、冷卻潤滑劑以及可受微生物影響或破環之其他物質。亦可在欲保護之材料的範疇內提及可被微生物之增殖減弱的生產設備及建築物之部分(例如水冷卻電路、冷卻及加熱系統以及通風及空調單元)。本發明範疇內之工業材料較佳地包括黏著劑、膠料、紙張及卡片、皮革、原木、塗料、冷卻潤滑劑及熱傳遞流體,更佳地原木。
式(I)化合物及包含其之組合物可防止有害影響,諸如腐壞、腐爛、變色、脫色或黴形成。
就原木處理而言,式(I)化合物及包含其之組合物亦可用以抵抗易在木材上或內部生長之真菌性病害。
木材意謂所有類型之原木物種,及欲用於建築之此原木之所有加工類型,例如實心原木、高密度原木、層壓原木板及膠合板。另外,式(I)化合物及包含其之組合物可用以保護與鹽水或微咸水形成接觸之物件(尤其為皮、螢幕、網、建築物、系泊船及信號傳導系統)免受積垢。
式(I)化合物及包含其之組合物亦可用於保護儲存貨物。應將儲存貨物理解為意謂蔬菜或動物來源之天然物質或其經處理產品,其具有天然來源且需要長期保護。蔬菜來源之儲存貨物(例如植物或植物部分,諸如莖稈、葉片、塊莖、種子、果實、穀粒)可在剛收穫後或在藉由(預)乾燥、濕潤、粉碎、研磨、按壓或焙烤之處理後受到保護。儲存貨物亦包括木材,其未經處理(諸如建築木材、電線桿及障壁)或呈成品形式(諸如傢俱)。動物來源之儲存貨物係例如獸皮、皮革、皮草及毛髮。式(I)化合物及包含其之組合物可防止有害影響,諸如腐壞、腐爛、變色、脫色或黴形成。
能夠降解或改變工業物質之微生物包括(例如)細菌、真菌、酵母、藻類及黏液生物生物體。式(I)化合物及包含其之組合物較佳地針對真菌,尤其黴菌、使原木變色及毀壞原木之真菌(子囊菌、擔子菌、半知菌及接合菌),以及針對黏液生物體及藻類起作用。實例包括以下屬之微生物:交鏈孢屬,諸如美洲留蘭香交鏈孢屬(Alternaria tenuis
);麴菌屬,諸如黑麯黴(Aspergillus niger
);毛殼菌屬(Chaetomium
),諸如球毛殼菌屬(Chaetomium globosum
);粉孢革菌屬(Coniophora
),諸如單純粉孢革菌屬(Coniophora puetana
);香菇屬(Lentinus
),諸如虎皮香菇屬(Lentinus tigrinus
);青黴菌屬,諸如灰綠青黴菌(Penicillium glaucum
);多孔菌屬(Polyporus
),諸如變色多孔菌(Polyporus versicolor
);短梗黴屬(Aureobasidium
),諸如出芽短梗黴菌(Aureobasidium pullulans
);核莖點黴屬(Sclerophoma
),諸如綠頂核莖點黴(Sclerophoma pityophila
);木黴菌屬(Trichoderma
),諸如綠色木黴菌屬(Trichoderma viride
);長喙殼菌(Ophiostoma spp .
);長喙殼屬(Ceratocystis spp .
);腐殖菌屬(Humicola spp .
);石座菌屬(Petriella spp .
);毛束黴屬(Trichurus spp .)
;革蓋菌屬(Coriolus spp .
);黏褶菌屬(Gloeophyllum spp .
);側耳屬(Pleurotus spp .
);臥孔菌屬(Poria spp .
);蟠龍介屬(Serpula spp .
)及乾酪菌屬(Tyromyces spp .
);分枝孢子菌屬(Cladosporium spp .
);擬青黴菌屬(Paecilomyces spp .
);白黴菌屬(Mucor spp .
);埃希氏桿菌屬(Escherichia
),諸如大腸桿菌(Escherichia coli
);假單胞菌屬(Pseudomonas
),諸如綠膿桿菌(Pseudomonas aeruginosa
);葡萄球菌屬(Staphylococcus
),諸如金黃色葡萄球菌(Staphylococcus aureus
);念珠菌屬(Candida spp .
)及酵母屬(Saccharomyces spp
.),諸如釀酒酵母(Saccharomyces cerevisae
)。
種子處理 式(I)化合物及包含其之組合物亦可用以保護種子免受非所需微生物影響,諸如植物病原性微生物,例如植物病原性真菌或植物病原性卵菌。如本文所用,術語種子
包括休眠種子、引發種子、預發芽種子及具有冒出之根及葉片之種子。
因此,本發明亦係關於一種用於保護種子免受非所需微生物影響之方法,其包含以下步驟:用式(I)化合物或組合物處理種子。
用式(I)化合物或組合物處理種子,保護種子免受植物病原性微生物影響,而且保護萌發種子、所冒出幼苗木及自經處理種子冒出後之植物。因此,本發明亦係關於一種用於保護種子、萌發種子且使幼苗冒出之方法。
種子處理可在播種之前、播種時或播種不久後進行。
當在播種前進行種子處理(例如,所謂的種子上施加)時,可如下進行種子處理:可將種子置放於具有所需量之式(I)化合物或組合物之混合器中,混合種子及式(I)化合物或組合物直至實現種子上之均勻分佈為止。適當時,可隨後乾燥種子。
本發明亦係關於塗佈有式(I)化合物或包含其之組合物的種子。
較佳地,種子在處理過程中不出現損害之足夠穩定之狀態下進行處理。一般而言,種子可在收穫與播種後不久之間的任何時間進行處理。習用使用已自植物分離且自穗軸、殼、梗、外殼、毛髮或果實之果肉釋放的種子。舉例而言,有可能使用已收穫、清潔及經乾燥至水分含量降至小於15重量%的種子。或者,亦有可能使用在乾燥之後例如已用水處理且隨後再次乾燥的種子、或剛好引發後之種子、或儲存於引發條件下之種子或預發芽種子、或在育苗盤、膠帶或紙張上播種之種子。
施加至種子之式(I)化合物或包含其之組合物之量通常使得種子發芽不減弱或所得植物不損害。此必須特別地確定,以防式(I)化合物在某些施加量下將呈現植物毒性效果。在判定待施加至種子以便用最少量的所用化合物達成最佳種子及發芽植物保護的式(I)化合物的量時,亦應考量轉殖基因植物之固有表型。
式(I)化合物可原樣直接施加至種子,亦即無需使用任何其他組分且無需稀釋。此外,包含其之組合物可施加至種子。
式(I)化合物及包含其之組合物適合於保護任何植物品種之種子。較佳種子為穀類(諸如,小麥、大麥、粗麥、栗、黑小麥及燕麥)、油菜、玉米、棉、大豆、水稻、馬鈴薯、向日葵、菜豆、咖啡、豆類、甜菜(例如,糖用甜菜及飼料甜菜)、花生、蔬菜(諸如,番茄、胡瓜、洋蔥及萵苣)、草坪及觀賞植物。更佳的為小麥、大豆、油菜、玉米及水稻之種子。
式(I)化合物及包含其之組合物可用於處理轉殖基因種子,尤其能夠表現針對害蟲、除草損害或非生物性逆境起作用之多肽或蛋白質的植物之種子,由此增加保護作用。能夠表現針對害蟲、除草損害或非生物性逆境起作用之多肽或蛋白質的植物之種子可含有至少一種允許表現該多肽或蛋白質之異源基因。轉殖基因種子中的此等異源基因可來源於例如以下屬之微生物:芽孢桿菌屬(Bacillus)、根瘤菌屬(Rhizobium)、假單胞菌屬(Pseudomonas)、沙雷菌屬(Serratia)、木黴菌屬(Trichoderma)、棍狀桿菌屬(Clavibacter)、叢枝菌根菌屬(Glomus)或膠黴屬(Gliocladium)。此等異源基因較佳地來源於芽孢桿菌屬,在此情況下基因產物有效抵抗歐洲玉米螟及/或西方玉米根蟲。尤佳地,異源基因來源於蘇力菌。
施加
式(I)化合物可原樣或例如以以下形式施加:備用溶液、乳液、水基或油基懸浮液、粉末、可濕潤粉末、糊、可溶粉末、粉塵、可溶顆粒、用於散佈之顆粒、懸乳劑濃縮物、浸漬有式(I)化合物之天然產物、浸漬有式(I)化合物之合成物質、肥料或聚合物質中之微膠囊劑。
以習用方式、例如藉由澆水、噴灑、霧化、散佈、撒粉、發泡、塗抹及類似者實現施加。亦可藉由超低量方法經由滴灌系統或浸液施加來部署式(I)化合物,以沿溝施加或將其噴射至田埂或土埂中。另外可藉助於傷口密封、塗層或其他傷口敷裹來施加式(I)化合物。
施加至植物、植物部分、果實、種子或土壤之式(I)化合物的有效及植物相容量將視各種因素而定,該等因素諸如所用化合物/組合物、處理之對象(植物、植物部分、果實、種子或土壤)、處理類型(撒粉、噴灑、拌種)、處理之用途(治癒性及保護性)、微生物類型、微生物之發展階段、微生物之敏感性、作物生長階段及環境條件。
當式(I)化合物用作殺真菌劑時,施加量可在相對廣範圍內變化,該範圍視施加種類而定。對於處理植物部分(諸如葉片),施加量的範圍可為0.1至10 000 g/ha,較佳地10至1000 g/ha,更佳地50至300 g/ha (在藉由澆水或滴注施加之情況下,甚至可降低施加量,尤其在使用諸如石棉或珍珠岩之惰性基質時)。對於處理種子,施加量的範圍可為0.1至200公克/100公斤種子,較佳地1至150公克/100公斤種子,更佳地2.5至25公克/100公斤種子,甚至更佳地2.5至12.5公克/100公斤種子。對於處理土壤,施加量可在0.1至10 000 g/ha,較佳1至5000 g/ha範圍內。
此等施加量僅為實例且並不意欲限制本發明之範疇。
可根據以下實例來進一步理解本發明教示之態樣,該等實例不應視為以任何方式限制本發明教示之範疇。實例
製備實例
在以下實例中,logP值及質量峰如表1中所定義。
製備實例 1 :
7,8-二氟-3-[3-氟-2-(6-氟吡啶-3-基)苄基]-2-甲基喹啉(化合物I.042)
在5 mL微波管中,稱重73 mg(0.51 mmol)(6-氟吡啶-3-基)硼酸、10 mg(0.047 mmol)乙酸鈀(II)及38 mg(0.094 mmol)二環己基(2',6'-二甲氧基雙苯基-2-基)膦。接著添加214 mg(1.41 mmol)氟化銫,隨後在2.9 mL 1,2-二甲氧基乙烷與甲醇之2:1混合物中添加含172 mg(0.47 mmol)3-(2-溴-3-氟苄基)-7,8-二氟-2-甲基喹啉之溶液。在微波下在80℃下加熱反應混合物1小時。將經冷卻之反應混合物轉移至2 g矽膠濾筒上且藉由8 mL二氯甲烷溶離三次。在真空中濃縮濾液且藉由製備型HPLC(梯度乙腈/水+0.1% HCO2
H)純化,得到117 mg(61%)7,8-二氟-3-[3-氟-2-(6-氟吡啶-3-基)苄基]-2-甲基喹啉。LogP=3.70。質量(M+H)=383。
製備實例 2 :
N-[2-(4-環丙基吡啶-3-基)-3-氟苯基]-7,8-二氟-2-甲基喹啉-3-胺(化合物I.104)
步驟 1 :
製備N-(2-溴-3-氟苯基)-7,8-二氟-2-甲基喹啉-3-胺
藉由氬氣將70 ml 1,4-二噁烷中之2.5 g(12.23 mmol)7,8-二氟-2-甲基喹啉-3-胺及3.32 g(12.84 mmol)1,2-二溴-3-氟苯與11.95 mg(36.69 mmol)碳酸銫及708 mg(1.22 mmol)9,9-二甲基-9H-二苯并哌喃-4,5-二基)雙-(二苯基磷酸酯)[Xantphos]一起之混合物脫氣30分鐘。添加896 mg(0.97 mmol)參(二亞苄基丙酮)鈀(0),且加熱回流反應混合物26小時。經冷卻之反應混合物經矽膠墊過濾,且用乙酸乙酯洗滌該墊。在真空下濃縮有機相且藉由矽膠管柱層析(300 g濾筒-梯度正庚烷/乙酸乙酯)純化,得到2.31 g(49%)N-(2-溴-3-氟苯基)-7,8-二氟-2-甲基喹啉-3-胺。LogP=3.28。質量(M+H)=367。
步驟 2 :
製備N-[2-(4-環丙基吡啶-3-基)-3-氟苯基]-7,8-二氟-2-甲基喹啉-3-胺(化合物I.104)
在25 mL微波管中,向用氬氣脫氣15分鐘之8 mL 1,4-二噁烷及1.5 mL水的溶液中依次添加130 mg(0.35 mmol)N-(2-溴-3-氟苯基)-7,8-二氟-2-甲基喹啉-3-胺、115 mg(0.70 mmol)(4-環丙基吡啶-3-基)硼酸、134 mg(0.88 mmol)氟化鈀、14.5 mg(0.035 mmol)參(二亞苄基丙酮)鈀(0)及14.5 mg(0.035 mmol)2-二環己基膦基-2',6'-二甲氧基二苯基[S-Phos]。在微波下在150℃下加熱反應混合物1小時。經冷卻之反應混合物用乙酸乙酯稀釋且用CeliteTM
墊過濾。用鹽水洗滌有機相且用硫酸鎂乾燥有機相。在真空下濃縮有機相且藉由矽膠管柱層析(12 g濾筒-梯度正庚烷/乙酸乙酯)純化,得到43 mg(29%)N-[2-(4-環丙基吡啶-3-基)-3-氟苯基]-7,8-二氟-2-甲基喹啉-3-胺。LogP=2.12。質量(M+H)=406。
製備實例 3
:製備5,6-二氟-N-[2-(3-氟吡啶-4-基)苯基]-3-甲基喹喏啉-2-胺(化合物I.014)
步驟 1
:製備2-(3-氟吡啶-4-基)苯胺
在50 mL微波管中,向用氬氣脫氣15分鐘之20 mL 1,4-二噁烷及3 mL水的溶液中依次添加900 mg(4.73 mmol)2-溴-3-氟苯胺、2.64 g(11.84 mmol)3-氟-4-(4,4,5,5-四甲基-1,3,2-二氧硼㖦-2-基)吡啶、1798 mg(11.84 mmol)氟化銫、216 mg(0.237 mmol)參(二亞苄基丙酮)鈀(0)及194 mg(0.474 mmol)S-Phos。在微波下在150℃下加熱反應混合物1小時。經冷卻之反應混合物用乙酸乙酯稀釋且在CeliteTM
墊上過濾。用鹽水洗滌有機相且用硫酸鎂乾燥有機相。在真空下濃縮有機相且藉由矽膠管柱層析(40 g濾筒-梯度正庚烷/乙酸乙酯)純化,得到775 mg(72%)2-(3-氟吡啶-4-基)苯胺。LogP=2.38。質量(M+H)=207。
步驟 2
:製備5,6-二氟-N-[2-(3-氟吡啶-4-基)苯基]-3-甲基喹喏啉-2-胺(化合物I.014)
向25 ml經脫氣之1,4-二噁烷中之295 mg(1.22 mmol)2-溴-5-氟-3-甲基喹喏啉及252 mg(1.22 mmol)2-(3-氟吡啶-4-基)苯胺與1.19 g(3.67 mmol)碳酸銫及70 mg(0.122 mmol)Xantphos一起之混合物中添加31 mg(0.61 mmol)鈀-(Pi-苯烯丙基)氯化二聚體。在回流下加熱反應混合物2.5小時。經冷卻之反應混合物用乙酸乙酯稀釋且在CeliteTM
墊上過濾。在真空下濃縮有機相且藉由矽膠管柱層析(12 g濾筒-梯度正庚烷/乙酸乙酯)純化,產生113 mg(25%)呈淡黃色固體之5,6-二氟-N-[2-(3-氟吡啶-4-基)苯基]-3-甲基喹喏啉-2-胺。LogP=2.83。質量(M+H)=367。
製備實例 4
:製備7,8-二氟-3-{[4-(2-氟吡啶-4-基)-3-噻吩基]甲基}-2-甲基喹啉(化合物I.138)
步驟 1
:製備3-溴-4-(氯甲基)噻吩
向20 mL二氯甲烷中之1 g(5.02 mmol)(4-溴基-3-噻吩基)甲醇及770 mg(7.53 mmol)三乙胺之混合物中添加867 mg(7.53 mmol)甲磺醯氯。在環境溫度下攪拌反應混合物隔夜。真空濃縮混合物,得到3.19 g呈橙色油狀之殘餘物。藉由矽膠管柱層析(40 g濾筒-梯度正庚烷/乙酸乙酯)純化殘餘物,產生1.01 g(95%)呈淡黃色油狀之3-溴-4-(氯甲基)噻吩。LogP=2.99。質量(M+H):無電離。藉由GC-mass測得的質量(M)=210。
步驟 2
:製備3-[(4-溴-3-噻吩基)甲基]-7,8-二氟-2-甲基喹啉
在5 mL微波管中,將99 mg(0.43 mmol)(7,8-二氟-2-甲基喹啉-3-基)硼酸及100 mg(0.47 mmol)3-溴-4-(氯甲基)噻吩溶解於4 mL 1,4-二噁烷中。添加1 mL水中含178 mg(1.29 mmol)碳酸鉀之溶液且用氬氣使反應混合物脫氣5分鐘。進一步添加24.8 mg(0.021 mmol)肆(三苯基-膦)鈀(0),且在微波下在100℃下加熱反應混合物20分鐘。再重複相同反應4次。將合併之5個反應混合物傾入100 mL水上且藉由乙酸乙酯再萃取。經硫酸鎂乾燥有機相且在真空中濃縮,得到978 mg呈橙色固體狀之殘餘物。藉由矽膠管柱層析(80 g濾筒-梯度正庚烷/乙酸乙酯)純化殘餘物,產生609 mg(80%)呈淡黃色固體狀之3-[(4-溴-3-噻吩基)甲基]-7,8-二氟-2-甲基喹啉。LogP=4.01。質量(M+H)=354。
步驟 3
:製備7,8-二氟-3-{[4-(2-氟吡啶-4-基)-3-噻吩基]甲基}-2-甲基喹啉(化合物I.138)
在5 mL微波管中,將100 mg(0.28 mmol)3-[(4-溴-3-噻吩基)甲基]-7,8-二氟-2-甲基喹啉及265 mg(1.12 mmol)2-氟-4-(4,4,5,5-四甲基-1,3,2-二氧硼㖦-2-基)吡啶溶解於5 mL 1,4-二噁烷中。添加129 mg(0.84 mmol)氟化銫以及12 mg(0.028 mmol)S-Phos且用氬氣將反應混合物脫氣5分鐘。再添加13 mg(0.014 mmol)參(二亞苄基丙酮)鈀(0),且在微波下在150℃下加熱反應混合物3小時。用矽膠墊過濾經冷卻之反應混合物,且用乙酸乙酯洗滌該墊。在真空下濃縮有機相且藉由矽膠管柱層析(40 g濾筒-梯度正庚烷/乙酸乙酯)純化,產生87 mg(78%)呈橙色固體之7,8-二氟-3-{[4-(2-氟吡啶-4-基)-3-噻吩基]甲基}-2-甲基喹啉。LogP=3.64。質量(M+H)=371。
表1以非限制性方式說明式(I)化合物之實例:
其中A可選自由以下基團組成之清單:A-G1、A-G2、A-G3、A-G4、A-G5、
A-G6及A-G7:
其中該基團A-Gn經由用「*」所鑑別之鍵連接至式(I)之L且該基團A-Gn經由用「#」所鑑別之鍵連接至式(I)之B環。
表1中所示之化合物係與上文所提供之實例類似而製備。
在表1中,logP值係根據EEC Directive 79/831 Annex V.A8,藉由HPLC (高效液相層析)在逆相管柱(C 18)上,使用以下所述方法測定:
溫度:40℃;移動相:0.1%甲酸水溶液及乙腈水溶液;線性梯度:10%乙腈至95%乙腈;
若多於一個LogP值在相同方法中可用,則所有值給出且由「;」分隔開。
校準係使用具有已知logP值(logP值之測定藉由在兩個連續烷酮之間使用線性內插法之滯留時間)之未分支烷-2-酮(包含3至16個碳原子)執行。使用200 nm至400 nm之UV光譜及層析信號之峰值測定λ最大值。 表 1 :
注意( 1 )
:作為不可分開的1:1混合物NMR 峰清單
實例 | L | M+H | logP | |||
I.001 | 喹啉-3-基 | NH | A-G3 | 吡啶-3-基 | 316 | 1.39 |
I.002 | 3-甲基喹喏啉-2-基 | NH | A-G2 | 3-氟吡啶-4-基 | 349 | 2.57 |
I.003 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 噠嗪-4-基 | 349 | 2.28 |
I.004 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 5-甲基吡啶-3-基 | 362 | 1.99 |
I.005 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-甲基吡啶-4-基 | 362 | 1.75 |
I.006 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 4-甲基吡啶-3-基 | 362 | 1.86 |
I.007 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 吡啶-4-基 | 365 | 2.00 |
I.008 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 吡啶-3-基 | 365 | 2.64 |
I.009 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 吡啶-3-基 | 366 | 2.28 |
I.010 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 吡啶-4-基 | 366 | 2.01 |
I.011 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 嘧啶-5-基 | 366 | 2.76 |
I.012 | 8-氟-2-甲基喹啉-3-基 | NH | A-G4 | 3-氟吡啶-4-基 | 366 | 2.95 |
I.013 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 嘧啶-5-基 | 367 | 2.61 |
I.014 | 5,6-二氟-3-甲基喹喏啉-2-基 | NH | A-G1 | 3-氟吡啶-4-基 | 367 | 2.83 |
I.015 | 5-氟-3-甲基喹喏啉-2-基 | NH | A-G2 | 3-氟吡啶-4-基 | 367 | 2.67 |
I.016 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 噠嗪-4-基 | 367 | 2.44 |
I.017 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 3,4-二氫-2H-哌喃-6-基 | 370 | 4.41 |
I.018 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 3,4-二氫-2H-哌喃-6-基 | 371 | 4.44 |
I.019 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-氰基吡啶-3-基 | 373 | 3.25 |
I.020 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 5-氰基吡啶-3-基 | 373 | 3.04 |
I.021 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 3-氰基吡啶-4-基 | 373 | 1.41 |
I.022 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 3-乙基吡啶-4-基 | 376 | 2.08 |
I.023 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 4-乙基吡啶-3-基 | 376 | 2.08 |
I.024 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-乙基吡啶-3-基 | 376 | 2.03 |
I.025 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 3,5-二甲基吡啶-4-基 | 376 | 2.05 |
I.026 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 1-甲基-6-側氧基-1,6-二氫吡啶-2-基 | 378 | 2.52 |
I.027 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 3-甲氧基吡啶-4-基 | 378 | 2.14 |
I.028 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-甲氧基吡啶-4-基 | 378 | 3.56 |
I.029 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-甲氧基吡啶-2-基 | 378 | 4.66 |
I.030 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 4-甲氧基吡啶-3-基 | 378 | 1.77 |
I.031 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-氟-5-甲基吡啶-3-基 | 380 | 3.69 |
I.032 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 5-甲基吡啶-3-基 | 380 | 2.26 |
I.033 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-甲基吡啶-4-基 | 380 | 1.88 |
I.034 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 3-氯吡啶-4-基 | 382 | 3.37 |
I.035 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-氯吡啶-2-基 | 382 | 4.97 |
I.036 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-氯吡啶-4-基 | 382 | 3.56 |
I.037 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-氯吡啶-3-基 | 382 | 3.62 |
I.038 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-氯吡啶-3-基 | 382 | 3.43 |
I.039 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 4-氯吡啶-3-基 | 382 | 3.22 |
I.040 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 5-氯吡啶-3-基 | 382 | 3.54 |
I.041 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 3-氟吡啶-4-基 | 383 | 3.40 |
I.042 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 6-氟吡啶-3-基 | 383 | 3.70 |
I.043 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 2-氟吡啶-3-基 | 383 | 3.55 |
I.044 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 2-氟吡啶-4-基 | 383 | 3.65 |
I.045 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-氟吡啶-3-基 | 384 | 3.46 |
I.046 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-氟吡啶-4-基 | 384 | 3.46 |
I.047 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-氟吡啶-3-基 | 384 | 3.35 |
I.048 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G5 | 3-氟吡啶-4-基 | 384 | 3.04 |
I.049 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G3 | 3-氟吡啶-4-基 | 3.24 | |
I.050 | 5,6-二氟-3-甲基喹喏啉-2-基 | CH2 | A-G2 | 3-氟吡啶-4-基 | 384 | 3.31 |
I.051 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 3-氟吡啶-4-基 | 3.29 | |
I.052 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2,5-二氟吡啶-4-基 / 2,5-二氟吡啶-3-基(1) | 384 | 3.62 |
I.053 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2,3-二氟吡啶-4-基 | 384 | 3.69 |
I.054 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2,6-二氟吡啶-4-基 | 384 | 3.91 |
I.055 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2,6-二氟吡啶-3-基 | 384 | 3.81 |
I.056 | 5,6-二氟-3-甲基喹喏啉-2-基 | NH | A-G2 | 3-氟吡啶-4-基 | 385 | 2.98 |
I.057 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 4-環丙基吡啶-3-基 | 388 | 2.05 |
I.058 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 3-環丙基吡啶-4-基 | 388 | 2.12 |
I.059 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-環丙基吡啶-3-基 | 388 | 2.80 |
I.060 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-丙基吡啶-3-基 | 390 | 2.21 |
I.061 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 3-丙基吡啶-4-基 | 390 | 2.31 |
I.062 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 4-丙基吡啶-3-基 | 390 | 2.41 |
I.063 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 3-氰基吡啶-4-基 | 391 | 1.46 |
I.064 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 5-氰基吡啶-3-基 | 391 | 3.16 |
I.065 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-乙氧吡啶-3-基 | 392 | 4.02 |
I.066 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-乙氧吡啶-3-基 | 392 | 4.24 |
I.067 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 3-乙基吡啶-4-基 | 394 | 2.41 |
I.068 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 4-乙基吡啶-3-基 | 394 | 2.41 |
I.069 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-乙基吡啶-3-基 | 394 | 2.41 |
I.070 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 3,5-二甲基吡啶-4-基 | 394 | 2.28 |
I.071 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-(甲基硫基)吡啶-3-基 | 394 | 3.81 |
I.072 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-(甲基硫基)吡啶-3-基 | 394 | 4.08 |
I.073 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 6-甲氧基吡啶-3-基 | 395 | 3.99 |
I.074 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 6-甲氧基吡啶-2-基 | 395 | 3.79 |
I.075 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 2-甲氧基吡啶-3-基 | 395 | 3.79 |
I.076 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-甲氧基吡啶-3-基 | 396 | 3.70 |
I.077 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-甲氧基吡啶-3-基 | 396 | 3.71 |
I.078 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G2 | 2-甲氧基嘧啶-5-基 | 396 | 3.25 |
I.079 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-氟-3-甲氧基吡啶-4-基 | 396 | 3.72 |
I.080 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-甲氧基吡啶-2-基 | 396 | 4.55 |
I.081 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 3-甲氧基吡啶-4-基 | 396 | 2.44 |
I.082 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 4-甲氧基吡啶-3-基 | 396 | 1.84 |
I.083 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-甲氧基吡啶-4-基 | 396 | 3.71 |
I.084 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-氯-5-甲基吡啶-3-基 | 396 | 3.69 |
I.085 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-氯-2-甲基吡啶-3-基 | 396 | 3.94 |
I.086 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-氯-4-甲基吡啶-3-基 | 396 | 3.98 |
I.087 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-氯-5-甲基吡啶-3-基 | 396 | 3.91 |
I.088 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-甲氧基嘧啶-5-基 | 397 | 3.08 |
I.089 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-氟-5-甲基吡啶-3-基 | 398 | 3.75 |
I.090 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 4-氯-5-氟吡啶-3-基 | 400 | 3.62 |
I.091 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-氯吡啶-4-基 | 400 | 3.69 |
I.092 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-氯吡啶-3-基 | 400 | 3.72 |
I.093 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 3-氯吡啶-4-基 | 400 | 3.46 |
I.094 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-氯吡啶-3-基 | 400 | 3.50 |
I.095 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 5-氯-2-氟吡啶-3-基 | 400 | 4.01 |
I.096 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 3-氯-2-氟吡啶-4-基 | 400 | 3.91 |
I.097 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-氯-5-氟吡啶-3-基 | 400 | 3.81 |
I.098 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2-氯-5-氟吡啶-4-基 | 400 | 3.91 |
I.099 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 5-氯吡啶-3-基 | 400 | 3.60 |
I.100 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2,6-二氟吡啶-4-基 | 402 | 3.98 |
I.101 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2,3-二氟吡啶-4-基 | 402 | 3.81 |
I.102 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2,5-二氟吡啶-4-基 / 2,5-二氟吡啶-3-基(1) | 402 | 3.77 |
I.103 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2,6-二氟吡啶-3-基 | 402 | 3.84 |
I.104 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 4-環丙基吡啶-3-基 | 406 | 2.12 |
I.105 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-環丙基吡啶-3-基 | 406 | 3.25 |
I.106 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 3-環丙基吡啶-4-基 | 406 | 2.49 |
I.107 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-異丙氧基吡啶-3-基 | 406 | 4.43 |
I.108 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2,6-二甲氧基吡啶-3-基 | 408 | 4.62 |
I.109 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-丙基吡啶-3-基 | 408 | 2.62 |
I.110 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 3-丙基吡啶-4-基 | 408 | 2.89 |
I.111 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 4-丙基吡啶-3-基 | 408 | 2.75 |
I.112 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-乙氧吡啶-3-基 | 410 | 4.09 |
I.113 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-乙氧吡啶-3-基 | 410 | 4.13 |
I.114 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-(甲基硫基)吡啶-3-基 | 412 | 3.91 |
I.115 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-(甲基硫基)吡啶-3-基 | 412 | 3.98 |
I.116 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 3-氯-2-甲氧基吡啶-4-基 | 412 | 4.09 |
I.117 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-氟-3-甲氧基吡啶-4-基 | 414 | 3.75 |
I.118 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-氯-5-甲基吡啶-3-基 | 414 | 3.75 |
I.119 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-氯-5-甲基吡啶-3-基 | 414 | 3.98 |
I.120 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-氯-2-甲基吡啶-3-基 | 414 | 4.01 |
I.121 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-氯-4-甲基吡啶-3-基 | 414 | 4.01 |
I.122 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 5-(三氟甲基)吡啶-3-基 | 416 | 3.65 |
I.123 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 6-(三氟甲基)吡啶-3-基 | 416 | 3.91 |
I.124 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 2,5-二氯吡啶-3-基 | 416 | 4.13 |
I.125 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 4,5-二氯吡啶-3-基 | 416 | 4.01 |
I.126 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-氯-5-氟吡啶-4-基 | 418 | 3.98 |
I.127 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2-氯-5-氟吡啶-3-基 | 418 | 3.87 |
I.128 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 5-氯-2-氟吡啶-3-基 | 418 | 4.05 |
I.129 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 3-氯-2-氟吡啶-4-基 | 418 | 3.98 |
I.130 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-異丙氧基吡啶-3-基 | 424 | 4.47 |
I.131 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2,6-二甲氧基吡啶-3-基 | 426 | 4.43 |
I.132 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 3-氯-2-甲氧基吡啶-4-基 | 430 | 4.09 |
I.133 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 5-(三氟甲基)吡啶-3-基 | 434 | 3.75 |
I.134 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 6-(三氟甲基)吡啶-3-基 | 434 | 3.94 |
I.135 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G1 | 5-溴-2-甲氧基吡啶-4-基 | 456 | 4.36 |
I.136 | 7,8-二氟-2-甲基喹啉-3-基 | NH | A-G2 | 2,5-二氟吡啶-3-基 | 3.71 | |
I.137 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G6 | 2-氟吡啶-4-基 | 366 | 2.52 |
I.138 | 7,8-二氟-2-甲基喹啉-3-基 | CH2 | A-G7 | 2-氟吡啶-4-基 | 371 | 3.64 |
I.139 | 8-氟喹啉-3-基 | CH2 | A-G7 | 2-氟吡啶-4-基 | 339 | 3.11 |
所選實例之1
H-NMR數據以1
H-NMR峰清單之形式陳述。對於每一信號峰值,所列δ值以ppm表示且信號強度在括號中表示。
尖銳信號的強度相當於所列印出NMR譜實例的信號高度(以cm表示)且展示信號的強度的實際關係。自寬信號可展示信號之若干峰值或中間值及其相較於頻譜中之最密集信號之相對強度。
1
H-NMR峰清單類似於經典1
H-NMR印刷圖且因此通常含有經典NMR說明中所列之所有峰。另外,其可如古典1
H-NMR印刷一樣顯示溶劑信號、目標化合物之立體異構體(其亦為本發明之目的)及/或雜質之峰。為在溶劑及/或水之δ範圍(delta-range)中展示化合物信號,溶劑之一般峰(例如d6-DMSO中之DMSO峰)及水之峰展示於吾人之1
H-NMR峰清單中且通常平均具有較高強度。
目標化合物之立體異構體之峰及/或雜質之峰通常平均具有比目標化合物(例如具有大於90%之純度)之峰低的強度。此類立體異構體及/或雜質對於特定製備方法可為典型的。因此其峰可經由「副產物指紋」幫助辨認吾人之製備方法之再現。
用已知方法(MestreC、ACD模擬,以及用憑經驗評估之期望值)計算目標化合物之峰的專家可視情況使用另外的強度過濾器按需要分離目標化合物之峰。此分離將類似於經典1
H-NMR解釋處之相關峰挑選。
具有峰清單之NMR數據描述的其他詳情可見於研究公開資料庫編號564025之公開案「Citation of NMR Peaklist Data within Patent Applications」中。
所選擇之式(I)化合物之NMR峰清單
使用實例
I.001: 1H-NMR(300.2 MHz, CDCl3): δ= 8.7057 (7.6);8.7039 (7.6);8.6985 (8.1);8.6081 (5.6);8.6027 (5.9);8.5919 (6.3);8.5864 (6.7);8.5808 (12.0);8.5715 (11.6);8.0205 (4.4);8.0166 (4.8);7.9936 (4.7);7.9906 (5.4);7.7943 (3.4);7.7885 (5.0);7.7811 (3.4);7.7680 (4.0);7.7622 (5.6);7.7549 (3.7);7.6399 (3.9);7.6356 (3.6);7.6325 (3.1);7.6147 (6.3);7.6084 (6.2);7.5621 (2.0);7.5562 (2.7);7.5392 (6.0);7.5333 (4.6);7.5291 (2.5);7.5130 (9.8);7.5057 (10.1);7.4857 (16.0);7.4799 (10.9);7.4681 (5.0);7.4625 (3.0);7.4570 (5.9);7.4394 (5.0);7.3644 (4.8);7.3619 (4.3);7.3482 (4.7);7.3457 (4.2);7.3381 (4.4);7.3357 (3.8);7.3219 (4.1);7.3195 (3.6);7.2984 (11.2);7.1981 (2.4);7.1881 (3.8);7.1717 (3.1);7.1596 (7.5);7.1567 (7.8);7.1467 (3.6);7.1333 (4.5);7.1272 (6.8);7.1175 (3.4);5.7495 (7.0);2.9841 (2.4);2.9091 (2.1);2.8083 (0.3);2.1190 (2.3);2.0512 (1.0);2.0349 (13.0);2.0182 (1.0);1.2943 (0.5);1.2878 (0.5);1.2710 (0.5);0.0433 (0.4);0.0326 (12.4);0.0216 (0.4) |
I.002: 1H-NMR(300.2 MHz, CDCl3): δ= 8.7126 (3.5);8.5976 (2.1);8.5815 (2.2);8.5550 (1.9);8.5271 (2.0);7.8989 (1.6);7.8718 (1.8);7.8404 (1.6);7.8128 (2.1);7.6553 (0.8);7.6286 (1.7);7.6157 (0.8);7.6052 (1.1);7.5934 (1.0);7.5879 (1.6);7.5661 (1.5);7.5602 (0.9);7.5389 (1.9);7.5160 (1.7);7.4929 (0.8);7.4886 (0.7);7.4656 (1.3);7.4478 (2.0);7.4296 (1.2);7.2984 (7.4);7.0746 (1.2);7.0446 (2.1);7.0164 (1.1);6.5274 (1.8);2.4188 (16.0);1.6383 (9.7);1.2919 (0.4);0.0364 (9.1) |
I.003: 1H-NMR(400.2 MHz, d6-DMSO): δ= 9.3181 (2.4);9.3151 (2.9);9.3123 (2.9);9.3092 (2.5);9.0425 (2.4);9.0395 (2.4);9.0291 (2.5);9.0261 (2.5);7.8267 (3.4);7.7596 (2.2);7.7536 (2.3);7.7462 (2.2);7.7402 (2.2);7.5837 (0.8);7.5798 (1.0);7.5644 (1.6);7.5604 (2.9);7.5419 (2.4);7.5381 (2.7);7.4860 (0.5);7.4692 (0.7);7.4613 (1.6);7.4481 (2.2);7.4314 (1.0);7.4232 (1.1);7.4059 (1.1);7.4005 (1.6);7.3979 (1.7);7.3819 (2.2);7.3789 (2.4);7.3724 (2.5);7.3630 (1.0);7.3601 (1.2);7.3527 (2.0);7.0810 (3.3);7.0786 (3.3);3.3490 (30.7);2.8932 (1.2);2.7354 (1.0);2.7344 (1.1);2.6266 (16.0);2.5296 (0.5);2.5161 (8.1);2.5118 (15.9);2.5073 (20.4);2.5027 (14.9);2.4983 (7.3);-0.0002 (1.3) |
I.004: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.3887 (2.8);8.3842 (2.8);8.1005 (2.6);8.0969 (2.7);7.9554 (0.5);7.6707 (2.8);7.6516 (3.4);7.4955 (0.7);7.4916 (0.8);7.4765 (1.7);7.4735 (1.6);7.4574 (1.4);7.4538 (1.8);7.4399 (2.0);7.4353 (2.1);7.4309 (2.3);7.4197 (3.7);7.4165 (3.5);7.4067 (1.1);7.3981 (1.2);7.3814 (1.0);7.3580 (0.4);7.3444 (2.1);7.3393 (2.6);7.3367 (2.2);7.3274 (2.2);7.3196 (1.9);7.3097 (1.0);6.9853 (3.3);6.9830 (3.3);3.3444 (9.9);2.8923 (3.1);2.7338 (2.7);2.5824 (16.0);2.5279 (0.6);2.5143 (10.9);2.5102 (21.0);2.5057 (26.6);2.5012 (19.3);2.4970 (9.5);2.1347 (13.0);-0.0002 (1.6) |
I.005: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2102 (2.7);8.1973 (2.8);7.6589 (3.5);7.5051 (0.8);7.5013 (0.9);7.4860 (1.7);7.4828 (1.7);7.4671 (1.2);7.4633 (1.3);7.4556 (0.5);7.4367 (2.0);7.4321 (4.1);7.4162 (4.2);7.4040 (1.3);7.3876 (1.0);7.3643 (0.4);7.3304 (4.5);7.3265 (4.6);7.3116 (3.5);7.2962 (1.0);7.2099 (1.8);7.2071 (1.8);7.1970 (1.8);7.1943 (1.7);7.0345 (3.5);3.3449 (20.6);2.8924 (1.9);2.7341 (1.7);2.6067 (16.0);2.5105 (19.5);2.5061 (24.8);2.5017 (18.3);2.3020 (15.4);-0.0002 (1.3) |
I.006: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.3400 (5.2);8.1306 (3.1);8.1181 (3.2);7.9554 (0.3);7.5238 (0.6);7.5204 (0.6);7.5098 (0.8);7.5062 (0.9);7.4974 (2.1);7.4895 (1.6);7.4836 (1.8);7.4800 (2.0);7.4701 (4.8);7.4629 (1.8);7.4575 (1.6);7.4553 (1.8);7.4400 (1.1);7.4322 (1.2);7.4142 (1.0);7.4093 (0.7);7.3910 (0.5);7.3079 (0.8);7.2949 (10.5);7.2888 (3.5);7.2775 (3.2);7.2617 (0.5);7.2592 (0.4);7.1344 (3.5);7.1321 (3.6);7.0650 (2.6);7.0524 (2.6);3.3512 (36.5);2.8928 (2.4);2.7342 (2.0);2.5290 (0.6);2.5156 (10.0);2.5113 (19.6);2.5067 (26.8);2.5023 (32.7);2.1772 (16.0);-0.0002 (1.3) |
I.007: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.5978 (5.0);8.5938 (3.3);8.5868 (3.2);8.5828 (5.2);7.9564 (0.3);7.7924 (3.0);7.7521 (0.6);7.7481 (0.7);7.7383 (0.8);7.7340 (0.8);7.7293 (1.0);7.7250 (1.0);7.7153 (0.9);7.7117 (0.9);7.6286 (0.8);7.6103 (0.9);7.6029 (1.0);7.5848 (1.0);7.5800 (0.7);7.5616 (0.5);7.4863 (0.7);7.4712 (0.9);7.4662 (1.4);7.4514 (1.4);7.4463 (1.1);7.4313 (0.9);7.3446 (4.3);7.3414 (3.1);7.3299 (4.2);7.3150 (1.3);7.2930 (2.0);7.2716 (0.9);7.0409 (2.1);7.0216 (2.0);6.6378 (0.4);6.6169 (0.4);4.0287 (6.7);3.6173 (0.6);3.5850 (2.4);3.3563 (72.8);2.8963 (2.2);2.7382 (1.9);2.7373 (1.9);2.5179 (10.8);2.5136 (21.2);2.5091 (27.4);2.5046 (20.3);2.5003 (10.4);2.4010 (16.0);-0.0002 (0.4) |
I.008: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.5556 (1.7);8.5518 (1.8);8.5436 (1.8);8.5398 (1.8);8.4795 (2.4);8.4752 (2.5);7.9561 (0.5);7.7724 (3.1);7.7474 (1.6);7.7423 (1.8);7.7381 (1.7);7.7235 (2.4);7.7175 (1.6);7.6255 (0.8);7.6072 (0.8);7.6000 (1.0);7.5819 (1.0);7.5770 (0.7);7.5584 (0.5);7.4883 (0.7);7.4733 (0.8);7.4683 (1.4);7.4534 (1.4);7.4485 (1.1);7.4334 (2.3);7.4205 (1.4);7.4141 (1.4);7.4019 (1.2);7.3159 (1.2);7.2935 (1.9);7.2719 (0.9);7.0707 (2.2);7.0516 (2.0);4.0343 (6.8);3.3635 (72.1);3.3616 (74.1);2.8965 (3.4);2.7380 (3.0);2.5315 (0.6);2.5183 (9.9);2.5142 (19.4);2.5097 (25.1);2.5053 (18.5);2.3882 (16.0) |
I.009: 1H-NMR(400.2 MHz, d6-DMSO): δ= 9.6188 (0.6);8.5487 (11.9);8.3119 (0.8);8.2839 (7.4);8.2806 (8.1);8.2721 (8.1);8.2687 (7.9);7.9543 (2.0);7.8645 (0.5);7.8455 (0.5);7.8044 (6.4);7.7848 (6.8);7.6848 (14.7);7.5502 (3.1);7.5359 (3.9);7.5303 (5.3);7.5273 (5.3);7.5165 (4.9);7.4961 (3.6);7.4757 (8.2);7.4702 (5.4);7.4592 (8.5);7.4552 (7.4);7.4440 (6.0);7.4391 (5.9);7.4265 (5.0);7.4028 (2.5);7.3790 (0.6);7.3608 (0.3);7.3468 (0.6);7.3259 (1.1);7.3051 (0.9);7.2974 (0.6);7.2718 (16.0);7.2353 (6.3);7.2232 (6.4);7.2166 (6.4);7.2044 (5.7);7.1471 (5.3);7.1253 (8.8);7.1013 (6.4);7.0959 (10.7);7.0756 (9.3);7.0444 (0.6);7.0364 (0.6);7.0261 (0.6);7.0170 (0.8);7.0063 (0.5);6.9971 (0.4);6.7082 (1.8);6.6872 (1.7);6.6372 (0.6);6.6162 (0.6);6.5550 (1.9);6.1299 (2.5);4.0122 (0.5);3.6522 (0.6);3.6155 (9.8);3.5832 (3.3);3.5565 (6.5);3.3603 (499.3);3.2019 (0.4);2.9817 (0.3);2.8941 (12.0);2.7540 (0.4);2.7356 (10.8);2.7140 (0.6);2.6955 (0.6);2.6763 (0.9);2.6334 (0.5);2.5856 (1.0);2.5746 (0.7);2.5371 (70.5);2.5116 (114.8);2.5073 (145.5);2.5030 (109.8);2.3760 (0.5);2.3602 (0.5);2.3384 (0.8);2.3340 (1.0);1.7152 (0.4);1.6458 (1.9);1.6014 (1.9);1.5534 (2.2);1.4127 (0.7);1.3784 (0.6);1.3586 (0.5);1.3390 (0.6);1.2999 (0.9);1.2597 (1.4);1.2375 (5.7);1.1856 (0.4);1.1508 (0.4);1.1143 (0.8);1.0588 (3.3);0.8698 (0.5);0.8528 (1.1);0.8353 (0.5);-0.0002 (2.2) |
I.010: 1H-NMR(300.2 MHz, CDCl3): δ= 8.7734 (2.6);8.7543 (2.6);7.7861 (2.9);7.7833 (2.8);7.4315 (0.6);7.4133 (3.8);7.3975 (4.4);7.3888 (2.8);7.3813 (2.7);7.3684 (1.3);7.3592 (2.4);7.3362 (1.4);7.2988 (4.1);7.0433 (2.1);7.0158 (1.8);6.9478 (1.1);6.9451 (1.0);6.9173 (2.0);6.8896 (1.0);6.8868 (0.9);5.4505 (1.9);5.3340 (0.7);2.5742 (16.0);2.0791 (0.3);1.7574 (0.6);1.2886 (0.7);0.0336 (4.4) |
I.011: 1H-NMR(400.2 MHz, d6-DMSO): δ= 9.1552 (7.0);8.8135 (11.5);7.9557 (0.4);7.7797 (3.2);7.7599 (0.7);7.7560 (0.8);7.7463 (0.8);7.7421 (0.9);7.7372 (1.0);7.7331 (1.0);7.7233 (0.9);7.7197 (0.9);7.6334 (0.8);7.6152 (0.9);7.6080 (1.0);7.5898 (1.0);7.5850 (0.7);7.5665 (0.5);7.5422 (0.7);7.5271 (0.9);7.5221 (1.4);7.5071 (1.4);7.5022 (1.1);7.4871 (0.9);7.3651 (1.2);7.3432 (1.9);7.3218 (1.0);7.1072 (2.1);7.0881 (2.0);4.1000 (6.7);3.3624 (66.4);2.8969 (2.3);2.7379 (2.1);2.5146 (19.4);2.5101 (25.1);2.5056 (18.5);2.5015 (9.5);2.4289 (16.0) |
