CN1688546A - Pyridinyl amides and imides for use as fungicides - Google Patents
Pyridinyl amides and imides for use as fungicides Download PDFInfo
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Abstract
Description
发明背景 Background of the invention
本发明涉及某些吡啶酰胺和吡啶酰亚胺，它们的N-氧化物、合适的农用盐和组合物，以及作为杀真菌剂的用法。This invention relates to certain pyridine amides and pyridine imides, their N-oxides, suitable agriculturally acceptable salts and compositions, and their use as fungicides.
由真菌类植物病原体造成的植物病害的控制在获得高的谷物收成中非常重要。植物病害对损坏观赏植物、蔬菜、农田、谷物和水果作物能造成明显减产，从而导致消费者费用增加。有许多商品可用作这种用途，但仍需要更有效、成本低、毒性小、更环保或作用模式不同的新型化合物。The control of plant diseases caused by fungal phytopathogens is very important in obtaining high cereal yields. Plant diseases can cause significant yield loss by damaging ornamental, vegetable, field, cereal and fruit crops, resulting in increased costs to consumers. There are many commercial products available for this purpose, but there remains a need for new compounds that are more effective, less expensive, less toxic, more environmentally friendly, or have a different mode of action.
WO 99/42447公开了作为杀真菌剂的一些通式i的苯甲酰胺。WO 99/42447 discloses certain benzamides of general formula i as fungicides.
其中尤其是R1为H、烷基或酰基；R2为H或烷基；和L为-(C＝O)-、-SO2-或-(C＝S)-。wherein especially R 1 is H, alkyl or acyl; R 2 is H or alkyl; and L is -(C=O)-, -SO 2 - or -(C=S)-.
本发明概述 SUMMARY OF THE INVENTION
本发明涉及包括所有几何的和立体的异构体、N-氧化物，以及它们合适的农用盐的通式I或通式II化合物：The present invention relates to compounds of formula I or II including all geometric and stereoisomers, N-oxides, and their suitable agriculturally acceptable salts:
其中in
A为取代的吡啶基环；A is a substituted pyridyl ring;
B为取代的吡啶基环；B is a substituted pyridyl ring;
W为C＝L或SOn；W is C=L or SOn ;
L为O或S；L is O or S;
R1和R2各自独立的是H；或C1-C6烷基、C2-C6链烯基、C2-C6炔基或C3-C6环烷基，每个都非必需的被取代；R 1 and R 2 are each independently H; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl, each of which is not required to be superseded;
R3为H；或C1-C6烷基、C2-C6链烯基、C2-C6炔基或C3-C6环烷基、C2-C6烷羰基、C2-C6烷氧基羰基、C2-C6烷氨基羰基或C3-C8二烷氨基羰基；R 3 is H; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl or C 3 -C 8 dialkylaminocarbonyl;
R4为C1-C6烷基、C2-C6链烯基、C2-C6炔基或C3-C6环烷基，每个都非必需的被取代；R 4 is C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl, each of which is optionally substituted;
X为O或S；和X is O or S; and
n为1或2；条件是当W为C＝O和R1、R2和R3为H时；则B为除4-三氟甲基-3-吡啶基、2-氯-4-吡啶基和2，6-二卤-4-吡啶基外的其他吡啶基环。n is 1 or 2; the condition is that when W is C=O and R 1 , R 2 and R 3 are H; then B is except 4-trifluoromethyl-3-pyridyl, 2-chloro-4-pyridine and other pyridyl rings other than 2,6-dihalo-4-pyridyl.
本发明还涉及包含杀真菌有效剂量的本发明化合物和选自表面活性剂、固体稀释剂或液体稀释剂的至少一种其他成分，和/或具有不同作用模式的至少一种其他杀菌剂的杀真菌剂组合物。The invention also relates to a fungicidally effective dose of a compound of the invention and at least one other component selected from surfactants, solid diluents or liquid diluents, and/or at least one other fungicide with a different mode of action. Fungal composition.
本发明还涉及由真菌类植物病原体造成的植物病害的控制方法，包括将有效杀真菌量的本发明化合物(例如此处描述的组合物)施用在植物或其一部分上，或使用到植物种子或秧苗上。The present invention also relates to a method for controlling plant diseases caused by fungal phytopathogens, comprising applying to plants or parts thereof, or to plant seeds or On the seedlings.
发明详述 Detailed description of the invention
如上所述，A和B各自独立的是取代的吡啶基环。与这些A和B基团相关的术语“取代的”指具有不会减弱杀真菌剂活性的至少一个非氢取代基的基团。掺入其中A被1-4个R5取代、b被1-4个R6取代的所述吡啶基环的通式I和通式II的实例包括在以下Exhibit 1中描述的环，其中m和p独立的是1-4的整数。注意(R5)m和A之间，以及(R6)p与B之间的连接点描述为活动点，且(R5)m和(R6)p可连接到吡啶基环的任何合适的碳原子上。As noted above, A and B are each independently a substituted pyridyl ring. The term "substituted" in relation to these A and B groups refers to groups having at least one non-hydrogen substituent which does not impair fungicidal activity. Examples of formulas I and II incorporating said pyridyl rings wherein A is substituted by 1-4 R 5 and b is substituted by 1-4 R 6 include the rings described in Exhibit 1 below, where m independently of p is an integer of 1-4. Note that the points of attachment between (R 5 ) m and A, and between (R 6 ) p and B are described as active points, and that (R 5 ) m and (R 6 ) p may be attached to any suitable location on the pyridyl ring. on the carbon atom.
Exhibit 1 Exhibit 1
与A连接时的R5和与B连接时的R6的实例包括：Examples of R5 when connected to A and R6 when connected to B include:
R5和R6各自独立的是C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6卤烷基、C2-C6卤链烯基、C2-C6卤炔基、C3-C6卤环烷基、卤素、CN、CO2H、CONH2、NO2、羟基、C1-C4烷氧基、C1-C4卤烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4卤烷基硫代基、C1-C4卤烷基亚硫酰基、C1-C4卤烷基磺酰基、C1-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基、C3-C6环烷氨基、C2-C6烷羰基、C2-C6烷氧基羰基、C2-C6烷氨基羰基、C3-C8二烷氨基羰基、C3-C6三烷基硅烷基；或R 5 and R 6 are independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkane C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, CO 2 H, CONH 2 , NO 2 , hydroxyl, C 1 - C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino , C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 dialkylaminocarbonyl, C 3 -C 6 trialkylsilyl; or
R5和R6各自独立的是苯基、苄基或苯氧基，各自非必需地用C1-C4烷基、C2-C4链烯基、C2-C4炔基、C3-C6环烷基、C1-C4卤烷基、C2-C4卤链烯基、C2-C4卤炔基、C3-C6卤环烷基、卤素、CN、NO2、C1-C4烷氧基、C1-C4卤烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基、C3-C6环烷氨基、C3-C6(烷基)环烷氨基、C2-C4烷羰基、C2-C6烷氧基羰基、C2-C6烷氨基羰基、C3-C8二烷氨基羰基或C3-C6三烷基硅烷基。R 5 and R 6 are each independently phenyl, benzyl or phenoxy, each optionally with C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, NO 2 , C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkane Sulfonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 3 -C 6 (alkyl) ring Alkylamino, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 dialkylaminocarbonyl or C 3 -C 6 trialkylsilyl .
其他R5和R6基团对于本领域普通技术人员是很显然的。例如每个R5和/或R6可以是NH2、NHCO(C1-C4烷基)或NHCO(C1-C4卤烷基)；或每个R5和/或R6可以是苯基、苄基或苯氧基，各自用C5-C8三烷基硅烷基炔基取代。Other R5 and R6 groups will be apparent to those of ordinary skill in the art. For example each R 5 and/or R 6 can be NH 2 , NHCO(C 1 -C 4 alkyl) or NHCO (C 1 -C 4 haloalkyl); or each R 5 and/or R 6 can be Phenyl, benzyl or phenoxy, each substituted with C 5 -C 8 trialkylsilylalkynyl.
值得注意的是通式I的化合物，其中Of note are compounds of general formula I, wherein
R5和R6各自独立的是C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6卤烷基、C2-C6卤链烯基、C2-C6卤炔基、C3-C6卤环烷基、卤素、CN、CO2H、CONH2、NO2、羟基、C1-C4烷氧基、C1-C4卤烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4卤烷基硫代基、C1-C4卤烷基亚硫酰基、C1-C4卤烷基磺酰基、C1-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基、C3-C6环烷氨基、C2-C6烷羰基、C2-C6烷氧基羰基、C2-C6烷氨基羰基、C3-C8二烷氨基羰基、C3-C6三烷基硅烷基；或R 5 and R 6 are independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkane C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, CO 2 H, CONH 2 , NO 2 , hydroxyl, C 1 - C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino , C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 dialkylaminocarbonyl, C 3 -C 6 trialkylsilyl; or
R5和R6各自独立的是苯基、苄基或苯氧基，各自非必需地用C1-C4烷基、C2-C4链烯基、C2-C4炔基、C3-C6环烷基、C1-C4卤烷基、C2-C4卤链烯基、C2-C4卤炔基、C3-C6卤环烷基、卤素、CN、NO2、C1-C4烷氧基、C1-C4卤烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基、C3-C6环烷氨基、C3-C6(烷基)环烷氨基、C2-C4烷羰基、C2-C6烷氧基羰基、C2-C6烷氨基羰基、C3-C8二烷氨基羰基、C5-C8三烷基硅烷基炔基或C3-C6三烷基硅烷基。R 5 and R 6 are each independently phenyl, benzyl or phenoxy, each optionally with C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, NO 2 , C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkane Sulfonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 3 -C 6 (alkyl) ring Alkylamino, C 2 -C 4 Alkylcarbonyl, C 2 -C 6 Alkoxycarbonyl, C 2 -C 6 Alkylaminocarbonyl, C 3 -C 8 Dialkylaminocarbonyl, C 5 -C 8 Trialkylsilyl Alkynyl or C 3 -C 6 trialkylsilyl.
如上所述，R1和R2各自独立的是H；或C1-C6烷基、C2-C6链烯基、C2-C6炔基或C3-C6环烷基，各自非必需的被取代；R4为C1-C6烷基、C2-C6链烯基、C2-C6炔基或C3-C6环烷基，各自非必需的被取代。与这些R1、R2和R4基团相关的术语“非必需的被取代”指未取代的基团，或带有不会减弱通过未取代的类似物而具有杀菌剂活性的至少一个非氢取代基团。非必需被取代的R1、R2和R4基团的实例是非必需的被一个或多个选自卤素、CN、NO2、羟基、C1-C4烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C2-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基和C3-C6环烷氨基的取代基取代的那些。尽管在上述实例中列出了这些取代基，但显然它们不是必须存在，因为它们是非必需的取代基。As mentioned above, each of R and R is independently H; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl, Each is optionally substituted; R 4 is C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl, each is optionally substituted . The term "optionally substituted" in relation to these R 1 , R 2 and R 4 groups refers to an unsubstituted group, or at least one non-essential group that does not impair the fungicidal activity of the unsubstituted analogue. Hydrogen substituents. Examples of optionally substituted R 1 , R 2 and R 4 groups are optionally substituted by one or more selected from halogen, CN, NO 2 , hydroxyl, C 1 -C 4 alkoxy, C 1 -C 4 Alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 2 -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino, C 2 -C 8 Those substituted with substituents of dialkylamino and C 3 -C 6 cycloalkylamino. Although these substituents are listed in the above examples, it is clear that they need not be present as they are optional substituents.
通式I和通式II的N-氧化物的实例分别以Exhibit 2中的I-10到I-16，以及II-10到II-16描述，其中R1、R2、R3、R4、R5、R6、W、X、m和p的定义如上所述。Examples of N-oxides of general formula I and general formula II are respectively described as I-10 to I-16 in Exhibit 2, and II-10 to II-16, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , W, X, m and p are as defined above.
Exhibit 2 Exhibit 2
在以上陈述中，单独使用或用于化合物名称如“烷基硫代基”或“卤烷基”中的术语“烷基”包括直链或支链烷基，如甲基、乙基、正丙基、异丙基，或不同的丁基、戊基或己基异构体。术语“1-2个烷基”指一个或两个合适位置可以是独立选择的烷基。“链烯基”包括直链或支链烯烃，如乙烯基、1-丙稀基、2-丙稀基，和不同的丁烯基、戊烯基和己烯基异构体。“链烯基”还包括多烯如1，2-丙二烯基和2，4-己二烯基。“炔基”包括直链或支链炔如乙炔基、1-丙炔基、2-丙炔基和不同的丁炔基、戊炔基和己炔基异构体。“炔基”还可包括由诸如2，5-己二炔基等含多个叁键的基团。“烷氧基”包括例如甲氧基、乙氧基、正丙氧基、异丙氧基和不同的丁氧基、戊氧基和己氧基异构体。“烷氧基烷基”指在烷基上取代的烷氧基。“烷氧基烷基”的实例包括CH3OCH2、CH3OCH2CH2、CH3CH2OCH2、CH3CH2CH2CH2OCH2和CH3CH2OCH2CH2。“烷氧基烷氧基”指在烷氧基上取代的烷氧基。术语“链烯基氧基”包括直链或支链的链烯基氧基。“链烯基氧基”的实例包括H2C＝CHCH2O、(CH3)2C＝CHCH2O、(CH3)CH＝CHCH2O、(CH3)CH＝C(CH3)CH2O和CH2＝CHCH2CH2O。“炔基氧基”包括直链或支链炔基氧基。“炔基氧基”的实例包括HC≡CCH2O、CH3C≡CCH2O和CH3C≡CCH2CH2O。“烷基硫代基”包括支链或直链烷基硫代基部分如甲基硫代基、乙基硫代基，和不同的丙基硫代基、丁基硫代基、戊基硫代基和己基硫代基异构体。“烷基硫代烷基”指在烷基上取代的烷基硫代基。“烷基硫代烷基”的实例包括CH3SCH2、CH3SCH2CH2、CH3CH2SCH2、CH3CH2CH2CH2SCH2和CH3CH2SCH2CH2。“烷基硫代烷氧基”指在烷氧基上取代的烷基硫代基。“烷基亚硫酰基”包括烷基亚硫酰基的两种对映体。“烷基亚硫酰基”的实例包括CH3S(O)、CH3CH2S(O)、CH3CH2CH2S(O)、(CH3)2CHS(O)和不同的丁基亚硫酰基、戊基亚硫酰基和己基亚硫酰基异构体。“烷基磺酰基”的实例包括CH3S(O)2、CH3CH2S(O)2、CH3CH2CH2S(O)2、(CH3)2CHS(O)2和不同的丁基磺酰基、戊基磺酰基和己基磺酰基异构体。“氰烷基”指用一个氰基取代的烷基。“氰烷基”的实例包括NCCH2、NCCH2CH2和CHCH(CN)CH2。“烷氨基”、“二烷氨基”、“链烯基硫代基”、“链烯基亚硫酰基”、“链烯基磺酰基”、“炔基硫代基”、“炔基亚硫酰基”、“炔基磺酰基”等与上述实例的定义类似。“环烷基”包括例如环丙基、环丁基、环戊基和环己基。术语“环烷氧基”包括通过一个氧原子连接的相同基团，如环戊氧基和环己氧基。In the above statements, the term "alkyl" used alone or in compound names such as "alkylthio" or "haloalkyl" includes linear or branched chain alkyl groups such as methyl, ethyl, n- Propyl, isopropyl, or the different butyl, pentyl, or hexyl isomers. The term "1-2 alkyl" means that one or two suitable positions may be independently selected alkyl groups. "Alkenyl" includes straight or branched chain alkenes such as vinyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl, and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" may also include groups containing multiple triple bonds such as 2,5-hexadiynyl. "Alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy, pentyloxy and hexyloxy isomers. "Alkoxyalkyl" refers to an alkoxy group substituted on an alkyl group. Examples of " alkoxyalkyl " include CH3OCH2 , CH3OCH2CH2 , CH3CH2OCH2 , CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2 . _ "Alkoxyalkoxy" refers to an alkoxy group substituted on an alkoxy group. The term "alkenyloxy" includes straight chain or branched alkenyloxy groups. Examples of "alkenyloxy" include H 2 C=CHCH 2 O, (CH 3 ) 2 C=CHCH 2 O, (CH 3 )CH=CHCH 2 O, (CH 3 )CH=C(CH 3 ) CH2O and CH2 = CHCH2CH2O . "Alkynyloxy" includes straight or branched chain alkynyloxy. Examples of " alkynyloxy" include HC≡CCH2O , CH3C≡CCH2O and CH3C≡CCH2CH2O . "Alkylthio" includes branched or straight chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio Substitute and hexylthio isomers. "Alkylthioalkyl" refers to an alkylthio group substituted on an alkyl group. Examples of " alkylthioalkyl " include CH3SCH2 , CH3SCH2CH2 , CH3CH2SCH2 , CH3CH2CH2CH2SCH2 , and CH3CH2SCH2CH2 . "Alkylthioalkoxy" refers to an alkylthio group substituted on an alkoxy group. "Alkylsulfinyl" includes both enantiomers of alkylsulfinyl. Examples of "alkylsulfinyl" include CH3S (O), CH3CH2S (O) , CH3CH2CH2S (O) , ( CH3 ) 2CHS (O) and the different butyl sulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 , (CH 3 ) 2 CHS(O) 2 and Different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Cyanoalkyl" refers to an alkyl group substituted with a cyano group. Examples of "cyanoalkyl" include NCCH2 , NCCH2CH2 and CHCH(CN) CH2 . "Alkylamino", "Dialkylamino", "Alkenylthio", "Alkenylsulfinyl", "Alkenylsulfonyl", "Alkynylthio", "Alkynylthio Acyl", "alkynylsulfonyl", etc. are defined similarly to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "cycloalkoxy" includes the same groups attached through an oxygen atom, such as cyclopentyloxy and cyclohexyloxy.
