CA2048974A1 - Azolylmethyloxiranes and fungicides containing them - Google Patents
Azolylmethyloxiranes and fungicides containing themInfo
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- CA2048974A1 CA2048974A1 CA002048974A CA2048974A CA2048974A1 CA 2048974 A1 CA2048974 A1 CA 2048974A1 CA 002048974 A CA002048974 A CA 002048974A CA 2048974 A CA2048974 A CA 2048974A CA 2048974 A1 CA2048974 A1 CA 2048974A1
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- alkyl
- phenyl
- naphthyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
O.Z. 0050/41868 Abstract of the Disclosure: Fungicides contain azolyl-methyloxiranes of the general formula I
where A and B are each alkyl, cycloalkyl, cycloalkenyl, biphenyl, naphthyl, hetaryl or phenyl, where these radicals may be substituted, D is alkyl and X is CH or N, or their plant-tolerated acid addition salts or metal complexes.
where A and B are each alkyl, cycloalkyl, cycloalkenyl, biphenyl, naphthyl, hetaryl or phenyl, where these radicals may be substituted, D is alkyl and X is CH or N, or their plant-tolerated acid addition salts or metal complexes.
Description
~0~97~
o.z. 0050~41868 AzolylmethYloxiranes and funaicide~ containina them The present invention relates to novel azolyl-methyloxirane~, processes for their preparation and fungicide~ containing them.
WQ have found that compound~ of the formula I
~x~N ~ B
N
where A and B are each Cl-Ca-alkyl, C3-Ca-cycloalkyl, C5-Ca-cycloalkenyl, biphenyl, naphthyl, hetaryl or phenyl, where each of these radicals may be monosubstituted to trisubstituted by halogen, nitro, phenoxy, amino, Cl-C4-alkyl, Cl-C4-alkoxy or Cl-C4-haloalkyl, D is Cl-Ca-alkyl and X i3 CH or N, and plant-tolerated acid addition salts and metal com-plexes thereof have a better fungicidal action than known azole compounds.
The compounds of the formula I contain centers of chirality and are obtained in general in the form of racemates or as diastereomer mixtures of erythro or threo forms. The erythro or threo diastereomers of the novel compounds can be ~eparated in a conventional manner, for example on the basis of their different solubilitie4 or by column chromatography, and isolated in pure form.
Pure enRntiomers can be obtained from such an isolated diastereomer by known methods. Both the pure dia~tereo-mer~ o~ enantiomers and the mixtures thereof obtained inthe synthesLs can be used as fungicides. The present invention relates to all the~e compounds.
Preferred azolylmethyloxiranes are those in which A and B have the following mesningss Cl-Ca-alkyl, preferably Cl-C~-alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl; among the Cl-Ca-alkyl radicals of more than 4 carbon atoms, n-pentyl and neopentyl are preferred;
phenyl or halogen-substituted phenyl, such as ~ ~Y
o.z. 0050~41868 AzolylmethYloxiranes and funaicide~ containina them The present invention relates to novel azolyl-methyloxirane~, processes for their preparation and fungicide~ containing them.
WQ have found that compound~ of the formula I
~x~N ~ B
N
where A and B are each Cl-Ca-alkyl, C3-Ca-cycloalkyl, C5-Ca-cycloalkenyl, biphenyl, naphthyl, hetaryl or phenyl, where each of these radicals may be monosubstituted to trisubstituted by halogen, nitro, phenoxy, amino, Cl-C4-alkyl, Cl-C4-alkoxy or Cl-C4-haloalkyl, D is Cl-Ca-alkyl and X i3 CH or N, and plant-tolerated acid addition salts and metal com-plexes thereof have a better fungicidal action than known azole compounds.
The compounds of the formula I contain centers of chirality and are obtained in general in the form of racemates or as diastereomer mixtures of erythro or threo forms. The erythro or threo diastereomers of the novel compounds can be ~eparated in a conventional manner, for example on the basis of their different solubilitie4 or by column chromatography, and isolated in pure form.
Pure enRntiomers can be obtained from such an isolated diastereomer by known methods. Both the pure dia~tereo-mer~ o~ enantiomers and the mixtures thereof obtained inthe synthesLs can be used as fungicides. The present invention relates to all the~e compounds.
Preferred azolylmethyloxiranes are those in which A and B have the following mesningss Cl-Ca-alkyl, preferably Cl-C~-alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl; among the Cl-Ca-alkyl radicals of more than 4 carbon atoms, n-pentyl and neopentyl are preferred;
phenyl or halogen-substituted phenyl, such as ~ ~Y
- 2 - o.z. 0050/41868 2-chlorophenyl, 3-chlorophenyl, 4 chlorophenyl, 2-fluoro~
phenyl, 3-fluorophenyl, 4-fluoxophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,3-dichlorophenyl,2,4-di-chlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-5 chloro-4-fluorophenyl or 2-chloro-6-fluorophenyl;
phenyl which is monosubstituted by nitro, pheno~y, amino or Cl-C4-alkyl, such a~ 3-nitrophenyl, 4~nitroph~nyl, 3-phenoxyphenyl, 4-phenoxyphenyl, 3-aminophenyl, 4-amino-phenyl, 4-ethylphenyl, 4-isopropylphenyl or 4-tert-butylphenyl;
phenyl which is substituted by two or three different radicals from among tho~e stated above, such as 2-chloro-.
6-methylphenyl;
phenyl which i~ mono~ubstituted or disub~tituted by Cl-C4-alkoxy, such a~ 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 4-tert-butoxyphenyl, 2,4-dimethoxyphenyl or 3,4-dLmethoxyphenyl;
p-biphenyl, l-naphthyl or 2-naphthyl;
hetaryl having 5 or 6 ring atoms, 6-membered rings having not more than three nitrogen atom~, such as pyridyl, 2-pyridyl, 2-pyridyl or 4-pyridyl, being particular ex-ample~, aY well as 5-membered rings having, preferably, one or two of the hetero atoms O, S and N, in particular furyl, 2-furyl, ~hienyl, 2-thienyl, 3-thienyl, oxazolyl, 4-oxazolyl, thiazolyl, 4 thiazolyll isoxazolyl, 4-isoxaz olyl, 5-isoxazolyl, Lmidazolyl or 5-Lmidazolyl;
C3-C0-cycloalkyl, preferably cyclopentyl or cyclohexyl, or C5-C~-cycloalkenyl, preferably 3-cyclohexenyl.
D i3 Cl-Ca-alkyl r preferably Cl-C4-alkyl, in particular methyl, ethyl, n-propyl, i~opropyl, n-butyl, sec-butyl or tert-butyl; among the Cl-C0-alkyl groups of more than 4 carbon atom~, n-pentyl and neopentyl are preferred.
Acid addition ~alts are, for example, the hydro-chloride3, bromides, ~ulfates, nitrate~, phosphate~, oxalate~ and dodecylbenzene~ulfonate~. The activity of - Z~14~397~
- _ 3 _ o.z. 0050/41868 the salts is due to the cation, so that the anion is in general unimportant. The novel active ingredient salts are prepared by reacting the azolylmethyloxiranes (I~
with suitable acids.
Metal complexes of the active ingredients I or of their salts can be formed with copper, zinc, tin, man-ganese, iron, cobalt or nickel by reacting the azolyl-methyloxiranes with corresponding metal salts.
The compound~ of the formula I can be prepared, for example, if a) a compound of the formula II
L ~ 3 II
where A, B and D have the abovementioned meanings and L i3 a nucleophilic leaving group, is reacted with a compound of the formula III
~e-N ~ III
~5N
where Me is hydrogen or a metal atom and X has the stated meanings, or b) a compound of the formula IV
~x~
N~_,N ~ IV
A
where A, B, D and X have the abovementioned mean-ings, i8 converted into an epoxide.
Where ~e is hydrogen, reaction a) is carrLed out in the presence or absence of a ~olvent or diluent and with or without the addition of an inorganic or organic base or of a reaction accelerator at from lO to 120C.
The preferred ~olvents and diluents include ketones, such as acetone, methyl ethyl ketone or cyclohexanone, nit-riles, such as acetonitrile or propionitrile, alcohol~, such as methanol, ethanol, isopropanol, n-butanol or 21~4~39'7~
- 4 - O.Z. 0050/41868 glycol, eqters, such as ethyl acetate, methyl acetate or butyl acetate, ethers, such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane or diisopropyl ether, amides, such as dimethylformamide, dimethylacetamide or 5N-methylpyrrolidone, and dimethyl sulfoxide, sulfolane or corresponding mixtures.
Suitable bases which may also be used a~ acid acceptors in the reaction are, for example, alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide 10or potassium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, ~odium bicarbonate or potassium bicarbonate, pyridine or 4-dimethylamino-pyridine. However, other conventional bases may al80 be used.
15Preferred reaction accelerators are metal hal-ides, such as sodium iodide or potassium iodide, quater-nary ammonium salts, such as tetrabutylammonium chloride, bromide, iodide or bisulfate, benzyltriethylammonium chloride or bromide, or crown ethers, such as 12-crown-204, 15-crown-5, 18-crown-6, dibenzo-18-crown-6 or dicyclo-hexano-18-crown-6.
The reaction i8 carried out in general at from 20 to 150C under atmospheric or superatmospheric pressure, continuou~ly or batchwise.
25If ~e i8 a metal atom, reaction a) is carried out in the presence or absence of a solvent or diluent and with or without the addition of a strong inorganic or organic base at from -10 to 120C. The preferred solvents and diluents include amides, such as dimethylformamide, 30diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide and sulfoxides, such as dimethyl sulfoxide or sulfolane.
Suitsble bases which may also be used as acid acceptors in the reaction are, for example, alkali metal 35hydrides, such as lithium hydride, sod~um hydride or potassium hydride, alkali metal amides, such as sodium amide or potassium amide, and sodium tert-butoxide or 2al4~97~
` - 5 - O.Z. 0050/41868 potassium tert-butoxide.
