CN1194267A - 1-phenyl-5-anilinotetrazole compounds - Google Patents
1-phenyl-5-anilinotetrazole compounds Download PDFInfo
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Abstract
The present invention relates to novel 1-Phenyl-5-anilinotetrazoles of the formula (I): wherein, R1, R2, R3, R4, m and n have the meaning provided in the specification, precesses for their preparation and their use as microbiocides, insecticides and/or herbicides.
Description
The present invention relates to new 1-phenyl-5-anilinotetrazole compounds, its preparation method and its purposes as microbicide, sterilant and/or weedicide.
At Collection of Czechoslovak Chemical Communications (1992), 57 (5), 1065-71; Synthetic Communications (1990), 20 (2), 217-26; Synthesis (1987), (9), 823-4; Monatschefte fuer Chemie (1983), 114 (1), 65-70; Journal of Organic Chemistry (1980), 45 (25), 5136-6; Ibid. (1977), 42 (23), 3709-13; Journal of Chemical Society, PerkinTransaction 1 (1977), (11), 1241-3; Chem.Zvesti (1979), 33 (4), put down in writing some 1-phenyl-5-anilino tetrazolium in the periodicals such as 521-7.But existing technical literature does not have to disclose its purposes as agricultural chemicals.
Find the 1-phenyl-5-anilino tetrazolium of new formula (I) now
Wherein R1 is a hydrogen, halogen, cyano group; nitro, the alkyl of C1-4, the haloalkyl of C1-4; the halogenated alkoxy of C1-4 or the halogenated alkylthio of C1-4, R2 are cyano group, nitro; the haloalkyl of C1-4, the alkyl sulphonyl of C1-4, haloalkyl-alkylsulfonyl of C1-4; alkoxyl group-carbonyl of C1-4, aminocarboxyl or amino thiocarbonyl, R3 are halogen; the haloalkyl of C1-4 or the halogenated alkoxy of C1-4, R4 are hydrogen, cyano group; the alkyl of C1-4, the alkyl-carbonyl of C1-4, alkoxyl group-carbonyl of C1-4; the alkyl sulphonyl of C1-4; alkyl-carbonyl of the alkoxy-C 1-4 of C1-4, phenyloxycarbonyl that can be replaced by nitro or the pyridyl carbonyl that can be replaced by halogen, n is 1; 2 or 3; and when n was 2 or 3, two or three R1 can be identical or different, and m is 1 or 2; and when m was 2, two R3 can be identical or different.
The 1-phenyl-5-anilinotetrazole compounds of new formula (I) of the present invention can obtain under the following situation: a) when R4 is hydrogen:
Make the compound of formula (II)
Wherein the definition of R1 and n as above, X is halogen or methylsulfonyl,
Compound with formula (III)
R2 wherein, the definition of R3 and m is the same,
A kind of thinner and, if suitable, in the presence of a kind of acid binding agent, react, or b) when R4 is the alkoxy carbonyl of the alkyl of C1-4 or C1-4:
Make the compound of formula (IV)
R1 wherein, R2, R3, the definition of m and n as above, and R5 is the alkyl of C1-4 or the alkoxy carbonyl of C1-4, reacts in the presence of a kind of thinner with sodiumazide, or c) when R4 is hydrogen:
Make the compound of formula (Ib)
R1 wherein, R2, R3, the definition of m and n as above, and R6 is the alkyl of C1-4 or the phenyl that can be replaced by nitro,
A kind of thinner and, if suitable, hydrolysis in the presence of a kind of alkali, or d) beyond R4 is the alkyl of dehydrogenation and C1-4 as above to the defined group of R4 the time:
Make the compound of formula (Ia)
R1 wherein, R2, R3, the definition of m and n as above, with the compound of formula V
R7-Y (V)
Wherein R7 be beyond the alkyl of dehydrogenation and C1-4 with the identical group of R4 as defined above, and Y is a halogen,
A kind of thinner and, if suitable, in the presence of a kind of acid binding agent, react, or e) when R4 is the alkyl-carbonyl of the alkoxy-C 1-4 of the alkyl-carbonyl of C1-4 or C1-4:
Make the compound of above-mentioned formula (Ia) and the compound of formula (VI)
Wherein R8 is the alkyl of the alkoxy-C 1-4 of the alkyl of C1-4 or C1-4,
Be with or without a kind of thinner and a kind of acid catalyst in the presence of react.
The 1-phenyl of formula of the present invention (I)-5-anilino tetrazolium has showed insecticidal activity and/or fungicidal activity and/or weeding activity.
Outstanding ground, the 1-phenyl of formula of the present invention (I)-5-anilino tetrazolium has very strong insecticidal activity, fungicidal activity and/or weeding activity.
In this manual, term " halogen ", the halogen in " haloalkyl " and " halogenated alkoxy " is represented fluorine, chlorine, bromine or iodine, preferred fluorine, chlorine or bromine.
" alkyl " can be straight or branched and comprise, for example, methyl, ethyl, propyl group, sec.-propyl, just-, different-, secondary-or tert-butyl etc.
" alkoxyl group " can be straight or branched and comprise, for example, methoxyl group, oxyethyl group, propoxy-, isopropoxy, just-, different-, secondary-or uncle-butoxy etc.
" haloalkyl " can be straight or branched and comprise, for example, trifluoromethyl, 2,2,2-trifluoroethyl, chloro ethyl etc.
" halogenated alkoxy " can be straight or branched and comprise, for example, trifluoromethoxy, 2,2,2-trifluoro ethoxy etc.
" haloalkyl sulfenyl " can be straight or branched and comprise, for example, trifluoromethyl sulfenyl, 2,2,2-trifluoroethyl sulfenyl etc.
" alkyl sulphonyl " can be straight or branched and comprise, for example, methylsulfonyl, ethylsulfonyl, third alkylsulfonyl, different third alkylsulfonyl etc.
" halogenated alkyl sulfonyl " can be straight or branched and comprise, for example, trifyl, 2,2,2-trifluoro ethylsulfonyl etc.
In the 1-phenyl-5-anilinotetrazole compounds of formula (I), preferred compound is that wherein R1 is a hydrogen, halogen; cyano group, nitro, the alkyl of C1-3; the fluoro-alkyl of C1-3, the fluoroalkane sulfenyl of the fluoroalkyl of C1-3 or C1-3, R2 are cyano group; nitro, the haloalkyl of C1-3, the alkyl sulphonyl of C1-3; the halogenated alkyl sulfonyl of C1-3; alkoxyl group-carbonyl of C1-3, aminocarboxyl or amino thiocarbonyl, R3 are halogen; the fluoro-alkyl of C1-3 or the fluoroalkyl of C1-4; R4 is a hydrogen, cyano group, the alkyl of C1-3; the alkyl-carbonyl of C1-3; alkoxyl group-carbonyl of C1-3, the alkyl sulphonyl of C1-3, alkyl-carbonyl of the alkoxy-C 1-2 of C1-2; phenyloxycarbonyl that can be replaced by nitro or the pyridyl carbonyl that can be replaced by chlorine; n is 1 or 2, and when n was 2, two R1 can be identical or different; and m is 1 or 2; and when m was 2, two R3 can be identical or different, compound.
The 1-phenyl-5-anilinotetrazole compounds of particularly preferred formula (I) is that wherein R1 is a hydrogen, fluorine, chlorine, bromine; cyano group, nitro, methyl, trifluoromethyl; trifluoromethoxy or trifluoromethyl sulfenyl, R2 are cyano group, nitro, trifluoromethyl; methylsulfonyl, ethylsulfonyl, trifyl, methoxycarbonyl; ethoxy carbonyl, aminocarboxyl or amino thiocarbonyl, R3 are fluorine; chlorine, bromine, trifluoromethyl or trifluoromethoxy; R4 is a hydrogen, cyano group, methyl; the methyl carbonyl, methoxycarbonyl, ethoxy carbonyl; methylsulfonyl, methoxymethyl carbonyl, phenyloxycarbonyl; 4-nitrophenoxy carbonyl or 2,6-two chloro-4-pyridyl carbonyls, n is 1 or 2; and when n was 2, two R1 can be identical or different, and m is 1 or 2; and when m was 2, two R3 can be identical or different, compound.
Can should be mentioned that the concrete example of the 1-phenyl of formula of the present invention (I)-5-anilino tetrazolium is the compound shown in the table of putting down in writing later 1.
In above-mentioned method (a), for example, if 5-chloro-1-phenyltetrazole and 4-amino-3-trifluoromethyl benzonitrile are used as reaction raw materials, reaction process can be used following The Representation Equation so:
In above-mentioned method (b), for example, if N '-(4-fluorophenyl)-N-(4-cyano group-2,5-difluorophenyl)-N-methyl-chloro carbonamidine and sodiumazide are used as reaction raw materials, reaction process can be used following The Representation Equation so:
In above-mentioned method (c), for example, if 1-(4-trifluoromethyl)-5-(2-chloro-4-trifluoromethyl-N-methoxycarbonyl-anilino) tetrazolium hydrolysis, reaction process can be used following The Representation Equation so:
In above-mentioned method (d), for example, if 1-(4-trifluoromethyl)-5-(4-cyano group-2,5-difluoroaniline base) tetrazolium and methylsulfonyl chloride are used as reaction raw materials, reaction process can be used following The Representation Equation so:
In above-mentioned method (e), for example, if 1-(4-Trifluoromethoxyphen-l)-5-(4-cyano group-2,5-difluoroaniline base) tetrazolium and diacetyl oxide are used as reaction raw materials, reaction process can be used following The Representation Equation so:
In method (a), the reaction raw materials of formula (II) is meant based on above-mentioned R1, the compound of the definition of n and X, and preferred substituted is based on the definition of above-mentioned preferred R1 and n, and X preferably represents chlorine and bromine.
