TW201927768A - Trisubstitutedsilylmethylheteroaryloxyquinolines and analogues - Google Patents
Trisubstitutedsilylmethylheteroaryloxyquinolines and analogues Download PDFInfo
- Publication number
- TW201927768A TW201927768A TW107146127A TW107146127A TW201927768A TW 201927768 A TW201927768 A TW 201927768A TW 107146127 A TW107146127 A TW 107146127A TW 107146127 A TW107146127 A TW 107146127A TW 201927768 A TW201927768 A TW 201927768A
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- Prior art keywords
- alkyl
- group
- halogen atoms
- haloalkyl
- substituted
- Prior art date
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- 238000000034 method Methods 0.000 claims abstract description 171
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- -1 1H-benzimidazol-1-yl ring Chemical group 0.000 claims description 164
- 125000005843 halogen group Chemical group 0.000 claims description 149
- 125000000623 heterocyclic group Chemical group 0.000 claims description 79
- 125000001424 substituent group Chemical group 0.000 claims description 73
- 125000003118 aryl group Chemical group 0.000 claims description 67
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 66
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 55
- 125000004649 C2-C8 alkynyl group Chemical group 0.000 claims description 42
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- 125000001309 chloro group Chemical group Cl* 0.000 claims description 26
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 25
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
本發明係關於真菌活性化合物、更具體而言三取代矽基甲基雜芳基氧基喹啉及其類似物、用於其等製備之方法及中間體及其作為真菌活性化合物、特定而言呈殺真菌劑組合物之形式的用途。本發明亦係關於使用該等化合物或包含其等之組合物控制植物之植物病原性真菌的方法。The present invention relates to fungal active compounds, more specifically tri-substituted silylmethylheteroaryloxyquinolines and their analogs, methods and intermediates used in the preparation thereof, and as fungal active compounds, specifically Use in the form of a fungicide composition. The present invention also relates to a method for controlling phytopathogenic fungi of a plant using these compounds or a composition containing the same.
已知一些雜芳基氧基喹啉展現殺真菌活性。Some heteroaryloxyquinolines are known to exhibit fungicidal activity.
WO2017/072283揭示可用作殺真菌劑之三取代矽基苯氧基雜環。WO2017 / 072283 discloses tri-substituted silylphenoxy heterocycles useful as fungicides.
在國際專利申請案WO 2013/002205中,某些雜芳基氧基喹啉屬類上包含於下式之許多化合物之寬揭示內容中:
其中,D及E可代表5至7員環或雜環環,X可代表O、NH或N-C1
-C8
-烷基,B (或Y)可代表C或N,且R在各個基團中可代表視情況經取代之烷氧基、視情況二取代胺基、視情況經取代且視情況氧化之烷基硫基或硝基。然而,WO2013/002205並未揭示或建議提供其中R代表三取代矽基甲基之化合物。In the international patent application WO 2013/002205, certain heteroaryloxyquinolines are included in the wide disclosure of many compounds of the formula:
Among them, D and E may represent a 5- to 7-membered ring or heterocyclic ring, X may represent O, NH or NC 1 -C 8 -alkyl, B (or Y) may represent C or N, and R is in each group Where may represent an optionally substituted alkoxy group, an optionally substituted diamino group, an optionally substituted alkylthio group or a nitro group. However, WO2013 / 002205 does not disclose or suggest providing compounds in which R represents a tri-substituted silylmethyl group.
在日本專利申請案JP-2014/166991中,某些雜芳基氧基喹啉屬類上包含於下式之許多化合物之寬揭示內容中:
其中A可代表5至7員環,D可代表5至7員烴或雜環環,X可代表O、S、未經取代或經取代之碳或氮原子,Z及B可獨立地代表C或N,且R可代表基團CR1
R2
R3
、C=O-R3
、CR3
=CRa
Rb
、CR3=
NRc
、C6
-C10
芳基、炔基或CN。然而,JP-2014/166991並未揭示或建議提供其中R代表三取代矽基甲基之化合物。In Japanese patent application JP-2014 / 166991, certain heteroaryloxyquinolines are included in the wide disclosure of many compounds of the following formula:
Where A can represent a 5 to 7-membered ring, D can represent a 5 to 7-membered hydrocarbon or heterocyclic ring, X can represent O, S, unsubstituted or substituted carbon or nitrogen atom, and Z and B can independently represent C Or N, and R may represent the groups CR 1 R 2 R 3 , C = OR 3 , CR 3 = CR a R b , CR 3 = NR c , C 6 -C 10 aryl, alkynyl or CN. However, JP-2014 / 166991 does not disclose or suggest providing a compound in which R represents a tri-substituted silylmethyl group.
在國際專利申請案WO 2011/081174中,某些雜芳基氧基喹啉屬類上包含於下式之許多化合物之寬揭示內容中:
其中A及D可代表5至7員環或雜環環,X可代表O、NH或N-C1
-C8
-烷基,Y或Z可代表C或N,且R在各個基團中可代表視情況經取代之烷氧基、視情況二取代胺基、視情況經取代且視情況氧化之烷基硫基或硝基。然而,WO 2011/081174並未揭示或建議提供其中R代表三取代矽基甲基之化合物。In the international patent application WO 2011/081174, certain heteroaryloxyquinolines are included in the wide disclosure of many compounds of the formula:
Wherein A and D may represent a 5- to 7-membered ring or heterocyclic ring, X may represent O, NH or NC 1 -C 8 -alkyl, Y or Z may represent C or N, and R may represent each group. Optionally substituted alkoxy, optionally disubstituted amino, optionally substituted alkylthio or nitro. However, WO 2011/081174 does not disclose or suggest providing compounds in which R represents a tri-substituted silylmethyl group.
在國際專利申請案WO 2012/161071中,某些苯氧基喹啉屬類上包含於下式之許多化合物之寬揭示內容中:
其中D可代表5至7員環,A1
、A2
、A3
及A4
可獨立地代表C或N,條件係An
中之至少一者係N,且R可代表視情況經取代之烷基或氰基。然而,WO 2012/161071並未揭示或建議提供其中R代表三取代矽基甲基之化合物。In the international patent application WO 2012/161071, certain phenoxyquinolines are included in the wide disclosure of many compounds of the formula:
Where D may represent a ring of 5 to 7, A 1 , A 2 , A 3 and A 4 may independently represent C or N, provided that at least one of A n is N, and R may represent a substituted one as appropriate. Alkyl or cyano. However, WO 2012/161071 does not disclose or suggest providing compounds in which R represents a tri-substituted silylmethyl group.
儘管到目前為止已開發若干種殺真菌化合物,但業內仍需要開發新的殺真菌劑。實際上,對殺真菌劑活性化合物之生態及經濟要求不斷增加,例如關於活性譜、毒性、選擇性、施用率、殘餘物之形成及有利的生產,持續需要開發至少在該等態樣中之一些中優於已知化合物及組合物之新穎殺真菌化合物及組合物。Although several fungicidal compounds have been developed so far, the industry still needs to develop new fungicides. In fact, the ecological and economic requirements for fungicide active compounds continue to increase, such as with regard to the spectrum of activity, toxicity, selectivity, application rates, formation of residues and favorable production, and there is a continuing need to develop at least among these aspects Some novel fungicidal compounds and compositions are superior to known compounds and compositions.
因此,本發明提供如本文下文所述之三取代矽基甲基雜芳基氧基喹啉及其類似物,其可用作殺真菌劑。Accordingly, the present invention provides tri-substituted silylmethylheteroaryloxyquinolines and analogs thereof as described herein below, which are useful as fungicides.
活性成分
本發明提供式(I)化合物,
其中
• A代表喹啉-3-基環,其中Q1
為C;喹喏啉-2-基環,其中Q1
為C;或1H-苯并咪唑-1-基環,其中Q1
為N;
• B代表包含1、2或3個獨立地選自由N、O及S組成之清單中雜原子之5或6員雜環基環;
• Q2
係C或N;
• Z選自由以下組成之群:氫原子、鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、包含最多9個可相同或不同之鹵素原子之C2
-C8
-鹵代烯基、C2
-C8
-炔基、包含最多9個可相同或不同之鹵素原子之C2
-C8
-鹵代炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、羥基、C1
-C8
-烷氧基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷氧基、芳基、雜環基、甲醯基、C1
-C8
-烷基羰基、(羥基亞胺基)C1
-C8
-烷基、(C1
-C8
-烷氧基亞胺基)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
-三烷基矽基、氰基及硝基,其中該等C1
-C8
-烷基、C2
-C8
-烯基、C2
-C8
-炔基及C1
-C8
-烷氧基可經一或多個Za
取代基取代,且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基及雜環基可經一或多個Zb
取代基取代;
• n代表0、1、2、3或4;
• p代表0、1、2、3、4或5;
• L代表O、S、SO、SO2
、CR4
R5
或NR6
,其中
○ R4
及R5
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、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C1
-C8
-烷氧基及包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷氧基,或其可與其所鏈接之碳原子一起形成羰基;
○ R6
選自由以下組成之群:氫原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、包含最多9個可相同或不同之鹵素原子之C2
-C8
-鹵代烯基、C3
-C8
-炔基、包含最多9個可相同或不同之鹵素原子之C3
-C8
-鹵代炔基、C3
-C7
-環烷基、包含最多9個可相同或不同之鹵素原子之C3
-C7
-鹵代環烷基、C3
-C7
-環烷基-C1
-C8
-烷基、甲醯基、C1
-C8
-烷基羰基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基羰基、C1
-C8
-烷氧基羰基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷氧基羰基、C1
-C8
-烷基磺醯基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基磺醯基、芳基-C1
-C8
-烷基及苯基磺醯基,
其中該等C1
-C8
-烷基、C2
-C8
-烯基、C3
-C8
-炔基可經一或多個R6a
取代基取代,且其中該等C3
-C7
-環烷基、C3
-C7
-環烷基-C1
-C8
-烷基、芳基-C1
-C8
-烷基及苯基磺醯基可經一或多個R6b
取代基取代;
• X獨立地選自由以下組成之群:鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、包含最多9個可相同或不同之鹵素原子之C2
-C8
-鹵代烯基、C2
-C8
-炔基、包含最多9個可相同或不同之鹵素原子之C2
-C8
-鹵代炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、羥基、C1
-C8
-烷氧基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷氧基、C1
-C6
-三烷基矽基、氰基及硝基,其中該等C1
-C8
-烷基、C2
-C8
-烯基、C2
-C8
-炔基及C1
-C8
-烷氧基可經一或多個Xa
取代基取代且該等C3
-C7
-環烷基及C4
-C7
-環烯基可經一或多個Xb
取代基取代;
• Y獨立地選自由以下組成之群:鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、包含最多9個可相同或不同之鹵素原子之C2
-C8
-鹵代烯基、C2
-C8
-炔基、包含最多9個可相同或不同之鹵素原子之C2
-C8
-鹵代炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、羥基、C1
-C8
-烷氧基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷氧基、芳基、雜環基、甲醯基、C1
-C8
-烷基羰基、(羥基亞胺基)C1
-C8
-烷基、(C1
-C8
-烷氧基亞胺基)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
-三烷基矽基、氰基及硝基,其中該等C1
-C8
-烷基、C2
-C8
-烯基、C2
-C8
-炔基及C1
-C8
-烷氧基可經一或多個Ya
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基及雜環基可經一或多個Yb
取代基取代;
• R1
選自由以下組成之群:C1
-C8
-烷基、C2
-C8
-烯基、C2
-C8
-炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、芳基及雜環基,其中該等C1
-C8
-烷基、C2
-C8
-烯基及C2
-C8
-炔基可經一或多個R1a
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基及雜環基可經一或多個R1b
取代基取代;
• R2
選自由以下組成之群:羥基、C1
-C8
-烷氧基、C1
-C8
-烷基、C2
-C8
-烯基、C2
-C8
-炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、芳基及雜環基,其中該等C1
-C8
-烷氧基、C1
-C8
-烷基、C2
-C8
-烯基及C2
-C8
-炔基可經一或多個R2a
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基及雜環基可經一或多個R2b
取代基取代;
• 當R1
及R2
獨立地代表C1
-C8
烷基或C2
-C8
烯基時,其可與其所鏈接之矽原子一起形成C3
-C8
-矽雜環烷基環或C4
-C8
-矽雜環烯基環,其中該C3
-C8
-矽雜環烷基環或C4
-C8
-矽雜環烯基環可經一或多個R1b
取代基取代;
• R3
選自由以下組成之群:氫原子、鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、C2
-C8
-炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、羥基、C1
-C8
-烷氧基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、羥基-C1
-C8
-烷基、C1
-C8
-烷氧基-C1
-C8
-烷基、C1
-C8
-烷基羰基氧基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基、雜環基氧基-C1
-C8
-烷基、胺基-C1
-C8
-烷基、C1
-C8
-烷基胺基-C1
-C8
-烷基、二-C1
-C8
-烷基胺基-C1
-C8
-烷基、芳基胺基-C1
-C8
-烷基、二-芳基胺基-C1
-C8
-烷基、雜環基胺基-C1
-C8
-烷基、C1
-C8
-烷基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷氧基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷基硫基-C1
-C8
-烷基、C1
-C8
-烷基亞磺醯基-C1
-C8
-烷基、C1
-C8
-烷基磺醯基-C1
-C8
-烷基及氰基-C1
-C8
-烷基,其中該等C1
-C8
-烷基、C2
-C8
-烯基及C2
-C8
-炔基可經一或多個R3a
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基及雜環基氧基-C1
-C8
-烷基可經一或多個R3b
取代基取代;
• 當該X鄰接至SiR1
R2
R3
時,R3
及X可與其分別連接之矽及碳原子一起形成5、6或7員部分飽和之雜環,其中該5、6或7員部分飽和之雜環可經一或多個R3b
取代基取代;
• 當R2
代表C1
-C8
-烷氧基且R3
代表C1
-C8
-烷氧基或C1
-C8
烷基時,其可與其鏈接之矽原子一起形成5、6或7員雜環,其中該5、6或7員雜環可經一或多個R2b
取代基取代;
• Za
、R1a
、R2a
、R3a
、R6a
、Xa
及Ya
獨立地選自由以下組成之群: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、C3
-C7
-環烷基、具有1至5個鹵素原子之C3
-C8
-鹵代環烷基、C1
-C8
-烷基胺基、二-C1
-C8
-烷基胺基、C1
-C8
-烷氧基、具有1至5個鹵素原子之C1
-C8
-鹵代烷氧基、C1
-C8
-烷基硫基、具有1至5個鹵素原子之C1
-C8
-鹵代烷基硫基、C1
-C8
-烷基羰基、具有1至5個鹵素原子之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個鹵素原子之C1
-C8
-鹵代烷氧基羰基、C1
-C8
-烷基羰基氧基、具有1至5個鹵素原子之C1
-C8
-鹵代烷基羰基氧基、C1
-C8
-烷基羰基胺基、具有1至5個鹵素原子之C1
-C8
-鹵代烷基羰基胺基、C1
-C8
-烷基亞磺醯基、具有1至5個鹵素原子之C1
-C8
-鹵代烷基亞磺醯基、C1
-C8
-烷基磺醯基及具有1至5個鹵素原子之C1
-C8
-鹵代烷基-磺醯基;
• Zb
、R1b
、R2b
、R3b
、R6b
、Xb
及Yb
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個鹵素原子之C1
-C8
-鹵代烷基、具有1至5個鹵素原子之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個鹵素原子之C1
-C8
-鹵代烷氧基、C1
-C8
-烷基硫基、具有1至5個鹵素原子之C1
-C8
-鹵代烷基硫基、C1
-C8
-烷基羰基、具有1至5個鹵素原子之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個鹵素原子之C1
-C8
-鹵代烷氧基羰基、C1
-C8
-烷基羰基氧基、具有1至5個鹵素原子之C1
-C8
-鹵代烷基羰基氧基、C1
-C8
-烷基羰基胺基、具有1至5個鹵素原子之C1
-C8
-鹵代烷基羰基胺基、C1
-C8
-烷基硫基、具有1至5個鹵素原子之C1
-C8
-鹵代烷基硫基、C1
-C8
-烷基亞磺醯基、具有1至5個鹵素原子之C1
-C8
-鹵代烷基亞磺醯基、C1
-C8
-烷基磺醯基及具有1至5個鹵素原子之C1
-C8
-鹵代烷基-磺醯基;
以及其鹽、N-氧化物、金屬錯合物、類金屬錯合物及光學活性異構體或幾何異構體。 Active ingredient <br/> The present invention provides a compound of formula (I),
Where A represents a quinolin-3-yl ring, where Q 1 is C; a quinazolin-2-yl ring, where Q 1 is C; or a 1H-benzimidazol-1-yl ring, where Q 1 is N ;
B represents a 5- or 6-membered heterocyclyl ring containing 1, 2, or 3 heteroatoms independently selected from the list consisting of N, O, and S;
• Q 2 is C or N;
• Z is selected from the group consisting of a hydrogen atom, a halogen atom, a C 1 -C 8 -alkyl group, a C 1 -C 8 -haloalkyl group containing up to 9 halogen atoms that may be the same or different, and a C 2 -C 8 - alkenyl group, may contain up to 9 identical or different halogen atoms C 2 -C 8 - haloalkenyl, C 2 -C 8 - alkynyl, C comprising up to 9 identical or different halogen atoms 2 -C 8 -haloalkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, hydroxyl, C 1 -C 8 -alkoxy, containing up to 9 may be the same or different C 1 -C 8 -haloalkoxy, aryl, heterocyclyl, formyl, C 1 -C 8 -alkylcarbonyl, (hydroxyimino) C 1 -C 8 -alkyl, halogen ( C 1 -C 8 -alkoxyimino) C 1 -C 8 -alkyl, carboxyl, C 1 -C 8 -alkoxycarbonyl, carbamoyl, C 1 -C 8 -alkylamino Fluorenyl, di-C 1 -C 8 -alkylaminomethyl, amine, C 1 -C 8 -alkylamino, di-C 1 -C 8 -alkylamino, thio, C 1 -C 8 - alkylthio, C 1 -C 8 - alkylsulfinyl acyl, C 1 -C 8 - alkylsulfonyl group, C 1 -C 6 - trialkyl silicon based, a cyano group and a nitro Group, wherein these C 1 -C 8 -alkyl, C 2 -C 8 - alkenyl, C 2 -C 8 - alkynyl group and C 1 -C 8 - alkoxy group may be substituted with one or more substituents Z a, and where such C 3 -C 7 - cycloalkyl Group, C 4 -C 7 -cycloalkenyl, aryl and heterocyclic group may be substituted with one or more Z b substituents;
• n represents 0, 1, 2, 3, or 4;
• p represents 0, 1, 2, 3, 4 or 5;
• L represents O, S, SO, SO 2 , CR 4 R 5 or NR 6 , wherein ○ R 4 and R 5 are independently selected from the group consisting of hydrogen atom, halogen atom, hydroxyl group, C 1 -C 8 alkane group, may contain up to 9 identical or different halogen atoms C 1 -C 8 - haloalkyl, C 1 -C 8 - alkoxy and C comprising up to 9 identical or different halogen atoms 1 -C 8 -Haloalkoxy, or it may form a carbonyl group with the carbon atom to which it is linked;
○ R 6 is selected from the group consisting of: hydrogen atom, C 1 -C 8 -alkyl, C 1 -C 8 -haloalkyl containing up to 9 halogen atoms which may be the same or different, C 2 -C 8 -ene group, may contain up to 9 identical or different halogen atoms C 2 -C 8 - haloalkenyl, C 3 -C 8 - alkynyl, C comprising up to 9 identical or different halogen atoms 3 -C 8 - haloalkynyl group, C 3 -C 7 - cycloalkyl, may contain up to 9 identical or different halogen atoms C 3 -C 7 - cycloalkyl haloalkyl, C 3 -C 7 - cycloalkyl, -C 1 -C 8 -alkyl, formyl, C 1 -C 8 -alkylcarbonyl, C 1 -C 8 -haloalkylcarbonyl containing up to 9 halogen atoms which may be the same or different, C 1 -C 8 -alkoxycarbonyl, C 1 -C 8 -haloalkoxycarbonyl containing up to 9 halogen atoms which may be the same or different, C 1 -C 8 -alkylsulfonyl, containing up to 9 may be the same or different C 1 -C 8 -haloalkylsulfonyl, aryl-C 1 -C 8 -alkyl and phenylsulfonyl of halogen atom,
Wherein the C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 3 -C 8 -alkynyl can be substituted with one or more R 6a substituents, and wherein the C 3 -C 7 -Cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 8 -alkyl, aryl-C 1 -C 8 -alkyl and phenylsulfonyl may be substituted with one or more R 6b Radical substitution
X is independently selected from the group consisting of: halogen atoms, C 1 -C 8 -alkyl groups, C 1 -C 8 -haloalkyl groups containing up to 9 halogen atoms which may be the same or different, C 2 -C 8- alkenyl group, comprising up to 9 halogen atoms may be the same or different C 2 -C 8 - haloalkenyl, C 2 -C 8 - alkynyl, C comprising up to 9 identical or different halogen atoms of 2 - C 8 -haloalkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, hydroxyl, C 1 -C 8 -alkoxy, containing up to 9 halogens which may be the same or different Atomic C 1 -C 8 -haloalkoxy, C 1 -C 6 -trialkylsilyl, cyano and nitro, wherein these C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl , C 2 -C 8 -alkynyl and C 1 -C 8 -alkoxy may be substituted with one or more X a substituents and these C 3 -C 7 -cycloalkyl and C 4 -C 7 -rings Alkenyl may be substituted with one or more X b substituents;
• Y is independently selected from the group consisting of halogen atoms, C 1 -C 8 -alkyl groups, C 1 -C 8 -haloalkyl groups containing up to 9 halogen atoms which may be the same or different, C 2 -C 8- alkenyl group, comprising up to 9 halogen atoms may be the same or different C 2 -C 8 - haloalkenyl, C 2 -C 8 - alkynyl, C comprising up to 9 identical or different halogen atoms of 2 - C 8 -haloalkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, hydroxyl, C 1 -C 8 -alkoxy, containing up to 9 halogens which may be the same or different Atomic C 1 -C 8 -haloalkoxy, aryl, heterocyclyl, formamyl, C 1 -C 8 -alkylcarbonyl, (hydroxyimino) C 1 -C 8 -alkyl, (C 1- C 8 -alkoxyimino) C 1 -C 8 -alkyl, carboxyl, C 1 -C 8 -alkoxycarbonyl, carbamoyl, C 1 -C 8 -alkylamine Radical, di-C 1 -C 8 -alkylaminomethyl, amine, C 1 -C 8 -alkylamino, di-C 1 -C 8 -alkylamino, thio, C 1- C 8 - alkylthio, C 1 -C 8 - alkylsulfinyl acyl, C 1 -C 8 - alkylsulfonyl group, C 1 -C 6 - trialkyl silicon based, a cyano group and a nitro group , Where these C 1 -C 8 -alkyl, C 2 -C 8 - alkenyl, C 2 -C 8 - alkynyl group and C 1 -C 8 - alkoxy group may be substituted with one or more substituents and Y a wherein those C 3 -C 7 - cycloalkyl, C 4 -C 7 -cycloalkenyl, aryl and heterocyclic groups may be substituted with one or more Y b substituents;
• R 1 is selected from the group consisting of: C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 3 -C 7 -cycloalkyl, C 4- C 7 -cycloalkenyl, aryl, and heterocyclyl, where the C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, and C 2 -C 8 -alkynyl can be passed through one or more R 1a substituents and wherein the C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, aryl and heterocyclic groups may be substituted with one or more R 1b substituents;
• R 2 is selected from the group consisting of: hydroxyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, aryl and heterocyclyl, wherein these C 1 -C 8 -alkoxy, C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl and C 2 -C 8 -alkynyl may be substituted with one or more R 2a substituents and wherein these C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, Aryl and heterocyclic groups may be substituted with one or more R 2b substituents;
• When R 1 and R 2 independently represent C 1 -C 8 alkyl or C 2 -C 8 alkenyl, they may form a C 3 -C 8 -silane ring or C 4 -C 8 -silyl ring, wherein the C 3 -C 8 -silyl ring or C 4 -C 8 -silyl ring may be substituted by one or more R 1b substituents Replace
• R 3 is selected from the group consisting of hydrogen atom, halogen atom, C 1 -C 8 -alkyl group, C 1 -C 8 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, hydroxyl, C 1 -C 8 -alkoxy, aryl, aromatic -C 1 -C 8 -alkyl, heterocyclyl, heterocyclyl -C 1 -C 8 -alkyl, hydroxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy-C 1- C 8 -alkyl, C 1 -C 8 -alkylcarbonyloxy-C 1 -C 8 -alkyl, aryloxy-C 1 -C 8 -alkyl, heterocyclyloxy-C 1- C 8 -alkyl, amino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylamino-C 1 -C 8 -alkyl, di-C 1 -C 8 -alkyl Amino-C 1 -C 8 -alkyl, arylamino-C 1 -C 8 -alkyl, di-arylamino-C 1 -C 8 -alkyl, heterocyclylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxycarbonylamino -C 1 -C 8 -alkyl, C 1 -C 8 -alkylthio-C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinamilide-C 1 -C 8 -alkyl, C 1 -C 8 -alkyl Sulfonyl-C 1 -C 8 -alkyl and cyano-C 1 -C 8 -alkane Group, wherein the C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl and C 2 -C 8 -alkynyl groups may be substituted with one or more R 3a substituents and wherein the C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, aryl, aryl-C 1 -C 8 -alkyl, heterocyclyl, heterocyclyl -C 1 -C 8 -alkyl, aryl Oxy-C 1 -C 8 -alkyl and heterocyclyloxy-C 1 -C 8 -alkyl may be substituted with one or more R 3b substituents;
• When the X is adjacent to SiR 1 R 2 R 3 , R 3 and X may form a 5, 6, or 7-membered partially saturated heterocyclic ring together with the silicon and carbon atoms to which they are connected respectively, wherein the 5, 6 or 7-membered portion A saturated heterocyclic ring may be substituted with one or more R 3b substituents;
• When R 2 represents C 1 -C 8 -alkoxy and R 3 represents C 1 -C 8 -alkoxy or C 1 -C 8 alkyl, it can form 5, 6, or 7-membered heterocyclic ring, wherein the 5, 6 or 7-membered heterocyclic ring may be substituted with one or more R 2b substituents;
• Z a , R 1a , R 2a , R 3a , R 6a , X a and Y a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxy, amine, thio, pentafluoro-λ 6 -thio, formamyl, carbamate, carbamate, C 3 -C 7 -cycloalkyl, C 3 -C 8 -halocycloalkyl having 1 to 5 halogen atoms, C 1 -C 8 -alkylamino, di-C 1 -C 8 -alkylamino, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkoxy having 1 to 5 halogen atoms Radical, C 1 -C 8 -alkylthio, C 1 -C 8 -haloalkylthio having 1 to 5 halogen atoms, C 1 -C 8 -alkylcarbonyl, C 1 -C 8 -haloalkylcarbonyl, C 1 -C 8 -alkylaminomethyl, di-C 1 -C 8 -alkylaminomethyl, C 1 -C 8 -alkoxycarbonyl, having 1-5 halogen atoms C 1 -C 8 - alkoxycarbonyl haloalkoxy, C 1 -C 8 - alkylcarbonyl group having 1-5 C atoms, halogen of 1 -C 8 - haloalkyl alkylcarbonyloxy, C 1 -C 8 - alkylcarbonyl group having a C 1 to 5 halogen atoms 1 -C 8 - alkylcarbonyl haloalkyl group, C 1 -C 8 - alkylsulfinyl acyl having from 1 to 5 Halogen The C 1 -C 8 - haloalkyl alkylsulfinyl acyl, C 1 -C 8 - alkylsulfonyl group and having a C 1 to 5 halogen atoms 1 -C 8 - haloalkyl - sulfo acyl;
• Z b , R 1b , R 2b , R 3b , R 6b , X b and Y b are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amine, thio, penta Fluoro-λ 6 -thio, formamyl, carbamate, carbamate, C 1 -C 8 -alkyl, C 3 -C 7 -cycloalkyl, those having 1 to 5 halogen atoms C 1 -C 8 -haloalkyl, C 3 -C 8 -halocycloalkyl having 1 to 5 halogen atoms, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 1- C 8 -alkylamino, di-C 1 -C 8 -alkylamino, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkoxy having 1 to 5 halogen atoms, C 1 -C 8 - alkylthio, having a C 1 to 5 halogen atoms 1 -C 8 - haloalkyl group, C 1 -C 8 - alkylcarbonyl group having a C 1 to 5 halogen atoms 1-- C 8 -haloalkylcarbonyl, C 1 -C 8 -alkylaminomethyl, di-C 1 -C 8 -alkylaminomethyl, C 1 -C 8 -alkoxycarbonyl, having 1 to 5 halogen atoms C 1 -C 8 - alkoxycarbonyl haloalkoxy, C 1 -C 8 - alkylcarbonyl group having a C 1 to 5 halogen atoms 1 -C 8 - haloalkyl alkylcarbonyloxy, C 1 - C 8 - alkylcarbonyl amine Having a C 1 to 5 halogen atoms 1 -C 8 - alkylcarbonyl haloalkyl group, C 1 -C 8 - alkylthio, having a C 1 to 5 halogen atoms 1 -C 8 - haloalkyl group , C 1 -C 8 -alkylsulfinyl sulfenyl, C 1 -C 8 -haloalkylsulfinyl sulfinyl having 1 to 5 halogen atoms, C 1 -C 8 -alkylsulfinyl sulfinyl and having 1 to C 1 -C 8 -haloalkyl-sulfofluorenyl with 5 halogen atoms;
And its salts, N-oxides, metal complexes, metalloid complexes, and optically active isomers or geometric isomers.
如本文所用,表述「一或多個取代基」係指取代基的數目在1到基於可用鍵結位點之數目的可能取代基最大數目之範圍內,前提係滿足穩定性及化學可行性之條件。As used herein, the expression "one or more substituents" means that the number of substituents ranges from 1 to the maximum number of possible substituents based on the number of available bonding sites, provided that stability and chemical feasibility are met. condition.
如本文所用,鹵素意指氟、氯、溴或碘;甲醯基意指-CH(=O);羧基意指-C(=O)OH;羰基意指-C(=O)-;胺甲醯基意指-C(=O)NH2 ;N-羥基胺甲醯基意指-C(=O)NHOH;三氟甲磺醯基意指-SO2 -CF3 ;SO代表亞碸基團;SO2 代表碸基團;雜原子意指硫、氮或氧;亞甲基意指基團-CH2 -;芳基通常意指苯基或萘基;除非提供不同含義,否則雜環基意指5至7員環、較佳5至6員環,其可係飽和、部分飽和或不飽和,包含1至4個獨立地選自由N、O、S組成之清單中雜原子。As used herein, halogen means fluorine, chlorine, bromine or iodine; formamyl means -CH (= O); carboxy means -C (= O) OH; carbonyl means -C (= O)-; amine Formamyl means -C (= O) NH 2 ; N-hydroxyamine formamyl means -C (= O) NHOH; trifluoromethanesulfonyl means -SO 2 -CF 3 ; SO stands for thallium SO 2 represents a fluorene group; heteroatom means sulfur, nitrogen or oxygen; methylene means the group -CH 2- ; aryl usually means phenyl or naphthyl; unless a different meaning is provided, hetero Cyclo means a 5- to 7-membered ring, preferably a 5- to 6-membered ring, which may be saturated, partially saturated or unsaturated, and contains 1 to 4 heteroatoms independently selected from the list consisting of N, O, and S.
如本文所用,術語「雜環基」涵蓋雜芳基。As used herein, the term "heterocyclyl" encompasses heteroaryl.
如本文在表述「5至7員環」中所用之術語「員」指定構成環之骨架原子的數目。The term "member" as used herein in the expression "5 to 7-membered ring" specifies the number of backbone atoms that make up the ring.
如本文所用,烷基、烯基及炔基以及含有該等術語之部分可為直鏈或具支鏈。As used herein, alkyl, alkenyl, and alkynyl, as well as moieties containing these terms, may be straight or branched.
當胺基或任何其他含胺基之基團的胺基部分經兩個可相同或不同之取代基取代時,該兩個取代基連同其鏈接之氮原子一起可形成5至7員雜環基,該雜環基可經取代或可包括其他雜原子,例如嗎啉基或六氫吡啶基。When the amine group of an amine group or any other amine group-containing group is substituted with two substituents which may be the same or different, the two substituents together with the nitrogen atom to which they are linked may form a 5- to 7-membered heterocyclic group The heterocyclic group may be substituted or may include other heteroatoms such as morpholinyl or hexahydropyridyl.
本發明之任何化合物可以一或多種光學或手性異構體形式存在,此取決於化合物中不對稱中心之數量。因此,本發明同樣係關於所有光學異構體及其外消旋或非外消旋(scalemic)混合物(術語「非外消旋」意指不同比例之對映異構體之混合物)以及呈所有比例之所有可能立體異構體之混合物。非鏡像異構體及/或光學異構體可根據自身已知之方法由熟習此項技術者分離。Any compound of the invention may exist in one or more optical or chiral isomer forms, depending on the number of asymmetric centers in the compound. Therefore, the present invention also relates to all optical isomers and their racemic or non-racemic mixtures (the term "non-racemic" means a mixture of enantiomers in different proportions) and all A mixture of all possible stereoisomers in proportion. Non-mirror isomers and / or optical isomers can be separated by those skilled in the art according to methods known per se.
本發明之任何化合物亦可以一或多種幾何異構體形式存在,此取決於化合物中雙鍵之數量。因此,本發明同樣係關於所有幾何異構體及呈所有比例之所有可能混合物。幾何異構體可根據自身已知之一般方法由熟習此項技術者分離。Any compound of the invention may also exist in one or more geometric isomers, depending on the number of double bonds in the compound. The invention therefore likewise relates to all geometric isomers and all possible mixtures in all proportions. Geometric isomers can be separated by those skilled in the art according to general methods known per se.
本發明之任何化合物亦可以一或多種幾何異構體形式存在,此取決於鏈或環之取代基的相對位置(順/反(syn/anti, cis/trans))。因此,本發明同樣係關於所有順/反(syn/anti或cis/trans)異構體及呈所有比例之所有可能順/反(syn/anti或cis/trans)混合物。順/反(syn/anti或cis/trans)異構體可根據自身已知之一般方法由熟習此項技術者分離。Any compound of the invention may also exist in one or more geometric isomers, depending on the relative position (syn / anti, cis / trans) of the substituents of the chain or ring. Therefore, the present invention also pertains to all syn / anti or cis / trans isomers and all possible syn / anti or cis / trans mixtures in all proportions. The cis / anti or cis / trans isomers can be separated by those skilled in the art according to general methods known per se.
當本發明化合物可以互變異構形式存在時,本發明亦涵蓋該化合物之任何互變異構形式,即使在此並未明確提及時。When a compound of the invention can exist in tautomeric forms, the invention also encompasses any tautomeric form of the compound, even if not explicitly mentioned herein.
式(I)化合物在本文中稱為「活性成分」。Compounds of formula (I) are referred to herein as "active ingredients".
在以上式(I)中,Z較佳選自由以下組成之群:氫原子、鹵素原子、羥基、C1 -C6 -烷基、包含最多9個可相同或不同之鹵素原子之C1 -C6 -鹵代烷基、C1 -C6 -烷氧基、包含最多9個可相同或不同之鹵素原子之C1 -C6 -鹵代烷氧基及氰基,更佳地Z係氫原子或C1 -C6 -烷基、甚至更佳Z係氫原子或甲基。In the above formula (I), Z is preferably selected from the group consisting of: a hydrogen atom, a halogen atom, a hydroxyl group, C 1 -C 6 - alkyl, C comprising up to 9 identical or different halogen atoms 1-- C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and cyano containing up to 9 halogen atoms which may be the same or different, more preferably Z is a hydrogen atom or C 1- C 6 -alkyl, even more preferably a Z-based hydrogen atom or a methyl group.
在以上式(I)中,n較佳為0、1或2,更佳地0或1。In the above formula (I), n is preferably 0, 1 or 2, and more preferably 0 or 1.
在以上式(I)中,p較佳為0、1、2或3,更佳0、1或2,甚至更佳0。In the above formula (I), p is preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and even more preferably 0.
在以上式(I)中,L較佳為O、C=O、CH(OH)、CH(OCH3 )、CH(OAc)、NH或CH2 ,更佳O、C=O、NH或CH2 ,甚至更佳O、CH2 及C=O。In the above formula (I), L is preferably O, C = O, CH (OH), CH (OCH 3 ), CH (OAc), NH or CH 2 , more preferably O, C = O, NH or CH 2 and even better O, CH 2 and C = O.
在以上式(I)中,X較佳獨立地係鹵素原子、C1 -C6 -烷基、包含最多9個可相同或不同之鹵素原子之C1 -C6 -鹵代烷基或C1 -C6 -烷氧基,更佳X獨立地係溴原子、氯原子、氟原子、甲基、甲氧基或三氟甲基、甚至更佳X獨立地係氯原子、氟原子或甲基。In the above formula (I), X is preferably independently a halogen atom, a C 1 -C 6 -alkyl group, a C 1 -C 6 -haloalkyl group or a C 1 -group containing up to 9 halogen atoms which may be the same or different C 6 -alkoxy, more preferably X is independently a bromine atom, a chlorine atom, a fluorine atom, a methyl group, a methoxy group or a trifluoromethyl group, and even more preferably X is independently a chlorine atom, a fluorine atom or a methyl group.
在以上式(I)中,Y較佳獨立地選自由以下組成之群:鹵素原子、C1 -C6 -烷基、包含最多9個可相同或不同之鹵素原子之C1 -C6 -鹵代烷基、C1 -C6 -烷氧基、包含最多9個可相同或不同之鹵素原子之C1 -C6 -鹵代烷氧基及氰基,更佳Y獨立地選自由以下組成之群:鹵素原子、C1 -C6 -烷基及包含最多9個可相同或不同之鹵素原子之C1 -C6 -鹵代烷基,甚至更佳Y獨立地係氟原子、氯原子、甲基或三氟甲基。In the above formula (I), Y is preferably independently selected from the group consisting of: a halogen atom, C 1 -C 6 - alkyl comprising up to 9 halogen atoms may be the same or different C 1 -C 6 - Haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and cyano containing up to 9 halogen atoms which may be the same or different, and more preferably Y is independently selected from the group consisting of: Halogen atom, C 1 -C 6 -alkyl group and C 1 -C 6 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, even more preferably Y is independently a fluorine atom, a chlorine atom, a methyl group or a tris Fluoromethyl.
在一些實施例中,Y係鹵素原子。In some embodiments, Y is a halogen atom.
在以上式(I)中,R1 較佳為C1 -C6 -烷基,更佳甲基。In the above formula (I), R 1 is preferably a C 1 -C 6 -alkyl group, and more preferably a methyl group.
在以上式(I)中,R2 較佳為C1 -C6 -烷基,更佳甲基。In the above formula (I), R 2 is preferably a C 1 -C 6 -alkyl group, and more preferably a methyl group.
在以上式(I)中,R3 較佳選自由以下組成之群:氫、羥基、C1 -C6 -烷基、包含最多9個可相同或不同之鹵素原子之C1 -C6 -鹵代烷基、C1 -C6 -烯基、C1 -C6 -烷氧基、芳基(例如苯基及C1 -C6 -烷基氧基-苯基)、芳基-C1 -C6 -烷基、雜環基及雜環基-C1 -C6 -烷基,更佳R3 選自由以下組成之群:氫、C1 -C6 -烷基、包含最多9個可相同或不同之鹵素原子之C1 -C6 -鹵代烷基、C1 -C6 -烯基、芳基及芳基-C1 -C6 -烷基,甚至更佳R3 係氫、甲基、乙基、氯甲基、乙烯基、烯丙基、苯基或苄基。In the above formula (I), R 3 is preferably selected from the group consisting of: hydrogen, hydroxy, C 1 -C 6 - alkyl group, it may contain up to 9 identical or different halogen atoms C 1 -C 6 - Haloalkyl, C 1 -C 6 -alkenyl, C 1 -C 6 -alkoxy, aryl (e.g. phenyl and C 1 -C 6 -alkyloxy-phenyl), aryl -C 1- C 6 -alkyl, heterocyclyl and heterocyclyl-C 1 -C 6 -alkyl, more preferably R 3 is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, containing up to 9 may C 1 -C 6 -haloalkyl, C 1 -C 6 -alkenyl, aryl and aryl-C 1 -C 6 -alkyl with identical or different halogen atoms, even more preferably R 3 hydrogen, methyl , Ethyl, chloromethyl, vinyl, allyl, phenyl or benzyl.
在以上式(I)中,Q1 較佳為碳原子。In the above formula (I), Q 1 is preferably a carbon atom.
在以上式(I)中,B較佳選自由以下組成之群:
較佳地,B選自由以下組成之群:B1
、B2
、B3
、B4
、B5
、B10
、B12
、B14
、B16
及B19
,
其中
R1
、R2
及R3
係如上文所揭示;
Q4
係O、S或NY7
,其中Y7
為氫原子或C1
-C8
-烷基;
X1
、X2
及X3
獨立地係氫原子或如上文所揭示之X,較佳地,X1
、X2
及X3
獨立地選自由以下組成之群:氫原子、C1
-C6
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基及C1
-C6
-烷氧基,更佳X獨立地係氫原子、溴原子、氯原子、氟原子、甲基、甲氧基或三氟甲基,甚至更佳X獨立地係氫原子、氯原子、氟原子或甲基。In the above formula (I), B is preferably selected from the group consisting of:
Preferably, B is selected from the group consisting of: B 1, B 2, B 3, B 4, B 5, B 10, B 12, B 14, B 16 and B. 19,
among them
R 1 , R 2 and R 3 are as disclosed above;
Q 4 is O, S or NY 7 , wherein Y 7 is a hydrogen atom or a C 1 -C 8 -alkyl group;
X 1 , X 2 and X 3 are independently a hydrogen atom or X as disclosed above, preferably X 1 , X 2 and X 3 are independently selected from the group consisting of hydrogen atom, C 1 -C 6 -Alkyl, C 1 -C 6 -haloalkyl and C 1 -C 6 -alkoxy containing up to 9 halogen atoms which may be the same or different, more preferably X is independently a hydrogen atom, a bromine atom, a chlorine atom, A fluorine atom, methyl, methoxy or trifluoromethyl, even more preferably X is independently a hydrogen atom, a chlorine atom, a fluorine atom or a methyl group.
在一些實施例中,B選自由以下組成之群:吡啶基、嘧啶基、吡唑基、吡咯基、咪唑基、噻吩基、噻唑基、異噻唑基及異噁唑基,較佳地,B選自由以下組成之群:吡啶基、嘧啶基、吡唑基、吡咯基、咪唑基、噻吩基及異噁唑基。In some embodiments, B is selected from the group consisting of pyridyl, pyrimidinyl, pyrazolyl, pyrrolyl, imidazolyl, thienyl, thiazolyl, isothiazolyl, and isoxazolyl, preferably, B It is selected from the group consisting of pyridyl, pyrimidinyl, pyrazolyl, pyrrolyl, imidazolyl, thienyl, and isoxazolyl.
在一些實施例中,B選自由以下組成之群:吡啶基、嘧啶基、噻吩基、呋喃基、吡咯基、吡唑基及咪唑基,較佳為吡啶基、嘧啶基及吡咯基。In some embodiments, B is selected from the group consisting of pyridyl, pyrimidinyl, thienyl, furyl, pyrrolyl, pyrazolyl, and imidazolyl, preferably pyridyl, pyrimidinyl, and pyrrolyl.
適宜基團(其中「#」表示B環至L基團之連接點且「*」表示B環至CH2 SiR1 R2 R3 基團之連接點)之非限制性實例包括表1之行「」中所列示之任何基團。suitable Non-limiting examples of groups (where "#" represents the point of attachment of the B ring to the L group and "*" represents the point of attachment of the B ring to the CH 2 SiR 1 R 2 R 3 group) include the line in Table 1 " ".
在一些實施例中,A係:
其中:
X1
為CY1
或N;
Y1
、Y2
、Y3
、Y4
及Y5
獨立地係氫原子或如上文所揭示之Y,較佳地,Y1
、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、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基、C1
-C6
-烷氧基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷氧基及氰基,更佳Y1
、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
-烷基及包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基,甚至更佳Y1
、Y2
、Y3
、Y4
及Y5
獨立地係氫原子、氟原子、氯原子、甲基或三氟甲基;及
Z係如上文所揭示,較佳地,Z選自由以下組成之群:氫原子、鹵素原子、羥基、未經取代或經取代之C1
-C6
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基、未經取代或經取代之C1
-C6
-烷氧基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷氧基及氰基,更佳Z係氫原子或未經取代或經取代之C1
-C6
-烷基,甚至更佳Z係氫原子或甲基。In some embodiments, A is:
among them:
X 1 is CY 1 or N;
Y 1 , Y 2 , Y 3 , Y 4 and Y 5 are independently a hydrogen atom or Y as disclosed above, preferably, Y 1 , Y 2 , Y 3 , Y 4 and Y 5 are independently selected from the following Composition group: hydrogen atom, halogen atom, C 1 -C 6 -alkyl group, C 1 -C 6 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, C 1 -C 6 -alkoxy group, C 1 -C 6 -haloalkoxy and cyano containing up to 9 halogen atoms which may be the same or different, more preferably Y 1 , Y 2 , Y 3 , Y 4 and Y 5 are independently selected from the group consisting of: Hydrogen, halogen, C 1 -C 6 -alkyl and C 1 -C 6 -haloalkyl containing up to 9 halogen atoms which may be the same or different, even more preferably Y 1 , Y 2 , Y 3 , Y 4 And Y 5 is independently a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a trifluoromethyl group; and
Z is as disclosed above, preferably, Z is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an unsubstituted or substituted C 1 -C 6 -alkyl group, containing up to 9 may be the same or C 1 -C 6 -haloalkyl with different halogen atoms, unsubstituted or substituted C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkane containing up to 9 halogen atoms which may be the same or different Oxygen and cyano, more preferably a Z-based hydrogen atom or an unsubstituted or substituted C 1 -C 6 -alkyl group, even more preferably a Z-based hydrogen atom or a methyl group.
在一些實施例中,A係:
其中:
X1
為CY1
或N;
Y1
、Y2
、Y3
、Y4
及Y5
獨立地係氫原子或鹵素原子;且
Z係氫原子或甲基,
適宜之非限制性實例包括表1之行「」中所列示之任何基團。In some embodiments, A is:
among them:
X 1 is CY 1 or N;
Y 1 , Y 2 , Y 3 , Y 4 and Y 5 are independently a hydrogen atom or a halogen atom; and
Z is a hydrogen atom or a methyl group,
suitable Non-limiting examples include the line in Table 1, ".