Suitable diluents for reaction b) are polar organic solvents, such as nitriles, eg. acetonitrile, sulfoxide~, eg. dimethyl sulfoxide, formamides, eg.
dimethylformamide, ketones, eg. acetone, ethers, eg.
diethyl ether or tetrahydrofuran, and in particular chlorohydrocarbons, eg. methylene chloride or chloroform.
The reaction is carried out in general at from 0 to 100C, preferably from 20 to 80C. In the presence of a ~olvent, it is expediently carried out at the boiling point of the particular solvent.
The starting compounds II are obtained by epoxi-dation of the corresponding olefins V:
L_~B V
A
; 15 (cf. G. Dittus in ~ouben-Weyl-~ller, Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, 1965, Vol. VI, 3, page 385 et ~eq.).
The compounds V are prepared by halogenating or oxidizing olefins of the formula VI
~ B VI
A
in the allyl position by known methods.
Suitable halogenating reagents are N-chloro- and N-bromosuccinimide in halohydrocarbons, ~uch as carbon tetrachloride, trichloroQthane or methylene chloride, at 25from 20 to 100C. Peresters, ~uch as tert-butyl per-benzoate or tert-butyl peracetate, in the presence of a heavy metal ~alt, eg. copper(I) chloride or copper(I) bromide, are used for allyl oxidation. The reaction i~
carried out in an inert solvent at from 10 to 100C.
30The resulting allyl halides or alcohols V are then converted into the corresponding epoxides II (L =
halogen or OH). For this purpose, the olefin~ V are oxidized with a peroxycarboxylic acid, ~uch a~ perbenzoic 204~3~7~
- 6 - O.Z. 0050/4186a acid, 3-chloroperbenzoic acid, 4-nitroperbenzoic acid, monoperphthalic acid, peracetic acid, perpropionic acid, permaleic acid, monopersuccinic acid, perpelargonic acid or trifluoroperacetic acid, in an inert solvent, prefer-ably chlorohydrocarbons, eg. methylene chloride, chloro-form, carbon tetrachloride or dichloroethane, or, if required, also in acetic acid, ethyl acetate, acetone or dimethylformamide, in the presence or absence of a buffer, such a~ sodium acetate, sodium carbonate or disodium hydrogen phosphate. The reaction is carried out at from 10 to loor and, if required, is catalyzed, for example with iodine, sodium tungstate or light. Also suitable for the oxidation are alkaline solution~ of hydrogen peroxide (about 30% strength) in methanol, ethanol, acetone or acetonitrile at from 25 to 30C, and alkyl hydroperoxides, eg. tert-butyl hydroperoxide, with the addition of a cataly~t, eg. sodium tungstate, per-tungstic acid, molybdenum hexacarbonyl or vanadyl acetyl-acetonate. Some of the ~tated oxidizing agents can be produced in situ.
While the resulting epoxy halides II (L = halo-gen) can be immediately reacted by proces3 a), the corresponding epoxy alcohols II (L = OH) are converted into reactive esters, which are then reacted with a compound III by procesa a).
The reactive esters which are reacted with III
are prepared by generally known methods (Houben-Weyl-M~ller, Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, 1955, Volume 9, pages 388, 663 and 671). Examples of such esters are methane~ulfonates, trifluoromethanesulfonates, 2,2,2-trifluoroethane-sulfonates, nonafluorobutaneaulfonate~, 4-methylbenzene-~ulfonates, 4-bromobenzenesulfonstes, 4-nitrobenzene-sulfonatea and bensenesulfonates.
The compounds IV are converted, for example with an oxidizing agent, into their epoxidea.
The compoundJ V can be prepared by generally ~.
2~4~
- 7 - O.Z. 0050/41868 known method~ of olefin synthesi~ (Houben-Weyl-Muller, Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, 1972, Vol. V, lb).
The Examples which follow illustrate the prepara-tion of the active ingredients.
I. Preparation of the starting material~
Method A
1-(4-Fluorophenyl)-2-(3-trifluoromethylphenyl)-buten-2-one F
27.8 g (0.224 mol) of 4-fluorobenzaldehyde and 2 ml of piperidine are added to a solution of S0 g (0.247 mol) of 3-trifluoromethylphenylacetone in 250 ml of toluene, and the mixture i~ heated with removal of the water formed in the reaction. Thereafter, the reaction ~olution i~ wa~hed once with 0.5 M hydrochloric acid and three times with water, dried over sodium sulfate and evaporated down under reduced pres~ure. The subsequent di~tillation of the remaining residue give~ 62 g (90%) of product boiling at 102-C under 0.1 mbar.
~ethod B
ci~-2-(1-Hydroxyethyl)-2-(3-trifluoromethylphenyl)-3-(4-fluorophenyl)-oxirane H~F
¢~
62 g (0.2 mol) of 1-(4-fluorophenyl)-2-(3-tri-fluoromethylphenyl)-buten-2-one are dis~olved in 300 ml of methanol, and 4 ml of concentrated ~odium hydroxide ~olution are added. The reaction ~olution i4 ~tirred at . - : . ,...... . , .. , , ~
Z1~4~39~
- 8 - O.Z. 0050/41868 0C while 1~.4 g of hydrogen peroxide are slowly added dropwise, the internal temperature not exceeding 30C.
After the end of the addition, stirring is continued for six hours at room temperature, after which 2.5 g of S sodium borohydride, dissolved in a little 10% strength sodium hydroxide solution, are added. After the reaction mixture has been stirred for 18 hours at room tempera-ture, 100 ml of water are added to the solution and the resulting emulsion is extracted by shaking with methylene chloride. The isolated organic phase i~ then dried over sodium sulfate and evaporated down. 60 g (92%) of product are obtained as a 1 : 1 diastereomer mixture.
Method C
cis-2~ Methylsulfonyloxyethyl)-2-(3-trifluoromethyl-phenyl)-3-(4-fluorophenyl)-oxirane H 3C--S~F
0~
17.6 g of methanesulfonyl chloride are added to a solution of 40 g (0.123 mol) of cis-2-(1-hydroxyethyl)-2-(3-trifluoromethylphenyl)-3-(4-fluorophenyl)-oxirane in 200 ml of methylene chloride and 21.5 ml of triethylamine at room temperature. After 24 hours, the reaction mixture is washed with aqueous sodium bicarbonate solu-tion and water, dried over sodium sulfate and evaporated down under reduced pressure. The residue give~ 45 g (91%) of product as a 1 : 1 diastereomer mixture. 5 II. Preparation of the end product~
cis-2-(1,2,4-Triazol-l-ylethyl)-2-(3-trifluoromethyl-phenyl)-3-(4-fluorophenyl)-oxirane ~N~ ~_F
Ç~
`` 204t397~
- g - O.Z. 0050/41868 15.6 g of potassium carbonate are added to a solution of 7.73 g (0.11 mol) of 1,2,4-triazole in 100 ml of N,N-dimethylformamide and the mixture is heated at 50C for 30 minute~. After the reaction mixture has been cooled to room temperature, 22.8 g (0.056 mol) of cis-2-(l-methylsulfonyloxyethyl)-2-(3-trifluoromethylphenyl)-3-(4-fluorophenyl)-oxirane, dissolved in 50 ml of N,N-dimethylformamide, are slowly added dropwise to the solution and stirring is carried out for 13 hours at room temperature. Thereafter, 100 ml of water are added and the mixture is extracted several times with methyl tert-butyl ether; the organic pha~e iq wa~hed with water, dried over sodium sulfate and evaporated down under reduced pre~sure.
Yield: 7.7 g (36%) (compound No. 1) The compound~:shown in the Table can be prepared similarly to Example 1.
