CN103180307A - 新颖的杀微生物剂 - Google Patents
新颖的杀微生物剂 Download PDFInfo
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- CN103180307A CN103180307A CN2011800521094A CN201180052109A CN103180307A CN 103180307 A CN103180307 A CN 103180307A CN 2011800521094 A CN2011800521094 A CN 2011800521094A CN 201180052109 A CN201180052109 A CN 201180052109A CN 103180307 A CN103180307 A CN 103180307A
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- Prior art keywords
- alkyl
- compound
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- hydrogen
- halogen
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- 229940124561 microbicide Drugs 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 308
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 90
- 150000002367 halogens Chemical class 0.000 claims abstract description 90
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 125000000714 pyrimidinyl group Chemical group 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000468 ketone group Chemical group 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- -1 nitro, formyl Chemical group 0.000 claims description 146
- 239000000126 substance Substances 0.000 claims description 131
- 239000001257 hydrogen Substances 0.000 claims description 97
- 229910052739 hydrogen Inorganic materials 0.000 claims description 97
- 239000000203 mixture Substances 0.000 claims description 77
- 239000000463 material Substances 0.000 claims description 48
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- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 33
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
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- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 8
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- 125000005493 quinolyl group Chemical group 0.000 claims description 5
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- 235000005282 vitamin D3 Nutrition 0.000 description 1
- 239000011647 vitamin D3 Substances 0.000 description 1
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 description 1
- 229940021056 vitamin d3 Drugs 0.000 description 1
- 229960005080 warfarin Drugs 0.000 description 1
- 239000002578 wasp venom Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- WCJYTPVNMWIZCG-UHFFFAOYSA-N xylylcarb Chemical compound CNC(=O)OC1=CC=C(C)C(C)=C1 WCJYTPVNMWIZCG-UHFFFAOYSA-N 0.000 description 1
- 229940023877 zeatin Drugs 0.000 description 1
- 239000005943 zeta-Cypermethrin Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- UUZYGGPKLYQGLZ-UHFFFAOYSA-M zinc;1-methanidyl-2-methoxybenzene;chloride Chemical compound [Zn+]Cl.COC1=CC=CC=C1[CH2-] UUZYGGPKLYQGLZ-UHFFFAOYSA-M 0.000 description 1
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
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Abstract
具有化学式(I)的化合物,其中G与它附接到其上的嘧啶环的两个碳原子一起表示含有选自下组的0至2个杂原子的一个5-至7-元的、脂肪族碳环或杂环的环系统,该组由以下各项组成:氮、氧和硫;并且其中所述5-至7-元的、脂肪族碳环或杂环的环系统可以经选自下组的取代基单-、双-或三取代,该组由以下各项组成:卤素、酮基、C1-C6烷基、C1-C6烷氧基、C1-C6烷基肟基和C1-C6亚烷基二氧基;并且其中其他取代基R1、R2、R3、R4、R5和R6是如在权利要求1中所定义的,以及这些具有化学式(I)的化合物作为杀微生物剂的用途。
Description
本发明涉及新颖的具有杀微生物活性、特别是杀真菌活性的2-(吡啶-2-基)-嘧啶。它进一步涉及包括这些化合物的组合物并且涉及它们在农业或园艺学中用于控制或预防植物被致植物病的微生物、优选地是真菌所侵染的用途。
在WO2006/010570以及WO2007/116079中描述了具有杀真菌活性的2-(吡啶-2-基)-嘧啶。所披露的化合物其特征为在吡啶的6位上的一个芳基取代基。
现在已经发现,在吡啶环的6位上具有一个脂肪族的取代基(例如,苄基或吡啶甲基基团)的新颖的2-(吡啶-2-基)-嘧啶具有增加的杀微生物活性。
因此本发明涉及具有化学式(I)的化合物
其中
G与它附接到其上的嘧啶环的两个碳原子一起表示单或双环的并且含有选自下组的0至2个杂原子的一个5-至8-元的、脂环族的或非芳香族的杂环系统,该组由以下各项组成:氮、氧和硫;并且其中所述5-至8-元的、脂环族的或非芳香族的杂环系统可以经选自下组的取代基单-、双-或三取代,该组由以下各项组成:卤素、羟基、酮基、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷氧基-C1-C6烷基、C1-C6烷基肟基和C1-C6亚烷基二氧基;
R1是可以经选自下组的取代基单-、双-或三取代的芳基或杂芳基,该组由以下各项组成:卤素、羟基、氰基、硝基、甲酰基、C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6卤代烷基、C2-C6卤代链烯基、C2-C6卤代炔基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6烷氧基-C1-C6烷基、C1-C6烷氧基-C1-C6烷氧基、C1-C6烷氧基-C1-C6烷氧基-C1-C6烷基、C1-C6烷氧基-C1-C6烷硫基、C1-C6烷硫基-C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基亚磺酰基、C1-C6烷基磺酰基、C1-C6烷基氨基、二C1-C6烷基氨基、C3-C6环烷基氨基、(C1-C6烷基)(C3-C6环烷基)氨基、二C3-C6环烷基氨基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基氨基羰基、二C1-C6烷基氨基羰基、C1-C6烷氧基羰基氧基、C1-C6烷基氨基羰基氧基、二C1-C6烷基氨基羰基氧基、C1-C6烷基羰基氧基、C1-C6烷基羰基氨基、C1-C6烷基羰基-C1-C6烷基氨基、C1-C6烷氧基亚氨基、C1-C6烷氧基亚氨基-C1-C6烷基、三C1-6烷基甲硅烷基、C1-C6烷氧基-C2-C6炔基、C1-C6烷氧基亚氨基-C2-C6炔基、C1-C6烷硫基-C2-C6炔基、羟基-C2-C6炔基、C1-C6烷硫基-C1-C6烷基或羟基-C1-C6烷基;
R2与R3彼此独立地是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;或
R2与R3一起形成一个3-至5-元的、脂肪族的碳环或一个3-至5-元的杂环,该杂环包含多达两个选自O、S以及N的杂原子;或
R2与R3一起形成一个羰基或C1-C6烷基肟基;
R4是氢、卤素、氰基、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;
R5是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;并且
R6是氢、卤素、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;
以及那些化合物的农艺学上可接受的盐、异构体、阻转异构体、结构异构体、立体异构体、非对映异构体、对映异构体、互变异构体以及N-氧化物;
其条件是当G是一个未经取代的、5或6元的、单环的脂环族环,并且R2与R3彼此独立地是氢、C1-C4烷基时,那么R1不能是苯基或经取代的苯基。
本发明涵盖了那些化合物的所有农艺学上可接受的盐、异构体、阻转异构体、结构异构体、立体异构体、非对映异构体、对映异构体、互变异构体以及N-氧化物。本发明涵盖了所有的此类异构体以及互变异构体以及它们的处于所有比例的混合物,连同同位素形式,例如氘化的化合物。由于围绕一个单键的旋转受限,还可能存在旋转对映异构现象。
取代基的定义中出现的烷基基团可以是直链或支链的,例如甲基、乙基、正丙基、正丁基、正戊基、正己基、异丙基、正丁基、仲丁基、异丁基或叔丁基。烷氧基、链烯基和炔基衍生自所提及的烷基。这些链烯基以及炔基基团可以是单-或二-不饱和的。该环烷基基团是例如环丙基、环丁基、环戊基或环己基。卤素通常是氟、氯、溴或碘,优选氟、溴或氯,更优选氯或氟。这相应地还适用于与其他含义结合的卤素,例如卤代烷基或卤代烷氧基。卤代烷基基团优选地具有一个从1至4个碳原子的链长。卤代烷基是,例如氟甲基、二氟甲基、三氟甲基、氯甲基、二氯甲基、三氯甲基、2,2,2-三氟乙基、2-氟乙基、2-氯乙基、五氟代乙基、1,1-二氟-2,2,2-三氯乙基、2,2,3,3-四氟乙基和2,2,2-三氯乙基;优选是三氯甲基、二氟氯甲基、二氟甲基、三氟甲基、以及二氯氟甲基。烷氧基是,例如甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基和叔丁氧基;优选是甲氧基和乙氧基。卤代烷氧基是,例如氟甲氧基、二氟甲氧基、三氟甲氧基、2,2,2-三氟乙氧基、1,1,2,2-四氟乙氧基、2-氟乙氧基、2-氯乙氧基、2,2-二氟乙氧基和2,2,2-三氯乙氧基;优选是二氟甲氧基、2-氯乙氧基、和三氟甲氧基。硫代烷基是例如甲硫基、乙硫基、丙硫基、叔丁硫基、己硫基。烷氨基是例如甲氨基、乙氨基、丙氨基、叔丁氨基、己基氨基,连同例如二甲氨基、二乙氨基、二丙氨基、二叔丁氨基、二己基氨基或三甲基氨基、三乙基氨基、三丙基氨基、三叔丁基氨基、三己基氨基或具有不同的烷基基团的2-至3-级取代的胺。芳基和杂芳基是例如苯基、萘基、吡啶基、喹啉基、哒嗪基、噌啉基、嘧啶基、喹唑啉基、吡嗪基、喹喔啉基、噻吩基、呋喃基、异噁唑基、异噻唑基、噻唑基、噁唑基、吡唑基、咪唑基、吡咯基、噁二唑基、噻二唑基。
优选地,当G是一个未经取代的、5或6元的、单环的脂环族环,并且R2与R3彼此独立地是氢、C1-C6烷基时,那么R1不能是苯基或经取代的苯基。
优选地本发明涉及具有化学式I的化合物,其中
G与它附接到其上的嘧啶环的两个碳原子一起表示单或双环的并且含有选自下组的0至2个杂原子的一个5-至8-元的、脂环族的或非芳香族的杂环系统,该组由以下各项组成:氮、氧和硫;并且其中所述5-至8-元的、脂环族的或非芳香族的杂环系统可以经选自下组的取代基单-、双-或三取代,该组由以下各项组成:卤素、羟基、酮基、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷氧基-C1-C6烷基、C1-C6烷基肟基和C1-C6亚烷基二氧基;
R1是可以经选自下组的取代基单-、双-或三取代的芳基或杂芳基,该组由以下各项组成:卤素、羟基、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C7环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷氧基-C1-C6烷基、C1-C6烷氧基-C1-C6烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷硫基烷基、C1-C6单烷基氨基、C1-C6二烷基氨基;
R2与R3彼此独立地是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;或
R2与R3一起形成一个3-至5-元的、脂肪族的碳环;或
R2与R3一起形成一个羰基或C1-C6烷基肟基;
R4是氢、卤素、氰基、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;并且
R5是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;
R6是氢、卤素、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;
在一个另外的实施例中
G与它附接到其上的嘧啶环的两个碳原子一起表示单或双环的并且含有选自下组的0至2个杂原子的一个5-至8-元的、脂环族的或非芳香族的杂环系统,该组由以下各项组成:氮、氧和硫;并且其中所述5-至8-元的、脂环族的或非芳香族的杂环系统可以经选自下组的取代基单-、双-或三取代,该组由以下各项组成:卤素、羟基、酮基、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷氧基-C1-C6烷基、C1-C6烷基肟基和C1-C6亚烷基二氧基;
R1是可以经选自下组的取代基单-、双-或三取代的芳基或杂芳基,该组由以下各项组成:卤素、羟基、氰基、硝基、甲酰基、C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6卤代烷基、C2-C6卤代链烯基、C2-C6卤代炔基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6烷氧基-C1-C6烷基、C1-C6烷氧基-C1-C6烷氧基、C1-C6烷氧基-C1-C6烷氧基-C1-C6烷基、C1-C6烷氧基-C1-C6烷硫基、C1-C6烷硫基-C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基亚磺酰基、C1-C6烷基磺酰基、C1-C6烷基氨基、二C1-C6烷基氨基、C3-C6环烷基氨基、(C1-C6烷基)(C3-C6环烷基)氨基、二C3-C6环烷基氨基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基氨基羰基、二C1-C6烷基氨基羰基、C1-C6烷氧基羰基氧基、C1-C6烷基氨基羰基氧基、二C1-C6烷基氨基羰基氧基、C1-C6烷基羰基氧基、C1-C6烷基羰基氨基、C1-C6烷基羰基-C1-C6烷基氨基、C1-C6烷氧基亚氨基、C1-C6烷氧基亚氨基-C1-C6烷基、三C1-6烷基甲硅烷基、C1-C6烷氧基-C2-C6炔基、C1-C6烷氧基亚氨基-C2-C6炔基、C1-C6烷硫基-C2-C6炔基、羟基-C2-C6炔基、C1-C6烷硫基-C1-C6烷基或羟基-C1-C6烷基;
R2与R3彼此独立地是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;或
R2与R3一起形成一个3-至5-元的、脂肪族的碳环或一个3-至5-元的杂环,该杂环包含多达两个选自O、S以及N的杂原子;或
R4是氢、卤素、氰基、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;
R5是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;并且
R6是氢、卤素、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;
以及那些化合物的农艺学上可接受的盐、异构体、阻转异构体、结构异构体、立体异构体、非对映异构体、对映异构体、互变异构体以及N-氧化物;
当G是一个未经取代的、5或6元的、单环的脂环族环,并且R2与R3彼此独立地是氢、C1-C4烷基时,那么R1不能是苯基或经取代的苯基。
并且在一个另外的、更优选的实施例中
G与它附接到其上的嘧啶环的两个碳原子一起表示单或双环的并且含有选自下组的0至2个杂原子的一个5-至8-元的、脂环族的或非芳香族的杂环系统,该组由以下各项组成:氮、氧和硫;并且其中所述5-至8-元的、脂环族的或非芳香族的杂环系统可以经选自下组的取代基单-、双-或三取代,该组由以下各项组成:卤素、羟基、酮基、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷氧基-C1-C6烷基、C1-C6烷基肟基和C1-C6亚烷基二氧基;
R1是可以经选自下组的取代基单-、双-或三取代的芳基或杂芳基,该组由以下各项组成:卤素、羟基、氰基、硝基、甲酰基、C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6卤代烷基、C2-C6卤代链烯基、C2-C6卤代炔基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6烷氧基-C1-C6烷基、C1-C6烷氧基-C1-C6烷氧基、C1-C6烷氧基-C1-C6烷氧基-C1-C6烷基、C1-C6烷氧基-C1-C6烷硫基、C1-C6烷硫基-C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基亚磺酰基、C1-C6烷基磺酰基、C1-C6烷基氨基、二C1-C6烷基氨基、C3-C6环烷基氨基、(C1-C6烷基)(C3-C6环烷基)氨基、二C3-C6环烷基氨基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基氨基羰基、二C1-C6烷基氨基羰基、C1-C6烷氧基羰基氧基、C1-C6烷基氨基羰基氧基、二C1-C6烷基氨基羰基氧基、C1-C6烷基羰基氧基、C1-C6烷基羰基氨基、C1-C6烷基羰基-C1-C6烷基氨基、C1-C6烷氧基亚氨基、C1-C6烷氧基亚氨基-C1-C6烷基、三C1-6烷基甲硅烷基、C1-C6烷氧基-C2-C6炔基、C1-C6烷氧基亚氨基-C2-C6炔基、C1-C6烷硫基-C2-C6炔基、羟基-C2-C6炔基、C1-C6烷硫基-C1-C6烷基或羟基-C1-C6烷基;
R2与R3彼此独立地是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;或
R2与R3一起形成一个3-至5-元的、脂肪族的碳环
R4是氢、卤素、氰基、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;
R5是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;并且
R6是氢、卤素、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;
以及那些化合物的农艺学上可接受的盐、异构体、阻转异构体、结构异构体、立体异构体、非对映异构体、对映异构体、互变异构体以及N-氧化物;
当G是一个未经取代的、5或6元的、单环的脂环族环,并且R2与R3彼此独立地是氢、C1-C4烷基时,那么R1不能是苯基或经取代的苯基。
更优选地本发明涉及具有化学式I的化合物,其中
G与它附接到其上的嘧啶环的两个碳原子一起表示单或双环的并且含有选自下组的0至2个杂原子的一个5-至8-元的、脂环族的或非芳香族的杂环系统,该组由以下各项组成:氮、氧和硫;并且其中所述5-至8-元的、脂环族的或非芳香族的杂环系统可以经选自下组的取代基单-、双-或三取代,该组由以下各项组成:卤素、酮基、C1-C6烷基、C1-C6烷氧基、C1-C6烷基肟基和C1-C6亚烷基二氧基;
