CA1241658A - 2-pyrazolylmethyl-oxirane useful as intermediates for producing fungicides - Google Patents
2-pyrazolylmethyl-oxirane useful as intermediates for producing fungicidesInfo
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- CA1241658A CA1241658A CA000547804A CA547804A CA1241658A CA 1241658 A CA1241658 A CA 1241658A CA 000547804 A CA000547804 A CA 000547804A CA 547804 A CA547804 A CA 547804A CA 1241658 A CA1241658 A CA 1241658A
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Abstract
Abstract The invention provides 2-pyrasolylmethyl-oxiranes of the general formula IIa
Description
This application is divided out of Canadian Patent Appli-cation Serial No. 451,607 filed April 10, 1984.
The present invention relates to novel 2-pyrazolylmethyl-oxiranes, processes for theix preparation and their use as inter-mediates in the preparation of fungicides.
Application Serial No. 451,607 is directed to 1-azolyl-3-pyrazolyl-2-propanol derivatives of the general formula fH /N
Aæ - CH2 - C - CH2 - N I (I) R
in which Az represents 1,2,4-triazol-1-yl or pyrazol-l-yl and rR
represents straight-chain or branched alkyl with 1 to 12 carbon a-toms, straight-chain or branched alkenyl or alkinyl with in each case 2 to 6 carbon atoms, or phenyl, phenylalkyl with 1 to 4 carbon atoms in the alkyl part, phenylalkenyl with 2 to 4 carbon atoms in the alkenyl part or ph~nylalkinyl with 2 to 4 carbon atoms in the alkinyl part, each of which is optionally mono-, di- or tri-substi-tuted in the phenyl part by identical or different substituents, from the group comprising halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with in each case 1 or 2 carbon atoms, alkox-yalkyl with 1 or 2 carbon atoms in each alkyl part and optionally halogen-substituted phenyl or represents naphthyl, or cycloalkyl which has 3 to 7 carbon atoms and is optionally substituted by alkyl with 1 to 4 carbon atoms], an acid addition salts and metal salt com-plexes thereof. The l-azolyl- 3-pyrazolyl-2-propanol derivatives of 5t~
The present invention relates to novel 2-pyrazolylmethyl-oxiranes, processes for theix preparation and their use as inter-mediates in the preparation of fungicides.
Application Serial No. 451,607 is directed to 1-azolyl-3-pyrazolyl-2-propanol derivatives of the general formula fH /N
Aæ - CH2 - C - CH2 - N I (I) R
in which Az represents 1,2,4-triazol-1-yl or pyrazol-l-yl and rR
represents straight-chain or branched alkyl with 1 to 12 carbon a-toms, straight-chain or branched alkenyl or alkinyl with in each case 2 to 6 carbon atoms, or phenyl, phenylalkyl with 1 to 4 carbon atoms in the alkyl part, phenylalkenyl with 2 to 4 carbon atoms in the alkenyl part or ph~nylalkinyl with 2 to 4 carbon atoms in the alkinyl part, each of which is optionally mono-, di- or tri-substi-tuted in the phenyl part by identical or different substituents, from the group comprising halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with in each case 1 or 2 carbon atoms, alkox-yalkyl with 1 or 2 carbon atoms in each alkyl part and optionally halogen-substituted phenyl or represents naphthyl, or cycloalkyl which has 3 to 7 carbon atoms and is optionally substituted by alkyl with 1 to 4 carbon atoms], an acid addition salts and metal salt com-plexes thereof. The l-azolyl- 3-pyrazolyl-2-propanol derivatives of 5t~
-2- 23189-5714D
the formula ( I ) are obtained by a process in which a) 2-azolylmethyl-oxiranes of the formula R - C - CH2 - Az / \ (II) in which Az and R have the abovementioned meaning, are reacted with azoles of the formula H-Az' in which Az' has the meanings of Az, but at least one of Az and Az' represent pyrazol-l-yl, in the presence of an alkali metal alcohol-ate and in the presence of a diluent, or b) 2-halogenomethyl-oxiranes of the formula R - C - CH2 - Hal / \ (IV) in which R has the abovementioned meaning and Hal represents halo-gen, are reacted with pyrazole of the formula ON
M - N TV) \, in which M represents hydrogen or an alkali metal, in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent, or c) dihalogenoalkanols of the formula OiH
Hal - CH2 - C - CH2 - Hal (VI) R
6S~3
the formula ( I ) are obtained by a process in which a) 2-azolylmethyl-oxiranes of the formula R - C - CH2 - Az / \ (II) in which Az and R have the abovementioned meaning, are reacted with azoles of the formula H-Az' in which Az' has the meanings of Az, but at least one of Az and Az' represent pyrazol-l-yl, in the presence of an alkali metal alcohol-ate and in the presence of a diluent, or b) 2-halogenomethyl-oxiranes of the formula R - C - CH2 - Hal / \ (IV) in which R has the abovementioned meaning and Hal represents halo-gen, are reacted with pyrazole of the formula ON
M - N TV) \, in which M represents hydrogen or an alkali metal, in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent, or c) dihalogenoalkanols of the formula OiH
Hal - CH2 - C - CH2 - Hal (VI) R
6S~3
-3- 23189-5714D
in which Hal and R have the abo~eme.ntioned meaning, are reacted with pyrazole of the formula (V) in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent.
If appropriate, an acid or a metal salt can then be add-ed on to the compounds of the formula (I) thus obtained.
Surprisingly, the compounds of the formula (I) exhibit a better fungicidal activity than 1,3-di-(1,2,4-triazol-1-yl)-2-(4-chlorophenylj-2-propanol, which is known from the prior art and is a closely related compound structurally and from the point of view of its action.
Particularly preferred compounds of the formula (I) are those in which Az represents 1,2,4-triazol-1-yl or pyrazol-l-yl and R represents ethyl, tert.-butyl, allyl or propargyl, or phenyl, benzyl, phenethyl, phenethenyl or phenethinyl, each of which is optionally monosubstituted or disubstituted in the phenyl part by identical or different substituents, substituents on the phenyl which may be mentioned in each case being: fluorine, chlorine, methyl, methoxy, methylthio, isopropoxy, methoxymethyl, phenyl which is optionally substituted by fluorine or chlorine, naphthyl, and cyclopropyl, cyclopentyl and cyclohexyl, each of which is optionally substituted by methyl or ethyl.
Very particularly preferred compounds of the formula (~) are those in which Az represents 1,2,4-triazol-1-yl or pyrazol-1-yl and R represents phenyl which is optionally monosubstituted or di-substituted by identical or different substituents, substituents which may be mentioned being: fluorine, chlorine, methyl and methoxy.
in which Hal and R have the abo~eme.ntioned meaning, are reacted with pyrazole of the formula (V) in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent.
If appropriate, an acid or a metal salt can then be add-ed on to the compounds of the formula (I) thus obtained.
Surprisingly, the compounds of the formula (I) exhibit a better fungicidal activity than 1,3-di-(1,2,4-triazol-1-yl)-2-(4-chlorophenylj-2-propanol, which is known from the prior art and is a closely related compound structurally and from the point of view of its action.
Particularly preferred compounds of the formula (I) are those in which Az represents 1,2,4-triazol-1-yl or pyrazol-l-yl and R represents ethyl, tert.-butyl, allyl or propargyl, or phenyl, benzyl, phenethyl, phenethenyl or phenethinyl, each of which is optionally monosubstituted or disubstituted in the phenyl part by identical or different substituents, substituents on the phenyl which may be mentioned in each case being: fluorine, chlorine, methyl, methoxy, methylthio, isopropoxy, methoxymethyl, phenyl which is optionally substituted by fluorine or chlorine, naphthyl, and cyclopropyl, cyclopentyl and cyclohexyl, each of which is optionally substituted by methyl or ethyl.
Very particularly preferred compounds of the formula (~) are those in which Az represents 1,2,4-triazol-1-yl or pyrazol-1-yl and R represents phenyl which is optionally monosubstituted or di-substituted by identical or different substituents, substituents which may be mentioned being: fluorine, chlorine, methyl and methoxy.
-4- 23189-5714D
Addition products of acids and those 1-azolyl-3-pyrazol-2-propanol derivatives of the formula (I) in which the substituen-ts Az and R have the meanings which have already been mentioned as preferred for these substituents are also preferred compounds.
Preferred acids which can be added on include hydrogen hal-ide acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, and furthermore phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, ma-leic acid, succinic acid, fumaric acid, tartaric acid, citric acid,salicylic acid, sorbic acid and lactic acid, and sulphonic acids, such as p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid.
Other preferred compounds are addition products of salts and metals of main groups II to IV and subgroups I and II and IV to VIII and those l-azolyl-3-pyrazolyl-2-propanol derivatives of the formula (It in which the substituents Az and R have the meanings which have already been mentioned as preferred for these substituents.
Particularly preferred salts here are those of copper, zinc, manganese, magnesium, tin, iron and nickel. Possible anions of these salts are those which are derived from acids leading to physiologically acceptable addition products. In this connection, particularly preferred acids of this type are the hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, and nitric acid and sulphuric acid.
If, for example, 2-(2~chlorophenyl)-2-(1,2,~-triazol-1-yl-methyl)-oxirane, potassium tert.-butylate and pyrazole are used 65~
Addition products of acids and those 1-azolyl-3-pyrazol-2-propanol derivatives of the formula (I) in which the substituen-ts Az and R have the meanings which have already been mentioned as preferred for these substituents are also preferred compounds.
Preferred acids which can be added on include hydrogen hal-ide acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, and furthermore phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, ma-leic acid, succinic acid, fumaric acid, tartaric acid, citric acid,salicylic acid, sorbic acid and lactic acid, and sulphonic acids, such as p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid.
Other preferred compounds are addition products of salts and metals of main groups II to IV and subgroups I and II and IV to VIII and those l-azolyl-3-pyrazolyl-2-propanol derivatives of the formula (It in which the substituents Az and R have the meanings which have already been mentioned as preferred for these substituents.
Particularly preferred salts here are those of copper, zinc, manganese, magnesium, tin, iron and nickel. Possible anions of these salts are those which are derived from acids leading to physiologically acceptable addition products. In this connection, particularly preferred acids of this type are the hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, and nitric acid and sulphuric acid.
If, for example, 2-(2~chlorophenyl)-2-(1,2,~-triazol-1-yl-methyl)-oxirane, potassium tert.-butylate and pyrazole are used 65~
-5- 23139-5714D
as starting substances, the course of the reaction in process (a) can be represented by the following equation:
~CH2 0 ¦ N-CH - I O -N
If, for example, 2 chloromethyl-2-(4-chlorophenyl)-oxirane and pyrazole are used as starting substances and potassium carbonate is used as the acid-binding agent, the course of the reaction in pro-cess (b) can be represented by the following equation:
Cl- CH2-- O K2CO3 = N OH
\ /N--If, for example, 1,3-dichloro-2-(4-chlorophenyl)-2-propan-ol and pyrazole are used as starting substances and potassium car-bonate is used as the acid-binding agent, the course of process (c) can be represented by the following equation:
so
as starting substances, the course of the reaction in process (a) can be represented by the following equation:
~CH2 0 ¦ N-CH - I O -N
If, for example, 2 chloromethyl-2-(4-chlorophenyl)-oxirane and pyrazole are used as starting substances and potassium carbonate is used as the acid-binding agent, the course of the reaction in pro-cess (b) can be represented by the following equation:
Cl- CH2-- O K2CO3 = N OH
\ /N--If, for example, 1,3-dichloro-2-(4-chlorophenyl)-2-propan-ol and pyrazole are used as starting substances and potassium car-bonate is used as the acid-binding agent, the course of process (c) can be represented by the following equation:
so
-6- 23l89-57l4D
OH / N-l Cl-CH2 - C - CH2Cl + 2 HN K CO
~3 _,_.21~
C1 1= N\ OH ON
lo Jl Formula (II) provides a general definition of the 2-azoly-lmethyl-oxiranes to be used as starting substances for process (a) according to the invention. In this formulal Az and R preferably represent those radicals which have already been mentioned as pre-ferred for these substituents in connection with the description of the substances of the formula (I).
Some of the azolylmethyl-oxiranes of the formula (II) are known (compare, for example, European 0,044,605 and European 0,061,835). The present invention is directed to novel 2 pyrazoly-lmethyl-oxiranes of the formula /N =
R - C - CH - N (IIa) ~Z4~6~B
OH / N-l Cl-CH2 - C - CH2Cl + 2 HN K CO
~3 _,_.21~
C1 1= N\ OH ON
lo Jl Formula (II) provides a general definition of the 2-azoly-lmethyl-oxiranes to be used as starting substances for process (a) according to the invention. In this formulal Az and R preferably represent those radicals which have already been mentioned as pre-ferred for these substituents in connection with the description of the substances of the formula (I).
Some of the azolylmethyl-oxiranes of the formula (II) are known (compare, for example, European 0,044,605 and European 0,061,835). The present invention is directed to novel 2 pyrazoly-lmethyl-oxiranes of the formula /N =
R - C - CH - N (IIa) ~Z4~6~B
-7- 23189-5714D
in which R represents straight-chain or branched alkyl with 1 to 12 carbon atoms, straight-chain or branched alkenyl or alkinyl with in each case 2 to 6 carbon atoms, or phenyl, phenylalkyl with 1 to 4 carbon atoms in the alkyl part, phenylalkenyl with 2 to a carbon atoms in the alkenyl part or phenylalkinyl with 2 to 4 carbon atoms in the alkinyl part, each of which is optionally mono-, di- or tri-substituted in the phenyl part by identical or different substitu-ents, from the group comprising halogen, alkyl with 1 -to 4 carbon atoms, alkoxy and alkylthio with in each case 1 or 2 carbon atoms, alkoxyalk~l with 1 or 2 carbon atoms in each alkyl part and option-ally halogen-substituted phenyl or represents naphthyl, or cycloalkyl which has 3 to 7 carbon atoms and is optionally substituted by alkyl with 1 to 4 carbon atoms.
Preferred values for R in the 2-pyrazolylmethyl-oxiranes of formula IIa are those which are already mentioned as preferred values for R in compounds of formula I.
The 2-pyrazolylmethyl-oxiranes of the formula (IIa) can be obtained by a process in which:
(i) 2-halogenomethyl-oxirane of the formula (IV) R / C - CH2 - Hal CH O (IV) in which R has the abovementioned meaning and Hal represents halogen, is reacted with pyrazole in the presence of an inert organic solvent, such as, for example, acetone, and in the presence of an acid-binding agent, such as, for example, potassium carbonate, at a temperature ~2~16~k~
-7a- 23189-5714D
between 20 and 120C (compare al.so the preparation examples); or (ii) a ketone of the formula / No -R-CO-CH2-N (VII) 6S~3
in which R represents straight-chain or branched alkyl with 1 to 12 carbon atoms, straight-chain or branched alkenyl or alkinyl with in each case 2 to 6 carbon atoms, or phenyl, phenylalkyl with 1 to 4 carbon atoms in the alkyl part, phenylalkenyl with 2 to a carbon atoms in the alkenyl part or phenylalkinyl with 2 to 4 carbon atoms in the alkinyl part, each of which is optionally mono-, di- or tri-substituted in the phenyl part by identical or different substitu-ents, from the group comprising halogen, alkyl with 1 -to 4 carbon atoms, alkoxy and alkylthio with in each case 1 or 2 carbon atoms, alkoxyalk~l with 1 or 2 carbon atoms in each alkyl part and option-ally halogen-substituted phenyl or represents naphthyl, or cycloalkyl which has 3 to 7 carbon atoms and is optionally substituted by alkyl with 1 to 4 carbon atoms.
Preferred values for R in the 2-pyrazolylmethyl-oxiranes of formula IIa are those which are already mentioned as preferred values for R in compounds of formula I.
The 2-pyrazolylmethyl-oxiranes of the formula (IIa) can be obtained by a process in which:
(i) 2-halogenomethyl-oxirane of the formula (IV) R / C - CH2 - Hal CH O (IV) in which R has the abovementioned meaning and Hal represents halogen, is reacted with pyrazole in the presence of an inert organic solvent, such as, for example, acetone, and in the presence of an acid-binding agent, such as, for example, potassium carbonate, at a temperature ~2~16~k~
-7a- 23189-5714D
between 20 and 120C (compare al.so the preparation examples); or (ii) a ketone of the formula / No -R-CO-CH2-N (VII) 6S~3
-8- 23189-5714D
in which R has the abovementioned meaning, either I) is reacted with dimethyloxosulphonium methylide of the formula + (VIII) ( 3)2 OCH2 in the presence of a diluent, such as, for example, dimethylsulph-oxide, at a temperature between 20 and 80C (in this context, com-pare the statements in I. Am. Chem. Soc. 87, 1363-1364 (1965)), or I) is reacted with trimethylsulphonium methylsulphate of the form-ula t 3)3S CH3SO41 ) (IX) in the presence of an inert organic solvent, such as, for example, acetonitrile, and in the presence of a base, such as, for example, sodium methylate, at temperatures between 0 and 60C, preferably at room temperature (compare also the statements in Heterocycles 8, 397 (1977)).
If appropriate, the oxiranes of the formula (IIa) thus obtained can be further reacted directly to obtain compounds of the formula (I), without being isolated.
The ketones of the formula (VII) required as starting sub-stances in the preparation of the 2-azolyl- methyl-oxiranes of the formula (II) are known (compare, for example DE-OS (German Published Specification) 2,431,407, DE-OS (German Published Specificaticn) 2,638,470 and DE-OS (German Published Specification) 2,820,361), or they are the subject of an earlier patent application which has been ~4~
in which R has the abovementioned meaning, either I) is reacted with dimethyloxosulphonium methylide of the formula + (VIII) ( 3)2 OCH2 in the presence of a diluent, such as, for example, dimethylsulph-oxide, at a temperature between 20 and 80C (in this context, com-pare the statements in I. Am. Chem. Soc. 87, 1363-1364 (1965)), or I) is reacted with trimethylsulphonium methylsulphate of the form-ula t 3)3S CH3SO41 ) (IX) in the presence of an inert organic solvent, such as, for example, acetonitrile, and in the presence of a base, such as, for example, sodium methylate, at temperatures between 0 and 60C, preferably at room temperature (compare also the statements in Heterocycles 8, 397 (1977)).
If appropriate, the oxiranes of the formula (IIa) thus obtained can be further reacted directly to obtain compounds of the formula (I), without being isolated.
The ketones of the formula (VII) required as starting sub-stances in the preparation of the 2-azolyl- methyl-oxiranes of the formula (II) are known (compare, for example DE-OS (German Published Specification) 2,431,407, DE-OS (German Published Specificaticn) 2,638,470 and DE-OS (German Published Specification) 2,820,361), or they are the subject of an earlier patent application which has been ~4~
-9- 23189-571~D
filed by the applicant Company (compare German Published Specifica-tion 30 48 266 published July 29, 19~2), or they can be prepared by processes which are known in principle.
The dimethyloxosulphonium methylide of the formula (VIII) required in process variant (ox is likewise known (compare J. em.
Chem. Soc. _, 1363-1364 (1965)~. In the above reaction, it is processed in the freshly prepared state by being produced in situ by reacting trimethyloxosulphonium iodide with sodium hydride or sodium amide, in particular with potassium tert.-butylate or sodium
filed by the applicant Company (compare German Published Specifica-tion 30 48 266 published July 29, 19~2), or they can be prepared by processes which are known in principle.
The dimethyloxosulphonium methylide of the formula (VIII) required in process variant (ox is likewise known (compare J. em.
Chem. Soc. _, 1363-1364 (1965)~. In the above reaction, it is processed in the freshly prepared state by being produced in situ by reacting trimethyloxosulphonium iodide with sodium hydride or sodium amide, in particular with potassium tert.-butylate or sodium
10 methylate, in the presence of a diluent.
The trimethylsulphonium methylsulphate of the formula (IX) required in process variant (~) is likewise known (compare Hetero-cycles 8, 397 (1977)). In the above reaction, it is likewise em-ployed in the freshly prepared state, by being produced in situ by reaction of dimethyl sulphide with dimethyl sulphate.
Formula (I'i7) provides a general definition of the 2-halo-genomethyl-oxiranes to be used as starting substances for process (b) for producing compounds of formula I or process (i) for producing compounds of formula IIa. In this formula, R preferably represents 20 those radicals which have already been mentioned as preferred for these substituents in connection with the description of the sub-stances of the formula (I). Hal preferably represents chlorine, bromine or iodine.
The 2-halogenomethyl-oxiranes of the formula (IV) are known, or they can be obtained in a generally known manner, by add-ing aqueous alkali metal hydroxide solution to dihalogenoalkanols of the formula tVI) (in this context, compare also J. Org. Chem.
27, 2242 (1961)).
Formula (V) provides a general definition of the azoles also to be used as starting substances for process (b). In this formula, M preferably represents hydrogen, sodium or potassium.
The azoles of the formula (V) are generally known com-pounds of organic chemistry. The alkali metal salts are obtained by reacting pyrazole, imidazole or 1,2,4-triazole with sodium ethy-late or potassium ethylate, or by reacting pyrazole, imidazole or lQ 1~2~4-triazole with the equivalent amount of the corresponding alkali metal hydride.
Formula (VI) provides a general definition of the dihalo-genoalkanols to be used as starting substances for process (c) for producing compounds of formula I or for producing compounds of form-ula (IV) by reaction with aqueous alkali metal hydroxide solution.
In this formula, R preferably represents those radicals which haze already been mentioned as preferred for this substituent. Hal pre-ferably represents chlorine.
The dihalogenoalkanols of the formula (VI) are known, or they can be obtained in a generally known manner, by reacting 1,3-dihalogenoacetones, such as, in particular, 1,3-dichloroacetone, with a corresponding Grignard reagent (in this context, compare also J. Org. Chem. 27, 2242 (1961)~.
Preferred possible diluents for process (a) are inert organic solvents. These include, preferably, nitriles, such as, in particular, acetonitrile; aro~.atic hydrocarbons, such as benz-ene, toluene and dichlorobenzene; formamides, such as, in particular, ~LZ4~S8 dimethylformamide; halogenated hydrocarbons, such as methylene chloride or carbon tetrachloride; and hexamethylphosphoric acid triamide.
Process (a) is carried out in the presence of an alkali metal alcoholate. Preferred alkali metal alcoholates include the methylates and ethylates of sodium and potassium and, in particular, also potassium tert.-butylate.
The reaction temperatures can be varied within a substan-tial range in carrying out process (a). In general, the reaction is carried out between about 30 and 150C, preferably between 80 and 100C.
In carrying out process (a) 1 to 4 mol of azole of the formula (III) and 1 to mol of alkali metal alcoholate are prefer-ably employed per mol of oxirane of the formula (II). The end prod-ucts are isolated in a generally customary manner.
In a preferred embodiment of process (a) the oxiranes of the formula (II) obtained according to process (~) or (~) are fur-ther reacted directly, without being isolated.
Preferred possible diluents for processes (b) and (c) are inert organic solvents. These include, preferably, ketones, such as, in particular , acetone and methyl ethyl ketone; nitriles, such as, in particular, acetonitrile; alcohols, such as, in particular, ethanol and isopropanol; ethers, such as, in particular, tetrahydro-furan or dioxane; formamides, such as, in particular, dimethylform-amide; and aromatic and halogenated hydrocarbons.
-12~ 23189-5714D
If appropri.ate, processes (b) and Ic) are carried out in the presence of an acid-binding agent. All the inorganic or organic acid-binding agents which can usually be employed can be added, such as alkali metal carbonates, for example sodium carbonate and potas-sium carbonate; or such as lower tertiary alkylamines, cycloalkyla-mines,cycl~Xenylami.nes or arylalkylamines, for example triethylam-ine, N,N-dimethylcyclohexylamine, dicyclohexylamine or N,N-dimeth-ylbenzylamine, and furthermore pyridine and diazabicyclooctane, and also an appropriate excess of azole.
The reaction temperatures can be varied within a substant-ial range in carrying out processes (b) and (c). In general, the reactions are carried out between about 20 and about 150C, prefer-ably at 20 to 120C.
In carrying out processes (b) and (c)2 to 4 mol of azole of the formula (V) and, if appropriate, 2 to 4 mol of acid-binding agent are employed per mol of the 2-halogenomethyloxiranes of the formula (IV) or of the dihalogenoalkanols of the formula (VI). The compounds of the formula (I) are isolated in a customary manner.
The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and they can be isolated in a known manner, for example by filtration, and if appropriate purified by washing with an inert organic solvent.
so The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to compounds of the formula (I).
The metal salt complexes can be isolated in a known manner, for ex-ample by filtration, and if necessary purified by recrystallisation.
The active compounds of the formula (I) according to the parent application exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms.
The active compounds are suitable for use as plant protection agents.
Funsicidal agents in plant protection are employed for combating Plasmodiophoromyce~es, Oomycetes, Chytridiomycetes, Zygomy-cetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds of the formula (I) can be used with particularly good success for combating cereal diseases such as Cochliobolus sativus, Erysiphe graminis, Puccinia and Pyrenophora teres; and furthermore for combating apple scab (Venturia inaequalis) and rice diseases, such as Pyricularia and Pellicularia.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for seed, and formulations 1'~416S~
used with burning equipment, such as fumiga-ting cartridges, fumig-ating cans, fumigating coils and the like, as well as ULV cold mis-t and warm mist formulations.
These formulations are produced in known manner, for ex-ample by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, op-tionally with the use of surfaceactive agents, that is, emulsifying .
agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as wel.l as their ethers and esters, ketones, such as acetone, methyl ethyl ketone,. methyl isolbutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsul-phoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellant, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide;
as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; as ~Z~
solid carriers for granules there are suitahle: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sep-iolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic materials such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/
or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl poly-glycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylc-ellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers i.n the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal pht-halocyanine dyestuffs, and trace nutrients such as salts of iron,manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compounds of the formula (I) can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungici.des, bactericides, insectic-ides, acaricides, nematicides, herbicides, bird repellants, growth ~Z4~L6~
-lh- 23l89-57l4D
factors, plant nutrients and agents for improving soil structure.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vaporising, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dres-sing or encrusting.
In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0.0001% by weight, pre-ferably between 0.5 and 0.001%.
In the treatment of seed, amounts of active compollnd of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
For the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the place of action.
Preparation examples:
Example 1 N OH N
= N/ Cl 65~
(Process a) A mixture of 3.4 g (50 mmol) of pyrazole, 2.8 g (25 mmol) of potassium tert.-butylate and 5.9 g (25 mmol) of 2-(2-chlorophen-yl)-2-(1,2,4-triazol-1-yl-methyl)-Q~irane in 200 ml of dimethylform-amide is heated at 100C for 36 hours. The reaction mixture is then concentrated in vacuo, the residue is dissolved in chloroform and the solution is filtered and washed with water. The chloroform solution is dried over sodium sulphate, filtered and concentrated in vacuo. the residue which remains is purified by chromatography (silica gel 60 Merck/chloroform)O 5.8 g (74% of theory) of 2-(2-chlorophenyl)-l-pyrazol-l-yl)-3-(1,2,4-triazol-1-yyl)-2-propanol of refractive index nD 1.5690 are obtained.
Preparation of the starting substance O - CH - N/
CH - o A solution of 68.5 g (0.33 mol) of 2-(2-chlorophenyl)-2-chloromethyl-oxirane in 50 ml of acetone is added dropwise to a mix-ture of 24.2 g (o.35 mol) of triazole and 48.3 g (o.35 mol) of pot-assium carbonate in 300 ml of acetone. The reaction mixture is heated under reflux for 20 hours and filtered and the filtrate is concentrated. The residue is dissolved in methylene chloride and the solution is washed with water, dried over sodium sulphate, fil-tered and concentrated again. The residue is purified by column chromatography (silica gel 60 Merc~/chloroform). 159 g (20.5~ of theory) of2-(2-chlorophenyl)-2-(1,2,4-triazol-1-yl-methyl)-ooxirane of refractive index nD 1.5572 are obtained.
:~21~6~
The following compounds of the general formula R ¦ (I) are obtained in a corresponding manner and according to the processes mentioned:
Example ¦ Melting No. R Az point (C) .. .. _ .. .. . .~
2 C lo N-- 118 Use examples The compound shown below is employed as the comparison substance in the use examples which follow:
=N` OH N
( A ) N -- CH -- C - CH -- N/
~11 Example A
Cochliobolus sativus test (barley) / protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether 4~L~513 To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with wat-er to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Cochliobolus sativus. The plants remain in an incuba-tion cabinet for 48 hours at 20C and 100% relative atomspheric humidity.
The plants are placed in a greenhouse at a temperature of about 20C and a relative atmospheric humidity of about 80%.
Evaluation is carried out 7 days after the inoculation.
In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples: 1.
Example B
Venturia test (apple)/protective Solvent: 4.7 parts by weight of acetone 0 Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
~20- 23139--5714D
To test for protective aetivity, young plants are sprayed with the preparation of aetive eompound until dripping wet.
After the spray coating has dried on, the plants are inoculated wi-th an aqueous eonidia suspension of the apple scab eausative organism (Venturia inaequalis) and then remain in an ineubation cabin at 20C
and 100~ relative atmospheric humidity for 1 day.
The plants are then placed in a greenhouse at 20C and a relative atmospheric humidity of about 70~.
Evaluation is earried out 12 days after the inoculation.
In this test, a clearly superior aetivity compared with the prior art is shown, for example, by the eompounds aeeording to the following preparation examples: 1.
The trimethylsulphonium methylsulphate of the formula (IX) required in process variant (~) is likewise known (compare Hetero-cycles 8, 397 (1977)). In the above reaction, it is likewise em-ployed in the freshly prepared state, by being produced in situ by reaction of dimethyl sulphide with dimethyl sulphate.
Formula (I'i7) provides a general definition of the 2-halo-genomethyl-oxiranes to be used as starting substances for process (b) for producing compounds of formula I or process (i) for producing compounds of formula IIa. In this formula, R preferably represents 20 those radicals which have already been mentioned as preferred for these substituents in connection with the description of the sub-stances of the formula (I). Hal preferably represents chlorine, bromine or iodine.
The 2-halogenomethyl-oxiranes of the formula (IV) are known, or they can be obtained in a generally known manner, by add-ing aqueous alkali metal hydroxide solution to dihalogenoalkanols of the formula tVI) (in this context, compare also J. Org. Chem.
27, 2242 (1961)).
Formula (V) provides a general definition of the azoles also to be used as starting substances for process (b). In this formula, M preferably represents hydrogen, sodium or potassium.
The azoles of the formula (V) are generally known com-pounds of organic chemistry. The alkali metal salts are obtained by reacting pyrazole, imidazole or 1,2,4-triazole with sodium ethy-late or potassium ethylate, or by reacting pyrazole, imidazole or lQ 1~2~4-triazole with the equivalent amount of the corresponding alkali metal hydride.
Formula (VI) provides a general definition of the dihalo-genoalkanols to be used as starting substances for process (c) for producing compounds of formula I or for producing compounds of form-ula (IV) by reaction with aqueous alkali metal hydroxide solution.
In this formula, R preferably represents those radicals which haze already been mentioned as preferred for this substituent. Hal pre-ferably represents chlorine.
The dihalogenoalkanols of the formula (VI) are known, or they can be obtained in a generally known manner, by reacting 1,3-dihalogenoacetones, such as, in particular, 1,3-dichloroacetone, with a corresponding Grignard reagent (in this context, compare also J. Org. Chem. 27, 2242 (1961)~.
Preferred possible diluents for process (a) are inert organic solvents. These include, preferably, nitriles, such as, in particular, acetonitrile; aro~.atic hydrocarbons, such as benz-ene, toluene and dichlorobenzene; formamides, such as, in particular, ~LZ4~S8 dimethylformamide; halogenated hydrocarbons, such as methylene chloride or carbon tetrachloride; and hexamethylphosphoric acid triamide.
Process (a) is carried out in the presence of an alkali metal alcoholate. Preferred alkali metal alcoholates include the methylates and ethylates of sodium and potassium and, in particular, also potassium tert.-butylate.
The reaction temperatures can be varied within a substan-tial range in carrying out process (a). In general, the reaction is carried out between about 30 and 150C, preferably between 80 and 100C.
In carrying out process (a) 1 to 4 mol of azole of the formula (III) and 1 to mol of alkali metal alcoholate are prefer-ably employed per mol of oxirane of the formula (II). The end prod-ucts are isolated in a generally customary manner.
In a preferred embodiment of process (a) the oxiranes of the formula (II) obtained according to process (~) or (~) are fur-ther reacted directly, without being isolated.
Preferred possible diluents for processes (b) and (c) are inert organic solvents. These include, preferably, ketones, such as, in particular , acetone and methyl ethyl ketone; nitriles, such as, in particular, acetonitrile; alcohols, such as, in particular, ethanol and isopropanol; ethers, such as, in particular, tetrahydro-furan or dioxane; formamides, such as, in particular, dimethylform-amide; and aromatic and halogenated hydrocarbons.
-12~ 23189-5714D
If appropri.ate, processes (b) and Ic) are carried out in the presence of an acid-binding agent. All the inorganic or organic acid-binding agents which can usually be employed can be added, such as alkali metal carbonates, for example sodium carbonate and potas-sium carbonate; or such as lower tertiary alkylamines, cycloalkyla-mines,cycl~Xenylami.nes or arylalkylamines, for example triethylam-ine, N,N-dimethylcyclohexylamine, dicyclohexylamine or N,N-dimeth-ylbenzylamine, and furthermore pyridine and diazabicyclooctane, and also an appropriate excess of azole.
The reaction temperatures can be varied within a substant-ial range in carrying out processes (b) and (c). In general, the reactions are carried out between about 20 and about 150C, prefer-ably at 20 to 120C.
In carrying out processes (b) and (c)2 to 4 mol of azole of the formula (V) and, if appropriate, 2 to 4 mol of acid-binding agent are employed per mol of the 2-halogenomethyloxiranes of the formula (IV) or of the dihalogenoalkanols of the formula (VI). The compounds of the formula (I) are isolated in a customary manner.
The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and they can be isolated in a known manner, for example by filtration, and if appropriate purified by washing with an inert organic solvent.
so The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to compounds of the formula (I).
The metal salt complexes can be isolated in a known manner, for ex-ample by filtration, and if necessary purified by recrystallisation.
The active compounds of the formula (I) according to the parent application exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms.
The active compounds are suitable for use as plant protection agents.
Funsicidal agents in plant protection are employed for combating Plasmodiophoromyce~es, Oomycetes, Chytridiomycetes, Zygomy-cetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds of the formula (I) can be used with particularly good success for combating cereal diseases such as Cochliobolus sativus, Erysiphe graminis, Puccinia and Pyrenophora teres; and furthermore for combating apple scab (Venturia inaequalis) and rice diseases, such as Pyricularia and Pellicularia.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for seed, and formulations 1'~416S~
used with burning equipment, such as fumiga-ting cartridges, fumig-ating cans, fumigating coils and the like, as well as ULV cold mis-t and warm mist formulations.
These formulations are produced in known manner, for ex-ample by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, op-tionally with the use of surfaceactive agents, that is, emulsifying .
agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as wel.l as their ethers and esters, ketones, such as acetone, methyl ethyl ketone,. methyl isolbutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsul-phoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellant, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide;
as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; as ~Z~
solid carriers for granules there are suitahle: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sep-iolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic materials such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/
or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl poly-glycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylc-ellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers i.n the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal pht-halocyanine dyestuffs, and trace nutrients such as salts of iron,manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compounds of the formula (I) can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungici.des, bactericides, insectic-ides, acaricides, nematicides, herbicides, bird repellants, growth ~Z4~L6~
-lh- 23l89-57l4D
factors, plant nutrients and agents for improving soil structure.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vaporising, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dres-sing or encrusting.
In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0.0001% by weight, pre-ferably between 0.5 and 0.001%.
In the treatment of seed, amounts of active compollnd of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
For the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the place of action.
Preparation examples:
Example 1 N OH N
= N/ Cl 65~
(Process a) A mixture of 3.4 g (50 mmol) of pyrazole, 2.8 g (25 mmol) of potassium tert.-butylate and 5.9 g (25 mmol) of 2-(2-chlorophen-yl)-2-(1,2,4-triazol-1-yl-methyl)-Q~irane in 200 ml of dimethylform-amide is heated at 100C for 36 hours. The reaction mixture is then concentrated in vacuo, the residue is dissolved in chloroform and the solution is filtered and washed with water. The chloroform solution is dried over sodium sulphate, filtered and concentrated in vacuo. the residue which remains is purified by chromatography (silica gel 60 Merck/chloroform)O 5.8 g (74% of theory) of 2-(2-chlorophenyl)-l-pyrazol-l-yl)-3-(1,2,4-triazol-1-yyl)-2-propanol of refractive index nD 1.5690 are obtained.
Preparation of the starting substance O - CH - N/
CH - o A solution of 68.5 g (0.33 mol) of 2-(2-chlorophenyl)-2-chloromethyl-oxirane in 50 ml of acetone is added dropwise to a mix-ture of 24.2 g (o.35 mol) of triazole and 48.3 g (o.35 mol) of pot-assium carbonate in 300 ml of acetone. The reaction mixture is heated under reflux for 20 hours and filtered and the filtrate is concentrated. The residue is dissolved in methylene chloride and the solution is washed with water, dried over sodium sulphate, fil-tered and concentrated again. The residue is purified by column chromatography (silica gel 60 Merc~/chloroform). 159 g (20.5~ of theory) of2-(2-chlorophenyl)-2-(1,2,4-triazol-1-yl-methyl)-ooxirane of refractive index nD 1.5572 are obtained.
:~21~6~
The following compounds of the general formula R ¦ (I) are obtained in a corresponding manner and according to the processes mentioned:
Example ¦ Melting No. R Az point (C) .. .. _ .. .. . .~
2 C lo N-- 118 Use examples The compound shown below is employed as the comparison substance in the use examples which follow:
=N` OH N
( A ) N -- CH -- C - CH -- N/
~11 Example A
Cochliobolus sativus test (barley) / protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether 4~L~513 To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with wat-er to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Cochliobolus sativus. The plants remain in an incuba-tion cabinet for 48 hours at 20C and 100% relative atomspheric humidity.
The plants are placed in a greenhouse at a temperature of about 20C and a relative atmospheric humidity of about 80%.
Evaluation is carried out 7 days after the inoculation.
In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples: 1.
Example B
Venturia test (apple)/protective Solvent: 4.7 parts by weight of acetone 0 Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
~20- 23139--5714D
To test for protective aetivity, young plants are sprayed with the preparation of aetive eompound until dripping wet.
After the spray coating has dried on, the plants are inoculated wi-th an aqueous eonidia suspension of the apple scab eausative organism (Venturia inaequalis) and then remain in an ineubation cabin at 20C
and 100~ relative atmospheric humidity for 1 day.
The plants are then placed in a greenhouse at 20C and a relative atmospheric humidity of about 70~.
Evaluation is earried out 12 days after the inoculation.
In this test, a clearly superior aetivity compared with the prior art is shown, for example, by the eompounds aeeording to the following preparation examples: 1.
Claims
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A 2-pyrazolylmethyl-oxirane of the formula in which R represents straight-chain or branched alkyl with 1 to 12 carbon atoms, straight-chain or branched alkenyl or alkinyl with in each case 2 to 6 carbon atoms, or phenyl, phenylalkyl with 1 to 4 carbon atoms in the alkyl part, phenylalkenyl with 2 to 4 carbon atoms in the alkenyl part or phenylalkinyl with 2 to 4 carbon atoms in the alkinyl part, each of which is optionally mono-, di- or tri-substituted in the phenyl part by identical or different substituents, from the group comprising halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with in each case 1 or 2 carbon atoms, alkoxy-alkyl with 1 or 2 carbon atoms in each alkyl part and optionally halogen-substituted phenyl or represents naphthyl, or cycloalkyl which has 3 to 7 carbon atoms and is optionally substituted by alkyl with 1 to 4 carbon atoms.
2. A compound according to claim 1 wherein R represents ethyl, tert.-butyl, allyl or propargyl, or phenyl, benzyl, phenethyl, phen-ethenyl or phenethinyl, each of which is optionally monosubstituted or disubstituted in the phenyl part by identical or different sub-stituents selected from fluorine, chlorine, methyl, methoxy, meth-ylthio, isopropoxy, methoxymethyl, phenyl which is optionally sub-stituted by fluorine or chlorine, naphthyl, and cyclopropyl, cyclopentyl and cyclohexyl, each of which is optionally substituted by methyl or ethyl.
3. A compound according to claim 1 wherein R represents phenyl which is optionally monosubstituted or disubstituted by identical or different substituents selected from fluorine, chlorine, methyl and methoxy.
4. A process for preparing a 2-pyrazolylmethyl-oxirane of the formula IIa as defined in claim 1 which process comprises i) reacting a 2-halogenomethyl-oxirane of the formula IV
in which R is as defined in claim 1 and Hal represents halogen, with pyrazole, or ii) reacting a ketone of the formula VII
in which R is as defined in claim 1, with either .alpha.) dimethyloxosulphonium methylide of the formula .delta. + .delta.-VIII
(CH3)2SOCH2 or .beta.) trimethylsulphonium methylsulphate of the formula CH3SO4(-) IX
A process according to claim 4(i) wherein the reaction is conducted in the presence of an inert organic solvent and in the presence of an acid binding agent.
6. A process according to claim 4(i) wherein the reaction is conducted at a temperature between 20 and 120°C.
7. A process according to claim 4(ii) wherein the reaction of the compound of formula (VII) with the compound of formula (VIII) is conducted in the presence of a diluent, at a temperature between 20 and 80°C.
8. A process according to claim 4(ii) wherein the reaction of the compound of formula (VII) with the compound of formula (IX) is conducted in the presence of an inert organic solvent and in the presence of a base.
9. A process according to claim 4(ii) wherein the reaction of the compound of formula (VII) with the compound of formula (IX) is conducted at a temperature between 0 and 60°C.
10. A process as claimed in claim 5 wherein the inert or-ganic solvent is acetone.
11. A process as claimed in claim 5 wherein the acid-bind-ing agent is potassium carbonate.
12. A process as claimed in claim 7 wherein the diluent is dimethylsulphoxide.
13. A process as claimed in claim 8 wherein the inert organic solvent is acetonitrile.
14. A process as claimed in claim 8 wherein the base is sodium methylate.
15. A process as claimed in claim 4(ii) wherein the reaction of the compound of formula (VII) with the compound of formula (IX) is conducted at room temperature.
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A 2-pyrazolylmethyl-oxirane of the formula in which R represents straight-chain or branched alkyl with 1 to 12 carbon atoms, straight-chain or branched alkenyl or alkinyl with in each case 2 to 6 carbon atoms, or phenyl, phenylalkyl with 1 to 4 carbon atoms in the alkyl part, phenylalkenyl with 2 to 4 carbon atoms in the alkenyl part or phenylalkinyl with 2 to 4 carbon atoms in the alkinyl part, each of which is optionally mono-, di- or tri-substituted in the phenyl part by identical or different substituents, from the group comprising halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with in each case 1 or 2 carbon atoms, alkoxy-alkyl with 1 or 2 carbon atoms in each alkyl part and optionally halogen-substituted phenyl or represents naphthyl, or cycloalkyl which has 3 to 7 carbon atoms and is optionally substituted by alkyl with 1 to 4 carbon atoms.
2. A compound according to claim 1 wherein R represents ethyl, tert.-butyl, allyl or propargyl, or phenyl, benzyl, phenethyl, phen-ethenyl or phenethinyl, each of which is optionally monosubstituted or disubstituted in the phenyl part by identical or different sub-stituents selected from fluorine, chlorine, methyl, methoxy, meth-ylthio, isopropoxy, methoxymethyl, phenyl which is optionally sub-stituted by fluorine or chlorine, naphthyl, and cyclopropyl, cyclopentyl and cyclohexyl, each of which is optionally substituted by methyl or ethyl.
3. A compound according to claim 1 wherein R represents phenyl which is optionally monosubstituted or disubstituted by identical or different substituents selected from fluorine, chlorine, methyl and methoxy.
4. A process for preparing a 2-pyrazolylmethyl-oxirane of the formula IIa as defined in claim 1 which process comprises i) reacting a 2-halogenomethyl-oxirane of the formula IV
in which R is as defined in claim 1 and Hal represents halogen, with pyrazole, or ii) reacting a ketone of the formula VII
in which R is as defined in claim 1, with either .alpha.) dimethyloxosulphonium methylide of the formula .delta. + .delta.-VIII
(CH3)2SOCH2 or .beta.) trimethylsulphonium methylsulphate of the formula CH3SO4(-) IX
A process according to claim 4(i) wherein the reaction is conducted in the presence of an inert organic solvent and in the presence of an acid binding agent.
6. A process according to claim 4(i) wherein the reaction is conducted at a temperature between 20 and 120°C.
7. A process according to claim 4(ii) wherein the reaction of the compound of formula (VII) with the compound of formula (VIII) is conducted in the presence of a diluent, at a temperature between 20 and 80°C.
8. A process according to claim 4(ii) wherein the reaction of the compound of formula (VII) with the compound of formula (IX) is conducted in the presence of an inert organic solvent and in the presence of a base.
9. A process according to claim 4(ii) wherein the reaction of the compound of formula (VII) with the compound of formula (IX) is conducted at a temperature between 0 and 60°C.
10. A process as claimed in claim 5 wherein the inert or-ganic solvent is acetone.
11. A process as claimed in claim 5 wherein the acid-bind-ing agent is potassium carbonate.
12. A process as claimed in claim 7 wherein the diluent is dimethylsulphoxide.
13. A process as claimed in claim 8 wherein the inert organic solvent is acetonitrile.
14. A process as claimed in claim 8 wherein the base is sodium methylate.
15. A process as claimed in claim 4(ii) wherein the reaction of the compound of formula (VII) with the compound of formula (IX) is conducted at room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000547804A CA1241658A (en) | 1983-04-12 | 1987-09-24 | 2-pyrazolylmethyl-oxirane useful as intermediates for producing fungicides |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3313073A DE3313073A1 (en) | 1983-04-12 | 1983-04-12 | 1-AZOLYL-3-PYRAZOLYL-2-PROPANOL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DEP3313073.6 | 1983-04-12 | ||
| CA000451607A CA1242444A (en) | 1983-04-12 | 1984-04-10 | 1-azolyl-3-pyrazolyl-2-propanol derivatives, processes for their preparation and their use as fungicides |
| CA000547804A CA1241658A (en) | 1983-04-12 | 1987-09-24 | 2-pyrazolylmethyl-oxirane useful as intermediates for producing fungicides |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000451607A Division CA1242444A (en) | 1983-04-12 | 1984-04-10 | 1-azolyl-3-pyrazolyl-2-propanol derivatives, processes for their preparation and their use as fungicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1241658A true CA1241658A (en) | 1988-09-06 |
Family
ID=25670352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000547804A Expired CA1241658A (en) | 1983-04-12 | 1987-09-24 | 2-pyrazolylmethyl-oxirane useful as intermediates for producing fungicides |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1241658A (en) |
-
1987
- 1987-09-24 CA CA000547804A patent/CA1241658A/en not_active Expired
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| Date | Code | Title | Description |
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| MKEX | Expiry |