9'7~
- 10 - O. Z . 0050/41868 TABLE
NV ~3 Example A B D X mp . / lH-NMR
[ ppm 1 1 3-CF3-C6H4 4-F-C6H4 CH3 N 1.68 (d), 3.72 (s) (2S)4 (g)~ 8-04, 3 2 3-CF3-C6H4 4-F-C6H4 CH3 CH 1 62 Id~, 4.39 ~s), 3-CF3-C6H4 4-F-C6H4 C4Hg N
63--CF3--C6H4 4--F--C6H4 C5Hl 1 N
8 3-cF3-c6H4 C6H5 CH3 N
9 3-CF3-C6H4 2-F-c6H4 CH3 N
Il 3-CF3-C6H4 3-F-C6H4 CH3 N
143-CF3-C6H4 2-Cl-C6H4 C3H7 N
153-CF3-C6H4 2-CI-C6H4 iso-c3H7 N
203-CF3-C6H4 2,4-cl2-c6H3 C~3 N
213-CF3-C6H4 2,4-C12-C6H3 C2H5 N
233-CF3-C6H4 4-cH3-c6H4 CH3 N
243-CF3-C6H4 2,4-(cH3)2-c6H3 CH3 N
253--CF3--C6H4 2-ocH3-c6H4 CH3 N
273-CF3-C6H4 2-cF3-c6H4 CH3 N
Z~ 7~
- 11 - O.Z. 0050/41868 Example A B D X mp. /lH-NMR
. . ~ ppm 1 3-CF.-C6H4 l-Naphthyl CH3 N
31 3-CF3-C6H4 2-Naphthyl CH3 N
32 3-CF3-C6H4 4-3iphenyl CH3 N
33 C6Hs C6H5 CH3 N
C6H5 2-CI-C6H4 C2H5 N 3 92' 1.06 (2 t~, 8 14 ~2~')7 ~9' 37 C6Hs 3-CI-C6H4 CH3 N
38 C6H5 4-CI~C6H4 CH3 N
39 C6Hs 4-CI-C6H4 C2H5 N
4I C6H5 2,4-C12-C6H3 CH3 N
42 C6H5 2,4-ct2-C6H3 C2H5 N
43 C6Hs 2-F-C6H4 CH3 N
C6H5 3-F-c6H4 CH3 N
47 C6H5 4-F-c6H4 C2H5 N
48 C6H5 4-F-c6H4 C3H7 N
49 C6H5 2-Br-C6H4 CH3 N
51 ~ C6H5 4-CH3-C6H4 CH3 N
58 C6H5 I-Naphthyl CH3 N
59 C6H5 2-Naphthyl CH3 N
C6H5 4-Biphenyl CH3 N
O. Z . ()050/41868 Example A 13 D X mp. /lH-NMR
_ ___ [pl~m]
63 C~H5 Cyclopentyl CH3 N
54 C6H5 Cyclohexyl CH3 N
CDH5 3-Cyclohexenyl C~13 N
C6H5 2-Furyl CH3 N
57 C6H5 2-Thienyl CH3 N
63 C6H5 3-Thienyl CH3 N
69 C6H5 2-Pyridyl CH3 N
C6H5 3-Pyridyl CH3 N
71 2-cl-c6H4 C5H5 CH3 N
72 2-Cl-C6H4 2-CI-C6H4 CH3 N
73 2-cl-C5H4 3-CI-C6H4 CH3 N
74 2-Cl-C6H4 4-CI-CsH4 CH3 N
2-Cl-C6H4 2,4-cl2-C6H3 CH3 N
76 2-cl-c6H4 2-F-C6H4 CH3 N
77 2-Cl-C6H4 4-F-C6H4 CH3 N
78 2-Cl-C6H4 2-Br-C6H4 CH3 N
79 2-Cl-C6H4 2-CH3-C6H4 CH3 N
84 2-CI-C6H4 2-Furyl CH3 N
2-CI-C6H4 2-Thienyl CH3 N
86 2-Cl-C6H4 3-Pyridyl CH3 N
3-cl-c6H4 2,4-C12-C6H3 CH3 N
92 3-CI-C6H4 4-F-C6H4 c~l3 N
93 3-cl-c6H4 2-CF3-C6H4 CH3 N
94 3-cl-c6H4 4-CF3-C6H4 CH3 N
4-cl-c6H4 C6~l5 CH3 N
96 4-CI-C5H4 2-cl-c6H4 CH3 N
97 4-cl-c6H4 2-CI-C6H4 C2H5 N
2~4~9~'1 - 13 - O. Z . 0050/41868 Example A B D X mp. /lH-NMR
[ ppm 913 4--Cl--c6H4 2--cl--C6H4 C3H7 N
99 4--CI--C6H4 2--CI--C~H4 iso--C3H7 N
100 4--Cl--C6H4 2--CI--C6H4 C4Hg N
103 4--Cl--C6H4 4--Cl-C6H4 C2H5 N
105 4-CI-C6H4 2,4-C12-C6H3 CH3 N
106 4-CI-C6H4 2,4-C12-C5H3 C2H5 N
107 4-CI-C6H4 2-F-c6H4 CH3 N
109 4-CI-C6H4 2-6r-C6H4 CH3 N
110 4-Cl-C6H4 2-CH3-C6H4 CH3 N
117 4-CI-C6H4 l-Naphthyl CH3 N
118 4-CI-C6H4 2-Naphthyl CH3 N
119 4-CI-C6H4 4-B:iphenyl CH3 N
l20 4-CI-C6H4 CH3 CH3 N
122 4-GI-C6H4 Cyclopentyl CH3 N
123 4-CI-C6H4 Cyclohexyl CH3 N
124 4-CI-C6H4 2-Furyl CH3 N
125 4-CI-C6H4 2-Thienyl CH3 N
126 4-CI-C6H4 3-Thienyl CH3 N
127 4-CI-C6H4 2-Pyridyl CH3 N
128 4-CI-C6H4 3-~yridyl CH3 N
2~4~3~7~
- 14 - O. Z . 0050/41868 Example A B D X mp. /lH-NMR
- rppm]
132 2-F-C5H4 2, 4-C1 2 - C6H3 CH3 N
136 2-F-C6H4 4_CF3_C6H4 CH3 N
137 3_F_C6H4 2-CI-C6H4 CH3 N
138 3_F_C6H4 4_CI_C6H4 CH3 N
139 3-F-C6H4 4~F~C6H4 CH3 N
140 4_F_C6H4 C6H5 CH3 N
141 4_F_C6H4 2-C1-C6H4 CH3 N
142 4_F_C6H4 2-CI-C6H4 C2H5 N
143 4_F_C6H4 2-CI-C6H4 C3H7 N
144 4_F_C6H4 2-CI-C6H4 ;SO-C3H7 N
145 4_F_C6H4 2-CI-C6H4 C4H9 N
147 4_F_C6H4 3_CI_C6H4 CH3 N
148 4_F_C6H4 4_CI_C6H4 CH3 N
150 4_F_C6H4 4 CI_C6H4 C3H7 N
ISI 4_F_C6H4 4_CI_C6H4 C4H9 N
152 4_F_C6H4 2,4-CI2-C6H3 CH3 N
153 4_F_C6H4 2,4-CI2-C6H3 CH3 N
154 4_F_C6H4 2-F-C6H4 CH3 N ~.
155 4-F-C6H4 4~F~C6H4 CH3 N
156 4-F-C6H4 2-Cr-C6H4 CH3 N
158 4_F_C6H4 4_CH3_C6H4 CH3 N
159 4-F-C6H4 2,4-(CH3 ) 2-C6H 3 CH 3 N
160 4_F_C6H4 2-OCH3-C6H4 CH3 N
161 4--F--C6H4 4~CH3--C6H4 CH3 N
163 4_F_C6H4 4_CF3_C6H4 CH3 N
164 4_F_C6H4 3_NO2_C6H4 CH3 N
165 4_F_C6H4 3_NH2_C6H4 CH3 N
166 4-F-C6H4 I-Naphthyl CH3 N
2C~4~39~
- 15 - O. Z . 0050/41868 Example A B D X mp . ~lH-NMR
[ ppm l 167 4-F-C6H4 2-Naphthyl CH3 N
168 4-F-C6H4 4-Biphenyl CH3 N
171 4-F-C6H4 Cyclopentyl CH3 N
172 4-F-C6H4 Cyclohe~yl CH3 N
173 4-F-C6H4 2-Furyl CH3 N
174 4-F-C6H4 2-Thienyl CH3 N
175 4-F-c6H4 3-Thienyl CH3 N
176 4-F-C6H4 2-Pyridyl CH3 N
177 4-F-C6H4 3-Pyridyl CH3 N
178 4-F-C6H4 4-Pyridyl CH3 N
179 2~4-cl2-c6H3 C6H5CH3 N
180 2,4-C12-C6H3 2-CI-C6H4 CH 3 N
181 2~4-cl2-c6H3 3-CI-C6H4 CH3 N
182 2,4-C12-C6H3 4-CI-C6H4 CH3 N
183 2,4-C12-C6H3 2,4-C12-C6H4 CH3 N
184 2,4-C12-C6H3 2-F-C6H4 CH3 N
185 2,4-C12-C6H3 4-F-C6H4 CH3 N
186 2,4-C12-C6H3 2-CF3-C6H4 CH3 N
187 2,4-C12-C6H3 4-CF3-C6H4 CH3 N
188 2,4-C12-C6H3 2-CH3-C6H4 CH3 N
189 2,4-C12-c6H3 4-cH3-c6H4 CH3 N
190 4-Br-C6H4 C6H5 CH3 N
191 4-Br-C6H4 2-CI-C6H4 CH3 N
192 4-Br-C6H4 4-cl-c6H4 CH3 N
193 4-Br-C6H4 2,4-C1 rC6H3 CH3 N
194 4-Br-C6H4 4-F-c6H4 CH3 N
195 4-Br-C6H4 2-CF3-C6H4 CH3 N
2~39~
- 16 - O.Z. 0050/41868 Example A B D X mp. /lH-N~tR
. .. _ r ~pm 1 202 4-CH3-C6H4 2-cl-c6H4 CH3 N
203 4-CH3-C6H4 4-Cl-C6H4 CH3 N
204 4-CH3-C5H4 2,4-CI7-C5H3 CH3 N
215 4-oCH3-C6H4 C6H5CH3 N
216 4-OCH3-C6H4 2-CI-c6H4 CH3 N 1 72, 1 /9 ~2 d), 217 4-OCH3-C6H4 4-Cl-C6H4 CH3 N 8.12 (45) 221 2-Cf3-C6H4 2-CI-C6H4 CH3 N
222 2-CF3-C6H4 4-Cl-C6H4 CH3 N
223 2-CF3-C6H4 2-f-C6H4 CH3 N
226 4-cF3-c6H4 2-CI-C6H4 CH3 N
227 4-CF3-C6H4 4-Cl-C6H4 CH3 N
228 4-CF3-C6H4 2-f-C6H4 CH3 N
230 1-Naphthyl 2-CI-C6H4 CH3 N
231 1-Naphthyl 4-CI-C6H4 CH3 N
232 I-Naphthyl 4-F-C6H4 CH3 N
233 2-Naphthyl 2-cl-C6H4 CH3 N
234 2-Naphthyl 4-Cl-C6H4 CH3 N
235 2-Naphthyl 4-F-C6H4 CH3 N
236 4-3iphenyl 2-CI-C6H4 CH3 N
21~4~7'~
- - 17 - O. Z . 0050/41868 Example A B D X mp. /lH-NMR
__ [ppm~
237 4-Biphenyl 4-CI-C6H4 CH3 N
242 CH3 4-F-c6H4 CH3 N
243 CH3 2,4-Clz-C6H3 CH3 N
244 Cyclohexyl C6H5 CH3 N
245 Cyclohexyl 2-CI-C6H4 CH3 N
246 Cyclohexyl 4-CI-C6H4 CH3 N
247 Cyclohexyl 2,4-C12-C6H3 CH3 N
248 Cyclohexyl 2-F-C6H4 CH3 N
249 Cyclohexyl 4-F-C6H4 CH3 N
250 2-Furyl C6H5CH3 N
251 2-Furyl 2-CI-C6H4 CH3 N
: 252 2-Furyl 2,4-C1 rC6H3 CH3 N
253 2-Furyl 4-CI-C6H4 CH3 N
254 2-Furyl 2-F-C6H4 CH3 N
255 2-Furyl 4-F-c6H4 CH3 N
256 2-Thienyl C6Hs CH3 N
257 2-Thienyl 2-CI-C6H4 CH3 N
258 2-Thienyl 4-CI-C6H4 CH3 N
259 2-Thienyl 2,4-C12-C6H3 CH3 N :
260 2-Thienyl 2-F-C6H4 CH3 N
261 2-Thienyl 4-F-c6H4 CH3 N
262 3-Thienyl C6H5CH3 N
263 3-Thienyl 2-CI-C6H4 CH3 N
264 3-Thienyl 4-cl-c6H4 CH3 N
265 3-Thienyl 2,4-C12-C6H3 CH3 N
266 3-Thienyl 4-F-c6H4 CH3 N
267 4-Pyridyl C6H5CH3 N
268 4-Pyridyl 2-CI-C6H4 CH3 N
269 4-Pyridyl 4-CI-C6H4 CH3 N
270 4-Pyridyl 2,4-C12-C6H3 CH3 N
271 4-Pyridyl 4-F-c6H4 CH3 N
20~B97fl - 18 - O.Z. 0050/41868 The novel compounds are suitable as fungicides.
