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HK1104548A - Substituted pyridine herbicides - Google Patents

Substituted pyridine herbicides Download PDF

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Publication number
HK1104548A
HK1104548A HK07109949.6A HK07109949A HK1104548A HK 1104548 A HK1104548 A HK 1104548A HK 07109949 A HK07109949 A HK 07109949A HK 1104548 A HK1104548 A HK 1104548A
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HK
Hong Kong
Prior art keywords
radical
alkoxy
group
formula
alkyl
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HK07109949.6A
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Chinese (zh)
Inventor
A.埃德蒙兹
A．德梅斯马克
C．卢西
J．谢策尔
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辛根塔参与股份公司
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Publication of HK1104548A publication Critical patent/HK1104548A/en

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Description

Substituted pyridine herbicides
The application is a divisional application of Chinese patent application No.200510119289.X, with an application date of 07/06/2001 and a priority date of 09/06/2000.
The present invention relates to novel herbicidally active pyridinones, to processes for their preparation, to compositions comprising these compounds and to their use in controlling weeds, particularly in crops of useful plants, or in inhibiting plant growth.
Pyridinones having herbicidal action are described, for example, in WO00/15615 and WO 00/39094.
We have now found novel pyridinones which have herbicidal and growth-inhibiting properties.
The present invention therefore provides compounds of formula I
Wherein
p is 0 or 1;
R1is C1-C6Alkylene radical, C3-C6Alkenylene or C3-C6Alkynylene chain, which may be substituted by halogen or R5Mono-or polysubstituted, wherein the unsaturated bonds of the chain are not directly connected to the substituents X1Connecting; with the proviso that when R2Is unsubstituted phenyl and X1When is-O (CO) -, R1Is not a methylene group;
X1is oxygen, -O (CO) -, - (CO) O-, -O (CO) O-, -N (R)6)-O-、-O-NR51-, thio, sulfinyl, sulfonyl, -SO2NR7-、-NR52SO2-or-NR8-；
R2Is C1-C8Alkyl radical, C3-C6Alkenyl or C3-C6Alkynyl, which is mono-or polysubstituted with: halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C1-C6Alkoxy radical, C1-C6Alkoxycarbonyl, C2-C6Alkenyl radical, C2-C6Haloalkenyl, C2-C6Alkynyl, C2-C6Halogenated alkynyl, C3-C6Cycloalkyl, C substituted by halogen3-C6Cycloalkyl radical, C3-C6Alkenyloxy radical, C3-C6Alkynyloxy, C1-C6Haloalkoxy, C3-C6Haloalkenyloxy, cyano-C1-C6Alkoxy radical, C1-C6alkoxy-C1-C6Alkoxy radical, C1-C6alkoxy-C1-C6alkoxy-C1-C6Alkoxy radical, C1-C6alkylthio-C1-C6Alkoxy radical, C1-C6alkylsulfinyl-C1-C6Alkoxy radical, C1-C6alkylsulfonyl-C1-C6Alkoxy radical, C1-C6alkoxycarbonyl-C1-C6Alkoxy radical, C1-C6Alkoxycarbonyl, C1-C6Alkylcarbonyl group, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylthio, C1-C6Haloalkylsulfinyl radical, C1-C6Haloalkylsulfonyl, which may be substituted by C1-C6Alkyl-substituted oxirane radicals, which may themselves be substituted by C1-C6Alkyl-substituted (3-oxetanyl) oxy, benzylthio, benzylsulfinyl, benzylsulfonyl, C1-C6Alkylamino radical, di (C)1-C6Alkyl) amino, R9S(O)2O、R10N(R11)SO2-, thiocyanato, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl;
in which the phenyl-or benzyl-containing radicals may themselves be substituted by one or more C1-C6Alkyl radical, C1-C6Haloalkyl group、C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro substituted; or
R2Is phenyl, which may be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro is mono-or polysubstituted; or
R2Is C3-C6Cycloalkyl radical, C1-C6Alkoxy-or C1-C6Alkyl-substituted C3-C6Cycloalkyl, 3-oxetanyl or C1-C6Alkyl-substituted 3-oxetanyl;
or if Q is Q2Or Q3Or is wherein R14And R22Is C2-C3Q of alkylene chain1Then R2Also a5 to 10 membered monocyclic or fused bicyclic ring system, which may be aromatic, saturated or partially saturated, and may contain 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, wherein the ring system is either directly or via C1-C4Alkylene radical, C2-C4alkenyl-C1-C4Alkylene radical, C2-C4alkynyl-C1-C4Alkylene, -N (R)12)-C1-C4Alkylene, -SO-C1-C4Alkylene or-SO2-C1-C4Alkylene is bonded to the substituent X1, where each ring system may not contain more than two oxygen atoms and more than two sulfur atoms, and the ring system itself may be mono-, di-and trisubstituted by: c1-C6Alkyl radical, C1-C6Haloalkyl, C2-C6Alkenyl radical, C2-C6Haloalkenyl, C2-C6Alkynyl, C2-C6Halogenated alkynyl, C1-C6Alkoxy, hydroxy, C1-C6Haloalkoxy, C3-C6Alkenyloxy radical, C3-C6Alkynyloxy, mercapto, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C3-C6Alkenylthio radical, C3-C6Haloalkenylthio group, C3-C6Alkynylthio, C2-C5Alkoxyalkylthio radical, C3-C5Acetylalkylthio, C3-C6Alkoxycarbonyl alkylthio radical, C2-C4Cyanoalkylthio, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl, aminosulfonyl, C1-C2Alkylaminosulfonyl, di (C)1-C2Alkyl) aminosulfonyl, di (C)1-C4Alkyl) amino, halogen, cyano, nitro, phenyl and benzylthio, where phenyl and benzylthio may themselves be bound by C on the phenyl ring1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3Haloalkoxy, halogen, cyano, or nitro substitution, wherein a substituent on the heterocyclic nitrogen is other than halogen; or
Under the following conditions R2Is hydrogen or unsubstituted C1-C8Alkyl groups:
a)R1by the group R5Is substituted, or
b) Q is a group Q2Or is or
c) Q is a group Q3Wherein X is1is-O (CO) -, - (CO) O-, -N (R)6)-O-、-O-NR51-、-SO2NR7-、-NR52SO2-or-NR8-, or
d) Q is a group Q1Wherein X is1is-N (R)6)-O-、-O-NR51-、-SO2NR7-、-NR52SO2-or-NR8-, or
e) Q is a group Q1Wherein Q is1R in (1)14And R22Is C2-C3Alkylene chain X1is-O (CO) -or- (CO) O-;
R3is C1-C3A haloalkyl group;
R4is hydrogen, halogen, C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3alkoxy-C1-C3Alkyl or C1-C3alkoxy-C1-C3An alkoxy group;
R5is hydroxy, C1-C6Alkoxy radical, C3-C6Cycloalkoxy, C1-C6alkoxy-C1-C6Alkoxy radical, C1-C6alkoxy-C1-C6alkoxy-C1-C6Alkoxy or C1-C2An alkylsulfonyloxy group;
R6、R7、R8、R9、R10、R11、R12、R51and R52Independently of one another are hydrogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxycarbonyl, C1-C6Alkylcarbonyl group, C1-C6alkoxy-C1-C6Alkyl radical, C1-C6Alkoxy, benzyl or phenyl substituted C1-C6alkoxy-C1-C6Alkyl, where phenyl and benzyl may themselves be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro is mono-or polysubstituted; wherein R is6And R9Not being hydrogen and hydrogen, C, respectively, at the same time1-C6Alkoxycarbonyl or C1-C6An alkylcarbonyl group;
q is Q1
Wherein
A1Is C (R)14R15)、NR16Or oxygen;
A2is C (R)17R18)、C(O)、-C＝N-O-R19Oxygen, sulfur, sulfinyl, sulfonyl, -NR20Or an ethylene group; with the proviso that if A2Is oxygen, C (O), sulfur, sulfinyl, -C ═ N-O-R19、-NR20Or C (R)17R18) Wherein R is17And R18Independently of one another is C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radicals, then A1Different from oxygen; if A is2Is thio, sulfinyl or C (R)17R18) Wherein R is17And R18Independently of one another is C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radicals, then A1Is different from NR16；
R14And R22Independently of one another are hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C4Alkenyl radical, C3-C4Alkynyl, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Alkylsulfonyloxy, C1-C4Alkoxy radical, C1-C4Alkoxycarbonyl or C1-C4An alkylcarbonyl group;
R15and R21Independently of one another are hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C4Alkenyl or C3-C4An alkynyl group;
R17is hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl or C1-C4An alkylsulfonyl group;
R18is hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C4Alkenyl radical, C3-C4Alkynyl, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl or C1-C4dialkoxyalkyl-C1-C4An alkyl group;
R20is C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C3-C4Alkenyl radical, C3-C4Alkynyl, C1-C4Alkylcarbonyl group, C1-C4Alkylcarbonyloxy, di (C)1-C4Alkyl) aminocarbonyl or benzyl, in which the phenyl radical may be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro is mono-or polysubstituted;
R19and R16Independently of one another are hydrogen, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C3-C4Alkenyl radical, C3-C4Alkynyl, benzyl or phenyl, where phenyl and benzyl may themselves be substituted by C1-C6Alkyl radical, C1-C6A halogenated alkyl group,C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro is mono-or polysubstituted;
or R14And R22Together form C2-C3An alkylene chain;
or R14And R15Together and/or R17And R18Together and/or R21And R22Together form C2-C4An alkylene chain which may be interrupted by oxygen and/or carbonyl groups and/or sulfur, with the proviso that the oxygen and sulfur atoms are separated by at least one methylene group;
or R14And R18Together form C2-C4An alkylene chain;
or R22And R18Together form C2-C4An alkylene chain;
or R18And R22Or R14Together form a direct bond;
or R16And R18Together form C2-C4An alkylene chain;
R13is hydroxy, O-M+(wherein M is+Is an alkali metal cation or an ammonium cation), halogen, C1-C12Alkylsulfonyloxy, amino, C1-C4Alkylthio radical, C1-C12Alkylsulfinyl radical, C1-C12Alkylsulfonyl radical, C1-C12Haloalkylthio, C1-C12Haloalkylsulfinyl radical, C1-C12Haloalkylsulfonyl group, C1-C6alkoxy-C1-C6Alkylthio radical, C1-C6alkoxy-C1-C6Alkylsulfinyl radical, C1-C6alkoxy-C1-C6Alkylsulfonyl radical, C3-C12Alkenylthio radical, C3-C12Alkenylsulfinyl, C3-C12Alkenylsulfonyl radical, C3-C12Alkynylthio, C3-C12Alkynylsulfinyl group, C3-C12Alkynylsulfonyl radical, C1-C4alkoxycarbonyl-C1-C4Alkylthio radical, C1-C4alkoxycarbonyl-C1-C4Alkylsulfinyl radical, C1-C4alkoxycarbonyl-C1-C4Alkylsulfonyl group, (C)1-C4Alkoxy group)2P(O)O、C1-C4Alkyl radical- (C)1-C4Alkoxy group) P (O) O, H (C)1-C4Alkoxy) P (O) O, R23R24N、R25R26NNH、R27R28NC(O)O-、R29R30NC(O)NH-、C1-C18Alkylcarbonyloxy, C2-C18Alkenylcarbonyloxy, C2-C18Alkynyl carbonyloxy, C3-C6Cycloalkyl carbonyloxy, C1-C12Alkoxycarbonyloxy, C1-C12Alkylthio carbonyloxy, C1--C12Alkylthiocarbamoyl, in which alkyl, alkenyl and alkynyl may be substituted by halogen, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl or cyano substitution;
or R13Is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenylsulfonyloxy or benzoyloxy, where the phenyl radical may itself be substituted by one or more halogen, nitro, cyano, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4Haloalkoxy substitution;
or R13Is a group Het1Thio, Het2-sulfinyl, Het3-sulfonyl, Het4- (CO) O or Het5-N(R33) (ii) a Wherein Het1、Het2、Het3、Het4And Het5Independently of one another, is a 5-to 10-membered monocyclic or fused bicyclic ring system, which may be aromatic or partially saturated, and may contain 1 to 4 heteroatoms from the group of nitrogen, oxygen and sulfur, where each ring system may not contain more than two oxygen atoms and more than two sulfur atoms, where the ring system itself may be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl, di (C)1-C4Alkyl) aminosulfonyl, di (C)1-C4Alkyl) amino, halogen, cyano, nitro or phenyl substitution, wherein the substituent on the heterocyclic nitrogen is other than halogen;
R23、R24、R25、R26、R27、R28、R29、R30and R33Independently of one another, hydrogen or C1-C6An alkyl group;
or R23And R24Together or R25And R26Together or R27And R28Together or R29And R30Together are pyrrolidinyl, piperidino, morpholino, thiomorpholino, which may be mono-or polysubstituted with methyl;
or Q is Q2
Wherein
R34Is hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl radical, C2-C4Alkenyl radical, C2-C4An alkynyl group or a benzyl group,wherein the phenyl group may be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro is mono-or polysubstituted; r35Is hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl radical, C3-C4Alkenyl radical, C3-C4Alkynyl or benzyl, wherein the phenyl radical may be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro is mono-or polysubstituted; r36Is hydroxy, O-M+(wherein M is+Is an alkali metal cation or an ammonium cation), halogen, C1-C12Alkylsulfonyloxy, amino, C1-C4Alkylthio radical, C1-C12Alkylsulfinyl radical, C1-C12Alkylsulfonyl radical, C1-C12Haloalkylthio, C1-C12Haloalkylsulfinyl radical, C1-C12Haloalkylsulfonyl group, C1-C6alkoxy-C1-C6Alkylthio radical, C1-C6alkoxy-C1-C6Alkylsulfinyl radical, C1-C6alkoxy-C1-C6Alkylsulfonyl radical, C3-C12Alkenylthio radical, C3-C12Alkenylsulfinyl, C3-C12Alkenylsulfonyl radical, C3-C12Alkynylthio, C3-C12Alkynylsulfinyl group, C3-C12Alkynylsulfonyl radical, C1-C4alkoxycarbonyl-C1-C4Alkylthio radical, C1-C4alkoxycarbonyl-C1-C4Alkylsulfinyl radical, C1-C4alkoxycarbonyl-C1-C4Alkylsulfonyl group, (C)1-C4Alkoxy group)2P(O)O、C1-C4Alkyl radical- (C)1-C4Alkoxy radical)P(O)O、H(C1-C4Alkoxy) P (O) O, R37R38N、R39R40NNH、R41R42NC(O)O-、R43R44NC(O)NH-、C1-C18Alkylcarbonyloxy, C2-C18Alkenylcarbonyloxy, C2-C18Alkynyl carbonyloxy, C3-C6Cycloalkyl carbonyloxy, C1-C12Alkoxycarbonyloxy, C1-C12Alkylthio carbonyloxy or C1-C12Alkylthiocarbamoyl, in which alkyl, alkenyl and alkynyl may be substituted by halogen, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl or cyano substitution;
or R36Is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenylsulfonyloxy or benzoyloxy, where the phenyl radical may itself be substituted by halogen, nitro, cyano, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4Haloalkoxy mono-or polysubstituted; or R36Is a group Het7Thio, Het8-sulfinyl, Het9-sulfonyl, Het10- (CO) O or Het11-N(R47) (ii) a Wherein Het7、Het8、Het9、Het10And Het11Independently of one another, is a 5-to 10-membered monocyclic or fused bicyclic ring system, which may be aromatic or partially saturated, and may contain 1 to 4 heteroatoms from the group of nitrogen, oxygen and sulfur, where each ring system may not contain more than two oxygen atoms and more than two sulfur atoms, where the ring system itself may be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6An alkylsulfonyl group,Two (C)1-C4Alkyl) aminosulfonyl, di (C)1-C4Alkyl) amino, halogen, cyano, nitro or phenyl substitution, wherein the substituent on the heterocyclic nitrogen is other than halogen;
R37、R38、R39、R40、R41、R42、R43、R44and R47Independently of one another, hydrogen or C1-C6An alkyl group;
or R37And R38Together or R39And R40Together or R41And R42Together or R43And R44Together are pyrrolidinyl, piperidino, morpholino, thiomorpholino, which may be mono-or polysubstituted with methyl;
or Q is Q3
Wherein
R49Is C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl or halogen substituted C3-C6A cycloalkyl group;
R50is C1-C3Alkylene which may be substituted by halogen, hydroxy, C1-C6Alkoxy radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C6Cycloalkyl radical, C1-C6alkoxy-C1-C6Alkoxy radical, C1-C6alkoxy-C1-C6alkoxy-C1-C6Alkoxy, (3-oxetanyl) oxy, C1-C6Alkyl-substituted (3-oxetanyl) oxy, or benzylthio, benzylsulfinyl, benzylsulfonyl, phenyl, phenoxy, phenylthio, benzenesulfinoAcyl or phenylsulfonyl, in which the phenyl-and benzyl-containing radicals may themselves be substituted by one or more C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro substituted;
or R50Is phenyl, wherein the phenyl-containing radical may itself be substituted by one or more C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro substituted;
or R50Is C3-C6Cycloalkyl radical, C1-C6Alkoxy or C1-C6Alkyl substituted C3-C6Cycloalkyl, 3-oxetanyl or C1-C6Alkyl-substituted 3-oxetanyl; and n is 0, 1 or 2;
and the agronomically acceptable salts/N-oxides/isomers/enantiomers of these compounds, with the exception of the following compounds: 3-hydroxy-2- (2-methoxymethoxymethyl-6-chlorodifluoromethyl-pyridine-3-carbonyl) -4, 4-dimethylcyclohex-2-en-1-one, 3-hydroxy-2- (2-methoxymethoxymethyl-6-difluoromethyl-pyridine-3-carbonyl) -4, 4-dimethylcyclohex-2-en-1-one, 3-hydroxy-2- (2-methoxymethoxymethyl-6-pentafluoroethyl-pyridine-3-carbonyl) -4, 4-dimethylcyclohex-2-en-1-one, 3-hydroxy-2- (2-methoxymethoxymethyl-6-trifluoromethyl- 1-oxy-pyridine-3-carbonyl) -4, 4-dimethylcyclohex-2-en-1-one.