在一些實施例中,本發明之化合物係式(I)化合物
其中:
• A代表喹啉-3-基環(Q1
為C)、喹喏啉-2-基環(Q1
為C)或1H-苯并咪唑-1-基環(Q1
為N);
• B選自由以下組成之群:吡啶基、嘧啶基、吡唑基、吡咯基、咪唑基、噻吩基、噻唑基、異噻唑基及異噁唑基,較佳B選自由以下組成之群:吡啶基、嘧啶基、吡唑基、吡咯基、咪唑基、噻吩基及異噁唑基;
• Q2
係C或N;
• Z選自由以下組成之群:氫原子、鹵素原子、羥基、C1
-C6
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基、C1
-C6
-烷氧基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷氧基及氰基,較佳地,Z係氫原子或C1
-C6
-烷基,更佳Z係氫原子或甲基;
• n係0、1或2,較佳0或1;
• p代表0、1、2或3,較佳0、1或2;
• L代表O、C=O、CH(OH)、CH(OCH3
)、CH(OAc)、NH或CH2
,更佳O、C=O、NH或CH2
;
• X獨立地選自由以下組成之群:鹵素原子、C1
-C6
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基及C1
-C6
-烷氧基,較佳X獨立地係溴原子、氯原子、氟原子、甲基、甲氧基或三氟甲基,更佳X獨立地係氯原子、氟原子或甲基;
• Y獨立地選自由以下組成之群:鹵素原子、C1
-C6
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基、C1
-C6
-烷氧基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷氧基及氰基,較佳地Y獨立地選自由以下組成之群:鹵素原子、C1
-C6
-烷基及包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基,更佳Y獨立地係氟原子、氯原子、甲基或三氟甲基;甚至更佳Y係氟原子或氯原子;
• R1
係C1
-C6
-烷基、較佳甲基;
• R2
係C1
-C6
-烷基、較佳甲基;
• R3
選自由以下組成之群:氫、羥基、C1
-C6
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基、C1
-C6
-烯基、C1
-C6
-烷氧基、芳基(例如苯基及C1
-C6
-烷基氧基-苯基)、芳基-C1
-C6
-烷基、雜環基及雜環基-C1
-C6
-烷基,較佳R3
選自由以下組成之群:氫、C1
-C6
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基、C1
-C6
-烯基、芳基及芳基-C1
-C6
-烷基,更佳R3
係氫、甲基、乙基、氯甲基、乙烯基、烯丙基、苯基或苄基。In some embodiments, the compound of the invention is a compound of formula (I)
among them:
• A represents a quinolin-3-yl ring (Q 1 is C), a quinazolin-2-yl ring (Q 1 is C), or a 1H-benzimidazol-1-yl ring (Q 1 is N);
• B is selected from the group consisting of pyridyl, pyrimidinyl, pyrazolyl, pyrrolyl, imidazolyl, thienyl, thiazolyl, isothiazolyl and isoxazolyl, preferably B is selected from the group consisting of Pyridyl, pyrimidinyl, pyrazolyl, pyrrolyl, imidazolyl, thienyl and isoxazolyl;
• Q 2 is C or N;
• Z is selected from the group consisting of hydrogen atom, halogen atom, hydroxyl group, C 1 -C 6 -alkyl group, C 1 -C 6 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, C 1- C 6 -alkoxy, C 1 -C 6 -haloalkoxy and cyano containing up to 9 halogen atoms which may be the same or different, preferably Z is a hydrogen atom or C 1 -C 6 -alkyl, More preferably, Z is a hydrogen atom or a methyl group;
N is 0, 1, or 2, preferably 0 or 1;
• p represents 0, 1, 2 or 3, preferably 0, 1 or 2;
L stands for O, C = O, CH (OH), CH (OCH 3 ), CH (OAc), NH or CH 2 , more preferably O, C = O, NH or CH 2 ;
X is independently selected from the group consisting of halogen atoms, C 1 -C 6 -alkyl groups, C 1 -C 6 -haloalkyl groups containing up to 9 halogen atoms which may be the same or different, and C 1 -C 6- Alkoxy, preferably X is independently a bromine atom, a chlorine atom, a fluorine atom, a methyl group, a methoxy group or a trifluoromethyl group, and more preferably X is independently a chlorine atom, a fluorine atom or a methyl group;
• Y is independently selected from the group consisting of halogen atoms, C 1 -C 6 -alkyl groups, C 1 -C 6 -haloalkyl groups containing up to 9 halogen atoms which may be the same or different, C 1 -C 6- Alkoxy, C 1 -C 6 -haloalkoxy and cyano containing up to 9 halogen atoms which may be the same or different, preferably Y is independently selected from the group consisting of: halogen atom, C 1 -C 6 -Alkyl and C 1 -C 6 -haloalkyl containing up to 9 halogen atoms which may be the same or different, more preferably Y is independently a fluorine atom, a chlorine atom, a methyl group or a trifluoromethyl group; even more preferably a Y system Fluorine atom or chlorine atom;
• R 1 is C 1 -C 6 -alkyl, preferably methyl;
• R 2 is C 1 -C 6 -alkyl, preferably methyl;
• R 3 is selected from the group consisting of: hydrogen, hydroxyl, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl containing up to 9 halogen atoms which may be the same or different, C 1 -C 6- Alkenyl, C 1 -C 6 -alkoxy, aryl (e.g. phenyl and C 1 -C 6 -alkyloxy-phenyl), aryl -C 1 -C 6 -alkyl, heterocyclyl heterocyclyl and -C 1 -C 6 - group consisting of alkyl, R 3 is preferably selected from the group consisting of: hydrogen, C 1 -C 6 - alkyl, C comprising up to 9 identical or different halogen atoms 1 -C 6 -haloalkyl, C 1 -C 6 -alkenyl, aryl and aryl-C 1 -C 6 -alkyl, more preferably R 3 hydrogen, methyl, ethyl, chloromethyl, vinyl , Allyl, phenyl or benzyl.
在一些實施例中,本發明之化合物係式(I)化合物,其中:
• A係A1
或A2
,較佳A1
,其中
○ X1
為CY1
或N;
○ Y1
、Y2
、Y3
、Y4
及Y5
獨立地係氫原子或如上文所揭示之Y,較佳地,Y1
、Y2
、Y3
、Y4
及Y5
獨立地選自由以下組成之群:氫原子、鹵素原子、經取代或未經取代之C1
-C6
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基、未經取代或經取代之C1
-C6
-烷氧基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷氧基及氰基,更佳Y1
、Y2
、Y3
、Y4
及Y5
獨立地選自由以下組成之群:氫原子、鹵素原子及未經取代或經取代之C1
-C6
-烷基,甚至更佳Y1
、Y2
、Y3
、Y4
及Y5
獨立地係氫原子、氟原子、氯原子、甲基或三氟甲基;
○ Z係如上文所揭示,較佳地,Z選自由以下組成之群:氫原子、鹵素原子、羥基、未經取代或經取代之C1
-C6
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷基、未經取代或經取代之C1
-C6
-烷氧基、包含最多9個可相同或不同之鹵素原子之C1
-C6
-鹵代烷氧基及氰基,更佳Z係氫原子或未經取代或經取代之C1
-C6
-烷基,甚至更佳Z係氫原子或甲基;及
• B係如上文所揭示,較佳B係吡啶、嘧啶或吡咯;
• L係如上文所揭示,較佳L係O、C=O、NH或CH2
;
• X係如上文所揭示,較佳X獨立地係鹵素原子或未經取代或經取代之C1
-C6
-烷基,更佳X獨立地係氯原子、氟原子或甲基;
• n係如上文所揭示,較佳n為0、1或2;
• R1
、R2
及R3
係如本文所揭示,較佳R1
係未經取代或經取代之C1
-C6
-烷基、更佳甲基;較佳R2
係未經取代或經取代之C1
-C6
-烷基、更佳甲基;較佳R3
選自由以下組成之群:羥基、未經取代或經取代之C1
-C6
-烷基、未經取代或經取代之C3
-C7
-環烷基、未經取代或經取代之芳基、未經取代或經取代之芳基-C1
-C6
-烷基、未經取代或經取代之雜環基及未經取代或經取代之雜環基-C1
-C6
-烷基,更佳R3
選自由以下組成之群:未經取代或經取代之C1
-C6
-烷基、未經取代或經取代之芳基、未經取代或經取代之芳基-C1
-C6
-烷基及未經取代或經取代之雜環基,甚至更佳R3
係甲基、苯基、噻吩基或苄基。In some embodiments, the compound of the present invention is a compound of formula (I), wherein:
• A is A 1 or A 2 , preferably A 1 , where ○ X 1 is CY 1 or N;
○ Y 1 , Y 2 , Y 3 , Y 4 and Y 5 are independently hydrogen atoms or Y as disclosed above, preferably, Y 1 , Y 2 , Y 3 , Y 4 and Y 5 are independently selected from A group consisting of: a hydrogen atom, a halogen atom, a substituted or unsubstituted C 1 -C 6 -alkyl group, a C 1 -C 6 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, Substituted or substituted C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and cyano containing up to 9 halogen atoms which may be the same or different, more preferably Y 1 , Y 2 , Y 3 , Y 4 and Y 5 are independently selected from the group consisting of a hydrogen atom, a halogen atom, and an unsubstituted or substituted C 1 -C 6 -alkyl group, even more preferably Y 1 , Y 2 , Y 3 , Y 4 and Y 5 are independently a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a trifluoromethyl group;
○ Z is as disclosed above, preferably, Z is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an unsubstituted or substituted C 1 -C 6 -alkyl group, containing up to 9 may be the same or halogen atoms different from C 1 -C 6 - haloalkyl, unsubstituted or substituted with of C 1 -C 6 - alkoxy group, may contain up to 9 identical or different halogen atoms C 1 -C 6 - Haloalkoxy and cyano, more preferably Z is a hydrogen atom or an unsubstituted or substituted C 1 -C 6 -alkyl group, even more preferably Z is a hydrogen atom or a methyl group; and B is as disclosed above, Preferred B is pyridine, pyrimidine or pyrrole;
L is as disclosed above, preferably L is O, C = O, NH or CH 2 ;
X is as disclosed above, preferably X is independently a halogen atom or an unsubstituted or substituted C 1 -C 6 -alkyl group, and more preferably X is independently a chlorine atom, a fluorine atom or a methyl group;
N is as disclosed above, preferably n is 0, 1 or 2;
• R 1 , R 2 and R 3 are as disclosed herein, preferably R 1 is unsubstituted or substituted C 1 -C 6 -alkyl, more preferably methyl; preferably R 2 is unsubstituted or Substituted C 1 -C 6 -alkyl, more preferably methyl; preferably R 3 is selected from the group consisting of: hydroxyl, unsubstituted or substituted C 1 -C 6 -alkyl, unsubstituted or Substituted C 3 -C 7 -cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted aryl-C 1 -C 6 -alkyl, unsubstituted or substituted hetero Cyclic and unsubstituted or substituted heterocyclyl-C 1 -C 6 -alkyl, more preferably R 3 is selected from the group consisting of: unsubstituted or substituted C 1 -C 6 -alkyl, Unsubstituted or substituted aryl, unsubstituted or substituted aryl-C 1 -C 6 -alkyl and unsubstituted or substituted heterocyclic group, even more preferably R 3 is methyl, benzene Group, thienyl or benzyl.
本發明化合物之取代基之上述較佳者可以各種方式組合。較佳特徵之該等組合由此提供本發明化合物之子類。本發明較佳化合物之該等子類之實例係:
- A之較佳特徵以及B、Q1
、Q2
、L、R1
、R2
、R3
、n、p、X、Y及Z之一或多個較佳特徵;
- B之較佳特徵以及A、Q1
、Q2
、L、R1
、R2
、R3
、n、p、X、Y及Z之一或多個較佳特徵;
- Q1
之較佳特徵以及A、B、Q2
、L、R1
、R2
、R3
、n、p、X、Y及Z之一或多個較佳特徵;
- Q2
之較佳特徵以及A、Q1
、L、R1
、R2
、R3
、n、p、X、Y及Z之一或多個較佳特徵;
- L之較佳特徵以及A、B、Q1
、Q2
、R1
、R2
、R3
、n、p、X、Y及Z之一或多個較佳特徵;
- R1
之較佳特徵以及A、B、Q1
、Q2
、L、R2
、R3
、n、p、X、Y及Z之一或多個較佳特徵;
- R2
之較佳特徵以及A、B、Q1
、Q2
、L、R1
、R3
、n、p、X、Y及Z之一或多個較佳特徵;
- R3
之較佳特徵以及A、B、Q1
、Q2
、L、R1
、R2
、n、p、X、Y及Z之一或多個較佳特徵;
- n之較佳特徵以及A、B、Q1
、Q2
、L、R1
、R2
、R3
、p、X、Y及Z之一或多個較佳特徵;
- p之較佳特徵以及A、B、Q1
、Q2
、L、R1
、R2
、R3
、n、X、Y及Z之一或多個較佳特徵;
- X之較佳特徵以及A、B、Q1
、Q2
、L、R1
、R2
、R3
、n、p、Y及Z之一或多個較佳特徵;
- Y之較佳特徵以及A、B、Q1
、Q2
、L、R1
、R2
、R3
、n、p、X及Z之一或多個較佳特徵;
- Z之較佳特徵以及A、B、Q1
、Q2
、L、R1
、R2
、R3
、n、p、X及Y之一或多個較佳特徵。The above-mentioned preferred ones of the substituents of the compounds of the present invention may be combined in various ways. These combinations of preferred features thus provide a subclass of the compounds of the invention. Examples of such subclasses of preferred compounds of the invention are:
-Preferred features of A and one or more preferred features of B, Q 1 , Q 2 , L, R 1 , R 2 , R 3 , n, p, X, Y, and Z;
-Preferred features of B and one or more preferred features of A, Q 1 , Q 2 , L, R 1 , R 2 , R 3 , n, p, X, Y and Z;
-Preferred features of Q 1 and one or more preferred features of A, B, Q 2 , L, R 1 , R 2 , R 3 , n, p, X, Y and Z;
-Preferred features of Q 2 and one or more preferred features of A, Q 1 , L, R 1 , R 2 , R 3 , n, p, X, Y and Z;
-Preferred features of L and one or more preferred features of A, B, Q 1 , Q 2 , R 1 , R 2 , R 3 , n, p, X, Y and Z;
-Preferred features of R 1 and one or more preferred features of A, B, Q 1 , Q 2 , L, R 2 , R 3 , n, p, X, Y and Z;
-Preferred features of R 2 and one or more preferred features of A, B, Q 1 , Q 2 , L, R 1 , R 3 , n, p, X, Y and Z;
-Preferred features of R 3 and one or more preferred features of A, B, Q 1 , Q 2 , L, R 1 , R 2 , n, p, X, Y and Z;
-preferred features of n and one or more preferred features of A, B, Q 1 , Q 2 , L, R 1 , R 2 , R 3 , p, X, Y, and Z;
-preferred features of p and one or more preferred features of A, B, Q 1 , Q 2 , L, R 1 , R 2 , R 3 , n, X, Y, and Z;
-Preferred features of X and one or more preferred features of A, B, Q 1 , Q 2 , L, R 1 , R 2 , R 3 , n, p, Y and Z;
-Preferred features of Y and one or more preferred features of A, B, Q 1 , Q 2 , L, R 1 , R 2 , R 3 , n, p, X and Z;
-One or more of the preferred characteristics of Z, and one or more of A, B, Q 1 , Q 2 , L, R 1 , R 2 , R 3 , n, p, X, and Y.
在本發明化合物之取代基之較佳特徵的該等組合中,該等較佳特徵亦可選自A、B、Q1 、Q2 、L、R1 、R2 、R3 、n、p、X、Y及Z中每一者之更佳特徵,以形成本發明化合物之最佳子類。In these combinations of preferred characteristics of the substituents of the compounds of the present invention, these preferred characteristics may also be selected from A, B, Q 1 , Q 2 , L, R 1 , R 2 , R 3 , n, p , X, Y, and Z each have better characteristics to form the best subclass of the compounds of the present invention.
製備活性化合物之方法
本發明亦包含製備式(I)化合物之方法。 Method for preparing an active compound <br/> The present invention also includes a method for preparing a compound of formula (I).
式(I)化合物(其中Q2
代表C)可藉由製程P1製備,其包含以下步驟:使式(II)之鹵代甲基雜芳基或其鹽中之一者:
其中A、B、Q1
、L、n、p、X、Y及Z係如本文所定義且Q2
代表C且U1
代表氯原子、溴原子、碘原子、甲磺醯基、甲苯磺醯基或三氟甲磺醯基;與式(IIIa)之二矽基衍生物反應:
其中R1
、R2
及R3
係如本文所定义。The compound of formula (I) (where Q 2 represents C) can be prepared by process P1, which comprises the following steps: one of the halomethylheteroaryl groups of the formula (II) or a salt thereof:
Wherein A, B, Q 1 , L, n, p, X, Y and Z are as defined herein and Q 2 represents C and U 1 represents a chlorine atom, a bromine atom, an iodine atom, a mesylsulfonyl group, a tosylsulfonium Or trifluoromethanesulfonyl; react with a disilyl derivative of formula (IIIa):
Wherein R 1 , R 2 and R 3 are as defined herein.
製程P1可在過渡金屬觸媒(例如鈀)之存在下且(若適當)在膦配體或N-雜環碳烯配體之存在下、(若適當)在鹼之存在下且(若適當)在溶劑之存在下根據已知製程來實施(Organic Letters (2003),5 , 3483, Organic Letters (2007),9 , 3785及其中之引用參考文獻)。Process P1 can be in the presence of a transition metal catalyst (such as palladium) and (if appropriate) in the presence of a phosphine ligand or N-heterocyclic carbene ligand, (if appropriate) in the presence of a base and (if appropriate) ) It is carried out according to a known process in the presence of a solvent (Organic Letters (2003), 5 , 3483, Organic Letters (2007), 9 , 3785 and references cited therein).
式(II)衍生物(其中A、B、Q1
、L、n、p、X、Y及Z係如本文所定義且Q2
代表C且U1
代表氯原子或溴原子)可根據已知製程藉由式(IV)之甲苯衍生物或其鹽中之一者之自由基鹵化來製備:
其中A、B、Q1
、L、n、p、X、Y及Z係如本文所定義且Q2
代表C。Derivatives of formula (II) (where A, B, Q 1 , L, n, p, X, Y, and Z are as defined herein and Q 2 represents C and U 1 represents a chlorine atom or a bromine atom) can be based on known The process is prepared by free radical halogenation of a toluene derivative of formula (IV) or one of its salts:
Wherein A, B, Q 1 , L, n, p, X, Y and Z are as defined herein and Q 2 represents C.
式(IV)之衍生物(其中A、Q1 、L、n、p、X、Y及Z係如本文所定義且Q2 代表C)可根據製程P3製備。Derivatives of formula (IV) (wherein A, Q 1 , L, n, p, X, Y and Z are as defined herein and Q 2 represents C) can be prepared according to process P3.
式(II)之衍生物(其中A、B、Q1
、L、n、p、X、Y及Z係如本文所定義且Q2
代表C且U1
代表氯原子、溴原子、碘原子、甲磺醯基、甲苯磺醯基或三氟甲磺醯基)可根據已知製程藉由式(V)之羥基甲基衍生物或其鹽中之一者之鹵化或磺化來製備:
其中A、B、Q1
、L、n、p、X、Y及Z係如本文所定義且Q2
代表C。Derivatives of formula (II) (wherein A, B, Q 1 , L, n, p, X, Y and Z are as defined herein and Q 2 represents C and U 1 represents a chlorine atom, a bromine atom, an iodine atom, Methanesulfonyl, tosylsulfonyl or trifluoromethanesulfonyl) can be prepared according to known processes by halogenation or sulfonation of a hydroxymethyl derivative of formula (V) or one of its salts:
Wherein A, B, Q 1 , L, n, p, X, Y and Z are as defined herein and Q 2 represents C.
式(IIIa)之二矽基衍生物係已知的或可藉由已知製程來製備。The two silicon-based derivatives of formula (IIIa) are known or can be prepared by known processes.
式(I)化合物(其中R3 代表羥基)可自式(I)化合物(其中R3 代表未經取代或經取代之C1 -C6 -烷氧基)(其自身藉由製程P1製備)根據已知製程藉由酸性水解來製備(Organic Letters (2003),5 , 3483)。Compounds of formula (I) (where R 3 represents a hydroxyl group) can be prepared from compounds of formula (I) (where R 3 represents an unsubstituted or substituted C 1 -C 6 -alkoxy group) (which is itself prepared by process P1) It is prepared by acidic hydrolysis according to known processes (Organic Letters (2003), 5 , 3483).
式(I)化合物(其中R3 代表氟原子)可自式(I)化合物(其中R3 代表未經取代或經取代之C1 -C6 -烷氧基)(其自身藉由製程P1製備)藉由已知製程來製備(Synlett (2012),23 , 1064及其中之引用參考文獻)或可自式(I)化合物(其中R3 代表羥基)藉由已知製程來製備(EP1908472)。Compounds of formula (I) (wherein R 3 represents a fluorine atom) can be prepared from compounds of formula (I) (wherein R 3 represents unsubstituted or substituted C 1 -C 6 -alkoxy) (by themselves prepared by process P1 ) Can be prepared by known processes (Synlett (2012), 23 , 1064 and cited references therein) or can be prepared by known processes from compounds of formula (I) (wherein R 3 represents a hydroxyl group) (EP1908472).
製程P1可在觸媒(例如金屬鹽或錯合物)之存在下實施。用於此目的之適宜金屬衍生物係過渡金屬觸媒,例如鈀。用於此目的之適宜金屬鹽或錯合物係(例如)氯化鈀、乙酸鈀、四(三苯基膦)鈀(0)、雙(二亞苄基丙酮)鈀(0)、參(二亞苄基-丙酮)二鈀(0)、雙(三苯基膦)二氯化鈀(II)、[1,1’-雙(二苯基膦基)-二茂鐵]二氯鈀(II)、雙(桂醯基)二氯二鈀(II)、雙(烯丙基)-二氯二鈀(II)或[1,1’-雙(二-第三丁基膦基)二茂鐵]二氯鈀(II)。The process P1 can be implemented in the presence of a catalyst (such as a metal salt or a complex). Suitable metal derivatives for this purpose are transition metal catalysts, such as palladium. Suitable metal salts or complexes for this purpose are, for example, palladium chloride, palladium acetate, tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0), Dibenzylidene-acetone) dipalladium (0), bis (triphenylphosphine) palladium (II) chloride, [1,1'-bis (diphenylphosphino) -ferrocene] dichloropalladium (II), bis (lauryl) dichlorodipalladium (II), bis (allyl) -dichlorodipalladium (II), or [1,1'-bis (di-third-butylphosphino) Ferrocene] Dichloropalladium (II).
亦可藉由將鈀鹽及配體或鹽單獨添加至反應中在反應混合物中生成鈀錯合物,該配體或鹽係例如三乙基膦、三-第三丁基膦、三-第三丁基鏻四氟硼酸鹽、三環己基膦、2-(二環己基膦基)聯苯、2-(二-第三丁基膦基)聯苯、2-(二環己基膦基)-2'-(N,N-二甲基胺基)聯苯、2-(第三丁基膦基)-2'-(N,N-二甲基胺基)聯苯、2-二-第三丁基膦基-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-(二苯基膦基)苯磺酸鈉、參-2-(甲氧基-苯基)膦、2,2'-雙(二苯基膦基)-1,1'-聯萘、1,4-雙(二苯基膦基)丁烷、1,2-雙(二苯基膦基)乙烷、1,4-雙(二環己基膦基)丁烷、1,2-雙(二環己基膦基)-乙烷、2-(二環己基膦基)-2'-(N,N-二甲基胺基)-聯苯、1,1’-雙(二苯基膦基)-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-嗎啉基苯基膦或氯化1,3-雙(2,4,6-三甲基苯基)咪唑鎓鹽。The palladium complex can also be formed in the reaction mixture by separately adding a palladium salt and a ligand or salt to the reaction. The ligand or salt is, for example, triethylphosphine, tri-third-butylphosphine, tri- Tributylphosphonium tetrafluoroborate, tricyclohexylphosphine, 2- (dicyclohexylphosphino) biphenyl, 2- (di-third-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2- (third butylphosphino) -2'-(N, N-dimethylamino) biphenyl, 2-di- Third butylphosphino-2 ', 4', 6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl, 2-di Cyclohexylphosphino-2,6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2 ', 6'-diisopropoxybiphenyl, triphenyl-phosphine, gins- (o-toluene Group) phosphine, sodium 3- (diphenylphosphino) benzenesulfonate, gins-2- (methoxy-phenyl) phosphine, 2,2'-bis (diphenylphosphino) -1,1 ' -Binaphthalene, 1,4-bis (diphenylphosphino) butane, 1,2-bis (diphenylphosphino) ethane, 1,4-bis (dicyclohexylphosphino) butane, 1 , 2-bis (dicyclohexylphosphino) -ethane, 2- (dicyclohexylphosphino) -2 '-(N, N-dimethylamino) -biphenyl, 1,1'-bis ( (Diphenylphosphino) -ferrocene, (R )-(-)-1-[(S) -2-diphenyl-phosphino) ferrocenyl] ethyldicyclohexylphosphine, p- (2,4-tert-butyl-phenyl) Phosphate, bis (1-adamantyl) -2-morpholinylphenylphosphine or 1,3-bis (2,4,6-trimethylphenyl) imidazolium chloride.
亦有利的係自商業目錄選擇適當觸媒及/或配體,例如Strem Chemicals之「Metal Catalysts for Organic Synthesis」或Strem Chemicals之「Phosphorous Ligands and Compounds」。It is also advantageous to select the appropriate catalyst and / or ligand from a commercial catalog, such as "Metal Catalysts for Organic Synthesis" by Strem Chemicals or "Phosphorous Ligands and Compounds" by Strem Chemicals.
用於實施製程P1之適宜鹼可係常用於該等反應之無機鹼及有機鹼。較佳者係使用鹼土金屬或鹼金屬氫氧化物,例如氫氧化鈉、氫氧化鈣、氫氧化鉀或其他氫氧化銨衍生物;鹼土金屬、鹼金屬或銨氟化物,例如氟化鉀、氟化銫或四丁基氟化銨;鹼土金屬或鹼金屬碳酸鹽,例如碳酸鈉、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,例如乙酸鈉、乙酸鋰、乙酸鉀或乙酸鈣;鹼金屬或鹼土金屬磷酸鹽,例如磷酸三鉀;鹼金屬醇鹽,例如第三丁醇鉀或第三丁醇鈉;三級胺,例如三甲胺、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-甲基六氫吡啶、N,N-二甲基胺基吡啶、二氮雜雙環辛烷(DABCO)、二氮雜雙環壬烯(DBN)或二氮雜雙環十一烯(DBU);以及芳香族鹼,例如吡啶、甲基吡啶、二甲基吡啶或三甲基吡啶。Suitable bases for implementing process P1 may be inorganic bases and organic bases commonly used in these reactions. Preferred are alkaline earth metal or alkali metal hydroxides, such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or other ammonium hydroxide derivatives; alkaline earth metal, alkali metal, or ammonium fluoride compounds such as potassium fluoride, fluorine Caesium or tetrabutylammonium fluoride; alkaline earth or alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, or cesium carbonate; alkali or alkaline earth metal acetates, such as sodium acetate, lithium acetate , Potassium acetate or calcium acetate; alkali metal or alkaline earth metal phosphates, such as tripotassium phosphate; alkali metal alkoxides, such as potassium tert-butoxide or sodium tert-butoxide; tertiary amines, such as trimethylamine, triethylamine, Tributylamine, N, N-dimethylaniline, N, N-dicyclohexylmethylamine, N, N-diisopropylethylamine, N-methylhexahydropyridine, N, N-dimethylamine Pyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU); and aromatic bases such as pyridine, methylpyridine, dimethylpyridine Or trimethylpyridine.
用於實施製程P1之適宜溶劑可為常用惰性有機溶劑。較佳者係使用視情況經鹵化之脂肪族、脂環族或芳香族烴,例如石油醚、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、氯仿、四氯化碳、二氯乙烷或三氯乙烷;醚,例如二乙醚、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,例如乙腈、丙腈、正丁腈或異丁腈或苄腈;醯胺,例如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,例如1,3-二甲基-3,4,5,6-四氫-2(1H)-嘧啶酮;酯,例如乙酸甲酯或乙酸乙酯;亞碸,例如二甲亞碸;或碸,例如環丁碸;及其混合物。A suitable solvent for implementing the process P1 may be a commonly used inert organic solvent. The preferred ones are halogenated aliphatic, cycloaliphatic or aromatic hydrocarbons, such as petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene Or decahydronaphthalene; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl Ether, methyltripentyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitrile , Such as acetonitrile, propionitrile, n-butyronitrile, or isobutyronitrile or benzonitrile; ammonium, such as N, N -dimethylformamide, N, N -dimethylacetamide, N -methylformamide Aniline, N -methylpyrrolidone or hexamethylphosphonium triamine; urea, such as 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidone; ester, Examples are methyl acetate or ethyl acetate; osmium, such as dimethylarsine; or osmium, such as cyclobutane; and mixtures thereof.
亦可有利的係利用共溶劑(例如水或醇,例如甲醇、乙醇、丙醇、異丙醇或第三丁醇)實施製程P1。It may also be advantageous to implement process P1 using a co-solvent (such as water or an alcohol, such as methanol, ethanol, propanol, isopropanol, or tertiary butanol).
製程P1可在惰性氣氛(例如氬或氮氣氛)中實施。在實施製程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莫耳鹼以及0.01至20莫耳%之鈀錯合物。亦可採用其他比率之反應組分。藉由已知方法來進行實驗處理。Process P1 can be performed in an inert atmosphere (such as an argon or nitrogen atmosphere). When implementing process P1, 1 mole or an excess of the compound of formula (III), 1 to 5 mole base, and 0.01 to 20 mole% palladium complex can be used per mole of the compound of formula (II). Other ratios of reaction components can also be used. Experimental treatment was performed by known methods.
式(I)化合物(其中Q2
代表C)可藉由製程P2製備,該製程P2包含以下步驟:使式(VI)化合物或其鹽中之一者:
其中A、B、Q1
、L、n、p、X、Y及Z係如本文所定義且Q2
代表C且U2
代表氯原子、溴原子、碘原子、甲磺醯基、甲苯磺醯基或三氟甲磺醯基;與式(IIIb)之硼衍生物反應:
其中W3
代表硼衍生物,例如硼酸、硼酸酯或三氟硼酸鉀衍生物;
R1
及R2
獨立地代表C1
-C8
-烷基、C2-
C8
-烯基、C3
-C7
-環烷基、芳基或雜環基;
其中該等C1
-C8
-烷基及C2
-C8
-烯基可經一或多個R1a
或R2a
取代基取代且其中該等C3
-C7
-環烷基、芳基及雜環基可經一或多個R1b
或R2b
取代基取代;且
R3
代表氫原子、鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、C2
-C8
-炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、C1
-C8
-烷氧基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、羥基-C1
-C8
-烷基、C1
-C8
-烷氧基-C1
-C8
-烷基、C1
-C8
-烷基羰基氧基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基、雜環基氧基-C1
-C8
-烷基、胺基-C1
-C8
-烷基、C1
-C8
-烷基胺基-C1
-C8
-烷基、二-C1
-C8
-烷基胺基-C1
-C8
-烷基、芳基胺基-C1
-C8
-烷基、二-芳基胺基-C1
-C8
-烷基、雜環基胺基-C1
-C8
-烷基、C1
-C8
-烷基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷氧基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷基硫基-C1
-C8
-烷基、C1
-C8
-烷基亞磺醯基-C1
-C8
-烷基、C1
-C8
-烷基磺醯基-C1
-C8
-烷基及氰基-C1
-C8
-烷基,其中該等C1
-C8
-烷基、C2
-C8
-烯基及C2
-C8
-炔基可經一或多個R3a
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基及雜環基氧基-C1
-C8
-烷基可經一或多個R3b
取代基取代。The compound of formula (I) (where Q 2 represents C) can be prepared by process P2, which comprises the following steps: one of the compound of formula (VI) or a salt thereof:
Wherein A, B, Q 1 , L, n, p, X, Y and Z are as defined herein and Q 2 represents C and U 2 represents a chlorine atom, a bromine atom, an iodine atom, a mesylsulfonyl group, a tosylsulfonium Or trifluoromethanesulfonyl; react with a boron derivative of formula (IIIb):
Wherein W 3 represents a boron derivative, such as a boric acid, a borate or a potassium trifluoroborate derivative;
R 1 and R 2 independently represent C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 3 -C 7 -cycloalkyl, aryl or heterocyclic group;
Wherein these C 1 -C 8 -alkyl and C 2 -C 8 -alkenyl may be substituted by one or more R 1a or R 2a substituents and wherein these C 3 -C 7 -cycloalkyl, aryl And heterocyclyl may be substituted with one or more R 1b or R 2b substituents; and
R 3 represents a hydrogen atom, a halogen atom, a C 1 -C 8 -alkyl group, a C 1 -C 8 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, a C 2 -C 8 -alkenyl group, a C 2 -C 8 -alkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, C 1 -C 8 -alkoxy, aryl, aryl-C 1 -C 8 -alkane Group, heterocyclyl, heterocyclyl-C 1 -C 8 -alkyl, hydroxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonyloxy-C 1 -C 8 -alkyl, aryloxy-C 1 -C 8 -alkyl, heterocyclyloxy -C 1 -C 8 -alkyl, amine -C 1 -C 8 -alkyl, C 1 -C 8 -alkylamino-C 1 -C 8 -alkyl, di-C 1 -C 8 -alkylamino -C 1 -C 8- Alkyl, arylamino-C 1 -C 8 -alkyl, di-arylamino-C 1 -C 8 -alkyl, heterocyclylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxycarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylthio -C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinylsulfenyl-C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinyl-C 1 -C 8 -Alkyl and cyano-C 1 -C 8 -alkyl, wherein these C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl and C 2 -C 8 -alkynyl may be substituted with one or more R 3a substituents and wherein these C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloolefin , Aryl, aryl-C 1 -C 8 -alkyl, heterocyclyl, heterocyclyl-C 1 -C 8 -alkyl, aryloxy-C 1 -C 8 -alkyl and heterocyclic The alkoxy-C 1 -C 8 -alkyl group may be substituted with one or more R 3b substituents.
R1a 、R2a 、R1b 、R2b 、R3a 及R3b 取代基係如本文所揭示。R 1a , R 2a , R 1b , R 2b , R 3a and R 3b substituents are as disclosed herein.
式(VI)之衍生物(其中A、B、Q1
、L、n、p、X、Y及Z係如本文所定義且Q2
代表C且U2
代表氯原子、溴原子或碘原子)可根據已知製程藉由式(VII)之苯胺或其鹽中之一者之重氮化來製備:
其中A、B、Q1
、L、n、p、X、Y及Z係如本文所定義且Q2
代表C (Patai's Chemistry of Functional Groups - Amino, Nitroso, Nitro and Related Groups - 1996)。Derivatives of formula (VI) (wherein A, B, Q 1 , L, n, p, X, Y and Z are as defined herein and Q 2 represents C and U 2 represents a chlorine atom, a bromine atom or an iodine atom) It can be prepared according to a known process by diazotization of one of aniline of formula (VII) or a salt thereof:
Wherein A, B, Q 1 , L, n, p, X, Y, and Z are as defined herein and Q 2 represents C (Patai's Chemistry of Functional Groups-Amino, Nitroso, Nitro and Related Groups-1996).
式(VII)之苯胺可根據已知製程藉由硝基之還原來製備(Patai's Chemistry of Functional Groups - Amino, Nitroso, Nitro and Related Groups - 1996)。Aniline of formula (VII) can be prepared by reduction of a nitro group according to a known process (Patai's Chemistry of Functional Groups-Amino, Nitroso, Nitro and Related Groups-1996).
式(IIIb)之硼衍生物係已知的或可藉由已知製程來製備。Boron derivatives of formula (IIIb) are known or can be prepared by known processes.
製程P2可在過渡金屬觸媒(例如鈀)之存在下且(若適當)在膦配體或N-雜環碳烯配體之存在下且(若適當)在鹼之存在下且(若適當)在溶劑之存在下實施。用於此目的之適宜鈀鹽或錯合物可如關於製程P1所揭示。Process P2 can be in the presence of a transition metal catalyst (e.g. palladium) and (if appropriate) in the presence of a phosphine ligand or N-heterocyclic carbene ligand and (if appropriate) in the presence of a base and (if appropriate) ) Is carried out in the presence of a solvent. Suitable palladium salts or complexes for this purpose may be as disclosed in relation to process P1.
用於實施製程P2之適宜鹼可如關於製程P1所揭示。Suitable bases for implementing process P2 may be as disclosed with respect to process P1.
用於實施製程P2之適宜溶劑可如關於製程P1所揭示。Suitable solvents for implementing process P2 may be as disclosed with respect to process P1.
亦可有利的係利用共溶劑(例如水或醇,例如甲醇、乙醇、丙醇、異丙醇或第三丁醇)實施本發明之製程P2。It may also be advantageous to implement the process P2 of the present invention using a co-solvent (such as water or an alcohol, such as methanol, ethanol, propanol, isopropanol, or third butanol).
製程P2可在惰性氣氛中實施。在實施製程P2時,每莫耳式(VI)化合物可採用1莫耳或過量之式(IIIb)化合物及1至5莫耳鹼以及0.01至20莫耳%之過渡金屬錯合物。亦可採用其他比率之反應組分。藉由已知方法來進行實驗處理。Process P2 can be implemented in an inert atmosphere. In the implementation of the process P2, 1 mole or an excess of the compound of the formula (IIIb) and 1 to 5 mole base and 0.01 to 20 mole% of the transition metal complex can be used per mole of the compound of formula (VI). Other ratios of reaction components can also be used. Experimental treatment was performed by known methods.
式(I)化合物(其中Q2
代表C)可藉由製程P3來製備,該製程P3包含以下步驟:使式(VI)化合物或其鹽中之一者:
其中A、B、Q1
、L、n、p、X、Y及Z係如本文所定義且Q2
代表C且U2
代表氯原子、溴原子、碘原子、甲磺醯基、甲苯磺醯基或三氟甲磺醯基;與式(IIIc)之有機金屬衍生物反應:
其中M1
代表鹼土金屬(例如鋰)、鎂衍生物(例如格氏試劑(Grignard reagent)或鋅衍生物(例如有機鋅試劑)。The compound of formula (I) (where Q 2 represents C) can be prepared by process P3, which comprises the following steps: one of the compound of formula (VI) or a salt thereof:
Wherein A, B, Q 1 , L, n, p, X, Y and Z are as defined herein and Q 2 represents C and U 2 represents a chlorine atom, a bromine atom, an iodine atom, a mesylsulfonyl group, a tosylsulfonium Or trifluoromethanesulfonyl; react with an organometallic derivative of formula (IIIc):
Wherein M 1 represents an alkaline earth metal (such as lithium), a magnesium derivative (such as a Grignard reagent) or a zinc derivative (such as an organic zinc reagent).
R1
及R2
獨立地代表C1
-C8
-烷基、C2-
C8
-烯基、C3
-C7
-環烷基、芳基或雜環基,其中該等C1
-C8
-烷基及C2
-C8
-烯基可經一或多個R1a
或R2a
取代基取代且其中該等C3
-C7
-環烷基、芳基及雜環基可經一或多個R1b
或R2b
取代基取代;且
R3
代表氫原子、鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、C2
-C8
-炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、C1
-C8
-烷氧基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、羥基-C1
-C8
-烷基、C1
-C8
-烷氧基-C1
-C8
-烷基、C1
-C8
-烷基羰基氧基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基、雜環基氧基-C1
-C8
-烷基、胺基-C1
-C8
-烷基、C1
-C8
-烷基胺基-C1
-C8
-烷基、二-C1
-C8
-烷基胺基-C1
-C8
-烷基、芳基胺基-C1
-C8
-烷基、二-芳基胺基-C1
-C8
-烷基、雜環基胺基-C1
-C8
-烷基、C1
-C8
-烷基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷氧基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷基硫基-C1
-C8
-烷基、C1
-C8
-烷基亞磺醯基-C1
-C8
-烷基、C1
-C8
-烷基磺醯基-C1
-C8
-烷基及氰基-C1
-C8
-烷基,其中該等C1
-C8
-烷基、C2
-C8
-烯基及C2
-C8
-炔基可經一或多個R3a
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基及雜環基氧基-C1
-C8
-烷基可經一或多個R3b
取代基取代。R 1 and R 2 independently represent C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 3 -C 7 -cycloalkyl, aryl or heterocyclyl, wherein these C 1 -C 8 -alkyl and C 2 -C 8 -alkenyl may be substituted by one or more R 1a or R 2a substituents and wherein the C 3 -C 7 -cycloalkyl, aryl and heterocyclic groups may be substituted by one Or more R 1b or R 2b substituents; and
R 3 represents a hydrogen atom, a halogen atom, a C 1 -C 8 -alkyl group, a C 1 -C 8 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, a C 2 -C 8 -alkenyl group, a C 2 -C 8 -alkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, C 1 -C 8 -alkoxy, aryl, aryl-C 1 -C 8 -alkane Group, heterocyclyl, heterocyclyl-C 1 -C 8 -alkyl, hydroxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonyloxy-C 1 -C 8 -alkyl, aryloxy-C 1 -C 8 -alkyl, heterocyclyloxy -C 1 -C 8 -alkyl, amine -C 1 -C 8 -alkyl, C 1 -C 8 -alkylamino-C 1 -C 8 -alkyl, di-C 1 -C 8 -alkylamino -C 1 -C 8- Alkyl, arylamino-C 1 -C 8 -alkyl, di-arylamino-C 1 -C 8 -alkyl, heterocyclylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxycarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylthio -C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinylsulfenyl-C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinyl-C 1 -C 8 -Alkyl and cyano-C 1 -C 8 -alkyl, wherein these C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl and C 2 -C 8 -alkynyl may be substituted with one or more R 3a substituents and wherein these C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloolefin , Aryl, aryl-C 1 -C 8 -alkyl, heterocyclyl, heterocyclyl-C 1 -C 8 -alkyl, aryloxy-C 1 -C 8 -alkyl and heterocyclic The alkoxy-C 1 -C 8 -alkyl group may be substituted with one or more R 3b substituents.
式(IIIc)之有機金屬衍生物係已知的或可藉由已知製程來製備。Organometallic derivatives of formula (IIIc) are known or can be prepared by known processes.
製程P3可在過渡金屬觸媒(例如鈀)之存在下且(若適當)在膦配體或N-雜環碳烯配體之存在下且(若適當)在鹼之存在下且(若適當)在溶劑之存在下實施。用於此目的之適宜鈀鹽或錯合物可如關於製程P1所揭示。Process P3 can be in the presence of a transition metal catalyst (e.g. palladium) and (if appropriate) in the presence of a phosphine ligand or N-heterocyclic carbene ligand and (if appropriate) in the presence of a base and (if appropriate) ) Is carried out in the presence of a solvent. Suitable palladium salts or complexes for this purpose may be as disclosed in relation to process P1.
用於實施製程P3之適宜鹼可如關於製程P1所揭示。Suitable bases for implementing process P3 may be as disclosed with respect to process P1.
用於實施製程P3之適宜溶劑可如關於製程P1所揭示。Suitable solvents for implementing process P3 may be as disclosed with respect to process P1.
製程P3可在惰性氣氛(例如氬或氮氣氛)中實施。在實施製程P3時,每莫耳式(VI)化合物可採用1莫耳或過量之式(IIIc)化合物及1至5莫耳鹼以及0.01至20莫耳%之過渡金屬錯合物。亦可採用其他比率之反應組分。藉由已知方法來進行實驗處理。Process P3 can be implemented in an inert atmosphere (such as an argon or nitrogen atmosphere). In the implementation of process P3, 1 mole or an excess of the compound of formula (IIIc) and 1 to 5 mole bases and 0.01 to 20 mole% of the transition metal complex can be used per mole of the compound of formula (VI). Other ratios of reaction components can also be used. Experimental treatment was performed by known methods.
式(I)化合物(其中Q1
代表C)可藉由製程P4來製備,其包含以下步驟:使式(VIII)之化合物或其鹽中之一者與式(IX)化合物反應,如以下反應方案中所圖解說明:
製程P4
其中L代表O、S或NR6
;
U3
代表氯原子、溴原子、碘原子、甲磺醯基、甲苯磺醯基或三氟甲磺醯基;
R1
及R2
獨立地代表C1
-C8
-烷基、C2-
C8
-烯基、C3
-C7
-環烷基、芳基或雜環基;
其中該等C1
-C8
-烷基及C2
-C8
-烯基可經一或多個R1a
或R2a
取代基取代且其中該等C3
-C7
-環烷基、芳基及雜環基可經一或多個R1b
或R2b
取代基取代;且
R3
代表氫原子、鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、C2
-C8
-炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、C1
-C8
-烷氧基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、羥基-C1
-C8
-烷基、C1
-C8
-烷氧基-C1
-C8
-烷基、C1
-C8
-烷基羰基氧基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基、雜環基氧基-C1
-C8
-烷基、胺基-C1
-C8
-烷基、C1
-C8
-烷基胺基-C1
-C8
-烷基、二-C1
-C8
-烷基胺基-C1
-C8
-烷基、芳基胺基-C1
-C8
-烷基、二-芳基胺基-C1
-C8
-烷基、雜環基胺基-C1
-C8
-烷基、C1
-C8
-烷基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷氧基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷基硫基-C1
-C8
-烷基、C1
-C8
-烷基亞磺醯基-C1
-C8
-烷基、C1
-C8
-烷基磺醯基-C1
-C8
-烷基及氰基-C1
-C8
-烷基;
其中該等C1
-C8
-烷基、C2
-C8
-烯基及C2
-C8
-炔基可經一或多個R3a
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基及雜環基氧基-C1
-C8
-烷基可經一或多個R3b
取代基取代,且
A、B、Q2
、n、p、X、Y、R6
、R1a
、R2a
、R1b
、R2b
、R3a
、R3b
及Z係如本文所定義。The compound of formula (I) (where Q 1 represents C) can be prepared by process P4, which comprises the following steps: reacting one of the compound of formula (VIII) or a salt thereof with a compound of formula (IX), as shown in the following reaction Illustrated in the plan:
Process P4
Where L represents O, S or NR 6 ;
U 3 represents a chlorine atom, a bromine atom, an iodine atom, a mesylsulfonyl group, a tosylsulfonyl group or a trifluoromethanesulfonyl group;
R 1 and R 2 independently represent C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 3 -C 7 -cycloalkyl, aryl or heterocyclic group;
Wherein these C 1 -C 8 -alkyl and C 2 -C 8 -alkenyl may be substituted by one or more R 1a or R 2a substituents and wherein these C 3 -C 7 -cycloalkyl, aryl And heterocyclyl may be substituted with one or more R 1b or R 2b substituents; and
R 3 represents a hydrogen atom, a halogen atom, a C 1 -C 8 -alkyl group, a C 1 -C 8 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, a C 2 -C 8 -alkenyl group, a C 2 -C 8 -alkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, C 1 -C 8 -alkoxy, aryl, aryl-C 1 -C 8 -alkane Group, heterocyclyl, heterocyclyl-C 1 -C 8 -alkyl, hydroxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonyloxy-C 1 -C 8 -alkyl, aryloxy-C 1 -C 8 -alkyl, heterocyclyloxy -C 1 -C 8 -alkyl, amine -C 1 -C 8 -alkyl, C 1 -C 8 -alkylamino-C 1 -C 8 -alkyl, di-C 1 -C 8 -alkylamino -C 1 -C 8- Alkyl, arylamino-C 1 -C 8 -alkyl, di-arylamino-C 1 -C 8 -alkyl, heterocyclylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxycarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylthio -C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinylsulfenyl-C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinyl-C 1 -C 8 -Alkyl and cyano-C 1 -C 8 -alkyl;
Wherein the C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl and C 2 -C 8 -alkynyl can be substituted with one or more R 3a substituents and wherein the C 3 -C 7- Cycloalkyl, C 4 -C 7 -cycloalkenyl, aryl, aryl-C 1 -C 8 -alkyl, heterocyclyl, heterocyclyl -C 1 -C 8 -alkyl, aryloxy -C 1 -C 8 -alkyl and heterocyclyloxy-C 1 -C 8 -alkyl may be substituted with one or more R 3b substituents, and
A, B, Q 2 , n, p, X, Y, R 6 , R 1a , R 2a , R 1b , R 2b , R 3a , R 3b and Z are as defined herein.
式(IX)化合物係商業購得的或可藉由熟知製程來製備。Compounds of formula (IX) are commercially available or can be prepared by well-known procedures.
製程P4可在過渡金屬觸媒(例如鈀)之存在下且(若適當)在膦配體或N-雜環碳烯配體之存在下;或銅且(若適當)在配體之存在下;且(若適當)在鹼之存在下且(若適當)在溶劑之存在下根據已知製程來實施(Organic Letters (2012),14 , 170, Organic Letters (2002), 4, 1623及其中之引用參考文獻)。Process P4 can be in the presence of a transition metal catalyst (such as palladium) and (if appropriate) in the presence of a phosphine ligand or an N-heterocyclic carbene ligand; or copper and (if appropriate) in the presence of a ligand ; And (if appropriate) in the presence of a base and (if appropriate) in the presence of a solvent according to known processes (Organic Letters (2012), 14 , 170, Organic Letters (2002), 4, 1623 and (Citing references).
適宜基於鈀之觸媒可如關於製程P1所揭示。Suitable palladium-based catalysts can be disclosed as for process P1.