The novel fungicidal compounds or the agents containing them can be applied, for example, in the form of directly sprayable solutions, powders, suspensions, including concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusting agents, broadcasting agents or granules, by spraying, atomizing, dusting, broadcasting or pouring.
The application forms depend on the intended uses; they should in any case ensure very fine distribution of the novel active ingredients.
Usually, the plants are sprayed or dusted with the active ingredients or the seeds of the plants are treated with the active ingredients.
The formulations are prepared in a known manner, for example by extending the active ingredient with solvents and/or carriers, if desired with the use of emulsifiers and dispersants; where water is used as a diluent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable assistants for this purpose are essentially solvents such as aromatics (eg. xylene), chlorinated aromatics (eg. chlorobenzenes), paraffins (eg. mineral oil fractions), alcohols (eg.
methanol or butanol), ketones (eg. cyclohexanone), amines (eg. ethanolamine or dimethylformamide) and water;
carriers, such as ground natural minerals (eg. kaolins, aluminas, talc or chalk) and ground synthetic minerals (eg. finely divided silica or silicate~); emulsifiers, such as nonionic and anionic emulsifiers (èg. polyoxy-ethylene fatty alcohol ethers, alkylsulfonates andarylsulfonates), and dispersants, such as ligninsulfite waste liquors and methylcellulose.
Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkylsulfonates, alkylarylsulfonates, ~04~3~7~
~ - 19 - O.Z. 0050~41868 alkylsulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octa-decanols, and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of naph-thalenesulfonic acids with phenol and formaldehyde, poly-oxyethylene octylphenol ethers, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxy-ethylene alkyl ethers or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, ligninsulfite waste liquors or methylcellulose.
lS Powders, broadcasting agents and dusting agents can be prepared by mixing or milling the active sub-stances together with a solid carrier.
Granules, for example coated, impregnated and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths, such as silica gel, silicas, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, kieselguhr, calcium sulfate, magnesium sulfate, magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate or ureas, and vegetable products, such as grain flour, bark meal, wood meal or nutshell meal, cellulosic powders and other solid carrier~.
Examples of such formulations are:
I. A solution of 90 parts by weight of compound No.
1 and 10 part~ by weight of N-methyl-~-pyrrolidone, which solution i~ suitable for use in the form of very small drops;
II. A mixture of 20 parts by weight of compound No.
1, 80 parts by weight of xylene, 10 parts by weight of the adduct of from 8 to 10 mol of ethylene oxide with 1 mol of oleic acid 21[)4~37~
- 20 - O.Z. 0050/41868 N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil; by finely distributing the solution in water, a dispersion is obtained.
III. An aqueous dispersion of 20 parts by weight of compound No. 1, 40 parts hy weight of cyclohexan-one, 30 part~ by weight of isobutanol and 20 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil;
IV. An aqueous dispersion of 20 par~s by weight of compound No. 1, 25 parts by weight of cyclohexan-ol, 65 parts by weight of a mineral oil fraction boiling within a range from 210 to 280C and 10 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil;
V. A mixture milled in a hammer mill and consisting of 80 parts by weight of compound No. 1, 3 parts by weight of the sodium salt of diisobutyl-naphthalene-~-sulfonic acid, 10 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor and 7 parts by weight of silica gel powder; by finely dis-tributing the mixture in water, a spray liquor is obtained;
VI. - A thorough mixture of 3 parts by weight of compound No. 1 and 97 parts by weight of finely divided kaolin; this dusting agent cantains 3~ by weight of active ingredient;
VII. A thorough mixture of 30 parts by weight of compound No. 1, 92 parts by weight of silica gel powder and 8 parts by weight of liquid paraffin, which has been sprayed onto the surface af the silica gel; this formulation gives the active ingredient good adhesion;
VIII. A stab1e aqueous dispersion of 40 parts by weight 2~ 7 ~
- 21 - o.~. 0050/41868 of compound No. 1, 10 parts by weight of the sodium salt of a phenolsulfonic acid/urea/formal-dehyde condensate, 2 part~ by weight of silica gel and 48 parts by weight of water, which can be further diluted;
IX. A stable oily dispersion of 20 parts by weight of compound No. 1, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenol-sulfonic acid/urea~formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil.
The novel compounds have excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class consisting of the Ascomyce~es and Basidiomycetes. Some of them have sy~temic activity and can be used as foliage and soil fungicides.
They are particularly important for controlling a large number of fungi on variou~ crops, such as wheat, rye, barley, oats, ricet corn, grass, cotton, soybean, coffee, ~ugar cane, grapevines, fruit trees, ornamentals and vegetable plants, such as cucumbers, beans and cucurbitaceae, and on the seeds of these plant~.
The compounds are u~ed by treating the fungi or the seeds, plants or materials to be protected from fungal attack or the soil with a fungicidal amount of the active ingredients.
Application is effected before or after infection of the materials, plants or seeds by the fungi.
The compounds I are especially suitable for controlling the following plant diseasess Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbitaceae, Podosphaera leucotricha on apples, Uncinula necator on grapevines, Puccinia species on cereals, ;~04~37~
- 22 - O.Z. 0050/41868 Rhizoctonia species on cotton and lawns, Ustilago species on cereals and sugar cane, Venturia inae~ualis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries and grape-vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Fusarium and Verticillium species on various plants, Plasmopara viticola on grapevines and Alternaria species on vegetables and fruit.
The novel compounds can also be used in material protection (wood preservation), for example against Paecilomyces variotii.
The fungicides contain in general from 0.1 to 95, preferably from 0.5 to 90, % by weight of active ingredient.
The application rates are from 0.02 to 3 kg of active ingredient per ha, depending on the type of effect desired.
In the treatment of seed, in general from 0.001 to 50 g, preferably from 0.01 to 10 g, of active in-gredient are required per kilogram of seed.
- In the application form as fungicide~, the novel agents can also be present together with other active ingredients, for example with herbicides, insecticides, growth regulators or fungicides or with fertilizers.
Mixing with fungicides results in many cases in an extension of the fungicidal action spectrum.
phenyl, 3-fluorophenyl, 4-fluoxophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,3-dichlorophenyl,2,4-di-chlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-5 chloro-4-fluorophenyl or 2-chloro-6-fluorophenyl;
phenyl which is monosubstituted by nitro, pheno~y, amino or Cl-C4-alkyl, such a~ 3-nitrophenyl, 4~nitroph~nyl, 3-phenoxyphenyl, 4-phenoxyphenyl, 3-aminophenyl, 4-amino-phenyl, 4-ethylphenyl, 4-isopropylphenyl or 4-tert-butylphenyl;
phenyl which is substituted by two or three different radicals from among tho~e stated above, such as 2-chloro-.
6-methylphenyl;
phenyl which i~ mono~ubstituted or disub~tituted by Cl-C4-alkoxy, such a~ 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 4-tert-butoxyphenyl, 2,4-dimethoxyphenyl or 3,4-dLmethoxyphenyl;
p-biphenyl, l-naphthyl or 2-naphthyl;
hetaryl having 5 or 6 ring atoms, 6-membered rings having not more than three nitrogen atom~, such as pyridyl, 2-pyridyl, 2-pyridyl or 4-pyridyl, being particular ex-ample~, aY well as 5-membered rings having, preferably, one or two of the hetero atoms O, S and N, in particular furyl, 2-furyl, ~hienyl, 2-thienyl, 3-thienyl, oxazolyl, 4-oxazolyl, thiazolyl, 4 thiazolyll isoxazolyl, 4-isoxaz olyl, 5-isoxazolyl, Lmidazolyl or 5-Lmidazolyl;
C3-C0-cycloalkyl, preferably cyclopentyl or cyclohexyl, or C5-C~-cycloalkenyl, preferably 3-cyclohexenyl.
D i3 Cl-Ca-alkyl r preferably Cl-C4-alkyl, in particular methyl, ethyl, n-propyl, i~opropyl, n-butyl, sec-butyl or tert-butyl; among the Cl-C0-alkyl groups of more than 4 carbon atom~, n-pentyl and neopentyl are preferred.
Acid addition ~alts are, for example, the hydro-chloride3, bromides, ~ulfates, nitrate~, phosphate~, oxalate~ and dodecylbenzene~ulfonate~. The activity of - Z~14~397~
- _ 3 _ o.z. 0050/41868 the salts is due to the cation, so that the anion is in general unimportant. The novel active ingredient salts are prepared by reacting the azolylmethyloxiranes (I~
with suitable acids.
Metal complexes of the active ingredients I or of their salts can be formed with copper, zinc, tin, man-ganese, iron, cobalt or nickel by reacting the azolyl-methyloxiranes with corresponding metal salts.
The compound~ of the formula I can be prepared, for example, if a) a compound of the formula II
L ~ 3 II
where A, B and D have the abovementioned meanings and L i3 a nucleophilic leaving group, is reacted with a compound of the formula III
~e-N ~ III
~5N
where Me is hydrogen or a metal atom and X has the stated meanings, or b) a compound of the formula IV
~x~
N~_,N ~ IV
A
where A, B, D and X have the abovementioned mean-ings, i8 converted into an epoxide.
Where ~e is hydrogen, reaction a) is carrLed out in the presence or absence of a ~olvent or diluent and with or without the addition of an inorganic or organic base or of a reaction accelerator at from lO to 120C.
The preferred ~olvents and diluents include ketones, such as acetone, methyl ethyl ketone or cyclohexanone, nit-riles, such as acetonitrile or propionitrile, alcohol~, such as methanol, ethanol, isopropanol, n-butanol or 21~4~39'7~
- 4 - O.Z. 0050/41868 glycol, eqters, such as ethyl acetate, methyl acetate or butyl acetate, ethers, such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane or diisopropyl ether, amides, such as dimethylformamide, dimethylacetamide or 5N-methylpyrrolidone, and dimethyl sulfoxide, sulfolane or corresponding mixtures.
Suitable bases which may also be used a~ acid acceptors in the reaction are, for example, alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide 10or potassium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, ~odium bicarbonate or potassium bicarbonate, pyridine or 4-dimethylamino-pyridine. However, other conventional bases may al80 be used.
15Preferred reaction accelerators are metal hal-ides, such as sodium iodide or potassium iodide, quater-nary ammonium salts, such as tetrabutylammonium chloride, bromide, iodide or bisulfate, benzyltriethylammonium chloride or bromide, or crown ethers, such as 12-crown-204, 15-crown-5, 18-crown-6, dibenzo-18-crown-6 or dicyclo-hexano-18-crown-6.
The reaction i8 carried out in general at from 20 to 150C under atmospheric or superatmospheric pressure, continuou~ly or batchwise.
25If ~e i8 a metal atom, reaction a) is carried out in the presence or absence of a solvent or diluent and with or without the addition of a strong inorganic or organic base at from -10 to 120C. The preferred solvents and diluents include amides, such as dimethylformamide, 30diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide and sulfoxides, such as dimethyl sulfoxide or sulfolane.
Suitsble bases which may also be used as acid acceptors in the reaction are, for example, alkali metal 35hydrides, such as lithium hydride, sod~um hydride or potassium hydride, alkali metal amides, such as sodium amide or potassium amide, and sodium tert-butoxide or 2al4~97~
` - 5 - O.Z. 0050/41868 potassium tert-butoxide.
Suitable diluents for reaction b) are polar organic solvents, such as nitriles, eg. acetonitrile, sulfoxide~, eg. dimethyl sulfoxide, formamides, eg.
dimethylformamide, ketones, eg. acetone, ethers, eg.
diethyl ether or tetrahydrofuran, and in particular chlorohydrocarbons, eg. methylene chloride or chloroform.
The reaction is carried out in general at from 0 to 100C, preferably from 20 to 80C. In the presence of a ~olvent, it is expediently carried out at the boiling point of the particular solvent.
The starting compounds II are obtained by epoxi-dation of the corresponding olefins V:
L_~B V
A
; 15 (cf. G. Dittus in ~ouben-Weyl-~ller, Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, 1965, Vol. VI, 3, page 385 et ~eq.).
The compounds V are prepared by halogenating or oxidizing olefins of the formula VI
~ B VI
A
in the allyl position by known methods.
Suitable halogenating reagents are N-chloro- and N-bromosuccinimide in halohydrocarbons, ~uch as carbon tetrachloride, trichloroQthane or methylene chloride, at 25from 20 to 100C. Peresters, ~uch as tert-butyl per-benzoate or tert-butyl peracetate, in the presence of a heavy metal ~alt, eg. copper(I) chloride or copper(I) bromide, are used for allyl oxidation. The reaction i~
carried out in an inert solvent at from 10 to 100C.
30The resulting allyl halides or alcohols V are then converted into the corresponding epoxides II (L =
halogen or OH). For this purpose, the olefin~ V are oxidized with a peroxycarboxylic acid, ~uch a~ perbenzoic 204~3~7~
- 6 - O.Z. 0050/4186a acid, 3-chloroperbenzoic acid, 4-nitroperbenzoic acid, monoperphthalic acid, peracetic acid, perpropionic acid, permaleic acid, monopersuccinic acid, perpelargonic acid or trifluoroperacetic acid, in an inert solvent, prefer-ably chlorohydrocarbons, eg. methylene chloride, chloro-form, carbon tetrachloride or dichloroethane, or, if required, also in acetic acid, ethyl acetate, acetone or dimethylformamide, in the presence or absence of a buffer, such a~ sodium acetate, sodium carbonate or disodium hydrogen phosphate. The reaction is carried out at from 10 to loor and, if required, is catalyzed, for example with iodine, sodium tungstate or light. Also suitable for the oxidation are alkaline solution~ of hydrogen peroxide (about 30% strength) in methanol, ethanol, acetone or acetonitrile at from 25 to 30C, and alkyl hydroperoxides, eg. tert-butyl hydroperoxide, with the addition of a cataly~t, eg. sodium tungstate, per-tungstic acid, molybdenum hexacarbonyl or vanadyl acetyl-acetonate. Some of the ~tated oxidizing agents can be produced in situ.
While the resulting epoxy halides II (L = halo-gen) can be immediately reacted by proces3 a), the corresponding epoxy alcohols II (L = OH) are converted into reactive esters, which are then reacted with a compound III by procesa a).
The reactive esters which are reacted with III
are prepared by generally known methods (Houben-Weyl-M~ller, Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, 1955, Volume 9, pages 388, 663 and 671). Examples of such esters are methane~ulfonates, trifluoromethanesulfonates, 2,2,2-trifluoroethane-sulfonates, nonafluorobutaneaulfonate~, 4-methylbenzene-~ulfonates, 4-bromobenzenesulfonstes, 4-nitrobenzene-sulfonatea and bensenesulfonates.
The compounds IV are converted, for example with an oxidizing agent, into their epoxidea.
The compoundJ V can be prepared by generally ~.
2~4~
- 7 - O.Z. 0050/41868 known method~ of olefin synthesi~ (Houben-Weyl-Muller, Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, 1972, Vol. V, lb).
The Examples which follow illustrate the prepara-tion of the active ingredients.
I. Preparation of the starting material~
Method A
1-(4-Fluorophenyl)-2-(3-trifluoromethylphenyl)-buten-2-one F
27.8 g (0.224 mol) of 4-fluorobenzaldehyde and 2 ml of piperidine are added to a solution of S0 g (0.247 mol) of 3-trifluoromethylphenylacetone in 250 ml of toluene, and the mixture i~ heated with removal of the water formed in the reaction. Thereafter, the reaction ~olution i~ wa~hed once with 0.5 M hydrochloric acid and three times with water, dried over sodium sulfate and evaporated down under reduced pres~ure. The subsequent di~tillation of the remaining residue give~ 62 g (90%) of product boiling at 102-C under 0.1 mbar.
~ethod B
ci~-2-(1-Hydroxyethyl)-2-(3-trifluoromethylphenyl)-3-(4-fluorophenyl)-oxirane H~F
¢~
62 g (0.2 mol) of 1-(4-fluorophenyl)-2-(3-tri-fluoromethylphenyl)-buten-2-one are dis~olved in 300 ml of methanol, and 4 ml of concentrated ~odium hydroxide ~olution are added. The reaction ~olution i4 ~tirred at . - : . ,...... . , .. , , ~
Z1~4~39~
- 8 - O.Z. 0050/41868 0C while 1~.4 g of hydrogen peroxide are slowly added dropwise, the internal temperature not exceeding 30C.
After the end of the addition, stirring is continued for six hours at room temperature, after which 2.5 g of S sodium borohydride, dissolved in a little 10% strength sodium hydroxide solution, are added. After the reaction mixture has been stirred for 18 hours at room tempera-ture, 100 ml of water are added to the solution and the resulting emulsion is extracted by shaking with methylene chloride. The isolated organic phase i~ then dried over sodium sulfate and evaporated down. 60 g (92%) of product are obtained as a 1 : 1 diastereomer mixture.
Method C
cis-2~ Methylsulfonyloxyethyl)-2-(3-trifluoromethyl-phenyl)-3-(4-fluorophenyl)-oxirane H 3C--S~F
0~
17.6 g of methanesulfonyl chloride are added to a solution of 40 g (0.123 mol) of cis-2-(1-hydroxyethyl)-2-(3-trifluoromethylphenyl)-3-(4-fluorophenyl)-oxirane in 200 ml of methylene chloride and 21.5 ml of triethylamine at room temperature. After 24 hours, the reaction mixture is washed with aqueous sodium bicarbonate solu-tion and water, dried over sodium sulfate and evaporated down under reduced pressure. The residue give~ 45 g (91%) of product as a 1 : 1 diastereomer mixture. 5 II. Preparation of the end product~
cis-2-(1,2,4-Triazol-l-ylethyl)-2-(3-trifluoromethyl-phenyl)-3-(4-fluorophenyl)-oxirane ~N~ ~_F
Ç~
`` 204t397~
- g - O.Z. 0050/41868 15.6 g of potassium carbonate are added to a solution of 7.73 g (0.11 mol) of 1,2,4-triazole in 100 ml of N,N-dimethylformamide and the mixture is heated at 50C for 30 minute~. After the reaction mixture has been cooled to room temperature, 22.8 g (0.056 mol) of cis-2-(l-methylsulfonyloxyethyl)-2-(3-trifluoromethylphenyl)-3-(4-fluorophenyl)-oxirane, dissolved in 50 ml of N,N-dimethylformamide, are slowly added dropwise to the solution and stirring is carried out for 13 hours at room temperature. Thereafter, 100 ml of water are added and the mixture is extracted several times with methyl tert-butyl ether; the organic pha~e iq wa~hed with water, dried over sodium sulfate and evaporated down under reduced pre~sure.
Yield: 7.7 g (36%) (compound No. 1) The compound~:shown in the Table can be prepared similarly to Example 1.
9'7~
- 10 - O. Z . 0050/41868 TABLE
NV ~3 Example A B D X mp . / lH-NMR
[ ppm 1 1 3-CF3-C6H4 4-F-C6H4 CH3 N 1.68 (d), 3.72 (s) (2S)4 (g)~ 8-04, 3 2 3-CF3-C6H4 4-F-C6H4 CH3 CH 1 62 Id~, 4.39 ~s), 3-CF3-C6H4 4-F-C6H4 C4Hg N
63--CF3--C6H4 4--F--C6H4 C5Hl 1 N
8 3-cF3-c6H4 C6H5 CH3 N
9 3-CF3-C6H4 2-F-c6H4 CH3 N
Il 3-CF3-C6H4 3-F-C6H4 CH3 N
143-CF3-C6H4 2-Cl-C6H4 C3H7 N
153-CF3-C6H4 2-CI-C6H4 iso-c3H7 N
203-CF3-C6H4 2,4-cl2-c6H3 C~3 N
213-CF3-C6H4 2,4-C12-C6H3 C2H5 N
233-CF3-C6H4 4-cH3-c6H4 CH3 N
243-CF3-C6H4 2,4-(cH3)2-c6H3 CH3 N
253--CF3--C6H4 2-ocH3-c6H4 CH3 N
273-CF3-C6H4 2-cF3-c6H4 CH3 N
Z~ 7~
- 11 - O.Z. 0050/41868 Example A B D X mp. /lH-NMR
. . ~ ppm 1 3-CF.-C6H4 l-Naphthyl CH3 N
31 3-CF3-C6H4 2-Naphthyl CH3 N
32 3-CF3-C6H4 4-3iphenyl CH3 N
33 C6Hs C6H5 CH3 N
C6H5 2-CI-C6H4 C2H5 N 3 92' 1.06 (2 t~, 8 14 ~2~')7 ~9' 37 C6Hs 3-CI-C6H4 CH3 N
38 C6H5 4-CI~C6H4 CH3 N
39 C6Hs 4-CI-C6H4 C2H5 N
4I C6H5 2,4-C12-C6H3 CH3 N
42 C6H5 2,4-ct2-C6H3 C2H5 N
43 C6Hs 2-F-C6H4 CH3 N
C6H5 3-F-c6H4 CH3 N
47 C6H5 4-F-c6H4 C2H5 N
48 C6H5 4-F-c6H4 C3H7 N
49 C6H5 2-Br-C6H4 CH3 N
51 ~ C6H5 4-CH3-C6H4 CH3 N
58 C6H5 I-Naphthyl CH3 N
59 C6H5 2-Naphthyl CH3 N
C6H5 4-Biphenyl CH3 N
O. Z . ()050/41868 Example A 13 D X mp. /lH-NMR
_ ___ [pl~m]
63 C~H5 Cyclopentyl CH3 N
54 C6H5 Cyclohexyl CH3 N
CDH5 3-Cyclohexenyl C~13 N
C6H5 2-Furyl CH3 N
57 C6H5 2-Thienyl CH3 N
63 C6H5 3-Thienyl CH3 N
69 C6H5 2-Pyridyl CH3 N
C6H5 3-Pyridyl CH3 N
71 2-cl-c6H4 C5H5 CH3 N
72 2-Cl-C6H4 2-CI-C6H4 CH3 N
73 2-cl-C5H4 3-CI-C6H4 CH3 N
74 2-Cl-C6H4 4-CI-CsH4 CH3 N
2-Cl-C6H4 2,4-cl2-C6H3 CH3 N
76 2-cl-c6H4 2-F-C6H4 CH3 N
77 2-Cl-C6H4 4-F-C6H4 CH3 N
78 2-Cl-C6H4 2-Br-C6H4 CH3 N
79 2-Cl-C6H4 2-CH3-C6H4 CH3 N
84 2-CI-C6H4 2-Furyl CH3 N
2-CI-C6H4 2-Thienyl CH3 N
86 2-Cl-C6H4 3-Pyridyl CH3 N
3-cl-c6H4 2,4-C12-C6H3 CH3 N
92 3-CI-C6H4 4-F-C6H4 c~l3 N
93 3-cl-c6H4 2-CF3-C6H4 CH3 N
94 3-cl-c6H4 4-CF3-C6H4 CH3 N
4-cl-c6H4 C6~l5 CH3 N
96 4-CI-C5H4 2-cl-c6H4 CH3 N
97 4-cl-c6H4 2-CI-C6H4 C2H5 N
2~4~9~'1 - 13 - O. Z . 0050/41868 Example A B D X mp. /lH-NMR
[ ppm 913 4--Cl--c6H4 2--cl--C6H4 C3H7 N
99 4--CI--C6H4 2--CI--C~H4 iso--C3H7 N
100 4--Cl--C6H4 2--CI--C6H4 C4Hg N
103 4--Cl--C6H4 4--Cl-C6H4 C2H5 N
105 4-CI-C6H4 2,4-C12-C6H3 CH3 N
106 4-CI-C6H4 2,4-C12-C5H3 C2H5 N
107 4-CI-C6H4 2-F-c6H4 CH3 N
109 4-CI-C6H4 2-6r-C6H4 CH3 N
110 4-Cl-C6H4 2-CH3-C6H4 CH3 N
117 4-CI-C6H4 l-Naphthyl CH3 N
118 4-CI-C6H4 2-Naphthyl CH3 N
119 4-CI-C6H4 4-B:iphenyl CH3 N
l20 4-CI-C6H4 CH3 CH3 N
122 4-GI-C6H4 Cyclopentyl CH3 N
123 4-CI-C6H4 Cyclohexyl CH3 N
124 4-CI-C6H4 2-Furyl CH3 N
125 4-CI-C6H4 2-Thienyl CH3 N
126 4-CI-C6H4 3-Thienyl CH3 N
127 4-CI-C6H4 2-Pyridyl CH3 N
128 4-CI-C6H4 3-~yridyl CH3 N
2~4~3~7~
- 14 - O. Z . 0050/41868 Example A B D X mp. /lH-NMR
- rppm]
132 2-F-C5H4 2, 4-C1 2 - C6H3 CH3 N
136 2-F-C6H4 4_CF3_C6H4 CH3 N
137 3_F_C6H4 2-CI-C6H4 CH3 N
138 3_F_C6H4 4_CI_C6H4 CH3 N
139 3-F-C6H4 4~F~C6H4 CH3 N
140 4_F_C6H4 C6H5 CH3 N
141 4_F_C6H4 2-C1-C6H4 CH3 N
142 4_F_C6H4 2-CI-C6H4 C2H5 N
143 4_F_C6H4 2-CI-C6H4 C3H7 N
144 4_F_C6H4 2-CI-C6H4 ;SO-C3H7 N
145 4_F_C6H4 2-CI-C6H4 C4H9 N
147 4_F_C6H4 3_CI_C6H4 CH3 N
148 4_F_C6H4 4_CI_C6H4 CH3 N
150 4_F_C6H4 4 CI_C6H4 C3H7 N
ISI 4_F_C6H4 4_CI_C6H4 C4H9 N
152 4_F_C6H4 2,4-CI2-C6H3 CH3 N
153 4_F_C6H4 2,4-CI2-C6H3 CH3 N
154 4_F_C6H4 2-F-C6H4 CH3 N ~.
155 4-F-C6H4 4~F~C6H4 CH3 N
156 4-F-C6H4 2-Cr-C6H4 CH3 N
158 4_F_C6H4 4_CH3_C6H4 CH3 N
159 4-F-C6H4 2,4-(CH3 ) 2-C6H 3 CH 3 N
160 4_F_C6H4 2-OCH3-C6H4 CH3 N
161 4--F--C6H4 4~CH3--C6H4 CH3 N
163 4_F_C6H4 4_CF3_C6H4 CH3 N
164 4_F_C6H4 3_NO2_C6H4 CH3 N
165 4_F_C6H4 3_NH2_C6H4 CH3 N
166 4-F-C6H4 I-Naphthyl CH3 N
2C~4~39~
- 15 - O. Z . 0050/41868 Example A B D X mp . ~lH-NMR
[ ppm l 167 4-F-C6H4 2-Naphthyl CH3 N
168 4-F-C6H4 4-Biphenyl CH3 N
171 4-F-C6H4 Cyclopentyl CH3 N
172 4-F-C6H4 Cyclohe~yl CH3 N
173 4-F-C6H4 2-Furyl CH3 N
174 4-F-C6H4 2-Thienyl CH3 N
175 4-F-c6H4 3-Thienyl CH3 N
176 4-F-C6H4 2-Pyridyl CH3 N
177 4-F-C6H4 3-Pyridyl CH3 N
178 4-F-C6H4 4-Pyridyl CH3 N
179 2~4-cl2-c6H3 C6H5CH3 N
180 2,4-C12-C6H3 2-CI-C6H4 CH 3 N
181 2~4-cl2-c6H3 3-CI-C6H4 CH3 N
182 2,4-C12-C6H3 4-CI-C6H4 CH3 N
183 2,4-C12-C6H3 2,4-C12-C6H4 CH3 N
184 2,4-C12-C6H3 2-F-C6H4 CH3 N
185 2,4-C12-C6H3 4-F-C6H4 CH3 N
186 2,4-C12-C6H3 2-CF3-C6H4 CH3 N
187 2,4-C12-C6H3 4-CF3-C6H4 CH3 N
188 2,4-C12-C6H3 2-CH3-C6H4 CH3 N
189 2,4-C12-c6H3 4-cH3-c6H4 CH3 N
190 4-Br-C6H4 C6H5 CH3 N
191 4-Br-C6H4 2-CI-C6H4 CH3 N
192 4-Br-C6H4 4-cl-c6H4 CH3 N
193 4-Br-C6H4 2,4-C1 rC6H3 CH3 N
194 4-Br-C6H4 4-F-c6H4 CH3 N
195 4-Br-C6H4 2-CF3-C6H4 CH3 N
2~39~
- 16 - O.Z. 0050/41868 Example A B D X mp. /lH-N~tR
. .. _ r ~pm 1 202 4-CH3-C6H4 2-cl-c6H4 CH3 N
203 4-CH3-C6H4 4-Cl-C6H4 CH3 N
204 4-CH3-C5H4 2,4-CI7-C5H3 CH3 N
215 4-oCH3-C6H4 C6H5CH3 N
216 4-OCH3-C6H4 2-CI-c6H4 CH3 N 1 72, 1 /9 ~2 d), 217 4-OCH3-C6H4 4-Cl-C6H4 CH3 N 8.12 (45) 221 2-Cf3-C6H4 2-CI-C6H4 CH3 N
222 2-CF3-C6H4 4-Cl-C6H4 CH3 N
223 2-CF3-C6H4 2-f-C6H4 CH3 N
226 4-cF3-c6H4 2-CI-C6H4 CH3 N
227 4-CF3-C6H4 4-Cl-C6H4 CH3 N
228 4-CF3-C6H4 2-f-C6H4 CH3 N
230 1-Naphthyl 2-CI-C6H4 CH3 N
231 1-Naphthyl 4-CI-C6H4 CH3 N
232 I-Naphthyl 4-F-C6H4 CH3 N
233 2-Naphthyl 2-cl-C6H4 CH3 N
234 2-Naphthyl 4-Cl-C6H4 CH3 N
235 2-Naphthyl 4-F-C6H4 CH3 N
236 4-3iphenyl 2-CI-C6H4 CH3 N
21~4~7'~
- - 17 - O. Z . 0050/41868 Example A B D X mp. /lH-NMR
__ [ppm~
237 4-Biphenyl 4-CI-C6H4 CH3 N
242 CH3 4-F-c6H4 CH3 N
243 CH3 2,4-Clz-C6H3 CH3 N
244 Cyclohexyl C6H5 CH3 N
245 Cyclohexyl 2-CI-C6H4 CH3 N
246 Cyclohexyl 4-CI-C6H4 CH3 N
247 Cyclohexyl 2,4-C12-C6H3 CH3 N
248 Cyclohexyl 2-F-C6H4 CH3 N
249 Cyclohexyl 4-F-C6H4 CH3 N
250 2-Furyl C6H5CH3 N
251 2-Furyl 2-CI-C6H4 CH3 N
: 252 2-Furyl 2,4-C1 rC6H3 CH3 N
253 2-Furyl 4-CI-C6H4 CH3 N
254 2-Furyl 2-F-C6H4 CH3 N
255 2-Furyl 4-F-c6H4 CH3 N
256 2-Thienyl C6Hs CH3 N
257 2-Thienyl 2-CI-C6H4 CH3 N
258 2-Thienyl 4-CI-C6H4 CH3 N
259 2-Thienyl 2,4-C12-C6H3 CH3 N :
260 2-Thienyl 2-F-C6H4 CH3 N
261 2-Thienyl 4-F-c6H4 CH3 N
262 3-Thienyl C6H5CH3 N
263 3-Thienyl 2-CI-C6H4 CH3 N
264 3-Thienyl 4-cl-c6H4 CH3 N
265 3-Thienyl 2,4-C12-C6H3 CH3 N
266 3-Thienyl 4-F-c6H4 CH3 N
267 4-Pyridyl C6H5CH3 N
268 4-Pyridyl 2-CI-C6H4 CH3 N
269 4-Pyridyl 4-CI-C6H4 CH3 N
270 4-Pyridyl 2,4-C12-C6H3 CH3 N
271 4-Pyridyl 4-F-c6H4 CH3 N
20~B97fl - 18 - O.Z. 0050/41868 The novel compounds are suitable as fungicides.
The novel fungicidal compounds or the agents containing them can be applied, for example, in the form of directly sprayable solutions, powders, suspensions, including concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusting agents, broadcasting agents or granules, by spraying, atomizing, dusting, broadcasting or pouring.
The application forms depend on the intended uses; they should in any case ensure very fine distribution of the novel active ingredients.
Usually, the plants are sprayed or dusted with the active ingredients or the seeds of the plants are treated with the active ingredients.
The formulations are prepared in a known manner, for example by extending the active ingredient with solvents and/or carriers, if desired with the use of emulsifiers and dispersants; where water is used as a diluent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable assistants for this purpose are essentially solvents such as aromatics (eg. xylene), chlorinated aromatics (eg. chlorobenzenes), paraffins (eg. mineral oil fractions), alcohols (eg.
methanol or butanol), ketones (eg. cyclohexanone), amines (eg. ethanolamine or dimethylformamide) and water;
carriers, such as ground natural minerals (eg. kaolins, aluminas, talc or chalk) and ground synthetic minerals (eg. finely divided silica or silicate~); emulsifiers, such as nonionic and anionic emulsifiers (èg. polyoxy-ethylene fatty alcohol ethers, alkylsulfonates andarylsulfonates), and dispersants, such as ligninsulfite waste liquors and methylcellulose.
Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkylsulfonates, alkylarylsulfonates, ~04~3~7~
~ - 19 - O.Z. 0050~41868 alkylsulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octa-decanols, and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of naph-thalenesulfonic acids with phenol and formaldehyde, poly-oxyethylene octylphenol ethers, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxy-ethylene alkyl ethers or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, ligninsulfite waste liquors or methylcellulose.
lS Powders, broadcasting agents and dusting agents can be prepared by mixing or milling the active sub-stances together with a solid carrier.
Granules, for example coated, impregnated and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths, such as silica gel, silicas, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, kieselguhr, calcium sulfate, magnesium sulfate, magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate or ureas, and vegetable products, such as grain flour, bark meal, wood meal or nutshell meal, cellulosic powders and other solid carrier~.
Examples of such formulations are:
I. A solution of 90 parts by weight of compound No.
1 and 10 part~ by weight of N-methyl-~-pyrrolidone, which solution i~ suitable for use in the form of very small drops;
II. A mixture of 20 parts by weight of compound No.
1, 80 parts by weight of xylene, 10 parts by weight of the adduct of from 8 to 10 mol of ethylene oxide with 1 mol of oleic acid 21[)4~37~
- 20 - O.Z. 0050/41868 N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil; by finely distributing the solution in water, a dispersion is obtained.
III. An aqueous dispersion of 20 parts by weight of compound No. 1, 40 parts hy weight of cyclohexan-one, 30 part~ by weight of isobutanol and 20 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil;
IV. An aqueous dispersion of 20 par~s by weight of compound No. 1, 25 parts by weight of cyclohexan-ol, 65 parts by weight of a mineral oil fraction boiling within a range from 210 to 280C and 10 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil;
V. A mixture milled in a hammer mill and consisting of 80 parts by weight of compound No. 1, 3 parts by weight of the sodium salt of diisobutyl-naphthalene-~-sulfonic acid, 10 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor and 7 parts by weight of silica gel powder; by finely dis-tributing the mixture in water, a spray liquor is obtained;
VI. - A thorough mixture of 3 parts by weight of compound No. 1 and 97 parts by weight of finely divided kaolin; this dusting agent cantains 3~ by weight of active ingredient;
VII. A thorough mixture of 30 parts by weight of compound No. 1, 92 parts by weight of silica gel powder and 8 parts by weight of liquid paraffin, which has been sprayed onto the surface af the silica gel; this formulation gives the active ingredient good adhesion;
VIII. A stab1e aqueous dispersion of 40 parts by weight 2~ 7 ~
- 21 - o.~. 0050/41868 of compound No. 1, 10 parts by weight of the sodium salt of a phenolsulfonic acid/urea/formal-dehyde condensate, 2 part~ by weight of silica gel and 48 parts by weight of water, which can be further diluted;
IX. A stable oily dispersion of 20 parts by weight of compound No. 1, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenol-sulfonic acid/urea~formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil.
The novel compounds have excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class consisting of the Ascomyce~es and Basidiomycetes. Some of them have sy~temic activity and can be used as foliage and soil fungicides.
They are particularly important for controlling a large number of fungi on variou~ crops, such as wheat, rye, barley, oats, ricet corn, grass, cotton, soybean, coffee, ~ugar cane, grapevines, fruit trees, ornamentals and vegetable plants, such as cucumbers, beans and cucurbitaceae, and on the seeds of these plant~.
The compounds are u~ed by treating the fungi or the seeds, plants or materials to be protected from fungal attack or the soil with a fungicidal amount of the active ingredients.
Application is effected before or after infection of the materials, plants or seeds by the fungi.
The compounds I are especially suitable for controlling the following plant diseasess Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbitaceae, Podosphaera leucotricha on apples, Uncinula necator on grapevines, Puccinia species on cereals, ;~04~37~
- 22 - O.Z. 0050/41868 Rhizoctonia species on cotton and lawns, Ustilago species on cereals and sugar cane, Venturia inae~ualis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries and grape-vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Fusarium and Verticillium species on various plants, Plasmopara viticola on grapevines and Alternaria species on vegetables and fruit.
The novel compounds can also be used in material protection (wood preservation), for example against Paecilomyces variotii.
The fungicides contain in general from 0.1 to 95, preferably from 0.5 to 90, % by weight of active ingredient.
The application rates are from 0.02 to 3 kg of active ingredient per ha, depending on the type of effect desired.
In the treatment of seed, in general from 0.001 to 50 g, preferably from 0.01 to 10 g, of active in-gredient are required per kilogram of seed.
- In the application form as fungicide~, the novel agents can also be present together with other active ingredients, for example with herbicides, insecticides, growth regulators or fungicides or with fertilizers.
Mixing with fungicides results in many cases in an extension of the fungicidal action spectrum.
Claims (5)
1. An azolylmethyloxirane of the formula I
I
where A and B axe each C1-C8-alkyl, C3-C8-cycloalkyl, C5-C8-cycloalkenyl, biphenyl, naphthyl, hetaryl or phenyl, where each of these radicals may be monosubstituted to trisubstituted by halogen, nitro, phenoxy, amino, C1-C4 alkyl, C1-C4-alkoxy or C1-C4-haloalkyl, D is C1-C8-alkyl and X is CH or N, and its plant-tolerated acid addition salts and metal complexes.
I
where A and B axe each C1-C8-alkyl, C3-C8-cycloalkyl, C5-C8-cycloalkenyl, biphenyl, naphthyl, hetaryl or phenyl, where each of these radicals may be monosubstituted to trisubstituted by halogen, nitro, phenoxy, amino, C1-C4 alkyl, C1-C4-alkoxy or C1-C4-haloalkyl, D is C1-C8-alkyl and X is CH or N, and its plant-tolerated acid addition salts and metal complexes.
2. An azolylmethyloxirane of the formula I as claimed in claim 1, wherein A and B are each phenyl which is unsubstituted or substituted by one or two sub-stituents selected from the group consisting of fluorine, chlorine, bromine and trifluoromethyl.
3. A fungicide containing a carrier and a fungicidal amount of an azolylmethyloxirane of the formula I
I
where A and B are each C1-C8-alkyl, C3-C8-cycloalkyl, C5-C8-cycloalkenyl, biphenyl, naphthyl, hetaryl or phenyl, where each of these radicals may be monosubstituted to trisubstituted by halogen, nitro, phenoxy, amino, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl, D is C1-C8-alkyl and X is CH or N, or its plant-tolerated acid addition salt and metal complex.
I
where A and B are each C1-C8-alkyl, C3-C8-cycloalkyl, C5-C8-cycloalkenyl, biphenyl, naphthyl, hetaryl or phenyl, where each of these radicals may be monosubstituted to trisubstituted by halogen, nitro, phenoxy, amino, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl, D is C1-C8-alkyl and X is CH or N, or its plant-tolerated acid addition salt and metal complex.
4. A method fox controlling fungi, wherein a fungi-cidal amount of an azolylmethyloxirane of the formula I
I
- 24 - O.Z. 0050/41868 where A and B are each C1-C8-alkyl, C3-C8-cycloalkyl, C5-C8-cycloalkenyl, biphenyl, naphthyl, hetaryl or phenyl, where each of these radicals may be monosubstituted to trisubstituted by halogen, nitro, phenoxy, amino, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl, D is C1-C8-alkyl and X is CH or N, or of its plant-tolerated acid addition salt or metal complex is allowed to act on the fungi or on the mater-ials, surfaces, plants or seeds threatened by fungal attack.
I
- 24 - O.Z. 0050/41868 where A and B are each C1-C8-alkyl, C3-C8-cycloalkyl, C5-C8-cycloalkenyl, biphenyl, naphthyl, hetaryl or phenyl, where each of these radicals may be monosubstituted to trisubstituted by halogen, nitro, phenoxy, amino, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl, D is C1-C8-alkyl and X is CH or N, or of its plant-tolerated acid addition salt or metal complex is allowed to act on the fungi or on the mater-ials, surfaces, plants or seeds threatened by fungal attack.
5. A compound of the formula I as claimed in claim 1, wherein A is 3-trifluoromethylphenyl, B is 4-fluoro-phenyl, D is methyl and X is N.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4028392.5 | 1990-09-07 | ||
| DE4028392A DE4028392A1 (en) | 1990-09-07 | 1990-09-07 | AZOLYL METHYLOXIRANES AND FUNGICIDES CONTAINING THEM |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2048974A1 true CA2048974A1 (en) | 1992-03-08 |
Family
ID=6413784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002048974A Abandoned CA2048974A1 (en) | 1990-09-07 | 1991-08-12 | Azolylmethyloxiranes and fungicides containing them |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0474045B1 (en) |
| JP (1) | JP3164608B2 (en) |
| KR (1) | KR920006351A (en) |
| AT (1) | ATE129243T1 (en) |
| AU (1) | AU637258B2 (en) |
| CA (1) | CA2048974A1 (en) |
| DE (2) | DE4028392A1 (en) |
| DK (1) | DK0474045T3 (en) |
| ES (1) | ES2079008T3 (en) |
| GR (1) | GR3018015T3 (en) |
| HU (1) | HU210748B (en) |
| ZA (1) | ZA917085B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7910614B2 (en) | 2006-07-25 | 2011-03-22 | Basf Se | Azolylmethyloxiranes, use thereof for controlling plant pathogenic fungi, and agents containing the same |
| US7994340B2 (en) | 2006-12-22 | 2011-08-09 | Basf Se | Azolylmethyloxiranes, their use for controlling phytopathogenic fungi, and compositions comprising them |
| US8236788B2 (en) | 2006-07-24 | 2012-08-07 | Basf Se | Azolylmethyloxiranes, use thereof for controlling plant pathogenic fungi, and agents containing the same |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10179891B2 (en) | 2012-07-25 | 2019-01-15 | Basf Se | Use of branched polyesters based on citric acid as additive in washing compositions, detergents or a formulation for water treatment |
| EP2746277A1 (en) * | 2012-12-19 | 2014-06-25 | Basf Se | Fungicidal imidazolyl and triazolyl compounds |
| EP2746275A1 (en) * | 2012-12-19 | 2014-06-25 | Basf Se | New substituted triazoles and imidazoles and their use as fungicides |
| EP2746279A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | Fungicidal imidazolyl and triazolyl compounds |
| EP2746276A1 (en) * | 2012-12-19 | 2014-06-25 | Basf Se | New substituted triazoles and imidazoles and their use as fungicides |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE640204A (en) * | 1962-11-20 | |||
| DE3218130A1 (en) * | 1982-05-14 | 1983-11-17 | Basf Ag, 6700 Ludwigshafen | AZOLYL METHYLOXIRANES, METHOD FOR THE PRODUCTION THEREOF AND FUNGICIDES CONTAINING THEM |
| DE3805376A1 (en) * | 1988-02-20 | 1989-08-31 | Basf Ag | NEW AZOLYL METHYLOXIRANES AND FUNGICIDES CONTAINING THEM |
| DE3807951A1 (en) * | 1988-03-10 | 1989-09-21 | Basf Ag | FUNGICIDAL IMIDAZOLYL METHYLOXIRANE |
| DE3907729A1 (en) * | 1989-03-10 | 1990-09-13 | Basf Ag | TRIFLUORMETHYLPHENYLAZOLYLMETHYLOXIRANE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PLANT PROTECTANT |
| ES2054128T3 (en) * | 1989-03-21 | 1994-08-01 | Basf Ag | AZOLYLMETILOXIRANES HERBICIDES AND PLANTS GROWTH REGULATORS. |
| DE3940492A1 (en) * | 1989-12-07 | 1991-06-13 | Basf Ag | 1-BROM-3-CHLORINE-1,2-DIARYL-2-PROPANOLE, METHOD FOR THE STEREOSELECTIVE PRODUCTION OF ERYTHRO-1-BROMO-3-CHLORINE-1,2-DIARYL-2-PROPANOLE AND THEIR REALIZATION TO AZOLYLMETHYLOXIRANES |
-
1990
- 1990-09-07 DE DE4028392A patent/DE4028392A1/en not_active Withdrawn
-
1991
- 1991-08-12 CA CA002048974A patent/CA2048974A1/en not_active Abandoned
- 1991-08-21 JP JP20926491A patent/JP3164608B2/en not_active Expired - Fee Related
- 1991-08-22 DK DK91114061.4T patent/DK0474045T3/en active
- 1991-08-22 ES ES91114061T patent/ES2079008T3/en not_active Expired - Lifetime
- 1991-08-22 EP EP91114061A patent/EP0474045B1/en not_active Expired - Lifetime
- 1991-08-22 DE DE59106715T patent/DE59106715D1/en not_active Expired - Lifetime
- 1991-08-22 AT AT91114061T patent/ATE129243T1/en not_active IP Right Cessation
- 1991-09-06 HU HU912893A patent/HU210748B/en not_active IP Right Cessation
- 1991-09-06 KR KR1019910015555A patent/KR920006351A/en not_active Application Discontinuation
- 1991-09-06 AU AU83685/91A patent/AU637258B2/en not_active Ceased
- 1991-09-06 ZA ZA917085A patent/ZA917085B/en unknown
-
1995
- 1995-11-08 GR GR950403126T patent/GR3018015T3/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8236788B2 (en) | 2006-07-24 | 2012-08-07 | Basf Se | Azolylmethyloxiranes, use thereof for controlling plant pathogenic fungi, and agents containing the same |
| US7910614B2 (en) | 2006-07-25 | 2011-03-22 | Basf Se | Azolylmethyloxiranes, use thereof for controlling plant pathogenic fungi, and agents containing the same |
| US7994340B2 (en) | 2006-12-22 | 2011-08-09 | Basf Se | Azolylmethyloxiranes, their use for controlling phytopathogenic fungi, and compositions comprising them |
Also Published As
| Publication number | Publication date |
|---|---|
| KR920006351A (en) | 1992-04-27 |
| DK0474045T3 (en) | 1996-02-05 |
| EP0474045B1 (en) | 1995-10-18 |
| JP3164608B2 (en) | 2001-05-08 |
| HUT58466A (en) | 1992-03-30 |
| DE4028392A1 (en) | 1992-03-12 |
| HU912893D0 (en) | 1992-01-28 |
| HU210748B (en) | 1995-07-28 |
| JPH04230680A (en) | 1992-08-19 |
| EP0474045A1 (en) | 1992-03-11 |
| GR3018015T3 (en) | 1996-02-29 |
| AU637258B2 (en) | 1993-05-20 |
| ATE129243T1 (en) | 1995-11-15 |
| AU8368591A (en) | 1992-03-12 |
| ES2079008T3 (en) | 1996-01-01 |
| ZA917085B (en) | 1993-03-08 |
| DE59106715D1 (en) | 1995-11-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |