GB2063260A - alpha -aryl-1 -H-imidazole-1-ethanol Derivatives and their Use as Fungicides - Google Patents
alpha -aryl-1 -H-imidazole-1-ethanol Derivatives and their Use as Fungicides Download PDFInfo
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- GB2063260A GB2063260A GB8036001A GB8036001A GB2063260A GB 2063260 A GB2063260 A GB 2063260A GB 8036001 A GB8036001 A GB 8036001A GB 8036001 A GB8036001 A GB 8036001A GB 2063260 A GB2063260 A GB 2063260A
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- 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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- 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
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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
- 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
-
- 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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
Compounds of the formula: <IMAGE> wherein R<0> is alkyl cycloalkyl or cycloalkylalkyl, said cycloalkyl and cycloalkylalkyl being optionally ring substituted by one or two alkyl groups, and R is hydrogen, halogen, alkyl, alkoxy, alkylthio or nitro, and R' is hydrogen, halogen, alkyl, alkoxy, alkylthio, -CF3 in the 3- position of Ring A, nitro, -CN, -C00R'', an optionally substituted phenyl group of the formula: <IMAGE> or an optionally substituted phenoxy group in the 4-position of Ring A and having the formula <IMAGE> R'' is hydrogen, alkyl or a cation, or R and R' together represent alkylenedioxy of 1 or 2 carbon atoms substituted onto adjacent carbon atoms of the phenyl Ring A, and Y<0> and Y are independently hydrogen, halogen, alkyl or alkoxy, with the proviso that when R<0> is n- butyl: a) at least one of R and R' is other than hydrogen and b) R or R' are not halo, are useful as fungicides.
Description
SPECIFICATION
Improvements in or Relating to Organic Compounds
The present invention relates to -aryl-1 H-imidazole-1-ethanols, more particularly a-alkyl or cycloalkyl-a-phenyl-1 H-imidazole-1 -ethanols, their use as fungicides and agricultural compositions for facilitating such use.
More specifically, the present invention provides compounds of formula I,
wherein RO is alkyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, cycloalkylalkyl in which the cycloalkyl is of 3 to 6 carbon atoms and the alkyl portion of 1 to 3 carbon atoms, said cycloalkyl and cycloalkylalkyl being optionally ring substituted by one or two alkyl groups of 1 to 3 carbon atoms, and
R is hydrogen, halogen having an atomic number of from 9 to 35, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms or nitro, and
R' is hydrogen, halogen having an atomic number of from 9 to 35, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, -CF3 in the 3-position of Ring A, nitro, -CN, -COOR", an optionally substituted phenyl group of the formula:
or an optionally substituted phenoxy group in the 4-position of Ring A and having the formula
R" is hydrogen or alkyl of 1 to 4 carbon atoms or
R and R' together represent alkylenedioxy of 1 or 2 carbon atoms substituted onto adjacent carbon atoms of the phenyl Ring A, and Y and Y are independently hydrogen, halogen having an atomic number of from 9 to 35, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms,
with the proviso that when Ra is n-butyl: a) at least one of R and R' is other than hydrogen and b)
R or R' are not halo.
Halogen atoms having an atomic number of from 9 to 35 are fluoro, chloro and bromo.
The invention also provides processes for the production of compounds of formula I comprising
a) reacting a compound of the formula II:
wherein RO, R and R' are as above defined with a compound of formula Ill
wherein X is an alkali metal in an inert organic solvent, b) obtaining a compound of formula la,
wherein RO and R are as defined above by oxidation of the CH3 group of a compound of formula
Ib,
wherein RO and R are as defined above, or c) obtaining a compound of formula Ic,
wherein R and RO are as defined above and Alk is C1~4alkyí, by esterification of a compound of formula la with an alcohol of formula IV Al k-OH IV wherein Alk is as defined above, or a reactive functional derivative thereof.
The process a) may be carried out at temperatures typically from OOC to 1 800, preferably 400C to 1200 C, in an inert organic solvent of conventional type, e.g. an amide of an organic carboxylic acid such as dimethylformamide. As is conventional, the compound of the formula Ill is preferably provided by reacting imidazole with a strong base such as an alkali metal hydride e.g. sodium hydride, in an inert organic solvent which is conveniently the same solvent which is to be used in process a).
The oxidation according to process b) may be carried out with the aid of oxidizing agent capable of oxidizing an CH3-group to a COOH group. Suitable oxidizing agents are potassium permanganate, manganese dioxide and the like, preferably potassium permanganate. The reaction is conveniently carried out in aqueous solution. A suitable reaction temperature for process b) is from 200 to 1 500C, preferably from 600 to 1200C.
The compounds of formula la are depending on the reaction conditions and the recovery steps obtained in free form or in salt form (H of COOH substituted by a cation). Free forms of compounds of formula la may be converted into salt forms in conventional manner and vice versa. The cation of the salt form of compounds of formula la is preferably an agriculturally acceptable cation such as Na+, K+ and NH4+.
The process c) may be carried out in accordance with known esterification procedures for compounds containing a potentially reactive hydroxyl group. The esterification with an alcohol of formula IV is conveniently carried out at a reaction temperature of from 300C to 800C, advantageously under anhydrous conditions and in the presence of an acid, such as hydrogen chloride. Suitable solvents for this reaction are inert organic solvents or an excess of the alcohol of formula IV.
Suitable reactive functional derivatives of an alcohol of formula IV are the corresponding diazoalkane, e.g. a diazoalkane of 1 to 3 carbon atoms, or an alkylhalide, particularly a chloride, bromide or iodide. The reaction with a diazoalkane is conveniently carried out under anhydrous conditions in an inert organic solvent. A suitable reaction temperature is then -200C to +40"C, more usually-50C to +200C. For the reaction with an alkylhalide the compounds of formula la are preferably in salt form, e.g. the alkali metal and silver salt form. Such reaction is conveniently carried out in an inert organic solvent at temperatures of from OOC to 1 000C, more usually 400C to 900C.
The reaction product of processes a), b) and c) may be recovered from the reaction mixture in which it is formed by working up by established procedures.
The compounds of formula I wherein R' is other than COOH may be prepared and used in the form of acid addition salt forms. The compounds of formula I are ethanol derivatives and can therefore exist in free form and in alternate forms such as an ethanolate salt form, e.g. a sodium ethanolate form, and in metal complex form, e.g. of metals from the groups Ib, lla, lib, Vlb, Vllb and Vlil of the periodic table, such as copper zinc, and with anions such as chloride, sulphate, nitrate, carbonate, acetate, citrate, dimethyldithioca rbamate and the like.