I.012: 1H-NMR(300.2 MHz, CDCl3): δ= 8.6104 (2.7);8.6049 (2.8);8.5373 (1.7);8.5339 (1.8);8.5210 (1.8);8.5176 (1.8);7.7579 (2.6);7.7536 (2.6);7.4654 (0.5);7.4593 (0.8);7.4379 (2.7);7.4324 (3.1);7.4198 (1.2);7.4106 (1.4);7.3987 (1.7);7.3957 (1.6);7.3825 (3.0);7.3676 (0.8);7.3616 (2.5);7.3536 (1.4);7.3325 (1.3);7.2990 (7.6);7.2810 (0.7);7.2737 (0.7);7.2678 (1.0);7.2623 (1.0);7.2433 (0.7);7.2378 (0.7);7.0277 (1.2);7.0194 (1.5);6.9929 (1.3);6.9846 (1.5);6.9560 (1.0);6.9476 (0.8);6.9291 (1.3);6.9205 (1.1);6.9013 (0.8);6.8930 (0.7);5.6154 (1.4);4.1934 (0.3);4.1695 (1.0);4.1457 (1.0);4.1219 (0.4);2.6506 (16.0);2.0820 (4.7);1.6458 (5.5);1.3197 (1.3);1.3069 (0.8);1.2959 (2.7);1.2721 (1.2);0.0471 (0.3);0.0361 (9.7);0.0254 (0.3) |
I.013: 1H-NMR(400.2 MHz, d6-DMSO): δ= 10.1518 (1.0);10.1442 (1.0);8.9091 (6.5);8.8326 (9.6);8.7558 (1.2);8.6398 (1.9);8.3893 (0.7);8.3144 (0.6);7.9546 (2.6);7.8494 (3.4);7.8392 (1.4);7.8211 (0.4);7.5869 (0.7);7.5727 (0.9);7.5672 (1.2);7.5641 (1.2);7.5505 (1.1);7.5382 (0.8);7.5177 (1.6);7.5009 (2.4);7.4808 (1.7);7.4575 (1.1);7.4338 (0.5);7.3479 (3.7);7.3320 (0.4);7.3242 (0.6);7.3117 (0.5);7.3042 (0.4);7.2916 (0.3);7.2066 (0.5);7.1865 (0.5);7.1748 (1.4);7.1525 (2.1);7.1302 (1.1);7.0911 (2.4);7.0713 (2.4);7.0552 (0.9);3.6158 (0.8);3.3787 (3.0);3.2021 (0.4);2.8948 (14.3);2.7360 (13.1);2.7208 (0.4);2.5617 (16.0);2.5111 (32.1);2.5068 (41.0);2.5026 (31.3);2.4214 (5.0);1.2603 (0.4);1.2376 (1.4);-0.0002 (1.1) |
I.014: 1H-NMR(300.2 MHz, CDCl3): δ= 8.6400 (2.8);8.6347 (2.8);8.5484 (1.7);8.5452 (1.8);8.5322 (1.8);8.5289 (1.8);8.4373 (1.8);8.4100 (1.9);7.6434 (0.8);7.6369 (0.8);7.6139 (1.4);7.5921 (0.8);7.5858 (0.9);7.5418 (0.6);7.5369 (0.5);7.5254 (0.6);7.5195 (0.6);7.5107 (1.2);7.5057 (1.4);7.4942 (1.2);7.4884 (1.3);7.4825 (1.3);7.4579 (1.1);7.4502 (1.4);7.4254 (3.4);7.4051 (3.9);7.3987 (2.2);7.3890 (1.7);7.3836 (1.9);7.3803 (1.7);7.3566 (1.7);7.3343 (0.6);7.3309 (0.6);7.2988 (17.6);6.6741 (1.4);5.3383 (0.7);2.5466 (16.0);1.6061 (13.7);1.2908 (0.9);0.0476 (0.7);0.0368 (19.6);0.0260 (0.8) |
I.015: 1H-NMR(300.2 MHz, CDCl3): δ= 8.7100 (3.0);8.7064 (2.9);8.6785 (0.4);8.5958 (1.9);8.5926 (2.0);8.5797 (1.9);8.5766 (1.8);8.4866 (1.8);8.4587 (1.9);7.6224 (1.3);7.6170 (0.9);7.6018 (1.0);7.5938 (3.2);7.5887 (2.1);7.5748 (2.4);7.5676 (1.0);7.5586 (1.1);7.5508 (1.4);7.5468 (1.1);7.5327 (1.2);7.5229 (0.5);7.5048 (0.6);7.4556 (1.2);7.4374 (1.8);7.4195 (1.2);7.2989 (9.7);7.2361 (0.9);7.2305 (0.9);7.2113 (0.8);7.2028 (1.1);7.1978 (1.0);7.1768 (0.8);7.1722 (0.8);7.1060 (1.0);7.1033 (1.0);7.0757 (1.9);7.0480 (0.9);7.0453 (0.9);6.6053 (1.5);5.3374 (0.3);2.4651 (16.0);1.6210 (10.8);0.0474 (0.4);0.0366 (10.8);0.0255 (0.4) |
I.016: 1H-NMR(400.2 MHz, d6-DMSO): δ= 9.2585 (2.4);9.2558 (2.5);9.2532 (2.4);9.0715 (2.4);9.0685 (2.3);9.0582 (2.5);9.0552 (2.4);7.8762 (3.3);7.7608 (1.3);7.7591 (1.4);7.7553 (1.4);7.7476 (1.4);7.7459 (1.4);7.7421 (1.4);7.5858 (0.6);7.5821 (0.6);7.5718 (0.7);7.5633 (1.7);7.5593 (1.2);7.5469 (1.9);7.5435 (2.2);7.5266 (1.7);7.5226 (1.1);7.5066 (1.3);7.4903 (0.9);7.4827 (1.0);7.4648 (0.9);7.4598 (0.6);7.4414 (0.5);7.3681 (3.3);7.1821 (1.2);7.1603 (1.8);7.1385 (1.0);7.1370 (1.0);7.1035 (2.3);7.0832 (2.1);3.3479 (29.8);2.8938 (1.3);2.7355 (1.1);2.5773 (16.0);2.5299 (0.4);2.5249 (0.7);2.5164 (8.2);2.5120 (16.2);2.5075 (20.8);2.5029 (15.1);2.4985 (7.3);-0.0002 (1.3) |
I.017: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.8962 (3.0);7.7684 (0.6);7.7642 (0.7);7.7547 (0.7);7.7503 (0.8);7.7456 (1.0);7.7414 (1.0);7.7317 (0.9);7.7279 (0.9);7.6310 (0.7);7.6127 (0.8);7.6053 (1.0);7.5872 (0.9);7.5824 (0.7);7.5640 (0.5);7.3507 (0.7);7.3358 (0.8);7.3308 (1.4);7.3161 (1.4);7.3108 (1.1);7.2960 (0.9);7.1538 (1.1);7.1320 (1.8);7.1105 (0.9);6.8627 (2.1);6.8437 (1.9);4.8253 (1.3);4.8159 (2.8);4.8065 (1.3);4.2115 (6.7);3.9355 (2.2);3.9231 (2.8);3.9104 (2.3);3.3679 (87.0);2.8970 (1.8);2.7386 (1.6);2.5840 (16.0);2.5324 (0.5);2.5190 (8.4);2.5147 (16.7);2.5102 (21.9);2.5057 (16.3);2.5016 (8.4);2.0684 (0.9);2.0527 (2.3);2.0430 (2.3);2.0274 (1.1);1.7725 (0.6);1.7575 (1.7);1.7439 (1.9);1.7316 (1.5);1.7161 (0.5) |
I.018: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9548 (0.4);7.7944 (3.3);7.6758 (0.6);7.6719 (0.7);7.6622 (0.7);7.6579 (0.8);7.6527 (1.0);7.6486 (1.1);7.6391 (1.0);7.6356 (1.0);7.5677 (0.8);7.5494 (0.8);7.5424 (1.0);7.5242 (1.0);7.5006 (0.6);7.4676 (3.3);7.4402 (0.4);7.4316 (0.4);7.4242 (0.4);7.3123 (0.8);7.2958 (1.1);7.2918 (1.6);7.2756 (1.7);7.2715 (1.1);7.2550 (0.9);6.9546 (2.3);6.9341 (2.1);6.8284 (1.2);6.8055 (1.9);6.7841 (1.1);4.9802 (1.0);4.9709 (2.1);4.9624 (1.1);3.8275 (2.0);3.8149 (2.7);3.8025 (2.2);3.3695 (96.3);3.2945 (0.4);3.2811 (0.3);2.8962 (2.7);2.7376 (2.3);2.6493 (16.0);2.5310 (0.6);2.5176 (10.9);2.5134 (21.7);2.5089 (28.4);2.5045 (21.2);1.9421 (0.9);1.9267 (2.2);1.9169 (2.2);1.9014 (1.1);1.5784 (0.6);1.5640 (1.7);1.5509 (2.0);1.5380 (1.5);1.5226 (0.6);1.2602 (0.4);1.2367 (1.1);-0.0002 (0.5) |
I.019: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.8225 (2.8);8.8207 (3.0);8.8171 (3.0);8.8153 (2.7);8.1147 (2.0);8.1092 (1.9);8.0945 (2.4);8.0890 (2.3);7.9565 (2.2);7.8974 (3.0);7.8957 (3.0);7.8773 (2.5);7.8755 (2.5);7.7603 (3.6);7.5597 (0.8);7.5558 (0.9);7.5404 (1.6);7.5367 (2.0);7.5177 (2.8);7.5005 (2.3);7.4971 (1.8);7.4879 (0.6);7.4712 (0.7);7.4637 (1.9);7.4547 (1.6);7.4503 (1.6);7.4390 (1.0);7.4305 (1.1);7.4137 (1.0);7.4079 (0.4);7.3854 (1.3);7.3827 (1.5);7.3667 (1.8);7.3638 (2.6);7.3585 (2.6);7.3478 (1.0);7.3450 (1.2);7.3388 (2.0);7.0863 (3.3);7.0842 (3.3);3.3492 (51.4);2.8947 (14.9);2.7363 (12.7);2.7354 (12.4);2.6017 (16.0);2.5304 (0.5);2.5170 (10.5);2.5126 (20.5);2.5080 (26.1);2.5035 (18.7);2.4990 (9.0);-0.0002 (0.9) |
I.020: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.8745 (3.8);8.8692 (3.8);8.7200 (4.0);8.7150 (4.0);8.4058 (2.4);8.4007 (4.1);8.3955 (2.2);7.9558 (2.0);7.7683 (3.6);7.5496 (0.8);7.5457 (0.9);7.5303 (1.6);7.5266 (2.3);7.5184 (1.8);7.5157 (1.8);7.5120 (1.4);7.5077 (1.9);7.4996 (2.7);7.4897 (0.8);7.4864 (0.8);7.4778 (1.4);7.4635 (1.3);7.4587 (1.2);7.4412 (0.9);7.4333 (1.1);7.4158 (1.0);7.4107 (0.5);7.3925 (0.4);7.3748 (1.2);7.3722 (1.5);7.3531 (4.4);7.3329 (2.5);7.0486 (3.4);3.3444 (38.5);2.8935 (13.6);2.7352 (11.6);2.7342 (11.8);2.5992 (16.0);2.5291 (0.6);2.5155 (11.3);2.5112 (21.9);2.5068 (27.7);2.5022 (20.0);2.4978 (9.7);-0.0002 (1.4) |
I.022: 1H-NMR(300.2 MHz, CDCl3): δ= 8.6155 (0.7);8.5984 (0.7);8.4862 (1.2);7.8102 (0.8);7.4483 (0.4);7.4202 (0.4);7.3816 (0.5);7.3683 (0.6);7.3526 (0.8);7.3387 (0.5);7.3290 (1.1);7.3124 (0.8);7.2990 (7.5);7.2821 (0.6);7.2769 (0.6);7.2075 (0.4);7.1826 (0.5);5.3380 (1.3);5.2050 (0.6);2.5630 (0.8);2.5377 (0.9);2.5127 (0.3);2.4836 (4.3);1.6097 (16.0);1.1394 (1.2);1.1142 (2.4);1.0890 (1.1);0.0478 (0.4);0.0374 (9.2) |
I.024: 1H-NMR(300.2 MHz, CDCl3): δ= 8.6729 (0.6);8.6670 (0.6);8.6567 (0.6);8.6509 (0.6);7.8038 (1.1);7.5755 (0.6);7.5695 (0.6);7.5500 (0.7);7.5440 (0.7);7.4397 (0.5);7.4164 (0.5);7.4120 (0.6);7.3788 (0.6);7.3639 (1.4);7.3607 (1.3);7.3478 (0.5);7.3372 (1.0);7.3165 (0.5);7.2988 (8.0);7.2793 (0.8);7.2724 (1.0);7.2546 (0.6);7.2453 (0.6);7.2292 (0.5);7.2034 (0.5);7.1994 (0.5);7.1784 (0.6);7.1755 (0.6);5.1946 (0.7);2.7733 (0.4);2.7482 (1.4);2.7231 (1.4);2.6980 (0.5);2.4783 (6.2);1.6206 (16.0);1.2912 (0.9);1.2198 (1.8);1.1947 (3.8);1.1696 (1.7);0.0370 (7.6) |
I.025: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1728 (4.2);7.6043 (0.3);7.6005 (0.4);7.5904 (0.4);7.5865 (0.4);7.5811 (0.6);7.5775 (0.6);7.5673 (0.6);7.5640 (0.6);7.5298 (0.5);7.5119 (0.5);7.5042 (0.6);7.4862 (2.4);7.4182 (0.5);7.4136 (0.5);7.3981 (0.8);7.3959 (0.8);7.3805 (0.7);7.3757 (0.6);7.1945 (0.4);7.1920 (0.5);7.1756 (1.1);7.1734 (1.2);7.1579 (1.0);7.1555 (1.0);7.1462 (1.5);7.1417 (1.5);7.1273 (0.6);7.1228 (0.5);7.1098 (1.3);7.0901 (1.2);7.0379 (1.8);3.3454 (32.0);2.8929 (0.8);2.7343 (0.7);2.7333 (0.7);2.5280 (0.4);2.5146 (8.0);2.5102 (15.6);2.5056 (19.8);2.5011 (14.1);2.4966 (6.7);2.4607 (9.6);2.0612 (16.0);-0.0002 (0.7) |
I.027: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2285 (4.5);8.0707 (2.8);8.0589 (2.9);7.4675 (0.8);7.4634 (0.8);7.4485 (3.4);7.4437 (2.8);7.4320 (3.7);7.4255 (1.6);7.4186 (1.1);7.3392 (3.2);7.3318 (1.8);7.3161 (4.3);7.2970 (1.6);7.2473 (1.5);7.2441 (1.4);7.2395 (3.2);7.2271 (7.2);7.2103 (0.9);7.2076 (0.8);3.7944 (16.0);3.3464 (24.5);2.8926 (1.4);2.7340 (1.2);2.5498 (14.7);2.5284 (0.5);2.5148 (8.3);2.5106 (16.3);2.5061 (20.9);2.5016 (15.4);2.4974 (7.7);-0.0002 (0.8) |
I.028: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9698 (2.3);7.9689 (2.3);7.9556 (3.4);7.6350 (2.7);7.5067 (0.6);7.5027 (0.7);7.4874 (1.4);7.4851 (1.2);7.4827 (1.1);7.4684 (1.1);7.4648 (1.3);7.4520 (1.6);7.4476 (1.8);7.4430 (2.0);7.4373 (1.6);7.4312 (2.8);7.4279 (2.8);7.4135 (0.9);7.3970 (0.8);7.3325 (1.3);7.3165 (3.5);7.2970 (2.7);7.0727 (2.6);7.0703 (2.6);7.0441 (1.8);7.0406 (1.9);7.0308 (1.8);7.0273 (1.8);6.8708 (3.1);6.8692 (3.0);3.7176 (16.0);3.3429 (27.6);2.8926 (7.9);2.7346 (6.8);2.7337 (6.6);2.6039 (12.9);2.5283 (0.5);2.5149 (9.1);2.5105 (17.8);2.5060 (22.8);2.5014 (16.4);2.4970 (8.0);-0.0002 (1.0) |
I.029: 1H-NMR(400.2 MHz, d6-DMSO): δ= 9.0649 (2.7);7.9577 (0.4);7.8046 (1.4);7.7854 (2.2);7.7650 (1.9);7.7570 (2.6);7.7238 (1.4);7.7203 (1.4);7.7044 (1.5);7.7008 (1.5);7.5936 (0.5);7.5900 (0.5);7.5796 (0.6);7.5760 (0.6);7.5703 (0.9);7.5670 (0.9);7.5565 (0.8);7.5535 (0.8);7.5243 (0.7);7.5063 (0.7);7.4988 (0.8);7.4809 (0.8);7.4760 (0.5);7.4575 (0.4);7.4240 (0.6);7.4203 (0.6);7.4033 (1.4);7.3900 (2.5);7.3860 (1.3);7.3820 (1.1);7.3720 (2.2);7.3243 (1.9);7.3060 (1.2);7.1665 (0.9);7.1637 (0.9);7.1473 (1.5);7.1292 (0.8);7.1263 (0.8);6.7828 (2.4);6.7625 (2.3);3.9106 (16.0);3.3489 (30.2);2.8950 (2.9);2.7368 (2.5);2.6864 (12.4);2.5309 (0.4);2.5174 (7.9);2.5132 (15.2);2.5087 (19.3);2.5042 (13.9);2.4999 (6.8);-0.0002 (1.1) |
I.030: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2476 (5.7);8.2227 (3.0);8.2084 (3.1);7.4480 (3.3);7.4368 (2.6);7.4312 (3.3);7.4180 (1.4);7.4136 (2.0);7.3308 (1.3);7.3269 (1.4);7.3112 (3.0);7.3076 (3.9);7.2903 (3.9);7.2503 (1.3);7.2473 (1.2);7.2319 (1.8);7.2290 (1.7);7.2132 (0.8);7.2103 (0.8);7.1969 (2.9);7.1939 (2.9);6.9169 (2.9);6.9024 (2.8);3.7145 (16.0);3.3490 (17.3);2.8924 (1.3);2.7344 (1.1);2.7333 (1.1);2.5222 (15.9);2.5148 (10.2);2.5103 (19.3);2.5057 (24.9);2.5012 (18.1);2.4967 (8.9);-0.0002 (0.5) |
I.031: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.0391 (2.3);7.9564 (0.6);7.9144 (1.2);7.9103 (1.1);7.8900 (1.2);7.8859 (1.1);7.6599 (3.4);7.4951 (0.8);7.4912 (0.9);7.4760 (2.2);7.4569 (1.7);7.4530 (3.1);7.4421 (3.0);7.4377 (3.0);7.4269 (1.3);7.4218 (2.9);7.4184 (3.0);7.4016 (1.0);7.3958 (0.4);7.3784 (0.4);7.3323 (1.7);7.3226 (2.2);7.3195 (2.7);7.3157 (2.5);7.3027 (1.7);7.2992 (2.1);7.0164 (3.2);7.0138 (3.2);3.6152 (1.5);3.3452 (35.3);2.8937 (4.0);2.7350 (3.4);2.5964 (16.0);2.5296 (0.5);2.5162 (9.6);2.5118 (19.1);2.5073 (24.7);2.5027 (17.9);2.4983 (8.7);2.0841 (10.6);-0.0002 (1.6) |
I.032: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.3006 (2.8);8.0903 (2.8);7.9553 (2.0);7.6755 (4.3);7.6125 (3.2);7.5743 (0.8);7.5704 (0.8);7.5605 (0.9);7.5564 (1.0);7.5512 (1.3);7.5473 (1.4);7.5373 (1.2);7.5338 (1.2);7.4868 (1.1);7.4777 (1.2);7.4686 (1.2);7.4612 (2.5);7.4574 (2.5);7.4412 (3.0);7.4372 (2.1);7.4203 (1.7);7.2891 (4.1);7.1198 (1.4);7.1178 (1.5);7.0966 (2.5);7.0943 (2.0);7.0756 (4.0);7.0558 (2.6);3.3460 (28.6);2.8927 (14.0);2.7345 (11.7);2.7334 (11.7);2.5290 (22.1);2.5149 (14.8);2.5105 (29.1);2.5059 (37.5);2.5013 (27.2);2.4968 (13.3);2.1076 (16.0);-0.0002 (1.7) |
I.033: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2223 (2.6);8.2097 (2.7);7.9543 (0.3);7.6563 (3.4);7.5755 (0.6);7.5717 (0.6);7.5616 (0.7);7.5576 (0.8);7.5524 (1.1);7.5486 (1.1);7.5384 (1.0);7.5351 (1.0);7.4929 (0.9);7.4753 (1.7);7.4672 (1.1);7.4591 (1.3);7.4550 (2.1);7.4438 (0.9);7.4388 (1.9);7.4347 (1.2);7.4260 (0.6);7.4183 (1.0);7.3277 (3.3);7.2536 (3.2);7.1385 (1.8);7.1257 (1.7);7.0943 (1.3);7.0728 (1.9);7.0537 (2.6);7.0341 (2.1);3.6132 (0.4);3.3395 (47.9);2.8921 (2.4);2.7336 (2.0);2.7326 (2.0);2.5453 (17.5);2.5271 (1.3);2.5222 (1.7);2.5136 (17.3);2.5092 (33.9);2.5047 (43.4);2.5001 (31.0);2.4956 (14.8);2.2710 (16.0);-0.0002 (2.3) |
I.034: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.4287 (5.6);8.2937 (3.3);8.2813 (3.5);7.9555 (1.8);7.6631 (3.1);7.5346 (0.8);7.5304 (0.8);7.5143 (1.5);7.5123 (1.6);7.4964 (1.2);7.4921 (1.4);7.4675 (3.8);7.4519 (2.5);7.4448 (4.1);7.4321 (3.4);7.4064 (0.3);7.3619 (1.3);7.3580 (1.4);7.3508 (0.3);7.3429 (2.3);7.3390 (2.1);7.3327 (0.4);7.3300 (0.4);7.3124 (2.5);7.2984 (1.9);7.2952 (2.6);7.2801 (2.1);7.2778 (1.8);7.2614 (0.8);7.2588 (0.8);7.2060 (0.3);7.1620 (3.1);7.1598 (3.1);3.3444 (35.1);2.8929 (12.5);2.7348 (10.4);2.7339 (10.6);2.6997 (1.4);2.5650 (16.0);2.5286 (0.6);2.5151 (10.7);2.5108 (21.2);2.5063 (27.2);2.5017 (19.7);2.4973 (9.6);-0.0002 (1.8) |
I.035: 1H-NMR(400.2 MHz, d6-DMSO): δ= 9.6057 (3.3);7.9848 (1.3);7.9652 (3.5);7.9457 (2.6);7.9109 (3.2);7.8925 (1.8);7.8615 (3.3);7.8320 (1.8);7.8285 (1.8);7.8123 (2.0);7.8088 (1.9);7.6126 (0.6);7.6092 (0.7);7.5990 (0.7);7.5950 (0.8);7.5895 (1.2);7.5854 (1.4);7.5786 (2.2);7.5606 (2.5);7.5355 (0.9);7.5174 (1.0);7.5099 (1.1);7.4957 (4.4);7.4769 (4.1);7.4569 (0.9);7.4534 (0.8);7.1966 (1.2);7.1940 (1.2);7.1764 (2.0);7.1589 (1.0);7.1563 (1.0);3.3474 (51.6);2.8956 (1.4);2.7889 (16.0);2.7365 (1.2);2.6737 (0.4);2.5312 (0.8);2.5177 (13.2);2.5134 (25.9);2.5090 (33.4);2.5044 (24.4);2.5001 (12.2);-0.0002 (1.9) |
I.036: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1908 (2.8);8.1786 (2.9);8.1779 (3.0);7.9555 (1.6);7.7649 (3.4);7.5870 (3.6);7.5850 (3.7);7.5460 (0.8);7.5421 (0.9);7.5268 (1.7);7.5238 (1.6);7.5079 (1.1);7.5039 (1.4);7.4935 (1.7);7.4892 (1.8);7.4842 (0.9);7.4732 (2.9);7.4699 (2.5);7.4613 (1.7);7.4500 (4.2);7.4467 (3.9);7.4373 (2.6);7.4336 (3.0);7.4244 (1.1);7.4073 (1.0);7.4015 (0.5);7.3840 (0.4);7.3519 (1.9);7.3450 (2.4);7.3421 (2.3);7.3348 (2.4);7.3250 (1.9);7.3223 (1.8);7.3169 (1.3);7.3140 (0.8);7.0793 (3.1);7.0768 (3.2);3.3641 (0.6);3.3606 (0.6);3.3450 (45.8);3.3316 (0.6);2.9038 (0.4);2.8932 (11.3);2.7449 (0.3);2.7349 (9.5);2.6997 (1.0);2.6240 (16.0);2.5154 (12.4);2.5110 (24.0);2.5064 (30.5);2.5018 (21.6);2.4974 (10.1);1.2309 (0.4);-0.0002 (1.5) |