R1是可以经选自下组的取代基单-、双-或三取代的芳基或杂芳基,该组由以下各项组成:卤素、羟基、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C7环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷氧基-C1-C6烷基、C1-C6烷氧基-C1-C6烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷硫基烷基、C1-C6单烷基氨基、C1-C6二烷基氨基,R2与R3彼此独立地是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;
R4是氢、卤素、氰基、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;并且
R5是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;
R6是氢、卤素、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;
以及那些化合物的农艺学上可接受的盐、异构体、阻转异构体、结构异构体、立体异构体、非对映异构体、对映异构体、互变异构体以及N-氧化物;
当G是一个未经取代的、5或6元的、单环的脂环族环,并且R2与R3彼此独立地是氢、C1-C4烷基时,那么R1不能是苯基或经取代的苯基。
例如G(它与它附接到其上的嘧啶环的两个碳原子一起表示含有选自下组的0至2个杂原子的一个5-至7-元的、脂肪族碳环或杂环的环系统,该组由以下各项组成:氮、氧和硫)是环戊烷、四氢呋喃、四氢噻吩、环己烷、四氢吡喃、2,2,1-二环庚烷、2,2,2-二环辛烷或环庚烷。
由嘧啶环与取代基G一起形成的、具有化学式(I)的化合物的优选的环系统选自下组,该组由以下各项组成
其中R5具有如对以上化学式I所作定义的含义,特别是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基。尤其优选的环系统是Q3、Q4、Q6、Q12和Q19。
作为Q11中的一个实例,G表示一个8元的、脂环族的环系统,该环系统是二环的。
优选地芳基是可以经选自下组的取代基单-、双-或三取代的苯基,该组由以下各项组成:卤素、C1-C4烷基、C1-C6卤代烷基、C1-C4烷氧基、C1-C6烷氧基-C1-C6烷氧基、C1-C4烷硫基和C1-C6卤代烷氧基。
优选地杂芳基芳基是可以经选自下组的取代基单-、双-或三取代的吡啶基或噻吩基,该组由以下各项组成:卤素、C1-C4烷基、C1-C6卤代烷基、C1-C4烷氧基、C1-C6烷氧基-C1-C6烷氧基、C1-C4烷硫基和C1-C6卤代烷氧基。
在本发明的一个优选实施例中,R1是可以经选自下组的取代基单-、双-或三取代的芳基,该组由以下各项组成:卤素、C1-C4烷基、C1-C6卤代烷基、C1-C4烷氧基和C1-C4烷硫基。
在具有化学式I的化合物的一个优选的组中,R1是可以经选自下组的取代基单-、双-或三取代的苯基、吡啶基或噻吩基,该组由以下各项组成:卤素、C1-C4烷基、C1-C6卤代烷基、C1-C4烷硫基和C1-C4烷氧基。
优选地该吡啶基取代基是吡啶-2-基或吡啶-3-基。优选地该噻吩基取代基是噻吩-2-基或噻吩-3-基。
R1是可以经选自下组的取代基单-或双-取代的苯基、萘基、吡啶基、喹啉基、哒嗪基、噌啉基、嘧啶基、喹唑啉基、吡嗪基、喹喔啉基、噻吩基、呋喃基、异噁唑基、异噻唑基、噻唑基、噁唑基、吡唑基、咪唑基、吡咯基、噁二唑基、噻二唑基,该组由以下各项组成:卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷硫基和C1-C4烷氧基;
更优选地R1是可任选地经卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷硫基或C1-C4烷氧基,优选地是经卤素、甲基、三卤代烷基、甲硫基或甲氧基单-或双-取代的苯基、吡啶基或噻吩基。
优选地R2与R3彼此独立地是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基,或R2与R3一起形成一个3-至5-元的、脂肪族的碳环或一个3-至5-元的杂环,该杂环包含多达两个选自O、S以及N的杂原子;
更优选地R2与R3彼此独立地是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基或R2与R3一起形成一个3-至5-元的、脂肪族的碳环;
甚至更优选地R2与R3彼此独立地是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基
当R2与R3一起形成一个3-至5-元的、脂肪族的碳环时;3-元的环是优选的。
在另外一组优选的具有化学式I的化合物中,
R1是可以经选自下组的取代基单-或双-取代的苯基、萘基、吡啶基、喹啉基、哒嗪基、噌啉基、嘧啶基、喹唑啉基、吡嗪基、喹喔啉基、噻吩基、呋喃基、异噁唑基、异噻唑基、噻唑基、噁唑基、吡唑基、咪唑基、吡咯基、噁二唑基、噻二唑基,该组由以下各项组成:卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷硫基和C1-C4烷氧基;
R2与R3是氢或C1-C4烷基;
R4是氢、C1-C4烷基或C1-C4烷氧基;
R5是氢、卤素或C1-C4烷基;并且
R6是氢、C1-C4烷基或C1-C4烷氧基。
优选地在另外一组优选的具有化学式I的化合物中,
R1是可以经卤素、C1-C4烷基、C1-C4烷硫基或C1-C4烷氧基取代的苯基或吡啶基或噻吩基;
R2与R3是氢或C1-C4烷基;
R4是氢、C1-C4烷基或C1-C4烷氧基;
R5是氢、卤素或C1-C4烷基;并且
R6是氢、C1-C4烷基或C1-C4烷氧基。
更优选地在另外一组优选的具有化学式I的化合物中,
R1是可以经卤素、C1-C4烷基或C1-C4烷氧基取代的苯基、吡啶基或噻吩基;
R2与R3是氢或C1-C4烷基;
R4是氢、C1-C4烷基或C1-C4烷氧基;
R5是氢、卤素或C1-C4烷基;并且
R6是氢。
最优选地在另外一组优选的具有化学式I的化合物中,
R1是可以经卤素、C1-C4烷基或C1-C4烷氧基取代的苯基;
R2与R3是氢或甲基;
R4是氢或甲基;
R5是氢或甲基;并且
R6是氢;
本发明的另外优选的实施例是实施例E1至E19,它们被定义为如下述的由选自下组的一个化学式表示的具有化学式I的化合物,该组由化学式T1至T19组成,其中在化学式T1至T19中:
R1是可以经选自下组的取代基单-或双-取代的苯基、萘基、吡啶基、喹啉基、哒嗪基、噌啉基、嘧啶基、喹唑啉基、吡嗪基、喹喔啉基、噻吩基、呋喃基、异噁唑基、异噻唑基、噻唑基、噁唑基、吡唑基、咪唑基、吡咯基、噁二唑基、噻二唑基,该组由以下各项组成:卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷硫基和C1-C4烷氧基;
R2与R3是氢或C1-C4烷基;
R4是氢、C1-C4烷基或C1-C4烷氧基
R5是氢、卤素或C1-C4烷基;并且
R6是氢、C1-C4烷基或C1-C4烷氧基。
优选地R1是可任选地经卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷硫基或C1-C4烷氧基,优选地是经卤素、甲基、三卤代烷基、甲硫基或甲氧基单-或双-取代的苯基、吡啶基或噻吩基。
例如,用具有化学式T1的化合物表示实施例E1
其中
R1是可以经卤素、C1-C4烷基或C1-C4烷氧基取代的苯基、吡啶基或噻吩基;
R2与R3是氢或C1-C4烷基;
R4是氢、C1-C4烷基或C1-C4烷氧基;
R5是氢、卤素或C1-C4烷基;并且
R6是氢、C1-C4烷基或C1-C4烷氧基。
该结构(T1)由具有化学式(I)的这些化合物所定义,其中由嘧啶环与取代基G一起形成的环系统是Q1的结构。同样地,该结构(T2)由具有化学式(I)的这些化合物所定义,其中由嘧啶环与取代基G一起形成的环系统是Q2的结构。
因此定义了实施例E2至E19。优选的实施例是实施例E3、E4、E6、E12和E19,特别是E3和E12。在所述实施例E1至E19中,这些取代基的以下含义是优选的:
R1是可以经卤素、C1-C4烷基或C1-C4烷氧基取代的苯基、吡啶基或噻吩基;
R2与R3是氢或C1-C4烷基;
R4是氢、C1-C4烷基或C1-C4烷氧基
R5是氢、卤素或C1-C4烷基;并且
R6是氢、C1-C4烷基或C1-C4烷氧基。
优选地,R6是氢、甲基或甲氧基。
更优选的实施例是实施例E3、E4、E6、E12和E19,特别是E3和E12。在所述实施例E1至E19中,这些取代基的以下含义是优选的:
R1是可以经卤素、C1-C4烷基或C1-C4烷氧基取代的苯基、吡啶基或噻吩基;
R2与R3是氢或C1-C4烷基;
R4是氢、C1-C4烷基或C1-C4烷氧基;
R5是氢、卤素或C1-C4烷基;并且
R6是氢。
在所述实施例E1至E19中,这些取代基的以下含义是更优选的:
R1是可以经卤素、C1-C4烷基或C1-C4烷氧基取代的苯基;
R2与R3是氢或C1-C4烷基;
R4是氢、C1-C4烷基或C1-C4烷氧基
R5是氢、卤素或C1-C4烷基;并且
R6是氢。
在所述实施例E1至E19中,这些取代基的以下含义是最优选的:
R1是可以经卤素、C1-C4烷基或C1-C4烷氧基取代的苯基;
R2与R3是氢或甲基;
R4是氢或甲基;
R5是氢或甲基;并且
R6是氢;
具有化学式I的化合物可以如在以下方案中所示的进行制备。
具有化学式I.1的化合物(其中R1、R2、R3、R4、R6以及G是如在化学式I下所定义的)可以通过具有化学式II的化合物(其中R1、R2、R3以及R4是如在化学式I下所定义的)与具有化学式III的化合物(其中G是如在化学式I下所定义的并且R7和R8是C1-C6烷基)在碱性条件下的转化而获得。
具有化学式II的化合物(其中R1、R2、R3、R4以及R6是如在化学式I下所定义的)可以通过用碱和铵盐来转化具有化学式IV的化合物(其中R1、R2、R3以及R4是如在化学式I下所定义的)而获得。
具有化学式IV的化合物(其中R1、R2、R3、R4以及R6是如在化学式I下所定义的)可以通过用氰化物和碱转化具有化学式V的化合物(其中R1、R2、R3、R4以及R6是如在化学式I下所定义的)而获得,该氰化物是例如氰化钠、氰化钾或三甲基甲硅烷基氰化物,该碱是例如三乙胺、乙基二异丙基胺或吡啶。
具有化学式V的化合物(其中R1、R2、R3、R4以及R6是如在化学式I下所定义的)可以通过用氧化剂转化具有化学式VI的化合物(其中R1、R2、R3以及R4是如在化学式I下所定义的)而获得,该氧化剂是例如间-氯过苯甲酸、过氧化氢或臭氧。
具有化学式VI的单和双取代的吡啶是已知化合物,或可以使用本领域常规的、并且普通技术人员熟悉的方法从已知化合物容易地获得。
具有化学式III的化合物(其中G如在化学式I下所定义的并且R7和R8是C1-C6烷基)可以通过用双(二烷基氨基)叔丁氧基甲烷或用N,N-二烷基甲酰胺二烷基缩醛转化具有化学式VII的化合物(其中G如在化学式I下所定义的)而获得。
具有化学式VII的酮是已知化合物,或可以使用本领域常规的、并且是普通技术人员熟悉的方法从已知化合物容易地获得。
可替代地,具有化学式I.1的化合物(其中R1、R2、R3、R4、R6以及G是如在化学式I下所定义的)可以通过用催化剂转化具有化学式VIII的化合物(其中R4和G是如在化学式I下所定义的,并且Hal是卤素,优选地是氯、溴或碘)与具有化学式IX的化合物(其中R1、R2和R3是如在化学式I下所定义的,并且R9是In、MgCl、MgBr、Sn(R10)3、ZnCl、ZnBr或B(OR10)2,其中R10彼此独立地是氢、C1-C6烷基,或者其中两个R10一起形成一个C3-C8环烷基)而获得,该催化剂是例如四三苯基膦钯、二氯化钯、[1,1-双(二苯基膦基)二茂铁]二氯钯(II)、乙酸钯或双(二苯基膦)氯化钯(II)。
具有化学式VIII的化合物(其中R4和G是如在化学式I下所定义的,并且Hal是卤素,优选地是氯、溴或碘)可以通过具有化学式X的化合物(其中R4是如在化学式I下所定义的,并且Hal是卤素,优选地是氯、溴或碘)与具有化学式III的化合物(其中G是如化学式I下所定义的并且R7和R8是C1-C6烷基)在碱性条件下进行转化而获得。
具有化学式X的化合物(其中R4是如在化学式I下所定义的,并且Hal是卤素,优选地是氯、溴或碘)可以通过用碱和铵盐转化具有化学式XI的化合物(其中R4是如在化学式I下所定义的,并且Hal是卤素,优选地是氯、溴或碘)而获得。
具有化学式XI的化合物(其中R4是如在化学式I下所定义的,并且Hal是卤素,优选地是氯、溴或碘)可以通过用氰化物转化具有化学式XII的化合物(其中R4是如在化学式I下所定义的,并且Hal是卤素,优选地是氯、溴或碘)而获得,该氰化物是例如氰化钠、氰化钾或三甲基甲硅烷基氰化物,该碱是例如三乙胺、乙基二异丙基胺或吡啶。
具有化学式XII的化合物(其中R4是如在化学式I下所定义的,并且Hal是卤素,优选地是氯、溴或碘)可以通过用氧化剂转化具有化学式XIII的化合物(其中R4是如在化学式I下所定义的,并且Hal是卤素,优选地是氯、溴或碘)而获得,该氧化剂是例如间-氯过苯甲酸、过氧化氢或臭氧。
具有化学式XIII的单和双取代的吡啶是已知化合物,或可以使用本领域常规的、并且普通技术人员熟悉的方法从已知化合物容易地获得。
可替代地,具有化学式I的化合物(其中R1、R2、R3、R4、R5和R6是如在化学式I下所定义的)可以通过用催化剂转化具有化学式XIV的化合物(其中R1、R2、R3和R4是如在化学式I下所定义的,并且R9是In、MgCl、MgBr、Sn(R10)3、ZnCl、ZnBr或B(OR10)2,其中R10彼此独立地是氢、C1-C6烷基,或者其中两个R10一起形成一个C3-C8环烷基)与具有化学式XV的化合物(其中R5是如在化学式I下所定义的,并且Hal是卤素,优选地是氯、溴或碘)而获得,该催化剂是例如四三苯基膦钯、二氯化钯、[1,1-双(二苯基膦基)二茂铁]二氯钯(II)、乙酸钯或双(二苯基膦)氯化钯(II)。
具有化学式XIV的金属取代的吡啶和具有化学式XV的2-卤代嘧啶是已知化合物,或可以使用本领域常规的、并且普通技术人员熟悉的方法从已知化合物容易地获得。
可替代地,具有化学式I的化合物(其中R1、R2、R3、R4和R5是如在化学式I下所定义的)可以通过用催化剂转化具有化学式XVI的化合物(其中R1、R2、R3和R4是如在化学式I下所定义的,并且Hal是卤素,优选地是氯、溴或碘)与具有化学式XVII的化合物(其中R5是如在化学式I下所定义的,并且R9是In、MgCl、MgBr、Sn(R10)3、ZnCl、ZnBr或B(OR10)2,其中R10彼此独立地是氢、C1-C6烷基,或者其中两个R10一起形成一个C3-C8环烷基)而获得,该催化剂是例如四三苯基膦钯、二氯化钯、[1,1-双(二苯基膦基)二茂铁]二氯钯(II)、乙酸钯或双(二苯基膦)氯化钯(II)。
具有化学式XVI的双和三取代的吡啶和具有化学式XVII的2-金属-取代的嘧啶是已知化合物,或可以使用本领域常规的、并且普通技术人员熟悉的方法从已知化合物容易地获得。
给出具有化学式I的化合物的这些反应有利地在非质子的惰性有机溶剂中进行。此类溶剂是烃,例如苯,甲苯,二甲苯或环己烷,氯化烃,例如二氯甲烷、三氯甲烷、四氯甲烷或氯苯,醚类,例如二乙基醚、乙二醇二甲基醚、二乙二醇二甲基醚、四氢呋喃或二噁烷,腈类,例如乙腈或丙腈,酰胺类,例如N,N-二甲基甲酰胺、二乙基甲酰胺或N-甲基吡咯烷酮。这些反应温度有利地在-20°C与+120°C之间。总体上,这些反应是轻微放热的并且按规则,它们可以在环境温度进行。为了缩短该反应时间,或者启动该反应,该混合物可以暂时地加热到该反应混合物的沸点。该反应时间还可以通过加入几滴碱作为反应催化剂而缩短。适当的碱具体是叔胺类,例如三甲胺、三乙胺、奎宁环、1,4-二氮杂二环[2.2.2]辛烷、1,5-二氮杂二环[4.3.0]壬-5-烯或1.5-二氮杂二环[5.4.0]十一-7-烯。然而,作为碱还可以使用无机碱,例如氢化物,例如氢化钠或氢化钙,氢氧化物,例如氢氧化钠或氢氧化钾,碳酸盐,例如碳酸钠和碳酸钾,或碳酸氢盐,例如碳酸氢钾和碳酸氢钠。这些碱可以按照这样使用或者还可以与一种催化量的相转移催化剂(例如冠醚,特别是18-冠-6)或一种四烷基铵盐一起使用。
具有化学式I的化合物以及适当时其互变异构体如果适当的话还能以水合物的形式获得和/或包括其他的溶剂,例如可以用于以固体形式存在的化合物结晶的那些。
现在已经发现了根据本发明的具有化学式I的化合物具有(用于实用的目的),一个非常有利的针对由致植物病的微生物(例如,真菌、细菌或病毒)引起的疾病的保护有用植物的活性谱。
因此本发明还涉及一种用于控制或预防有用植物受致植物病的微生物侵染的方法,其中将具有化学式I的化合物作为活性成分施用到这些植物、其部分或其场所上。根据本发明的具有化学式I的化合物显著地区别在于在低比率应用下优异的活性、良好的植物耐受性并且是环境安全的。它们具有非常有用的治疗、预防和系统特性,并且用于保护众多有用植物。具有化学式I的化合物可以被用于抑制或破坏在多种不同的有用植物作物的植物或植物部分(果实、花、叶子、茎、块茎、根)上发生的疾病,同时还保护了稍后生长的那些植物部分例如免于致植物病的微生物侵害。
还有可能使用具有化学式I的化合物作为用于处理植物繁殖材料,特别是种子(果实、块茎、谷粒)以及植物插条(例如稻)的拌种剂,用于保护对抗真菌侵染连同对抗在土壤中存在的致植物病的真菌。
此外,根据本发明的具有化学式I的化合物可以用于控制相关领域的真菌,例如在工业材料(包括木材以及与木材有关的工业产品)的保护中,在食品保存中或在卫生管理中。
具有化学式I的化合物是例如有效地针对以下类别的致植物病的真菌:半知菌(例如葡萄孢属、梨孢属、长蠕孢属、镰孢霉属、壳针孢属、尾孢属和链格孢霉属)和担子菌(例如丝核菌属、驼孢锈菌属、柄锈菌属)。此外,它们还对子囊菌纲(例如黑星菌属和白粉菌属、叉丝单囊壳属、念珠菌属、钩丝壳属)和卵菌纲(例如疫霉属、腐霉属、单轴霉属)有效。此外,新颖的具有化学式I的化合物针对以下项是有效的:致植物病的细菌和病毒(例如,针对黄单胞菌属物种、假单胞菌属物种、梨火疫病菌连同针对烟草花叶病毒)。具有化学式I的化合物针对亚洲大豆锈菌病(大豆锈菌病)也是有效的。
在本发明的范围内,有待保护的有用植物典型地包括以下植物种类:谷物(小麦、大麦、黑麦、燕麦、稻、玉米、高粱以及相关种类);甜菜(糖萝卜以及饲用甜菜);梨果、核果以及无核小水果(苹果、梨、李子、桃、扁桃、樱桃、草莓、覆盆子和黑莓);豆科植物(豆、滨豆、豌豆、大豆);油科作物(油菜、芥菜、罂粟、橄榄、向日葵、椰子、蓖麻油植物、可可豆、落花生);瓜类植物(南瓜、黄瓜、甜瓜);纤维植物(棉花、亚麻、大麻、黄麻纤维);柑橘属水果(桔子、柠檬、葡萄柚、柑橘);蔬菜(菠菜、莴苣、芦笋、甘蓝、胡萝卜、洋葱、番茄、马铃薯、红椒);樟科(鳄梨、肉桂、樟脑)或多种植物,例如烟草、坚果、咖啡、茄子、甘蔗、茶、胡椒、藤本植物、蛇麻、香蕉以及天然橡胶植物,连同观赏植物。
术语“有用植物”理解为还包括由于常规育种方法或基因工程已经使之耐受除草剂如溴苯腈或多种除草剂类别(如,例如HPPD抑制剂、ALS抑制剂,例如氟嚓磺隆、氟磺隆和三氟啶磺隆、EPSPS(5-烯醇-丙酮酰-莽草酸-3-磷酸-合酶)抑制剂、GS(谷氨酰胺合成酶)抑制剂或PPO(原卟啉原-氧化酶)抑制剂)的有用植物。一个通过常规育种方法(诱变)被赋予对咪唑啉酮类(例如甲氧咪草烟)的耐受性的作物实例是夏季油菜(卡诺拉(Canola))。通过遗传工程方法已经被赋予了对多种除草剂或多种除草剂类别的耐受性的作物的实例包括草甘膦和草丁膦抗性玉米品种,它们在 和商标名下是可商购的。
术语“有用植物”应理解为还包括已经通过使用重组DNA技术转化使其能合成一种或多种选择性作用毒素的有用植物,所述毒素例如像已知来自于产生毒素的细菌,尤其是芽抱杆菌属的那些细菌。
此类植物的实例是:(玉米品种,表达一种CryIA(b)毒素);YieldGard(玉米品种,表达一种CryIIIB(b1)毒素);YieldGard(玉米品种,表达一种CryIA(b)以及一种CryIIIB(b1)毒素);(玉米品种,表达一种Cry9(c)毒素);Herculex(玉米品种,表达一种CryIF(a2)毒素以及实现对除草剂草丁膦铵的耐受性的酶膦丝菌素N-乙酰转移酶(PAT));NuCOTN(棉花品种,表达一种CryIA(c)毒素);(棉花品种,表达一种CryIA(c)毒素);(棉花品种,表达一种CryIA(c)以及一种CryIIA(b)毒素);(棉花品种,表达一种VIP毒素);(马铃薯品种,表达一种CryIIIA毒素); GT Advantage(GA21耐草甘膦性状),AgrisureCB Advantage(Bt11玉米螟(CB)性状)、RW(玉米根虫性状)以及
术语“作物”应理解为还包括已经通过使用重组DNA技术转化使其能合成一种或多种选择性作用毒素的作物植物,所述毒素例如像已知来自于产生毒素的细菌,尤其是芽抱杆菌属的那些细菌。
可通过此类转基因植物表达的毒素包括,例如来自于枯草芽孢杆菌或日本甲虫芽孢杆菌的杀虫蛋白质;或来自于苏云金芽孢杆菌的杀虫蛋白质,如δ-内毒素,例如Cry1Ab、Cry1Ac、Cry1F、Cry1Fa2、Cry2Ab、Cry3A、Cry3Bb1或Cry9C,或营养期杀虫蛋白(Vip),例如Vip1、Vip2、Vip3或Vip3A;或线虫共生细菌的杀虫蛋白质,例如光杆状茵属或致病杆菌属,如发光光杆状茵、嗜线虫致病杆菌;由动物产生的毒素,如蝎毒素、蜘蛛毒素、黄蜂毒素和其他昆虫特异性神经毒素;由真菌产生的毒素,如链霉菌毒素;植物凝集素,如豌豆凝集素、大麦凝集素或雪花莲凝集素;凝集素类;蛋白酶抑制剂,如胰蛋白酶抑制剂、丝氨酸蛋白酶抑制剂、马铃薯贮存蛋白(patatin)、半胱氨酸蛋白酶抑制剂、木瓜蛋白酶抑制剂;核糖体失活蛋白(RIP),如蓖麻蛋白、玉米-RIP、相思豆毒蛋白、丝瓜籽毒蛋白、皂草毒素蛋白或异株泻根毒蛋白;类固醇代谢酶,如3-羟基类固醇氧化酶、蜕皮类固醇-UDP-糖基-转移酶、胆固醇氧化酶、蜕皮激素抑制剂、HMG-COA-还原酶,离子通道阻断剂,如钠通道或钙通道阻断剂,保幼激素酯酶,利尿激素受体、茋合酶、联苄合酶、几丁酶和葡聚糖酶。
