1-PYRIDYL-PYRAZOLYL AMIDE COMPOUNDS AND PREPARATION AND USES THEREOF

Abstract

This invention provides 1-pyridyl pyrazole amide compounds represented by Formula (I) and preparation and uses thereof, wherein each substituent is defined in the disclosure. The compounds of Formula (I) of this invention possess excellent insecticidal activities, especially very strong activities against pests such as aphids, armyworms and diamondback moths, etc., and can be used to control various pests. This invention also provides synthetic intermediates represented by Formula (II) for preparing compounds of Formula (I) wherein each substituent is defined in the specification.

##STR00001##

Claims

1. A 1-pyridyl-pyrazolyl amide compound, wherein the 1-pyridyl-pyrazolyl amide compound and its isomer thereof are represented by general Formula (I): ##STR00030## wherein: I. R is C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.12 alkenyl, C.sub.2-C.sub.12 alkynyl, C.sub.3-C.sub.8 cycloalkyl or C.sub.3-C.sub.8 heterocyclic group; II. R.sup.1 is halogen, C.sub.1-C.sub.6 alkyl or C.sub.1-C.sub.6 alkoxy; III. R.sup.2 is halogen, cyano, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy or nitro; IV. R.sup.3 is H, C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.12 alkenyl, C.sub.2-C.sub.12 alkynyl, C.sub.3-C.sub.8 cycloalkyl or C.sub.3-C.sub.8 heterocyclic group; V. R.sup.4 is C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.12 alkenyl, C.sub.2-C.sub.12 alkynyl, C.sub.3-C.sub.8 cycloalkyl or C.sub.3-C.sub.8 heterocyclic group; VI. X.sup.1, X.sup.2 and X.sup.3 are identical or different, and they represent H, halogen, C.sub.1-C.sub.6 alkyl or C.sub.1-C.sub.6 alkoxy; VII. W.sup.1 and W.sup.2 are identical or different, and they represent oxygen or sulfur; in above definition of Formula (I), the terms used whether alone or in compound words, represent the following substituents: halogen: represents fluorine, chlorine, bromine or iodine; alkyl: represents straight-chain or branched-chain alkyl; cycloalkyl: represents saturated or unsaturated cycloalkyl; alkenyl: represents straight-chain or branched-chain alkenyl; alkynyl: represents straight-chain or branched-chain alkynyl; halo-: represents the hydrogen atoms are partially or entirely substituted by halogen atoms; heterocyclic group: represents saturated or unsaturated heterocyclic group containing one or more than one identical or different hetero-atoms selected from N, O and/or S, including furanyl, thiophenyl, pyrrolyl, piperidinyl, piperazinyl, pyrazinyl, pyridazinyl, oxazolyl, thiazolyl, pyrazolyl, imidazolyl, tetrazolyl or triazolyl.

2. The 1-pyridyl-pyrazolyl amide compound according to claim 1, wherein I. R is C.sub.1-C.sub.12 alkyl or C.sub.3-C.sub.5 cycloalkyl; II. R.sup.1 is halogen or CH.sub.3; III. R.sup.2 is halogen, CF.sub.3, nitro or CN; IV. R.sup.3 is H, C.sub.1-C.sub.12 alkyl or C.sub.3-C.sub.5 cycloalkyl; V. R.sup.4 is C.sub.1-C.sub.12 alkyl or C.sub.3-C.sub.5 cycloalkyl; VI. X.sup.1, X.sup.2 and X.sup.3 are identical or different, and they represent H, halogen or CF.sub.3; VII. W.sup.1 and W.sup.2 are identical or different, and they represent oxygen or sulfur.

3. The 1-pyridyl-pyrazolyl amide compounds according to claim 1, wherein the compound represented by Formula (I) is: N-[2,4-dichloro-6-[(methylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(ethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(propylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(isopropylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(cyclopropylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(butylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(tert-butylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(methylamino)carbonyl]phenyl]-N-ethyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(ethylamino)carbonyl]phenyl]-N-ethyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(dimethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(methyl(ethyl)amino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(methyl(isopropyl)amino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide N-[2,4-dichloro-6-[(methyl(cyclopropyl)amino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(diethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(dipropylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(dimethylamino)carbonyl]phenyl]-N-ethyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(methyl(ethyl)amino)carbonyl]phenyl]-N-ethyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(dimethylamino)carbonyl]phenyl]-N-propyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(methyl(propyl)amino)carbonyl]phenyl]-N-propyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(dimethylamino)thioxomethyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(methyl(isopropyl)amino)thioxomethyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(diethylamino)thioxomethyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2,4-dichloro-6-[(diethylamino)thioxomethyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carbothioamide; N-[2-bromo-4-chloro-6-[(methylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(ethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(propylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(isopropylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(isopropylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(cyclopropylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(butylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(butylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(dimethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(methyl(ethyl)amino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(methyl(propyl)amino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(methyl(isopropyl)amino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(methyl(cyclopropyl)amino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(methyl(tert-butyl)amino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(diethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(dimethylamino)carbonyl]phenyl]-N-ethyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(methyl(ethyl)amino)carbonyl]phenyl]-N-ethyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(diethylamino)carbonyl]phenyl]-N-ethyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-bromo-4-chloro-6-[(dimethylamino)carbonyl]phenyl]-N-propyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-methyl-4-chloro-6-[(methylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-methyl-4-chloro-6-[(ethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-methyl-4-chloro-6-[(dimethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-methyl-4-chloro-6-[(methyl(ethyl)amino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-methyl-4-chloro-6-[(methyl(propyl)amino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-methyl-4-chloro-6-[(dimethylamino)thioxomethyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-methyl-4-bromo-6-[(diethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide; N-[2-methyl-4-bromo-6-[(diethylamino)carbonyl]phenyl]-N-ethyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide.