The alkyl groups appearing in the definition of substituents may be straight-chain or branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, nonyl, octyl, decyl, undecyl and dodecyl and their branched isomers. Alkoxy, alkenyl and alkynyl groups are derived from the alkyl groups. Alkenyl and alkynyl groups may be mono-or polyunsaturated.
Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine and chlorine. This also applies correspondingly to halogen in combination with other meanings, for example haloalkyl or halophenyl.
The haloalkyl group preferably has a chain length of 1 to 6 carbon atoms. Haloalkyl groups are, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2, 2, 2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1-difluoro-2, 2, 2-trichloroethyl, 2, 2, 3, 3-tetrafluoroethyl and 2, 2, 2-trichloroethyl; preferred are trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
Suitable haloalkenyl groups are alkenyl groups which are mono-or polysubstituted by halogen, fluorine, chlorine, bromine and iodine, in particular fluorine and chlorine, for example 2, 2-difluoro-1-methylethenyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2, 3, 3-trifluoropropenyl, 2, 3, 3-trichloropropenyl and 4, 4, 4-trifluorobut-2-en-1-yl. At C mono-, di-or trisubstituted by halogen3-C20Among the alkenyl groups, those having a chain length of 3 to 5 carbon atoms are preferred.
Suitable haloalkynyl radicals are alkynyl radicals which are mono-or polysubstituted by halogen, the halogens being bromine, iodine, in particular fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3, 3, 3-trifluoropropynyl and 4, 4, 4-trifluorobut-2-yn-1-yl. Among the alkynyl groups which are mono-or polysubstituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.
In the context of the present invention, the alkali metal cation M+(e.g. in R)13In the definition of) is preferably a sodium cation or a potassium cation.
The alkoxy group preferably has a chain length of 1 to 6 carbon atoms. Alkoxy radicals are, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and the isomeric pentoxy and hexoxy radicals; methoxy and ethoxy are preferred.
The alkylcarbonyl group is preferably acetyl or propionyl.
Alkoxycarbonyl, for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl.
The haloalkoxy group preferably has a chain length of 1 to 8 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2, 2, 2-trifluoroethoxy, 1, 2, 2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2, 2-difluoroethoxy and 2, 2, 2-trichloroethoxy; difluoromethoxy, 2-chloroethoxy and trifluoromethoxy are preferred.
Alkylthio groups preferably have a chain length of 1 to 8 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio.
Alkylsulfinyl is, for example, methanesulfinyl, ethanesulfinyl, propanesulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preference is given to methylsulfinyl and ethylsulfinyl.
Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably a methanesulfonyl group or an ethanesulfonyl group.
The alkoxyalkoxy group preferably has a chain length of 1 to 8 carbon atoms. Examples of alkoxyalkoxy are methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy or butoxybutoxy.
Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomeric butylamine. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino. Preferred alkylamino groups have a chain length of 1 to 4 carbon atoms.
The alkoxyalkyl group preferably has a chain length of 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
The alkylthioalkyl preferably has a chain length of 1 to 8 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.
Cycloalkyl groups preferably have 3 to 8 ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Phenyl groups and phenyl groups as part of substituents, such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, may be substituted. In this case, the substituents may be located in ortho, meta and/or para positions. Preferred substituent positions are ortho and para to the ring attachment point.
The compounds of the formula I may exist in different tautomeric forms, for example if R13Is hydroxy, then there are preferred formulae I' and I "
The invention also covers the salts which can be formed from the compounds of the formula I, preferably with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Suitable salt formers are described, for example, in WO 98/41089.
The invention also encompasses salts which may be formed from the compounds of formula I with amines, alkali and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides, the hydroxides of lithium, sodium, potassium, magnesium or calcium, in particular those of sodium or potassium, are the salt-forming agents worth emphasizing.
Examples of amines suitable for the formation of ammonium salts are ammonia and primary, secondary and tertiary C1-C18Alkylamine, C1-C4Hydroxyalkylamine and C2-C4Alkoxyalkyl amines, for example methylamine, ethylamine, N-propylamine, isopropylamine, the four isomeric butylamine, N-pentylamine, isopentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, di-N-pentylamine, diisopentylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, N-propanolamine, isopropanolamine, N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, N-butenyl-2-amine, N-pentenyl-2-amine, 2, 3-dimethylbutyl-2-amine, butenyl-2-amine, isopentenyl-2-amine, and the like, Dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-pentylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines such as pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine ; primary arylamines such as aniline, methoxyaniline, ethoxyaniline, o, m, p-toluidine, phenylenediamine, benzidine, naphthylamine, and o, m, p-chloroaniline; in particular triethylamine, isopropylamine and diisopropylamine.
Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [ N (R)aRbRcRd)]OH, wherein Ra、Rb、RcAnd RdIndependently of one another is C1-C4An alkyl group. Utensil for cleaning buttockOther suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
Compounds of formula I wherein p is 0 are preferred.
Preferred compounds of the formula I are those in which R1is-CH2-、-CH2CH2-、-CF2、-CH＝CHCH2-、-CH(CH3) -or-C ≡ CCH2-, particularly preferably-CH2-, in which the free valency on the left is in each case attached to the pyridine ring.
Further preferred are compounds of formula I wherein X1Is oxygen, sulfonyl or a radical-NR52SO2-, in particular oxygen.
Particular preference is given to compounds of the formula I in which R2is-CH2OCH3、-CH2OCH2CH3、-CH2CH2OCH3、-CH2CH2SO2CH3or-CH2CH2OCH2CH2OCH3Is preferably-CH2CH2OCH3Highlighting compounds wherein X1Is oxygen, R1is-CH2-. Within this group, preference is given to compounds in which Q is Q1，R13Is a hydroxyl group.
Further emphasis is given to compounds of the formula I in which R2Is that
If at these preferred R2In the meaning, no free valency is indicated, e.g. inIn the case of (b), then the point of attachment is the carbon atom represented by "CH".
In a further preferred compound of the formula I, R3Is CF3、CF2CF3、CF2Cl、CF2H or CCl3Particularly preferred is CF3Wherein R is4Hydrogen or methyl is preferred, and hydrogen is particularly preferred.
R6、R7、R8、R9、R10、R11、R12、R51And R52Independently of one another, especially hydrogen, C1-C4Alkyl radical, C1-C6alkoxy-C1-C6Alkyl or by C1-C6Alkoxy-substituted C1-C6alkoxy-C1-C6Alkyl, wherein in preferred compounds of formula I, additionally Q is Q2，R1Is methylene.
Very preferably, Q is Q1，R13Is hydroxy or halogen, especially hydroxy. Within this group, compounds are emphasized in which
a)A1Is C (R)14R15) Or NR16，A2Is C (R)17R18) C (O) or oxygen; or
b)A1Is C (R)14R15)，A2Is C (R)17R18)，R14And R22Together form C2-C3Alkylene chains, preferably ethylene chains, in which R is15、R17、R18And R21Hydrogen is particularly preferred; or
c)A2Is C (O) or C (R)17R18)，A1Is C (R)14R15)，R14、R15、R17And R18Independently of one another, hydrogen, methyl, ethyl, methoxycarbonyl or ethylAn oxycarbonyl group; or
d)R14And R15Or R21And R22Together form C2Alkylene chain (cyclopropyl ring), A2Is CH2，R21And R22Or R14And R15Independently of one another are hydrogen, C1-C4Alkyl, methoxycarbonyl or ethoxycarbonyl; or
e)A2Is C (R)17R18)，A1Is C (R)14R15)，R18And R14Together form C2-C3An alkylene chain.
In a further highlighted group of compounds of formula I, Q is Q3，R49Is cyclopropyl, R50-S(O)nIs methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl.
The compounds of the formula I can be prepared by processes known per se, for example those described in WO 97/46530 or WO00/15615 or WO 00/39094, for example in the case of the compounds of the formula I,
wherein R is1、R2、R3、R4And X1Is as defined under formula I, Q is a group
For example,
a) reacting a compound of formula Ia in an inert organic solvent in the presence of a base
Wherein R is1、R2、R3、R4And X1 is as defined under formula I, Y1Is a leaving group, such as halogen or cyano, with a compound of formula II,
wherein R is22、R21、A2And A1Is as defined under formula I,
to give compounds of the formulae IIIa and IIIb
They are then isomerized, for example in the presence of a base and a catalytic amount of Dimethylaminopyridine (DMAP) or a cyanide source, for example acetone cyanohydrin; or
b) Reacting a compound of formula Ib in an inert organic solvent in the presence of a base and a coupling agent
Wherein R is1、R2、R3、R4And X1Is as defined under formula I, with a compound of formula II,
wherein R is22、R21、A1And A2Is as defined under formula I to give a compound of formula IIIa or IIIb
They are then isomerized, for example as described under route a).
The preparation of compounds of the formula I, in which Q is a radical, is carried out in analogy to known methods (for example WO 97/46530)
Wherein the content of the first and second substances,
a) reacting a compound of formula Ia in an inert organic solvent in the presence of a base
Wherein R is1、R2、R3、R4And X1Is as defined under formula I, Y1Is a leaving group, such as halogen or cyano,
with a compound of the formula IIa,
wherein R is34And R35The definition is the same as that of the above,
to give the compound of the formula IIIc
Wherein R is1、R2、R3、R4、R34、R35And X1Is as defined under formula I,
this compound is then isomerized, for example in the presence of a base and a catalytic amount of a cyanide source; or
b) Reacting a compound of formula Ib in an inert organic solvent in the presence of a base and a coupling agent
Wherein R is1、R2、R3、R4And X1Is as defined under formula I,
with a compound of the formula IIa,
wherein R is34And R35The definition is the same as that of the above,
to give the compound of the formula IIIc
This compound is then isomerized as described under pathway a).
The preparation of the compounds of the formula I, in which Q is a radical, is carried out analogously to known processes, for example as described in WO00/15615, WO 00/39094 or WO 97/43270
Wherein n is O, R50And R49The definition is the same as that of the above,
wherein
a) In the presence of a base, carbon disulphide and an alkylating agent of formula V,
R50-Y2 (V)
wherein R is50Is as defined under formula I, Y2Is a leaving group, e.g. halogen or sulfonate, to a compound of formula IV
Wherein X1、R1、R2、R3、R4And R49The definition is the same as that of the above,
into compounds of the formula VI
Wherein R is1、R2、R3、R4、R50、X1And R49The definition is the same as that of the above,
this compound is then cyclized with hydroxylamine hydrochloride, if appropriate in a solvent, in the presence of a base, for example sodium acetate, to give the isomeric compounds of the formulae Ic and Id
These compounds are then oxidized with an oxidizing agent, for example peracids such as m-chloroperbenzoic acid (m-CPBA) or peracetic acid, to give the corresponding sulfoxides (n ═ 1) and sulfones (n ═ 2) of the formulae Ie and If, respectively. Using a suitable mobile phase, isomers of formulae Ic and Id (where n ═ 0) or isomers of formulae Ie and If (where n ═ 1 or 2) can be isolated and purified by column chromatography.