在本发明背景下,δ-内毒素例如Cry1Ab、Cry1Ac、Cry1F、Cry1Fa2、Cry2Ab、Cry3A、Cry3Bb1或Cry9C,或营养期杀虫蛋白(Vip),例如Vip1、Vip2、Vip3或Vip3A应理解为显然还包括混合毒素、截短的毒素和修饰的毒素。混合毒素是通过那些蛋白的不同结构域的新组合重组产生的(参见,例如WO02/15701)。截短的毒素例如截短的Cry1Ab是已知的。在修饰的毒素的情况下,天然存在的毒素的一个或多个氨基酸被置换。在此类氨基酸置换中,优选将非天然存在的蛋白酶识别序列插入毒素中,例如在Cry3A055的情况下,一种组织蛋白酶-G-识别序列被插入Cry3A毒素(见WO03/018810)。
此类毒素或能够合成此类毒素的转基因植物的实例披露于例如EP-A-0374753、WO93/07278、WO95/34656、EP-A-0427529、EP-A-451878和WO03/052073中。
用于制备此类转基因植物的方法对于本领域的普通技术人员是已知的并且描述在例如以上提及的公开物中。CryI-型脱氧核糖核酸及其制备已知于例如WO95/34656、EP-A-0367474、EP-A-0401979和WO90/13651。
包含在转基因植物中的毒素使得植物对有害昆虫有耐受性。此类昆虫可以存在于任何昆虫分类群,但尤其是在甲虫(鞘翅目)、双翅昆虫(双翅目)和蝴蝶(鳞翅目)中经常发现。
含有一个或多个编码杀虫剂抗性和表达一种或多种毒素的基因的转基因植物是已知的并且其中一些是可商购的。此类植物的实例是:(玉米品种,表达CryIAb毒素);YieldGard(玉米品种,表达Cry3Bb1毒素);YieldGard(玉米品种,表达Cry1AB以及Cry3Bb1毒素);(玉米品种,表达Cry9C毒素);Herculex(玉米品种,表达Cry1Fa2毒素以及实现对除草剂草丁膦铵的耐受性的酶膦丝菌素N-乙酰转移酶(PAT));NuCOTN(棉花品种,表达Cry1Ac毒素);Bollgard(棉花品种,表达Cry1Ac毒素);Bollgard(棉花品种,表达Cry1Ac和Cry2Ab毒素);(棉花品种,表达Vip3A和Cry1Ab毒素);(马铃薯品种,表达Cry3A毒素); GT Advantage(GA21耐草甘膦性状),CB Advantage(Bt11玉米螟(CB)性状)以及
此类转基因作物的其他实例是:
1.Bt11玉米,来自先正达种子公司(Syngenta Seeds SAS),Chemin del'Hobit27,F-31790St.Sauveur,法国,登记号C/FR/96/05/10。遗传修饰的玉蜀黍,通过转基因表达截短的Cry1Ab毒素,使之能抵抗欧洲玉米螟(玉米螟和粉茎螟)的侵袭。Bt11玉米还转基因表达PAT酶以达到对除草剂草丁膦铵盐的耐受性。
2.Bt176玉米,来自先正达种子公司(Syngenta Seeds SAS),Chemin del'Hobit27,F-31790St.Sauveur,法国,登记号C/FR/96/05/10。遗传修饰的玉蜀黍,通过转基因表达Cry1Ab毒素,使之能抵抗欧洲玉米螟(玉米螟和粉茎螟)的侵袭。Bt176玉米还转基因表达PAT酶以达到对除草剂草丁膦铵盐的耐受性。
3.MIR604玉米,来自先正达种子公司(Syngenta Seeds SAS),Cheminde l'Hobit27,F-31790St.Sauveur,法国,登记号C/FR/96/05/10。通过转基因表达修饰的Cry3A毒素使之具有昆虫抗性的玉米。此毒素是通过插入组织蛋白酶-G-蛋白酶识别序列而修饰的Cry3A055。此类转基因玉米的制备描述于WO03/018810中。
4.MON863玉米,来自孟山都公司(Monsanto Europe S.A.),270-272Avenue de Tervuren,B-1150布鲁塞尔,比利时,登记号C/DE/02/9。MON863表达Cry3Bb1毒素,并且对某些鞘翅目昆虫有抗性。
5.IPC531棉花,来自孟山都公司270-272Avenue de Tervuren,B-1150布鲁塞尔,比利时,登记号C/ES/96/02。
6.1507玉米,来自先锋环球公司(Pioneer Overseas Corporation)AvenueTedesco,7B-1160布鲁塞尔,比利时,登记号C/NL/00/10。遗传修饰的玉米,表达蛋白质Cry1F以达到对某些鳞翅目昆虫的抗性和表达PAT蛋白质以达到对除草剂草丁膦铵盐的耐受性。
7.NK603×MON810玉米,来自孟山都公司(Monsanto EuropeS.A.),270-272Avenue de Tervuren,B-1150布鲁塞尔,比利时,登记号C/GB/02/M3/03。通过将遗传修饰的品种NK603和MON810杂交,由常规育种的杂交玉米品种构成。NK603×MON810玉米转基因表达由土壤杆菌属菌株CP4获得的CP4EPSPS蛋白质,使之耐除草剂(含有草甘膦),以及由苏云金芽孢杆菌库尔斯塔克亚种(Bacillus thuringiensissubsp.kurstaki)获得的Cry1Ab毒素,使之耐某些鳞翅目昆虫,包括欧洲玉米螟。
如在此使用的,术语有用植物“场所”意在包括有用植物生长的地方,在这里这些有用植物的植物繁殖材料得以播下或者在这里这些有用植物的植物繁殖材料将被放置于土壤中。这样的所在地的一个实例是作物植物在其上生长的田地。
术语“植物繁殖材料”应被理解为是指植物的生殖的部分,例如种子,这些部分可以被用于该植物的繁殖,以及营养性材料,例如插条或块茎(例如马铃薯)。可以提及,例如种子(在严格意义上)、根、果实、块茎、球茎、根茎以及植物的多个部分。还可以提及有待在萌发后或出土后移植的萌发的植物以及幼小的植物。这些幼小的植物可以通过浸渍进行完全或部分地处理从而在移植之前进行保护。优选地“植物繁殖材料”应被理解为是指种子。
具有化学式I的化合物能以未修饰的形式使用,或者优选地与配制领域中常规使用的载体以及佐剂一起使用。
因此本发明还涉及针对致植物病微生物进行控制和保护的组合物,这些组合物包括具有化学式I的化合物和惰性载体,并且涉及控制或预防有用植物被致植物病微生物侵染的方法,其中一种组合物,包括作为活性成分的具有化学式I的化合物和惰性载体,被施用至这些植物、其部分或其场所。
为了这个目标,用已知方式将具有化学式I的化合物和惰性载体方便地配制为可乳化的浓缩物、可包衣的膏、直接可喷洒的或可稀释的溶液、稀释乳液、可湿性粉、可溶性粉、尘剂、颗粒,以及还有封装物(例如在聚合物物质中)。对于这些组合物的类型,应用的方法,例如喷雾、雾化、尘化、播撒、包衣或倾倒,可以依据预期的目的以及主要环境进行选择。这些组合物还可以含有其他佐剂,例如稳定剂、消泡剂、黏度调节剂、粘合剂、增粘剂连同肥料、微量营养素供体或用于获得特殊效果的其他配制品。
适合的载体和佐剂(助剂)可以是固体或液体的并且是在配制品技术中有用的物质,例如天然或再生的矿物质、溶剂、分散剂、湿润剂、增粘剂、增稠剂、粘合剂或肥料。例如在WO97/33890中说明了此类载体。
具有化学式I的化合物或包含作为活性成分的具有化学式I化合物以及一种惰性载体的组合物可以被施用到待处理的植物场所或植物上(与其他化合物同时地或顺序地)。这些其他化合物可以是例如肥料或微量营养素供体或影响植物生长的其他制品。它们还可以是选择性的除草剂,连同杀昆虫剂、杀真菌剂、杀细菌剂、杀线虫剂、杀软体动物剂或几种这些制剂的混合物,如果希望的话与配制领域所使用的常规的载体、表面活性剂或促进施用的佐剂一起。
一种优选的用于施用具有化学式I的化合物或包含作为活性成分的具有化学式I的化合物以及一种惰性载体的组合物的方法是叶施用。施用频率和施用比率取决于受相应的病原体侵染的风险。然而,具有化学式I的化合物还可以通过用一种液体配制品浸泡该植物的场所或者通过将处于固体形式的化合物施用至土壤,例如以颗粒的形式(土壤施用)而经由土壤通过根(内吸作用)透入该植物。在水稻作物中,可以将此类颗粒施用到水浸没的稻田中。具有化学式I的化合物还可以通过用杀真菌剂的液体配制品浸渍种子或块茎、或用一种固体配制品对其进行包衣而施用到种子(包衣)上。
以一种已知方式制备一种配制品(即,含具有化学式I化合物以及如果希望的话一种固体或液体佐剂或,如果还希望的话,另外的其他的杀生物的活性成分的组合物),该方式典型地是通过将该化合物与增充剂,例如溶剂、固体载体以及,可任选地,表面活性化合物(表面活性剂)进行密切地混合和/或研磨。
本发明另外涉及多种混合物,这些混合物包括至少一种具有化学式I的化合物,和至少一种另外的其他杀生物活性成分以及任选地另外的成分。该另外的其他杀生物活性成分是已知的,例如从《农药手册》(The PesticideManual)[(《农药手册》)(The Pesticide Manual)-(《全球纲要》)(AWorld Compendium);第十三版(新版(2003年11月2日));编者:C.D.S.Tomlin(托姆林);The British Crop Protection Council(英国农作物保护委员会),ISBN-10:1901396134;ISBN-13:978-1901396133]或其电子版(《农药手册V4.2》)(“e-Pesticide Manual V4.2”),或者来自网站http://www.alanwood.net/pesticides/,或者优选地是以下列出的另外的杀有害生物剂之一。
具有TX的这些化合物与另外的活性成分(B)的以下混合物是优选的(缩写“TX”是指选自下组的一种化合物,该组由以下各项组成:具有来自本发明的表1至57中说明的A.1.1至A.1.215行的化学式的化合物,因此缩写“TX”是指选自化合物T.1.1.1至T57.1.215的至少一种化合物或选自表A1(化合物1至46)的至少一种化合物:
一种佐剂,该佐剂选自由以下物质组成的组:石油(别名(628)+TX),
一种杀螨剂,该杀螨剂选自由以下物质组成的组:1,1-二(4-氯苯基)-2-乙氧基乙醇(IUPAC名称)(910)+TX、2,4-二氯苯基苯磺酸酯(IUPAC/化学文摘名)(1059)+TX、2-氟-N-甲基-N-1-萘乙酰胺(IUPAC名称)(1295)+TX、4-氯苯基苯基砜(IUPAC名称)(981)+TX、阿维菌素(abamectin)(1)+TX、灭螨醌(3)+TX、乙酰虫腈[CCN]+TX、氟丙菊酯(9)+TX、涕灭威(16)+TX、涕灭砜威(863)+TX、α-氯氰菊酯(202)+TX、赛硫磷(870)+TX、磺胺螨酯[CCN]+TX、氨基硫代盐(872)+TX、胺吸磷(875)+TX、胺吸磷草酸氢盐(875)+TX、双甲脒(24)+TX、杀螨特(881)+TX、三氧化二砷(882)+TX、AVI382(化合物代码)+TX、AZ60541(化合物代码)+TX、益棉磷(44)+TX、保棉磷(azinphos-methyl)(45)+TX、偶氮苯(IUPAC名称)(888)+TX、三唑锡(azacyclotin)(46)+TX、偶氮磷(azothoate)(889)+TX、苯茵灵(62)+TX、苯诺沙磷(benoxafos)(别名)[CCN]+TX、苯螨特(benzoximate)(71)+TX、苯甲酸苄酯(IUPAC名称)[CCN]+TX、联苯肼酯(74)+TX、氟氯菊酯(76)+TX、乐杀螨(907)+TX、溴灭菊酯(别名)+TX、溴烯杀(bromocyclene)(918)+TX、溴硫磷(920)+TX、乙基溴硫磷(921)+TX,溴螨酯(bromopropylate)(94)+TX、噻嗪酮(99)+TX、丁酮威(103)+TX、丁酮砜威(104)+TX、丁酮威(butylpyridaben)(别名)+TX、石硫合剂(calcium polysulfide)(IUPAC名称)(111)+TX、毒杀芬(campheechlor)(941)+TX、氯灭杀威(carbanolate)(943)+TX、甲萘威(115)+TX、克百威(carbofuran)(118)+TX、卡波硫磷(947)+TX、CGA50’439(研究代码)(125)+TX、灭螨猛(chinomethionat)(126)+TX、杀螨醚(chlorbenside)(959)+TX、杀虫脒(964)+TX、杀虫脒盐酸盐(964)+TX、溴虫腈(130)+TX、敌螨(968)+TX、杀螨酯(chlorfenson)(970)+TX、敌螨特(chlorfensulphide)(971)+TX、氯芬磷(131)+TX、乙酯杀螨醇(chlorobenzilate)(975)+TX、伊托明(chloromebuform)(977)+TX、灭虫脲(chloromethiuron)(978)+TX、丙酯杀螨醇(chloropropylate)(983)+TX、毒死蜱(145)+TX、甲基毒死蜱(146)+TX、虫螨磷(chlorthiophos)(994)+TX、瓜菊酯(cinerin)I(696)+TX、瓜菊酯11(696)+TX、瓜叶菊素(cinerins)(696)+TX、四螨嗪(158)+TX、氯氰碘柳胺(别名)[CCN]+TX、库马磷(174)+TX、克罗米通(别名)[CCN]+TX、巴毒磷(crotoxyphos)(1010)+TX、硫杂灵(1013)+TX、果虫磷(cyanthoate)(1020)+TX、丁氟螨酯(CAS登记号:400882-07-7)+TX、三氯氟氰菊酯(196)+TX、三环锡(199)+TX、氯氰菊酯(201)+TX、DCPM(1032)+TX、DDT(219)+TX、田乐磷(demephion)(1037)+TX、田乐磷-O(1037)+TX、田乐磷-S(1037)+TX、内吸磷(demeton)(1038)+TX、甲基内吸磷(224)+TX、内吸磷-O(1038)+TX、甲基内吸磷-O(224)+TX、内吸磷-S(1038)+TX、甲基内吸磷-S(224)+TX、内吸磷-S-甲基磺隆(demeton-S-methylsulphon)(1039)+TX、杀螨隆(226)+TX、氯亚胺硫磷(dialifos)(1042)+TX、二嗪磷(227)+TX、苯氟磺胺(230)+TX、敌敌畏(236)+TX、甲氟磷(dicliphos)(别名)+TX、开乐散(242)+TX、百治磷(243)+TX、遍地克(1071)+TX、甲氟磷(dimefox)(1081)+TX、乐果(262)+TX、二甲杀螨霉素(dinactin)(别名)(653)+TX、消螨酚(dinex)(1089)+TX、消螨酚(dinex-diclexine)(1089)+TX、消螨通(dinobuton)(269)+TX、敌螨普(dinocap)(270)+TX、敌螨普-4[CCN]+TX、敌螨普-6[CCN]+TX、二硝酯(1090)+TX、硝戊酯(dinopenton)(1092)+TX、硝辛酯(dinosulfon)(1097)+TX、硝丁酯(dinoterbon)(1098)+TX、敌恶磷(1102)+TX、二苯砜(IUPAC名称)(1103)+TX、双硫仑(别名)[CCN]+TX、乙拌磷(278)+TX、DNOC(282)+TX、苯氧炔螨(dofenapyn)(1113)+TX、多拉克汀(别名)[CCN]+TX、硫丹(294)+TX、因毒磷(endothion)(1121)+TX、EPN(297)+TX、依立诺克丁(别名)[CCN]+TX、乙硫磷(309)+TX、益硫磷(ethoate-methyl)(1134)+TX、乙螨唑(etoxazole)(320)+TX,乙嘧硫磷(etrimfos)(1142)+TX、抗螨唑(fenazaflor)(1147)+TX、喹螨醚(328)+TX、苯丁锡(fenbutatin oxide)(330)+TX、苯硫威(fenothiocarb)(337)+TX、甲氰菊酯(342)+TX、吡螨胺(fenpyrad)(别名)+TX、唑螨酯(fenpyroximate)(345)+TX、芬螨酯(fenson)(1157)+TX、氟硝二苯胺(fentrifanil)(1161)+TX、氰戊菊酯(349)+TX、氟虫腈(354)+TX、嘧螨酯(fluacrypyrim)(360)+TX、氟佐隆(1166)+TX、氟螨噻(flubenzimine)(1167)+TX、氟螨脲(366)+TX、氟氰戊菊酯(flucythrinate)(367)+TX、联氟螨(fluenetil)(1169)+TX、氟虫脲(370)+TX、氟氯苯菊酯(flumethrin)(372)+TX、氟杀螨(fluorbenside)(1174)+TX、氟胺氰菊酯(fluvalinate)(1184)+TX、FMC1137(研究代码)(1185)+TX、抗螨脒(405)+TX、抗螨脒盐酸盐(405)+TX、安硫磷(formothion)(1192)+TX、胺甲威(formparanate)(1193)+TX、γ-HCH(430)+TX、果绿啶(glyodin)(1205)+TX、苄螨醚(halfenprox)(424)+TX、庚烯醚(heptenophos)(432)+TX、十六碳烷基环丙烷羧酸酯(IUPAC/化学文摘名)(1216)+TX、噻螨酮(441)+TX、碘甲烷(IUPAC名称)(542)+TX、水胺硫磷(isocarbophos)(别名)(473)+TX、异丙基0-(甲氧基氨基硫代磷酰基)水杨酸酯(IUPAC名称)(473)+TX、伊维菌素(别名)[CCN]+TX、茉莉菊酯(jasmolin)I(696)+TX、茉莉菊酯II(696)+TX、碘硫磷(jodfenphos)(1248)+TX、林丹(430)+TX、禄芬隆(490)+TX、马拉硫磷(492)+TX、苄丙二腈(malonoben)(1254)+TX、灭蚜磷(mecarbam)(502)+TX、地胺磷(mephosfolan)(1261)+TX、甲硫芬(别名)[CCN]+TX、虫螨畏(methacrifos)(1266)+TX、甲胺磷(527)+TX、杀扑磷(529)+TX、灭虫威(530)+TX、灭多虫(531)+TX、溴甲烷(537)+TX、速灭威(metolcarb)(550)+TX、速灭磷(556)+TX、自克威(mexacarbate)(1290)+TX、米尔螨素(557)+TX、杀螨茵素肟(milbemycin oxime)(别名)[CCN]+TX、丙胺氟磷(mipafox)(1293)+TX、久效磷(561)+TX、茂硫磷(morphothion)(1300)+TX、莫昔克丁(别名)[CCN]+TX、二溴磷(naled)(567)+TX、NC-184(化合物代码)+TX、NC-152(化合物代码)+TX、氟蚊灵(nifluridide)(1309)+TX、尼柯霉素(别名)[CCN]+TX、戊氰威(nitrilacarb)(1313)+TX、戊氰威(nitrilacarb)1:1氯化锌络合物(1313)+TX、NNI-0101(化合物代码)+TX、NNI-0250(化合物代码)+TX、氧乐果(氧乐果)(594)+TX、杀线威(602)+TX、亚异砜磷(oxydeprofos)(1324)+TX、砜拌磷(oxydisulfoton)(1325)+TX、pp'-DDT(219)+TX、对硫磷(615)+TX、氯菊酯(626)+TX、石油(别名)(628)+TX、芬硫磷(1330)+TX、稻丰散(631)+TX、甲拌磷(636)+TX、伏杀硫磷(637)+TX、硫环磷(phosfolan)(1338)+TX、亚胺硫磷(638)+TX、磷胺(639)+TX、辛硫磷(642)+TX、甲基嘧啶磷(652)+TX、氯化松节油(polychloroterpenes)(传统名称)(1347)+TX,杀螨霉素(polynactins)(别名)(653)+TX、丙氯诺(1350)+TX、丙溴磷(662)+TX、蜱虱威(promacyl)(1354)+TX、克螨特(671)+TX、胺丙畏(propetamphos)(673)+TX、残杀威(678)+TX、乙噻唑磷(prothidathion)(1360)+TX、发硫磷(prothoate)(1362)+TX、除虫菊酯I(696)+TX、除虫菊酯II(696)+TX、除虫菊素(pyrethrins)(696)+TX、哒螨灵(699)+TX、哒嗪硫磷(pyridaphenthion)(701)+TX、嘧螨醚(pyrimidifen)(706)+TX、嘧硫磷(1370)+TX、喹硫磷(quinalphos)(711)+TX、喹硫磷(quintiofos)(1381)+TX、R-1492(研究代码)(1382)+TX、RA-17(研究代码)(1383)+TX、鱼藤酮(722)+TX、八甲磷(schradan)(1389)+TX、硫线磷(sebufos)(别名)+TX、塞拉菌素(selamectin)(别名)[CCN]+TX、SI-0009(化合物代码)+TX、苏硫磷(sophamide)(1402)+TX、螺螨酯(738)+TX、螺甲螨酯(739)+TX、SSI-121(研究代码)(1404)+TX、舒非仑(别名)[CCN]+TX、氟虫胺(sulfluramid)(750)+TX、治螟磷(sulfotep)(753)+TX、硫黄(754)+TX、S21-121(研究代码)(757)+TX、氟胺氰菊酯(398)+TX,吡螨胺(763)+TX、TEPP(1417)+TX、叔丁威(terbam)(别名)+TX、司替罗磷(777)+TX、三氯杀螨砜(tetradifon)(786)+TX、杀螨霉素(tetranactin)(别名)(653)+TX、杀螨硫醚(tetrasul)(1425)+TX、久效威(thiafenox)(别名)+TX、抗虫威(thiocarboxime)(1431)+TX、久效威(thiofanox)(800)+TX、甲基乙拌磷(thiometon)(801)+TX、克杀螨(1436)+TX、苏力菌素(thuringiensin)(别名)[CCN]+TX、威茵磷(triamiphos)(1441)+TX、苯噻螨(triarathene)(1443)+TX、三唑磷(820)+TX、唑呀威(triazuron)(别名)+TX、敌百虫(824)+TX、氯苯乙丙磷(trifenofos)(1455)+TX、甲杀螨霉素(trinactin)(别名)(653)+TX、灭蚜硫磷(847)+TX、氟吡唑虫(vaniliprole)[CCN]和YI-5302(化合物代码)+TX,