The compound that is used as the formula (II) of reaction raw materials comprises: 5-chloro-1-phenyltetrazole; 5-chloro-1-(4-fluorophenyl) tetrazolium; 5-chloro-1-(4-chloro-phenyl-) tetrazolium; 5-chloro-1-(4-bromophenyl) tetrazolium; 5-chloro-1-(4-trifluoromethyl) tetrazolium; 5-chloro-1-(4-Trifluoromethoxyphen-l) tetrazolium, 5-chloro-1-(3-chloro-4-trifluoromethyl) tetrazolium, 5-methylsulfonyl-1-(3-fluorophenyl) tetrazolium etc.
Compound of formula (II) and preparation method thereof is at JP56-86175, and is on the books among DE-A-1251327 and the GB-A-1128025, and perhaps this compound can be used with the similar methods described in these reference synthetic.
In method of the present invention (a), the reaction raw materials of formula (III) is meant based on above-mentioned R1, the compound of the definition of R2 and m, and preferred substituted is based on above-mentioned preferred R1, the definition of R2 and m.
The compound that is used as the formula (III) of reaction raw materials is well-known in organic chemistry filed; the example comprises; for example; 4-amino-3-trifluoromethyl-benzonitrile; 4-amino-2,5-two fluoro-benzonitriles, 2-chloro-4-trifluoromethyl-aniline; 2-chloro-4-trifluoromethyl sulfonyl aniline, 2-chloro-4-methylsulfonyl aniline etc.
In method of the present invention (b), the reaction raw materials of formula (IV) is meant based on above-mentioned R1, R2, R3, m, the compound of the definition of n and R5, preferred substituted is based on above-mentioned preferred R1, R2, R3, the definition of m and n, and R5 preferably represents the alkyl of C1-3 or the alkoxy carbonyl of C1-3.
In above-mentioned method (b), example as the compound of the formula (IV) of reaction raw materials comprises: N '-(4-fluoro phenyl)-N-(4-cyano group-2, the 5-difluorophenyl)-the N-methyl chloride is for carbonamidine, N '-(4-trifluoromethyl)-N-(4-cyano group-2, the 5-difluorophenyl)-and the N-methyl chloride is for carbonamidine, and N '-(4-trifluoromethyl)-N-(2-chloro-4-trifluoromethyl)-N-methyl chloride is for carbonamidine etc.
The compound of formula (IV) can be used for example Journal of Organic Chemistry, and (1977), 42 (23), the method production described in the 3709-3713 etc. also can be used, and for example, following method is synthetic.
Make the compound of formula (VII)
Wherein the definition of R1 and n as above, with the compound of formula (VIII)
R2 wherein, R3, the definition of m and R5 as above, a kind of thinner with, if suitable, in the presence of a kind of suitable acid binding agent, react.
The compound of the compound of formula (VII) and formula (VIII) is well-known in organic chemistry filed.
In method of the present invention (c), the reaction raw materials of formula (Ib) is meant based on above-mentioned R1, R2, R3, R6, the compound of the definition of m and n, preferred substituted is based on above-mentioned preferred R1, R2, R3, the definition of m and n, and R6 preferably represents the alkyl of C1-3, phenyl or 4-nitrophenyl.
The compound that is used as the formula (Ib) of reaction raw materials of the present invention can be synthetic with above-mentioned method (b), its concrete example comprises: 1-(4-fluoro phenyl)-5-(2-chloro-4-trifluoromethyl-N-methoxycarbonyl anilino) tetrazolium, 1-(4-trifluoromethyl)-5-(2-chloro-4-trifluoromethyl-N-methoxycarbonyl anilino) tetrazolium, 1-(4-Trifluoromethoxyphen-l)-5-(2-chloro-4-trifluoromethyl-N-methoxycarbonyl anilino) tetrazolium etc.
In method of the present invention (d) with (e), the reaction raw materials of formula (Ia) is meant based on above-mentioned R1, R2, and R3, the compound of the definition of m and n, preferred substituted is based on above-mentioned preferred definition
Can be with above-mentioned method (a) or (c) synthesize as the compound of the formula (Ia) of reaction raw materials of the present invention.
The concrete example of the compound of formula (Ia) comprising: 1-(4-trifluoromethyl)-5-(4-cyano group-2,5-difluoromethyl anilino) tetrazolium, 1-(4-Trifluoromethoxyphen-l)-5-(4-cyano group-2,5-difluoromethyl anilino) tetrazolium etc.
In method of the present invention (d); the reaction raw materials of formula V is meant the compound based on the definition of above-mentioned R7 and Y; R7 preferably represents cyano group; the alkyl-carbonyl of C1-3; alkoxyl group-carbonyl of C1-3; the alkyl sulphonyl of C1-3, phenyloxycarbonyl that can be replaced by nitro or the pyridyl carbonyl that can be replaced by chlorine, Y preferably represents chlorine or bromine.
The compound that is used as the formula V of reaction raw materials is well-known in organic chemistry filed, and its example comprises Acetyl Chloride 98Min., propionyl chloride, methoxyacetyl chloride, methyl chlorocarbonate, chloro ethyl formate, cyanogen bromide, methylsulfonyl chloride etc.
In method of the present invention (e), the reaction raw materials of formula (VI) is meant the compound based on the definition of above-mentioned R8, preferably represents the alkyl of the alkoxy-C 1-2 of the alkyl of C1-3 or C1-2.
The compound that is used as the formula (VI) of reaction raw materials is well-known in organic chemistry filed, and its example comprises diacetyl oxide.
The reaction of aforesaid method (a) can be carried out in a kind of suitable diluent.The example of suitable diluent is an aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon (they can be chlorinated) is pentane, hexane, hexanaphthene, sherwood oil, V.M.. naphtha, benzene,toluene,xylene, methylene dichloride, chloroform, tetracol phenixin, 1 for example, 2-methylene dichloride, chlorinated benzene and dichlorobenzene; Ethers is ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, dioxy oxane, glycol dimethyl ether (DME), tetrahydrofuran (THF) (THF) and diethylene glycol dimethyl ether (DGM) for example; Ketone is acetone, methylethylketone (MEK), methyl isopropyl Ketone and methyl iso-butyl ketone (MIBK) (MIBK) for example; Nitrile is acetonitrile, propionitrile and vinyl cyanide for example; The ester class is ethyl acetate and pentyl acetate for example; The carboxylic acyloxy amine is dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), N-Methyl pyrrolidone, 1 for example, 3-dimethyl-2-imidazolidone and hexamethylphosphoric acid triamide (HMPA); Sulfone and sulfoxide class be dimethyl sulfoxide (DMSO) (DMSO) and tetramethylene sulfone for example; Deng.
The reaction of method (a) can be carried out in the presence of a kind of acid binding agent.The example of suitable acid binding agent is a mineral alkali, for example the oxyhydroxide of basic metal or alkaline-earth metal, carbonate and supercarbonate and alkoxide such as sodium bicarbonate, saleratus, yellow soda ash, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium tert-butoxide and potassium tert.-butoxide; Inorganic base metal amides, for example Lithamide, sodium amide and potassium amide; Organic bases, for example alcoholate, tertiary amine, dialkyl amido aniline and pyridine such as triethylamine, 1,1,4,4-Tetramethyl Ethylene Diamine (TMEDA), N, accelerine, N, N-Diethyl Aniline, pyridine, 4-Dimethylamino pyridine (DMAP), 1,4-diazabicyclo [2,2,2] octane (DABCO) and 1,8-diazabicyclo [5,4,0] undecane-7-alkene (DBU); Organolithium compound, for example lithium methide, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, phenyl lithium, lithium dimethylcuprate, lithium diisopropylamine, cyclohexyl sec.-propyl Lithamide, dicyclohexyl Lithamide, n-Butyl Lithium-DABCO, n-Butyl Lithium-DBO and n-Butyl Lithium-TMEDA.
The reaction of method (a) can be carried out under the temperature of quite wide scope, but generally may adopt about-20-100 ℃ temperature of reaction, preferably approximately-5-80 ℃, and preferred reaction should carry out under normal pressure, carries out but also can be chosen under pressurization or the decompression.
Be implementation method (a) that for example the compound of 1 mole formula (II) can, react, and obtain needed compound for example in the tetrahydrofuran (THF) at a kind of solvent with the compound of the formula (III) of 1-1.1 molar weight in the presence of a kind of acid binding agent.
The reaction of above-mentioned method (b) can be carried out at diluent free or in a kind of suitable diluent.The example of suitable diluent is an aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon (they can be chlorinated) is pentane, hexane, hexanaphthene, sherwood oil, V.M.. naphtha, benzene,toluene,xylene, methylene dichloride, chloroform, tetracol phenixin, 1 for example, 2-methylene dichloride, chlorinated benzene and dichlorobenzene; Ethers is ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, Er Yang oxane, glycol dimethyl ether (DME), tetrahydrofuran (THF) (THF) and diethylene glycol dimethyl ether (DGM) for example; Ketone is acetone, methylethylketone (MEK), methyl isopropyl Ketone and methyl iso-butyl ketone (MIBK) (MIBK) for example; Nitrile is acetonitrile, propionitrile and vinyl cyanide for example; The ester class is ethyl acetate and pentyl acetate for example; The carboxylic acyloxy amine is dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), N-Methyl pyrrolidone, 1 for example, 3-dimethyl-2-imidazolone and hexamethylphosphoric acid triamide (HMPA); Sulfone and sulfoxide class be dimethyl sulfoxide (DMSO) (DMSO) and tetramethylene sulfone etc. for example.
The reaction of method (b) can be carried out under the temperature of quite wide scope, but generally may adopt about 0-120 ℃ temperature of reaction, preferably approximately 20-100 ℃, and preferred reaction should carry out under normal pressure, carries out but also can be chosen under pressurization or the decompression.
Be implementation method (b) that for example the compound of 1 mole formula (IV) can for example react in the mixed solvent of acetone and water at a kind of solvent with the sodiumazide of 1-1.5 molar weight, and obtains needed compound.
The reaction of above-mentioned method (c) can be carried out in a kind of suitable diluent.The example of preferred suitable diluent is water or alcohols for example methyl alcohol, ethanol, Virahol, butanols and ethylene glycol, but also can be with other thinner, its example is an aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon (they can be chlorinated) is pentane, hexane, hexanaphthene, sherwood oil, V.M.. naphtha, benzene,toluene,xylene, methylene dichloride, chloroform, tetracol phenixin, 1 for example, 2-methylene dichloride, chlorinated benzene and dichlorobenzene; Ethers is ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, Er Yang oxane, glycol dimethyl ether (DME), tetrahydrofuran (THF) (THF) and diethylene glycol dimethyl ether (DGM) for example; Ketone is acetone, methylethylketone (MEK), methyl isopropyl Ketone and methyl iso-butyl ketone (MIBK) (MIBK) for example; Nitrile is acetonitrile, propionitrile and vinyl cyanide for example; The ester class is ethyl acetate and pentyl acetate for example; The carboxylic acyloxy amine is dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), N-Methyl pyrrolidone, 1 for example, 3-dimethyl-2-imidazolone and hexamethylphosphoric acid triamide (HMPA); Sulfone and sulfoxide class be dimethyl sulfoxide (DMSO) (DMSO) and tetramethylene sulfone etc. for example.
The reaction of method (c) can preferably be carried out in the presence of a kind of mineral alkali.The example of suitable mineral alkali is oxyhydroxide, carbonate and supercarbonate such as sodium bicarbonate, saleratus, yellow soda ash, salt of wormwood, lithium hydroxide, sodium hydroxide, potassium hydroxide and the calcium hydroxide of basic metal or alkaline-earth metal.
The reaction of method (c) can be carried out under the temperature of quite wide scope, but generally may adopt about 0-150 ℃ temperature of reaction, preferably approximately 20-100 ℃, and preferred reaction should carry out under normal pressure, carries out but also can be chosen under pressurization or the decompression.
Be implementation method (c) that for example the compound of 1 mole formula (Ib) can for example react in the methyl alcohol at a kind of solvent with a kind of alkali of 1-3 molar weight, and obtains needed compound.
The reaction of aforesaid method (d) can be carried out in a kind of suitable diluent.The example of suitable diluent is an aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon (they can be chlorinated) is pentane, hexane, hexanaphthene, sherwood oil, V.M.. naphtha, benzene,toluene,xylene, methylene dichloride, chloroform, tetracol phenixin, 1 for example, 2-methylene dichloride, chlorinated benzene and dichlorobenzene; Ethers is ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, Er Yang oxane, glycol dimethyl ether (DME), tetrahydrofuran (THF) (THF) and diethylene glycol dimethyl ether (DGM) for example; Ketone is acetone, methylethylketone (MEK), methyl isopropyl Ketone and methyl iso-butyl ketone (MIBK) (MIBK) for example; Nitrile is acetonitrile, propionitrile and vinyl cyanide for example; The ester class is ethyl acetate and pentyl acetate for example; The carboxylic acyloxy amine is dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), N-Methyl pyrrolidone, 1 for example, 3-dimethyl-2-imidazolone and hexamethylphosphoric acid triamide (HMPA); Sulfone and sulfoxide class be dimethyl sulfoxide (DMSO) (DMSO) and tetramethylene sulfone etc. for example.
The reaction of method (d) can be carried out in the presence of a kind of acid binding agent.The example of suitable acid binding agent is a mineral alkali, for example the oxyhydroxide of basic metal or alkaline-earth metal, carbonate and supercarbonate such as sodium bicarbonate, saleratus, yellow soda ash, salt of wormwood, lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; Metal hydride, for example lithium hydride, sodium hydride, potassium hydride KH and hydrolith; Organic bases, for example alcoholate, tertiary amine, dialkyl amido aniline and pyridine such as sodium tert-butoxide, potassium tert.-butoxide, triethylamine, 1,1,4,4-Tetramethyl Ethylene Diamine (TMEDA), N, accelerine, N, N-Diethyl Aniline, pyridine, 4-Dimethylamino pyridine (DMAP), 1,4-diazabicyclo [2,2,2] octane (DABCO) and 1,8-diazabicyclo [5,4,0] undecane-7-alkene (DBU); Organolithium compound, for example lithium methide, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, phenyl lithium, lithium dimethylcuprate, lithium diisopropylamine, cyclohexyl sec.-propyl Lithamide, dicyclohexyl Lithamide, n-Butyl Lithium-DABCO, n-Butyl Lithium-DBO and n-Butyl Lithium-TMEDA.
The reaction of method (d) can be carried out under the temperature of quite wide scope, but generally may adopt about 0-120 ℃ temperature of reaction, preferably approximately 10-100 ℃, and preferred reaction should carry out under normal pressure, carries out but also can be chosen under pressurization or the decompression.
Be implementation method (d) that for example the compound of 1 mole formula (Ia) can, react, and obtain needed compound for example in the tetrahydrofuran (THF) at a kind of solvent with the compound of the formula V of 1-1.5 molar weight in the presence of a kind of acid binding agent.
The reaction of aforesaid method (e) can be carried out at diluent free or in a kind of suitable diluent or solvent.The example of suitable diluent is an aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon (they can be chlorinated) is pentane, hexane, hexanaphthene, sherwood oil, V.M.. naphtha, benzene,toluene,xylene, methylene dichloride, chloroform, tetracol phenixin, 1 for example, 2-methylene dichloride, chlorinated benzene and dichlorobenzene; Ethers is ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, Er Yang oxane, glycol dimethyl ether (DME), tetrahydrofuran (THF) (THF) and diethylene glycol dimethyl ether (DGM) for example; Ketone is acetone, methylethylketone (MEK), methyl isopropyl Ketone and methyl iso-butyl ketone (MIBK) (MIBK) for example; Nitrile is acetonitrile, propionitrile and vinyl cyanide for example; Alcohols is methyl alcohol, ethanol, Virahol, butanols and ethylene glycol for example; The ester class is ethyl acetate and pentyl acetate for example; The carboxylic acyloxy amine is dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), N-Methyl pyrrolidone, 1 for example, 3-dimethyl-2-imidazolone and hexamethylphosphoric acid triamide (HMPA); Sulfone and sulfoxide class be dimethyl sulfoxide (DMSO) (DMSO) and tetramethylene sulfone etc. for example.
The reaction of method (e) can be carried out in the presence of a kind of acid catalyst.The example of suitable acid catalyst is mineral acid example hydrochloric acid, sulfuric acid, nitric acid, Hydrogen bromide, Sodium sulfhydrate; Organic acid is formic acid, acetate, trifluoroacetic acid, propionic acid, methylsulfonic acid, Phenylsulfonic acid, tosic acid for example; For example a kind of pyridine hydrochloride of organic amine salt hydrochlorate, triethylamine hydrochloride etc.
The reaction of method (e) can be carried out under the temperature of quite wide scope, but generally may adopt about 0-150 ℃ temperature of reaction, preferably approximately 20-120 ℃, and preferred reaction should carry out under normal pressure, carries out but also can be chosen under pressurization or the decompression.
Be implementation method (e) that the compound of for example excessive formula (VI) (also can be used as solvent simultaneously) can react with the compound of formula (Ia), and obtains needed compound in the presence of a kind of acid catalyst.
The 1-phenyl of formula of the present invention (I)-5-anilino tetrazolium has showed powerful microbiocidal activity, insecticidal activity and/or weeding activity, and the 1-phenyl of formula of the present invention (I)-5-anilino tetrazolium do not show phytotoxicity to the plant of cultivation, so they can be used as microbicide, sterilant and/or weedicide.
The 1-phenyl of formula of the present invention (I)-5-anilino tetrazolium has showed powerful microbiocidal activity, can be used to resist harmful microorganism in practice, and the 1-phenyl of formula (I)-5-anilino tetrazolium is suitable as plant protection product and uses.
Mycocide in the plant protection is used to kill knee Pseudomonas, oomycetes genus, Chytridium, joint Pseudomonas, arthroderma, Basidiomycotina and Dendrochium.
Sterilant in the plant protection is used to kill pseudomonas class, Rhizobiaceae, enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
Below said some that are included under the above-mentioned subject heading can cause mycosis and bacteriosis organism not as determinate example:
Xanthomonas, for example rice field Xanthomonas campestris; Rhodopseudomonas, for example angular leaf spot of cucumber pseudomonas syringae; Erwinia is for example separated the starch Erwinia; Pythium, for example ultimate corruption is mould; Swollen stalk mould genus, for example phytophthora infestan; False Peronospora, for example false downy mildew of Cuba; Plasmopara, for example grape is given birth to Plasmopara; Peronospora, for example rape pea downy mildew; White powdery mildew belongs to, for example happy powdery mildew; Monofilament shell Pseudomonas, for example Siberian cocklebur monofilament shell bacterium; Caulococcus, for example apple mildew bar coccus; Venturia, for example venturia inaequalis; The nuclear cavity Pseudomonas, bacterium, for example wheat class circle nuclear cavity bacteria; (conidium type: drechslera, synonym: Helminthosporium); Revolve the spore Pseudomonas, for example to revolve spore mould for standing grain; Uromyces, for example Kidney bean uromyce; Puccinia, for example Puccinia recondita; Tilletia, for example wheat net fungus tilletia; Ustilago, for example naked smut belongs to, the oat ustilago; The film lead fungi belongs to, and for example assistant is helped Mu Shi film lead fungi; Pyricularia belongs to, for example, and Pyricularia oryzae; Fusarium, for example machete sickle spore; Staphlosporonites, for example gray botrytis; Septoria, for example clever withered septoria musiva; The bead chamber belongs to, for example clever withered ball cavity bacteria; Cercospora, for example grey tail spore; Alternaria, for example black spot of cabbage chain lattice spore; False Cercosporalla, for example Pseudocercosporella herpotrichoides.
Because plant has good tolerance to the 1-phenyl-5-anilino tetrazolium that can resist the formula (I) under the plant illness concentration, can be to plant, the over-ground part of vegetative reproduction original seed and seed and soil is taked treatment measures.
The 1-phenyl of formula (I)-5-anilino tetrazolium is low to the toxicity of warm-blooded animal; can be used to tackle arthropod; particularly agriculture; forestry; the insect that runs in the protection of stored goods and material and the health field, they have the activity of killing general sensitivity and resistance species and all or some etap.
Above-mentioned insect comprises:
Etc. sufficient guiding principle, for example two comb beach louses tides worm, armadillidum vulgare and pillworm;
Diplopoda, for example little Monas;
Chilopoda, for example food fruit DIWUGONG and common house centipede;
Symphyla, for example immaculate common house centipede;
Collembola, for example sweet taste silverfish;
Collembola, for example spinosity springtail;
Orthoptera, oriental cockroach for example, America Lian, leucophaea maderae, Groton bug, tame Xi, mole cricket, migratory locusts, migratory locusts class, the negative locust of long volume and desert locust;
Dermaptera, for example European earwig;
Isoptera, for example Reticulitermes;
Anoplura, for example huge Phylloxera spp, goitre woolly aphid belong to, stop lice, blood lice and long volume lice and belong to;
Mallophaga, for example Trichodectes and Damalinea spp.;
Thysanoptera, for example greenhouse Hercinothrips spp and cotton thrips;
Heteroptera, for example brown scutteleerid, middle red stinkbug, beet are intended lace bug, bed bug, Rhodniusprolixus and Reduvius;
Homoptera, wild cabbage aleyrodid for example, whitefly in bt cotton, Trialeurodes vaporariorum Westwood, cotten aphid, brevicoryne brassicae, the latent knurl aphid of tea Fischer, Aphis, Doralis pomi, eriosoma lanigerum, mealy plum aphid, grain aphid, knurl volume Aphis, the hops wart closes, the volume aphid, the grain Rhopalosiphum spp, Empoasca spp belongs to, two leafhopper belong to, rice green leafhopper, brown apricot scale, sweet-scented osmanthus olive a red-spotted lizard, rice small brown rice planthopper, Nilaparvata lugen (brown planthopper), California red scale, Folium seu Cortex Nerii circle a red-spotted lizard, mealybug belongs to and the leaf lice belongs to;
Lepidopteran, pink bollworm for example, loose looper, winter geometrid moth, France half white thin moth, cherry ermine moth, small cabbage moth, tent caterpillar, brown-tail moth, Euproctis, cotton lyonetid, tangerine leaf lyonetid, cutworm, the real moth of cotton spot, genus heliothis, beet leaves moth, lopper worm, small noctuid tiltedly twists noctuid, and prodenia litura belongs to, cabbage looper, carpocapsa pononella, Pier, snout moth's larva belongs to, wild snout moth's larva, meal moth, galleria mellonella waxmoth, polypody leaf roll snout moth's larva, netted cigarette moth, spruce bunworm, grape codling moth (Clysia ambiguella), the green leaf roller of tea long paper moth and oak;
Coleoptera, furniture death watch beetle for example, lesser grain borer, bean weevil, house longhorn beetle, the purple flea beetle of alder, colorado potato bug, horseradish daikon leaf beetle, the chrysomelid genus of bar, rape blue flea beetle, mexican bean ladybird, latent food first, saw chest ostomatid, Anthonomus spp belongs to, Sitophilus, vine black ear beak resembles, banana root weevil, wild cabbage pod weevil, alfalfa weevil, khapra beetle belongs to, and khapra beetle belongs to, Anthrenus, attagenus piceus, the powder moth, pollen beetle, Ptinus, golden yellow ptinid, wheat ptinid, Tribolium, the bloom first, click beetle belongs to, wireworm, strontium cockchafer.June chafer and Costelytra zealandica;
Hymenoptera, sawfly for example, tenthredinidae, the field ant belongs to, MonomoriumMayr and Vespa;
Diptera, Aedes for example, Anopheles, Culex, fruit bat, fly belongs to, Fannia, calliphora erythrocephala, lucilia, Carysomyia, cuterbrid belongs to, Gasterophilus, Hippobosca, the chela fly belongs to, Oestrus, Hypoderma, Gadfly, Tannia spp, garden march fly, Sweden's wheat stem chloropid fly, the wheat fly belongs to, beet fly, Mediterranean fruitfly, dacus oleae and marsh daddy-longlegs.
The 1-phenyl of formulas more of the present invention (I)-5-anilino tetrazolium can be used as the medicament of defoliating agent, siccative, destruction broad leaved plant, is particularly useful as herbicide.
Generalized weeds are interpreted as referring to that all are grown in the plant in the place that should not grow.It all can weedicide still be that the effect of selective herbicide mainly depends on usage quantity that material of the present invention plays a part.
For example, active compound of the present invention can be used for following plants:
Broadleaf weed belongs to: sinapis, separate row Vegetable spp, Bedstraw, Stellaria, Matricaria, chamomile belongs to, ox achyranthes chrysanthemum spp, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, japanese bearbind belongs to, sweet potato belongs to, Polygonum, Daubentonia, Ambrosia, Cirsium, bristlethistle, sonchus L, Solanum Han Lepidium, Leaf of Chinese Deciduous Cypress belongs to, ball is combed mould genus, lamium, Veronica, fiber crops belong to fennel, thorn acid belongs to, graceful snake Polyalthia, the Jin Lepidium, the weasel hemp nettle belongs to, papaver and bachelor's-button.
Dicotyledonous cultivated plant belongs to: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, linum, sweet potato belong to, vetch, Nicotiana, tomato genus, Arachis, Btassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weed belongs to: Echinochloa, abdominal cavity Turbatrix, Panicum, knotgrass, ladder forage spp, annual bluegrass genus, festuca, genus, Brachiaria, lolium temulentum genus, Brome, Avena, Cyperus, jowar genus, Agropyron, Cynodon, Monochoria, genus fimbristylis, arrowhead genus, Eleocharis, Fischer grass genus, Paspalum, ischaemum, cusp Pittosporum, talon eria, creeping bentgrass belong to, amur foxtail belongs to and Apeva.
The unifacial leaf cultivated plant belongs to: Oryza, Zea, Triticum, Hordeum, Avena, Secale, jowar genus, Panicum, saccharum, Ananas, Asparagus and allium.
Yet the 1-phenyl of formula of the present invention (I)-5-anilino tetrazolo is not limited to be used for these platymisciums, can also spread in the same way to be used for other plant.
According to the concentration of using, the 1-phenyl of formula (I)-5-anilino tetrazolium is for example removed the weeds on the industrial belt that has or do not have trees, railway, path and square applicable to the totipotency weeding.Equally, the 1-phenyl of formula (I)-5-anilino tetrazolium also can be used for removing for example weeds in forest, ornamental trees, orchard, vineyard, citrus clump, walnut garden, banana plantation, cafetal, tea plantation, rubber plantation, oil palm plantation, cocoa plantation, mushy fruit plantation and the hops planting site of perennial cultivation plant, also is used for optionally removing the weeds of annual cultivated plant.
The 1-phenyl of formula (I)-5-anilino tetrazolium can change prescription commonly used into, for example solution, emulsion, wettable powder, suspension, powder, foam, paste, granula, tablet, smoke substance, embedding the natural and synthetic materials of active compound, with the thin capsule of polymkeric substance parcel, seed with coated composition and the formulation example of using combustion equipment as stifling tablet, fumigation tank and stifling coil pipe and cold mist of ULV and hot mist preparation.
These preparations can be produced with currently known methods, for example the 1-phenyl-5-anilino tetrazolium by wushu (I) and developping agent are that the gas of liquid or liquefaction or solid diluent or carrier mix, and can also use tensio-active agent is emulsifying agent and/or dispersion agent and/or whipping agent.For example make when using water as developping agent, organic solvent also can be used as secondary solvent.
As liquid solvent, diluent or carrier, be mainly suitable aromatic hydrocarbon (for example dimethylbenzene, toluene or alkylnaphthalene), chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbon (for example chlorobenzene, vinylchlorid or methylene dichloride), aliphatic hydrocarbon (for example hexanaphthene or paraffin such as mineral oil composition), alcohols (for example butanols or ethylene glycol and ethers thereof and ester class), ketone (for example acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone), or intensive polar solvent (for example dimethyl formamide and dimethyl sulfoxide (DMSO) and water).
The diluent for gases of liquefaction or carrier are meant and are the liquid of gas, for example aerosol propellant such as halohydrocarbon and butane, propane, nitrogen and carbonic acid gas under normal temperature and normal pressures.
Spendable solid carrier is the ground natural mineral, (for example kaolin, clay, talcum, chalk, quartz, U.S.'s atlapulgite, polynite or diatomite) and ground synthetic mineral (for example high dispersive type silica gel, aluminium and silicate).Spendable solid particulate carrier is for grinding and fractionated natural crystal (for example calcite, marble, float stone, sepiolite and rhombspar) and synthetic is inorganic and organic particle and organic materials particle (for example sawdust, Exocarpium cocois (Cocos nucifera L), mealie and tobacco rods).
Spendable emulsifying agent and/or whipping agent are non-ionic type and anionic emulsifier for example polyoxyethylene carboxylate, polyoxyethylene-fatty alcohol-ether such as alkylaryl polyglycol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate and white protein hydrolysate.
The example of dispersion agent comprises: xylogen sulfite waste lye and methylcellulose gum.
The example of spendable tackiness agent is carboxymethyl cellulose and powdery, granular or the glue lactous is natural and synthetic polymer for example Sudan Gum-arabic, polyvinyl alcohol and polyvinyl acetate in the preparation.