单独使用或在化合物名称如“卤烷基”中使用的术语“卤素”包括氟、氯、溴或碘。术语“1-2卤素”指取代基的一个或两个合适位置可以是独立选择的卤素的那些。此外，当用于化合物名称如“卤烷基”中时，所述烷基可以部分或全部被相同或不同的卤素原子取代。“卤烷基”的实例包括F3C、ClCH2、CF3CH2和CF3CCl2。术语“卤链烯基”、“卤炔基”、“卤烷氧基”、“卤烷基硫代基”等与术语“卤烷基”的定义类似。“卤链烯基”的实例包括(Cl)2C＝CHCH2和CF3CH2CH＝CHCH2。“卤炔基”的实例包括HC≡CCHCl、CF3C≡C、CCl3C≡C和FCH2C≡CCH2。“卤烷氧基”的实例包括CF3O、CCl3CH2O、HCF2CH2CH2O和CF3CH2O。“卤烷基硫代基”的实例包括CCl3S、CF3S、CCl3CH2S和ClCH2CH2CH2S。“卤烷基亚硫酰基”的实例包括CF3S(O)、CCl3S(O)、CF3CH2S(O)和CF3CF2S(O)。“卤烷基磺酰基”的实例包括CF3S(O)2、CCl3S(O)2、CF3CH2S(O)2和CF3CF2S(O)2。“卤烷氧基烷氧基”的实例包括CF3OCH2O、ClCH2CH2OCH2CH2O、Cl3CCH2OCH2O，以及支链烷基衍生物。“烷羰基”的实例包括C(O)CH3、C(O)CH2CH2CH3和C(O)CH(CH3)2。“烷氧基羰基”的实例包括CH3OC(＝O)、CH3CH2OC(＝O)、CH3CH2CH2OC(＝O)、(CH3)2CHOC(＝O)，和不同的丁氧基羰基或戊氧基羰基异构体。The term "halogen" used alone or in a compound name such as "haloalkyl" includes fluorine, chlorine, bromine or iodine. The term "1-2 halo" refers to those in which one or both suitable positions of a substituent may be independently selected halo. In addition, when used in a compound name such as "haloalkyl", the alkyl group may be partially or completely substituted with the same or different halogen atoms. Examples of "haloalkyl" include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 . The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", "haloalkylthio" and the like are defined similarly to the term "haloalkyl". Examples of "haloalkenyl" include (Cl) 2 C═CHCH 2 and CF 3 CH 2 CH═CHCH 2 . Examples of "haloalkynyl" include HC≡CCHCl, CF3C≡C , CCl3C≡C and FCH2C≡CCH2 . Examples of " haloalkoxy" include CF3O , CCl3CH2O , HCF2CH2CH2O and CF3CH2O . Examples of "haloalkylthio" include CCl3S , CF3S , CCl3CH2S and ClCH2CH2CH2S . Examples of "haloalkylsulfinyl" include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O). Examples of "haloalkylsulfonyl" include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 . Examples of "haloalkoxyalkoxy" include CF3OCH2O, ClCH2CH2OCH2CH2O , Cl3CCH2OCH2O , and branched alkyl derivatives . Examples of "alkylcarbonyl" include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 . Examples of "alkoxycarbonyl" include CH 3 OC(=O), CH 3 CH 2 OC(=O), CH 3 CH 2 CH 2 OC(=O), (CH 3 ) 2 CHOC(=O), and different butoxycarbonyl or pentyloxycarbonyl isomers.
本领域普通技术人员可以理解的是，不是所有含氮杂环都能形成N-氧化物，因为氮要求合适的孤电子对，以氧化形成氧化物。本领域普通技术人员能知道可形成N-氧化物的含氮杂环，也能知道叔胺能形成N-氧化物。制备杂环和叔胺的N-氧化物的合成方法是本领域普通技术人员公知的，包括杂环和叔胺与诸如过乙酸和m-氯过苯甲酸(MCPBA)等过氧酸、过氧化氢、诸如叔丁基氢过氧化物等烷基氢过氧化物、过硼酸钠和诸如二甲基二环氧乙烷等二环氧乙烷的氧化。N-氧化物的这些制备方法已在文献中广泛描述和评述，参见例如：T.L.Gilchrist在Comprehensive Organic Synthesis，第7卷，第748-75O页，S.V.Ley，编，Pergamon Press中描述的；M.Tisler和B.Stanovnik在Comprehensive Heterocyclic Chemistry，第3卷，第18-20页，A.J.Boulton和A.Mckillop，编，Pergamon Press中描述的；M.R.Grimmett和B.R.T.Keene在Advances in HeterocyclicChemistry，第43卷，第149-161页，A.R.Katritzky，编，AcademicPress中描述的；M.Tisler和B.Stanovnik在Advances inHeterocyclic Chemistry，第9卷，第285-291页，A.R.Katritzky和A.J.Boulton，编，Academic Press中描述的；以及G.W.H.Cheeseman和E.S.G.Werstiuk在Advances in Heterocyclic Chemistry，第22，第390-392页，A.R.Kartitzky和A.J.Boulton，编，Academic Press中描述的。Those of ordinary skill in the art will understand that not all nitrogen-containing heterocyclic rings can form N-oxides, because nitrogen requires a suitable lone pair of electrons to oxidize to form oxides. Those of ordinary skill in the art will be aware of nitrogen-containing heterocycles that can form N-oxides, and will also know that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are well known to those of ordinary skill in the art and include combinations of heterocycles and tertiary amines with peroxyacids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), peroxygen Oxidation of hydrogen, alkyl hydroperoxides such as tert-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These preparations of N-oxides have been extensively described and reviewed in the literature, see for example: T.L. Gilchrist in Comprehensive Organic Synthesis, Vol. 7, pp. 748-750, S.V. Ley, ed., Pergamon Press; M. Described by Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, Vol. 3, pp. 18-20, A.J. Boulton and A. Mckillop, eds., Pergamon Press; M.R. Grimmett and B.R.T. Keene in Advances in Heterocyclic Chemistry, Vol. 43, pp. pp. 149-161, described in A.R. Katritzky, eds., Academic Press; described by M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, Vol. 9, pp. 285-291, A.R. Katritzky and A.J. Boulton, eds., Academic Press and as described by G.W.H. Cheeseman and E.S.G. Werstiuk in Advances in Heterocyclic Chemistry, pp. 22, pp. 390-392, A.R. Kartitzky and A.J. Boulton, eds., Academic Press.
取代基中的碳原子总数用“Ci-Cj”前缀表示，其中i和j为1-8的数。例如C1-C3烷基磺酰基表示从甲基磺酰基到丙基磺酰基；C2烷氧基烷基表示CH3OCH2；C3烷氧基烷基表示例如CH3CH(OCH3)、CH3OCH2CH2或CH3CH2OCH2；和C4烷氧基烷基表示用含有总共4个碳原子的烷氧基取代的烷基的各种异构体，例如包括CH3CH2CH2OCH2和CH3CH2OCH2CH2。The total number of carbon atoms in a substituent is indicated by the "C i -C j " prefix, where i and j are numbers from 1-8. For example, C 1 -C 3 alkylsulfonyl means from methylsulfonyl to propylsulfonyl; C 2 alkoxyalkyl means CH 3 OCH 2 ; C 3 alkoxyalkyl means for example CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2 ; and C 4 alkoxyalkyl denotes various isomers of alkyl substituted with alkoxy containing a total of 4 carbon atoms, including for example CH 3CH2CH2OCH2 and CH3CH2OCH2CH2 . _ _ _ _
当一种化合物用带有可超过1的指示所述取代基数量的下标的取代基时，所述取代基(当它们超过1时)独立的选自定义的取代基。此外，当下标指示一个范围如(R)i-j时，取代基的数量可选自i和j之间(包括i和j)的整数。When a compound has substituents bearing subscripts which may exceed 1 to indicate the number of said substituents, said substituents (when they exceed 1) are independently selected from defined substituents. Furthermore, when the subscript indicates a range such as (R) ij , the number of substituents may be selected from integers between i and j inclusive.
当一个基团包含可以是氢的取代基时，如R1或R2时，那么当该取代基为氢时，可以认为等同于未取代基团。When a group contains a substituent which may be hydrogen, such as R1 or R2 , then when the substituent is hydrogen, it can be considered equivalent to the unsubstituted group.
本发明的化合物可以一种或多种立体异构体存在。不同立体异构体包括对映体、非对映体、阻转异构体和几何异构体。本领域普通技术人员可以理解的是，当一种立体异构体相对其他立体异构体而言含量更高，或当其与其他立体异构体分开时，可以更有活性和/或可表现出有益的效果。此外，熟练技工知道如何分离、富集和/或有选择地制备所述立体异构体。因此，本发明包括选自通式I的化合物、其N-氧化物和其农业上合适的盐。本发明的化合物可以立体异构体混合物、单独的立体异构体或以光活性形态存在。尤其是当通式I和通式II的R1和R2不同时，所述通式在与其共同连接的碳原子处具有手性中心。本发明包括外消旋混合物。此外，本发明包括与以下通式的对映体中的外消旋混合物比较其中一种对映体含量更高的化合物The compounds of the invention may exist as one or more stereoisomers. Different stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Those of ordinary skill in the art will appreciate that one stereoisomer may be more active and/or expressive when it is present in greater abundance relative to the other stereoisomer or when it is separated from the other stereoisomer. have beneficial effects. Furthermore, the skilled artisan knows how to separate, enrich and/or selectively prepare said stereoisomers. Accordingly, the present invention includes compounds selected from the group of formula I, N-oxides thereof and agriculturally suitable salts thereof. The compounds of the invention may exist as mixtures of stereoisomers, as individual stereoisomers or in optically active forms. Especially when R 1 and R 2 of formula I and formula II are different, said formulas have a chiral center at the carbon atom to which they are jointly attached. The present invention includes racemic mixtures. Furthermore, the present invention includes compounds having a higher content of one of the enantiomers as compared to the racemic mixture of the enantiomers of the general formula
包括实际上纯净的通式I’和通式II’的对映体。本发明还包括与以下通式的对映体中的外消旋混合物比较其中一种对映体含量更高的化合物Enantiomers of general formula I' and general formula II' are included in virtually pure form. The present invention also includes compounds having a higher content of one of the enantiomers as compared to the racemic mixture of the enantiomers of the general formula
包括实际上纯净的通式I”和通式II”的对映体。Enantiomers of general formula I" and general formula II" are included in virtually pure form.
当对映体富集时，一种对映体可以比其他对映体的量更多，且富集的程度可用对映体过量的表达(“ee”)来定义，即定义为100(2x-1)，其中x为混合物中主对映体的摩尔百分数(如20％的ee对应60∶40比值的对映体)。When enantiomerically enriched, one enantiomer can be present in greater amounts than the other, and the degree of enrichment can be defined by the expression of enantiomeric excess ("ee"), which is defined as 100 (2x -1), where x is the mole percent of the main enantiomer in the mixture (eg 20% ee corresponds to a 60:40 ratio of enantiomers).
相对于R1、R2的相对位置而言更有活性的对映体，A和通过氮连接的其他分子对应于2，4-二氯-N-[(1R)-1-[3-氯-5-(三氟甲基)-2-吡啶基]乙基]-3-吡啶甲酰胺的对映体的构型，当其在CDCl3溶液中时，在(+)或右旋方向旋转平面偏振光(即索引表B的化合物31的主对映体)。The more active enantiomer with respect to the relative position of R 1 , R 2 , A and other molecules linked through nitrogen corresponds to 2,4-dichloro-N-[(1R)-1-[3-chloro - The configuration of the enantiomers of 5-(trifluoromethyl)-2-pyridyl]ethyl]-3-pyridinecarboxamide, which rotates in the (+) or dextrorotatory direction when in CDCl3 solution Plane polarized light (ie the main enantiomer of compound 31 in Index Table B).
本发明组合物优选具有更活性异构体至少50％的对映体过量；更优选至少75％的对映体过量；特别优选至少90％的对映体过量；最优选至少94％的对映体过量。The compositions of the present invention preferably have an enantiomeric excess of the more active isomer of at least 50%; more preferably at least 75% enantiomeric excess; especially preferably at least 90% enantiomeric excess; most preferably at least 94% enantiomeric excess body overdose.
通式II的化合物对于该结构中的C＝N键而言，也可以是(E)-或(Z)-异构体，或是(E)-与(Z)-异构体的混合物存在。本发明包括几何异构体的混合物以及单一异构体。For the C=N bond in the structure, the compound of general formula II can also be (E)- or (Z)-isomer, or a mixture of (E)- and (Z)-isomer exists . The present invention includes mixtures of geometric isomers as well as individual isomers.
本发明化合物的盐包括与无机酸或有机酸如氢溴酸、盐酸、硝酸、磷酸、硫酸、乙酸、丁酸、富马酸、乳酸、马来酸、丙二酸、草酸、丙酸、水杨酸、酒石酸、4-甲苯磺酸或戊酸的酸加成盐。当本发明化合物含有诸如酸性基的羧酸或酚时，本发明化合物的盐还包括与有机碱(如吡啶、氨或三乙胺)或无机碱(如钠、钾、锂、钙、镁或钡的氢化物、氢氧化物或碳酸盐)形成的盐。Salts of the compounds of the present invention include compounds with inorganic or organic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, water Acid addition salts of citric acid, tartaric acid, 4-toluenesulfonic acid or valeric acid. When the compound of the present invention contains a carboxylic acid or phenol such as an acidic group, the salt of the compound of the present invention also includes an organic base (such as pyridine, ammonia or triethylamine) or an inorganic base (such as sodium, potassium, lithium, calcium, magnesium or Barium hydride, hydroxide or carbonate) salts.
就活性更好和/或容易合成而言，优选的化合物是：In terms of better activity and/or ease of synthesis, preferred compounds are:
Preferred 1：优选的是通式I和通式II的化合物，其中Preferred 1: preferred is the compound of general formula I and general formula II, wherein
A为1-4个R5取代的吡啶基环；A is 1-4 R 5 substituted pyridyl rings;
B为1-4个R6取代的吡啶基环；B is 1-4 R 6 substituted pyridyl rings;
R1和R2各自独立的是H；或C1-C6烷基、C2-C6链烯基、C2-C6炔基或C3-C6环烷基，各自非必需的用一个或多个选自卤素、CN、NO2、羟基、C1-C4烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C2-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基和C3-C6环烷氨基的取代基取代；R 1 and R 2 are each independently H; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, or C 3 -C 6 cycloalkyl, each optional With one or more selected from halogen, CN, NO 2 , hydroxyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 - Substituents of C 4 alkylsulfonyl, C 2 -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino and C 3 -C 6 cycloalkylamino;
R4是C1-C6烷基、C2-C6链烯基、C2-C6炔基或C3-C6环烷基，各自非必需的用一个或多个选自卤素、CN、NO2、羟基、C1-C4烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C2-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基和C3-C6环烷氨基的取代基取代；和R 4 is C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl, each optionally with one or more selected from halogen, CN, NO 2 , hydroxyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 2 Substituents of -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino and C 3 -C 6 cycloalkylamino; and
R5和R6各自独立的是C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6卤烷基、C2-C6卤链烯基、C2-C6卤炔基、C3-C6卤环烷基、卤素、CN、CO2H、CONH2、NO2、羟基、C1-C4烷氧基、C1-C4卤烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4卤烷基硫代基、C1-C4卤烷基亚硫酰基、C1-C4卤烷基磺酰基、C1-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基、C3-C6环烷氨基、C2-C6烷羰基、C2-C6烷氧基羰基、C2-C6烷氨基羰基、C3-C8二烷氨基羰基、C3-C6三烷基硅烷基；或R 5 and R 6 are independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkane C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, CO 2 H, CONH 2 , NO 2 , hydroxyl, C 1 - C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino , C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 dialkylaminocarbonyl, C 3 -C 6 trialkylsilyl; or
R5和R6各自独立的是苯基、苄基或苯氧基，各自非必需地用C1-C4烷基、C2-C4链烯基、C2-C4炔基、C3-C6环烷基、C1-C4卤烷基、C2-C4卤链烯基、C2-C4卤炔基、C3-C6卤环烷基、卤素、CN、NO2、C1-C4烷氧基、C1-C4卤烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基、C3-C6环烷氨基、C3-C6(烷基)环烷氨基、C2-C4烷羰基、C2-C6烷氧基羰基、C2-C6烷氨基羰基、C3-C8二烷氨基羰基或C3-C6三烷基硅烷基。R 5 and R 6 are each independently phenyl, benzyl or phenoxy, each optionally with C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, NO 2 , C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkane Sulfonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 3 -C 6 (alkyl) ring Alkylamino, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 dialkylaminocarbonyl or C 3 -C 6 trialkylsilyl .
值得注意的是这样的Preferred 1化合物，其中Of note is the Preferred 1 compound, where
每个R5独立的是C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6卤烷基、C2-C6卤链烯基、C2-C6卤炔基、C3-C6卤环烷基、卤素、CN、CO2H、CONH2、NO2、羟基、C1-C4烷氧基、C1-C4卤烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4卤烷基硫代基、C1-C4卤烷基亚硫酰基、C1-C4卤烷基磺酰基、C1-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基、C3-C6环烷氨基、C2-C6烷羰基、C2-C6烷氧基羰基、C2-C6烷氨基羰基、C3-C8二烷氨基羰基、C3-C6三烷基硅烷基；条件是当A为2-吡啶基时，R5是除C1-C6卤烷基外的其他基；和Each R 5 is independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, CO 2 H, CONH 2 , NO 2 , hydroxyl, C 1 -C 4 Alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 Haloalkylthio, C 1 -C 4 Haloalkylsulfinyl, C 1 -C 4 Haloalkylsulfonyl, C 1 -C 4 Alkoxycarbonyl, C 1 -C 4 Alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 di Alkylaminocarbonyl, C 3 -C 6 trialkylsilyl; with the proviso that when A is 2-pyridyl, R is a group other than C 1 -C 6 haloalkyl; and
每个R6独立的是C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6卤烷基、C2-C6卤链烯基、C2-C6卤炔基、C3-C6卤环烷基、卤素、CN、CO2H、CONH2、NO2、羟基、C1-C4烷氧基、C1-C4卤烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4卤烷基硫代基、C1-C4卤烷基亚硫酰基、C1-C4卤烷基磺酰基、C1-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基、C3-C6环烷氨基、C2-C6烷羰基、C2-C6烷氧基羰基、C2-C6烷氨基羰基、C3-C8二烷氨基羰基、C3-C6三烷基硅烷基；或Each R 6 is independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, CO 2 H, CONH 2 , NO 2 , hydroxyl, C 1 -C 4 Alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 Haloalkylthio, C 1 -C 4 Haloalkylsulfinyl, C 1 -C 4 Haloalkylsulfonyl, C 1 -C 4 Alkoxycarbonyl, C 1 -C 4 Alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 di Alkylaminocarbonyl, C 3 -C 6 trialkylsilyl; or
R5和R6各自独立的是苯基、苄基或苯氧基，各自非必需地用C1-C4烷基、C2-C4链烯基、C2-C4炔基、C3-C6环烷基、C1-C4卤烷基、C2-C4卤链烯基、C2-C4卤炔基、C3-C6卤环烷基、卤素、CN、NO2、C1-C4烷氧基、C1-C4卤烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基、C3-C6环烷氨基、C3-C6(烷基)环烷氨基、C2-C4烷羰基、C2-C6烷氧基羰基、C2-C6烷氨基羰基、C3-C8二烷氨基羰基或C3-C6三烷基硅烷基取代。R 5 and R 6 are each independently phenyl, benzyl or phenoxy, each optionally with C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, NO 2 , C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkane Sulfonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 3 -C 6 (alkyl) ring Alkylamino, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 dialkylaminocarbonyl or C 3 -C 6 trialkylsilyl replace.
Preferred 2：其中W为C＝O的通式I的Preferred 1化合物。Preferred 2: Preferred 1 compound of general formula I wherein W is C=O.
值得注意的是其中A为取代的3-吡啶基环的Preferred 2化合物。同样应注意的是这样的Preferred 2化合物，其中Of note are Preferred 2 compounds wherein A is a substituted 3-pyridyl ring. Also of note are Preferred 2 compounds where
每个R5独立的是C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6卤烷基、C2-C6卤链烯基、C2-C6卤炔基、C3-C6卤环烷基、卤素、CN、CO2H、CONH2、NO2、羟基、C1-C4烷氧基、C1-C4卤烷氧基、C1-C4烷基硫代基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、C1-C4卤烷基硫代基、C1-C4卤烷基亚硫酰基、C1-C4卤烷基磺酰基、C1-C4烷氧基羰基、C1-C4烷氨基、C2-C8二烷氨基、C3-C6环烷氨基、C2-C6烷羰基、C2-C6烷氧基羰基、C2-C6烷氨基羰基、C3-C8二烷氨基羰基、C3-C6三烷基硅烷基；条件是当A为2-吡啶基时，R5是除C1-C6卤烷基外的其他基。Each R 5 is independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, CO 2 H, CONH 2 , NO 2 , hydroxyl, C 1 -C 4 Alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 Haloalkylthio, C 1 -C 4 Haloalkylsulfinyl, C 1 -C 4 Haloalkylsulfonyl, C 1 -C 4 Alkoxycarbonyl, C 1 -C 4 Alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 di Alkylaminocarbonyl, C 3 -C 6 trialkylsilyl; the proviso is that when A is 2-pyridyl, R 5 is other groups except C 1 -C 6 haloalkyl.
Preferred 3：Preferred 2化合物，其中Preferred 3: Preferred 2 compounds, where
A为用1-4个R5取代的2-吡啶基环；和A is a 2-pyridyl ring substituted with 1-4 R 5 ; and
B用1-4个R6取代，但至少一个R6与W邻位连接。B is substituted with 1-4 R6s , but at least one R6 is ortho-bonded to W.
应注意的是下列Preferred 3化合物，其中R5为Cl、Br、CH3、OCF3、OCHF2、OCH2CF3、OCF2CF3、OCF2CF2H、OCHFCF3、SCF3、SCHF2、SCH2CF3、SCF2CF3、SCF2CF2H、SCHFCF3、SOCF3、SOCHF2、SOCH2CF3、SOCF2CF3、SOCF2CF2H、SOCHFCF3、SO2CF3、SO2CHF2、SO2CH2CF3、SO2CF2CF3、SO2CF2CF2H或SO2CHFCF3。同样应注意的是这样的Preferred 3化合物，其中B为其一个R6在每个位置与W邻位键连接(和非必需的1-2个其他R6)的3-吡啶基或4-吡啶基环。It should be noted that the following Preferred 3 compounds where R 5 is Cl, Br, CH 3 , OCF 3 , OCHF 2 , OCH 2 CF 3 , OCF 2 CF 3 , OCF 2 CF 2 H, OCHFCF 3 , SCF 3 , SCHF 2 , SCH 2 CF 3 , SCF 2 CF 3 , SCF 2 CF 2 H, SCHFF 3 , SOCF 3 , SOCHF 2 , SOCH 2 CF 3 , SOCF 2 CF 3 , SOCF 2 CF 2 H, SOCHFCF 3 , SO 2 CF 3 , SO2CHF2 , SO2CH2CF3 , SO2CF2CF3 , SO2CF2CF2H , or SO2CHFCF3 . _ _ Also of note are Preferred 3 compounds in which B is a 3-pyridyl or 4-pyridine in which one R6 is bonded at each position to an ortho bond to W (and optionally 1-2 other R6s ) base ring.
Preferred 4：Preferred 3的化合物，其中B为其一个R6在每个位置与W邻位连接，和非必需的1-2个其他R6且R6为卤素或甲基的3-吡啶基或4-吡啶基环。Preferred 4: A compound of Preferred 3, wherein B is 3-pyridyl in which one R6 is connected ortho to W at each position, and optionally 1-2 other R6 and R6 is halogen or methyl, or 4-pyridyl ring.
Preferred 5：其中B为3-吡啶基环的Preferred 4化合物，其中一个R6为Cl且位于与W邻位连接的2-位置上，另一个R6选自Cl或甲基并位于与W邻位连接于4-位置上，第三个非必需的R6为6-位置上的甲基。Preferred 5: Preferred 4 compound wherein B is a 3-pyridyl ring, wherein one R is Cl and is located at the 2-position connected to the ortho position of W, and the other R is selected from Cl or methyl and is located at ortho to W is attached at the 4-position and the third optional R6 is a methyl group at the 6-position.
Preferred 6：其中A为3-氯-5-CF3-2-吡啶基的Preferred 5化合物。Preferred 6: Compound of Preferred 5 wherein A is 3-chloro-5- CF3-2 -pyridyl.
Preferred 7：其中R1为H且R2为CH3的Preferred 3化合物，但尤其是Preferred 4化合物。Preferred 7: Preferred 3 compounds, but especially Preferred 4 compounds, where R 1 is H and R 2 is CH 3 .
Preferred 8：通式II的Preferred 1化合物，其中Preferred 8: Preferred 1 compound of general formula II, wherein
A为用1-4个R5取代的2-吡啶基环；和A is a 2-pyridyl ring substituted with 1-4 R 5 ; and
B用1-4个R6取代，但至少一个R6与共同连接到X和B的碳原子邻位键连接。B is substituted with 1-4 R 6 , but at least one R 6 is bonded ortho to the carbon atom jointly bound to X and B.
Preferred 9：其中X为S的Preferred 5化合物。Preferred 9: Preferred 5 compound where X is S.
本发明的优选化合物包括其中R1为H或CH3、R2为H和(在通式I中)R3为H的Preferred 1到Preferred 9的化合物。Preferred compounds of the invention include compounds of Preferred 1 to Preferred 9 wherein R 1 is H or CH 3 , R 2 is H and (in formula I) R 3 is H.
特别优选的是选自以下的化合物Particularly preferred are compounds selected from
2，4-二氯-N-[[3-氯-5-(三氟甲基)-2-吡啶基]甲基]-3-吡啶甲酰胺、2，4-二氯-N-[1-[3-氯-5-(三氟甲基)-2-吡啶基]乙基]-3-吡啶甲酰胺、2，4-二氯-N-[[3-氯-5-(三氟甲基)-2-吡啶基]甲基]-6-甲基-3-吡啶甲酰胺，和2，4-二氯-N-[1-[3-氯-5-(三氟甲基)-2-吡啶基]乙基]-6-甲基-3-吡啶甲酰胺。2,4-dichloro-N-[[3-chloro-5-(trifluoromethyl)-2-pyridyl]methyl]-3-pyridinecarboxamide, 2,4-dichloro-N-[1 -[3-Chloro-5-(trifluoromethyl)-2-pyridyl]ethyl]-3-pyridinecarboxamide, 2,4-dichloro-N-[[3-chloro-5-(trifluoro Methyl)-2-pyridyl]methyl]-6-methyl-3-pyridinecarboxamide, and 2,4-dichloro-N-[1-[3-chloro-5-(trifluoromethyl) -2-pyridyl]ethyl]-6-methyl-3-pyridinecarboxamide.
同样特别优选的是选自以下的化合物Also particularly preferred are compounds selected from the group consisting of
2，4-二氯-N-[(3，5-二氯-2-吡啶基)甲基]-3-吡啶甲酰胺、2，4-二氯-N-[1-(3，5-二氯-2-吡啶基)乙基]-3-吡啶甲酰胺、2，4-二氯-N-[(3，5-二氯-2-吡啶基)甲基]-6-甲基-3-吡啶甲酰胺、2，4-二氯-N-[1-(3，5-二氯-2-吡啶基)乙基]-6-甲基-3-吡啶甲酰胺、N-[(5-溴-3-氯-2-吡啶基)甲基]-2，4-二氯-3-吡啶甲酰胺、N-[1-(5-溴-3-氯-2-吡啶基)乙基]-2，4-二氯-3-吡啶甲酰胺、N-[(5-溴-3-氯-2-吡啶基)甲基]-2，4-二氯-6-甲基-3-吡啶甲酰胺，和N-[1-(5-溴-3-氯-2-吡啶基)乙基]-2，4-二氯-6-甲基-3-吡啶甲酰胺。2,4-dichloro-N-[(3,5-dichloro-2-pyridyl)methyl]-3-pyridinecarboxamide, 2,4-dichloro-N-[1-(3,5- Dichloro-2-pyridyl)ethyl]-3-pyridinecarboxamide, 2,4-dichloro-N-[(3,5-dichloro-2-pyridyl)methyl]-6-methyl- 3-pyridinecarboxamide, 2,4-dichloro-N-[1-(3,5-dichloro-2-pyridyl)ethyl]-6-methyl-3-pyridinecarboxamide, N-[( 5-bromo-3-chloro-2-pyridyl)methyl]-2,4-dichloro-3-pyridinecarboxamide, N-[1-(5-bromo-3-chloro-2-pyridyl)ethyl Base]-2,4-dichloro-3-pyridinecarboxamide, N-[(5-bromo-3-chloro-2-pyridyl)methyl]-2,4-dichloro-6-methyl-3 - pyridinecarboxamide, and N-[1-(5-bromo-3-chloro-2-pyridyl)ethyl]-2,4-dichloro-6-methyl-3-pyridinecarboxamide.
本发明还涉及含有有效杀真菌量的本发明化合物和选自表面活性剂、固体稀释剂或液体稀释剂的至少一种其他成分的杀真菌剂组合物。本发明优选的组合物是包含上述优选的化合物的那些组合物。The present invention also relates to fungicidal compositions comprising a fungicidally effective amount of a compound of the present invention and at least one other ingredient selected from the group consisting of surfactants, solid diluents or liquid diluents. Preferred compositions of the invention are those comprising the preferred compounds described above.
本发明还涉及由真菌类植物病原体造成的植物病害的控制方法，包括将有效杀真菌量的本发明化合物(例如此处描述的组合物)施用在植物或其一部分上，或施用到植物种子或秧苗上。优选的使用方法是涉及上述优选化合物的方法。The present invention also relates to a method for controlling plant diseases caused by fungal phytopathogens comprising applying to plants or parts thereof, or to plant seeds or On the seedlings. Preferred methods of use are those involving the preferred compounds described above.
通式I和通式II的化合物可通过一种或多种以下方法和方案1-6中描述的变化制备。以下通式1-4的化合物中A、B、L、W、R1到R6、X和n的定义如上所述。通式1a、1b和1c的化合物是通式1的子系统。通式Ia、Ib和Ic的化合物是通式I的化合物的子系统，且通式Ia、Ib和Ic的所有取代基与通式I的以上定义相同。通式IIa的化合物是通式II的化合物的子系统，且通式IIa的所有取代基与通式II的以上定义相同。Compounds of general formula I and general formula II can be prepared by one or more of the following methods and variations described in Schemes 1-6. A, B, L, W, R1 to R6, X and n in the compounds of the following general formulas 1-4 are as defined above. Compounds of general formula 1a, 1b and 1c are subsystems of general formula 1 . Compounds of general formula Ia, Ib and Ic are subsystems of compounds of general formula I, and all substituents of general formula Ia, Ib and Ic are the same as defined above for general formula I. Compounds of general formula IIa are subsystems of compounds of general formula II, and all substituents of general formula IIa are the same as defined above for general formula II.
通式I的化合物可用以下方案1-5中描述的方法制备。通式Ic和IIa的化合物可用以下方案6中描述的方法制备。Compounds of general formula I can be prepared by the methods described in Schemes 1-5 below. Compounds of general formula Ic and IIa can be prepared by the method described in Scheme 6 below.
通式Ia的化合物通过在2摩尔当量的碱(如三乙胺或碳酸钾)存在下，在惰性溶剂中用合适的酰氯处理通式I的铵盐来制备。合适的溶剂选自诸如四氢呋喃、二甲氧基乙烷或二乙醚等醚类；诸如甲苯或二甲苯等烃类；和诸如二氯甲烷或氯仿等卤化碳类。Compounds of general formula Ia are prepared by treating the ammonium salt of general formula I with the appropriate acid chloride in an inert solvent in the presence of 2 molar equivalents of a base such as triethylamine or potassium carbonate. Suitable solvents are selected from ethers such as tetrahydrofuran, dimethoxyethane or diethyl ether; hydrocarbons such as toluene or xylene; and halocarbons such as methylene chloride or chloroform.
方案1 plan 1
作为选择，通式Ia的化合物可通过在诸如1，3-二环己基碳化二亚胺(DCC)或1-[3-(二甲氨基)丙基]-3-乙基碳化二亚胺盐酸盐(EDC)等有机脱水剂存在下，将通式I的铵盐与合适的羧酸反应来合成，如方案2中描述的。合适的溶剂选自诸如四氢呋喃、二甲氧基乙烷或二乙醚等醚类；诸如甲苯或二甲苯等烃类；和诸如二氯甲烷或氯仿等卤化碳类。Alternatively, the compound of general formula Ia can be obtained by adding a compound such as 1,3-dicyclohexylcarbodiimide (DCC) or 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide salt The ammonium salt of general formula I is synthesized by reacting the ammonium salt of general formula I with a suitable carboxylic acid in the presence of an organic dehydrating agent such as dihydrochloride (EDC), as described in Scheme 2. Suitable solvents are selected from ethers such as tetrahydrofuran, dimethoxyethane or diethyl ether; hydrocarbons such as toluene or xylene; and halocarbons such as methylene chloride or chloroform.
方案2 Scenario 2
其中A为带有所指出的取代基的2-吡啶基，且R1、R2和R3为氢的中间产物盐1a可用与WO99/42447中类似的方法，通过在诸如氢化钠的强碱存在下，在诸如N，N-二甲基甲酰胺的极性、非质子传递溶剂中，将方案3中所示的商购亚胺酯5与R5取代的2，3-二氯吡啶(通式4)反应，然后在酸性介质中加热来制备。通式1b的化合物可通过类似的方法制备，其中在酸性介质中加热前，先将步骤1得到的中间阴离子用诸如甲基碘化物的烷基化剂处理。应注意其中R5为CF3的化合物。The intermediate salt 1a, wherein A is 2-pyridyl with the indicated substituents, and R 1 , R 2 and R 3 are hydrogen, can be obtained in a strong base such as sodium hydride in a manner similar to that in WO99/42447. Commercially available imidate 5 shown in Scheme 3 was combined with R substituted 2,3-dichloropyridine ( Formula 4) reaction, and then heated in an acidic medium to prepare. Compounds of general formula 1b can be prepared in a similar manner by treating the intermediate anion obtained in step 1 with an alkylating agent such as methyl iodide before heating in an acidic medium. Attention should be paid to compounds in which R5 is CF3 .
方案3 Option 3
带有一个氨甲基的通式1c的化合物(其中A为取代的吡啶基环)可通过用氢化铝锂在甲苯中还原通式2的腈(其中A为取代的吡啶基环)，得到相应的氨甲基中间产物来合成(方案4)。A compound of general formula 1c (wherein A is a substituted pyridyl ring) with an aminomethyl group can be obtained by reducing a nitrile of general formula 2 (wherein A is a substituted pyridyl ring) in toluene with lithium aluminum hydride to give the corresponding The aminomethyl intermediates were synthesized (Scheme 4).
方案4 Option 4
A为取代的吡啶基环A is a substituted pyridyl ring
作为选择，通式1c的化合物(其中A如上定义和R1和R2为氢的化合物)可通过在诸如甲醇等质子溶剂中，将通式3的化合物与氨反应来合成。通式1c的化合物也可以通过将通式3的化合物与邻苯二甲酰亚胺的钾盐反应，然后在醇溶剂中与氨基乙醇或肼反应，以提供要求亚胺的钾盐反应，然后在醇溶剂中与氨基乙醇或肼反应，以提供要求的氨基甲基中间产物，通式1c来制备(方案5)。Alternatively, compounds of general formula 1c (compounds wherein A is as defined above and R1 and R2 are hydrogen) can be synthesized by reacting compounds of general formula 3 with ammonia in a protic solvent such as methanol. The compound of general formula 1c can also be reacted by reacting the compound of general formula 3 with the potassium salt of phthalimide, and then reacting with aminoethanol or hydrazine in an alcoholic solvent to provide the potassium salt reaction of the desired imine, and then Reaction with aminoethanol or hydrazine in an alcoholic solvent provides the desired aminomethyl intermediate, prepared by general formula 1c (Scheme 5).
方案5 Option 5
LG为Cl，Br，-OSO2Me，-OSO2-p-TolLG is Cl, Br, -OSO 2 Me, -OSO 2 -p-Tol
通式IIa的化合物(其中R1、R2、A和B与上述定义相同且X为S)可如方案6概述的那样合成。下面所示通式Ib的酰胺(其中R3为H的通式I的化合物)可通过将酰胺与Lawessond’s的试剂或五硫化二磷在合适的溶剂中接触而转化为通式Ic的硫代酰胺(参见March；J.Advanced Organic Chemistry，第4版，pp893-4)。然后可用合适的烷基化剂，在诸如碳酸钾、氢化钠或氢氧化钾的碱存在下，将硫代酰胺烷基化。合适溶剂可包括(但不限于)诸如四氢呋喃、二甲氧基乙烷或二乙醚等醚类；诸如甲苯或二甲苯等烃类；和诸如二氯甲烷或氯仿等卤化碳类。Compounds of general formula Ha, wherein R 1 , R 2 , A and B are as defined above and X is S, can be synthesized as outlined in Scheme 6. Amides of general formula Ib shown below (compounds of general formula I wherein R is H) can be converted to thioamides of general formula Ic by contacting the amide with Lawessond's reagent or phosphorus pentasulfide in a suitable solvent (see March ; J. Advanced Organic Chemistry, 4th Ed., pp893-4). The thioamide can then be alkylated with a suitable alkylating agent in the presence of a base such as potassium carbonate, sodium hydride or potassium hydroxide. Suitable solvents may include, but are not limited to, ethers such as tetrahydrofuran, dimethoxyethane, or diethyl ether; hydrocarbons such as toluene or xylene; and halocarbons such as methylene chloride or chloroform.
方案6 Option 6
已经知道：上述制备通式I的化合物的某些试剂和反应条件可不与中间产物中存在的某些官能度相容。在这些实例中，在合成中插入保护/去保护顺序或官能团互变有助于获得要求的产物。使用和选择保护基团对于化学合成领域的普通技术人员是很明显的(参见例如Greene，T.W.；Wuts，P.G.M.Protective Groups in OrganicSynthesis，第二版；Wiley：纽约，1991)。本领域普通技术人员知道：在某些情况下，引入任何单个方案中描述的给定试剂后，也许要进行未详细描述的其他合成路径，以完成通式I的化合物的合成。本领域普通技术人员还知道：也许要以除上述方案中提出的特定顺序外的其他顺序将几个步骤结合，以制备通式I的化合物。It is known that certain reagents and reaction conditions described above for the preparation of compounds of general formula I may not be compatible with certain functionalities present in the intermediate products. In these instances, insertion of protection/deprotection sequences or functional group interconversions during the synthesis was helpful in obtaining the desired products. The use and selection of protecting groups will be apparent to those of ordinary skill in the art of chemical synthesis (see for example Greene, T.W.; Wuts, P.G.M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). Those of ordinary skill in the art are aware that in some cases, following the introduction of a given reagent described in any single scheme, other synthetic routes not described in detail may be followed to complete the synthesis of compounds of general formula I. Those of ordinary skill in the art also recognize that several steps may be combined in an order other than the specific order set forth in the above schemes to prepare compounds of general formula I.
本领域普通技术人员还知道：通式I的化合物和此处描述的中间产物可进行各种亲电子反应、亲核反应、自由基间的反应、有机金属反应、氧化反应和还原反应，以增加取代基或改性现有取代基。Those of ordinary skill in the art also know: the compound of general formula I and the intermediate product described here can carry out various electrophilic reaction, nucleophilic reaction, reaction between free radicals, organometallic reaction, oxidation reaction and reduction reaction, to increase substitution groups or modify existing substituents.
不必进行其他工作，可认为本领域普通技术人员用上述方法能利用本发明达到其全部目的。因此以下实施例仅用于举例说明，而不以任何方式限制本发明。除色谱溶剂混合物或另有说明外，百分比均为重量百分比。除另有说明外，色谱溶剂混合物的份数和百分数均为体积数。1H NMR谱从四甲基硅烷的低磁场以ppm给出；s为单峰、d为双峰、t为三峰、q为四峰、m为多峰、dd为双双峰、dt为三双峰、br为宽单峰。No further work is required, and it is believed that one of ordinary skill in the art can utilize the present invention to achieve its full purpose by using the methods described above. Therefore the following examples are for illustration only and do not limit the invention in any way. Percentages are by weight unless chromatographic solvent mixtures or otherwise stated. Parts and percentages of chromatographic solvent mixtures are by volume unless otherwise indicated. 1 H NMR spectra are given in ppm downfield from tetramethylsilane; s is singlet, d is doublet, t is triplet, q is quadruplet, m is multimodal, dd is doublet doublet, dt is triplet Doublet, br is a broad singlet.
实施例1 Example 1
2，4-二氯-N-[[3-氯-5-(三氟甲基)-2-吡啶基]甲基] 2,4-dichloro-N-[[3-chloro-5-(trifluoromethyl)-2-pyridyl]methyl]
-6-甲基-3-吡啶甲酰胺 -6-Methyl-3-pyridinecarboxamide
(检索表B的化合物8)的制备 (compound 8 of retrieval form B) preparation
步骤A：2，4-二氯-N-[[3-氯-5-(三氟甲基)-2-吡啶基]甲基]-6-甲基Step A: 2,4-Dichloro-N-[[3-chloro-5-(trifluoromethyl)-2-pyridyl]methyl]-6-methyl -3-吡啶甲酰胺的制备- Preparation of 3-pyridinecarboxamide
化合物8用2-氨基甲基-3-氯-5-三氟甲基吡啶盐酸盐制备(按WO99/42447描述的方法制备)。将2mL二氯甲烷中的2，4-二氯-6-甲基-3-吡啶甲酰氯(0.65g)在室温下加入10mL二氯甲烷中的2-氨基甲基-3-氯-5-三氟甲基吡啶盐酸盐(0.79g)和三乙胺(0.68g)溶液中。室温下搅拌反应混合物一夜。然后将反应混合物倒入1英寸硅胶管塞顶部，用30mL二氯甲烷洗脱，旋转蒸发洗脱剂，得到0.69g本发明的化合物酰胺(化合物8)。1H NMR(CDCl3；300MHz)δ2.57(s，3H)、4.96(m，2H)、7.22(s，1H)、7.48(bs，1H)、8.00(s，1H)、8.71(s，1H)。Compound 8 was prepared from 2-aminomethyl-3-chloro-5-trifluoromethylpyridine hydrochloride (prepared as described in WO99/42447). 2,4-Dichloro-6-methyl-3-pyridinecarbonyl chloride (0.65 g) in 2 mL of dichloromethane was added to 2-aminomethyl-3-chloro-5- Trifluoromethylpyridine hydrochloride (0.79g) and triethylamine (0.68g) solution. The reaction mixture was stirred overnight at room temperature. The reaction mixture was then poured onto the top of a 1 inch silica gel tube plug, eluted with 30 mL of dichloromethane, and the eluent was rotovapped to afford 0.69 g of the compound amide of the invention (compound 8). 1 H NMR (CDCl 3 ; 300MHz) δ2.57(s, 3H), 4.96(m, 2H), 7.22(s, 1H), 7.48(bs, 1H), 8.00(s, 1H), 8.71(s, 1H).
实施例2 Example 2
2，4-二氯-N-[[3-氯-5-(三氟甲基)-2-吡啶基]甲基] 2,4-dichloro-N-[[3-chloro-5-(trifluoromethyl)-2-pyridyl]methyl]
-3-吡啶甲酰胺的制备 - Preparation of 3-pyridinecarboxamide
步骤A：2，4-二氯吡啶的制备Step A: Preparation of 2,4-dichloropyridine
将6.7g 4-硝基吡啶N-氧化物在POCl3中的溶液回流3小时，然后冷却到室温。真空下除去溶剂，剩下油状残余物。小心加入饱和碳酸氢钠溶液(200mL)，随后用二氯甲烷(2X)提取。然后在真空下除去二氯甲烷，通过硅胶管塞过滤得到油脂，并用己烷中的20％乙酸乙酯洗脱。真空下除去溶剂，得到1.6g油脂。1H NMR(CDCl3；300MHz)δ7.25(dd，1H，J为1.7，5.4Hz)、7.38(d，1H，J为1.7Hz)、8.31(d，1H，J为5.4Hz)。A solution of 6.7 g of 4-nitropyridine N-oxide in POCl3 was refluxed for 3 hours and then cooled to room temperature. The solvent was removed in vacuo to leave an oily residue. Sat. sodium bicarbonate solution (200 mL) was added carefully, followed by extraction with dichloromethane (2X). The dichloromethane was then removed under vacuum and the oil was filtered through a plug of silica gel and eluted with 20% ethyl acetate in hexanes. The solvent was removed in vacuo to yield 1.6 g of grease. 1 H NMR (CDCl 3 ; 300 MHz) δ 7.25 (dd, 1H, J is 1.7, 5.4 Hz), 7.38 (d, 1H, J is 1.7 Hz), 8.31 (d, 1H, J is 5.4 Hz).
步骤B：2，4-二氯-3-吡啶甲醛的制备Step B: Preparation of 2,4-dichloro-3-pyridinecarbaldehyde
在氮气下将1.6g 2，4-二氯吡啶在5mL干四氢呋喃(THF)中的溶液加入-70℃的25mL THF中的6mL二异丙基氨基化锂中，随后在该温度下搅拌3小时。然后在-70℃下加入1mL干燥的N，N-二甲基甲酰胺，随后在该温度下搅拌1小时。然后加入25mL饱和氯化铵溶液，并在室温下搅拌反应混合物过夜。用25mL水稀释反应混合物，并用乙酸乙酯(2X)提取。在真空下蒸馏合并的有机相，得到固体并溶解在5mL二氯甲烷中，并用硅胶过滤，用100％的二氯甲烷洗脱。真空下除去溶剂，得到标题所示的固体中间产物。1H NMR(CDCl3；300MHz)δ7.41(d，1H，J为5.3Hz)、8.42(d，1H，J为5.2Hz)、10.5(s，1H)。A solution of 1.6 g of 2,4-dichloropyridine in 5 mL of dry tetrahydrofuran (THF) was added to 6 mL of lithium diisopropylamide in 25 mL of THF at -70 °C under nitrogen, followed by stirring at this temperature for 3 h . Then 1 mL of dry N,N-dimethylformamide was added at -70°C, followed by stirring at this temperature for 1 hour. Then 25 mL of saturated ammonium chloride solution was added and the reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with 25 mL of water and extracted with ethyl acetate (2X). The combined organic phases were distilled under vacuum to give a solid which was dissolved in 5 mL of dichloromethane and filtered through silica gel eluting with 100% dichloromethane. The solvent was removed in vacuo to afford the title solid intermediate. 1 H NMR (CDCl 3 ; 300 MHz) δ 7.41 (d, 1H, J at 5.3 Hz), 8.42 (d, 1H, J at 5.2 Hz), 10.5 (s, 1H).
步骤C：2，4-二氯烟酸的制备Step C: Preparation of 2,4-dichloronicotinic acid
将来自步骤B的0.40g醛的溶液溶解在6mL THF中，然后加入0.27g亚氯酸钠和0.29g氨基磺酸在6mL水中的溶液。在室温下搅拌反应混合物过夜。用1N氢氧化钠(10mL)稀释反应混合物，并用二乙醚(1X)提取。然后用浓盐酸酸化水层，用二氯甲烷(2X)提取，并用硫酸镁干燥合并的二氯甲烷提取液。真空下除去二氯甲烷，得到0.22g固体。1H NMR(CDCl3；300MHz)δ7.38(d，1H，J为5.4Hz)、8.40(d，1H，J为5.5Hz)、8.60(bs，1H)。A solution of 0.40 g of the aldehyde from Step B was dissolved in 6 mL of THF, then a solution of 0.27 g of sodium chlorite and 0.29 g of sulfamic acid in 6 mL of water was added. The reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with 1N sodium hydroxide (10 mL) and extracted with diethyl ether (1X). The aqueous layer was then acidified with concentrated hydrochloric acid, extracted with dichloromethane (2X), and the combined dichloromethane extracts were dried over magnesium sulfate. The dichloromethane was removed in vacuo to give 0.22 g of a solid. 1 H NMR (CDCl 3 ; 300 MHz) δ 7.38 (d, 1H, J at 5.4 Hz), 8.40 (d, 1H, J at 5.5 Hz), 8.60 (bs, 1H).
步骤D：2，4-二氯-N-[[3-氯-5-(三氟甲基)-2-吡啶基]甲基]-3-吡啶Step D: 2,4-Dichloro-N-[[3-chloro-5-(trifluoromethyl)-2-pyridyl]methyl]-3-pyridine 甲酰胺的制备Preparation of formamide
将来自步骤C的0.22g酸的溶液在亚硫酰氯中回流1小时，随后真空下除去溶剂得到油脂状物。将该油脂溶解在1mL二氯甲烷中，并在室温下加入2-氨甲基-3-氯-5-三氟甲基吡啶盐酸盐(0.25g)和三乙铵(0.20g)在9mL二氯甲烷中的溶液。在室温下搅拌反应混合物过夜。然后通过硅胶过滤反应混合物，并用100％的二氯甲烷洗脱。真空下除去溶剂，得到固体标题化合物，熔点为122-124℃。A solution of 0.22 g of the acid from Step C was refluxed in thionyl chloride for 1 hour, then the solvent was removed in vacuo to give a grease. Dissolve the oil in 1 mL of dichloromethane, and add 2-aminomethyl-3-chloro-5-trifluoromethylpyridine hydrochloride (0.25 g) and triethylammonium (0.20 g) in 9 mL of solution in dichloromethane. The reaction mixture was stirred overnight at room temperature. The reaction mixture was then filtered through silica gel and eluted with 100% dichloromethane. The solvent was removed in vacuo to give the title compound as a solid, mp 122-124°C.
实施例3 Example 3
2，4-二氯-N-[1-[3-氯-5-(三氟甲基)-2-吡啶基]乙基] 2,4-dichloro-N-[1-[3-chloro-5-(trifluoromethyl)-2-pyridyl]ethyl]
-3-吡啶甲酰胺的制备 - Preparation of 3-pyridinecarboxamide
步骤A：3-氯-α-甲基-5-(三氟甲基)-2-吡啶甲胺的制备Step A: Preparation of 3-chloro-α-methyl-5-(trifluoromethyl)-2-pyridinemethanamine
在室温下将N-(二苯基亚甲基)甘氨酸乙酯(2.25g)加入到氢化钠在20mL干燥N，N-二甲基甲酰氨中的悬浮液(0.74g 60％的油状分散体)中，产生剧烈的气体排放。室温下搅拌5分钟后，加入2g 2，3-二氯-5-三氟甲基吡啶，随后在室温下搅拌1小时。然后加入0.80mL甲基碘，随后在室温下搅拌一夜。将反应混合物倒入冰水中，用二乙醚(2X)提取，并在真空下蒸馏除去溶剂，留下油状物。然后将该油脂在6N HCl中回流过夜。将反应混合物冷却到室温，用固体碳酸钠使其变成碱性，并用二乙醚(2X)提取。用硫酸镁干燥合并的提取物，真空下蒸馏除去溶剂，留下1.5g油脂。1H NMR(CDCl3；300MHz)δ1.4(d，3H，J为6.6Hz)、4.6(bs，1H)、7.88(m，1H)、8.75(bs，1H)。N-(diphenylmethylene)glycine ethyl ester (2.25 g) was added to a suspension of sodium hydride in 20 mL of dry N,N-dimethylformamide (0.74 g of a 60% oil dispersion) at room temperature body), severe gas emissions are generated. After stirring at room temperature for 5 minutes, 2 g of 2,3-dichloro-5-trifluoromethylpyridine was added, followed by stirring at room temperature for 1 hour. Then 0.80 mL of methyl iodide was added, followed by stirring overnight at room temperature. The reaction mixture was poured into ice water, extracted with diethyl ether (2X), and the solvent was distilled off in vacuo to leave an oil. The grease was then refluxed overnight in 6N HCl. The reaction mixture was cooled to room temperature, made basic with solid sodium carbonate, and extracted with diethyl ether (2X). The combined extracts were dried over magnesium sulfate and the solvent was distilled off in vacuo, leaving 1.5 g of oil. 1 H NMR (CDCl 3 ; 300 MHz) δ 1.4 (d, 3H, J at 6.6 Hz), 4.6 (bs, 1H), 7.88 (m, 1H), 8.75 (bs, 1H).
步骤B：2，4-二氯-N-[1-[3-氯-5-(三氟甲基)-2-吡啶基]乙基]-3-吡Step B: 2,4-Dichloro-N-[1-[3-chloro-5-(trifluoromethyl)-2-pyridyl]ethyl]-3-pyridine 啶甲酰胺的制备Preparation of pyridinecarboxamide
将实施例1步骤C中制备的2，4-二氯烟酰氯(0.40g)在室温下加入到步骤A得到的胺中间产物(0.66g)和三乙胺(0.70g)在30mL二氯甲烷中的溶液中，随后搅拌一夜。真空下蒸馏反应混合物以除去溶剂，通过硅胶过滤并用100％二氯甲烷作为洗脱剂得到油脂。然后在真空下除去溶剂，得到红色油脂状标题化合物，即本发明的化合物。1HNMR(CDCl3；300MHz)δ1.62(d，3H，J为6.7Hz)、5.48(m，1H)、7.35(d，1H，J为5.2Hz)、7.40(d，1H，J为6.9)、7.99(d，1H，J为1.8Hz)、8.34(d，1H，J为5.2)、8.70(s，1H)。2,4-dichloronicotinoyl chloride (0.40 g) prepared in step C of Example 1 was added to the amine intermediate (0.66 g) and triethylamine (0.70 g) obtained in step A at room temperature in 30 mL of dichloromethane solution, followed by stirring overnight. The reaction mixture was distilled under vacuum to remove solvent and filtered through silica gel using 100% dichloromethane as eluent to give an oil. The solvent was then removed in vacuo to afford the title compound, a compound of the invention, as a red oil. 1 HNMR (CDCl 3 ; 300MHz) δ1.62 (d, 3H, J is 6.7Hz), 5.48 (m, 1H), 7.35 (d, 1H, J is 5.2Hz), 7.40 (d, 1H, J is 6.9 ), 7.99 (d, 1H, J is 1.8Hz), 8.34 (d, 1H, J is 5.2), 8.70 (s, 1H).
实施例4 Example 4
(+)-2，4-二氯-N-[1-[3-氯-5-(三氟甲基)-2-吡啶基]乙基](+)-2,4-dichloro-N-[1-[3-chloro-5-(trifluoromethyl)-2-pyridyl]ethyl]
-3-吡啶甲酰胺的制备 - Preparation of 3-pyridinecarboxamide
步骤A：3-氯-α-甲基-5-(三氟甲基)-2-吡啶甲胺的拆分Step A: Resolution of 3-chloro-α-methyl-5-(trifluoromethyl)-2-pyridinemethanamine
将(-)-氯甲酸薄荷酯(0.92g)在室温下加入到实施例3步骤A制备的α-甲基胺(1g)和三乙胺(1.2mL)在25mL THF中的溶液中，随后在室温下搅拌30分钟。然后真空除去溶剂，得到包含通过柱色谱(以5％二乙醚的己烷溶液作为洗脱剂)分离的两种氨基甲酸薄荷酯非对映体的油脂，得到0.20g更极性的非对映体油脂状物。然后在5mL三氟乙酸中回流该油脂4小时，以裂开氨基甲酸薄荷酯。将反应混合物冷却到室温，并用水(30mL)稀释，用固体碳酸钠使其变成碱性，并用二氯甲烷提取。通过硫酸镁干燥有机层，真空蒸馏得到60mg油脂状对映体富集的胺中间产物。1H NMR(CDCl3；300MHz)δ1.41(d，3H，J为6.7Hz)、1.9(bs，2H)、4.60(m，1H)、7.88(m，1H)、8.74(s，1H)。(-)-Menthyl chloroformate (0.92 g) was added to a solution of α-methylamine (1 g) and triethylamine (1.2 mL) prepared in Step A of Example 3 at room temperature in 25 mL of THF, followed by Stir at room temperature for 30 minutes. The solvent was then removed in vacuo to give an oil containing the two menthyl carbamate diastereomers separated by column chromatography (5% diethyl ether in hexane as eluent) to yield 0.20 g of the more polar diastereomer Body fat. The lipid was then refluxed in 5 mL of trifluoroacetic acid for 4 hours to cleave the menthyl carbamate. The reaction mixture was cooled to room temperature and diluted with water (30 mL), made basic with solid sodium carbonate and extracted with dichloromethane. The organic layer was dried over magnesium sulfate and vacuum distilled to give 60 mg of the enantiomerically enriched amine intermediate as an oil. 1 H NMR (CDCl 3 ; 300MHz) δ1.41(d, 3H, J is 6.7Hz), 1.9(bs, 2H), 4.60(m, 1H), 7.88(m, 1H), 8.74(s, 1H) .
步骤B：(+)-2，4-二氯-N-[1-[3-氯-5-(三氟甲基)-2-吡啶基]乙Step B: (+)-2,4-Dichloro-N-[1-[3-chloro-5-(trifluoromethyl)-2-pyridyl]B 基]-3-吡啶甲酰胺的制备Preparation of base]-3-pyridinecarboxamide
将实施例1步骤C中制备的2，4-二氯烟酰氯(0.56g)在室温下加入到步骤A得到的对映体富集的胺(60mg)和三乙胺(54mg)在10mL二氯甲烷中的溶液中，随后搅拌一夜。然后通过硅胶过滤反应混合物并用100％二氯甲烷作为洗脱剂。在真空下除去溶剂，得到本标题的固体化合物，即本发明的化合物，熔点为110-111℃。约2mg本标题化合物在1mL CDCl3中的溶液的旋光仪测定表明平面偏振光在(+)或右旋方向。The 2,4-dichloronicotinoyl chloride (0.56 g) prepared in Step C of Example 1 was added to the enantiomerically enriched amine (60 mg) and triethylamine (54 mg) obtained in Step A at room temperature in 10 mL of diethylamine solution in methyl chloride, followed by stirring overnight. The reaction mixture was then filtered through silica gel using 100% dichloromethane as eluent. The solvent was removed in vacuo to give the title compound, a compound of the invention, as a solid, mp 110-111°C. Polarimeter measurements of a solution of approximately 2 mg of the title compound in 1 mL of CDCl3 showed plane polarized light in the (+) or dextrorotatory direction.
用已在实施例4步骤A中获得的相反的对映体中富集的3-氯-α-甲基-5-(三氟甲基)-2-吡啶甲胺，以类似方式制备实施例4的对映体(-)-2，4-二氯-N-[1-[3-氯-5-(三氟甲基)-2-吡啶基]乙基]-3-吡啶甲酰胺。Using 3-chloro-α-methyl-5-(trifluoromethyl)-2-picolylmethanamine enriched in the opposite enantiomer already obtained in step A of Example 4, the example was prepared in a similar manner Enantiomer of 4 (-)-2,4-dichloro-N-[1-[3-chloro-5-(trifluoromethyl)-2-pyridyl]ethyl]-3-pyridinecarboxamide.
实施例5 Example 5
N-[1-(5-溴-3-氯-2-吡啶基)乙基]-2，4-二氯-3-吡啶甲酰胺的制备Preparation of N-[1-(5-bromo-3-chloro-2-pyridyl)ethyl]-2,4-dichloro-3-pyridinecarboxamide
步骤A：5-溴-3-氯-2(1H)-吡啶酮的制备Step A: Preparation of 5-bromo-3-chloro-2(1H)-pyridone
将6.2g氯酸钾的100mL水溶液加入到预热至50-60℃的25g 5-溴-2-吡啶酮的100mL浓HCl溶液中，搅拌5分钟形成浓的沉淀物。然后加入60mL水以有利于搅拌，并室温搅拌混合物一夜。过滤反应混合物，用水(2X)捣碎，真空干燥沉淀物得到17.7g要求的固体中间物。NMR(CDCl3；300MHz)：δ7.53(d，1H，J为2.6Hz)、7.75(d，1H，J为2.5Hz)。Add 6.2 g of potassium chlorate in 100 mL of aqueous solution to 25 g of 5-bromo-2-pyridone in 100 mL of concentrated HCl solution preheated to 50-60° C., and stir for 5 minutes to form a concentrated precipitate. Then 60 mL of water was added to facilitate stirring, and the mixture was stirred at room temperature overnight. The reaction mixture was filtered, triturated with water (2X), and the precipitate dried in vacuo to yield 17.7 g of the desired solid intermediate. NMR (CDCl 3 ; 300 MHz): δ 7.53 (d, 1H, J at 2.6 Hz), 7.75 (d, 1H, J at 2.5 Hz).
步骤B：5-溴-2，3-二氯吡啶的制备Step B: Preparation of 5-bromo-2,3-dichloropyridine
将步骤A的产物(17.7g)和10g PCl5与100mL POCl3混和，洗涤回流混合物4小时。减压浓缩反应混合物，以除去大部分POCl3，小心倒入温水中，冷却到室温然后用二氯甲烷(2X)提取。通过硫酸镁干燥合并的提取物，浓缩得到油脂状物，并进行柱色谱(8∶2/己烷∶EtOAc)得到4.2g要求的油脂状中间产物。NMR(CDCl3；300MHz)：δ7.94(d，1H，J为2.2Hz)、8.37(d，1H，J为2.3Hz)。The product from Step A (17.7 g) and 10 g of PCl 5 were mixed with 100 mL of POCl 3 and the refluxed mixture was washed for 4 hours. The reaction mixture was concentrated under reduced pressure to remove most of the POCl3 , poured carefully into warm water, cooled to room temperature and extracted with dichloromethane (2X). The combined extracts were dried over magnesium sulfate, concentrated to an oil, and column chromatographed (8:2/hexanes:EtOAc) to give 4.2 g of the desired oily intermediate. NMR (CDCl 3 ; 300 MHz): δ 7.94 (d, 1H, J at 2.2 Hz), 8.37 (d, 1H, J at 2.3 Hz).
步骤C：5-溴-3-氯-α-甲基-2-吡啶甲胺盐酸盐的制备Step C: Preparation of 5-bromo-3-chloro-α-methyl-2-pyridinemethanamine hydrochloride
在氮气下将4.1g步骤B的标题化合物加入到氢化钠在30mL干N，N-二甲基甲酰胺中的悬浮液(60％油状悬浮液)中，冷却到0℃。在不用外源性热源的条件下分批加入N-(二苯基亚甲基)甘氨酸乙酯(4.6g)，室温搅拌混合物3小时。然后以低于30℃加入3.4mL甲基碘，室温搅拌反应混合物一夜。用水稀释反应混合物并用二乙醚(2X)提取。用饱和盐水冲洗混和的提取液，在真空中浓缩成油脂，然后在50mL 12N HCl中回流4小时。真空浓缩反应混合物成油脂，冷却并用二乙醚制浆一夜。然后倒掉醚，在真空炉中干燥残余物，得到1.3g要求的固体中间物。NMR(CDCl3；300MHz)：1.40和1.46(2双峰，3H，J为7.0Hz)、4.7(m，1H)、8.48(d，1H，J为1.8)、8.6(bs，3H)、8.79(d，1H，J为1.9Hz)。Add 4.1 g of the title compound from Step B to a suspension of sodium hydride in 30 mL of dry N,N-dimethylformamide (60% oily suspension) under nitrogen and cool to 0°C. Ethyl N-(diphenylmethylene)glycine (4.6 g) was added in portions without exogenous heat source, and the mixture was stirred at room temperature for 3 hours. Then 3.4 mL of methyl iodide was added below 30 °C and the reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with water and extracted with diethyl ether (2X). The combined extracts were washed with saturated brine, concentrated to oil in vacuo, and then refluxed in 50 mL of 12N HCl for 4 hours. The reaction mixture was concentrated in vacuo to a grease, cooled and slurried with diethyl ether overnight. The ether was then poured off and the residue was dried in a vacuum oven to yield 1.3 g of the desired solid intermediate. NMR (CDCl 3 ; 300MHz): 1.40 and 1.46 (2 doublets, 3H, J at 7.0Hz), 4.7 (m, 1H), 8.48 (d, 1H, J at 1.8), 8.6 (bs, 3H), 8.79 (d, 1H, J at 1.9 Hz).
步骤D：N-[1-(5-溴-3-氯-2-吡啶基)乙基]-2，4-二氯-3-吡啶甲酰胺Step D: N-[1-(5-Bromo-3-chloro-2-pyridyl)ethyl]-2,4-dichloro-3-pyridinecarboxamide 的制备preparation of
将步骤C的产物(0.80g)、1.21mL三乙胺和0.62g 2，4-二氯烟酰氯在20℃以下按顺序混和到25mL二氯甲烷中，室温搅拌混合物一夜。真空浓缩反应混合物，制备本标题的固体化合物，即本发明的化合物。NMR(CDCl3；300MHz)：δ1.59(d，3H，J为6.6Hz)、5.75(m，1H)、7.3(bs，1H)、7.34(d，1H，J为5.2Hz)、7.91(d，1H，J为1.9Hz)、8.33(d，1H，J为5.4Hz)、8.49(d，1H，J为1.9Hz)。The product of step C (0.80 g), 1.21 mL of triethylamine and 0.62 g of 2,4-dichloronicotinoyl chloride were sequentially mixed into 25 mL of dichloromethane at below 20° C., and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated in vacuo to produce the title compound, a compound of the invention, as a solid. NMR (CDCl 3 ; 300MHz): δ1.59 (d, 3H, J is 6.6Hz), 5.75 (m, 1H), 7.3 (bs, 1H), 7.34 (d, 1H, J is 5.2Hz), 7.91 ( d, 1H, J at 1.9 Hz), 8.33 (d, 1H, J at 5.4 Hz), 8.49 (d, 1H, J at 1.9 Hz).
实施例6 Example 6
2，4-二氯-N-[1-(3，5-二氯-2-吡啶基)乙基]-3-吡啶甲酰胺的制备Preparation of 2,4-dichloro-N-[1-(3,5-dichloro-2-pyridyl)ethyl]-3-pyridinecarboxamide
实施例6的制备方法与实施例5类似，用2-溴-3，5-二氯吡啶作原料，以实施例5的步骤C(制备3，5-二氯-α-甲基-2-吡啶甲胺)和D中描述的类似条件处理该原料，得到固体的本标题化合物，即本发明化合物。NMR(CDCl3；300MHz)：δ1.58(d，3H，J为6.6Hz)、5.7-5.8(m，1H)、7.4(m，2H)、7.77(m，1H)、8.35(m，1H)、8.40(m，1H)。The preparation method of embodiment 6 is similar to embodiment 5, with 2-bromo-3,5-dichloropyridine as raw material, with step C of embodiment 5 (preparation of 3,5-dichloro-α-methyl-2- Pyridinemethanamine) and similar conditions described in D to give the title compound, a compound of the invention, as a solid. NMR (CDCl 3 ; 300MHz): δ1.58(d, 3H, J is 6.6Hz), 5.7-5.8(m, 1H), 7.4(m, 2H), 7.77(m, 1H), 8.35(m, 1H ), 8.40 (m, 1H).
通过此处描述的方法与本领域公知方法一起，可制备下表1-9的化合物。以下简写用于下表中：t为叔、s为仲、n为正、i为异、c为环、Me为甲基、Et为乙基、Pr为丙基、i-Pr为异丙基、Bu为丁基、Ph为苯基、OMe为甲氧基、OEt为乙氧基、SMe为甲基硫代基、SEt为乙基硫代基、CN为氰基、NO2为硝基、TMS为三甲基硅烷基、S(O)Me为甲基亚硫酰基和S(O)2Me为甲基磺酰基。取代基M、Q和R与指定位置的独立R5取代基等同。取代基T、U和V与指定位置的独立R6取代基等同。The compounds of Tables 1-9 below can be prepared by the methods described herein together with methods well known in the art. The following abbreviations are used in the table below: t is tertiary, s is secondary, n is normal, i is iso, c is ring, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl , Bu is butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, SEt is ethylthio, CN is cyano, NO2 is nitro, TMS is trimethylsilyl, S(O)Me is methylsulfinyl and S(O) 2Me is methylsulfonyl. The substituents M, Q and R are equivalent to the independent R substituents at the indicated positions. The substituents T, U and V are equivalent to the independent R substituents at the indicated positions.
表1 Table 1
表2 Table 2
表3 table 3
表4 Table 4
T和V均为Cl，U为H
T和V均为Cl，U为Me
T为Cl，V和U均为Me
表5 table 5
T和V均为Cl，U为H
T和V均为Cl，U为Me
T为Cl，V和U均为Me
表6 Table 6
T和V均为Cl，U为H
T和V均为Cl，U为Me
T为Cl，V和U均为Me
表7 Table 7
T和V均为Cl，U为H
T和V均为Cl，U为Me
T为Cl，V和U均为Me
表8 Table 8
T和V均为Cl，U为H
T和V均为Cl，U为Me
T为Cl，V和U均为Me
表9 Table 9
T和V均为Cl，U为H
T和V均为Cl，U为Me
T为Cl，V和U均为Me
表10 Table 10
表11 Table 11
表12 Table 12
制剂/实用性Formulation/Availability
本发明化合物通常可用作具有包含至少一种液体稀释剂、固体稀释剂或表面活性剂的农业载体的制剂或组合物。配方或组合物成分的选择与活性成分的物理性能、应用模式和诸如土壤类型、水分和温度等环境因素一致。有用的制剂包括诸如溶液(包括可乳化的浓缩物)、悬浮液、乳液(包括微乳液和/或悬浮乳液(suspoemulsions))等液体，它们可非必需的增稠成凝胶。有用的配方还包括诸如粉剂、粉末、颗粒、丸、片、膜等固体，它们可分散在水中(“可润湿的”)或可溶于水。活性成分可以是被(微)包封的，可进一步形成悬浮液或固体制剂；作为选择，活性成分的整个制剂都可以包敷(或“包涂”)。包敷能控制或延时释放活性成分。喷雾剂可延伸到合适介质中，并以每公顷约100到几百升的量应用。高强度组合物主要用作进一步制剂的中间产物。The compounds of the invention are generally useful as formulations or compositions with an agricultural carrier comprising at least one liquid diluent, solid diluent or surfactant. The choice of formulation or composition ingredients is consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions), which may optionally be thickened into gels. Useful formulations also include solids such as dusts, powders, granules, pellets, tablets, films, etc., which are dispersible in water ("wettable") or soluble in water. The active ingredient may be (micro)encapsulated, which may further form a suspension or solid formulation; alternatively, the entire formulation of the active ingredient may be coated (or "coated"). The coating provides controlled or delayed release of the active ingredient. Sprays can be spread into suitable media and applied at rates of about 100 to several hundred liters per hectare. High-strength compositions are mainly used as intermediates for further formulations.
该制剂可典型的含有有效量(如0.01-99.99wt％)的活性成分和以下近似范围内的稀释剂和/或表面活性剂，并加到100wt％的量。
典型的固体稀释剂描述在Watkins等的Handbook ofInsecticide Dust Diluents and Carriers，第二版，Dorland Books，Caldwell，新泽西中。典型的液体稀释剂描述在Marsden的SolventsGuide，第二版，Interscience，纽约，1950中。McCutcheon’sDetergents and Emulsifiers Annual，Allured Publ.Corp.，Ridgewood，新泽西，以及Sisely和Wood的Encyclopedia of SurfaceActive Agents，Chemical Publ.Co.，Inc.，纽约，1964中列出了表面活性剂并推荐采用。所有配方均可含有少量添加剂，以减少起泡、结块、腐蚀、微生物生长等，或含有增稠剂以增加粘性。Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Edition, Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden's Solvents Guide, Second Edition, Interscience, New York, 1950. Surfactants are listed and recommended in McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, and Sisely and Wood's Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbial growth, etc., or thickeners to increase viscosity.
表面活性剂包括例如聚乙氧基化的醇、聚乙氧基化的烷基酚、聚乙氧基化的脱水山梨醇脂肪酸酯、磺基琥珀酸二烷基酯、烷基硫酸盐、烷基苯磺酸酯、有机硅氧烷、N，N-二烷基牛磺酸盐、木素磺酸盐、萘磺酸盐甲醛缩合物、聚羧酸酯，以及聚氧乙烯/聚氧丙烯嵌段共聚物。固体稀释剂包括例如粘土如膨润土、蒙脱石、硅镁土和高岭土；淀粉、糖、二氧化硅、滑石、硅藻土、尿素、碳酸钙、碳酸钠和碳酸氢钠，以及硫酸钠。液体稀释剂包括例如水、N，N-二甲基甲酰胺、二甲亚砜、N-烷基吡咯烷酮、乙二醇、聚丙二醇、石蜡、烷基苯、烷基萘；橄榄油、蓖麻油、亚麻子油、桐油、芝麻油、玉米油、花生油、棉籽油、大豆油、菜油和可可油；脂肪酸酯；酮如环己酮、2-庚酮、异佛尔酮和4-羟基-4-甲基-2-戊酮；以及醇如甲醇、环己醇、癸醇和四氢糠醇。Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, Alkylbenzenesulfonates, organosiloxanes, N,N-dialkyltaurines, lignosulfonates, naphthalenesulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxy Propylene block copolymer. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite, and kaolin; starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate, and sodium bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N,N-dimethylformamide, dimethylsulfoxide, N-alkylpyrrolidones, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene; olive oil, castor oil , linseed oil, tung oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, and cocoa butter; fatty acid esters; ketones such as cyclohexanone, 2-heptanone, isophorone, and 4-hydroxy-4 - methyl-2-pentanone; and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
包括可乳化的提浓物的溶液可通过简单混和这些成分制备。微细粉或粉末可通过掺和并通常是在锤磨机或流体动力磨研磨来制备。悬浮液一般通过湿式磨制备；参见例如US 3060084。优选的悬浮液提浓物包括除含有活性成分外，还含有5-20％非离子表面活性剂(例如聚乙氧基化的脂肪醇)，并非必须的与50-65％液体稀释剂和高达5％的阴离子表面活性剂结合的那些。颗粒和小颗粒可通过将活性材料喷在预先形成的颗粒载体上或通过聚结技术来制备。参见Browning的“Agglomeration”，Chemical Engineering，1967年12月4日，147-48页；Perry’s Chemical Engineer’s Handbook，第四版，McGraw-Hill，纽约，1963，8-57页及以下，以及WO 91/13546。小颗粒可如US 4172714中描述的制备。水分散性和水溶性颗粒可如US5180587、US 5232701和US 5208030中教导的方法制备。膜可如GB2095558和US 3299566中教导的方法制备。Solutions including emulsifiable concentrates can be prepared by simply mixing the ingredients. Fine powders or powders can be prepared by blending and grinding, usually in a hammer mill or hydrodynamic mill. Suspensions are generally prepared by wet milling; see eg US 3060084. A preferred suspension concentrate comprises, in addition to the active ingredient, 5-20% nonionic surfactant (e.g. polyethoxylated fatty alcohol), optionally with 50-65% liquid diluent and up to 5% of those bound with anionic surfactants. Granules and granules can be prepared by spraying the active material onto preformed particulate carriers or by agglomeration techniques. See Browning, "Agglomeration," Chemical Engineering, Dec. 4, 1967, pp. 147-48; Perry's Chemical Engineer's Handbook, Fourth Edition, McGraw-Hill, New York, 1963, pp. 8-57ff., and WO 91/ 13546. Small particles can be prepared as described in US 4172714. Water-dispersible and water-soluble granules can be prepared as taught in US5180587, US5232701 and US5208030. Membranes can be prepared as taught in GB2095558 and US 3299566.
考虑配方工艺的其他配方见US 3235361的6段16行-7段19行以及实施例10-41；US 3309192的5段43行-7段62行以及实施例8、12、15、39、41、52、53、58、132、138-140、162-164、166、167和169-182；US 2891855的3段66行-5段17行以及实施例1-4；Klingman，Weed Control as a Science，John Wiley andSons，Inc.，纽约，1961，pp81-96；和Hance等的Weed ControlHandbook，第8版，Blackwell Scientific Publications，牛津，1989。For other formulations considering the formula process, see US 3235361, 6 paragraphs 16 lines-7 paragraphs 19 lines and Examples 10-41; US 3309192 5 paragraphs 43 lines-7 paragraphs 62 lines and Examples 8, 12, 15, 39, 41 , 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; US 2891855 3 paragraphs 66 lines-5 paragraphs 17 lines and embodiment 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp81-96; and Hance et al., Weed Control Handbook, 8th Edition, Blackwell Scientific Publications, Oxford, 1989.
在以下实施例中，所有百分数均指重量，所有制剂用常用方法制备。化合物数指Index Tables A-D中的化合物。In the following examples, all percentages are by weight and all formulations were prepared by conventional methods. Compound numbers refer to compounds in Index Tables A-D.
实施例A Example A
可润湿粉末wettable powder
化合物8 65.0％Compound 8 65.0%
十二烷基苯酚聚乙二醇醚 2.0％ Laurylphenol Polyethylene Glycol Ether 2.0%
木素磺酸钠 4.0％Sodium lignosulfonate 4.0%
硅铝酸钠 6.0％Sodium aluminosilicate 6.0%
蒙脱石(煅烧的) 23.0％Montmorillonite (calcined) 23.0%
实施例B Example B
颗粒particles
化合物8 10.0％Compound 8 10.0%
attapulgite颗粒(低挥发性物质，0.71/0.30mm；attapulgite particles (low volatile matter, 0.71/0.30mm;
U.S.S.No.25-50筛) 90.0％U.S.S.No. 25-50 sieve) 90.0%
实施例C Example C
挤压颗粒extruded pellets
化合物8 25.0％Compound 8 25.0%
无水硫酸钠 10.0％Anhydrous Sodium Sulfate 10.0%
木素磺酸钙粗料 5.0％Calcium lignosulfonate coarse material 5.0%
烷基萘磺酸钠 1.0％Sodium alkylnaphthalene sulfonate 1.0%
钙/镁膨润土 59.0％Calcium/magnesium bentonite 59.0%
实施例D Example D
可乳化的提浓物emulsifiable concentrate
化合物8 20.0％Compound 8 20.0%
油溶性磺酸酯与聚氧乙烯醚的混合物 10.0％Mixture of oil-soluble sulfonate and polyoxyethylene ether 10.0%
异佛尔酮 70.0％Isophorone 70.0%
值得注意的是包含15-25％活性成分、10-20％非离子表面活性剂、0-5％阴离子表面活性剂、0-10％有机稀释剂和45-60％水的悬浮提浓物。Of note are suspension concentrates comprising 15-25% active ingredient, 10-20% nonionic surfactant, 0-5% anionic surfactant, 0-10% organic diluent and 45-60% water.
实施例E Example E
化合物2 20.0％Compound 2 20.0%
聚乙氧基化的脂肪醇 非离子表面活性剂 15.0％Polyethoxylated Fatty Alcohol Nonionic Surfactant 15.0%
褐煤蜡的酯衍生物 3.0％Ester derivatives of montan wax 3.0%
木素磺酸钙 阴离子表面活性剂 2.0％Calcium Lignosulfonate Anionic Surfactant 2.0%
聚乙氧基化的/聚丙氧基化的Polyethoxylated/Polypropoxylated
聚乙二醇嵌段共聚物 表面活性剂 1.0％Polyethylene glycol block copolymer Surfactant 1.0%
丙二醇 稀释剂 6.4％Propylene Glycol Thinner 6.4%
聚(二甲基硅氧烷) 消泡剂 0.6％Poly(dimethylsiloxane) defoamer 0.6%
灭菌剂 0.1％Sterilizer 0.1%
水 稀释剂 51.9％Water Thinner 51.9%
该制剂的成分一起混和成浆状，加入化合物2并在掺和机中该将混合物均质化。然后将所得浆料湿磨形成悬浮提浓物。The ingredients of the formulation were blended together into a slurry, compound 2 was added and the mixture was homogenized in the blender. The resulting slurry is then wet milled to form a suspension concentrate.
实施例F Example F
化合物5 20.0％Compound 5 20.0%
聚乙氧基化的脂肪醇 非离子表面活性剂 15.0％Polyethoxylated fatty alcohol Nonionic surfactant 15.0%
褐煤蜡的酯衍生物 3.0％Ester derivatives of montan wax 3.0%
木素磺酸钙 阴离子表面活性剂 2.0％Calcium Lignosulfonate Anionic Surfactant 2.0%
聚乙氧基化的/聚丙氧基化的Polyethoxylated/Polypropoxylated
聚乙二醇嵌段共聚物 表面活性剂 1.0％Polyethylene glycol block copolymer Surfactant 1.0%
丙二醇 稀释剂 6.4％Propylene Glycol Thinner 6.4%
聚(二甲基硅氧烷) 消泡剂 0.6％Poly(dimethylsiloxane) defoamer 0.6%
灭菌剂 0.1％Sterilizer 0.1%
水 稀释剂 51.9％Water Thinner 51.9%
该制剂的成分一起混和成浆状，加入化合物5并在掺和机中该将混合物均质化。然后将所得浆料湿磨形成悬浮提浓物。The ingredients of the formulation were blended together into a slurry, compound 5 was added and the mixture was homogenized in the blender. The resulting slurry is then wet milled to form a suspension concentrate.
实施例G Example G
化合物8 20.0％Compound 8 20.0%
聚乙氧基化的脂肪醇 非离子表面活性剂 15.0％Polyethoxylated fatty alcohol Nonionic surfactant 15.0%
褐煤蜡的酯衍生物 3.0％Ester derivatives of montan wax 3.0%
木素磺酸钙 阴离子表面活性剂 2.0％Calcium Lignosulfonate Anionic Surfactant 2.0%
聚乙氧基化的/聚丙氧基化的Polyethoxylated/Polypropoxylated
聚乙二醇嵌段共聚物 表面活性剂 1.0％Polyethylene glycol block copolymer Surfactant 1.0%
丙二醇 稀释剂 6.4％Propylene Glycol Thinner 6.4%
聚(二甲基硅氧烷) 消泡剂 0.6％Poly(dimethylsiloxane) defoamer 0.6%
灭菌剂 0.1％Sterilizer 0.1%
水 稀释剂 51.9％Water Thinner 51.9%
该制剂的成分一起混和成浆状，加入化合物8并在掺和机中该将混合物均质化。然后将所得浆料湿磨形成悬浮提浓物。The ingredients of the formulation were blended together into a slurry, compound 8 was added and the mixture was homogenized in the blender. The resulting slurry is then wet milled to form a suspension concentrate.
实施例H Example H
化合物28 20.0％Compound 28 20.0%
聚乙氧基化的脂肪醇 非离子表面活性剂 15.0％Polyethoxylated fatty alcohol Nonionic surfactant 15.0%
褐煤蜡的酯衍生物 3.0％Ester derivatives of montan wax 3.0%
木素磺酸钙 阴离子表面活性剂 2.0％Calcium Lignosulfonate Anionic Surfactant 2.0%
聚乙氧基化的/聚丙氧基化的Polyethoxylated/Polypropoxylated
聚乙二醇嵌段共聚物 表面活性剂 1.0％Polyethylene glycol block copolymer Surfactant 1.0%
丙二醇 稀释剂 6.4％Propylene Glycol Thinner 6.4%
聚(二甲基硅氧烷) 消泡剂 0.6％Poly(dimethylsiloxane) defoamer 0.6%
灭菌剂 0.1％Sterilizer 0.1%
水 稀释剂 51.9％Water Thinner 51.9%
该制剂的成分一起混和成浆状，加入化合物28并在掺和机中该将混合物均质化。然后将所得浆料湿磨形成悬浮提浓物。The ingredients of the formulation were blended together into a slurry, compound 28 was added and the mixture was homogenized in the blender. The resulting slurry is then wet milled to form a suspension concentrate.
实施例I Example I
化合物29 20.0％Compound 29 20.0%
聚乙氧基化的脂肪醇 非离子表面活性剂 15.0％Polyethoxylated fatty alcohol Nonionic surfactant 15.0%
褐煤蜡的酯衍生物 3.0％Ester derivatives of montan wax 3.0%
木素磺酸钙 阴离子表面活性剂 2.0％Calcium Lignosulfonate Anionic Surfactant 2.0%
聚乙氧基化的/聚丙氧基化的Polyethoxylated/Polypropoxylated
聚乙二醇嵌段共聚物 表面活性剂 1.0％Polyethylene glycol block copolymer Surfactant 1.0%
丙二醇 稀释剂 6.4％Propylene Glycol Thinner 6.4%
聚(二甲基硅氧烷) 消泡剂 0.6％Poly(dimethylsiloxane) defoamer 0.6%
灭菌剂 0.1％Sterilizer 0.1%
水 稀释剂 51.9％Water Thinner 51.9%
该制剂的成分一起混和成浆状，加入化合物29并在掺和机中该将混合物均质化。然后将所得浆料湿磨形成悬浮提浓物。The ingredients of the formulation were blended together into a slurry, compound 29 was added and the mixture was homogenized in the blender. The resulting slurry is then wet milled to form a suspension concentrate.
实施例J Example J
化合物30 20.0％Compound 30 20.0%
聚乙氧基化的脂肪醇 非离子表面活性剂 15.0％Polyethoxylated fatty alcohol Nonionic surfactant 15.0%
褐煤蜡的酯衍生物 3.0％Ester derivatives of montan wax 3.0%
木素磺酸钙 阴离子表面活性剂 2.0％Calcium Lignosulfonate Anionic Surfactant 2.0%
聚乙氧基化的/聚丙氧基化的Polyethoxylated/Polypropoxylated
聚乙二醇嵌段共聚物 表面活性剂 1.0％Polyethylene glycol block copolymer Surfactant 1.0%
丙二醇 稀释剂 6.4％Propylene Glycol Thinner 6.4%
聚(二甲基硅氧烷) 消泡剂 0.6％Poly(dimethylsiloxane) defoamer 0.6%
灭菌剂 0.1％Sterilizer 0.1%
水 稀释剂 51.9％Water Thinner 51.9%
该制剂的成分一起混和成浆状，加入化合物30并在掺和机中该将混合物均质化。然后将所得浆料湿磨形成悬浮提浓物。The ingredients of the formulation were blended together into a slurry, compound 30 was added and the mixture was homogenized in the blender. The resulting slurry is then wet milled to form a suspension concentrate.
实施例K Example K
化合物31 20.0％Compound 31 20.0%
聚乙氧基化的脂肪醇 非离子表面活性剂 15.0％Polyethoxylated fatty alcohol Nonionic surfactant 15.0%
褐煤蜡的酯衍生物 3.0％Ester derivatives of montan wax 3.0%
木素磺酸钙 阴离子表面活性剂 2.0％Calcium Lignosulfonate Anionic Surfactant 2.0%
聚乙氧基化的/聚丙氧基化的Polyethoxylated/Polypropoxylated
聚乙二醇嵌段共聚物 表面活性剂 1.0％Polyethylene glycol block copolymer Surfactant 1.0%
丙二醇 稀释剂 6.4％Propylene Glycol Thinner 6.4%
聚(二甲基硅氧烷) 消泡剂 0.6％Poly(dimethylsiloxane) defoamer 0.6%
灭菌剂 0.1％Sterilizer 0.1%
水 稀释剂 51.9％Water Thinner 51.9%
该制剂的成分一起混和成浆状，加入化合物31并在掺和机中该将混合物均质化。然后将所得浆料湿磨形成悬浮提浓物。The ingredients of the formulation were blended together into a slurry, compound 31 was added and the mixture was homogenized in the blender. The resulting slurry is then wet milled to form a suspension concentrate.
实施例L Example L
化合物35 20.0％Compound 35 20.0%
聚乙氧基化的脂肪醇 非离子表面活性剂 15.0％Polyethoxylated fatty alcohol Nonionic surfactant 15.0%
褐煤蜡的酯衍生物 3.0％Ester derivatives of montan wax 3.0%
木素磺酸钙 阴离子表面活性剂 2.0％Calcium Lignosulfonate Anionic Surfactant 2.0%
聚乙氧基化的/聚丙氧基化的Polyethoxylated/Polypropoxylated
聚乙二醇嵌段共聚物 表面活性剂 1.0％Polyethylene glycol block copolymer Surfactant 1.0%
丙二醇 稀释剂 6.4％Propylene Glycol Thinner 6.4%
聚(二甲基硅氧烷) 消泡剂 0.6％Poly(dimethylsiloxane) defoamer 0.6%
灭菌剂 0.1％Sterilizer 0.1%
水 稀释剂 51.9％Water Thinner 51.9%
该制剂的成分一起混和成浆状，加入化合物35并在掺和机中该将混合物均质化。然后将所得浆料湿磨形成悬浮提浓物。The ingredients of the formulation were blended together into a slurry, compound 35 was added and the mixture was homogenized in the blender. The resulting slurry is then wet milled to form a suspension concentrate.
实施例M Example M
化合物36 20.0％Compound 36 20.0%
聚乙氧基化的脂肪醇 非离子表面活性剂 15.0％Polyethoxylated Fatty Alcohol Nonionic Surfactant 15.0%
褐煤蜡的酯衍生物 3.0％Ester derivatives of montan wax 3.0%
木素磺酸钙 阴离子表面活性剂 2.0％Calcium Lignosulfonate Anionic Surfactant 2.0%
聚乙氧基化的/聚丙氧基化的Polyethoxylated/Polypropoxylated
聚乙二醇嵌段共聚物 表面活性剂 1.0％Polyethylene glycol block copolymer Surfactant 1.0%
丙二醇 稀释剂 6.4％Propylene Glycol Thinner 6.4%
聚(二甲基硅氧烷) 消泡剂 0.6％Poly(dimethylsiloxane) Defoamer 0.6%
灭菌剂 0.1％Sterilizer 0.1%
水 稀释剂 51.9％Water Thinner 51.9%
该制剂的成分一起混和成浆状，加入化合物36并在掺和机中该将混合物均质化。然后将所得浆料湿磨形成悬浮提浓物。The ingredients of the formulation were blended together into a slurry, compound 36 was added and the mixture was homogenized in the blender. The resulting slurry is then wet milled to form a suspension concentrate.
实施例N Example N
化合物37 20.0％Compound 37 20.0%
聚乙氧基化的脂肪醇 非离子表面活性剂 15.0％Polyethoxylated Fatty Alcohol Nonionic Surfactant 15.0%
褐煤蜡的酯衍生物 3.0％Ester derivatives of montan wax 3.0%
木素磺酸钙 阴离子表面活性剂 2.0％Calcium Lignosulfonate Anionic Surfactant 2.0%
聚乙氧基化的/聚丙氧基化的Polyethoxylated/Polypropoxylated
聚乙二醇嵌段共聚物 表面活性剂 1.0％Polyethylene glycol block copolymer Surfactant 1.0%
丙二醇 稀释剂 6.4％Propylene Glycol Thinner 6.4%
聚(二甲基硅氧烷) 消泡剂 0.6％Poly(dimethylsiloxane) Defoamer 0.6%
灭菌剂 0.1％Sterilizer 0.1%
水 稀释剂 51.9％Water Thinner 51.9%
该制剂的成分一起混和成浆状，加入化合物37并在掺和机中该将混合物均质化。然后将所得浆料湿磨形成悬浮提浓物。The ingredients of the formulation were blended together into a slurry, compound 37 was added and the mixture was homogenized in the blender. The resulting slurry is then wet milled to form a suspension concentrate.
本发明的化合物可用作植物病害控制剂。因此本发明还包括控制由真菌植物病原体产生的植物病害的方法，包括向需保护的植物或其一部分，或向需保护的植物种子或秧苗上施予有效量的本发明化合物或含有所述化合物的杀真菌剂组合物。本发明的化合物和组合物提供对由担子菌、子囊菌、卵菌和半知菌纲中的广谱真菌植物病原体产生的病害的控制。它们在控制广谱植物病害，尤其是观赏植物、蔬菜、田野、谷物和水果作物的页状病原体上是有效的。这些病原体包括葡萄生单轴菌(Plasmopara viticola)、蔓延疫霉(Phytophthorainfestans)、斜尖状孢子菌属tabacina(Peronospora tabacina)、古巴假霜菌(Pseudoperonospora cubensis)、瓜果腐霉(Pythiumaphanidermatum)、甘蓝黑斑病链格孢菌(Alternaria brassicae)、颖枯壳针孢(Septoria nodorum)、小麦壳针孢(Septoria tritici)、Cercosporidium personatum、变灰尾孢菌(Cercospora arachidicola)、麦类眼斑病菌(Pseudocercosporella herpotrichoides)、菾菜生尾孢(Cercospora beticola)、灰色葡萄孢(Botrytis cinerea)、果生链核盘菌(Monilinia fructicola)、稻梨孢菌(Pyriculariaoryzae)、苹果白粉病柄球菌(Podosphaera leucotricha)、苹果黑星菌(Venturia inaequalis)、禾白粉菌(Erysiphe graminis)、裸黑粉菌(Uncinula necartur)、隐匿柄锈菌(Puccinia recondita)、禾柄锈菌(Puccinia graminis)、咖啡驻孢锈菌(Hemileia vastatrix)、鸭茅条形柄锈菌(Puccinia striiformis)、落花生柄锈菌(Pucciniaarachidis)、立枯丝核菌(Rhizoctonia solani)、苍耳单丝壳菌(Sphaerotheca fuliginea)、尖镰孢(Fusarium oxysporum)、大丽花轮枝孢(Verticillium dahliae)、瓜果腐霉(Pythiumaphanidermatum)、大雄疫霉(Phytophthora megasperma)、核盘菌(Sclerotinia sclerotiorum)、齐整小核菌(Sclerotium rolfsii)、蓼白粉菌(Erysiphe polygoni)、圆核腔菌(Pyrenophora teres)、禾顶囊壳(Gaeumannomvces graminis)、Rynchosporium secalis、粉红镰孢(Fusarium roseum)、莴苣盘梗霉(Bremia lactucae)，以及与这些病原体紧密相关的其他属种病原体。The compounds of the present invention are useful as plant disease controlling agents. The present invention therefore also includes a method for controlling plant diseases produced by fungal plant pathogens, comprising administering an effective amount of a compound of the present invention or containing said compound to the plant to be protected or a part thereof, or to the seed or seedling of a plant to be protected. fungicide composition. The compounds and compositions of the present invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the class Basidiomycetes, Ascomycetes, Oomycetes and Deuteromycetes. They are effective in controlling a broad spectrum of plant diseases, especially phyllopathogens of ornamental, vegetable, field, cereal and fruit crops. These pathogens include Plasmopara viticola, Phytophthorainfestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythiumaphanidermatum, cabbage Alternaria brassicae, Septoria nodorum, Septoria tritici, Cercosporidium personatum, Cercospora arachidicola, Eyespot Pseudocercosporella herpotrichoides), Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyriculariaoryzae, Podosphaera leucotricha , Venturia inaequalis, Erysiphe graminis, Uncinula necartur, Puccinia recondita, Puccinia graminis, Coffee spore rust (Hemileia vastatrix), Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerotheca fuliginea, Fusarium oxysporum ( Fusarium oxysporum), Verticillium dahliae, Pythiumaphanidermatum, Phytophthora megasperma, Sclerotinia sclerotiorum, Sclerotium rolfsii, Powdery mildew ( Erysiphe polygoni), Pyrenophora teres, Gaeumannomvces graminis, Rynchosporium secalis, Fusarium roseum, Bremia lactucae, and others closely related to these pathogens Species of pathogens.
本发明的化合物也可与一种或多种其他杀虫剂、杀真菌剂、杀线虫剂、杀细菌剂、杀螨剂、生长调节剂、化学消毒剂、化学信息物质、拒斥剂、引诱剂、信息素、助食剂或其他生物活性化合物混合，形成提供更广谱的农作物保护的多成分农药。可与本发明的化合物一起配制的这种农作物保护剂的实例是：杀虫剂如阿维菌素、乙酰甲胺磷、保棉磷、联苯菊酯、噻嗪酮、克百威、chlorfenapyr、毒死蜱、毒死蜱-甲基、氟氯氰菊酯、高效氟氯氰菊酯、氯氟氰菊酯、高效氯氟氰菊酯、溴氰菊酯、丁醚脲、二嗪磷、除虫脲、乐果、S-氰戊菊酯、苯氧威、甲氰菊酯、氰戊菊酯、氟虫腈、氟氰戊菊酯、氟胺氰菊酯、地虫硫磷、吡虫啉、异柳磷、马拉硫磷、四聚乙醛、甲胺磷、杀扑磷、灭多威、烯虫酯、甲氧滴滴涕、甲基7-氯-2，5-二氢-2-[[N-(甲氧基羰基)-N-[4-(三氟甲氧基)苯基]氨基]羰基]茚并[1，2-e][1，3，4]噁二嗪-4α(3H)-甲酸酯(indoxacarb)、久效磷、杀线威、对硫磷、对硫磷-甲基、氯菊酯、甲拌磷、伏杀硫磷、亚胺硫磷、磷胺、抗蚜威、丙溴磷、鱼藤酮、硫丙磷、虫酰肼、七氟菊酯、特丁磷、杀虫威、硫双威、四溴菊酯、敌百虫和杀铃脲；杀真菌剂如噻二唑素、嘧菌酯、苯菌灵、灭瘟素、波尔多液(三碱硫酸铜)、糠菌唑、carpropamid(KTU 3616)、敌菌丹、克菌丹、多菌灵、氯苯甲醚、百菌清、氧氯化铜、诸如硫酸铜和氢氧化铜的铜盐、cyazofamid、霜脲氰、环丙唑醇、嘧菌环胺(CGA219417)、(S)-3，5-二氯-N-(3-氯-1-乙基-1-甲基-2-氧代丙基)-4-甲基苯并酰胺(RH 7281)、diclocymet(S-2900)、哒菌酮、氯硝胺、苯醚甲环唑、烯酰吗啉、烯唑醇、烯唑醇-M、多果定、敌瘟磷、氟环唑(BAS 480F)、易灵、fenamidone、氯苯嘧啶醇、腈苯唑、fencaramid(SZX0722)、拌种咯、苯锈啶、丁苯吗啉、三苯基乙酸锡、三苯基氢氧化锡、氟啶胺、咯菌腈、flumetover(RPA 403397)、氟喹唑、氟硅唑、氟酰胺、粉唑醇、灭菌丹、三乙膦酸铝、呋霜灵、furametapyr(S-82658)、己唑醇、种菌唑、异稻瘟净、异菌脲、稻瘟灵、iprovalicarb、春雷霉素、醚菌酯、代森锰锌、代森锰、mefenoxam、灭锈胺、甲霜灵、metonazole、metominostrobin/fenominostrobin(SSF-126)、腈菌唑、neo-asozin(甲烷胂酸铁)、噁霜灵、戊菌唑、戊菌隆、烯丙苯噻唑、咪鲜胺、霜霉威、丙环唑、丙森锌、pyrclostrobin、啶斑肟、嘧霉胺、咯喹酮、quinoxyfen、spiroxamine、硫、戊唑醇、四氟醚唑、噻菌灵、thifluzamide、甲基硫菌灵、福美双、三唑酮、三唑醇、三环唑、trifloxystrobin、灭菌唑、有效霉素、乙烯菌核利、代森锌和zoxamid；杀线虫剂如涕灭砜威和苯线磷；杀细菌剂如链霉素；杀螨虫剂如双甲脒、灭螨猛、乙酯杀螨醇、三环锡、三氯杀螨醇、dienochlor、特苯噁唑、喹螨醚、苯丁锡、甲氰菊酯、唑螨酯、噻螨酮、炔螨特、哒螨灵和吡螨胺；以及生物试剂如苏云金芽孢杆菌、苏云金芽孢杆菌δ-内毒素、杆状病毒(baculovirus)，以及昆虫病原细菌、病毒和真菌。这些不同混和组分与本发明的化合物的重量比典型的为100∶1-1∶100，优选30∶1-1∶30，更优选10∶1-1∶10，最优选4∶1-1∶4。The compounds of the present invention may also be combined with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemical disinfectants, semiochemicals, repellants, attractants additives, pheromones, food aids or other bioactive compounds to form multi-ingredient pesticides that provide broader spectrum crop protection. Examples of such crop protection agents which may be formulated with the compounds of the invention are: Insecticides such as abamectin, acephate, acetophos, bifenthrin, buprofezin, carbofuran, chlorfenapyr , chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, beta-cyfluthrin, cyhalothrin, beta-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, S- Fenvalerate, Fenoxycarb, Fenvalerate, Fenvalerate, Fipronil, Flucyvalerate, Fluvalinate, Tefenthion, Imidacloprid, Isofenphos, Malathion , Metaldehyde, Methamidophos, Methaphos, Methomyl, Methoprene, Methoxychlor, Methyl 7-Chloro-2,5-Dihydro-2-[[N-(Methoxycarbonyl )-N-[4-(trifluoromethoxy)phenyl]amino]carbonyl]indeno[1,2-e][1,3,4]oxadiazine-4α(3H)-carboxylate ( indoxacarb), monocrotophos, oxacarb, parathion, parathion-methyl, permethrin, phorate, phosthion, imophos, phosphamide, pirimicarb, profenofos , rotenone, thioprofos, tebufenozide, tefluthrin, terbufos, dimecarb, thiodicarb, perbromethrin, trichlorfon and triflumuron; fungicides such as thiadiazol, Azoxystrobin, benomyl, blasticidin, Bordeaux mixture (tribasic copper sulfate), furfurazole, carpropamid (KTU 3616), captafate, captan, carbendazim, chloroanisole, chlorothalon Qing, copper oxychloride, copper salts such as copper sulfate and copper hydroxide, cyazofamid, cymoxanil, cyproconazole, cyprodinil (CGA219417), (S)-3,5-dichloro-N- (3-Chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide (RH 7281), diclocymet (S-2900), pyridoxetone, clonamide, Difenoconazole, dimethomorph, diniconazole, diniconazole-M, dodine, fenfofos, flueconazole (BAS 480F), Yiling, fenamidone, chlorpyrimidinol, nibenazole , fencaramid (SZX0722), seed dressing, fenpropidin, fenpropimorph, triphenyltin acetate, triphenyltin hydroxide, fluazinam, fludioxonil, flumetover (RPA 403397), fluquinazole, Flusilazole, Fluoramide, Fenconazole, Foldan, Aluminum Triethylphosphonate, Falaxyl, Furametapyr (S-82658), Hexaconazole, Conconazole, Isofridazine, Iprodione, Rice Plague, iprovalicarb, kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxam, mefenoxam, metalaxyl, metonazole, metominostrobin/fenominostrobin (SSF-126), myclobutanil, neo-asozin (Iron methane arsenate), oxadaxyl, penconazole, penburon, allyl benzothiazole, prochloraz, propamocarb, propiconazole, propine zinc, pyrclostrobin, pyrimethanil, pyrimethanil, Quinoxyfen, quinoxyfen, spiroxamine, sulfur, tebuconazole, tetrafluconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, triadimefon, triadimolol, tricyclazole, trifluxystrobin, sterilizing azoles, validamycin, vinclozolin, zoxamid and zoxamid; nematocides such as aldisulfonecarb and fenamiphos; bactericides such as streptomycin; Ethylfofol, tricyclotin, dicofol, dienochlor, terbenoxazole, fenazaquin, fenbutatin, fenpropathrin, fenpyrid, hexymethoxone, propyzafen, pyridaben, and pyridaben amines; and biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta-endotoxin, baculovirus, and entomopathogenic bacteria, viruses and fungi. The weight ratio of these different mixing components to the compound of the present invention is typically 100:1-1:100, preferably 30:1-1:30, more preferably 10:1-1:10, most preferably 4:1-1 : 4.
值得注意的是与能提供更广谱的农作物保护的其他杀真菌剂的结合，所述杀菌剂包括嘧菌酯、醚菌酯、pyrclostrobin、trifloxystrobin、苯菌灵、多菌灵、百菌清、烯酰吗啉、灭菌丹、代森锰锌、代森锰、quinoxyfen、有效霉素、乙烯菌核利、苯锈啶、丁苯吗啉、糠菌唑、环丙唑醇、苯醚甲环唑、氟环唑(epoxyconazole)、氟硅唑、种菌唑、叶菌唑、丙环唑、戊唑醇和灭菌唑。Of note is the combination with other fungicides that provide broader spectrum crop protection, including azoxystrobin, kresoxim-methyl, pyrclostrobin, trifloxystrobin, benomyl, carbendazim, chlorothalonil, Dimethomorph, folpet, mancozeb, maneb, quinoxyfen, validamycin, vinclozolin, fenpropidin, fenpropimorph, furfurazole, cyproconazole, diphenoxymethyl Cycloconazole, epoxyconazole, flusilazole, bacconazole, metconazole, propiconazole, tebuconazole, and fenconazole.
值得注意的是与作用模式不同的(如mitochondrial呼吸抑制、通过干扰核蛋白体RNA的合成或抑制β-微管蛋白的合成来抑制蛋白质合成)其他杀真菌剂的结合，对抵抗力管理是尤其有益的。实例包括通式I和/或通式II的化合物(如化合物8)与嘧菌酯、醚菌酯、pyrclostrobin、trifloxystrobin、多菌灵、易灵、fenamidone、苯菌灵、霜脲氰、烯酰吗啉、灭菌丹、三乙膦酸铝、甲霜灵、代森锰锌、代森锰的混合物。这些混合物对抵抗力管理是尤其有益的，特别是当该混合物的杀真菌剂控制相同或相似的病害时。Of note is the combination of other fungicides with a different mode of action (e.g. mitochondrial respiratory inhibition, inhibition of protein synthesis by interfering with ribosomal RNA synthesis or inhibition of β-tubulin synthesis), especially for resistance management benefit. Examples include compounds of general formula I and/or general formula II (such as compound 8) with azoxystrobin, kresoxim-methyl, pyrclostrobin, trifloxystrobin, carbendazim, elizidine, fenamidone, benomyl, cymoxanil, enoyl A mixture of morpholine, folpet, aluminum triethylphosphonate, metalaxyl, mancozeb, and maneb. These blends are particularly beneficial for resistance management, especially when the fungicides of the blend control the same or similar diseases.
值得注意的是与其他控制葡萄疾病的杀真菌剂的结合，所述杀真菌剂包括二硫代氨基甲酸酯如代森锰锌、代森锰、丙森锌和代森锌；phthalimids如灭菌丹、铜盐如硫酸铜和氢氧化铜；strobilurins如嘧菌酯、pyrclostrobin和trifloxystrobin；苯酰胺如甲霜灵；磺酸盐如三乙膦酸铝；吗啉类如烯酰吗啉，以及其他杀菌剂如霜脲氰、易灵和fenamidone。Of note is the combination with other fungicides for grape disease control, including dithiocarbamates such as mancozeb, maneb, propineb, and zinc; phthalimids such as Capulant, copper salts such as copper sulfate and copper hydroxide; strobilurins such as azoxystrobin, pyrclostrobin, and trifloxystrobin; benzamides such as metalaxyl; sulfonates such as aluminum triethronate; morpholines such as dimethomorph, and Other fungicides such as cymoxanil, Yiling and fenamidone.
值得注意的是与其他控制马铃薯疾病的杀真菌剂的结合，所述杀真菌剂包括二硫代氨基甲酸酯如代森锰锌、代森锰、丙森锌和代森锌；铜盐如硫酸铜和氢氧化铜；strobilurins如pyrclostrobin和trifloxystrobin；苯酰胺如甲霜灵；氨基甲酸酯如霜霉威；苯吡拉明(phenylpyriylamine)如氟啶胺；吗啉类如烯酰吗啉，以及其他杀真菌剂如百菌清、cyazofamid、霜脲氰、易灵、fenamidone、zoxamid和iprovalicarb。Of note is the combination with other fungicides for potato disease control, including dithiocarbamates such as mancozeb, maneb, propineb, and zinc; copper salts such as copper sulfate and copper hydroxide; strobilurins such as pyrclostrobin and trifloxystrobin; benzamides such as metalaxyl; carbamates such as propamocarb; phenylpyriylamine such as fluazinam; morpholines such as dimethomorph, As well as other fungicides such as chlorothalonil, cyazofamid, cymoxanil, Yiling, fenamidone, zoxamid and iprovalicarb.
尤其值得注意的是化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与嘧菌酯的混合物；化合物2、化合物5、化合物8、化合物28、化合化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与醚菌酯的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与pyrclostrobin的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与trifloxystrobin的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与多菌灵的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与百菌清的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与烯酰吗啉的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与灭菌丹的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与代森锰锌的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与代森锰的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与quinoxyfen的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与有效霉素的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与乙烯菌核利的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与苯锈啶的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与丁苯吗啉的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与糠菌唑的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与环丙唑醇的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与苯醚甲环唑的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与氟环唑的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与氟硅唑的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与种菌唑的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与叶菌唑的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与丙环唑的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与戊唑醇的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与灭菌唑的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与易灵的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与fenamidone的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与苯菌灵的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与霜脲氰的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与烯酰吗啉的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与灭菌丹的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与三乙膦酸铝的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与甲霜灵的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与＿＿的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与丙森锌的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与代森锌的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与硫酸铜的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与氢氧化铜的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与霜霉威的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与cyazofamid的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与zoxamid的混合物；化合物2、化合物5、化合物8、化合物28、化合物29、化合物30、化合物31、化合物35、化合物36或化合物37与iprovalicarb的混合物。Of particular note are compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and the mixture of azoxystrobin; compound 2, compound 5, compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35, Compound 36 or Compound 37 and the mixture of Kresoxim-methyl; Compound 2, Compound 5, Compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35. The mixture of compound 36 or compound 37 and pyrclostrobin; the mixture of compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and trifloxystrobin; compound 2, compound 5. The mixture of compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and carbendazim; compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, The mixture of compound 31, compound 35, compound 36 or compound 37 and chlorothalonil; compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and enoyl A mixture of morpholine; a mixture of compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and folpet; compound 2, compound 5, compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35, Compound 36 or Compound 37 and the mixture of Mancozeb; Compound 2, Compound 5, Compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35. The mixture of compound 36 or compound 37 and maneb; the mixture of compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and quinoxyfen; compound 2 , compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or the mixture of compound 37 and validamycin; compound 2, compound 5, compound 8, compound 28, compound 29, compound 30. The mixture of compound 31, compound 35, compound 36 or compound 37 and vinylclozolin; compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 The mixture with fenpropidin; the mixture of compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and fenpropimorph; compound 2, compound 5, Compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35, Compound 36 or Compound 37 and the mixture of Fuconazole; Compound 2, Compound 5, Compound 8, Compound 28, Compound 29, Compound 30, Compound 31 , compound 35, compound 36 or compound 37 and the mixture of cyproconazole; The mixture of epazole; the mixture of compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and epoxiconazole; compound 2, compound 5, compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35, Compound 36 or Compound 37 and the mixture of flusilazole; Compound 2, Compound 5, Compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35 , the mixture of compound 36 or compound 37 and baconazole; the mixture of compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and metconazole; compound 2. The mixture of compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and propiconazole; compound 2, compound 5, compound 8, compound 28, compound 29, The mixture of compound 30, compound 31, compound 35, compound 36 or compound 37 and tebuconazole; compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 Mixture with Fenconazole; Compound 2, Compound 5, Compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35, Compound 36 or Compound 37 and Yiling; Compound 2, Compound 5, Compound 8 , compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and the mixture of fenamidone; compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, The mixture of compound 36 or compound 37 and benomyl; the mixture of compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and cymoxanil; compound 2 , Compound 5, Compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35, Compound 36 or Compound 37 and the mixture of Dimethomorph; Compound 2, Compound 5, Compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35, Compound 36 or Compound 37 and the mixture of Folpet; Compound 2, Compound 5, Compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35, Compound 36 or Compound 37 Mixture with aluminum triethylphosphonate; Compound 2, Compound 5, Compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35, Compound 36 or Compound 37 and metalaxyl; Compound 2, Compound 5 , Compound 8, Compound 28, Compound 29, Compound 30, Compound 31, Compound 35, Compound 36 or Compound 37 and a mixture of ____; Compound 2, Compound 5, Compound 8, Compound 28, Compound 29, Compound 30, Compound 31, The mixture of compound 35, compound 36 or compound 37 and zinc; the mixture of compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and zinc ; compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 with copper sulfate mixture; compound 2, compound 5, compound 8, compound 28, compound 29 , compound 30, compound 31, compound 35, compound 36 or compound 37 and the mixture of copper hydroxide; compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound The mixture of 37 and propamocarb; the mixture of compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or compound 37 and cyazofamid; compound 2, compound 5, compound 8 , compound 28, compound 29, compound 30, compound 31, compound 35, compound 36 or a mixture of compound 37 and zoxamid; compound 2, compound 5, compound 8, compound 28, compound 29, compound 30, compound 31, compound 35, Mixture of Compound 36 or Compound 37 with iprovalicarb.
植物病害控制一般通过在感染前或感染后，将有效量的本发明化合物施用到需保护的植物的某一部分如根、茎、叶、果实、种子、块茎或球根上，或需保护的植物生长的培养基(土壤或砂子)上。该化合物也可施用到种子上，以保护种子和秧苗。Plant disease control is generally carried out by applying an effective amount of the compound of the present invention to a certain part of the plant to be protected, such as root, stem, leaf, fruit, seed, tuber or bulb, before or after infection, or to the growth of the plant to be protected. medium (soil or sand). The compound can also be applied to seeds for seed and seedling protection.
这些化合物的施用率可受许多环境因素影响，由实际使用条件决定。当以低于1g/公顷到5000g/公顷活性成分的用量处理时，通常可保护叶子。当以每公斤种子0.1-10g的量处理种子时，通常可保护种子和秧苗。The application rates of these compounds can be influenced by many environmental factors and will be determined by actual use conditions. Foliage is generally protected when treated at rates from less than 1 g/ha to 5000 g/ha of active ingredient. Seeds and seedlings are generally protected when seeds are treated at 0.1-10 g/kg seed.
以下测试表明本发明化合物在具体病原体上的控制效果。然而该化合物提供的病原体控制保护并不限于这些种类。见Index Tables A-E对化合物的描述。用于Index Tables的以下缩写如下：Me为甲基、Et为乙基、Ph为苯基、OMe为甲氧基、OBt为乙氧基。缩写“dec”指化合物熔化时会分解。缩写“Ex.”表示“实施例”，随后的数字指化合物在该实施例中制备。The following tests demonstrate the control efficacy of the compounds of the invention on specific pathogens. The protection against pathogen control provided by the compounds is not limited to these species, however. See Index Tables A-E for compound descriptions. The following abbreviations used in Index Tables are as follows: Me is methyl, Et is ethyl, Ph is phenyl, OMe is methoxy, OBt is ethoxy. The abbreviation "dec" refers to the fact that the compound decomposes when melted. The abbreviation "Ex." means "Example", followed by a number indicating that the compound was prepared in that Example.
INDEX TABLE A INDEX TABLE A
INDEX TABLE B INDEX TABLE B
* 1H NMR数据参见Index Table E * 1 H NMR data see Index Table E
INDEX TABLE C INDEX TABLE C
INDEX TABLE D INDEX TABLE D
* 1H NMR数据参见Index Table E * 1 H NMR data see Index Table E
INDEX TABLE E
a 1H NMR数据为来自四甲基硅烷的ppm低场数据。偶合通过(s)-单峰、(d)-双峰、(t)-三峰、(q)-四峰、(m)-多峰、(dd)-双双峰、(dt)-双三峰、(brs)-宽单峰表示。 a1H NMR data are ppm downfield data from tetramethylsilane. Coupling via (s)-singlet, (d)-doublet, (t)-triplet, (q)-quatrette, (m)-multiplet, (dd)-doublet doublet, (dt)-doublet triplet , (brs)-broad singlet representation.
本发明的生物实施例 Biological Examples of the Invention
制备测试悬浮液的一般方法：先将测试化合物溶解于为最终容积3％量的丙酮中，然后以要求的浓度(以ppm计)悬浮在含有250ppm表面活性剂Trem_014(多元醇酯)的丙酮和纯净水(50/50混和比)中。然后将所得测试悬浮液用于以下测试。以500g/公顷的当量将200ppm的测试悬浮液喷洒在测试植物上直至流淌。General method for preparing the test suspension: first dissolve the test compound in acetone in an amount of 3% of the final volume, and then suspend in the required concentration (in ppm) containing 250ppm surfactant Trem_014 (polyol ester) Acetone and purified water (50/50 mixing ratio). The resulting test suspension was then used in the following tests. The test plants were sprayed with 200 ppm of the test suspension at an equivalent of 500 g/ha until runnable.
测试A Test A
将测试悬浮液喷洒在小麦秧苗上至流淌。次日，用Erysiphegraminis f.sp.tritici，的孢子粉尘(小麦粉末状霉病的致病剂)培植秧苗，并在20℃的生长室中培养7天，然后作出病害分级。The test suspension was sprayed onto wheat seedlings until runny. The next day, the seedlings were inoculated with spore dust of Erysiphegraminis f.sp.tritici, the causative agent of wheat powdery mildew, and cultured in a growth chamber at 20° C. for 7 days, and then the disease classification was made.
测试B test B
将测试悬浮液喷洒在小麦秧苗上至流淌。次日，用Pucciniarecondita的孢子悬浮液(小麦叶斑的致病剂)培植秧苗，并在20℃的饱和气氛中培养24小时，转移到20℃的生长室中6天，然后作出病害分级。The test suspension was sprayed onto wheat seedlings until runny. The next day, the seedlings were inoculated with a spore suspension of Pucciniarecondita (the causative agent of wheat leaf spot) and incubated in a saturated atmosphere at 20°C for 24 hours, transferred to a growth chamber at 20°C for 6 days, and then disease graded.
测试C test C
将测试悬浮液喷洒在稻谷秧苗上至流淌。次日，用Pyriculariaoryzae的孢子悬浮液(稻瘟病的致病剂)培植秧苗，并在27℃的饱和气氛中培养24小时，转移到30℃的生长室中5天，然后作出病害分级。The test suspension was sprayed onto rice seedlings until runny. The next day, the seedlings were inoculated with a spore suspension of Pyricularia eryzae (the causative agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 hours, transferred to a growth chamber at 30°C for 5 days, and then disease grading was made.
测试D test D
将测试悬浮液喷洒在番茄秧苗上至流淌。次日，用Phytophthorainfestans的孢子悬浮液(马铃薯和番茄晚疫病的致病剂)培植秧苗，并在20℃的饱和气氛中培养24小时，转移到20℃的生长室中5天，然后作出病害分级。The test suspension was sprayed onto tomato seedlings until runny. The next day, seedlings were inoculated with a spore suspension of Phytophthorainfestans (causative agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 hours, transferred to a growth chamber at 20°C for 5 days, and then disease graded .
测试E Test E
将测试悬浮液喷洒在葡萄秧苗上至流淌。次日，用Plasmoparaviticola的孢子悬浮液(葡萄霜霉病的致病剂)培植秧苗，并在20℃的饱和气氛中培养24小时，转移到20℃的生长室中6天，然后在20℃的饱和气氛中培养24小时，随后作出病害分级。The test suspension was sprayed onto the grape seedlings until runny. The next day, the seedlings were planted with the spore suspension of Plasmoparaviticola (causative agent of grape downy mildew), and cultivated in a saturated atmosphere at 20°C for 24 hours, transferred to a growth chamber at 20°C for 6 days, and then placed in a 20°C Incubate in saturated atmosphere for 24 hours, then make disease classification.
测试F Test F
用Phytophthora infestans的孢子悬浮液(马铃薯和番茄晚疫病的致病剂)培植番茄(或马铃薯)秧苗，并在20℃的饱和气氛中培养24小时。第二天喷洒测试悬浮液至流淌，将处理后的植物移至20℃生长室中5天，随后作出病害分级。Tomato (or potato) seedlings were inoculated with a spore suspension of Phytophthora infestans (causative agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 hours. The next day the test suspensions were sprayed to runny and the treated plants were moved to a growth chamber at 20°C for 5 days before disease grading was made.
测试G Test G
用Plasmopara viticola的孢子悬浮液(葡萄霜霉病的致病剂)培植葡萄秧苗，并在20℃的饱和气氛中培养24小时。第二天喷洒测试悬浮液至流淌，将处理后的植物移至20℃的生长室中6天，然后在20℃的饱和气氛中培养24小时，随后作出病害分级。Grape seedlings were inoculated with a spore suspension of Plasmopara viticola (the causative agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 hours. The next day the test suspensions were sprayed to runny and the treated plants were moved to a growth chamber at 20°C for 6 days and then incubated in a saturated atmosphere at 20°C for 24 hours before disease grading.
测试A-E的结果列于表A。在该表中，100级指100％的病害控制，0级指无病害控制(相对于控制而言)。横杠(-)指无测试结果。ND指病害控制由于植物毒性而不确定。除以下所示测试外，本发明的化合物(如化合物2、5、8、28、29、30、31、35、36和37)被认为特别是对于葡萄霜霉病具有显著的疗效。The results of Tests A-E are listed in Table A. In this table, a rating of 100 means 100% disease control and a rating of 0 means no disease control (relative to control). A bar (-) means no test result. ND means disease control is not sure due to phytotoxicity. In addition to the tests shown below, the compounds of the present invention (such as compounds 2, 5, 8, 28, 29, 30, 31, 35, 36 and 37) are considered to have significant curative effect especially against grape downy mildew.
表A Table A
化合物编号 测试A 测试B 测试C 测试D 测试E 测试F 测试G Compound No. Test A Test B Test C Test D Test E Test F Test G
1 0 0 0 90 291 0 0 0 0 90 29
2 0 ND - 100 - 992 0 ND - 100 - 99
3 21 28 0 7 83 21 28 0 0 7 8
4 - - - 99 -4 - - - - - 99 -
5 - 19 - - 98 995 - 19 - - - 98 99
6 0 0 - 19 -6 0 0 0 - 19 -
7 0 0 - - -7 0 0 0 - - - -
8 0 8 - 100 100 968 0 8 8 - 100 100 96
9 0 28 0 7 09 0 28 0 7 0
10 0 9 74 16 010 0 9 74 16 0
11 0 9 0 7 811 0 9 0 0 7 8
12 0 19 0 7 2412 0 19 0 0 7 24
13 0 9 0 3 2313 0 9 0 0 3 23
14 0 19 90 100 9814 0 19 90 100 98
15 0 38 30 7 815 0 38 30 7 8
16 0 9 100 34 816 0 9 100 34 8
17 13 0 0 25 017 13 0 0 0 25 0
18 0 9 80 32 018 0 9 80 32 0
19 0 9 0 7 819 0 9 0 0 7 8
20 0 28 87 25 820 0 28 87 25 8
21 69 68 88 16 821 69 68 88 16 8
22 0 0 0 7 022 0 0 0 0 0 7 0
23 72 9 7 32 823 72 9 7 7 32 8
24 0 0 7 25 824 0 0 0 7 25 8
25 0 9 13 79 1625 0 9 13 79 16
26 0 32 0 25 026 0 32 0 25 0
27 0 0 0 32 1627 0 0 0 0 32 16
28 - - 0 100 100 97# 37* 28 - - 0 100 100 97# 37 *
29 - - 0 100 100 100* 29 - - 0 100 100 100 *
30 - - 0 100 100 100* 30 - - 0 100 100 100 *
31 - - 0 100 100 100** 31 - - 0 100 100 100 **
32 0 0 0 32 -32 0 0 0 0 32 -
33 91 - - 71 -33 91 - - - 71 -
34 0 44 - 31 -34 0 44 - 31 -
35 0 30 - 100 100 100* 35 0 30 - 100 100 100 *
36 0 38 0 100 100 10036 0 38 0 100 100 100
37 0 19 0 100 100 10037 0 19 0 100 100 100
38 - - - - 69* 0** 38 - - - - 69 * 0 **
#100ppm在马铃薯秧苗上 *100ppm. **20ppm.#100ppm on potato seedlings * 100ppm. ** 20ppm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103249721A (en) * | 2010-10-18 | 2013-08-14 | 拉夸里亚创药株式会社 | Arylamine Derivatives as TTX-S Blockers |
| CN103965187A (en) * | 2008-01-25 | 2014-08-06 | 杜邦公司 | Fungicidal Hetercyclic Compounds |
| CN106316931A (en) * | 2015-07-10 | 2017-01-11 | 沈阳中化农药化工研发有限公司 | 2-phenyl nicotinic acid derivative with insecticidal/acaricidal activity |
| CN108516955A (en) * | 2018-07-09 | 2018-09-11 | 上海凯爱网络科技有限公司 | A kind of 5- trifluoromethyls -2- pyridine amides and the preparation method and application thereof |
| CN111454202A (en) * | 2019-01-18 | 2020-07-28 | 山东省联合农药工业有限公司 | Heteroaryl formanilide compound containing pentafluorothio and preparation method and application thereof |
| CN117143013A (en) * | 2023-11-01 | 2023-12-01 | 苏州开元民生科技股份有限公司 | Synthesis method of 2-chloronicotinic acid |
-
2001
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965187A (en) * | 2008-01-25 | 2014-08-06 | 杜邦公司 | Fungicidal Hetercyclic Compounds |
| CN103249721A (en) * | 2010-10-18 | 2013-08-14 | 拉夸里亚创药株式会社 | Arylamine Derivatives as TTX-S Blockers |
| CN103249721B (en) * | 2010-10-18 | 2016-10-12 | 拉夸里亚创药株式会社 | Arylamine Derivatives as TTX-S Blockers |
| CN106316931A (en) * | 2015-07-10 | 2017-01-11 | 沈阳中化农药化工研发有限公司 | 2-phenyl nicotinic acid derivative with insecticidal/acaricidal activity |
| CN106316931B (en) * | 2015-07-10 | 2020-05-05 | 沈阳中化农药化工研发有限公司 | 2-phenylnicotinic acid derivatives with insecticidal and acaricidal activity |
| CN108516955A (en) * | 2018-07-09 | 2018-09-11 | 上海凯爱网络科技有限公司 | A kind of 5- trifluoromethyls -2- pyridine amides and the preparation method and application thereof |
| CN111454202A (en) * | 2019-01-18 | 2020-07-28 | 山东省联合农药工业有限公司 | Heteroaryl formanilide compound containing pentafluorothio and preparation method and application thereof |
| CN111454202B (en) * | 2019-01-18 | 2021-10-01 | 山东省联合农药工业有限公司 | Heteroaryl formanilide compound containing pentafluorothio and preparation method and application thereof |
| CN117143013A (en) * | 2023-11-01 | 2023-12-01 | 苏州开元民生科技股份有限公司 | Synthesis method of 2-chloronicotinic acid |
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