一种杀藻剂,该杀藻剂选自由以下物质组成的组:3-苯并[b]噻吩-2-基-5,6-二氢-1,4,2-噁噻嗪-4-氧化物[CCN]+TX、二辛酸铜(IUPAC名称)(170)+TX、硫酸铜(172)+TX、cybutryne[CCN]+TX、二氢萘醌(dichlone)(1052)+TX、双氯酚(232)+TX、茵多酸(295)+TX、三苯锡(fentin)(347)+TX、熟石灰[CCN]+TX、代森钠(nabam)(566)+TX、灭藻醌(quinoclamine)(714)+TX、醌萍胺(quinonamid)(1379)+TX、西玛津(730)+TX、三苯锡乙酸盐(IUPAC名称)(347)和氢氧化三苯锡(IUPAC名称)(347)+TX,
一种驱蠕虫剂,该驱蠕虫剂选自由以下物质组成的组:阿维菌素(1)+TX、克芦磷酯(1011)+TX、多拉克汀(别名)[CCN]+TX、依马克丁(291)+TX、依马克丁苯甲酸酯(291)+TX、依立诺克丁(别名)[CCN]+TX、伊维菌素(别名)[CCN]+TX、米尔倍霉素(别名)[CCN]+TX、莫昔克丁(别名)[CCN]+TX、哌嗪[CCN]+TX、塞拉菌素(selamectin)(别名)[CCN]+TX、多杀菌素(737)和硫菌灵(thiophanate)(1435)+TX,
一种杀鸟剂,该杀鸟剂选自由以下物质组成的组:氯醛糖(127)+TX、异狄氏剂(1122)+TX、倍硫磷(346)+TX、吡啶-4-胺(IUPAC名称)(23)和士的宁(745)+TX,
一种杀细菌剂,该杀细菌剂选自由以下物质组成的组:1-羟基-1H-吡啶-2-硫酮(IUPAC名称)(1222)+TX、4-(喹喔啉-2-基氨基)苯磺酰胺(IUPAC名称)(748)+TX、8-羟基喹啉硫酸盐(446)+TX、溴硝醇(97)+TX、二辛酸铜(IUPAC名称)(170)+TX、氢氧化铜(IUPAC名称)(169)+TX、甲酚[CCN]+TX、双氯酚(232)+TX、双吡硫翁(1105)+TX、多地辛(1112)+TX、敌磺钠(fenaminosulf)(1144)+TX、甲醛(404)+TX、汞加芬(别名)[CCN]+TX、春雷霉素(483)+TX、春雷霉素盐酸盐水合物(483)+TX、二(二甲基二硫代氨基甲酸盐)镍(IUPAC名称)(1308)+TX、三氯甲基吡啶(nitrapyrin)(580)+TX、辛噻酮(octhilinone)(590)+TX、奥索利酸(606)+TX、土霉素(611)+TX、羟基喹啉硫酸钾(446)+TX、烯丙苯噻唑(probenazole)(658)+TX、链霉素(744)+TX、链霉素倍半硫酸盐(744)+TX、叶枯酞(766)+TX扣硫柳汞(别名)[CCN]+TX,
一种生物试剂,该生物试剂选自由以下物质组成的组:棉褐带卷蛾颗粒体病毒(Adoxophyes orana GV)(别名)(12)+TX、放射形土壤杆菌(别名)(13)+TX、捕食螨(Amblyseius spp.)(别名)(19)+TX、芹菜夜蛾核多角体病毒(Anagrapha falcifera NPV)(别名)(28)+TX、Anagrusatomus(别名)(29)+TX、蚜虫寄生蜂(Aphelinus abdominalis)(别名)(33)+TX、棉蚜寄生蜂(Aphidius colemani)(别名)(34)+TX、食蚜瘿蚊(Autographa californica NPV)(别名)(35)+TX、苜蓿银纹夜蛾核多角体病毒(Bacillus firmus)(别名)(38)+TX、坚强芽孢杆菌(Bacillusfirmus)(别名)(48)+TX、球形芽孢杆菌(Bacillus sphaericus Neide)(学名)(49)+TX、苏云金杆菌(学名)(51)+TX、苏云金杆菌(Bacillus thuringiensis Berliner)(学名)(51)+TX、苏云金杆菌艾扎外亚种(Bacillus thuringiensis subsp.aizawai)(学名)(51)+TX、、苏云金杆菌以色列亚种(Bacillus thuringiensis subsp.israelensis)(学名)(51)、苏云金杆菌日本亚种(Bacillus thuringiensis subsp.japonensis)(学名)(51)+TX、苏云金杆菌库尔斯塔克亚种(Bacillus thuringiensis subsp.kurstaki)(学名)(51)+TX、苏云金杆菌拟步行亚种.(Bacillus thuringiensis subsp.tenebrionis)(学名)(51)+TX、球孢白僵茵(Beauveria bassiana)(别名)(53)+TX,布氏白僵茵(Beauveria brongniartii)(别名)(54)+TX、草蜻蛉(Chrysoperla carnea)(别名)(151)+TX、孟氏隐唇瓢虫(Cryptolaemus montrouzieri)(别名)(178)+TX、苹果蠹蛾颗粒体病毒(Cydia pomonella GV)(别名)(191)+TX、西伯利亚离颚茧蜂(Dacnusasibirica)(别名)(212)+TX、豌豆潜叶蝇姬小蜂(Diglyphus isaea)(别名)(254)+TX、丽蚜小蜂(Encarsia formosa)(学名)(293)+TX、桨角蚜小蜂(Eretmocerus eremicus)(别名)(300)+TX、玉米穗夜蛾核多角体病毒(Helicoverpa zea)(别名)(431)+TX、嗜茵异小杆线虫(Heterorhabditis bacteriophora)和H.megidis(别名)(433)+TX、会聚长足瓢虫(Hippodamia convergens)(别名)(442)+TX、橘粉介壳虫寄生蜂(Leptomastix dactylopii)(别名)(488)+TX、盲蝽(Macrolophuscaliginosus)(别名)(491)+TX,甘蓝夜蛾核多角体病毒(Mamestrabrassicae NPV)(别名)(494)+TX、Metaphycus helvolus(别名)(522)+TX、黄绿绿僵茵(Metarhizium anisopliae var.acridum)(学名)(523)+TX、金龟子绿僵菌小孢变种(Metarhizium anisopliae var.anisopliae)(学名)(523)+TX、松黄叶蜂(Neodiprion sertifer)核多角体病毒和红头松树叶蜂(N.lecontei)核多角体病毒(别名)(575)+TX、小花蝽(别名)(596)+TX、玫烟色拟青霉(Paecilomyces fumosoroseus)(别名)(613)+TX、智利捕植螨(Phytoseiulus persimilis)(别名)(644)+TX、甜菜夜蛾(Spodoptera exigua multicapsid)多核衣壳核多角体病毒(学名)(741)+TX、毛蚊线虫(Steinernema bibionis)(别名)(742)+TX、小卷蛾斯氏线虫(Steinernema feltiae)(别名)(742)+TX、夜蛾斯氏线虫(别名)(742)+TX、Steinernema glaseri(别名)(742)+TX、Steinernemariobrave(另I1名)(742)+TX、Steinernema riobravis(别名)(742)+TX、Steinernema scapterisci(别名)(742)+TX、斯氏线虫(Steinernemaspp.)(别名)(742)+TX、赤眼蜂(别名)(826)+TX、西方盲走螨(Typhlodromus occidentalis)(别名)(844)和蜡蚧轮枝茵(Verticilliumlecanii)(别名)(848)+TX,
一种土壤消毒剂,该土壤消毒剂选自由以下物质组成的组:碘甲烷(IUPAC名祢)(542)和溴甲烷(537)+TX,
一种化学不育剂,该化学不育剂选自由以下物质组成的组:唑磷嗪(apholate)[CCN]+TX、bisazir(别名)[CCN]+TX、白消安(别名)[CCN]+TX、除虫脲(250)+TX、dimatif(别名)[CCN]+TX、六甲蜜胺(hemel)[CCN]+TX、六甲磷(hempa)[CCN]+TX、甲基涕巴(metepa)[CCN]+TX、甲硫涕巴(methiotepa)[CCN]+TX、不育特(methylapholate)[CCN]+TX、不孕啶(morzid)[CCN]+TX、氟幼脲(penfluron)(别名)[CCN]+TX、涕巴(tepa)[CCN]+TX、硫代六甲磷(thiohempa)(别名)[CCN]+TX、硫涕巴(别名)[CCN]+TX、曲他胺(别名)[CCN]和尿烷亚胺(别名)[CCN]+TX,
一种昆虫信息素,该昆虫昆虫信息素选自由以下物质组成的组:(E)-癸-5-烯-1-基乙酸酯与(E)-癸-5-烯-1-醇(IUPAC名称)(222)+TX、(E)-十三碳-4-烯-1-基乙酸酯(IUPAC名称)(829)+TX、(E)-6-甲基庚-2-烯-4-醇(IUPAC名称)(541)+TX、(E,Z)-十四碳-4,10-二烯-1-基乙酸酯(IUPAC名称)(779)+TX、(Z)-十二碳-7-烯-1-基乙酸酯(IUPAC名称)(285)+TX、(Z)-十六碳-11-烯醛(IUPAC名称)(436)+TX、(Z)-十六碳-11-烯-1-基乙酸酯(IUPAC名称)437)+TX、(Z)-十六碳-13-烯-11-炔-1-基乙酸酯(IUPAC名称)438)+TX、(Z)-二十-13-烯-10-酮(IUPAC名称)448)+TX、(Z)-十四碳-7-烯-1-醛(IUPAC名称)(782)+TX、(Z)-十四碳-9-烯-1-醇(IUPAC名称)(783)+TX、(Z)-十四碳-9-烯-1-基乙酸酯(IUPAC名称)(784)+TX、(7E,9Z)-十二碳-7,9-二烯-1-基乙酸酯(IUPAC名称)(283)+TX、(9Z,11E)-十四碳-9,11-二烯-1-基乙酸酯(IUPAC名称)(780)+TX、(9Z,12E)-十四碳-9,12-二烯-1-基乙酸酯(IUPAC名称)(781)+TX、14-甲基十八-1-烯(IUPAC名称)(545)+TX、4-甲基壬醛-5-醇与4-甲基壬醛-5-酮(IUPAC名称)(544)+TX、α-multistriatin(别名)[CCN]+TX、西部松小蠹集合信息素(brevicomin)(别名)[CCN]+TX、十二碳二烯醇(codlelure)(别名)[CCN]+TX、十二碳二烯醇(codlemone)(别名)(167)+TX、诱蝇酮(cuelure)(别名)(179)+TX、环氧十九烷(disparlure)(277)+TX、十二碳-8-烯-1基乙酸酯(IUPAC名称)(286)+TX、十二碳-9-烯-1-基乙酸酯(IUPAC名称)(287)+TX、十二碳-8+TX、10-二烯-1-基乙酸酯(IUPAC名称)(284)+TX、dominicalure(别名)[CCN]+TX、4-甲基辛酸乙酯(IUPAC名称)(317)+TX、丁香酚(别名)[CCN]+TX、南部松小蠹集合信息素(frontalin)(别名)[CCNl+TX、诱虫十六酯(gossyplure)(别名)(420)+TX、诱杀烯混剂(grandlure)(421)+TX、诱杀烯混剂I(别名)(421)+TX、诱杀烯混剂II(别名)(421)+TX、诱杀烯混剂III(别名)(421)+TX、诱杀烯混剂IV(别名)(421)+TX、醋酸十六烯酯(hexalure)[CCN]+TX、齿小蠹二烯醇(ipsdienol)(别名)[CCN]+TX、小蠢烯醇(ipsenol)(别名)[CCN]+TX、金龟子性诱剂(japonilure)(别名)(481)+TX、lineatin(别名)[CCN]+TX、litlure(别名)[CCN]+TX、粉纹夜蛾性诱剂(looplure)(别名)[CCN]+TX、诱杀酯(medlure)[CCN]+TX、megatomoic acid(别名)[CCN]+TX、诱虫醚(methyl eugenol)(别名)(540)+TX、诱虫烯(muscalure)(563)+TX、十八-2,13-二烯-1-基乙酸酯(IUPAC名称)(588)+TX、十八-3,13-二烯-1-基乙酸酯(IUPAC名称)(589)+TX、贺康彼(orfralure)(别名)[CCN]+TX、oryctalure(别名)(317)+TX、非乐康(ostramone)(别名)[CCN]+TX、诱虫环(siglure)[CCN]+TX、sordidin(别名)(736)+TX、食菌甲诱醇(sulcatol)(别名)[CCN]+TX、十四-11-烯-1-基乙酸酯(IUPAC名称)(785)+TX、特诱酮(839)+TX、特诱酮A(别岩)(839)+TX、特诱酮B1,(别名)(839)+TX、特诱酮B2(别名)(839)+TX、特诱酮C(别名)(839)和trunc-call(别名)[CCN]+TX,
一种昆虫驱避剂,该昆虫驱避剂选自由以下物质组成的组:2-(辛基硫代)乙醇(IUPAC名称)(591)+TX、避蚊酮(butopyronoxyl)(933)+TX、丁氧基(聚丙二醇)(936)+TX、己二酸二丁酯(IUPAC名称)(1046)+TX、邻苯二甲酸二丁酯(1047)+TX、丁二酸二丁酯(IUPAC名称)(1048)+TX、避蚊胺[CCN]+TX、避蚊胺[CCN]+TX、驱蚊酯(dimethyl carbate)[CCN]+TX、乙基己二醇(1137)+TX、己脲[CCN]+TX、甲喹丁(methoquin-butyl)(1276)+TX、甲基新癸酰胺[CCN]+TX、草氨酸盐(oxamate)[CCN]和羟哌酯[CCN]+TX,
一种杀昆虫剂,该杀昆虫剂选自由以下物质组成的组:1-二氯-1-硝基乙烷(IUPAC/化学文摘名称)(1058)+TX、1,1-二氯-2,2-二(4-乙基苯基)乙烷(IUPAC名称)(1056)+TX、1,2-二氯丙烷(IUPAC/化学文摘名称)(1062)+TX、带有1,3-二氯丙烯的1,2-二氯丙烷(IUPAC名称)(1063)+TX、1-溴-2-氯乙烷(IUPAC/化学文摘名称)(916)+TX、乙酸2,2,2-三氯-1-(3,4-二氯苯基)乙基酯(IUPAC名称)(1451)+TX、2,2-二氯乙烯基2-乙基亚磺酰基乙基甲基磷酸酯(IUPAC名称)(1066)+TX、二甲基氨基甲酸2-(1,3-二硫杂环戊烷-2-基)苯基酯(IUPAC/化学文摘名称)(1109)+TX、硫氰酸2-(2-丁氧基乙氧基)乙基酯(IUPAC/化学文摘名称)(935)+TX、甲基氨基甲酸2-(4,5-二甲基-1,3-二氧环戊烷-2-基)苯基酯(IUPAC/化学文摘名称)(1084)+TX、2-(4-氯-3,5-二甲苯基氧基)乙醇(IUPAC名称)(986)+TX、2-氯乙烯基二乙基磷酸酯(IUPAC名称)(984)+TX、2-咪唑啉酮(IUPAC名称)(1225)+TX、2-异戊酰基茚满-1,3-二酮(IUPAC名称)(1246)+TX、甲基氨基甲酸2-甲基(丙-2-炔基)氨基苯基酯(IUPAC名称)(1284)+TX、月桂酸2-硫氰基乙基酯(IUPAC名称)(1433)+TX、3-溴-1-氯丙-1-烯(IUPAC名称)(917)+TX、二甲基氨基甲酸3-甲基-1-苯基吡唑-5-基酯(IUPAC名称)(1283)+TX、甲基氨基甲酸4-甲基(丙-2-炔基)氨基-3,5-二甲苯基酯(IUPAC名称)(1285)+TX、二甲基氨基甲酸5,5-二甲基-3-氧代环己-1-烯基酯(IUPAC名称)(1085)+TX、阿维菌素(1)+TX、乙酰甲胺磷(2)+TX、啶虫脒(4)+TX、家蝇磷(别名)[CCN]+TX、乙酰虫腈[CCN]+TX、氟丙菊酯(9)+TX、丙烯腈(IUPAC名称)(861)+TX、棉铃威(15)+TX、涕灭威(16)+TX、涕灭砜威(863)+TX、氯甲桥萘(864)+TX、烯丙菊酯(17)+TX、阿洛氨菌素(别名)[CCN]+TX、除害威(866)+TX、α-氯氰菊酯(202)+TX、α-蜕皮激素(别名)[CCN]+TX、磷化铝(640)+TX、赛硫磷(870)+TX、硫代酰胺(872)+TX、灭害威(873)+TX、胺吸磷(875)+TX、胺吸磷草酸氢盐(875)+TX、双甲脒(24)+TX、新烟碱(877)+TX、乙基杀扑磷(883)+TX、AVI382(化合物代码)+TX、AZ60541(化合物代码)+TX、印楝素(别名)(41)+TX、甲基吡啶磷(42)+TX、谷硫磷-乙基(44)+TX、谷硫磷-甲基(45)+TX、偶氮磷(889)+TX、苏云金芽孢杆菌δ-内毒素类(别名)(52)+TX、六氟硅酸钡(别名)[CCN]+TX、多硫化钡(IUPAC/化学文摘名称)(892)+TX、熏菊酯[CCN]+TX、贝螺杀(Bayer)22/190(研究代码)(893)+TX、Bayer22408(研究代码)(894)+TX、噁虫威(58)+TX、丙硫克百威(60)+TX、杀虫磺(66)+TX、β-氟氯氰菊酯(194)+TX、β-氯氰菊酯(203)+TX、联苯菊酯(76)+TX、生物烯丙菊酯(78)+TX、生物烯丙菊酯S-环戊烯基异构体(别名)(79)+TX、戊环苄呋菊酯(bioethanomethrin)[CCN]+TX、生物氯菊酯(908)+TX、除虫菊酯(80)+TX、二(2-氯乙基)醚(IUPAC名称)(909)+TX、双三氟虫脲(83)+TX、硼砂(86)+TX、溴灭菊酯(别名)+TX、溴苯烯磷(914)+TX、溴杀烯(918)+TX、溴-DDT(别名)[CCN]+TX、溴硫磷(920)+TX、溴硫磷-乙基(921)+TX、合杀威(924)+TX、噻嗪酮(99)+TX、畜虫威(926)+TX、butathiofos(927)+TX、丁酮威(103)+TX、丁酯膦(932)+TX、丁酮砜威(104)+TX、丁基哒螨灵(别名)+TX、硫线磷(109)+TX、砷酸钙[CCN]+TX、氰化钙(444)+TX、多硫化钙(IUPAC名称)(111)+TX、毒杀芬(941)+TX、氯灭杀威(943)+TX、甲萘威(115)+TX、克百威(118)+TX、二硫化碳(IUPAC/化学文摘名称)(945)+TX、四氯化碳(IUPAC名称)(946)+TX、三硫磷(947)+TX、丁硫克百成(119)+TX、杀螟丹(123)+TX、杀螟丹盐酸盐(123)+TX、西伐丁(别名)(725)+TX、冰片丹(960)+TX、氯丹(128)+TX、开蓬(963)+TX、杀虫脒(964)+TX、杀虫脒盐酸盐(964)+TX、氯氧磷(129)+TX、溴虫腈(130)+TX、毒虫畏(131)+TX、定虫隆(132)+TX、氯甲磷(136)+TX、氯仿[CCN]+TX、三氯硝基甲烷(141)+TX、氯辛硫磷(989)+TX、灭虫吡啶(990)+TX、毒死蜱(145)+TX、毒死蜱-甲基(146)+TX、虫螨磷(994)+TX、环虫酰肼(150)+TX、灰菊素I(696)+TX、灰菊素II(696)+TX、灰菊素类(696)+TX、顺式苄呋菊酯(cis-resmethrin)(别名)+TX、顺式苄呋菊酯(cismethrin)(80)+TX、功夫菊酯(别名)+TX、除线威(999)+TX、氯氰碘柳胺(别名)[CCN]+TX、噻虫胺(165)+TX、乙酰亚砷酸铜[CCN]+TX、砷酸铜[CCN]+TX、油酸铜[CCN]+TX、蝇毒磷(174)+TX、畜虫磷(1006)+TX、克罗米通(别名)[CCN]+TX、巴毒磷(1010)+TX、克芦磷酯(1011)+TX、冰晶石(别名)(177)+TX、CS708(研究代码)(1012)+TX、苯腈膦(1019)+TX、杀螟睛(184)+TX、果虫磷(1020)+TX、乙氰菊酯(188)+TX、氟氯氰菊酯(193)+TX、三氯氟氰菊酯(196)+TX、氯氰菊酯(201)+TX、苯氰菊酯(206)+TX、环丙马秦(209)+TX、畜蜱磷(别名)[CCN]+TX、d-柠檬烯(别名)[CCN]+TX、d-四甲菊酯(别名)(788)+TX、DAEP(1031)+TX、棉隆(216)+TX、DDT(219)+TX、decarbofuran(1034)+TX、溴氰菊酯(223)+TX、田乐磷(1037)+TX、田乐磷-O(1037)+TX、田乐磷-S(1037)+TX、内吸磷(1038)+TX、内吸磷-甲基(224)+TX、内吸磷-O(1038)+TX、内吸磷-O-甲基(224)+TX、内吸磷-S(1038)+TX、内吸磷-S-甲基(224)+TX、内吸磷-S-甲基砜(1039)+TX、丁醚脲(226)+TX、氯亚胺硫磷(1042)+TX、二胺磷(1044)+TX、二嗪磷(227)+TX、异氯磷(1050)+TX、除线磷(1051)+TX、敌敌畏(236)+TX、dicliphos(别名)+TX、dicresyl(别名)[CCN]+TX、百治磷(243)+TX、地昔尼尔(244)+TX、狄氏刑(1070)+TX、二乙基5-甲基吡唑-3-基磷酸酯(IUPAC名称)(1076)+TX、除虫脲(250)+TX、二羟丙茶碱(dilor)(别名)[CCN]+TX、四氟甲醚菊酯[CCN]+TX、甲氟磷(1081)+TX、地麦威(1085)+TX、乐果(262)+TX、苄菊酯(1083)+TX、甲基毒虫畏(265)+TX、敌蝇威(1086)+TX、消螨酚(1089)+TX、消螨酚-diclexine(1089)+TX、丙硝酚(1093)+TX、戊硝酚(1094)+TX、达诺杀(1095)+TX、呋虫胺(271)+TX、苯虫醚(1099)+TX、蔬果磷(1100)+TX、二氧威(1101)+TX、敌恶磷(1102)+TX、乙拌磷(278)+TX、苯噻乙双硫磷(dithicrofos)(1108)+TX、DNOC(282)+TX、多拉克汀(别名)[CCN]+TX、DSP(1115)+TX、蜕皮激素(别名)[CCN]+TX、EI1642(研究代码)(1118)+TX、甲氧基阿维菌素(291)+TX、甲氧基阿维菌素苯甲酸盐(291)+TX、EMPC(1120)+TX、烯炔菊酯(292)+TX、硫丹(294)+TX、因毒磷(1121)+TX、异狄氏剂(1122)+TX、EPBP(1123)+TX、EPN(297)+TX、保幼醚(1124)+TX、依立诺克丁(别名)[CCN]+TX、高氰戊菊酯(302)+TX、牛津郡丙硫磷(etaphos)(别名)[CCN]+TX、乙硫苯威(308)+TX、乙硫磷(309)+TX、乙虫腈(310)+TX、益硫磷-甲基(1134)+TX、灭线磷(312)+TX、甲酸乙酯(IUPAC名称)[CCN]+TX、乙基-DDD(别名)(1056)+TX、二溴化乙烯(316)+TX、二氯化乙烯(化学名称)(1136)+TX、环氧乙烷[CCN]+TX、醚菊酯(319)+TX、乙嘧硫磷(1142)+TX、EXD(1143)+TX、氨磺磷(323)+TX、苯线磷(326)+TX、抗螨唑(1147)+TX、皮蝇磷(1148)+TX、苯硫威(1149)+TX、芬氟司林(1150)+TX、杀螟硫磷(335)+TX、丁苯威(336)+TX、嘧酰虫胺(fenoxacrim)(1153)+TX、苯氧威(340)+TX、吡氯氰菊酯(1155)+TX、甲氰菊酯(342)+TX、吡螨胺(fenpyrad)(别名)+TX、丰索磷(1158)+TX、倍硫磷(346)+TX、倍硫磷-乙基[CCN]+TX、氰戊菊酯(349)+TX、氟虫腈(354)+TX、氟啶虫酰胺(358)+TX、氟虫酰胺(CAS登记号:272451-65-7)+TX、flucofuron(1168)+TX、氟环脲(366)+TX、氟氰戊菊酯(367)+TX、联氟螨(1169)+TX、嘧虫胺[CCN]+TX、氟虫脲(370)+TX、三氟醚菊酯(1171)+TX、氟氯苯菊酯(372)+TX、氟胺氰菊酯(1184)+TX、FMC1137(研究代码)(1185)+TX、地虫磷(1191)+TX、伐虫脒(405)+TX、伐虫脒盐酸盐(405)+TX、安硫磷(1192)+TX、藻螨威(formparanate)(1193)+TX、丁苯硫磷(1194)+TX、福司吡酯(1195)+TX、噻唑酮磷(408)+TX、丁硫环磷(1196)+TX、呋线威(412)+TX、抗虫菊(1200)+TX、γ-氯氟氰菊酯(197)+TX、γ-HCH(430)+TX、双胍盐(422)+TX、双胍醋酸盐(422)+TX、GY-81(研究代码)(423)+TX、苄螨醚(424)+TX、氯虫酰肼(425)+TX、HCH(430)+TX、HEOD(1070)+TX、飞布达(1211)+TX、庚烯磷(432)+TX、速杀硫磷[CCN]+TX、氟铃脲(439)+TX、HHDN(864)+TX、氟蚁腙(443)+TX、氢氰酸(444)+TX、烯虫乙酯(445)+TX、hyquincarb(1223)+TX、吡虫啉(458)+TX、炔咪菊酯(460)+TX、茚虫威(465)+TX、碘甲烷(IUPAC名称)(542)+TX、IPSP(1229)+TX、氯唑磷(1231)+TX、碳氯灵(1232)+TX、水胺硫磷(别名)(473)+TX、异艾氏剂(1235)+TX、异柳磷(1236)+TX、移栽灵(1237)+TX、异丙威(472)+TX、O-(甲氧基氨基硫代磷酰基)水杨酸异丙酯(IUPAC名称)(473)+TX、稻瘟灵(474)+TX、异拌磷(1244)+TX、恶唑磷(480)+TX、伊维菌素(别名)[CCN]+TX、茉酮菊素I(696)+TX、茉酮菊素II(696)+TX、碘硫磷(1248)+TX、保幼激素I(别名)[CCN]+TX、保幼激素II(别名)[CCN]+TX、保幼激素III(别名)[CCN]+TX、氯戊环(1249)+TX、烯虫炔酯(484)+TX、γ-三氯氟氰菊酯(198)+TX、砷酸铅[CCN]+TX、雷皮菌素(CCN)+TX、对溴磷(1250)+TX、林旦(430)+TX、lirimfos(1251)+TX、虱螨脲(490)+TX、噻唑磷(1253)+TX、间异丙基苯基甲基氨基甲酸酯(IUPAC名称)(1014)+TX、磷化镁(IUPAC名称)(640)+TX、马拉硫磷(492)+TX、特螨腈(1254)+TX、叠氮磷(1255)+TX、灭蚜磷(502)+TX、四甲磷(1258)+TX、灭蚜硫磷(1260)+TX、地安磷(1261)+TX、氯化亚汞(513)+TX、mesulfenfos(1263)+TX、氰氟虫腙(CCN)+TX、威百亩(519)+TX、威百亩钾(别名)(519)+TX、威百亩钠(519)+TX、虫螨畏(1266)+TX、甲胺磷(527)+TX、甲烷磺酰氟(IUPAC/化学文摘名称)(1268)+TX、杀扑磷(529)+TX、灭虫威(530)+TX、杀虫乙烯磷(1273)+TX、灭多威(531)+TX、烯虫酯(532)+TX、甲喹丁(1276)+TX、甲醚菊酯(别名)(533)+TX、甲氧滴滴涕(534)+TX、甲氧苯酰(535)+TX、溴甲烷(537)+TX、异硫氰酸甲酯(543)+TX、甲基氯仿(别名)[CCN]+TX、二氯甲烷[CCN]+TX、甲氧苄氟菊酯[CCN]+TX、速灭威(550)+TX、恶虫酮(1288)+TX、速灭磷(556)+TX、兹克威(1290)+TX、密灭汀(557)+TX、米尔倍霉素(别名)[CCN]+TX、丙胺氟磷(1293)+TX、灭蚁灵(1294)+TX、久效磷(561)+TX、茂硫磷(1300)+TX、莫昔克丁(别名)[CCN]+TX、萘酞磷(别名)[CCN]+TX、二溴磷(567)+TX、萘(IUPAC/化学文摘名称)(1303)+TX、NC-170(研究代码)(1306)+TX、NC-184(化合物代码)+TX、烟碱(578)+TX、硫酸烟碱(578)+TX、氟蚁灵(1309)+TX、烯啶虫胺(579)+TX、硝乙脲噻唑(nithiazine)(1311)+TX、戊氰威(1313)+TX、戊氰威1:1氯化锌络合物(1313)+TX、NNI-0101(化合物代码)+TX、NNI-0250(化合物代码)+TX、降烟碱(传统名称)(1319)+TX、双苯氟脲(585)+TX、多氟脲(586)+TX、O-5-二氯-4-碘苯基O-乙基乙基硫代膦酸酯(IUPAC名称)(1057)+TX、O,O-二乙基O-4-甲基-2-氧代-2H-色烯-7-基硫代膦酸酯(IUPAC名称)(1074)+TX、O,O-二乙基O-6-甲基-2-丙基嘧啶-4-基硫代膦酸酯(IUPAC名称)(1075)+TX、O,O,O',O'-四丙基二硫代焦磷酸酯(IUPAC名称)(1424)+TX、油酸(IUPAC名称)(593)+TX、氧化乐果(594)+TX、杀线威(602)+TX、砜吸磷-甲基(609)+TX、异亚砜磷(1324)+TX、砜拌磷(1325)+TX、pp'-DDT(219)+TX、对-二氯苯[CCN]+TX、对硫磷(615)+TX、对硫磷-甲基(616)+TX、氟幼脲(别名)[CCN]+TX、五氯苯酚(623)+TX、月桂酸五氯苯基酯(IUPAC名称)(623)+TX、氯菊酯(626)+TX、石油油料类(别名)(628)+TX、PH60-38(研究代码)(1328)+TX、芬硫磷(1330)+TX、苯醚菊酯(630)+TX、稻丰散(631)+TX、甲拌磷(636)+TX、伏杀硫磷(637)+TX、硫环磷(1338)+TX、亚胺硫磷(638)+TX、对氯硫磷(1339)+TX、磷胺(639)+TX、磷化氢(IUPAC名称)(640)+TX、辛硫磷(642)+TX、辛硫磷-甲基(1340)+TX、pirimetaphos(1344)+TX、抗蚜威(651)+TX、虫螨磷-乙基(1345)+TX、虫螨磷-甲基(652)+TX、聚氯二环戊二烯异构体类(IUPAC名称)(1346)+TX、聚氯萜类(传统名称)(1347)+TX、亚砷酸钾[CCN]+TX、硫氰酸钾[CCN]+TX、丙炔菊酯(655)+TX、早熟素I(别名)[CCN]+TX、早熟素II(别名)[CCN]+TX、早熟素III(别名)[CCN]+TX、乙酰嘧啶磷(primidophos)(1349)+TX、丙溴磷(662)+TX、丙氟菊酯[CCN]+TX、蜱虱威(1354)+TX、猛杀威(1355)+TX、丙虫磷(1356)+TX、胺丙畏(673)+TX、残杀威(678)+TX、乙噻唑磷(1360)+TX、丙硫磷(686)+TX、发硫磷(1362)+TX、protrifenbute[CCN]+TX、吡蚜酮(688)+TX、吡唑硫磷(689)+TX、定菌磷(693)+TX、pyresmethrin(1367)+TX、除虫菊酯I(696)+TX、除虫菊酯II(696)+TX、除虫菊酯类(696)+TX、哒螨灵(699)+TX、啶虫丙醚(700)+TX、哒嗪硫磷(701)+TX、嘧螨醚(706)+TX、嘧硫磷(1370)+TX、吡丙醚(708)+TX、苦木提取物(quassia)(别名)[CCN]+TX、喹硫磷(quinalphos)(711)+TX、喹硫磷-甲基(1376)+TX、畜宁磷(1380)+TX、喹硫磷(quintiofos)(1381)+TX、R-1492(研究代码)(1382)+TX、雷复尼特(别名)[CCN]+TX、苄呋菊酯(719)+TX、鱼藤酮(722)+TX、RU15525(研究代码)(723)+TX、RU25475(研究代码)(1386)+TX、尼亚那(ryania)(别名)(1387)+TX、利阿诺定(传统名称)(1387)+TX、沙巴藜芦(别名)(725)+TX、八甲磷(1389)+TX、硫线磷(别名)+TX、塞拉菌素(别名)[CCN]+TX、SI-0009(化合物代码)+TX、SI-0205(化合物代码)+TX、SI-0404(化合物代码)+TX、SI-0405(化合物代码)+TX、氟硅菊酯(728)+TX、SN72129(研究代码)(1397)+TX、亚砷酸钠[CCN]+TX、氰化钠(444)+TX、氟化钠(IUPAC/化学文摘名称)(1399)+TX、六氟硅酸钠(1400)+TX、五氯酚钠(623)+TX、硒酸钠(IUPAC名称)(1401)+TX、硫氰酸钠[CCN]+TX、苏硫磷(1402)+TX、多杀菌素(737)+TX、螺甲螨酯(739)+TX、螺虫乙酯(spirotetrmat)[CCN]+TX、sulcofuron(746)+TX、sulcofuron-sodium(746)+TX、氟虫胺(750)+TX、治螟磷(753)+TX、氟啶虫胺腈[CCN]+TX、磺酰氟(756)+TX、硫丙磷(1408)+TX、焦油类(别名)(758)+TX、τ-氟胺氰菊酯(398)+TX、噻螨威(1412)+TX、TDE(1414)+TX、虫酰肼(762)+TX、吡螨胺(763)+TX、丁基嘧啶磷(764)+TX、氟苯脲(768)+TX、七氟菊酯(769)+TX、双硫磷(770)+TX、TEPP(1417)+TX、环戊烯丙菊酯(1418)+TX、terbam(别名)+TX、特丁硫磷(773)+TX、四氯乙烷[CCN]+TX、杀虫畏(777)+TX、四甲菊酯(787)+TX、θ-氯氰菊酯(204)+TX、噻虫啉(791)+TX、thiafenox(别名)+TX、噻虫嗪(792)+TX、thicrofos(1428)+TX、克虫威(1431)+TX、杀虫环(798)+TX、杀虫环草酸氢盐(798)+TX、硫双威(799)+TX、久效威(800)+TX、甲基乙拌磷(801)+TX、虫线磷(1434)+TX、杀虫单(thiosultap)(803)+TX、杀虫双(thiosultap-sodium)(803)+TX、苏云金素(别名)[CCN]+TX、唑虫酰胺(809)+TX、四溴菊酯(812)+TX、四氟苯菊酯(813)+TX、transpermethrin(1440)+TX、威菌磷(1441)+TX、唑蚜威(818)+TX、三唑磷(820)+TX、唑呀威(别名)+TX、敌百虫(824)+TX、三氯甲基对硫磷-3(别名)[CCN]+TX、毒壤膦(1452)+TX、三氯丙氧磷(1455)+TX、杀铃脲(835)+TX、混杀威(840)+TX、烯虫硫酯(1459)+TX、蚜灭磷(847)+TX、vaniliprole[CCN]+TX、藜芦定(别名)(725)+TX、藜芦碱(别名)(725)+TX、XMC(853)+TX、灭杀威(854)+TX、YI-5302(化合物代码)+TX、zeta-氯氰菊酯(205)+TX、zetamethrin(别名)+TX、磷化锌(640)+TX、丙硫恶唑磷(zolaprofos)(1469)、以及ZXI8901(研究代码)(858)+TX,氰虫酰胺[736994-63-19]+TX、氯虫酰胺[500008-45-7]+TX、唑螨氰[560121-52-0]+TX、丁氟螨酯[400882-07-7]+TX、氟虫吡喹[337458-27-2]+TX、乙基多杀菌素[187166-40-1+187166-15-0]+TX、螺虫乙酯[203313-25-1]+TX、氟啶虫胺腈[946578-00-3]+TX、丁烯氟虫腈[704886-18-0]+TX、氯氟醚菊酯[915288-13-0]+TX、四氟醚菊酯[84937-88-2]+TX,
一种杀软体动物剂,该杀软体动物剂选自由以下物质组成的组:二(三丁基锡)氧化物(IUPAC名称)(913)+TX、溴乙酰胺[CCN]+TX、砷酸钙[CCN]+TX、除线威(cloethocarb)(999)+TX、乙酰亚砷酸铜[CCN]+TX、硫酸铜(172)+TX、三苯锡(347)+TX、磷酸铁(IUPAC名称)(352)+TX、四聚乙醛(518)+TX、灭虫威(530)+TX、氯硝柳胺(576)+TX,氯硝柳胺乙醇胺盐(576)+TX、五氯酚(623)+TX、五氯苯氧化钠(623)+TX、噻螨威(tazimcarb)(1412)+TX、硫双威(799)+TX、三丁基氧化锡(913)+TX、杀螺吗啉(trifenmorph)(1454)+TX、混杀威(trimethacarb)(840)+TX、醋酸三苯基锡(IUPAC名称)(347)和三苯基氢氧化锡(IUPAC名称)(347)+TX、皮瑞普(pyriprole)[394730-71-3]+TX,
一种杀线虫剂,该杀线虫剂选自由以下物质组成的组:AKD-3088(化合物代码)+TX、1,2-二溴-3-氯丙烷(IUPAC/化学文摘名)(1045)+TX、1,2-二氯丙烷(IUPAC/化学文摘名)(1062)+TX、1,2-二氯丙烷与1,3-二氯丙烯(IUPAC名称)(1063)+TX、1,3-二氯丙烯(233)+TX、3,4-二氯四氢噻吩1,1-二氧化物(IUPAC/化学文摘名)(1065)+TX、3-(4-氯苯基)-5-甲基绕丹宁(IUPAC名称)(980)+TX、5-甲基-6-硫代-1,3,5-噻二嗪烷-3-基乙酸(IUPAC名称)(1286)+TX、6-异戊烯基氨基嘌呤(别名)(210)+TX、阿维菌素(1)+TX、乙酰虫腈[CCN]+TX、棉铃威(15)+TX、涕灭威(aldicarb)(16)+TX、涕灭砜威(aldoxycarb)(863)+TX、AZ60541(化合物代码)+TX、benclothiaz[CCN]+TX、苯茵灵(62)+TX、丁基哒螨酮(butylpyridaben)(别名)+TX、硫线磷(cadusafos)(109)+TX、克百威(carbofuran)(118)+TX、二硫化碳(945)+TX、丁硫克百威(119)+TX、氯化苦(141)+TX、毒死蜱(145)+TX、除线威(cloethocarb)(999)+TX、细胞分裂素(cytokinins)(别名)(210)+TX,棉隆(216)+TX、DBCP(1045)+TX、DCIP(218)+TX、除线特(diamidafos)(1044)+TX、除线磷(dichlofenthion)(1051)+TX、二克磷(dicliphos)(别名)+TX、乐果(262)+TX、依马克丁(别名)[CCN]+TX、依马克丁苯甲酸酯(291)+TX、依立诺克丁(291)+TX、(别名)[CCN]+TX312)+TX、二溴乙烷(316)+TX、苯线磷(fenamiphos)(326)+TX、吡螨胺(别名)+TX、丰索磷(fenpyrad)(1158)+TX、噻唑磷(fosthiazate)(408)+TX、丁硫环磷(fosthietan)(1196)+TX、糠醛(别名)[CCN]+TX、GY-81(研究代码)(423)+TX、速杀硫磷(heterophos)[CCN]+TX、碘甲烷(IUPAC名称)(542)+TX、isamidofos(1230)+TX、氯唑磷(isazofos)(1231)+TX、激动素(kinetin)(别名)[CCN]+TX、糠氨基嘌呤(mecarphon)(别名)(210)+TX、甲基灭蚜磷(mecarphon)(1258)+TX、威百亩(519)+TX、威百亩钾盐(别名)(519)+TX、威百亩钠盐(519)+TX、溴甲烷(537)+TX、异硫氰酸甲酯(543)+TX、杀螨菌素肟(milbemycin oxime)(别名)[CCN]+TX、莫昔克丁(剔名)[CCN]+TX、疣孢漆斑茵(Myrothecium verrucaria)组分(别名)(565)+TX、NC-184(化合物代码)+TX、杀线威(602)+TX、甲拌磷(636)+TX、磷胺(639)+TX、磷虫威(phosphocarb)[CCN]+TX、硫线磷(sebufos)(别名)+TX、塞拉菌素(selamectin)(别名)[CCN]+TX、多杀菌素(737)+TX、叔丁威(terbam)(别名)+TX、特丁磷(terbufos)(773)+TX、四氯噻吩(IUPAC/化学文摘名)(1422)+TX、thiaf enox(别名)+TX、虫线磷(thionazin)(1434)+TX、三唑磷(triazophos)(820)+TX、triazuron(别名)+TX、二甲苯酚[CCN]+TX、YI-5302(化合物代码)和玉米素(别名)(210)+TX、fluensulfone[318290-98-1]+TX,
一种硝化作用抑制剂,该硝化作用抑制剂选自由以下物质组成的组:乙基黄原酸钾[CCN]以及氯啶(nitrapyrin)(580)+TX,
一种植物激活剂,该植物激活剂选自由以下物质组成的组:噻二唑素(acibenzolar)(6)+TX、噻二唑素-S-甲基(6)+TX、烯丙苯噻唑(probenazole)(658)和大虎杖(Reynoutria sachalinensis)提取物(别名)(720)+TX,
一种杀鼠剂,该杀鼠剂选自由以下物质组成的组:2-异戊酰茚满-1,3-二酮(IUPAC名称)(1246)+TX、4-(喹喔啉-2-基氨基)苯磺酰胺(IUPAC名称)(748)+TX、α-氯代醇[CCN]+TX、磷化铝(640)+TX、安妥(880)+TX、三氧化二砷(882)+TX、碳酸钡(891)+TX、双鼠脲(912)+TX、溴鼠隆(89)+TX、溴敌隆(91)+TX、溴鼠胺(92)+TX、氰化钙(444)+TX、氮醛糖(127)+TX、氯鼠酮(140)+TX、维生素D3(别名)(850)+TX、氯灭鼠灵(1004)+TX、克灭鼠(1005)+TX、杀鼠萘(175)+TX、杀鼠嘧啶(1009)+TX、鼠得克(246)+TX、噻鼠灵(249)+TX、敌鼠钠(273)+TX、维生素D2(301)+TX、氟鼠灵(357)+TX、氟乙酰胺(379)+TX、鼠朴定(1183)+TX、盐酸鼠朴定(1183)+TX、β-HCH(430)+TX、HCH(430)+TX、氢氰酸(444)+TX、碘代甲烷(IUPAC名称)(542)+TX、林旦(430)+TX、磷化镁(IUPAC名称)(640)+TX、甲基溴(537)+TX、鼠特灵(1318)+TX、毒鼠磷(1336)+TX、磷化氢(IUPAC名称)(640)+TX、磷[CCN]+TX、杀鼠酮(1341)+TX、亚砷酸钾[CCN]+TX、灭鼠优(1371)+TX、海葱糖苷(1390)+TX、亚砷酸钠[CCN]+TX、氰化钠(444)+TX、氟乙酸钠(735)+TX、士的宁(745)+TX、硫酸铊[CCN]+TX、杀鼠灵(851)以及磷化锌(640)+TX,
一种增效剂,该增效剂选自由以下物质组成的组:2-(2-丁氧基乙氧基)乙基胡椒基酯(IUPAC名称)(934)+TX、5-(1,3-苯并二氧杂环戊烯-5-基)-3-己基环己-2-烯酮(IUPAC名称)(903)+TX、具有橙花叔醇的法呢醇(别名)(324)+TX、MB-599(研究代码)(498)+TX、MGK264(研究代码)(296)+TX,增效醚(piperonyl butoxide)(649)+TX、增效醛(piprotal)(1343)+TX、增效酯(propyl isomer)(1358)+TX、S421(研究代码)(724)+TX、增效散(sesamex)(1393)+TX、sesasmolin(1394)和亚砜(1406)+TX,
一种动物驱避剂,该动物驱避剂选自由以下物质组成的组:蒽醌(32)+TX、氯醛糖(127)+TX、环烷酸铜[CCN]+TX、王铜(171)+TX、二嗪磷(227)+TX、二环戊二烯(化学名称)(1069)+TX、双胍盐(guazatine)(422)+TX、双胍醋酸盐(422)+TX、灭虫威(530)+TX、吡啶-4-胺(IUPAC名称)(23)+TX、塞仑(804)+TX、混杀威(trimethacarb)(840)+TX、环烷酸锌[CCN]和福美锌(856)+TX,
一种杀病毒剂,该杀病毒剂选自由以下物质组成的组:衣马宁(imanin)(别名)[CCN]和利巴韦林(别名)[CCN]+TX,
一种创伤保护剂,该创伤保护剂选自由以下物质组成的组:氧化汞(512)+TX、辛噻酮(octhilinone)(590)和甲基硫茵灵(802)+TX,
以及生物活性的化合物,该化合物选自由以下物质组成的组:阿扎康唑(60207-31-0]+TX、联苯三唑醇[70585-36-3]+TX、糠菌唑[116255-48-2]+TX、环唑醇[94361-06-5]+TX、苯醚甲环唑[119446-68-3]+TX、烯唑醇[83657-24-3]+TX、氟环唑[106325-08-0]+TX、腈苯唑[114369-43-6]+TX、氟喹唑[136426-54-5]+TX、氟硅唑[85509-19-9]+TX、粉唑醇[76674-21-0]+TX、己唑醇[79983-71-4]+TX、抑霉唑[35554-44-0]+TX、亚胺唑[86598-92-7]+TX、种菌唑[125225-28-7]+TX、叶菌唑[125116-23-6]+TX、腈菌唑[88671-89-0]+TX、稻瘟酯[101903-30-4]+TX、戊菌唑[66246-88-6]+TX、丙硫菌唑[178928-70-6]+TX、啶斑肟(pyrifenox)[88283-41-4]+TX、丙氯灵[67747-09-5]+TX、丙环唑[60207-90-1]+TX、硅氟唑(simeconazole)[149508-90-7]+TX、戊唑醇[107534-96-3]+TX、氟醚唑[112281-77-3]+TX、三唑酮[43121-43-3]+TX、三唑酮[55219-65-3]+TX、氟菌唑[99387-89-0]+TX、灭菌唑[131983-72-7]+TX、三环苯嘧醇[12771-68-5]+TX、氯苯嘧啶醇[60168-88-9]+TX、氟氯苯嘧啶醇[63284-71-9]+TX、乙嘧酚磺酸酯(bupirimate)[41483-43-6]+TX、甲菌定(dimethirimol)[5221-53-4]+TX、乙菌定(ethirimol)[23947-60-6]+TX、十二环吗啉[1593-77-7]+TX、苯锈啶(fenpropidine)[67306-00-7]+TX、丁苯吗啉[67564-91-4]+TX、螺环菌胺[118134-30-8]+TX、十三吗啉[81412-43-3]+TX、嘧菌环胺[121552-61-2]+TX、嘧菌胺[110235-47-7]+TX、嘧霉胺(pyrimethanil)[53112-28-0]+TX、拌种咯[74738-17-3]+TX、咯菌腈(fludioxonil)[131341-86-1]+TX、苯霜灵(benalaxyl)[71626-11-4]+TX、呋霜灵(furalaxyl)[57646-30-7]+TX、甲霜灵[57837-19-1]+TX、R-甲霜灵[70630-17-0]+TX、呋酰胺[58810-48-3]+TX、恶霜灵(Oxadixyl)[77732-09-3]+TX、苯菌灵[17804-35-2]+TX、多菌灵[10605-21-7]+TX、咪菌威(debacarb)[62732-91-6]+TX、麦穗宁[3878-19-1]+TX、噻苯达唑[148-79-8]+TX、乙菌利(chlozolinate)[84332-86-5]+TX、菌核利(dichlozoline)[24201-58-9]+TX、异菌脲(Iprodione)[36734-19-7]+TX、myclozoline[54864-61-8]+TX、腐霉利(procymidone)[32809-16-8]+TX、乙烯菌核利(vinclozoline)[50471-44-8]+TX、(S)-[3-(4-氯-2-氟-苯基)-5-(2,4-二氟-苯基)-异噁唑-4-基]-吡啶-3-基-甲醇(WO2010069881)+TX、3-(4-氯-2-氟-苯基)-5-(2,4-二氟-苯基)-异噁唑-4-基]-吡啶-3-基-甲醇(WO2010069881)+TX、啶酰菌胺(boscalid)[188425-85-6]+TX、萎锈灵[5234-68-4]+TX、甲呋酰苯胺[24691-80-3]+TX、氟酰胺(Flutolanil)[66332-96-5]+TX、灭锈胺[55814-41-0]+TX、氧化萎锈灵[5259-88-1]+TX、吡噻菌胺(penthiopyrad)[183675-82-3]+TX、噻呋菌胺[130000-40-7]+TX、双胍盐[108173-90-6]+TX、多果定(dodine)[2439-10-3][112-65-2](游离键)+TX、双胍辛胺(iminoctadine)[13516-27-3]+TX、嘧菌酯[131860-33-8]+TX、醚菌胺[149961-52-4]+TX、烯肟菌酯{Proc.BCPC,Int.Congr.,Glasgow.2003,1,93}+TX、氟嘧菌酯[361377-29-9]+TX甲基醚菌酯[143390-89-0]+TX、苯氧菌胺[133408-50-1]+TX、肟菌酯[141517-21-7]+TX、肟醚菌胺[248593-16-0]+TX、啶氧菌酯[117428-22-5]+TX、唑菌胺酯[175013-18-0]+TX、福美铁[14484-64-1]+TX、代森锰锌[8018-01-7]+TX、代森锰[12427-38-2]+TX、代森联[9006-42-2]+TX、甲代森锌(propineb)[12071-83-9]+TX、塞仑[137-26-8]+TX、代森锌[12122-67-7]+TX、福美锌[137-30-4]+TX、敌菌丹(captafol)[2425-06-1]+TX、克菌丹[133-06-2]+TX、苯氟磺胺[1085-98-9]+TX、唑啶草(fluoroimide)[41205-21-4]+TX、灭菌丹[133-07-3]+TX、甲苯氟磺胺[731-27-1]+TX、波尔多(bordeaux)混合物[8011-63-0]+TX、氢氧化铜(copperhydroxid)[20427-59-2]+TX、氯化铜(copperoxychlorid)[1332-40-7]+TX、硫酸铜(coppersulfat)[7758-98-7]+TX、氧化铜(copperoxid)[1317-39-1]+TX、代森锰铜(mancopper)[53988-93-5]+TX、喹啉铜(oxine-copper)[10380-28-6]+TX、敌螨普(dinocap)[131-72-6]+TX、酞菌酯(nitrothal-isopropyl)[10552-74-6]+TX、克瘟散[17109-49-8]+TX、异稻瘟净(iprobenphos)[26087-47-8]+TX、稻瘟灵(isoprothiolane)[50512-35-1]+TX、氯瘟磷(phosdiphen)[36519-00-3]+TX、克菌磷(pyrazophos)[13457-18-6]+TX、甲基托氯磷(tolclofos-methyl)[57018-04-9]+TX、苯并噻二唑(acibenzolar-S-methyl)[135158-54-2]+TX、敌菌灵[101-05-3]+TX、苯噻菌胺[413615-35-7]+TX、灭瘟素(blasticidin)-S[2079-00-7]+TX、灭螨猛(chinomethionat)[2439-01-2]+TX、地茂散(chloroneb)[2675-77-6]+TX、百菌清[1897-45-6]+TX、环氟菌胺[180409-60-3]+TX、霜脲氰[57966-95-7]+TX、二氯萘醌(dichlone)[117-80-6]+TX、双氯氰菌胺(diclocymet)[139920-32-4]+TX、哒菌酮(diclomezine)[62865-36-5]+TX、氯硝胺(dicloran)[99-30-9]+TX、乙霉威(diethofencarb)[87130-20-9]+TX、烯酰吗啉[110488-70-5]+TX、SYP-LI90(Flumorph)[211867-47-9]+TX、二噻农(dithianon)[3347-22-6]+TX、噻唑菌胺(ethaboxam)[162650-77-3]+TX、土菌灵(etridiazole)[2593-15-9]+TX、恶唑菌酮[131807-57-3]+TX、咪唑菌酮(fenamidone)[161326-34-7]+TX、稻瘟酰胺(Fenoxanil)[115852-48-7]+TX、三苯锡(fentin)[668-34-8]+TX、嘧菌腙(ferimzone)[89269-64-7]+TX、氟啶胺(fluazinam)[79622-59-6]+TX、氟吡菌胺(fluopicolide)[239110-15-7]+TX、磺菌胺(flusulfamide)[106917-52-6]+TX、环酰菌胺[126833-17-8]+TX、福赛得(fosetyl-aluminium)[39148-24-8]+TX、恶霉灵(hymexazol)[10004-44-1]+TX、丙森锌[140923-17-7]+TX、IKF-916(赛座灭(Cyazofamid))[120116-88-3]+TX、春雷霉素(kasugamycin)[6980-18-3]+TX、磺菌威(methasulfocarb)[66952-49-6]+TX、苯菌酮[220899-03-6]+TX、戊菌隆(pencycuron)[66063-05-6]+TX、苯酞[27355-22-2]+TX、多氧霉素(polyoxins)[11113-80-7]+TX、噻菌灵(probenazole)[27605-76-1]+TX、百维威(propamocarb)[25606-41-1]+TX、碘喹唑酮(proquinazid)[189278-12-4]+TX、乐喹酮(pyroquilon)[57369-32-1]+TX、喹氧灵[124495-18-7]+TX、五氯硝苯[82-68-8]+TX、硫[7704-34-9]+TX、噻酰菌胺[223580-51-6]+TX、咪唑嗪(triazoxide)[72459-58-6]+TX、三环唑[41814-78-2]+TX、嗪氨灵[26644-46-2]+TX、有效霉素[37248-47-8]+TX、苯酰菌胺(zoxamide)(RH7281)[156052-68-5]+TX、双炔酰菌胺(mandipropamid)[374726-62-2]+TX、吡蚜酮(isopyrazam)[881685-58-1]+TX、sedaxane[874967-67-6]+TX、3-二氟甲基-1-甲基-1H-吡唑-4-羧酸(9-二氯亚甲基-1,2,3,4-四氢-1,4-桥亚甲基-萘-5-基)-酰胺(在WO2007/048556中披露的)+TX、3-二氟甲基-1-甲基-1H-吡唑-4-羧酸[2-(2,4-二氯苯基)-2-甲氧基-1-甲基-乙基]-酰胺(在中WO2008/148570披露的)+TX、1-[4-[4-[(5S)5-(2,6-二氟苯基)-4,5-二氢-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+TX、1-[4-[4-[5-(2,6-二氟苯基)-4,5-二氢-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[1003318-67-9],两者均在WO2010/123791、WO2008/013925、WO2008/013622和WO2011/051243中第20页披露)+TX、3-二氟甲基-1-甲基-1H-吡唑-4-羧酸(3’,4’,5’-三氟-二苯-2-基)-酰胺(披露在WO2006/087343中)+TX。
已经发现,与组分TX组合使用组分(B)出人意料地并且实质地可以增强组分TX针对真菌的效果,反之亦然。此外,本发明的方法针对更宽的此类真菌谱是有效的,当单独使用时,这一方法的活性成分可以对抗这些真菌。
总体而言,组分TX与组分(B)的重量比是从2000:1至1:1000。此类重量比的一个非限制性实例是,具有化学式I的化合物:具有化学式B-2的化合物为10:1。组分TX与组分(B)的重量比优选是从100:1至1:100;更优选是从20:1至1:50。
组分TX与组分(B)的活性成分混合物包括具有化学式I的化合物以及一种另外的、其他杀生物活性成分或组合物或者如果希望的话包括一种优选地以下面混合比的固体或液体佐剂:从1000:1至1:1000,尤其是从50:1至1:50,更尤其是以从20:1至1:20的比率,更尤其是以从10:1至1:10的比率,非常尤其是以从5:1与1:5的比率,尤其优选项是从2:1至1:2的比率,并且从4:1至2:1的比率同样是优选的,最重要的是1:1、或5:1、或5:2、或5:3、或5:4、或4:1、或4:2、或4:3、或3:1、或3:2、或2:1、或1:5、或2:5、或3:5、或4:5、或1:4、或2:4、或3:4、或1:3、或2:3、或1:2、或1:600、或1:300、或1:150、或1:35、或2:35、或4:35、或1:75、或2:75、或4:75、或1:6000、或1:3000、或1:1500、或1:350、或2:350、或4:350、或1:750、或2:750、或4:750的比率。那些混合比率被理解为包括,一方面是重量比,并且还有另一方面是摩尔比。
已经发现,出人意料地,组分TX与组分(B)的某些重量比能够提高协同活性。因此,本发明的一个另外的方面是组合物,其中组分TX和组分(B)以产生协同效应的量存在于该组合物中。该协同活性从以下事实中是明显的:包括组分TX和组分(B)的组合物的杀真菌活性大于组分TX和组分(B)的杀真菌活性之和。该协同活性以两种方式延伸了组分TX和组分(B)的作用范围。第一,组分TX和组分(B)的施用比率降低了,同时其作用保持同样地好,这意味着甚至在这样一种低施用比率范围中,这两种单独的组分已经变得总体无效的情况下,该活性成分混合物仍达到高度的植物病原菌控制。第二,存在可以被控制的植物病原菌谱的实质性扩展。
存在一种协同效应,无论何时,活性成分组合的作用大于单独组分的作用之和。对于给定的活性成分组合,预期的作用E服从所谓的科尔比(COLBY)公式并且可以按以下进行计算(科尔比(COLBY),S.R.,“alculating synergistic and antagonistic responses of herbicide combination”(“计算除草剂组合的协同和拮抗反应”):
ppm=每升喷洒混合物的活性成分(=a.i.)的毫克数
X=活性成分A)的%作用,使用p ppm的活性成分
Y=活性成分B)的%作用,使用q ppm的活性成分。
如果实际观察到的(O)作用大于预期的作用(E),那么该组合的作用是超级加性的,即存在一种协同效应。在数学方面,协同作用对应于(O-E)的差的正值。在纯互补性添加活性物(期待的活性)的情况下,所述差(O-E)为零。所述差(O-E)的负值标志着与期待的活性相比,活性的损失。
然而,除了相对于杀真菌活性的实际协同作用外,根据本发明的组合物还可以具有另外的出人意料的有利特性。可以提及的此类有利的特性的实例是:更有利的可降解性;改进的毒理学的和/或生态毒理学的行为;或有用的植物的改进的特征,包括:出苗、作物产量、根系统更发达、分蘖增加、株高增加、叶片更大、基部叶片死亡更少、分蘖更强、叶子颜色更绿、所需肥料更少、所需种子更少、分蘖更多产、开花更早、谷粒成熟更早、植物倒伏(伏到(lodging))更少、芽生长增强、改进的植物活力以及发芽早。
根据本发明的一些组合物具有一种内吸作用并且可以被用作叶、土壤、以及种子处理的杀真菌剂。
使用根据本发明的组合物,有可能抑制或破坏致植物病的微生物,这些微生物发生于多种不同的有用植物的植物或植物部分(果实、花、叶子、茎、块茎、根),同时还保护了稍后生长的植物部分免于被致植物病的微生物侵袭。
根据本发明的组合物可以被施用至致植物病的微生物、有用植物、其场所、其繁殖材料、储存货物或受微生物攻击威胁的工业材料。
可以在有用植物、其繁殖材料、储存货物或工业材料被微生物感染之前或之后施用根据本发明的组合物。
本发明的一个另外方面是控制在有用植物上或在其繁殖材料上由植物病原菌引起的疾病的方法,它包括将根据本发明的组合物施用至这些有用植物、其场所或其繁殖材料。优选的是以下方法,它包括将根据本发明的组合物施用至这些有用植物或至其场所,更优选地是施用至这些有用植物。另外优选的是以下方法,它包括将根据本发明的组合物施用至这些有用植物的繁殖材料。
贯穿本文件,表述“组合物”代表组分TX和(B)的不同混合物或组合,例如以一种单一的“掺水即用”的形式,以组合的喷洒混合物(该混合物由这些单一活性成分的单独配制品构成)(例如一种“桶混制剂”),以及当以一种顺序的方式(即,一个在另一个的适当短的时期之后,例如几小时或几天)施用时,以这些单独活性成分的组合使用。对于使本发明工作,施用组分TX和(B)的顺序并不是必要的。
根据本发明的组合物还可以包括多于一种的活性组分(B),例如,如果希望扩展疾病控制谱。例如,在农业实践中将两种或三种组分(B)与组分TX组合可以是有利的。一个实例是一种组合物,该组合物包括具有化学式(I)的化合物、嘧菌酯和环唑醇。
尽管优选地是将商用的产品配制为浓缩物,最终的使用者通常使用稀释的配制品。
有利的施用比率通常是从5g至2kg的活性成分(a.i.)/公顷(ha),优选地从10g至1kg a.i./ha,最优选地从20g至600g a.i./ha。在用作种子浸湿剂时,方便的施用比率是从10mg至1g的活性物质/kg的种子。可以通过试验确定用于所希望的作用的施用比率。它取决于例如作用类型、该有用植物的发育阶段以及施用(地点、时间安排、施用方法),并且可以由于这些参数在宽泛的限制内变化。
以上说明的具有化学式(I)的化合物或其一种药物盐还可以具有有利的对于处理和/或预防动物中的微生物侵染的活性谱。“动物”可以是任何动物,例如昆虫、哺乳动物、爬行动物、鱼、两栖动物,优选是哺乳动物,最优选是人类。“处理”意思是对具有微生物侵染的动物使用以降低或减慢或停止该侵染的增大或扩散,或降低该侵染或治疗该侵染。“预防”意思是对没有明显的微生物侵染迹象的动物使用以预防任何将来的侵染,或降低或减慢任何将来的侵染的增大或扩散。
根据本发明,提供了具有化学式(I)的化合物在制造一种用于处理和/或预防动物中的微生物侵染的药物中的用途。还提供了具有化学式(I)的化合物作为一种药用试剂的用途。还提供了具有化学式(I)的化合物作为在动物处理中的一种抗微生物剂的用途。根据本发明,还提供了一种药用组合物,该组合物包括作为活性成分的一种具有化学式(I)的化合物,或其一种药学上可接受的盐,以及一种药学上可接受的稀释剂或载体。该组合物可以被用于处理和/或预防动物中的抗微生物侵染。该药用组合物可以处于一种适于口服给药的形式,例如片剂、锭剂、硬胶囊、水性悬浮液、油状的悬浮液、乳液、可分散粉剂、可分散的颗粒、糖浆和酏剂。可替代地,该药用组合物可以处于一种适于局部施用的形式,例如一种喷雾剂、膏状物或洗剂。可替代地,该药用组合物可以处于一种适于肠胃外给药(例如注射)的形式。可替代地,该药用组合物可以是处于可吸入形式,例如一种气溶胶喷雾剂。
具有化学式(I)的化合物针对多种能够引起动物内的微生物侵染的微生物物种是有效的。此类微生物物种的实例是引起曲霉病的那些,例如烟曲霉、黄曲霉、土曲霉、构巢曲霉和黑曲霉;引起芽生菌病的那些,例如皮炎芽生菌;引起念珠菌病的那些,例如白色念珠菌、光滑念珠菌、热带念珠菌、近平滑念珠菌、克柔念珠菌和葡萄牙念珠菌;引起球孢子菌病的那些,例如粗球孢子菌;引起隐球菌病的那些,例如新生隐球菌;引起组织胞浆菌病的那些,例如荚膜组织胞浆菌;以及引起接合菌病的那些,例如伞枝梨头霉、微小根毛霉和无根根霉。另外的实例是镰孢霉属物种,例如尖孢镰刀菌和茄病镰刀菌,以及足放线病菌属物种,例如尖端赛多孢子菌和多育赛多孢子菌。仍另外的实例是小孢子菌属物种、发癣菌属物种、表皮癣菌属物种、毛霉属物种、孢子丝菌属物种、瓶霉菌属物种、分支孢子菌属物种、霉样真霉属物种、副球孢子菌属物种和组织胞浆菌属物种。
以下非限制性的实例更详细地展示了以上描述的发明而非对其进行限制。
制备实例:
实例P1:2-[6-(6-氯吡啶-3-基甲基)-吡啶-2-基]-5,6,7,8-四氢喹唑啉的制
备:
a)2-(6-溴吡啶-2-基)-5,6,7,8-四氢喹唑啉的制备:
将甲醇钠(16.5g的在甲醇中的30%溶液)添加到6-溴代甲吡啶酰亚胺酰胺盐酸盐(bromopicolinimidamide hydrochloride)(在JP01052772中描述;6.4g,32mmol)在350ml甲醇中的溶液里。将该反应在室温搅拌30min,然后添加2-(二甲氨基)亚甲基-环己酮(在Tetrahedron(《四面体》)1994,50,2255中描述;14.1g,92mmol)并且将该反应混合物加热至回流,持续2h。将该混合物冷却,用水稀释并且用甲基叔丁基醚进行萃取。将合并的有机层用硫酸钠干燥,过滤并在真空中蒸发,将剩余物通过乙醚/己烷的结晶作用进行纯化,以给出呈黄色晶体的2-(6-溴吡啶-2-基)-5,6,7,8-四氢喹唑 啉,m.p.126°C-128°C。
b)将2-(6-溴吡啶-2-基)-5,6,7,8-四氢喹唑啉(150mg,0.5mmol)与双(三苯基膦)二氯化钯(II)(40mg,0.05mmol)在5ml的四氢呋喃中的混合物加热至回流。然后在该温度逐滴添加2-氯-5-吡啶基甲基氯化锌(1.1ml的在四氢呋喃中的0.5M溶液)。将该反应混合物加热至回流,持续另外一小时,然后冷却,倾倒入水中并且用乙酸乙酯进行萃取。将合并的有机层用盐水洗涤,用硫酸钠干燥、过滤并且在真空中进行蒸发。将该剩余物用硅胶柱层析(使用环己烷/二氯甲烷4:1作为洗脱液)进行纯化,以给出呈米色粉末状的2-[6-(6-氯吡啶-3-基甲基)-吡啶-2-基]-5,6,7,8-四氢喹唑啉,m.p.115°C-120°C。
实例P2:2-[6-(2-甲苄基)-吡啶-2-基]-7,8-二氢-5H-吡喃并[4,3-d]嘧啶的制
备:
a)2-(6-溴吡啶-2-基)-7,8-二氢-5H-吡喃并[4,3-d]嘧啶的制备:
将甲醇钠(3.6g的在甲醇中的30%溶液)添加到6-溴代甲吡啶酰亚胺酰胺盐酸盐(在JP01052772中描述;4.2g,18mmol)在35ml甲醇中的溶液里。将该反应在室温搅拌30min,然后添加3-(二甲氨基)亚甲基-2H-5,6-二氢吡喃-4-酮(在WO2004/060890中描述;3.3g,21mmol)并且将该反应混合物加热至回流,持续2h。将该混合物冷却,用水稀释并且用甲基叔丁基醚进行萃取。将合并的有机层用硫酸钠干燥,过滤并在真空中蒸发,将剩余物通过乙醚/己烷的结晶作用进行纯化,以给出呈棕色粉末状的2-(6-溴吡啶-2-基)-7,8-二氢-5H-吡喃并[4,3-d]嘧啶,m.p.156°C-158°C。
b)将2-(6-溴吡啶-2-基)-7,8-二氢-5H-吡喃并[4,3-d]嘧啶(120mg,0.41mmol)与双(三苯基膦)二氯化钯(II)(29mg,0.04mmol)在4ml的四氢呋喃中的混合物加热至回流。然后在该温度逐滴添加2-甲苄基氯化锌(0.95ml的在四氢呋喃中的0.5M溶液)。将该反应混合物加热至回流,持续另外一小时,然后冷却,倾倒入水中并且用乙酸乙酯进行萃取。将合并的有机层用盐水洗涤,用硫酸钠干燥、过滤并且在真空中进行蒸发。将该剩余物用硅胶柱层析(使用四氢呋喃/己烷1:1作为洗脱液)进行纯化,以给出呈黄色粉末状的2-[6-(2-甲苄基)-吡啶-2-基]-7,8-二氢-5H-吡喃并[4,3-d]嘧啶,m.p.132°C-133°C。
实例P3:2-[6-(2-甲氧苄基)-吡啶-2-基]-7,7-二甲基-5,6,7,8-四氢喹唑啉的
制备:
a)2-(6-溴吡啶-2-基)-7,7-二甲基-5,6,7,8-四氢喹唑啉的制备:
将甲醇钠(1.3g的在甲醇中的30%溶液)添加到6-溴代甲吡啶酰亚胺酰胺盐酸盐(在JP01052772中描述;1.5g,6.3mmol)在25ml甲醇中的溶液里。将该反应在室温搅拌30min,然后添加1-二甲氨基-亚甲基-5,5-二甲基-环己-2-酮(在Bull.Chem.Soc.Jpn.(《日本化学学会公报》)1987,60,3285中描述;1.4g,7.6mmol)并且将该反应混合物加热至回流,持续2h。将该混合物冷却,用水稀释并且用甲基叔丁基醚进行萃取。将合并的有机层用硫酸钠干燥,过滤并在真空中蒸发,将剩余物通过乙醚/己烷的结晶作用进行纯化,以给出呈灰色粉末状的2-(6-溴吡啶-2-基)-7,7-二甲基-5,6,7,8-四氢喹唑 啉,m.p.175°C-177°C。
b)将2-(6-溴吡啶-2-基)-7,7-二甲基-5,6,7,8-四氢喹唑啉(120mg,0.37mmol)与双(三苯基膦)二氯化钯(II)(29mg,0.04mmol)在4ml的四氢呋喃中的混合物加热至回流。然后在该温度逐滴添加2-甲氧苄基氯化锌(0.9ml的在四氢呋喃中的0.5M溶液)。将该反应混合物加热至回流,持续另外一小时,然后冷却,倾倒入水中并且用乙酸乙酯进行萃取。将合并的有机层用盐水洗涤,用硫酸钠干燥、过滤并且在真空中进行蒸发。将该剩余物用硅胶柱层析(使用四氢呋喃/己烷1:1作为洗脱液)进行纯化,以给出呈黄色粉末状的2-[6-(2-甲氧苄基)-吡啶-2-基]-7,7-二甲基-5,6,7,8-四氢喹唑啉,m.p.251°C-252°C。
实例P4:2-(6-苄基-吡啶-2-基)-6,7,8,9-四氢-5H-环庚嘧啶的制备:
a)2-苄基-吡啶的制备:在氮气下,将无水乙酰丙酮钴(II)(0.454g,1.8mmol)吸收在包含无水二噁烷(50mL)的两颈烧瓶中。在0°C下,将氯化苄基镁(2M醚溶液,26.54mL,53mmol)添加到生成的红色溶液中。将该混合物在25°C搅拌大约5min,并且然后逐滴添加2-氯吡啶(2g,17.7mmol)。在相同温度搅拌30min之后,将该反应混合物倾倒入水(50mL)中。将该产物用乙酸乙酯(3mL x150mL)进行萃取。将合并的有机萃取物用无水硫酸钠干燥并且在减压下进行浓缩。将该粗产物通过柱层析(硅胶柱,20%在己烷中的乙酸乙酯)纯化,给出呈粘性液体的2-苄基吡啶。
1HNMR(400MHZ,CDCl3):δ8.58-8.54(m,1H),7.59-7.55(ddd,J=7.70Hz和1.83Hz,1H),7.4-7.2(m,5H),7.14-6.19(m,2H),4.2(s,2H)。
b)2-苄基吡啶-1-氧化物的制备:在0°C,向100ml圆底烧瓶中的2-苄基吡啶(1g,6mmol)在二氯甲烷(30ml)中的溶液里分若干小份经10min添加3-氯过苯甲酸(50%,1.5g,9mmol)。在添加完成之后,将该反应混合物在室温进行搅拌直到该反应完成。将过量的过酸用5%无水焦亚硫酸钠溶液分解并且将该反应物质在减压下浓缩并使用5%在二氯甲烷中的甲醇作为洗脱液进行柱层析(硅胶柱),以给出呈粘性液体的所希望的产物。
1HNMR(400MHZ,CDCl3):δ8.34-8.29(m,1H),7.38-7.33(m,2H),7.32-7.25(m,3H),7.18-7.14(m,2H),6.97-6.92(m,1H),4.2(s,2H)。
c)6-苄基-吡啶-2-腈的制备:向在两颈烧瓶中的2-苄基-吡啶-1-醇(0.9g,5mmol)在二氯甲烷中的溶液里添加氰化三甲基甲硅烷(0.96g,10mmol),随后逐滴添加氨基甲酰氯化物(0.8g,7mmol)。允许将该反应混合物在室温搅拌两天并且用饱和碳酸氢钠溶液洗涤,并且最终用二氯甲烷(3mL x50mL)进行萃取。将有机层用无水硫酸钠干燥,在减压下浓缩,随后使用快速层析法进行纯化。获得呈粘性液体的所希望的产物。
HNMR(400MHZ,CDCl3):δ7.67-7.61(dd,J=7.79Hz,1H),7.48-7.44(dd,J=7.69Hz,1H),7.28-7.22(m,3H),7.21-7.14(m,3H),4.2(s,2H)。
d)6-苄基-吡啶-2-盐酸甲脒的制备:向在两颈烧瓶中的2-氰基-6-苄基吡啶(0.5g,2.6mmol)在甲醇(10mL)中的溶液里添加新制备的甲醇钠(0.278g,5mmol)并且允许将该反应混合物搅拌3小时。在相同的温度,向该反应混合物中添加氯化铵(0.418g,8mmol)并且允许将该反应混合物再搅拌3小时。该反应完成之后,在减压下将甲醇从该反应混合物中蒸发出,以得到呈白色固体的所希望的盐酸脒。
1HNMR(400MHZ,DMSO-d6):δ8.33-8.28(d,J=7.63Hz,1H),8.08-8.02(dd,J=8.02Hz,1H),7.66-7.63(d,J=7.76Hz,1H),7.38-7.34(m,2H),7.33-7.28(m,2H),7.24-7.18(m,1H),4.2(s,2H)。
e)2-(6-苄基-吡啶-2-基)-6,7,8,9-四氢-5H-环庚嘧啶的制备:在室温,向在两颈烧瓶中的6-苄基吡啶-2-盐酸甲脒(0.2g,0.9mmol)在甲醇中的溶液里添加甲醇钠(0.1g,1.9mmol)。然后将2-(1-二甲氨基-亚甲基)-环庚酮(0.239g,1.4mmol)添加到该反应混合物中并且允许将该反应混合物在60°C加热持续6小时。该反应完成之后,将甲醇从该反应混合物中蒸发出,将该残余物质用水洗涤并且用乙酸乙酯(3mL x20mL)进行萃取。将有机层用无水硫酸钠干燥并且在减压下进行浓缩。使用15%在己烷中的乙酸乙酯作为洗脱液将该粗产物通过柱层析(硅胶柱)进行纯化,给出呈棕色胶质的所希望的产物。
1HNMR(400MHZ,CDCl3):δ8.6(s,1H),8.30-8.27(d,J=7.95Hz,1H),7.73-7.67(dd,J=7.8Hz,1H),7.36-7.28(m,4H),7.26-7.20(m,1H),7.06(d,J=7.8Hz,1H),4.4(s,2H),3.2(m,2H),2.8(m,2H),1.9(m,2H),1.8(m,4H)
实例P5:2-[6-(6-甲氧基-吡啶-3-基甲基)-吡啶-2-基]-6,7,8,9-四氢-5H-环庚
嘧啶的制备:
a)2-(6-甲氧基-吡啶-3-基甲基)-吡啶-1-氧化物的制备:称取Pd2(dba)3(70mg,0.08mmol)、X-phos(70g,16mmol)、NaOtBu(0.8g,8mmol)以及2-甲基吡啶N-氧化物(.58g,5.3mmol)并放入具有磁搅拌棒的微波小瓶中。将该烧瓶用橡胶隔片加盖并用氮气进行清洗。然后经由注射器添加5-溴-2-甲氧基吡啶(0.5g,2.67mmol)和无水甲苯(10mL)并且将该混合物用氮气进行除气。然后用微波管帽代替该橡胶隔片并且然后将该混合物在110°C置于微波合成器中60min(最大功率-200w,压力-3bar)。该反应完成之后,将该反应混合物用50mL的二氯甲烷稀释,经硅藻土过滤并且然后在减压下进行蒸发。使用8%在二氯甲烷中的甲醇将该残余物通过快速层析法纯化,以给出呈粘性油的所希望的产物。
1HNMR(400MHZ,CDCl3):δ8.2-8.3(m,1H),8.09(d,J=2.3Hz,1H),7.54(dd,J=8.51Hz,1H),7.16-7.2(m,3H),7.0-7.06(m,1H),4.17(s,2H),3.9(S,3H)。
b)6-(6-甲氧基-吡啶-3-基甲基)-吡啶-2-腈的制备:向在两颈烧瓶中的2-(6-甲氧基-吡啶-3-基甲基)-吡啶-1-氧化物(.2g,1mmol)在二氯甲烷(10ml)中的溶液里添加氰化三甲基甲硅烷(0.18g,1.8mmol),随后逐滴添加氨基甲酰氯化物(0.147g,1.4mmol)。允许将该反应混合物在室温搅拌两天。该反应完成之后,将该反应混合物用饱和碳酸氢钠溶液洗涤并且用二氯甲烷进行萃取。将该有机层用硫酸钠干燥,在减压下浓缩,并且通过快速层析法进行纯化。获得呈粘性液体的所希望的产物。
1HNMR(400MHZ,CDCl3):δ8.07(d,J=2.43Hz,1H),7.73(dd,J=7.6Hz,J=8Hz,1H),7.55(dd,J=0.8Hz,1.2Hz,1H),7.48(dd,J=2.8Hz,J=2.4,1H),7.32(dd,J=0.8Hz,each,1H),6.71(d,J=8.46Hz,1H),4.1(s,2H),3.8(s,3H)。
c)6-[(6-甲氧基-3-吡啶基)甲基]吡啶-2-盐酸甲脒的制备:向在两颈烧瓶中的6-(6-甲氧基-吡啶-3-基甲基)-吡啶-2-腈(0.1g,0.4mmol)在甲醇(5mL)中的溶液里添加新制备的甲醇钠(0.048g,0.8mmol)并且允许将该反应混合物搅拌3小时。向该反应混合物中添加氯化铵(0.07g,1.3mmol)并且允许将该反应混合物在室温搅拌3小时。该反应完成之后,将甲醇从该反应混合物中蒸发出,以得到呈白色固体的所希望的产物。
1HNMR(400MHZ,DMSO-d6):δ8.3(d,J=2Hz,1H),8.2(d,J=2.23Hz,1H),8.08(dd,J=7.6Hz,J=8Hz,1H),7.73(dd,J=2.4Hz each,J=2H),7.68(d,J=7.92Hz,3H),6.75(d,J=8.4Hz,1H),4.1(s,2H),3.8(s,3H)。
d)2-[6-(6-甲氧基-吡啶-3-基甲基)-吡啶-2-基]-6,7,8,9-四氢-5H-环庚嘧啶的制备:
在室温,向在两颈烧瓶中的6-[(6-甲氧基-3-吡啶基)甲基]吡啶-2-盐酸甲脒(0.2g,0.8mmol)在甲醇中的溶液里添加甲醇钠(0.09g,1.6mmol)。然后将2-(1-二甲氨基-亚甲基)-环庚酮(0.207g,1.2mmol)添加到该反应混合物中并且允许将该反应混合物在60°C加热持续6小时。该反应完成之后,从该反应混合物中浓缩甲醇并且将该残余物用水洗涤并且用乙酸乙酯(30mL)进行萃取。将该有机层用硫酸钠干燥并且浓缩。使用15%在己烷中的乙酸乙酯将该产物通过快速层析法进行纯化,给出呈棕色胶粘物质的所希望的产物。
1HNMR(400MHZ,CDCL3):δ8.6(s,1H),8.3(d,J=7.95Hz,1H),8.1(d,J=2.39Hz,1H),7.7(dd,J=8Hz each,1H),7.5(dd,J=2.8Hz each,1H),7.05(d,J=7.69Hz,1H),6.7(d,J=8.35Hz,1H),4.4(s,2H),3.8(s,3H),3.2(m,2H),2.8(m,2H),1.9(m,2H),1.8(m,4H)
下表A定义了用于具有化学式I的化合物的取代基R1、R2、R3、R4和R5的化学名称,而R6的含义在表1至57中给出:
表A:具有化学式I的化合物的取代基R
1
、R
2
、R
3
、R
4
和R
5
的化学名
称:
表1:该表披露了具有以下化学式的215个化合物T1.1.1至T1.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。例如,具体化合物T1.1.23是具有化学式T1的化合物,其中每一变量R1、R2、R3、R4和R5具有表A的A.1.23行中给定的具体含义并且R6是H,并且因此具有以下化学式:
根据相同系统,同样类似指定了在表1中披露的所有其他215个具体化合物连同在表2至19中披露的所有具体化合物。
表2:该表披露了具有以下化学式的215个化合物T2.1.1至T2.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表3:该表披露了具有以下化学式的215个化合物T3.1.1至T3.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表4:该表披露了具有以下化学式的215个化合物T4.1.1至T4.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表5:该表披露了具有以下化学式的215个化合物T5.1.1至T5.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表6:该表披露了具有以下化学式的215个化合物T6.1.1至T6.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表7:该表披露了具有以下化学式的215个化合物T7.1.1至T7.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表8:该表披露了具有以下化学式的215个化合物T8.1.1至T8.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表9:该表披露了具有以下化学式的215个化合物T9.1.1至T9.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表10:该表披露了具有以下化学式的215个化合物T10.1.1至T10.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表11:该表披露了具有以下化学式的215个化合物T11.1.1至T11.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表12:该表披露了具有以下化学式的215个化合物T12.1.1至T12.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表13:该表披露了具有以下化学式的215个化合物T13.1.1至T13.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表14:该表披露了具有以下化学式的215个化合物T14.1.1至T14.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表15:该表披露了具有以下化学式的215个化合物T15.1.1至T15.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表16:该表披露了具有以下化学式的215个化合物T16.1.1至T16.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表17:该表披露了具有以下化学式的215个化合物T17.1.1至T17.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表18:该表披露了具有以下化学式的215个化合物T18.1.1至T18.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表19:该表披露了具有以下化学式的215个化合物T19.1.1至T19.1.215
其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是H。
表20:该表披露了具有化学式(T1)的215个化合物T20.1.1至T20.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表21:该表披露了具有化学式(T2)的215个化合物T21.1.1至T21.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表22:该表披露了具有化学式(T3)的215个化合物T22.1.1至T22.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表23:该表披露了具有化学式(T4)的215个化合物T23.1.1至T23.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表24:该表披露了具有化学式(T5)的215个化合物T24.1.1至T24.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表25:该表披露了具有化学式(T6)的215个化合物T25.1.1至T25.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表26:该表披露了具有化学式(T7)的215个化合物T26.1.1至T26.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表27该表披露了具有化学式(T8)的215个化合物T27.1.1至T27.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表28:该表披露了具有化学式(T9)的215个化合物T28.1.1至T28.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表29:该表披露了具有化学式(T10)的215个化合物T29.1.1至T29.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表30:该表披露了具有化学式(T11)的215个化合物T30.1.1至T30.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表31:该表披露了具有化学式(T12)的215个化合物T31.1.1至T31.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表32:该表披露了具有化学式(T13)的215个化合物T32.1.1至T32.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表33:该表披露了具有化学式(T14)的215个化合物T33.1.1至T33.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表34:该表披露了具有化学式(T15)的215个化合物T34.1.1至T34.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表35:该表披露了具有化学式(T16)的215个化合物T35.1.1至T35.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表36:该表披露了具有化学式(T17)的215个化合物T36.1.1至T36.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表37:该表披露了具有化学式(T18)的215个化合物T37.1.1至T37.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表38:该表披露了具有化学式(T19)的215个化合物T38.1.1至T38.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是CH3。
表39:该表披露了具有化学式(T1)的215个化合物T39.1.1至T39.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表40:该表披露了具有化学式(T2)的215个化合物T40.1.1至T40.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表41:该表披露了具有化学式(T3)的215个化合物T41.1.1至T41.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表42:该表披露了具有化学式(T4)的215个化合物T42.1.1至T42.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表43:该表披露了具有化学式(T5)的215个化合物T43.1.1至T43.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表44:该表披露了具有化学式(T6)的215个化合物T44.1.1至T44.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表45:该表披露了具有化学式(T7)的215个化合物T45.1.1至T45.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表46:该表披露了具有化学式(T8)的215个化合物T46.1.1至T46.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表47该表披露了具有化学式(T9)的215个化合物T47.1.1至T47.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表48:该表披露了具有化学式(T10)的215个化合物T48.1.1至T48.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表49:该表披露了具有化学式(T11)的215个化合物T49.1.1至T49.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表50:该表披露了具有化学式(T12)的215个化合物T50.1.1至T50.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表51:该表披露了具有化学式(T13)的215个化合物T51.1.1至T51.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表52:该表披露了具有化学式(T14)的215个化合物T52.1.1至T52.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表53:该表披露了具有化学式(T15)的215个化合物T53.1.1至T53.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表54:该表披露了具有化学式(T16)的215个化合物T54.1.1至T54.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表55:该表披露了具有化学式(T17)的215个化合物T55.1.1至T55.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表56:该表披露了具有化学式(T18)的215个化合物T56.1.1至T56.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表57:该表披露了具有化学式(T19)的215个化合物T57.1.1至T57.1.215,其中对于这215个具体化合物中的每一个,每一变量R1、R2、R3、R4和R5具有相应行中给定的具体含义,该行适当地选自表A的A.1.1至A.1.215的215行并且R6是OCH3。
表A1:示出对于表1至57的化合物的选择的m.p.和/或LCMS数据以及保留时间/MW。
贯穿本说明书,以摄氏度给出温度并且“m.p.”是指熔点。
使用的这些分析方法在此如下所述:
方法U:来自安捷伦公司(Agilent)的6410-三四极杆质谱仪(6410-Triple Quad Mass Spectrometer)(三四极杆质谱仪)
电离法:电喷射
极性:正离子和负离子同时扫描
毛细管(V)4000,Frag(V)100.00,
源参数
气体温度(°C)350,气体流速(l/min)11;喷雾器(psi):35
质量范围:80Da至800Da
DAD波长范围(nm):190至400
方法:具有以下HPLC梯度条件的安捷伦1200系列(Agilent1200series)
(溶液A:水,0.1%甲酸以及溶剂B:乙腈,0.1%甲酸)
柱型:沃特斯公司(Waters)的XTerra MS C-18;柱长:30mm;柱内径:4.6mm;颗粒尺寸:3.5微米;温度:30°C。
方法A:来自沃特斯公司的ZQ质谱仪(单四极杆质谱仪)
仪器参数:离子化法:电喷射;极性:正(负)离子
毛细管(kV)3.00,锥孔(V)30.00,提取器(V)2.00,源温度(°C)100,脱溶剂气温度(°C)250,锥孔反吹气流(L/Hr)50,脱溶剂气流(L/Hr)400
质量范围:100Da至900Da(LC8非极性的:150Da-1000Da)
来自安捷伦公司的HP1100HPLC:溶剂脱气装置,四元泵(ZCQ)/二元泵(ZDQ),加热的管柱室以及二极管阵列检测器。
温度:60°C
DAD波长范围(nm):200至500
溶剂梯度:
A=水+0.05%HCOOH
B=乙腈/甲醇(4:1,v:v)+0.04%HCOOH
具有化学式I的化合物的配制品实例:
实例F-1.1至F-1.2:可乳化的浓缩物
可以通过用水稀释此类浓缩物来制备任何希望浓度的乳液。
实例F-2:可乳化的浓缩物
可以通过用水稀释此类浓缩物来制备任何希望浓度的乳液。
实例F-3.1至F-3.4:溶液
这些溶液适合以微滴的形式使用。
实例F-4.1至F-4.4:颗粒:
将该新颖的化合物溶解在二氯甲烷中,将溶液喷洒到载体上,并且然后通过真空蒸馏除去溶剂。
实例F-5.1和F-5.2:尘剂
通过立即混合所有组分获得备用尘剂。
实例F-6.1至F-6.3:可湿性粉
混合所有组分,并且在适合的研磨机中充分研磨该混合物以给出可湿性粉,可以用水将该粉稀释为具有任何希望的浓度的悬浮液。
实例F7:可流动的种子处理浓缩物
将这种精细研磨的活性成分与这些佐剂充分混合,从而给出一种悬浮液浓缩物,通过用水稀释可以从该浓缩物获得任何所希望的稀释体的悬浮液。使用此类稀释体,可以对活的植物连同植物繁殖材料进行处理并且对其针对微生物侵染通过喷洒、倾倒或浸渍进行保护。
生物学实例:
生物学实例1:针对茄链格孢菌的杀真菌活性/番茄/叶圆片(早枯病)
将番茄栽培品种Baby的叶圆片置于多孔板(24孔规格)中的琼脂上,并且用稀释在水中的配制的测试化合物喷雾。在施用后2天以后,用真菌的孢子悬液接种这些叶圆片。在气候室中的12h光照/12h黑暗的一个光方案下,在23°C/21°C(白天/夜晚)和80%rh培育接种的叶圆片,并且在未处理的对照叶圆片上出现适当的疾病破坏水平时(施用后5-7天以后),作为与未处理的相比时的疾病控制百分比来评估化合物的活性。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物3、5、6、7、19、21、25以及33在200ppm处给出至少80%的疾病控制。
生物学实例2:针对小麦白粉病菌(Blumeria graminis f.sp.Tritici,
Erysiphe graminis f.sp.Tritici)的杀真菌活性/小麦/叶圆片预防(小麦上的白
粉病)
将小麦栽培品种Kanzler的叶片段置于多孔板(24孔规格)的琼脂上,并且用稀释在水中的配制的测试化合物喷雾。在施用后1天之后,通过在测试板上方摇动白粉病感染的植物来接种这些叶圆片。在人工气候室中在24h黑暗随后是12h光照/12h黑暗的一个光方案下,在20°C和60%rh培育接种的叶圆片,并且在未处理的对照叶片段上出现适当的疾病破坏水平时(施用后6-8天以后),作为与未处理的相比时的疾病控制百分比来评估化合物的活性。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物1、2、3、4、5、6、7、9、11、18、19、21、22、25、26、27、28、29、30、31、32、33、34、35、36、37、39、41、42、43以及44在200ppm处给出至少80%的疾病控制。
生物学实例3:针对灰葡萄孢菌(Botryotinia fuckelian,Botrytis cinerea)
的杀真菌活性/液体培养(灰霉病)
将来自冷冻储存的真菌分生孢子直接混入营养肉汤(Vogels(沃格尔)肉汤)中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24°C孵育并且在施用后3-4天之后通过光度法测定对生长的抑制。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物1、2、3、4、5、6、7、9、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、32、33、34、35、36、37、41、42、43、44以及45在200ppm处给出至少80%的疾病控制。
生物学实例4:针对燕麦全蚀病菌的杀真菌活性/液体培养(谷物的全蚀
病)
将来自冷冻储存的真菌丝状片段直接混入营养肉汤(PDB(马铃薯葡萄糖肉汤))中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24°C孵育并且在施用后4-5天之后通过光度法测定对生长的抑制。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物1、2、3、4、5、6、7、9、11、14、17、18、19、20、21、22、23、24、26、27、28、29、30、31、32、33、34、35、36、37、39、41、42、43、44以及45在200ppm处给出至少80%的疾病控制。
生物学实例5:针对瓜类小丛壳(瓜类炭疽菌)的杀真菌活性/液体培养
(炭疽病)
将来自冷冻储存的真菌分生孢子直接混入营养肉汤(PDB(马铃薯葡萄糖肉汤))中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24°C下孵育并且在施用后3-4天以后通过光度法测量对生长的抑制。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物1、2、3、4、5、6、7、9、11、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、39、41、42、43、44以及45在200ppm处给出至少80%的疾病控制。
生物学实例6:针对雪腐明梭孢(雪霉叶枯菌)的杀真菌活性/液体培养
(谷类根腐病)
将来自冷冻储存的真菌分生孢子直接混入营养肉汤(PDB(马铃薯葡萄糖肉汤))中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24°C孵育并且在施用后4-5天之后通过光度法测定对生长的抑制。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物1、3、4、5、6、7、9、11、13、14、15、16、17、19、21、23、24、25、26、27、28、29、30、32、33、34、35、36、37、41、42、43、44以及45在200ppm处给出至少80%的疾病控制。
生物学实例7:针对落花生球腔菌(落花生尾孢)的杀真菌活性/液体培
养(早褐斑病)
将来自冷冻储存的真菌分生孢子直接混入营养肉汤(PDB(马铃薯葡萄糖肉汤))中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24°C孵育并且在施用后4-5天之后通过光度法测定对生长的抑制。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物1、2、3、4、5、6、7、9、11、12、13、14、15、16、17、18、19、20、21、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、39、41、42、43、44以及45在200ppm处给出至少80%的疾病控制。
生物学实例8:针对禾生球腔菌(小麦壳针孢)的杀真菌活性/液体培养
(壳针孢属斑纹病(Septoria blotch))
将来自冷冻储存的真菌分生孢子直接混入营养肉汤(PDB(马铃薯葡萄糖肉汤))中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24°C孵育并且在施用后4-5天之后通过光度法测定对生长的抑制。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物1、2、3、4、5、6、7、11、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、39、41、42、43、44以及45在200ppm处给出至少80%的疾病控制。
生物学实例9:针对颖枯壳针孢(Phaeosphaeria nodorum,Septoria
nodorum)的杀真菌活性/小麦/叶圆片预防(稃枯病)
将小麦栽培品种Kanzler的叶片段置于多孔板(24孔规格)的琼脂上,并且用稀释在水中的配制的测试化合物喷雾。在施用后2天以后,用真菌的孢子悬液接种这些叶圆片。在气候室中的12h光照/12h黑暗的一个光方案下,在20°C和75%rh培育接种的测试叶圆片,并且在未处理的对照叶圆片上出现适当的疾病破坏水平时(施用后5-7天以后),作为与未处理的相比时的疾病控制百分比来评估化合物的活性。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物1、2、3、4、5、6、7、9、11、13、15、16、17、18、19、21、22、24、25、26、27、28、29、30、31、32、33、34、35、36、37、39、41、42、43、44以及45在200ppm处给出至少80%的疾病控制。
生物学实例10:针对致病疫霉菌的杀真菌活性/番茄/叶圆片预防(晚疫
病)
将番茄叶圆片置于多孔板(24孔规格)中的水琼脂培养基上,并且用稀释在水中的配制的测试化合物喷雾。在施用后1天之后,用真菌的孢子悬液接种这些叶圆片。在气候室中,在24h黑暗随后是12h光照/12h黑暗的光方案下,在16°C和75%rh培育这些接种的叶圆片,并且化合物活性被评估为,在未处理的对照叶圆片中出现适当水平的疾病损害时(施用后5-7天以后),与未处理的相比时的疾病控制百分比。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物2、21、29、30、33以及36在200ppm处给出至少80%的疾病控制。
生物学实例11:针对葡萄生单轴霉的杀真菌活性/葡萄/叶圆片预防(晚
疫病)
将葡萄藤叶圆片置于多孔板(24孔规格)中的水琼脂上,并且用稀释在水中的配制的测试化合物喷雾。在施用后1天之后,用真菌的孢子悬液接种这些叶圆片。在气候室中,在12h光照/12h黑暗的光方案下,在19°C和80%rh培育这些接种的叶圆片,并且化合物活性被评估为,在未处理的对照叶圆片中出现适当水平的疾病损害时(施用后6-8天以后),与未处理的相比时的疾病控制百分比。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物14、33以及34在200ppm处给出至少80%的疾病控制。
生物学实例12:针对小麦隐匿柄锈菌(Puccinia recondita f.sp.tritici)的
杀真菌活性/小麦/叶圆片预防(褐锈病)
将小麦栽培品种Kanzler的叶片段置于多孔板(24孔规格)的琼脂上,并且用稀释在水中的配制的测试化合物喷雾。在施用后1天之后,用真菌的孢子悬液接种这些叶圆片。在气候室中的12h光照/12h黑暗的一个光方案下,在19°C和75%rh培育接种的叶片段,并且在未处理的对照叶片段上出现适当的疾病破坏水平时(施用后7-9天以后),作为与未处理的相比时的疾病控制百分比来评估化合物的活性。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物1、2、3、4、5、6、7、9、11、18、19、21、22、24、25、26、27、28、29、30、31、32、33、34、35、37、39、41、42以及44在200ppm处给出至少80%的疾病控制。
生物学实例13:针对大麦网斑病菌的杀真菌活性/大麦/叶圆片预防(网
斑病)
将大麦栽培品种Hasso的叶片段置于多孔板(24孔规格)内的琼脂上,并且用稀释在水中的配制的测试化合物喷雾。在施用后2天以后,用真菌的孢子悬液接种这些叶片段。在气候室中的12h光照/12h黑暗的一个光方案下,在20°C和65%rh培育接种的叶片段,并且在未处理的对照叶片段上出现适当的疾病破坏水平时(施用后5-7天以后),作为与未处理的相比时的疾病控制百分比来评估化合物的活性。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物1、2、3、4、5、6、7、9、11、14、15、16、17、18、19、21、22、25、26、27、28、29、30、31、32、33、34、35、36、37、39、41、42、43、44以及45在200ppm处给出至少80%的疾病控制。
生物学实例14:针对水稻枯纹病菌(立枯丝核菌)的杀真菌活性/液体培
养(根腐病,猝倒病)
将新鲜的液体培养的真菌的菌丝体片段直接混入营养肉汤(PDB马铃薯葡萄糖肉汤)中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌材料的营养肉汤。将这些测试板在24°C孵育并且在施用后3-4天之后通过光度法测定对生长的抑制。
在本测试中当在相同条件下与未处理的对照叶圆片(它们显示出广泛的疾病发展)对比时,化合物1、2、3、4、5、11、13、14、15、17、18、19、21、24、26、28、29、30、31、32、33、34、35、36、37、41、42、44以及45在200ppm处给出至少80%的疾病控制。
Claims (13)
1.一种具有化学式I的化合物
其中
G与它附接到其上的嘧啶环的两个碳原子一起表示单或双环的并且含有选自下组的0至2个杂原子的一个5-至8-元的、脂环族的或非芳香族的杂环系统,该组由以下各项组成:氮、氧和硫;并且其中所述5-至8-元的、脂环族的或非芳香族的杂环系统可以经选自下组的取代基单-、双-或三取代,该组由以下各项组成:卤素、羟基、酮基、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷氧基-C1-C6烷基、C1-C6烷基肟基和C1-C6亚烷基二氧基;
R1是可以经选自下组的取代基单-、双-或三取代的芳基或杂芳基,该组由以下各项组成:卤素、羟基、氰基、硝基、甲酰基、C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6卤代烷基、C2-C6卤代链烯基、C2-C6卤代炔基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6烷氧基-C1-C6烷基、C1-C6烷氧基-C1-C6烷氧基、C1-C6烷氧基-C1-C6烷氧基-C1-C6烷基、C1-C6烷氧基-C1-C6烷硫基、C1-C6烷硫基-C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基亚磺酰基、C1-C6烷基磺酰基、C1-C6烷基氨基、二C1-C6烷基氨基、C3-C6环烷基氨基、(C1-C6烷基)(C3-C6环烷基)氨基、二C3-C6环烷基氨基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基氨基羰基、二C1-C6烷基氨基羰基、C1-C6烷氧基羰基氧基、C1-C6烷基氨基羰基氧基、二C1-C6烷基氨基羰基氧基、C1-C6烷基羰基氧基、C1-C6烷基羰基氨基、C1-C6烷基羰基-C1-C6烷基氨基、C1-C6烷氧基亚氨基、C1-C6烷氧基亚氨基-C1-C6烷基、三C1-6烷基甲硅烷基、C1-C6烷氧基-C2-C6炔基、C1-C6烷氧基亚氨基-C2-C6炔基、C1-C6烷硫基-C2-C6炔基、羟基-C2-C6炔基、C1-C6烷硫基-C1-C6烷基或羟基-C1-C6烷基;
R2与R3彼此独立地是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;或
R2与R3一起形成一个3-至5-元的、脂肪族的碳环或一个3-至5-元的杂环,该杂环包含多达两个选自O、S以及N的杂原子;或
R2与R3一起形成一个羰基或C1-C6烷基肟基;
R4是氢、卤素、氰基、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;
R5是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基;并且
R6是氢、卤素、C1-C6烷基、C1-C6烷氧基或C1-C6烷硫基;
以及那些化合物的农艺学上可接受的盐、异构体、阻转异构体、结构异构体、立体异构体、非对映异构体、对映异构体、互变异构体以及N-氧化物;
其条件是当G是一个未经取代的、5或6元的、单环的脂环族环,并且R2与R3彼此独立地是氢、C1-C4烷基时,那么R1不能是苯基或经取代的苯基。
3.根据权利要求1所述的具有化学式I的化合物,其中R2和R3彼此独立地是氢、羟基、卤素、C1-C6烷基或C1-C6烷氧基,或R2与R3一起形成一个3-至5-元的、脂肪族的碳环或一个3-至5-元的杂环,该杂环包含多达两个选自O、S以及N的杂原子;
4.根据权利要求2所述的具有化学式I的化合物,其中R5是氢、卤素、羟基、C1-C4烷基或C1-C4烷氧基。
5.根据权利要求2所述的具有化学式I的化合物,其中该环系统选自Q3、Q4、Q6、Q12和Q19。
6.根据权利要求1所述的具有化学式I的化合物,其中
R1是可以经选自下组的取代基单-或双-取代的苯基、萘基、吡啶基、喹啉基、哒嗪基、噌啉基、嘧啶基、喹唑啉基、吡嗪基、喹喔啉基、噻吩基、呋喃基、异噁唑基、异噻唑基、噻唑基、噁唑基、吡唑基、咪唑基、吡咯基、噁二唑基、噻二唑基,该组由以下各项组成:卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷硫基和C1-C4烷氧基;
R2与R3是氢或C1-C4烷基;
R4是氢、C1-C4烷基或C1-C4烷氧基;
R5是氢、卤素或C1-C4烷基;并且
R6是氢、C1-C4烷基或C1-C4烷氧基。
7.根据权利要求1所述的具有化学式I的化合物,其中
R1是可以经卤素、C1-C4烷基、C1-C4烷硫基或C1-C4烷氧基取代的苯基或吡啶基或噻吩基;
R2与R3是氢或C1-C4烷基;
R4是氢、C1-C4烷基或C1-C4烷氧基;
R5是氢、卤素或C1-C4烷基;并且
R6是氢、C1-C4烷基或C1-C4烷氧基。
8.根据权利要求7所述的具有化学式I的化合物,其中
R1是可以经卤素、C1-C4烷基或C1-C4烷氧基取代的苯基、吡啶基或噻吩基;
R2与R3是氢或C1-C4烷基;
R4是氢、C1-C4烷基或C1-C4烷氧基;
R5是氢、卤素或C1-C4烷基;并且
R6是氢。
9.根据权利要求8所述的具有化学式I的化合物,其中
R1是可以经卤素、C1-C4烷基或C1-C4烷氧基取代的苯基;
R2与R3是氢或甲基;
R4是氢或甲基;
R5是氢或甲基;并且
R6是氢;
10.一种用于控制或预防有用植物受到致植物病的微生物侵染的方法,其中将根据权利要求1所述的具有化学式I的化合物或包括该化合物作为活性成分的一种组合物施用到这些植物、其部分或其场所。
11.一种用于控制并且保护对抗致植物病的微生物的组合物,该组合物包括根据权利要求1所述的具有化学式I的化合物以及至少一种助剂。
12.一种用于控制有用植物或其植物繁殖材料上的致植物病的疾病的方法,该方法包括将一种杀真菌有效量的保护植物繁殖材料的组合物施用到所述植物繁殖材料上,该组合物包括如在权利要求1中定义的具有化学式(I)的化合物,连同一种适合用于此的载体。
13.一种组合物,包括一种杀真菌有效量的如权利要求1中所定义的具有化学式(I)的化合物,可任选地包括至少一种另外的活性成分。
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