4. A compound of formula (II) as a synthetic intermediate for preparing the 1-pyridyl-pyrazolyl amide compound represented by Formula (I) of claim 1, ##STR00031## wherein: R is C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.12 alkenyl, C.sub.2-C.sub.12 alkynyl, C.sub.3-C.sub.8 cycloalkyl or C.sub.3-C.sub.8 heterocyclic group; R.sup.1 is halogen, C.sub.1-C.sub.6 alkyl or C.sub.1-C.sub.6 alkoxy; R.sup.2 is halogen, cyano, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy or nitro; R.sup.3 is H, C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.12 alkenyl, C.sub.2-C.sub.12 alkynyl, C.sub.3-C.sub.8 cycloalkyl or C.sub.3-C.sub.8 heterocyclic group; R.sup.4 is C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.12 alkenyl, C.sub.2-C.sub.12 alkynyl, C.sub.3-C.sub.8 cycloalkyl or C.sub.3-C.sub.8 heterocyclic group; W.sup.1 represents oxygen or sulfur; in above definition of Formula (II), the terms used whether alone or in compound words, represent the following substituents: halogen: represents fluorine, chlorine, bromine or iodine; alkyl: represents straight-chain or branched-chain alkyl; cycloalkyl: represents saturated or unsaturated cycloalkyl; alkenyl: represents straight-chain or branched-chain alkenyl; alkynyl: represents straight-chain or branched-chain alkynyl; halo-: represents the hydrogen atoms are partially or entirely substituted by halogen atoms; heterocyclic group: represents saturated or unsaturated heterocyclic group containing one or more than one identical or different hetero-atoms selected from N, O and/or S, including furanyl, thiophenyl, pyrrolyl, piperidinyl, piperazinyl, pyrazinyl, pyridazinyl, oxazolyl, thiazolyl, pyrazolyl, imidazolyl, tetrazolyl or triazolyl.

5. A compound of formula (II) as a synthetic intermediate for preparing the 1-pyridyl-pyrazolyl amide compound represented by Formula (I) of claim 1, ##STR00032## wherein the compound of formula (II) represents: N-methyl-3,5-dichloro-2-(methylamino)benzamide; N-ethyl-3,5-dichloro-2-(methylamino)benzamide; N-propyl-3,5-dichloro-2-(methylamino)benzamide; N-isopropyl-3,5-dichloro-2-(methylamino)benzamide; N-cyclopropyl-3,5-dichloro-2-(methylamino)benzamide; N-butyl-3,5-dichloro-2-(methylamino)benzamide; N-methyl-3,5-dichloro-2-(ethylamino)benzamide; N-ethyl-3,5-dichloro-2-(ethylamino)benzamide; N,N-dimethyl-3,5-dichloro-2-(methylamino)benzamide; N-methyl-N-ethyl-3,5-dichloro-2-(methylamino)benzamide; N-methyl-N-isopropyl-3,5-dichloro-2-(methylamino)benzamide; N-methyl-N-cyclopropyl-3,5-dichloro-2-(methylamino)benzamide; N,N-diethyl-3,5-dichloro-2-(methylamino)benzamide; N,N-dipropyl-3,5-dichloro-2-(methylamino)benzamide; N,N-dimethyl-3,5-dichloro-2-(ethylamino)benzamide; N-methyl-N-ethyl-3,5-dichloro-2-(ethylamino)benzamide; N,N-dimethyl-3,5-dichloro-2-(propylamino)benzamide; N-methyl-N-propyl-3,5-dichloro-2-(propylamino)benzamide; N,N-dimethyl-3,5-dichloro-2-(methylamino)benzothioamide; N-methyl-N-isopropyl-3,5-dichloro-2-(methylamino)benzothioamide; N,N-diethyl-3,5-dichloro-2-(methylamino)benzothioamide; N-methyl-3-bromo-5-chloro-2-(methylamino)benzamide; N-ethyl-3-bromo-5-chloro-2-(methylamino)benzamide; N-propyl-3-bromo-5-chloro-2-(methylamino)benzamide; N-isopropyl-3-bromo-5-chloro-2-(methylamino)benzamide; N-cyclopropyl-3-bromo-5-chloro-2-(methylamino)benzamide; N-butyl-3-bromo-5-chloro-2-(methylamino)benzamide; N,N-dimethyl-3-bromo-5-chloro-2-(methylamino)benzamide; N-methyl-N-ethyl-3-bromo-5-chloro-2-(methylamino)benzamide; N-methyl-N-propyl-3-bromo-5-chloro-2-(methylamino)benzamide; N-methyl-N-isopropyl-3-bromo-5-chloro-2-(methylamino)benzamide; N-methyl-N-cyclopropyl-3-bromo-5-chloro-2-(methylamino)benzamide; N-methyl-N-tert-butyl-3-bromo-5-chloro-2-(methylamino)benzamide; N,N-diethyl-3-bromo-5-chloro-2-(methylamino)benzamide; N,N-dimethyl-3-bromo-5-chloro-2-(ethylamino)benzamide; N-methyl-N-ethyl-3-bromo-5-chloro-2-(ethylamino)benzamide; N,N-diethyl-3-bromo-5-chloro-2-(ethylamino)benzamide; N,N-dimethyl-3-bromo-5-chloro-2-(propylamino)benzamide; N-methyl-3-methyl-5-chloro-2-(methylamino)benzamide; N-ethyl-3-methyl-5-chloro-2-(methylamino)benzamide; N,N-dimethyl-3-methyl-5-chloro-2-(methylamino)benzamide; N-methyl-N-ethyl-3-methyl-5-chloro-2-(methylamino)benzamide; N,N-dimethyl-3-methyl-5-chloro-2-(methylamino)benzothioamide; N,N-diethyl-3-methyl-5-bromo-2-(methylamino)benzamide N,N-diethyl-3-methyl-5-bromo-2-(ethylamino)benzamide; N-methyl-N-propyl-3-methyl-5-chloro-2-(methylamino)benzamide.

6. The 1-pyridyl-pyrazolyl amide compound according to claim 1, wherein the 1-pyridyl-pyrazolyl amide compound represented by Formula (I) exists as one or more isomers, the isomers include enantiomers, diastereomers, geometric isomers, rotational isomers and tautomers; the 1-pyridyl-pyrazolyl amide compound represented by Formula (I) exists as geometric isomers, and the geometric isomer is represented by Z-isomer or E-isomer, the compound includes the Z-isomer, the E-isomer or their mixture in any proportion; the 1-pyridyl-pyrazolyl amide compound represented by Formula (I) exists as stereoisomers, and the stereoisomer is represented by R-isomer or S-isomer, the compound includes the R-isomer, the S-isomer or their mixture in any proportion; the 1-pyridyl-pyrazolyl amide compound represented by Formula (I) exists as rotational isomers, and the rotational isomer is represented by I-isomer or I′-isomer, the compound includes the I-isomer, the I′-isomer or their mixture in any proportion; or the 1-pyridyl-pyrazolyl amide compound represented by Formula (I) exists as keto-enol tautomers, and the keto-enol tautomer is represented by I-isomer or I″-isomer, the compound includes the I-isomer, the I″ isomers or their mixture in any proportion.

7. The 1-pyridyl pyrazole amide compound according to claim 1, wherein a method for preparing the 1-pyridyl-pyrazolyl amide compound represented by Formula (I) comprises the following steps: ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## in a solvent or a mixture of any two solvents, at certain temperatures from −10° C. to the reflux temperature of the solvent used, reacting the compound of Formula (II) with a compound of Formula (III) to afford the compound of Formula (I), the addition of a base accelerates or facilitates the reaction, the solvent is selected from tetrahydrofuran, 1,4-dioxane, acetone, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide, the base is selected from triethylamine, N,N-dimethylaniline, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide or sodium bicarbonate; in a solvent or a mixture of any two solvents, at certain temperatures from −15° C. to the reflux temperature of the solvent used, reacting a compound of Formula (IV) with a compound of Formula (V) to afford a compound of Formula (VI), the solvent is selected from water, tetrahydrofuran, 1,4-dioxane, acetone, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide; in a solvent or a mixture of any two solvents, at certain temperatures from −15° C. to the reflux temperature of the solvent used, in the presence of a base, reacting the compound of Formula (VI) with a compound of Formula (VII) to afford a compound of Formula (I W.sup.1=W.sup.2=0), the solvent is selected from tetrahydrofuran, 1,4-dioxane, acetone, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide, the base is selected from triethylamine, N,N-dimethylaniline, pyridine, methylpyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide or sodium bicarbonate; in a solvent or a mixture of any two solvents, at certain temperatures from −15° C. to the reflux temperature of the solvent used, reacting a compound of Formula (I W.sup.1=W.sup.2=O) with P.sub.2S.sub.5 to afford a compound of Formula (I W.sup.1=S or O, W.sup.2=O or S), the solvent is selected from tetrahydrofuran, 1,4-dioxane, acetone, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide; in a solvent or a mixture of any two solvents, at certain temperatures from −15° C. to the reflux temperature of the solvent used, in the presence of a base, reacting a compound of Formula (VIII) with the compound of Formula (VII) to afford the compound of Formula (IX), the solvent is selected from tetrahydrofuran, 1,4-dioxane, acetone, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide, the base is selected from triethylamine, N,N-dimethylaniline, pyridine, methylpyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide or sodium bicarbonate; in a solvent or a mixture of any two solvents, at certain temperatures from −15° C. to the reflux temperature of the solvent used, in the presence of a base, reacting the compound of Formula (IX) with the compound of Formula (V) to afford a compound of Formula (II W.sup.1=O), the solvent is selected from water, tetrahydrofuran, 1,4-dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide; in a solvent or a mixture of any two solvents, at certain temperatures from −15° C. to the reflux temperature of the solvent used, reacting the compound of Formula (II W.sup.1=O) with P.sub.2S.sub.5 to afford a compound of Formula (II W.sup.1=S), the solvent is selected from tetrahydrofuran, 1,4-dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide; in a solvent or a mixture of any two solvents, at certain temperatures from 25° C. to the reflux temperature of the solvent used, in the presence of a base, routine hydrolysis of a compound of Formula (X) and then treating the reaction mixture with dilute acid solution such as dilute hydrochloric acid solution to afford a compound of Formula (XI), the solvent is selected from water, ethanol, methanol, tetrahydrofuran, 1,4-dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide, the base is selected from triethylamine, N,N-dimethylaniline, pyridine, methylpyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide or sodium bicarbonate; in solvent-free or a solvent, at certain temperatures from 15° C. to the reflux temperature of the solvent used, reacting the compound of Formula (XI) with an acyl halide reagent to afford the compound of Formula (III), the solvent is selected from tetrahydrofuran, 1,4-dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate or acetonitrile, the acyl halide reagent is selected from sulfoxide chloride, phosgene, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus pentabromide or oxalyl chloride; in a solvent or a mixture of any two solvents, at certain temperatures from −15° C. to the reflux temperature of the solvent used, in the presence of a base, treating a mixture of a compound of Formula (XII) and a compound of Formula (III W.sup.2=O) with methylsulfonyl chloride to afford the compound of Formula (IV), the solvent is selected from tetrahydrofuran, 1,4-dioxane, acetone, toluene, xylene, acetonitrile, dichloromethane, dichloroethane or N,N-dimethylformamide, the base is pyridine or methylpyridine; in a solvent or a mixture of any two solvents, at −15° C. to 25° C., reacting the compound of Formula (XII) with phosgene, diphosgene or triphosgene for 2 to 10 hours, and then at certain temperatures from 15° C. to the reflux temperature for 2 to 10 hours, to afford the compound of Formula (VIII), the solvent is selected from tetrahydrofuran, acetone, 1,4-dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate or acetonitrile; wherein R, R.sup.1, R.sup.2, R.sup.3, R.sup.4, X.sup.1, X.sup.2, X.sup.3, W.sup.1 and W.sup.2 are the same as defined in claim 1, L is a leaving group including chlorine or bromine.