Intermediates of formulae Ia, Ib, IV and VI are novel and are particularly useful in the preparation of compounds of formula I. They therefore also form part of the subject matter of the present invention. The novel intermediates of formulae Ia, Ib, IV and VI together correspond to formula XX
Wherein
Q is hydroxy, halogen, cyano or C1-C6Alkoxy, or a group of the formula
or-CH2(CO)R49(ii) a And
R1、R3、R4、R49、R50、X1and p is as defined under formula I, R2Is C1-C8Alkyl radical, C3-C6Alkenyl or C3-C6Alkynyl, which is mono-or polysubstituted with: halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C1-C6Alkoxy radical, C1-C6Alkoxycarbonyl, C2-C6Alkenyl radical, C2-C6Haloalkenyl, C2-C6Alkynyl, C2-C6Halogenated alkynyl, C3-C6Cycloalkyl, C substituted by halogen3-C6Cycloalkyl radical, C3-C6Alkenyloxy radical, C3-C6Alkynyloxy, C1-C6Haloalkoxy, C3-C6Haloalkenyloxy, cyano-C1-C6Alkoxy radical, C1-C6alkoxy-C1-C6Alkoxy radical, C1-C6alkoxy-C1-C6alkoxy-C1-C6Alkoxy radical, C1-C6alkylthio-C1-C6Alkoxy radical, C1-C6alkylsulfinyl-C1-C6Alkoxy radical, C1-C6alkylsulfonyl-C1-C6Alkoxy radical, C1-C6alkoxycarbonyl-C1-C6Alkoxy radical, C1-C6Alkoxycarbonyl, C1-C6Alkylcarbonyl group, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylthio, C1-C6Haloalkylsulfinyl radical, C1-C6Haloalkylsulfonyl, which may be substituted by C1-C6Alkyl-substituted oxirane radicals, which may themselves be substituted by C1-C6Alkyl-substituted (3-oxetanyl) oxy, benzylthio, benzylsulfinyl, benzylsulfonyl, C1-C6Alkylamino radical, di (C)1-C6Alkyl) amino, R9S(O)2O、R10N(R11)SO2-, thiocyanato, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl;
in which the phenyl-or benzyl-containing radicals may themselves be substituted by one or more C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro substituted; or
R2Is phenyl, which may be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro is mono-or polysubstituted; or
R2Is C3-C6Cycloalkyl radical, C1-C6Alkoxy-or C1-C6Alkyl-substituted C3-C6Cycloalkyl, 3-oxetanyl or C1-C6Alkyl-substituted 3-oxetanyl;
or if X1is-N (R)6)-O-、-O-NR51-、-SO2NR7-or-NR52SO2-, and R6、R7、R51And R52Is as defined under formula I, then R2May additionally be hydrogen, unsubstituted C1-C6Alkyl or a 5-to 10-membered monocyclic or fused bicyclic ring system, which may be aromatic, saturated or partially saturated, and may contain 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, wherein the ring system is direct or via C1-C4Alkylene radical, C2-C4alkenyl-C1-C4Alkylene radical, C2-C4alkynyl-C1-C4Alkylene, -N (R)12)-C1-C4Alkylene, -SO-C1-C4Alkylene or-SO2-C1-C4Alkylene and substituent X1(ii) a linkage wherein each ring system may not contain more than two oxygen atoms and more than two sulfur atoms, wherein the ring system itself may be mono-, di-and tri-substituted with: c1-C6Alkyl radical, C1-C6Haloalkyl, C2-C6Alkenyl radical, C2-C6Haloalkenyl, C2-C6Alkynyl, C2-C6Halogenated alkynyl, C1-C6Alkoxy, hydroxy, C1-C6Haloalkoxy, C3-C6Alkenyloxy radical, C3-C6Alkynyloxy, mercapto, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C3-C6Alkenylthio radical, C3-C6Haloalkenylthio group, C3-C6Alkynylthio, C2-C5Alkoxyalkylthio radical, C3-C5Acetylalkylthio, C3-C6Alkoxycarbonyl alkylthio radical, C2-C4Cyanoalkylthio, C1-C6Alkylsulfinyl radical, C1-C6Haloalkyl groupSulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl, aminosulfonyl, C1-C2Alkylaminosulfonyl, di (C)1-C2Alkyl) aminosulfonyl, di (C)1-C4Alkyl) amino, halogen, cyano, nitro, phenyl and benzylthio, where phenyl and benzylthio may themselves be bound by C on the phenyl ring1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3Haloalkoxy, halogen, cyano or nitro, wherein the substituents on the heterocyclic nitrogen are other than halogen.
The following reaction schemes 1 and 2 illustrate the preparation of the compounds of formula I in more detail.
Reaction scheme 1
Route a):
reaction scheme 1 is preferably used to prepare a compound having a group Q1Wherein R is13Compounds of the formula I which are hydroxy and have a group Q2Wherein R is36A compound of formula I which is hydroxy.
Reaction scheme 2
Compounds of the formula I in which p is 1, i.e. the corresponding oxides of the formula I N, can be prepared in the presence of anhydrides, for example trifluoroacetic anhydride, in such a way that p is0 with a suitable oxidizing agent, e.g. H2O2A urea adduct. Such oxidations are known in the literature, for example j.med.chem. (journal of medicinal chemistry), 32(12), 2561-73, 1989 or WO 00/15615.
According to scheme 1, route a), a carboxylic acid derivative of formula Ia, wherein Y is1Is a leaving group, e.g. halogen, e.g. iodine, bromine, especially chlorine, N-oxophthalimide or N, O-dimethylhydroxyamino, or part of an activated ester, e.g.
(from Dicyclohexylcarbodiimide (DCC) and the corresponding carboxylic acid
Generate) or(generated from N-ethyl-N' - (3-dimethylaminopropyl) carbodiimide (EDC) and the corresponding carboxylic acid) for the preparation of compounds of formula I, wherein Q represents a group Q1And Q2，R13And R36Is a hydroxyl group. The starting material is reacted with a diketone derivative of the formula II or a pyrazole of the formula IIa in an inert organic solvent, for example a halogenated hydrocarbon such as dichloromethane, a nitrile such as acetonitrile, or an aromatic hydrocarbon such as toluene, in the presence of a base such as an alkylamine such as triethylamine, an aromatic amine such as pyridine or 4-Dimethylaminopyridine (DMAP) to give an enol ether of the formula IIIa, IIIb or IIIc. The esterification can be carried out at a temperature of from 0 ℃ to 110 ℃.
Conversion of ester derivatives of formulae IIIa, IIIb and IIIc to derivatives of formula I (wherein R13And R36Is ｃA hydroxyl group) can be carried out, for example, analogously to what is described in EP-A-0353187, EP-A-0316491 or WO 97/46530, in the presence of ｃA base, for example an alkylamine, for example triethylamine, in the presence of ｃA carbonate, for example potassium carbonate, and in the presence of catalytic amounts of DMAP or of ｃA cyanide source, for example acetone cyanohydrin or potassium cyanide. In particular, if a cyanide compound of the formula Ia (Y) is used1Cyano) or inIn the presence of catalytic amounts of acetone cyanohydrin or potassium cyanide, then the two reaction steps can be carried out in situ without isolation of intermediate III.
Following reaction scheme 1, route b), the desired derivative of formula I (wherein R13And R36Is a hydroxyl group) can be obtained, for example, analogously to what is described in E.Haslem, Tetrahedron (Tetrahedron), 2409-2433, 36, 1980 by esterifying a carboxylic acid of the formula Ib with a diketone derivative of the formula II or a pyrazole IIa in an inert solvent, for example a halogenated hydrocarbon, for example dichloromethane, a nitrile, for example acetonitrile, or an aromatic hydrocarbon, for example toluene, in the presence of a base, for example an alkylamine, for example triethylamine, and in the presence of a coupling agent, for example 2-chloro-1-methylpyridinium iodide. Depending on the solvent used, the esterification is carried out at a temperature of from 0 ℃ to 110 ℃ as described under route a), initially giving the isomeric esters of formula IIIa, IIIb or IIIc, which can be isomerized as described under route a), for example in the presence of a base and a catalytic amount of DMAP or a cyanide source, for example acetone cyanohydrin, to give the desired derivative of formula I (wherein R is13And R36Is a hydroxyl group). In scheme 1 (pathway a), activated carboxylic acid derivatives of formula Ia (where Y is1Is a leaving group, such as halogen, e.g. bromine, iodine, or especially chlorine), can be prepared by known standard methods, such as those described in c.ferri, "Reaktionen der organischen Synthesis" (organic Synthesis reactions), georgThieme Verlag, Stuttgart, 1978, 460, and the like. Such reactions are generally known and described in the literature, with respect to the leaving group Y1May be different.
Wherein Q represents a group Q3The preparation of compounds of the formula I can be carried out according to reaction scheme 2, for example analogously to Synthesis 1991, 301, supra, 1988, 793 or Tetrahedron 32, 3055, 1976, in the presence of a base, for example a carbonate, for example potassium carbonate, in the presence of a metal hydride, for example sodium hydride or aluminum potassium fluoride, and in the presence of an alkylating agent of the formula V, where Y is2Is a leaving group, e.g. halogen, e.g. iodine, bromine, especially chlorine, CH3SO2O-orReacting the beta-diketone derivative of formula IV with carbon disulphide. The reaction is conveniently carried out in a solvent, for example an amide, such as N, N-Dimethylformamide (DMF), a sulfoxide, such as dimethyl sulfoxide (DMSO), or a nitrile, such as acetonitrile. The ketene dithioacetal of the formula VI formed is cyclized with the aid of hydroxylamine hydrochloride in the presence of a base, for example sodium acetate, in a solvent, for example an alcohol, for example ethanol, or an ether, for example tetrahydrofuran, to give the isomeric compounds of the formulae Ic and Id, where n is 0. The cyclization reaction is carried out at a temperature of 0 ℃ to 100 ℃. If appropriate, compounds of formulae Ic and Id in which n is 0 can be oxidized by known standard methods, for example as described in H.O.House, "Modern synthetic reactions", W.A.Benjamin, Inc., Menlo Park, California, 1972, p334-335 and 353-354, to give the corresponding sulfones and sulfoxides of formulae Ie and If (n ═ 1 or 2).
The compounds of formula IV in scheme 2 can be obtained by standard methods, e.g. from the corresponding compounds of formula Ia
Wherein R is1、R2、R3、R4And X1As defined above, Y1Is a leaving group, for example halogen, for example obtained by claisen condensation, or from a compound of formula Ia by reaction with a ketocarboxylate of formula VII,
wherein R is49Is as defined under formula I, M+Is an alkali metal ion (see, for example, WO 96/26192).
Wherein R is1In particular C1-C2Alkyl compounds of the formula I can also be prepared, for example, in this wayThe N-oxide of IX is heated under known reaction conditions in the presence of an acid anhydride (see, for example, Konno, K.; Hashimoto, K.; Shirahama, H.; Matsumoto, T.; Heterocycles 1986, 24, 2169 or WO 00/15615) and the product (Ig) obtained is hydrolyzed in a protic solvent, for example water or a water/methanol mixture, if appropriate in the presence of a base, for example lithium hydroxide or sodium hydroxide, and then in the presence of a base, for example sodium hydride or potassium hydroxide, if appropriate in a phase-transfer catalyst or a crown ether, and in the presence of an alkylating agent R2-Y3In the presence of (b), wherein R2Is as defined under formula I, Y3Is a leaving group, e.g. halogen or mesylate, in an aprotic inert solvent, e.g. tetrahydrofuran or dimethylformamide, to convert the resulting alcohol X to the corresponding derivative of formula Ih (wherein X is1Is oxygen). Wherein R is2Is C1-C6Compounds of the formula I which are alkoxymethyl or 2-tetrahydropyranyl or 2-tetrahydrofuranyl may be prepared, for example, by reacting an alcohol of the formula X with an alcohol of the formula VE in the presence of an acidic catalyst, for example p-toluenesulfonic acid, in an inert solvent, for example dichloromethane1Treatment with vinyl ethers, in which R03、R04And R05Is C1-C6Alkyl, or R03And R05Together form C2-C3An alkylene chain. Such reactions are generally known from the literature (see, for example, Synthesis, p.169, 1973). Two reaction lines are demonstrated using the following examples.
Reaction scheme 3
Wherein R is1In particular C1-C2Alkyl or C1-C2Haloalkyl compounds of the formula I can, for example, also be prepared under known halogenation conditions, for example using N-bromosuccinimide or N-chlorosuccinimide, in the presence of light and free-radical initiators, for exampleBenzoyl peroxide, oxidation of R therein13Especially chlorine, C1-C4Compounds of the formula XI which are alkoxycarbonyloxy or benzoylcarbonyloxy (prepared analogously to WO00/15615 or WO 00/39094) to give 1-bromo or 1-chloro, 1-dibromo or 1, 1-dichloro compounds, which are then functionalized again to the corresponding derivatives of the formula I, for example by reaction with a nucleophile R in the presence of a base such as sodium hydride, potassium hydroxide or potassium carbonate2Reaction of-Z, wherein Z is, for example, -SH, -OH, -C (O) OH, -O-N (R)51)H、-N(R6)-OH、-SO2N(R52) H or-N (R)8)H，R2、R52、R8、R6And R51Is as defined under formula I, followed by an aqueous post-treatment. These reaction lines are also demonstrated using the following examples.
Reaction scheme 4
Wherein Q represents Q1Or Q2And wherein R13Or R36Compounds of the formula I which are different from hydroxyl or halogen can be prepared by conversion processes which are generally known from the literature, for example from the compounds in which R is present in the presence of suitable bases13Or R36Starting from compounds of formula I which are hydroxy, they are acylated or carbamylated with the appropriate acid chloride, or they may be prepared by reaction of a compound of formula I wherein R is13And R36Nucleophilic substitution reactions on the chloride of formula I, which is chlorine, can likewise be obtained in a known manner by reaction with chlorinating agents, such as phosgene, thionyl chloride or oxalyl chloride. The starting materials used are, for example, appropriately substituted amines or direct hydroxylamines, or alkylsulfonamides, mercaptans, thiophenols, phenols, heterocyclic amines or heterocyclic mercaptans, in the presence of bases, for example 5-ethyl-2-methylpyridine, diisopropylethylamine, triethylamine, sodium hydrogencarbonate, sodium acetate or potassium carbonate.
Can be similar toIn which R is oxidized by known standard methods13And R36Compounds of formula I containing a sulphur group, for example using a peracid such as m-chloroperbenzoic acid (m-CPBA) or peracetic acid, give the corresponding sulfones and sulfoxides of formula I. The degree of oxidation (SO-or SO) on the sulfur atom can be controlled by the amount of oxidizing agent2-)。
Obtained wherein R13And R36The derivatives of the formula I which are different from the hydroxyl radical can likewise exist in different isomeric forms and can, if appropriate, be isolated in pure form. Thus, the present invention also encompasses all such stereoisomeric forms. Examples of such isomeric forms are of formulae I ', I ' and I ', wherein Q represents a group Q1。
Compounds of the formulae II and IIｃA are known and can be prepared analogously, as described, for example, in WO 92/07837, JP 10265441, DE-A-3818958, EP-A-0338992, DE-A-3902818, EP-A-O278742, WO 98/29412, JP 02059566, US-A-5,089,046, GB-A-2205316, WO 00/27821 or EP-A-0384736.