用於此目的之適宜銅鹽或錯合物及其水合物係(例如)銅金屬、碘化銅(I)、氯化銅(I)、溴化銅(I)、氯化銅(II)、溴化銅(II)、氧化銅(II)、氧化銅(I)、乙酸銅(II)、乙酸銅(I)、噻吩-2-甲酸銅(I)、氰化銅(I)、硫酸銅(II)、雙(2,2,6,6-四甲基-3,5-庚二酮酸)銅、三氟甲烷磺酸銅(II)、六氟磷酸四(乙腈)銅(I)、四氟硼酸四(乙腈)-銅(I)。Suitable copper salts or complexes for this purpose and hydrates thereof (e.g. copper metal, copper (I) iodide, copper (I) chloride, copper (I) bromide, copper (II) chloride) , Copper (II) bromide, copper (II) oxide, copper (I) oxide, copper (II) acetate, copper (I) acetate, copper thiophene-2-carboxylate (I), copper (I) cyanide, sulfuric acid Copper (II), bis (2,2,6,6-tetramethyl-3,5-heptanedione) copper, copper (II) trifluoromethanesulfonate, copper (I) hexafluorophosphate ), Tetrafluoroborate tetra (acetonitrile) -copper (I).
亦可能藉由將銅鹽及配體或鹽單獨添加至反應在反應混合物中產生銅錯合物,該銅鹽及配體或鹽係(例如)乙二胺、N,N-二甲基乙二胺、N,N’-二甲基乙二胺、外消旋-反式-1,2-二胺基環己烷、外消旋-反式-N,N’-二甲基環己烷-1,2-二胺、1,1’-聯萘基-2,2’-二胺、N,N,N’,N’-四甲基乙二胺、脯胺酸、N,N-二甲基甘胺酸、喹啉-8-醇、吡啶、2-胺基吡啶、4-(二甲基胺基)吡啶、2,2’-聯吡啶、2,6-二(2-吡啶基)吡啶、2-吡啶甲酸、2-(二甲基胺基甲基)-3-羥基吡啶、1,10-菲咯啉、3,4,7,8-四甲基-1,10-菲咯啉、2,9-二甲基-1,10-菲咯啉、4,7-二甲氧基-1,10-菲咯啉、N,N'-雙[(E)-吡啶-2-基亞甲基]環己烷-1,2-二胺、N-[(E)-苯基亞甲基]、N-[(E)-苯基亞甲基]-環己胺、1,1,1-參(羥基甲基)乙烷、乙二醇、2,2,6,6-四甲基庚烷-3,5-二酮、2-(2,2-二甲基丙醯基)環己酮、乙醯基丙酮、二苯甲醯基甲烷、2-(2-甲基丙醯基)環己酮、聯苯-2-基(二-第三丁基 )磷烷、伸乙基雙-(二苯基膦)、N,N-二乙基柳基醯胺、2-羥基苯甲醛 肟、側氧基[(2,4,6-三甲基苯基)胺基]乙酸或1H-吡咯-2-甲酸。It is also possible to produce copper complexes in the reaction mixture by adding copper salts and ligands or salts separately to the reaction. The copper salts and ligands or salts are, for example, ethylenediamine, N, N-dimethylethyl Diamine, N, N'-dimethylethylenediamine, racemic-trans-1,2-diaminocyclohexane, racemic-trans-N, N'-dimethylcyclohexane Alkan-1,2-diamine, 1,1'-binapthyl-2,2'-diamine, N, N, N ', N'-tetramethylethylenediamine, proline, N, N -Dimethylglycine, quinoline-8-ol, pyridine, 2-aminopyridine, 4- (dimethylamino) pyridine, 2,2'-bipyridine, 2,6-bis (2- Pyridyl) pyridine, 2-picolinic acid, 2- (dimethylaminomethyl) -3-hydroxypyridine, 1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10 -Phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-dimethoxy-1,10-phenanthroline, N, N'-bis [(E) -pyridine 2-ylmethylene] cyclohexane-1,2-diamine, N-[(E) -phenylmethylene], N-[(E) -phenylmethylene] -cyclohexylamine , 1,1,1-ginseng (hydroxymethyl) ethane, ethylene glycol, 2,2,6,6-tetramethylheptane-3,5-dione, 2- (2,2-dimethyl Propylpropanyl) cyclohexanone, ethanylacetone, benzophenymethane, 2- (2-methylpropanyl) cyclohexanone, -2-yl (B - tert-butyl) phosphine, ethyl-bis stretch - (diphenylphosphine), N, N- diethyl Liu Amides group, 2-hydroxybenzaldehyde oxime, oxo [(2,4,6-trimethylphenyl) amino] acetic acid or 1H-pyrrole-2-carboxylic acid.
亦有利的是自Strem Chemicals之商業目錄(例如「Metal Catalysts for Organic Synthesis」)或綜述(Chemical Society Reviews (2014),43 , 3525, Coordination Chemistry Reviews (2004),248 , 2337及其中之參考文獻)選擇適當觸媒及/或配體。Also advantageous are commercial catalogs (e.g., "Metal Catalysts for Organic Synthesis") or reviews from Strem Chemicals (Chemical Society Reviews (2014), 43 , 3525, Coordination Chemistry Reviews (2004), 248 , 2337 and references therein). Select the appropriate catalyst and / or ligand.
用於實施製程P4之適宜鹼可如關於製程P1所揭示。Suitable bases for implementing process P4 may be as disclosed with respect to process P1.
用於實施製程P4之適宜溶劑可如關於製程P1所揭示。Suitable solvents for implementing process P4 may be as disclosed with respect to process P1.
製程P4可在惰性氣氛(例如氬或氮氣氛)中實施。在實施製程P4時,每莫耳式(VIII)化合物可採用1莫耳或過量之式(IX)化合物及1至5莫耳鹼以及0.01至20莫耳%之過渡金屬錯合物。亦可採用其他比率之反應組分。藉由已知方法來進行實驗處理。Process P4 can be performed in an inert atmosphere (such as an argon or nitrogen atmosphere). When implementing the process P4, 1 mole or an excess of the compound of formula (IX) and 1 to 5 mole base and 0.01 to 20 mole% of the transition metal complex can be used per mole of the compound of formula (VIII). Other ratios of reaction components can also be used. Experimental treatment was performed by known methods.
式(I)化合物(其中Q1
代表C)可藉由製程P5來製備,其包含以下步驟:使式(X)化合物或其鹽中之一者與式(XI)化合物反應,如以下反應方案中所圖解說明:
製程P5
其中L代表CR4
R5
;
R4
及R5
獨立地代表氫原子或未經取代或經取代之C1
-C8
烷基;
U4
代表溴原子、氯原子、碘原子、甲磺醯基、甲苯磺醯基或三氟甲磺醯基;
W1
代表硼衍生物,例如硼酸、硼酸酯或三氟硼酸鉀衍生物;
R1
及R2
獨立地代表C1
-C8
-烷基、C2-
C8
-烯基、C3
-C7
-環烷基、芳基或雜環基;
其中該等C1
-C8
-烷基及C2
-C8
-烯基可經一或多個R1a
或R2a
取代基取代且其中該等C3
-C7
-環烷基、芳基及雜環基可經一或多個R1b
或R2b
取代基取代;且
R3
代表氫原子、鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、C2
-C8
-炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、C1
-C8
-烷氧基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、羥基-C1
-C8
-烷基、C1
-C8
-烷氧基-C1
-C8
-烷基、C1
-C8
-烷基羰基氧基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基、雜環基氧基-C1
-C8
-烷基、胺基-C1
-C8
-烷基、C1
-C8
-烷基胺基-C1
-C8
-烷基、二-C1
-C8
-烷基胺基-C1
-C8
-烷基、芳基胺基-C1
-C8
-烷基、二-芳基胺基-C1
-C8
-烷基、雜環基胺基-C1
-C8
-烷基、C1
-C8
-烷基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷氧基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷基硫基-C1
-C8
-烷基、C1
-C8
-烷基亞磺醯基-C1
-C8
-烷基、C1
-C8
-烷基磺醯基-C1
-C8
-烷基及氰基-C1
-C8
-烷基;
其中該等C1
-C8
-烷基、C2
-C8
-烯基及C2
-C8
-炔基可經一或多個R3a
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基及雜環基氧基-C1
-C8
-烷基可經一或多個R3b
取代基取代,且
A、B、Q2
、n、p、X、Y、R1a
、R2a
、R1b
、R2b
、R3a
、R3b
及Z係如本文所定義。The compound of formula (I) (where Q 1 represents C) can be prepared by process P5, which comprises the following steps: reacting one of the compound of formula (X) or a salt thereof with a compound of formula (XI), as shown in the following reaction scheme Illustrated in:
Process P5
Where L represents CR 4 R 5 ;
R 4 and R 5 independently represent a hydrogen atom or an unsubstituted or substituted C 1 -C 8 alkyl group;
U 4 represents a bromine atom, a chlorine atom, an iodine atom, a mesylsulfonyl group, a tosylsulfonyl group or a trifluoromethanesulfonyl group;
W 1 represents a boron derivative, such as a boric acid, borate or potassium trifluoroborate derivative;
R 1 and R 2 independently represent C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 3 -C 7 -cycloalkyl, aryl or heterocyclic group;
Wherein these C 1 -C 8 -alkyl and C 2 -C 8 -alkenyl may be substituted by one or more R 1a or R 2a substituents and wherein these C 3 -C 7 -cycloalkyl, aryl And heterocyclyl may be substituted with one or more R 1b or R 2b substituents; and
R 3 represents a hydrogen atom, a halogen atom, a C 1 -C 8 -alkyl group, a C 1 -C 8 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, a C 2 -C 8 -alkenyl group, a C 2 -C 8 -alkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, C 1 -C 8 -alkoxy, aryl, aryl-C 1 -C 8 -alkane Group, heterocyclyl, heterocyclyl-C 1 -C 8 -alkyl, hydroxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonyloxy-C 1 -C 8 -alkyl, aryloxy-C 1 -C 8 -alkyl, heterocyclyloxy -C 1 -C 8 -alkyl, amine -C 1 -C 8 -alkyl, C 1 -C 8 -alkylamino-C 1 -C 8 -alkyl, di-C 1 -C 8 -alkylamino -C 1 -C 8- Alkyl, arylamino-C 1 -C 8 -alkyl, di-arylamino-C 1 -C 8 -alkyl, heterocyclylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxycarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylthio -C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinylsulfenyl-C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinyl-C 1 -C 8 -Alkyl and cyano-C 1 -C 8 -alkyl;
Wherein the C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl and C 2 -C 8 -alkynyl can be substituted with one or more R 3a substituents and wherein the C 3 -C 7- Cycloalkyl, C 4 -C 7 -cycloalkenyl, aryl, aryl-C 1 -C 8 -alkyl, heterocyclyl, heterocyclyl -C 1 -C 8 -alkyl, aryloxy -C 1 -C 8 -alkyl and heterocyclyloxy-C 1 -C 8 -alkyl may be substituted with one or more R 3b substituents, and
A, B, Q 2 , n, p, X, Y, R 1a , R 2a , R 1b , R 2b , R 3a , R 3b and Z are as defined herein.
式(XI)化合物可藉由已知製程來製備(Journal of the American Chemical Society (1957),79 , 6540;Journal of Organic Chemistry (2000), (65), 4913;Tetrahedron Letters (2002),43 , 8569)。Compounds of formula (XI) can be prepared by known processes (Journal of the American Chemical Society (1957), 79 , 6540; Journal of Organic Chemistry (2000), (65), 4913; Tetrahedron Letters (2002), 43 , 8569).
製程P5可在過渡金屬觸媒(例如鈀)之存在下且(若適當)在膦配體或N-雜環碳烯配體之存在下且(若適當)在鹼之存在下且(若適當)在溶劑之存在下實施。用於此目的之適宜鈀鹽或錯合物可如關於製程P1所揭示。Process P5 can be in the presence of a transition metal catalyst (e.g., palladium) and (if appropriate) in the presence of a phosphine ligand or N-heterocyclic carbene ligand and (if appropriate) in the presence of a base and (if appropriate) ) Is carried out in the presence of a solvent. Suitable palladium salts or complexes for this purpose may be as disclosed in relation to process P1.
用於實施製程P5之適宜鹼可如關於製程P1所揭示。Suitable bases for implementing process P5 may be as disclosed with respect to process P1.
用於實施製程P5之適宜溶劑可如關於製程P1所揭示。Suitable solvents for implementing process P5 may be as disclosed with respect to process P1.
亦可有利的係利用共溶劑(例如水或醇,例如甲醇、乙醇、丙醇、異丙醇或第三丁醇)實施本發明之製程P5。It may also be advantageous to implement the process P5 of the present invention using a co-solvent (such as water or an alcohol, such as methanol, ethanol, propanol, isopropanol, or tertiary butanol).
製程P5可在惰性氣氛(例如氬或氮氣氛)中實施。在實施製程P5時,每莫耳式(X)化合物可採用1莫耳或過量之式(XI)化合物及1至5莫耳鹼以及0.01至20莫耳%之過渡金屬錯合物。亦可採用其他比率之反應組分。藉由已知方法來進行實驗處理。Process P5 can be performed in an inert atmosphere (such as an argon or nitrogen atmosphere). In the implementation of process P5, 1 mole or an excess of the compound of formula (XI) and 1 to 5 mole bases and 0.01 to 20 mole% of the transition metal complex can be used per mole of the compound (X). Other ratios of reaction components can also be used. Experimental treatment was performed by known methods.
式(I)化合物(其中Q1
代表C)可藉由製程P6來製備,其包含以下步驟:使式(VIII)化合物或其鹽中之一者與式(XII)化合物反應,如以下反應方案中所圖解說明:
製程P6
其中L代表CR4
R5
;
R4
及R5
獨立地代表氫原子、C1
-C8
-烷氧基或C1
-C8
烷基;
U3
代表溴原子、氯原子、碘原子、甲磺醯基、甲苯磺醯基或三氟甲磺醯基;
W2
代表硼衍生物,例如硼酸、硼酸酯或三氟硼酸鉀衍生物;
R1
及R2
獨立地代表C1
-C8
-烷基、C2-
C8
-烯基、C3
-C7
-環烷基、芳基或雜環基;
其中該等C1
-C8
-烷基及C2
-C8
-烯基可經一或多個R1a
或R2a
取代基取代且其中該等C3
-C7
-環烷基、芳基及雜環基可經一或多個R1b
或R2b
取代基取代;且
R3
代表氫原子、鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、C2
-C8
-炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、C1
-C8
-烷氧基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、羥基-C1
-C8
-烷基、C1
-C8
-烷氧基-C1
-C8
-烷基、C1
-C8
-烷基羰基氧基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基、雜環基氧基-C1
-C8
-烷基、胺基-C1
-C8
-烷基、C1
-C8
-烷基胺基-C1
-C8
-烷基、二-C1
-C8
-烷基胺基-C1
-C8
-烷基、芳基胺基-C1
-C8
-烷基、二-芳基胺基-C1
-C8
-烷基、雜環基胺基-C1
-C8
-烷基、C1
-C8
-烷基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷氧基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷基硫基-C1
-C8
-烷基、C1
-C8
-烷基亞磺醯基-C1
-C8
-烷基、C1
-C8
-烷基磺醯基-C1
-C8
-烷基及氰基-C1
-C8
-烷基;
其中該等C1
-C8
-烷基、C2
-C8
-烯基及C2
-C8
-炔基可經一或多個R3a
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基及雜環基氧基-C1
-C8
-烷基可經一或多個R3b
取代基取代,且
A、B、Q2
、n、p、X、Y、R1a
、R2a
、R1b
、R2b
、R3a
、R3b
及Z係如本文所定義。The compound of formula (I) (where Q 1 represents C) can be prepared by process P6, which includes the following steps: reacting one of the compound of formula (VIII) or a salt thereof with a compound of formula (XII), as shown in the following reaction scheme Illustrated in:
Process P6
Where L represents CR 4 R 5 ;
R 4 and R 5 independently represent a hydrogen atom, a C 1 -C 8 -alkoxy group or a C 1 -C 8 alkyl group;
U 3 represents a bromine atom, a chlorine atom, an iodine atom, a mesylsulfonyl group, a tosylsulfonyl group or a trifluoromethanesulfonyl group;
W 2 represents a boron derivative, such as a boric acid, borate or potassium trifluoroborate derivative;
R 1 and R 2 independently represent C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 3 -C 7 -cycloalkyl, aryl or heterocyclic group;
Wherein these C 1 -C 8 -alkyl and C 2 -C 8 -alkenyl may be substituted by one or more R 1a or R 2a substituents and wherein these C 3 -C 7 -cycloalkyl, aryl And heterocyclyl may be substituted with one or more R 1b or R 2b substituents; and
R 3 represents a hydrogen atom, a halogen atom, a C 1 -C 8 -alkyl group, a C 1 -C 8 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, a C 2 -C 8 -alkenyl group, a C 2 -C 8 -alkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, C 1 -C 8 -alkoxy, aryl, aryl-C 1 -C 8 -alkane Group, heterocyclyl, heterocyclyl-C 1 -C 8 -alkyl, hydroxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonyloxy-C 1 -C 8 -alkyl, aryloxy-C 1 -C 8 -alkyl, heterocyclyloxy -C 1 -C 8 -alkyl, amine -C 1 -C 8 -alkyl, C 1 -C 8 -alkylamino-C 1 -C 8 -alkyl, di-C 1 -C 8 -alkylamino -C 1 -C 8- Alkyl, arylamino-C 1 -C 8 -alkyl, di-arylamino-C 1 -C 8 -alkyl, heterocyclylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxycarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylthio -C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinylsulfenyl-C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinyl-C 1 -C 8 -Alkyl and cyano-C 1 -C 8 -alkyl;
Wherein the C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl and C 2 -C 8 -alkynyl can be substituted with one or more R 3a substituents and wherein the C 3 -C 7- Cycloalkyl, C 4 -C 7 -cycloalkenyl, aryl, aryl-C 1 -C 8 -alkyl, heterocyclyl, heterocyclyl -C 1 -C 8 -alkyl, aryloxy -C 1 -C 8 -alkyl and heterocyclyloxy-C 1 -C 8 -alkyl may be substituted with one or more R 3b substituents, and
A, B, Q 2 , n, p, X, Y, R 1a , R 2a , R 1b , R 2b , R 3a , R 3b and Z are as defined herein.
式(XII)化合物可自式(XI)藉由已知製程製備(Tetrahedron Letters (2003),44 , 233及Chemistry Letters (2002), 780)。Compounds of formula (XII) can be prepared from formula (XI) by known processes (Tetrahedron Letters (2003), 44 , 233 and Chemistry Letters (2002), 780).
製程P6可在過渡金屬觸媒(例如鈀)之存在下且(若適當)在膦配體或N-雜環碳烯配體之存在下且(若適當)在鹼之存在下且(若適當)在溶劑之存在下實施。用於此目的之適宜鈀鹽或錯合物可如關於製程P1所揭示。Process P6 can be in the presence of a transition metal catalyst (e.g. palladium) and (if appropriate) in the presence of a phosphine ligand or N-heterocyclic carbene ligand and (if appropriate) in the presence of a base and (if appropriate) ) Is carried out in the presence of a solvent. Suitable palladium salts or complexes for this purpose may be as disclosed in relation to process P1.
用於實施製程P6之適宜鹼可如關於製程P1所揭示。Suitable bases for implementing process P6 may be as disclosed with respect to process P1.
用於實施製程P6之適宜溶劑可如關於製程P1所揭示。Suitable solvents for implementing process P6 may be as disclosed with respect to process P1.
亦可有利的係利用共溶劑(例如水或醇,例如甲醇、乙醇、丙醇、異丙醇或第三丁醇)實施本發明之製程P6。It may also be advantageous to implement the process P6 of the present invention using a co-solvent (such as water or an alcohol, such as methanol, ethanol, propanol, isopropanol, or third butanol).
製程P6可在惰性氣氛(例如氬或氮氣氛)中實施。在實施製程P6時,每莫耳式(VIII)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%之過渡金屬錯合物。亦可採用其他比率之反應組分。藉由已知方法來進行實驗處理。Process P6 can be implemented in an inert atmosphere (such as an argon or nitrogen atmosphere). When implementing process P6, 1 mole or an excess of the compound of formula (XII) and 1 to 5 mole bases and 0.01 to 20 mole% of the transition metal complex can be used per mole of the compound of formula (VIII). Other ratios of reaction components can also be used. Experimental treatment was performed by known methods.
式(I)化合物(其中Q1
代表N)可藉由製程P7來製備,其包含以下步驟:使式(XIII)化合物或其鹽中之一者與式(XI)化合物反應,如以下反應方案中所圖解說明:
製程P7
其中L代表CR4
R5
;
R4
及R5
獨立地代表氫原子或C1
-C8
烷基;
U4
代表溴原子、氯原子、碘原子、甲磺醯基、甲苯磺醯基或三氟甲磺醯基;
R1
及R2
獨立地代表C1
-C8
-烷基、C2-
C8
-烯基、C3
-C7
-環烷基、芳基或雜環基;
其中該等C1
-C8
-烷基及C2
-C8
-烯基可經一或多個R1a
或R2a
取代基取代且其中該等C3
-C7
-環烷基、芳基及雜環基可經一或多個R1b
或R2b
取代基取代;且
R3
代表氫原子、鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、C2
-C8
-炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、C1
-C8
-烷氧基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、羥基-C1
-C8
-烷基、C1
-C8
-烷氧基-C1
-C8
-烷基、C1
-C8
-烷基羰基氧基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基、雜環基氧基-C1
-C8
-烷基、胺基-C1
-C8
-烷基、C1
-C8
-烷基胺基-C1
-C8
-烷基、二-C1
-C8
-烷基胺基-C1
-C8
-烷基、芳基胺基-C1
-C8
-烷基、二-芳基胺基-C1
-C8
-烷基、雜環基胺基-C1
-C8
-烷基、C1
-C8
-烷基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷氧基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷基硫基-C1
-C8
-烷基、C1
-C8
-烷基亞磺醯基-C1
-C8
-烷基、C1
-C8
-烷基磺醯基-C1
-C8
-烷基及氰基-C1
-C8
-烷基;
其中該等C1
-C8
-烷基、C2
-C8
-烯基及C2
-C8
-炔基可經一或多個R3a
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基及雜環基氧基-C1
-C8
-烷基可經一或多個R3b
取代基取代,且
A、B、Q2
、n、p、X、Y、R1a
、R2a
、R1b
、R2b
、R3a
、R3b
及Z係如本文所定義。The compound of formula (I) (where Q 1 represents N) can be prepared by the process P7, which comprises the following steps: reacting one of the compound of formula (XIII) or a salt thereof with a compound of formula (XI), as shown in the following reaction scheme Illustrated in:
Process P7
Where L represents CR 4 R 5 ;
R 4 and R 5 independently represent a hydrogen atom or a C 1 -C 8 alkyl group;
U 4 represents a bromine atom, a chlorine atom, an iodine atom, a mesylsulfonyl group, a tosylsulfonyl group or a trifluoromethanesulfonyl group;
R 1 and R 2 independently represent C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 3 -C 7 -cycloalkyl, aryl or heterocyclic group;
Wherein these C 1 -C 8 -alkyl and C 2 -C 8 -alkenyl may be substituted by one or more R 1a or R 2a substituents and wherein these C 3 -C 7 -cycloalkyl, aryl And heterocyclyl may be substituted with one or more R 1b or R 2b substituents; and
R 3 represents a hydrogen atom, a halogen atom, a C 1 -C 8 -alkyl group, a C 1 -C 8 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, a C 2 -C 8 -alkenyl group, a C 2 -C 8 -alkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, C 1 -C 8 -alkoxy, aryl, aryl-C 1 -C 8 -alkane Group, heterocyclyl, heterocyclyl-C 1 -C 8 -alkyl, hydroxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonyloxy-C 1 -C 8 -alkyl, aryloxy-C 1 -C 8 -alkyl, heterocyclyloxy -C 1 -C 8 -alkyl, amine -C 1 -C 8 -alkyl, C 1 -C 8 -alkylamino-C 1 -C 8 -alkyl, di-C 1 -C 8 -alkylamino -C 1 -C 8- Alkyl, arylamino-C 1 -C 8 -alkyl, di-arylamino-C 1 -C 8 -alkyl, heterocyclylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxycarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylthio -C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinylsulfenyl-C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinyl-C 1 -C 8 -Alkyl and cyano-C 1 -C 8 -alkyl;
Wherein the C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl and C 2 -C 8 -alkynyl can be substituted with one or more R 3a substituents and wherein the C 3 -C 7- Cycloalkyl, C 4 -C 7 -cycloalkenyl, aryl, aryl-C 1 -C 8 -alkyl, heterocyclyl, heterocyclyl -C 1 -C 8 -alkyl, aryloxy -C 1 -C 8 -alkyl and heterocyclyloxy-C 1 -C 8 -alkyl may be substituted with one or more R 3b substituents, and
A, B, Q 2 , n, p, X, Y, R 1a , R 2a , R 1b , R 2b , R 3a , R 3b and Z are as defined herein.
式(XI)化合物可藉由已知製程來製備(Journal of the American Chemical Society (1957),79 , 6540;Journal of Organic Chemistry (2000), (65), 4913;Tetrahedron Letters (2002),43 , 8569)。Compounds of formula (XI) can be prepared by known processes (Journal of the American Chemical Society (1957), 79 , 6540; Journal of Organic Chemistry (2000), (65), 4913; Tetrahedron Letters (2002), 43 , 8569).
式(XIII)化合物或其互變異構物係商業購得的或可藉由熟知製程來製備。Compounds of formula (XIII) or tautomers thereof are commercially available or can be prepared by well-known procedures.
製程P7可(若適當)在適宜鹼之存在下且(若適當)在溶劑之存在下實施。Process P7 can be carried out (if appropriate) in the presence of a suitable base and (if appropriate) in the presence of a solvent.
用於實施製程P7之適宜鹼可如關於製程P1所揭示。Suitable bases for implementing process P7 may be as disclosed with respect to process P1.
用於實施製程P7之適宜溶劑可如關於製程P1所揭示。Suitable solvents for implementing process P7 may be as disclosed with respect to process P1.
製程P7可在惰性氣氛中實施。在實施製程P7時,每莫耳式(XIII)化合物可採用1莫耳或過量之式(XI)化合物及1至5莫耳鹼。亦可採用其他比率之反應組分。藉由已知方法來進行實驗處理。Process P7 can be implemented in an inert atmosphere. In the implementation of process P7, one mole or an excess of the compound of formula (XI) and one to five moles of base can be used per mole of the compound (XIII). Other ratios of reaction components can also be used. Experimental treatment was performed by known methods.
式(I)化合物(其中Q2
代表N)可藉由製程P8來製備,其包含以下步驟:使式(XIV)化合物或其鹽中之一者與式(IIId)化合物反應,如以下反應方案中所圖解說明:
製程P8
其中A、B、Q1
、L、n、p、X、Y、Z、R1
、R2
及R3
係如本文所定義且Q2
代表N且U5
代表氯原子、溴原子、碘原子、甲磺醯基或甲苯磺醯基,
式(XIV)化合物可藉由已知製程或根據製程P4、P5、P6或P7製備。The compound of formula (I) (where Q 2 represents N) can be prepared by process P8, which comprises the following steps: reacting one of the compound of formula (XIV) or a salt thereof with a compound of formula (IIId), as shown in the following reaction scheme Illustrated in:
Process P8
Wherein A, B, Q 1 , L, n, p, X, Y, Z, R 1 , R 2 and R 3 are as defined herein and Q 2 represents N and U 5 represents a chlorine atom, a bromine atom, an iodine atom , Methanesulfonyl or tosylsulfonyl,
Compounds of formula (XIV) can be prepared by known processes or according to processes P4, P5, P6 or P7.
式(IIId)化合物係商業購得的或可藉由熟知製程來製備。Compounds of formula (IIId) are commercially available or can be prepared by well-known processes.
製程P8可(若適當)在適宜鹼之存在下且(若適當)在溶劑之存在下實施。Process P8 can be carried out (if appropriate) in the presence of a suitable base and (if appropriate) in the presence of a solvent.
用於實施製程P8之適宜鹼可如關於製程P1所揭示。Suitable bases for implementing process P8 may be as disclosed with respect to process P1.
用於實施製程P8之適宜溶劑可如關於製程P1所揭示。Suitable solvents for implementing process P8 may be as disclosed with respect to process P1.
製程P8可在惰性氣氛(例如氬或氮氣氛)中實施。在實施製程P8時,每莫耳式(XIV)化合物可採用1莫耳或過量之式(IIId)化合物及1至5莫耳鹼。亦可採用其他比率之反應組分。藉由已知方法來進行實驗處理。Process P8 can be implemented in an inert atmosphere (such as an argon or nitrogen atmosphere). In the implementation of the process P8, 1 mole or an excess of the compound of the formula (IIId) and 1 to 5 mole of base can be used per mole of the compound (XIV). Other ratios of reaction components can also be used. Experimental treatment was performed by known methods.
式(I)化合物(其中Q1
代表C且L代表CH(OH)或C=O)可藉由製程P9來製備,其包含以下步驟:使式(XV)化合物或其鹽中之一者與式(XVI)化合物反應,如以下反應方案中所圖解說明:
製程P9
其中
代表單鍵或雙鍵;
U6
代表氫原子、氯原子、溴原子、C1
-C6
-烷氧基或N-(C1
-C6
-烷氧基)-C1
-C6
-胺基;
M2
代表鹼土金屬(例如鋰)或鎂衍生物(例如格氏試劑);
R1
及R2
獨立地代表C1
-C8
-烷基、C2-
C8
-烯基、C3
-C7
-環烷基、芳基或雜環基;
其中該等C1
-C8
-烷基及C2
-C8
-烯基可經一或多個R1a
或R2a
取代基取代且其中該等C3
-C7
-環烷基、芳基及雜環基可經一或多個R1b
或R2b
取代基取代;且
R3
代表氫原子、鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、C2
-C8
-炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、C1
-C8
-烷氧基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、羥基-C1
-C8
-烷基、C1
-C8
-烷氧基-C1
-C8
-烷基、C1
-C8
-烷基羰基氧基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基、雜環基氧基-C1
-C8
-烷基、胺基-C1
-C8
-烷基、C1
-C8
-烷基胺基-C1
-C8
-烷基、二-C1
-C8
-烷基胺基-C1
-C8
-烷基、芳基胺基-C1
-C8
-烷基、二-芳基胺基-C1
-C8
-烷基、雜環基胺基-C1
-C8
-烷基、C1
-C8
-烷基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷氧基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷基硫基-C1
-C8
-烷基、C1
-C8
-烷基亞磺醯基-C1
-C8
-烷基、C1
-C8
-烷基磺醯基-C1
-C8
-烷基及氰基-C1
-C8
-烷基;
其中該等C1
-C8
-烷基、C2
-C8
-烯基及C2
-C8
-炔基可經一或多個R3a
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基及雜環基氧基-C1
-C8
-烷基可經一或多個R3b
取代基取代,且
A、B、Q2
、n、p、X、Y、R6
、R1a
、R2a
、R1b
、R2b
、R3a
、R3b
及Z係如本文所定義。Compounds of formula (I) (wherein Q 1 represents C and L represents CH (OH) or C = O) can be prepared by process P9, which comprises the following steps: one of the compound of formula (XV) or a salt thereof and The reaction of a compound of formula (XVI) is illustrated in the following reaction scheme:
Process P9
among them
Stands for single or double bond;
U 6 represents a hydrogen atom, a chlorine atom, a bromine atom, a C 1 -C 6 -alkoxy group or an N- (C 1 -C 6 -alkoxy) -C 1 -C 6 -amino group;
M 2 represents an alkaline earth metal (such as lithium) or a magnesium derivative (such as a Grignard reagent);
R 1 and R 2 independently represent C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 3 -C 7 -cycloalkyl, aryl or heterocyclic group;
Wherein these C 1 -C 8 -alkyl and C 2 -C 8 -alkenyl may be substituted by one or more R 1a or R 2a substituents and wherein these C 3 -C 7 -cycloalkyl, aryl And heterocyclyl may be substituted with one or more R 1b or R 2b substituents; and
R 3 represents a hydrogen atom, a halogen atom, a C 1 -C 8 -alkyl group, a C 1 -C 8 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, a C 2 -C 8 -alkenyl group, a C 2 -C 8 -alkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, C 1 -C 8 -alkoxy, aryl, aryl-C 1 -C 8 -alkane Group, heterocyclyl, heterocyclyl-C 1 -C 8 -alkyl, hydroxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonyloxy-C 1 -C 8 -alkyl, aryloxy-C 1 -C 8 -alkyl, heterocyclyloxy -C 1 -C 8 -alkyl, amine -C 1 -C 8 -alkyl, C 1 -C 8 -alkylamino-C 1 -C 8 -alkyl, di-C 1 -C 8 -alkylamino -C 1 -C 8- Alkyl, arylamino-C 1 -C 8 -alkyl, di-arylamino-C 1 -C 8 -alkyl, heterocyclylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxycarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylthio -C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinylsulfenyl-C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinyl-C 1 -C 8 -Alkyl and cyano-C 1 -C 8 -alkyl;
Wherein the C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl and C 2 -C 8 -alkynyl can be substituted with one or more R 3a substituents and wherein the C 3 -C 7- Cycloalkyl, C 4 -C 7 -cycloalkenyl, aryl, aryl-C 1 -C 8 -alkyl, heterocyclyl, heterocyclyl -C 1 -C 8 -alkyl, aryloxy -C 1 -C 8 -alkyl and heterocyclyloxy-C 1 -C 8 -alkyl may be substituted with one or more R 3b substituents, and
A, B, Q 2 , n, p, X, Y, R 6 , R 1a , R 2a , R 1b , R 2b , R 3a , R 3b and Z are as defined herein.
式(XV)化合物係商業購得的或可藉由熟知製程來製備。Compounds of formula (XV) are commercially available or can be prepared by well-known processes.
式(XVI)之有機金屬衍生物可根據熟知製程藉由自式(XVII)之衍生物之鹵素-金屬交換來製備
其中
U7
代表氯原子、溴原子或碘原子;且
R1
及R2
獨立地代表C1
-C8
-烷基、C2-
C8
-烯基、C3
-C7
-環烷基、芳基或雜環基;
其中該等C1
-C8
-烷基及C2
-C8
-烯基可經一或多個R1a
或R2a
取代基取代且其中該等C3
-C7
-環烷基、芳基及雜環基可經一或多個R1b
或R2b
取代基取代;且
R3
代表氫原子、鹵素原子、C1
-C8
-烷基、包含最多9個可相同或不同之鹵素原子之C1
-C8
-鹵代烷基、C2
-C8
-烯基、C2
-C8
-炔基、C3
-C7
-環烷基、C4
-C7
-環烯基、C1
-C8
-烷氧基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、羥基-C1
-C8
-烷基、C1
-C8
-烷氧基-C1
-C8
-烷基、C1
-C8
-烷基羰基氧基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基、雜環基氧基-C1
-C8
-烷基、胺基-C1
-C8
-烷基、C1
-C8
-烷基胺基-C1
-C8
-烷基、二-C1
-C8
-烷基胺基-C1
-C8
-烷基、芳基胺基-C1
-C8
-烷基、二-芳基胺基-C1
-C8
-烷基、雜環基胺基-C1
-C8
-烷基、C1
-C8
-烷基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷氧基羰基胺基-C1
-C8
-烷基、C1
-C8
-烷基硫基-C1
-C8
-烷基、C1
-C8
-烷基亞磺醯基-C1
-C8
-烷基、C1
-C8
-烷基磺醯基-C1
-C8
-烷基及氰基-C1
-C8
-烷基;
其中該等C1
-C8
-烷基、C2
-C8
-烯基及C2
-C8
-炔基可經一或多個R3a
取代基取代且其中該等C3
-C7
-環烷基、C4
-C7
-環烯基、芳基、芳基-C1
-C8
-烷基、雜環基、雜環基-C1
-C8
-烷基、芳基氧基-C1
-C8
-烷基及雜環基氧基-C1
-C8
-烷基可經一或多個R3b
取代基取代,且
B、Q2
、n、R1a
、R2a
、R1b
、R2b
、R3a
、R3b
且X係如本文所定義。Organometallic derivatives of formula (XVI) can be prepared by halogen-metal exchange from derivatives of formula (XVII) according to well-known processes
among them
U 7 represents a chlorine atom, a bromine atom or an iodine atom; and
R 1 and R 2 independently represent C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 3 -C 7 -cycloalkyl, aryl or heterocyclic group;
Wherein these C 1 -C 8 -alkyl and C 2 -C 8 -alkenyl may be substituted by one or more R 1a or R 2a substituents and wherein these C 3 -C 7 -cycloalkyl, aryl And heterocyclyl may be substituted with one or more R 1b or R 2b substituents; and
R 3 represents a hydrogen atom, a halogen atom, a C 1 -C 8 -alkyl group, a C 1 -C 8 -haloalkyl group containing up to 9 halogen atoms which may be the same or different, a C 2 -C 8 -alkenyl group, a C 2 -C 8 -alkynyl, C 3 -C 7 -cycloalkyl, C 4 -C 7 -cycloalkenyl, C 1 -C 8 -alkoxy, aryl, aryl-C 1 -C 8 -alkane Group, heterocyclyl, heterocyclyl-C 1 -C 8 -alkyl, hydroxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonyloxy-C 1 -C 8 -alkyl, aryloxy-C 1 -C 8 -alkyl, heterocyclyloxy -C 1 -C 8 -alkyl, amine -C 1 -C 8 -alkyl, C 1 -C 8 -alkylamino-C 1 -C 8 -alkyl, di-C 1 -C 8 -alkylamino -C 1 -C 8- Alkyl, arylamino-C 1 -C 8 -alkyl, di-arylamino-C 1 -C 8 -alkyl, heterocyclylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkoxycarbonylamino-C 1 -C 8 -alkyl, C 1 -C 8 -alkylthio -C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinylsulfenyl-C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfinyl-C 1 -C 8 -Alkyl and cyano-C 1 -C 8 -alkyl;
Wherein the C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl and C 2 -C 8 -alkynyl can be substituted with one or more R 3a substituents and wherein the C 3 -C 7- Cycloalkyl, C 4 -C 7 -cycloalkenyl, aryl, aryl-C 1 -C 8 -alkyl, heterocyclyl, heterocyclyl -C 1 -C 8 -alkyl, aryloxy -C 1 -C 8 -alkyl and heterocyclyloxy-C 1 -C 8 -alkyl may be substituted with one or more R 3b substituents, and
B, Q 2 , n, R 1a , R 2a , R 1b , R 2b , R 3a , R 3b and X are as defined herein.
式(XVII)化合物可藉由已知製程或根據製程P1、P2、P3或P8來製備。Compounds of formula (XVII) can be prepared by known processes or according to processes P1, P2, P3 or P8.
用於實施製程P9之適宜溶劑可為常用惰性有機溶劑。較佳者係使用視情況鹵化之脂肪族、脂環族或芳香族烴,例如石油醚、戊烷、己烷、庚烷、環己烷、甲基環己烷、苯、甲苯、二甲苯或十氫萘;醚,例如二乙醚、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茴香醚;及其混合物。A suitable solvent for implementing the process P9 may be a commonly used inert organic solvent. Preferred are the use of optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or Decahydronaphthalene; ethers such as diethyl ether, diisopropyl ether, methyl tertiary butyl ether, methyl tertiary pentyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethyl Oxyethane, 1,2-diethoxyethane or anisole; and mixtures thereof.
製程P9可在惰性氣氛(例如氬或氮氣氛)中實施。在實施製程P9時,每莫耳式(XV)化合物可採用1莫耳或過量之式(XVI)化合物。亦可採用其他比率之反應組分。藉由已知方法來進行實驗處理。Process P9 can be implemented in an inert atmosphere (such as an argon or nitrogen atmosphere). When implementing the process P9, 1 mole or an excess of the compound of the formula (XVI) can be used per mole of the compound (XV). Other ratios of reaction components can also be used. Experimental treatment was performed by known methods.
製程P1、P2、P3、P4、P5、P6、P7、P8及P9通常在大氣壓下實施。其亦可在高壓或減壓下操作。Processes P1, P2, P3, P4, P5, P6, P7, P8, and P9 are usually implemented at atmospheric pressure. It can also be operated under high pressure or reduced pressure.
在實施製程P1、P2、P3、P4、P5、P6、P7、P8及P9時,反應溫度可在相當寬範圍內變化。一般而言,該等製程可在自-78℃至200℃、較佳-78℃至150℃之溫度下實施。控制製程溫度之方法係使用微波技術。When the processes P1, P2, P3, P4, P5, P6, P7, P8, and P9 are implemented, the reaction temperature can be changed within a relatively wide range. Generally, these processes can be carried out at a temperature from -78 ° C to 200 ° C, preferably -78 ° C to 150 ° C. The method of controlling the process temperature uses microwave technology.
通常,將反應混合物在減壓下濃縮。可藉由已知方法(例如層析或結晶)使剩餘殘餘物與可能仍存在之任何雜質分離。Generally, the reaction mixture was concentrated under reduced pressure. The remaining residue can be separated from any impurities that may still be present by known methods, such as chromatography or crystallization.
藉由係以常用方法來進行實驗處理。通常,使用水處理反應混合物且分離出有機相,並在乾燥之後在減壓下濃縮。若適當,可藉由常用方法(例如層析、結晶或蒸餾)使剩餘殘餘物與可能仍存在之任何雜質分離。The experimental treatment is performed by a common method. Generally, the reaction mixture is treated with water and the organic phase is separated and, after drying, concentrated under reduced pressure. If appropriate, the remaining residue can be separated from any impurities that may still be present by common methods such as chromatography, crystallization or distillation.
式(I)化合物可根據上述一般製備製程來製備。然而應理解,基於一般知識及可取得出版物,熟習此項技術者將能夠根據期望合成之每一化合物的具體細節來修改該等方法。The compound of formula (I) can be prepared according to the above general preparation process. It should be understood, however, that based on general knowledge and available publications, those skilled in the art will be able to modify these methods based on the specific details of each compound desired to be synthesized.
組合物及調配物
本發明進一步係關於組合物、特定而言用於控制不期望植物病原微生物之組合物。組合物可施用於微生物及/或及其棲息地中。 Compositions and formulations <br/> The present invention further relates to compositions, particularly compositions for controlling unwanted plant pathogenic microorganisms. The composition can be applied to microorganisms and / or their habitat.
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宜之助劑,例如載劑及/或表面活性劑。The composition generally comprises at least one compound of formula (I) and at least one agriculturally suitable adjuvant, such as a carrier and / or a surfactant.
載劑係固體或液體、天然或合成合成之有機或無機物質,其通常係惰性的。載劑通常改良化合物至(例如)植物、植物部分或種子之施用。適宜固體載劑之實例包括(但不限於)銨鹽;天然石粉,例如高嶺土、黏土、滑石、白堊、石英、鎂鋁海泡石、蒙脫石及矽藻土;及合成石粉,例如精細二氧化矽、氧化鋁及矽酸鹽。用於製備顆粒之通常可用固體載劑的實例包括(但不限於)破碎並分級之天然岩石,例如方解石、大理石、浮石、海泡石及白雲石;無機及有機粉末之合成顆粒及有機材料之顆粒,例如紙、鋸屑、椰子殼、玉米穗軸及菸草桿。適宜液體載劑之實例包括(但不限於)水、有機溶劑及其組合。適宜溶劑之實例包括極性及非極性有機化學液體,例如來自以下種類:芳香族及非芳香族烴(例如,環己烷、石蠟、烷基苯、二甲苯、甲苯烷基萘、氯化芳香族或氯化脂肪族烴,例如,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,例如丁醇或二醇)、酮(例如,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、未經取代及經取代胺、醯胺(例如,二甲基甲醯胺)、內醯胺(例如,N-烷基吡咯啶酮)及內酯、碸及亞碸(例如,二甲亞碸)。載劑亦可為液化氣態增量劑,亦即,在標準溫度及標準壓力下為氣態之液體,例如氣溶膠推進劑,例如,鹵代烴、丁烷、丙烷、氮及二氧化碳。載劑之量通常在組合物之1重量%至99.99重量%、較佳5重量%至99.9重量%、更佳10重量%至99.5重量%且最佳20重量%至99重量%之範圍內。Carriers are solid or liquid, natural or synthetic organic or inorganic substances, which are usually inert. Vehicles generally improve the application of the compound to, for example, a plant, plant part, or seed. Examples of suitable solid carriers include, but are not limited to, ammonium salts; natural stone flours, such as kaolin, clay, talc, chalk, quartz, magnesia sepiolite, montmorillonite, and diatomaceous earth; and synthetic stone flours, such as fine Silica, alumina and silicate. Examples of commonly used solid carriers for the preparation of granules include, but are not limited to, broken and classified natural rocks, such as calcite, marble, pumice, sepiolite, and dolomite; synthetic particles of inorganic and organic powders, and organic materials Pellets, such as paper, sawdust, coconut husks, corn cobs, and tobacco rods. Examples of suitable liquid carriers include, but are not limited to, water, organic solvents, and combinations thereof. Examples of suitable solvents include polar and non-polar organic chemical liquids, such as from the following: aromatic and non-aromatic hydrocarbons (e.g., cyclohexane, paraffin, alkylbenzene, xylene, tolylnaphthalene, chlorinated aromatics Or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride, or dichloromethane, alcohols and polyols (which may also be substituted, etherified, and / or esterified as appropriate, such as butanol or glycol), ketones ( For example, acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), esters (including fats and oils), and (poly) ethers, unsubstituted and substituted amines, amidine (for example, dimethylamine Methylformamide), lactam (eg, N-alkylpyrrolidone), and lactones, amidines, and fluorenes (eg, dimethylarsine). The carrier can also be a liquefied gaseous extender, that is, a liquid that is gaseous at standard temperature and pressure, such as an aerosol propellant, such as halogenated hydrocarbons, butane, propane, nitrogen, and carbon dioxide. The amount of the carrier is usually in the range of 1% to 99.99% by weight, preferably 5% to 99.9% by weight, more preferably 10% to 99.5% by weight, and most preferably 20% to 99% by weight of the composition.
表面活性劑可為離子(陽離子或陰離子)或非離子表面活性劑,例如離子或非離子乳化劑、泡沫形成劑、分散劑、潤濕劑及其任何混合物。適宜表面活性劑之實例包括(但不限於)聚丙烯酸之鹽、木質素磺酸之鹽、酚磺酸或萘磺酸之鹽、乙烯及/或環氧丙烷與脂肪醇、脂肪酸或脂肪胺之縮聚物(聚氧乙烯脂肪酸酯、聚氧乙烯脂肪醇醚,例如烷基芳基聚二醇醚)、經取代之酚(較佳烷基酚或芳基酚)、磺基琥珀酸酯之鹽、牛磺酸衍生物(較佳烷基牛磺酸鹽)、聚乙氧基化醇或酚之磷酸酯、多元醇之脂肪酯及含有硫酸鹽、磺酸鹽及磷酸鹽之化合物的衍生物(例如,烷基磺酸鹽、烷基硫酸鹽、芳基磺酸鹽)及蛋白質水解產物、亞硫酸紙漿廢液(lignosulfite waste liquor)及甲基纖維素。當式(I)化合物及/或載劑不溶於水且施用係利用水進行時,通常使用表面活性劑。因此,表面活性劑之量通常在組合物之5重量%至40重量%之範圍內。Surfactants can be ionic (cationic or anionic) or non-ionic surfactants, such as ionic or non-ionic emulsifiers, foam formers, dispersants, wetting agents and any mixtures thereof. Examples of suitable surfactants include, but are not limited to, salts of polyacrylic acid, salts of ligninsulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, ethylene and / or propylene oxide with fatty alcohols, fatty acids or fatty amines Polycondensates (polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, such as alkylaryl polyglycol ethers), substituted phenols (preferably alkylphenols or arylphenols), sulfosuccinates Derivatives of salts, taurine derivatives (preferably alkyl taurates), phosphate esters of polyethoxylated alcohols or phenols, fatty esters of polyols, and compounds containing sulfates, sulfonates and phosphates (E.g., alkyl sulfonates, alkyl sulfates, aryl sulfonates) and protein hydrolysates, lignosulfite waste liquor, and methyl cellulose. When the compound of formula (I) and / or the vehicle are insoluble in water and the application is performed with water, a surfactant is usually used. Therefore, the amount of the surfactant is usually in the range of 5% to 40% by weight of the composition.