The example of spendable dyestuff is inorganic dyestuff (for example ferric oxide, titanium oxide and Prussian orchid) and organic dye (for example alizarine dyestuff, azoic dyestuff or metal phthalocyanine dyestuff) and trace nutrient substance (for example salt of iron, manganese, boron, copper, cobalt, molybdenum and zinc).
Preparation contains the active compound of 0.1-95% weight percent generally, preferably contains the active compound of 0.5-90% weight percent.
The 1-phenyl of formula of the present invention (I)-5-anilino tetrazolium can be present in the use formulation that its commercial available prescription neutralization makes with these prescriptions with other active compound blended mode, and the example of other active compound is sterilant, attractive substance, chemosterilant, miticide, nematocides, mycocide, growth regulatory substance or weedicide.The example of mixable sterilant comprises organophosphate, carbamate, carboxylicesters, hydrochloric ether and by the insect killing substance of microorganisms producing.
When the 1-of wushu (I) phenyl-when 5-anilino tetrazolium mixes mutually with weedicide, can exemplify following known weedicide:
Be used for controlling 4-amino-6-(1, the 1-dimethyl ethyl)-3-ethyl sulfenyl-1,2 of cereal raise crop weeds, 4-triazine-5 (4H)-ketone; 1-amino-6-ethyl sulfenyl-3-(2, the 2-dimethyl propyl)-1,3,5-triazines-2,4 (1H, 3H)-diketone, N-(2-[4-morpholinodithio base)-N, N '-dimethyl urea etc.;
Be used for controlling 4-amino-3-methyl-6-phenyl-1,2 of the weeds of cane planting, 4-triazine-5 (4H)-ketone etc.;
Be used for controlling the weeds of soybean planting 4-amino-6-(1,1-dimethyl ethyl-3-methyl sulfenyl-1,2,4-triazine-5 (4H)-ketone etc.
The 1-phenyl of formula of the present invention (I)-5-anilino tetrazolium can also with have synergistic medicament and mix use, having synergistic medicament is the active compound that can promote compound, and added have synergistic medicament itself and unnecessaryly have an activity.
The 1-phenyl of formula of the present invention (the I)-content of 5-anilino tetrazolium in its commercial formulation can change in very wide scope, for example is in the weight percentage ranges of 0.0000001-100%, preferably between 0.00001% and 1% weight percent.
Can be by the general mode that is suitable for used formulation, 1-phenyl-5-anilino tetrazolium with formula of the present invention (I) tackles insect, aspect killing the health product insect and storing grain pest, the 1-phenyl of formula of the present invention (I)-5-anilino tetrazolium is to the excellent stability of the alkali on the material of lime treatment, and the residual action on wooden and soil is also fabulous.
When the 1-of formula of the present invention (I) phenyl-5-anilino tetrazolium is used as weedicide, can use in any stage before plant emerges and after emerging, also can mix soil prior to seeding.
The usage quantity of the 1-phenyl of formula (I)-5-anilino tetrazolium can change in sizable scope, and mainly change according to the needed character that works, but when the 1-of formula (I) phenyl-5-anilino tetrazolium is used as weedicide, the usage quantity of the 1-phenyl of formula (I)-5-anilino tetrazolium for example can be about 0.001kg/ha-5kg/ha, preferably approximately 0.1kg/ha-2kg/ha.
Then, the following examples just illustrate the present invention, and they should not be counted as limiting the scope of the invention.Synthetic embodiment 1
At room temperature 4-amino-3-trifluoromethyl benzonitrile (0.9g) is joined sodium hydride (0.5g; 60% oil solution) in the tetrahydrofuran solution (25ml), mixture at room temperature stirs about 10 minutes till no longer producing hydrogen, toward wherein adding 5-chloro-1-phenyltetrazole (0.9g), mixture is stirred 2 hours then.Reaction mixture is poured in the 100ml frozen water, the pressure reducing and steaming organic layer, join gac in the water layer and filter water layer, with concentrated hydrochloric acid pH value of filtrate is adjusted to 2-3 then, filter crystallization and water and normal hexane washing that collecting precipitation goes out, obtain 1-phenyl-5-(4-cyano group-2-trifluoromethylbenzene amido)-tetrazolium (1.5g).
Fusing point: 154-156 ℃.Synthetic embodiment 2
4-methylamino-2,5-difluoro benzonitrile joins sodium hydride (0.4g; 60% oil solution) in the tetrahydrofuran solution (25ml), continues down to stir about 10 minutes till no longer producing hydrogen, toward wherein adding dichloride-4-fluorophenyl isocyanic ester, at room temperature continue to stir 3 hours then at 0-5 ℃.In reaction soln, add gac, filtering solution then, pressure reducing and steaming filtrate, residue is dissolved in acetone (30ml), to the aqueous solution that wherein adds sodiumazide (0.6g) (6ml), mixture heating up is refluxed 3 hours.After reaction was finished, to wherein adding entry (80ml), the pressure reducing and steaming organic layer filtered crystallization and water and normal hexane washing that collecting precipitation goes out then, obtains 1-(4-fluorophenyl)-5-(4-cyano group-2,5-two fluoro-methylphenylamine bases)-tetrazolium (2.3g).
Fusing point: 162.5 ℃.Synthetic embodiment 3
Join sodium hydride (0.4g at a 0-5 ℃ of following N-(2-chloro-4-trifluoromethyl) Urethylane (2.0g); 60% oil solution) in the tetrahydrofuran solution (25ml), continues down to stir about 10 minutes till no longer producing hydrogen, toward wherein adding dichloride-4-trifluoromethylbenzene based isocyanate (1.9g), at room temperature continue to stir 3 hours then at 0-5 ℃.In reaction soln, add gac, filtering solution then, pressure reducing and steaming filtrate, residue is dissolved in acetone (30ml), to the aqueous solution that wherein adds sodiumazide (0.65g) (7ml), mixture heating up is refluxed 3 hours.After reaction is finished, to wherein adding entry (80ml) and using dichloromethane extraction.Behind anhydrous magnesium sulfate drying, the pressure reducing and steaming methylene dichloride, the gained residue is dissolved in ethanol (15ml), then to wherein adding hexane (30ml), the crystallization that the filtration collecting precipitation goes out is also used ethanol: the mixing solutions washing of normal hexane (1: 2) obtains 1-(4-trifluoromethyl)-5-(2-chloro-4-trifluoromethyl-N-methoxycarbonyl anilino)-tetrazolium (1.8g).
Fusing point: 111-112 ℃.Synthetic embodiment 4
At room temperature stir 1-(4-trifluoromethyl)-5-(2-chloro-4-trifluoromethyl-N-methoxycarbonyl-anilino) tetrazolium (1.2g), the mixing solutions of methyl alcohol (15ml) and potassium hydroxide (0.4g) 3 hours, after reaction is finished, to wherein adding hydrochloric acid (5%; 80ml), the crystallization that the filtration collecting precipitation goes out also washes with water, obtains 1-(4-trifluoromethyl)-5-(2-chloro-4-trifluoromethylbenzene amido)-tetrazolium (1.0g).
Fusing point: 115.5-116.5 ℃.Synthetic embodiment 5
At room temperature 1-(4-trifluoromethyl)-5-(4-cyano group-2,5-difluorophenyl amino) tetrazolium (1.5g) is joined sodium hydride (0.2g; 60% oil solution) in the tetrahydrofuran solution (25ml), at room temperature continuing to stir about 5 minutes till no longer producing hydrogen, toward wherein adding methylsulfonyl chloride (0.5g), at room temperature continuing to stir 24 hours then.After reaction was finished, the pressure reducing and steaming solvent was also using twice of ethyl acetate extraction in the water adding residue.Organic layer is behind anhydrous magnesium sulfate drying; the pressure reducing and steaming solvent; the gained residue is dissolved in the ethanol of heat; the crystallization that the cooled and filtered collecting precipitation goes out is also successively washed with cold ethanol and normal hexane; obtain 1-(4-trifluoromethyl)-5-(4-cyano group-2,5-two fluoro-N-methylsulfonyl-anilinos)-tetrazolium (1g).
Fusing point: 129.5-130.5 ℃.Synthetic embodiment 6
Stir diacetyl oxide (15ml) down at 70-80 ℃; 1-(4-Trifluoromethoxyphen-l)-5-(4-cyano group-2; 5-difluoroaniline base) tetrazolium (1.5g); and the mixing solutions of the vitriol oil (1ml) 1 hour; after reaction is finished, behind the unreacted diacetyl oxide of pressure reducing and steaming, residue water and normal hexane washing; obtain 1-(4-Trifluoromethoxyphen-l)-5-(4-cyano group-2,5-two fluoro-N-ethanoyl-anilinos) tetrazolium (1.55g).
Fusing point: 108-110.5 ℃.
Following table 1 has been listed the compound that obtains according among compound that obtains with the described same method of synthetic embodiment 1-6 and the above-mentioned synthetic embodiment 1-6.
Table 1
Fusing point (℃) or compound sequence number R
1N R
2R
3M R
4Refractive index (n
20 D)
1 H 4-CN 2-CF
3 H 154-156
2 4-F 4-CN 2，5-F
2 CH
3 162.5
3 4-CF
3 4-CF
3 2-Cl COOCH
3 111-112
4 4-CF
3 4-CF
3 2-Cl H 115.5-116.5
5 4-CF
3 4-CN 2，5-F
2 SO
2CH
3 129.5-130.5
6 4-OCF
3 4-CN 2，5-F
2 COCH
3 108-110.5
7 H 4-CN 2，5-F
2 H 171-172.5
8 2-Cl 4-CN 2，5-F
2 H 165-167.5
9 4-OCF
3 4-CN 2，5-F
2 H 165-167.5
10 3-CN 4-CN 2，5-F
2 H 196-197
11 3-F 4-CN 2，5-F
2 H 172-175.5
12 4-F 4-CN 2，5-F
2 H 165-167
13 2-F 4-CN 2，5-F
2 H 174-177
14 3-CF
3 4-CN 2，5-F
2 H 195.5-199.5
15 3-Cl-4-OCF
3 4-CN 2，5-F
2 H 136-136.5
16 4-CF
3 4-CN 2，5-F
2 H 171-172
17 3-CF
3-4-Cl?4-CN 2，5-F
2 H 210-211
18 2-CF
3 4-CN 2，5-F
2 H 184.5-186.5
19 2，4-Cl
2 4-CN 2，5-F
2 H 182-186.5
20 4-Cl 4-CN 2，5-F
2 H 185-188
Table 1 (continuing)
Fusing point (℃) or compound sequence number R
1N R
2R
3M R
4Refractive index (n
20 D) 21 3,4-Cl
24-CN 2,5-F
2H 216-217.5 (decomposed) 22 2,3-Cl
24-CN 2,5-F
2H 141-144.523 4-Br 4-CN 2,5-F
2H 185-19024 H 4-CN 2,5-F
2SO
2CH
3127.5-13025 H 4-CN 2,5-F
2 
159-16226 4-OCF
34-CN 2,5-F
2SO
2CH
393-94.527 4-CF
34-CN 2,5-F
2COCH
3110-11128 4-OCF
34-CN 2,5-F
2 129.5-130.529 4-F 4-CN 2,5-F
2COCH
3117.5-121.530 4-OCF
34-CN 2-CF
3H 137-13831 4-F 4-CN 2-CF
3H 149.5-15132 3-CF
34-CN 2-CF
3H 176.5-178.533 3-Cl-4-CF
34-CN 2-CF
3H 170-17134 4-CF
34-CN 2-CF
3H 152-15235 3-CF
3-4-Cl 4-CN 2-CF
3H 200-204.536 4-Cl 4-CN 2-CF
3H 159.5-162.537 3,4-Cl
24-CN 2-CF
3H 175-176.538 2,3-Cl
24-CN 2-CF
3H 142-14739 4-Br 4-CN 2-CF
3H 168-171.540 2,6-Cl
24-CN 2-CF
3H 1.4720
Table 1 (continuing)
Fusing point (℃) or compound sequence number R
1N R
2R
3M R
4Refractive index (n
20 D) 41 3-Cl-4-CF
34-CN 2-CF
3H 172-174 (decomposition) 42 3-Cl 4-CN 2-CF
3H-43 3-F 4-CN 2-CF
3H 149-15144 H 4-CN 2,5-F
2COOCH
3113.5-11545 3-CN 4-CF
32,6-Cl
2H 173-17746 4-F 4-CF
32,6-Cl
2H 167-16947 4-OCF
34-CF
32,6-Cl
2H 128-13248 4-OCF
34-CN 2,5-F
2COOC
2H
587.5-88.549 H 4-CN 2,5-F
2COCH
2OCH
385-88.550 4-OCF
34-CF
32-Cl-6-Br H 121-12451 H 4-CN 2,5-F
2CH
3132-132.552 3-CF
34-CF
32,6-Cl
2H 187-188 (decomposition) 53 4-NO
24-CN 2,5-F
2H 178-180.554 3-Cl-4-OCF
34-CF
32,6-Cl
2H 148-15255 4-CF
34-CF
32,6-Cl
2H 139.5-14056 3-CF
3-4-Cl 4-CF
32,6-Cl
2H 132-13657 4-OCF
32-CN 3-F H 153-155.558 4-CF
32-CN 3-F H 145.5-146.559 4-OCF
32-CN 5-F H 138.5-140.560 4-OCF
34-CN 2,5-F
2 143.5-146.561 4-OCF
34-CN 2,5-F
2 129.5-131.5
Table 1 (continuing)
Fusing point (℃) or compound sequence number R
1N R
2R
3M R
4Refractive index (n
20 D) 62 4-CF
32-CN 5-F H 217-21863 4-CF
32-CN 5-Cl H 141-14264 4-CF
34-CN 2,6-Cl
2H 191.5-193
(decomposition) 65 4-CF
34-CF
32-Cl-6-Br H 192-19366 4-CF
34-CN 2,5-F
2COOCH
3148.5-149.567 3-CF
3-4-Cl 4-CF
32-Cl-6-Br H 162-16368 4-OCF
34-CN 2,5-F
2CH
3111.5-112.569 4-OCF
34-CN 2-F H 201.5-202.5 (decomposition) 70 4-CF
34-CN 2-F H 119-12471 4-CF
32-CN 3-F H 215-21672 4-CF
34-CN 2-Cl H 209-209.573 4-OCF
34-CN 2-Cl H 183-18674 4-Cl 4-CN 2,5-F
2CH
3148-149.575 4-OCF
34-CN 2,5-F
2CN 155-15776 4-Cl 4-CF
32,6-Cl
2H 156-16077 3,4-Cl
24-CN 2,5-F
2CH
3150.5-15278 2,3-Cl
24-CN 2,5-F
2CH
3148.5-149.579 3,4-Cl
24-CF
32,6-Cl
2H 151-15580 3,4-Cl
24-CN 2-Cl H 230.5-232.5 (decomposition) 81 3-Cl-4-CH
34-CN 2-CF
3H 148.5-15282 4-CF
34-CN 3-Cl H 207-210.5 (decomposition) 83 3-Cl-4-OCF
34-CN 3-Cl H 199-201.5 (decomposition)
Table 1 (continuing)
Fusing point (℃) or compound sequence number R
1N R
2R
3M R
4Refractive index (n
20 D) 84 4-Br 4-CN 2,5-F
2CH
3166-166.585 3-Cl-4-CF
34-CN 2-Cl H 204.5-207.5 (decomposition) 86 2-CH
3-4-Cl 4-CN 2-CF
3H 153-155.587 2-Cl 4-CN 3-Cl H 219-223 (decomposition) 88 4-CH
34-CN 2-CF
3H 109.5-11289 3-CH
3-4-Br 4-CN 2-CF
3H 101.5-10490 2-Cl-5-CF
34-CN 2-CF
3H91 3-Cl-4-CF
34-CF
32-F-6-Cl H 117-12192 4-CF
34-CF
32-F-6-Cl H 127.5-13093 3-Cl-4-OCF
34-CF
32-F-6-Cl H 86.5-87.594 4-CF
32-CN 3-Cl H 192-19595 4-Cl 4-CN 2-F H 193-19496 4-Br 4-CN 2-F H 182-18697 4-Cl 2-CN 3-F H 173.5-174 (decomposition) 98 4-Br 2-CN 3-F H99 4-Br 4-CF32-Cl H 103.5-104.5100 3-F 4-CN 2-CF
3H 139.5-142.5101 4-CF
34-CN 2-Cl CH
3112-114102 4-CF
34-CN 2-OCF
3H 120-123.5103 4-Cl 4-SO
2CF
32-Cl H 181-5.186.5 (decomposition) 104 4-Br 4-SO
2CF
32-Cl H 176-180105 4-CF
34-SO
2CF
32-Cl H 159-162106 4-F 4-SO
2CF
32-Cl H 148-151
Table 1 (continuing)
Fusing point (℃) or compound sequence number R
1N R
2R
3M R
4Refractive index (n
20 D) 107 H 4-SO
2CF
32-Cl H-108 4-CF
34-SO
2CF
32-Cl CH
3-109 4-CF
34-SO
2CH
32-Cl H-110 4-Cl 4-SO
2CH
32-F H-111 4-Cl 4-SO
2CH
32-Cl H-112 4-Br 4-SO
2C
2H
52-Cl H-113 4-Cl 4-SO
2CH
32,5-F
2H-114 4-CF
34-NO
22-Cl H-115 4-CF
34-SO
2CH
32-Cl CH
3-116 4-CF
34-CN 2,5-F
2C
2H
5-117 4-CF
34-CN 2-CF
3CH
3-118 3,4-F
24-CN 2,5-F
2CH
3123-125119 4-CF
32-CF
34-Cl H 97-98120 4-CF
32-CF
34-Cl COOCH
3115-119121 4-CF
32-CF
34-Br H 107-109122 4-CF
32-CF
34-Br COOCH
3115-117123 4-Cl 4-CN 2-OCF
3H 134-135124 4-SCF
34-CN 2-CF
3H 157-158125 4-SCF
34-CN 2-Cl H 153-156126 4-Cl 2-CN 4-CF
3H 149-153127 4-SCF
34-CN 2,5-F
2H 157128 4-Cl 4-CF
32,5-Cl
2H 150.5-156.5129 4-Cl 4-CF
32,5-F
2COOCH
31.5259130 4-Cl 4-CF
32,5-F
2H-131 4-Cl 4-CF
32,5-Cl
2H-132 3-Cl-4-CH
34-CN 3-F H 152-157133 H 4-NO
22-Cl H-
Table 1 (continuing)
Fusing point (℃) or compound sequence number R
1N R
2R
3M R
4Refractive index (n
20 D) 134 4-CF
34-NO
22-Cl H-135 4-CF
34-COOCH
32-Cl H-136 4-CF
32-COOCH
34-Cl H-137 4-Cl 4-NO
22-Cl H-138 4-Br 4-COOCH
32-Cl H-139 4-Cl 4-CONH
22-Cl H-140 4-CF
34-CSNH
22,5-F
2H-141 4-Cl 4-CSNH
22,5-F
2H-142 4-CF
34-COOC
2H
52,5-F
2H-143 4-Cl 4-COOC
2H
52,5-F
2H-144 4-Cl 4-NO
22-F H-145 4-CF
34-NO
22-Cl CH
3-146 4-Cl 4-COOCH
32-Cl CH
3-147 4-CF
32-COOCH
34-Cl CH
3-148 4-Cl 4-COOCH
32,5-F
2CH
3-149 4-Cl 4-COOCH
32,5-F
2H-150 4-OCF
34-NO
22-Cl H-151 H 4-COOCH
32-Cl H-152 4-CF
34-COOCH
32-F H-purposes EXAMPLE Example 1 bactericidal assay (anti-microbial activity on substratum) test method
In this test, used following pathogenic microorganism:
The plant pathogenic moulds:
The grey matter botrytis,
Nuclear clump mould sclerotinite,
The plant malignant bacteria:
Wild xanthomonas
The animal malignant bacteria:
Aurococcus,
Potato-glucose agar medium is used for cultivation in advance and the test of mould, the semisynthetic substratum of potato is used for cultivation in advance and the test of bacterium, every kind of test compound that is dissolved in small amount of methanol is suspended in the distilled water and is added in every kind of substratum with the concentration of 10ppm, each 15ml of every kind of substratum that has added compound is poured into culture dish (diameter: solidify 9cm), cultivate every kind of test microorganism then on culture dish.For mould, bore (diameter: 4mm) cut off the rhizomorph of cultivating in advance, cultivating on the rhizomorph test medium that cuts off with fork; For bacterium, streak culture carrying out on a spot of cell inoculation to a substratum with a platinum loop.Cultivate after 7 days, and the little cultivation of other pathogenic microorganism was measured the diameter of rhizomorph (mould) or the degree of cell growth (bacterium) after 2 days, obtained cytostatic percentage ratio on substratum.The result
Sequence number of the present invention is 9,11,12,14, and 16,20,23,27 and 36 compound is 9,11,12,14 to Pyriculariaoryzae, sequence number, 16,20,23,27, and 36 and 39 compound is to the grey matter botrytis; Sequence number is 9,16,20,23 and 36 compound is 9 to nuclear clump mould sclerotinite, sequence number, 16,20,23,27,36 and 39 compound is 9,16,20 to wild xanthomonas, sequence number, 23,36 and 39 compound has showed anti-microbial activity more than 99% or 99% respectively to aurococcus.The preparation of sterilization embodiment 2 (to the culture dish test of grey mould) wettable powder
Active compound: 30-40 weight part
Carrier: the mixture of diatomite and kaolin (1: 5), 55-65 weight part
Emulsifying agent: polyoxyethylene alkyl phenyl ether, 5 weight parts
The active compound of above-mentioned quantity, carrier and emulsifying agent grind, are mixed and made into wettable powder, and this pulvis is diluted with water to the concentration of specified active compound.Test method
About three Kidney beans (Cultivar: late type) plant at a vinyon basin (diameter: 7cm), in 15-25 ℃ greenhouse, cultivate, when treating seedling length to one leaf, use the every kind of test compound that is diluted to above-mentioned prescribed concentration by the amount of per three basin 25ml.With the rhizomorph of the disconnected grey matter botrytis of cultivating in advance of fork drilling, make a rhizomorph dish with substratum, be used for inoculation.Behind the administered compound 1 day, the rhizomorph dish is inoculated into the plant of handling and places humidity-temperature incubation chamber of 20 ℃.Inoculate after 4 days, the incidence in every basin is classified and according to following criterion evaluation calculation control rate, listed the average assessment result of three basins.
The area (%) of spotted ratio of incidence or spot
0 0
0.5 ＜2
1 2-＜5
2 5-＜10
3 10-＜20
4 20-＜40
5 〉=40 inverse amplification factors (%)=(the incidence ÷ that 1-is subject to processing the zone is not subject to processing regional incidence) * 100 results
Sequence number of the present invention is that 9,16,20,23 and 28 compound has showed the inverse amplification factor more than 95% or 95% when the concentration of 250ppm.The preparation solvent of insecticidal test example 1 (to the test of Spodoptera litura larvae that blur spot is arranged) test solution: the xylol emulsifying agent of 3 weight parts: the polyoxyethylene alkyl phenyl ether of 1 weight part
When producing the preparation of suitable active compound, the solvent of the emulsifying agent that contains above-mentioned quantity of the active compound of 1 weight part and above-mentioned quantity, mixture is diluted with water to specified concentration.Test method
In the aqueous solution of the active compound of wild cabbage (Caulis et Folium Brassicae capitatae) leaf immersion prescribed concentration.Solution places culture dish (diameter: 9cm), discharge three instar larvaes of 10 common cutworms (prodenia litura that blur spot is arranged) to the wild cabbage leaf of handling after dry air.Then culture dish is placed 25 ℃ incubator.After 7 days, check that the number of dead larva is so that calculate dead percentage ratio.Successively carried out twice test, dead percentage ratio is listed with mean value.The result
Sequence number of the present invention is 1-5,7-24, and 26-39,41-52,60,63,65-67,69-75,77-81,84-86,88-106, the compound of 118-130 have showed 100% lethality rate when the concentration of 1000ppm.Sterilant test example 2 (to the test of aulacophora femoralis larva) test method
In the aqueous solution of the active compound of cucumber leaf immersion prescribed concentration.Solution places culture dish (diameter: 9cm), discharge two instar larvaes of 10 aulacophora femoralises to the cucumber leaf of handling after dry air.Then culture dish is placed 25 ℃ incubator.After 7 days, check that the number of dead larva is so that calculate dead percentage ratio.Successively carried out twice test, dead percentage ratio is listed with mean value.The result
Sequence number of the present invention is 1-5,7-40, and 41-44,47-49,51,60-62,66,69-75,77,78,81,83-90,93-106, the compound of 118-130 have showed 100% lethality rate when the concentration of 1000ppm.The preparation carrier of weeding test example 1 (to the herbicidal effect test of weeds in paddy field) active agent preparation: acetone 5 weight part emulsifying agents: benzyloxy polyglycol ether 1 weight part
Formulations of active ingredients is by what obtain the carrier of the active compound of 1 weight part and above-mentioned quantity and emulsifier mix, and the preparation dilute with water specified quantity makes test preparation.Test method
In the greenhouse, divide the rice seedling of per 3 2.5 leaf age phases (15cm height) plantation of two places in 1/2000 are the big flowerpot (25 * 25 * 9) that fills paddy soil, plant the seed of Xiao Hua, Monochoria korsakowii, wide leaf weeds (common Brittle Falsepimpernel Herb, India's toothcup, long shoot waterwort, this cloth of Roc are spent more water amaranth, Ha Mierte horsefly eye etc.) and reed grass down then, it is dark to 2-3cm to water on soil.The plantation paddy rice was pressed the active agent preparations of the every kind of specified quantity for preparing with above-mentioned preparation method's similar methods after 7 days to used for ponds.
On the same day after 3 weeks of dispenser, check herbicidal effect and, in trial period, keep the depth of water of 3cm the phytotoxicity degree in crops.Herbicidal effect is decided to be 100% when dead fully, and herbicidal effect is not decided to be 0% when observing herbicidal effect or not having phytotoxicity.The result
In this test, sequence number of the present invention is 5,6,9,11,12,16,26,27,48 and 66 instantiation compound has showed Xiao Hua, Monochoria korsakowii, wide leaf weeds and reed grass has been had weeding rate more than 90% or 90% when using the active compound of 0.5kg/ha amount.Weeding test example 2 (to the preceding soil treatment test of emerging of the weeds that plow) test method
In the greenhouse, the seed of Mason's knotweed and recessed amaranth is planted the top layer of the soil that plows in being contained in the 120cm2 flowerpot that covers with soil respectively, being evenly distributed in the upper soll layer of testing flowerpot by test preparation with every kind of specified quantity of weeding test example 1 similar methods preparation.
4 week of distribution preparation back inspection herbicidal effect.The result
In this test, sequence number of the present invention is 5,6,16,27, and 28,48 and 66 instantiation compound has showed the weeding rate to Mason's knotweed and recessed amaranth 100% when using the active compound of 0.5kg/ha amount.Weeding test example 3 (to the back foliage applying test of emerging of the weeds that plow) test method
In the greenhouse, the seed of Mason's knotweed and recessed amaranth is planted respectively in the 120cm2 flowerpot that plows soil and cover with soil is housed, sowing and blinding (the average 2-leaf in weeds carried out during the phase) after 10 days, being distributed to the blade face part of testing the test plant in the flowerpot equably by preparation with every kind of specified quantity of weeding test example 1 similar methods preparation.3 week of distribution preparation back inspection herbicidal effect.The result
In this test, sequence number of the present invention be 5,28,48 and 66 instantiation compound when using the active compound of 0.5kg/ha amount, showed Mason's knotweed and recessed amaranth 90% or 90% above weeding rate.Example of formulations 1 (granula)
Water (25 parts) is added in the mixture of kneaded No. 3 compounds of the present invention (10 parts), otaylite (montmorillonite) (30 parts), talcum (58 parts) and sulfonated lignin (2 parts); make 10-40 purpose particle with the extrusion type tablets press; dry under 40-50 ℃ then, make particle.Example of formulations 2 (granula)
The clay pit (95 parts) that is in the 0.2-2mm particle size distribution is joined in the impeller, under rotation, No. 1 compound of the present invention (5 parts) is sprayed with a kind of liquid diluent, make it reach uniform humidity, dry under 40-50 ℃ then, make particle.Example of formulations 3 (emulsion)
Under agitation, No. 3 compounds of the present invention (30 parts), xylol (5 parts), polyoxyethylene alkyl phenyl ether (8 parts) and alkyl benzene calcium sulfonate (7 parts) are mixed, obtain a kind of emulsion.Example of formulations 4 (wettable powder)
With pulverulence the condenses (3 parts) of the mixture (1: 5) (80 parts) of No. 5 compounds of the present invention (15 parts), a kind of white carbon black (fine powder of the amorphous silica of aquation) and powdered clay, alkyl phenyl sodium sulfonate (2 parts) and a kind of sodium alkyl naphthalene sulfonate and formaldehyde is mixed, make wettable powder.Example of formulations 5 (wetting properties granula)
By thorough mixing No. 2 compounds of the present invention (20 parts), sodium lignosulfonate (30 parts), montmorillonite (15 parts) and the good diatomite powder (35 parts) of calcining, add then water and by the mesh of 0.3mm extrude, drying, make the wetting properties granula.
Claims (14)
1. the 1-phenyl-5-anilinotetrazole compounds of following formula
Wherein R1 is a hydrogen, halogen, cyano group; nitro, the alkyl of C1-4, the haloalkyl of C1-4; the halogenated alkoxy of C1-4 or the halogenated alkylthio of C1-4, R2 are cyano group, nitro; the haloalkyl of C1-4, the alkyl sulphonyl of C1-4, haloalkyl-alkylsulfonyl of C1-4; alkoxyl group-carbonyl of C1-4, aminocarboxyl or amino thiocarbonyl, R3 are halogen; the haloalkyl of C1-4 or the halogenated alkoxy of C1-4, R4 are hydrogen, cyano group; the alkyl of C1-4, the alkyl-carbonyl of C1-4, alkoxyl group-carbonyl of C1-4; the alkyl sulphonyl of C1-4; alkyl-carbonyl of the alkoxy-C 1-4 of C1-4, phenyloxycarbonyl that can be replaced by nitro or the pyridyl carbonyl that can be replaced by halogen, n is 1; 2 or 3; and when n was 2 or 3, two or three R1 can be identical or different, and m is 1 or 2; and when m was 2, two R3 can be identical or different.
2. the 1-phenyl-5-anilinotetrazole compounds of the formula of claim 1 (I), wherein R1 is a hydrogen, halogen; cyano group, nitro, the alkyl of C1-3; the fluoro-alkyl of C1-3, the fluoroalkane sulfenyl of the fluoroalkyl of C1-3 or C1-3, R2 are cyano group; nitro; the haloalkyl of C1-3, the alkyl sulphonyl of C1-3, haloalkyl-alkylsulfonyl of C1-3; alkoxyl group-carbonyl of C1-3; aminocarboxyl or amino thiocarbonyl, R3 are halogen, the fluoro-alkyl of C1-3 or the fluoroalkyl of C1-3; R4 is a hydrogen; cyano group, the alkyl of C1-3, the alkyl-carbonyl of C1-3; alkoxyl group-carbonyl of C1-3; the alkyl sulphonyl of C1-3, alkyl-carbonyl of the alkoxy-C 1-2 of C1-2, phenyloxycarbonyl that can be replaced by nitro or the pyridyl carbonyl that can be replaced by chlorine; n is 1 or 2; and when n was 2, two or three R1 can be identical or different, and m is 1 or 2; and when m was 2, two R3 can be identical or different.
3. the 1-phenyl-5-anilinotetrazole compounds of the formula of claim 1 (I), wherein R1 is a hydrogen, fluorine, chlorine; bromine, cyano group, nitro, methyl; trifluoromethyl, trifluoromethoxy or trifluoromethyl sulfenyl, R2 are cyano group, nitro; trifluoromethyl, methylsulfonyl, ethylsulfonyl, trifyl; methoxycarbonyl, ethoxy carbonyl, aminocarboxyl or amino thiocarbonyl; R3 is a fluorine, chlorine, bromine; trifluoromethyl or trifluoromethoxy, R4 are hydrogen, cyano group; methyl, methyl carbonyl, methoxycarbonyl; ethoxy carbonyl, methylsulfonyl, methoxymethyl carbonyl; phenyloxycarbonyl, 4-nitrophenoxy carbonyl or 2,6-two chloro-4-pyridyl carbonyls; n is 1 or 2, and when n was 2, two R1 can be identical or different; and m is 1 or 2, and when m was 2, two R3 can be identical or different.
4. the method for the 1-phenyl-5-anilinotetrazole compounds of preparation formula (I),
Wherein R1 is a hydrogen, halogen, cyano group; nitro, the alkyl of C1-4, the haloalkyl of C1-4; the halogenated alkoxy of C1-4 or the halogenated alkylthio of C1-4, R2 are cyano group, nitro; the haloalkyl of C1-4, the alkyl sulphonyl of C1-4, haloalkyl-alkylsulfonyl of C1-4; alkoxyl group-carbonyl of C1-4; aminocarboxyl or amino thiocarbonyl, R3 are halogen, the haloalkyl of C1-4 or the halogenated alkoxy of C1-4; R4 is a hydrogen; cyano group, the alkyl of C1-4, the alkyl-carbonyl of C1-4; alkoxyl group-carbonyl of C1-4; the alkyl sulphonyl of C1-4, alkyl-carbonyl of the alkoxy-C 1-4 of C1-4, phenyloxycarbonyl that can be replaced by nitro or the pyridyl carbonyl that can be replaced by halogen; n is 1; 2 or 3, and when n was 2 or 3, two or three R1 can be identical or different; and m is 1 or 2; and when m was 2, two R3 can be identical or different, it is characterized by: a) when R4 is hydrogen: the compound that makes formula (II)
Wherein the definition of R1 and n as above, X is halogen or methylsulfonyl, with the compound of formula (III)
R2 wherein, the definition of R3 and m is the same, a kind of thinner and, if suitable, in the presence of a kind of acid binding agent, react, perhaps b) when R4 is the alkoxy carbonyl of the alkyl of C1-4 or C1-4:
Make the compound of formula (IV)
R1 wherein, R2, R3, the definition of m and n as above, and
R5 is the alkyl of C1-4 or the alkoxy carbonyl of C1-4,
React in the presence of a kind of inert solvent with sodiumazide, perhaps c) when R4 is hydrogen: the compound that makes formula (Ib)
R1 wherein, R2, R3, the definition of m and n as above, and R6 is the alkyl of C1-4 or the phenyl that can be replaced by nitro,
A kind of inert solvent and, if suitable, hydrolysis in the presence of a kind of alkali, perhaps d) during group as defined above beyond R4 is the alkyl of dehydrogenation and C1-4:
Make the compound of formula (Ia)
R1 wherein, R2, R3, the definition of m and n as above,
Compound with formula (IV)
R7-Y (V)
Wherein R7 be beyond the alkyl of dehydrogenation and C1-4 with the identical group of R4 as defined above, and Y is a halogen, preferred chlorine or bromine,
If at a kind of inert solvent and suitable, in the presence of a kind of acid binding agent, react, perhaps e) when R4 is the alkyl-carbonyl of the alkoxy-C 1-4 of the alkyl-carbonyl of C1-4 or C1-4:
Make the compound of above-mentioned formula (Ia) and the compound of formula (VI)
Wherein R8 is the alkyl of the alkoxy-C 1-4 of the alkyl of C1-4 or C1-4, inert solvent and, if suitable, in the presence of a kind of acid catalyst, react.
5. insecticides is characterized in that composition contains the 1-phenyl of a kind of formula of claim 1 (I)-5-anilino tetrazolium at least.
6. Synergistic microbicidal compositions is characterized in that composition contains the 1-phenyl of a kind of formula of claim 1 (I)-5-anilino tetrazolium at least.
7. herbicidal composition is characterized in that composition contains the 1-phenyl of a kind of formula of claim 1 (I)-5-anilino tetrazolium at least.
8. kill the method for harmful insect, it is characterized in that the 1-phenyl-5-anilino tetrazolium of the formula (I) of claim 1.
9. kill the harmful microbe method, it is characterized in that the 1-phenyl-5-anilino tetrazolium of the formula (I) of claim 1.
10. kill the method for removing injurious weed, it is characterized in that the 1-phenyl-5-anilino tetrazolium of the formula (I) of claim 1.
11. the 1-phenyl of the formula of claim 1 (I)-5-anilino tetrazolium is used for the kill harmful microorganism.
12. the 1-phenyl of the formula of claim 1 (I)-5-anilino tetrazolium is used for the kill harmful insect.
13. the 1-phenyl of the formula of claim 1 (I)-5-anilino tetrazolium is used to remove injurious weed.
14. prepare the method for pesticide composition, it is characterized in that making the 1-phenyl-5-anilino tetrazolium of the formula (I) of claim 1 to mix with developping agent and/or tensio-active agent.
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|---|---|---|---|
| CN98106411A CN1194267A (en) | 1997-01-28 | 1998-01-27 | 1-phenyl-5-anilinotetrazole compounds |
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|---|---|---|---|
| JP27300/97 | 1997-01-28 | ||
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103282354A (en) * | 2010-09-01 | 2013-09-04 | 拜耳知识产权有限责任公司 | N-(tetrazol-5-l)- and n-(triazol-5-yl)arylcarboxamides and use thereof as herbicides |
| CN104011031A (en) * | 2011-11-03 | 2014-08-27 | 拜耳知识产权有限责任公司 | 5-phenyl-substituted N-(tetrazol-5-yl) aryl carboxylic acid amides and N-(triazol-5-yl) aryl carboxylic acid amides, and use thereof as herbicides |
-
1998
- 1998-01-27 CN CN98106411A patent/CN1194267A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103282354A (en) * | 2010-09-01 | 2013-09-04 | 拜耳知识产权有限责任公司 | N-(tetrazol-5-l)- and n-(triazol-5-yl)arylcarboxamides and use thereof as herbicides |
| CN103282354B (en) * | 2010-09-01 | 2016-05-04 | 拜耳知识产权有限责任公司 | N-(tetrazolium-5-yl)-and N-(triazole-5-yl) aryl carboxamides and as the purposes of herbicide |
| CN104011031A (en) * | 2011-11-03 | 2014-08-27 | 拜耳知识产权有限责任公司 | 5-phenyl-substituted N-(tetrazol-5-yl) aryl carboxylic acid amides and N-(triazol-5-yl) aryl carboxylic acid amides, and use thereof as herbicides |
| CN104011031B (en) * | 2011-11-03 | 2016-07-06 | 拜耳知识产权有限责任公司 | N-(tetrazolium-5-base) aryl carboxylic acid amides of 5-phenyl-replacement and N-(triazole-5-base) aryl carboxylic acid amides, and the purposes as herbicide |
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