I.037: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.4662 (3.1);8.4611 (3.0);8.4600 (3.0);7.9554 (0.4);7.9303 (2.0);7.9240 (1.9);7.9096 (2.2);7.9033 (2.1);7.6899 (3.5);7.5197 (0.8);7.5158 (0.9);7.5004 (1.6);7.4967 (2.0);7.4772 (2.6);7.4719 (1.9);7.4560 (3.9);7.4439 (1.9);7.4288 (1.1);7.4203 (1.2);7.4035 (1.0);7.3802 (0.4);7.3641 (4.3);7.3433 (5.2);7.3338 (2.6);7.3243 (1.2);7.3142 (2.0);7.0298 (3.4);3.6145 (0.3);3.3439 (45.4);2.8930 (2.8);2.7339 (2.4);2.6022 (16.0);2.5288 (0.8);2.5151 (12.9);2.5109 (24.9);2.5064 (31.8);2.5019 (23.2);2.4976 (11.5);-0.0002 (1.2) |
I.038: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1161 (2.6);8.1113 (2.9);8.1043 (2.9);8.0994 (2.8);7.9551 (2.6);7.8564 (2.6);7.8516 (2.6);7.8374 (2.9);7.8326 (2.7);7.6194 (4.4);7.5061 (1.1);7.5022 (1.2);7.4865 (2.3);7.4838 (2.4);7.4680 (5.7);7.4527 (3.6);7.4432 (1.6);7.4273 (1.4);7.4043 (0.6);7.3862 (1.6);7.3824 (2.2);7.3658 (2.8);7.3626 (2.7);7.2919 (6.3);7.2727 (6.3);7.2557 (1.3);7.2530 (1.1);7.2409 (2.8);7.2290 (2.7);7.2219 (2.6);7.2101 (2.6);7.1571 (4.4);3.6136 (0.5);3.3425 (44.6);2.8924 (16.0);2.7343 (13.6);2.7332 (14.1);2.6993 (0.6);2.6700 (0.4);2.5479 (21.0);2.5279 (0.9);2.5101 (29.9);2.5056 (38.2);2.5011 (28.2);2.3162 (0.6);-0.0002 (2.3) |
I.040: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.5456 (3.7);8.5411 (3.8);8.3180 (3.6);8.3122 (3.8);8.0042 (2.1);7.9989 (3.4);7.9938 (2.1);7.9543 (2.2);7.7465 (3.3);7.5345 (0.7);7.5307 (0.9);7.5151 (1.6);7.5130 (1.6);7.5109 (1.6);7.5026 (1.6);7.4978 (2.1);7.4929 (1.8);7.4821 (3.0);7.4696 (0.7);7.4586 (1.4);7.4432 (1.9);7.4255 (0.9);7.4174 (1.0);7.4001 (0.9);7.3767 (0.4);7.3648 (1.6);7.3484 (4.3);7.3294 (3.2);7.0246 (3.3);7.0224 (3.3);3.3425 (55.9);2.8918 (14.7);2.7323 (12.8);2.5970 (16.0);2.5271 (0.9);2.5135 (17.8);2.5093 (35.3);2.5048 (45.8);2.5003 (33.8);2.4960 (17.0);1.2322 (0.4);-0.0002 (0.4) |
I.041: 1H-NMR(300.2 MHz, CDCl3): δ= 8.5732 (2.3);8.4926 (1.4);8.4769 (1.4);7.5981 (2.6);7.4765 (0.5);7.4714 (0.5);7.4600 (1.2);7.4533 (0.6);7.4460 (1.1);7.4410 (1.8);7.4330 (1.6);7.4231 (1.1);7.4144 (1.4);7.4066 (2.1);7.3869 (1.4);7.3847 (1.4);7.3746 (1.3);7.3521 (1.2);7.3440 (0.6);7.3214 (0.6);7.2984 (4.0);7.2283 (1.1);7.2106 (2.5);7.1919 (1.2);7.1834 (1.8);7.1556 (0.8);6.9534 (1.8);6.9277 (1.6);4.0768 (0.9);4.0213 (2.4);3.9590 (2.4);3.9035 (0.9);2.5397 (16.0);2.0100 (0.4);1.7260 (2.4);1.2974 (0.6);1.2926 (0.6);1.2765 (5.2);0.9141 (0.6);0.0330 (2.9) |
I.042: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1870 (2.5);8.1823 (2.6);8.1138 (1.2);7.9667 (0.8);7.9600 (1.1);7.9463 (1.5);7.9405 (1.4);7.9260 (0.8);7.9199 (0.8);7.8055 (0.3);7.8006 (0.4);7.7821 (3.6);7.7690 (0.6);7.7646 (0.5);7.7553 (0.7);7.7514 (0.8);7.7413 (0.8);7.7371 (0.9);7.7324 (1.1);7.7287 (1.1);7.7187 (1.0);7.6336 (1.1);7.6152 (1.3);7.6091 (1.3);7.5908 (1.2);7.5666 (0.5);7.4944 (0.7);7.4791 (1.0);7.4747 (1.5);7.4596 (1.6);7.4546 (1.2);7.4394 (0.9);7.3849 (0.4);7.3673 (0.6);7.3476 (0.4);7.3206 (1.2);7.2976 (1.9);7.2763 (1.0);7.2208 (1.5);7.2142 (1.5);7.1998 (1.5);7.1930 (1.4);7.0940 (0.4);7.0761 (1.4);7.0653 (2.6);7.0467 (2.7);6.7082 (0.6);6.6871 (0.5);4.2165 (2.9);4.0547 (6.9);3.6179 (3.0);3.3448 (33.3);3.3414 (38.2);2.8971 (4.0);2.7388 (3.6);2.6098 (6.5);2.5135 (27.1);2.5092 (33.7);2.5048 (24.7);2.4160 (16.0);1.6101 (0.3);1.5566 (0.3);1.2357 (0.6);1.0547 (0.5);-0.0002 (0.6) |
I.043: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2446 (1.6);8.2325 (1.6);8.0248 (0.9);8.0202 (0.9);8.0064 (1.1);8.0011 (1.6);7.9959 (1.0);7.9820 (1.0);7.9773 (0.9);7.9563 (0.8);7.7549 (3.3);7.7111 (0.7);7.7074 (0.7);7.6971 (0.8);7.6933 (0.9);7.6881 (1.1);7.6845 (1.2);7.6743 (1.0);7.6710 (1.0);7.6262 (0.8);7.6082 (0.9);7.6006 (1.1);7.5828 (1.0);7.5779 (0.7);7.5595 (0.5);7.5317 (0.7);7.5164 (0.9);7.5117 (1.4);7.4965 (1.5);7.4918 (1.2);7.4765 (1.0);7.4330 (1.0);7.4282 (1.1);7.4208 (1.1);7.4153 (1.7);7.4099 (1.1);7.4025 (1.0);7.3976 (1.0);7.3315 (1.2);7.3095 (2.0);7.2876 (1.0);7.1089 (2.3);7.0897 (2.1);4.1139 (1.1);4.0723 (2.7);4.0254 (2.7);3.9838 (1.0);3.6170 (1.5);3.3455 (51.1);2.8960 (4.7);2.7375 (4.3);2.5128 (20.8);2.5085 (26.8);2.5042 (20.1);2.3931 (16.0);1.2363 (0.3);-0.0002 (0.4) |
I.044: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.3120 (1.4);8.2552 (2.6);8.2425 (2.7);7.9539 (0.4);7.8131 (3.3);7.7537 (0.7);7.7397 (0.9);7.7349 (1.1);7.7310 (1.0);7.7207 (1.0);7.7179 (1.0);7.6360 (0.8);7.6174 (0.9);7.6107 (1.0);7.5928 (1.0);7.5691 (0.5);7.5059 (0.7);7.4907 (0.8);7.4858 (1.4);7.4707 (1.4);7.4661 (1.1);7.4508 (0.9);7.3302 (1.7);7.3242 (1.8);7.3103 (3.3);7.2873 (1.0);7.2428 (3.2);7.0395 (2.2);7.0204 (2.1);4.0668 (7.0);3.3375 (111.7);2.8946 (2.4);2.7356 (2.2);2.6747 (0.4);2.5099 (48.8);2.5057 (62.6);2.5015 (47.4);2.4277 (16.0);2.3326 (0.4);1.2383 (1.1);-0.0002 (2.1) |
I.045: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.3137 (0.5);8.2394 (2.6);8.0610 (5.1);8.0247 (0.7);8.0192 (0.8);8.0043 (1.5);7.9989 (1.4);7.9839 (0.8);7.9782 (0.8);7.9560 (2.3);7.7171 (0.8);7.7129 (0.9);7.6973 (4.4);7.6806 (1.0);7.6765 (0.9);7.5786 (1.0);7.5731 (0.9);7.5610 (1.6);7.5537 (2.1);7.5363 (2.0);7.5124 (0.6);7.4913 (1.2);7.4745 (1.9);7.4703 (2.7);7.4537 (2.5);7.4502 (2.3);7.4335 (1.1);7.4269 (0.6);7.3393 (0.8);7.3255 (3.9);7.3194 (2.3);7.3014 (1.7);7.2810 (0.8);7.1327 (1.3);7.1112 (2.2);7.0898 (1.2);7.0596 (4.0);7.0540 (2.2);7.0390 (3.8);7.0325 (1.8);6.9797 (1.5);6.9761 (1.6);6.9592 (1.2);6.9558 (1.5);6.9293 (0.9);6.9237 (1.5);6.9183 (0.8);6.9004 (0.9);6.8948 (1.5);6.8893 (0.8);6.7333 (0.7);6.7283 (0.7);6.7128 (1.3);6.7069 (1.2);6.6923 (0.7);6.6862 (0.6);3.5119 (0.7);3.3432 (44.5);3.3395 (52.9);2.8959 (15.3);2.7377 (13.4);2.7150 (0.4);2.6883 (16.0);2.5568 (17.6);2.5167 (18.4);2.5125 (36.8);2.5080 (48.1);2.5035 (36.0);1.2612 (0.4);1.2360 (2.0);0.8526 (0.4);-0.0002 (1.6) |
I.046: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.0642 (4.0);8.0517 (2.9);7.9550 (1.1);7.7475 (3.1);7.6940 (0.3);7.6894 (0.3);7.6759 (0.3);7.5790 (0.8);7.5549 (1.4);7.5411 (1.1);7.5117 (0.9);7.5035 (0.9);7.4912 (1.7);7.4858 (1.2);7.4752 (2.1);7.4600 (1.2);7.4546 (1.4);7.4367 (0.6);7.3896 (3.4);7.3550 (1.5);7.3420 (1.6);7.3195 (0.6);7.3018 (0.6);7.2400 (3.1);7.1186 (1.1);7.0952 (1.8);7.0735 (1.1);7.0531 (2.3);7.0329 (2.1);6.9788 (0.5);6.9752 (0.5);6.9584 (0.4);6.9549 (0.5);6.9223 (0.5);6.8934 (0.5);6.7132 (0.4);6.7082 (0.4);3.6561 (0.5);3.6174 (0.4);3.3711 (103.7);3.3684 (101.5);2.8962 (7.1);2.7375 (6.1);2.6876 (5.3);2.5835 (1.1);2.5724 (16.0);2.5315 (0.7);2.5180 (13.7);2.5137 (27.7);2.5093 (36.5);2.5048 (27.4);1.2610 (0.4);1.2365 (1.4);-0.0002 (0.6) |
I.047: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.3100 (0.7);8.0336 (7.6);8.0241 (7.2);8.0216 (7.6);7.9765 (4.0);7.9718 (3.9);7.9577 (5.7);7.9530 (8.5);7.9481 (4.7);7.9340 (4.4);7.9293 (3.9);7.7603 (16.0);7.5471 (2.4);7.5307 (3.2);7.5229 (8.5);7.5091 (11.8);7.4956 (6.0);7.4881 (12.9);7.4714 (12.2);7.4509 (4.8);7.3619 (16.0);7.2396 (4.4);7.2349 (4.8);7.2275 (4.8);7.2219 (7.5);7.2164 (4.9);7.2090 (4.5);7.2042 (4.4);7.0902 (5.6);7.0683 (9.6);7.0464 (5.2);7.0251 (11.1);7.0049 (10.4);4.0131 (0.4);3.6171 (0.4);3.4464 (0.4);3.3700 (412.0);3.3679 (399.6);2.8956 (9.0);2.7371 (7.9);2.7158 (0.5);2.6991 (0.3);2.6923 (0.5);2.6872 (0.4);2.6825 (0.6);2.6778 (0.8);2.6736 (0.6);2.6424 (0.6);2.6346 (0.3);2.5980 (1.1);2.5757 (0.6);2.5345 (79.1);2.5175 (46.4);2.5133 (90.4);2.5089 (117.5);2.5045 (87.6);2.3731 (0.5);2.3402 (0.5);2.3358 (0.7);2.3313 (0.6);1.3012 (0.6);1.2606 (1.1);1.2369 (4.2);0.8694 (0.3);0.8528 (0.9);0.8348 (0.4);-0.0002 (2.3) |
I.049: 1H-NMR(300.1 MHz, d6-DMSO): δ= 8.4146 (9.2);8.4085 (9.4);8.2588 (6.0);8.2558 (6.1);8.2425 (6.3);8.2395 (6.2);7.6529 (10.4);7.4852 (5.4);7.4684 (6.2);7.4639 (7.7);7.4541 (12.6);7.4482 (7.7);7.4289 (9.2);7.4208 (9.3);7.4135 (8.9);7.4040 (10.4);7.3955 (16.0);7.3697 (5.9);7.0552 (9.8);7.0517 (9.4);3.3507 (19.3);2.9873 (0.7);2.5510 (49.1);2.5203 (6.8);2.5144 (12.7);2.5084 (16.7);2.5025 (11.5);2.4967 (5.2);2.0808 (10.7);-0.0004 (0.4) |
I.050: 1H-NMR(300.2 MHz, CDCl3): δ= 8.5830 (0.4);7.2988 (3.9);4.3044 (0.4);4.2338 (0.5);4.1671 (0.4);2.5514 (2.1);1.9731 (0.4);1.6254 (6.0);1.3082 (16.0);1.2900 (0.4);1.2791 (6.8);0.0360 (3.9) |
I.051: 1H-NMR(300.2 MHz, d6-DMSO): δ= 8.4611 (10.9);8.4569 (11.0);8.3125 (7.1);8.2980 (7.0);7.8066 (10.1);7.5834 (2.5);7.5522 (10.7);7.5428 (7.5);7.5302 (14.8);7.5103 (12.8);7.5036 (9.2);7.4979 (6.9);7.4922 (8.1);7.4760 (4.1);7.4571 (2.1);7.4321 (11.8);7.2975 (0.6);7.1123 (5.2);7.0836 (8.0);7.0527 (5.1);7.0388 (8.7);7.0117 (7.7);6.9570 (0.8);6.9349 (0.6);6.9137 (0.6);6.8749 (0.6);6.8160 (0.5);6.8033 (0.5);6.7709 (0.5);6.7390 (0.5);6.6697 (0.5);6.5754 (0.4);5.7648 (0.8);2.7651 (0.4);2.5544 (58.2);2.5244 (8.4);2.5187 (15.8);2.5127 (20.9);2.5068 (15.3);2.3399 (0.3);2.0841 (16.0);1.2286 (0.6);-0.0003 (1.2) |
I.052: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.0632 (2.6);7.9872 (1.1);7.9797 (2.5);7.9762 (2.4);7.9562 (3.0);7.7391 (2.5);7.7122 (2.2);7.5525 (0.6);7.5487 (0.6);7.5332 (1.7);7.5304 (1.5);7.5211 (1.1);7.5100 (2.2);7.5064 (2.0);7.5014 (1.8);7.4940 (2.7);7.4862 (1.7);7.4830 (1.7);7.4779 (1.8);7.4696 (1.5);7.4610 (0.9);7.4457 (2.6);7.4264 (2.4);7.3235 (1.1);7.3174 (1.2);7.3120 (1.3);7.3058 (1.2);7.2957 (3.8);7.2920 (3.7);7.2758 (4.0);7.2726 (3.6);7.2604 (3.3);7.1956 (2.1);3.3500 (73.8);2.8940 (16.0);2.7356 (13.9);2.7346 (13.6);2.7003 (0.4);2.5822 (12.0);2.5731 (10.4);2.5293 (0.7);2.5158 (13.9);2.5117 (26.6);2.5072 (33.7);2.5027 (24.6);2.4987 (12.3);-0.0002 (1.0) |
I.053: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9557 (2.0);7.8635 (2.0);7.8612 (2.0);7.8509 (2.1);7.8485 (2.0);7.7057 (3.4);7.5475 (0.8);7.5436 (0.9);7.5282 (2.0);7.5253 (1.7);7.5236 (1.6);7.5183 (0.8);7.5153 (0.8);7.5087 (2.8);7.4990 (1.6);7.4949 (1.6);7.4832 (1.1);7.4747 (1.3);7.4596 (2.1);7.4517 (0.8);7.4429 (1.9);7.3976 (1.8);7.3855 (2.9);7.3733 (1.7);7.2959 (3.3);7.2885 (2.8);7.2861 (3.0);7.2834 (2.2);7.2698 (2.5);7.2660 (2.3);7.2633 (1.8);7.2533 (1.2);7.2505 (0.9);3.6148 (1.6);3.3440 (38.1);2.8934 (13.6);2.7351 (11.4);2.7340 (11.6);2.5736 (16.0);2.5288 (0.7);2.5153 (11.9);2.5109 (23.4);2.5064 (29.9);2.5018 (21.6);2.4973 (10.4);-0.0002 (1.8) |
I.054: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9555 (0.9);7.7790 (3.5);7.5553 (0.8);7.5516 (1.0);7.5359 (1.8);7.5333 (1.8);7.5195 (2.3);7.5156 (2.8);7.4995 (3.1);7.4965 (2.6);7.4893 (2.3);7.4767 (2.1);7.4634 (1.4);7.4549 (1.3);7.4378 (1.0);7.4240 (0.4);7.4148 (0.5);7.3344 (1.7);7.3258 (2.4);7.3231 (2.6);7.3171 (2.6);7.3057 (2.0);7.3033 (2.1);7.2994 (1.6);7.2438 (14.8);7.1739 (3.4);3.3373 (40.2);2.8925 (5.8);2.7331 (5.1);2.6318 (16.0);2.5598 (1.0);2.5098 (35.4);2.5054 (45.2);2.5009 (33.9);1.2320 (0.4) |
I.055: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1542 (0.6);8.1338 (1.5);8.1102 (1.4);8.0898 (0.6);7.9554 (2.0);7.6308 (3.2);7.5135 (0.5);7.5077 (0.9);7.5038 (1.0);7.4981 (0.7);7.4892 (3.9);7.4735 (2.3);7.4698 (1.8);7.4651 (1.9);7.4471 (1.0);7.4404 (0.3);7.4242 (1.6);7.4072 (1.8);7.2879 (1.1);7.2853 (1.6);7.2745 (2.1);7.2715 (2.8);7.2689 (2.6);7.2544 (1.7);7.2510 (2.6);7.1963 (3.0);7.0593 (1.4);7.0538 (1.6);7.0391 (1.4);7.0335 (1.5);3.3380 (30.4);2.8926 (14.2);2.7339 (11.9);2.7331 (11.7);2.5601 (16.0);2.5276 (0.6);2.5142 (13.3);2.5098 (26.6);2.5053 (34.3);2.5007 (24.6);2.4962 (11.9);1.2325 (0.3) |
I.056: 1H-NMR(300.2 MHz, CDCl3): δ= 8.7057 (1.4);8.7021 (1.4);8.5933 (0.8);8.5901 (0.8);8.5771 (0.8);8.5739 (0.8);8.4209 (0.8);8.3931 (0.9);7.6203 (0.3);7.5924 (0.8);7.5790 (0.3);7.5713 (0.8);7.5644 (0.9);7.5585 (0.6);7.5479 (0.5);7.5423 (0.8);7.5210 (0.5);7.4959 (0.4);7.4886 (0.6);7.4635 (0.5);7.4485 (0.6);7.4310 (1.0);7.4124 (0.5);7.2989 (10.4);7.1134 (0.5);7.1106 (0.5);7.0829 (0.9);7.0552 (0.4);7.0527 (0.4);6.5837 (0.7);2.4764 (7.0);2.0483 (0.6);1.6070 (16.0);0.0362 (9.1);0.0251 (0.4) |
I.057: 1H-NMR(300.2 MHz, CDCl3): δ= 8.5236 (0.6);8.5059 (0.6);8.4569 (1.0);7.7653 (0.6);7.7615 (0.6);7.4262 (0.6);7.4176 (0.4);7.3977 (0.5);7.3925 (0.4);7.3522 (0.7);7.3318 (0.6);7.3210 (0.3);7.2988 (8.6);7.2401 (0.3);7.2358 (0.3);6.7358 (0.5);6.7179 (0.5);5.4059 (0.4);5.3378 (0.6);2.5131 (3.5);1.6113 (16.0);1.2913 (0.6);0.0370 (7.7) |
I.059: 1H-NMR(300.2 MHz, CDCl3): δ= 8.5290 (1.5);8.5232 (1.6);8.5131 (1.6);8.5073 (1.6);7.7439 (2.6);7.7396 (2.7);7.5350 (1.8);7.5290 (1.9);7.5095 (2.1);7.5036 (2.2);7.4948 (0.6);7.4724 (1.4);7.4677 (1.3);7.4497 (1.4);7.4449 (1.8);7.4363 (2.2);7.4312 (2.4);7.4222 (1.5);7.4171 (1.4);7.4098 (1.1);7.4050 (0.8);7.3968 (1.8);7.3922 (1.7);7.3772 (0.5);7.3589 (0.6);7.3456 (3.0);7.3251 (2.6);7.3139 (1.5);7.2990 (9.6);7.2942 (1.8);7.2837 (0.4);7.2615 (1.5);7.2560 (1.2);7.2382 (1.3);7.2361 (1.3);7.2332 (1.3);7.2305 (1.1);7.2134 (0.8);7.2077 (0.7);7.1587 (2.0);7.1427 (2.0);7.1332 (1.8);7.1172 (1.8);5.4859 (1.8);5.3376 (0.9);2.5206 (16.0);1.9237 (0.6);1.9127 (0.7);1.8970 (1.3);1.8812 (0.8);1.8701 (0.7);1.8542 (0.3);1.6233 (12.6);1.2321 (0.4);1.2277 (0.4);1.2225 (0.4);1.2119 (0.8);1.2068 (0.5);1.2011 (0.6);1.1962 (0.8);1.1913 (0.6);1.1854 (0.6);1.1800 (0.6);1.1755 (0.5);1.1643 (0.4);1.0855 (0.4);1.0747 (0.5);1.0695 (0.5);1.0646 (0.7);1.0586 (0.6);1.0541 (0.9);1.0488 (0.6);1.0438 (0.4);1.0380 (0.8);1.0337 (0.5);1.0278 (0.4);1.0227 (0.5);1.0176 (0.4);1.0067 (0.4);0.9141 (0.4);0.9028 (0.4);0.8927 (0.4);0.8835 (0.8);0.8726 (0.6);0.8628 (0.6);0.8562 (0.8);0.8454 (0.5);0.8355 (0.4);0.8244 (0.3);0.7302 (0.4);0.7195 (0.4);0.7089 (0.5);0.7032 (0.6);0.6992 (0.8);0.6929 (0.6);0.6894 (0.5);0.6823 (0.6);0.6789 (0.5);0.6723 (0.7);0.6628 (0.4);0.0484 (0.4);0.0375 (11.7);0.0267 (0.5) |
I.060: 1H-NMR(300.2 MHz, CDCl3): δ= 8.6741 (1.5);8.6682 (1.6);8.6581 (1.6);8.6520 (1.6);8.1413 (0.9);7.7981 (2.6);7.7940 (2.7);7.5814 (1.5);7.5754 (1.6);7.5558 (1.8);7.5499 (1.8);7.4733 (0.5);7.4679 (0.6);7.4457 (1.3);7.4412 (1.1);7.4225 (1.1);7.4170 (1.2);7.3937 (0.5);7.3891 (0.5);7.3778 (1.8);7.3686 (3.4);7.3589 (1.5);7.3484 (1.3);7.3438 (1.5);7.3387 (2.1);7.3167 (1.2);7.2991 (23.2);7.2868 (0.8);7.2731 (3.0);7.2672 (2.0);7.2581 (1.7);7.2487 (1.5);7.2325 (1.5);7.2078 (1.3);7.2037 (1.3);7.1834 (1.5);7.1797 (1.6);7.1589 (0.7);7.1546 (0.7);5.3377 (0.4);5.1889 (1.8);2.7280 (1.0);2.7199 (1.2);2.7108 (0.5);2.7012 (2.0);2.6952 (2.0);2.6866 (0.6);2.6764 (1.2);2.6686 (1.2);2.4772 (16.0);2.4523 (0.7);2.0834 (1.1);1.8380 (1.7);1.7600 (0.7);1.7395 (0.6);1.7257 (0.5);1.7143 (0.9);1.7014 (0.9);1.6889 (1.1);1.6768 (1.2);1.6628 (1.2);1.6523 (1.1);1.6382 (0.8);1.6257 (0.7);1.3209 (0.4);1.2971 (1.0);1.2923 (0.8);1.2733 (0.4);0.8524 (4.4);0.8279 (9.1);0.8033 (3.9);0.0481 (0.9);0.0373 (26.6);0.0263 (0.9) |
I.061: 1H-NMR(300.2 MHz, CDCl3): δ= 8.6358 (0.6);8.5626 (0.4);8.5461 (0.4);7.8102 (0.4);7.3721 (0.6);7.3415 (0.4);7.2986 (6.9);7.1934 (0.4);7.1771 (0.6);2.4813 (2.4);1.6041 (16.0);0.8364 (0.7);0.8119 (1.3);0.7875 (0.6);0.0375 (7.8) |
I.062: 1H-NMR(300.2 MHz, CDCl3): δ= 8.6029 (2.8);8.5860 (2.9);8.4920 (4.1);7.8073 (2.6);7.8031 (2.6);7.4812 (0.5);7.4757 (0.6);7.4530 (1.3);7.4300 (1.1);7.4245 (1.2);7.4125 (0.6);7.3950 (0.6);7.3902 (0.5);7.3787 (1.6);7.3646 (3.3);7.3608 (3.3);7.3482 (1.3);7.3376 (2.5);7.3158 (1.7);7.3074 (3.1);7.2990 (41.0);7.2768 (2.2);7.2713 (2.0);7.2110 (1.3);7.2069 (1.3);7.1862 (1.6);7.1827 (1.7);7.1618 (0.7);7.1579 (0.7);5.2008 (1.8);2.5287 (2.1);2.5030 (4.3);2.4826 (16.0);1.7230 (0.9);1.6877 (1.0);1.6416 (0.8);1.6170 (0.7);1.5918 (0.6);1.5722 (1.0);1.5476 (1.6);1.5230 (1.7);1.5018 (1.4);1.4768 (0.8);1.4570 (0.4);1.2932 (0.7);0.8260 (4.3);0.8017 (8.7);0.7771 (3.8);0.1080 (0.9);0.0488 (2.2);0.0379 (53.7);0.0271 (2.1) |
I.064: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.8271 (2.4);8.8247 (2.7);8.8224 (2.7);8.7436 (4.1);8.7386 (4.2);8.4235 (1.8);8.4188 (2.9);8.4148 (1.6);7.9559 (2.2);7.8276 (3.4);7.6055 (0.6);7.6018 (0.6);7.5916 (0.7);7.5877 (0.8);7.5824 (1.0);7.5787 (1.1);7.5685 (1.0);7.5652 (1.0);7.5316 (0.9);7.5237 (1.0);7.5150 (1.2);7.5110 (1.8);7.5058 (1.1);7.4947 (2.1);7.4907 (1.3);7.4798 (1.1);7.4743 (1.5);7.4567 (0.5);7.3588 (3.3);7.1541 (1.2);7.1327 (2.0);7.1113 (1.0);7.1095 (1.1);7.0744 (2.3);7.0542 (2.1);3.3435 (36.9);2.8939 (16.0);2.7354 (13.5);2.7343 (13.3);2.5560 (16.5);2.5298 (1.1);2.5244 (1.1);2.5157 (11.8);2.5113 (23.5);2.5068 (30.3);2.5022 (21.8);2.4977 (10.4);-0.0002 (1.7) |
I.065: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1847 (3.2);8.1790 (3.2);7.9562 (1.6);7.7585 (1.9);7.7524 (1.8);7.7371 (2.0);7.7310 (1.9);7.6021 (3.7);7.4623 (0.8);7.4586 (0.9);7.4505 (0.7);7.4423 (2.0);7.4381 (2.1);7.4265 (4.8);7.4104 (4.5);7.3988 (1.3);7.3824 (1.1);7.3588 (0.4);7.3330 (1.7);7.3163 (4.8);7.2976 (3.1);6.9640 (3.8);6.6080 (3.1);6.5866 (3.1);4.1756 (1.6);4.1581 (5.0);4.1405 (5.0);4.1229 (1.6);3.3454 (33.7);2.8933 (9.4);2.7351 (8.6);2.5971 (16.0);2.5112 (21.3);2.5070 (26.4);2.5027 (19.6);1.1781 (5.1);1.1605 (10.5);1.1430 (5.0);-0.0002 (0.9) |
I.066: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9558 (2.0);7.9367 (3.0);7.9320 (3.3);7.9244 (3.2);7.9196 (3.2);7.6221 (3.0);7.6173 (3.1);7.6038 (3.4);7.5991 (3.1);7.4577 (0.5);7.4458 (1.2);7.4419 (1.5);7.4344 (1.9);7.4218 (3.7);7.4154 (4.2);7.4084 (3.6);7.4037 (3.3);7.3987 (5.8);7.3767 (0.4);7.3580 (2.4);7.3542 (2.4);7.3388 (3.8);7.3345 (4.0);7.3321 (4.0);7.3294 (4.0);7.3111 (2.6);7.3094 (2.6);7.2949 (5.2);7.2570 (2.1);7.2541 (2.0);7.2384 (3.0);7.2358 (2.9);7.2199 (1.3);7.2169 (1.2);7.1730 (5.2);6.8565 (3.1);6.8441 (3.1);6.8382 (3.1);6.8258 (2.9);4.2453 (1.8);4.2277 (5.8);4.2101 (5.9);4.1925 (1.9);3.3430 (45.2);2.8927 (13.2);2.7341 (11.5);2.5268 (25.4);2.5150 (14.8);2.5107 (28.8);2.5062 (37.3);2.5017 (27.4);2.4975 (13.7);1.2125 (7.7);1.1950 (16.0);1.1773 (7.4);-0.0002 (2.0) |
I.068: 1H-NMR(300.2 MHz, CDCl3): δ= 19.1321 (0.4);9.6695 (0.4);8.7245 (0.6);8.7010 (0.7);8.6605 (0.6);8.6499 (0.7);8.6441 (0.8);8.6231 (0.9);8.5853 (0.7);8.5150 (0.8);8.4717 (0.5);7.8788 (0.7);7.8449 (0.7);7.3736 (4.8);7.3542 (4.9);7.3219 (5.4);7.2985 (6.5);7.2705 (9.7);7.0624 (0.6);6.9772 (1.0);6.9546 (0.8);6.9188 (0.7);6.8885 (0.7);6.8448 (0.5);6.7993 (0.4);5.1995 (0.8);5.1718 (0.6);5.1350 (0.4);2.7041 (0.5);2.6533 (0.8);2.5806 (2.0);2.5678 (2.1);2.5358 (2.3);2.5030 (2.2);2.4755 (2.5);1.8409 (0.5);1.6064 (16.0);1.5771 (16.0);1.4117 (0.5);1.3784 (0.7);1.2920 (1.1);1.2011 (1.8);1.1930 (1.7);1.1739 (2.0);1.1470 (1.8);0.0587 (5.7);0.0370 (7.7);0.0090 (11.5) |
I.069: 1H-NMR(300.2 MHz, CDCl3): δ= 8.7283 (0.6);8.7225 (0.6);8.7123 (0.6);8.7064 (0.6);7.8744 (1.1);7.6291 (0.6);7.6232 (0.6);7.6036 (0.7);7.5977 (0.7);7.4264 (0.4);7.4219 (0.5);7.4090 (0.4);7.4024 (0.8);7.3794 (0.5);7.3703 (1.1);7.3488 (1.0);7.3433 (0.5);7.3367 (0.7);7.3207 (0.9);7.3108 (0.6);7.2989 (6.3);7.0232 (0.8);6.9957 (0.7);6.8996 (0.4);6.8972 (0.4);6.8702 (0.7);6.8430 (0.4);5.3373 (1.1);5.1712 (0.8);2.7655 (0.7);2.7593 (0.7);2.7401 (0.7);2.7344 (0.7);2.4972 (6.4);1.6242 (16.0);1.2917 (0.4);1.2658 (1.8);1.2407 (3.5);1.2155 (1.6);0.0367 (6.5) |
I.070: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2746 (2.1);7.7945 (2.1);7.7137 (0.4);7.7100 (0.4);7.7000 (0.5);7.6959 (0.5);7.6908 (0.6);7.6869 (0.6);7.6769 (0.6);7.6736 (0.6);7.6002 (0.5);7.5820 (0.6);7.5746 (0.6);7.5567 (0.6);7.5516 (0.4);7.5331 (0.3);7.3797 (0.5);7.3591 (1.0);7.3421 (1.0);7.3216 (0.5);7.1321 (2.2);6.9276 (0.8);6.9062 (1.4);6.8849 (0.7);6.6936 (1.5);6.6732 (1.5);3.3457 (19.4);2.5111 (12.2);2.5067 (15.3);2.5022 (11.0);2.4981 (5.4);2.4767 (9.9);2.1007 (16.0);-0.0002 (0.9) |
I.071: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.4992 (2.4);8.4948 (2.4);7.9552 (1.4);7.7983 (0.3);7.7880 (0.3);7.7378 (1.5);7.7320 (1.4);7.7169 (1.6);7.7112 (1.6);7.6264 (2.9);7.4801 (1.0);7.4653 (2.1);7.4616 (2.2);7.4542 (2.0);7.4510 (2.0);7.4426 (3.1);7.4348 (3.4);7.4183 (1.1);7.4099 (1.1);7.3931 (0.9);7.3698 (0.4);7.3522 (1.3);7.3360 (1.6);7.3159 (2.4);7.2964 (1.6);7.1563 (2.2);7.1356 (2.1);7.0118 (2.9);3.6140 (1.1);3.3459 (33.4);2.8925 (9.0);2.7342 (7.9);2.6018 (12.4);2.5104 (19.1);2.5061 (23.6);2.5017 (17.2);2.3963 (16.0);-0.0002 (0.7) |
I.072: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1620 (1.6);8.1577 (1.7);8.1500 (1.7);8.1456 (1.6);7.9533 (0.5);7.7130 (0.3);7.6966 (0.3);7.6931 (0.3);7.6138 (0.6);7.5411 (1.6);7.5368 (1.7);7.5223 (1.9);7.5179 (1.7);7.4781 (0.7);7.4741 (0.8);7.4537 (3.1);7.4397 (1.3);7.4360 (1.7);7.4206 (1.0);7.4112 (1.9);7.3952 (2.4);7.3870 (0.5);7.3715 (0.8);7.3647 (1.4);7.3606 (1.3);7.3455 (1.7);7.3417 (1.5);7.2925 (1.7);7.2747 (1.3);7.2726 (1.3);7.2508 (3.4);7.2481 (3.4);7.2321 (1.6);7.2294 (1.5);7.2134 (0.7);7.2105 (0.6);7.1573 (0.3);6.9344 (1.6);6.9223 (1.6);6.9156 (1.6);6.9035 (1.5);3.3332 (67.2);2.8907 (3.7);2.7309 (3.1);2.6759 (0.4);2.6671 (2.9);2.5283 (13.5);2.5205 (3.1);2.5117 (31.2);2.5073 (62.8);2.5027 (81.6);2.4982 (58.8);2.4937 (28.3);2.3397 (16.0);2.3298 (0.8);2.3252 (0.5);1.2342 (0.6);-0.0002 (0.6) |
I.073: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.0687 (2.2);8.0629 (2.2);7.9567 (0.6);7.7830 (2.4);7.7457 (0.5);7.7417 (0.6);7.7316 (0.6);7.7277 (0.7);7.7228 (0.8);7.7188 (0.8);7.7088 (0.7);7.7055 (0.7);7.6304 (1.8);7.6246 (1.4);7.6088 (1.9);7.6036 (1.9);7.5869 (0.8);7.5821 (0.6);7.5635 (0.4);7.4426 (0.5);7.4276 (0.7);7.4227 (1.1);7.4079 (1.1);7.4028 (0.9);7.3878 (0.7);7.2771 (0.9);7.2555 (1.5);7.2341 (0.7);7.0263 (1.7);7.0074 (1.5);6.8399 (2.2);6.8390 (2.2);6.8187 (2.2);6.8176 (2.1);4.0512 (5.0);3.8382 (16.0);3.3443 (35.1);2.8961 (4.2);2.7372 (3.6);2.5309 (0.4);2.5175 (7.7);2.5132 (15.3);2.5087 (19.9);2.5042 (14.8);2.4999 (7.7);2.4097 (12.5);-0.0002 (0.4) |
I.074: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1352 (1.3);8.1306 (1.4);8.1226 (1.6);8.1138 (3.1);7.9573 (0.7);7.8041 (0.7);7.7998 (0.7);7.7902 (0.7);7.7854 (0.8);7.7813 (1.0);7.7771 (0.9);7.7675 (0.9);7.7635 (0.8);7.6785 (2.3);7.6583 (1.2);7.6489 (0.8);7.6381 (0.9);7.6326 (1.0);7.6216 (1.4);7.6167 (1.9);7.6037 (1.7);7.5988 (1.4);7.5894 (1.1);7.5831 (0.7);7.5653 (0.6);7.4758 (0.3);7.4472 (0.5);7.4320 (0.8);7.4277 (1.0);7.4127 (1.2);7.4076 (0.9);7.4028 (0.6);7.3924 (0.8);7.3838 (1.1);7.3664 (1.4);7.3470 (0.9);7.3259 (0.5);7.2386 (0.8);7.2159 (1.3);7.1944 (0.7);7.0938 (0.9);7.0839 (1.8);7.0755 (3.2);7.0628 (2.3);7.0596 (2.4);7.0523 (2.4);7.0418 (2.2);7.0298 (1.4);7.0173 (1.4);7.0118 (1.2);6.9992 (1.1);6.7077 (1.0);6.6867 (1.0);4.2157 (7.1);4.0472 (0.8);4.0061 (1.7);3.9427 (1.6);3.9016 (0.8);3.6175 (5.8);3.5570 (12.2);3.3444 (62.0);2.8966 (4.3);2.7385 (3.9);2.6096 (16.0);2.5135 (29.1);2.5091 (36.6);2.5048 (26.6);2.3778 (10.7);1.6436 (0.5);1.6112 (0.6);1.5562 (0.6);1.2352 (0.7);1.0554 (1.0);-0.0002 (0.5) |
I.075: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1342 (1.6);8.1295 (1.8);8.1216 (2.0);8.1166 (3.1);7.9565 (0.4);7.8037 (0.4);7.7993 (0.5);7.7897 (0.5);7.7850 (0.7);7.7810 (0.8);7.7771 (0.8);7.7670 (0.7);7.7632 (0.7);7.6751 (3.1);7.6570 (1.5);7.6444 (1.0);7.6377 (0.8);7.6303 (0.8);7.6207 (1.7);7.6159 (2.1);7.6028 (2.2);7.5980 (1.9);7.5886 (1.3);7.5812 (1.0);7.5633 (0.9);7.5397 (0.4);7.4478 (0.6);7.4325 (0.8);7.4278 (1.3);7.4129 (1.3);7.4080 (1.2);7.4033 (0.6);7.3930 (0.9);7.3841 (0.8);7.3666 (1.0);7.3471 (0.6);7.2379 (1.0);7.2157 (1.7);7.1940 (0.9);7.0857 (2.1);7.0726 (2.3);7.0676 (2.6);7.0590 (1.8);7.0505 (1.7);7.0409 (1.6);7.0304 (1.9);7.0179 (1.8);7.0124 (1.8);6.9998 (1.6);6.7098 (0.3);4.3062 (0.4);4.2151 (4.9);4.0472 (1.0);4.0060 (2.2);3.9427 (2.2);3.9015 (1.0);3.6180 (1.8);3.5545 (16.0);3.3681 (148.4);2.8969 (2.3);2.7384 (2.1);2.6746 (1.0);2.6087 (11.0);2.5147 (27.7);2.5105 (36.3);2.5061 (27.9);2.3769 (13.8);1.2338 (0.4) |
I.076: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9548 (0.4);7.9480 (1.6);7.9433 (1.8);7.9356 (1.8);7.9308 (1.8);7.6311 (1.5);7.6264 (1.6);7.6129 (1.7);7.6081 (1.7);7.5026 (2.7);7.4924 (0.8);7.4832 (2.6);7.4676 (2.2);7.4580 (1.0);7.4420 (0.9);7.4350 (0.8);7.4183 (1.1);7.4146 (1.3);7.3980 (1.3);7.3943 (1.0);7.3776 (0.7);7.3175 (2.9);7.0209 (3.4);7.0002 (4.0);6.9787 (1.0);6.8661 (1.7);6.8537 (1.7);6.8479 (1.8);6.8354 (1.6);3.7590 (16.0);3.3404 (25.1);2.8939 (2.5);2.7357 (2.2);2.6876 (1.0);2.5120 (22.4);2.5067 (21.9);2.5022 (16.1);2.4979 (8.5);1.2364 (0.8);-0.0002 (0.5) |
I.077: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1565 (2.1);8.1543 (1.9);7.9548 (1.2);7.7092 (1.1);7.7047 (1.2);7.6880 (1.2);7.6834 (1.2);7.5784 (2.7);7.5680 (0.7);7.5641 (0.6);7.5536 (0.6);7.5500 (0.7);7.5445 (0.9);7.5409 (0.9);7.5304 (0.8);7.5275 (0.8);7.4855 (0.6);7.4673 (0.7);7.4599 (0.8);7.4417 (0.8);7.4370 (1.1);7.4167 (1.5);7.4002 (1.3);7.3963 (0.9);7.3797 (0.7);7.3083 (2.7);7.0980 (0.9);7.0765 (1.5);7.0552 (0.8);7.0536 (0.8);7.0271 (1.8);7.0070 (1.6);6.6918 (2.3);6.6906 (2.4);6.6705 (2.2);6.6692 (2.2);3.7149 (16.0);3.3365 (24.3);2.8946 (8.2);2.7360 (7.0);2.6878 (1.0);2.5510 (12.9);2.5292 (0.6);2.5156 (8.8);2.5113 (17.7);2.5068 (23.2);2.5023 (17.4);2.4981 (9.0);1.2372 (0.8);-0.0002 (0.8) |
I.078: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.5715 (10.9);7.9560 (1.0);7.7866 (3.1);7.7484 (0.7);7.7338 (0.9);7.7290 (1.1);7.7259 (1.0);7.7150 (1.0);7.6372 (0.7);7.6187 (0.8);7.6122 (1.0);7.5937 (0.9);7.5704 (0.5);7.4947 (0.6);7.4747 (1.3);7.4597 (1.3);7.4550 (1.1);7.4397 (0.8);7.3247 (1.1);7.3019 (1.8);7.2805 (0.9);7.0639 (2.0);7.0447 (1.9);4.1063 (6.3);3.8992 (16.0);3.3502 (68.5);2.8968 (5.5);2.7380 (5.2);2.5131 (19.4);2.5091 (25.0);2.5050 (20.0);2.4433 (14.1) |
I.079: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.7524 (2.0);7.7494 (2.1);7.7400 (2.2);7.7369 (2.1);7.5209 (0.5);7.5043 (0.7);7.4970 (2.0);7.4867 (2.1);7.4828 (2.5);7.4728 (1.4);7.4644 (2.9);7.4441 (4.8);7.4244 (0.5);7.3884 (1.3);7.3844 (1.8);7.3677 (2.0);7.3646 (1.9);7.2965 (3.3);7.2944 (3.4);7.2673 (3.1);7.2562 (6.6);7.2375 (4.7);7.2206 (1.0);7.2182 (0.8);3.7574 (10.7);3.7516 (10.5);3.6150 (1.4);3.3442 (31.4);2.8936 (0.8);2.7346 (0.7);2.5734 (16.0);2.5289 (0.5);2.5153 (10.2);2.5111 (20.0);2.5067 (25.7);2.5022 (18.9);2.4981 (9.5);-0.0002 (1.6) |
I.080: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1267 (2.8);7.7466 (2.6);7.7384 (1.7);7.7198 (2.0);7.7176 (1.9);7.6991 (1.7);7.6292 (0.5);7.6253 (0.5);7.6154 (0.5);7.6114 (0.6);7.6062 (0.8);7.6023 (0.8);7.5923 (0.8);7.5889 (0.7);7.5415 (0.6);7.5234 (0.7);7.5158 (0.8);7.4978 (0.7);7.4930 (0.5);7.4746 (0.4);7.4194 (0.6);7.4030 (0.7);7.3989 (1.2);7.3826 (1.3);7.3784 (0.8);7.3620 (0.6);7.1857 (1.1);7.1799 (1.1);7.1674 (1.0);7.1616 (1.1);7.0551 (1.8);7.0346 (1.6);6.9884 (0.9);6.9867 (0.9);6.9639 (1.2);6.9427 (0.8);6.7175 (2.2);6.7164 (2.3);6.6969 (2.2);6.6956 (2.2);3.8416 (16.0);3.3441 (28.2);2.8941 (1.1);2.7358 (1.0);2.7347 (1.0);2.5983 (12.4);2.5297 (0.4);2.5161 (8.0);2.5118 (15.8);2.5072 (20.4);2.5027 (14.8);2.4983 (7.3);-0.0002 (1.4) |
I.081: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1999 (3.6);8.0804 (1.7);8.0687 (1.7);7.9547 (0.6);7.5356 (0.4);7.5119 (2.5);7.4955 (3.6);7.4855 (1.5);7.4692 (1.0);7.4574 (0.7);7.4452 (0.6);7.4369 (1.2);7.4203 (1.2);7.4000 (0.6);7.3634 (2.4);7.2525 (1.4);7.2408 (1.4);7.0272 (1.0);7.0106 (2.1);7.0060 (2.0);6.9911 (1.6);6.9848 (1.1);3.7904 (16.0);3.7050 (0.4);3.6562 (0.8);3.6138 (0.4);3.3466 (55.9);2.8923 (4.7);2.7341 (3.8);2.7331 (3.8);2.5473 (0.4);2.5200 (16.1);2.5144 (13.2);2.5099 (24.4);2.5054 (31.1);2.5008 (22.2);2.4963 (10.6);-0.0002 (0.5) |
I.082: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2333 (4.8);8.2283 (3.1);8.2137 (2.6);7.9550 (1.6);7.5339 (0.4);7.5180 (0.6);7.5102 (1.9);7.5033 (1.4);7.4952 (1.6);7.4797 (3.9);7.4625 (1.0);7.4471 (0.8);7.4392 (0.4);7.4305 (0.9);7.4268 (1.4);7.4102 (1.5);7.4065 (1.0);7.3898 (0.8);7.3445 (3.0);7.0292 (1.1);7.0098 (3.7);6.9896 (2.4);6.8862 (2.8);6.8716 (2.7);3.7241 (16.0);3.3471 (8.2);2.8926 (10.8);2.7342 (9.4);2.7333 (9.1);2.5550 (0.4);2.5278 (0.7);2.5143 (11.6);2.5100 (22.7);2.5054 (30.2);2.5007 (32.8);-0.0002 (1.6) |
I.083: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9957 (2.2);7.9837 (2.2);7.9825 (2.3);7.9547 (1.6);7.6062 (2.6);7.5802 (0.5);7.5770 (0.5);7.5667 (0.5);7.5628 (0.6);7.5574 (0.8);7.5538 (0.8);7.5433 (0.8);7.5404 (0.8);7.5052 (0.6);7.4871 (0.7);7.4796 (0.8);7.4667 (0.9);7.4564 (0.6);7.4505 (0.8);7.4464 (1.3);7.4383 (0.5);7.4302 (1.3);7.4261 (0.8);7.4096 (0.7);7.3884 (2.5);7.0881 (0.9);7.0663 (1.4);7.0447 (0.8);7.0429 (0.8);7.0179 (1.8);6.9977 (1.6);6.9605 (1.6);6.9473 (1.6);6.8278 (2.8);3.7044 (16.0);3.3456 (56.8);2.8920 (11.2);2.7337 (9.3);2.7326 (9.6);2.5470 (12.7);2.5277 (0.6);2.5142 (11.4);2.5098 (22.7);2.5053 (29.3);2.5007 (21.2);2.4963 (10.4) |