適宜助劑之其他實例包括防水劑、乾燥劑、黏合劑(黏結劑、增黏劑、固定劑,例如羧甲基纖維素、呈粉末、顆粒或乳液形式之天然及合成聚合物,例如阿拉伯膠、聚乙烯醇及聚乙酸乙烯酯,天然磷脂,例如,腦磷脂及卵磷脂及合成磷脂、聚乙烯基吡咯啶酮及填充體)、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(例如,無機顏料,例如氧化鐵、氧化鈦及普魯士藍(Prussian Blue);有機染料,例如茜素、偶氮及金屬酞青素染料)、消泡劑(例如聚矽氧消泡劑及硬脂酸鎂)、防腐劑(例如雙氯酚及苄醇半縮甲醛)、二次增稠劑(纖維素衍生物、丙烯酸衍生物、黃原膠、改質黏土及精細二氧化矽)、膠黏劑、吉貝素(gibberellin)及加工助劑、礦物質及植物油、香料、蠟、營養物(包括痕量營養物,例如鐵、錳、硼、銅、鈷、鉬及鋅之鹽)、保護性膠體、觸變物質、滲透劑、螯合劑及錯合物形成劑。Other examples of suitable auxiliaries include water repellents, desiccants, adhesives (binders, tackifiers, fixatives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or emulsions, such as gum arabic , Polyvinyl alcohol and polyvinyl acetate, natural phospholipids, such as brain phospholipids and lecithin and synthetic phospholipids, polyvinyl pyrrolidone and fillers, thickeners, stabilizers (such as low temperature stabilizers, preservatives, Antioxidants, light stabilizers or other agents that improve chemical and / or physical stability), dyes or pigments (e.g. inorganic pigments such as iron oxide, titanium oxide and Prussian Blue; organic dyes such as alizarin, Azo and metal phthalocyanin dyes), defoamers (such as polysiloxane defoamers and magnesium stearate), preservatives (such as bischlorophenol and benzyl alcohol hemiformal), secondary thickeners (fibers Derivatives, acrylic derivatives, xanthan gum, modified clay and fine silica), adhesives, gibberellin and processing aids, minerals and vegetable oils, spices, waxes, nutrients (including Trace nutrients, such as , Salts of manganese, boron, copper, cobalt, molybdenum and zinc,), protective colloid, thixotropic substances, penetrants, chelating agents and complexes are formed.
助劑之選擇與式(I)化合物之期望施用芳基及/或及物理性質有關。此外,助劑可經選擇以賦予組合物或自其製備之使用形式特定性質(技術、物理及/或生物性質)。助劑之選擇可允許針對具體需求定製組合物。The choice of adjuvant is related to the desired application of the aryl and / or physical properties of the compound of formula (I). In addition, auxiliaries can be selected to impart specific properties (technical, physical, and / or biological properties) to the composition or the form of use prepared therefrom. The choice of auxiliaries may allow the composition to be tailored to specific needs.
組合物可呈任何常用形式,例如溶液(例如,水溶液)、乳液、可濕潤粉末、基於水及基於油之懸浮液、粉末、粉塵、糊劑、可溶性粉末、可溶性顆粒、用於撒播之顆粒、懸乳劑濃縮物、浸漬有式(I)化合物之天然或合成產物、肥料以及於聚合物質中之微膠囊。式(I)化合物可以懸浮、乳化或溶解形式製備。The composition can be in any of the usual forms, such as solutions (e.g., aqueous solutions), emulsions, wettable powders, water-based and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble particles, particles for spreading, Suspension concentrates, natural or synthetic products impregnated with a compound of formula (I), fertilizers, and microcapsules in a polymeric substance. Compounds of formula (I) can be prepared in suspended, emulsified or dissolved form.
組合物可作為即用調配物提供給最終使用者,即,組合物可藉由適宜裝置(例如噴灑或撒施裝置)直接施用於植物或種子。或者,組合物可以濃縮液形式提供給最終使用者,其在使用之前必須較佳用水稀釋。The composition can be provided to the end user as a ready-to-use formulation, ie, the composition can be applied directly to the plant or seed by a suitable device, such as a spraying or spraying device. Alternatively, the composition may be provided to the end user in the form of a concentrate, which must preferably be diluted with water before use.
組合物可以習用方式製備,例如藉由將式(I)化合物與一或多種適宜助劑(例如本文上文所揭示者)混合。The composition may be prepared in a conventional manner, for example by mixing a compound of formula (I) with one or more suitable auxiliaries, such as those disclosed herein above.
組合物通常含有0.01至99重量%、0.05至98重量%、較佳0.1至95重量%、更佳0.5至90重量%、最佳1至80重量%之式(I)化合物。組合物可能包含兩種或更多種式(I)化合物。在此情形中,所列示範圍係指本發明化合物之總量。The composition usually contains 0.01 to 99% by weight, 0.05 to 98% by weight, preferably 0.1 to 95% by weight, more preferably 0.5 to 90% by weight, and most preferably 1 to 80% by weight. The composition may comprise two or more compounds of formula (I). In this case, the listed range refers to the total amount of the compound of the present invention.
混合物 / 組合
式(I)化合物及包含其等之組合物可與其他活性成分混合,例如殺真菌劑、殺菌劑、殺蟎劑、殺線蟲劑、殺蟲劑、除草劑、肥料、生長調節劑、安全劑或訊息化合物。此可允許擴展活性譜或以防止產生抗性。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。 Mixtures / combinations <br/> Compounds of formula (I) and compositions containing them can be mixed with other active ingredients, such as fungicides, fungicides, acaricides, nematicides, insecticides, herbicides, fertilizers , Growth regulators, safeners, or messaging compounds. This may allow the spectrum of activity to be extended or to prevent the development of resistance. Examples of known fungicides, insecticides, acaricides, nematicides and fungicides are disclosed in the Pesticide Manual, 17th edition.
可與式(I)化合物及組合物混合物之尤佳殺真菌劑的實例係:
1) 麥角固醇生物合成之抑制劑,例如(1.001) 環唑醇(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) 硫酸依滅列、(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) 克啉菌(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-1,3-二氧戊環-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-1,3-二氧戊環-2-基}甲基)-1H-1,2,4-三唑、(1.039) 硫氰酸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-基酯、(1.040) 硫氰酸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-基酯、(1.041) 硫氰酸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-基酯、(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-2,6,6-三甲基庚-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) 氯氟醚菌唑(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-(烯丙基硫基)-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-(烯丙基硫基)-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-(烯丙基硫基)-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-甲亞胺基甲醯胺、(1.078) N'-{5-溴-6-[(順式-4-異丙基環己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲亞胺基甲醯胺、(1.079) N'-{5-溴-6-[(反式-4-異丙基環己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲亞胺基甲醯胺、(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-甲亞胺基甲醯胺、(1.081) Ipfentrifluconazole。
2) 呼吸鏈複合體I或II之抑制劑,例如(2.001) 苯并烯氟菌唑(benzovindiflupyr)、(2.002) 聯苯吡菌胺(bixafen)、(2.003) 白克列(boscalid)、(2.004) 萎鏽靈(carboxin)、(2.005) 氟派瑞(fluopyram)、(2.006) 福多寧(flutolanil)、(2.007) 氟克殺(fluxapyroxad)、(2.008) 福拉比(furametpyr)、(2.009) 異丙噻菌胺(Isofetamid)、(2.010) 亞派佔(isopyrazam) (反差向異構鏡像異構物1R,4S,9S)、(2.011) 亞派佔(反差向異構鏡像異構物1S,4R,9R)、(2.012) 亞派佔(反差向異構外消旋物1RS,4SR,9SR)、(2.013) 亞派佔(順差向異構外消旋物1RS,4SR,9RS及反差向異構外消旋物1RS,4SR,9SR之混合物)、(2.014) 亞派佔(順差向異構鏡像異構物1R,4S,9R)、(2.015) 亞派佔(順差向異構鏡像異構物1S,4R,9S)、(2.016) 亞派佔(順差向異構外消旋物1RS,4SR,9RS)、(2.017) 戊苯吡菌胺(penflufen)、(2.018) 吡噻菌胺(penthiopyrad)、(2.019) 氟唑菌醯羥胺(pydiflumetofen)、(2.020) 吡唑氟醯胺(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-甲氧基丙-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-硫代甲醯胺、(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-4,5-二甲基苄基)-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) pyrapropoyne。
3) 呼吸鏈複合體III之抑制劑,例如(3.001) 唑嘧菌胺(ametoctradin)、(3.002) 安美速(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) 醚菌胺(dimoxystrobin)、(3.008) 烯肟菌酯(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,3-二甲基戊-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) 2-甲基丙酸(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-4,9-二側氧基-1,5-二氧雜壬-7-基酯、(3.026) 甲哌喹(mandestrobin)、(3.027) N-(3-乙基-3,5,5-三甲基環己基)-3-甲醯胺基-2-羥基苯甲醯胺、(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,3-二甲基戊-3-烯醯胺、(3.029) {5-[3-(2,4-二甲基苯基)-1H-吡唑-1-基]-2-甲基苄基}胺基甲酸甲酯、(3.030) 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) 萬黴靈(diethofencarb)、(4.003) 噻唑菌胺(ethaboxam)、(4.004) 氟比來(fluopicolide)、(4.005) 賓克隆(pencycuron)、(4.006) 腐絕(thiabendazole)、(4.007) 甲基多保淨(thiophanate-methyl)、(4.008) 座賽胺(zoxamide)、(4.009) 3-氯-4-(2,6-二氟苯基)-6-甲基-5-苯基嗒嗪、(4.010) 3-氯-5-(4-氯苯基)-4-(2,6-二氟苯基)-6-甲基嗒嗪、(4.011) 3-氯-5-(6-氯吡啶-3-基)-6-甲基-4-(2,4,6-三氟苯基)嗒嗪、(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)-3,6-二甲基嗒嗪、(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) 波爾多混合液(bordeaux mixture)、(5.002) 四氯丹(captafol)、(5.003) 克菌丹(captan)、(5.004) 百菌清(chlorothalonil)、(5.005) 氫氧化銅、(5.006) 環烷酸銅、(5.007) 銅氧化物、(5.008) 氧氯化銅、(5.009) 硫酸銅(2+)、(5.010) 腈硫醌、(5.011) 多果定(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) 代森聯鋅(metiram zinc)、(5.017) 快得寧(oxine-copper)、(5.018) 甲基鋅乃浦(propineb)、(5.019) 硫及硫製劑,包括多硫化鈣、(5.020) 福雙美(thiram)、(5.021) 鋅乃浦(zineb)、(5.022) 吉闌(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]二硫雜[2,3-c][1,2]噻唑-3-甲腈。
6) 能夠誘導宿主防禦之化合物,例如(6.001) 阿拉酸式苯-S-甲基(acibenzolar-S-methyl)、(6.002) 異噻菌胺(isotianil)、(6.003) 噻菌靈(probenazole)、(6.004) 噻醯菌胺(tiadinil)。
7) 胺基酸及/或蛋白質生物合成之抑制劑,例如(7.001) 賽普洛(cyprodinil)、(7.002) 嘉賜黴素(kasugamycin)、(7.003) 嘉賜黴素鹽酸鹽水合物、(7.004) 土黴素(oxytetracycline)、(7.005) 派美尼(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) 矽噻菌胺(silthiofam)。
9) 細胞壁合成之抑制劑,例如(9.001) 苯噻菌胺(benthiavalicarb)、(9.002) 達滅芬(dimethomorph)、(9.003) 氟嗎啉(flumorph)、(9.004) 丙森鋅(iprovalicarb)、(9.005) 雙炔醯菌胺(mandipropamid)、(9.006) 吡嗎啉(pyrimorph)、(9.007) 霜黴滅(valifenalate)、(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) 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2,2,2-三氟乙基酯。
12) 核酸合成之抑制劑,例如(12.001) 本達樂(benalaxyl)、(12.002) 右本達樂(benalaxyl-M) (精苯霜靈(kiralaxyl))、(12.003) 滅達樂(metalaxyl)、(12.004) 右滅達樂(精甲霜靈(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) 能夠作為解聯劑之化合物,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(Abscisic acid)、(15.002) 佈生(benthiazole)、(15.003) 苯噻唑嗪(bethoxazin)、(15.004) 卡巴西黴素(capsimycin)、(15.005) 香旱芹酮(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) 氟噻唑菌腈(flutianil)、(15.012) 三乙膦酸鋁(fosetyl- aluminum)、(15.013) 三乙膦酸鈣、(15.014) 三乙膦酸鈉、(15.015) 異硫氰酸甲酯、(15.016) 滅芬農(metrafenone)、(15.017) 米多黴素(mildiomycin)、(15.018) 納他黴素(natamycin)、(15.019) 福美鎳(nickel dimethyldithiocarbamate)、(15.020) 酞菌酯(nitrothal-isopropyl)、(15.021) 氧莫卡比(oxamocarb)、(15.022) 氟噻唑吡乙酮(oxathiapiprolin)、(15.023) 氧芬森(oxyfenthiin)、(15.024) 五氯苯酚及鹽、(15.025) 磷酸及其鹽、(15.026) 霜黴威乙膦酸鹽(propamocarb-fosetylate)、(15.027) 吡氟草酮(pyriofenone) (綠芬酮(chlazafenone))、(15.028) 異丁乙氧喹啉(tebufloquin)、(15.029) 克枯爛(tecloftalam)、(15.030) 甲磺菌胺(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}六氫吡啶-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}六氫吡啶-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)六氫吡啶-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)六氫吡啶-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)六氫吡啶-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) 甲烷磺酸2-{(5R)-3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}-3-氯苯基酯、(15.040) 甲烷磺酸2-{(5S)-3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}-3-氯苯基酯、(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) 甲烷磺酸2-{3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}-3-氯苯基酯、(15.044) 甲烷磺酸2-{3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}苯基酯、(15.045) 2-苯基苯酚及鹽、(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(互變異構形式:4-胺基-5-氟嘧啶-2(1H)-酮)、(15.049) 4-側氧基-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-苯并氧氮雜環庚烷呯、(15.055) {6-[({[(Z)-(1-甲基-1H-四唑-5-基)(苯基)亞甲基]胺基}氧基)甲基]吡啶-2-基}胺基甲酸丁-3-炔-1-基酯、(15.056) (2Z)-3-胺基-2-氰基-3-苯基丙烯酸乙酯、(15.057) 吩嗪-1-甲酸、(15.058) 3,4,5-三羥基苯甲酸丙酯、(15.059) 喹啉-8-醇、(15.060) 喹啉-8-醇硫酸鹽(2:1)、(15.061) {6-[({[(1-甲基-1H-四唑-5-基)(苯基)亞甲基]胺基}氧基)甲基]吡啶-2-基}胺基甲酸第三丁基酯、(15.062) 5-氟-4-亞胺基-3-甲基-1-[(4-甲基苯基)磺醯基]-3,4-二氫嘧啶-2(1H)-酮、(15.063) 胺比芬(aminopyrifen)。Examples of particularly preferred fungicides that can be mixed with compounds and compositions of formula (I) are:
1) Inhibitors of ergosterol biosynthesis, such as (1.001) Cyproconazole, (1.002) Difenoconazole, (1.003) Epoxiconazole, (1.004) Cyclopyramide ( fenhexamid), (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) protection Flutriafol, (1.010) imazalil, (1.011) ezulline sulfate, (1.012) ipconazole, (1.013) metconazole, (1.014) myclobutanil , (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1.019) Pyrisoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023) triadimenol, (1.024) tridemorph, (1.025) ) Triticonazole, (1.026) (1R, 2S, 5S) -5- (4-chlorobenzyl) -2- (chloromethyl) -2-methyl-1- (1H-1,2, 4-triazol-1-ylmethyl) ring Alcohol, (1.027) (1S, 2R, 5R) -5- (4-chlorobenzyl) -2- (chloromethyl) -2-methyl-1- (1H-1,2,4-triazole- 1-ylmethyl) cyclopentanol, (1.028) (2R) -2- (1-chlorocyclopropyl) -4-[(1R) -2,2-dichlorocyclopropyl] -1- (1H -1,2,4-triazol-1-yl) but-2-ol, (1.029) (2R) -2- (1-chlorocyclopropyl) -4-[(1S) -2,2-di Chlorocyclopropyl] -1- (1H-1,2,4-triazol-1-yl) but-2-ol, (1.030) (2R) -2- [4- (4-chlorophenoxy) 2- (trifluoromethyl) phenyl] -1- (1H-1,2,4-triazol-1-yl) propan-2-ol, (1.031) (2S) -2- (1-chloro Cyclopropyl) -4-[(1R) -2,2-dichlorocyclopropyl] -1- (1H-1,2,4-triazol-1-yl) but-2-ol, (1.032) (2S) -2- (1-chlorocyclopropyl) -4-[(1S) -2,2-dichlorocyclopropyl] -1- (1H-1,2,4-triazol-1-yl ) But-2-ol, (1.033) (2S) -2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl] -1- (1H-1,2,4 -Triazol-1-yl) propan-2-ol, (1.034) (R)-[3- (4-chloro-2-fluorophenyl) -5- (2,4-difluorophenyl) -1 , 2-oxazol-4-yl] (pyridin-3-yl) methanol, (1.035) (S)-[3- (4-chloro-2-fluorophenyl) -5- (2,4-difluoro (Phenyl) -1,2-oxazol-4-yl] (pyridin-3-yl) methanol, (1.036) [3- (4-chloro-2-fluorophenyl) -5- (2,4-di (Fluorophenyl) -1,2-oxazol-4-yl] (pyridin-3-yl) methanol, (1.037) 1-(((2R, 4S) -2- [2 -Chloro-4- (4-chlorophenoxy) phenyl] -4-methyl-1,3-dioxolane-2-yl} methyl) -1H-1,2,4-triazole, (1.038) 1-(((2S, 4S) -2- [2-chloro-4- (4-chlorophenoxy) phenyl] -4-methyl-1,3-dioxolane-2- (Yl) methyl) -1H-1,2,4-triazole, (1.039) thiocyanate 1-((3- (2-chlorophenyl) -2- (2,4-difluorophenyl) ring Oxyethane-2-yl] methyl} -1H-1,2,4-triazol-5-yl ester, (1.040) thiocyanate 1-{[rel (2R, 3R) -3- (2- (Chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl} -1H-1,2,4-triazol-5-yl ester, (1.041) sulfur 1-{[rel (2R, 3S) -3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl} -1H- 1,2,4-triazol-5-yl ester, (1.042) 2-[(2R, 4R, 5R) -1- (2,4-dichlorophenyl) -5-hydroxy-2,6,6 -Trimethylhept-4-yl] -2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.043) 2-[(2R, 4R, 5S) -1- (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylhept-4-yl] -2,4-dihydro-3H-1,2,4-triazole-3 -Thione, (1.044) 2-[(2R, 4S, 5R) -1- (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylhept-4-yl] -2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.045) 2-[(2R, 4S, 5S) -1- (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylhept-4-yl] -2,4-dihydro-3H-1,2 , 4-triazole-3-thione, (1.046) 2-[(2S, 4R, 5R) -1- (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethyl Heptyl-4-yl] -2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.047) 2-[(2S, 4R, 5S) -1- (2, 4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylhept-4-yl] -2,4-dihydro-3H-1,2,4-triazole-3-thione , (1.048) 2-[(2S, 4S, 5R) -1- (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylhept-4-yl] -2, 4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S, 4S, 5S) -1- (2,4-dichlorophenyl) -5- Hydroxy-2,6,6-trimethylhept-4-yl] -2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.050) 2- [1- ( 2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylhept-4-yl] -2,4-dihydro-3H-1,2,4-triazole-3- Thione, (1.051) 2- [2-chloro-4- (2,4-dichlorophenoxy) phenyl] -1- (1H-1,2,4-triazol-1-yl) propane- 2-alcohol, (1.052) 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -1- (1H-1,2,4-triazol-1-yl) but-2- Alcohol, (1.053) 2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl] -1- (1H-1,2,4-triazol-1-yl) butyl -2-ol, (1.054) 2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl] -1- (1H-1,2,4-triazole-1- ) Pentyl-2-ol, (1.055) Mefentrifluconazole, (1.056) 2-((3- (2 -Chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl} -2,4-dihydro-3H-1,2,4-triazole-3 -Thione, (1.057) 2-{[rel (2R, 3R) -3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl } -2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.058) 2-{[rel (2R, 3S) -3- (2-chlorophenyl)- 2- (2,4-difluorophenyl) oxirane-2-yl] methyl} -2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059 ) 5- (4-chlorobenzyl) -2- (chloromethyl) -2-methyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol, (1.060 ) 5- (allylthio) -1-{[3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl}- 1H-1,2,4-triazole, (1.061) 5- (allylthio) -1-{[rel (2R, 3R) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl] methyl} -1H-1,2,4-triazole, (1.062) 5- (allylthio) -1-{[rel ( 2R, 3S) -3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxirane-2-yl] methyl} -1H-1,2,4-triazole , (1.063) N '-(2,5-dimethyl-4-{[3- (1,1,2,2-tetrafluoroethoxy) phenyl] thio} phenyl) -N-ethyl -N-methylimidoformamidine, (1.064) N '-(2,5-dimethyl-4-{[3- (2,2,2-trifluoroethoxy) phenyl] sulfur ) Phenyl) -N-ethyl-N- Iminomethoxamine, (1.065) N '-(2,5-dimethyl-4-{[3- (2,2,3,3-tetrafluoropropoxy) phenyl] thio} benzene ) -N-ethyl-N-methylimidoformamidine, (1.066) N '-(2,5-dimethyl-4-{[3- (pentafluoroethoxy) phenyl] sulfur Phenyl) -N-ethyl-N-methylimidoformamidine, (1.067) N '-(2,5-dimethyl-4- {3-[(1,1,2,2 -Tetrafluoroethyl) thio] phenoxy} phenyl) -N-ethyl-N-methyliminoformamidine, (1.068) N '-(2,5-dimethyl-4- { 3-[(2,2,2-trifluoroethyl) thio] phenoxy} phenyl) -N-ethyl-N-methyliminoformamidine, (1.069) N '-(2, 5-dimethyl-4- {3-[(2,2,3,3-tetrafluoropropyl) thio] phenoxy} phenyl) -N-ethyl-N-methyliminoformamidine Amine, (1.070) N '-(2,5-dimethyl-4- {3-[(pentafluoroethyl) thio] phenoxy} phenyl) -N-ethyl-N-methylimine Methylformamide, (1.071) N '-(2,5-dimethyl-4-phenoxyphenyl) -N-ethyl-N-methimidoformamide, (1.072) N'- (4-{[3- (difluoromethoxy) phenyl] thio} -2,5-dimethylphenyl) -N-ethyl-N-methyliminoformamidine, (1.073) N '-(4- {3-[(difluoromethyl) thio] phenoxy} -2,5-dimethylphenyl) -N-ethyl-N-methyliminoformamidine, N '-[5-bromo-6- (2,3-dihydro-1H-inden-2-yloxy) -2-methylpyridin-3-yl] -N-ethyl-N-methyliminoformamidine, (1.075) N ' -{4-[(4,5-dichloro-1,3-thiazol-2-yl) oxy] -2,5-dimethylphenyl} -N-ethyl-N-methyliminomethyl Hydrazine, (1.076) N '-{5-bromo-6-[(1R) -1- (3,5-difluorophenyl) ethoxy] -2-methylpyridin-3-yl} -N -Ethyl-N-methyliminoformamidine, (1.077) N '-{5-bromo-6-[(1S) -1- (3,5-difluorophenyl) ethoxy] -2 -Methylpyridin-3-yl} -N-ethyl-N-methyliminoformamidine, (1.078) N '-{5-bromo-6-[(cis-4-isopropylcyclohexyl ) Oxy] -2-methylpyridin-3-yl} -N-ethyl-N-methylimidoformamidine, (1.079) N '-{5-bromo-6-[(trans-4 -Isopropylcyclohexyl) oxy] -2-methylpyridin-3-yl} -N-ethyl-N-methyliminoformamidine, (1.080) N '-{5-bromo-6- [1- (3,5-difluorophenyl) ethoxy] -2-methylpyridin-3-yl} -N-ethyl-N-methyliminoformamidine, (1.081) Ipfentrifluconazole.
2) Inhibitors of the respiratory chain complex I or II, such as (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, ( 2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, ( 2.009) Isofetamid, (2.010) isopyrazam (contrast isomeric mirror isomers 1R, 4S, 9S), (2.011) apyrazine (contrast isomeric mirror isomers) (1S, 4R, 9R), (2.012) subgroup (contrast isomeric racemate 1RS, 4SR, 9SR), (2.013) subgroup (substance isomeric racemate 1RS, 4SR, 9RS) And contrast isomers racemates 1RS, 4SR, 9SR), (2.014) subgroups (surplus isomeric mirror isomers 1R, 4S, 9R), (2.015) subgroups (surplus anisotropy Conformational isomers 1S, 4R, 9S), (2.016) sub-petroleum (surplus isomeric racemate 1RS, 4SR, 9RS), (2.017) penflufen, (2.018) pyridine Penthiopyrad, (2.019) pydiflumetofen, (2.020) Pyraziflumid (2.021) sedaxane, (2.022) 1,3-dimethyl-N- (1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl ) -1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R) -1,1,3-trimethyl-2,3-dihydro-1H- Inden-4-yl] -1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S) -1,1,3-trimethyl-2,3- Dihydro-1H-inden-4-yl] -1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3- (trifluoromethyl) -N- [2 '-(trifluoromethyl (Yl) biphenyl-2-yl] -1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6- (trifluoromethyl) -N- (1,1,3-trimethyl- 2,3-dihydro-1H-inden-4-yl) benzamide, (2.027) 3- (difluoromethyl) -1-methyl-N- (1,1,3-trimethyl- 2,3-dihydro-1H-inden-4-yl) -1H-pyrazole-4-carboxamide, (2.028) 3- (difluoromethyl) -1-methyl-N-[(3R) -1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl] -1H-pyrazole-4-carboxamide, (2.029) 3- (difluoromethyl)- 1-methyl-N-[(3S) -1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl] -1H-pyrazole-4-carboxamide, ( 2.030) Fluindapyr, (2.031) 3- (difluoromethyl) -N-[(3R) -7-fluoro-1,1,3-trimethyl-2,3-dihydro -1H-inden-4-yl] -1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3- (difluoromethyl) -N-[(3S) -7 -Fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl] -1-methyl-1H-pyrazole-4-carboxamide, (2.033) 5, 8-difluoro-N- [2- (2-fluoro-4-{[4- (trifluoromethyl) pyridin-2-yl] oxy} phenyl) ethyl] quinazolin-4-amine, (2.034) N- (2-cyclopentyl-5-fluorobenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4- Formamidine, (2.035) N- (2-tert-butyl-5-methylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H -Pyrazole-4-carboxamide, (2.036) N- (2-third butylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl- 1H-pyrazole-4-carboxamide, (2.037) N- (5-chloro-2-ethylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1- Methyl-1H-pyrazole-4-carboxamide, (2.038) isoflucypram, (2.039) N-[(1R, 4S) -9- (dichloromethylene) -1,2,3,4-tetram Hydrogen-1,4-methylnaphthyl-5-yl] -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.040) N-[(1S, 4R ) -9- (dichloromethylene) -1,2,3,4-tetrahydro-1,4-methylnaphthyl-5-yl] -3- (difluoromethyl) -1-methyl- 1H-pyrazole-4-carboxamide, (2.041) N- [1- (2,4-dichlorophenyl) -1-methoxyprop-2-yl] -3- (difluoromethyl) 1-methyl-1H-pyrazole-4-carboxamide, (2.042) N- [2-chloro-6- (tri (Methyl) benzyl] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043) N- [3- Chloro-2-fluoro-6- (trifluoromethyl) benzyl] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-methyl Amidine, (2.044) N- [5-chloro-2- (trifluoromethyl) benzyl] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H -Pyrazole-4-carboxamide, (2.045) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-N- [5-methyl-2- (trifluoro (Methyl) benzyl] -1H-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (2-fluoro-6-iso (Propylbenzyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (2-iso (Propyl-5-methylbenzyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.048) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N -(2-isopropylbenzyl) -1-methyl-1H-pyrazole-4-thiomethaneamine, (2.049) N-cyclopropyl-3- (difluoromethyl) -5-fluoro -N- (2-isopropylbenzyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3- (difluoromethyl) -5-fluoro -N- (5-fluoro-2-isopropylbenzyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3- (difluoromethyl) -N- (2-ethyl-4,5-dimethyl ) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3- (difluoromethyl) -N- (2-ethyl-5 -Fluorobenzyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3- (difluoromethyl) -N- (2-ethyl Methyl-5-methylbenzyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-cyclopropyl-N- (2-cyclopropyl-5- (Fluorobenzyl) -3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N- (2-cyclopropyl Methyl-5-methylbenzyl) -3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N- (2-cyclopropylbenzyl) -3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoyne.
3) Inhibitors of respiratory chain complex III, such as (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) methanoate ( coumethoxystrobin), (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dioxystrobin, (3.008) enoxastrobin, (3.009) (famoxadone), (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) Kresoxim-methyl, (3.014) ) Metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin , (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E) -2- {2-[({(((1E) -1- (3-(((E ) -1-fluoro-2-phenylvinyl] oxy} phenyl) ethylene) amino} oxy) methyl] phenyl} -2- (methoxyimino) -N-methyl Acetylamine, (3.022) (2E, 3Z) -5-{[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxy} -2- (Methoxyimino) -N, 3-dimethylpent-3-enamine, (3.023) (2R) -2- {2-[(2,5-dimethylphenoxy) methyl Phenyl] phenyl} -2-methoxy-N-methylacetamide, (3.024) (2S) -2- {2-[(2,5-dimethylphenoxy) methyl] phenyl } -2-methoxy-N-methylacetamide, (3.025) 2-methylpropanoic acid (3S, 6S, 7R, 8R) -8-benzyl-3-[({3-[(iso Butanyloxy) methoxy] -4-methoxypyridin-2-yl} carbonyl) amino] -6-methyl-4,9-dioxo-1,5-dioxanon-7 -Yl ester, (3.026) mandestrobin, (3.027) N- (3-ethyl-3,5,5-trimethylcyclohexyl) -3-carboxamino-2-hydroxybenzyl Hydrazine, (3.028) (2E, 3Z) -5-{[1- (4-chloro-2-fluorophenyl) -1H-pyrazol-3-yl] oxy} -2- (methoxyoxy (Amino) -N, 3-dimethylpent-3-enamidamine, (3.029) {5- [3- (2,4-dimethylphenyl) -1H-pyrazol-1-yl]- 2-methylbenzyl} carbamate, (3.030) metyltetraprole, (3.031) florylpicoxamid.
4) Inhibitors of mitosis and cell division, such as (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide , (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) 3-chloro- 4- (2,6-difluorophenyl) -6-methyl-5-phenylpyrazine, (4.010) 3-chloro-5- (4-chlorophenyl) -4- (2,6-di (Fluorophenyl) -6-methylpyrazine, (4.011) 3-chloro-5- (6-chloropyridin-3-yl) -6-methyl-4- (2,4,6-trifluorophenyl ) Dazine, (4.012) 4- (2-bromo-4-fluorophenyl) -N- (2,6-difluorophenyl) -1,3-dimethyl-1H-pyrazole-5-amine (4.013) 4- (2-bromo-4-fluorophenyl) -N- (2-bromo-6-fluorophenyl) -1,3-dimethyl-1H-pyrazole-5-amine, ( 4.014) 4- (2-bromo-4-fluorophenyl) -N- (2-bromophenyl) -1,3-dimethyl-1H-pyrazole-5-amine, (4.015) 4- (2 -Bromo-4-fluorophenyl) -N- (2-chloro-6-fluorophenyl) -1,3-dimethyl-1H-pyrazole-5-amine, (4.016) 4- (2-bromo 4-fluorophenyl) -N- (2-chlorophenyl) -1,3-dimethyl-1H-pyrazole-5-amine, (4.017) 4- (2-bromo-4-fluorophenyl) ) -N- (2-fluorophenyl) -1,3-dimethyl-1H -Pyrazole-5-amine, (4.018) 4- (2-chloro-4-fluorophenyl) -N- (2,6-difluorophenyl) -1,3-dimethyl-1H-pyrazole -5-amine, (4.019) 4- (2-chloro-4-fluorophenyl) -N- (2-chloro-6-fluorophenyl) -1,3-dimethyl-1H-pyrazole-5 -Amine, (4.020) 4- (2-chloro-4-fluorophenyl) -N- (2-chlorophenyl) -1,3-dimethyl-1H-pyrazole-5-amine, (4.021) 4- (2-chloro-4-fluorophenyl) -N- (2-fluorophenyl) -1,3-dimethyl-1H-pyrazole-5-amine, (4.022) 4- (4-chloro (Phenyl) -5- (2,6-difluorophenyl) -3,6-dimethylpyrazine, (4.023) N- (2-bromo-6-fluorophenyl) -4- (2-chloro 4-fluorophenyl) -1,3-dimethyl-1H-pyrazole-5-amine, (4.024) N- (2-bromophenyl) -4- (2-chloro-4-fluorophenyl) ) -1,3-dimethyl-1H-pyrazole-5-amine, (4.025) N- (4-chloro-2,6-difluorophenyl) -4- (2-chloro-4-fluorobenzene Group) -1,3-dimethyl-1H-pyrazole-5-amine.
5) Compounds capable of multi-site action, such as (5.001) Bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil ( chlorothalonil), (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper sulfate (2+), (5.010) nitrile thioquinone, (5.011) dodine, (5.012) folpet, (5.013) zinc manganese (mancozeb), (5.014) maneb, (5.015) to avoid rotten (metiram), (5.016) metiram zinc, (5.017) oxine-copper, (5.018) methyl zinc propineb, (5.019) sulfur and sulfur preparations, including calcium polysulfide, ( 5.020) thiram, (5.021) zineb, (5.022) ziram, (5.023) 6-ethyl-5,7-dioxo-6,7-di Hydrogen-5H-pyrrolo [3 ', 4': 5,6] [1,4] dithia [2,3-c] [1,2] thiazole-3-carbonitrile.
6) Compounds that can induce host defenses, such as (6.001) acibenzolar-S-methyl, (6.002) isotianil, (6.003) probenazole , (6.004) tiadinil.
7) Inhibitors of amino acid and / or protein biosynthesis, such as (7.001) cyprodinil, (7.002) kasugamycin, (7.003) Jiacimycin hydrochloride hydrate, ( 7.004) oxytetracycline, (7.005) pirimethanil, (7.006) 3- (5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinoline -1-yl) quinoline.
8) Inhibitors of ATP production, such as (8.001) silthiofam.
9) Inhibitors of cell wall synthesis, such as (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E) -3- (4-tert-butylphenyl) ) -3- (2-chloropyridin-4-yl) -1- (morpholin-4-yl) prop-2-en-1-one, (9.009) (2Z) -3- (4-tert-butyl Phenyl) -3- (2-chloropyridin-4-yl) -1- (morpholin-4-yl) prop-2-en-1-one.
10) Inhibitors of lipid and membrane synthesis, such as (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.
11) Inhibitors of melanin biosynthesis, such as (11.001) tricyclazole, (11.002) {3-methyl-1-[(4-methylbenzyl) amino] but-2-yl } 2,2,2-trifluoroethyl aminoformate.
12) Inhibitors of nucleic acid synthesis, such as (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl (12.004) Dexteryl Dal (Mefenoxam).
13) Inhibitors of signal transduction, such as (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.
14) Compounds that can be used as decoupling agents, such as (14.001) fluazinam and (14.002) meptyldinocap.
15) Other compounds, such as (15.001) Abscisic acid, (15.002) benthiazole, (15.003) bethoxazin, (15.004) capsimycin, (15.005) Carvone, (15.006) chinomethionat, (15.007) cufraneb, (15.008) cyflufenamid, (15.009) cymoxanil, (15.010) Ciproflamine, (15.011) flutianil, (15.012) foamyl-aluminum, (15.013) calcium triethylphosphonate, (15.014) sodium triethylphosphonate, ( 15.015) Methyl isothiocyanate, (15.016) metrafenone, (15.017) Mildiomycin, (15.018) Natamycin, (15.019) Nickel dimethyldithiocarbamate , (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) oxathiapiprolin, (15.023) oxyfenthiin, (15.024) five Chlorophenol and salts, (15.025) phosphoric acid and its salts, (15.026) propamocarb-fosetylate, (15.027) pyriofenone ( Chlazafenone), (15.028) tebufloquin, (15.029) tecloftalam, (15.030) tolnifanide, (15.031) 1- (4- {4-[(5R) -5- (2,6-difluorophenyl) -4,5-dihydro-1,2-oxazole-3-yl] -1,3-thiazol-2-yl} Hexahydropyridin-1-yl) -2- [5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl] ethanone, (15.032) 1- (4- {4- [ (5S) -5- (2,6-difluorophenyl) -4,5-dihydro-1,2-oxazol-3-yl] -1,3-thiazol-2-yl} hexahydropyridine- 1-yl) -2- [5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl] ethanone, (15.033) 2- (6-benzylpyridin-2-yl) Quinazoline, (15.034) dipymetitrone, (15.035) 2- [3,5-bis (difluoromethyl) -1H-pyrazol-1-yl] -1- [4- (4- {5- [2 -(Prop-2-yn-1-yloxy) phenyl] -4,5-dihydro-1,2-oxazol-3-yl} -1,3-thiazol-2-yl) hexahydropyridine -1-yl] ethanone, (15.036) 2- [3,5-bis (difluoromethyl) -1H-pyrazol-1-yl] -1- [4- (4- {5- [2- Chloro-6- (prop-2-yn-1-yloxy) phenyl] -4,5-dihydro-1,2-oxazol-3-yl} -1,3-thiazol-2-yl) Hexahydropyridin-1-yl] ethanone, (15.037) 2- [3,5-bis (difluoromethyl) -1H-pyrazol-1-yl] -1- [4- (4- {5- [2-fluoro-6- (prop-2-yn-1-yloxy) phenyl] -4,5-dihydro-1, 2-oxazol-3-yl} -1,3-thiazol-2-yl) hexahydropyridin-1-yl] ethanone, (15.038) 2- [6- (3-fluoro-4-methoxybenzene ) -5-methylpyridin-2-yl] quinazoline, (15.039) methanesulfonic acid 2-{(5R) -3- [2- (1-{[3,5-bis (difluoromethyl) ) -1H-pyrazol-1-yl] ethenyl} hexahydropyridin-4-yl) -1,3-thiazol-4-yl] -4,5-dihydro-1,2-oxazole-5 -Yl} -3-chlorophenyl ester, (15.040) methanesulfonic acid 2-{(5S) -3- [2- (1-{[3,5-bis (difluoromethyl) -1H-pyrazole -1-yl] ethenyl} hexahydropyridin-4-yl) -1,3-thiazol-4-yl] -4,5-dihydro-1,2-oxazol-5-yl} -3- Chlorophenyl ester, (15.041) Ipflufenoquin, (15.042) 2- {2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl) oxy] phenyl} propan-2-ol , (15.043) methanesulfonic acid 2- {3- [2- (1-{[3,5-bis (difluoromethyl) -1H-pyrazol-1-yl] ethylfluorenyl} hexahydropyridine-4 -Yl) -1,3-thiazol-4-yl] -4,5-dihydro-1,2-oxazol-5-yl} -3-chlorophenyl ester, (15.044) methanesulfonic acid 2- { 3- [2- (1-{[3,5-bis (difluoromethyl) -1H-pyrazol-1-yl] ethenyl} hexahydropyridin-4-yl) -1,3-thiazole- 4-yl] -4,5-dihydro-1,2-oxazol-5-yl} phenyl ester, (15.045) 2-phenylphenol and salts, (15.046) 3- (4,4,5- (Trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) (5.047) quinofumelin, (15.048) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2 (1H) -one), (15.049) 4-oxo-4-[(2-phenylethyl) amino] butanoic acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5 -Chloro-N'-phenyl-N '-(prop-2-yn-1-yl) thiophene-2-sulfohydrazine, (15.052) 5-fluoro-2-[(4-fluorobenzyl) oxy ] Pyrimidin-4-amine, (15.053) 5-fluoro-2-[(4-methylbenzyl) oxy] pyrimidin-4-amine, (15.054) 9-fluoro-2,2-dimethyl-5 -(Quinolin-3-yl) -2,3-dihydro-1,4-benzoxazepine, (15.055) {6-[({((((Z)-(1-methyl -1H-tetrazol-5-yl) (phenyl) methylene] amino} oxy) methyl] pyridin-2-yl} amino-3-butyn-1-yl formate, (15.056) (2Z) -3-Amino-2-cyano-3-phenylethyl acrylate, (15.057) phenazine-1-carboxylic acid, (15.058) propyl 3,4,5-trihydroxybenzoate, (15.059 ) Quinoline-8-ol, (15.060) quinoline-8-alcohol sulfate (2: 1), (15.061) {6-[((((1-methyl-1H-tetrazol-5-yl) (Phenyl) methylene] amino} oxy) methyl] pyridin-2-yl} aminocarboxylic acid third butyl ester, (15.062) 5-fluoro-4-imino-3-methyl- 1-[(4-methylphenyl) sulfonyl]- 3,4-dihydropyrimidin-2 (1H) -one, (15.063) aminopyrifen.
如上所述類別(1)至(15)之所有指定混合夥伴均可以自由化合物及/或(若其官能基使其能夠如此)其農業上上可接受之鹽的形式存在。All specified mixing partners of categories (1) to (15) as described above can exist in the form of free compounds and / or (if their functional group enables it) their agriculturally acceptable salts.
式(I)化合物及組合物亦可與一或多種生物控制劑組合。The compounds and compositions of formula (I) may also be combined with one or more biological control agents.
可與式(I)化合物及包含其等之組合物組合之生物控制劑的實例係:
(A) 選自以下群組之抗細菌劑:
(A1) 細菌,例如(A1.1) 枯草芽孢桿菌(Bacillus subtilis
),特定而言菌株QST713/AQ713 (自Bayer CropScience LP, US作為SERENADE OPTI或SERENADE ASO獲得,具有NRRL登錄號B21661且闡述於美國專利第6,060,051號中);(A1.2) 解澱粉芽孢桿菌(Bacillus amyloliquefaciens
),特定而言菌株D747 (自Certis, US作為Double Nickel™獲得,具有登錄號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
),特定而言菌株BU F-33 (具有NRRL登錄號50185);(A1.4) 解澱粉枯草桿菌變種菌株FZB24 (自Novozymes, US作為Taegro®獲得);(A1.5) 類芽孢桿菌屬(Paenibacillus
sp.)菌株,具有登錄號NRRL B-50972或登錄號NRRL B-67129且闡述於國際專利公開案第WO 2016/154297號中;及
(A2) 真菌,例如(A2.1) 出芽短梗黴(Aureobasidium pullulans),特定而言菌株DSM14940之芽生孢子;(A2.2) 菌株DSM 14941之出芽短梗黴芽生孢子;(A2.3) 出芽短梗黴,特定而言菌株DSM14940及DSM14941之芽生孢子混合物;
(B) 選自以下之群之殺真菌劑:
(B1) 細菌,例如(B1.1) 枯草桿菌,特定而言菌株QST713/AQ713 (自Bayer CropScience LP, US作為SERENADE OPTI或SERENADE ASO獲得,具有NRRL登錄號B21661且闡述於美國專利第6,060,051號中);(B1.2) 短小芽孢桿菌,特定而言菌株QST2808 (自Bayer CropScience LP, US作為SONATA®獲得,具有登錄號NRRL B-30087且闡述於美國專利第6,245,551號中);(B1.3) 短小芽孢桿菌,特定而言菌株GB34 (自Bayer AG, DE作為Yield Shield®獲得);(B1.4) 短小芽孢桿菌,特定而言菌株BU F-33 (具有NRRL登錄號50185);(B1.5) 解澱粉芽孢桿菌,特定而言菌株D747 (自Certis, US作為Double Nickel™獲得,具有登錄號FERM BP-8234且揭示於美國專利第7,094,592號中);(B1.6) 枯草桿菌Y1336 (自Bion-Tech, Taiwan作為BIOBAC®
WP獲得,在臺灣Taiwan以登記號4764、5454、5096及5277登記為生物殺真菌劑);(B1.7) 解澱粉芽孢桿菌菌株MBI 600 (自BASF SE作為SUBTILEX獲得);(B1.8) 枯草桿菌菌株GB03 (自Bayer AG, DE作為Kodiak®獲得);(B1.9) 解澱粉枯草桿菌變種菌株FZB24 (自Novozymes Biologicals Inc., Salem, Virginia或Syngenta Crop Protection, LLC, Greensboro, North Carolina作為殺真菌劑TAEGRO®
或TAEGRO®
ECO (EPA登記號70127-5)獲得);(B1.10) 蕈狀桿菌(Bacillus mycoides
),分離株J (自Certis USA作為BmJ TGAI或WG獲得);(B1.11) 地衣芽孢桿菌(Bacillus licheniformis
),特定而言菌株SB3086 (自Novozymes作為EcoGuard TM Bio殺真菌劑及Green Releaf獲得);(B1.12) 類芽孢桿菌屬菌株,具有登錄號NRRL B-50972或登錄號NRRL B-67129且闡述於國際專利公開案第WO 2016/154297號中。Examples of biological control agents that can be combined with compounds of formula (I) and compositions containing them are:
(A) an antibacterial agent selected from the group:
(A1) Bacteria, such as (A1.1) Bacillus subtilis , specifically strains QST713 / AQ713 (obtained from Bayer CropScience LP, US as SERENADE OPTI or SERENADE ASO, with NRRL accession number B21661 and described in the United States (Patent No. 6,060,051); (A1.2) Bacillus amyloliquefaciens , specifically strain D747 (obtained from Certis, US as Double Nickel ™, with accession number FERM BP-8234 and disclosed in US Patent No. No. 7,094,592); (A1.3) Bacillus pumilus , specifically strain BU F-33 (with NRRL accession number 50185); (A1.4) Amylolyticus subtilis variant strain FZB24 (from Novozymes, US is available as Taegro®); (A1.5) Paenibacillus sp. Strains have accession number NRRL B-50972 or accession number NRRL B-67129 and are described in International Patent Publication No. WO 2016/154297 Medium; and
(A2) Fungi, such as (A2.1) Aureobasidium pullulans, specifically spores of strain DSM14940; (A2.2) Sprouts spores of DSM 14941; (A2.3) S. budding, specifically spore mixtures of strains DSM14940 and DSM14941;
(B) Fungicides selected from the group consisting of:
(B1) Bacteria, such as (B1.1) Bacillus subtilis, specifically strains QST713 / AQ713 (obtained from Bayer CropScience LP, US as SERENADE OPTI or SERENADE ASO, with NRRL accession number B21661 and described in US Patent No. 6,060,051 ); (B1.2) Bacillus pumilus, specifically strain QST2808 (obtained as SONATA® from Bayer CropScience LP, US, with accession number NRRL B-30087 and described in US Patent No. 6,245,551); (B1.3) ) Bacillus pumilus, specifically strain GB34 (obtained as Yield Shield® from Bayer AG, DE); (B1.4) Bacillus pumilus, specifically strain BU F-33 (with NRRL accession number 50185); (B1 .5) Bacillus amyloliquefaciens, specifically strain D747 (obtained from Certis, US as Double Nickel ™ with accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592); (B1.6) Bacillus subtilis Y1336 (Obtained as BIOBAC ® WP from Bion-Tech, Taiwan and registered as a biocide with registration numbers 4764, 5454, 5096, and 5277 in Taiwan); (B1.7) Bacillus amyloliquefaciens strain MBI 600 (from BASF SE (Obtained as SUBTILEX); (B1.8) Bacillus subtilis Strain GB03 (obtained from Bayer AG, DE as Kodiak®); (B1.9) A. subtilis variant strain FZB24 (from Novozymes Biologicals Inc., Salem, Virginia or Syngenta Crop Protection, LLC, Greensboro, North Carolina as fungicidal Agent TAEGRO ® or TAEGRO ® ECO (EPA registration number 70127-5)); (B1.10) Bacillus mycoides , isolate J (obtained from Certis USA as BmJ TGAI or WG); (B1.11 ) Bacillus licheniformis , specifically strain SB3086 (obtained from Novozymes as EcoGuard ™ Bio fungicide and Green Releaf); (B1.12) Bacillus-like strains with registration number NRRL B-50972 or registration No. NRRL B-67129 and is described in International Patent Publication No. WO 2016/154297.
