CA1262735A - Pyrazolecarboxamide derivative and fungicide containing it as active ingredient - Google Patents
Pyrazolecarboxamide derivative and fungicide containing it as active ingredientInfo
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- CA1262735A CA1262735A CA000496744A CA496744A CA1262735A CA 1262735 A CA1262735 A CA 1262735A CA 000496744 A CA000496744 A CA 000496744A CA 496744 A CA496744 A CA 496744A CA 1262735 A CA1262735 A CA 1262735A
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- carboxamide
- pyrazole
- methyl group
- methyl
- group
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Abstract
ABSTRACT OF THE DISCLOSURE
There is disclosed a pyrazolecarboxamide derivative having controlling effects on plant diseases which is represented by the formula (I):
There is disclosed a pyrazolecarboxamide derivative having controlling effects on plant diseases which is represented by the formula (I):
Description
2~735 PYRAZOLECARBOXAMIDE DERIVATIVE AND
FUNGICID:E: CONTAINING IT AS ACTIVE IN(GREDIENT
The present invention relates to a pyrazole-carboxamide derivative (referred -to as "present compound" hereinafter) represented by -the formula ~ N ~ R 1 ~ ~ C H 2 ~\ C ~-- C \CH3 [ I]
1 R 2 (F)n wherein R and R which are identical or different represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a trifluoromethyl group, R3 represents a hydrogen atom or a methyl group and n r~presents 0 or 1, and a fungicide containing the derivative as an active ingredient.
The inventors have made extensive researches on pyrazolecarboxamide compounds and as a result~
found that the present compound represented by the formula [I] has preventive, curative and systemic controlling effects on plant microbes.
The following are plant diseases on which the present compound has an excellent controlling effect; E~u~Q~nni3_~QL~Li and Rhizoctonla ory3~e, R solani III B on rice plant; Puccinia s-triiformis, P. graminis, P. recondita, P. hordei, Rh_zoctonia cerealis, Typhula incarnataL T. ishikariensis, Ustilaqo tritici and U. nuda on wheat; Rhizoctonia .__ solani and Cortic _miEæl~L3i on various crops;
Rhizoctonia solani on potato and beet; Gy ~r~}~
ha_,~eanum on pear; Venturia inaequaris on apple;
Rhizoctonia 9 _ nl orticium rolEsii, Uromyces trlfolii and Typhula incarnata, T. ishikariensis on pasture and lawn.
- 2 ~
The present compound can be produced, for example, by the followiny methods.
[Method A]
M Rl CH~ N ~ ~ H2N - Ar ~ lCI - X
[II~ [III]
~CH3 ~ N \ ~ C -N ~ A
R2 o [I]
wherein Rl and R are as defined above, X represents a halogen atom and Ar represents a group having the formula: CH
R3 \ / ~
CH ~ CH3 ~ C ~ CH3 (F)n (wherein R3 and n are as defined above).
That is, a carboxylic acid halide represent-ed by the formula [II] (e.g., carboxylic acid chloride, carboxylic acid bromide and carboxylic acid fluoride) is reacted with a ~-aminoindane derivative represented by the formula [III] to obtain the present compound represented by the Formula [I].
Reaction solvents are not essential for the above method, but generally inert solvents are used.
As examples of the solvents, the following may be listed; hydrocarbons such as benzene, toluene, xylene, etc., halogenated hydrocarbons such as chloroform, dichloromethane, chlorobenzene, etc.,
FUNGICID:E: CONTAINING IT AS ACTIVE IN(GREDIENT
The present invention relates to a pyrazole-carboxamide derivative (referred -to as "present compound" hereinafter) represented by -the formula ~ N ~ R 1 ~ ~ C H 2 ~\ C ~-- C \CH3 [ I]
1 R 2 (F)n wherein R and R which are identical or different represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a trifluoromethyl group, R3 represents a hydrogen atom or a methyl group and n r~presents 0 or 1, and a fungicide containing the derivative as an active ingredient.
The inventors have made extensive researches on pyrazolecarboxamide compounds and as a result~
found that the present compound represented by the formula [I] has preventive, curative and systemic controlling effects on plant microbes.
The following are plant diseases on which the present compound has an excellent controlling effect; E~u~Q~nni3_~QL~Li and Rhizoctonla ory3~e, R solani III B on rice plant; Puccinia s-triiformis, P. graminis, P. recondita, P. hordei, Rh_zoctonia cerealis, Typhula incarnataL T. ishikariensis, Ustilaqo tritici and U. nuda on wheat; Rhizoctonia .__ solani and Cortic _miEæl~L3i on various crops;
Rhizoctonia solani on potato and beet; Gy ~r~}~
ha_,~eanum on pear; Venturia inaequaris on apple;
Rhizoctonia 9 _ nl orticium rolEsii, Uromyces trlfolii and Typhula incarnata, T. ishikariensis on pasture and lawn.
- 2 ~
The present compound can be produced, for example, by the followiny methods.
[Method A]
M Rl CH~ N ~ ~ H2N - Ar ~ lCI - X
[II~ [III]
~CH3 ~ N \ ~ C -N ~ A
R2 o [I]
wherein Rl and R are as defined above, X represents a halogen atom and Ar represents a group having the formula: CH
R3 \ / ~
CH ~ CH3 ~ C ~ CH3 (F)n (wherein R3 and n are as defined above).
That is, a carboxylic acid halide represent-ed by the formula [II] (e.g., carboxylic acid chloride, carboxylic acid bromide and carboxylic acid fluoride) is reacted with a ~-aminoindane derivative represented by the formula [III] to obtain the present compound represented by the Formula [I].
Reaction solvents are not essential for the above method, but generally inert solvents are used.
As examples of the solvents, the following may be listed; hydrocarbons such as benzene, toluene, xylene, etc., halogenated hydrocarbons such as chloroform, dichloromethane, chlorobenzene, etc.,
- 3 - ~ 2~3~
ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, etc., ketones such as acetone, methyl isoblltyl ketone, etc., esters such as ethyl acetate, etc., nitriles such as acetonitrile, etc., dimethylsulfoxide, sulfolane, dimethylformamide, dimethylacetamide, etc. and mixtures thereof.
The reaction may be carried out in the presence of an acid accepting agent. Examples of the acid accepting agent are organic bases such as triethylamine, pyridine, N,N-dimethylaniline, 4-dimethylaminopyridine, etc. and inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. and the like.
15 Reaction temperature has no special limi-tation, ~ut usually is 0C - 150C.
Amount of the starting compounds used in this reaction is generally 0.8 - 1.5 mol of the 4-aminoindane derivative represented by the formula [III] per 1 mol of the carboxylic acid halide re-presented by the formula [II].
[Method B~
1' 2' R ~ ~CH2~ ~ R ~ OCN - Ar ---Il 11 O O [V]
[IV]
~ R
O = C ~ H CH3NHNH2 CH - C - N - Ar --~
O = C O
\ R2 ' [VI]
2~
~N R
3 ~ ~1 ~ C ~N - Ar R2 ' o [VII]
wherein Ar is as defined above and Rl and R2 which are identical or differen-t represent a methyl group or an ethyl group.
That is, firstly a diketone represented by the formula [IV] is reacted with an isocyanate represented by the formula [V] to obtain a carbamoyl diketone represented by the formula [~I], which is then reacted with methylhydrazine to obtain the present compound.
Reaction solvent is not essential for the reaction of the diketone represented by t~e formula [IV] with the isocyanate represented by the formula ~V], but ordinarily inert solvents are used.
As examples of the solvents, the following are listed; hydrocarbons such as benzene, toluene, etc., halogenated hydrocarbons such as chloroform, dichloromethane, chlorobenzene, etc., ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, etc., ketones such as acetone, methyl isobutyl ketone, etc., nitriles such as acetonitrile, etc., dimethyl sulfoxide, sulfolAne, dimethylformamide, dimethylacetamide, etc. and mixtures thereof.
Organic bases such as triethylamine, pyricline, etc., inorganic bases such as sodium hydride, potassium carbonate, etc. and the like may be used as a reaction assistant in this reac-tion.
Reaction temperature has no special limitation, but the object can be sufEiciently - 5 - ~6~73~
achieved by employing the range of 0C - 100C.
Amount of the starting compounds used in this reaction is usually 0.7 - 1.3 mol of the iso-cyanate represented by the formula [V] per 1 mol of the di~etone represented by the formula [IV].
Solvent is not essential for -the reaction of thus obtained carbamoyl diketone represented by the formula [VI] wi-th methylhydrazine, but normally inert solvent is used. As examples of the solvent, the following may be listed; hydrocarbons such as benzene, toluene, etc., ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, etc., alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc., water, and the like and mixtures thereof.
Reaction temperature has no special limi-tation, but generally is 0C - 100C or up to the boiling point of the solvent used.
Amount of the reactant compounds used in this reaction is usually 0.9 - 1.5 mol of methyl-hydrazine per 1 mol of the carbamoyldiketone represent-ed by the formula [VI].
[~ethod C]
,N Rl",N~ R
CH3 ~ N r ~ OCN - Ar-~ CH3 - N ~ H
C- N - Ar O O O
[VIII] [V] ~IX]
1"
POCQ~ CH ,N ~ R
3 ~ C -N - Ar CQ O
[X]
6 ~ r~
wherein Ar is as defined above and Rl represents a methyl group, an ethyl group or a trifluoromethyl group.
That is~ firstly a pyrazoline~5-one re~
presented by the formula [VIII] is reacted with an isocyanate represented by the formula [V] to obtain a 4-carbamoylpyrazoline-5-one represented by the formula [[X], which is then reacted with phosphorus oxychloride to obtain a chlorine-substituted pyrazolecarboxamide compound represented by the formula [X] .
Solvent is not essential for the reaction of pyrazoline-5-one represented by the formula [VIII]
with isocyanate represen~ed by the formula [V], but normally inert solvent is used. As examples of the solvent, the following may be listed; hydrocarbons such as benzene, toluene, etc., halogenated hydrocarbons such as chloroform, dichloromethane/ chlorobenzene, etc., ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, etc., ketones such as acetone, methyl isobutyl ketone, etc., nitriles such as acetonitrile, etc., dimethyl sul foxid e, sulfolane, dimethyl f ormamide, dimethylacetamide, etc. and mixtures thereof. Furthermore, organic bases such as triethylamine, pyridine, etc. and inorganic bases such as sodium hydride, potassium carbonate, etc. may also be used as a reaction assistant in this reaction.
Reaction temperature has no special limi-tation, but usually the object can be sufficien-tly achieved by employing a temperature of 0C - 100C.
Amount of the starting compounds used in this reaction is usually 0.7 - 1.3 mol of the iso-cyanate represented by the formula [V~ per 1 mol of the pyrazoline-5-one represented by the formula ~VIII].
Normally solvent is not necessary for the subsequent reaction of thus obtained carbamoyl pyrazoline-5-one represented by the formula [IX] wi-th phosphorus oxychloride, but inert solvent may be used.
As e~amples of the solvent there are hydrocarbons such as benzene, toluene, etc., halogenated hydro-carbons such as chloroform, dichloromethane, chloro-benzene, etc., ethers such as diethyl ether, diiso-propyl ether, tetrahydro~uran, dioxane, dimethoxy-ethane, etc. ~urthermore, an acid accepting agentsuch as N,N-dimethylaniline, N,N-diethylaniline, 4-dimethylaminopyridine, etc. may be used as reaction assistants in this reaction.
Reaction temperature for this reaction has no special limitation, but usually is the range of from room temperature to the reflux temperature of the reaction mixture.
Amount of the reactant compounds used in this reaction is ordinarily 1.0 - 20 mols, preferably 20 5.0 - 10 mols of phosphorus oxychloride per 1 mol of the carbamoylpyrazoline-5-one represented by the formula [IX].
[Method D]
CH3 - N~ H Reduction or fluorinat~on CQ
[X]
CH - N~ H
Y O
[XI]
3~
wherein Rl is as defined above and Y represents a hydrogen atom or a fluorine atom.
That is, the chlorine-substi-tuted pyrazole-carboxamide compound ob-tained by [method C] is sub-S jected to reduction reaction to replace a chlorineatom with a hydrogen atom or is subjected to chlorine/
fluorine replacing reaction with a fluorinating agent to obtain the pyrazolecarboxamide compound represented by the formula [XI].
The reduction reaction in this method is, for example, a catalytic reduction using a catalyst such as palladium-carbon. Typically the carboxamide compound represented by the formula [X~ is subjected to catalytic reduction in hydrocarbons such as benzene, toluene, etc., esters such as ethyl acetate, etc., alcohols such as methyl alcohol, ethyl alcohol, etc. using as a catalyst palladium-carbon (Pd-C) in an amount of 5 - 50~ by weight of the carboxamide compound under a hydrogen pressure of 1 - 2 atm. in the presence of an acid accepting agent such as anhydrous sodium acetate, anhydrous ammonium acetate or the like.
Fluorinatin~ agents used in the chlorine/
fluorine replacing reaction include potassium fluoride, cesium fluoride and the like. Amount of the fluorinating agent is usually 1.0 - 5.0 mols per 1 mol of the chlorine-substituted pyrazolecarboxami~e compound represented by the formula [X].
Normally, inert solvent is used in this reaction. As examples of the solvent, the following may ~e listed; hydrocarbons such as toluene, xylene, etc., ethers such as bis(2-methoxyethyl)ether, etc., dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide~ e-tc. and mixtures thereof.
Reaction temperature is usually 100 -200C.
As reaction assistants, there may be used calcium Eluoride and well-known phase transfer catalyst.
As phase transfer catalyst, the following may be illustrated; for example, Crown ether, quaternary ammonium salts such as tetraalkyl ammonium halides, phosphoni.um salts such as tetraalkylphosphonium halides, e-tc.
[Method E]
N Rl CH3,c ~ 2`CH ~ Acid CH N~C ~'' ~ (F) Rearrangement R2 o [XII]
~CH2 C ~ 3 N2~ R ~ / \CH
25 ~C N~
(F)n [I]
wherein Rl, R , R3 and n are as defined above.
That is, a tetrahydroquinoline represented by the formula [XII] is subjected to rearrangement in the presence of an acid catalyst to obtain the pyrazolecarboxamide derivative represented by the formula [I].
In this method, there may be used protonic acid and Lewis acid often used as catalyst in Friedel-73~;
Crafts reac-tion as the acids. However, the object can be fully attained by using lnorganic acids such as sulfuric acid, phosphoric acid, polyphosphoric acid and the like and use of these acids is very advantageous because -they also act as reaction solvents. Furthermore, if necessary, halogenated hydrocarbon -type inert solvents such as carbon tetra-chloride may also be used. Reaction temperature is usually 0C - 135C.
The tetrahydroquinoline represented by -the formula [XII] used as a startin~ compound in this method may be syn-thesized, for example, by a method similar to the methods described in E. Krovenagel et al "Chem. Ber.", 55, 23~9 (1922) and W. H. Cliffe et al "J. Chem. Soc.", (C) 514 (1966).
Examples of the present compounds will be shown below but the present compounds are not of cour~e limited to these examples.
1,3-Dimethyl-N-(l,l-dimethylindane-~-yl~pyrazole 4-carboxamide,1,5-Dimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide, 1,3,5-Trimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-
ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, etc., ketones such as acetone, methyl isoblltyl ketone, etc., esters such as ethyl acetate, etc., nitriles such as acetonitrile, etc., dimethylsulfoxide, sulfolane, dimethylformamide, dimethylacetamide, etc. and mixtures thereof.
The reaction may be carried out in the presence of an acid accepting agent. Examples of the acid accepting agent are organic bases such as triethylamine, pyridine, N,N-dimethylaniline, 4-dimethylaminopyridine, etc. and inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. and the like.
15 Reaction temperature has no special limi-tation, ~ut usually is 0C - 150C.
Amount of the starting compounds used in this reaction is generally 0.8 - 1.5 mol of the 4-aminoindane derivative represented by the formula [III] per 1 mol of the carboxylic acid halide re-presented by the formula [II].
[Method B~
1' 2' R ~ ~CH2~ ~ R ~ OCN - Ar ---Il 11 O O [V]
[IV]
~ R
O = C ~ H CH3NHNH2 CH - C - N - Ar --~
O = C O
\ R2 ' [VI]
2~
~N R
3 ~ ~1 ~ C ~N - Ar R2 ' o [VII]
wherein Ar is as defined above and Rl and R2 which are identical or differen-t represent a methyl group or an ethyl group.
That is, firstly a diketone represented by the formula [IV] is reacted with an isocyanate represented by the formula [V] to obtain a carbamoyl diketone represented by the formula [~I], which is then reacted with methylhydrazine to obtain the present compound.
Reaction solvent is not essential for the reaction of the diketone represented by t~e formula [IV] with the isocyanate represented by the formula ~V], but ordinarily inert solvents are used.
As examples of the solvents, the following are listed; hydrocarbons such as benzene, toluene, etc., halogenated hydrocarbons such as chloroform, dichloromethane, chlorobenzene, etc., ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, etc., ketones such as acetone, methyl isobutyl ketone, etc., nitriles such as acetonitrile, etc., dimethyl sulfoxide, sulfolAne, dimethylformamide, dimethylacetamide, etc. and mixtures thereof.
Organic bases such as triethylamine, pyricline, etc., inorganic bases such as sodium hydride, potassium carbonate, etc. and the like may be used as a reaction assistant in this reac-tion.
Reaction temperature has no special limitation, but the object can be sufEiciently - 5 - ~6~73~
achieved by employing the range of 0C - 100C.
Amount of the starting compounds used in this reaction is usually 0.7 - 1.3 mol of the iso-cyanate represented by the formula [V] per 1 mol of the di~etone represented by the formula [IV].
Solvent is not essential for -the reaction of thus obtained carbamoyl diketone represented by the formula [VI] wi-th methylhydrazine, but normally inert solvent is used. As examples of the solvent, the following may be listed; hydrocarbons such as benzene, toluene, etc., ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, etc., alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc., water, and the like and mixtures thereof.
Reaction temperature has no special limi-tation, but generally is 0C - 100C or up to the boiling point of the solvent used.
Amount of the reactant compounds used in this reaction is usually 0.9 - 1.5 mol of methyl-hydrazine per 1 mol of the carbamoyldiketone represent-ed by the formula [VI].
[~ethod C]
,N Rl",N~ R
CH3 ~ N r ~ OCN - Ar-~ CH3 - N ~ H
C- N - Ar O O O
[VIII] [V] ~IX]
1"
POCQ~ CH ,N ~ R
3 ~ C -N - Ar CQ O
[X]
6 ~ r~
wherein Ar is as defined above and Rl represents a methyl group, an ethyl group or a trifluoromethyl group.
That is~ firstly a pyrazoline~5-one re~
presented by the formula [VIII] is reacted with an isocyanate represented by the formula [V] to obtain a 4-carbamoylpyrazoline-5-one represented by the formula [[X], which is then reacted with phosphorus oxychloride to obtain a chlorine-substituted pyrazolecarboxamide compound represented by the formula [X] .
Solvent is not essential for the reaction of pyrazoline-5-one represented by the formula [VIII]
with isocyanate represen~ed by the formula [V], but normally inert solvent is used. As examples of the solvent, the following may be listed; hydrocarbons such as benzene, toluene, etc., halogenated hydrocarbons such as chloroform, dichloromethane/ chlorobenzene, etc., ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, etc., ketones such as acetone, methyl isobutyl ketone, etc., nitriles such as acetonitrile, etc., dimethyl sul foxid e, sulfolane, dimethyl f ormamide, dimethylacetamide, etc. and mixtures thereof. Furthermore, organic bases such as triethylamine, pyridine, etc. and inorganic bases such as sodium hydride, potassium carbonate, etc. may also be used as a reaction assistant in this reaction.
Reaction temperature has no special limi-tation, but usually the object can be sufficien-tly achieved by employing a temperature of 0C - 100C.
Amount of the starting compounds used in this reaction is usually 0.7 - 1.3 mol of the iso-cyanate represented by the formula [V~ per 1 mol of the pyrazoline-5-one represented by the formula ~VIII].
Normally solvent is not necessary for the subsequent reaction of thus obtained carbamoyl pyrazoline-5-one represented by the formula [IX] wi-th phosphorus oxychloride, but inert solvent may be used.
As e~amples of the solvent there are hydrocarbons such as benzene, toluene, etc., halogenated hydro-carbons such as chloroform, dichloromethane, chloro-benzene, etc., ethers such as diethyl ether, diiso-propyl ether, tetrahydro~uran, dioxane, dimethoxy-ethane, etc. ~urthermore, an acid accepting agentsuch as N,N-dimethylaniline, N,N-diethylaniline, 4-dimethylaminopyridine, etc. may be used as reaction assistants in this reaction.
Reaction temperature for this reaction has no special limitation, but usually is the range of from room temperature to the reflux temperature of the reaction mixture.
Amount of the reactant compounds used in this reaction is ordinarily 1.0 - 20 mols, preferably 20 5.0 - 10 mols of phosphorus oxychloride per 1 mol of the carbamoylpyrazoline-5-one represented by the formula [IX].
[Method D]
CH3 - N~ H Reduction or fluorinat~on CQ
[X]
CH - N~ H
Y O
[XI]
3~
wherein Rl is as defined above and Y represents a hydrogen atom or a fluorine atom.
That is, the chlorine-substi-tuted pyrazole-carboxamide compound ob-tained by [method C] is sub-S jected to reduction reaction to replace a chlorineatom with a hydrogen atom or is subjected to chlorine/
fluorine replacing reaction with a fluorinating agent to obtain the pyrazolecarboxamide compound represented by the formula [XI].
The reduction reaction in this method is, for example, a catalytic reduction using a catalyst such as palladium-carbon. Typically the carboxamide compound represented by the formula [X~ is subjected to catalytic reduction in hydrocarbons such as benzene, toluene, etc., esters such as ethyl acetate, etc., alcohols such as methyl alcohol, ethyl alcohol, etc. using as a catalyst palladium-carbon (Pd-C) in an amount of 5 - 50~ by weight of the carboxamide compound under a hydrogen pressure of 1 - 2 atm. in the presence of an acid accepting agent such as anhydrous sodium acetate, anhydrous ammonium acetate or the like.
Fluorinatin~ agents used in the chlorine/
fluorine replacing reaction include potassium fluoride, cesium fluoride and the like. Amount of the fluorinating agent is usually 1.0 - 5.0 mols per 1 mol of the chlorine-substituted pyrazolecarboxami~e compound represented by the formula [X].
Normally, inert solvent is used in this reaction. As examples of the solvent, the following may ~e listed; hydrocarbons such as toluene, xylene, etc., ethers such as bis(2-methoxyethyl)ether, etc., dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide~ e-tc. and mixtures thereof.
Reaction temperature is usually 100 -200C.
As reaction assistants, there may be used calcium Eluoride and well-known phase transfer catalyst.
As phase transfer catalyst, the following may be illustrated; for example, Crown ether, quaternary ammonium salts such as tetraalkyl ammonium halides, phosphoni.um salts such as tetraalkylphosphonium halides, e-tc.
[Method E]
N Rl CH3,c ~ 2`CH ~ Acid CH N~C ~'' ~ (F) Rearrangement R2 o [XII]
~CH2 C ~ 3 N2~ R ~ / \CH
25 ~C N~
(F)n [I]
wherein Rl, R , R3 and n are as defined above.
That is, a tetrahydroquinoline represented by the formula [XII] is subjected to rearrangement in the presence of an acid catalyst to obtain the pyrazolecarboxamide derivative represented by the formula [I].
In this method, there may be used protonic acid and Lewis acid often used as catalyst in Friedel-73~;
Crafts reac-tion as the acids. However, the object can be fully attained by using lnorganic acids such as sulfuric acid, phosphoric acid, polyphosphoric acid and the like and use of these acids is very advantageous because -they also act as reaction solvents. Furthermore, if necessary, halogenated hydrocarbon -type inert solvents such as carbon tetra-chloride may also be used. Reaction temperature is usually 0C - 135C.
The tetrahydroquinoline represented by -the formula [XII] used as a startin~ compound in this method may be syn-thesized, for example, by a method similar to the methods described in E. Krovenagel et al "Chem. Ber.", 55, 23~9 (1922) and W. H. Cliffe et al "J. Chem. Soc.", (C) 514 (1966).
Examples of the present compounds will be shown below but the present compounds are not of cour~e limited to these examples.
1,3-Dimethyl-N-(l,l-dimethylindane-~-yl~pyrazole 4-carboxamide,1,5-Dimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide, 1,3,5-Trimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-
4-carboxamide, 1,3-Dimethyl-5-fluoro-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide,
5-Chloro-1,3-dimethyl-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide, 5-~romo-1,3-dimethyl-N-(l/l-dimethylindane-4-yl) pyrazole-4-carboxamide, 1,3-Dimethyl 5-iodo-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide, 1,5-Dimethyl-3-fluoro-N-(l,l-dimethylindane-4-yl) pyrazole~4-carboxamide, 3~Fluoro-1,5-dimethyl-N-(l,l-dimethylindane-4-yl) ;6~
pyrazole-4-carboxamide, 3-Chloro-1,5-dimethyl-N-(l,l-dimethylindane-4-yl) pyrazole-~-carboxamide, 3-~3romo 1,S-dimethyl-N-(l,l-dimethylindane~4-yl) pyrazole-4-carboxamide, 1,5-Di.methyl-3-iodo-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide, 3,5-Difluoro-l-methyl-N-(l,l--dimethylindane-4-yl) pyrazole-4-carboxamide, 3,5-Dichloro-l-methyl-N-(l,l-dimethylindane-4-yl~
pyrazole-4-carboxamide, 3,5-Dibromo-l-methyl-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide, 3,5-Diiodo-l-methyl-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxami~e, 1 Methyl-3-trifluoromethyl-N-(l,l-dimethylindane-4~yl) pyrazole-4-carboxamide, l-Methyl-5-trifluoromethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide, 3-Fluoro-l-methyl-5-trifluoromethyl-N-(l,l-dimethyl-indane-4-yl)pyrazole-4-carboxamide, 5-Fluoro-l-methyl-3-trifluoromethyl-N-~l,l-dimethyl-indane-4-yl)pyrazole-4-carboxamide, 3-Chloro-l-methyl-5-trifluoromethyl-N-(l,l-dimethyl-indane-4-yl)pyrazole-4-carboxamide, 5-Chloro-l-methyl-3-trifluoromethyl-N-(l,l-dimethyl-indane-4-yl)pyrazole-~-carboxamide, 5-Bromo-l-methyl-3-trifluoromethyl-N-(l,l dimethyl-indane~4-yl)pyrazole-~-carboxamide, 5-Iodo-l-methyl-3-trifluoromethyl-N-(l,l-dimethyl-indane-4-yl)pyrazole-4-carboxamide, 1,3-Dimethyl-5-tri~luoromethyl-N-(l,l-dimethylin~ane-4-yl)pyrazole-4-carboxamide, 1,5-Dimethyl-3-trifluoromethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide, - 12 ~ 2~35 3,5-Bis(tri~luoromethyl)-1-methyl-N-(l,l-dimethyl-indane-4-yl)pyrazole-4-carboxamide, 1,3-Dimethyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 5 1,5-Dimethyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 1,3,5-Trimethyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,5-Dimethyl-3-fluoro-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,3-Dimekhyl-5-fluoro-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 3-Chloro-1,5-dimethyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 15 5-Chloro-1,3-dimethyl-N-(1,1 3-trimethylindane-4-yl) pyrazole-4-carboxamide, 5-Bromo-1,3-dimethyl N-tl,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,3-Dimethyl-5-iodo-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 3-Bromo-1,5-dimethyl-N-tl,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,5-Dimethyl-3-iodo-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 25 3,5-Difluoro-l-methyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 3,5-Dichloro-l-methyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 3,5~Dibromo--l-methyl-N-(1,1,3-trimethyli.ndane-4~yl) 3~ pyrazole-4-carboxamide, 3,5-D:i.iodo-l-methyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, l-Methyl-3--trifluoromethyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, l~Methyl-5-trifluoromethyl-N-tl,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 3-Fluoro-l-methyl-5-trifluoromethyl-N-(],1,3-tri-methylindane-4-yl)pyrazole-4-carboxamide, 5-Fluoro-l-methyl-3-trifluoromethyl-N-(1,1,3-tri-methylindane-~-yl)pyrazole-4-carboxamide, 3-Chloro-l-methyl-5-trifluoromethyl-N-(1,1,3-tri methylindane-4-yl)pyrazole-4-carboxamide !
5-Chloro-l-methyl-3-trifluoromethyl-N-(1,1,3-tri-methylindane-4-yl)pyrazole-4-carboxamide, 5-Bromo-l-me-thyl-3-trifluoromethyl-N-(1,1,3-tri-methylindane-4-yl)pyrazole-4-carboxamide, 5-Iodo-l-methyl-3-trifluoromethyl-N-(1,1,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 1,3-Dimethyl-5-tri~luoromethyl-N-(1,1,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 1,5-Dimethyl-3-trifluoromethyl-N-(1,1,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 3,5-Bis(trifluoromethyl)-l-methyl-N-(1,l.,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 3-Ethyl-l-methyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide, 5-Ethyl-l-methyl-N-(1,1-dimethylindane-4-yl)pyrazole-4-carboxamide, 3-Ethyl-1-methyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 5-Ethyl-1-methyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,3-Dimethyl-5-ethyl-N-(1,1-dimethylindane-4-yl) pyrazole-4-carboxamide, 1,3-Dimethyl-5-ethyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,5-Dj.methyl-3 ethyl-N-(1,1-dimethylindane-4-yl) pyrazole-4-carboxamide, 1,5-Dimethyl-3-ethyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 3-Ethyl-5-~luoro-1-methyl-N-(l,l-dimethylindane-4-
pyrazole-4-carboxamide, 3-Chloro-1,5-dimethyl-N-(l,l-dimethylindane-4-yl) pyrazole-~-carboxamide, 3-~3romo 1,S-dimethyl-N-(l,l-dimethylindane~4-yl) pyrazole-4-carboxamide, 1,5-Di.methyl-3-iodo-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide, 3,5-Difluoro-l-methyl-N-(l,l--dimethylindane-4-yl) pyrazole-4-carboxamide, 3,5-Dichloro-l-methyl-N-(l,l-dimethylindane-4-yl~
pyrazole-4-carboxamide, 3,5-Dibromo-l-methyl-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide, 3,5-Diiodo-l-methyl-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxami~e, 1 Methyl-3-trifluoromethyl-N-(l,l-dimethylindane-4~yl) pyrazole-4-carboxamide, l-Methyl-5-trifluoromethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide, 3-Fluoro-l-methyl-5-trifluoromethyl-N-(l,l-dimethyl-indane-4-yl)pyrazole-4-carboxamide, 5-Fluoro-l-methyl-3-trifluoromethyl-N-~l,l-dimethyl-indane-4-yl)pyrazole-4-carboxamide, 3-Chloro-l-methyl-5-trifluoromethyl-N-(l,l-dimethyl-indane-4-yl)pyrazole-4-carboxamide, 5-Chloro-l-methyl-3-trifluoromethyl-N-(l,l-dimethyl-indane-4-yl)pyrazole-~-carboxamide, 5-Bromo-l-methyl-3-trifluoromethyl-N-(l,l dimethyl-indane~4-yl)pyrazole-~-carboxamide, 5-Iodo-l-methyl-3-trifluoromethyl-N-(l,l-dimethyl-indane-4-yl)pyrazole-4-carboxamide, 1,3-Dimethyl-5-tri~luoromethyl-N-(l,l-dimethylin~ane-4-yl)pyrazole-4-carboxamide, 1,5-Dimethyl-3-trifluoromethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide, - 12 ~ 2~35 3,5-Bis(tri~luoromethyl)-1-methyl-N-(l,l-dimethyl-indane-4-yl)pyrazole-4-carboxamide, 1,3-Dimethyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 5 1,5-Dimethyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 1,3,5-Trimethyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,5-Dimethyl-3-fluoro-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,3-Dimekhyl-5-fluoro-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 3-Chloro-1,5-dimethyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 15 5-Chloro-1,3-dimethyl-N-(1,1 3-trimethylindane-4-yl) pyrazole-4-carboxamide, 5-Bromo-1,3-dimethyl N-tl,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,3-Dimethyl-5-iodo-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 3-Bromo-1,5-dimethyl-N-tl,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,5-Dimethyl-3-iodo-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 25 3,5-Difluoro-l-methyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 3,5-Dichloro-l-methyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 3,5~Dibromo--l-methyl-N-(1,1,3-trimethyli.ndane-4~yl) 3~ pyrazole-4-carboxamide, 3,5-D:i.iodo-l-methyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, l-Methyl-3--trifluoromethyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, l~Methyl-5-trifluoromethyl-N-tl,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 3-Fluoro-l-methyl-5-trifluoromethyl-N-(],1,3-tri-methylindane-4-yl)pyrazole-4-carboxamide, 5-Fluoro-l-methyl-3-trifluoromethyl-N-(1,1,3-tri-methylindane-~-yl)pyrazole-4-carboxamide, 3-Chloro-l-methyl-5-trifluoromethyl-N-(1,1,3-tri methylindane-4-yl)pyrazole-4-carboxamide !
5-Chloro-l-methyl-3-trifluoromethyl-N-(1,1,3-tri-methylindane-4-yl)pyrazole-4-carboxamide, 5-Bromo-l-me-thyl-3-trifluoromethyl-N-(1,1,3-tri-methylindane-4-yl)pyrazole-4-carboxamide, 5-Iodo-l-methyl-3-trifluoromethyl-N-(1,1,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 1,3-Dimethyl-5-tri~luoromethyl-N-(1,1,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 1,5-Dimethyl-3-trifluoromethyl-N-(1,1,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 3,5-Bis(trifluoromethyl)-l-methyl-N-(1,l.,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 3-Ethyl-l-methyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide, 5-Ethyl-l-methyl-N-(1,1-dimethylindane-4-yl)pyrazole-4-carboxamide, 3-Ethyl-1-methyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 5-Ethyl-1-methyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,3-Dimethyl-5-ethyl-N-(1,1-dimethylindane-4-yl) pyrazole-4-carboxamide, 1,3-Dimethyl-5-ethyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 1,5-Dj.methyl-3 ethyl-N-(1,1-dimethylindane-4-yl) pyrazole-4-carboxamide, 1,5-Dimethyl-3-ethyl-N-(1,1,3-trimethylindane-4-yl) pyrazole-4-carboxamide, 3-Ethyl-5-~luoro-1-methyl-N-(l,l-dimethylindane-4-
6~2 ~'3 3 yl)pyrazole-4 carboxamide, 5-Ethyl-3-fluoro-1-methyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide, 3-Ethyl-5-fluoro-1-methyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-~-carboxamide, 5-Ethyl-3-fluoro-1-methyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 5-Chloro-3-ethyl-1-methyl-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide, 3-Chloro-5-ethyl 1-methyl-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide, 5-Chloro-3-ethyl-1-methyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 3-~hloro-5-ethyl-1-methyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 5-Bromo-3-ethyl-1-methyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide, 3-Bromo-5-ethyl-1-methyl-N-(l,l-dimethylindane 4-yl)pyrazole-4-carboxamide, 20 5-8romo-3-ethyl-1-meth~l-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 3-8romo-5-ethyl-1-methyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 3-Ethyl-S-iodo-l-methyl-N-(l,l-dimethylindane-4-yi) pyrazole-4-carboxamide, 5-Ethyl-3-iodo-1-methyl-N-(1,1-dimethylindane-4-yl) pyrazole-4-carboxamide, 3-Ethyl-5-iodo-1-methyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide, 30 5-Ethyl-3 iodo-1-methyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-~-carboxamide, 3-Ethyl-l-methyl-5-trifluoromethyl-N-(l,l-dimethyl-indane-4-yl)pyrazole-4-carboxamide, 5-Ethyl-l-methyl-3-trifluoromethyl-N-(l,l-dimethyl-indane-4-yl)pyrazole~4-carboxamide, - 15 - ~2~273 ~
3-Ethyl-1-methyl-5-trifluoromethyl-N-(1,1,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 5-Ethyl-l-methyl-3-trifluoromethyl-N-(1,1,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 1,3,5-trimethyl-N-(1,1-dimethyl-5-fluoroindane-4-yl) pyrazole-4-carboxamide, 5-Chloro-1,3-dimethyl-N-(l,l-dimethyl-5-fluoroindane-4-yl)pyrazole-4-carboxamide, 1,3-Dimethyl-5-fluoro-N-(l,l-dimethyl-5 fluoroindane-4-yl)pyrazole-4-carboxamide, 1,5-Dimethyl-3-trifluoromethyl-N-(l,l-dimethyl-5-fluoroindane-4-yl)pyrazole-4-carboxamide, 1,3,5-Trimethyl-N-(l,l-dimethyl-7-fluoroindane-4-yl) pyrazole-4-carboxamide, 5-Chloro-1~3-dimethyl-N-(l,l-dimethyl 7-fluoroindane-4-yl)pyrazole-4-carboxamide, 1,3-Dimethyl-5-fluoro-N-(l,l-dimethyl-7-fluoroindane-4-yl)pyraæole-4-carboxamide, 1,5-Dimethyl-3-trifluoromethyl-N-(l,l-dimethyl-7-fluoroindane-4-yl)pyrazole-4-carboxamide, Production of the present compounds will be explained by the following synthesis examples.
Synthesis Example 1 [Synthesis of compound (6)~
To a solution of 1.61 g of l,l-dimethyl-4- aminoindane and 2 ml of pyridine in 50 ml of toluene was added with stirring at room temperature a solution of 2.47 g of 5-chloro-1-methyl-3-trifluoromethyl-pyrazole-4-carboxylic acid chloride in 10 ml of toluene, followed by stirring at room temperature for 12 hours. Thereafter, the reaction solution was pour-ed into a cold water to result in separation into two layers. The aqueous layer was extracted with ethyl acetate and the ethyl acetate layer was combined with the organic layer. The resultant organic layer was dried over anhydrous magnesium sulfate and the ~262t735 solvent was distilled off. The residue was recrystal~
lized using toluene to obtain 3.01 g of 5-chloro-1-methyl-3-trifluoromethyl-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide having a melting point of 119.9C.
Synthesis Example 2 [Synthesis of compound (1)]
To a solution of 600 mg (6.0 mmol) of acetylacetone and 1.12 g (6.0 mmol) of 1,1 dimethyl-indane-4-yl isocyanate in 10 ml of toluene was added dropwise 730 mg (7.2 mmol) of trie-thylamine at room temperature with stirring, followed by further stirring at room temperature for 12 hours. Then the reaction solution was concentrated under reduced pressure to obtain crude 3-(1,1-dimethylindane-4-yl carbamoyl) pentane-2,4-dione. Then, thus obtained crude 3-(1,1-dimethylindane-4-yl carbamoyl~pentane-2,4-dione was dissolved in 10 ml of ethanol. To the solution was added 276 mg (6.0 mmol) of methylhydrazine, followed by stirring at room temperature for 6 hours and then for further one hour under reflux with heating.
~fter left standing for cooling, the solvent was distilled off under reduced pressure and the residue was recrystallized with methanol to obtain 1.25 g of 1,3,5-trimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide which had a melting point of 151.6C.
Synthesis Example 3 [Synthesis of compound (2)]
1.12 g (10 mmol) of 1,3-dimethylpyrazoline-5-one was suspended in 10 ml of toluene containing 1.11 g of triethylamine. To the suspension was added dropwise a solution of lu87 g of l,l-dimethylindane-4-yl isocyanate in 2 ml of toluene with stirring at room tem~erature, followed by further stirring at room temperature for 12 hours. Thereater, the - 17 ~627~
reaction mixture was extracted with water three times.
The aqueous layers were made acidic with concentrated hydrochloric acid and cooled with ice. The precipi-tate produced was filtered and air-dried to obtain 1.81 g of 1,3-dimethyl-5~oxo-N-(1,1-dimethylindane-4-yl)4,5-dihydropyrazole-4-carboxamide (mp 141.4C).
Then, thus obtained 1,3-dimethyl-5-oxo-N-(l,l-dimethyl-indane-4-yl)-4,5-dihydropyrazole-4-carboxamide was added to a mixture of 5 ml of phosphorus oxychloride 10 and 907 mg of N,N-diethylaniline. The resultant mixture was stirred under re~lux with heating fox 1.5 hour. The obtained reaction mixture was poured into ice water and extracted with chloroeorm three times. The chloroform layer was washed with water 15 and dried over anhydrous magnesium sulEate. Thereafter, the solvent was distilled off under reduced pressure and the residue was recrystallized with ethanol to obtain 0.96 g of 5- chloro-1,3-dimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide (mp 20 175.2C).
Synthesis Example 4 [Synthesis of compound (3)]
270 mg of 5-chloro-1,3-dimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide obtained 25 in Synthesis Example 3 was dissolved in 6 ml of eth~nol and subjected to catalytic reduction using 40 mg of PdtC (596) as a catalyst in the presence of 150 mg of anhydrous sodium acetate. After completion of the reaction, the catalyst and a precipitate 30 were filtered off with Celite and the filtrate was concentrated under reduced pressure and the residue was subjected to silica gel column chromatography to obtain 156 m~ of 1,3-dimethyl-N-(1,1 dimethyl-indane-4-yl)pyrazole-4-carboxamide (mp 146.8C).
~ 18 ~
Synthesis Example 5 [Synthesis of compound (5)]
1.0 g of potassium fluoride powder, 15 ml of sulfolane and 20 ml of toluene were charged in a reactor and water in the reaction system was removed by molecular sieves under reflux with heating, then toluene was distilled off and the content was cooled.
Then, thexeto was added 318 mg of 5-chloro-1,3-dimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide and the mixture was heated in a nitrogen atmosphere at 180 200C for 16 hours. After cooling, to the reaction mixture were added water and ether to result in separation into two layers. The aqueous layer was extracted with ether and the ether layer was combined with the ether layer obtained in the above. The resultant ether layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfateO Then, the solvent was distilled off and the residue was subjected to silica gel column chromatography to obtain 140 mg of 5-fluoro-1,3-dimethyl-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide (mp 138.5C).
19F-NMR spectrum (Solvent : CDCQ3, External standard :
CF3C02H) 48 ppm (in the higher magnetic field side against external standard of CF3C02H) Synthesis Example 6 [Synthesis of compound (11)]
To a solution of 1.75 g of 1,1,3-trimethyl-4-aminoindane and 2 ml of triethylamine in 50 ml of tetrahydrofuran was with stirring at room temperature added dropwise a solution of 1.73 g of 1,3,5-tri-methylpyrazole-4-carboxylic acid chloride in 10 ml of tetrahydrofuran, followed by stirring at room temperature for 12 hours. Then, the reaction solution was poured into a cold water to result in separation into two layers. The aqueous layer was extracted with e-thyl acetate and the ethyl acetate layer was combined wi-th the organic layer. The resultant organic layer was dried over anhydrous magnesium sulfate and -the solvent was dis-tilled off. The residue was recrystallized with toluene to obtain 2.55 g of 1,3,5-trimethyl-N-(1,1,3-trimethylinclane-4-yl)pyrazole-~-carboxamide (mp 176.2C).
Synthesis Example 7 [Synthesis of compound (15)]
100 g of potassium fluoride powder, 300 ml of sulfolane, 100 ml of toluene and 5 g of 18-Crown-6 were charged in a reactor and water in the system was removed by molecular sieves under reflux with heatin~, followed by distilling off of toluene and cooling the residue. Then, thereto was added 42 g of 5 chloro-1,3-dimethyl-N-(1,1,3-trimethylindane-~-yl)pyrazole carboxamide and the mixture was stirred wi-th heating at 180 - 200C for 10 hours in a nitrogen atmosphere. After cooling, water and ether were added to the reaction mixture to result in separation into two layers. The aqueous layer was extracted with ether and the ether layer was combined with the ether layer obtained above. The resultant ether layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. Then the solvent was distilled off and the residue was recrystallized with cyclohexane-toluene mixed solvent to obtain 31.5 g of 1,3-dimethyl-5-30 fluoro~N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide ~mp 136.9C).
Synthesis Example 8 [Synthesis of compound (11)]
.
5 cc of 85% aqueous sulfuric acid was added to 0.31 g of N-(1,3,5-trimethylpyrazole-4-yl carbonyl)-- 20 ~ 7~5 2,2,4-trime~hyl-1,2,3,4-tetrahydroquinoline a~ room temperature, followed by stirring at the same temper-ature for 24 hours. The reaction mixture was poured into ice water. The precipitated crystal was filter-ed and washed with n-hexane. Af-ter dryi.ng, the crystal was recrystallized from n-hexane-ethyl acetate to obta.in 0.17 g of the objective 1,3,5-trimethyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide.
Representative examples of the present compounds which can be produced by these methods are shown in Table 1.
Table 1 Compounds represented by the formula:
C3 ~ ~ C~ \
(F)n . _ .
No. Rl R2 R3 n Position Physical 19F-NMR(ppm) _ _ (1) CH3 CH3 H 0 _ mp.151.6C
(2) CH3 CQ H 0 _ mp.l7502C
~ _ .. .. __ (3) CH3 H H 0 _ mp.l46.8C
.... .. _ _ . .. _ . .__ .. ..... _ (4) CH3 CH3 H 1 5~. ~. mp.193.3C
(S) CH3 F H 0 _ mp.138.5C 48.0 2~3~;
_ .
(6 ~ C F 3 C Q H O _mp .119.9 C - 17.0
3-Ethyl-1-methyl-5-trifluoromethyl-N-(1,1,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 5-Ethyl-l-methyl-3-trifluoromethyl-N-(1,1,3-trimethyl-indane-4-yl)pyrazole-4-carboxamide, 1,3,5-trimethyl-N-(1,1-dimethyl-5-fluoroindane-4-yl) pyrazole-4-carboxamide, 5-Chloro-1,3-dimethyl-N-(l,l-dimethyl-5-fluoroindane-4-yl)pyrazole-4-carboxamide, 1,3-Dimethyl-5-fluoro-N-(l,l-dimethyl-5 fluoroindane-4-yl)pyrazole-4-carboxamide, 1,5-Dimethyl-3-trifluoromethyl-N-(l,l-dimethyl-5-fluoroindane-4-yl)pyrazole-4-carboxamide, 1,3,5-Trimethyl-N-(l,l-dimethyl-7-fluoroindane-4-yl) pyrazole-4-carboxamide, 5-Chloro-1~3-dimethyl-N-(l,l-dimethyl 7-fluoroindane-4-yl)pyrazole-4-carboxamide, 1,3-Dimethyl-5-fluoro-N-(l,l-dimethyl-7-fluoroindane-4-yl)pyraæole-4-carboxamide, 1,5-Dimethyl-3-trifluoromethyl-N-(l,l-dimethyl-7-fluoroindane-4-yl)pyrazole-4-carboxamide, Production of the present compounds will be explained by the following synthesis examples.
Synthesis Example 1 [Synthesis of compound (6)~
To a solution of 1.61 g of l,l-dimethyl-4- aminoindane and 2 ml of pyridine in 50 ml of toluene was added with stirring at room temperature a solution of 2.47 g of 5-chloro-1-methyl-3-trifluoromethyl-pyrazole-4-carboxylic acid chloride in 10 ml of toluene, followed by stirring at room temperature for 12 hours. Thereafter, the reaction solution was pour-ed into a cold water to result in separation into two layers. The aqueous layer was extracted with ethyl acetate and the ethyl acetate layer was combined with the organic layer. The resultant organic layer was dried over anhydrous magnesium sulfate and the ~262t735 solvent was distilled off. The residue was recrystal~
lized using toluene to obtain 3.01 g of 5-chloro-1-methyl-3-trifluoromethyl-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide having a melting point of 119.9C.
Synthesis Example 2 [Synthesis of compound (1)]
To a solution of 600 mg (6.0 mmol) of acetylacetone and 1.12 g (6.0 mmol) of 1,1 dimethyl-indane-4-yl isocyanate in 10 ml of toluene was added dropwise 730 mg (7.2 mmol) of trie-thylamine at room temperature with stirring, followed by further stirring at room temperature for 12 hours. Then the reaction solution was concentrated under reduced pressure to obtain crude 3-(1,1-dimethylindane-4-yl carbamoyl) pentane-2,4-dione. Then, thus obtained crude 3-(1,1-dimethylindane-4-yl carbamoyl~pentane-2,4-dione was dissolved in 10 ml of ethanol. To the solution was added 276 mg (6.0 mmol) of methylhydrazine, followed by stirring at room temperature for 6 hours and then for further one hour under reflux with heating.
~fter left standing for cooling, the solvent was distilled off under reduced pressure and the residue was recrystallized with methanol to obtain 1.25 g of 1,3,5-trimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide which had a melting point of 151.6C.
Synthesis Example 3 [Synthesis of compound (2)]
1.12 g (10 mmol) of 1,3-dimethylpyrazoline-5-one was suspended in 10 ml of toluene containing 1.11 g of triethylamine. To the suspension was added dropwise a solution of lu87 g of l,l-dimethylindane-4-yl isocyanate in 2 ml of toluene with stirring at room tem~erature, followed by further stirring at room temperature for 12 hours. Thereater, the - 17 ~627~
reaction mixture was extracted with water three times.
The aqueous layers were made acidic with concentrated hydrochloric acid and cooled with ice. The precipi-tate produced was filtered and air-dried to obtain 1.81 g of 1,3-dimethyl-5~oxo-N-(1,1-dimethylindane-4-yl)4,5-dihydropyrazole-4-carboxamide (mp 141.4C).
Then, thus obtained 1,3-dimethyl-5-oxo-N-(l,l-dimethyl-indane-4-yl)-4,5-dihydropyrazole-4-carboxamide was added to a mixture of 5 ml of phosphorus oxychloride 10 and 907 mg of N,N-diethylaniline. The resultant mixture was stirred under re~lux with heating fox 1.5 hour. The obtained reaction mixture was poured into ice water and extracted with chloroeorm three times. The chloroform layer was washed with water 15 and dried over anhydrous magnesium sulEate. Thereafter, the solvent was distilled off under reduced pressure and the residue was recrystallized with ethanol to obtain 0.96 g of 5- chloro-1,3-dimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide (mp 20 175.2C).
Synthesis Example 4 [Synthesis of compound (3)]
270 mg of 5-chloro-1,3-dimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide obtained 25 in Synthesis Example 3 was dissolved in 6 ml of eth~nol and subjected to catalytic reduction using 40 mg of PdtC (596) as a catalyst in the presence of 150 mg of anhydrous sodium acetate. After completion of the reaction, the catalyst and a precipitate 30 were filtered off with Celite and the filtrate was concentrated under reduced pressure and the residue was subjected to silica gel column chromatography to obtain 156 m~ of 1,3-dimethyl-N-(1,1 dimethyl-indane-4-yl)pyrazole-4-carboxamide (mp 146.8C).
~ 18 ~
Synthesis Example 5 [Synthesis of compound (5)]
1.0 g of potassium fluoride powder, 15 ml of sulfolane and 20 ml of toluene were charged in a reactor and water in the reaction system was removed by molecular sieves under reflux with heating, then toluene was distilled off and the content was cooled.
Then, thexeto was added 318 mg of 5-chloro-1,3-dimethyl-N-(l,l-dimethylindane-4-yl)pyrazole-4-carboxamide and the mixture was heated in a nitrogen atmosphere at 180 200C for 16 hours. After cooling, to the reaction mixture were added water and ether to result in separation into two layers. The aqueous layer was extracted with ether and the ether layer was combined with the ether layer obtained in the above. The resultant ether layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfateO Then, the solvent was distilled off and the residue was subjected to silica gel column chromatography to obtain 140 mg of 5-fluoro-1,3-dimethyl-N-(l,l-dimethylindane-4-yl) pyrazole-4-carboxamide (mp 138.5C).
19F-NMR spectrum (Solvent : CDCQ3, External standard :
CF3C02H) 48 ppm (in the higher magnetic field side against external standard of CF3C02H) Synthesis Example 6 [Synthesis of compound (11)]
To a solution of 1.75 g of 1,1,3-trimethyl-4-aminoindane and 2 ml of triethylamine in 50 ml of tetrahydrofuran was with stirring at room temperature added dropwise a solution of 1.73 g of 1,3,5-tri-methylpyrazole-4-carboxylic acid chloride in 10 ml of tetrahydrofuran, followed by stirring at room temperature for 12 hours. Then, the reaction solution was poured into a cold water to result in separation into two layers. The aqueous layer was extracted with e-thyl acetate and the ethyl acetate layer was combined wi-th the organic layer. The resultant organic layer was dried over anhydrous magnesium sulfate and -the solvent was dis-tilled off. The residue was recrystallized with toluene to obtain 2.55 g of 1,3,5-trimethyl-N-(1,1,3-trimethylinclane-4-yl)pyrazole-~-carboxamide (mp 176.2C).
Synthesis Example 7 [Synthesis of compound (15)]
100 g of potassium fluoride powder, 300 ml of sulfolane, 100 ml of toluene and 5 g of 18-Crown-6 were charged in a reactor and water in the system was removed by molecular sieves under reflux with heatin~, followed by distilling off of toluene and cooling the residue. Then, thereto was added 42 g of 5 chloro-1,3-dimethyl-N-(1,1,3-trimethylindane-~-yl)pyrazole carboxamide and the mixture was stirred wi-th heating at 180 - 200C for 10 hours in a nitrogen atmosphere. After cooling, water and ether were added to the reaction mixture to result in separation into two layers. The aqueous layer was extracted with ether and the ether layer was combined with the ether layer obtained above. The resultant ether layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. Then the solvent was distilled off and the residue was recrystallized with cyclohexane-toluene mixed solvent to obtain 31.5 g of 1,3-dimethyl-5-30 fluoro~N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide ~mp 136.9C).
Synthesis Example 8 [Synthesis of compound (11)]
.
5 cc of 85% aqueous sulfuric acid was added to 0.31 g of N-(1,3,5-trimethylpyrazole-4-yl carbonyl)-- 20 ~ 7~5 2,2,4-trime~hyl-1,2,3,4-tetrahydroquinoline a~ room temperature, followed by stirring at the same temper-ature for 24 hours. The reaction mixture was poured into ice water. The precipitated crystal was filter-ed and washed with n-hexane. Af-ter dryi.ng, the crystal was recrystallized from n-hexane-ethyl acetate to obta.in 0.17 g of the objective 1,3,5-trimethyl-N-(1,1,3-trimethylindane-4-yl)pyrazole-4-carboxamide.
Representative examples of the present compounds which can be produced by these methods are shown in Table 1.
Table 1 Compounds represented by the formula:
C3 ~ ~ C~ \
(F)n . _ .
No. Rl R2 R3 n Position Physical 19F-NMR(ppm) _ _ (1) CH3 CH3 H 0 _ mp.151.6C
(2) CH3 CQ H 0 _ mp.l7502C
~ _ .. .. __ (3) CH3 H H 0 _ mp.l46.8C
.... .. _ _ . .. _ . .__ .. ..... _ (4) CH3 CH3 H 1 5~. ~. mp.193.3C
(S) CH3 F H 0 _ mp.138.5C 48.0 2~3~;
_ .
(6 ~ C F 3 C Q H O _mp .119.9 C - 17.0
(7) CF3 CH3 H 0 _mp .189.4 ~C -18.5 . .. _ .. _ _
(8) CF3 H H 0 _mp .144.1 C -18.8 _ . . .___
(9) CH3 CF3 H 0 _mp .139.9 C - 20.7
10 (10) H CF3 H 0 _mp.106.0C -21.0 .
(11) C~I3 CH3 CH3 ~mp .176.2C
_ ~ . l
_ ~ . l
(12) c~3 H C~13 ~mp.156.2C
~ _
~ _
(13) H CH3 CH3 ~mp .161.0 C
.. . _
.. . _
(14) CH3 CQ CH3 ~mp .134.4C
_ _ ,_.
20 (15) CH3 F CH3 ~mp.l36.9C 48.2 __ _ _ ... _.
(16) CF3 CH3 CH3 ~mp .161.8 C -18.3 _ 25 (17) C~I3 CF3 CH3 ~mp.l40.3C -20.3 _ (18) CF3 CQ CH3 ~mp .157.4 C 16.9 _ _ __ ,. .
(19) CF3 H CH3 ~mp .166.2C 18.8 ~ _ (20) C2~5 CH3 H 0 _mp.l26.8C
.. _.. __. . . ,, (21) C2H5 CQ H 0 _mp.l40.3C
~ _ (22~ C zH5 F H O _mp .105.6C 47.8 - 22 ~ 3~
_ . .... .
(23) C2H5 CQ CH3 ~ mp.125.7C
. _ _ _ ~ . . _ _ 124) C2H5 F CH3 0 _ mp. 9B.3C 48.1 * Trifluoroace-tlc acid was used as an external standard. Nega-tive value indicates lower magnetic field side.
~ hen the present compound is used as an active ingredient of fungicides, it may be used as it is without adding any o-ther components, but generally, it is formulated into emulsifiable concentrates, wettable powders, suspension formulations, granules, dusts, liquids and the like by mixing with a solid or liquid carrier, a surface active agent and other auxiliaries for formulation.
The conten-t of the present compound contain-ed as an active ingredient in these formulations is 0.1to 99.9~, preferably 0.2 to 80~ by weight.
The solid carriers include for example fine powders or granules of kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn starch powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrated silicon dioxide and the like. The liquid carrier includes for example aromatic hydrocarbons such as xylene, methylnaphthalene and the like, alcohols such as isopropanol, ethylene glycol r cellosolve and the like, ketones such as acetone, cyclohexanone, isophorone and the like, vegetable oils such as soy-bean oil, cotton seed oil and the like, dimethyl sulfoxide, acetonitrile, water and the like.
The surface active agents used for emul-sification, dispersion, wetting, etc. include for - 23 ~ 5 example anionic surface active agents such as salts of alkyl sulfate, alkyl (aryl) sulfonates, dialkyl~
sulfosuccinates, salts of polyoxyethylene alkylaryl ether phosphoric acid esters, naphthalenesulfonic acid/~ormalin condensates, etc. and nonionic surface active agents such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. The auxiliaries for formulation include for example lignosulfonates, alginates, polyvinyl alcohol, gum arabic, CMC (carboxy-methyl cellulose), PAP (acid isopropyl phosphate), etc.
The following are formulation examples, where the present compounds used are indicated by the numbers given in Table 1 and parts are by weight.
Formulation Example 1 Fifty parts of each of the present compounds 20 (1) - (24), 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrated silicon dioxide are thoroughly pulverized and mixed to obtain a wettable powder.
Formulation Example 2 Ten parts of each of the present compounds (1) - (24), 14 parts of polyoxyethylenestyrylphenyl ether, 6 parts o calcium dodecylbenzenesulfonate and 70 parts o~ xylene are thoroughly mixed to obtain an emulsifiable concentrate.
Formulation Exam ~ 3 Two parts of each of the present compounds (1) - (24), 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignosulfonate, 30 parts ~ 3-3 of bentonite, and 65 parts of kaolin clay are thoroughly pulverized and mixed, well kneaded with watex, then granulated and dried to obtain a granule.
Formulation Example_~
Twentyfive parts of each of the present compounds (1) - (24), 3 parts of polyoxyethylene-sorbitan monooleate, 3 parts of CMC and 69 par-ts of water are mixed and wet-pulverized to particle size of not more than 5 microns to obtain a suspension formulation.
Formulation Example 5 Two parts of each of the present compounds (1) - (24), 88 parts of kaolin clay and 10 parts of talc are thoroughly pulverized and mixed to obtain a dust.
These formulations as such or dilut~d with, for example, water are applied to soil ox directly to plants. In more detail, they are used in various forms, e~g., sprinkling, spraying or dusting on plants or sprinkling, spraying, dusting or granule-sprinkling onto soil surface or if necessary, subsequent fur-ther soil-mixingY
Fungicidal effects can be expected to be further increased by using them in admixture wi-th other fungicides. Furthermore, these formula-tions may also be used in admixture with insecticides, acaricides, nematocides, herbicides, plant growth regulating agent, fertilizers, soil improvers and the like.
The present compounds can be uséd as an active ingredient of fungicides to be used for paddy field, plowland, orchard, pasture, turf and the like.
When the present compound is used as an active ingredient of fungicide, its dosage is ~2~2~3~
generally 0.5 to 100 g, preferably 1 to 50 g per are, although it depends on weather conditions, form of formulations, time, method and place of applica-tion, diseases to be controlled, crops to be treated, etc.
When the emulsifiable concentrate, wettable powder, suspension formulation, liquid formulation, etc. are diluted with water for use, the concentration is 0.001~ to 1~, preferably 0.005~ to 0.5~. Granule and dust are used as they are without dilution.
The effect of the present compounds as an active ingredient of fungicides will be shown by the following test examples. The present compounds used are indicated by the compound number given in Table 1 and the compounds used for comparison are indicated by the compound number given in Table 2.
Table 2 _ Compound No. Chemical formula Note CH3 Commercially A ~ ~ OC3H7~i) fungicide mepronil Commercially CCQ -CH-NHCHO
3 1 avallable B ~ N) triforine CCQ3-C~-NHCHO
- 26 - ~ ~273 Commerc la 11 y CN ~ CN available C CQ ~ CQ TpNngicide O Commercially CQ ~ O-CH-C-C(CH3)3 available D ,N ~ fungicide ~ N triadimefon Test Example 1 Test for preventive controlling effect on sheath blight (Rhizoctonia ~^ solani) of rice.
Sandy loam was filled in a plastic pot and rice (var.: Kinki No. 33) was sowed and cultivated in a greenhouse for 60 days to grow to seedlings in the 6 - 7 leaf stages. The test compounds were formulated into emulsifiable concentrates in accordance with the Formulation Example 2 and they were diluted with water to a given concentration. These were foliar-sprayed onto the seedlings to allow them to thoroughlydeposit on the leaf surface. After ~ hours ~rom the spraying, the seedlings were inoculated by putting agar piece containing Rhizoctonia solani. After inoculation, the seedlings were grown at 28C for ~
days under hlghly humid condltion and the controlling effects were observed. The results are shown in Table 3.
The controlling effect is determined by observing with the naked eye the condition of disease of test plants on examination, namely, the degree of - 27 ~ 27 ~S
fungus colon~ and infected area of leaf and stem and grading the condition of diseases into the following six steps 0, 1, 2, 3, 4 and 5:
5 ...... No infected area and fungus colony are noticed.
4 ...... Infec-ted area and fungus colony are noticed in about 10% of leaf and stem.
3 O~ Infected area and fungus colony are noticed in about 30~ of leaf and stem.
2 ...... Infected area and fungus colony are noticed in about 50% of leaf and stem.
1 ...... Infected area and fungus colony are noticed in about 70~ of leaf and stem.
0 ...... Infected area and fungus colony are noticed in more than about 70~ and no difference is noticed from the condition of disease when no compound is used.
The above grading is applied to all of the following test examples.
Table 3 Concentration of Test compounds active ingredient Controlling effect (ppm) (1) 10 5 (2) 10 5 (3) 10 5 (4) 10 5 (5) 10 5 (6) 10 5 (7) 10 5 (g) 50 5 (9) 50 5 (10) 100 5 - 28 - ~2 (11) 10 5 (12) 10 5 (13) 50 5 (14) 10 5
_ _ ,_.
20 (15) CH3 F CH3 ~mp.l36.9C 48.2 __ _ _ ... _.
(16) CF3 CH3 CH3 ~mp .161.8 C -18.3 _ 25 (17) C~I3 CF3 CH3 ~mp.l40.3C -20.3 _ (18) CF3 CQ CH3 ~mp .157.4 C 16.9 _ _ __ ,. .
(19) CF3 H CH3 ~mp .166.2C 18.8 ~ _ (20) C2~5 CH3 H 0 _mp.l26.8C
.. _.. __. . . ,, (21) C2H5 CQ H 0 _mp.l40.3C
~ _ (22~ C zH5 F H O _mp .105.6C 47.8 - 22 ~ 3~
_ . .... .
(23) C2H5 CQ CH3 ~ mp.125.7C
. _ _ _ ~ . . _ _ 124) C2H5 F CH3 0 _ mp. 9B.3C 48.1 * Trifluoroace-tlc acid was used as an external standard. Nega-tive value indicates lower magnetic field side.
~ hen the present compound is used as an active ingredient of fungicides, it may be used as it is without adding any o-ther components, but generally, it is formulated into emulsifiable concentrates, wettable powders, suspension formulations, granules, dusts, liquids and the like by mixing with a solid or liquid carrier, a surface active agent and other auxiliaries for formulation.
The conten-t of the present compound contain-ed as an active ingredient in these formulations is 0.1to 99.9~, preferably 0.2 to 80~ by weight.
The solid carriers include for example fine powders or granules of kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn starch powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrated silicon dioxide and the like. The liquid carrier includes for example aromatic hydrocarbons such as xylene, methylnaphthalene and the like, alcohols such as isopropanol, ethylene glycol r cellosolve and the like, ketones such as acetone, cyclohexanone, isophorone and the like, vegetable oils such as soy-bean oil, cotton seed oil and the like, dimethyl sulfoxide, acetonitrile, water and the like.
The surface active agents used for emul-sification, dispersion, wetting, etc. include for - 23 ~ 5 example anionic surface active agents such as salts of alkyl sulfate, alkyl (aryl) sulfonates, dialkyl~
sulfosuccinates, salts of polyoxyethylene alkylaryl ether phosphoric acid esters, naphthalenesulfonic acid/~ormalin condensates, etc. and nonionic surface active agents such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. The auxiliaries for formulation include for example lignosulfonates, alginates, polyvinyl alcohol, gum arabic, CMC (carboxy-methyl cellulose), PAP (acid isopropyl phosphate), etc.
The following are formulation examples, where the present compounds used are indicated by the numbers given in Table 1 and parts are by weight.
Formulation Example 1 Fifty parts of each of the present compounds 20 (1) - (24), 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrated silicon dioxide are thoroughly pulverized and mixed to obtain a wettable powder.
Formulation Example 2 Ten parts of each of the present compounds (1) - (24), 14 parts of polyoxyethylenestyrylphenyl ether, 6 parts o calcium dodecylbenzenesulfonate and 70 parts o~ xylene are thoroughly mixed to obtain an emulsifiable concentrate.
Formulation Exam ~ 3 Two parts of each of the present compounds (1) - (24), 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignosulfonate, 30 parts ~ 3-3 of bentonite, and 65 parts of kaolin clay are thoroughly pulverized and mixed, well kneaded with watex, then granulated and dried to obtain a granule.
Formulation Example_~
Twentyfive parts of each of the present compounds (1) - (24), 3 parts of polyoxyethylene-sorbitan monooleate, 3 parts of CMC and 69 par-ts of water are mixed and wet-pulverized to particle size of not more than 5 microns to obtain a suspension formulation.
Formulation Example 5 Two parts of each of the present compounds (1) - (24), 88 parts of kaolin clay and 10 parts of talc are thoroughly pulverized and mixed to obtain a dust.
These formulations as such or dilut~d with, for example, water are applied to soil ox directly to plants. In more detail, they are used in various forms, e~g., sprinkling, spraying or dusting on plants or sprinkling, spraying, dusting or granule-sprinkling onto soil surface or if necessary, subsequent fur-ther soil-mixingY
Fungicidal effects can be expected to be further increased by using them in admixture wi-th other fungicides. Furthermore, these formula-tions may also be used in admixture with insecticides, acaricides, nematocides, herbicides, plant growth regulating agent, fertilizers, soil improvers and the like.
The present compounds can be uséd as an active ingredient of fungicides to be used for paddy field, plowland, orchard, pasture, turf and the like.
When the present compound is used as an active ingredient of fungicide, its dosage is ~2~2~3~
generally 0.5 to 100 g, preferably 1 to 50 g per are, although it depends on weather conditions, form of formulations, time, method and place of applica-tion, diseases to be controlled, crops to be treated, etc.
When the emulsifiable concentrate, wettable powder, suspension formulation, liquid formulation, etc. are diluted with water for use, the concentration is 0.001~ to 1~, preferably 0.005~ to 0.5~. Granule and dust are used as they are without dilution.
The effect of the present compounds as an active ingredient of fungicides will be shown by the following test examples. The present compounds used are indicated by the compound number given in Table 1 and the compounds used for comparison are indicated by the compound number given in Table 2.
Table 2 _ Compound No. Chemical formula Note CH3 Commercially A ~ ~ OC3H7~i) fungicide mepronil Commercially CCQ -CH-NHCHO
3 1 avallable B ~ N) triforine CCQ3-C~-NHCHO
- 26 - ~ ~273 Commerc la 11 y CN ~ CN available C CQ ~ CQ TpNngicide O Commercially CQ ~ O-CH-C-C(CH3)3 available D ,N ~ fungicide ~ N triadimefon Test Example 1 Test for preventive controlling effect on sheath blight (Rhizoctonia ~^ solani) of rice.
Sandy loam was filled in a plastic pot and rice (var.: Kinki No. 33) was sowed and cultivated in a greenhouse for 60 days to grow to seedlings in the 6 - 7 leaf stages. The test compounds were formulated into emulsifiable concentrates in accordance with the Formulation Example 2 and they were diluted with water to a given concentration. These were foliar-sprayed onto the seedlings to allow them to thoroughlydeposit on the leaf surface. After ~ hours ~rom the spraying, the seedlings were inoculated by putting agar piece containing Rhizoctonia solani. After inoculation, the seedlings were grown at 28C for ~
days under hlghly humid condltion and the controlling effects were observed. The results are shown in Table 3.
The controlling effect is determined by observing with the naked eye the condition of disease of test plants on examination, namely, the degree of - 27 ~ 27 ~S
fungus colon~ and infected area of leaf and stem and grading the condition of diseases into the following six steps 0, 1, 2, 3, 4 and 5:
5 ...... No infected area and fungus colony are noticed.
4 ...... Infec-ted area and fungus colony are noticed in about 10% of leaf and stem.
3 O~ Infected area and fungus colony are noticed in about 30~ of leaf and stem.
2 ...... Infected area and fungus colony are noticed in about 50% of leaf and stem.
1 ...... Infected area and fungus colony are noticed in about 70~ of leaf and stem.
0 ...... Infected area and fungus colony are noticed in more than about 70~ and no difference is noticed from the condition of disease when no compound is used.
The above grading is applied to all of the following test examples.
Table 3 Concentration of Test compounds active ingredient Controlling effect (ppm) (1) 10 5 (2) 10 5 (3) 10 5 (4) 10 5 (5) 10 5 (6) 10 5 (7) 10 5 (g) 50 5 (9) 50 5 (10) 100 5 - 28 - ~2 (11) 10 5 (12) 10 5 (13) 50 5 (14) 10 5
(15) 10 5
(16) iO 5
(17) 100 5
(18) 10 5
(19) 10 5
(20) 50 5
(21) 50 5
(22) 10 5
(23) 100 5
(24) 10 5 _ Test Example 2 Test for systemic controlling effect on sheath blight (Rhizoctonia solani) of rice.
~andy loam was filled in a 130 ml plastic pot and rice (var.: Kinki No. 33) was sowed and cultivated in a gxeenhouse for 8 weeks to grow to seedlings in the 6 - 7 leaf stages. The test compounds formulated to emulsifiable concentrates in accordance with Formulation ~xample 2 and they were diluted with water and drenched in a given amount to the soil.
After drench, the seedlings were grown in a green-house for 7 days and inoculated by putting agar piececontaining Rhizoct_nia solanl. After inoculation, the seedlings were grown at 2~C for 4 days under a highly humid condition and the controlling effect was observed. The results are shown in Table 4.
- 29 - ~ ~273 Table 4 Test compounds Dosage of compound Controlling ëffect 10 l (11) 1 5 (12) 1 5 (13) 1 5 (14) 1 5 (15) 1 5 (16) 1 5 (19) 1 5 (20) 1 5 _ _ _ _ _ Test Example 3 Controlling effect on sheath blight (Rhizoctonia solani) o rice by submerged application Sandy loam was filled in a 1/10000 a Wagner's pot and rice (var.: Kinki No. 33) was sowed and cultivated in a greenhouse for 80 days -to grow to seedlings of the 9 - 10 leaf stages. The -test com-pounds were formulated into wettable powders in accordance with Formulation Example 1 and diluted with water and drenched in a given amount to the soil.
After drench, the seedlings were grown for 7 days in a greenhouse and inoculated by putting agar piece - containing ~ lzoctonia solani. After inoculation, the seedlings were grown at 28C for 4 days under a hi~hly humid condition and controlling effect was observed. The results are shown in Table 5.
s Table 5 Dosage of active Test compounds . . Controlling effect lngredlent (g/lOa) (6) 100 5 (7) 100 5 15 (11) 100 5 (12) 100 5 (13) 100 5 (14) 100 5 (15) 100 5 20 (16) 100 5 (19) 100 5 _ .
Test Example 4 Test for curative controlling effect on brown rust (~iLLa recondita) of wheat Sandy loam was filled in a plastic pot and wheat (var.: Norin No. 73) was sowed and grown in a greenhouse for 10 days to seedlings of the 2 - 3 leaf stages, which were inoculated with Puccinia recQn~ita by dusting. After inoculation, the seedlings were grown at 23C or one day under a high:Ly humid - 31 - ~ 3~
condition and onto these seedlings was foliar-sprayed the test compound formulated to wettable powder in accordance with Formulation Example 1 and diluted with water to a given concentration, so that the compound was thoroughly deposited on the leaf surface. After spraying, the seedlings were cultivated at 23C for 7 days under illumination and the controlling effect was observed. The results are shown in Table 6.
Table 6 Concentration of Test compounds active ingredient Controlling effect 1~ r~h ~
Test Example 5 Test for curative controlling effect on brown rust (Puccinia ~1 recondita) of wheat Sandy loam was filled in a plastic pot and wheat (var.: Norin No. 73) was sowed and grown in a greenhouse for 10 days to seedlings of the 2 - 3 leaf stages, which were inoculated with ~uccinia r ondita by dusting. After inoculation, the seedlings were grown at 23C for one day under a highly humid condition and onto these seedlings was foliar sprayed ~,62t7;3 ~
the test compound formulated to emulsifiable concen-trate in accordance with Formulation Example 2 and diluted with water to a given concentration, so that the compound was thoroughly deposited on the leaf surface. After spraying, the seedlings were grown at 23C for 7 days under illumination and the controlling effect was examined. The results are shown in Table 7.
Table 7 . Concentration of Test compounds active ingredient Controlling effect (ppm) ~O ~
(14) 50 5 ~
I (17) 16 35 5 - 33 - ~6~73~
Sr ~ r lo-- t- ~
15 l _est Example 6 Test for controlling effect on southern blight (~Corticium rolfsii) of kidney bean.
Sandy loam well mixed with ~s~5i~Lh~
rolfsii which was previously cultured in bran medium was filled in a 250 ml plastic pot and kidney bean ~var.: Taishokintoki) was sowed. The test compound was formulated into a wettable powder and diluted with water. A given amount of the test compound was drenched into the soil. A~ter the drench, cultivation was made for 3 weeks in a greenhouse and controlling effect was examined by observing the degree of disease of the stem in the vicinity of the soil surface. The results are shown in Table 8.
~i27;3 ~
Table 8 Dosage of active _ Test compounds ingredient Controlling effect ~ 1~ =~-' Test Æxample 7 Test for preventive controlling effect on scab (Venturia inaequalis) of apple Sandy loam was filled in a plastic pot and seed of apple was sowed and cultivated in a green-house for 30 days. Onto the seedlings of the 5 leaf stage was foliar-sprayed the test compound formulated into a wettable powder in accordance with Eormulation Example 1 and diluted with water to a given concen-tration so that thé test compound was thoroughly deposited on the leaf surface. After 4 hours from the spraying, the seedlings were inoculated by spray-ing a suspension of spores of Venturia inae~ualis.
AEter inoculation the seedlings were grown at 15C for 14 days under a highly humid condition and the controlling effect was observed. The results are shown in Table 9.
3~;i Table 9 _ Concentration of Test compounds Active ingredient Controlling effect (ppm) _ _ (8) 500 5 (11) SOO 5 (18) 500 5 (19) O ____
~andy loam was filled in a 130 ml plastic pot and rice (var.: Kinki No. 33) was sowed and cultivated in a gxeenhouse for 8 weeks to grow to seedlings in the 6 - 7 leaf stages. The test compounds formulated to emulsifiable concentrates in accordance with Formulation ~xample 2 and they were diluted with water and drenched in a given amount to the soil.
After drench, the seedlings were grown in a green-house for 7 days and inoculated by putting agar piececontaining Rhizoct_nia solanl. After inoculation, the seedlings were grown at 2~C for 4 days under a highly humid condition and the controlling effect was observed. The results are shown in Table 4.
- 29 - ~ ~273 Table 4 Test compounds Dosage of compound Controlling ëffect 10 l (11) 1 5 (12) 1 5 (13) 1 5 (14) 1 5 (15) 1 5 (16) 1 5 (19) 1 5 (20) 1 5 _ _ _ _ _ Test Example 3 Controlling effect on sheath blight (Rhizoctonia solani) o rice by submerged application Sandy loam was filled in a 1/10000 a Wagner's pot and rice (var.: Kinki No. 33) was sowed and cultivated in a greenhouse for 80 days -to grow to seedlings of the 9 - 10 leaf stages. The -test com-pounds were formulated into wettable powders in accordance with Formulation Example 1 and diluted with water and drenched in a given amount to the soil.
After drench, the seedlings were grown for 7 days in a greenhouse and inoculated by putting agar piece - containing ~ lzoctonia solani. After inoculation, the seedlings were grown at 28C for 4 days under a hi~hly humid condition and controlling effect was observed. The results are shown in Table 5.
s Table 5 Dosage of active Test compounds . . Controlling effect lngredlent (g/lOa) (6) 100 5 (7) 100 5 15 (11) 100 5 (12) 100 5 (13) 100 5 (14) 100 5 (15) 100 5 20 (16) 100 5 (19) 100 5 _ .
Test Example 4 Test for curative controlling effect on brown rust (~iLLa recondita) of wheat Sandy loam was filled in a plastic pot and wheat (var.: Norin No. 73) was sowed and grown in a greenhouse for 10 days to seedlings of the 2 - 3 leaf stages, which were inoculated with Puccinia recQn~ita by dusting. After inoculation, the seedlings were grown at 23C or one day under a high:Ly humid - 31 - ~ 3~
condition and onto these seedlings was foliar-sprayed the test compound formulated to wettable powder in accordance with Formulation Example 1 and diluted with water to a given concentration, so that the compound was thoroughly deposited on the leaf surface. After spraying, the seedlings were cultivated at 23C for 7 days under illumination and the controlling effect was observed. The results are shown in Table 6.
Table 6 Concentration of Test compounds active ingredient Controlling effect 1~ r~h ~
Test Example 5 Test for curative controlling effect on brown rust (Puccinia ~1 recondita) of wheat Sandy loam was filled in a plastic pot and wheat (var.: Norin No. 73) was sowed and grown in a greenhouse for 10 days to seedlings of the 2 - 3 leaf stages, which were inoculated with ~uccinia r ondita by dusting. After inoculation, the seedlings were grown at 23C for one day under a highly humid condition and onto these seedlings was foliar sprayed ~,62t7;3 ~
the test compound formulated to emulsifiable concen-trate in accordance with Formulation Example 2 and diluted with water to a given concentration, so that the compound was thoroughly deposited on the leaf surface. After spraying, the seedlings were grown at 23C for 7 days under illumination and the controlling effect was examined. The results are shown in Table 7.
Table 7 . Concentration of Test compounds active ingredient Controlling effect (ppm) ~O ~
(14) 50 5 ~
I (17) 16 35 5 - 33 - ~6~73~
Sr ~ r lo-- t- ~
15 l _est Example 6 Test for controlling effect on southern blight (~Corticium rolfsii) of kidney bean.
Sandy loam well mixed with ~s~5i~Lh~
rolfsii which was previously cultured in bran medium was filled in a 250 ml plastic pot and kidney bean ~var.: Taishokintoki) was sowed. The test compound was formulated into a wettable powder and diluted with water. A given amount of the test compound was drenched into the soil. A~ter the drench, cultivation was made for 3 weeks in a greenhouse and controlling effect was examined by observing the degree of disease of the stem in the vicinity of the soil surface. The results are shown in Table 8.
~i27;3 ~
Table 8 Dosage of active _ Test compounds ingredient Controlling effect ~ 1~ =~-' Test Æxample 7 Test for preventive controlling effect on scab (Venturia inaequalis) of apple Sandy loam was filled in a plastic pot and seed of apple was sowed and cultivated in a green-house for 30 days. Onto the seedlings of the 5 leaf stage was foliar-sprayed the test compound formulated into a wettable powder in accordance with Eormulation Example 1 and diluted with water to a given concen-tration so that thé test compound was thoroughly deposited on the leaf surface. After 4 hours from the spraying, the seedlings were inoculated by spray-ing a suspension of spores of Venturia inae~ualis.
AEter inoculation the seedlings were grown at 15C for 14 days under a highly humid condition and the controlling effect was observed. The results are shown in Table 9.
3~;i Table 9 _ Concentration of Test compounds Active ingredient Controlling effect (ppm) _ _ (8) 500 5 (11) SOO 5 (18) 500 5 (19) O ____
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A pyrazolecarboxamide derivative re-presented by the formula (I):
(I) wherein R1 and R2 which are identical or different represent each a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a trifluoromethyl group, R3 represents a hydrogen atom or a methyl group and n represents 0 or 1.
(I) wherein R1 and R2 which are identical or different represent each a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a trifluoromethyl group, R3 represents a hydrogen atom or a methyl group and n represents 0 or 1.
2. A pyrazolecarboxamide derivative according to claim 1, wherein R1 is a methyl group or a trifluoromethyl group and R2 is a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group.
3. A pyrazolecarboxamide derivative according to claim 1, wherein R1 is a methyl group or a trifluoromethyl group and R2 is a hydrogen atom, a fluorine atom, a chlorine atom or a methyl group.
4. A pyrazolecarboxamide derivative according to claim 1, wherein R1 is a methyl group or a trifluoromethyl group and R2 is a fluorine atom or a methyl group.
5. A pyrazolecarboxamide derivative according to claim 1, wherein R1 is a methyl group or a trifluoromethyl group, R2 is a fluorine atom or a methyl group and n is 0.
6. A pyrazolecarboxamide derivative according to claim 1, wherein both of R1 and R2 are a methyl group, R3 is a hydrogen atom and n is 0.
7. A pyrazolecarboxamide derivative according to claim 1, wherein R1 is a methyl group, R2 is a fluorine atom, R3 is a hydrogen atom and n is 0.
8. A pyrazolecarboxamide derivative according to claim 1, wherein R1 is a trifluoromethyl group, R2 is a methyl group, R3 is a hydrogen atom and n is 0.
9. A pyrazolecarboxamide derivative according to claim 1, wherein all of R1, R2 and R3 are a methyl group and n is 0.
10. A pyrazolecarboxamide derivative according to claim 1, wherein both of R1 and R3 are a methyl group and R2 is a fluorine atom and n is 0.
11. A pyrazolecarboxamide derivative according to claim 1, wherein R1 is a trifluoromethyl group, R2 is a hydrogen atom, R3 is a methyl group and n is 0.
12. A pyrazolecarboxamide derivative according to claim 1, wherein both of R1 and R3 are a methyl group, R2 is a hydrogen atom and n is 0.
13. A fungicidal composition which comprises as an active ingredient a fungicidally effective amount of a pyrazole-carboxamide derivative represented by the formula (I):
(I) wherein R1 and R2 which are identical or different represent each a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a trifluoromethyl group, R3 represents a hydrogen atom or a methyl group and n represents 0 or 1x, and an inert carrier.
(I) wherein R1 and R2 which are identical or different represent each a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a trifluoromethyl group, R3 represents a hydrogen atom or a methyl group and n represents 0 or 1x, and an inert carrier.
14. A fungicidal composition according to claim 13, wherein the pyrazolecarboxamide derivative has the formula (I) whereln R1 is a methyl group or a trifluoromethyl group and R2 is a hydrogen atom, a chlorine atom, a fluorine atom or a methyl group.
15. A fungicidal composition according to claim 13, wherein the pyrazolecarboxamide derivative has the formula (I) wherein R1 is a methyl group or a trifluoromethyl group and R2 is a fluorine atom or a methyl group and n is 0.
16. A method for controlling plant microbes by applying a pyrazolecarboxamide derivative represented by the formula (I):
(I) wherein R1 and R2 which are identical or different represent each a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a trifluoromethyl group, R3 represents a hydrogen atom or a methyl group and n represents 0 or 1.
(I) wherein R1 and R2 which are identical or different represent each a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a trifluoromethyl group, R3 represents a hydrogen atom or a methyl group and n represents 0 or 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP121947/85 | 1985-06-05 | ||
| JP12194785A JPH064592B2 (en) | 1985-06-05 | 1985-06-05 | Pyrazolcarboxamide compound and fungicide containing the same as an active ingredient |
| JP15093585A JPH064593B2 (en) | 1985-07-08 | 1985-07-08 | Pyrazolcarboxamide derivative and fungicide containing the same as an active ingredient |
| JP150935/85 | 1985-07-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1262735A true CA1262735A (en) | 1989-11-07 |
Family
ID=26459188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000496744A Expired CA1262735A (en) | 1985-06-05 | 1985-12-03 | Pyrazolecarboxamide derivative and fungicide containing it as active ingredient |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1262735A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8765756B2 (en) | 2010-08-10 | 2014-07-01 | Sumitomo Chemical Company, Limited | Plant disease controlling composition and use thereof |
-
1985
- 1985-12-03 CA CA000496744A patent/CA1262735A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8765756B2 (en) | 2010-08-10 | 2014-07-01 | Sumitomo Chemical Company, Limited | Plant disease controlling composition and use thereof |
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