8. An use of the 1-pyridyl pyrazole amide compound according to claim 1, wherein the compound possesses insecticidal activity comprising contacting the pests or their environment with the compound of Formula (I) at a dosage of 15 to 5000 g per hectare.

9. (canceled)

10. An insecticidal composition, comprising a biologically effective amount of a compound according to claim 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, in which the weight percentage of the active ingredient is in the range of 0.5-99%.

11. The 1-pyridyl-pyrazolyl amide compound according to claim 1, wherein: the hydrogen atoms in alkyl, alkenyl, alkynyl, cycloalkyl or heterocyclic group defined in I, II, III, IV, V and VI are partially or entirely substituted by identical or different substituting groups, selected from the following: halogen, cyano, hydroxyl, amino, mercapto, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 alkylamino, C.sub.1-C.sub.6 alkylsulfinyl, C.sub.1-C.sub.6 alkylsulfonyl or C.sub.3-C.sub.8 heterocyclic group.

12. The compound of formula (II) as the synthetic intermediate for preparing the 1-pyridyl-pyrazolyl amide compound represented by Formula (I) of claim 4, wherein: the hydrogen atoms in alkyl, alkenyl, alkynyl, cycloalkyl or heterocyclic group defined in R, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are partially or entirely substituted by identical or different substituting groups selected from the following: halogen, cyano, hydroxyl, amino, mercapto, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 alkylamino, C.sub.1-C.sub.6 alkylsulfinyl, C.sub.1-C.sub.6 alkylsulfonyl or C.sub.3-C.sub.8 heterocyclic group.

13. The compound of formula (II) as the synthetic intermediate for preparing the 1-pyridyl-pyrazolyl amide compound represented by Formula (I) of claim 4, wherein a method for preparing the compound of formula (II) comprises the following steps: ##STR00039## ##STR00040## ##STR00041## ##STR00042## in a solvent or a mixture of any two solvents, at certain temperatures from −15° C. to the reflux temperature of the solvent used, in the presence of a base, reacting a compound of Formula (VIII) with the compound of Formula (VII) to afford the compound of Formula (IX), the solvent is selected from tetrahydrofuran, 1,4-dioxane, acetone, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide, the base is selected from triethylamine, N,N-dimethylaniline, pyridine, methylpyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide or sodium bicarbonate; in a solvent or a mixture of any two solvents, at certain temperatures from −15° C. to the reflux temperature of the solvent used, in the presence of a base, reacting the compound of Formula (IX) with the compound of Formula (V) to afford a compound of Formula (II W.sup.1=O), the solvent is selected from water, tetrahydrofuran, 1,4-dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide; in a solvent or a mixture of any two solvents, at certain temperatures from −15° C. to the reflux temperature of the solvent used, reacting the compound of Formula (II W.sup.1=O) with P.sub.2S.sub.5 to afford a compound of Formula (II W.sup.1=S), the solvent is selected from tetrahydrofuran, 1,4-dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide; in a solvent or a mixture of any two solvents, at certain temperatures from 25° C. to the reflux temperature of the solvent used, in the presence of a base, routine hydrolysis of a compound of Formula (X) and then treating the reaction mixture with dilute acid solution such as dilute hydrochloric acid solution to afford a compound of Formula (XI), the solvent is selected from water, ethanol, methanol, tetrahydrofuran, 1,4-dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate, acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide, the base is selected from triethylamine, N,N-dimethylaniline, pyridine, methylpyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide or sodium bicarbonate; in solvent-free or a solvent, at certain temperatures from 15° C. to the reflux temperature of the solvent used, reacting the compound of Formula (XI) with an acyl halide reagent to afford the compound of Formula (III), the solvent is selected from tetrahydrofuran, 1,4-dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate or acetonitrile, the acyl halide reagent is selected from sulfoxide chloride, phosgene, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus pentabromide or oxalyl chloride; in a solvent or a mixture of any two solvents, at certain temperatures from −15° C. to the reflux temperature of the solvent used, in the presence of a base, treating a mixture of a compound of Formula (XII) and a compound of Formula (III W.sup.2=O) with methylsulfonyl chloride to afford the compound of Formula (IV), the solvent is selected from tetrahydrofuran, 1,4-dioxane, acetone, toluene, xylene, acetonitrile, dichloromethane, dichloroethane or N,N-dimethylformamide, the base is pyridine or methylpyridine; in a solvent or a mixture of any two solvents, at −15° C. to 25° C., reacting the compound of Formula (XII) with phosgene, diphosgene or triphosgene for 2 to 10 hours, and then at certain temperatures from 15° C. to the reflux temperature for 2 to 10 hours, to afford the compound of Formula (VIII), the solvent is selected from tetrahydrofuran, acetone, 1,4-dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloromethane, hexane, ethyl acetate or acetonitrile; wherein R, R.sup.1, R.sup.2, R.sup.3, R.sup.4, X.sup.1, X.sup.2, X.sup.3, W.sup.1 and W.sup.2 are the same as defined in claim 4, L is a leaving group including chlorine or bromine.

14. An use of the 1-pyridyl pyrazole amide compound according to claim 2, wherein the compound possesses insecticidal activity comprising contacting the pests or their environment with the compound of Formula (I) at a dosage of 15 to 5000 g per hectare.

15. An use of the 1-pyridyl pyrazole amide compound according to claim 3, wherein the compound possesses insecticidal activity comprising contacting the pests or their environment with the compound of Formula (I) at a dosage of 15 to 5000 g per hectare.

16. An insecticidal composition, comprising a biologically effective amount of a compound according to claim 2 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, in which the weight percentage of the active ingredient is in the range of 0.5-99%.

17. An insecticidal composition, comprising a biologically effective amount of a compound according to claim 3 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, in which the weight percentage of the active ingredient is in the range of 0.5-99%.

Description

DESCRIPTION OF EMBODIMENTS

Example 1 Preparation of Compound 1 in Table 1 and Compound II-1 in Table 3

[0190] ##STR00022##

2-amino-3,5-dichlorobenzoic Acid (Method 1)

[0191] A mixture of 2-amino-5-chlorobenzoic acid (0.10 mol) and N-chlorosuccinimide (0.13 mol) or 2-aminobenzoic acid (0.10 mol) and N-chlorosuccinimide (0.25 mol) in glacial acetic acid (150 mL) was heated to reflux for 4-8 hours until the reaction was complete. The reaction mixture was cooled to room temperature, the title compound 2-amino-3,5-dichlorobenzoic acid in greater than 85% yield was afforded by routine post-treatments such as filtration, water washing and drying.

2-amino-3,5-dichlorobenzoic Acid (Method 2)

[0192] Excess chlorine was introduced into a solution of 2-amino-5-chlorobenzoic acid (0.10 mol) or 2-aminobenzoic acid (0.10 mol) in glacial acetic acid (150 mL) under room temperature and stirring conditions, the reaction mixture was then stirred at temperatures from 25° C. to the reflux temperature until the reaction was complete. the title compound 2-amino-3,5-dichlorobenzoic acid in greater than 80% yield was afforded by routine post-treatments.

6,8-dichloro-2H-3,1-benzooxazine-2,4(1H)-dione (Method 1)

[0193] To a solution of 2-amino-3,5-dichlorobenzoic acid (0.05 mol) in tetrahydrofuran (50 mL) was slowly added dropwise a solution of phosgene (0.07 mol) in tetrahydrofuran under −10 to −5° C. and stirring conditions. The reaction mixture was stirred at room temperature for 2-5 hours, then heated to reflux and continued stirring 2-5 hours until the reaction was complete. The reaction mixture was cooled to room temperature, filtered to afford the title compound; the filtrate was concentrated to a ⅓ of the volume, cooled to afford a second crop of the title compound, which was also collected by filtration. The combined total yield was greater than 85%.

6,8-dichloro-2H-3,1-benzooxazine-2,4(1H)-dione (Method 2)

[0194] To a solution of 2-amino-3,5-dichlorobenzoic acid (0.05 mol) in tetrahydrofuran (80 mL) was slowly introduced phosgene (0.07 mol) under −10 to −5° C. and stirring conditions. The reaction mixture was stirred at room temperature for 2-4 hours, then heated to reflux and continued stirring 3-5 hours. The reaction mixture was cooled to room temperature, filtered to afford the title compound; the filtrate was concentrated to a ⅓ of the volume, cooled to afford a second crop of the title compound, which was also collected by filtration. The combined total yield was greater than 85%.

6,8-dichloro-2H-3,1-benzooxazine-2,4(1H)-dione (Method 3)

[0195] To a solution of 2-amino-3,5-dichlorobenzoic acid (0.05 mol) in tetrahydrofuran (80 mL) was added a catalytic amount of pyridine, and then was slowly added in batches triphosgene (0.03 mol) under −10 to −5° C. and stirring conditions. The reaction mixture was stirred at room temperature for 2-5 hours, then heated to reflux and continued stirring 2-5 hours. The reaction mixture was cooled to room temperature, filtered to afford the title compound; the filtrate was concentrated to a ⅓ of the volume, cooled to afford a second crop of the title compound, which was also collected by filtration. The combined total yield was greater than 65%.

6,8-dichloro-1-methyl-2H-3,1-benzooxazine-2,4(1H)-dione

[0196] To a mixture of 6,8-dichloro-2H-3,1-benzooxazine-2,4(1H)-dione (0.02 mol) and sodium hydride (0.03 mol) in N,N-dimethylformamide (25 mL) was slowly added dropwise iodomethane (0.03 mol) under room temperature and stirring conditions. the reaction mixture was continued stirring 6-10 hours until the reaction was complete. the title compound in greater than 70% yield was afforded by routine post-treatments such as the reaction mixture extracted with ethyl acetate, washed with ice water, dried, concentrated and purified, etc.

N-methyl-3,5-dichloro-2-(methylamino)benzamide

[0197] A mixture of 6,8-dichloro-1-methyl-2H-3,1-benzooxazine-2,4(1H)-dione (0.01 mol) and methylamine aqueous solution (33%, 10 mL) was stirred at room temperature for 2-6 hours until the reaction was complete. the title compound in about 70% yield was afford by routine post-treatments such as the reaction mixture extracted with ethyl acetate, washed with ice water, dried, concentrated and purified, etc.

N-[2,4-dichloro-6-[(methylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide

[0198] A mixture of N-methyl-3,5-dichloro-2-(methylamino)benzamide (5.0 mmol) and 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carbonyl chloride (5.5 mmol) in toluene (20 mL) or a mixture of toluene (5 mL) and xylene (15 mL) were refluxed for 2-6 hours with stirring until the reaction was complete. The reaction mixture was cooled to room temperature, the resulting crude products were collected by filtration and recrystallized from petroleum ether and ethyl acetate to afford the title compound in greater than 80% yield.

Example 2 Preparation of Compound 2 in Table 1 and Compound II-2 in Table 3

[0199] ##STR00023##

N-ethyl-3,5-dichloro-2-(methylamino)benzamide

[0200] A mixture of 6,8-dichloro-1-methyl-2H-3,1-benzooxazine-2,4(1H)-dione (0.01 mol) and ethylamine aqueous solution (65%, 10 mL) was stirred at room temperature for 2-6 hours until the reaction was complete. the title compound in about 70% yield was afford by routine post-treatments such as the reaction mixture extracted with ethyl acetate, washed with ice water, dried, concentrated and purified, etc.

N-[2,4-dichloro-6-[(ethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide

[0201] A mixture of N-ethyl-3,5-dichloro-2-(methylamino)benzamide (5.0 mmol) and 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carbonyl chloride (5.5 mmol) in toluene (20 mL) or a mixture of toluene (5 mL) and xylene (15 mL) were refluxed for 2-6 hours with stirring until the reaction was complete. The reaction mixture was cooled to room temperature, the resulting crude products were collected by filtration and recrystallized from petroleum ether and ethyl acetate to afford the title compound in greater than 80% yield.

Example 3 Preparation of Compound 9 in Table 1 and Compound II-9 in Table 3

[0202] ##STR00024##

N-[2,4-dichloro-6-[(methylamino)carbonyl]phenyl]-N-ethyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide

[0203] A mixture of N-methyl-3,5-dichloro-2-(ethylamino)benzamide (5.0 mmol) and 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carbonyl chloride (5.5 mmol) in toluene (20 mL) or a mixture of toluene (5 mL) and xylene (15 mL) were refluxed for 2-6 hours with stirring until the reaction was complete. The reaction mixture was cooled to room temperature, the resulting crude products were collected by filtration and recrystallized from petroleum ether and ethyl acetate to afford the title compound in greater than 70% yield.

Example 4 Preparation of Compound 10 in Table 1 and Compound II-10 in Table 3

[0204] ##STR00025##

6,8-dichloro-1-ethyl-2H-3,1-benzooxazine-2,4(1H)-dione

[0205] To a mixture of 6,8-dichloro-2H-3,1-benzooxazine-2,4(1H)-dione (0.02 mol) and sodium hydride (0.03 mol) in N,N-dimethylformamide (25 mL) was slowly added dropwise iodoethane (0.03 mol) under room temperature and stirring conditions. The reaction mixture was continued stirring 6-18 hours until the reaction was complete. The reaction mixture was poured into ice water and the resulting crude products were collected by filtration, washed with water and dried to afford the title compound in 80% yield.

N-ethyl-3,5-dichloro-2-(ethylamino)benzamide

[0206] A mixture of 6,8-dichloro-1-ethyl-2H-3,1-benzooxazine-2,4(1H)-dione (0.01 mol) and ethylamine aqueous solution (65%, 10 mL) was stirred at room temperature for 2-6 hours until the reaction was complete. The reaction mixture was acidified with dilute hydrochloric acid to PH of about 7, the title compound in about 60% yield was afford by routine post-treatments such as the reaction mixture extracted with dichloromethane, washed with ice water, dried, concentrated and purified, etc.

N-[2,4-dichloro-6-[(ethylamino)carbonyl]phenyl]-N-ethyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide

[0207] A mixture of N-ethyl-3,5-dichloro-2-(ethylamino)benzamide (5.0 mmol) and 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carbonyl chloride (5.5 mmol) in toluene (20 mL) or a mixture of toluene (5 mL) and xylene (15 mL) were refluxed for 2-6 hours with stirring until the reaction was complete. The reaction mixture was cooled to room temperature, the resulting crude products were collected by filtration and recrystallized from petroleum ether and ethyl acetate to afford the title compound in greater than 70% yield.

Example 5 Preparation of Compound 11 in Table 1 and Compound II-11 in Table 3 (Method 1)

[0208] ##STR00026##

N,N-dimethyl-3,5-dichloro-2-(methylamino)benzamide

[0209] A mixture of 6,8-dichloro-1-methyl-2H-3,1-benzooxazine-2,4(1H)-dione (0.01 mol) and dimethylamine aqueous solution (30%, 10 mL) was stirred at room temperature for 2-6 hours until the reaction was complete. the title compound in about 70% yield was afford by routine post-treatments such as the reaction mixture extracted with ethyl acetate, washed with ice water, dried, concentrated and purified, etc.

N-[2,4-dichloro-6-[(dimethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide

[0210] A mixture of N,N-dimethyl-3,5-dichloro-2-(methylamino)benzamide (5.0 mmol) and 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carbonyl chloride (5.5 mmol) in toluene (20 mL) or a mixture of toluene (5 mL) and xylene (15 mL) were refluxed for 2-6 hours with stirring until the reaction was complete. The reaction mixture was cooled to room temperature, the resulting crude products were collected by filtration and recrystallized from petroleum ether and ethyl acetate to afford the title compound in greater than 80% yield.

Example 6 Preparation of Compound 11 in Table 1 (Method 2)

[0211] ##STR00027##

6,8-dichloro-2-[1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazol-5-yl]-4H-3,1-benzooxazine-4-one

[0212] To a mixture of 2-amino-3,5-dichlorobenzoic acid (0.1 mol), 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-carboxylic acid (0.1 mol) and pyridine (0.4 mol) in acetonitrile (50 mL) was slowly added dropwise methanesulfonyl chloride (0.4 mol) under −10 to 0° C. and stirring conditions. The reaction mixture was stirred 3-5 hours at this temperature, then allowed to warm naturally to room temperature, and stirred 2-5 hours until the reaction was complete. The reaction mixture was added ice water, the resulting crude products were collected by filtration, washed with water, dried to afford the title compound in greater than 80% yield.

N-[2,4-dichloro-6-[(dimethylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide

[0213] To a solution of 6,8-dichloro-2-[1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazol-5-yl]-4H-3,1-benzooxazine-4-one (0.01 mol) in tetrahydrofuran (15 mL) was slowly added dropwise dimethylamine aqueous solution (33%, 15 mL) under −10 to 0° C. and stirring conditions. The reaction mixture was stirred 2-5 hours at this temperature, then allowed to warm naturally to room temperature, and stirred 2-3 hours until the reaction was complete. The reaction mixture was poured into ice water, the resulting title product in greater than 80% yield was collected by filtration.

N-[2,4-dichloro-6-[(dimethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide

[0214] To a solution of N-[2,4-dichloro-6-[(dimethylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide (0.015 mol) in N,N-dimethylformamide (30 mL) or a mixture of N,N-dimethylformamide (25 mL) and tetrahydrofuran (5 mL) was added in batches sodium hydride (0.025 mol) under cooling in an ice-water bath and stirring conditions. The mixture was stirred 15-30 minutes and then iodomethane (0.025 mol) was slowly added dropwise. The reaction mixture was stirred 1-3 hours at this temperature, then allowed to warm naturally to room temperature, and stirred 2-5 hours until the reaction was complete. The reaction mixture was poured slowly into saturated ice brine, the resulting crude products were collected by filtration and recrystallized from ethanol to afford the title compound in about 80% yield.

Example 7 Preparation of Compound 15 in Table 1 and Compound II-15 in Table 3 (Method 1)

[0215] ##STR00028##

N,N-diethyl-3,5-dichloro-2-(methylamino)benzamide

[0216] A mixture of 6,8-dichloro-1-methyl-2H-3,1-benzooxazine-2,4(1H)-dione (0.01 mol), diethylamine (0.02 mol) and water (20 mL) was stirred at room temperature for 2-6 hours until the reaction was complete. the title compound in about 65% yield was afford by routine post-treatments such as the reaction mixture extracted with dichloromethane, washed with ice water, dried, concentrated and purified, etc.

N-[2,4-dichloro-6-[(diethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide

[0217] A mixture of N,N-diethyl-3,5-dichloro-2-(methylamino)benzamide (5.0 mmol) and 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carbonyl chloride (5.5 mmol) in toluene (20 mL) or a mixture of toluene (5 mL) and xylene (15 mL) were refluxed for 2-6 hours with stirring until the reaction was complete. The reaction mixture was cooled to room temperature, the resulting crude products were collected by filtration and recrystallized from petroleum ether and ethyl acetate to afford the title compound in greater than 70% yield.

Example 8 Preparation of Compound 15 in Table 1 (Method 2)

[0218] ##STR00029##

N-[2,4-dichloro-6-[(diethylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide

[0219] To a mixture of 6,8-dichloro-2-[1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazol-5-yl]-4H-3,1-benzooxazine-4-one (0.02 mol) in water (40 mL) was slowly added dropwise diethylamine (0.04 mol) under −10 to 0° C. and stirring conditions. The reaction mixture was stirred 2-5 hours at this temperature, then allowed to warm naturally to room temperature, and stirred 2-5 hours until the reaction was complete. The reaction mixture was added ice water, the title compound in about 70% yield was afford by routine post-treatments such as the reaction mixture extracted with dichloromethane, washed with ice water, dried, concentrated and purified, etc.

N-[2,4-dichloro-6-[(diethylamino)carbonyl]phenyl]-N-methyl-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide

[0220] To a solution of N-[2,4-dichloro-6-[(diethylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-3-bromo-1H-pyrazole-5-carboxamide (0.015 mol) in N,N-dimethylformamide (30 mL) or a mixture of N,N-dimethylformamide (25 mL) and tetrahydrofuran (5 mL) was added in batches sodium hydride (0.025 mol) under cooling in an ice-water bath and stirring conditions. The mixture was stirred 15-30 minutes and then iodomethane (0.025 mol) was slowly added dropwise. The reaction mixture was stirred 1-3 hours at this temperature, then allowed to warm naturally to room temperature, and stirred 2-5 hours until the reaction was complete. The reaction mixture was poured slowly into saturated ice brine, the resulting crude products were collected by filtration and recrystallized from ethanol to afford the title compound in greater than 70% yield.

[0221] Other compounds of this invention can be prepared by the procedures described in examples 1-8 or together with methods known in relevant references.

BIOLOGICAL EXAMPLES OF THE INVENTION

[0222] The biological tests indicate that the compounds of this invention possess excellent insecticidal activity. Some results are as follows.

Example 9 Test Against Armyworm (Mythimna separata (Walker))

[0223] Potter tower method: the test compound was dissolved in an appropriate solvent such as N,N-dimethylformamide, and then diluted with 0.2% aqueous solution of Tween 80 to the desired concentration, Those without the test compounds were set as blank controls. The fresh and tender corn leaves were taken and cut into fragments of basically the same size, then put into a Petri dish (diameter 90 mm) padded with filter paper in advance. Ten third-instar larvae of test insects were transferred into the dish and then placed under the Potter spray tower for being sprayed, each concentration treatment was sprayed at the amount of 1 mL and replicated 3 times. The dish was covered and then placed in a chamber for culture and observed regularly, after 72 hours, the dead insects was investigated and recorded and the mean mortality was calculated. Activity (mortality) is divided into four levels A, B, C and D as a percentage relative to the blank control, 100≥mortality (%)≥90 is level A, 90>mortality (%)≥70 is level B, 70>mortality (%)≥50 is level C, and 50>mortality (%)≥0 is level D. The results show that the compounds of this invention possess excellent activity against armyworm, and some compounds still have high activity at very low concentration. Some results are listed below:

[0224] At 500 mg/L, the following compounds of this invention as well as D1, D2 and D3 provided level A activity against armyworm: 1, 2, 3, 5, 6, 7, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, etc.

[0225] At 50 mg/L, the following compounds of this invention as well as D1, D2 and D3 provided level A activity against armyworm: 1, 2, 3, 5, 6, 7, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 47, 48, 49, etc.

[0226] At 12.5 mg/L, the following compounds of this invention as well as D1 and D2 provided level A activity and D3 provided level B activity against armyworm: 1, 2, 3, 5, 6, 10, 11, 12, 14, 15, 17, 22, 23, 25, 26, 28, 29, 32, 37, 40, 42, etc.

[0227] Further screening results showed that the compounds of this invention, such as 1, 2, 5, 9, 10, 11, 12, 14, 15, 32 and 40 etc., provided excellent activity against armyworm, and their activity against armyworm could rank with that of chlorantraniliprole (D1); The activity of some compounds of this invention against armyworm was better than that of chlorantraniliprole (D1). For example, at 1.25 mg/L, the activity of compound 1 of this invention against armyworm was 75%, and the activity of chlorantraniliprole (D1) against armyworm was less than 50% under the same conditions.

Example 10 Test Against Spodoptera litura (Fabricius)

[0228] The test compound was dissolved in an appropriate solvent such as N,N-dimethylformamide, and then diluted with 0.2% aqueous solution of Tween 80 to the desired concentration, Those without the test compounds were set as blank controls, the treatments were replicated 3 times. The cabbage leaves were perforated to get 18 mm diameter leaf discs by a hole puncher, 5 leaf discs were dipped in the test solution for 10 seconds and then put into a Petri dish (diameter 90 mm) padded with moisturizing filter paper, after air-drying, the leaf discs were infested with no less than ten second-instar larvae of test insects which were starved for 4 hours, and then the dish was covered and placed in a chamber for culture. After 72 hours, the number of dead insects was investigated, the mortality was calculated, and the regression equation, correlation coefficient (r) and the median lethal concentration (LC.sub.50) were obtained using Probit analysis method.

[0229] The results show that the compounds of this invention possess excellent activity against Spodoptera litura, and some compounds such as compounds 1, 2, 9, 10, 11, 12, 15, 32, etc. as well as chlorantraniliprole (D1) still have high activity at very low concentration. The activity against Spodoptera litura of some compounds of this invention is better than that of chlorantraniliprole (D1). For example, the median lethal concentration LC.sub.50 value of compounds 1, 2, 10, 15, etc. of this invention against Spodoptera litura is lower than that of chlorantraniliprole (D1) under the same conditions.

Example 11 Test Against Diamondback Moth (Plutella xylostella (Linnaeus))

[0230] The test compound was dissolved in an appropriate solvent such as N,N-dimethylformamide, and then diluted with 0.2% aqueous solution of Tween 80 to the desired concentration, Those without the test compounds were set as blank controls, the treatments were replicated 3 times. The cabbage leaves were perforated to get 18 mm diameter leaf discs by a hole puncher, 5 leaf discs were dipped in the test solution for 10 seconds and then put into a Petri dish (diameter 90 mm) padded with moisturizing filter paper, after air-drying, the leaf discs were infested with no less than ten second-instar larvae of test insects which were starved for 4 hours, and then the dish was covered and placed in a chamber for culture. After 72 hours, the number of dead insects was investigated, the mortality was calculated, and the regression equation, correlation coefficient (r) and the median lethal concentration (LC.sub.50) were obtained using Probit analysis method.

[0231] The results show that the compounds of this invention possess excellent activity against diamondback moth, and some compounds such as compounds 1, 2, 9, 10, 11, 12, 15, 32, etc. as well as chlorantraniliprole (D1) still have high activity at very low concentration, for example, the lethal medium concentration LC.sub.50 values of compounds 1, 2, 11 etc. of this invention against diamondback moth are lower than 1.00 mg/L. The activity against diamondback moth of some compounds of this invention is better than that of chlorantraniliprole (D1).

Example 12 Test Against Aphid (Aphidoidea)

[0232] For evaluating the activity of the compounds of this invention against Homoptera pests, Aphis fabae, wheat aphids, etc. were selected as the test insects, and the activity of the compounds of this invention against aphids was measured by leaf dip method indoors.

[0233] Leaf dip method (Aphis fabae): the test compound was dissolved in an appropriate solvent such as N,N-dimethylformamide, and then diluted with 0.2% aqueous solution of Tween 80 to the desired concentration, Those without the test compounds were set as blank controls, the treatments were replicated 3 times. Horsebean seedlings with no less than twenty 3-day-old Aphis fabae per plant was cut from the stem, 5 horsebean seedlings with the insects were dipped in the test solution for 5 seconds, then inserted into a sponge filled with water after sucked dry using filter paper, then covered with a glass tube and placed in a chamber for culture. After 24 hours, the number of living and dead insects were investigated and the results were averaged. Activity (mortality) is divided into four levels A, B, C and D as a percentage relative to the blank control, 100≥mortality (%)≥90 is level A, 90>mortality (%)≥70 is level B, 70>mortality (%)≥50 is level C, and 50>mortality (%)≥0 is level D. The results show that the compounds of this invention possess excellent activity against Aphis fabae, and some compounds still have excellent activity at very low concentration. Some results are listed below:

[0234] At 500 mg/L, the following compounds of this invention as well as D1, D2 and D3 provided level A activity against Aphis fabae: 1, 2, 3, 5, 6, 7, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, etc.

[0235] At 200 mg/L, the following compounds of this invention as well as D2 and D3 provided level A activity against Aphis fabae: 1, 2, 3, 5, 6, 7, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 46, 47, 49, etc.

[0236] At 50 mg/L, the following compounds of this invention as well as D2 and D3 provided level A activity and D1 provided level D activity against Aphis fabae: 1, 2, 3, 5, 6, 7, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 25, 26, 27, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 47, etc.

[0237] At 12.5 mg/L, the following compounds of this invention as well as D2 and D3 provided level A activity against Aphis fabae: 1, 2, 3, 5, 6, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 25, 26, 27, 31, 32, 33, 34, 35, 37, 38, 39, 40, 41, 42, 47, etc.

[0238] For further comparing the activity of the compounds of this invention with that of D2, D3 as well as the leading insecticide for controlling aphids imidacloprid (D4), compounds 1, 2, 5, 10, 11, 12, 15, 32, 33, 47, etc. selected as the representative compounds of this invention as well as D2, D3 and imidacloprid were further tested. The results show that the compounds of this invention possessed excellent activity against Aphis fabae, for example, the LC.sub.50 values of compounds 1, 2, 10, 11, 15, 31, 34, etc. as well as imidacloprid against Aphis fabae were less than 1.0 mg/L, and the LC.sub.50 values of D2 and D3 against Aphis fabae were greater than 1.0 mg/L.

[0239] Studies on the biological activity also show that the activity of some compounds of this invention against Aphis fabae is better than that of imidacloprid (D4) under the same conditions.

[0240] Studies on the biological activity against wheat aphids also show that the compounds of this invention possess excellent insecticidal activity against wheat aphids.