在一些實施例中,生物控制劑係產生豐原素(fengycin)或製磷脂菌素(plipastatin)型化合物、伊枯草菌素(iturin)型化合物及/或表面活性素(surfactin)型化合物之枯草桿菌或解澱粉芽孢桿菌菌株。關於背景,參見以下綜述文章: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桿菌QST713 (自Bayer CropScience LP, US作為SERENADE OPTI或SERENADE ASO獲得,具有NRRL登錄號B21661且闡述於美國專利第6,060,051號中)、解澱粉芽孢桿菌菌株D747 (作為獲得Double Nickel™ 自Certis, US,具有登錄號FERM BP-8234且揭示於美國專利第7,094,592號中);枯草桿菌MBI600 (自Becker Underwood, US作為SUBTILEX®
獲得,EPA登記號71840-8);枯草桿菌Y1336 (自Bion-Tech, Taiwan作為BIOBAC®
WP獲得,在臺灣(Taiwan)以登記號4764、5454、5096及5277登記為生物殺真菌劑); 解澱粉芽孢桿菌,特定而言菌株FZB42 (自ABiTEP, DE作為RHIZOVITAL®
獲得);及解澱粉枯草桿菌變種FZB24 (自Novozymes Biologicals Inc., Salem, Virginia或Syngenta Crop Protection, LLC, Greensboro, North Carolina作為殺真菌劑TAEGRO®
或TAEGRO®
ECO (EPA登記號70127-5)獲得);且
(B2) 真菌,例如:(B2.1) 盾殼黴(Coniothyrium minitans
),特定而言菌株CON/M/91-8 (登錄號DSM-9660;例如來自Bayer之Contans ®);(B2.2) 核果梅奇酵母菌(Metschnikowia fructicola
),特定而言菌株NRRL Y-30752 (例如Shemer®);(B2.3) 赫色小球殼孢(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
),闡述於國際申請案第PCT/IT2008/000196號中之菌株SC1);(B2.6) 哈氏木黴菌(Trichoderma harzianum rifai
)菌株KRL-AG2 (亦稱為菌株T-22,/ATCC 208479,例如PLANTSHIELD T-22G, 來自BioWorks, US之Rootshield®及TurfShield);(B2.14) 粉紅黏帚黴(Gliocladium roseum
),來自W.F. Stoneman Company LLC之菌株321U;(B2.35) 黃藍狀菌(Talaromyces flavus
),菌株V117b;(B2.36) 棘孢木黴菌(Trichoderma asperellum
),來自Isagro之菌株ICC 012;(B2.37) 棘孢木黴菌,菌株SKT-1 (例如來自Kumiai Chemical Industry之ECO-HOPE®);(B2.38) 深綠木黴,菌株CNCM I-1237 (例如Esquive® WP 來自之Agrauxine, FR);(B2.39) 深綠木黴,菌株編號V08/002387;(B2.40) 深綠木黴,菌株NMI編號V08/002388;(B2.41) 深綠木黴,菌株NMI編號V08/002389;(B2.42) 深綠木黴,菌株NMI編號V08/002390;(B2.43) 深綠木黴,菌株LC52 (例如Agrimm Technologies Limited之Tenet);(B2.44) 深綠木黴,菌株ATCC 20476 (IMI 206040);(B2.45) 深綠木黴,菌株T11 (IMI352941/ CECT20498);(B2.46)鉤狀木黴菌(Trichoderma hamatum
);(B2.47) 哈氏木黴菌;(B2.48) 哈氏木黴菌T39 (例如來自Makhteshim, US之Trichodex®);(B2.49) 哈氏木黴菌,特定而言菌株KD (例如來自Biological Control Products, SA之Trichoplus (自Becker Underwood獲得));(B2.50) 哈氏木黴菌,菌株ITEM 908 (例如Trianum-P 來自之Koppert);(B2.51) 哈氏木黴菌,菌株TH35 (例如Mycontrol之Root-Pro);(B2.52) 綠木黴(Trichoderma virens
)(亦稱為綠黏帚黴(Gliocladium virens
)),特定而言菌株GL-21 (例如Certis, US之SoilGard 12G);(B2.53) 綠色木黴(Trichoderma viride
),菌株TV1 (例如Koppert之Trianum-P);(B2.54) 白粉寄生孢(Ampelomyces quisqualis),特定而言菌株AQ 10 (例如IntrachemBio Italia之AQ 10®);(B2.56) 出芽短梗黴,特定而言菌株DSM14940之芽生孢子;(B2.57) 出芽短梗黴,特定而言菌株DSM 14941之芽生孢子;(B2.58) 出芽短梗黴,特定而言菌株DSM14940及DSM 14941之芽生孢子之混合物(例如bio-ferm, CH之Botector®);(B2.64) 枝孢樣分枝孢子菌(Cladosporium cladosporioides
),菌株H39 (Stichting Dienst Landbouwkundig Onderzoek);(B2.69) 鏈孢黏帚黴(Gliocladium catenulatum
)(同義詞:粉紅黏帚黴鏈狀專化型(Clonostachys rosea f. catenulate
))菌株J1446 (例如AgBio Inc.之Prestop ®以及例如Kemira Agro Oy之Primastop®);(B2.70) 蠟蚧輪枝菌(Lecanicillium lecanii
)(先前稱為蠟蚧輪枝菌(Verticillium lecanii
))菌株KV01之分生孢子(例如Koppert/Arysta之Vertalec®);(B2.71) 蠕形青黴(Penicillium vermiculatum
);(B2.72) 異常畢赤酵母(Pichia anomala
),菌株WRL-076 (NRRL Y-30842);(B2.75) 深綠木黴,菌株SKT-1 (FERM P-16510);(B2.76) 深綠木黴,菌株SKT-2 (FERM P-16511);(B2.77) 深綠木黴,菌株SKT-3 (FERM P-17021);(B2.78) 蓋姆斯木黴(Trichoderma gamsii
)(先前稱為綠色木黴(T. viride
)),菌株ICC080 (IMI CC 392151 CABI,例如AGROBIOSOL DE MEXICO, S.A. DE C.V.之BioDerma);(B2.79) 哈氏木黴菌,菌株DB 103 (例如Dagutat Biolab之T-Gro 7456);(B2.80) 多孢木黴(Trichoderma polysporum
),菌株IMI 206039 (例如BINAB Bio-Innovation AB, Sweden之Binab TF WP);(B2.81) 子座木黴(Trichoderma stromaticum
)(例如Ceplac, Brazil之Tricovab);(B2.83) 奧德曼細基格孢(Ulocladium oudemansii
),特定而言菌株HRU3 (例如Botry-Zen Ltd, NZ之Botry-Zen®);(B2.84) 黑白輪枝菌(Verticillium albo-atrum
)(先前稱為大麗輪枝菌(V. dahliae
)),菌株WCS850 (CBS 276.92;例如Tree Care Innovations之Dutch Trig);(B2.86) 厚垣輪枝菌(Verticillium chlamydosporium
);(B2.87) 棘孢木黴菌菌株ICC 012及蓋姆斯木黴菌株ICC 080之混合物(稱為例如來自Bayer CropScience LP, US之BIO-TAMTM
之產品)。In some embodiments, the biological control agent is a Bacillus subtilis which produces fengycin or plipastatin-type compounds, iturin-type compounds, and / or surfactin-type compounds Or Bacillus amyloliquefaciens strains. For background, see the following review article: Ongena, M. et al., " Bacillus Lipopeptides: Versatile Weapons for Plant Disease Biocontrol", Trends in Microbiology, Volume 16, Issue 3, March 2008, pages 115-125. Bacillus strains capable of producing lipopeptides include Bacillus subtilis QST713 (obtained from Bayer CropScience LP, US as SERENADE OPTI or SERENADE ASO with NRRL accession number B21661 and described in U.S. Patent No. 6,060,051), Bacillus amyloliquefaciens strain D747 ( as Double Nickel ™ obtained from Certis, US, having the accession number FERM BP-8234 and is disclosed in the U.S. Patent No. 7,094,592); Bacillus subtilis MBI600 (from Becker Underwood, US SUBTILEX ® as obtained, EPA registration No. 71840-8); Bacillus subtilis Y1336 (obtained as BIOBAC ® WP from Bion-Tech, Taiwan and registered as a biofungicide with registration numbers 4764, 5454, 5096, and 5277 in Taiwan); Bacillus amyloliquefaciens, specifically the strain FZB42 ( since ABiTEP, DE obtained as RHIZOVITAL ®); and amyloliquefaciens subtilisin variant FZB24 (from Novozymes Biologicals Inc., Salem, Virginia, or Syngenta Crop Protection, LLC, Greensboro, North Carolina as fungicides TAEGRO ® or TAEGRO ® ECO (EPA Accession number 70127-5)); and
(B2) Fungi, such as: (B2.1) Coniothyrium minitans , specifically strain CON / M / 91-8 (accession number DSM-9660; for example, Contans® from Bayer); (B2.2 ) Metschnikowia fructicola , specifically strain NRRL Y-30752 (eg Shemer®); (B2.3) Microsphaeropsis ochracea (eg Microx® from Prophyta); ( B2.5) Trichoderma spp. , Including Trichoderma atroviride , described in strain SC1 in International Application No. PCT / IT2008 / 000196; (B2.6) Trichoderma harzianum ( Trichoderma harzianum rifai ) strain KRL-AG2 (also known as strain T-22, / ATCC 208479, such as PLANETSHIELD T-22G, Rootshield® and TurfShield from BioWorks, US); (B2.14) Gliocladium pink roseum ), strain 321U from WF Stoneman Company LLC; (B2.35) Talaromyces flavus , strain V117b; (B2.36) Trichoderma asperellum , strain ICC 012 from Isagro; (B2.37) Trichoderma echinococcus, strain SKT-1 (e.g. from Kumiai Chemical Industry (ECO-HOPE®); (B2.38) Trichoderma dark green, strain CNCM I-1237 (for example, Agrauxine, FR from Equive® WP); (B2.39) Trichoderma dark green, strain number V08 / 002387; ( B2.40) Trichoderma deep green, strain NMI number V08 / 002388; (B2.41) Trichoderma deep green, strain NMI number V08 / 002389; (B2.42) Trichoderma deep green, strain NMI number V08 / 002390; (B2.43) Trichoderma deep green, strain LC52 (e.g. Tenet from Agrimm Technologies Limited); (B2.44) Trichoderma deep green, strain ATCC 20476 (IMI 206040); (B2.45) Trichoderma deep green, strain T11 (IMI352941 / CECT20498); (B2.46) Trichoderma hamatum ; (B2.47) Trichoderma; (B2.48) Trichoderma T39 (e.g. Trichodex® from Makhteshim, US ); (B2.49) Trichoderma harzianum, specifically strain KD (eg Trichoplus from Biological Control Products, SA (obtained from Becker Underwood)); (B2.50) Trichoderma harzianum, strain ITEM 908 (for example Koppert from Trianum-P); (B2.51) Trichoderma harzianum, strain TH35 (eg Root-Pro of Mycontrol); (B2.52) Trichoderma virens (also known as Trichoderma virens ) Gliocladium v irens )), specifically strain GL-21 (such as SoilGard 12G from Certis, US); (B2.53) Trichoderma viride , strain TV1 (such as Triumum-P from Koppert); (B2.54) Ampelomyces quisqualis, specifically strain AQ 10 (for example, AQ 10® of IntrachemBio Italia); (B2.56) Brevibacterium sp., Specifically budding spores of strain DSM14940; (B2.57) sprouting short T. spp., Spores of strain DSM 14941; (B2.58) S. spores, a mixture of spores of strains DSM14940 and DSM 14941 (e.g., Botector® of bio-ferm, CH); (B2 .64) Cladosporium cladosporioides , strain H39 (Stichting Dienst Landbouwkundig Onderzoek); (B2.69) Gliocladium catenulatum (synonym: chain specialization type of Gliocladium catenulatum ) ( Clonostachys rosea f. Catenulate )) strain J1446 (e.g. Prestop® from AgBio Inc. and e.g. Primastop® from Kemira Agro Oy); (B2.70) Lecanicillium lecanii (formerly known as Lecanicillium lecanii ) Conidia of Verticillium lecanii ) strain KV01 (For example, Vertalec® of Koppert / Arysta); (B2.71) Penicillium vermiculatum ; (B2.72) Pichia anomala , strain WRL-076 (NRRL Y-30842); (B2.71) B2.75) Trichoderma deep green, strain SKT-1 (FERM P-16510); (B2.76) Trichoderma deep green, strain SKT-2 (FERM P-16511); (B2.77) Trichoderma deep green , Strain SKT-3 (FERM P-17021); (B2.78) Trichoderma gamsii (formerly known as T. viride ), strain ICC080 (IMI CC 392151 CABI, eg AGROBIOSOL BioDerma of DE MEXICO, SA DE CV); (B2.79) Trichoderma harzianum, strain DB 103 (eg T-Gro 7456 from Dagutat Biolab); (B2.80) Trichoderma polysporum , strain IMI 206039 (e.g. Binab TF WP of BINAB Bio-Innovation AB, Sweden); (B2.81) Trichoderma stromaticum (e.g. Tricovab of Ceplac, Brazil); (B2.83) Oldmannia spp. ( Ulocladium oudemansii ), specifically the strain HRU3 (eg Botry-Zen® of Botry-Zen Ltd, NZ); (B2.84) Verticillium albo-atrum (formerly known as Verticillium albo-atrum ) V. dahliae)), Strain WCS850 (CBS 276.92; e.g. Tree Care Innovations of Dutch Trig); (B2.86) chlamydospores Verticillium (Verticillium chlamydosporium) bacteria; (B2.87) aculeatus strain of Trichoderma Trichoderma strain ICC 012 and ICC Gaimu Si 080 mixture (referred to as, for example, the product of BIO-TAM ™ from Bayer CropScience LP, US).
可與式(I)化合物及包含其等之組合物組合之生物控制劑的其他實例係:
選自由以下組成之群之細菌:蠟狀芽孢桿菌、特定而言蠟狀芽孢桿菌菌株CNCM I-1562及堅強芽孢桿菌(Bacillus firmus
),菌株I-1582 (登錄號CNCM I-1582);枯草芽孢桿菌菌株OST 30002 (登錄號NRRL B-50421);蘇雲金芽孢桿菌(Bacillus thuringiensis
),特定而言蘇雲金芽孢桿菌以色列亞種(B. thuringiensis
subspeciesisraelensis
)(血清型H-14),菌株AM65-52 (登錄號ATCC 1276),蘇雲金芽孢桿菌鯰澤亞種(B. thuringiensis subsp. aizawai
),特定而言菌株ABTS-1857 (SD-1372),蘇雲金芽孢桿菌庫爾斯塔克亞種(B. thuringiensis subsp. kurstaki
)菌株HD-1,蘇雲金芽孢桿菌擬步甲亞種(B. thuringiensis subsp. tenebrionis
)菌株NB 176 (SD-5428);穿刺巴斯德芽菌(Pasteuria penetrans
),巴斯德芽菌屬(腎形腎狀線蟲(Rotylenchulus reniformis nematode))-PR3 (登錄號ATCC SD-5834);細黃鏈黴菌(Streptomyces microflavus
)菌株AQ6121 (= QRD 31.013, NRRL B-50550),及鮮黃鏈黴菌(Streptomyces galbus
)菌株AQ 6047 (登錄號NRRL 30232);
選自由以下組成之群之真菌及酵母:球孢白殭菌(Beauveria bassiana
),特定而言菌株ATCC 74040;臘蚧輪刺孢菌屬(Lecanicillium spp
.),特定而言菌株HRO LEC 12;黑殭菌(Metarhizium anisopliae
),特定而言菌株F52 (DSM3884或ATCC 90448);玫煙色擬青黴(Paecilomyces fumosoroseus
)(現稱:玫煙色棒束孢(Isaria fumosorosea
)),特定而言菌株IFPC 200613或菌株Apopka 97 (登錄號ATCC 20874);及淡紫擬青黴(Paecilomyces lilacinus
),特定而言淡紫擬青黴菌株251 (AGAL 89/030550);
選自由以下組成之群之病毒:小角紋捲葉蛾(Adoxophyes orana
)(夏果捲葉蛾(summer fruit tortrix))顆粒體病毒(GV)、蘋果蠧蛾(Cydia pomonella
)(蘋果捲葉蛾(codling moth))顆粒體病毒(GV)、棉鈴蟲(Helicoverpa armigera
)(番茄夜蛾(cotton bollworm))核多角體病毒(NPV)、甜菜葉蛾(Spodoptera exigua
)(甜菜葉蛾(beet armyworm))mNPV、草地貪夜蛾(Spodoptera frugiperda
) (秋行軍蟲(fall armyworm)) mNPV及海灰翅夜蛾(Spodoptera littoralis
)(非洲斜紋夜蛾(African cotton leafworm)) NPV。
可作為「接種劑」添加至植物或植物部分或植物器官且借助其特定性質促進植物生長及植物健康之細菌及真菌。實例係:土壤桿菌屬(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
.)、伯克氏菌屬(Burkholderia spp
.)、特定而言洋蔥伯克氏菌(Burkholderia cepacia
)(先前稱為洋蔥假單胞菌(Pseudomonas cepacia
))、巨孢囊黴屬(Gigaspora spp
.)、或單孢巨孢囊黴(Gigaspora monosporum
)、球囊黴屬(Glomus spp
.)、蠟蘑屬(Laccaria spp
.)、布氏乳桿菌(Lactobacillus buchneri
)、類球囊黴屬(Paraglomus spp.
)、彩色豆馬勃(Pisolithus tinctorius
)、假單胞菌屬(Pseudomonas spp.
)、根瘤菌屬(Rhizobium spp
.)、特定而言三葉草根瘤菌(Rhizobium trifolii
)、須腹菌屬(Rhizopogon spp.
)、硬皮馬勃屬(Scleroderma spp.
)、乳牛肝菌屬(Suillus spp
.)及鏈黴菌屬(Streptomyces spp.
)。
可用作生物控制劑之植物提取物及由微生物形成之產物(包括蛋白質及二次代謝物),例如大蒜(Allium sativum
)、苦艾(Artemisia absinthium
)、印楝素(azadirachtin)、Biokeeper WP、黑桂皮(Cassia nigricans
)、苦皮藤(Celastrus angulatus
)、美洲土荊芥(Chenopodium anthelminticum
)、幾丁質、Armour-Zen、歐洲鱗毛蕨(Dryopteris filix-mas
)、問荊(Equisetum arvense
)、Fortune Aza、Fungastop、Heads Up (藜麥(Chenopodium quinoa
)皂素提取物)、除蟲菊屬/除蟲菊酯(Pyrethrum/Pyrethrins
)、苦木(Quassia amara
)、櫟屬(Quercus
)、石鹼木屬(Quillaja
)、Regalia、「Requiem™殺蟲劑」、魚藤精(rotenone)、魚尼丁屬/蘭尼啶(ryania
/ryanodine)、康福利草(Symphytum officinale
)、菊蒿(Ta nacetum vulgare
)、瑞香酚(thymol)、Triact 70、TriCon、旱金蓮(Tropaeoulum majus
)、異株蕁麻(Urtica dioica
)、藜蘆鹼(Veratrin)、槲寄生(Viscum album
)、十字花科(Brassicaceae
)提取物,特定而言油菜粉或芥菜粉。Other examples of biological control agents that can be combined with compounds of formula (I) and compositions comprising them are:
Bacteria selected from the group consisting of Bacillus cereus, specifically Bacillus cereus strains CNCM I-1562 and Bacillus firmus , strain I-1582 (accession number CNCM I-1582); Bacillus subtilis Bacillus strain OST 30002 (accession number NRRL B-50421); Bacillus thuringiensis , specifically B. thuringiensis subspecies israelensis (serotype H-14), strain AM65-52 ( ATCC 1276), B. thuringiensis subsp. Aizawai , specifically strain ABTS-1857 (SD-1372), B. thuringiensis subsp. kurstaki ) strain HD-1, B. thuringiensis subsp. tenebrionis strain NB 176 (SD-5428); Pasteuria penetrans , Pasteuria (kidney-shaped nematode reniform (Rotylenchulus reniformis nematode)) - PR3 ( Accession No. ATCC SD-5834); Huang fine Streptomyces (Streptomyces microflavus) strain AQ6121 (= QRD 31.013, NRRL B -50550), and the bright yellow streptavidin (Streptomyces galbus) strain AQ 6047 (accession number NRRL 30232);
The fungus is selected from the group consisting of yeast and:; (. Lecanicillium spp) bassiana (Beauveria bassiana), for a particular strain ATCC 74040 December stab Verticillium spp, In particular strains HRO LEC 12; black Metarhizium anisopliae , specifically strain F52 (DSM3884 or ATCC 90448); Paecilomyces fumosoroseus (now known as: Isaria fumosorosea ), specifically strain IFPC 200613 Or strain Apopka 97 (accession number ATCC 20874); and Paecilomyces lilacinus , specifically Paecilomyces lilacinus strain 251 (AGAL 89/030550);
A virus selected from the group consisting of: Adoxophyes orana (summer fruit tortrix) granulovirus (GV), Cydia pomonella (codling moth) granules Virus (GV), Helicoverpa armigera (cotton bollworm), nuclear polyhedrovirus (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda ( Spodoptera frugiperda ) (fall armyworm) mNPV and Spodoptera littoralis (African cotton leafworm) NPV.
Bacteria and fungi that can be added to plants or plant parts or plant organs as "inoculants" and promote plant growth and plant health by virtue of their specific properties. Examples: Agrobacterium spp. , Azorhizobium caulinodans , Azospirillum spp. , Azotobacter spp ., Bradyrhizobium spp . ), Burkholderia spp ., Burkholderia cepacia (previously known as Pseudomonas cepacia ), Gigaspora spp . , Or Gigaspora monosporum , Glomus spp ., Laccaria spp ., Lactobacillus buchneri , Paraglomus spp. ), Pisolithus tinctorius , Pseudomonas spp. , Rhizobium spp ., Rhizobium trifolii , Rhizopogon spp. ), Scleroderma spp. , Suillus spp ., And Streptomyces spp .
Plant extracts that can be used as biological control agents and products (including proteins and secondary metabolites) formed by microorganisms, such as garlic ( Allium sativum ), absinthe ( Artemisia absinthium ), azadirachtin, Biokeeper WP, Cassia nigricans , Celastrus angulatus , Chenopodium anthelminticum , Chitin, Armour-Zen, Dryopteris filix-mas , Equisetum arvense , Fortune Aza, Fungastop, Heads Up (quinoa (Chenopodium quinoa) saponin extract), pyrethrum genus / pyrethrin (pyrethrum / pyrethrins), quassia (quassia amara), Quercus (Quercus), soda wood Quillaja , Regalia, "Requiem ™ Insecticide", rotenone, ryania / ryanodine, Symphytum officinale , Ta nacetum vulgare ), Daphne phenol (thymol), Triact 70, TriCon , nasturtium (Tropaeoulum majus), Urtica dioica (Urtica dioica), veratridine (Veratrin), mistletoe (Viscum album), cruciferous (family Brassicaceae) extract It was In particular rapeseed meal or mustard powder.
可與式(I)化合物及包含其等之組合物混合之殺蟲劑、殺蟎劑及殺線蟲劑之實例分別係:
(1) 乙醯膽鹼酯酶(AChE)抑制劑,例如胺基甲酸酯,例如棉鈴威(alanycarb)、得滅克(aldicarb)、免敵克(bendiocarb)、免扶克(benfuracarb)、佈嘉信(butocarboxim)、丁酮碸威(butoxycarboxim)、加保利(carbaryl)、加保扶(carbofuran)、丁基加保扶(carbosulfan)、乙硫苯威(ethiofencarb)、丁基滅必蝨(fenobucarb)、覆滅蟎(formetanate)、呋線威(furathiocarb)、滅必蝨(isoprocarb)、滅賜克(methiocarb)、納乃得(methomyl)、治滅蟲(metolcarb)、歐殺滅(oxamyl)、比加普(pirimicarb)、安丹(propoxur)、硫敵克(thiodicarb)、久效威(thiofanox)、唑蚜威(triazamate)、混殺威(trimethacarb)、XMC及滅爾蝨(xylylcarb);或有機磷酸酯,例如毆殺松(acephate)、甲基吡啶磷(azamethiphos)、益棉磷(azinphos-ethyl)、穀速松(azinphos-methyl)、硫線磷(cadusafos)、氯氧磷(chlorethoxyfos)、毒蟲畏(chlorfenvinphos)、氯甲磷(chlormephos)、甲基陶斯松(chlorpyrifos-methyl)、蠅毒磷(coumaphos)、殺螟腈(cyanophos)、滅賜松(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)、飛達松(heptenophos)、新煙磷(imicyafos)、亞芬松(isofenphos)、O-(甲氧基胺基硫代磷醯基)柳酸異丙基酯、加福松(isoxathion)、馬拉松(malathion)、滅加松(mecarbam)、達馬松(methamidophos)、滅大松(methidathion)、美文松(mevinphos)、亞素靈(monocrotophos)、二溴磷(naled)、歐滅松(omethoate)、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)、亞特松(pirimiphos-methyl)、佈飛松(profenofos)、撲達松(propetamphos)、普硫松(prothiofos)、白克松(pyraclofos)、必芬松(pyridaphenthion)、拜裕松(quinalphos)、治螟磷(sulfotep)、丁基嘧啶磷(tebupirimfos)、亞培松(temephos)、託福松(terbufos)、樂本松(tetrachlorvinphos)、硫滅松(thiometon)、三落松(triazophos)、三氯松(trichlorfon)及繁米松(vamidothion)。
(2) GABA門控氯離子通道阻斷劑,例如環戊二烯-有機氯類,例如可氯丹(chlordane)及安殺番(endosulfan),或苯基吡唑類(fiproles),例如益斯普(ethiprole)及芬普尼(fipronil)。
(3) 鈉通道調節劑,例如擬除蟲菊酯(pyrethroids),例如阿納寧(acrinathrin)、亞烈寧(allethrin)、d-順式-反式亞烈寧、d-反式亞烈寧、畢芬寧(bifenthrin)、百亞烈寧(bioallethrin)、百亞烈寧s-環戊烯基異構物、百列滅寧(bioresmethrin)、賽保寧(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、ζ-賽滅寧、賽酚寧(cyphenothrin) [(1R)-反式-異構物]、第滅寧(deltamethrin)、益避寧(empenthrin) [(EZ)-(1R)-異構物]、益化利(esfenvalerate)、依芬寧(etofenprox)、芬普寧(fenpropathrin)、芬化利(fenvalerate)、護賽寧(flucythrinate)、福滅寧(flumethrin)、τ-福化利(tau-fluvalinate)、合芬寧(halfenprox)、依普寧(imiprothrin)、剋特寧(kadethrin)、莫福寧(momfluorothrin)、百滅寧(permethrin)、酚丁滅寧(phenothrin) [(1R)-反式-異構物]、普亞列寧(prallethrin)、除蟲菊酯類(pyrethrins) (除蟲菊(pyrethrum))、列滅寧(resmethrin)、矽護芬(silafluofen)、汰福寧(tefluthrin)、治滅寧(tetramethrin)、治滅寧[(1R)-異構物)]、泰滅寧(tralomethrin)及拜富寧(transfluthrin)或DDT或甲氧滴滴涕(methoxychlor)。
(4) 菸鹼型乙醯膽鹼受體(nAChR)競爭性調節劑,例如新菸鹼類(neonicotinoids),例如亞滅培(acetamiprid)、可尼丁(clothianidin)、達特南(dinotefuran)、益達胺(imidacloprid)、烯啶蟲胺(nitenpyram)、賽果培(thiacloprid)及賽速安(thiamethoxam)或尼古丁或碸蟲啶(sulfoxaflor)或氟吡呋喃酮(flupyradifurone)。
(5) 菸鹼型乙醯膽鹼受體(nAChR)別位調節劑,例如多殺菌素(spinosyns),例如賜諾特(spinetoram)及賜諾殺(spinosad)。
(6) 麩胺酸鹽門控氯離子通道(GluCl)別位調節劑,例如阿維菌素(avermectins)/米爾貝黴素(milbemycins),例如阿巴汀(abamectin)、因滅汀(emamectin benzoate)、雷皮菌素(lepimectin)及密滅汀(milbemectin)。
(7) 仿生保幼激素類,例如保幼激素類似物,例如烯蟲乙酯(hydroprene)、烯蟲炔酯(kinoprene及甲氧普烯(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,例如鹵代烷,例如溴甲烷或其他鹵代烷;或氯化苦(chloropicrine)或磺醯氟或硼砂或吐酒石(tartar emetic)或異氰酸甲酯發生劑,例如棉隆(diazomet)及威百畝(metam)。
(9) 弦音器官之調節劑,例如派滅淨(pymetrozine)或氟尼胺(flonicamid)。
(10) 蟎生長抑制劑,例如克芬蟎(clofentezine)、合賽多(hexythiazox)及氟蟎嗪(diflovidazin)或依殺蟎(etoxazole)。
(11) 昆蟲腸道膜之微生物干擾物,例如蘇雲金芽孢桿菌以色列亞種、球形芽孢桿菌(Bacillus sphaericus
)、蘇雲金芽孢桿菌鯰澤亞種、蘇雲金芽孢桿菌庫爾斯塔克亞種、蘇雲金芽孢桿菌擬步甲亞種及B.t.
植物蛋白:Cry1Ab、Cry1Ac、Cry1Fa、Cry1A.105、Cry2Ab、Vip3A、mCry3A、Cry3Ab、Cry3Bb、Cry34Ab1/35Ab1。
(12)粒線體ATP合酶之抑制劑,例如ATP干擾物,例如殺蟎隆(diafenthiuron)或有機錫化合物,例如三唑錫(azocyclotin)、三環錫(cyhexatin)及芬佈賜(fenbutatin oxide)或毆傾多(propargite)或三氯殺蟎碸(tetradifon)。
(13)經由破壞質子梯度之氧化磷酸化之解聯劑,例如克凡派(chlorfenapyr)、DNOC及氟蟲胺(sulfluramid)。
(14) 菸鹼型乙醯膽鹼受體通道阻斷劑,例如免速達(bensultap)、培丹鹽酸鹽(cartap hydrochloride)、殺蟲環(thiocyclam)及殺蟲雙鈉(thiosultap-sodium)。
(15)幾丁質生物合成之抑制劑,0型,例如雙三氟蟲脲(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)、伏蟲隆(teflubenzuron)及三伏隆(triflumuron)。
(16)幾丁質生物合成之抑制劑,1型,例如布芬淨(buprofezin)。
(17) 蛻皮干擾物(特定而言對於雙翅目(Diptera),即雙翅類昆蟲),例如滅蠅胺(cyromazine)。
(18) 蛻皮激素受體激動劑,例如可芬諾(chromafenozide)、氯蟲醯肼(halofenozide)、甲氧蟲醯肼(methoxyfenozide)及得芬諾(tebufenozide)。
(19) 章魚胺受體激動劑,例如三亞蟎(amitraz)。
(20) 線粒體複合物III電子傳輸抑制劑,例如伏蟻腙(hydramethylnone)或亞醌蟎(acequinocyl)或嘧蟎酯(fluacrypyrim)。
(21) 線粒體複合物I電子傳輸抑制劑,例如來自METI殺蟎劑之群,例如芬殺蟎(fenazaquin)、芬普蟎(fenpyroximate)、畢汰芬(pyrimidifen)、畢達本(pyridaben)、得芬瑞(tebufenpyrad)及脫芬瑞(tolfenpyrad)或魚藤精(rotenone)(Derris)。
(22) 電壓依賴性鈉通道阻斷劑,例如因得克(indoxacarb)或美氟綜(metaflumizone)。
(23)乙醯基CoA羧化酶之抑制劑,例如特窗酸(tetronic acid)及特氨酸(tetramic acid)衍生物,例如賜派芬(spirodiclofen)、賜滅芬(spiromesifen)及賜派滅(spirotetramat)。
(24) 線粒體複合物IV電子傳輸抑制劑,例如膦,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) 線粒體複合物II電子傳輸抑制劑,例如β
-酮腈(β
-ketonitrile)衍生物,例如賽派芬(cyenopyrafen)及賽芬蟎(cyflumetofen);及羧醯苯胺,例如pyflubumide。
(26) 蘭諾定(Ryanodine)受體調節劑,例如二醯胺,例如剋安勃(chlorantraniliprole)、賽安勃(cyantraniliprole)及氟大滅(flubendiamide),
其他活性化合物,例如啶喃環丙蟲酯(Afidopyropen)、阿福拉納(Afoxolaner)、印楝素(Azadirachtin)、苯克賽(Benclothiaz)、苯蟎特(benzoximate)、必芬蟎(Bifenazate)、溴蟲氟苯雙醯胺(Broflanilide)、新殺蟎(Bromopropylate)、蟎離丹(Chinomethionat)、右旋反式氯丙炔菊酯(Chloroprallethrin)、冰晶石(Cryolite)、環溴蟲醯胺(Cyclaniliprole)、環氧蟲啶(Cycloxaprid)、氯氟氰蟲醯胺(Cyhalodiamide)、Dicloromezotiaz、大克蟎(Dicofol)、ε-美特寧(ε-Metofluthrin)、ε-莫福寧(ε-Momfluthrin)、Flometoquin、三氟咪啶醯胺(Fluazaindolizine)、聯氟碸(Fluensulfone)、嘧蟲胺(Flufenerim)、氟菌蟎酯(Flufenoxystrobin)、丁蟲腈(Flufiprole)、氟己芬(Fluhexafon)、氟派瑞(Fluopyram)、氟雷拉納(Fluralaner)、氟唑醯胺(Fluxametamide)、呋喃蟲醯肼(Fufenozide)、戊吡蟲胍(Guadipyr)、七氟甲醚菊酯(Heptafluthrin)、氯噻啉(Imidaclothiz)、依普同(Iprodione)、κ-畢芬寧(κ-Bifenthrin)、κ-特福寧(κ-Tefluthrin)、洛替拉納(Lotilaner)、氯氟醚菊酯(Meperfluthrin)、派蟲啶(Paichongding)、啶蟲丙醚(Pyridalyl)、Pyrifluquinazon、嘧蟎胺(Pyriminostrobin)、螺蟎雙酯(Spirobudiclofen)、四甲扶寧(Tetramethylfluthrin)、氟氰蟲醯胺(Tetraniliprole)、四氯蟲醯胺(Tetrachlorantraniliprole)、提格拉納(Tigolaner)、噻唑沙芬(Tioxazafen)、硫氟肟醚(Thiofluoximate)、三氟苯嘧啶(Triflumezopyrim)及碘甲烷;基於堅強芽孢桿菌之其他製劑(I-1582、BioNeem、Votivo)以及以下化合物:1-{2-氟-4-甲基-5-[(2,2,2-三氟乙基)亞磺醯基]苯基}-3-(三氟甲基)-1H-1,2,4-三唑-5-胺(自WO2006/043635得知) (CAS 885026-50-6)、{1'-[(2E)-3-(4-氯苯基)丙-2-烯-1-基]-5-氟螺[吲哚-3,4'-六氫吡啶]-1(2H)-基}(2-氯吡啶-4-基)甲酮(自WO2003/106457得知) (CAS 637360-23-7)、2-氯-N-[2-{1-[(2E)-3-(4-氯苯基)丙-2-烯-1-基]六氫吡啶-4-基}-4-(三氟甲基)苯基]異菸鹼醯胺(自WO2006/003494得知) (CAS 872999-66-1)、3-(4-氯-2,6-二甲基苯基)-4-羥基-8-甲氧基-1,8-二氮雜螺[4.5]癸-3-烯-2-酮(自WO 2010052161得知) (CAS 1225292-17-0)、碳酸3-(4-氯-2,6-二甲基苯基)-8-甲氧基-2-側氧基-1,8-二氮雜螺[4.5]癸-3-烯-4-基酯乙基酯(自EP2647626得知) (CAS 1440516-42-6)、4-(丁-2-炔-1-基氧基)-6-(3,5-二甲基六氫吡啶-1-基)-5-氟嘧啶(自WO2004/099160得知) (CAS 792914-58-0)、PF1364 (自JP2010/018586得知) (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(自WO2012/029672得知) (CAS 1363400-41-2)、(3E)-3-[1-[(6-氯-3-吡啶基)甲基]-2-吡啶亞基]-1,1,1-三氟-丙-2-酮(自WO2013/144213得知) (CAS 1461743-15-6)、N-[3-(苄基胺甲醯基)-4-氯苯基]-1-甲基-3-(五氟乙基)-4-(三氟甲基)-1H-吡唑-5-甲醯胺(自WO2010/051926得知) (CAS 1226889-14-0)、5-溴-4-氯-N-[4-氯-2-甲基-6-(甲基胺甲醯基)苯基]-2-(3-氯-2-吡啶基)吡唑-3-甲醯胺(自CN103232431得知) (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-(順式-1-氧離子基-3-硫雜環丁基)-苯甲醯胺、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-(反式-1-氧離子基-3-硫雜環丁基)-苯甲醯胺及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-(順式-1-氧離子基-3-硫雜環丁基)苯甲醯胺(自WO 2013/050317 A1得知) (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)亞磺醯基]-丙醯胺、(+)-N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亞磺醯基]-丙醯胺及(-)-N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亞磺醯基]-丙醯胺(自WO 2013/162715 A2、WO 2013/162716 A2、US 2014/0213448 A1得知) (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)亞磺醯基]-1H-吡唑-3-甲腈(自CN 101337937 A得知) (CAS 1105672-77-2)、3-溴-N-[4-氯-2-甲基-6-[(甲基胺基)硫代甲基]苯基]-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲醯胺(硫代苯甲醯胺(Liudaibenjiaxuanan),自CN 103109816 A得知) (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(自WO 2012/034403 A1得知) (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(自WO 2011/085575 A1得知) (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(自CN 101337940 A得知) (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(自CN 101715774 A得知) (CAS 1232543-85-9);環丙烷甲酸3-(2,2-二氯乙烯基)-2,2-二甲基-4-(1H-苯並咪唑-2-基)苯基酯(自CN 103524422 A得知) (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]-茚並[1,2-e][1,3,4]噁二嗪-4a(3H)-甲酸甲酯(自CN 102391261 A得知) (CAS 1370358-69-2);6-去氧-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-吡喃甘露醣(自US 2014/0275503 A1得知) (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-嗒嗪-3-基)-3-氮雜-二環[3.2.1]辛烷(CAS 1253850-56-4)、(8-反式)-8-(2-環丙基甲氧基-4-三氟甲基-苯氧基)-3-(6-三氟甲基-嗒嗪-3-基)-3-氮雜-二環[3.2.1]辛烷(CAS 933798-27-7)、(8-順式)-8-(2-環丙基甲氧基-4-三氟甲基-苯氧基)-3-(6-三氟甲基-嗒嗪-3-基)-3-氮雜-二環[3.2.1]辛烷(自WO 2007040280 A1、WO 2007040282 A1得知) (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]-丙醯胺(自WO 2015/058021 A1、WO 2015/058028 A1得知) (CAS 1477919-27-9)及N-[4-(胺基硫代甲基)-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(自CN 103265527 A得知) (CAS 1452877-50-7)、5-(1,3-二噁烷-2-基)-4-[[4-(三氟甲基)苯基]甲氧基]-嘧啶(自WO 2013/115391 A1得知) (CAS 1449021-97-9)、3-(4-氯-2,6-二甲基苯基)-4-羥基-8-甲氧基-1-甲基-1,8-二氮雜螺[4.5]癸-3-烯-2-酮(自WO 2010/066780 A1、WO 2011/151146 A1得知) (CAS 1229023-34-0)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-1-甲基-1,8-二氮雜螺[4.5]癸烷-2,4-二酮(自WO 2014/187846 A1得知) (CAS 1638765-58-8)、碳酸3-(4-氯-2,6-二甲基苯基)-8-甲氧基-1-甲基-2-側氧基-1,8-二氮雜螺[4.5]癸-3-烯-4-基酯乙基酯(自WO 2010/066780 A1、WO 2011151146 A1得知) (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(自DE 3639877 A1、WO 2012029672 A1得知) (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(自WO 2016005276 A1得知) (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(自WO 2011/105506 A1、WO 2016/133011 A1得知) (CAS 1332838-17-1)。
可與式(I)化合物及包含其等之組合物混合之安全劑實例係(例如)解草嗪(benoxacor)、解草酯(cloquintocet (-mexyl))、解草安腈(cyometrinil)、環丙磺醯胺(cyprosulfamide)、二氯丙烯胺(dichlormid)、解草唑(fenchlorazole (-ethyl))、解草啶(fenclorim)、解草安(flurazole)、氟草肟(fluxofenim)、解草噁唑(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)。Examples of insecticides, acaricides and nematicides that can be mixed with compounds of formula (I) and compositions containing them are:
(1) Acetylcholinesterase (AChE) inhibitors, such as carbamates, such as alanycarb, aldicarb, bendiocarb, benfuracarb, Butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, butyl carbamazepine (butylcarboxim) fenobucarb, formetanate, furathiocarb, isoprocarb, metiocarb, metomyl, metolcarb, oxamyl , Pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb ; Or organic phosphates, such as acephate, azamethiphos, azinphos-ethyl, azonphos-methyl, cadusafos, chlorox (chlorethoxyfos), chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, Cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, methylmethoxam (dimethylvinphos), disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenitrothion (fenthion), fosthiazate, heptenophos, imicyafos, isofenphos, O- (methoxyaminothiophosphoryl) isopropyl salicylate Esters, isoxathion, marathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, dibromophos naled), omethoate, oxydemeton-methyl, parathion-methyl, phenthoate, phorate, phosalone, benefit Phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos , Prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, TOEFL Terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, and vamidomion.
(2) GABA-gated chloride channel blockers, such as cyclopentadiene-organochlorines, such as chlordane and endosulfan, or fiproles, such as beneficial Ethiprole and fipronil.
(3) Sodium channel modulators, such as pyrethroids, such as acrinathrin, allethrin, d-cis-trans-arenein, d-trans-arenein , Bifenthrin, bioallethrin, s-cyclopentenyl isomers, bioresmethrin, cycloprothrin, cyfluthrin, β-Severin, Cyhalothrin, λ-Seronine, γ-Seronin, Cypermethrin, α-Serinin, β-Serinin, θ-Serinin, ζ-cyphenidin, cyphenothrin [(1R) -trans-isomer], deltamethrin, empenthrin [(EZ)-(1R) -isomer ], Esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, τ-fuhuali (tau -fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin ((1R)- Trans-isomers], prallethrin Pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, zimethonin (( 1R) -isomer)], tralomethrin and transfluthrin or DDT or methoxychlor.
(4) Competitive regulators of nicotinic acetylcholine receptor (nAChR), such as neonicotinoids, such as acetamiprid, clothianidin, and dinotefuran , Imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or flupyradifurone.
(5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators, such as spinosyns, such as spinetoram and spinosad.
(6) Glutamate-gated chloride channel (GluCl) allosteric modulators, such as avermectins / milbemycins, such as abamatein, emamectin benzoate), lepimectin and milbemectin.
(7) Bionic juvenile hormones, such as juvenile hormone analogs, such as hydroprene, kinoprene and metoprene, or fenoxycarb or beiprip芬 (pyriproxyfen).
(8) Various non-specific (multi-site) inhibitors, such as haloalkanes, such as methyl bromide or other haloalkanes; or chloropicrine or sulfofluorene or borax or tartar emetic or methyl isocyanate Ester generators, such as diazomet and metam.
(9) Modulators of string organs, such as pymetrozine or flonicamid.
(10) Mite growth inhibitors, such as clofentezine, hexythiazox and diflovidazin or etoxazole.
(11) Microbial interferents of insect intestinal membranes, such as Bacillus thuringiensis subspecies, Bacillus sphaericus , Bacillus thuringiensis subspecies, Bacillus thuringiensis Kurstak subspecies, Bacillus thuringiensis Sub-species of Paecarina and Bt plant proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Ab1 / 35Ab1.
(12) Inhibitors of mitochondrial ATP synthase, such as ATP interferences, such as diafenthiuron or organotin compounds, such as azocyclotin, cyhexatin, and fenbutatin oxide) or propargite or tetradifon.
(13) Decoupling agents such as chlorfenapyr, DNOC, and sulfluramid via oxidative phosphorylation that disrupts the proton gradient.
(14) Nicotinic acetylcholine receptor channel blockers, such as bensultap, cartap hydrochloride, thiocyclam, and thiosultap-sodium .
(15) Inhibitors of chitin biosynthesis, type 0, such as bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenon ( flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, and triflumuron.
(16) Inhibitors of chitin biosynthesis, type 1, such as bufofezin.
(17) Moulting disturbances (specifically for Diptera, ie dipterous insects), such as cyromazine.
(18) Ecdysone receptor agonists, such as chromafenozide, halofenozide, methoxyfenozide, and tebufenozide.
(19) Octopamine receptor agonists, such as amitraz.
(20) Mitochondrial complex III electron transport inhibitors, such as hydramethylnone or acequinocyl or fluacrypyrim.
(21) Mitochondrial complex I electron transport inhibitors, such as from the group of METI acaricides, such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, Tebufenpyrad and tolfenpyrad or rotenone (Derris).
(22) Voltage-dependent sodium channel blockers, such as indoxacarb or metaflumizone.
(23) Inhibitors of ethynyl CoA carboxylase, such as tetronic acid and tetramic acid derivatives, such as spirodiclofen, spiritomefen, and pie Off (spirotetramat).
(24) Mitochondrial complex IV electron transport inhibitors, such as phosphines, such as aluminum phosphide, calcium phosphide, phosphine, and zinc phosphide; or cyanides, such as calcium cyanide, potassium cyanide, and sodium cyanide.
(25) Mitochondrial complex II electron transport inhibitors, for example β - ketonitriles (β -ketonitrile) derivatives, e.g. race Pal-Fin (cyenopyrafen) and Saifun mites (Cyflumetofen and); and 2carboxamide aniline, e.g. pyflubumide.