The desired intermediate of formula Ib (or Ik, Il or Im) is synthesized analogously to known methods, for example as described in WO00/15615, WO 00/39094 or WO 97/46530, or they can be prepared, for example, according to generally known transformation methods, such as Stille (see, for example, Angew. chem. (applied chemistry) 1986, 98(6), 504-19), Heck (see, for example, Angew. chem. (applied chemistry) 1994, 106(23/24), 2473-506), Sonogashira (see, for example, "Comprehensive Organometallic Synthesis", Pergamon Verlag, Oxford, Vol 3, 1991, page 521, etc.) or Wittig (e.g., C.Ferri "Reaktion der organic Synthesis", Georg Thieme Verlag, Stuttgart, 1978, page 354, etc.), from halogen derivatives of the formula XIV (prepared as described in WO00/15615 or WO 00/39094) or halogen derivatives (prepared analogously to EP 522392):
reaction scheme 5
Wherein R is1、R2、R3、R4And X1Intermediates of formula Ib as defined under formula I can also be prepared according to the method of reaction scheme 6:
reaction scheme 6
Starting from vinyl or allyl compounds of the formula XVIII (prepared as described In WO00/15615 or WO 00/39094) using generally known oxidation methods, such as dihydroxylation, Wacker oxidation, epoxidation, hydroboration and subsequent oxidation, intermediates of the formulae II, In, Iq and Ir are obtained, which are converted by methods known to the person skilled In the art (e.g. activation of alcohols to sulfonates, alkylation, for example using an alkylating agent R)2-Y3Or R5-Y3Wherein R is2And R5Is as defined under formula I, Y3Is a leaving group, e.g. halogen), in the presence of a base, or by nucleophilic reactions, e.g. with nucleophiles Z-R2Reaction of in which Z and R2These intermediates may be converted to compounds of formula I, as defined above.
Wherein R is1Is C1-C2Alkyl and R2、R3、R4And X1The intermediate of formula Ib, which is defined as under formula I, can also be prepared by reacting R wherein R is as defined in formula I in the presence of a base, such as sodium hydride or an alkaline earth metal oxide or carbonate, in an inert solvent, such as dimethylformamide or THF, at a temperature between-5 and 160 deg.C3And R4Is as defined under formula I and Y4Is halogenWith nucleophiles R of the formula XIVa2-Z reaction, wherein Z is-SH, -OH, -C (O) OH, -O-N (R)51)H、-N(R6)-OH、-SO2N(R52) H or-N (R)8)H，R2、R52、R8、R6And R51As defined under formula I, or for the preparation of the corresponding sulfinyl or sulfonyl derivatives of formula Iu, with an oxidizing agent, such as m-chloroperbenzoic acid or sodium periodate or sodium perborate, in an inert solvent, such as dichloromethane, the temperature being controlled according to the degree of oxidation, as known to the skilled person (for example-30 ℃ to +50 ℃ for n ═ 1, and-20 ℃ to +100 ℃ for n ═ 2, respectively), to give compounds of formula Iv. In the following reaction scheme 7, Z ═ OH, SH, SO2N(R52) H and N (R)8) This is explained in more detail in the case of H:
reaction scheme 7
Wherein Q represents a group OR02(R02＝C1-C6Alkyl) intermediates of formula I can be converted to products of formula Ib by hydrolysis, for example using a base, e.g. LiOH, in a protic solvent, e.g. H2O or H2An O/methanol mixture.
With respect to the preparation of all others according to R1、R2、R3、R4And X1There are a number of suitable known standard methods for functionalizing compounds of formula I, such as alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, and the choice of a suitable preparation depends on the nature (reactivity) of the substituents in the intermediates.
The reaction to give the compounds of the formula I is advantageously carried out in an aprotic organic solvent. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as methylene chloride, chloroform, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N, N-dimethylformamide, diethylformamide or N-methylpyrrolidone. The reaction temperature is advantageously between-20 ℃ and +120 ℃. In general, the reaction is slightly exothermic and can generally be carried out at room temperature. To shorten the reaction time, or to start the reaction, the mixture may simply be heated to the boiling point of the reaction mixture. The reaction time can also be shortened by adding a few drops of base as a reaction catalyst. Suitable bases are, in particular, tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1, 4-diazabicyclo [2.2.2] octane, 1, 5-diazabicyclo [4.3.0] non-5-ene or 1, 5-diazabicyclo [5.4.0] undec-7-ene. However, it is also possible to use inorganic bases, such as hydrides, for example sodium hydride or calcium hydride, hydroxides, for example sodium hydroxide or potassium hydroxide, carbonates, for example sodium carbonate and potassium carbonate, or bicarbonates, for example potassium bicarbonate and sodium bicarbonate. These bases may be used alone or together with catalytic amounts of phase transfer catalysts, for example crown ethers, especially 18-crown-6, or tetraalkylammonium salts.
The compounds of the formula I can be isolated in a conventional manner by concentration and/or evaporation of the solvent, and purified by recrystallization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
All methods of application customary in agriculture, such as pre-emergence application, post-emergence application and seed treatment, as well as various methods and techniques, such as controlled release of active ingredients, are suitable for the application of the compounds of the formula I according to the invention or of the compositions comprising them. For this purpose, a solution of the active ingredient is applied to granules of mineral carrier or polymeric particles (urea/formaldehyde) and dried. If appropriate, further coating agents (coated particles) can be applied so that the active ingredient is released in a controlled manner for a specific time.
The compounds of the formula I can be employed as herbicides by themselves, i.e. in synthetically prepared form. However, they are preferably processed in customary manner with the auxiliaries customary in the formulation art, for example to give emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on page WO 97/344859-13. The method of application, e.g. spraying, atomizing, dusting, wetting, spreading or pouring, and the type of composition are chosen to suit the intended purpose and the prevailing circumstances.
Formulations, i.e. compositions, preparations or products comprising the active ingredient of formula I or at least one active ingredient of formula I and usually one or more solid or liquid formulation auxiliaries, are prepared in a known manner, for example by thoroughly mixing and/or grinding the active ingredient with the formulation auxiliaries, for example solvents or solid carriers. Furthermore, a surface-active compound (surfactant) may be additionally used in preparing the formulation. Examples of solvents and solid carriers are described, for example, on page 6 of WO 97/34485.
Suitable surface-active compounds are nonionic, cationic and/or anionic surfactants and surfactant mixtures, which, depending on the nature of the active ingredient of the formula I to be formulated, have good emulsifying, dispersing and wetting properties. Examples of suitable anionic, nonionic and cationic surfactants are described, for example, in WO 97/34485 p.7-8. Particularly described in "McCutcheon's Detergents and Emulsifiers Annual" (McCutcheon Detergents and Emulsifiers) MC Publishing Corp., Ridgewood New Jersey, 1981; stache, H., "Tensid-Taschenbuch" (surfactant guide), CarlHanser Verlag, Munich/Vienna, 1981; surfactants commonly used in the formulation field in "encyclopedia of Surfactants", Vol I-III, chemical publishing Co., New York, 1980-81 are furthermore also suitable for preparing the herbicidal compositions according to the invention.
Typically, the herbicidal formulation comprises from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of the herbicide, from 1 to 99.9% by weight, especially from 5 to 99.8% by weight, of the solid or liquid formulation adjuvant and from 0 to 25% by weight, especially from 0.1 to 25% by weight, of the surfactant. Although concentrated compositions are more preferred commercial products, dilute compositions are often used by the end consumer. The composition may also contain further additives such as stabilizers, for example epoxidized or non-epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), defoamers, for example silicone oils, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients.
In general, the active ingredients of the formula I are applied to the plants or their environment in an amount of from 0.001 to 4kg/ha, in particular from 0.005 to 2 kg/ha. The dosage required to achieve the desired effect can be determined experimentally. This depends on the type of action, the developmental stage of the crop and weed and the application (location, time, method), which vary widely due to these factors.
The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, which make them useful in crops of useful plants, in particular cereals, cotton, soybeans, sugar beet, sugar cane, cultivated crops, oilseed rape, maize and rice, and also for the non-selective control of weeds. Crops are also understood to include those which have been rendered herbicide tolerant by means of conventional planting or genetic engineering methods. The weeds to be controlled can be monocotyledonous and dicotyledonous weeds, for example Stellaria, Arabidopsis, agrostis, digitaria, Avena, Setaria, Brassica, Crataegus, Solanum, Echinochloa, Scirpus, Potentilla, Sagittaria, Bromus, Alopecurus, sorghum saccharum Sorghumhalepense (Sorghumuhalepen), Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The following examples illustrate the invention in more detail, but do not limit it.
Preparation example
Example H1: 2-Bromomethyl-6-trifluoromethylnicotinic acid ethyl ester
434.4g (1.866mol) of ethyl 2-methyl-6-trifluoromethylnicotinate (prepared analogously to Heterocycles 129, 46, 1997) were heated with 398.5g (2.239mol) of N-bromosuccinimide in 3500ml of carbon tetrachloride at 75 ℃ in the presence of 30.6g (0.1866mol) of α, α -azoisobutyronitrile and irradiated with 150 watt lamps. After 3 hours, the reaction was terminated, the mixture was cooled to 15 ℃ and the precipitated succinimide was removed by filtration. After evaporation of the solvent, the residue was distilled under reduced pressure. Ethyl 2-bromomethyl-6-trifluoromethylnicotinate is obtained as an oily product (260.2g, 44.7% of theory, b.p.74 ℃/0.04 mmHg).
Example H2: 2- (2-methoxyethoxymethyl) -6-trifluoromethylnicotinic acid
177.2g of ethyl 2-bromomethyl-6-trifluoromethylnicotinate are dissolved in 3000ml of toluene and reacted with 398ml (1.704mol) of 21% sodium ethoxide in ethanol at room temperature. After 8 hours at room temperature, 1500ml of ethanol and 100ml of 30% aqueous sodium hydroxide solution were added with vigorous stirring, and the reaction mixture was stirred at this temperature for a further 4 hours. The reaction mixture was poured into water, extracted with ethyl acetate and the aqueous phase was acidified to pH 1. Extraction with ethyl acetate, drying over sodium sulfate, evaporation under reduced pressure and trituration with hexane gave pure 2- (2-methoxyethoxymethyl) -6-trifluoromethylnicotinic acid as white crystals, m.p. 62-63 ℃.
Example H3: 4-hydroxy-3- [2- (2-methoxyethoxymethyl) -6-trifluoromethylpyridine -3-carbonyl]-bicyclo [3.2.1]Oct-3-en-2-ones
24.9g (0.1mol) of 2- (2-methoxyethoxymethyl) -6-trifluoromethylnicotinic acid are dissolved in 200ml of dichloromethane and 20ml of oxalyl chloride, and then 0.1ml of dimethylformamide is added dropwise. After the evolution of strong gas had ceased triethylamine (27.9ml, 0.2mol), dimethylaminopyridine (1.22g, 0.01mol) and 15.2g (0.11mol) bicyclo [3.2.1] octane-2, 4-dione were added at a temperature of 0 to 5 ℃. After 3 hours at 22 ℃ the reaction mixture was extracted with 2N hydrochloric acid. The dichloromethane phase is separated off, washed with water and then extracted with 10% aqueous sodium hydrogencarbonate, dried over sodium sulfate and concentrated. 36.9g (100% of theory) of 4-oxobicyclo [3.2.1] oct-2-en-2-yl 2- (2-methoxyethoxymethyl) -6-trifluoromethylnicotinate are obtained as an oil which is used further without purification.
36.9g (0.1mol) 4-oxobicyclo [3.2.1] oct-2-en-2-yl 2- (2-methoxyethoxymethyl) -6-trifluoromethylnicotinate and 27.9ml (0.2mol) triethylamine were dissolved in 400ml acetonitrile. At a temperature of 22 ℃ 0.92ml (0.01 mol) of acetone cyanohydrin are added. After 18 hours at 22 ℃ the reaction mixture was poured into a water/2N hydrochloric acid mixture and extracted with ethyl acetate. The ethyl acetate phase is washed with water and then with concentrated sodium chloride solution, dried over sodium sulfate, concentrated and the residue triturated with hexane. Filtration gave 27.9g (75.6% of theory) of 4-hydroxy-3- [2- (2-methoxyethoxymethyl) -6-trifluoromethylpyridine-3-carbonyl ] -bicyclo [3.2.1] oct-3-en-2-one as white crystals (m.p.55 ℃ -56 ℃).
Example H4: 3- (2-hydroxy-4-oxobicyclo [ 3.2.1)]Oct-2-ene-3-carbonyl) -6- Trifluoromethylpyridin-2-ylmethyl acetate
5.0g (1mmol) of 4-hydroxy-3- (2-methyl-1-oxy-6-trifluoromethylpyridine-3-carbonyl) bicyclo [3.2.1]Oct-3-en-2-one (prepared as described in WO 00/15615) was dissolved in 100ml of toluene and heated in the presence of 6.9ml (0.073mol) of acetic anhydride at reflux temperature for 10 hours. The mixture was then partitioned between water and ethyl acetate, the organic phase was dried over sodium sulfate and concentrated under reduced pressure. The residue remaining was purified by silica gel chromatography. Elution with a mixture of toluene, ethanol, dioxane, triethylamine and water (100: 40: 20: 5 parts by volume) gave a viscous oil which was dissolved in ethyl acetate and washed successively with 10% hydrochloric acid and water. Organic solution is treated with Na2SO4Drying and concentration gave 2.14g (38%) of pure 3- (2-hydroxy-4-oxobicyclo [3.2.1]]Oct-2-ene-3-carbonyl) -6-trifluoromethylpyridin-2-ylmethyl acetate as an oil.
1H-NMR(250 MHz，
CDCl3)：17.06(s)，1H；7.67(s)，2H；5.27(d，J＝12.5Hz)，1H；5.20(d，J＝12.5Hz)，1H；3.18，(t，J＝5.0Hz)，1H；2.92，(t，J＝5.0Hz)，1H；2.29-1.98(m)，4H；2.00，(s)，3H；1.81-1.73 ppm(m)，2H.
Example H5: 4-hydroxy-3- (2-oxiranylmethoxymethyl-6-trifluoromethylpyridine -3-carbonyl) bicyclo [3.2.1]Oct-3-en-2-ones
5g (0.013mol) of 3- (2-hydroxy-4-oxobicyclo [3.2.1] oct-2-ene-3-carbonyl) -6-trifluoromethylpyridin-2-ylmethyl acetate are dissolved in 60ml of methanol/water (3: 1 mixture) and 1.4g (0.046mol) of lithium hydroxide hydrate are added in portions at a temperature of 22 ℃. After 3 hours at 22 ℃ the reaction mixture was poured into ethyl acetate and 10% hydrochloric acid and the organic phase was washed three times with water, dried over sodium sulfate and concentrated. 4.1g of 4-hydroxy-3- (2-hydroxymethyl-6-trifluoromethylpyridine-3-carbonyl) bicyclo [3.2.1] oct-3-en-2-one are obtained as an oil which can be reacted further without purification.
1.5g of 4-hydroxy-3- (2-hydroxymethyl-6-trifluoromethylpyridine-3-carbonyl) bicyclo [3.2.1] oct-3-en-2-one are dissolved in 15ml of dimethylformamide and treated batchwise at room temperature with 0.4g of sodium hydride (80% oil suspension, 0.013 mol). After 15 minutes at a temperature of 22 ℃, 3ml (0.036mol) of epibromohydrin are added dropwise and the reaction mixture is stirred at this temperature for a further 18 hours. Then ethyl acetate was added and the mixture was acidified to pH3 with 10% hydrochloric acid and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and the crude product is purified by chromatography (mobile phase: toluene/ethanol/dioxane/triethylamine/water 100: 40: 20: 5 parts by volume). The title compound (triethylamine salt) was obtained as a pale yellow resin, released in analogy to example H4. Trituration with hexane afforded 600mg of pure 4-hydroxy-3- (2-oxiranylmethoxymethyl-6-trifluoromethylpyridine-3-carbonyl) bicyclo [3.2.1] oct-3-en-2-one, m.p. 54-56 ℃.
Example H6: (5-hydroxy-1, 3-dimethyl-1H-pyrazol-4-yl) - [2- (2-methoxy-l-methyl-) Ethoxymethyl) -6-trifluoromethylpyridin-3-yl]Ketone
1.0g (0.004mol) of 2- (2-methoxyethoxymethyl) -6-trifluoromethylnicotinic acid was dissolved in 10ml of oxalyl chloride. 3 drops of dimethylformamide were added and the mixture was stirred at room temperature for 1 hour. The mixture was then concentrated using a rotary evaporator and the residue (2- (2-methoxyethoxymethyl) -6-trifluoromethylnicotinoyl chloride) was dissolved in 10ml of dichloromethane. At a temperature of 0 ℃ 0.84ml (0.006mol) triethylamine and 0.45g (0.004mol)2, 5-dimethyl-2, 4-dihydropyrazol-3-one are added. After 2 hours at 22 ℃ the solvent was removed using a vacuum rotary evaporator and the remaining residue was dissolved in 10ml of acetonitrile and mixed with 0.1ml of acetone cyanohydrin and 1.13ml (0.008mol) of triethylamine for the rearrangement of the intermediate (2, 5-dimethyl-2H-pyrazol-3-yl 2- (2-methoxyethoxymethyl) -6-trifluoromethylnicotinate). The reaction solution was stirred at room temperature for 4 hours, and then concentrated. The remaining slurry was purified by silica gel chromatography. Elution with a mixture of toluene, ethanol, dioxane, triethylamine and water (100: 40: 20: 5 parts by volume) gave a viscous oil which was dissolved in ethyl acetate and washed with 10% hydrochloric acid and water in that order. Organic solution is treated with Na2SO4Drying and concentration gave 0.93g of (5-hydroxy-1, 3-dimethyl-1H-pyrazol-4-yl) - [2- (2-methoxyethoxymethyl) -6-trifluoromethylpyridin-3-yl]Methanone, as a viscous oil.
1H NMR(300 MHz，CDCl3，δin ppm)：7.81，(d，J＝6Hz)，1H；7.74，(d，J＝6Hz)，1H；4.84，(s)，2H；2H：3.71，(s)，3H；3.59，(t，J＝6Hz)2H；3.38，(dd，J4.0，3.0Hz)，1H；3.26，(s)，3H；1.82 ppm，(s)，1H.
Preferred compounds of formula I and their intermediates are listed in the table below.
In the following table, the radical R1The left-hand valency of (a) is attached to the pyridine ring. If at substituent R2In which no play is indicatedIonic valency, e.g. inIn the case of (3), the point of attachment is at the "CH" carbon atom.
In the following table, the compounds of formula I are represented as follows:
A-Q
wherein formula A
Represents the following groups:
radical (I) R1 R2 R4 R3 X1 p
A1A2A3A4A5A6A7A8A9A10 CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2 CH3CH2CH3(CH3)2CHPhCH2CH3CH3CH3CH3OCH2CH3CH2OCH2CH3OCH2CH2 H CF3H CF3H CF3H CF3H CF3H CF3H CF3H CF3H CF3H CF3 OOOOSSOSO2OOO OOOOOOOOOO
In the table below, in the case of rings, for the substituent A1And A2The ring point of attachment of (A) being at the carbon atom marked "C", e.g.In the case of an open chain structure, "(CH)3)2C' for example represents
In the formula A-Q, Q represents Q1
Q1Represents the following group B:
or Q in the formula A-Q represents Q2
Q2Represents the following group C:
or of the formula A-QIn (A) Q represents Q3
Q3Represents the following group D (R)49The point of attachment to the heterocycle is a "CH" group):
table 1: intermediates for the preparation of compounds of formula I represented by the formula
A-Q
Wherein Q represents a hydroxyl group:
OH OH OH OH OH OH OH OH OH OH OH OH
-A13A25A37A49A61A73 -A14A26A38A50A62A74 -A15A27A39A51A63A75 -A16A28A40A52A64A76 -A17A29A41A53A65A77 -A18A30A42A54A66A78 -A19A31A43A55A67A79 A8A20A32A44A56A68A80 A9A21A33A45A57A69A81 A1OA22A34A46A58A70A82 A11A23A35A47A59A71A83 A12A24A36A48A60A72A84
OH OH OH OH OH OH OH OH OH OH OH OH
A85-A109A121A133A145A157A169A181A193A205A217A229A241A253A265A277A289A301A313A325A337A349A361A373A385A397A409A421A433A445A457A469 A86-A110A122A134A146A158A170A182A194A206A218A230A242A254A266A278A290A302A314A326A338A350A362A374A386A398A410A422A434A446A458A470 A87A99A111A123A135A147A159A171A183A195A207A219A231A243A255A267A279A291A303A315A327A339A351A363A375A387A399A411A423A435A447A459A471 A88A100A112A124A136A148A160A172A184A196A208A220A232A244A256A268A280A292A304A316A328A340A352A364A376A388A400A412A424A436A448A460A472 A89A101A113A125A137A149A161A173A185A197A209A221A233A245A257A269A281A293A305A317A329A341A353A365A377A389A401A413A425A437A449A461A473 A90A102A114A126A138A150A162A174A186A198A210A222A234A246A258A270A282A294A306A318A330A342A354A366A378A390A402A414A426A438A450A462A474 -A103A115A127A139A151A163A175A187A199A211A223A235A247A259A271A283A295A307A319A331A343A355A367A379A391A403A415A427A439A451A463A475 -A104A116A128A140A152A164A176A188A200A212A224A236A248A260A272A284A296A308A320A332A344A356A368A380A392A404A416A428A440A452A464A476 -A105A117A129A141A153A165A177A189A201A213A225A237A249A261A273A285A297A309A321A333A345A357A369A381A393A405A417A429A441A453A465A477 -A106A118A130A142A154A166A178A190A202A214A226A238A250A262A274A286A298A310A322A334A346A358A370A382A394A406A418A430A442A454A466A478 -A107A119A131A143A155A167A179A191A203A215A227A239A251A263A275A287A299A311A323A335A347A359A371A383A395A407A419A431A443A455A467A479 -A108A120A132A144A156A168A180A192A204A216A228A240A252A264A276A288A300A312A324A336A348A360A372A384A396A408A420A432A444A456A468A480
OH OH OH OH OH OH OH OH OH OH OH OH
A481A493A505A517A529A541-A565A577A589A601A613A625-A649A661A685A697A709A721A733A745A757A769A781A793A805A817A829 A482A494A506A518A530A542A554A566A578A590A602A614A626-A650A662A686A698A710A722A734A746A758A770A782A794A806A818A830 A483A495A507A519A531A543A555A567A579A591A603A615A627-A651A663A687A699A711A723A735A747A759A771A783A795A807A819A831 A484A496A508A520A532A544A556A568A580A592A604A616A628-A652A664A688A700A712A724A736A748A760A772A784A796A808A820A832 A485A497A509A521A533A545A557A569A581A593A605A617A629-A653A665A689A701A713A725A737A749A761A773A785A797A809A821- A486A498A510A522A534-A558A570A582A594A606A618A630-A654A666A690A702A714A726A738A750A762A774A786A798A810A822- A487A499A511A523A535-A559A571A583A595A607A619A631-A655A667A691A703A715-A739A751A763A775A787A799A811A823- A488A500A512A524A536-A560A572A584A596A608A620A632A644A656A668A692A704A716-A740A752A764A776A788A800A812A824- A489A501A513A525A537-A561A573A585A597A609A621A633A645A657A669A693A705A717-A741A753A765A777A789A801A813A825- A490A502A514A526A538-A562A574A586A598A610A622A634A646A658A670A694A706A718-A742A754A766A778A790A802A814A826- A491A503A515A527A539-A563A575A587A599A611A623A635A647A659A671A695A707A719-A743A755A767A779A791A803A815A827- A492A504A516A528A540-A564A576A588A600A612A624A636A648A660A672A696A708A720-A744A756A768A780A792A804A816A828-
table 2: a compound of formula I represented by
A-Q
Wherein Q represents Q1，Q1Represents a group B52:
B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52
A1A13A25A37A49A61A73A85A97A109A121A133A145A157A169A181A193A205A217A229A241A253A265A277A289A301A313 A2A14A26A38A50A62A74A86A98A110A122A134A146A158A170A182A194A206A218A230A242A254A266A278A290A302A314 A3A15A27A39A51A63A75A87A99A111A123A135A147A159A171A183A195A207A219A231A243A255A267A279A291A303A315 A4A16A28A40A52A64A76A88A100A112A124A136A148A160A172A184A196A208A220A232A244A256A268A280A292A304A316 A5A17A29A41A53A65A77A89A101A113A125A137A149A161A173A185A197A209A221A233A245A257A269A281A293A305A317 A6A18A30A42A54A66A78A90A102A114A126A138A150A162A174A186A198A210A222A234A246A258A270A282A294A306A318 A7A19A31A43A55A67A79A91A103A115A127A139A151A163A175A187A199A211A223A235A247A259A271A283A295A307A319 A8A20A32A44A56A68A80A92A104A116A128A140A152A164A176A188A200A212A224A236A248A260A272A284A296A308A320 A9A21A33A45A57A69A81A93A105A117A129A141A153A165A177A189A201A213A225A237A249A261A273A285A297A309A321 A10A22A34A46A58A70A82A94A106A118A130A142A154A166A178A190A202A214A226A238A250A262A274A286A298A310A322 A11A23A35A47A59A71A83A95A107A119A131A143A155A167A179A191A203A215A227A239A251A263A275A287A299A311A323 A12A24A36A48A60A72A84A96A108A120A132A144A156A168A180A192A204A216A228A240A252A264A276A288A300A312A324
B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52
A325A337A349A361A373A385A397A409A421A433A445A457A469A481A493A505A517A529A541A553A565A577A589A601A613A625A637A649A661A673A685A697A709 A326A338A350A362A374A386A398A410A422A434A446A458A470A482A494A506A518A530A542A554A566A578A590A602A614A626A638A650A662A674A686A698A710 A327A339A351A363A375A387A399A411A423A435A447A459A471A483A495A507A519A531A543A555A567A579A591A603A615A627A639A651A663A675A687A699A711 A328A340A352A364A376A388A400A412A424A436A448A460A472A484A496A508A520A532A544A556A568A580A592A604A616A628A640A652A664A676A688A700A712 A329A341A353A365A377A389A401A413A425A437A449A461A473A485A497A509A521A533A545A557A569A581A593A605A617A629A641A653A665A677A689A701A713 A330A342A354A366A378A390A402A414A426A438A450A462A474A486A498A510A522A534A546A558A570A582A594A606A618A630A642A654A666A678A690A702A714 A331A343A355A367A379A391A403A415A427A439A451A463A475A487A499A511A523A535A547A559A571A583A595A607A619A631A643A655A667A679A691A703A715 A332A344A356A368A380A392A404A416A428A440A452A464A476A488A500A512A524A536A548A560A572A584A596A608A620A632A644A656A668A680A692A704A716 A333A345A357A369A381A393A405A417A429A441A453A465A477A489A501A513A525A537A549A561A573A585A597A609A621A633A645A657A669A681A693A705A717 A334A346A358A370A382A394A406A418A430A442A454A466A478A490A502A514A526A538A550A562A574A586A598A610A622A634A646A658A670A682A694A706A718 A335A347A359A371A383A395A407A419A431A443A455A467A479A491A503A515A527A539A551A563A575A587A599A611A623A635A647A659A671A683A695A707A719 A336A348A360A372A384A396A408A420A432A444A456A468A480A492A504A516A528A540A552A564A576A588A600A612A624A636A648A660A672A684A696A708A720
B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52
A721A733A745A757A769A781A793A805A817A829 A722A734A746A758A770A782A794A806A818A830 A723A735A747A759A771A783A795A807A819A831 A724A736A748A760A772A784A796A808A820A832 A725A737A749A761A773A785A797A809A821- A726A738A750A762A774A786A798A810A822- A727A739A751A763A775A787A799A811A823- A728A740A752A764A776A788A800A812A824- A729A741A753A765A777A789A801A813A825- A730A742A754A766A778A790A802A814A826- A731A743A755A767A779A791A803A815A827- A732A744A756A768A780A792A804A816A828-
table 3: a compound of formula I represented by
A-Q
Wherein Q represents Q1, Q1 represents the group B39:
B39 B39 B39 B39 B39 B39 B39 B39 B39 B39 B39 B39
A1A13A25A37A49A61A73A85A97A109A121A133A145 A2A14A26A38A50A62A74A86A98A110A122A134A146 A3A15A27A39A51A63A75A87A99A111A123A135A147 A4A16A28A40A52A64A76A88A100A112A124A136A148 A5A17A29A41A53A65A77A89A101A113A125A137A149 A6A18A30A42A54A66A78A90A102A114A126A138A150 A7A19A31A43A55A67A79A91A103A115A127A139A151 A8A20A32A44A56A68A80A92A104A116A128A140A152 A9A21A33A45A57A69A81A93A105A117A129A141A153 A10A22A34A46A58A70A82A94A106A118A130A142A154 A11A23A35A47A59A71A83A95A107A119A131A143A155 A12A24A36A48A60A72A84A96A108A120A132A144A156
B39 B39 B39 B39 B39 B39 B39 B39 B39 B39 B39 B39
A157A169A181A193A205A217A229A241A253A265A277A289A301A313A325A337A349A361A373A385A397A409A421A433A445A457A469A481A493A505A517A529A541 A158A170A182A194A206A218A230A242A254A266A278A290A302A314A326A338A350A362A374A386A398A410A422A434A446A458A470A482A494A506A518A530A542 A159A171A183A195A207A219A231A243A255A267A279A291A303A315A327A339A351A363A375A387A399A411A423A435A447A459A471A483A495A507A519A531A543 A160A172A184A196A208A220A232A244A256A268A280A292A304A316A328A340A352A364A376A388A400A412A424A436A448A460A472A484A496A508A520A532A544 A161A173A185A197A209A221A233A245A257A269A281A293A305A317A329A341A353A365A377A389A401A413A425A437A449A461A473A485A497A509A521A533A545 A162A174A186A198A210A222A234A246A258A270A282A294A306A318A330A342A354A366A378A390A402A414A426A438A450A462A474A486A498A510A522A534A546 A163A175A187A199A211A223A235A247A259A271A283A295A307A319A331A343A355A367A379A391A403A415A427A439A451A463A475A487A499A511A523A535A547 A164A176A188A200A212A224A236A248A260A272A284A296A308A320A332A344A356A368A380A392A404A416A428A440A452A464A476A488A500A512A524A536A548 A165A177A189A201A213A225A237A249A261A273A285A297A309A321A333A345A357A369A381A393A405A417A429A441A453A465A477A489A501A513A525A537A549 A166A178A190A202A214A226A238A250A262A274A286A298A310A322A334A346A358A370A382A394A406A418A430A442A454A466A478A490A502A514A526A538A550 A167A179A191A203A215A227A239A251A263A275A287A299A311A323A335A347A359A371A383A395A407A419A431A443A455A467A479A491A503A515A527A539A551 A168A180A192A204A216A228A240A252A264A276A288A300A312A324A336A348A360A372A384A396A408A420A432A444A456A468A480A492A504A516A528A540A552
B39 B39 B39 B39 B39 B39 B39 B39 B39 B39 B39 B39
A553A565A577A589A601A613A625A637A649A661A673A685A697A709A721A733A745A757A769A781A793A805A817A829 A554A566A578A590A602A614A626A638A650A662A674A686A698A710A722A734A746A758A770A782A794A806A818A830 A555A567A579A591A603A615A627A639A651A663A675A687A699A711A723A735A747A759A771A783A795A807A819A831 A556A568A580A592A604A616A628A640A652A664A676A688A700A712A724A736A748A760A772A784A796A808A820A832 A557A569A581A593A605A617A629A641A653A665A677A689A701A713A725A737A749A761A773A785A797A809A821- A558A570A582A594A606A618A630A642A654A666A678A690A702A714A726A738A750A762A774A786A798A810A822- A559A571A583A595A607A619A631A643A655A667A679A691A703A715A727A739A751A763A775A787A799A811A823- A560A572A584A596A608A620A632A644A656A668A680A692A704A716A728A740A752A764A776A788A800A812A824- A561A573A585A597A609A621A633A645A657A669A681A693A705A717A729A741A753A765A777A789A801A813A825- A562A574A586A598A610A622A634A646A658A670A682A694A706A718A730A742A754A766A778A790A802A814A826- A563A575A587A599A611A623A635A647A659A671A683A695A707A719A731A743A755A767A779A791A803A815A827- A564A576A588A600A612A624A636A648A660A672A684A696A708A720A732A744A756A768A780A792A804A816A828-
table 4: a compound of formula I represented by
A-Q
Wherein Q represents Q1，Q1Represents a group B3：
B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3
B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3
-A13A25A37A49A61A73A85-A109A121A133A145A157A169A181A193A205A217A229A241A253A265A277A289A301A313A325A337A349A361A373 -A14A26A38A50A62A74A86-A110A122A134A146A158A170A182A194A206A218A230A242A254A266A278A290A302A314A326A338A350A362A374 -A15A27A39A51A63A75A87A99A111A123A135A147A159A171A183A195A207A219A231A243A255A267A279A291A303A315A327A339A351A363A375 -A16A28A40A52A64A76A88A100A112A124A136A148A160A172A184A196A208A220A232A244A256A268A280A292A304A316A328A340A352A364A376 -A17A29A41A53A65A77A89A101A113A125A137A149A161A173A185A197A209A221A233A245A257A269A281A293A305A317A329A341A353A365A377 -A18A30A42A54A66A78A90A102A114A126A138A150A162A174A186A198A210A222A234A246A258A270A282A294A306A318A330A342A354A366A378 -A19A31A43A55A67A79-A103A115A127A139A151A163A175A187A199A211A223A235A247A259A271A283A295A307A319A331A343A355A367A379 A8A20A32A44A56A68A80-A104A116A128A140A152A164A176A188A200A212A224A236A248A260A272A284A296A308A320A332A344A356A368A380 A9A21A33A45A57A69A81-A105A117A129A141A153A165A177A189A201A213A225A237A249A261A273A285A297A309A321A333A345A357A369A381 A10A22A34A46A58A70A82-A106A118A130A142A154A166A178A190A202A214A226A238A250A262A274A286A298A310A322A334A346A358A370A382 A11A23A35A47A59A71A83-A107A119A131A143A155A167A179A191A203A215A227A239A251A263A275A287A299A311A323A335A347A359A371A383 A12A24A36A48A60A72A84-A108A120A132A144A156A168A180A192A204A216A228A240A252A264A276A288A300A312A324A336A348A360A372A384
B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3
A385A397A409A421A433A445A457A469A481A493A505A517A529A541-A565A577A589A601A613A625-A649A661A685A697A709A721A733A745A757A769A781 A386A398A410A422A434A446A458A470A482A494A506A518A530A542A554A566A578A590A602A614A626-A650A662A686A698A710A722A734A746A758A770A782 A387A399A411A423A435A447A459A471A483A495A507A519A531A543A555A567A579A591A603A615A627-A651A663A687A699A711A723A735A747A759A771A783 A388A400A412A424A436A448A460A472A484A496A508A520A532A544A556A568A580A592A604A616A628-A652A664A688A700A712A724A736A748A760A772A784 A389A401A413A425A437A449A461A473A485A497A509A521A533A545A557A569A581A593A605A617A629-A653A665A689A701A713A725A737A749A761A773A785 A390A402A414A426A438A450A462A474A486A498A510A522A534-A558A570A582A594A606A618A630-A654A666A690A702A714A726A738A750A762A774A786 A391A403A415A427A439A451A463A475A487A499A511A523A535-A559A571A583A595A607A619A631-A655A667A691A703A715-A739A751A763A775A787 A392A404A416A428A440A452A464A476A488A500A512A524A536-A560A572A584A596A608A620A632A644A656A668A692A704A716-A740A752A764A776A788 A393A405A417A429A441A453A465A477A489A501A513A525A537-A561A573A585A597A609A621A633A645A657A669A693A705A717-A741A753A765A777A789 A394A406A418A430A442A454A466A478A490A502A514A526A538-A562A574A586A598A610A622A634A646A658A670A694A706A718-A742A754A766A778A790 A395A407A419A431A443A455A467A479A491A503A515A527A539-A563A575A587A599A611A623A635A647A659A671A695A707A719-A743A755A767A779A791 A396A408A420A432A444A456A468A480A492A504A516A528A540-A564A576A588A600A612A624A636A648A660A672A696A708A720-A744A756A768A780A792
B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3
A793A805A817A829 A794A806A818A830 A795A807A819A831 A796A808A820A832 A797A809A821- A798A810A822- A799A811A823- A800A812A824- A801A813A825- A802A814A826 A803A815A827 A804A816A828
Table 5: compounds of formula I represented by the following formula
A-Q
Wherein Q represents Q2，Q2Represents a group C5：
C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5
A1A13A25A37A49A61A73A85A97A109A121A133A145A157A169A181A193A205A217 A2A14A26A38A50A62A74A86A98A110A122A134A146A158A170A182A194A206A218 A3A15A27A39A51A63A75A87A99A111A123A135A147A159A171A183A195A207A219 A4A16A28A40A52A64A76A88A100A112A124A136A148A160A172A184A196A208A220 A5A17A29A41A53A65A77A89A101A113A125A137A149A161A173A185A197A209A221 A6A18A30A42A54A66A78A90A102A114A126A138A150A162A174A186A198A210A222 A7A19A31A43A55A67A79A91A103A115A127A139A151A163A175A187A199A211A223 A8A20A32A44A56A68A80A92A104A116A128A140A152A164A176A188A200A212A224 A9A21A33A45A57A69A81A93A105A117A129A141A153A165A177A189A201A213A225 A10A22A34A46A58A70A82A94A106A118A130A142A154A166A178A190A202A214A226 A11A23A35A47A59A71A83A95A107A119A131A143A155A167A179A191A203A215A227 A12A24A36A48A60A72A84A96A108A120A132A144A156A168A180A192A204A216A228
C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5
A229A241A253A265A277A289A301A313A325A337A349A361A373A385A397A409A421A433A445A457A469A481A493A505A517A529A541A553A565A577A589A601A613 A230A242A254A266A278A290A302A314A326A338A350A362A374A386A398A410A422A434A446A458A470A482A494A506A518A530A542A554A566A578A590A602A614 A231A243A255A267A279A291A303A315A327A339A351A363A375A387A399A411A423A435A447A459A471A483A495A507A519A531A543A555A567A579A591A603A615 A232A244A256A268A280A292A304A316A328A340A352A364A376A388A400A412A424A436A448A460A472A484A496A508A520A532A544A556A568A580A592A604A616 A233A245A257A269A281A293A305A317A329A341A353A365A377A389A401A413A425A437A449A461A473A485A497A509A521A533A545A557A569A581A593A605A617 A234A246A258A270A282A294A306A318A330A342A354A366A378A390A402A414A426A438A450A462A474A486A498A510A522A534A546A558A570A582A594A606A618 A235A247A259A271A283A295A307A319A331A343A355A367A379A391A403A415A427A439A451A463A475A487A499A511A523A535A547A559A571A583A595A607A619 A236A248A260A272A284A296A308A320A332A344A356A368A380A392A404A416A428A440A452A464A476A488A500A512A524A536A548A560A572A584A596A608A620 A237A249A261A273A285A297A309A321A333A345A357A369A381A393A405A417A429A441A453A465A477A489A501A513A525A537A549A561A573A585A597A609A621 A238A250A262A274A286A298A310A322A334A346A358A370A382A394A406A418A430A442A454A466A478A490A502A514A526A538A550A562A574A586A598A610A622 A239A251A263A275A287A299A311A323A335A347A359A371A383A395A407A419A431A443A455A467A479A491A503A515A527A539A551A563A575A587A599A611A623 A240A252A264A276A288A300A312A324A336A348A360A372A384A396A408A420A432A444A456A468A480A492A504A516A528A540A552A564A576A588A600A612A624
C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5
A625A637A649A661A673A685A697A709A721A733A745A757A769A781A793A805A817A829 A626A638A650A662A674A686A698A710A722A734A746A758A770A782A794A806A818A830 A627A639A651A663A675A687A699A711A723A735A747A759A771A783A795A807A819A831 A628A640A652A664A676A688A700A712A724A736A748A760A772A784A796A808A820A832 A629A641A653A665A677A689A701A713A725A737A749A761A773A785A797A809A821- A630A642A654A666A678A690A702A714A726A738A750A762A774A786A798A810A822- A631A643A655A667A679A691A703A715A727A739A751A763A775A787A799A811A823- A632A644A656A668A680A692A704A716A728A740A752A764A776A788A800A812A824- A633A645A657A669A681A693A705A717A729A741A753A765A777A789A801A813A825- A634A646A658A670A682A694A706A718A730A742A754A766A778A790A802A814A826- A635A647A659A671A683A695A707A719A731A743A755A767A779A791A803A815A827- A636A648A660A672A684A696A708A720A732A744A756A768A780A792A804A816A828-
Table 6: a compound of formula I represented by
A-Q
Wherein Q represents Q2，Q2Represents a group C2:
C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2
A1A13A25A37A49 A2A14A26A38A50 A3A15A27A39A51 A4A16A28A40A52 A5A17A29A41A53 A6A18A30A42A54 A7A19A31A43A55 A8A20A32A44A56 A9A21A33A45A57 A10A22A34A46A58 A11A23A35A47A59 A12A24A36A48A60
C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2
A61A73A85A97A109A121A133A145A157A169A181A193A205A217A229A241A253A265A277A289A301A313A325A337A349A361A373A385A397A409A421A433A445 A62A74A86A98A110A122A134A146A158A170A182A194A206A218A230A242A254A266A278A290A302A314A326A338A350A362A374A386A398A410A422A434A446 A63A75A87A99A111A123A135A147A159A171A183A195A207A219A231A243A255A267A279A291A303A315A327A339A351A363A375A387A399A411A423A435A447 A64A76A88A100A112A124A136A148A160A172A184A196A208A220A232A244A256A268A280A292A304A316A328A340A352A364A376A388A400A412A424A436A448 A65A77A89A101A113A125A137A149A161A173A185A197A209A221A233A245A257A269A281A293A305A317A329A341A353A365A377A389A401A413A425A437A449 A66A78A90A102A114A126A138A150A162A174A186A198A210A222A234A246A258A270A282A294A306A318A330A342A354A366A378A390A402A414A426A438A450 A67A79A91A103A115A127A139A151A163A175A187A199A211A223A235A247A259A271A283A295A307A319A331A343A355A367A379A391A403A415A427A439A451 A68A80A92A104A116A128A140A152A164A176A188A200A212A224A236A248A260A272A284A296A308A320A332A344A356A368A380A392A404A416A428A440A452 A69A81A93A105A117A129A141A153A165A177A189A201A213A225A237A249A261A273A285A297A309A321A333A345A357A369A381A393A405A417A429A441A453 A70A82A94A106A118A130A142A154A166A178A190A202A214A226A238A250A262A274A286A298A310A322A334A346A358A370A382A394A406A418A430A442A454 A71A83A95A107A119A131A143A155A167A179A191A203A215A227A239A251A263A275A287A299A311A323A335A347A359A371A383A395A407A419A431A443A455 A72A84A96A108A120A132A144A156A168A180A192A204A216A228A240A252A264A276A288A300A312A324A336A348A360A372A384A396A408A420A432A444A456
C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2
A457A469A481A493A505A517A529A541A553A565A577A589A601A613A625A637A649A661A673A685A697A709A721A733A745A757A769A781A793A805A817A829 A458A470A482A494A506A518A530A542A554A566A578A590A602A614A626A638A650A662A674A686A698A710A722A734A746A758A770A782A794A806A818A830 A459A471A483A495A507A519A531A543A555A567A579A591A603A615A627A639A651A663A675A687A699A711A723A735A747A759A771A783A795A807A819A831 A460A472A484A496A508A520A532A544A556A568A580A592A604A616A628A640A652A664A676A688A700A712A724A736A748A760A772A784A796A808A820A832 A461A473A485A497A509A521A533A545A557A569A581A593A605A617A629A641A653A665A677A689A701A713A725A737A749A761A773A785A797A809A821- A462A474A486A498A510A522A534A546A558A570A582A594A606A618A630A642A654A666A678A690A702A714A726A738A750A762A774A786A798A810A822- A463A475A487A499A511A523A535A547A559A571A583A595A607A619A631A643A655A667A679A691A703A715A727A739A751A763A775A787A799A811A823- A464A476A488A500A512A524A536A548A560A572A584A596A608A620A632A644A656A668A680A692A704A716A728A740A752A764A776A788A800A812A824- A465A477A489A501A513A525A537A549A561A573A585A597A609A621A633A645A657A669A681A693A705A717A729A741A753A765A777A789A801A813A825- A466A478A490A502A514A526A538A550A562A574A586A598A610A622A634A646A658A670A682A694A706A718A730A742A754A766A778A790A802A814A826- A467A479A491A503A515A527A539A551A563A575A587A599A611A623A635A647A659A671A683A695A707A719A731A743A755A767A779A791A803A815A827- A468A480A492A504A516A528A540A552A564A576A588A600A612A624A636A648A660A672A684A696A708A720A732A744A756A768A780A792A804A816A828-
table 7: a compound of formula I represented by
A-Q
Wherein Q represents Q2，Q2Represents a group D1, D2 or D3:
D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3
-A13A25A37A49A61A73A85-A109A121A133A145A157A169A181A193A205A217A229A241A253A265A277 -A14A26A38A50A62A74A86-A110A122A134A146A158A170A182A194A206A218A230A242A254A266A278 -A15A27A39A51A63A75A87A99A111A123A135A147A159A171A183A195A207A219A231A243A255A267A279 -A16A28A40A52A64A76A88A100A112A124A136A148A160A172A184A196A208A220A232A244A256A268A280 -A17A29A41A53A65A77A89A101A113A125A137A149A161A173A185A197A209A221A233A245A257A269A281 -A18A30A42A54A66A78A90A102A114A126A138A150A162A174A186A198A210A222A234A246A258A270A282 -A19A31A43A55A67A79-A103A115A127A139A151A163A175A187A199A211A223A235A247A259A271A283 A8A20A32A44A56A68A80-A104A116A128A140A152A164A176A188A200A212A224A236A248A260A272A284 A9A21A33A45A57A69A81-A105A117A129A141A153A165A177A189A201A213A225A237A249A261A273A285 A10A22A34A46A58A70A82-A106A118A130A142A154A166A178A190A202A214A226A238A250A262A274A286 A11A23A35A47A59A71A83-A107A119A131A143A155A167A179A191A203A215A227A239A251A263A275A287 A12A24A36A48A60A72A84-A108A120A132A144A156A168A180A192A204A216A228A240A252A264A276A288
D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3
A289A301A313A325A337A349A361A373A385A397A409A421A433A445A457A469A481A493A505A517A529A541-A565A577A589A601A613A625-A649 A290A302A314A326A338A350A362A374A386A398A410A422A434A446A458A470A482A494A506A518A530A542A554A566A578A590A602A614A626-A650 A291A303A315A327A339A351A363A375A387A399A411A423A435A447A459A471A483A495A507A519A531A543A555A567A579A591A603A615A627-A651 A292A304A316A328A340A352A364A376A388A400A412A424A436A448A460A472A484A496A508A520A532A544A556A568A580A592A604A616A628-A652 A293A305A317A329A341A353A365A377A389A401A413A425A437A449A461A473A485A497A509A521A533A545A557A569A581A593A605A617A629-A653 A294A306A318A330A342A354A366A378A390A402A414A426A438A450A462A474A486A498A510A522A534-A558A570A582A594A606A618A630-A654 A295A307A319A331A343A355A367A379A391A403A415A427A439A451A463A475A487A499A511A523A535-A559A571A583A595A607A619A631-A655 A296A308A320A332A344A356A368A380A392A404A416A428A440A452A464A476A488A500A512A524A536-A560A572A584A596A608A620A632A644A656 A297A309A321A333A345A357A369A381A393A405A417A429A441A453A465A477A489A501A513A525A537-A561A573A585A597A609A621A633A645A657 A298A310A322A334A346A358A370A382A394A406A418A430A442A454A466A478A490A502A514A526A538-A562A574A586A598A610A622A634A646A658 A299A311A323A335A347A359A371A383A395A407A419A431A443A455A467A479A491A503A515A527A539-A563A575A587A599A611A623A635A647A659 A300A312A324A336A348A360A372A384A396A408A420A432A444A456A468A480A492A504A516A528A540-A564A576A588A600A612A624A636A648A660
D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3 D1/D2/ D3
A661A685A697A709A721A733A745A757A769A781A793A805A817A829 A662A686A698A710A722A734A746A758A770A782A794A806A818A830 A663A687A699A711A723A735A747A759A771A783A795A807A819A831 A664A688A700A712A724A736A748A760A772A784A796A808A820A832 A665A689A701A713A725A737A749A761A773A785A797A809A821- A666A690A702A714A726A738A750A762A774A786A798A810A822- A667A691A703A715-A739A751A763A775A787A799A811A823- A668A692A704A716-A740A752A764A776A788A800A812A824- A669A693A705A717-A741A753A765A777A789A801A813A825- A670A694A706A718-A742A754A766A778A790A802A814A826- A671A695A707A719-A743A755A767A779A791A803A815A827- A672A696A708A720-A744A756A768A780A792A804A816A828-
table 8: a compound of formula Ip:
wherein R is1、R2、R3、R4、X1And p has the same meaning as given for the group a, n is 0, 1 or 2:
A A A A A A A A A A A A
-A13A25A37A49A61A73A85-A109A121A133A145A157A169A181A193A205A217A229A241A253A265A277A289A301A313A325A337A349A361A373 -A14A26A38A50A62A74A86-A110A122A134A146A158A170A182A194A206A218A230A242A254A266A278A290A302A314A326A338A350A362A374 -A15A27A39A51A63A75A87A99A111A123A135A147A159A171A183A195A207A219A231A243A255A267A279A291A303A315A327A339A351A363A375 -A16A28A40A52A64A76A88A100A112A124A136A148A160A172A184A196A208A220A232A244A256A268A280A292A304A316A328A340A352A364A376 -A17A29A41A53A65A77A89A101A113A125A137A149A161A173A185A197A209A221A233A245A257A269A281A293A305A317A329A341A353A365A377 -A18A30A42A54A66A78A90A102A114A126A138A150A162A174A186A198A210A222A234A246A258A270A282A294A306A318A330A342A354A366A378 -A19A31A43A55A67A79-A103A115A127A139A151A163A175A187A199A211A223A235A247A259A271A283A295A307A319A331A343A355A367A379 A8A20A32A44A56A68A80-A104A116A128A140A152A164A176A188A200A212A224A236A248A260A272A284A296A308A320A332A344A356A368A380 A9A21A33A45A57A69A81-A105A117A129A141A153A165A177A189A201A213A225A237A249A261A273A285A297A309A321A333A345A357A369A381 A10A22A34A46A58A70A82-A106A118A130A142A154A166A178A190A202A214A226A238A250A262A274A286A298A310A322A334A346A358A370A382 A11A23A35A47A59A71A83-A107A119A131A143A155A167A179A191A203A215A227A239A251A263A275A287A299A311A323A335A347A359A371A383 A12A24A36A48A60A72A84-A108A120A132A144A156A168A180A192A204A216A228A240A252A264A276A288A300A312A324A336A348A360A372A384
A A A A A A A A A A A A
A385A397A409A421A433A445A457A469A481A493A505A517A529A541-A565A577A589A601A613A625-A649A661A685A697A709A721A733A745A757A769A781 A386A398A410A422A434A446A458A470A482A494A506A518A530A542A554A566A578A590A602A614A626-A650A662A686A698A710A722A734A746A758A770A782 A387A399A411A423A435A447A459A471A483A495A507A519A531A543A555A567A579A591A603A615A627-A651A663A687A699A711A723A735A747A759A771A783 A388A400A412A424A436A448A460A472A484A496A508A520A532A544A556A568A580A592A604A616A628-A652A664A688A700A712A724A736A748A760A772A784 A389A401A413A425A437A449A461A473A485A497A509A521A533A545A557A569A581A593A605A617A629-A653A665A689A701A713A725A737A749A761A773A785 A390A402A414A426A438A450A462A474A486A498A510A522A534-A558A570A582A594A606A618A630-A654A666A690A702A714A726A738A750A762A774A786 A391A403A415A427A439A451A463A475A487A499A511A523A535-A559A571A583A595A607A619A631-A655A667A691A703A715-A739A751A763A775A787 A392A404A416A428A440A452A464A476A488A500A512A524A536-A560A572A584A596A608A620A632A644A656A668A692A704A716-A740A752A764A776A788 A393A405A417A429A441A453A465A477A489A501A513A525A537-A561A573A585A597A609A621A633A645A657A669A693A705A717-A741A753A765A777A789 A394A406A418A430A442A454A466A478A490A502A514A526A538-A562A574A586A598A610A622A634A646A658A670A694A706A718-A742A754A766A778A790 A395A407A419A431A443A455A467A479A491A503A515A527A539-A563A575A587A599A611A623A635A647A659A671A695A707A719-A743A755A767A779A791 A396A408A420A432A444A456A468A480A492A504A516A528A540-A564A576A588A600A612A624A636A648A660A672A696A708A720-A744A756A768A780A792
A A A A A A A A A A A A
A793A805A817A829 A794A806A818A830 A795A807A819A831 A796A808A820A832 A797A809A821- A798A810A822- A799A811A823- A800A812A824- A801A813A825- A802A814A826- A803A815A827- A804A816A828-
table 9: a compound of formula I represented by
A-Q
Wherein A represents A10:
A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10
B1B13B25B37B49B61B73B85B97B109 B2B14B26B38B50B62B74B86B98B110 -B15B27-B51B63B75B87B99- B4B16B28B40-B64B76B88B100- B5B17B29B41B53B65B77B89B101- B6B18B30B42B54B66B78B90B102- B7B19B31B43B55B67B79B91B103- B8B20B32B44B56B68B80B92B104- B9B21B33B45B57B69B81B93B105- B10B22B34B46B58B70B82B94B106- B11B23B35B47B59B71B83-B107- B12B24B36B48B60B72B84B96B108-
table 10: a compound of formula I represented by
A-Q
Wherein A represents A10:
A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10
C1C13C25 -C14C26 C3C15C27 C4C16- -C17- C6C18- C7C19- C8C20- C9C21- C10C22- C11C23- C12C24-
table 11: a compound of formula I represented by
A-Q
Wherein A represents A10:
A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10
- - - D4 D5 D6 D7 D8 D9 D10 D11 D12
table 12: a compound of formula I represented by
A-Q
Wherein A represents A556:
A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556
B1B13B25B37B49B61B73B85B97 B2B14B26B38B50B62B74B86B98 -B15B27-B51B63B75B87B99 B4B16B28B40-B64B76B88B100 B5B17B29B41B53B65B77B89B101 B6B18B30B42B54B66B78B90B102 B7B19B31B43B55B67B79B91B103 B8B20B32B44B56B68B80B92B104 B9B21B33B45B57B69B81B93B105 B10B22B34B46B58B70B82B94B106 B11B23B35B47B59B71B83B107 B12B24B36B48B60B72B84B96B108
A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556
B109 B110 - - - - - - - - - -
table 13: a compound of formula I represented by
A-Q
Wherein A represents A556:
A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556
C1C13C25 -C14C26 C3C15C27 C4C16- -C17- C6C18- C7C19- C8C20- C9C21- C10C22- C11C23- C12C24-
table 14: a compound of formula I represented by
A-Q
Wherein A represents A556:
A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556
- - - D4 D5 D6 D7 D8 D9 D10 D11 D12
table 15: a compound of formula I represented by
A-Q
Wherein A represents A646:
A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646
B1B13B25B37B49B61B73B85B97B109 B2B14B26B38B50B62B74B86B98B110 -B15B27-B51B63B75B87B99- B4B16B28B40-B64B76B88B100- B5B17B29B41B53B65B77B89B101- B6B18B30B42B54B66B78B90B102- B7B19B31B43B55B67B79B91B103- B8B20B32B44B56B68B80B92B104- B9B21B33B45B57B69B81B93B105- B10B22B34B46B58B70B82B94B106- B11B23B35B47B59B71B83B107- B12B24B36B48B60B72B84B96B108-
table 16: a compound of formula I represented by
A-Q
Wherein A represents A646:
A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646
C1C13C25 -C14C26 C3C15C27 C4C16- -C17- C6C18- C7C19- C8C20- C9C21- C10C22- C11C23- C12C24-
table 17: a compound of formula I represented by
A-Q
Wherein A represents A646:
A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646
- - - D4 D5 D6 D7 D8 D9 D10 D11 D12
table 18: physical number of the compound of formula I shown in the above tableAccording to (melting point given in degrees Celsius)：
Compound (I) m.p. (range) Physical state
A1-C2 138-140 Crystallization of
A2-C2A833-B52(K+)A833-B52(H4)A830-B52A829-B52A829-B1A10-B52(H3)A10-B1A10-B3A10-B14A10-B39A736-B52A10-C2(H6)A57-B52(H5)A18-B52A8-B52A19-B52A1-C5A2-C5A10-C5A11-C5A11-B52A834-B52A835-B52A854-B52A90-B52 138-140145-150----54-5671-73--99-100100-102-54-5671-7495-9853-5532-3432-33-38-39----- Crystalline oil amorphous/liquid oil crystalline viscous crystalline resin crystalline viscous resin crystalline
Compound (I) m.p. (range) Physical state
A33-B52A556-B52A646-B52A868-B52A855-B52A817-B52A819-B52A856-B52A857-B52A63-B52A20-B52A858-B52A836-B52A859-B52A818-B52A837-B52A28-B52A28-B52(Et3NH+)A838-B52A839-B52A860-B52A860-B113A861-B52A840-B52A841-B52A842-B52A843-B52A866-B100A844-B52A866-B112A867-B112A856-B112A20-C5A10-C28A11-C28 113-115--106-107------------------90-93-41-43--96-98---79-81- Crystalline viscous crystalline solid viscous resin solid resin crystalline viscous crystalline viscous crystalline oil crystalline viscous crystalline viscous resin
Compound (I) m.p. (range) Physical state
A10-B52(Et3NH+)A862-B52A24-B52A845-B52A837-B52(Et3NH+)A67-B52A863-B52A10-B17A846-B52A847-B52A848-B52A56-B52A26-B52A849-B52A10-B4A865-B52A850-B52A10-C29A10-B111A3-C5A834-C5A851-B52A852-B52A10-B25A853-B52A27-B52A864-C5A864-B52A834-B39A-852-OHA-851-OHA-835-OHA-24-OHA-858-OH -102-10540-44--68-6980-8040-42--------63-64-76-78-------149-150110-112-102-103--- Viscous crystalline viscous crystalline glassy viscous crystalline resin glassy viscous amorphous/liquid viscous oil crystalline oil solid oil
Compound (I) m.p. (range) Physical state
A-859-OHA-864-OHA-851-OHA-848-OHA-27-OHA-855-OHA-90-OHA-124-OHA-834-OHA-852-OHA-851-OHA-835-OHA10-OHA830-OHA831-OHA829-OHA832-OH --73-7481-82-102-104111-114117-119--102-103-62-63157-158188-189131-134110-112 Oil solid crystalline oil crystallization crystalline oil crystalline crystallization crystalline oil crystallization crystalline crystals
Table 19: the physical data (melting points given in degrees Celsius) for the compounds of formula I shown in the table above:
in the formula, the terminal valency denotes methyl (excluding alkynyl and alkenyl) or hydrogen (in the case of alkynyl or alkenyl), for exampleCan also be drawn asCan also be drawn as
Biological examples
Example B1: pre-emergence herbicidal action (pre-emergence action)
Monocot and dicot test plants were grown in standard flowerpot soil. Immediately after planting, an aqueous suspension of the test substance (prepared according to WO 97/34485 from a wettable powder (example F3, b)) or an emulsion (prepared according to WO 97/34485 from an emulsifiable concentrate (example F1, c)) is sprayed at an optimum dose (500 l water/ha). The test plants are then grown under optimal conditions in the greenhouse.
After 4 weeks of testing, the test was evaluated using a 9-point rating scale (1: complete lesion, 9: no effect). Grades 1 to 4 (in particular grades 1 to 3) indicate good to very good herbicidal action.
Table B1: pre-emergent effect ("NT" means "not tested"):
compound (I) g/ha Panicum genus Genus digitaria Barnyard grass Abutilon genus Amaranthus Chenopodium genus
A10-B1A10-B52，(H3)A830-B52A1-C2A833-B52(K+)A833-B52，(H4)A10-B1A10-B3A10-B14A10-B39A736-B52A10-C2(H6)A57-B52(H5)A18-B52A8-B52A19-B52A1-C5A2-C5A10-C5A11-C5A11-B52A834-B52A835-B52A556-B52A646-B52A819-B52A63-B52A20-B52A836-B52A837-B52A28-B52A28-B52(Et3NH+) 250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250 21461121311311112121111117211111 21932121614311112232112119312222 21332121312311111211111117111222 11541111111112112111112111535123 11432111111212122111221222332231 1141111111111NTNTNT1111112111NTNT3NTNTNT
Compound (I) g/ha Panicum genus Genus digitaria Barnyard grass Abutilon genus Amaranthus Chenopodium genus
A838-B52A839-B52A840-B52A841-B52A842-B52A843-B52A844-B52A20-C5A10-C28A11-C28A10-B52(Et3NH+)A24-B52A845-B52A837-B52(Et3NH+)A67-B52A10-B17A846-B52A847-B52A848-B52A56-B52A26-B52A849-B52A10-B4A850-B52A10-C29A10-B111A3-C5A834-C5A851-B52A852-B52A10-B25A853-B52A27-B52 250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250 111111111211111111111121211111111 332262223211112113121232212311112 222122222121122112111211112111223 112121111211113424731231111114114 112121111111112211111112111211111 111111111111111114111111NTNTNTNT12123
The same results are obtained when the compounds of formula I are formulated according to the other examples of WO 97/34485.
Example B2: post-emergence herbicidal action
Monocot and dicot test plants were grown in standard flowerpot soil. At the 2 to 3 leaf stage of the test plants, an aqueous suspension (prepared according to WO 97/34485 from a wettable powder (example F3, b)) or an emulsion (prepared according to WO 97/34485 from an emulsifiable concentrate (example F1, c)) of the test substance is sprayed at the optimum dose (500 l water/ha). The test plants are then grown under optimal conditions in the greenhouse.
After 2 to 3 weeks of the test, the test was evaluated using a 9-point rating scale (1: complete lesion, 9: no effect). Grades 1 to 4 (in particular grades 1 to 3) indicate good to very good herbicidal action.
Table B2: post-emergence action:
compound (I) g/ha Panicum genus Genus digitaria Barnyard grass Abutilon Xanthium genus lpopur. Amaranthus Chenopodium genus
A10-B1A10-B52，(H3)A830-B52A829-B52A829-B1A1-C2A833-B52(K+)A833-B52，(H4)A10-B3A10-B14A10-B39A736-B52A10-C2(H6)A57-B52(H5)A18-B52A8-B52A19-B52 250250250250250250250250250250250250250250250250250 21427733121121111 21969833123141111 22347444333232212 21537333121121111 22464421122212222 22546332222232211 22422232121111111 11422433111111111
Compound (I) g/ha Panicum genus Genus digitaria Barnyard grass Abutilon Xanthium genus lpopur. Amaranthus Chenopodium genus
A1-C5A2-C5A10-C5A11-C5A11-B52A834-B52A835-B52A854-B52A90-B52A33-B52A556-B52A646-B52A855-B52A817-B52A819-B52A856-B52A857-B52A63-B52A20-B52A858-B52A836-B52A859-B52A818-B52A837-B52A28-B52A28-B52(Et3NH+)A838-B52A839-B52A860-B52A861-B52A840-B52A841-B52A842-B52A843-B52 250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250 4121111122112122211221211122222232 2222111222222232222222222222133433 2222222232222222222222322232254453 2222222222122222222222222212233333 4222223233222222222232223322223333 2222222242222221222232224222223336 2112112132222222222122211222222123 1111111111111111121211111111111111
Compound (I) g/ha Panicum genus Tang style foodBelong to Barnyard grass Abutilon Xanthium genus lpopur. Amaranthus Chenopodium genus
A844-B52A856-B112A20-C5A10-C28A11-C28A10-B52(E13NH+)A862-B52A24-B52A845-B52A837-B52(Et3NH+)A67-B52A863-B52A10-B17A846-B52A847-B52A848-B52A56-B52A26-B52A849-B52A10-B4A850-B52A10-C29A10-B111A3-C5A851-B52A852-B52A10-B25A27-B52A864-C5A864-B52 250250250250250250250250250250250250250250250250250250250250250250250250250250250250250250 232432222222211212212223333112 333442222222122222212324344222 454442322223221222322333444222 323332322222222222212233333322 333332222222222222222233333222 333332522233214222212133333422 332222222222223112222223232212 111111111111121111211111111511
The same results are obtained when the compounds of formula I are formulated according to the other examples of WO 97/34485.

Claims (5)

1. A compound of formula I
Wherein
p is 0 or 1;
R1is C1-C6Alkylene radical, C3-C6Alkenylene or C3-C6Alkynylene chain, which chain may be substituted by halogen or R5Mono-or polysubstituted, wherein the unsaturated bonds of the chain are not directWith substituent X1Connecting; with the proviso that when R2Is unsubstituted phenyl and X1When is-O (CO) -, R1Is not a methylene group;
X1is oxygen, -O (CO) -, - (CO) O-, -O (CO) O-, -N (R)6)-O-、-O-NR51-, thio, sulfinyl, sulfonyl, -SO2NR7-、-NR52SO2-or-NR8-；
R2Is a5 to 10 membered monocyclic or fused bicyclic ring system, which may be aromatic, saturated or partially saturated and may contain 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, wherein the ring system is direct or via C1-C4Alkylene radical, C2-C4alkenyl-C1-C4Alkylene radical, C2-C4alkynyl-C1-C4Alkylene, -N (R)12)-C1-C4Alkylene, -SO-C1-C4Alkylene or-SO2-C1-C4Alkylene and substituent X1(ii) a linkage wherein each ring system may not contain more than two oxygen atoms and more than two sulfur atoms, and the ring system itself may be mono-, di-and tri-substituted with: c1-C6Alkyl radical, C1-C6Haloalkyl, C2-C6Alkenyl radical, C2-C6Haloalkenyl, C2-C6Alkynyl, C2-C6Halogenated alkynyl, C1-C6Alkoxy, hydroxy, C1-C6Haloalkoxy, C3-C6Alkenyloxy radical, C3-C6Alkynyloxy, mercapto, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C3-C6Alkenylthio radical, C3-C6Haloalkenylthio group, C3-C6Alkynylthio, C2-C5Alkoxyalkylthio radical, C3-C5Acetylalkylthio, C3-C6Alkoxycarbonyl alkylthio radical, C2-C4Cyanoalkylthio, C1-C6Alkylsulfinyl radical, C1-C6HalogenatedAlkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl, aminosulfonyl, C1-C2Alkylaminosulfonyl, di (C)1-C2Alkyl) aminosulfonyl, di (C)1-C4Alkyl) amino, halogen, cyano, nitro, phenyl and benzylthio, where phenyl and benzylthio may themselves be bound by C on the phenyl ring1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3Haloalkoxy, halogen, cyano, or nitro, wherein a substituent on a heterocyclic nitrogen is other than halogen;
R3is C1-C3A haloalkyl group;
R4is hydrogen, halogen, C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3alkoxy-C1-C3Alkyl or C1-C3alkoxy-C1-C3An alkoxy group;
R5is hydroxy, C1-C6Alkoxy radical, C3-C6Cycloalkoxy, C1-C6alkoxy-C1-C6Alkoxy radical, C1-C6alkoxy-C1-C6alkoxy-C1-C6Alkoxy or C1-C2An alkylsulfonyloxy group;
R6、R7、R8、R9、R11、R12、R51and R52Independently of one another are hydrogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxycarbonyl, C1-C6Alkylcarbonyl group, C1-C6alkoxy-C1-C6Alkyl radical, C1-C6Alkoxy, benzyl or phenyl substituted C1-C6alkoxy-C1-C6Alkyl, where phenyl and benzyl may themselves be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro is mono-or polysubstituted; wherein R is6And R9Not being hydrogen and hydrogen, C, respectively, at the same time1-C6Alkoxycarbonyl or C1-C6An alkylcarbonyl group; q is Q1
Wherein
A1Is C (R)14R15)、NR16Or oxygen;
A2is C (R)17R18)、C(O)、-C＝N-O-R19Oxygen, sulfur, sulfinyl, sulfonyl, -NR20Or an ethylene group; with the proviso that if A2Is oxygen, C (O), sulfur, sulfinyl, -C ═ N-O-R19-NR20Or C (R)17R18) Wherein R is17And R18Independently of one another is C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radicals, then A1Is not oxygen; and if A2Is thio, sulfinyl or C (R)17R18) Wherein R is17And R18Independently of one another is C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radicals, then A1Is not NR16；
R15And R21Independently of one another are hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C4Alkenyl or C3-C4An alkynyl group;
R17is hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl or C1-C4An alkylsulfonyl group;
R18is hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C4Alkenyl radical, C3-C4Alkynyl, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl or C1-C4dialkoxyalkyl-C1-C4An alkyl group;
R20is C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C3-C4Alkenyl radical, C3-C4Alkynyl, C1-C4Alkylcarbonyl group, C1-C4Alkylcarbonyloxy, di (C)1-C4Alkyl) aminocarbonyl or benzyl, in which the phenyl radical may be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro is mono-or polysubstituted;
R19and R16Independently of one another are hydrogen, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C3-C4Alkenyl radical, C3-C4Alkynyl, benzyl or phenyl, where phenyl and benzyl may themselves be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, halogen, cyano, hydroxy or nitro is mono-or polysubstituted;
R14and R22Together form C2-C3An alkylene chain;
or R17And R18Together form C2-C4An alkylene chain which may be interrupted by oxygen and/or carbonyl groups and/or sulfur, provided that the oxygen and sulfur atoms are separated by at least one methylene group;
or R16And R18Together form C2-C4An alkylene chain; r13Is hydroxy, O-M+Wherein M is+Is an alkali metal cation or ammonium cation, halogen, C1-C12Alkylsulfonyloxy, amino, C1-C4Alkylthio radical, C1-C12Alkylsulfinyl radical, C1-C12Alkylsulfonyl radical, C1-C12Haloalkylthio, C1-C12Haloalkylsulfinyl radical, C1-C12Haloalkylsulfonyl group, C1-C6alkoxy-C1-C6Alkylthio radical, C1-C6alkoxy-C1-C6Alkylsulfinyl radical, C1-C6alkoxy-C1-C6Alkylsulfonyl radical, C3-C12Alkenylthio radical, C3-C12Alkenylsulfinyl, C3-C12Alkenylsulfonyl radical, C3-C12Alkynylthio, C3-C12Alkynylsulfinyl group, C3-C12Alkynylsulfonyl radical, C1-C4alkoxycarbonyl-C1-C4Alkylthio radical, C1-C4alkoxycarbonyl-C1-C4Alkylsulfinyl radical, C1-C4alkoxycarbonyl-C1-C4Alkylsulfonyl group, (C)1-C4Alkoxy group)2P(O)O、C1-C4Alkyl radical- (C)1-C4Alkoxy group) P (O) O, H (C)1-C4Alkoxy) P (O) O, R23R24N、R25R26NNH、R27R28NC(O)O-、R29R30NC(O)NH-、C1-C18Alkylcarbonyloxy, C2-C18Alkenylcarbonyloxy, C2-C18Alkynyl carbonyloxy, C3-C6Cycloalkyl carbonyloxy, C1-C12Alkoxycarbonyloxy, C1-C12Alkylthio carbonyloxy, C1-C12Alkylthiocarbamoyl, in which alkyl, alkenyl and alkynyl may be substituted by halogen, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl or cyano substitution;
or R13Is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenylsulfonyloxy or benzoyloxy, where the phenyl radical may itself be substituted by one or more halogen, nitro, cyano, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4Alkoxy substitution;
or R13Is a group Het1Thio, Het2-sulfinyl, Het3-sulfonyl, Het4- (CO) O or Het5-N(R33) (ii) a Wherein Het1、Het2、Het3、Het4And Het5Independently of one another, is a 5-to 10-membered monocyclic or fused bicyclic ring system, which may be aromatic or partially saturated, and may contain 1 to 4 heteroatoms from the group of nitrogen, oxygen and sulfur, where each ring system may not contain more than two oxygen atoms and more than two sulfur atoms, where the ring system itself may be substituted by C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl, di (C)1-C4Alkyl) aminosulfonyl, di (C)1-C4Alkyl) amino, halo, cyano, nitro or phenyl substitution, wherein a substituent on a heterocyclic nitrogen is other than halo;
R23、R24、R25、R26、R27、R28、R29、R30and R33Independently of one another, hydrogen or C1-C6An alkyl group; or R23And R24Together or R25And R26Together or R27And R28Together or R29And R30Together being pyrroleAlkyl, piperidino, morpholino, thiomorpholino, which may be mono-or polysubstituted by methyl; and
n is 0, 1 or 2; and
the compounds are agriculturally acceptable salts/N-oxides/isomers/enantiomers.
2. A process for the preparation of a compound of formula I as claimed in claim 1, which process comprises, for the preparation of formula I wherein R1、R2、R3、R4And X1Is as defined under formula I and Q is a group Q1The compound of the formula (I) in (1),
a) reacting a compound of formula Ia in an inert organic solvent in the presence of a base
Wherein R is1、R2、R3、R4And X1Is as defined under formula I, Y1Is a leaving group which is a substituent of the group,
with a compound of the formula II,
wherein R is22、R21、A2And A1Is as defined under formula I,
to give compounds of the formulae IIIa and IIIb
These compounds are then isomerized in the presence of a base and a catalytic amount of Dimethylaminopyridine (DMAP) or a cyanide source, such as acetone cyanohydrin; or
b) Reacting a compound of formula Ib in an inert organic solvent in the presence of a base and a coupling agent
Wherein R is1、R2、R3、R4And X1Is as defined under formula I,
with a compound of the formula II,
wherein R is22、R21、A1And A2Is as defined under formula I,
to give compounds of the formulae IIIa and IIIb
These compounds are then isomerized as described under pathway a).
3. A herbicidal and plant growth inhibiting composition comprising a herbicidally effective amount of a compound of formula I on an inert carrier.
4. A method for controlling the growth of undesired plants, wherein a herbicidally effective amount of an active compound of the formula I or of a composition comprising it is applied to the plants or their habitat.
5. Method for inhibiting the growth of plants, wherein a herbicidally effective amount of an active compound of the formula I or of a composition comprising this active compound is applied to the plants or their habitat.
HK07109949.6A 2000-06-09 2007-09-13 Substituted pyridine herbicides HK1104548A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1151/00 2000-06-09

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Publication Number Publication Date
HK1104548A true HK1104548A (en) 2008-01-18

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