I.084: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9549 (1.7);7.9011 (3.0);7.8968 (3.2);7.8953 (3.1);7.6790 (3.3);7.6744 (3.2);7.6732 (3.1);7.6291 (4.0);7.5083 (0.6);7.4931 (1.7);7.4887 (1.8);7.4841 (2.2);7.4725 (4.3);7.4552 (2.3);7.4506 (2.3);7.4312 (1.2);7.4258 (0.5);7.4081 (0.5);7.3484 (1.7);7.3447 (1.8);7.3295 (2.7);7.3256 (2.6);7.2848 (2.9);7.2704 (2.3);7.2674 (3.4);7.2521 (2.6);7.2495 (2.3);7.2335 (1.1);7.2307 (1.0);7.1511 (3.9);3.3449 (55.8);2.8924 (11.5);2.7333 (9.9);2.5492 (19.6);2.5282 (0.7);2.5146 (12.4);2.5103 (24.9);2.5058 (32.5);2.5012 (23.8);2.4968 (11.9);2.0769 (16.0);-0.0002 (1.8) |
I.085: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9545 (1.9);7.8268 (0.5);7.8182 (0.4);7.8108 (0.4);7.7987 (0.5);7.7942 (0.5);7.7867 (0.6);7.6849 (3.4);7.6646 (3.6);7.6341 (1.0);7.6249 (0.5);7.6147 (0.5);7.5940 (0.6);7.5465 (0.8);7.5377 (1.1);7.5337 (1.0);7.5247 (1.8);7.5106 (1.4);7.5010 (3.6);7.4875 (1.2);7.4804 (0.9);7.4759 (1.5);7.4692 (1.9);7.4627 (2.2);7.4566 (2.0);7.4527 (2.0);7.4438 (1.2);7.4382 (1.8);7.4337 (1.5);7.4230 (1.4);7.4187 (1.3);7.4102 (0.7);7.4061 (0.6);7.3889 (0.7);7.3587 (0.7);7.3482 (0.9);7.3412 (1.1);7.3155 (1.1);7.3114 (1.3);7.2966 (2.6);7.2924 (2.3);7.2702 (1.6);7.2678 (1.8);7.2519 (1.8);7.2494 (2.1);7.2339 (2.9);7.2151 (2.1);7.1966 (3.4);7.1691 (2.9);7.1489 (2.7);7.0496 (0.5);7.0177 (0.5);6.9295 (0.7);6.8888 (0.6);6.5849 (0.7);6.5529 (0.6);3.3404 (78.3);2.8917 (13.3);2.7331 (11.1);2.7322 (11.3);2.6736 (0.3);2.5339 (17.1);2.5135 (20.8);2.5092 (40.7);2.5047 (52.3);2.5001 (38.0);2.4957 (18.7);2.3282 (16.0);1.2324 (0.3) |
I.086: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1905 (6.7);7.9545 (1.7);7.8268 (1.0);7.8180 (1.0);7.8112 (0.8);7.7986 (1.2);7.7941 (1.0);7.7867 (1.2);7.6341 (1.7);7.6250 (0.9);7.6146 (0.9);7.5940 (1.0);7.5602 (0.7);7.5386 (2.0);7.5240 (2.1);7.4918 (2.4);7.4814 (5.1);7.4743 (3.7);7.4672 (4.7);7.4630 (3.0);7.4546 (2.0);7.4496 (2.4);7.4230 (2.4);7.4180 (2.0);7.4099 (1.2);7.4058 (1.0);7.3889 (1.5);7.3812 (0.4);7.3729 (0.6);7.3672 (0.4);7.3587 (1.2);7.3483 (1.8);7.3410 (2.0);7.3282 (0.4);7.3250 (0.3);7.3068 (0.9);7.3019 (1.2);7.2879 (3.3);7.2828 (3.4);7.2768 (7.5);7.2577 (2.1);7.2362 (2.8);7.2153 (5.6);7.0493 (0.8);7.0174 (0.9);6.9295 (1.2);6.8889 (1.1);6.5848 (1.3);6.5528 (1.1);3.3377 (59.2);2.8914 (11.7);2.7321 (9.9);2.6731 (0.4);2.5247 (19.4);2.5132 (24.7);2.5089 (48.4);2.5044 (62.5);2.4998 (45.5);2.4954 (22.3);2.3357 (0.4);2.3276 (0.5);2.1873 (16.0);1.2320 (0.4);-0.0002 (0.5) |
I.087: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2551 (2.9);8.2496 (3.0);7.9553 (1.9);7.8765 (2.8);7.8712 (2.7);7.8274 (0.5);7.8182 (0.5);7.8115 (0.5);7.7988 (0.6);7.7947 (0.5);7.7877 (0.7);7.6802 (3.5);7.6346 (0.9);7.6255 (0.5);7.6152 (0.5);7.5947 (0.6);7.5445 (0.5);7.5397 (0.5);7.5250 (0.7);7.5024 (0.9);7.4990 (1.0);7.4801 (3.0);7.4638 (2.8);7.4553 (3.3);7.4508 (3.4);7.4410 (2.2);7.4344 (3.3);7.4184 (1.4);7.4101 (1.6);7.3890 (0.9);7.3596 (0.7);7.3484 (1.0);7.3356 (1.8);7.3161 (4.9);7.2966 (2.9);7.0493 (0.6);7.0385 (3.6);7.0179 (0.5);6.9298 (0.6);6.8892 (0.5);6.5851 (0.6);6.5532 (0.6);3.3386 (34.3);2.8921 (11.8);2.7333 (10.8);2.6730 (0.4);2.5974 (16.0);2.5096 (34.0);2.5053 (42.9);2.5011 (31.8);2.3316 (0.4);2.1818 (14.6);-0.0002 (0.4) |
I.088: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.6204 (8.3);7.7339 (3.1);7.6047 (0.5);7.6014 (0.6);7.5907 (0.6);7.5875 (0.7);7.5818 (0.9);7.5786 (1.0);7.5679 (0.8);7.5652 (0.8);7.5180 (0.7);7.4998 (0.7);7.4926 (0.9);7.4749 (1.4);7.4544 (1.5);7.4380 (1.4);7.4175 (0.7);7.3864 (3.0);7.1204 (1.0);7.0985 (1.7);7.0769 (0.9);7.0075 (2.0);6.9873 (1.8);3.7977 (16.0);3.3660 (79.3);2.8965 (1.6);2.7381 (1.5);2.5733 (13.5);2.5318 (0.5);2.5182 (8.4);2.5142 (16.5);2.5097 (21.3);2.5053 (15.9);1.2370 (0.7) |
I.089: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9870 (2.9);7.9561 (2.3);7.8687 (1.5);7.8444 (1.5);7.6886 (4.2);7.5948 (0.8);7.5911 (0.8);7.5810 (0.9);7.5771 (1.0);7.5718 (1.3);7.5681 (1.3);7.5578 (1.2);7.5546 (1.2);7.5126 (1.0);7.4945 (1.1);7.4869 (1.3);7.4700 (2.0);7.4641 (0.9);7.4535 (1.4);7.4495 (2.2);7.4332 (2.1);7.4292 (1.4);7.4126 (1.1);7.3491 (4.1);7.0985 (1.5);7.0772 (2.4);7.0559 (1.2);7.0540 (1.3);7.0321 (2.8);7.0119 (2.6);3.6158 (1.3);3.3560 (96.9);2.8943 (16.0);2.7359 (13.7);2.7349 (13.3);2.5487 (20.6);2.5302 (0.9);2.5167 (13.8);2.5123 (27.1);2.5078 (34.8);2.5032 (25.0);2.4988 (12.0);2.0689 (13.4);-0.0002 (0.3) |
I.090: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.4389 (10.6);8.4379 (10.6);8.4172 (16.0);7.9552 (0.9);7.8929 (0.5);7.8902 (0.5);7.8129 (0.6);7.6482 (7.1);7.5368 (2.0);7.5327 (2.2);7.5287 (1.3);7.5170 (4.2);7.5145 (4.6);7.5038 (3.9);7.4983 (3.9);7.4941 (6.2);7.4779 (2.2);7.4695 (2.4);7.4525 (2.1);7.4467 (0.9);7.4293 (0.9);7.4053 (3.2);7.4011 (3.6);7.3851 (5.3);7.3814 (4.2);7.3509 (0.4);7.3322 (0.6);7.3298 (0.7);7.3114 (0.6);7.2934 (2.5);7.2907 (3.5);7.2753 (8.2);7.2555 (8.1);7.2487 (6.8);7.2081 (0.6);7.2055 (0.7);7.1867 (0.6);6.9791 (0.4);3.6644 (0.5);3.6144 (0.8);3.3462 (130.2);2.8932 (6.2);2.7349 (5.2);2.7338 (5.2);2.6993 (3.0);2.6799 (0.3);2.6753 (0.4);2.6707 (0.4);2.5499 (34.2);2.5288 (1.5);2.5240 (2.2);2.5153 (27.5);2.5109 (55.0);2.5063 (71.1);2.5017 (51.1);2.4972 (24.7);2.3533 (0.6);2.3377 (0.3);2.3331 (0.4);2.3285 (0.3);1.2310 (0.3);-0.0002 (2.6) |
I.091: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2124 (2.8);8.2114 (2.8);8.1997 (2.9);8.1986 (2.9);8.0682 (0.4);7.7986 (3.3);7.5950 (0.6);7.5911 (0.6);7.5811 (0.7);7.5770 (0.8);7.5662 (4.2);7.5550 (1.0);7.5186 (0.8);7.5107 (0.9);7.5022 (1.1);7.4981 (1.8);7.4927 (1.1);7.4819 (2.1);7.4777 (1.3);7.4669 (1.1);7.4614 (1.4);7.4437 (0.5);7.4068 (1.4);7.4042 (2.1);7.3915 (2.0);7.3760 (3.2);7.1269 (1.2);7.1053 (1.8);7.0835 (1.0);7.0816 (1.1);7.0691 (2.2);7.0488 (2.0);3.3445 (33.3);2.8938 (1.5);2.7355 (1.3);2.7344 (1.3);2.6880 (1.3);2.5743 (16.0);2.5296 (0.6);2.5247 (0.8);2.5161 (10.0);2.5116 (20.0);2.5071 (25.8);2.5025 (18.6);2.4980 (8.9);-0.0002 (2.0) |
I.092: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.4191 (2.2);8.4167 (2.4);8.4143 (2.2);7.9564 (0.4);7.8980 (1.4);7.8934 (1.3);7.8773 (1.5);7.8727 (1.4);7.7227 (3.4);7.5861 (0.6);7.5825 (0.6);7.5720 (0.7);7.5684 (0.8);7.5630 (1.1);7.5594 (1.1);7.5489 (1.0);7.5459 (1.0);7.5114 (0.8);7.4943 (1.4);7.4858 (1.1);7.4783 (1.2);7.4742 (1.9);7.4680 (1.2);7.4623 (0.9);7.4579 (1.8);7.4539 (1.2);7.4445 (0.6);7.4374 (0.9);7.4025 (3.0);7.4012 (3.1);7.3818 (2.8);7.3805 (2.9);7.3577 (3.2);7.3556 (3.2);7.1335 (1.1);7.1121 (1.9);7.0907 (1.0);7.0888 (1.0);7.0435 (2.2);7.0233 (2.0);3.3461 (35.6);2.8938 (2.6);2.7357 (2.2);2.7346 (2.2);2.6883 (0.9);2.5604 (16.0);2.5297 (0.6);2.5249 (0.9);2.5163 (10.0);2.5119 (19.8);2.5074 (25.6);2.5028 (18.5);2.4983 (8.9);-0.0002 (1.7) |
I.093: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.4984 (5.8);8.3815 (3.6);8.3691 (3.8);8.0676 (0.7);7.9558 (2.3);7.6974 (3.7);7.5961 (0.6);7.5934 (0.6);7.5820 (0.7);7.5789 (0.8);7.5703 (1.5);7.5590 (1.3);7.5564 (1.3);7.5438 (1.2);7.5262 (1.1);7.5181 (1.4);7.5151 (1.4);7.4951 (5.1);7.4833 (3.4);7.4777 (2.7);7.4740 (1.6);7.4600 (3.9);7.0672 (1.3);7.0457 (2.3);7.0228 (1.2);6.9784 (2.7);6.9582 (2.6);3.6625 (0.7);3.6145 (0.4);3.3432 (40.6);2.8932 (16.0);2.7341 (13.9);2.6873 (2.2);2.5405 (18.6);2.5292 (1.0);2.5152 (12.8);2.5109 (25.8);2.5064 (33.6);2.5018 (24.8);2.4974 (12.4);-0.0002 (2.3) |
I.094: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2115 (2.3);8.2067 (2.6);8.1996 (2.6);8.1948 (2.5);7.9554 (2.3);7.9079 (2.4);7.9030 (2.4);7.8889 (2.7);7.8840 (2.5);7.6718 (3.8);7.5997 (0.6);7.5963 (0.6);7.5858 (0.7);7.5821 (0.8);7.5765 (1.3);7.5733 (1.4);7.5627 (1.2);7.5596 (1.2);7.5401 (1.1);7.5224 (1.1);7.5146 (1.2);7.4968 (1.1);7.4892 (1.2);7.4718 (4.9);7.4686 (5.5);7.4519 (2.0);7.4480 (1.3);7.4313 (1.0);7.3226 (2.6);7.3107 (2.5);7.3037 (2.5);7.2917 (2.4);7.0590 (1.3);7.0573 (1.4);7.0361 (2.4);7.0150 (1.2);7.0130 (1.2);6.9609 (2.6);6.9406 (2.4);3.3566 (99.8);2.8935 (16.0);2.7351 (13.3);2.7343 (13.4);2.6873 (0.9);2.5303 (19.4);2.5160 (12.7);2.5116 (24.9);2.5070 (31.9);2.5024 (22.9);2.4980 (11.1);-0.0002 (2.3) |
I.095: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1178 (1.4);8.1113 (1.7);8.0975 (1.4);8.0910 (1.6);8.0383 (2.3);8.0354 (2.5);8.0320 (2.2);8.0289 (1.9);7.9549 (2.3);7.7254 (3.3);7.5249 (1.1);7.5209 (1.1);7.5165 (0.8);7.5055 (3.2);7.4892 (2.2);7.4826 (1.5);7.4719 (1.0);7.4638 (1.2);7.4480 (2.3);7.4310 (1.9);7.2880 (4.0);7.2686 (3.5);7.2530 (1.1);7.2505 (0.8);7.1984 (3.2);3.3374 (29.8);2.8921 (16.0);2.7332 (13.6);2.6693 (0.3);2.5647 (16.0);2.5269 (0.8);2.5135 (16.5);2.5092 (31.4);2.5047 (39.6);2.5002 (28.3);2.4958 (13.7);1.9105 (0.4);1.2323 (0.3) |
I.096: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9847 (2.5);7.9721 (2.7);7.8265 (0.4);7.8180 (0.4);7.8112 (0.4);7.7986 (0.5);7.7942 (0.4);7.7865 (0.6);7.6534 (3.3);7.6341 (0.5);7.5298 (1.2);7.5268 (1.2);7.5197 (0.5);7.5111 (2.3);7.5058 (4.0);7.4890 (3.5);7.4800 (1.7);7.4633 (1.8);7.4407 (0.4);7.4231 (0.5);7.4180 (0.6);7.4068 (3.2);7.3942 (3.0);7.3882 (2.1);7.3837 (1.8);7.3677 (2.1);7.3644 (2.0);7.3482 (0.7);7.3412 (0.5);7.2782 (3.4);7.2685 (3.1);7.2518 (2.5);7.2483 (2.4);7.2352 (1.0);3.3373 (52.7);2.8916 (1.7);2.7322 (1.6);2.6728 (0.3);2.5704 (16.0);2.5267 (0.9);2.5129 (17.6);2.5089 (34.9);2.5044 (45.4);2.4999 (33.5);2.4956 (16.8);1.2322 (0.3) |
I.097: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1908 (3.7);8.1833 (3.8);7.9545 (2.3);7.9306 (1.6);7.9231 (1.5);7.9087 (1.7);7.9012 (1.4);7.6578 (3.3);7.5369 (0.6);7.5135 (2.3);7.4970 (2.7);7.4811 (1.1);7.4723 (2.1);7.4561 (1.0);7.4327 (0.4);7.3948 (1.4);7.3908 (1.6);7.3748 (2.2);7.3717 (2.0);7.2769 (1.7);7.2666 (2.4);7.2595 (2.5);7.2419 (4.7);3.3370 (35.7);2.8919 (14.8);2.7327 (13.4);2.5694 (16.0);2.5264 (0.9);2.5088 (32.2);2.5044 (41.1);2.5000 (30.3);1.2324 (0.4) |
I.098: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2490 (3.6);8.2455 (3.7);7.9530 (1.8);7.7513 (3.3);7.6226 (3.1);7.6095 (3.1);7.5493 (0.9);7.5455 (1.4);7.5299 (2.2);7.5272 (2.2);7.5105 (1.8);7.5070 (2.2);7.4966 (1.0);7.4793 (1.0);7.4712 (1.1);7.4622 (0.5);7.4469 (2.0);7.4293 (2.2);7.2918 (4.7);7.2725 (4.9);7.2524 (3.9);3.3341 (123.4);2.8908 (12.8);2.7310 (10.8);2.6762 (0.5);2.6715 (0.8);2.5756 (16.0);2.5251 (2.3);2.5117 (43.3);2.5073 (85.8);2.5028 (110.4);2.4983 (79.7);2.4939 (38.7);2.3341 (0.5);2.3295 (0.7);2.3251 (0.5);1.2344 (0.9);-0.0002 (0.8) |
I.099: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.4811 (1.9);8.4779 (2.5);8.3243 (3.1);8.3184 (3.2);7.9961 (1.5);7.9920 (2.4);7.9879 (1.5);7.9810 (0.4);7.9546 (2.2);7.8035 (2.6);7.5922 (0.5);7.5883 (0.5);7.5784 (0.5);7.5743 (0.6);7.5690 (0.8);7.5653 (0.8);7.5551 (0.8);7.5518 (0.7);7.5155 (0.6);7.5042 (0.7);7.4990 (0.9);7.4950 (1.4);7.4862 (0.8);7.4786 (2.1);7.4748 (1.1);7.4584 (1.2);7.4372 (0.4);7.3413 (2.5);7.1472 (0.9);7.1452 (0.9);7.1239 (1.6);7.1025 (0.8);7.1005 (0.8);7.0825 (1.8);7.0623 (1.7);3.3401 (8.9);3.0036 (0.5);2.8921 (16.0);2.7333 (13.8);2.7320 (13.3);2.6854 (0.4);2.5846 (1.1);2.5513 (13.3);2.5270 (0.9);2.5221 (1.4);2.5136 (17.2);2.5091 (34.0);2.5046 (43.6);2.5000 (31.0);2.4955 (14.8);1.8875 (1.0) |
I.100: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9548 (2.2);7.7786 (3.2);7.6158 (0.6);7.6130 (0.6);7.5985 (0.7);7.5928 (1.1);7.5896 (1.1);7.5791 (1.0);7.5760 (1.0);7.5486 (0.8);7.5307 (0.8);7.5230 (1.0);7.5111 (1.0);7.4956 (4.0);7.4820 (0.7);7.4743 (1.6);7.4703 (1.1);7.4537 (0.8);7.2581 (9.2);7.0951 (1.2);7.0731 (1.7);7.0502 (1.0);7.0056 (2.2);6.9852 (2.1);3.3380 (16.4);2.8923 (15.4);2.7327 (13.2);2.5848 (16.0);2.5270 (0.9);2.5135 (19.2);2.5092 (38.0);2.5047 (49.2);2.5002 (36.0);2.4958 (18.1);2.3314 (0.4);1.2325 (0.4) |
I.101: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9549 (2.3);7.9375 (1.9);7.9355 (1.9);7.9249 (2.0);7.9229 (1.9);7.7934 (3.1);7.6173 (0.5);7.6009 (0.6);7.5924 (1.2);7.5785 (1.1);7.5613 (3.2);7.5515 (1.0);7.5432 (1.0);7.5328 (0.9);7.5260 (1.0);7.5159 (1.1);7.5123 (1.6);7.5022 (0.6);7.4955 (1.5);7.4921 (1.0);7.4750 (0.8);7.4507 (1.4);7.4389 (2.3);7.4271 (1.3);7.0778 (1.1);7.0556 (1.8);7.0334 (1.0);6.9646 (2.2);6.9442 (2.0);3.3401 (32.2);2.8925 (16.0);2.7330 (13.9);2.5527 (15.5);2.5272 (0.9);2.5136 (17.0);2.5094 (33.2);2.5049 (42.6);2.5004 (30.9);2.4961 (15.2) |
I.102: 1H-NMR(300.2 MHz, CDCl3): δ= 8.1744 (2.9);7.6678 (2.8);7.4724 (0.6);7.4512 (0.8);7.4448 (1.4);7.4236 (1.5);7.4175 (1.2);7.3961 (1.2);7.3862 (2.7);7.3655 (2.4);7.3537 (1.3);7.3334 (1.2);7.2987 (2.8);7.0696 (1.1);7.0572 (1.6);7.0452 (1.1);6.9861 (3.4);6.9582 (4.3);6.9307 (1.0);5.4748 (1.7);5.3342 (3.1);2.6479 (16.0);1.6885 (0.6);1.2881 (0.4);0.0334 (3.4) |
I.103: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2152 (0.6);8.1948 (1.4);8.1719 (1.4);8.1515 (0.6);7.9554 (2.3);7.7291 (3.3);7.6021 (0.5);7.5878 (0.6);7.5847 (0.6);7.5766 (1.3);7.5623 (1.2);7.5561 (1.0);7.5387 (0.9);7.5307 (1.0);7.5134 (0.9);7.5079 (0.5);7.4944 (1.0);7.4827 (3.3);7.4741 (1.8);7.4573 (1.6);7.4537 (1.1);7.4367 (0.8);7.1321 (1.4);7.1265 (1.4);7.1117 (1.4);7.1061 (1.4);7.0675 (1.1);7.0462 (1.9);7.0249 (1.0);7.0233 (1.0);6.9564 (2.2);6.9361 (2.1);3.3383 (37.9);2.8928 (16.0);2.7338 (13.3);2.7330 (13.6);2.5452 (15.9);2.5278 (0.8);2.5142 (14.7);2.5098 (28.7);2.5053 (36.8);2.5008 (26.6);2.4964 (13.0) |
I.105: 1H-NMR(300.2 MHz, CDCl3): δ= 8.5841 (0.8);8.5782 (0.8);8.5681 (0.8);8.5623 (0.8);7.8375 (1.3);7.8334 (1.4);7.5893 (0.7);7.5837 (0.7);7.5635 (0.8);7.5583 (0.8);7.4234 (0.4);7.4131 (0.3);7.4076 (0.3);7.3960 (1.5);7.3840 (1.1);7.3751 (1.1);7.3680 (0.7);7.3640 (0.8);7.3535 (0.8);7.3470 (0.6);7.3318 (0.7);7.2990 (12.3);7.2141 (1.1);7.1982 (1.1);7.1886 (1.0);7.1726 (0.9);7.0991 (1.1);7.0717 (0.9);6.9485 (0.6);6.9456 (0.6);6.9198 (0.9);6.9177 (0.9);6.8920 (0.5);6.8890 (0.5);5.4046 (1.0);5.3383 (3.5);2.5261 (8.5);1.8852 (0.6);1.8699 (0.3);1.5981 (16.0);1.2833 (0.4);1.2598 (0.3);1.2523 (0.4);1.2412 (0.4);1.2366 (0.4);1.2313 (0.4);1.2255 (0.3);1.2197 (0.4);1.0931 (0.4);1.0872 (0.3);1.0822 (0.5);1.0773 (0.4);1.0665 (0.4);1.0622 (0.3);0.9533 (0.4);0.9417 (0.5);0.9325 (0.4);0.9260 (0.4);0.9209 (0.4);0.9149 (0.3);0.7908 (0.3);0.7861 (0.4);0.7592 (0.4);0.0485 (0.7);0.0377 (16.2);0.0268 (0.6) |
I.106: 1H-NMR(300.2 MHz, CDCl3): δ= 8.5663 (2.7);8.5499 (2.7);8.3545 (4.0);7.8531 (3.0);7.8497 (3.0);7.4367 (0.6);7.4328 (0.6);7.4152 (1.2);7.4062 (1.5);7.4022 (1.6);7.3939 (1.2);7.3878 (3.2);7.3662 (2.2);7.3540 (1.6);7.3392 (1.1);7.3321 (1.4);7.3234 (0.5);7.2989 (2.9);7.2396 (2.3);7.2232 (2.3);7.0603 (2.1);7.0329 (1.8);6.9202 (1.2);6.9175 (1.2);6.8907 (2.1);6.8633 (1.1);6.8606 (1.0);5.3103 (2.2);2.5158 (16.0);1.8536 (0.5);1.7745 (0.6);1.7648 (0.6);1.7470 (0.9);1.7362 (0.4);1.7289 (0.6);1.7190 (0.6);1.3020 (5.9);1.2867 (0.8);1.2747 (4.0);0.9958 (0.4);0.9805 (0.7);0.9748 (0.6);0.9657 (0.8);0.9586 (0.8);0.9522 (0.8);0.9462 (0.5);0.9360 (0.9);0.9306 (0.6);0.9196 (0.7);0.9027 (0.9);0.8868 (0.9);0.8665 (1.9);0.8534 (0.8);0.8440 (1.8);0.8344 (0.9);0.8152 (0.7);0.8039 (0.5);0.7843 (0.3);0.7749 (0.3);0.7568 (0.4);0.7520 (0.6);0.7449 (0.9);0.7346 (0.9);0.7309 (0.9);0.7139 (0.8);0.7079 (0.4);0.6975 (0.4);0.1073 (0.4);0.0311 (3.1) |
I.107: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1502 (2.6);8.1444 (2.6);7.9555 (0.3);7.7049 (1.6);7.6987 (1.5);7.6836 (1.7);7.6774 (1.6);7.6281 (3.0);7.4557 (0.6);7.4520 (0.7);7.4331 (1.6);7.4177 (4.4);7.4014 (3.7);7.3900 (1.1);7.3738 (0.8);7.3195 (3.9);7.3006 (3.4);7.2842 (0.7);6.9437 (3.0);6.5143 (2.6);6.4929 (2.5);5.0755 (0.4);5.0601 (1.2);5.0447 (1.6);5.0292 (1.2);5.0138 (0.4);3.3443 (29.2);2.8929 (2.2);2.7344 (1.9);2.5958 (13.0);2.5107 (17.4);2.5063 (22.1);2.5019 (16.3);1.1012 (16.0);1.0858 (15.7);-0.0002 (1.2) |
I.108: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.5446 (3.3);7.5245 (3.5);7.4467 (1.4);7.4390 (2.2);7.4247 (2.8);7.4146 (1.0);7.3956 (0.6);7.3916 (0.8);7.3758 (1.2);7.3731 (1.2);7.3578 (1.0);7.3536 (1.1);7.3090 (1.3);7.3053 (1.3);7.2899 (2.1);7.2857 (2.1);7.2828 (2.1);7.2801 (2.1);7.2598 (4.0);7.2092 (1.2);7.2061 (1.3);7.1996 (2.8);7.1968 (2.8);7.1910 (1.8);7.1883 (1.5);7.1721 (0.7);7.1693 (0.6);6.2785 (3.5);6.2584 (3.5);3.8565 (0.8);3.8021 (0.9);3.7840 (15.4);3.7247 (16.0);3.3449 (30.6);2.8928 (0.4);2.7342 (0.4);2.5528 (12.9);2.5288 (0.5);2.5155 (8.1);2.5111 (15.7);2.5065 (20.0);2.5020 (14.3);2.4976 (6.8);-0.0002 (1.1) |
I.109: 1H-NMR(300.2 MHz, CDCl3): δ= 8.7234 (1.4);8.7175 (1.4);8.7073 (1.5);8.7014 (1.4);7.8748 (2.6);7.8711 (2.6);7.6234 (1.5);7.6174 (1.5);7.5978 (1.8);7.5918 (1.7);7.4557 (0.5);7.4514 (0.5);7.4383 (0.6);7.4326 (0.6);7.4252 (1.2);7.4206 (1.3);7.4018 (2.3);7.3784 (2.1);7.3699 (1.4);7.3565 (1.6);7.3492 (1.8);7.3395 (0.6);7.3292 (2.4);7.3132 (1.9);7.2987 (33.8);7.2909 (1.0);7.2877 (1.5);7.0401 (2.0);7.0125 (1.7);6.9044 (1.0);6.9013 (1.0);6.8754 (1.8);6.8478 (1.0);6.8447 (0.9);5.3375 (2.4);5.1731 (1.8);4.1711 (0.3);4.1475 (0.4);2.7311 (1.6);2.7050 (3.1);2.6798 (2.0);2.4932 (16.0);2.0828 (1.6);1.7608 (0.8);1.7436 (0.8);1.7358 (1.5);1.7185 (1.5);1.7108 (1.7);1.6929 (1.8);1.6853 (1.5);1.6677 (2.2);1.6339 (6.5);1.3206 (0.5);1.2966 (1.4);1.2919 (1.1);1.2729 (0.6);0.8984 (4.3);0.8740 (8.8);0.8494 (3.9);0.0477 (1.2);0.0444 (0.8);0.0369 (39.2);0.0260 (1.4) |
I.110: 1H-NMR(300.2 MHz, CDCl3): δ= 8.7023 (2.1);8.6267 (1.4);8.6101 (1.6);7.8747 (1.6);7.4255 (0.7);7.4217 (0.8);7.4080 (1.0);7.4034 (1.3);7.3812 (1.3);7.3720 (0.8);7.3594 (0.9);7.3517 (0.9);7.3317 (0.5);7.2986 (6.6);7.2417 (1.3);7.2251 (1.3);7.0328 (1.3);7.0051 (1.0);6.8966 (0.6);6.8939 (0.6);6.8675 (1.1);6.8398 (0.6);6.8371 (0.5);5.3362 (0.3);5.1723 (1.1);2.5800 (1.0);2.5544 (2.1);2.5287 (1.2);2.4971 (9.0);1.6451 (16.0);1.5933 (0.4);1.5816 (0.4);1.5684 (0.7);1.5566 (0.7);1.5432 (0.7);1.5317 (0.8);1.5175 (0.4);1.5070 (0.6);0.8874 (2.4);0.8734 (0.5);0.8630 (4.8);0.8494 (0.7);0.8385 (2.1);0.0363 (7.6) |
I.111: 1H-NMR(300.2 MHz, CDCl3): δ= 8.6382 (1.7);8.6212 (1.7);8.5045 (2.8);7.8724 (2.8);7.4533 (0.5);7.4488 (0.4);7.4360 (0.6);7.4306 (0.6);7.4227 (1.2);7.4182 (1.4);7.4054 (1.7);7.4002 (1.4);7.3946 (1.5);7.3837 (1.0);7.3777 (1.8);7.3687 (2.5);7.3636 (2.4);7.3512 (2.9);7.3410 (1.5);7.3300 (1.0);7.3095 (0.6);7.2986 (4.5);7.0150 (1.8);6.9875 (1.5);6.8964 (1.0);6.8676 (1.9);6.8400 (0.9);5.3324 (0.4);5.2119 (1.8);2.5485 (1.5);2.5225 (3.0);2.4965 (16.0);1.7717 (0.5);1.6445 (0.4);1.6242 (0.8);1.5996 (1.4);1.5755 (1.6);1.5530 (1.3);1.5293 (0.7);1.2882 (0.7);0.8873 (4.4);0.8628 (8.7);0.8383 (3.8);0.0326 (4.0) |
I.112: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.1198 (3.7);7.9558 (2.2);7.6779 (2.1);7.6733 (2.0);7.6566 (2.2);7.6519 (2.1);7.6257 (5.0);7.5618 (0.9);7.5582 (0.9);7.5477 (1.0);7.5442 (1.1);7.5387 (1.5);7.5352 (1.6);7.5247 (1.4);7.5219 (1.4);7.4849 (1.2);7.4669 (1.4);7.4593 (1.4);7.4418 (2.4);7.4253 (1.6);7.4214 (2.5);7.4052 (2.4);7.4011 (1.5);7.3847 (1.2);7.2775 (4.7);7.1038 (1.6);7.0825 (2.7);7.0612 (1.5);7.0592 (1.6);7.0490 (3.2);7.0289 (2.9);6.6260 (4.2);6.6248 (4.2);6.6046 (4.0);6.6034 (4.0);4.1646 (2.2);4.1470 (7.2);4.1294 (7.3);4.1119 (2.2);3.3439 (53.6);3.3297 (0.6);2.8931 (15.3);2.7351 (12.8);2.7342 (12.9);2.5514 (23.0);2.5289 (0.9);2.5154 (15.8);2.5111 (30.5);2.5065 (38.4);2.5020 (27.2);2.4975 (12.9);1.1597 (7.6);1.1421 (16.0);1.1245 (7.4);-0.0002 (2.3) |
I.113: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9556 (2.0);7.9329 (3.1);7.9281 (3.4);7.9205 (3.3);7.9157 (3.2);7.6279 (3.0);7.6231 (3.0);7.6096 (3.3);7.6048 (3.0);7.5023 (0.5);7.4838 (5.3);7.4668 (6.4);7.4549 (2.7);7.4506 (3.4);7.4476 (3.7);7.4374 (1.4);7.4286 (0.4);7.4209 (1.7);7.4170 (2.4);7.4006 (2.5);7.3966 (1.6);7.3892 (0.5);7.3802 (1.3);7.3100 (4.9);7.3081 (4.9);7.0371 (6.5);7.0165 (7.4);6.9948 (1.6);6.8469 (3.2);6.8345 (3.2);6.8287 (3.2);6.8163 (3.1);4.3406 (0.5);4.3231 (1.8);4.3140 (0.8);4.3055 (1.8);4.2964 (2.4);4.2879 (0.6);4.2788 (2.4);4.2612 (0.7);4.1629 (0.7);4.1453 (2.3);4.1362 (0.6);4.1277 (2.3);4.1187 (1.8);4.1102 (0.8);4.1010 (1.8);4.0834 (0.5);3.3421 (42.2);2.8924 (13.9);2.7337 (11.7);2.5125 (39.9);2.5112 (39.1);2.5059 (40.2);2.5013 (28.9);2.4969 (14.1);1.2450 (7.7);1.2274 (16.0);1.2098 (7.4);-0.0002 (2.8) |
I.114: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.4235 (2.0);7.7982 (0.3);7.7876 (0.4);7.6646 (1.0);7.6606 (1.0);7.6436 (1.5);7.6373 (3.2);7.5782 (0.4);7.5745 (0.5);7.5643 (0.5);7.5605 (0.6);7.5550 (0.8);7.5515 (0.8);7.5410 (0.8);7.5382 (0.7);7.4999 (0.6);7.4813 (0.9);7.4742 (1.0);7.4668 (0.8);7.4622 (0.9);7.4547 (1.2);7.4376 (0.9);7.4337 (1.5);7.4174 (1.3);7.4134 (0.8);7.3969 (0.7);7.3888 (0.5);7.3482 (0.6);7.3401 (2.5);7.1860 (2.0);7.1843 (2.0);7.1651 (1.9);7.1634 (1.9);7.1127 (0.9);7.0914 (1.4);7.0700 (0.7);7.0681 (0.7);7.0202 (1.7);7.0001 (1.5);3.6140 (0.5);3.3428 (26.6);2.8926 (1.7);2.7346 (1.4);2.7336 (1.4);2.5549 (12.0);2.5284 (0.5);2.5149 (8.6);2.5105 (17.0);2.5059 (21.8);2.5013 (15.6);2.4969 (7.4);2.3908 (16.0);-0.0002 (1.6) |
I.115: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.2994 (1.7);8.2951 (1.8);8.2872 (1.9);8.2829 (1.8);7.9556 (1.9);7.6277 (2.9);7.6017 (1.9);7.5972 (1.9);7.5827 (2.7);7.5788 (2.2);7.5708 (1.0);7.5421 (0.7);7.5242 (0.8);7.5167 (0.9);7.4992 (0.8);7.4755 (0.4);7.4328 (0.6);7.4124 (1.3);7.3956 (1.4);7.3732 (3.0);7.0386 (1.6);7.0264 (1.7);7.0198 (1.6);7.0076 (1.6);6.9778 (1.0);6.9563 (1.7);6.9346 (0.9);6.8862 (2.0);6.8659 (1.8);3.3449 (36.3);2.8928 (11.9);2.7336 (10.4);2.5105 (35.6);2.5059 (30.9);2.5014 (21.7);2.3711 (16.0) |
I.116: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9553 (1.2);7.8971 (3.3);7.8843 (3.5);7.5448 (2.8);7.4905 (0.8);7.4865 (0.8);7.4728 (3.3);7.4705 (3.1);7.4539 (3.6);7.4484 (1.5);7.4409 (1.0);7.3234 (1.2);7.3074 (1.7);7.3040 (1.7);7.2494 (3.2);7.2309 (5.8);7.2119 (0.8);7.2094 (0.6);6.9972 (3.3);6.9844 (3.2);3.7653 (16.0);3.3463 (38.7);2.8929 (7.7);2.7340 (6.7);2.5574 (13.4);2.5285 (0.5);2.5150 (9.4);2.5108 (18.2);2.5064 (23.3);2.5019 (17.1);2.4976 (8.5);-0.0002 (1.0) |
I.117: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.0681 (0.4);7.9557 (2.2);7.8083 (2.9);7.8049 (3.0);7.7959 (3.2);7.7925 (3.1);7.6170 (0.8);7.6139 (0.8);7.6031 (0.9);7.5994 (1.0);7.5937 (1.6);7.5906 (1.8);7.5798 (1.5);7.5769 (1.6);7.5609 (1.7);7.5511 (4.8);7.5440 (1.7);7.5357 (1.6);7.5179 (1.5);7.5123 (1.2);7.5026 (4.9);7.4436 (1.1);7.4268 (1.4);7.4230 (2.4);7.4063 (2.4);7.4026 (1.6);7.3858 (1.2);7.2805 (4.0);7.2681 (3.8);7.0062 (1.7);6.9849 (2.9);6.9637 (1.6);6.9619 (1.6);6.8756 (3.3);6.8552 (3.1);3.8243 (13.9);3.8176 (13.9);3.6151 (0.7);3.3469 (77.9);2.8938 (16.0);2.7353 (13.1);2.7342 (13.4);2.6875 (1.2);2.5453 (23.9);2.5291 (1.0);2.5244 (1.3);2.5157 (15.6);2.5112 (31.5);2.5067 (41.1);2.5021 (29.9);2.4976 (14.6);-0.0002 (0.8) |
I.118: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9965 (2.7);7.9949 (2.9);7.9906 (2.9);7.9891 (2.8);7.9556 (2.3);7.7187 (3.0);7.7140 (2.9);7.6902 (3.6);7.6132 (0.7);7.6098 (0.7);7.5993 (0.8);7.5954 (0.9);7.5901 (1.2);7.5867 (1.2);7.5761 (1.1);7.5731 (1.1);7.5432 (1.0);7.5252 (1.1);7.5176 (1.1);7.4997 (1.1);7.4946 (0.7);7.4774 (1.6);7.4615 (4.8);7.4405 (1.9);7.4366 (1.2);7.4199 (1.1);7.3482 (0.3);7.0381 (1.3);7.0170 (2.4);6.9957 (1.1);6.9939 (1.2);6.9636 (2.6);6.9434 (2.4);3.6147 (1.0);3.3572 (87.1);2.8934 (16.0);2.7352 (13.4);2.7341 (13.6);2.6871 (0.4);2.5287 (19.0);2.5160 (11.6);2.5116 (22.7);2.5071 (29.2);2.5025 (21.0);2.4980 (10.1);2.1168 (15.1) |
I.120: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9546 (2.3);7.7349 (2.9);7.7146 (3.2);7.6481 (0.6);7.6446 (0.6);7.6346 (0.8);7.6307 (0.7);7.6252 (1.0);7.6216 (1.0);7.6115 (0.9);7.6082 (0.9);7.5590 (0.8);7.5421 (3.6);7.5287 (3.3);7.5174 (1.0);7.5105 (0.6);7.4919 (0.5);7.4500 (0.7);7.4330 (1.0);7.4295 (1.5);7.4127 (1.5);7.4092 (1.0);7.3922 (0.8);7.2566 (2.5);7.2362 (2.4);7.0348 (1.1);7.0136 (1.9);6.9923 (1.0);6.9907 (1.0);6.8871 (2.1);6.8668 (1.9);3.3370 (20.2);2.8920 (16.0);2.7334 (13.7);2.7321 (13.6);2.6736 (0.3);2.6404 (1.2);2.5169 (20.1);2.5137 (20.9);2.5090 (35.8);2.5044 (45.1);2.4999 (32.2);2.4954 (15.4);2.3312 (0.4);2.3265 (0.4);2.3107 (11.3) |
I.122: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.8811 (2.7);8.8768 (2.8);8.6269 (2.5);8.6239 (2.5);8.2316 (2.6);7.9570 (1.6);7.8226 (3.4);7.5720 (0.7);7.5681 (1.0);7.5518 (3.8);7.5329 (4.3);7.4583 (0.5);7.4417 (0.6);7.4338 (1.6);7.4211 (2.2);7.4012 (5.4);7.3820 (4.5);7.3651 (1.1);7.3621 (0.9);7.3559 (0.5);6.9768 (3.2);6.9746 (3.3);3.3490 (49.7);2.8946 (11.0);2.7363 (9.4);2.7352 (9.3);2.5793 (16.0);2.5306 (0.5);2.5258 (0.8);2.5171 (10.0);2.5127 (20.2);2.5081 (26.3);2.5035 (19.2);2.4991 (9.5);-0.0002 (1.1) |
I.123: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.8056 (2.7);8.8014 (2.7);8.1217 (1.3);8.1173 (1.3);8.1015 (1.5);8.0969 (1.4);7.9557 (0.4);7.7464 (3.4);7.7322 (2.8);7.7118 (2.5);7.5481 (0.7);7.5447 (0.9);7.5278 (4.1);7.5091 (4.2);7.4825 (0.5);7.4664 (0.6);7.4587 (1.7);7.4470 (1.8);7.4319 (0.9);7.4237 (1.1);7.4069 (0.9);7.3831 (0.4);7.3739 (1.4);7.3558 (2.0);7.3478 (2.4);7.3390 (1.1);7.3362 (1.1);7.3277 (1.9);7.0993 (3.4);7.0975 (3.3);3.3397 (32.9);2.8927 (3.0);2.7337 (2.7);2.5956 (16.0);2.5278 (0.7);2.5143 (14.1);2.5102 (27.3);2.5057 (34.8);2.5013 (25.2);2.4970 (12.3) |
I.126: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.3300 (3.5);8.3277 (3.6);7.9539 (2.2);7.8696 (2.9);7.6981 (2.5);7.6855 (2.5);7.6189 (0.5);7.6158 (0.5);7.6048 (0.5);7.6017 (0.6);7.5957 (1.0);7.5928 (1.0);7.5819 (0.9);7.5790 (0.9);7.5609 (0.8);7.5434 (0.8);7.5328 (1.1);7.5120 (4.5);7.4951 (1.8);7.4915 (1.0);7.4746 (0.7);7.0773 (1.0);7.0559 (1.7);7.0345 (0.9);7.0325 (0.9);6.9763 (2.0);6.9558 (1.8);3.3359 (24.1);2.8914 (16.0);2.7327 (13.0);2.7315 (13.6);2.6726 (0.4);2.5573 (14.5);2.5261 (1.2);2.5214 (1.8);2.5127 (22.2);2.5082 (45.6);2.5036 (59.9);2.4990 (43.4);2.4945 (21.2);2.3304 (0.4);1.2332 (0.5);-0.0002 (0.4) |
I.127: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.3111 (3.2);8.3036 (3.4);8.0455 (1.5);8.0380 (1.4);8.0239 (1.6);8.0164 (1.3);7.9534 (2.4);7.7134 (3.0);7.6440 (0.5);7.6410 (0.5);7.6266 (0.7);7.6181 (1.0);7.6069 (0.9);7.5737 (3.4);7.5544 (0.8);7.5469 (0.9);7.5290 (0.8);7.5056 (0.4);7.4817 (0.6);7.4613 (1.4);7.4445 (1.4);7.4240 (0.7);7.0314 (1.1);7.0098 (1.8);6.9872 (0.9);6.9018 (2.0);6.8814 (1.9);3.3379 (15.6);2.8912 (16.0);2.7315 (14.5);2.6721 (0.4);2.5495 (14.1);2.5077 (47.0);2.5033 (60.8);2.4988 (45.2);2.3299 (0.4);1.6439 (0.4);1.2316 (0.4) |
I.129: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.0973 (2.3);8.0848 (2.4);7.9549 (2.3);7.6710 (3.0);7.6412 (0.5);7.6378 (0.5);7.6272 (0.6);7.6237 (0.6);7.6179 (1.0);7.6147 (1.1);7.6007 (3.7);7.5816 (0.8);7.5640 (0.8);7.5562 (0.9);7.5385 (0.8);7.5332 (0.5);7.5152 (0.4);7.5001 (0.7);7.4830 (3.6);7.4702 (2.8);7.4629 (1.6);7.4591 (1.0);7.4422 (0.8);7.0319 (1.1);7.0106 (1.8);6.9892 (1.0);6.9874 (1.0);6.8973 (2.1);6.8769 (2.0);3.3376 (22.7);2.8924 (16.0);2.7333 (13.2);2.7326 (13.4);2.5497 (14.9);2.5272 (0.8);2.5137 (15.5);2.5093 (30.9);2.5048 (40.1);2.5002 (29.0);2.4958 (14.1);1.9054 (0.3) |
I.130: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.0876 (2.3);7.9553 (1.5);7.6871 (3.1);7.6220 (1.3);7.6171 (1.2);7.6008 (1.3);7.5957 (1.3);7.5451 (0.5);7.5416 (0.5);7.5308 (0.6);7.5275 (0.7);7.5218 (1.0);7.5186 (1.0);7.5078 (0.9);7.5051 (0.9);7.4719 (0.7);7.4539 (0.8);7.4462 (0.9);7.4399 (0.9);7.4279 (1.0);7.4234 (1.4);7.4196 (1.6);7.4035 (1.6);7.3992 (1.0);7.3827 (0.8);7.2354 (2.9);7.0955 (1.0);7.0742 (1.7);7.0721 (1.7);7.0664 (2.1);7.0507 (1.3);7.0463 (1.9);6.5196 (2.6);6.4983 (2.6);5.0423 (0.5);5.0269 (1.2);5.0115 (1.7);4.9961 (1.2);4.9807 (0.5);3.3543 (79.8);2.8935 (10.4);2.7352 (9.0);2.7341 (8.4);2.5539 (14.2);2.5292 (0.6);2.5157 (11.0);2.5113 (21.5);2.5068 (27.4);2.5022 (19.7);2.4978 (9.5);1.0750 (16.0);1.0596 (15.8);-0.0002 (0.3) |
I.131: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.5294 (3.0);7.5179 (0.6);7.5094 (4.6);7.4948 (1.7);7.4842 (1.0);7.4681 (0.8);7.4065 (2.7);7.3803 (0.6);7.3642 (3.2);7.3435 (1.3);7.3395 (0.8);7.3231 (0.7);6.9725 (1.0);6.9613 (2.0);6.9515 (1.9);6.9411 (1.8);6.9307 (0.9);6.2784 (3.6);6.2583 (3.6);3.7810 (15.6);3.7030 (16.0);3.3438 (35.6);2.5297 (13.3);2.5150 (8.3);2.5106 (16.4);2.5060 (21.2);2.5014 (15.3);2.4969 (7.4);-0.0002 (1.2) |
I.132: 1H-NMR(400.2 MHz, d6-DMSO): δ= 7.9922 (3.5);7.9794 (3.7);7.9557 (1.9);7.6053 (0.5);7.5913 (0.6);7.5879 (0.6);7.5794 (1.3);7.5679 (3.9);7.5584 (1.2);7.5475 (3.0);7.5331 (1.0);7.5157 (0.8);7.5103 (0.4);7.4924 (0.4);7.4560 (0.7);7.4392 (0.9);7.4354 (1.4);7.4188 (1.5);7.4150 (0.9);7.3982 (0.7);7.0356 (3.5);7.0228 (3.4);6.9945 (1.0);6.9730 (1.7);6.9517 (0.9);6.8832 (2.0);6.8628 (1.9);3.7983 (16.0);3.3500 (56.1);2.8936 (13.0);2.7349 (11.0);2.5371 (13.9);2.5157 (9.7);2.5113 (18.8);2.5068 (24.0);2.5022 (17.2);2.4978 (8.2) |
I.133: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.8257 (3.8);8.6215 (3.4);8.6184 (3.4);8.2330 (3.4);7.9566 (2.4);7.9092 (4.6);7.5632 (1.3);7.5565 (1.0);7.5465 (2.3);7.5429 (3.1);7.5368 (1.7);7.5331 (1.7);7.5264 (2.8);7.5226 (2.8);7.5060 (1.2);7.4789 (1.1);7.4609 (1.2);7.4533 (1.3);7.4353 (1.2);7.4302 (0.8);7.4119 (0.6);7.2782 (4.5);7.1943 (1.6);7.1727 (2.6);7.1706 (2.5);7.1639 (3.3);7.1492 (1.9);7.1436 (2.9);3.3455 (72.8);2.8942 (16.0);2.7357 (14.0);2.7348 (13.4);2.5350 (21.8);2.5252 (2.1);2.5160 (17.0);2.5117 (33.2);2.5072 (42.4);2.5027 (30.8);2.4983 (15.2);-0.0002 (2.0) |
I.134: 1H-NMR(400.2 MHz, d6-DMSO): δ= 8.7560 (2.5);8.1017 (1.2);8.0792 (1.3);7.9556 (2.3);7.7948 (3.2);7.7494 (2.5);7.7293 (2.3);7.5759 (0.5);7.5725 (0.6);7.5620 (0.6);7.5584 (0.7);7.5528 (1.0);7.5494 (1.1);7.5359 (1.0);7.5213 (0.8);7.5107 (0.9);7.5046 (1.1);7.5008 (1.6);7.4929 (1.0);7.4844 (2.4);7.4805 (1.3);7.4637 (1.3);7.4441 (0.4);7.3937 (3.1);7.1428 (1.1);7.1212 (1.8);7.0996 (1.0);7.0980 (0.9);7.0527 (2.1);7.0324 (2.0);3.3430 (55.4);2.8931 (16.0);2.7345 (13.6);2.7333 (13.5);2.5543 (15.5);2.5283 (0.9);2.5148 (15.0);2.5105 (29.8);2.5059 (38.5);2.5014 (27.9);2.4969 (13.6) |
I.137: 1H-NMR(300.2 MHz, CDCl3): δ= 8.7345 (1.5);8.7295 (1.5);8.7190 (1.6);8.7141 (1.5);8.3173 (2.3);8.3002 (2.3);7.6450 (2.9);7.5223 (1.2);7.5173 (1.2);7.4964 (2.3);7.4910 (2.0);7.4801 (0.7);7.4727 (1.2);7.4677 (1.2);7.4554 (1.1);7.4499 (1.1);7.4338 (1.1);7.4123 (2.8);7.4013 (1.7);7.3971 (2.1);7.3861 (1.5);7.3802 (1.4);7.3709 (1.7);7.3489 (0.5);7.3149 (1.2);7.3103 (1.7);7.3038 (1.5);7.2986 (4.3);7.2935 (1.8);7.2874 (1.0);7.1173 (2.7);5.3313 (1.0);4.1911 (7.0);2.5891 (16.0);1.2859 (0.7);0.0302 (3.8) |
實例 A : 對稻梨孢 ( Pyricularia oryzae ) 菌之活體外
細胞測試
溶劑: 二甲亞碸(dimethyl sulfoxide)
培養基: 14.6 g無水D-葡萄糖(VWR),
7.1 g真菌蛋白腖(Oxoid),
1.4 g顆粒狀的酵母提取物(Merck),QSP 1公升
接種物: 孢子懸浮液
將所測試化合物溶解於二甲亞碸及用於製備所需濃度範圍之溶液中用於檢定之二甲亞碸最終濃度為≤1%。
製備稻梨孢菌之孢子懸浮液且稀釋至所需孢子密度。
評估化合物抑制液體培養基檢定中孢子出芽及菌絲體生長的能力。以所需濃度將化合物添加至具有孢子之培養基。在培育5天之後,藉由菌絲體生長之光譜量測來測定化合物之真菌毒性。藉由比較含有所測試化合物之孔中之吸光度值與無所測試化合物之對照孔中之吸光度來測定真菌生長之抑制。
在此測試中,根據本發明之以下化合物在所測試化合物之濃度為20 ppm時展示介於70%與79%之間的功效:I.015;I.020;I.026;I.030;I.032;I.057;I.079;I.085;I.086;I.087;I.107;I.122;I.123;I.134。
在此測試中,根據本發明之以下化合物在所測試化合物之濃度為20 ppm時展示介於80%與89%之間的功效:I.004;I.006;I.010;I.012;I.024;I.033;I.036;I.048;I.052;I.053;I.055;I.066;I.095;I.100;I.106;I.115;I.120;I.131;I.133。
在此測試中,根據本發明之以下化合物在所測試化合物之濃度為20 ppm時展示介於90%與100%之間的功效:I.009;I.018; I.022; I.023; I.025; I.027; I.028; I.034; I.035; I.038; I.040; I.044; I.045; I.046; I.047; I.049; I.058; I.059; I.060; I.061; I.062; I.067; I.068; I.069; I.070; I.072; I.074; I.075; I.076; I.077; I.080; I.081; I.083; I.084; I.090; I.091; I.093; I.094; I.096; I.097; I.099; I.101; I.103; I.104; I.105; I.108; I.109; I.110; I.111; I.113; I.117; I.118; I.119; I.125; I.126; I.127; I.129。
實例 B : 對豆刺盤孢菌 ( Colletotrichum lindemuthianum ) 之活體外細胞測試
溶劑: 二甲亞碸(dimethyl sulfoxide)
培養基: 14.6 g無水D -葡萄糖(VWR),
7.1 g真菌蛋白腖(Oxoid),
1.4 g顆粒狀的酵母提取物(Merck),QSP 1公升
接種物: 孢子懸浮液
將所測試化合物溶解於二甲亞碸及用於製備所需濃度範圍之溶液中用於檢定之二甲亞碸最終濃度為≤1%。
製備豆刺盤孢菌之孢子懸浮液且稀釋至所需孢子密度。
評估化合物抑制液體培養基檢定中孢子出芽及菌絲體生長的能力。以所需濃度將化合物添加至具有孢子之培養基。在培養6天之後,藉由菌絲體生長之光譜量測來測定化合物之真菌毒性。藉由比較含有所測試化合物之孔中之吸光度值與無所測試化合物之對照孔中之吸光度來測定真菌生長之抑制。
在此測試中,根據本發明之以下化合物在所測試化合物之濃度為20 ppm時展示介於70%與79%之間的功效:I.018;I.032;I.040;I.043;I.050;I.059;I.065;I.072;I.073;I.080;I.084;I.085;I.086;I.087;I.088;I.089;I.094;I.095;I.099;I.103;I.107;I.112;I.118;I.120;I.132。
在此測試中,根據本發明之以下化合物在所測試化合物之濃度為20 ppm時展示介於80%與89%之間的功效:I.004;I.005;I.009;I.011;I.014;I.016;I.019;I.022;I.023;I.028;I.031;I.036;I.037;I.038;I.042;I.044;I.047;I.048;I.054;I.055;I.063;I.068;I.074;I.075;I.076;I.078;I.083;I.090;I.092;I.100;I.111;I.113;I.115;I.116;I.119;I.122;I.125;I.133。
在此測試中,根據本發明之以下化合物在所測試化合物之濃度為20 ppm時展示介於90%與100%之間的功效:I.001;I.002;I.007;I.008;I.010;I.012;I.015;I.024;I.025;I.027;I.033;I.034;I.041;I.045;I.046;I.049;I.051;I.052;I.053;I.056;I.057;I.058;I.060;I.061;I.062;I.066;I.067;I.069;I.070;I.071;I.079;I.081;I.091;I.093;I.096;I.101;I.104;I.105;I.106;I.108;I.109;I.110;I.114;I.117;I.126;I.129;I.131。
實例 C : 對十字花科小球腔菌 ( Leptnosphaeria nodorum ) 之活體外細胞測試
溶劑: 二甲亞碸(dimethyl sulfoxide)
培養基: 14.6 g無水D -葡萄糖(VWR),
7.1 g真菌蛋白腖(Oxoid),
1.4 g顆粒狀的酵母提取物(Merck),QSP 1公升
接種物: 孢子懸浮液
將所測試化合物溶解於二甲亞碸及用於製備所需濃度範圍之溶液中用於檢定之二甲亞碸最終濃度為≤1%。
製備十字花科小球腔菌之孢子懸浮液且稀釋至所需孢子密度。
評估化合物抑制液體培養基檢定中孢子出芽及菌絲體生長的能力。以所需濃度將化合物添加至具有孢子之培養基。在培養6天之後,藉由菌絲體生長之光譜量測來測定化合物之真菌毒性。藉由比較含有所測試化合物之孔中之吸光度值與無所測試化合物之對照孔中之吸光度來測定真菌生長之抑制。
在此測試中,以下根據本發明之化合物在所測試化合物之濃度為20 ppm時展示介於80%與89%之間的功效:I.001。
在此測試中,根據本發明之以下化合物在所測試化合物之濃度為20 ppm時展示介於90%與100%之間的功效:I.007;I.008;I.009;I.010;I.011;I.017;I.018;I.041;I.042;I.043;I.044;I.045;I.046;I.047;I.074;I.075;I.076;I.077。
實例 D : 對 灰葡萄孢菌 ( Botrytis cinerea )( 灰黴 ) 之活體內預防性測試
溶劑: 按體積計之5%二甲亞碸
按體積計之10%丙酮
乳化劑: 每mg活性成分1 µL Tween® 80
使所測試化合物在二甲亞碸/丙酮/Tween®
80之混合物中可溶且均質化,且接著用水稀釋至所需濃度。
藉由噴灑如上文所描述製備之所測試化合物處理小黃瓜之幼株。僅用丙酮/二甲亞碸/Tween®
80之水溶液處理對照植株。
在24小時之後,植株因用灰葡萄孢菌孢子之水性懸浮液噴灑葉片而受到污染。經污染之小黃瓜植株在17℃下且在90%之相對濕度下培育4至5天。經污染之甘藍菜植株在20℃下且在100%之相對濕度下培育4至5天。
在接種後4至5天對測試進行評估。0%意謂對應於對照物植株之功效,而100%之功效意謂未觀測到疾病。
在此測試中,以下根據本發明之化合物在所測試化合物之濃度為500 ppm時展示介於70%與79%之間的功效:I.001。
在此測試中,以下根據本發明之化合物在所測試化合物之濃度為500 ppm時展示介於80%與89%之間的功效:I.017;I.078。
在此測試中,以下根據本發明之化合物在所測試化合物之濃度為500 ppm時展示介於90%與100%之間的功效:I.002;I.007;I.008;I.010;I.011;I.014;I.015;I.018;I.022;I.023;I.024;I.041;I.042;I.043;I.044;I.045;I.049;I.056;I.057;I.058;I.059;I.060;I.061;I.062;I.067;I.068;I.069;I.074;I.075;I.076;I.104;I.105;I.109;I.110。
實例 E : 蘋果黑星病菌 ( 蘋果 ) 之 活體內預防性測試
溶劑: 24.5重量份之丙酮
24.5重量份二甲亞碸
乳化劑:1重量份聚氧化乙烯脫水山梨糖醇單油酸酯
為產生所測試化合物之適合製劑,將1重量份化合物與規定量之溶劑及乳化劑混合,且將濃縮物用水稀釋至所需濃度。
為測試預防性活性,以規定施加速率用活性化合物製劑噴霧幼株。
在噴塗已乾燥之後,對植株接種引起蘋果瘡痂病(蘋果黑星病菌)之病原之水性分生孢子懸浮液,且隨後在約20℃及100%之相對大氣濕度下的培育箱中保持1天。
接著將植株置放於在約21℃及約90%之相對大氣濕度下的溫室中。
在接種後10天對測試進行評估。0%意謂對應於未處理對照物之功效的功效,而100%之功效意謂未觀測到病害。
在此測試中,本發明之以下化合物在100 ppm活性成分之濃度下顯示90%至100%功效:I.041; I.043;I.044。
實例 F : 對圓核腔菌 ( Pyrenophora teres ) ( 大麥 ) 之 活體內預防性測試
溶劑: 24.5重量份之丙酮
24.5重量份二甲亞碸
乳化劑:1重量份聚氧化乙烯脫水山梨糖醇單油酸酯
為了產生所測試化合物之適合製劑,將1重量份所測試化合物或化合物組合與所陳述量之溶劑及乳化劑混合,且將濃縮物用水稀釋至所需濃度。
為測試預防性活性,以規定施加速率用活性化合物製劑噴霧幼株。
在噴塗已乾燥之後,對該等植株噴灑大麥網斑病菌之孢子懸浮液。使植株在約20℃及約100%之相對大氣濕度的培育箱中保持48小時。
將植株置放置在約20℃之溫度及約80%之相對大氣濕度下的溫室中。
在接種後8天對測試進行評價。0%意謂對應於未處理對照物之功效的功效,而100%之功效意謂未觀測到病害。
在此測試中,以下根據本發明之化合物在所測試化合物之濃度為500 ppm時展示介於70%與79%之間的功效:I.007。
在此測試中,以下根據本發明之化合物在所測試化合物之濃度為500 ppm時展示介於80%與89%之間的功效:I.067。
在此測試中,以下根據本發明之化合物在所測試化合物之濃度為500 ppm時展示介於90%與100%之間的功效:I.041。
Claims (15)
- 一種式(I)化合物 其中 A為苯基或包含1、2或3個獨立地選自由N、O及S組成之清單之雜原子的5或6員不飽和雜環基環,其中該環A分別連接至基團B及基團L之兩個連接點為相鄰碳原子; B為部分飽和或不飽和6員雜環基環,其包含1、2、3或4個在由N、O及S組成之清單中獨立選擇之雜原子; Q1 為CY1 或N,其中: Y1 選自由以下組成之群:氫原子、鹵素原子、C1 -C8 烷基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷基、C2 -C8 烯基、包含至多9個可相同或不同之鹵素原子的C2 -C8 鹵代烯基、C2 -C8 炔基、包含至多9個可相同或不同之鹵素原子的C2 -C8 鹵代炔基、C3 -C7 環烷基、C4 -C7 環烯基、羥基、C1 -C8 烷氧基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷氧基、甲醯基、胺基、C1 -C8 烷胺基、二-C1 -C8 烷胺基、硫基、C1 -C8 烷基硫基、C1 -C8 烷基亞磺醯基、C1 -C8 烷基磺醯基、C1 -C6 三烷基矽烷基、氰基及硝基, 其中該C3 -C7 環烷基及C4 -C7 環烯基可經一或多個Ya 取代基取代; Y2 、Y3 、Y4 及Y5 獨立地選自由以下組成之群:氫原子、鹵素原子、C1 -C8 烷基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷基、C2 -C8 烯基、包含至多9個可相同或不同之鹵素原子的C2 -C8 鹵代烯基、C2 -C8 炔基、包含至多9個可相同或不同之鹵素原子的C2 -C8 鹵代炔基、C3 -C7 環烷基、C4 -C7 環烯基、羥基、C1 -C8 烷氧基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷氧基、甲醯基、胺基、C1 -C8 烷胺基、二-C1 -C8 烷胺基、硫基、C1 -C8 烷基硫基、C1 -C8 烷基亞磺醯基、C1 -C8 烷基磺醯基、C1 -C6 三烷基矽烷基、氰基及硝基, 其中該C3 -C7 環烷基及C4 -C7 環烯基可經一或多個Ya 取代基取代; Z選自由以下組成之群:氫原子、鹵素原子、羥基、C1 -C8 烷基、C2 -C8 烯基、C2 -C8 炔基、包含至多9個可相同或不同之鹵素原子的C2 -C8 鹵代炔基、C1 -C8 烷氧基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷基、包含至多9個可相同或不同之鹵素原子的C2 -C8 鹵代烯基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷氧基、C3 -C7 環烷基、C4 -C7 環烯基、甲醯基、C1 -C8 烷胺基、二-C1 -C8 烷胺基、硫基、C1 -C8 烷基硫基、C1 -C8 烷基亞磺醯基、C1 -C8 烷基磺醯基、C1 -C6 三烷基矽烷基、氰基及硝基, 其中該C3 -C7 環烷基及C4 -C7 環烯基可經一或多個Za 取代基取代; m為0、1、2、3或4; n為0、1、2、3或4; L為CR1 R2 或NR3 ,其中 R1 及R2 獨立地選自由以下組成之群:氫原子、鹵素原子、C1 -C8 烷氧基及C1 -C8 烷基; R3 係選自由以下組成之群:氫原子、C1 -C8 烷基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷基、C2 -C8 烯基、包含至多9個可相同或不同之鹵素原子的C2 -C8 鹵代烯基、C3 -C8 炔基、包含至多9個可相同或不同之鹵素原子的C3 -C8 鹵代炔基、C3 -C7 環烷基、包含至多9個可相同或不同之鹵素原子的C3 -C7 鹵代環烷基、C3 -C7 環烷基-C1 -C8 烷基、C1 -C8 烷基羰基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷基羰基、C1 -C8 烷氧羰基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷氧羰基、C1 -C8 烷基磺醯基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷基磺醯基、芳基-C1 -C8 烷基及苯磺醯基, 其中該C3 -C7 環烷基、C3 -C7 環烷基-C1 -C8 烷基、芳基-C1 -C8 烷基及苯磺醯基可經一或多個R3a 取代基取代; W獨立地選自由以下組成之群:鹵素原子、羥基、C1 -C8 烷基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷基、C1 -C8 烷氧基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷氧基、C1 -C8 羥基烷基、C1 -C8 烷氧基-C1 -C8 烷基、C2 -C8 烯基、包含至多9個可相同或不同之鹵素原子的C2 -C8 鹵代烯基、C2 -C8 炔基、包含至多9個可相同或不同之鹵素原子的C2 -C8 鹵代炔基、C3 -C7 環烷基、C4 -C8 環烯基、芳基、芳基-C1 -C8 烷基、雜環基、雜環基-C1 -C8 烷基、芳氧基、雜芳氧基、芳硫基、芳基亞磺醯基、芳基磺醯基、雜芳硫基、雜芳基亞磺醯基、雜芳基磺醯基、芳胺基、雜芳胺基、芳氧基-C1 -C8 烷基、雜芳氧基-C1 -C8 烷基、芳硫基-C1 -C8 烷基、芳基亞磺醯基-C1 -C8 烷基、芳基磺醯基-C1 -C8 烷基、雜芳基硫基-C1 -C8 烷基、雜芳基亞磺醯基-C1 -C8 烷基、雜芳基磺醯基-C1 -C8 烷基、芳胺基-C1 -C8 烷基、雜芳胺基-C1 -C8 烷基、芳基-C1 -C8 烷氧基、雜芳基-C1 -C8 烷氧基、芳基-C1 -C8 烷基硫基、芳基-C1 -C8 烷基亞磺醯基、芳基-C1 -C8 烷基磺醯基、雜芳基-C1 -C8 烷基硫基、雜芳基-C1 -C8 烷基亞磺醯基、雜芳基-C1 -C8 烷基磺醯基、芳基-C1 -C8 烷基胺基、雜芳基-C1 -C8 烷基胺基、甲醯基、C1 -C8 烷基羰基、(羥亞胺基)C1 -C8 烷基、(C1 -C8 -烷氧亞胺基)C1 -C8 烷基、羧基、C1 -C8 烷氧基羰基、胺甲醯基、C1 -C8 烷基胺甲醯基、二-C1 -C8 烷基胺甲醯基、胺基、C1 -C8 烷基胺基、二-C1 -C8 烷基胺基、硫基、C1 -C8 烷基硫基、C1 -C8 烷基亞磺醯基、C1 -C8 烷基磺醯基、C1 -C6 三烷基矽烷基、三(C1 -C8 烷基)矽氧基、三(C1 -C8 烷基)矽氧基-C1 -C8 烷基、側氧基、氰基及硝基, 其中該C3 -C7 環烷基、C4 -C8 環烯基、雜環基、芳基及該芳基-C1 -C8 烷基、雜環基-C1 -C8 烷基、芳氧基、雜芳氧基、芳基硫基、芳基亞磺醯基、芳基磺醯基、雜芳基硫基、雜芳基亞磺醯基、雜芳基磺醯基、芳基胺基、雜芳基胺基、芳氧基-C1 -C8 烷基、雜芳氧基-C1 -C8 烷基、芳基硫基-C1 -C8 烷基、芳基亞磺醯基-C1 -C8 烷基、芳基磺醯基-C1 -C8 烷基、雜芳基硫基-C1 -C8 烷基、雜芳基亞磺醯基-C1 -C8 烷基、雜芳基磺醯基-C1 -C8 烷基、芳基胺基-C1 -C8 烷基、雜芳基胺基-C1 -C8 烷基、芳基-C1 -C8 烷氧基、雜芳基-C1 -C8 烷氧基、芳基-C1 -C8 烷基硫基、芳基-C1 -C8 烷基亞磺醯基、芳基-C1 -C8 烷基磺醯基、雜芳基-C1 -C8 烷基硫基、雜芳基-C1 -C8 烷基亞磺醯基、雜芳基-C1 -C8 烷基磺醯基、芳基-C1 -C8 烷基胺基、雜芳基-C1 -C8 烷基胺基基團的該芳基、雜環基及雜芳基部分可經一或多個Wa 取代基取代; X獨立地選自由以下組成之群:鹵素原子、羥基、C1 -C8 烷基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷基、C1 -C8 烷氧基、包含至多9個可相同或不同之鹵素原子的C1 -C8 鹵代烷氧基、C2 -C8 烯基、包含至多9個可相同或不同之鹵素原子的C2 -C8 鹵代烯基、C2 -C8 炔基、包含至多9個可相同或不同之鹵素原子的C2 -C8 鹵代炔基、C3 -C7 環烷基、C4 -C7 環烯基、甲醯基、胺基、C1 -C8 烷基胺基、二-C1 -C8 烷基胺基、硫基、C1 -C8 烷基硫基、C1 -C8 烷基亞磺醯基、C1 -C8 烷基磺醯基、C1 -C6 三烷基矽烷基、氰基、硝基及C1 -C8 羥基烷基, 其中該C3 -C7 環烷基及C4 -C7 環烯基可經一或多個Xa 取代基取代; Za 、R3a 、Wa 、Xa 及Ya 獨立地選自由以下組成之群:鹵素原子、硝基、羥基、氰基、羧基、胺基、硫基、五氟-λ6 -硫基、甲醯基、胺甲醯基、胺基甲酸酯、C1 -C8 烷基、C3 -C7 環烷基、具有1至5個鹵素原子的C1 -C8 鹵代烷基、具有1至5個鹵素原子的C3 -C8 -鹵代環烷基、C2 -C8 烯基、C2 -C8 炔基、C1 -C8 烷基胺基、二-C1 -C8 烷基胺基、C1 -C8 烷氧基、具有1至5個鹵素原子的C1 -C8 鹵代烷氧基、C1 -C8 烷基硫基、具有1至5個鹵素原子的C1 -C8 鹵代烷基硫基、C1 -C8 烷基羰基、具有1至5個鹵素原子的C1 -C8 鹵代烷基羰基、C1 -C8 烷基胺甲醯基、二-C1 -C8 烷基胺甲醯基、C1 -C8 烷氧基羰基、具有1至5個鹵素原子的C1 -C8 鹵代烷氧基羰基、C1 -C8 烷基羰氧基、具有1至5個鹵素原子的C1 -C8 鹵代烷基羰氧基、C1 -C8 烷基羰基胺基、具有1至5個鹵素原子的C1 -C8 鹵代烷基羰基胺基、C1 -C8 烷基硫基、具有1至5個鹵素原子的C1 -C8 鹵代烷基硫基、C1 -C8 烷基亞磺醯基、具有1至5個鹵素原子的C1 -C8 鹵代烷基亞磺醯基、C1 -C8 烷基磺醯基及具有1至5個鹵素原子的C1 -C8 鹵代烷基-磺醯基; 以及其鹽、N-氧化物、金屬錯合物、類金屬錯合物及光活性異構體或幾何異構體; 其限制條件為式(I)化合物不為: 2-{2-[(6,7-二甲基-3-側氧基-3,4-二氫喹喏啉-2-基)甲基]苯基}-3,5-二側氧基-2,3,4,5-四氫-1,2,4-三嗪-6-甲腈[713527-70-9],及 3,5-二側氧基-2-{2-[(3-側氧基-3,4-二氫喹喏啉-2-基)甲基]苯基}-2,3,4,5-四氫-1,2,4-三嗪-6-甲腈[426815-75-0]。
- 如請求項1之式(I)化合物,其中A選自由以下組成之群:苯基、噻吩基、吡啶基及嘧啶基。
- 如前述請求項中任一項之式(I)化合物,其中B選自由以下組成之群:二氫哌喃基、二氫吡啶基、吡啶基及嘧啶基。
- 如前述請求項中任一項之式(I)化合物,其中L為CR1 R2 ,其中R1 及R2 為氫原子,或L為NR3 ,其中R3 為氫原子。
- 如前述請求項中任一項之式(I)化合物,其中X獨立地為鹵素原子。
- 如前述請求項中任一項之式(I)化合物,其中n為0或1。
- 如前述請求項中任一項之式(I)化合物,其中W獨立地選自由以下組成之群:鹵素原子、C1 -C6 烷基、包含至多9個可相同或不同之鹵素原子的C1 -C6 鹵代烷基、C1 -C6 烷氧基、C1 -C6 羥基烷基、C1 -C6 烷基硫基、C2 -C6 烯基、C1 -C6 烷氧基羰基、C3 -C7 環烷基、芳基、芳基-C1 -C6 烷基、雜環基、羧基、三(C1 -C6 烷基)矽氧基-C1 -C6 烷基、雜芳基-C1 -C6 烷基、C1 -C6 烷氧基-C1 -C6 烷基、側氧基及氰基。
- 如前述請求項中任一項之式(I)化合物,其中W獨立地選自由以下組成之群:鹵素原子、C1 -C6 烷基、包含至多9個可相同或不同之鹵素原子的C1 -C6 鹵代烷基、C1 -C6 烷氧基、C1 -C6 烷基硫基、C3 -C7 環烷基、側氧基及氰基。
- 如前述請求項中任一項之式(I)化合物,其中m為0、1或2。
- 如前述請求項中任一項之式(I)化合物,其中Z為氫原子或C1 -C6 烷基。
- 如前述請求項中任一項之式(I)化合物,其中Y2 、Y3 、Y4 及Y5 獨立地為氫原子或鹵素原子。
- 如前述請求項中任一項之式(I)化合物,其中Q1 為N或CY1 ,其中Y1 為氫原子。
- 一種組合物,其包含至少一種如請求項1至13中任一項之式(I)化合物及至少一種農業上適合之助劑。
- 一種用於控制非所需植物病原性微生物之方法,其包含以下步驟:將一或多種如請求項1至13中任一項之式(I)化合物或如請求項14之組合物施加至植物、植物部分、種子、果實或該等植物生長的土壤。
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CA (1) | CA3116629A1 (zh) |
MX (1) | MX2021004449A (zh) |
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2019
- 2019-10-17 US US17/285,840 patent/US20210386069A1/en not_active Abandoned
- 2019-10-17 KR KR1020217014688A patent/KR20210081370A/ko not_active Withdrawn
- 2019-10-17 CN CN201980068747.1A patent/CN112996782A/zh active Pending
- 2019-10-17 WO PCT/EP2019/078260 patent/WO2020079173A1/en unknown
- 2019-10-17 AR ARP190102961A patent/AR116747A1/es not_active Application Discontinuation
- 2019-10-17 CA CA3116629A patent/CA3116629A1/en not_active Abandoned
- 2019-10-17 EP EP19790197.8A patent/EP3867241A1/en not_active Withdrawn
- 2019-10-17 MX MX2021004449A patent/MX2021004449A/es unknown
- 2019-10-17 JP JP2021521012A patent/JP2022512719A/ja active Pending
- 2019-10-17 TW TW108137518A patent/TW202028187A/zh unknown
- 2019-10-17 BR BR112021007312-4A patent/BR112021007312A2/pt not_active Application Discontinuation
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US20210386069A1 (en) | 2021-12-16 |
CN112996782A (zh) | 2021-06-18 |
EP3867241A1 (en) | 2021-08-25 |
CA3116629A1 (en) | 2020-04-23 |
BR112021007312A2 (pt) | 2021-07-20 |
AR116747A1 (es) | 2021-06-09 |
MX2021004449A (es) | 2021-07-07 |
WO2020079173A1 (en) | 2020-04-23 |
KR20210081370A (ko) | 2021-07-01 |
JP2022512719A (ja) | 2022-02-07 |
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