(26) Ryanodine receptor modulators, such as dioxamine, such as chlorantraniliprole, cyantraniliprole, and flubendiamide,
Other active compounds, such as Afidopyropen, Afoxolaner, Azadirachtin, Benclothiaz, benzoximate, Bifenazate Bromolanate, Bromolanate, Chinomethionat, Chloroprallethrin, Cryolite, Cypromethoxam (Cyclaniliprole), Cycloxaprid, Cyhalodiamide, Dicloromezotiaz, Dicofol, ε-Metofluthrin, ε-Mofinin (ε- Momfluthrin), Flometoquin, Fluazaindolizine, Fluensulfone, Flufenerim, Flufenoxystrobin, Flufiprole, Fluhexafon , Fluopyram, Fluralaner, Flumetetamide, Fufenozide, Guadipyr, Heptafluthrin, Imidaclothiz, Iprodione, κ-Bifenthrin, κ-Tefal Κ-Tefluthrin, Lotilaner, Meperfluthrin, Paichongding, Pyridalyl, Pyrifluquinazon, Pyriminostrobin, Snail mite Spirobudiclofen, Tetramethylfluthrin, Tetraniliprole, Tetrachlorantraniliprole, Tigolaner, Tioxazafen, Thioxazafen (Thiofluoximate), Triflumezopyrim, and methyl iodide; other preparations based on Bacillus robustus (I-1582, BioNeem, Votivo) and the following compounds: 1- {2-fluoro-4-methyl-5- [ (2,2,2-trifluoroethyl) sulfinamidino] phenyl} -3- (trifluoromethyl) -1H-1,2,4-triazol-5-amine (obtained from WO2006 / 043635 (CAS 885026-50-6), (1 '-[(2E) -3- (4-chlorophenyl) prop-2-en-1-yl] -5-fluorospiro [indole-3, 4'-hexahydropyridine] -1 (2H) -yl} (2-chloropyridin-4-yl) methanone (known from WO2003 / 106457) (CAS 637360-23-7), 2-chloro-N- [2- {1-[(2E) -3- (4-chlorophenyl) prop-2-en-1-yl] hexahydropyridin-4-yl} -4- (trifluoromethyl) phenyl] Isonicotinamide (as known from WO2006 / 003494) (CAS 872999-66-1) 3- (4-chloro-2,6-dimethylphenyl) -4-hydroxy-8-methoxy-1,8-diazaspiro [4.5] dec-3-en-2-one (from WO 2010052161) (CAS 1225292-17-0), 3- (4-chloro-2,6-dimethylphenyl) carbonate, 8-methoxy-2- pendantoxy-1,8-di Azaspiro [4.5] dec-3-en-4-yl ester ethyl ester (known from EP 2647626) (CAS 1440516-42-6), 4- (but-2-yn-1-yloxy)- 6- (3,5-dimethylhexahydropyridin-1-yl) -5-fluoropyrimidine (known from WO2004 / 099160) (CAS 792914-58-0), PF1364 (known from JP2010 / 018586) ( CAS 1204776-60-2), N-[(2E) -1-[(6-chloropyridin-3-yl) methyl] pyridine-2 (1H) -subunit] -2,2,2-trifluoro Acetylamine (known from WO2012 / 029672) (CAS 1363400-41-2), (3E) -3- [1-[(6-chloro-3-pyridyl) methyl] -2-pyridine subunit] -1,1,1-trifluoro-propan-2-one (known from WO2013 / 144213) (CAS 1461743-15-6), N- [3- (benzylaminemethylamidino) -4-chlorobenzene Propyl] -1-methyl-3- (pentafluoroethyl) -4- (trifluoromethyl) -1H-pyrazole-5-carboxamide (known from WO2010 / 051926) (CAS 1226889-14- 0), 5-bromo-4-chloro-N- [4-chloro-2-methyl-6- (methylaminomethylmethyl) phenyl] -2- (3-chloro-2-pyridyl) pyridine Azole-3-carboxamide (known from CN103232431) (CAS 1449220-44-3), 4- [5- (3,5-dichlorophenyl) -4,5-dihydro-5- (trifluoromethyl) -3-isoxazolyl) -2-methyl-N- (cis-1-oxyion Methyl-3-thiacyclobutyl) -benzidine, 4- [5- (3,5-dichlorophenyl) -4,5-dihydro-5- (trifluoromethyl) -3- Isoxazolyl] -2-methyl-N- (trans-1-oxoyl-3-thietanyl) -benzidine and 4-[(5S) -5- (3,5 -Dichlorophenyl) -4,5-dihydro-5- (trifluoromethyl) -3-isoxazolyl] -2-methyl-N- (cis-1-oxoionyl-3- Thiacyclobutyl) benzidine (as known from WO 2013/050317 A1) (CAS 1332628-83-7), N- [3-chloro-1- (3-pyridyl) -1H-pyrazole- 4-yl] -N-ethyl-3-[(3,3,3-trifluoropropyl) sulfenamidinyl] -propanamide, (+)-N- [3-chloro-1- (3 -Pyridyl) -1H-pyrazol-4-yl] -N-ethyl-3-[(3,3,3-trifluoropropyl) sulfinamidinyl] -propanilamine and (-)-N -[3-Chloro-1- (3-pyridyl) -1H-pyrazol-4-yl] -N-ethyl-3-[(3,3,3-trifluoropropyl) sulfenamidine] -Propanamide (known from WO 2013/162715 A2, WO 2013/162716 A2, US 2014/0213448 A1) (CAS 1477923-37-7), 5-[((2E) -3-chloro-2-propene -1-yl] amino] -1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-[(trifluoromethyl) sulfinamidinyl] -1H-pyrazole -3-carbonitrile (known from CN 101337937 A) (CAS 1105672-77-2), 3-bromo-N- [4-chloro-2-methyl-6-[(methylamino) thiomethyl] phenyl] -1- (3-chloro- 2-pyridyl) -1H-pyrazole-5-carboxamide (Liudaibenjiaxuanan, known from CN 103109816 A) (CAS 1232543-85-9); N- [4-chloro- 2-[[(1,1-dimethylethyl) amino] carbonyl] -6-methylphenyl] -1- (3-chloro-2-pyridyl) -3- (fluoromethoxy) -1H-pyrazole-5-carboxamide (as known from WO 2012/034403 A1) (CAS 1268277-22-0), N- [2- (5-amino-1,3,4-thiadiazole 2-yl) -4-chloro-6-methylphenyl] -3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxamide (since WO 2011 / 085575 A1) (CAS 1233882-22-8), 4- [3- [2,6-dichloro-4-[(3,3-dichloro-2-propen-1-yl) oxy] benzene Oxy] propoxy] -2-methoxy-6- (trifluoromethyl) -pyrimidine (known from CN 101337940 A) (CAS 1108184-52-6); (2E)-and 2 (Z) -2- [2- (4-cyanophenyl) -1- [3- (trifluoromethyl) phenyl] ethylene] -N- [4- (difluoromethoxy) phenyl]- Hydrazine (as known from CN 101715774 A) (CAS 1232543-85-9); cyclopropanecarboxylic acid 3- (2,2-dichlorovinyl) -2,2-dimethyl-4- (1H- Benzimidazol-2-yl) phenyl ester (as known from CN 103524422 A) (CAS 1542271-46-4) (4aS) -7-chloro-2,5-dihydro-2-[[(methoxycarbonyl) [4-[(trifluoromethyl) thio] phenyl] amino] carbonyl] -indeno [ 1,2-e] [1,3,4] oxadiazine-4a (3H) -formic acid methyl ester (known from CN 102391261 A) (CAS 1370358-69-2); 6-deoxy-3-O -Ethyl-2,4-di-O-methyl-1- [N- [4- [1- [4- (1,1,2,2,2-pentafluoroethoxy) phenyl]- 1H-1,2,4-triazol-3-yl] phenyl] carbamate] -α-L-pyranomannose (as known from US 2014/0275503 A1) (CAS 1181213-14-8 ); 8- (2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy) -3- (6-trifluoromethyl-daphrazin-3-yl) -3-aza-di Cyclo [3.2.1] octane (CAS 1253850-56-4), (8-trans) -8- (2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy) -3- (6-trifluoromethyl-pyridazin-3-yl) -3-aza-bicyclo [3.2.1] octane (CAS 933798-27-7), (8-cis) -8- (2 -Cyclopropylmethoxy-4-trifluoromethyl-phenoxy) -3- (6-trifluoromethyl-pyridazin-3-yl) -3-aza-bicyclo [3.2.1] Octane (known from WO 2007040280 A1, WO 2007040282 A1) (CAS 934001-66-8), N- [3-chloro-1- (3-pyridyl) -1H-pyrazol-4-yl] -N -Ethyl-3-[(3,3,3-trifluoropropyl) thio] -propanamide (as known from WO 2015/058021 A1, WO 2015/058028 A1) (CAS 1477 919-27-9) and N- [4- (aminothiomethyl) -2-methyl-6-[(methylamino) carbonyl] phenyl] -3-bromo-1- (3- (Chloro-2-pyridyl) -1H-pyrazole-5-carboxamide (known from CN 103265527 A) (CAS 1452877-50-7), 5- (1,3-dioxan-2-yl) -4-[[4- (trifluoromethyl) phenyl] methoxy] -pyrimidine (known from WO 2013/115391 A1) (CAS 1449021-97-9), 3- (4-chloro-2, 6-dimethylphenyl) -4-hydroxy-8-methoxy-1-methyl-1,8-diazaspiro [4.5] dec-3-en-2-one (from WO 2010/066780 A1, WO 2011/151146 A1) (CAS 1229023-34-0), 3- (4-chloro-2,6-dimethylphenyl) -8-methoxy-1-methyl-1, 8-Diazaspiro [4.5] decane-2,4-dione (known from WO 2014/187846 A1) (CAS 1638765-58-8), 3- (4-chloro-2,6-dicarbonate (Methylphenyl) -8-methoxy-1-methyl-2- pendantoxy-1,8-diazaspiro [4.5] dec-3-en-4-yl ester ethyl ester (from WO (2010/066780 A1, WO 2011151146 A1) (CAS 1229023-00-0), N- [1-[(6-chloro-3-pyridyl) methyl] -2 (1H) -pyridine subunit]- 2,2,2-trifluoro-acetamidamine (known from DE 3639877 A1, WO 2012029672 A1) (CAS 1363400-41-2), [N (E)]-N- [1-[(6-chloro -3-pyridyl) methyl] -2 (1H) -pyridinyl] -2,2,2-trifluoro-ethyl Amidine (as known from WO 2016005276 A1) (CAS 1689566-03-7), [N (Z)]-N- [1-[(6-chloro-3-pyridyl) methyl] -2 (1H) -Pyridineylidene] -2,2,2-trifluoro-acetamidamine (CAS 1702305-40-5), 3-endo-3- [2-propoxy-4- (trifluoromethyl) phenoxy Group] -9-[[5- (trifluoromethyl) -2-pyridyl] oxy] -9-azabicyclo [3.3.1] nonane (from WO 2011/105506 A1, WO 2016/133011 (A1 learned) (CAS 1332838-17-1).
Examples of safeners that can be mixed with compounds of formula (I) and compositions containing them are, for example, benoxacor, cloquintocet (-mexyl), cyometrinil, Cyprosulfamide, dichlormid, fenchlorazole (-ethyl), fenclorim, flurazole, fluofenim, fluoxenim Furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalenedicarboxylic anhydride, oxabetrinil, 2-methoxy- N-({4-[(methylaminomethylamido) amino] phenyl} sulfoamido) benzamide (CAS 129531-12-0), 4- (dichloroethenyl) -1- Oxa-4-azaspiro [4.5] decane (CAS 71526-07-3), 2,2,5-trimethyl-3- (dichloroethylfluorenyl) -1,3-oxazoline ( CAS 52836-31-4).
可與式(I)化合物及包含其等之組合物混合之除草劑實例係:
禾耐斯(Acetochlor)、亞喜芬(acifluorfen)、亞喜芬鈉、苯草醚(aclonifen)、拉草(alachlor)、草毒死(allidochlor)、亞汰草(alloxydim)、亞汰草鈉、草殺淨(ametryn)、胺唑草酮(amicarbazone)、醯草胺(amidochlor)、醯嘧磺隆(amidosulfuron)、4-胺基-3-氯-6-(4-氯-2-氟-3-甲基苯基)-5-氟吡啶-2-甲酸、環丙嘧啶酸(aminocyclopyrachlor)、環丙嘧啶酸鉀、環丙嘧啶酸甲酯、氯胺吡啶酸(aminopyralid)、殺草強(amitrole)、胺基磺酸銨、莎稗磷(anilofos)、磺草靈(asulam)、草脫淨(atrazine)、草芬定(azafenidin)、四唑嘧磺隆(azimsulfuron)、氟丁醯草胺(beflubutamid)、草除靈(benazolin)、草除靈乙酯、倍尼芬(benfluralin)、呋草黃(benfuresate)、免速隆(bensulfuron)、免速隆甲酯、地散磷(bensulide)、本達隆(bentazone)、苯并雙環酮(benzobicyclon)、吡草酮(benzofenap)、氟吡草酮(bicyclopyron)、必芬諾(bifenox)、畢拉草(bilanafos)、畢拉草鈉、雙草醚(bispyribac)、雙草醚鈉、克草(bromacil)、溴芬諾(bromobutide)、溴酚肟(bromofenoxim)、溴苯腈(bromoxynil)、溴苯腈丁酸酯、溴苯腈鉀、溴苯腈庚酸酯及溴苯腈辛酸酯、羥草酮(busoxinone)、丁基拉草(butachlor)、氟丙嘧草酯(butafenacil)、抑草磷(butamifos)、丁烯草胺(butenachlor)、比達寧(butralin)、丁苯草酮(butroxydim)、丁草特(butylate)、唑草胺(cafenstrole)、長殺草(carbetamide)、唑草酮(carfentrazone)、唑酮草酯(carfentrazone-ethyl)、克爛本(chloramben)、滅落寧(chlorbromuron)、伐草克(chlorfenac)、伐草克鈉、燕麥酯(chlorfenprop)、整形素(chlorflurenol)、整形素甲酯、殺草敏(chloridazon)、氯嘧磺隆(chlorimuron)、氯嘧磺隆乙酯、氯酞醯亞胺(chlorophthalim)、綠麥隆(chlorotoluron)、大克草(chlorthal-dimethyl)、氯磺隆(chlorsulfuron)、吲哚酮(cinidon)、吲哚酮草酯(cinidon-ethyl)、環庚草醚(cinmethylin)、西速隆(cinosulfuron)、氯醯草膦(clacyfos)、剋草同(clethodim)、炔草酯(clodinafop)、炔草炔丙酯、可滅蹤(clomazone)、克普草(clomeprop)、畢克草(clopyralid)、氯酯磺草胺酸(cloransulam)、氯酯磺草胺酸甲酯、苄草隆(cumyluron)、氰胺(cyanamide)、草淨津(cyanazine)、草滅特(cycloate)、cyclopyrimorate、環磺隆(cyclosulfamuron)、環殺草(cycloxydim)、賽伏草(cyhalofop)、丁基賽伏草、環丙津(cyprazine)、2,4-滴(2,4-D)、2,4-滴丁氧基乙酯(2,4-D-butotyl)、2,4-滴丁酯、2,4-滴二甲基銨、2,4-滴二醇胺、2,4-滴乙酯、2,4-滴2-乙基己酯、2,4-滴異丁酯、2,4-滴異辛酯、2,4-滴異丙基銨、2,4-滴鉀、2,4-滴三異丙醇銨及2,4-滴三醇胺、2,4-滴丁酸(2,4-DB)、2,4-滴丁酸丁酯、2,4-滴丁酸二甲基銨、2,4-滴丁酸異辛酯、2,4-滴丁酸鉀及2,4-滴丁酸鈉、殺草隆(daimuron) (汰草龍(dymron))、得拉本(dalapon)、棉隆(dazomet)、正癸醇、甜菜安(desmedipham)、脫甲苯磺醯基吡唑特(detosyl-pyrazolate, DTP)、汰克草(dicamba)、二氯苯腈(dichlobenil)、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(dichlorprop)、2,4-滴丙酸-P、禾草靈(diclofop)、禾草靈甲酯、禾草靈-P-甲酯、雙氯磺草胺(diclosulam)、野燕枯(difenzoquat)、吡氟醯草胺(diflufenican)、氟吡草腙(diflufenzopyr)、氟吡草腙鈉、噁唑隆(dimefuron)、呱草丹(dimepiperate)、克草胺(dimethachlor)、異戊乙淨(dimethametryn)、汰草滅(dimethenamid)、汰草滅-P、地美曲殺福隆(dimetrasulfuron)、撻乃安(dinitramine)、地樂消(dinoterb)、大芬滅(diphenamid)、敵草快(diquat)、敵草快二溴鹽、汰硫草(dithiopyr)、達有龍(diuron)、DNOC、草多索(endothal)、EPTC、禾草畏(esprocarb)、丁氟消草(ethalfluralin)、胺苯磺隆(ethametsulfuron)、胺苯磺隆甲酯、乙嗪草酮(ethiozin)、呋草黃(ethofumesate)、氯氟草醚(ethoxyfen)、氯氟草醚乙酯、亞速隆(ethoxysulfuron)、乙氧苯草胺(etobenzanid)、F-9600、F-5231 (即,N-{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}乙烷磺醯胺)、F-7967 (即,3-[7-氯-5-氟-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)、芬殺草(fenoxaprop)、芬殺草-P、芬殺草乙酯、芬殺草-P-乙酯、苯磺噁唑草(fenoxasulfone)、酚醌草酮(fenquinotrione)、四唑醯草胺(fentrazamide)、麥草伏(flamprop)、麥草伏-M-異丙酯、麥草伏-M-甲酯、伏速隆(flazasulfuron)、雙氟磺草胺(florasulam)、伏寄普(fluazifop)、伏寄普-P、伏寄普丁酯、伏寄普-P-丁酯、氟唑磺隆(flucarbazone)、氟唑磺隆鈉、氟吡磺隆(flucetosulfuron)、貝殺靈(fluchloralin)、氟噻草胺(flufenacet)、氟噠嗪草(flufenpyr)、氟噠嗪草乙酯、唑嘧磺草胺(flumetsulam)、氟烯草酸(flumiclorac)、氟烯草酸戊酯、丙炔氟草胺(flumioxazin)、伏草隆(fluometuron)、抑草丁(flurenol)、抑草丁丁酯、抑草丁二甲基銨及抑草丁甲酯、乙羧氟草醚(fluoroglycofen)、乙羧氟草醚乙酯、克林草(flupropanate)、氟啶嘧磺隆(flupyrsulfuron)、氟啶嘧磺隆甲基鈉、氟啶酮(fluridone)、氟草吡酮(flurochloridone)、氟氯比(fluroxypyr)、氟氯比異辛酯、呋草酮(flurtamone)、嗪草酸(fluthiacet)、嗪草酸甲酯、氟磺胺草醚(fomesafen)、氟磺胺草醚鈉(fomesafen-sodium)、甲醯胺磺隆(foramsulfuron)、蔓草磷(fosamine)、固殺草(glufosinate)、固殺草銨、固殺草-P-鈉、固殺草-P-銨、固殺草-P-鈉、草甘膦(glyphosate)、草甘膦銨、草甘膦異丙基銨、草甘膦二銨、草甘膦二甲基銨、草甘膦鉀、草甘膦鈉及草甘膦三甲基硫鹽(glyphosate-trimesium)、H-9201 (即,O-(2,4-二甲基-6-硝基苯基)O-乙基異丙基硫代磷醯胺酯)、氟氯吡啶酯(halauxifen)、氟氯吡啶甲酯、氟硝磺醯胺(halosafen)、氯吡嘧磺隆(halosulfuron)、氯吡嘧磺隆甲酯、合氧氟(haloxyfop)、合氧氟-P、合氧氟-乙氧基乙酯、合氧氟-P-乙氧基乙酯、合氧氟甲酯、合氧氟-P-甲酯、菲殺淨(hexazinone)、HW-02 (即,(2,4-二氯苯氧基)乙酸1-(二甲氧基磷醯基)乙基酯)、咪草酯(imazamethabenz)、甲基咪草酯、咪草啶酸(imazamox)、咪草啶酸銨、甲咪唑煙酸(imazapic)、甲咪唑煙酸銨、咪唑煙酸(imazapyr)、咪唑煙酸異丙基銨、滅草喹(imazaquin)、滅草喹銨、普施特(imazethapyr)、普施特銨、咪唑磺隆(imazosulfuron)、茚草酮(indanofan)、三嗪茚草胺(indaziflam)、碘甲磺隆(iodosulfuron)、碘甲磺隆甲基鈉、碘苯腈(ioxynil)、辛醯碘苯腈(ioxynil-octanoate)、碘苯腈鉀及碘苯腈鈉、三唑醯草胺(ipfencarbazone)、異丙隆(isoproturon)、愛速隆(isouron)、異噁醯草胺(isoxaben)、異噁唑草酮(isoxaflutole)、卡靈草(karbutilate)、KUH-043 (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、乳氟草靈(lactofen)、環草啶(lenacil)、理有龍(linuron)、MCPA、MCPA-丁氧基乙酯、MCPA二甲基銨、MCPA-2-乙基己基酯、MCPA異丙基銨、MCPA鉀及MCPA鈉、MCPB、MCPB甲酯、MCPB乙酯及MCPB鈉、2甲4氯丙酸(mecoprop)、2甲4氯丙酸鈉及2甲4氯丙酸丁氧基乙酯、2甲4氯丙酸-P、2甲4氯丙酸-P-丁氧基乙酯、2甲4氯丙酸二甲基銨、2甲4氯丙酸2-乙基己酯及2甲4氯丙酸鉀、滅芬草(mefenacet)、麥夫迪(mefluidide)、甲基二磺隆(mesosulfuron)、甲基二磺隆甲酯、硝草酮(mesotrione)、甲苯噻隆(methabenzthiazuron)、威百畝(metam)、唑醯草胺(metamifop)、苯嗪草酮(metamitron)、滅草胺(metazachlor)、嗪吡嘧磺隆(metazosulfuron)、甲苯噻隆、甲硫嘧磺隆(methiopyrsulfuron)、甲硫唑草啉(methiozolin)、異硫氰酸甲酯、撲多草(metobromuron)、莫多草(metolachlor)、S-莫多草、磺草唑胺(metosulam)、甲氧隆(metoxuron)、滅必淨(metribuzin)、甲磺隆(metsulfuron)、甲磺隆甲酯、稻得壯(molinat)、綠穀隆(monolinuron)、單嘧磺隆(monosulfuron)、單嘧磺隆酯、MT-5950 (即,N-(3-氯-4-異丙基苯基)-2-甲基戊醯胺)、NGGC-011、滅落脫(napropamide)、NC-310 (即,[5-(苄基氧基)-1-甲基-1H-吡唑-4-基](2,4-二氯苯基)甲酮)、草不隆(neburon)、煙嘧磺隆(nicosulfuron)、壬酸(天竺葵酸(pelargonic acid))、噠草伏(norflurazon)、油酸(脂肪酸)、坪草丹(orbencarb)、甲嘧啶磺隆(orthosulfamuron)、安磺靈(oryzalin)、丙炔噁草酮(oxadiargyl)、噁草酮(oxadiazon)、環氧嘧磺隆(oxasulfuron)、去稗安(oxaziclomefon)、乙氧氟草醚(oxyfluorfen)、巴拉刈(paraquat)、巴拉刈二氯化物、克草猛(pebulate)、施得圃(pendimethalin)、平速爛(penoxsulam)、五氯苯酚、環戊噁草酮(pentoxazone)、烯草胺(pethoxamid)、石油、甜菜寧(phenmedipham)、毒莠定(picloram)、氟吡草胺(picolinafen)、唑啉草酯(pinoxaden)、戊草淨(piperophos)、普拉草(pretilachlor)、氟嘧磺隆(primisulfuron)、氟嘧磺隆甲酯、氨氟樂靈(prodiamine)、環苯草酮(profoxydim)、撲滅通(prometon)、佈滅淨(prometryn)、毒草胺(propachlor)、除草靈(propanil)、噁草酸(propaquizafop)、撲滅津(propazine)、苯胺靈(propham)、普樂寶(propisochlor)、丙苯磺隆(propoxycarbazone)、丙苯磺隆鈉、丙嗪嘧磺隆(propyrisulfuron)、戊炔草胺(propyzamide)、苄草丹(prosulfocarb)、氟磺隆(prosulfuron)、雙唑草腈(pyraclonil)、派芬草(pyraflufen)、乙基派芬草(pyraflufen-ethyl)、吡唑氟磺草胺(pyrasulfotole)、吡唑特(pyrazolynate、pyrazolate)、草剋星(pyrazosulfuron)、草剋星乙酯、苄草唑(pyrazoxyfen)、草醚(pyribambenz)、異丙酯草醚(pyribambenz-isopropyl)、丙酯草醚、嘧啶肟草醚(pyribenzoxim)、稗草丹(pyributicarb)、達草特(pyridafol)、必汰草(pyridate)、環酯草醚(pyriftalid)、嘧草醚(pyriminobac)、甲基嘧草醚、吡丙醚(pyrimisulfan)、嘧硫草醚(pyrithiobac)、嘧硫草醚鈉、派羅克殺草碸(pyroxasulfone)、啶磺草胺(pyroxsulam)、快克草(quinclorac)、喹草酸(quinmerac)、莫克草(quinoclamine)、喹禾靈(quizalofop)、喹禾靈乙酯、喹禾靈-P、喹禾靈-P-乙酯、喹禾糠酯(quizalofop-P-tefuryl)、碸嘧磺隆(rimsulfuron)、苯嘧磺草胺(saflufenacil)、烯禾啶(sethoxydim)、環草隆(siduron)、草滅淨(simazine)、西草淨(simetryn)、SL-261、磺草酮(sulcotrion)、甲磺草胺(sulfentrazone)、甲嘧磺隆(sulfometuron)、甲嘧磺隆甲酯、磺醯磺隆(sulfosulfuron)、SYN-523、SYP-249 (即,5-[2-氯-4-(三氟甲基)苯氧基]-2-硝基苯甲酸1-乙氧基-3-甲基-1-側氧基丁-3-烯-2-基酯)、SYP-300 (即,1-[7-氟-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、特丁噻草隆(tebuthiuron)、特呋三酮(tefuryltrione)、環磺酮(tembotrione)、得殺草(tepraloxydim)、特草定(terbacil)、特草靈(terbucarb)、特丁通(terbumeton)、特丁津(terbuthylazin)、特丁淨(terbutryn)、欣克草(thenylchlor)、噻草啶(thiazopyr)、噻酮磺隆(thiencarbazone)、噻酮磺隆甲酯、(thifensulfuron)、噻吩磺隆甲酯、殺丹(thiobencarb)、特芬斯(tiafenacil)、tolpyralate、苯唑草酮(topramezone)、肟草酮(tralkoxydim)、氟酮磺草胺(triafamone)、野麥畏(tri-allate)、醚苯磺隆(triasulfuron)、三嗪氟草胺(triaziflam)、苯磺隆(tribenuron)、苯磺隆甲酯、綠草定(triclopyr)、草達津(trietazine)、三氟啶磺隆(trifloxysulfuron)、三氟啶磺隆鈉、三氟草嗪(trifludimoxazin)、三福林(trifluralin)、氟胺磺隆(triflusulfuron)、氟胺磺隆甲酯、三嗪氟磺隆(tritosulfuron)、硫酸脲、滅草猛(vernolate)、XDE-848、ZJ-0862 (即,3,4-二氯-N-{2-[(4,6-二甲氧基嘧啶-2-基)氧基]苄基}苯胺)及以下化合物:
Examples of herbicides that can be mixed with compounds of formula (I) and compositions containing them are:
Acetochlor, acifluorfen, sodium axifen, aclofen, alachlor, allidochlor, alloxydim, sodium apyr , Ametryn, amidcarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6- (4-chloro-2-fluoro -3-methylphenyl) -5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, potassium cyclopropylpyrimidate, methyl cyclopropylpyrimidate, aminopyralid, aminopyralid (amitrole), ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, flubutazone Beflubutamid, benazolin, benzyl ethyl, benfluralin, benfuresate, bensulfuron, bensulfuron methyl ester, diphosphine ( bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyron, bifenox, bilanafos, biloba Sodium, bispyribac, Sodium glometazone, bromacil, bromobutide, bromofenoxim, bromoxynil, bromobenzonitrate, potassium bromobenzonitrile, bromobenzonitrile enanthate, and Bromoxynil octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, bidanin ( butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, g Chloramben, chlorbromuron, chlorfenac, sodium chlorfenac, chlorfenprop, chlorflurenol, methyl renin, chloridazon, chlorine Chlorimuron, chlorosulfuron ethyl, chlorophthalim, chlorotoluron, chlorthal-dimethyl, chlorsulfuron, indolinone (chlorimuron) cinidon), cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, cloxaton ( clethodim), clodinafop, propargyl, clomazone, clomeprop, clopyralid, cloransulam, chlorosulfen Methyl oxalate, cumyluron, cyanamide, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cycloxydim Cyhalofop, butyl safflower, cyprazine, 2,4-D (2,4-D), 2,4-D-butoxyethyl (2,4-D-butotyl ), 2,4-dibutyl ester, 2,4-dimethylammonium, 2,4-diethylene glycol amine, 2,4-diethyl acetate, 2,4-di 2-ethylhexyl ester, 2 , 4-drop isobutyl ester, 2,4-drop isooctyl ester, 2,4-drop isopropylammonium, 2,4-drop potassium, 2,4-drop triisopropanolate, and 2,4-drop Triolamine, 2,4-dibutyric acid (2,4-DB), 2,4-dibutyl butyrate, dimethyl ammonium 2,4-dibutyrate, isooctyl 2,4-dibutyrate Ester, potassium 2,4-dibutyrate and sodium 2,4-dibutyrate, daimuron (dymron), dalapon, dazomet, n-decane Alcohol, desmedipham, detosyl-pyrazolate (DTP), tilak grass ( dicamba), dichlobenil, 2- (2,4-dichlorobenzyl) -4,4-dimethyl-1,2-oxazolin-3-one, 2- (2,5 -Dichlorobenzyl) -4,4-dimethyl-1,2-oxazolin-3-one, 2,4-dichlorprop, 2,4-dipropionic acid-P, grass Diclofop, diclofop, diclofop, p-methyl, diclosulam, difenzoquat, diflufenican, diflufenican (diflufenzopyr), diflufenzopy sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P , Dimetrasulfuron, dimitramine, dinoterb, diphenamid, diquat, dibromide, thiosulfur ( dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron methyl ester , Ethiozin, ethofumesate, ethoxyfen, chloroflufenamate, ethoxysulfuron Etobenzanid, F-9600, F-5231 (i.e., N- {2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -5- pendantoxy-4 , 5-dihydro-1H-tetrazol-1-yl] phenyl} ethanesulfonamide), F-7967 (i.e., 3- [7-chloro-5-fluoro-2- (trifluoromethyl) -1H-benzimidazol-4-yl] -1-methyl-6- (trifluoromethyl) pyrimidine-2,4 (1H, 3H) -dione), fenoxaprop, fenoxadi -P, fenfenpyr-ethyl, fenfenpyr-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, flamprop, Syringa-M-isopropyl ester, Syringa-M-methyl ester, flazasulfuron, florasulam, fluazifop, voxyl-P, voxyl Esters, voroprol-P-butyl esters, flucarbazone, flufluazone sodium, flucetosulfuron, fluchloralin, flufenacet, fludoxazone Flufenpyr, flufenpyr, ethyl, flumetsulam, flumiclorac, amyl flufenoxal, flumioxazin, fluometuron , Flurenol, curcumin , Chlorfenapyr and methamphetamine methyl ester, fluoroglycofen, acetofluoracet ethyl ester, flupropanate, flupyrsulfuron, fluoxuridine Fomesulfuron methyl sodium, fluridone, flurochloridone, fluroxypyr, isooctyl, flurtamone, fluthiacet, hydrazine Methyl oxalate, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate, glufosinate, Glyphosate-P-Sodium, Glyphosate-P-Ammonium, Glyphosate-P-Sodium, glyphosate, glyphosate ammonium, glyphosate isopropylammonium, glyphosate diammonium, Glyphosate dimethyl ammonium, glyphosate potassium, glyphosate sodium, and glyphosate-trimesium, H-9201 (i.e., O- (2,4-dimethyl-6 -Nitrophenyl) O-ethylisopropylthiophosphoramidate), halauxifen, flucloperidyl methyl ester, halosafen, clopisulfuron ( halosulfuron), clomisulfuron methyl ester, haloxyfop , Oxyfluoro-P, oxyfluoro-ethoxyethyl, oxyfluoro-P-ethoxyethyl, oxyfluoromethyl, oxyfluoro-P-methyl, hexazinone , HW-02 (i.e., (2,4-dichlorophenoxy) acetate 1- (dimethoxyphosphatino) ethyl), imazamethabenz, methyl imazamet, imazam Imazamox, imazamox, amazapic, imazapic, amazapyr, imazapyr, imazaquin, imazaquin, imazamo Quinamin, imazethapyr, prostam, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron Methyl sodium, ioxynil, ioxynil-octanoate, potassium iodobenzonitrile and sodium iodobenzonitrile, ipfencarbazone, isoproturon, iso Isouron, isoxaben, isoxaflutole, karbutilate, KUH-043 (i.e., 3-(([5- (difluoromethyl)- 1-methyl-3- (trifluoromethyl) -1H-pyrazol-4-yl] methyl} sulfonyl) -5,5-dimethyl-4,5-dihydro-1,2- Azole), ketospiradox, lactofen, lenacil, linuron, MCPA, MCPA-butoxyethyl, MCPA dimethylammonium, MCPA-2-ethylhexyl Esters, MCPA isopropylammonium, MCPA potassium and MCPA sodium, MCPB, MCPB methyl ester, MCPB ethyl ester and MCPB sodium, 2 methyl 4 chloropropionic acid (mecoprop), 2 methyl 4 chloropropionate and 2 methyl 4 chloropropane Acid butoxy ethyl ester, 2 methyl 4 chloropropionic acid-P, 2 methyl 4 chloropropionic acid-P-butoxy ethyl ester, 2 methyl 4 chloropropionic acid dimethyl ammonium, 2 methyl 4 chloropropionic acid 2- Ethylhexyl ester and 2 methyl 4 chloropropionate, mefenacet, mefluidide, mesosulfuron, methyl disulfuron methyl, mesotrione , Methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, tolmethoxone , Methiopyrsulfuron, methiozolin, methyl isothiocyanate, metobromuron, metolachlor, S-modomochlor, sulfamethoxam (metosulam), metoxuron, metribuzin, a Metsulfuron, methylsulfuron methyl ester, molinat, monolinuron, monosulfuron, monosulfuronate, MT-5950 (i.e., N- (3- Chloro-4-isopropylphenyl) -2-methylpentamidine), NGGC-011, napropamide, NC-310 (i.e., [5- (benzyloxy) -1-methyl -1H-pyrazol-4-yl] (2,4-dichlorophenyl) methanone), neburon, nicosulfuron, nonanoic acid (pelargonic acid) , Norflurazon, oleic acid (fatty acid), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon ), Oxasulfuron, oxaziclomefon, oxyfluorfen, paraquat, paraquat dichloride, pebulate, Shidepu ( pendimethalin, penoxsulam, pentachlorophenol, pentoxazone, pethoxamid, petroleum, phenmedipham, picloram, picolinafen ), Pinoxaden, piperophos, general Pretilachlor, primisulfuron, methyl flusulfuron methyl, prodiamine, profoxydim, prometon, prometryn, Propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, profensulfuron sodium , Propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, ethyl pie Pyraflufen-ethyl, pyrazulfotole, pyrazolate, pyrazolate, pyrazosulfuron, pyroxacin ethyl, pyrazoxyfen, pyrribambenz , Pyribambenz-isopropyl, Pyribenzim-isopropyl, Pyribenzoxim, Piributicarb, Pyridafol, Pyridate, Cyclopsin (pyriftalid), pyriminobac, pyriminobac, pyrimisulfan, pyrimisulfan Ether (pyrithiobac), sodium sulfamethoxam, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinol Quizalofop, quinoxaline ethyl ester, quinoxaline-P, quinoxaline-P-ethyl ester, quizalofop-P-tefuryl, rimsulfuron, phenylsulfuron Saflufenacil, sethoxydim, siduron, simazine, simetryn, SL-261, sulcotrion, mesotrione ( sulfentrazone), sulfometuron, methylsulfuron methyl, sulfosulfuron, SYN-523, SYP-249 (i.e., 5- [2-chloro-4- (trifluoromethyl) ) Phenoxy] -2-nitrobenzoic acid 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl ester), SYP-300 (that is, 1- [7 -Fluoro-3-oxo-4- (prop-2-yn-1-yl) -3,4-dihydro-2H-1,4-benzoxazin-6-yl] -3-propyl -2-thioimidazolidine-4,5-dione), 2,3,6-TBA, TCA (trichloroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione ), Tembotrione, tepraloxydim Terbacil, terbucarb, terbumeton, terbuthylazin, terbutryn, thenylchlor, thiazopyr, thiazopyr Ketosulfuron (thiencarbazone), thifensulfuron methyl, thifensulfuron, thiophenesulfon methyl, thiobencarb, tiafenacil, tolpyralate, topramezone, oxame (tralkoxydim), triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron Esters, triclopyr, triazazine, trifloxysulfuron, trifloxysulfuron sodium, trifludimoxazin, trifluralin, fluflurane Triflusulfuron, methyl flusulfuron methyl, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862 (i.e., 3,4-dichloro-N- {2-[(4,6-dimethoxypyrimidin-2-yl) oxy] benzyl} aniline) and the following compounds:
植物生長調節劑之實例係:
阿拉酸式苯、阿拉酸式苯-S-甲基、5-胺基乙醯丙酸、環丙嘧啶醇(ancymidol)、6-苄基胺基嘌呤、油菜素內酯(Brassinolid)、兒茶素(catechine)、矮壯素(chlormequat chloride)、坐果安(cloprop)、環丙酸醯胺(cyclanilide)、3-(環丙-1-烯基)丙酸、丁醯肼、棉隆、正癸醇、調呋酸(dikegulac)、調呋酸鈉、茵多酸(endothal)、茵多酸二鉀、茵多酸二鈉及茵多酸單(N,N-二甲基烷基銨)、乙烯利(ethephon)、氟節胺(flumetralin)、抑草丁、抑草丁丁酯、呋嘧醇(flurprimidol)、氯吡苯脲(forchlorfenuron)、赤黴酸(gibberellic acid)、抗倒胺(inabenfide)、吲哚-3-乙酸(IAA)、4-吲哚-3-基丁酸、亞賜圃(isoprothiolane)、噻菌靈(probenazole)、茉莉酸(jasmonic acid)、馬來醯肼、助壯素(mepiquat chloride)、1-甲基環丙烯、茉莉酸甲酯、2-(1-萘基)乙醯胺、1-萘基乙酸、2-萘基氧基乙酸、硝基苯酚鹽混合物、巴克素(paclobutrazol)、N-(2-苯基乙基)-β-丙胺酸、N-苯基酞醯胺酸、調環酸(prohexadione)、調環酸鈣、茉莉酸丙酯(prohydrojasmone)、柳酸、獨腳金內酯(strigolactone)、四氯硝基苯(tecnazene)、噻苯隆(thidiazuron)、三十醇、抗倒酯(trinexapac, trinexapac-ethyl)、tsitodef、烯效唑(uniconazole)、烯效唑-P。Examples of plant growth regulators are:
Alamate benzene, Alamate benzene-S-methyl, 5-aminoacetamidopropionic acid, ancymidol, 6-benzylaminopurine, Brassinolid, catechin (Catechine), chlormequat chloride, cloprop, cyclanilide, 3- (cycloprop-1-enyl) propionic acid, butanhydrazine, cotton, Decanol, dikegulac, sodium furoate, endothal, dipotassium indoate, disodium indoate, and mono (N, N-dimethylalkylammonium) , Ethephon, flumetralin, currotrim, butrobutyl, flurprimidol, forchlorfenuron, gibberellic acid, antipyridamine inabenfide), indole-3-acetic acid (IAA), 4-indole-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, maleic hydrazine, Mepiquat chloride, 1-methylcyclopropene, methyl jasmonate, 2- (1-naphthyl) acetamidamine, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenolate Mixture, palobutrazol, N- (2-phenylethyl) -β-propane Acid, N-phenylphthalocyanine, prohexadione, calcium cyclic acid, propyl jasmonate (prohydrojasmone), salicylic acid, strigolactone, tetrachloronitrobenzene (tecnazene ), Thidiazuron, triacontanol, trinexapac (trinexapac-ethyl), tsitodef, uniconazole, uniconazole-P.
方法及用途
式(I)化合物及包含其等之組合物具有強效殺微生物活性及/或植物防禦調節潛力。其可用於控制不希望微生物,例如不希望之真菌及細菌。其特定而言可用於作物保護(其控制造成植物病害之微生物)或用於保護材料(例如工業材料、木料、儲存貨物),如本文下文更詳細闡述。更具體而言,式(I)化合物及包含其等之組合物可用於保護種子、正發芽種子、已顯現之幼苗、植物、植物部分、果實、收穫的物品及/或植物生長之土壤免受不希望之微生物的侵害。Methods and uses Compounds of formula (I) and compositions comprising them have potent microbicidal activity and / or plant defense regulation potential. It can be used to control unwanted microorganisms, such as unwanted fungi and bacteria. It can be used in particular for crop protection (which controls microorganisms that cause plant diseases) or for protecting materials (eg industrial materials, wood, storage goods), as explained in more detail below herein. More specifically, compounds of formula (I) and compositions containing them can be used to protect seeds, germinating seeds, emerging seedlings, plants, plant parts, fruits, harvested items, and / or plant growing soil Unwanted microorganisms.
如本文所用,控制(Control, controlling)涵蓋保護性、治癒性及根除性處理不希望之微生物。不希望之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,更具體而言植物病原性細菌、植物病原性病毒、植物病原性卵菌或植物病原性真菌。如本文下文所詳述,該等植物病原性微生物係廣泛植物病害之致病原。As used herein, Control (controlling) encompasses the protection, healing, and eradication of unwanted microorganisms. Unwanted microorganisms may be pathogenic bacteria, pathogenic viruses, pathogenic oomycetes, or pathogenic fungi, more specifically phytopathogenic bacteria, phytopathogenic viruses, phytopathogenic oomycetes, or phytopathogenic fungi. As detailed herein below, these phytopathogenic microorganisms are pathogens of a wide range of plant diseases.
更具體而言,式(I)化合物及包含其等之組合物可用作殺真菌劑。出於說明書之目的,術語「殺真菌劑」係指可用於作物保護中以控制不希望真菌(例如根腫菌綱(Plasmodiophoromycetes)、壺菌綱(Chytridiomycetes)、接合菌綱(Zygomycetes)、子囊菌綱(Ascomycetes)、擔子菌綱(Basidiomycetes)及不完全菌綱(Deuteromycetes))及/或以控制卵菌之化合物或組合物。More specifically, compounds of formula (I) and compositions containing them are useful as fungicides. For the purposes of this specification, the term "fungicide" refers to crop protection that can be used to control unwanted fungi (e.g. Plasmodiophoromycetes, Chytridiomycetes, Zygomycetes, Ascomycetes). Ascomycetes, Basidiomycetes and Deuteromycetes) and / or compounds or compositions for controlling oomycetes.
式(I)化合物及包含其等之組合物亦可用作抗細菌劑。特定而言,其可用於作物保護中以(例如)控制不希望之細菌,例如假單胞菌科(Pseudomonadaceae)、根瘤菌科(Rhizobiaceae)、黃單胞菌科(Xanthomonadaceae)、腸桿菌科(Enterobacteriaceae)、棒狀桿菌科(Corynebacteriaceae)及鏈黴菌科(Streptomycetaceae)。Compounds of formula (I) and compositions containing them can also be used as antibacterial agents. In particular, it can be used in crop protection to, for example, control unwanted bacteria, such as Pseudomonadaceae, Rhizobiaceae, Xanthomonadaceae, Enterobacteriaceae ( Enterobacteriaceae), Corynebacteriaceae and Streptomycetaceae.
式(I)化合物及包含其等之組合物亦可在作物保護中用作抗病毒劑。舉例而言,式(I)化合物及包含其等之組合物可對植物病毒引起之病害具有效應,例如菸草嵌紋病毒(tobacco mosaic virus, TMV)、菸草脆裂病毒(tobacco rattle virus)、菸草矮化病毒(tobacco stunt virus, TStuV)、菸草捲葉病毒(tobacco leaf curl virus, VLCV)、菸草脈綠嵌紋病毒(tobacco vein-banding mosaic virus, TVBMV)、菸草壞死性矮病毒(tobacco necrotic dwarf virus, TNDV)、菸草條斑病毒(tobacco streak virus, TSV)、馬鈴薯病毒X (potato virus X, PVX)、馬鈴薯病毒Y、S、M及A、馬鈴薯黃斑嵌紋病毒(potato aucuba mosaic virus, PAMV)、馬鈴薯帚頂病毒(potato mop-top virus, PMTV)、馬鈴薯葉捲病毒(potato leaf-roll virus, PLRV)、紫苜蓿嵌紋病毒(alfalfa mosaic virus, AMV)、胡瓜嵌紋病毒(cucumber mosaic virus, CMV)、胡瓜綠斑嵌紋病毒(cucumber green mottlemosaic virus, CGMMV)、胡瓜黃化病毒(cucumber yellows virus, CuYV)、西瓜嵌紋病毒(watermelon mosaic virus, WMV)、番茄斑點萎凋病毒(tomato spotted wilt virus, TSWV)、番茄輪斑病毒(tomato ringspot virus, TomRSV)、甘蔗嵌紋病毒(sugarcane mosaic virus, SCMV)、稻穀萎病毒(rice dwarf virus)、稻穀條斑病毒(rice stripe virus)、稻穀黑條萎病毒(rice black-streaked dwarf virus)、草莓斑紋病毒(strawberry mottle virus, SMoV)、草莓鑲脈病毒(strawberry vein banding virus, SVBV)、草莓輕型黃邊病毒(strawberry mild yellow edge virus, SMYEV)、草莓皺縮病毒(strawberry crinkle virus, SCrV)、蠶豆萎凋病毒(broad beanwilt virus, BBWV)及甜瓜壞疽斑點病毒(melon necrotic spot virus, MNSV)。The compounds of formula (I) and compositions comprising them can also be used as antiviral agents in crop protection. For example, compounds of formula (I) and compositions containing the same may have effects on diseases caused by plant viruses, such as tobacco mosaic virus (TMV), tobacco virus (tobacco rattle virus), tobacco Tobacco stunt virus (TStuV), Tobacco leaf curl virus (VLCV), Tobacco vein-banding mosaic virus (TVBMV), Tobacco necrotic dwarf virus (TNDV), tobacco streak virus (TSV), potato virus X (PVX), potato viruses Y, S, M and A, potato aucuba mosaic virus (PAMV) ), Potato mop-top virus (PMTV), potato leaf-roll virus (PLRV), alfalfa mosaic virus (AMV), cucumber mosaic virus (cucumber mosaic virus (CMV), cucumber green mottlemosaic virus (CGMMV), cucumber yellows virus (CuYV), watermelon mosaic virus (WMV), fan Tomato spotted wilt virus (TSWV), tomato ringspot virus (TomRSV), sugarcane mosaic virus (SCMV), rice dwarf virus, rice stripe virus (rice dwarf virus) rice stripe virus, rice black-streaked dwarf virus, strawberry mottle virus (SMoV), strawberry vein banding virus (SVBV), strawberry light yellow edge virus (strawberry Mild yellow edge virus (SMYEV), strawberry crinkle virus (SCrV), broad beanwilt virus (BBWV), and melon necrotic spot virus (MNSV).
本發明亦係關於控制不希望微生物(例如不希望真菌、卵菌及細菌)之方法,其包含以下步驟:將至少一種式(I)化合物或至少一種組合物施用至該等微生物及/或其棲息地(施用至植物、植物部分、種子、果實或植物生長之土壤)。The invention also relates to a method for controlling unwanted microorganisms, such as unwanted fungi, oomycetes and bacteria, comprising the steps of applying at least one compound of formula (I) or at least one composition to such microorganisms and / or Habitat (applied to plants, plant parts, seeds, fruits, or soil on which plants grow).
通常,當式(I)化合物及包含其等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,將有效且植物相容量之式(I)化合物及包含其等之組合物施用至植物、植物部分、種子、果實或植物生長之土壤或基質。可用於種植植物之適宜基質包括基於無機之基質,例如礦物棉,特定而言石羊毛、珍珠岩、沙或砂礫;有機基質,例如泥炭土、松樹皮或鋸屑;及基於石油之基質,例如,聚合發泡體或塑膠珠粒。有效且植物相容量 意指足以控制或消滅存在或耕地上易於出現之真菌且不會引起該等作物之任何明顯植物毒性症狀之量。此一量可端視欲控制之真菌、作物類型、作物生長階段、氣候條件及所用之各別式(I)化合物或組合物在款範圍內變化。此量可藉由在熟習此項技術者能力範圍內之系統田間試驗確定。Generally, when a compound of formula (I) and a composition comprising the same are used in a curative or protective method to control phytopathogenic fungi and / or phytopathogenic oomycetes, formula (I) The compounds and compositions comprising them are applied to plants, plant parts, seeds, fruits or soil or substrates on which plants grow. Suitable substrates that can be used for growing plants include inorganic-based substrates, such as mineral wool, specifically stone wool, perlite, sand, or grit; organic substrates such as peat soil, pine bark, or sawdust; and petroleum-based substrates, such as, Polymer foam or plastic beads. Effective and phytophagic capacity means an amount sufficient to control or eliminate the presence or susceptibility of fungi on the arable land without causing any significant phytotoxic symptoms of these crops. This amount of fungus, crop type, crop growth stage, climatic conditions, and the respective compound (I) of the compound or composition to be controlled can be varied within the scope of the paragraph. This amount can be determined by systematic field trials within the capabilities of those skilled in the art.
植物及植物部分
式(I)化合物及包含其等之組合物可施用至任何植物或植物部分。 Plants and plant parts <br/> The compounds of formula (I) and compositions comprising them can be applied to any plant or plant part.
植物 意指所有植物及植物種群,例如期望及不期望之野生植物或作物植物(包括天然作物植物)。作物植物可為可藉由習用育種及最優化方法或藉由生物技術及基因工程方法或該等方法之組合獲得之植物,其包括基因改造之植物(GMO或轉基因植物)及受植物育種者權(plant breeders' right)保護或不受其保護之植物栽培品種。 Plant means all plants and plant populations, such as desired and undesired wild plants or crop plants (including natural crop plants). Crop plants can be plants that can be obtained by conventional breeding and optimization methods or by biotechnology and genetic engineering methods or a combination of these methods, including genetically modified plants (GMO or genetically modified plants) and plant breeder rights (plant breeders' right) Plant cultivars that are protected or unprotected.
基因改造之植物 (GMO)
基因改造之植物(GMO或轉基因植物)係異源基因已穩定整合於基因體中之植物。表述「異源基因」本質上意指在植物外部提供或組裝且引入細胞核、葉綠體或粒線體基因體中時之基因。此基因藉由表現所關注蛋白質或多肽或藉由下調植物中所存在之其他基因或使其沉默(使用例如反義技術、共抑制技術、RNA干擾-RNAi-技術或微小RNA-miRNA-技術)使得轉化植物具有新的或經改良農業或其他性質。位於基因體中之異源基因亦稱為轉基因。植物基因體中由其特定位置界定之轉基因稱作轉化或轉基因事件。 Genetically Modified Plant (GMO)
Genetically modified plants (GMO or transgenic plants) are plants in which a heterologous gene has been stably integrated into the genome. The expression "heterologous gene" essentially means a gene that is provided or assembled outside a plant and introduced into the nucleus, chloroplast, or mitochondrial genome. This gene is expressed by the protein or polypeptide of interest or by down-regulating or silencing other genes present in the plant (using, for example, antisense technology, co-suppression technology, RNA interference-RNAi-technology or microRNA-miRNA-technology) The transformed plants are rendered with new or improved agricultural or other properties. Heterologous genes located in the genome are also called transgenes. A transgene that is defined by a specific location in a plant genome is called a transformation or transgenic event.
植物栽培品種 應理解為意指具有新性質(「特性」)且已藉由習用育種、藉由誘變或藉助重組DNA技術獲得之植物。其可為栽培品種、變種、生物或基因型。 Plant cultivars are understood to mean plants that have new properties ("traits") and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA technology. It can be a cultivar, variety, organism or genotype.
植物部分 應理解為意指植物之地上及地下之所有部分及器官,例如枝條、葉、針葉、莖、桿、花、子實體、果實、種子、根、塊莖及根莖。該等植物部分亦包括所收穫材料及營養性及生殖性繁殖材料,例如插條、塊莖、根莖、插穗及種子。 Plant parts are understood to mean all parts and organs above and below the plant, such as branches, leaves, needles, stems, rods, flowers, fruiting bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested materials and vegetative and reproductive propagation materials such as cuttings, tubers, rhizomes, cuttings and seeds.
可根據本文所述之方法處理之植物包括以下:棉花、亞麻、葡萄藤、果實、蔬菜,例如薔薇科屬種(Rosaceae sp. )(例如仁果類,例如,蘋果及梨;以及核果類,例如,杏子、櫻桃、杏仁及桃子;及漿果類,例如,草莓)、茶藨子科屬種(Ribesioidae sp. )、胡桃科屬種(Juglandaceae sp. )、樺木科屬種(Betulaceae sp. )、漆樹科屬種(Anacardiaceae sp. )、山毛櫸科屬種(Fagaceae sp. )、桑科屬種(Moraceae sp. )、木樨科屬種(Oleaceae sp. )、獼猴桃科屬種(Actinidiaceae sp. )、樟科屬種(Lauraceae sp. )、芭蕉科屬種(Musaceae sp. )(例如香蕉樹及種植園)、茜草科屬種(Rubiaceae sp. ) (例如咖啡)、山茶科屬種(Theaceae sp. )、梧桐科屬種(Sterculiceae sp. )、芸香科屬種(Rutaceae sp. )(例如檸檬、柑橘及葡萄柚);茄科屬種(Solanaceae sp. )(例如番茄)、百合科屬種(Liliaceae sp. )、菊科屬種(Asteraceae sp. ) (例如萵苣)、繖形花科屬種(Umbelliferae sp. )、十字花科屬種(Cruciferae sp. )、藜科屬種(Chenopodiaceae sp. )、葫蘆科屬種(Cucurbitaceae sp. ) (例如胡瓜)、蔥科屬種(Alliaceae sp. ) (例如韭菜、洋蔥)、蝶形花科屬種(Papilionaceae sp. )(例如豌豆);主要農作物,例如禾本亞目屬種(Gramineae sp. ) (例如玉蜀黍、草坪、榖物類,例如,小麥、黑麥、稻穀、大麥、燕麥、粟及黑小麥)、菊科屬種(例如向日葵)、蕓苔科屬種(Brassicaceae sp. )(例如白球甘藍、紫甘藍、青花菜、花椰菜、抱子甘藍、小白菜、球莖甘藍、蘿蔔及油菜籽、芥菜、山葵及水芹)、豆科屬種(Fabaceae sp. ) (例如豆、花生)、蝶形花科屬種(Papilionaceae sp. )(例如大豆)、茄科屬種(例如馬鈴薯)、藜科屬種(例如甜菜、飼用甜菾菜、葉用甜菜、根甜菜);用於花園及林地之有用植物及觀賞植物;及該等植物中每一者之基因改造變種。Plants that can be treated according to the methods described herein include the following: cotton, flax, vines, fruits, vegetables, such as Rosaceae sp. (Such as kernels, such as apples and pears; and stone fruits, For example, apricots, cherries, almonds, and peaches; and berries such as strawberries), Ribesioidae sp. , Juglandaceae sp. , Betulaceae sp. , Anacardiaceae sp. , Fagaceae sp. , Moraceae sp. , Oleaceae sp. , Actinidiaceae sp. , Lauraceae sp. , Musaceae sp. (Such as banana trees and plantations), Rubiaceae sp. (Such as coffee), Theaceae sp. . ), Sterculiceae sp. , Rutaceae sp. (E.g. lemon, citrus and grapefruit); Solanaceae sp. (E.g. tomato), Liliaceae (Liliaceae sp.), Asteraceae species (Asteraceae sp.) (such as lettuce), Shaped flowers Division species (Umbelliferae sp.), Cruciferous species (Cruciferae sp.), Chenopodiaceae species (Chenopodiaceae sp.), Cucurbitaceae species (Cucurbitaceae sp.) (For example cucumber), Alliaceae species ( Alliaceae sp. ) (E.g. leek, onion), Papilionaceae sp. (E.g. pea); major crops, e.g. Gramineae sp. (E.g. maize, lawn, loquat Species, for example, wheat, rye, rice, barley, oats, millet, and triticale), Asteraceae (e.g., sunflower), Brassicaceae sp. (E.g., white cabbage, purple cabbage, blue flower Vegetables, broccoli, brussels sprouts, pakchoi, cabbage, radishes and rapeseeds, mustard, wasabi and cress), Fabaceae sp. (E.g. beans, peanuts), butterfly family ( Papilionaceae sp. ) (E.g. soybeans), Solanaceae (e.g. potatoes), Chenopodiaceae (e.g. beets, forage sweet amaranth, leaf beets, root beets); useful plants and ornamentals for gardens and woodlands Plants; and genetically modified variants of each of these plants.
可藉由上述方法處理之植物及植物栽培品種包括抵抗一或多種生物性逆境之植物及植物栽培品種,即,該等植物對諸如以下動物及微生物害蟲顯示較佳防禦:線蟲、昆蟲、蟎、植物病原性真菌、細菌、病毒及/或類病毒。Plants and plant cultivars that can be treated by the methods described above include plants and plant cultivars that are resistant to one or more biological adversities, that is, these plants show better defenses against animals and microbial pests such as nematodes, insects, mites, Phytopathogenic fungi, bacteria, viruses and / or viroids.
可藉由上述方法處理之植物及植物栽培品種包括彼等抵抗一或多種非生物性逆境之植物。非生物性逆境條件可包括(例如)乾旱、低溫暴露、熱暴露、滲透壓逆境、淹水、土壤鹽度增加、礦物暴露增加、臭氧暴露、強光暴露、氮營養素之有限利用度、磷營養素之有限利用度、避蔭。Plants and plant cultivars that can be treated by the methods described above include plants that resist one or more abiotic stresses. Abiotic stress conditions can include, for example, drought, low temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, strong light exposure, limited availability of nitrogen nutrients, phosphorus nutrients Limited utilization, avoid shade.
可藉由上述方法處理之植物及植物栽培品種包括彼等特徵在於增強之產量特性之植物。該等植物中增加之產量可係(例如)改良之植物生理、生長及發育(例如水利用效率、水保持效率、改良之氮利用、增強之碳同化、改良之光合作用、提高發芽效率及加速成熟)之結果。產量可進一步受改良之植物結構(在逆境及非逆境條件下)影響,包括(但不限於)提早開花、對產生雜交種子之開花控制、幼苗勢、植株大小、節間數及距離、根系生長、種子大小、果實大小、莢果大小、莢果數或穗數、每個莢果或穗之種子數、種子質量、提高種子飽實度、降低種子散佈、減少莢果開裂及抗倒伏性。其他產量性狀包括種子組成(例如碳水化合物含量及組成(例如棉或澱粉)、蛋白質含量、油含量及組成)、營養價值、抗營養化合物減少、改良之加工性及更佳之儲存穩定性。Plants and plant cultivars that can be treated by the methods described above include plants that are characterized by enhanced yield characteristics. The increased yield in these plants can be, for example, improved plant physiology, growth, and development (e.g., water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency, and accelerated Mature). Yield can be further affected by improved plant structure (under adversity and non-adversity conditions), including (but not limited to) early flowering, control of flowering to produce hybrid seeds, seedling vigor, plant size, number of internodes and distance, root growth , Seed size, fruit size, pod size, number of pods or ears, number of seeds per pod or ear, seed quality, improving seed fullness, reducing seed spread, reducing pod cracking and lodging resistance. Other yield traits include seed composition (such as carbohydrate content and composition (such as cotton or starch), protein content, oil content and composition), nutritional value, reduced anti-nutritional compounds, improved processability, and better storage stability.
可藉由上述方法處理之植物及植物栽培品種包括為已表現出雜種或雜交優勢特徵之雜交植物的植物及植物栽培品種,該等雜交植物導致通常更高之產量、優勢、健康及對生物性及非生物性逆境之抗性。Plants and plant cultivars that can be treated by the methods described above include plants and plant cultivars that are hybrid plants that have exhibited characteristics of heterosis or hybridization, which hybrid plants lead to generally higher yields, advantages, health, and biological And resistance to abiotic stress.
可藉由以上所揭示之方法處理之植物及植物栽培品種(藉由植物生物技術方法獲得,例如遺傳工程)包括彼等為除草劑耐受性植物(即,耐受一或多種給定除草劑之植物)之植物及植物栽培品種。該等植物可藉由遺傳轉變或藉由選擇含有賦予該除草劑耐受性之突變之植物獲得。Plants and plant cultivars (obtained by plant biotechnology methods, such as genetic engineering) that can be treated by the methods disclosed above include those that are herbicide-tolerant plants (i.e., tolerant to one or more given herbicides) Plant) and plant cultivars. The plants can be obtained by genetic transformation or by selecting plants containing mutations that confer tolerance to the herbicide.
可藉由上述方法處理之植物及植物栽培品種(藉由植物生物技術方法獲得,例如遺傳工程)包括為抗昆蟲轉基因植物(即,耐受某些目標昆蟲攻擊之植物)之植物及植物栽培品種。該等植物可藉由遺傳轉變或藉由選擇含有賦予該昆蟲抗性之突變的植物來獲得。Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods described above include plants and plant cultivars that are insect-resistant genetically modified plants (i.e., plants that are resistant to attack by certain target insects) . The plants can be obtained by genetic transformation or by selecting plants containing mutations that confer resistance to the insect.
可藉由上述方法處理之植物及植物栽培品種(藉由植物生物技術方法獲得,例如遺傳工程)包括為抗病性轉基因植物(即,耐受某些目標昆蟲攻擊之植物)之植物及植物栽培品種。該等植物可藉由遺傳轉變或藉由選擇含有賦予該昆蟲抗性之突變的植物來獲得。Plants and plant cultivars that can be treated by the methods described above (obtained by plant biotechnology methods, such as genetic engineering) include plants and plant cultivation that are disease-resistant transgenic plants (i.e. plants that are resistant to attack by certain target insects) Variety. The plants can be obtained by genetic transformation or by selecting plants containing mutations that confer resistance to the insect.
可藉由上述方法處理之植物及植物栽培品種(藉由植物生物技術方法獲得,例如遺傳工程)包括耐受非生物性逆境之植物及植物栽培品種。該等植物可藉由遺傳轉變或藉由選擇含有賦予該逆境抗性之突變之植物來獲得。Plants and plant cultivars that can be treated by the methods described above (obtained by plant biotechnology methods, such as genetic engineering) include plants and plant cultivars that are resistant to abiotic stress. The plants can be obtained by genetic transformation or by selecting plants containing mutations that confer resistance to the stress.
可藉由上文所揭示之方法處理之植物及植物栽培品種(藉由植物生物技術方法獲得,例如遺傳工程)包括已顯示改變所收穫產物之數量、品質及/或儲存穩定性及/或改變所收穫產物之具體成分之性質之植物及植物栽培品種。Plants and plant cultivars (obtained by plant biotechnology methods, such as genetic engineering) that can be treated by the methods disclosed above include those that have been shown to alter the quantity, quality, and / or storage stability of harvested products and / or changes Plants and plant cultivars with specific properties of the harvested products.
可藉由上述方法處理之植物及植物栽培品種(藉由植物生物技術方法獲得,例如遺傳工程)包括具有改變之纖維特性之植物及植物栽培品種(例如棉花植物)。該等植物可藉由遺傳轉變或藉由選擇含有賦予該等改變之纖維特性之突變的植物來獲得。Plants and plant cultivars (obtained by plant biotechnology methods, such as genetic engineering) that can be treated by the methods described above include plants and plant cultivars (such as cotton plants) with altered fiber characteristics. The plants can be obtained by genetic transformation or by selecting plants that contain mutations that confer fiber characteristics to the changes.
可藉由上述方法處理之植物及植物栽培品種(藉由植物生物技術方法獲得,例如遺傳工程)包括具有改變之油組成(oil profile)特性之植物及植物栽培品種(例如油菜籽或相關芸薹屬植物)。該等植物可藉由遺傳轉變或藉由選擇含有賦予該等改變之油組成特性之突變的植物來獲得。Plants and plant cultivars (obtained by plant biotechnology methods, such as genetic engineering) that can be treated by the methods described above include plants and plant cultivars (such as rapeseed or related brassica) with altered oil profile characteristics Genus). The plants can be obtained by genetic transformation or by selecting plants that contain mutations that confers such altered oil composition.
可藉由上述方法處理之植物及植物栽培品種(藉由植物生物技術方法獲得,例如遺傳工程)包括具有改變之落粒特性之植物及植物栽培品種(例如油菜籽或相關芸薹屬植物)。該等植物可藉由遺傳轉變或藉由選擇含有賦予該等改變之落粒特性之突變的植物來獲得且包括具有延遲或減少落粒之植物(例如,油菜籽植物)。Plants and plant cultivars (obtained by plant biotechnology methods, such as genetic engineering) that can be treated by the methods described above include plants and plant cultivars (such as rapeseed or related Brassica plants) that have altered seeding characteristics. Such plants can be obtained by genetic transformation or by selecting plants that contain mutations that confer such altered seeding characteristics and include plants with delayed or reduced seeding (e.g., rapeseed plants).
可藉由上述方法處理之植物及植物栽培品種(藉由植物生物技術方法獲得,例如遺傳工程)包括具有改變之轉譯後蛋白質修飾模式之植物及植物栽培品種(例如菸草植物)。Plants and plant cultivars (obtained by plant biotechnology methods, such as genetic engineering) that can be treated by the methods described above include plants and plant cultivars (such as tobacco plants) with altered patterns of post-translational protein modification.
病原體
可根據本發明治療之真菌病害之病原體之非限制性實例包括:
由白粉病病原體引起之病害,例如布氏白粉菌屬(Blumeria
species),例如禾本科布氏白粉菌(Blumeria graminis
);叉絲單囊殼屬(Podosphaera
species),例如白叉絲單囊殼菌(Podosphaera leucotricha
);單囊殼屬(Sphaerotheca
species),例如單囊殼菌(Sphaerotheca fuliginea
);鈎絲殼屬(Uncinula
species),例如葡萄鉤絲殼菌(Uncinula necator
);
由銹病病原體引起之病害,例如膠銹菌屬(Gymnosporangium
species),例如褐色膠鏽菌(Gymnosporangium sabinae
);駝孢銹菌屬(Hemileia
species),例如咖啡駝孢銹菌(Hemileia vastatrix
);層銹菌屬(Phakopsora
species),例如豆薯層銹菌(Phakopsora pachyrhizi
)或山螞蝗層銹菌(Phakopsora meibomiae
);銹病菌屬(Puccinia
species),例如隱匿柄鏽菌(Puccinia recondita
)、禾柄鏽菌(Puccinia graminis
)或條形柄鏽菌(Puccinia striiformis
);單胞銹菌屬(Uromyces
species),例如菜豆單胞銹病菌(Uromyces appendiculatus
);
由來自卵菌之群之病原體引起之病害,例如白銹菌屬(Albugo
species),例如十字花科白銹菌(Albugo candida
);盤梗黴屬(Bremia
species),例如萵苣盤梗黴(Bremia lactucae
);霜黴屬(Peronospora
species),例如豌豆霜黴(Peronospora pisi
)或蕓苔霜黴(P. brassicae
);疫黴屬(Phytophthora
species),例如馬鈴薯晚疫黴(Phytophthora infestans
);單軸黴屬(Plasmopara
species),例如葡萄生單軸黴(Plasmopara viticola
);假單軸黴屬(Pseudoperonospora
species),例如葎草假單軸黴(Pseudoperonospora humuli
)或古巴假單軸黴(Pseudoperonospora cubensis
);腐黴屬(Pythium
species),例如終極腐黴(Pythium ultimum
);
由例如以下引起之葉斑枯病及葉枯病:鏈隔孢菌屬(Alternaria
species),例如茄鏈隔孢菌(Alternaria solani
);尾孢菌屬(Cercospora
species),例如甜菜生尾孢菌(Cercospora beticola
);枝孢菌屬(Cladiosporium
species),例如胡瓜枝孢菌(Cladiosporium cucumerinum
);旋孢腔菌屬(Cochliobolus
species),例如育旋孢腔菌(Cochliobolus sativus) (分生孢子形式:內臍蠕孢屬(Drechslera
),同義詞:長蠕孢黴屬(Helminthosporium
))或宮部氏旋孢腔菌(Cochliobolus miyabeanus
);炭疽刺盤孢菌屬(Colletotrichum
species),例如菜豆炭疽刺盤孢菌(Colletotrichum lindemuthianium
);棒狀桿孢菌屬(Corynespora
species),例如鐵刀木棒狀桿孢菌(Corynespora cassiicola
);鏽斑病菌屬(Cycloconium species),例如油橄欖鏽斑病菌(Cycloconium oleaginum);間座殼菌屬(Diaporthe
species),例如柑橘間座殼菌(Diaporthe citri
);痂囊腔菌屬(Elsinoe
species),例如柑橘痂囊腔菌(Elsinoe fawcettii
);盤長孢黴屬(Gloeosporium
species),例如悅色盤長孢黴(Gloeosporium laeticolor
);小叢殼屬(Glomerella
species),例如圍小叢殻菌(Glomerella cingulata
);球座腔菌屬(Guignardia
species),例如葡萄球座腔菌(Guignardia bidwelli
);小球腔菌屬(Leptosphaeria
species),例如斑點小球腔菌(Leptosphaeria maculans
);巨座殼屬(Magnaporthe
species),例如灰巨座殼(Magnaporthe grisea
);微座孢屬(Microdochium
species),例如雪黴微座孢(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),例如穎枯暗球腔菌(Phaeosphaeria nodorum
);核腔菌屬(Pyrenophora
species),例如圓核腔菌(Pyrenophora teres
)或偃麥草核腔菌(Pyrenophora tritici repentis
);柱隔孢菌屬(Ramularia
species),例如柱隔孢葉斑病菌(Ramularia collo-cygni
)或白斑柱隔孢菌(Ramularia areola
);喙孢屬(Rhynchosporium
species),例如黑麥喙孢(Rhynchosporium secalis
);殼針孢菌屬(Septoria
species),例如芹菜殼針孢菌(Septoria apii
)或番茄殼針孢菌(Septoria lycopersici
);殼多孢菌屬(Stagonospora
species),例如穎枯殼多孢菌(Stagonospora nodorum
);核瑚菌屬(Typhula
species),例如肉孢核瑚菌(Typhula incarnata
);黑星菌屬(Venturia
species),例如蘋果黑星菌(Venturia inaequalis
);
由例如以下引起之根莖部病害:皮殼菌屬(Corticium
species),例如禾皮殼菌(Corticium graminearum
);鐮孢菌屬(Fusarium
species),例如尖鐮孢菌(Fusarium oxysporum
);頂囊殼屬(Gaeumannomyces
species),例如禾頂囊殼(Gaeumannomyces graminis
);根腫菌屬(Plasmodiophora
species),例如蕓苔根腫菌(Plasmodiophora brassicae
);絲核菌屬(Rhizoctonia
species),例如立枯絲核菌(Rhizoctonia solani
);帚枝黴屬(Sarocladium
species),例如稻帚枝黴(Sarocladium oryzae
);小核菌屬(Sclerotium species),例如稻腐小核菌(Sclerotium oryzae
);Tapesia
屬,例如Tapesia acuformis
;根串珠黴屬(Thielaviopsis species),例如根串珠黴(Thielaviopsis basicola
);
由(例如)以下引起之肉穗花序及散穗花序病害(包括玉米穗軸):鏈隔孢菌屬,例如鏈隔孢菌屬;麴黴屬(Aspergillus
species),例如黃麴黴(Aspergillus flavus
);分枝孢子菌屬(Cladosporium
species),例如枝孢樣分枝孢子菌;麥角菌屬(Claviceps
species),例如黑麥角菌(Claviceps purpurea
);鐮孢菌屬,例如禾稈鐮孢菌(Fusarium culmorum
);赤黴菌屬(Gibberella species),例如玉蜀黍赤黴菌(Gibberella zeae
);明梭孢屬(Monographella species),例如雪腐明梭孢(Monographella nivalis);殼多孢菌屬,例如穎枯殼多孢菌;
由黑粉菌引起之病害,例如黑粉菌屬(Sphacelotheca
species),例如高粱絲黑粉菌(Sphacelotheca reiliana
);腥黑粉菌屬(Tilletia
species),例如小麥網腥黑粉菌(Tilletia caries
)或小麥矮腥黑粉菌(Tilletia controversa
);條黑粉菌屬(Urocystis
species),例如隱條黑粉菌(Urocystis occulta
);黑粉菌屬(Ustilago
species),例如麥散黑穗菌(Ustilago nuda);
由例如以下引起之果腐病:麴黴屬,例如黃麴黴;葡萄孢菌屬(Botrytis
species),例如灰色葡萄孢菌(Botrytis cinerea
);鏈核盤菌屬(Monilinia
species),例如核果鏈核盤菌(Monilinia laxa
);青黴菌屬(Penicillium
species),例如擴展青黴(Penicillium expansum
)或產紫青黴(Penicillium purpurogenum
);根黴屬(Rhizopus
species),例如匍枝根黴(Rhizopus stolonifer
);核盤菌屬(Sclerotinia
species),例如核盤菌(Sclerotinia sclerotiorum
);輪黴菌屬(Verticilium
species),例如黑白輪黴菌(Verticilium alboatrum
);
由例如以下引起之經種子及土壤傳播之腐爛及枯萎病以及幼苗病害:鏈隔孢菌屬,例如嗜甘藍鏈隔孢菌(Alternaria brassicicola
);絲囊黴屬(Aphanomyces
species),例如腐絲囊黴(Aphanomyces euteiches
);囊二孢菌屬(Ascochyta
species),例如小扁豆囊二孢菌(Ascochyta lentis
);麴黴屬,例如黃麴黴;分枝孢子菌屬,例如多主分枝孢子菌(Cladosporium herbarum
);旋孢腔菌屬,例如育旋孢腔菌(分生孢子形式:內臍蠕孢屬,雙孔孢菌屬(Bipolaris)同義詞:長蠕孢黴屬);炭疽刺盤孢菌屬,例如球炭疽刺盤孢菌(Colletotrichum coccodes
);鐮孢菌屬,例如禾稈鐮孢菌;赤黴菌屬,例如玉蜀黍赤黴菌;殼球孢屬(Macrophomina species),例如菜豆殼球孢菌(Macrophomina phaseolina);微座孢屬,例如雪黴微座孢;明梭孢屬,例如雪腐明梭孢;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(Phomopsis sojae
);疫黴屬,例如惡疫黴(Phytophthora cactorum
);核腔菌屬,例如麥類核腔菌(Pyrenophora graminea
);梨孢黴屬(Pyricularia
species),例如稻梨孢黴(Pyricularia oryzae
);腐黴屬,例如終極腐黴;絲核菌屬,例如立枯絲核菌;根黴屬,例如稻根黴(Rhizopus oryzae
);小核菌屬,例如齊整小核菌(Sclerotium rolfsii
);殼針孢菌屬,例如穎枯殼針孢菌(Septoria nodorum
);核瑚菌屬,例如肉孢核瑚菌;輪黴菌屬(Verticillium
species),例如大麗輪枝菌(Verticillium dahliae
);
由例如以下引起之癌性病害、癭及天狗巢病(witches’ broom):叢赤殼屬(Nectria
species),例如癌腫叢赤殼菌(Nectria galligena
);
由例如以下引起之枯萎病:輪黴菌屬,例如長孢輪枝菌(Verticillium longisporum
);鐮孢菌屬,例如尖孢鐮刀菌;
由例如以下引起之葉、花及果實變形: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化性病害:埃斯卡菌屬種(Esca
species),例如根黴格孢菌(Phaeomoniella chlamydospora
)、雞腿蘑絲抱菌(Phaeoacremonium aleophilum
)或地中海嗜藍孢孔菌(Fomitiporia mediterranea
);靈芝屬(Ganoderma
species),例如狹長孢靈芝(Ganoderma boninense
);
由例如以下引起之植物塊莖病害:絲核菌屬,例如立枯絲核菌;長蠕孢黴屬,例如茄長蠕孢黴(Helminthosporium solani
);
由細菌病原體引起之病害,例如黃單胞菌屬(Xanthomonas
species),例如野油菜黃單胞菌稻致病變種(Xanthomonas campestris pv. oryzae
);假單胞菌屬,例如丁香假單胞菌黃瓜致病變種(Pseudomonas syringae pv. lachrymans
);歐文氏菌屬(Erwinia
species),例如解澱粉歐文氏菌(Erwinia amylovora
);韌皮部桿菌屬(Liberibacter
species),例如韌皮部桿菌亞洲種(Liberibacter asiaticus
);木質桿菌屬(Xyella
species),例如苛養木桿菌(Xylella fastidiosa
);羅爾斯頓菌屬(Ralstonia
species),例如青枯羅爾斯頓菌(Ralstonia solanacearum
);迪基氏菌屬(Dickeya
species),例如茄迪基氏菌(Dickeya solani
);棒形桿菌屬(Clavibacter species),例如密執安棒形桿菌(Clavibacter michiganensis);鏈黴菌屬,例如瘡痂鏈黴菌(Streptomyces scabies
)。 Pathogens <br/> Non-limiting examples of pathogens of fungal diseases that can be treated according to the present invention include:
Diseases caused by powdery mildew pathogens, such as Blumeria species, such as Blumeria graminis , Podosphaera species, such as ( Podosphaera leucotricha ); Sphaerotheca species, such as Sphaerotheca fuliginea ; Uncinula species, such as Uncinula necator ;
Diseases caused by rust pathogens, such as Gymnosporangium species, such as Gymnosporangium sabinae ; Hemileia species, such as Hemileia vastatrix ; layered rust Phakopsora species, such as Phakopsora pachyrhizi or Phakopsora meibomiae ; Puccinia species, such as Puccinia recondita , Puccinia recondita Puccinia graminis or Puccinia striiformis ; Uromyces species, such as Uromyces appendiculatus ;
Diseases caused by pathogens from the group of oomycetes , such as Albugo species, such as Albugo candida ; Bremia species, such as Bremia lactucae ); Peronospora species, such as Peronospora pisi or P. brassicae ; Phytophthora species, such as Phytophthora infestans ; Uniaxial mold Plasmopara species, such as Plasmopara viticola ; Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis ; rot Geotrichum (Pythium species), for example, Pythium ultimum (Pythium ultimum);
Leaf blight and leaf blight caused by, for example: Alternaria species, such as Alternaria solani ; Cercospora species, such as Cercospora beet ( Cercospora beticola ); Cladiosporium species, such as Cladiosporium cucumerinum ; Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera , synonym: Helminthosporium ) or Cochliobolus miyabeanus ; Colletotrichum species, such as Pleurotus anthracis ( Colletotrichum lindemuthianium ); Corynespora species, such as Corynespora cassiicola ; Cycloconium species, such as Cycloconium oleaginum; mesenchyme genus (Diaporthe species), e.g. citrus seat globosum (Diaporthe citri); Elsinochrome genus (Elsinoe species), citrus scab e.g. Chamber bacteria (Elsinoe fawcettii); Gloeosporium Rhizopus (Gloeosporium species), e.g. color Yue Gloeosporium sp (Gloeosporium laeticolor); Glomerella genus (Glomerella species), for example around Glomerella bacteria (Glomerella cingulata); Ball Guignardia species, such as Guignardia bidwelli ; Leptosphaeria species, such as Leptosphaeria maculans ; Magnaporthe species, For example, Magnaporthe grisea ; Microdochium species, such as Microdochium nivale ; Mycosphaerella species, such as Mycosphaerella graminicola , groundnut Mycosphaerella arachidicola or Mycosphaerella fijiensis ; Phaeosphaeria species, such as Phaeosphaeria nodorum ; Pyrenophora species, such as round Pyrenophora teres or Pyrenophora tritici repentis ; Ramul aria species), such as Ramularia collo-cygni or Ramularia areola ; Rhynchosporium species, such as Rhynchosporium secalis ; Septoria species, such as Septoria apii or Septoria lycopersici ; Stagonospora species, such as Stagonospora nodorum ; nuclear Typhula species, such as Typhula incarnata ; Venturia species, such as Venturia inaequalis ;
Rhizome diseases caused by, for example: Corticium species, such as Corticium graminearum ; Fusarium species, such as Fusarium oxysporum ; apical capsid Gaeumannomyces species, such as Gaeumannomyces graminis ; Plasmodiophora species, such as Plasmodiophora brassicae ; Rhizoctonia species, such as Rhizoctonia Rhizoctonia solani ; Sarocladium species, such as Sarocladium oryzae ; Sclerotium species, such as Sclerotium oryzae ; Tapesia , such as Tapesia acuformis ; Thielaviopsis species, such as Thielaviopsis basicola ;
Diseases of panicles and loose spikes (including corn cobs) caused by, for example: Alternaria, such as Alternaria, and Aspergillus species, such as Aspergillus flavus ); Cladosporium species, such as Cladosporium species; Claviceps species, such as Claviceps purpurea ; Fusarium, such as Fusarium graminearum Fusarium culmorum ; Gibberella species, such as Gibberella zeae ; Monographella species, such as Monographella nivalis; for example Fusarium solani
Diseases caused by powdery mildew, such as Sphacelotheca species, such as Sphacelotheca reiliana ; Tilletia species, such as Tilletia caries Or wheat Tilletia controversa ; Urocystis species, such as Urocystis occulta ; Ustilago species, such as Ustilago nuda);
Fruit rot caused by, for example: Pythium spp., Such as P. flavus; Botrytis species, such as Botrytis cinerea ; Monilinia species, such as stone fruit chain Sclerotinia sclerotiorum ( Monilinia laxa ); Penicillium species, such as Penicillium expansum or Penicillium purpurogenum ; Rhizopus species, such as Rhizopus stolonifer ; Sclerotinia species, such as Sclerotinia sclerotiorum ; Verticilium species, such as Verticilium alboatrum ;
Seed and soil-borne rot and fusarium and seedling diseases caused by, for example: Alternaria, such as Alternaria brassicicola ; Aphanomyces species, such as silk rot Aphanomyces euteiches ; Ascochyta species, such as Ascochyta lentis ; Pythium, such as Pseudomonas spp .; Mycosporium , such as Mycosporium multiprime ( Cladosporium herbarum ); Spirospira , such as conidium (Conidia form: Helminthosporium, Bipolaris synonym: Helminthosporium); Anthracnose anthracis Genus , such as Colletotrichum coccodes ; Fusarium, such as Fusarium graminearum; Gibberella, such as Gibberella maize; Macrophomina species, such as Coccodium legume Macrophomina phaseolina; Microsporum, such as Microsporum spp .; Clostridium , such as Clostridium snow rot; Penicillium, such as Penicillium sp Phyllosticta ma lingam); genus Phomopsis (Phomopsis species), e.g. soybean Phomopsis (Phomopsis sojae); Phytophthora, for example Phytophthora cactorum (Phytophthora cactorum); Pyrenophora species, such as Pyrenophora bacteria ( Pyrenophora graminea ); Pyricularia species, such as Pyricularia oryzae ; Pythium, such as Ultimate Pythium; Rhizoctonia, such as Rhizoctonia solani, Rhizopus, such as Rhizopus oryzae ; Rhizopus spp., Such as Sclerotium rolfsii ; Schizophyllum spp., Such as Septoria nodorum ; Rhizopus spp., Such as Sarcocystis spp. Bacteria; Verticillium species, such as Verticillium dahliae ;
Cancerous diseases, slugs, and witches' broom caused by, for example: Nectria species, such as Nectria galligena ;
Fusarium caused by, for example: the genus Rotulina , such as Verticillium longisporum ; the genus Fusarium, such as Fusarium oxysporum;
Deformation of leaves, flowers and fruits caused by, for example: Exobasidium species, such as Exobasidium vexans ; Taphrina species, such as Taphrina deformans ;
Degenerative diseases of woody plants caused by, for example: Esca species such as Phaeomoniella chlamydospora , Phaeoacremonium aleophilum or Mediterranean cyanopore Fomitiporia mediterranea ; Ganoderma species, such as Ganoderma boninense ;
Tuber diseases of plants caused by, for example: Rhizoctonia spp., Such as Rhizoctonia solani , and Helminthosporium solani , such as Helminthosporium solani ;
Diseases caused by bacterial pathogens, such as Xanthomonas species, such as Xanthomonas campestris pv. Oryzae ; Pseudomonas, such as P. syringae cucumber Pathogenic species ( Pseudomonas syringae pv. Lachrymans ); Erwinia species, such as Erwinia amylovora ; Liberibacter species, such as Liberibacter asiaticus ; woody Xyella species, such as Xylella fastidiosa ; Ralstonia species, such as Ralstonia solanacearum ; Dickeya species, For example, Dickeya solani ; Clavibacter species, such as Clavibacter michiganensis; Streptomyces, such as Streptomyces scabies .
大豆之病害:
由例如以下引起之葉、莖、莢及種子上之真菌病害:鏈隔孢葉斑病(Alternaria spec. atrans tenuissima
)、炭疽病(Anthracnose
) (黑棉狀似膠黏炭疽刺盤孢菌平頭變種(Colletotrichum gloeosporioides dematium var. truncatum
))、褐斑病(大豆殼針孢菌(Septoria glycines
))、尾孢菌葉斑病及葉枯病(菊池氏尾孢菌(Cercospora kikuchii
))、笄黴菌(choanephora
)葉枯病(三孢漏斗笄黴(Choanephora infundibulifera trispora
)(同義詞))、疏毛核菌黴(dactuliophora
)葉斑病(大豆疏毛核菌黴(Dactuliophora glycines
))、露菌病(東北霜黴(Peronospora manshurica
))、內臍蠕孢屬
疫病(大豆內臍蠕孢(Drechslera glycini
))、斑點病(frogeye leaf spot) (大豆尾孢菌(Cercospora sojina
))、小光腔菌屬(leptosphaerulina
)葉斑病(三葉草小光腔菌(Leptosphaerulina trifolii
))、葉點黴屬(phyllosticta
)葉斑病(大豆生葉點黴(Phyllosticta sojaecola
))、莢莖枯萎病(大豆擬莖點黴)、白粉病(擴散叉絲殼(Microsphaera diffusa
))、棘殼孢黴(pyrenochaeta
)葉斑病(大豆棘殼孢黴(Pyrenochaeta glycines
))、絲核菌地上部分、葉及網枯病(rhizoctonia aerial, foliage, and web blight) (立枯絲核菌)、銹病(豆薯層銹菌、山螞蝗層銹菌)、瘡痂病(大豆痂圓孢菌(Sphaceloma glycines
))、匍柄黴屬(stemphylium
)葉枯病(匐柄黴(Stemphylium botryosum
))、猝死症候群(桿狀鐮孢菌(Fusarium virguliforme
))、靶斑病(target spot)(鐵刀木棒狀桿孢菌)。
由例如以下引起之根及莖基上之真菌病害:黑根腐病(black root rot)(野百合麗赤殼菌(Calonectria crotalariae
))、炭腐病(菜豆殼球孢菌)、鐮孢菌枯萎病或枯萎、根腐病及莢及莖腐病(尖鐮孢菌、直喙鐮孢菌(Fusarium orthoceras
)、半裸鐮孢菌(Fusarium semitectum
)、木賊鐮孢菌(Fusarium equiseti
))、細圓盤黴(mycoleptodiscus)根腐病(陸生細圓盤黴(Mycoleptodiscus terrestris
))、新赤殼屬(neocosmospora) (侵管新赤殼菌(Neocosmospora vasinfecta
))、莢及莖枯病(菜豆間座殼菌(Diaporthe phaseolorum
))、莖潰瘍病(菜豆間座殼菌北方大豆變種(Diaporthe phaseolorum var. caulivora
))、疫黴腐病(大雄疫黴(Phytophthora megasperma
))、莖褐腐病(大豆瓶黴菌(Phialophora gregata
))、腐敗病(pythium rot) (瓜果腐黴(Pythium aphanidermatum
)、畸雌腐黴(Pythium irregulare
)、
德巴利腐黴(Pythium debaryanum
)、
結群腐黴(Pythium myriotylum
)、
終極腐黴)、絲核菌根腐病、莖腐病及猝倒病(立枯絲核菌)、核盤菌莖腐病(核盤菌)、核盤菌屬南方疫病(sclerotinia southern blight)(齊整核盤菌(Sclerotinia rolfsii
))、根串珠黴根腐病(根串珠黴)。Diseases of soybean:
Fungal diseases on leaves, stems, pods, and seeds caused by, for example: Alternaria spec. Atrans tenuissima , Anthracnose (black cotton-like gummy anthracnose Discrete flathead variants) ( Colletotrichum gloeosporioides dematium var. Truncatum )), brown spot disease ( Septoria glycines ), Cercospora leaf spot and leaf blight ( Cercospora kikuchii ) choanephora ) leaf blight ( Choanephora infundibulifera trispora (synonym)), dactuliophora leaf spot ( Dactuliophora glycines ), dermatophytosis (Northeast China) downy mildew (Peronospora manshurica)), umbilical Helminthosporium blight (Helminthosporium soybean umbilical (Drechslera glycini)), scab (frogeye leaf spot) (soybean Cercospora (Cercospora sojina)), little light chamber genus ( Leptosphaerulina) leaf spot (bacteria clover little light chamber (Leptosphaerulina trifolii)), the genus Phyllosticta (Phyllosticta) leaf spot (Phyllosticta raw soybean (Phyllosticta sojaecola)), pod stem blight (Phomopsis soybean ), Powdery mildew (diffusion cross fuliginea (Microsphaera diffusa)), Pyrenochaeta sp (Pyrenochaeta) leaf spot (Pyrenochaeta sp soybean (Pyrenochaeta glycines)), Rhizoctonia aerial parts, and leaf blight network (Rhizoctonia aerial, foliage, and web blight) (Rhizotonia solani), rust (Puccinia striiformis, Puccinia striiformis), scab ( Sphaceloma glycines ), Phytophthora ( stemphylium ) leaf blight ( Stemphylium botryosum ), Sudden Death Syndrome ( Fusarium virguliforme ), target spot ( Coronadium lanceolata ).
Fungal diseases on roots and stems caused by, for example: black root rot ( Calonectria crotalariae ), charcoal rot (Phaseolus coccine ), Fusarium Fusarium or Fusarium, Root Rot and Pod and Stem Rot (Fusarium oxysporum, Fusarium orthoceras , Fusarium semitectum , Fusarium equiseti ), fine Mycoleptodiscus root rot ( Mycoleptodiscus terrestris ), neocosmospora ( Neocosmospora vasinfecta ), pods and stem blight (Phaseolus vulgaris) Diaporthe phaseolorum ), stem ulcer ( diaporthe phaseolorum var. Caulivora ), Phytophthora rot ( Phytophthora megasperma ), stem brown rot (soybean bottle Phialophora gregata ), pythium rot (Pythium aphanidermatum ), Pythium irregulare , Pythium debaryanum , Pythium myriotylum , Ultimate Pythium), Rhizoctonia sclerotiorum rot, stem rot and cataplexy (Rhizobium solani), Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia sclerotinia southern blight) ( Sclerotinia rolfsii )).
黴菌毒素
另外,式(I)化合物及包含其等之組合物可減少所收穫物質及自其製備之食物及飼料中之黴菌毒素含量。黴菌毒素特定包括(但不限於)以下:脫氧雪腐鐮刀菌烯醇(deoxynivalenol) (DON)、雪腐鐮刀菌烯醇(nivalenol)、15-Ac-DON、3-Ac-DON、T2-及HT2-毒素、伏馬毒素(fumonisins)、玉米赤黴烯酮(zearalenon)、串珠鐮刀菌素(moniliformin)、鐮菌素(fusarin)、二乙醯藨草鐮刀菌烯醇(diacetoxyscirpenol) (DAS)、白僵菌素(beauvericin)、恩鐮孢菌素(enniatin)、層出鐮孢菌素(fusaroproliferin)、鍵刀菌烯醇(fusarenol)、赭麴毒素(ochratoxins)、棒麴黴素(patulin)、麥角生物鹼(ergot alkaloids)及黃麴毒素(aflatoxins),該等可由例如以下真菌產生:鐮孢菌屬,例如銳形鐮孢菌(F. acuminatum
)、亞洲鐮孢菌(F. asiaticum
)、燕麥鐮孢菌(F. avenaceum
)、魯克威爾鐮孢菌(F. crookwellense
)、禾稈鐮孢菌(F. culmorum
)、禾穀鐮孢菌(F. graminearum
) (玉蜀黍赤黴菌)、木賊鐮孢菌、藤倉鐮孢菌(F. fujikoroi
)、香蕉鐮孢菌(F. musarum
)、尖鐮孢菌、層出鐮孢菌(F. proliferatum
)、早熟禾鐮孢菌(F. poae
)、假禾穀鐮孢菌(F. pseudograminearum
)、接骨木鐮孢菌(F. sambucinum
)、藨草鐮孢菌(F. scirpi
)、半裸鐮孢菌、茄鐮孢菌(F. solani
)、擬枝孢鐮孢菌(F. sporotrichoides
)、F. langsethiae
、亞黏團鐮孢菌(F. subglutinans
)、三線鐮孢菌(F. tricinctum
)、輪枝鐮孢菌(F. verticillioides
)等,以及麴黴屬,例如黃麴黴、寄生麯黴(A. parasiticus
)、紅綬麯黴(A. nomius
)、赭麯黴(A. ochraceus
)、棒麯黴(A. clavatus
)、土麴黴(A. terreus
)、雜色麯黴(A. versicolor
);青黴菌屬,例如疣梗青黴(P. verrucosum
)、鮮綠青黴(P. viridicatum
)、(P. citrinum
)、擴展青黴、棒形青黴(P. claviforme
)、婁地青黴(P. roqueforti
);麥角菌屬,例如黑麥角菌、紡錘麥角菌(C. fusiformis
)、雀稗麥角菌(C. paspali
)、非洲麥角菌(C. africana
)、葡萄穗黴孢菌屬(Stachybotrys
spec.)及其他。 Mycotoxins <br/> In addition, compounds of formula (I) and compositions containing them can reduce mycotoxins in harvested materials and foods and feeds prepared therefrom. Mycotoxins specifically include (but are not limited to) the following: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2-toxin, fumonisins, zearalenon, moniliformin, fusarin, diacetoxyscirpenol (DAS) , Beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins, patulin ), ergot alkaloids (ergot alkaloids) and aflatoxin (Aflatoxins), for example, by such fungi: Fusarium, for example Fusarium sharp shape (F. acuminatum), Asian Fusarium (F. asiaticum), oat Fusarium (F. avenaceum) bacteria, Luke Will Fusarium (F. crookwellense), straw Fusarium (F. culmorum) fungus, Fusarium graminearum (F. graminearum) (Gibberella Fungus ), Fusarium equisetum , F. fujikoroi , F. musarum , Fusarium oxysporum, Fusarium laminaria ( F. proliferatum ), F. poae , F. pseudograminearum , F. sambucinum , F. scirpi , Fusarium semitectum, Fusarium solani (F. solani), Fusarium intended Cladosporium (F. sporotrichoides), F. langsethiae, sticky alkylene group Fusarium (F. subglutinans), Fusarium three lines (F tricinctum ), F. verticillioides , etc., as well as genus P. spp . , such as P. flavus , A. parasiticus , A. nomius , A. ochraceus , A. clavatus , A. terreus , A. versicolor ; Penicillium, such as P. verrucosum , P. viridicatum , ( P. citrinum ), Penicillium extendedum, P. claviforme , P. roqueforti ; ergot genus, such as ergot ergot, C. fusiformis , cypress C. paspali , C. africana , Stachybotrys spec. And others.
材料保護
式(I)化合物及包含其等之組合物亦可用於保護材料、尤其用於保護工業材料免於受到植物病原性真菌之侵害及破壞。 Material protection <br/> The compounds of formula (I) and compositions containing them can also be used to protect materials, especially industrial materials from phytopathogenic fungi.
另外,式(I)化合物及包含其等之組合物可單獨或與其他活性成分組合用作抗結垢組合物。In addition, the compound of formula (I) and a composition containing the same may be used as an anti-scaling composition alone or in combination with other active ingredients.
工業材料 在本上下文中應理解為意指經製備用於工業之無生命材料。舉例而言,欲保護免於微生物蝕變或破壞之工業材料可為黏結劑、黏合劑、紙、壁紙及板/紙板、紡織品、地毯、皮革、木材、纖維及紙巾、油漆及塑膠物品、冷卻潤滑劑及可感染或被微生物破壞之其他材料。可因微生物繁殖而受損之生產工廠及建築物之部分(例如冷卻水環路、冷卻及加熱系統及通風及空氣調節單元)亦可在欲保護材料之範圍內提及。本發明範圍內之工業材料較佳包括黏結劑、上漿劑、紙及卡片、皮革、木材、油漆、冷卻潤滑劑及傳熱液,更佳木材。 Industrial materials are understood in this context to mean inanimate materials prepared for industrial use. For example, industrial materials to be protected from microbial alteration or destruction can be adhesives, adhesives, paper, wallpaper and board / cardboard, textiles, carpets, leather, wood, fiber and paper towels, paint and plastic items, cooling Lubricants and other materials that can be infected or destroyed by microorganisms. Parts of production plants and buildings (such as cooling water loops, cooling and heating systems, and ventilation and air-conditioning units) that can be damaged by the growth of microorganisms can also be mentioned within the scope of the material to be protected. Industrial materials within the scope of the present invention preferably include binders, sizing agents, paper and cards, leather, wood, paint, cooling lubricants, and heat transfer fluids, and more preferably wood.
式(I)化合物及包含其等之組合物可預防不良效應,例如腐敗、腐爛、變色、脫色或形成黴菌。Compounds of formula (I) and compositions containing them prevent adverse effects such as spoilage, decay, discoloration, discoloration or mold formation.
在處理木材之情形中,式(I)化合物及包含其等之組合物可用於抵抗易於在木料上或內部生長之真菌病害。In the case of treating wood, the compounds of formula (I) and compositions comprising them can be used to combat fungal diseases that tend to grow on or in the wood.
木料意指所有類型之木材種類及意欲用於建築之此木材的所有類型加工產品,例如實木、高密度木材、層壓木材及膠合板。另外,式(I)化合物及包含其等之組合物可用於保護與鹹水或半鹹水接觸之物體(尤其船體、篩、網、建築物、繫泊設備及信號傳導系統)免於結垢。Timber means all types of wood species and all types of processed products of this wood intended for construction, such as solid wood, high density wood, laminated wood and plywood. In addition, the compounds of formula (I) and compositions containing them can be used to protect objects (especially hulls, screens, nets, buildings, moorings, and signal transmission systems) in contact with saline or brackish water from scaling.
式(I)化合物及包含其等之組合物亦可用於保護儲存貨物。儲存貨物應理解為意指為天然來源且期望長期保護之植物或動物來源之天然產物或其經加工產物。植物來源之儲存貨物(例如植物或植物部分,例如莖、葉、塊莖、種子、果實、穀粒)可在新鮮收穫或藉由(預)乾燥、潤濕、粉碎、碾磨、壓榨或烘烤處理之後進行保護。儲存貨物亦包括未加工之木料(例如建築用木材、電線桿及障壁)或呈成品之形式(例如家具)。動物來源之儲存貨物係(例如)獸皮、皮革、毛皮及毛髮。式(I)化合物及包含其等之組合物可防止不良效應,例如腐敗、腐爛、變色、脫色或形成黴菌。Compounds of formula (I) and compositions containing them may also be used to protect storage cargo. Storage goods should be understood to mean natural products of plant or animal origin, or processed products thereof, of natural origin and long-term protection is desired. Plant-derived storage goods (e.g. plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains) can be harvested fresh or by (pre-) drying, wetting, crushing, milling, pressing or baking Protect after processing. Stored goods also include unprocessed wood (such as construction timber, power poles and barriers) or in the form of finished products (such as furniture). Storage goods of animal origin are, for example, animal skins, leather, fur, and hair. Compounds of formula (I) and compositions containing them prevent adverse effects such as decay, decay, discoloration, discoloration or mold formation.
能夠降解或改變工業材料之微生物包括例如細菌、真菌、酵母、藻類及黏液生物體。式(I)化合物及包含其等之組合物較佳對真菌、尤其黴菌、使木材褪色及破壞木材之真菌(子囊菌綱、擔子菌綱、不完全菌綱及接合菌綱)及對黏液生物體及藻類起作用。實例包括以下屬之微生物:鏈隔孢菌屬,例如極細鏈隔孢菌(Alternaria tenuis );麴黴屬,例如黑麯黴;毛殼菌屬(Chaetomium ),例如球毛殼菌(Chaetomium globosum );孢革菌屬(Coniophora ),例如粉孢革菌(Coniophora puetana );香菇屬(Lentinus ),例如虎皮香菇(Lentinus tigrinus );青黴菌屬,例如灰綠青黴菌(Penicillium glaucum );多孔菌屬(Polyporus ),例如變色多孔菌(Polyporus versicolor );短梗黴屬(Aureobasidium ),例如出芽短梗黴;核莖點黴屬(Sclerophoma ),例如喜松核莖點黴(Sclerophoma pityophila );木黴菌屬,例如綠木黴菌(Trichoderma viride );長喙殼菌屬(Ophiostoma spp. )、長喙黴屬(Ceratocystis spp. )、腐質黴屬屬(Humicola spp. )、彼得殼屬(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. )、鈣皮菌屬(Serpula spp. )及乾酪菌屬(Tyromyces spp. )、分枝孢子菌屬、擬青黴屬(Paecilomyce s spp. )、毛黴屬(Mucor spp. );埃希氏菌屬(Escherichia ),例如大腸桿菌;假單胞菌屬,例如綠膿桿菌;葡萄球菌屬(Staphylococcus ),例如金黃色葡萄球菌(Staphylococcus aureus );念珠菌屬(Candida spp .)及酵母屬(Saccharomyces spp .),例如釀酒酵母(Saccharomyces cerevisae )。Microorganisms capable of degrading or altering industrial materials include, for example, bacteria, fungi, yeast, algae, and slime organisms. Compounds of formula (I) and compositions containing them are preferred against fungi, especially molds, fungi that discolor and destroy wood (Ascomycetes, Basidiomycetes, Incomplete Mycetes, and Zygomycetes) and against myxoid Body and algae work. Examples include microorganisms of the genus Streptomyces, for example, Streptomyces extremely fine (Alternaria tenuis ); Pythium, such as Aspergillus niger; Chaetomium (Chaetomium ), Such asChaetomium globosum ); Sporothrix (Coniophora ), Such as DermatospiraConiophora puetana ); LentinusLentinus ), Such as Tiger Skin Mushroom (Lentinus tigrinus ); Penicillium, such as Penicillium gray-green (Penicillium glaucum ); PolyporusPolyporus ), For examplePolyporus versicolor );Aureobasidium ), Such as S. budding; Phytophthora spp.Sclerophoma ), Such as P. spp.Sclerophoma pityophila ); Trichoderma, such as Trichoderma green (Trichoderma viride );Ophiostoma spp. )Ceratocystis spp. ), Humicola (Humicola spp. ), Peter Shell (Petriella spp. TrichodermaTrichurus spp. )Coriolus spp. ), MyxoplasmaGloeophyllum spp. ), PleurotusPleurotus spp. ), PorconiaPoria spp. ), CalderiumSerpula spp. ) And Caseus (Tyromyces spp. ), Mycospora, Paecilomyces (Paecilomyce s spp. MucorMucor spp. ); Escherichia (Escherichia ), Such as E. coli; Pseudomonas, such as Pseudomonas aeruginosa; Staphylococcus (Staphylococcus ), Such as Staphylococcus aureus (Staphylococcus aureus ); CandidaCandida spp .) And Saccharomyces (Saccharomyces spp .), Such as Saccharomyces cerevisiae (Saccharomyces cerevisae ).
種子處理
式(I)化合物及包含其等之組合物亦可用於保護種子免於不希望微生物侵害,例如植物病原微生物,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、催芽的種子、預萌芽種子及顯現出根及葉之種子。 Seed treatment <br/> Compounds of formula (I) and compositions containing them can also be used to protect seeds from unwanted microorganisms, such as phytopathogenic microorganisms, such as phytopathogenic fungi or phytopathogenic oomycetes. As used herein, the term seed includes dormant seeds, germinated seeds, pre-germinated seeds, and seeds that exhibit roots and leaves.
因此,本發明亦係關於保護種子免於不希望微生物侵害之方法,其包含用式(I)化合物或組合物處理種子之步驟。Therefore, the invention also relates to a method for protecting seeds from unwanted microorganisms, which comprises the step of treating the seeds with a compound or composition of formula (I).
種子用式(I)化合物或組合物進行處理保護種子免於植物病原微生物侵害,而且保護萌芽種子、出土幼苗及自經處理種子萌發之植物。因此,本發明亦係關於保護種子、萌芽種子及出土幼苗之方法。Seed treatment with a compound or composition of formula (I) protects the seed from plant pathogenic microorganisms, and protects germinating seeds, unearthed seedlings, and plants germinated from the treated seeds. Therefore, the present invention also relates to a method for protecting seeds, germinating seeds and unearthed seedlings.
種子處理可在播種之前、播種時及播種之後不久實施。Seed treatment can be performed before, during, and shortly after sowing.
當在播種之前實施種子處理(例如所謂的拌種施用)時,種子處理可如下實施:可將種子與期望量之式(I)化合物或組合物一起放置於混合器中,將種子及式(I)化合物或組合物混合,直至達成種子上之均勻分佈為止。若適當,然後可將種子乾燥。When seed treatment (for example, so-called seed dressing application) is performed before sowing, seed treatment can be performed as follows: The seed can be placed in a mixer with a desired amount of a compound or composition of formula (I), and the seed and formula ( I) Compounds or compositions are mixed until a uniform distribution on the seeds is achieved. If appropriate, the seeds can then be dried.
本發明亦係關於經式(I)化合物或包含其等之組合物塗佈之種子。The invention also relates to seeds coated with a compound of formula (I) or a composition comprising them.
較佳地,種子係在其足夠穩定之狀態下處理,以使得在處理過程中不會發生損害。一般而言,種子可以在收穫與播種後不久之間之任何時間進行處理。慣常使用已自植物分離且沒有穗軸、殼、桿、外皮、毛或果肉之種子。舉例而言,可使用已經收穫、清洗並乾燥至水分含量小於15重量%之種子。或者,亦可使用例如在乾燥後已經水處理且然後再次乾燥之種子、或剛剛催芽之種子、或儲存於催芽條件中之種子或預萌芽種子、或播種於育苗盤、膠帶或紙上之種子。Preferably, the seeds are treated in a state where they are sufficiently stable so that no damage occurs during the treatment. Generally, seeds can be treated at any time between harvest and shortly after sowing. It is customary to use seeds that have been separated from the plant and have no cobs, husks, stalks, rinds, hairs or pulp. For example, seeds that have been harvested, washed and dried to a moisture content of less than 15% by weight can be used. Alternatively, for example, seeds which have been water-treated after drying and then dried again, or seeds that have just been germinated, or seeds stored in germination conditions or pre-germinated seeds, or seeds that are sown on seedling trays, tapes, or paper.
施用至種子之式(I)化合物或包含其等之組合物之量通常使得種子之萌芽不會受損或所得植物不會受到損害。特定地,在式(I)化合物在某些施用率下將展現植物毒性效應之情形中必須確保這一點。在確定施加至種子之式(I)化合物之量時應慮及轉基因植物之固有表型,以利用最小量之所用化合物達成最佳種子及萌發植物保護。The amount of the compound of formula (I) or a composition comprising the same applied to the seed is generally such that the germination of the seed is not damaged or the resulting plant is not damaged. In particular, this must be ensured in cases where compounds of formula (I) will exhibit phytotoxic effects at certain application rates. In determining the amount of the compound of formula (I) to be applied to the seed, the inherent phenotype of the transgenic plant should be taken into account to achieve the best seed and germinated plant protection with the smallest amount of the compound used.
式(I)化合物可如此直接施用至種子,即,不需要使用任何其他組分且不需要稀釋。而且,包含其等之組合物亦可施用至種子。The compound of formula (I) can be applied directly to the seed in such a way that no other components need to be used and no dilution is required. Moreover, compositions containing them can also be applied to seeds.
式(I)化合物及包含其等之組合物適於保護任何植物品種之種子。較佳種子係以下之種子:穀類(例如,小麥、大麥、黑麥、粟、黑小麥及燕麥)、油菜籽、玉蜀黍、玉米、大豆、稻穀、馬鈴薯、向日葵、豆類、咖啡、豌豆、甜菜(例如甜菜及飼用甜菾菜)、花生、蔬菜(例如,番茄、胡瓜、洋蔥及萵苣)、草坪及觀賞植物。更佳者係小麥、大豆、油菜籽、玉蜀黍及稻穀之種子。The compounds of formula (I) and compositions comprising them are suitable for protecting the seeds of any plant variety. Preferred seeds are the following: cereals (e.g., wheat, barley, rye, millet, triticale, and oats), rapeseed, maize, corn, soybeans, rice, potatoes, sunflower, beans, coffee, peas, beets ( Examples include sugar beet and fodder for food), peanuts, vegetables (for example, tomatoes, courgettes, onions, and lettuce), lawns, and ornamental plants. More preferred are seeds of wheat, soybeans, rapeseed, maize and rice.
式(I)化合物及包含其等之組合物可用於處理轉基因種子、特定而言能夠表現對抗害蟲、除草劑損害或非生物性逆境之多肽或蛋白質之植物種子,由此增加保護效應。能夠表現對抗害蟲、除草劑損害或非生物性逆境之多肽或蛋白質之植物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。轉基因種子中之該等異源基因可來源於(例如)物種芽孢桿菌屬(Bacillus )、根瘤菌屬、假單胞菌屬、沙雷氏菌屬(Serratia )、木黴菌屬、棒形桿菌屬、球囊黴屬或黏帚黴屬(Gliocladium )之微生物。該等異源基因較佳來源於芽孢桿菌屬,在此情形中基因產物有效對抗歐洲玉米螟及/或西方玉米根蟲。特別較佳地,異源基因來源於蘇雲金芽孢桿菌。Compounds of formula (I) and compositions comprising them can be used to treat genetically modified seeds, particularly plant seeds capable of expressing polypeptides or proteins against pests, herbicide damage or abiotic stress, thereby increasing the protective effect. Plant seeds capable of expressing a polypeptide or protein that is resistant to pests, herbicide damage, or abiotic stress may contain at least one heterologous gene that allows expression of the polypeptide or protein. The transgenic seed may be derived from such a heterologous gene (e.g.) species of Bacillus (Bacillus), Rhizobium, Pseudomonas, Serratia (SERRATIA), Trichoderma, genus rod , Microorganisms of the genus Glomus or Gliocladium . The heterologous genes are preferably derived from Bacillus, in which case the gene product is effective against European corn borer and / or western corn rootworm. Particularly preferably, the heterologous gene is derived from Bacillus thuringiensis.
施用
式(I)化合物可如此或例如呈以下形式施用:即用型溶液、乳液、水或油基懸浮液、粉末、可濕潤粉末、糊劑、可溶粉末、粉塵、可溶性顆粒、用於撒播之顆粒、懸乳劑濃縮物、用式(I)化合物浸漬之天然產物、用式(I)化合物浸漬之合成物質、肥料或於聚合物質中之微膠囊。 Application <br/> The compound of formula (I) can be applied as such or, for example, in the form of ready-to-use solutions, emulsions, water or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble particles , Granules for spreading, suspoemulsion concentrates, natural products impregnated with compounds of formula (I), synthetic substances impregnated with compounds of formula (I), fertilizers or microcapsules in polymeric substances.
施用係以慣用方式(例如)藉由灌溉、噴灑、霧化、撒播、撒粉、起泡沫、鋪展及諸如此類完成。亦可能藉由超低體積法、經由滴灌系統或浸液施用使式(I)化合物展開,以將其沿溝(in-furrow)施用或將其注射於土壤、莖或桿。進一步可藉助傷口密封、塗料或其他傷口敷料施用式(I)化合物。Application is done in a customary manner, for example, by irrigation, spraying, atomizing, scattering, dusting, foaming, spreading, and the like. It is also possible to unfold the compound of formula (I) by ultra-low volume method, via a drip irrigation system or immersion application, to apply it in-furrow or to inject it into soil, stem or rod. Compounds of formula (I) can further be applied by means of wound seals, coatings or other wound dressings.
施用至植物、植物部分、果實、種子或土壤之式(I)化合物之有效且植物相容量將取決於各種因素,例如所採用之化合物/組合物、處理之對象(植物、植物部分、果實、種子或土壤)、處理之類型(撒粉、噴灑、拌種)、處理之目的(治癒性及保護性)、微生物之類型、微生物之發育階段、微生物之敏感性、作物生長階段及環境條件。The effectiveness of the compounds of formula (I) applied to plants, plant parts, fruits, seeds or soil and the plant phase capacity will depend on various factors, such as the compound / composition used, the object to be treated (plant, plant part, fruit, (Seed or soil), type of treatment (dusting, spraying, seed dressing), purpose of treatment (curative and protective), type of microorganism, development stage of microorganism, sensitivity of microorganism, growth stage of crop and environmental conditions.
當式(I)化合物用作殺真菌劑時,施用率可端視施用類型在相對較寬範圍內變化。對於植物部分(例如葉)之處理,施用率可在0.1至10 000 g/ha、較佳10至1000 g/ha、更佳50至300 g/ha之範圍內(在藉由灌溉或滴液施用之情形中,甚至可降低施用率,尤其當施用惰性物質(例如,岩棉或珍珠岩)時)。對於種子處理,施用率可在0.1至200 g/100 kg種子、較佳1至150 g/100 kg種子、更佳2.5至25 g/100 kg種子、甚至更佳2.5至12.5 g/100 kg種子之範圍內。對於土壤處理,施用率可在0.1至10 000 g/ha、較佳1至5000 g/ha之範圍內。When a compound of formula (I) is used as a fungicide, the application rate can be varied within a relatively wide range depending on the type of application. For the treatment of plant parts (such as leaves), the application rate can be in the range of 0.1 to 10 000 g / ha, preferably 10 to 1000 g / ha, more preferably 50 to 300 g / ha (in the case of irrigation or dripping) In the case of application, the application rate can even be reduced, especially when inert substances (e.g. rock wool or perlite) are applied). For seed treatment, the application rate can be from 0.1 to 200 g / 100 kg seeds, preferably from 1 to 150 g / 100 kg seeds, more preferably from 2.5 to 25 g / 100 kg seeds, and even more preferably from 2.5 to 12.5 g / 100 kg seeds Within range. For soil treatment, the application rate may be in the range of 0.1 to 10 000 g / ha, preferably 1 to 5000 g / ha.
該等施用率僅係實例且並不意欲限制本發明之範圍。These application rates are examples only and are not intended to limit the scope of the invention.
根據以下實例可以進一步理解本教示之各態樣,該等實例不應解釋為以任何方式限制本教示之範圍。The various aspects of the teaching can be further understood from the following examples, which should not be construed as limiting the scope of the teaching in any way.
實例
表1以非限制性方式說明本發明式(I)化合物之實例:
本文下文表1中所提及之式(I)化合物係根據本文下文結合具體實例以及本文所揭示製程之一般描述之詳述程序製備。 Examples <br/> Table 1 illustrates, in a non-limiting manner, examples of compounds of formula (I) according to the invention:
The compounds of formula (I) mentioned in Table 1 below are prepared according to the detailed procedures described below in conjunction with specific examples and the general description of the processes disclosed herein.
在表1中,除非另有規定,否則M+H (ApcI+)意指分子離子峰加1 a.m.u. (原子質量單位),如在質譜中經由正大氣壓力化學電離所觀測。In Table 1, unless otherwise specified, M + H (ApcI +) means the molecular ion peak plus 1 a.m.u. (atomic mass unit), as observed in a mass spectrum via positive atmospheric pressure chemical ionization.
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)在反相管柱(C 18)上使用下述方法測定:
溫度:40℃;流動相:0.1%甲酸水溶液及乙腈;線性梯度自10%乙腈至95%乙腈;
使用具有已知logP值之非具支鏈烷-2-酮(包含3至16個碳原子)來進行校準(使用兩個連續烷酮之間之線性內插藉由滯留時間來確定logP值)。使用200 nm至400 nm之UV光譜及層析信號之峰值來測定λ-max值。In Table 1, logP values were determined by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18) according to EEC Directive 79/831 Annex V.A8 using the following method:
Temperature: 40 ℃; mobile phase: 0.1% formic acid aqueous solution and acetonitrile; linear gradient from 10% acetonitrile to 95% acetonitrile;
Calibration using non-branched alkan-2-ones (containing 3 to 16 carbon atoms) with a known logP value (use linear interpolation between two consecutive alkanones to determine logP value by residence time) . The UV spectrum of 200 nm to 400 nm and the peak of the chromatographic signal were used to determine the λ-max value.
在表1中,「#」表示B環至L基團之連接點且「*」表示B環至CH2 SiR1 R2 R3 基團之連接點。In Table 1, "#" indicates the point of attachment of the B ring to the L group and "*" indicates the point of attachment of the B ring to the CH 2 SiR 1 R 2 R 3 group.
表 1
:
注意(1)
:在中性條件下 Table 1 :
表2提供表1之所選數量之化合物的NMR數據(1 H)。Table 2 provides NMR data ( 1 H) for the selected number of compounds in Table 1.
所選實例之1 H-NMR數據係以1 H-NMR峰列表形式闡明。對於每一信號峰,列示δ值(以ppm計)及信號強度(在圓括號內)。The 1 H-NMR data of the selected examples are clarified as a list of 1 H-NMR peaks. For each signal peak, the delta value (in ppm) and signal intensity (in parentheses) are listed.
尖銳信號之強度與該等信號在NMR光譜之印刷實例中之高度(以cm計)相關且顯示信號強度之真實關係。自寬信號可顯示信號之若干峰或中間部分及其與光譜中最密集信號相比之相對強度。 The intensity of sharp signals is related to the height (in cm) of these signals in the printed example of the NMR spectrum and shows a true relationship of signal intensity. A self-width signal can show several peaks or middle portions of the signal and their relative intensity compared to the densest signal in the spectrum.
1 H-NMR峰列表類似於經典1 H-NMR圖譜且因此通常含有所有峰,該等峰均以經典NMR解釋列示。另外,其可顯示溶劑、目標化合物之立體異構體(其亦係本發明之目標)之類似經典1 H-NMR圖譜信號及/或雜質之峰。為顯示在溶劑及/或水之δ範圍中之化合物信號,溶劑之常見峰(例如DMSO於d6-DMSO中之峰及水峰)顯示於該等1 H-NMR峰列表中且通常平均具有高強度。 The 1 H-NMR peak list is similar to the classical 1 H-NMR spectrum and therefore usually contains all peaks, all of which are listed in classical NMR interpretation. In addition, it can show solvents, the stereoisomers of the target compounds (which are also the object of the present invention) similar to the classical 1 H-NMR spectrum signals and / or peaks of impurities. In order to show the signal of compounds in the δ range of solvents and / or water, common peaks of solvents (such as DMSO in d6-DMSO and water peaks) are shown in these 1 H-NMR peak lists and usually have high averages. strength.
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低於目標化合物(例如純度> 90%)之峰之強度。該等立體異構體及/或雜質對於特定製備方法可能係典型的。因此,其峰可有助於經由「副產物指紋圖譜」識別其製備方法之重現。The peaks of the stereoisomers and / or impurities of the target compound generally have an average intensity lower than the peaks of the target compound (eg, purity> 90%). These stereoisomers and / or impurities may be typical for a particular preparation method. Therefore, its peak can help to identify the reproducibility of its preparation method by "by-product fingerprint".
專業人士利用已知方法(MestreC、ACD-模擬、以及利用經驗評價預期值)計算目標化合物之峰,並可(如需要)視情況使用額外強度濾波器分離目標化合物之峰。此分離將類似於以經典1 H-NMR解釋挑選相關峰。Professionals use known methods (MestreC, ACD-simulation, and empirical evaluation of expected values) to calculate the peak of the target compound, and if necessary, use additional intensity filters to isolate the peaks of the target compound. This separation will be similar to picking related peaks with classical 1 H-NMR interpretation.
NMR-數據闡述之其他細節與峰列表參見出版物Research Disclosure Database編號564025之「Citation of NMR Peaklist Data within Patent Applications」。
表 3
:NMR峰列表
Table 3 : List of NMR peaks
製備實例
製備實例 1
:製備N-{2-氟-3-[(三甲基矽基)甲基]吡啶-4-基}喹啉-3-胺(化合物I.02)
步驟 1
:製備N-(3-溴-2-氟吡啶-4-基)喹啉-3-胺
在氬下,將0.5 g (3.46 mmol)喹啉-3-胺溶解於5 mL NMP [N-甲基吡咯啶酮]中。添加1.9 mL LDA [二異丙基胺基鋰]溶液(2 M於THF中;1.1當量)並將混合物在室溫下攪拌1小時。然後,進一步添加溶於5 mL NMP中之0.814 g (3.98 mmol) 3-溴-2,4-二氟吡啶并將反應混合物攪拌過夜。將反應混合物傾倒於水中並藉由乙酸乙酯萃取。有機相藉由氯化鋰飽和水溶液洗滌並經硫酸鎂乾燥。在真空下濃縮,獲得1.31 g褐色殘餘物。此殘餘物藉由管柱層析在矽膠上(梯度正庚烷/乙酸乙酯)純化,以獲得401 mg (36%)呈淺橙色固體之N-(3-溴-2-氟吡啶-4-基)喹啉-3-胺。LogP = 2.25。質量(M+H) = 318。 Preparation example
Preparation Example 1 : Preparation of N- {2-fluoro-3-[(trimethylsilyl) methyl] pyridin-4-yl} quinolin-3-amine (Compound I.02)
Step 1 : Prepare N- (3-bromo-2-fluoropyridin-4-yl) quinolin-3-amine under argon, dissolve 0.5 g (3.46 mmol) of quinolin-3-amine in 5 mL of NMP [N -Methylpyrrolidone]. 1.9 mL of LDA [lithium diisopropylamino] solution (2 M in THF; 1.1 equivalents) was added and the mixture was stirred at room temperature for 1 hour. Then, 0.814 g (3.98 mmol) of 3-bromo-2,4-difluoropyridine dissolved in 5 mL of NMP was further added and the reaction mixture was stirred overnight. The reaction mixture was poured into water and extracted with ethyl acetate. The organic phase was washed with a saturated aqueous solution of lithium chloride and dried over magnesium sulfate. Concentrated under vacuum to obtain 1.31 g of a brown residue. This residue was purified by column chromatography on silica gel (gradient n-heptane / ethyl acetate) to obtain 401 mg (36%) of N- (3-bromo-2-fluoropyridine-4 as a light orange solid -Yl) quinolin-3-amine. LogP = 2.25. Mass (M + H) = 318.
步驟 2
:製備N-{2-氟-3-[(三甲基矽基)甲基]吡啶-4-基}喹啉-3-胺
在乾燥5 mL RadleysTM
小瓶中,在氬下,在-78℃下將0.718 mL氯化鋅溶液(0.7 M於THF中;0.5 mmol)添加至0.393 mL三甲基矽基甲基氯化鎂溶液(1.2 M於THF中;0.47 mmol)中並在-78℃下攪拌1小時。使混合物緩慢恢復至室溫。添加溶於4 mL THF中之100 mg (0.314 mmol) N-(3-溴-2-氟吡啶-4-基)喹啉-3-胺,隨後添加14 mg (0.016 mmol)參(二亞苄基丙酮)二鈀及9.4 mg (0.031 mmol)四氟硼酸三-第三丁基鏻鹽。在微波下在100℃下將反應混合物加熱30分鐘。然後將冷卻之混合物經沙過濾且後者藉由乙酸乙酯洗滌。有機相用水洗滌並經硫酸鎂乾燥。在真空下濃縮,獲得38 mg橙色油。藉由製備型HPLC (梯度乙腈 / 水 + 0.1% HCO2
H)純化,獲得13 mg (12%)呈黃色油狀物之N-{2-氟-3-[(三甲基矽基)甲基]吡啶-4-基}喹啉-3-胺。LogP = 3.19.質量(M+H) = 326。 Step 2 : Preparation of N- {2-fluoro-3-[(trimethylsilyl) methyl] pyridin-4-yl} quinolin-3-amine in a dry 5 mL Radleys TM vial under argon at 0.718 mL of zinc chloride solution (0.7 M in THF; 0.5 mmol) was added to -0.393 mL of trimethylsilylmethylmagnesium chloride solution (1.2 M in THF; 0.47 mmol) at -78 ° C. Stir for 1 hour. The mixture was allowed to slowly return to room temperature. 100 mg (0.314 mmol) of N- (3-bromo-2-fluoropyridin-4-yl) quinolin-3-amine dissolved in 4 mL of THF were added, followed by 14 mg (0.016 mmol) of ginsyl (dibenzylidene) Acetone) dipalladium and 9.4 mg (0.031 mmol) of tri-tert-butylphosphonium tetrafluoroborate. The reaction mixture was heated under microwave at 100 ° C for 30 minutes. The cooled mixture was then filtered through sand and the latter was washed with ethyl acetate. The organic phase was washed with water and dried over magnesium sulfate. Concentrated under vacuum to give 38 mg of an orange oil. Purified by preparative HPLC (gradient acetonitrile / water + 0.1% HCO 2 H) to obtain 13 mg (12%) of N- {2-fluoro-3-[(trimethylsilyl) methyl as a yellow oil. [] Pyridin-4-yl} quinolin-3-amine. LogP = 3.19. Mass (M + H) = 326.
製備實例 2
:製備(1-{[二甲基(苯基)矽基]甲基}-1H-吡咯-2-基)(喹啉-3-基)甲酮(化合物I.32)
向溶於4 mL DMA [二甲基乙醯胺]中之300 mg (1.35 mmol) 1H-吡咯-2-基(喹啉-3-基)甲酮溶液中添加280 mg (1.485 mmol) (氯甲基)(二甲基)苯基矽烷及1.35 mL KHMDS [雙(三甲基矽基)醯胺鉀]溶液(1 M於THF中;1.35 mmol)。將反應混合物在100℃下加熱3小時。將冷卻之反應混合物傾倒於水中並藉由乙酸乙酯萃取。有機相藉由氯化鋰飽和水溶液洗滌並經硫酸鎂乾燥。在真空下濃縮,獲得578 mg橙褐色油狀物。此殘餘物藉由管柱層析在矽膠上(梯度正庚烷/乙酸乙酯)純化,以獲得274 mg (54%)呈褐色油狀物之(1-{[二甲基(苯基)矽基]甲基}-1H-吡咯-2-基)(喹啉-3-基)甲酮。LogP = 4.41。質量(M+H) = 371。 Preparation Example 2 : Preparation of (1-{[dimethyl (phenyl) silyl] methyl} -1H-pyrrole-2-yl) (quinolin-3-yl) methanone (Compound I.32)
To a solution of 300 mg (1.35 mmol) of 1H-pyrrole-2-yl (quinolin-3-yl) methanone in 4 mL of DMA [dimethylacetamide] was added 280 mg (1.485 mmol) (chlorine Methyl) (dimethyl) phenylsilane and 1.35 mL of KHMDS [potassium bis (trimethylsilyl) amidamine] (1 M in THF; 1.35 mmol). The reaction mixture was heated at 100 ° C for 3 hours. The cooled reaction mixture was poured into water and extracted with ethyl acetate. The organic phase was washed with a saturated aqueous solution of lithium chloride and dried over magnesium sulfate. Concentration under vacuum gave 578 mg of an orange-brown oil. This residue was purified by column chromatography on silica gel (gradient n-heptane / ethyl acetate) to obtain 274 mg (54%) of (1-{[dimethyl (phenyl)) as a brown oil. Silyl] methyl} -1H-pyrrole-2-yl) (quinolin-3-yl) methanone. LogP = 4.41. Mass (M + H) = 371.
製備實例 3
:製備(5-氯-1-{[二甲基(苯基)矽基]甲基}-1H-吡咯-2-基)(喹啉-3-基)甲酮(化合物I.48)、(4-氯-1-{[二甲基(苯基)矽基]甲基}-1H-吡咯-2-基)(喹啉-3-基)甲酮(化合物I.47)及(4,5-二氯-1-{[二甲基(苯基)矽基]甲基}-1H-吡咯-2-基)(喹啉-3-基)甲酮(化合物I.56)
向220 mg (0.594 mmol) (1-{[二甲基(苯基)矽基]甲基}-1H-吡咯-2-基)(喹啉-3-基)甲酮於10 ml戊烯穩定之氯仿中之溶液中添加114 mg (0.831 mmol) N-氯琥珀醯亞胺。將反應混合物回流加熱11小時。將冷卻之反應混合物傾倒於水中並藉由二氯甲烷萃取。有機相用水洗滌並經硫酸鎂乾燥。在真空下濃縮,獲得280 mg橙褐色油狀物。藉由製備型HPLC (梯度乙腈 / 水 + 0.1% HCO2
H)純化,獲得40 mg (16%) (5-氯-1-{[二甲基(苯基)矽基]甲基}-1H-吡咯-2-基)(喹啉-3-基)甲酮(LogP = 5.32;質量(M+H) = 405)、67 mg (26%) (4-氯-1-{[二甲基(苯基)矽基]甲基}-1H-吡咯-2-基)(喹啉-3-基)甲酮(LogP = 5.00;質量(M+H) = 405)及101 mg (37%) (4,5-二氯-1-{[二甲基(苯基)矽基]甲基}-1H-吡咯-2-基)(喹啉-3-基)甲酮(LogP = 5.84;質量(M+H) = 439)。 Preparation Example 3 : Preparation of (5-chloro-1-{[dimethyl (phenyl) silyl] methyl} -1H-pyrrole-2-yl) (quinolin-3-yl) methanone (Compound I. 48), (4-chloro-1-{[dimethyl (phenyl) silyl] methyl) -1H-pyrrole-2-yl) (quinolin-3-yl) methanone (Compound I.47) And (4,5-dichloro-1-{[dimethyl (phenyl) silyl] methyl} -1H-pyrrole-2-yl) (quinolin-3-yl) methanone (Compound I.56 )
Stable to 220 mg (0.594 mmol) (1-{[dimethyl (phenyl) silyl] methyl} -1H-pyrrole-2-yl) (quinolin-3-yl) methanone in 10 ml pentene To the solution in chloroform was added 114 mg (0.831 mmol) of N-chlorosuccinimide. The reaction mixture was heated at reflux for 11 hours. The cooled reaction mixture was poured into water and extracted with dichloromethane. The organic phase was washed with water and dried over magnesium sulfate. Concentrated under vacuum to give 280 mg of an orange-brown oil. Purified by preparative HPLC (gradient acetonitrile / water + 0.1% HCO 2 H) to obtain 40 mg (16%) (5-chloro-1-{[dimethyl (phenyl) silyl] methyl} -1H -Pyrrole-2-yl) (quinolin-3-yl) methanone (LogP = 5.32; mass (M + H) = 405), 67 mg (26%) (4-chloro-1-{[dimethyl (Phenyl) silyl] methyl} -1H-pyrrole-2-yl) (quinolin-3-yl) methanone (LogP = 5.00; mass (M + H) = 405) and 101 mg (37%) (4,5-dichloro-1-{[dimethyl (phenyl) silyl] methyl} -1H-pyrrole-2-yl) (quinolin-3-yl) methanone (LogP = 5.84; mass (M + H) = 439).
製備實例 4
:製備{4,5-二氯-1-[(三甲基矽基)甲基]-1H-咪唑-2-基}(7,8-二氟喹啉-3-基)甲醇(化合物I.51)
步驟 1
:製備2-溴-4,5-二氯-1-[(三甲基矽基)甲基]-1H-咪唑
在0℃下向1.5 g (6.94 mmol) 2-溴-4,5-二氯-1H-咪唑及1.14 g (9 mmol) (氯甲基)(三甲基)矽烷於10 mL DMA中之溶液中逐滴添加6.9 mL (6.94 mmol) 1 M KHMDS [雙(三甲基矽基)醯胺鉀]於THF中之溶液。將反應混合物在100℃下加熱4小時。將冷卻之反應混合物傾倒於水中並藉由乙酸乙酯萃取三次。有機相用10% LiCl水溶液洗滌並經硫酸鎂乾燥。在真空下濃縮,獲得2.13 g (98%)純2-溴-4,5-二氯-1-[(三甲基矽基)-甲基]-1H-咪唑。LogP = 4.11。質量(M+H) = 300。 Preparation Example 4 : Preparation of {4,5-dichloro-1-[(trimethylsilyl) methyl] -1H-imidazol-2-yl} (7,8-difluoroquinolin-3-yl) methanol (Compound I.51)
Step 1 : Preparation of 2-bromo-4,5-dichloro-1-[(trimethylsilyl) methyl] -1H-imidazole at 0 ° C to 1.5 g (6.94 mmol) of 2-bromo-4,5 -Dichloro-1H-imidazole and 1.14 g (9 mmol) (chloromethyl) (trimethyl) silane in a solution of 10 mL DMA was added dropwise 6.9 mL (6.94 mmol) 1 M KHMDS [bis (trimethyl A solution of phenylsilyl) potassium ammonium] in THF. The reaction mixture was heated at 100 ° C for 4 hours. The cooled reaction mixture was poured into water and extracted three times with ethyl acetate. The organic phase was washed with a 10% aqueous LiCl solution and dried over magnesium sulfate. Concentration under vacuum gave 2.13 g (98%) of pure 2-bromo-4,5-dichloro-1-[(trimethylsilyl) -methyl] -1H-imidazole. LogP = 4.11. Mass (M + H) = 300.
步驟 2
:製備{4,5-二氯-1-[(三甲基矽基)甲基]-1H-咪唑-2-基}(7,8-二氟喹啉-3-基)甲醇
在氬下,將860 mg (2.84 mmol) 2-溴-4,5-二氯-1-[(三甲基矽基)甲基]-1H-咪唑溶解於10 mL THF中並冷卻至-70℃,隨後逐滴添加1.14 mL (2.84 mmol) 2.5 M BuLi於己烷中之溶液,而不超過溫度-70℃。將反應混合物在-70℃下攪拌20分鐘。然後在-70℃下逐滴添加500 mg (2.58 mmol) 7,8-二氟喹啉-3-甲醛於5 mL THF中之溶液並將反應混合物在-70℃下再攪拌30分鐘。使反應混合物恢復至室溫,傾倒於水中並藉由1 N HCl水溶液中和(pH = 7)。水相用二氯甲烷重新萃取且有機相用鹽水洗滌並經硫酸鎂乾燥。在真空下濃縮,獲得1.28 g油狀物。此殘餘物藉由管柱層析在矽膠上(梯度正庚烷/乙酸乙酯)純化,以獲得474 mg (44%) {4,5-二氯-1-[(三甲基矽基)甲基]-1H-咪唑-2-基}(7,8-二氟喹啉-3-基)甲醇。LogP = 3.74。質量(M+H) = 416。 Step 2 : Preparation of {4,5-dichloro-1-[(trimethylsilyl) methyl] -1H-imidazol-2-yl} (7,8-difluoroquinolin-3-yl) methanol Under argon, 860 mg (2.84 mmol) of 2-bromo-4,5-dichloro-1-[(trimethylsilyl) methyl] -1H-imidazole was dissolved in 10 mL of THF and cooled to -70 ° C. Then, 1.14 mL (2.84 mmol) of 2.5 M BuLi in hexane was added dropwise without exceeding a temperature of -70 ° C. The reaction mixture was stirred at -70 ° C for 20 minutes. Then a solution of 500 mg (2.58 mmol) of 7,8-difluoroquinoline-3-carboxaldehyde in 5 mL of THF was added dropwise at -70 ° C and the reaction mixture was stirred for another 30 minutes at -70 ° C. The reaction mixture was allowed to return to room temperature, poured into water and neutralized with 1 N aqueous HCl (pH = 7). The aqueous phase was re-extracted with dichloromethane and the organic phase was washed with brine and dried over magnesium sulfate. Concentrated under vacuum to obtain 1.28 g of an oil. This residue was purified by column chromatography on silica gel (gradient n-heptane / ethyl acetate) to obtain 474 mg (44%) {4,5-dichloro-1-[(trimethylsilyl) Methyl] -1H-imidazol-2-yl} (7,8-difluoroquinolin-3-yl) methanol. LogP = 3.74. Mass (M + H) = 416.
製備實例 5
:製備3-({4,5-二氯-1-[(三甲基矽基)甲基]-1H-咪唑-2-基}甲基)-7,8-二氟喹啉(化合物I.46)
在0℃下向100 mg (0.24 mmol) {4,5-二氯-1-[(三甲基矽基)甲基]-1H-咪唑-2-基}(7,8-二氟喹啉-3-基)甲醇於5 mL三氟乙酸中之溶液中添加70 mg (0.60 mmol)三乙基矽烷。將反應混合物在60℃下過夜加熱。將冷卻之反應混合物傾倒於水中並藉由1 M NaOH水溶液使pH至8。水相用二氯甲烷重新萃取兩次且合併之有機相用鹽水洗滌兩次並經硫酸鎂乾燥。在真空下濃縮並藉由製備型HPLC (梯度乙腈 / 水 + 0.1% HCO2H)純化粗產物,獲得呈油狀物之39 mg (36%) 3-({4,5-二氯-1-[(三甲基-矽基)甲基]-1H-咪唑-2-基}甲基)-7,8-二氟喹啉。LogP = 4.18.質量(M+H) = 400。 Preparation Example 5 : Preparation of 3-({4,5-dichloro-1-[(trimethylsilyl) methyl] -1H-imidazol-2-yl} methyl) -7,8-difluoroquinoline (Compound I.46)
100 mg (0.24 mmol) {4,5-dichloro-1-[(trimethylsilyl) methyl] -1H-imidazol-2-yl} (7,8-difluoroquinoline) at 0 ° C To a solution of 3--3-yl) methanol in 5 mL of trifluoroacetic acid was added 70 mg (0.60 mmol) of triethylsilane. The reaction mixture was heated at 60 ° C overnight. The cooled reaction mixture was poured into water and the pH was brought to 8 with a 1 M aqueous NaOH solution. The aqueous phase was re-extracted twice with dichloromethane and the combined organic phases were washed twice with brine and dried over magnesium sulfate. Concentrate in vacuo and purify the crude product by preparative HPLC (gradient acetonitrile / water + 0.1% HCO2H) to obtain 39 mg (36%) 3-({4,5-dichloro-1- [ (Trimethyl-silyl) methyl] -1H-imidazol-2-yl} methyl) -7,8-difluoroquinoline. LogP = 4.18. Mass (M + H) = 400.
生物數據
實例 A :對稻梨孢黴之活體外細胞測試
溶劑: 二甲亞碸
培養基: 14.6 g無水D-葡萄糖(VWR),
7.1 g真菌用蛋白腖(Oxoid),
1.4 g顆粒狀酵母提取物(Merck),QSP 1公升
接種體: 孢子懸浮液
將測試化合物溶於二甲亞碸中且溶液用於準備所需濃度範圍。分析中所用二甲亞碸之最終濃度為 ≤ 1%。 Biological data
Example A : In vitro cell test on P. oryzae <br/> Solvent: Dimethylphosphine medium: 14.6 g of anhydrous D-glucose (VWR),
7.1 g of fungal peptone (Oxoid),
1.4 g granular yeast extract (Merck), QSP 1 liter inoculum: Spore suspension The test compound is dissolved in dimethylarsine and the solution is used to prepare the required concentration range. The final concentration of dimethylarsine used in the analysis was ≤ 1%.
製備稻梨孢黴之孢子懸浮液並稀釋至期望孢子密度。A spore suspension of P. oryzae was prepared and diluted to the desired spore density.
在液體培養分析中評估化合物抑制孢子萌發及菌絲體生長之能力。將化合物以期望濃度添加至含有孢子之培養基中。培育5天後,藉由菌絲體生長之光譜量測測定化合物之真菌毒性。藉由比較含有測試化合物之孔中之吸光度值與不含測試化合物之對照孔中之吸光度測定真菌生長之抑制。The ability of the compounds to inhibit spore germination and mycelial growth was evaluated in liquid culture analysis. The compound is added to the spore-containing medium at the desired concentration. After 5 days of incubation, the fungal toxicity of the compounds was determined by spectrometry of mycelial growth. Inhibition of fungal growth was determined by comparing absorbance values in wells containing test compounds with absorbance in control wells without test compounds.
在此測試中,以下本發明之化合物在20 ppm測試化合物之濃度下顯示介於70%與79%之間之效能:I.26;I.34。In this test, the following compounds of the present invention showed efficacy between 70% and 79% at a concentration of 20 ppm test compound: I.26; I.34.
在此測試中,以下本發明之化合物在20 ppm測試化合物之濃度下顯示介於80%與89%之間之效能:I.09;I.10;I.17;I.27;I.30;I.44;I.46。In this test, the following compounds of the present invention showed efficacy between 80% and 89% at a concentration of 20 ppm test compound: I.09; I.10; I.17; I.27; I.30 ; I.44; I.46.
在此測試中,以下本發明之化合物在20 ppm測試化合物之濃度下顯示介於90%與100%之間之效能:I.02;I.03;I.04;I.05;I.11;I.12;I.14;I.16;I.19;I.20;I.22;I.23;I.24;I.25;I.28;I.29;I.31;I.33;I.36;I.38;I.39;I.45;I.48;I.51;I.60;I.61。In this test, the following compounds of the present invention showed efficacy between 90% and 100% at a concentration of 20 ppm test compound: I.02; I.03; I.04; I.05; I.11 ; I.12; I.14; I.16; I.19; I.20; I.22; I.23; I.24; I.25; I.28; I.29; I.31; I .33; I.36; I.38; I.39; I.45; I.48; I.51; I.60; I.61.
實例 B :對菜豆炭疽刺盤孢菌之活體外細胞測試
溶劑: 二甲亞碸
培養基: 14.6 g無水D-葡萄糖(VWR),
7.1 g真菌用蛋白腖(Oxoid),
1.4 g顆粒狀酵母提取物(Merck),QSP 1公升
接種體: 孢子懸浮液
將測試化合物溶於二甲亞碸中且溶液用於準備所需濃度範圍。分析中所用二甲亞碸之最終濃度為 ≤ 1%。 Example B : In vitro cell test on Anopheles anthracis, <br/> solvent: Dimethylphosphine medium: 14.6 g of anhydrous D-glucose (VWR),
7.1 g of fungal peptone (Oxoid),
1.4 g granular yeast extract (Merck), QSP 1 liter inoculum: Spore suspension The test compound is dissolved in dimethylarsine and the solution is used to prepare the required concentration range. The final concentration of dimethylarsine used in the analysis was ≤ 1%.
製備菜豆炭疽刺盤孢菌之孢子懸浮液並稀釋至期望孢子密度。A spore suspension of Phaseolus anthracis was prepared and diluted to the desired spore density.
在液體培養分析中評估化合物抑制孢子萌發及菌絲體生長之能力。將化合物以期望濃度添加至含有孢子之培養基中。培育6天後,藉由菌絲體生長之光譜量測測定化合物之真菌毒性。藉由比較含有測試化合物之孔中之吸光度值與不含測試化合物之對照孔中之吸光度測定真菌生長之抑制。The ability of the compounds to inhibit spore germination and mycelial growth was evaluated in liquid culture analysis. The compound is added to the spore-containing medium at the desired concentration. After 6 days of incubation, the fungal toxicity of the compounds was determined by spectrometry of mycelial growth. Inhibition of fungal growth was determined by comparing absorbance values in wells containing test compounds with absorbance in control wells without test compounds.
在此測試中,以下本發明之化合物在20 ppm測試化合物之濃度下顯示介於70%與79%之間之效能:I.05;I.10;I.36。In this test, the following compounds of the present invention showed efficacy between 70% and 79% at a concentration of 20 ppm test compound: I.05; I.10; I.36.
在此測試中,以下本發明之化合物在20 ppm測試化合物之濃度下顯示介於80%與89%之間之效能:I.04;I.11;I.12;I.14;I.18;I.38;I.46;I.48。In this test, the following compounds of the present invention showed efficacy between 80% and 89% at a concentration of 20 ppm test compound: I.04; I.11; I.12; I.14; I.18 ; I.38; I.46; I.48.
在此測試中,以下本發明之化合物在20 ppm測試化合物之濃度下顯示介於90%與100%之間之效能:I.01;I.02;I.03;I.22;I.23;I.24;I.25;I.26;I.27;I.28;I.29;I.31;I.32;I.37;I.39;I.53;I.61。In this test, the following compounds of the invention show efficacy between 90% and 100% at a concentration of 20 ppm test compound: I.01; I.02; I.03; I.22; I.23 I.24; I.25; I.26; I.27; I.28; I.29; I.31; I.32; I.37; I.39; I.53; I.61.
實例 C : 對灰色葡萄孢菌 ( 灰黴菌 ) 之活體內預防性測試
溶劑: 5體積% 二甲亞碸
10體積% 丙酮
乳化劑: 1 µL Tween® 80/mg活性成分
將測試化合物在二甲亞碸/丙酮/Tween® 80之混合物中溶解並均質化且然後於水中稀釋至期望濃度。 Example C : In vivo preventive test against Botrytis cinerea ( Botrytis cinerea ) <br/> Solvent: 5% by volume
10% by volume of acetone emulsifier: 1 µL of Tween® 80 / mg active ingredient The test compound is dissolved and homogenized in a mixture of dimethylsulfine / acetone / Tween® 80 and then diluted to the desired concentration in water.
藉由噴灑如上所述製備之測試化合物處理黃瓜之幼株。對照植株僅用丙酮/二甲亞碸/ Tween® 80之水溶液進行處理。Young plants of cucumber were treated by spraying the test compound prepared as described above. Control plants were treated with only acetone / dimethylarsine / Tween® 80 in water.
在24小時後,藉由用灰色葡萄孢菌孢子之水性懸浮液噴灑葉子使植株受到污染。在17℃及90%相對濕度下將受污染之黃瓜植株培育4至5天。After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Botrytis spores. The contaminated cucumber plants were grown at 17 ° C and 90% relative humidity for 4 to 5 days.
在接種4至5天後,對測試進行評估。0%意指功效與對照植株之功效相當,而100%之功效意指未觀察到病害。The test is evaluated 4 to 5 days after the inoculation. 0% means that the efficacy is comparable to that of the control plants, while 100% means that no disease is observed.
在此測試中,以下本發明之化合物在500 ppm測試化合物之濃度下顯示介於70%與79%之間之效能:I.44。In this test, the following compounds of the present invention showed efficacy between 70% and 79% at a concentration of 500 ppm test compound: I.44.
在此測試中,以下本發明之化合物在500 ppm測試化合物之濃度下顯示介於80%與89%之間之效能:I.08;I.11;I.37;I.53。In this test, the following compounds of the present invention showed efficacy between 80% and 89% at a concentration of 500 ppm test compound: I.08; I.11; I.37; I.53.
在此測試中,以下本發明之化合物在500 ppm測試化合物之濃度下顯示介於90%與100%之間之效能:I.01;I.13;I.14;I.16;I.18;I.23;I.24;I.25;I.29。In this test, the following compounds of the present invention showed efficacy between 90% and 100% at a concentration of 500 ppm test compound: I.01; I.13; I.14; I.16; I.18 ; I.23; I.24; I.25; I.29.
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