Any saltform of compounds of formula I is preferably in the form of an agriculturally acceptable salt form.
The acid addition salt forms, the ethanolate salt form and the metal complex form can be prepared from the corresponding free form in conventional manner and vice versa.
The compounds of formula 11may be prepared by reacting a compound of the formula V
wherein RO, R, R' and R"' are as above defined, with the reaction product of a strong base and trimethylsulfonium iodide which provides a reagent which may be represented by the formula VI
which process is carried out in an inert organic solvent. This process is a known type reaction for the preparation of epoxy derivatives from ketones.
Many of the compounds of the formula V are known and those which are not known per se may be prepared from known materials by procedures analogous to those known for preparation of the known compounds. Many of the compounds II are also known.
The compounds of the formula I are useful as fungicides in combatting phytophathogenic fungi, including particularly powdery mildews and rust fungi, as indicated by standard in vivo and in vitro tests of the type hereinafter illustrated. For such use the compounds of the formula I may be applied to plants, seed or soil in a manner conventional in the use of fungicidal agents. As will be appreciated, the amount of the compound of the formula I to be applied will vary depending upon known factors such as the particular compound employed, whether the treatment is prophylactic or therapeutic, whether the compound is applied as a foliar spray, a soil treatment or a seed dressing, the species of fungus under treatment and the time of application.However, in general, satisfactory results are obtained when the compound is applied to a crop locus, either on crops or to soil, at a rate of from about 0.01 to 5, preferably about 0.01 to 2 kg (active ingredient)/hectare. The treatment may be repeated as required, e.g. at 8 to 30 day intervals. When employed as a seed dressing, satisfactory results are obtained when the compound is employed at a rate of from about 0.05 to 0.5, preferably about 0.1 to 0.3 g/kg seed.
The term "soil" as used herein is intended to embrace any conventional growing medium whether natural or artificial.
The invention also provides, as an additional feature, fungicidal compositions, comprising as fungicide, a compound of formula I in free form or in agriculturally acceptable salt or metal complex form and an inert carrier or diluent. In general, such compositions contain from about 0.01 to preferably from about 0.1 to 60% by weight of active agent. They may be in concentrate form, for dilution down prior to application, or in dilute, ready to apply, form. As examples of particular forms may be given wettable powder, emulsion concentrate, dusting spraying, granulate and delayed release forms, incorporating conventional carriers and such other diluents and/or adjuvants acceptable in the agricultural art. Application forms of those compositions generally contain between about 0.01 and 1 0% by weight of a compound of formula I as active agent.Concentrate forms of composition for fungicide use generally contain between about 2 to 80%, preferably between about 5 and 70%, by weight of a compound of formula I as active agent. Emulsion concentrate forms generally contain from about 10 to 70%, preferably about 20 to 60% by weight of active ingredient. Solid, particulate compositions are preferred.
The compositions particularly adapted for spraying preferably include a surfactant such as a liquid polyglycol ether, a fatty alkyl sulphate or a lignin sulphonate.
In addition to conventional carrier and surface-active materials, formulations of the compound I of the invention may also contain further additives with special purposes e.g. stabilizers, deactivators (for solid formulations on carriers with an active surface), agents for improving the adhesion to plants, corrosion inhibitors, anti-foaming agents and colorants.
Moreover, further fungicides, bactericides or other beneficially-acting materials, such as insecticides, may be present in the formulations and are contemplated as further embodiments of this invention.
Examples of the production of fungicide formulations are as follows: a) Wettable Powder Formulation
50 parts of a compound of formula I, e.g. cr-t-butyl-g-(p-methylphenyl)-1 H-imidazole-1 -ethanol are ground with 2 parts of lauryl sulphate, 3 parts sodium lignin sulphonate and 45 parts of finely divided kaolinite until the mean particle size is below 5 microns. The resulting wettable powder so obtained is diluted with water before use to a concentration of between 0.01% to 5% active agent. The
resulting spray liquor may be applied by foliar spray as well as by root drench application.
b) Granulate Formulation
Onto 94.5 parts by weight of a quartz sand in a tumbler mixer is sprayed 0.5 parts by weight of a binder (non-ionic tenside) and the whole thoroughly mixed. 5 Parts by weight of a compound of formula 1, e.g. powered a-t-butyl-p-(p-methylphenyl)-1 H-imidazole-1-ethanol are then added and thorough mixing continued to obtain a granulate formulation with a particle size in the range of from 0.3 to 0.7 mm. The granulate may be applied by incorporation into the soil adjacent the plants to be treated.
c) Emulsion Concentrate
25 Parts by weight of a compound of formula I, e.g. a-t-butyl-a-(p-methylphenyl)-1 H-imidazole1-ethanol are mixed with 30 parts by weight of iso-octyl phenyl octaglycol ether and 45 parts by weight of a petroleum fraction with a boiling range of 210--2800C. (D20: 0.92). The concentrate is diluted with water to the desired concentration.
d) Seed Dressing
45 Parts of a compound of formula I, e.g. a-t-butyl-a-(p-methylphenyl)-1 H-imidazole-1 -ethanol are mixed with 1.5 parts of diamylphenoldecaglycolether ethylene oxide adduct, 2 parts of spindle oil, 51 parts of fine talcum and 0.5 parts of colorant rhodamin B. The mixture is ground in a contraplex mill at 10,000 rpm until an average particle size of less than 20 microns is obtained. The resulting dry seed dressing powder has good adherence and may be applied to seeds, e.g. by mixing for 2 to 5 minutes in a slowly turning vessel.
Fungi against which the compounds of the formula I are indicated to be particularly of interest include by way of illustration the following:
A) Basidiomycetes, comprising
A. 1 ) those of the Order Uredinales such as those of the genus Uromyces in plants such as beans, e.g. Uromyces appendiculatus, and ornamentals, e.g. Uromyces dianthi, those of the genus Hemileia in plants such as coffee, e.g. Hemileia vastatrix, those of the genus Puccinia in plants such as cereals (e.g.
wheat, oats, barley) e.g. Puccinia graminis, Puccinia recondita and Puccinia striiformis, or ornamentals, e.g. Puccinia pelargoniizonalis, those of the genus Phakopsora in plants such as soya, e.g. Phakopsora pachyrhizi, those of the genus Melamspora in plants such as flax, e.g. Melampsora lini, and those of the genus Tranzschelia, e.g. tranzschelia pruni in plums;
A.2) those of the Order Ustilaginales such as those of the genus Ustilago in plants such as barley, wheat, corn and sugarcane, e.g. U. maydis on corn and U. nuda on barley, and
A.3) those of the genus Stereum in pip and stone fruit trees, e.g. Stereum purpureum in apple and prune.
B) Ascomycetes, comprising
B. 1 ) those of the Order Erysiphales such as those of the genus Erysiphe in plants such as cucumber, barley, wheat and sugarbeet, e.g. Erysiphe graminis f.sp. tritici on wheat and Erysiphe cichoraceareum on cucumbers: those of the genus Spohaerotheca on cucumbers and roses, e.g.
Spohaerotheca pannosa on roses; those of the genus Podosphaera in apples, pears and prunes, e.g.
Podosphaera leucotricha on apples; those of the genus Uncinula on plants such as grapes, e.g.
Uncinula necator on grapevines; those of the "genus" Oidium on a wide variety of plants; ant those of the genus Levelliula in plants such as cotton and other Malvaceae, e.g. Leveillula taurica on cotton.
C. Oomycetes, comprising C.1) those of the genus Phytophthora spp., e.g. Ph. cactorum, Ph. parasitica and Ph. cinamomi on susceptible plants; and
C.2) those of the genusAphanomyces in plants such as pea and sugar beet, e.g. Aphanomyces euteiches in sugar beet, and
D) Deuteromycetes, comprising
D.1) those of the genus Helminthosporium in plants such as barley and corn, e.g. Helm. Sativum;
D.2) those of the genus Septoria in plants such as wheat, tomato and celery, e.g. Sept. tritici in wheat, tomato and celery, e.g. Sept. tritici in wheat;
D.3) those of the genus Rhizoctonia in plants such as cotton and potato, e.g. This. solani in cotton;
D.4) those of the genus Fusarium spp, e.g.F. oxysporum f. sp. lycopersici in tomato, F. oxysporum f. sp. vasinfectum in cotton, F. oxysporum f. sp. cubense in banana, F. solani in vegetables, F. culmorum in cereals and F. graminearum in cereals;
D.5) those of the genus Thielaviopsis in plants such as cotton, tobacco etc., e.g. Thielaviopsis basicola in cotton; D.6) those of the genus Phoma in plants such as sugar beet, rape etc., e.g. Phoma betae in sugar beet;
D.7) those of the genus Piricularia spp., e.g. P. oryzae on rice; and
D.8) those of the genus Colletotrichum spp., e.g. C. llndemuthianum in beans.
The following conventional tests are illustrative of the manner by which the fungicidal activity of the compounds of the formula I may be indicated.
Test Method A: ln vivo employing bean rust (Uromyces appendiculatus). Phaseolus vulgaris (pole bean plant) is
cultivated in a mixture of peat and sand in plastic pots of 6 cm diameter for 9 days. The plants are
sprayed with a spray liquor containing 0.0008 to 0.05% (e.g. at 0.0008%, 0.003%, 0.012% and
0.05%) active ingredient. Treatment comprises foliar spraying to near run-off or soil drenching (28 ml
of spray liquor per pot). After drying, the plants are inoculated with a spore suspension spray (500.000
to 700,000 spores/ml) and incubated for 7 days in an incubation chamber at 100% relative humidity
and 210. The efficacy of the active agent treatment is determined by comparing the number of
pustules/leaf with that on untreated, similarly inoculated check plants. The compounds of formula I,
particularly the compounds of the examples hereinafter e.g. the compounds of the Examples 1 2A, 2Z-2 and 2Z-1 1, used in the wettable powder formulation given above provide a significant degree of fungicidal activity in the above test, both by contact as well as root-systemic action.
Analogous tests are run on the following crop/fungi with similar results.
Coffee: coffee leaf rust (Hemileia vastatrix)
Wheat: black stem rust (Puccinia graminis)
Wheat: brown leaf rust (Puccinia recondita)
Wheat: yellow or stripe rust (Puccinia striiformis) Flax: flax rust (Melamspora Lini)
Pelargonium: Pelargonium rust (Puccinia pelargonllzonalls) Snapdragon: Snapdragon rust (Puccinia antirrhini).
Test Method B:
In vivo employing cucumber powder mildew (Erysiphe cichoracearum). Cucumis sativus (cucumber) is cultivated in a mixture of peat and sand in plastic pots of 6 cm diameter for 7 days. The plants are sprayed with a spray liquor containing 0.0008 to 0.05% (e.g. at 0.0008%, 0.003%. 0.012% and 0.05%) active ingredient. Treatment comprises foliar spraying to near run-off or soil drenching (28 ml of spray liquor per pot). After drying, the plants are inoculated by dusting them with freshly collected conidia and are then incubated for 7 days in an incubation chamber at 6080% relative humidity and 25--300C. The efficacy of the active ingredient is determined by comparing the degree of fungal attack with that on untreated, similarly inoculated check plants.The compounds of formula I particularly the compounds of the Examples hereinafter, e.g. the compounds of the Examples 1, 2A. 2C, 2D, 2G, 2J, 2Q, 2T, 2Z-1, 2Z-2, 2Z-5, 2Z-6, 2Z-7, 2Z-9, 2Z-1 1 and 2Z-12, used in the wettable powder formulation given above provide a significant degree of fungicidal activity, both by contact as well as root systemic action.
Tests analogous to Test Method B are made with similar results on the following crop/fungi:
Wheat: wheat powdery mildew (Erys. gram. f. sp. triticl3 Barley: barley powder mildew (Erys. gram. f. sp. horde')
Apple: apple powdery mildew (Podos. leucotricha)
Grape: grapevine powdery mildew (Uncinula necator)
Test method B, above, as regards cucumber powdery mildew and the preferred compound of Example 1, hereinafter is repeated (both foliar spray and soil drench) but at the lower concentrations of 0.0002% and 0.00005% with the result that 100% and 80%, respectively, control of the fungi is still obtained by spray application and 55% and 10%, respectively by soil drenching thereby still further indicating the outstanding potency provided by the invention.
Test Method C: ln vitro test employing Ustilago maydis (corn smut). Different concentrations of the active ingredient are incorporated in malt agar plates to give concentrations of 0.8 to 200 ppm a.i. (e.g. at 0.8, 3.2, 12.5, 50 and 200 ppm). The plates are then inoculated by spraying a spore suspension of U.
maydis onto them or placing an agar plug containing the fungus in the centre of the plate. The plates are incubated at room temperature for 2-5 days. The efficacy of the active agent treatment is determined by comparing the growth of the fungus with that in untreated, similarly inoculated plates.
The compounds of Example 1, 2C and 2Z-8 hereinafter provide some to good control in Test Method C at the higher concentration. The compound of Example 1 showed also good control at the lower and higher concentrations in analogous test on Fusarium oxysporum f. sp.
Additional tests analogous to Test Method C at 1 3, 50 and 200 ppm a.i. show except where noted a 100% control with the compound of Example 1 hereinafter at at least one test dosage on the following: Phytophthora cactorum (maximum control 85%); Phytophthora cinamomi (maximum control 65%); Aphanomyces euteiches; Stereum purpureum; Thielaviopsis basicola (maximum control 80%); Piricularia oryzae (maximum control 70%); and Colletotrichum lindemuthianum (maximum control 65%).
Fungi of the aforementioned genera cause considerabie damage in agriculture and are different to prevent or control. In addition to combatting such fungi, the compounds of the formula I are indicated to be non-phytotoxic at effective doses in plants subject to such fungi and are further indicated to be of particular interest as also acting to combat fungi by systemic action as determined, for example, in the combatting of Uromyces appendiculatus on beans.
Additional tests analogous to Test Methods A and B at doses of 32, 124 and 500 ppm a.i.
conducted with the compound of Example 1 hereinafter show by spray application at 60%, 80% and 90% control, respectively of Helminthosporium on barley with no phytotoxicity.
Test Method D:
In vivo, employing Rhizoctonia solani. The fungus is cultivated in a sterile mixture of Zonolite and corn meal (10:1 w/w) to which water is added in a ratio of about 1:1 (w/w); cultivation lasts for 14 days at 25 C. The fungus is then mixed into a semi-sterile mixture of peat and sand which then is
treated with a suspension containing the formulated active ingredient to give concentration of 10 to 1 60 ppm (e.g. 10, 40 and 1 60 ppm) calculated per volume substrate. The substrate is transferred to
pots of 5 cm diameter which are planted with cotton seedlings (cotyledonous stage).The planted pots
are incubated at 240C and 60-70% relative humidity in an incubation chamber for 14 days, after
which disease attack is determined by comparing the fungal attack on roots and hypocotyl with that on
untreated, similarly inoculated check plants. The compound of Example 1, hereinafter, used in the
wettable powder formulation given above provides 100% disease control with no phytotoxicity at the lower dose.
A test analogous to Test Method D is run with Phoma betae on sugar beet to give 100% control
with 20% phytotoxicity at the lower dose.
From the foregoing it will be evident to those skilled in the art that the compounds of the present
invention are also indicated to be of particular interest with regard to the control of important soil- and
seed-borne fungi, e.g. Helminthosporium, Phoma, Rhizoctonia and Thielaviopsis, in addition to their
considerable interest and value in the control of powdery mildews and rusts.
The particular value and advantages of the invention are confirmed and/or further indicated in
more detailed evaluations of the compound of Example 1 hereinafter which exhibits the following
outstanding and in some cases remarkable properties: 1) a persistency of action that still produces
70% control of Uromyces app. on pole beans at spray concentrations of 0.012% on application 8 days
before inoculation; 2) a good stability of aqueous spray suspensions as indicated by 100% control of
Uromyces app. on pole beans on application 3 days after preparation of the suspension (0.012% concentration); 3) rapid and lasting penetration of the active substance into leaves of plants to be
protected as indicated by 80% control at the 0.012% concentration after washing the leaves of
grapevine for 1 5 minutes 2 hours after application of the active ingredient followed by infestation with
Uncinula, 4) a 65% control in simulated rain washing of the leaves of coffee plants at a rain rate of 50
MM/hour first applied two hours after application of the active ingredient for 1 5 minutes followed by
drying and a second application of rain for 1 5 minutes again, followed by infestation of the coffee plant
with Hemileia vastatrix, and 5) a 60% control in simulated rain washing of the leaves of pole beans at a
rain rate of 50 MM/hour first applied 2 hours after application of the active ingredient for 1 0 minutes,
followed by infestation of the pole bean plants with Uromyces app. In still further evaluation of the
preferred compound of Example 1 hereinafter a fungicidal activity of 100% compared with untreated
standard is obtained on application of the active ingredient at a concentration of 0.012% 1 day after
pole beans are infested with Uromyces app. and a 60% control 2 days after infestation.
Other compounds of the formula I as given in Example 2, hereinafter, also show very good to
outstanding fungicidal activity in evaluation procedures as above described.
Preferred compounds of the formula I have one or more and preferably all of the following
features: a) RO branched alkyl of 3 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms or
cycloalkylmethyl in which the cycloalkyl portion is of 3 to 6 carbon atoms; b) R is hydrogen, halogen
having a atomic number of from 9 to 35 or C1-C4aIkyl; c) R' is hydrogen, halogen having an atomic
number of from 9 to 35, C1-C4alkyl, C1-C4alkoxy or C1-C4alkylthio or d) R' is one of the groups
located at the para-position of Ring A.The more preferred among the above-mentioned preferred compounds of the formula I have one or more and preferably all of the following features: a) RO is branched alkyl of 3 to 5 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; b) R is hydrogen, fluoro or chloro and c) R' is hydrogen, halogen having an atomic number of from 9 to 35, C 1-C2alkyl or C1- C2alkoxy; or d) R is hydrogen and R' is
located at the para-position of Ring A, more preferably with YO and Y being hydrogen.
In general RO is preferably propyl or a branched butyl, i.e. n-propyl, isopropyl, sec.-butyl, isobutyl or t-butyl or cyclopropyl or cyclopentyl but most preferably RO is t-butyl.
In general, it is preferred that at least one of R and R' be other than hydrogen, particularly alkyl, e.g. methyl or ethyl, or phenyl at the para-position of Ring A, usually with the other being hydrogen or halogen.
The following Examples further illustrate the present invention. All temperatures are in centrigrade.
Example 1 a-t-butyl-,o'-(p-methylphenyl)-1 H-imidazole-l -ethanol A 0.82 g portion of 61.4% sodium hydride is washed three times with petroleum ether and then added to 10 ml of dimethylformamide while maintaining stirring. To the resulting suspension is added slowly with stirring 1.43 g of imidazole dissolved in 10 ml of dimethylformamide resulting in bubbling and an exotherm. After heating the resulting mixture at 400 with stirring for 30 minutes the bubbling ceases and then 4.0 g of 2-t-butyl-2-(4-methylphenyl)-oxirane is added followed by heating at 700 for
1.5 hours.The resulting reaction mixture is then poured onto water, extracted with ethyl acetate, the organic phase washed with water, dried and evaporated to an oil which is cooled to room temperature to obtain a solid which is recrystallized from hexane/carbon tetrachloride (10:90) to obtain α-t-butyl-α- (p-methylphenyl)-1H-imidazole-1-ethanol, m.p. 135-137 .
Example 2
Following the procedure of Example 1 the following additional compounds of the invention are obtained:
A) -n-butyl--(p-methylphenyl)-1 H-imidazole-1 -ethanol, m.p. 136-138 .
B) -t-butyl-a-(p-chlorophenyl)-1 H-imidazole-1 -ethanol.
C) α-t-butyl-α-(o,p-dichlorophenyl)-1H-imidazole-1-ethanol, m.p. 141-142 .
D) α-butyl-α-phenyl-1H-imidazole-1-ethanol, m.p. 124-125 .
E) α-n-propyl-α-(p-methylphenyl)-1H-imidazole-1-ethanol, m.p. 156-157 .
F) -t-butyl-a-(p-fluorophenyl)-l H-imidazole-1 -ethanol.
G) -t-butyl--(p-methoxyphenyl)-1 H-imidazole-1 -ethanol, m.p. 153-155 .
H) α-t-butyl-α-(m-nitrophenyl)-1 H-i midazole- 1 -ethanol.
1) α-t-butyl-α-(m-trifluoromethylphenyl)-1H-imidazole-1-ethanol.
J) a-t-butyl--(m-cyanophenyl)-1 H-imidazole-1-ethanol, m.p. 156-157 .
K) α-t-butyl-α-(m,p-methylenedioxyphenyl)-1 H-imidazole-1 -ethanol.
L) -t-butyl--(p-biphenylyl)-1 H-imidazole- 1-ethanol, m.p. 174-1750.
M) a-t-butyl--(p-phenoxyphenyl)-1 H-imidazole- 1-ethanol.
N) α-1-propyl-α-(p-chlorophenyl)-1 H-imidazole-1 -ethanol.
O) α-t-butyl-α-(m,p-dichlorophenyl)-1H-imidazole-1-ethanol.
P) α-i-butyl-α-(p-methylphenyl)-1H-imidazole-1-ethanol.
Q) α-n-propyl-α-phenyl-1H-imidazole-1-ethanol, m.p. 119-120 .
R) a-ethyl-a-(p-chlorophenyl)-l H-imidazole-1 -ethanol, m.p. 167-168 .
S) α-neopentyl-α-phenyl-1H-imidazole-1-ethanol, m.p. 169-170 .
T) α-cyclopropyl-α-(p-chlorophenyl)-1H-imidazole-1-ethanol, m.p. 132-134 .
U) a-n-penl-a-phenyl- 1 H-imidazole- 1-ethanol, m.p. 146-147 .
V) α-cyclopropyl-α-(p-methylphenyl)-1 K-imidazole-1 -ethanol.
W) α-cyclopentyl-α-(p-methylphenyl)-1 H-imidazole- 1 -ethanol.
X) α-t-butyl-α-(p-methylthiophenyl)-1H-imidazole-1-ethanol.
Y) α-sec.-butyl-α-(p-methylphenyl)-1 H-imidazole- 1-ethanol.
Z) α-i-butyl-α-(p-methylphenyl-1 H-imidazole- 1-ethanol.
Z-1) α-t-butyl-α-(m-btomop-methylphenyl)-1H-imidazole-1-ethanol, m.p. 139-142 .
Z-2) α-t-butyl-α-(m-fluoro-methylphenyl)-1H-imidazole-1-ethanol, m.p. 150-152 .
Z-3) α-t-butyl-α-(m-chloro-methylphenyl)-1H-imidazole-1-ethanol, m.p. 152-156 .
Z-4) α-t-butyl-α-(m-chloro-m-methoxyphenyl)-1 H-imidazole-1 -ethanol.
Z-5) -n-butyl-as-phenyl-1 H-imidazole-1 -ethanol, m.p. 138-139 .
Z-6) α-cyclopentyl-α-phenyl-1 H-imidazole-1 -ethanol, m.p. 144-1450.
Z-7) α-isopentyl-α-phenyl-1H-imidazole-1-ethanol 169-170 .
Z-8) α-n-butyl-α-(o,p-dichlorophenyl)-1 H-imidazole-1 -ethanol.
Z-9) α-tert.-butyl-α-(m,m'-dichlorophenyl)-1H-imidazole-1-ethanol, m.p.159-161 .
Z-10) α-tert.-butyl-α-(m,p-dimethylphenyl)-1H-imidazole-1-ethanol, 145-146 .
Z-11) α-tert.-butyl-α-(p-ethylphenyl)-1H-imidazole-1-ethanol, m.p. 115-118 .
Z-12) α-tert.-butyl-α-(m-methylphenyl)-1H-imidazole-1-ethanol, m.p. 90-92 .
Z-13) α-tert.-butyl-α-(p-tert.-butylphenyl)-1H-imidazole-1-ethanol, m.p. 155-157 .
Z-14) α-tert.-butyl-α-(m-methoxyphenyl)-1H-imidazole-1-ethanol, m.p. 153-155 .
Z-15) α-tert.-butyl-α-(m-methoxyphenyl)-1H-imidazole-1-ethanol, m.p. 114-115 .
Z-16) α-tert.-butyl-α-(p-cyanophenyl)-1H-imidazole-1-ethanol, m.p. 143-145 .
Z-17) α-tert.-butyl-α-(p-methylphenyl)-1H-imidazole-1-ethanol, m.p. 104-105 .
Z-18) α-(1-methylbutyl)-α-(p-methylphenyl)-1H-imidazole-1-ethanol, m.p. 119-122 .
Example 3
A 2.2 g portion of 61.4% sodium hydride is washed three times with petroleum ether, then 70 ml of dimethylsulfoxide added and the mixture heated with stirring to 700 and carried to 850 by the exotherm after which the mixture is heated at 750 for 40 minutes. The resulting mixture is cooled to 0 in an ice/salt bath and then under a nitrogen blanket there is added dropwise a solution of 7.0 g of trimethylsulfonium iodide in 50 ml of dimethylsulfoxide and 20 ml tetrahydrofuran while maintaining the temperature below 1 80. To the resulting mixture is then added with stirring under the nitrogen blanket a solution of 3.0 g of t-butyl-p-methylphenyl ketone in 30 ml of tetrahydrofuran while maintaining the temperature below 1 00. The resulting mixture is stirred at 0 for 30 minutes and then at room temperature for 2 hours. The resulting reaction mixture is then poured onto 400 ml of water, extracted with methylene chloride, the organic phase washed with water and then brine, dried and evaporated to obtain a yellow oil of 2-(t-butyl)-2-(4-methylphenyl)-oxirane.
Claims (48)
1. A compound of formula I
wherein RO is alkyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, cycloalkylalkyl in which the cycloalkyl is of 3 to 6 carbon atoms and the alkyl portion of 1 to 3 carbon atoms, said cycloalkyl and cycloalkylalkyl being optionally ring substituted by one or two alkyl groups of 1 to 3 carbon atoms, and
R is hydrogen, halogen having an atomic number of from 9 to 35, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms or nitro, and
R' is hydrogen, halogen having an atomic number of from 9 to 35, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, -CF3 in the 3-position of Ring A, nitro, -CN, -COOR", an optionally substituted phenyl group of the formula::
or an optionally substituted phenoxy group in the 4-position of Ring A and having the formula
R" is hydrogen, alkyl of 1 to 4 carbon atoms or a cation, or
R and R' together represent alkylenedioxy of 1 or 2 carbon atoms substituted onto adjacent carbon atoms of the phenyl Ring A, and
Y and Y are independently hydrogen, halogen having an atomic number of from 9 to 35, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms,
with the proviso that when R is n-butyl: a) at least one of R and R' is other than hydrogen and b)
R or R' are not halo.
2. A compound of Claim 1 in which R is hydrogen, halogen having an atomic number of from 9 to 35 or C1-C4alkyl and R' is hydrogen, halogen having an atomic number of from 9 to 35, C1-C4alkyl, C1-C4alkoxy, or a group located at the para-position of Ring A and having the formula
in which Y and Y are as defined in Claim 1.
3. A conipound of Claim 2 in which R is hydrogen, fluoro or chloro and R' is hydrogen, halogen having an atomic number of from 9 to 35, C1-C2al kyl or C1-C2alkoxy or p-phenoxy.
4. A compound according to any one of Claims 1 to 3 in which R is branched alkyl of 4 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms.
5. A compound of Claim 4 in which R is branched butyl, cyclopropyl or cyclopentyl.
6. A compound of Claim 4 in which R is t-butyl.
7. A compound of Claim 1 which is cr-t-butyl--(p-methylphenyl)-1 H-imidazole-1 -ethanol.
8. The compound of Claim 1 which is a-t-butyl-a-phenyl-1 H-imidazole-1 -ethanol.
9. The compound of Claim 1 which is a-t-butyl-a-(p-fluorophenyl)-1 H-imidazole-1 -ethanol.
10. The compound of Claim 1 which is cr-t-butyl--(p-chlorophenyl)-1 H-imidazole-1 -ethanol.
11. The compound of Claim 1 which is a-t-butyl-a-(o,p-dichlorophenyl)-1 H-imidazole-1 -ethanol.
12. The compound of Claim 1 which is -t-butyl--(p-biphenylyl)-1 H-imidazole-1 -ethanol.
13. The compound of Claim 1 which is -n-butyl--(p-methylphenyl)-1 H-imidazole-1 -ethanol.
14. The compound of Claim 1 which is -t-butyl--(p-phenoxyphenyl)-1 H-imidazole-1 -ethanol.
15. The compound of Claim 1 which is ct-cyciopropyl-ct-(p-methylphenyl)-l H-imidazole-1- ethanol.
16. The compound of Claim 1 which is a-cyclopentyl-a-(p-methylphenyl)-1 H-imidazole-1 ethanol.
17. The compound of Claim 1 which is a-n-prnpyl-a-(p-methylphenyl)-1 H-imidazole-1 -ethanol.
18. The compound of Claim 1 which is a-t-butyl--(p-methoxyphenyl)-1 H-imidazole-1 -ethanol.
19. The compound of Claim 1 which is -t-butyl--(m-cyanophenyl)-1 H-imidazole-1 -ethanol.
20. The compound of Claim 1 which is a-n-propyl-cg-phenyl-1 H-imidazole-1 -ethanol.
21. The compound of Claim 1 which is a-ethyl--(p-chlorophenyl)-1 H-imidazole-1 -ethanol.
22. The compound of Claim 1 which is α-cyclopropyl-α-(p-chlorophenyl)-1 H-imidazole-1- ethanol.
23. The compound of Claim 1 which is a-n-pentyl-a-phenyl-1 H-imidazole-1-ethanol.
24. The compound of Claim 1 which is a-t-butyl-a-(m-bromo-p-methylphenyl)-1 H-imidazole-1 ethanol.
25. The compound of Claim 1 which is α-t-butyl-α-(m-fluoro-p-methylphenyl)-1 H-imidazole-1- ethanol.
26. The compound of Claim 1 which is Z-1) α-t-butyl-α-(m-chloro-p-methylphenyl)-1 H-imidazole-1 ethanol.
27. The compound of Claim 1 which is -n-butyl--phenyl-1 H-imidazole-1 -ethanol.
28. The compound of Claim 1 which is a-cyclopentyl-sg-phenyl-1 H-imidazole-1 -ethanol.
29. The compound of Claim 1 which is a-isopentyl-a-phenyl-1 H-imidazole-1 -ethanol.
30. The compound of Claim 1 which is cg-n-butyl--(o,p-dichlorophenyl)-1 H-imidazole-1 -ethanol.
31. The compound of Claim 1 which is α-tert.-butyl-α-(m,m-dichlorophenyl)-1 H-imidazole-1ethanol.
32. The compound of Claim 1 which is α-tert.-butyl-α-(m,p-dimethylphenyl)-1 H-imidazole-1 ethanol.
33. The compound of Claim 1 which is a-tert.-butyl--(p-ethylphenyl)-1 H-imidazole-1-ethanol.
34. The compound of Claim 1 which is α-tert.-butyl-α-(m-methylphenyl)-1 H-imidazole-1ethanol.
35. A compound according to any one of Claims 1 to 34 in free form.
36. A compound according to any one of Claims 1 to 34 in salt or metal complex form.
37. The method of combatting phytopathogenic fungus in plants or soil comprising applying to said plants or soil 0.01 to 5 kg per hectare of a compound claimed in any one of Claims 1 to 36.
38. The method of Claim 30, wherein the application rate is from 0.1 to 2 kg per hectare of a compound claimed in any one of Claims 1 to 36.
39. The method of combatting phytopathogenic fungus in seeds comprising applying to the seeds 0.05 to 0.5 g per kg seed of a compound claimed in any one of Claims 1 to 36.
40. The method of Claim 40, wherein the application rate is from 0.1 to 0.3 g per kg seed of a compound claimed in any one of Claims 1 to 36.
41. A fungicidal composition comprising a compound claimed in any one of Claims 1 to 36 in free form or in agriculturally acceptable salt or metal complex form in association with a fungicide carrier or diluent.
42. The composition of Claim 42, comprising from 0.01 to 90% by weight of a compound claimed in any one of claims 1 to 36 in free form or in agriculturally acceptable salt or metal complex form.
43. An application form of the composition of Claim 43, comprising from 0.01 to 10% by weight of a compound claimed in any one of Claims 1 to 36 in free form or in agriculturally acceptable salt or metal complex form.
44. A concentrate form of the composition by weight of a compound claimed in any one of
Claims 1 to 36 in free form or in agriculturally acceptable salt or metal complex form.
45. A process for the production of compounds of formula I, stated in Claim 1, which comprises
a) reacting a compound of the formula II:
wherein RO, R and R' are as above defined, with a compound of formula Ill
wherein X is an alkali metal in an inert organic solvent, b) obtaining a compound of formula la,
wherein RO and R are as defined above by oxidation of the CH3 group of a compound of formula Ib,
wherein RO and R are as defined above, or c) obtaining a compound of formula Ic,
wherein R and RO are as defined above and Alk is C,,alkyl, by esterification of a compound of formula la with an alcohol of formula IV Al k-OH IV
wherein Alk is as defined above, or a reactive functional derivative thereof.
46. A process according to Claim 45, substantially as hereinbefore described with reference to any one of the Examples.
47. A compound of formula I, stated in Claim 1 whenever obtained by a process according to
Claim 45 or 46.
48. The method of combatting phytopathogenic fungus in plants, seeds or soil with a non
phytotoxic fungicidally effective amount of a compound claimed in any one of Claims 1 to 36 or 47 in
free form or in agriculturally acceptable salt or metal complex form.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9380079A | 1979-11-13 | 1979-11-13 | |
| US17098280A | 1980-07-18 | 1980-07-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2063260A true GB2063260A (en) | 1981-06-03 |
Family
ID=26787919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8036001A Withdrawn GB2063260A (en) | 1979-11-13 | 1980-11-10 | alpha -aryl-1 -H-imidazole-1-ethanol Derivatives and their Use as Fungicides |
Country Status (11)
| Country | Link |
|---|---|
| AU (1) | AU6426480A (en) |
| BR (1) | BR8007389A (en) |
| DE (1) | DE3042303A1 (en) |
| DK (1) | DK480780A (en) |
| ES (1) | ES496713A0 (en) |
| FR (1) | FR2469404A1 (en) |
| GB (1) | GB2063260A (en) |
| IL (1) | IL61455A0 (en) |
| IT (1) | IT8050118A0 (en) |
| NL (1) | NL8006171A (en) |
| PL (1) | PL227787A1 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2535321A1 (en) * | 1982-10-28 | 1984-05-04 | Sandoz Sa | NOVEL ETHANOL DERIVATIVES, THEIR PREPARATION AND THEIR USE AS FUNGICIDES |
| GB2136423A (en) * | 1983-03-04 | 1984-09-19 | Sandoz Ltd | Fungicidal 1h-azole-1-ethanol derivatives |
| US4609668A (en) * | 1983-09-01 | 1986-09-02 | Sandoz Ltd. | Fungicidal α-(alkynylphenyl)azole ethanol compounds |
| EP0212605A2 (en) * | 1985-08-29 | 1987-03-04 | Hoechst Aktiengesellschaft | Azolyl-cyclopropyl-ethanol derivatives, processes for their preparation and their use |
| EP0319960A2 (en) * | 1987-12-09 | 1989-06-14 | Ss Pharmaceutical Co., Ltd. | Imidazole derivative |
| US5164513A (en) * | 1987-12-09 | 1992-11-17 | Ss Pharmaceutical Co., Ltd. | Imidazole derivative |
| CN102258033A (en) * | 2011-08-19 | 2011-11-30 | 陕西美邦农药有限公司 | Novel pesticidal composition containing prothioconazole and triazole |
| CN102599171A (en) * | 2012-01-20 | 2012-07-25 | 联保作物科技有限公司 | Sterilizing composition and preparation thereof |
| US8658564B2 (en) | 2007-06-06 | 2014-02-25 | Bayer Cropscience Ag | Fungicide active ingredient combinations |
| WO2014095548A1 (en) * | 2012-12-19 | 2014-06-26 | Basf Se | Substituted [1,2,4]triazole compounds and their use as fungicides |
| WO2014095381A1 (en) * | 2012-12-19 | 2014-06-26 | Basf Se | Fungicidal imidazolyl and triazolyl compounds |
| WO2014095672A1 (en) | 2012-12-19 | 2014-06-26 | Basf Se | Substituted [1,2,4]triazole compounds and their use as fungicides |
| WO2014108288A2 (en) * | 2013-01-08 | 2014-07-17 | Basf Se | Substituted [1,2,4]triazole compounds |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2606408B1 (en) * | 1983-09-01 | 1989-11-24 | Sandoz Sa | NEW ETHANOL DERIVATIVE, ITS PREPARATION AND ITS USE AS A FUNGICIDE |
| DE10347090A1 (en) | 2003-10-10 | 2005-05-04 | Bayer Cropscience Ag | Synergistic fungicidal drug combinations |
| DE10349501A1 (en) | 2003-10-23 | 2005-05-25 | Bayer Cropscience Ag | Synergistic fungicidal drug combinations |
| DE102005026482A1 (en) | 2005-06-09 | 2006-12-14 | Bayer Cropscience Ag | Active substance combination, useful e.g. for combating unwanted phytopathogenic fungus, comprises herbicides e.g. glyphosate and active substances e.g. strobilurin, triazoles, valinamide and carboxamide |
| ATE484194T1 (en) | 2005-06-09 | 2010-10-15 | Bayer Cropscience Ag | ACTIVE INGREDIENTS COMBINATIONS |
| DE102005035300A1 (en) | 2005-07-28 | 2007-02-01 | Bayer Cropscience Ag | Synergistic fungicidal composition containing a carboxamide, azole and optionally strobilurin, for control of e.g. Puccinia or Erysiphe by treatment of plants, seeds or soil |
| DE102006023263A1 (en) | 2006-05-18 | 2007-11-22 | Bayer Cropscience Ag | Synergistic drug combinations |
| DE102007045920B4 (en) | 2007-09-26 | 2018-07-05 | Bayer Intellectual Property Gmbh | Synergistic drug combinations |
| KR20120051015A (en) | 2009-07-16 | 2012-05-21 | 바이엘 크롭사이언스 아게 | Synergistic active substance combinations containing phenyl triazoles |
| EP2910126A1 (en) | 2015-05-05 | 2015-08-26 | Bayer CropScience AG | Active compound combinations having insecticidal properties |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU557755A3 (en) * | 1968-08-19 | 1977-05-05 | Янссен Фармасьютика Н.В. (Фирма) | Method for preparing imidazole derivatives |
| EP0023103A1 (en) * | 1979-07-04 | 1981-01-28 | Pfizer Limited | Antifungal imidazole derivatives, process for their preparation and pharmaceutical compositions thereof |
| DE2946956A1 (en) * | 1979-11-21 | 1981-06-19 | Bayer Ag, 5090 Leverkusen | HYDROXYBUTYL-IMIDAZOLE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DE2946957A1 (en) * | 1979-11-21 | 1981-06-04 | Bayer Ag, 5090 Leverkusen | ANTIMICROBIAL AGENTS |
-
1980
- 1980-11-08 DE DE19803042303 patent/DE3042303A1/en not_active Withdrawn
- 1980-11-10 GB GB8036001A patent/GB2063260A/en not_active Withdrawn
- 1980-11-10 IT IT8050118A patent/IT8050118A0/en unknown
- 1980-11-11 DK DK480780A patent/DK480780A/en unknown
- 1980-11-11 AU AU64264/80A patent/AU6426480A/en not_active Abandoned
- 1980-11-11 IL IL61455A patent/IL61455A0/en unknown
- 1980-11-11 ES ES496713A patent/ES496713A0/en active Granted
- 1980-11-12 BR BR8007389A patent/BR8007389A/en unknown
- 1980-11-12 NL NL8006171A patent/NL8006171A/en not_active Application Discontinuation
- 1980-11-12 PL PL22778780A patent/PL227787A1/xx unknown
- 1980-11-12 FR FR8024030A patent/FR2469404A1/en active Pending
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2535321A1 (en) * | 1982-10-28 | 1984-05-04 | Sandoz Sa | NOVEL ETHANOL DERIVATIVES, THEIR PREPARATION AND THEIR USE AS FUNGICIDES |
| GB2136423A (en) * | 1983-03-04 | 1984-09-19 | Sandoz Ltd | Fungicidal 1h-azole-1-ethanol derivatives |
| TR22432A (en) * | 1983-03-04 | 1987-06-02 | Sandoz Ltd | NEW AZOLE COMPOUNDS, USED AS A YOENTEM AND FUNGICID FOR THEIR PREPARATION |
| AU571490B2 (en) * | 1983-03-04 | 1988-04-21 | Syngenta Participations Ag | Alpha-aryl-alpha(cycloalkyl-alkyl) -1h-azole-1-ethanols |
| US4609668A (en) * | 1983-09-01 | 1986-09-02 | Sandoz Ltd. | Fungicidal α-(alkynylphenyl)azole ethanol compounds |
| TR22423A (en) * | 1983-09-01 | 1987-05-18 | Sandoz Ltd | NEW OC-ARIL 1H-AZOL-1-ETANOLES, A YOENTEM FOR THEIR PREPARATION AND THEIR USE AS FUNGUSITS |
| EP0212605A2 (en) * | 1985-08-29 | 1987-03-04 | Hoechst Aktiengesellschaft | Azolyl-cyclopropyl-ethanol derivatives, processes for their preparation and their use |
| EP0212605A3 (en) * | 1985-08-29 | 1987-08-26 | Hoechst Aktiengesellschaft | Azolyl-cyclopropyl-ethanol derivatives, processes for their preparation and their use |
| US5164513A (en) * | 1987-12-09 | 1992-11-17 | Ss Pharmaceutical Co., Ltd. | Imidazole derivative |
| US4925953A (en) * | 1987-12-09 | 1990-05-15 | Ss Pharmaceutical Co., Ltd. | Imidazole derivative |
| EP0319960A3 (en) * | 1987-12-09 | 1990-12-27 | Ss Pharmaceutical Co., Ltd. | Imidazole derivative |
| US5082948A (en) * | 1987-12-09 | 1992-01-21 | Ss Pharmaceutical Co., Ltd. | Imidazole derivative |
| EP0319960A2 (en) * | 1987-12-09 | 1989-06-14 | Ss Pharmaceutical Co., Ltd. | Imidazole derivative |
| US8658564B2 (en) | 2007-06-06 | 2014-02-25 | Bayer Cropscience Ag | Fungicide active ingredient combinations |
| CN102258033A (en) * | 2011-08-19 | 2011-11-30 | 陕西美邦农药有限公司 | Novel pesticidal composition containing prothioconazole and triazole |
| CN102599171A (en) * | 2012-01-20 | 2012-07-25 | 联保作物科技有限公司 | Sterilizing composition and preparation thereof |
| WO2014095381A1 (en) * | 2012-12-19 | 2014-06-26 | Basf Se | Fungicidal imidazolyl and triazolyl compounds |
| WO2014095548A1 (en) * | 2012-12-19 | 2014-06-26 | Basf Se | Substituted [1,2,4]triazole compounds and their use as fungicides |
| WO2014095672A1 (en) | 2012-12-19 | 2014-06-26 | Basf Se | Substituted [1,2,4]triazole compounds and their use as fungicides |
| CN105164111A (en) * | 2012-12-19 | 2015-12-16 | 巴斯夫欧洲公司 | Substituted [1,2,4]triazole compounds and their use as fungicides |
| US10071971B2 (en) | 2012-12-19 | 2018-09-11 | Basf Se | Substituted [1,2,4]triazole compounds and their use as fungicides |
| CN105164111B (en) * | 2012-12-19 | 2018-11-20 | 巴斯夫欧洲公司 | Replace [1,2,4] triazole and its purposes as fungicide |
| WO2014108288A2 (en) * | 2013-01-08 | 2014-07-17 | Basf Se | Substituted [1,2,4]triazole compounds |
| WO2014108288A3 (en) * | 2013-01-08 | 2014-09-12 | Basf Se | Substituted imidazole and (1,2,4)triazole compounds as fungicides |
| CN105008332A (en) * | 2013-01-08 | 2015-10-28 | 巴斯夫欧洲公司 | Substituted imidazole and (1,2,4)triazole compounds as fungicides |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6426480A (en) | 1981-05-21 |
| NL8006171A (en) | 1981-06-01 |
| IT8050118A0 (en) | 1980-11-10 |
| ES8204423A1 (en) | 1982-05-01 |
| DE3042303A1 (en) | 1981-08-27 |
| IL61455A0 (en) | 1980-12-31 |
| BR8007389A (en) | 1981-05-26 |
| PL227787A1 (en) | 1981-11-13 |
| DK480780A (en) | 1981-05-14 |
| ES496713A0 (en) | 1982-05-01 |
| FR2469404A1 (en) | 1981-05-22 |
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Legal Events
| Date | Code | Title | Description |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |