CA1066188A - Combating fungi with 1-(diaryloxy)-1-imidazol(1')yl-3,3-dimethyl-butan(2)ones and derivatives - Google Patents
Combating fungi with 1-(diaryloxy)-1-imidazol(1')yl-3,3-dimethyl-butan(2)ones and derivativesInfo
- Publication number
- CA1066188A CA1066188A CA240,505A CA240505A CA1066188A CA 1066188 A CA1066188 A CA 1066188A CA 240505 A CA240505 A CA 240505A CA 1066188 A CA1066188 A CA 1066188A
- Authority
- CA
- Canada
- Prior art keywords
- imidazolyl
- phenoxy
- dimethylbutan
- compound
- chlorophenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
COMBATING FUNGI WITH 1- (DIARYLOXY) -1-IMIDAZOL(I')YL-3,3-DIMETHYL-BUTAN(2)ONES AND DERIVATIVES
Abstract of the Disclosure Fungicidal compositions containing, and methods of combating fungi using, 1-(diaryloxy)-1-imidazol(1')yl-3,3-dimethyl-butan(2)ones and derivatives of the formula (I) in which X and Y each independently is halogen, alkyl, alkoxy, haloalkylthio, nitro, amino, alkylamino or dialkylamino, Z is a direct bond, oxygen, sulfur, methylene, sulfonyl, alkoxymethylene or keto, A is -CO-, -CHOH- or -(OH)-, R is alkyl, and a and b each independently is an integer from O to 3.
* * * * * * * * * * * * * * * * * * * * * * * * * *
Abstract of the Disclosure Fungicidal compositions containing, and methods of combating fungi using, 1-(diaryloxy)-1-imidazol(1')yl-3,3-dimethyl-butan(2)ones and derivatives of the formula (I) in which X and Y each independently is halogen, alkyl, alkoxy, haloalkylthio, nitro, amino, alkylamino or dialkylamino, Z is a direct bond, oxygen, sulfur, methylene, sulfonyl, alkoxymethylene or keto, A is -CO-, -CHOH- or -(OH)-, R is alkyl, and a and b each independently is an integer from O to 3.
* * * * * * * * * * * * * * * * * * * * * * * * * *
Description
~o66~s8 The present invention relates to and has for its objects the provision of particular new fungicidal compos-itions containing, and methods of combating fungi using, l-(diaryloxy)-l-imidazoL~ -dimethyl-butan-2-ones and derivatives, which compositions are in the form of mix-tures of such compounds with solid and liquid dispersible carrier vehicles. Oth~r and further objects will become apparent from a study of the within specification and ac-companying examples.
lQ It has been disclosed in German Published Spec-ification DOS 2,201,063 that triazolyl-O,N-acetals such as, for example, l-(p-chlorophenoxy)-1-[1,2,4-triazolyl-(1)~-3,3-dimethylbutan-2-one (Compound A), possess a very good fungicidal activity. Furthermore, it is known from Patent Specification 3,321,366 and German Published Specification DOS 1,795,24~ that tris-phenyl-imidazolyl-(l)-(Compound B) and -1,2,4-triazolyl-(1)-methane (Compound C) exhibit a fungicidal action against phytophathogenic fungi. However, the effect of these compounds is not always entirely satis-factory in some fields of use9 especially if low amounts and low concentrations are used.
It has been iound that compounds which are diaryloxy-imidazolyl-O,N-acetals or ~alts thereof, the diaryloxy-imidazolyl-O,N-acetal~ being oi the generPl formula Le A 16 091 -2- ~
g~
10661~8 ~ z ~3 O-CH-A-C(CH3)3 X Y (I) a b ~ ~
N
in which X and Y each independently is halogen, alkyl, alkoxy, haloalkyl-thio, nitro, amino, alkylamino, or dialkylamino, Z is a direct bond, oxygen, sulfur, methylene, sulfonyl, alkoxymethylene or keto, A is -CO-, -CHOH- or -C(OH)-, R is alkyl, A is an integer from 1 to 3 and may also be O if Z is not a direct bond, and b is an integer from O to 3, exhibit powerful fungi-cidal properties against phytopathogenic fungi, and are thus useful as the active ingredient in fungicidal compositions for plant protection use.
Surprisingly, the diaryloxy-imidazolyl-O,N-acetals to be used according to the invention exhibit a substantially greater fungicidal action than the azole derivatives known in the art, for example tris-phenyl-1,2,4-triazolyl-(l)-methane, tris-phenyl-imidazolyl-(l)-methane and l-(p-chloro-phenoxy)-1-[1,2,4-triazolyl-(1)]-3,3-dimethylbutan-2-one. The very good action against species of Erysiphe, Fusicladium and Uromyces should be singled out for particular mention. The compounds usable according to the invention thus represent an enrichment of the art.
X and Y are preferably fluorine, chlorine or bromine, alkyl with up to 4 carbon atoms, (for example methyl, ethyl, isopropyl and ter-tiary butyl), alkoxy with up to 4, especially with 1 or 2, carbon atoms, (for example methoxy), ,~
;
~066~8B
haloalkylthio with up to 4 carbon atom~ and up to 5 halogen atom~, especially with 1 or 2 carbon atoma and up to 3 identi-cal or di~ierent halogen atoms, preierred halogene being fluorine, and chlorine, (for example triiluoromethylthio), nitro, amlno or alkylamino or dialkylamino with up to 4, especially with 1 or 2, carbon atoms in each alkyl moiety, (~or example ethylamino and dimethylamino). The indices a and b are preierably 0, 1 or 2. When Z i~ alkoxymethylene it is preierably methoxymethylene or etho~ymethylene. When A is a -C(OH)- group, R is preferably methyl or ethyl.
R
If the active compound i~ used in the iorm of a salt, it is usually preferable that the acid forming the salt should be a physiologically tolerated acid. Preierred acids include the hydrogen halide acids, ior example hydro-chloric acid and hydrobromic acid, phosphoric acid, nitricacid, the monofunctional and biiunctional carboxylic acids and the hydroxycarboxylic acids, ior example acetic acid, maleic acid, succinic acid, iumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and 1,5-naphthaleneaisu~fonic acid.
~ he following may be mentioned as example~ of the active compounds to be used according to the invention: 1-[imidazolyl-(1)]-1-[4'-(3"-methylphenyl)-phenoxy]-3,3-di-methylbutan-2-one, l-[imidazolyl-(1)]-1-[4'-(2"-chlorophenyl)-3'-chlorophenoxy)]-3,3-dimethylbutan-2-ones, l-[imidazolyl-(1)]-~ 4'-(2"-bromo-4"-chlorophenyl)-(2'-bromophenoxy)]-3,3-dimethylbutan-2-one, l-[imidazolyl-(1)]-1 -[4'-(4"-nitrophenyl)-(2',6'-dichloropheno~y)]-3,3-dimethylbutan-2-one, l-[imidazo-Le A 16 091 _4_ ~066188 lyl-(l)]-1-[4'-(4"-ethoxyphenyl)-(2'-bro~no-6'-chloropheno~cy)]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(3"-a~ino-phenyl)-(2'-metbylphenoxy)]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(2"-methylphenoxy)-(2'-chlorophenoxy)]-c 3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-~4'-(3"-chloro-phenoxy)-phenoxy]-3,3_dimethylbutan_2_one, l-[lmldazolyl-(l)]-1-[4'-phenoxy-2',6'-dibromophenoxy]-3,3-dimethylbutan-2-one, l-[imidazolyl-(1)]-1-~4'-(3"-nitrophenylthio)-(2'-bromophen-o~y)]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(2"-methoxyphenylthio)-(2'-chlorophenoxy)]-3,3-dimethylbutan-
lQ It has been disclosed in German Published Spec-ification DOS 2,201,063 that triazolyl-O,N-acetals such as, for example, l-(p-chlorophenoxy)-1-[1,2,4-triazolyl-(1)~-3,3-dimethylbutan-2-one (Compound A), possess a very good fungicidal activity. Furthermore, it is known from Patent Specification 3,321,366 and German Published Specification DOS 1,795,24~ that tris-phenyl-imidazolyl-(l)-(Compound B) and -1,2,4-triazolyl-(1)-methane (Compound C) exhibit a fungicidal action against phytophathogenic fungi. However, the effect of these compounds is not always entirely satis-factory in some fields of use9 especially if low amounts and low concentrations are used.
It has been iound that compounds which are diaryloxy-imidazolyl-O,N-acetals or ~alts thereof, the diaryloxy-imidazolyl-O,N-acetal~ being oi the generPl formula Le A 16 091 -2- ~
g~
10661~8 ~ z ~3 O-CH-A-C(CH3)3 X Y (I) a b ~ ~
N
in which X and Y each independently is halogen, alkyl, alkoxy, haloalkyl-thio, nitro, amino, alkylamino, or dialkylamino, Z is a direct bond, oxygen, sulfur, methylene, sulfonyl, alkoxymethylene or keto, A is -CO-, -CHOH- or -C(OH)-, R is alkyl, A is an integer from 1 to 3 and may also be O if Z is not a direct bond, and b is an integer from O to 3, exhibit powerful fungi-cidal properties against phytopathogenic fungi, and are thus useful as the active ingredient in fungicidal compositions for plant protection use.
Surprisingly, the diaryloxy-imidazolyl-O,N-acetals to be used according to the invention exhibit a substantially greater fungicidal action than the azole derivatives known in the art, for example tris-phenyl-1,2,4-triazolyl-(l)-methane, tris-phenyl-imidazolyl-(l)-methane and l-(p-chloro-phenoxy)-1-[1,2,4-triazolyl-(1)]-3,3-dimethylbutan-2-one. The very good action against species of Erysiphe, Fusicladium and Uromyces should be singled out for particular mention. The compounds usable according to the invention thus represent an enrichment of the art.
X and Y are preferably fluorine, chlorine or bromine, alkyl with up to 4 carbon atoms, (for example methyl, ethyl, isopropyl and ter-tiary butyl), alkoxy with up to 4, especially with 1 or 2, carbon atoms, (for example methoxy), ,~
;
~066~8B
haloalkylthio with up to 4 carbon atom~ and up to 5 halogen atom~, especially with 1 or 2 carbon atoma and up to 3 identi-cal or di~ierent halogen atoms, preierred halogene being fluorine, and chlorine, (for example triiluoromethylthio), nitro, amlno or alkylamino or dialkylamino with up to 4, especially with 1 or 2, carbon atoms in each alkyl moiety, (~or example ethylamino and dimethylamino). The indices a and b are preierably 0, 1 or 2. When Z i~ alkoxymethylene it is preierably methoxymethylene or etho~ymethylene. When A is a -C(OH)- group, R is preferably methyl or ethyl.
R
If the active compound i~ used in the iorm of a salt, it is usually preferable that the acid forming the salt should be a physiologically tolerated acid. Preierred acids include the hydrogen halide acids, ior example hydro-chloric acid and hydrobromic acid, phosphoric acid, nitricacid, the monofunctional and biiunctional carboxylic acids and the hydroxycarboxylic acids, ior example acetic acid, maleic acid, succinic acid, iumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and 1,5-naphthaleneaisu~fonic acid.
~ he following may be mentioned as example~ of the active compounds to be used according to the invention: 1-[imidazolyl-(1)]-1-[4'-(3"-methylphenyl)-phenoxy]-3,3-di-methylbutan-2-one, l-[imidazolyl-(1)]-1-[4'-(2"-chlorophenyl)-3'-chlorophenoxy)]-3,3-dimethylbutan-2-ones, l-[imidazolyl-(1)]-~ 4'-(2"-bromo-4"-chlorophenyl)-(2'-bromophenoxy)]-3,3-dimethylbutan-2-one, l-[imidazolyl-(1)]-1 -[4'-(4"-nitrophenyl)-(2',6'-dichloropheno~y)]-3,3-dimethylbutan-2-one, l-[imidazo-Le A 16 091 _4_ ~066188 lyl-(l)]-1-[4'-(4"-ethoxyphenyl)-(2'-bro~no-6'-chloropheno~cy)]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(3"-a~ino-phenyl)-(2'-metbylphenoxy)]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(2"-methylphenoxy)-(2'-chlorophenoxy)]-c 3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-~4'-(3"-chloro-phenoxy)-phenoxy]-3,3_dimethylbutan_2_one, l-[lmldazolyl-(l)]-1-[4'-phenoxy-2',6'-dibromophenoxy]-3,3-dimethylbutan-2-one, l-[imidazolyl-(1)]-1-~4'-(3"-nitrophenylthio)-(2'-bromophen-o~y)]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(2"-methoxyphenylthio)-(2'-chlorophenoxy)]-3,3-dimethylbutan-
2-one, 1-[imidazolyl-(1)}-1-[4~4"bromophenylthio)-(3'-chloro-pheno~y)]-3,3-dimethylbutan-2-one, l-[imidazolyl-(1)]-1-[4'-(2"-chlorophenylsul fonyl )-phenoxy]-3,3-diEnethylbutan-2-one, l-[imidazolyl-(1)]-1-[4'-(4"-ethylphenylsulfonyl )-(2',6'-dichlorophenoxy)]-3,3-dimethylbutan-2-one, l-[imidazolyl-(1)~-1-[4'-(2"-ch~orophenylcarbonyl)_(2'-bromophenoxy)]_
3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(2",6"-dichlorophenylcarbonyl)-(2'-chlorophenoxy)]-3,3-dimethyl-butan-2-one, 1-[imidazolyl-(1)]-1-[4'-(2"-nitrophenylcarbonyl)-phenoxy]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(4"-bromobenzyl)-(3'-bromophenoxy)]-3,3-dimethylbutan-2-one, l-[imidazolyl-(l)J~ 4'-(4"-trifluoromethylthiobenzyl)-(2',3'-dichlorophenoxy)]-3,3-dimethylbutan-2-one, l-[imidazolyl-(1)]-1-[4'-(3",5"-dichlorobenzyl)-(2'-methylphenoxy)]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(4"-tert.-butylbenzyl)-phenoxy]-3,3-dimethylbutan-2-one and l-[imidaz-olyl-(l)]-l-[4'-(2"-ethylaminobenzyl)-(2'-nitrophenoxy~]-3,3-dimethylbutan-2-one, and their salts with the acids specified above.
Le A 16 091 ~066188 Active compounds to be used according to the invention are prepared in German Application P 24 29 514.5, filed 3une 20, 1974 and laid open for inspection in December 1975.
Those compounds to be used according to the present invention in which, in formula I, A is a carbonyl group, can be prepared according to a method described in our Canadian Patent Application Serial No. 240,533, filed November 26, 1975; the method is given below as (a). Methods (b) and (c) below are applicable respectively to compounds in which A is a -CH(OH)-group and to compounds in which A is a -~(OH)-group.
(a) A haloether-ketone is reacted with an imidazole, for example in equimolar amounts, if appropriate in the presence of an inorganic acid-binding agent, for example potassium carbonate, or in the presence of an organic acid-binding agent, for example triethylamine or excess imidazole, and in the presence of a polar solvent, for example acetonitrile, at tem-peratures of 20 to 150C; the resulting reaction mixture is evaporated in vacuo; the residue is taken up with an organic solvent, for example methy-lene chloride; the solution is extracted by shaking with water; and the organic phase is distilled in vacuo. The oil which remains after the sol-vent has passed over is purified according to customary methods (see Example 7C hereinbelow).
106618t3 (b) A compound obtained according to method (a), i~
reduced, for example by a generally c~,tomary method. The reduction ca.n be e~fected for example (1) with hydrogen in the presence of a catalyst, for example Raney nickel, and a polar solvent, ~or example methanol, at 20-~0C; or (2) with aluminum isopropylate in the presence o~ an inert solvent at 20-120C, with subsequent hydroly~i~; or (3) with a complex hydride (for example sodium borohydride or lithium alanate) in thepresence of a polar solvent, ~or example methanol, at l.0 0-30C, followed by hydrolysis, ~or example with hydrochloric acid; or (4) with formamidinesulfinic acid and alkali metal hydroxide, ~or example sodium hydroxide, in aqueous solution at 20-100C in the presence of a polar solvent, for example ethanol.
(c) A compound obtained according to method (a) is subjected to reductive alkylation, especially by means of a Grignard reagent, such as an alkyl-magne~ium halide (pre-ferably an iodide or bromide), for example with methyl-magnesium iodide in anhydrous diethyl ether at 20-80C, and the product is hydrolyzed, ~or example with aqueous ammonium chloride solution. The compounds of the ~ormula I, thus obtained, may be isolated according to customary methods and purified if appropriate (see Example 9A hereinbelow).
The salts o~ the compounds oi the formula I can be 2~ obtained in a simple ma~ner in accordance with customary methods of forming salts, ~or example by dissolving the ba~e in ether;
for example diethyl ether, and adding the acid, ~or example hydrogen chloride, and they can be isolated in a known manner, ~or example by filtering o~P, and can be purified if desired (see Example 9B hereinbelow).
Le A 16 091 -7-The haloether-ketones to be used as 8tarting materials have not previously been disclosed but can be pre-pared according to processes whlch have been known for a long time, for example by reacting the corresponding phenol derivative with a haloketone (the so-called "Williamson ether synthesi~"). The active hydrogen atom which still remains i~ then replaced by halogen in the usual manner (see Example 7A an~ ~ he~einbelow).
~he fungicidal active compounds according to the in-vention have a very broad spectrum of action and can be used against parasitic fungi which infect above-ground part~ of plants or attack the plants through the soil, and also Qgainst seed-borne pathogens.
Fungitoxic agEnts are employed in plant protection for 1~ combating fungi from very diverse classes of fungi, such as Archim.ycetes, PhYcom.vcetes, Ascomvcetes, LasidiomYcetes and un~i ImPerfecti .
As has in part already been mentioned, the active com-pounds to be used according to the invention display a 20 particularly good activ$ty against parasitic fungi on above-ground parts of plants, such as species o~ Er~siphe and species of Venturia, as well as against epecie~ o~ ricularia and species of Pellicularia. Good eiiecte are achieved ag~inst the pathogens o~ apple scab (Fusiclad$um dendriticum), of 25 powdsry mildew oi cereals (~E_siPhe ~raminis) and of bean rust (Uromyces Phaseoli). A point to be singled out particularly is that these active compounds not only display a protective action but are also curatively active, that iB to say active on application after con.tamination with the ~pores of the 30 fungus. Furthermore, the systemic action of the compounds Le A 16 091 should be pointed out. Thus it proves possible to protect plants against fungal iniection if the active compound is ~upplied to the above-ground parts of the plant ~ia the ~oil and the root. As plant protection agents, these compounds can be used for the treatment of soil, ior the treatment o*
seed and ior the treatment oi above-ground parts oi plants.
The active compounds to be used according to the invention are well tolerated by plants. ~hey have only a low toxicity to warm-blooded animals and because of their low oaor and their good toleration by human skin they are not unpleasant to handle.
The active compound~ to be u~ed according to the present invention can be converted into the usual iormulations, such as solutions, emulsions, ~uspensions, powders, pastes and granulates. These may be produced in known manner, ior example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of suriace-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-iorming agents. In the case oi the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
AB liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydro-carbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or parafiins, for example mineral oil iraction~, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such a9 acetone, methyl ethyl ketone, methyl i80-Le A 16 091 -9-~3i66~88 butyl ketone or cyclohexanone, or ~trongly polar solYent8, such as dimethyl formamide, dimethyl ~ulphoxide or aceto-nitrile, as well as water.
Ly liquefied gaseou~ diluent~ or carriers are meant liquid~ which wolld be ga~eous at normal temperature~ and pressure~, e.g. aero~ol propell~nt~, 9uch as halogenated hydrocarbons, e.g. ~reon.
The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesti-cide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following ~ay be chiefly conside~ed for use as conventional carrier vehicles for Le A 16 091 -10-this purpose: aerosol propellants which are gas ous at normal temperatures and pressures, such as Freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chloro-benzenes, etc.), cycloalkanes, (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters ~ad~ ~har~l~
Le A 16 091 -11-10661~8 of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.
Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or li~uid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as ot'ner fungicides, or insecticides, acaricides, nematocides, bactericides, ro-denticides, herbicides, fertilizers, growth-regulating agents, bird repellents, plant nutrients, agents for improving soil stnlcture, etc., if desired or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.
As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95% by weight, and preferablyO.5-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10%, preferably 0.01-1%, by we~ght of Le A 16 091 -12-~066188 the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water, preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-95%, and preferably 0.01-95%, by weight of the mixture.
The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compos-itions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound.
Le A 16 091 -13-~066~
When u~ed Be lea~ ~ungicides, the concentratione o~
active compound in compositione used ~or application can be varied within a ~ubstantial range. They are in general from 0.1 to 0.00001 per cent by weight, pre~erably 0.05 to 0.0001~.
In the treatment o~ ~eed, amount~ oi active compound of 0.001 to 50 g per kilogram o~ ~eed, preferably 0.01 to 10 g, are in general applied to the ~eed.
For the treatment of 90il, amounts o~ active compound of 1 to 1,000 g per cubic meter of 80il, preferably of 10 to 200 g, are generally applied to the ~oil.
At somewhat higher concentrations, the active compounds alao po~sess plant growth-regulating properties.
Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. fungi, which comprises applying to at least one of correspondingly (a) such fungi, and (b) the corresponding habitat thereof, i.e. the locus to be protected, e.g. to à
growing crop, to an area where a crop is to be grown or to a domestic animal, a correspondingly combative or toxic amount, i.e. a fungicidally effective amount, of the part-icular active compound of the invention alone or together with a carrier vehicle as noted above. The instant form-ulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dry dressing, moist dressing, wet dressing, slurry dressing encrusting and the like.
Le A 16 091 -14-It will be realized, of course, that the concen-tration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concen-tration ranges.
The unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:
Example 1.
Mycelium growth test Nutrient medium used:
20 parts by weight of agar-agar 200 part~ by weight oi potato decoction 5 parts by weight of malt 15 part~ by weight of dextrose 5 parts by weight of peptone 2 parts by weight of disodium hydrogen phosphate 0-3 part by weight of calcium nitrate Proportion of solvent mixture to nutrient medium:
2 parts by weight of solvent mi~ture 100 parts by weight o~ agar nutrient medium Composition o~ solvent mixture 0.19 part by weight o~ dimethyl~ormamide or acetone 0.01 part by weight of emulsi~ier (alkylaryl polyglycol ether) 1.80 parts bY weiRht oi water 2 parts by weight oi solvent mixture Le A 16 091 -15-106611~8 The amount o~ active compound required ~or the desired concentration of active compound in the nutrient medium was mixed with the stated amount of solvent mixture. The concentrate was thoroughly mixed, in the ~tated proportion, with the liquid nutrient medium which had been cooled to 42C and was then poured into Petri dishes of 9 cm di-ameter. Control plates to which the preparation had not been added were also set up.
When the nutrient medium had cooled and solidified, the plateæ were inoculated with the species of ~ungi stated in Table 1 and incubated at about 21C.
Evaluation wa~ carried out after 4 - 10 days, dependent upon the speed of growth of the fungi. When evaluation was carried out the radial growth of the mycelium on the treated nutrient media was compared with the growth on the control nutrient media. In the evaluation of the iungu8 growth, the iollowing characteristic values are used:
1 no fungus growth up to 3 very strong inhibition oi growth up to 5 medium inhibition of growth up to 7 slight inhibition o~ growth 9 growth equal to that of the untreated control.
The active compounds, the active compound concen-trations and results can be ~een from the table which follows:
Le A 16 091 -16-1066~88 aBzLIo SBUO-mOl~UB
BFlB¦noF~ 1~ ,1 ,~
SF~Bn ~aBUi s~'m~ua~
~-IO~
Blo~lsnT~
a~a~d so OA~ 1 mnau ~nF.IOdSOII~U~ H o~
sue~selaul~
o~dol~li~ ~ ~1 ~1 a~z~o ~FI~ln~FlFa c~
lIln I~BOqlB
umFIIF~F~a~ ~ ~ u~
salaulo sl.-~A'I~og ~ N
~i~qBAlW
snloqFI~~ o~ N ~-J
IU~IOS
~oZF~
mnu~
~n~7;:)FI~o~allo~ o~
el'eJLFU~ IBS~ 0 OF~oï-al~s BFUF~O'Iel~s ~ L~
mn.Iom [no ~nF-Issn,~
~dd ' punod -~o~ a~F~s ~o UoF~Bl~uaouo~ ~11 ;o~ uf ~ u ~~~
Le A 16 091 -17-1066~
aBzAlo s~uo~ol~usX
1~
Bl:l~ ~1 ,~ .
a~u ~Fm ~U3 ~tllO
~a ool~nm a~dso~ ,, umaulm~
u~nl~odSol~uFwl~H ,~
suaosalaulo elo~dol~F~a ,1 ,, a~zA:~Io ~, ~FI'eln~FIFa U~
~TT~
~alaul~ ~F~ ~
snu~aq~
snloqoFl~ob mnm~.-~ln ~nF~l'a . ' ~u~los - ~FUo~oozl~N ~ ~1 mnu~a,~,~oa mn~oFI~o~allo;
a~ Fu ~n}~I~sn,~
mn.IoF~o~alos ~FuF~
nlo~no m~ ~sn,a 31 ~ N 11 ~ ~ 'punodmoo al~F~ ,~
+~ o uoF~ uaouo"
o~ z;~ Z51 .IP~ ~ =o l Le A 16 091 -18-1066~88 OBZA~O SBUOmO~T~UBX
~ F~BB~B
BFI~In~llaa 8 'FIBn ~ aBU~ sFIn ~uë,ll.
lI~n.IO~OBO
BlO~ dO~ a B~OO~Bn~l alas~dsoo~
mnau~ms Od~o~uF~l aH N
6ua~sa~Iaulo BlOl~olsF~a aBZLIO
sF~ n~F~F
lIml~BOqlB
~nn~ F~al~
~alauFo Eil~ SF~o~
SnU-BaqB~I~
snl-oqoFI~oo~ ~1 ~n~F~In mnF~A;a I~BIOS
BFUo~oOZF~
mnusa,~,~E
mn~o~l~o~allo~
els~Fu mnFIssn,~
mnlo-~o,Ialos BFUF~OIalo$ u~
mn.IoT~no mnFIssn,~ u~
d~ n ' punotI~oo a~F~os l ,~o UoF~B~uaouo~
o ~lo ~
Le A 16 091 1~)66~88 Exam~le 2 Shoot treatment test/powdery mildew of cereal/protective (leaf-destru~tive mycosi~) To produce a suitable preparation of active compound, 0.25 g part by weight o~ active compound was taken up in ?5 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether emulsifier and 975 parts by weight of water were added. The concentrate was diluted with water to the desired final concentration of the spray liquor.
To test for protective activity, ~ingle-leaved young barley plants of the Amsel variety were sprayed with the preparation of active compound until dew-moist. After drying, the barley plants were dusted with spores of Ervsi~he r~minis var. hordei.
After 6 days' dwell time of the plants at a temperature of 21-22C and 80-90~o atmospheric humidity the occurrence of mildew pustules on the plants was evaluated. ~he degree of ~fection is expressed as a percentage of the infection of the untreated control plants. 0% denotes no infection and lOO~o denotes the same degree of infection as in the case of the untreated control. The more active the compound, the lower is the degree of mildew infection.
~he active compounds, active compound concentrations in the spray liquor and degrees of infection can be seen from thetable which follows.
Le A 16 091 20 1066181E~
Table 2 Shoot treatment test/powdery mildew o~ cereal/
protective Active Active com- In~ection compounds pound concen- .n % f in % bg weight treated .
untreated - 100 0.01 50.0 .N~ ((kcn)wn) 0.001 68.8 N ~
Cl ~ 0-ICH-C0-C(CH3)~ 0 001 317 5 L~ (14) Cl Br ~ 0-CIH-CO-C(CH~)~ 0.01 16.
~N (7) 0 ~ 0-ICH-C0-C(CH3)~ 0.01 16.3 . (8a) 0-CH-C0-C(CH~)~ 6.3 ~`11 (10) Le A 16 091 -21-106618~3 Table 2 (continued) Shoot treatment te~t/powdery mildew of cereal/
protective Active Acti~e com- Infection compound~ pound con- in % of the centration in untreated the spray liquor control in ~ by weight H ~ 3 0-CH-CH-CtCH~), OCH~ N OH 0.01 0.0 0.00132.5 ~ 13) Cl Cl ~ O-CH-CO-C(CH~)~
N 0,01 0.0 ~ ~ (4) 0-00133.8 am~le 3 Erysiphe test/~ystemic Solvent: 4,7 part~ by weight of acetone Dispersing agent: 0.3 part by weight of alkylaryl polyglycol 15ether Water: 95 parts by weight The amount of active compound required to give the desired concentration Or active compound in the watering liquid wa~ mixed with the stated amount of solvent and the concentrate wa~ diluted with the stated amount of water which contained the stated additi~es.
Cucumber plants grown in standard 80il, in the 1-2 leaf ~tage, were watered three times within one week with 10 ml of the watering liquid, o~ the stated concentration of actiYe compound, per 100 cc Or ~oil.
The plants treated in this way were inoculated, after treatment, with conidia of the rungus Erlvci~he cichoracearum.
Le A 16 091 -22-The plants were then get up in a greenhouga at 2~-24C and 70% relative atmospheric humidity After 12 days, the infection of the cucumber plants was determined as a per-centage of the untreated, but also inoculated, control plants.
0~0 denotes no infection and 100% denotes that the infection was exactly as great as in the case of the control plants.
The active compounds, active compound concentrations and re~ult~ can be seen from the table which follows.
Table 3 Erysiphe test/systemic Active Infection in ~ of the compound infection of the un-treated control at an active compound con-centration of 100 ppm 25 ppm 1~1 100 ~3c,~
.N~
L~ (known) (B) Cl ~ 0-1CH-C0-C(CH~)~ 25 ~ ~ (14) _xamPle 4 Fusicladium test (apple scab) (Protective) Solvent: 4.7 parts by weight of acetone Emulsiiier:0.~ part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount oi active compound required ior the Le A 16 091 -23-~06618~
desired concentration oi the active compound in the spray liquid wa~ mixed with the gtated amount of solvent, and the concentrate wa~ diluted with the 8tated amount oi water which contained the stated additions.
Young apple seedling~ in the 4-6 leaf stage were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20C and àt a relative atmospheric humidity of 70~0. They were then inoculated with an aqueous conidium suspension of the apple scab causative organism (Fusicladium dendriticum) and incubated for 18 hour~ in a humidity chamber at 18-20C
and at a relative atmospheric humidity of 100%.
The plants then again were put in the greenhouse for 14 days, 15 day3 after inoculation, the infection of the seed-lings was determined as a percentage oi the untreated but also inoculated control plants.
O~o means no infection; 100% means that the infection was exactly as great as in the case of the control plants.
The active compound~, the concentrations of the active compounds and the results can be seen from the ~ollowing table:
Table4 ~usicladium test/protective Active compound Infection in % of the iniection oi the un-treated control at an active compound con-centration (in ~o) of 0.002~
. ~
C ~ (known) 66 ~ (B) Le A 16 091 -24-1066~88 ~able 4(continued) Fu~icladium test/protective Active compound Infection in % of the infection of the un-treated control at an : active compound con-centration (in Yo) of 0.0025 Cl ~ 0-CH-C0-C(CH~)~ 35 ~ (14) NO2 ~ 0-~H-C0-C(CH~)~
~ ~ . HCl 29 ~xample 5 Fusicladium test (apple scab) [Curative]
Solvent: 4.7 parts by weight of acetone Emulsifier: 0.~ part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the ~tated additions.
Young apple seedling~ in the 4-6 leaf stage were in-oculated with an aqueous conidium suspen~ion of the apple ~cab cau~ati~e organi~m (Fusicladium dendriticum ) and incubated for 18 hour3 in a humidity chamber at 18-20C
and at a relative atmospheric humidity o~ lOO~o. The plants then were wt in a greenhouse and were allowed to dry.
After standing for-a suitable period of time, the plants were sprayed dripping wet with the spray liquid prepared in Le A 16 091 -25-~06618~3 the manner described above. The plants then again were put ;n the ~reenhouse.
15 days after inoculation, the infection of the ap~e ~eedlings wa~ determined a~ a percentage o~ the un-treated but also inoculated control plant~.
O~o means no infection; 100% means that the infection was exactly as great as in the case of the control plantæ.
The active compounds, the concentrations of the active compounds, the period of time between inoculation and ~praying ~lnd the results obtained can be seen from the following table:
Table S
Fu~icladium test/curative Active Dwell Infection in % of the compound time in infection of the un-hours treated control at an active compound 42 concentration (in ~) of -?~ 0.0062 _ ~' ~C~3 100 ~=) N (known) - ~ ~ (B) C1 ~ 0-CH-C0-C(CH~)~ _ 21 - L~ (14) Example _6 Uromyces test (bean rus~/ protective Solvent: 4.7 part~ by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight Le A 16 091 -26-~066188 The amount oi active compound required ior the deelred concentratlon of active compound in the spray liquor was mixed with the stated ~mount oi the solvent and the con-centrate was diluted with the stated amount of water which contained the stated additives.
The y~ung bean plant~, which were in the 2-leaf stage, were sprayed with the spray liquor until dripping wet. The plants remained in a greenhouse for 24 hours at 20-22C and a relative atmospheric humidity of 70% in order to dry. They were then inoculated with an aqueous uredospore suspension of the causative organi~m of bean rust (Uro~vces R aseoli ) and lncubated rOr 24 hour~ in a dark humidlty chamber at 20-22C and 100% relative atmospheric humidity.
The plants were then set up in a greenhouse under intensive illumination for 9 days at 20-22C and a relative atmospheric humidity of 70-80%.
10 days after the inoculation, the infection of the plants was determined in ~ of the untreated but also in-oculated control plants.
0~O denote~ no infection and 100% denotes that the infection was just as high as in the case of the c~ntrol plants.
The active compounds, active compound concentrations and results can be seen from the table which follows:
~able 6 Uromyces test/protective Active compound Infection in % of the in-fection of the untreated control at an active compound concentration (in%) of 0.00156 Cl ~ 0-CH-C0-C(CH~)~ 91 ~ ~ (known) (A) Le A 16 091 -27-Table 6 (continued) Uromyce~ te~t/protective Active compound Infection in % of the in~ection of the untreated control at an active com-pound concentration (in ~o) _ _ _ 0.001~6 Cl ~ O-CH-CO-C(CH3 )3 10 ~ ~ (14) Cl ~ O-cH-lcH-c(cH~ )3 34 ,N~ OH
~ I (11) CH~ ~ O-ICH-CO-C(CH~)~ 70 ~ ~ (6) Br ~ O-CH-CO-C(CH~)~
L~
SO~ ~ O-CH-CH-C(CH~)I 75 ~N~ OH
(2) CH2 ~ 0-CH-ICH-C(CH~)~ 70 N~ OH
~ 1 (12) Cl Br ~ O-CH-CO-C(CH~ )3 70 Cl ~ (5) .
Le A 16 091 -28-: 1066188 ~able 6 (continued) Uromyces test/protective Active compound Iniection in ~ o~ the inrection of the un-tre~ted control at an active compound concen-tration ~in %) Or 0.00156 o~ o-cH-co-C(CH~), ~ ~ (8) Cl Cl ~ 0-CH-C0-C(CH~)~ 0 ~ ~ (4) Exam~le 7 ~ S2 ~ 0-CH2-C0-C(C~ ) S2 ~ 0-fH-C0-C(CH3)3 Br ~ S2 ~ f-cH-co-c(cH3)3 ~1 (1) N
(preparation according to method (a)) 44 g (0.107 mole)of 1-bromo-1-(4'-phenylsulfn~1~
phenoxy)- 3,3-dimethylbutan-2-one in 500 ml o~ absolute acetonitrile were heated with 34 g (0.5 mole)of imidazole ior 26 hour~ under re~lux. The solvent wa~ then distilled Oir in a water pump vacuum and the residue wa~ taken up in Le A 16 091 -29-100 ml of water, The re~ulting precipitate was wa~hed with twice 100 ml of water and recrystallized irom benzene. 26 g (66~ of theory) of 1-[lmidazolyl-(1)]-1-[4'-(phenylsul fonyl)-phenoxy]-3,~-dimethylbutan-2-one of melting point 146C were obtained, Intermediate product:
S2 ~ 0-fH-C0-C(CH3)3 Br 49 g of bromine were added dropwise at room temperature to 99.6g(0.3 mol~ ~f 1-(4~-phenyl~ulfonyl-phen-oxy)-3,~-dimethylbutan-2-one suspended in 600 ml of c~rbon tetrachloride. After the mixture had lo~t its cOlcr, the resulting precipitate wa~ filtered off, washed with petroleum ether and recrystallized ~rom benzene, 89 g (72~o of theory) of l-bromo-1-(4'-phenyl~ulfonyl--phenoxy)-3,3-dimethylbutan-2-one of melting point 157-162C were obtained.
Starting material:
~ S2 ~ 0-CH2-C0-C(CH3)3 280 g (2 moles) of powdered pota~ium hydroxide were ~uspended in 2 liters of methyl ethyl ketone. 467 g (2 moles)of 4-phenylsulfonyl -phenol were added and the mixture wa~ heated to the boil, Thereafter 269 g (2 moles) of ~-chloropinacolone were added dropwi~e over the course of 1 hour and the mixture was heated for 15 hour~ under reflux, After cooling, the ~olid re~idue was filtered ~f, washed and recry~ta~iæed from ligroin. 687 g (85% of theory) of 1-(4'-phenyl~ulfonyl -phenoxy)-3,3-dimethylbutan-2-one o~
melting point 105-108C were obtained, Le A 16 091 -30-. _ ~
~066~8 ~xamPle 8 2~ 0-TH-~H-C(CH3)3 ~ (2) (preparation according to method (b)(3)) 1.6 g to.o42 mol~ of sodium borohydride were added in portions to 11 g (0.028 mol~ of 1-[imidazolyl-(1)]-1-[4'-(phenylsulfonyl) -phenoxy~-3,3-dimethylbutan-2-one suspended in 100 ml of methanol, at a temperature of -5C. The re-~ction mixture was stirred for 17 hours at room temperature, 6.5 m] of concentrated hydrochloric acid were then added and the mixture was again stirred ior 17 hour~ at room temperature.
It was then extracted by shaking with three times 200 ml oi methylene chloride. The combined organic phases were drl~d over sodium sulfate. The solvent was di~tilled ofi in a water pump vacuum. 50 ml oi n-pentane was added to the residue and the crystals were iiltered off. 10 g (90~o bi theory) oi l-[imidazolyl-(1)]-1-[4'-(phenylsul-fonyl) -phenoxy]-3,3-dimethylbutan-2-ol of melting point 198C were obtained.
ExamPle 9 fH3 (A) Cl ~ ~ o-fH- ,C_c ( CH3)3 ~' l 20(preparation according to method (c)) 2.4 g (0.1 mol~ of magnesium filings were suspended in 30 ml oi ether. A solution oi 14.2 g (0.1 mol~ o~ methyl Le A 16 091 -31-10661~8 iodide in 50 ml o~ absolute ether was added drapwise thereto.
After 2 hours, a solution o~ 18.4 g (0.05 mol) of 1-[4'-(4"-chlorophenyl)-phenoxy]~ midazolyl~ -3~3-dimethylbutan-2-one in 100 ml of absolute tetrahydrofurane was added drop-wise at 10C and the mixture was stirred for a further 15 hours at room temperature. Thereafter, the reaction mixture was stirred, at oC, into a solution of 10 g of ammonium chloride in 500 ml of water and the mixture was left to stand overnight. The ether phase was separated off, washed with twice 100 ml of water and dried over sodium sulfate, and the solvent was distilled off in a water pump vacuum. An oil remained, which crystallized on trituration with hot petroleum ether. It was recrystall~ ed ~rom 40 ml of ethyl acetate. 16.6 g (86% o~ theory) of 1-[4'-(4"-chlorophenyl)-phenoxy]-1-[imidazolyl-(1)]-2-methyl-3,3-dimethylbutan-2-ol of melting point 177C were obtained.
(B) ~ 0-CH-C-C(CH~)~
L ~ OH . HCl (3a) (preparation oi a salt1 5 g (0.013 mol~ of 1-[4'-(4"-chlorophenyl)-phenoxy]-l-[imidazolyl-(1)]-2-methyl-3,3-dimethylbutan-2-ol were dissolved in 25 ml of acetone and 25 ml of methylene chloride.
20 ml of ethereal hydrochloric acid were added thereto, the solvent was distilled off in a water pump vacuum and the residue was boiled up with acetone. 4.7 g (86~ of theory) oi 1=~4'-(4"-chlorophenyl)-phenoxy]-1-[imidazolyl-(1)]-2-methyl-3,3-dimethylbutan-2-ol hydrochloride of melting point 220-224C (decomposition) were obtained.
Le A 16 091 -32-~066188 The following compounds of the general formula Z - ~ 0-~H-A-C(CH3)3 X~ Yb ~ N
were obtained analogously to ~xample~ 7 to 9:
Le A 16 091 ~066~88 -o`
h~
O O
~:
L~
L O ~ ~ ~a L~ ~ ~L~ L~) L~ ~ ~ D ,D ~ ~ p 5 Ll) L~
h ~1 O
h U
C) L~ _ _ -- ~ O ~ ~ ~
O h _ _ _ ~_ _ _ _ P~ a) O g ~ N ~ 0 Ir~ O Lr~ N
t--~I 0 1~ J ~_1 o ~ I ~ t-- 0 U~ ~1 0 0 ~1 ~ 0 1~ t-- 0 U~
r-- ~ o ¢ 8 ~ c~ ~) ~~ ~O~ ~o) ~c r~
~ ~ I v,,,,, ,o ~ JO ~U O O O O O O O O O O O
rl ~
c~
P~ I I I ~
~J N~D I h ~ I I I I I I I I I I I
N m .~ ~ 1 o ~1 o o ~1 o ~ ,~ o o v v m~ ~ m~
Le A 16 091 -34-1066~88 bD I
h O
~
h O O
~ Y
h O
P~ h ~d O
.
~ V
~ ~ m ~ . _ ~ ' ~
_ C~ ~
C) cd O O '' _ ~
-~ ~ ~ o~ P~
a~ ~ 0~ ~ o o ~ P:
.~ O ~ O ~ ~
0~ ~ C) o------a~
c~ o ~d a) o ~ o ~ ~ o ~ ~ ~ ~ U~
.,, o--_I o,1 a) ,~ ~1 O h~I t ~ 0 r- I I
IO ~ I I I ~ 0 co~,1a~ ~ o o ¢ 8 8 8 8 u 8 ~ o o o o o o o o ~ l l l l l l l l ~,~ ~
o Le A 16 091 35 1(~661~8 Other compounds which can be similarly prepared from appropriate starting materials and thereafter converted to salts, if desired, include:
Table 8 Compound X a Y b ` Z A
No.
2~4-di-cH3 2 2-F 1 _ -C(C2H5)(0H) 16 3-C3H7-i 1 2-oCH3 1 -S- -CO-17 4-NH(C2H5) 1 3-SCF3 1 -O- -CO-18 4-SCC12F ( 3)2 -CO-It will be appreciated that the instant specification and examples are set forth by way of illustrat~ n and not limitation, and that various difications and changes may be made without departing from the spirit and scope of the present inventionO
Le A 16 091
Le A 16 091 ~066188 Active compounds to be used according to the invention are prepared in German Application P 24 29 514.5, filed 3une 20, 1974 and laid open for inspection in December 1975.
Those compounds to be used according to the present invention in which, in formula I, A is a carbonyl group, can be prepared according to a method described in our Canadian Patent Application Serial No. 240,533, filed November 26, 1975; the method is given below as (a). Methods (b) and (c) below are applicable respectively to compounds in which A is a -CH(OH)-group and to compounds in which A is a -~(OH)-group.
(a) A haloether-ketone is reacted with an imidazole, for example in equimolar amounts, if appropriate in the presence of an inorganic acid-binding agent, for example potassium carbonate, or in the presence of an organic acid-binding agent, for example triethylamine or excess imidazole, and in the presence of a polar solvent, for example acetonitrile, at tem-peratures of 20 to 150C; the resulting reaction mixture is evaporated in vacuo; the residue is taken up with an organic solvent, for example methy-lene chloride; the solution is extracted by shaking with water; and the organic phase is distilled in vacuo. The oil which remains after the sol-vent has passed over is purified according to customary methods (see Example 7C hereinbelow).
106618t3 (b) A compound obtained according to method (a), i~
reduced, for example by a generally c~,tomary method. The reduction ca.n be e~fected for example (1) with hydrogen in the presence of a catalyst, for example Raney nickel, and a polar solvent, ~or example methanol, at 20-~0C; or (2) with aluminum isopropylate in the presence o~ an inert solvent at 20-120C, with subsequent hydroly~i~; or (3) with a complex hydride (for example sodium borohydride or lithium alanate) in thepresence of a polar solvent, ~or example methanol, at l.0 0-30C, followed by hydrolysis, ~or example with hydrochloric acid; or (4) with formamidinesulfinic acid and alkali metal hydroxide, ~or example sodium hydroxide, in aqueous solution at 20-100C in the presence of a polar solvent, for example ethanol.
(c) A compound obtained according to method (a) is subjected to reductive alkylation, especially by means of a Grignard reagent, such as an alkyl-magne~ium halide (pre-ferably an iodide or bromide), for example with methyl-magnesium iodide in anhydrous diethyl ether at 20-80C, and the product is hydrolyzed, ~or example with aqueous ammonium chloride solution. The compounds of the ~ormula I, thus obtained, may be isolated according to customary methods and purified if appropriate (see Example 9A hereinbelow).
The salts o~ the compounds oi the formula I can be 2~ obtained in a simple ma~ner in accordance with customary methods of forming salts, ~or example by dissolving the ba~e in ether;
for example diethyl ether, and adding the acid, ~or example hydrogen chloride, and they can be isolated in a known manner, ~or example by filtering o~P, and can be purified if desired (see Example 9B hereinbelow).
Le A 16 091 -7-The haloether-ketones to be used as 8tarting materials have not previously been disclosed but can be pre-pared according to processes whlch have been known for a long time, for example by reacting the corresponding phenol derivative with a haloketone (the so-called "Williamson ether synthesi~"). The active hydrogen atom which still remains i~ then replaced by halogen in the usual manner (see Example 7A an~ ~ he~einbelow).
~he fungicidal active compounds according to the in-vention have a very broad spectrum of action and can be used against parasitic fungi which infect above-ground part~ of plants or attack the plants through the soil, and also Qgainst seed-borne pathogens.
Fungitoxic agEnts are employed in plant protection for 1~ combating fungi from very diverse classes of fungi, such as Archim.ycetes, PhYcom.vcetes, Ascomvcetes, LasidiomYcetes and un~i ImPerfecti .
As has in part already been mentioned, the active com-pounds to be used according to the invention display a 20 particularly good activ$ty against parasitic fungi on above-ground parts of plants, such as species o~ Er~siphe and species of Venturia, as well as against epecie~ o~ ricularia and species of Pellicularia. Good eiiecte are achieved ag~inst the pathogens o~ apple scab (Fusiclad$um dendriticum), of 25 powdsry mildew oi cereals (~E_siPhe ~raminis) and of bean rust (Uromyces Phaseoli). A point to be singled out particularly is that these active compounds not only display a protective action but are also curatively active, that iB to say active on application after con.tamination with the ~pores of the 30 fungus. Furthermore, the systemic action of the compounds Le A 16 091 should be pointed out. Thus it proves possible to protect plants against fungal iniection if the active compound is ~upplied to the above-ground parts of the plant ~ia the ~oil and the root. As plant protection agents, these compounds can be used for the treatment of soil, ior the treatment o*
seed and ior the treatment oi above-ground parts oi plants.
The active compounds to be used according to the invention are well tolerated by plants. ~hey have only a low toxicity to warm-blooded animals and because of their low oaor and their good toleration by human skin they are not unpleasant to handle.
The active compound~ to be u~ed according to the present invention can be converted into the usual iormulations, such as solutions, emulsions, ~uspensions, powders, pastes and granulates. These may be produced in known manner, ior example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of suriace-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-iorming agents. In the case oi the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
AB liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydro-carbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or parafiins, for example mineral oil iraction~, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such a9 acetone, methyl ethyl ketone, methyl i80-Le A 16 091 -9-~3i66~88 butyl ketone or cyclohexanone, or ~trongly polar solYent8, such as dimethyl formamide, dimethyl ~ulphoxide or aceto-nitrile, as well as water.
Ly liquefied gaseou~ diluent~ or carriers are meant liquid~ which wolld be ga~eous at normal temperature~ and pressure~, e.g. aero~ol propell~nt~, 9uch as halogenated hydrocarbons, e.g. ~reon.
The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesti-cide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following ~ay be chiefly conside~ed for use as conventional carrier vehicles for Le A 16 091 -10-this purpose: aerosol propellants which are gas ous at normal temperatures and pressures, such as Freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chloro-benzenes, etc.), cycloalkanes, (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters ~ad~ ~har~l~
Le A 16 091 -11-10661~8 of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.
Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or li~uid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as ot'ner fungicides, or insecticides, acaricides, nematocides, bactericides, ro-denticides, herbicides, fertilizers, growth-regulating agents, bird repellents, plant nutrients, agents for improving soil stnlcture, etc., if desired or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.
As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95% by weight, and preferablyO.5-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10%, preferably 0.01-1%, by we~ght of Le A 16 091 -12-~066188 the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water, preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-95%, and preferably 0.01-95%, by weight of the mixture.
The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compos-itions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound.
Le A 16 091 -13-~066~
When u~ed Be lea~ ~ungicides, the concentratione o~
active compound in compositione used ~or application can be varied within a ~ubstantial range. They are in general from 0.1 to 0.00001 per cent by weight, pre~erably 0.05 to 0.0001~.
In the treatment o~ ~eed, amount~ oi active compound of 0.001 to 50 g per kilogram o~ ~eed, preferably 0.01 to 10 g, are in general applied to the ~eed.
For the treatment of 90il, amounts o~ active compound of 1 to 1,000 g per cubic meter of 80il, preferably of 10 to 200 g, are generally applied to the ~oil.
At somewhat higher concentrations, the active compounds alao po~sess plant growth-regulating properties.
Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. fungi, which comprises applying to at least one of correspondingly (a) such fungi, and (b) the corresponding habitat thereof, i.e. the locus to be protected, e.g. to à
growing crop, to an area where a crop is to be grown or to a domestic animal, a correspondingly combative or toxic amount, i.e. a fungicidally effective amount, of the part-icular active compound of the invention alone or together with a carrier vehicle as noted above. The instant form-ulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dry dressing, moist dressing, wet dressing, slurry dressing encrusting and the like.
Le A 16 091 -14-It will be realized, of course, that the concen-tration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concen-tration ranges.
The unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:
Example 1.
Mycelium growth test Nutrient medium used:
20 parts by weight of agar-agar 200 part~ by weight oi potato decoction 5 parts by weight of malt 15 part~ by weight of dextrose 5 parts by weight of peptone 2 parts by weight of disodium hydrogen phosphate 0-3 part by weight of calcium nitrate Proportion of solvent mixture to nutrient medium:
2 parts by weight of solvent mi~ture 100 parts by weight o~ agar nutrient medium Composition o~ solvent mixture 0.19 part by weight o~ dimethyl~ormamide or acetone 0.01 part by weight of emulsi~ier (alkylaryl polyglycol ether) 1.80 parts bY weiRht oi water 2 parts by weight oi solvent mixture Le A 16 091 -15-106611~8 The amount o~ active compound required ~or the desired concentration of active compound in the nutrient medium was mixed with the stated amount of solvent mixture. The concentrate was thoroughly mixed, in the ~tated proportion, with the liquid nutrient medium which had been cooled to 42C and was then poured into Petri dishes of 9 cm di-ameter. Control plates to which the preparation had not been added were also set up.
When the nutrient medium had cooled and solidified, the plateæ were inoculated with the species of ~ungi stated in Table 1 and incubated at about 21C.
Evaluation wa~ carried out after 4 - 10 days, dependent upon the speed of growth of the fungi. When evaluation was carried out the radial growth of the mycelium on the treated nutrient media was compared with the growth on the control nutrient media. In the evaluation of the iungu8 growth, the iollowing characteristic values are used:
1 no fungus growth up to 3 very strong inhibition oi growth up to 5 medium inhibition of growth up to 7 slight inhibition o~ growth 9 growth equal to that of the untreated control.
The active compounds, the active compound concen-trations and results can be ~een from the table which follows:
Le A 16 091 -16-1066~88 aBzLIo SBUO-mOl~UB
BFlB¦noF~ 1~ ,1 ,~
SF~Bn ~aBUi s~'m~ua~
~-IO~
Blo~lsnT~
a~a~d so OA~ 1 mnau ~nF.IOdSOII~U~ H o~
sue~selaul~
o~dol~li~ ~ ~1 ~1 a~z~o ~FI~ln~FlFa c~
lIln I~BOqlB
umFIIF~F~a~ ~ ~ u~
salaulo sl.-~A'I~og ~ N
~i~qBAlW
snloqFI~~ o~ N ~-J
IU~IOS
~oZF~
mnu~
~n~7;:)FI~o~allo~ o~
el'eJLFU~ IBS~ 0 OF~oï-al~s BFUF~O'Iel~s ~ L~
mn.Iom [no ~nF-Issn,~
~dd ' punod -~o~ a~F~s ~o UoF~Bl~uaouo~ ~11 ;o~ uf ~ u ~~~
Le A 16 091 -17-1066~
aBzAlo s~uo~ol~usX
1~
Bl:l~ ~1 ,~ .
a~u ~Fm ~U3 ~tllO
~a ool~nm a~dso~ ,, umaulm~
u~nl~odSol~uFwl~H ,~
suaosalaulo elo~dol~F~a ,1 ,, a~zA:~Io ~, ~FI'eln~FIFa U~
~TT~
~alaul~ ~F~ ~
snu~aq~
snloqoFl~ob mnm~.-~ln ~nF~l'a . ' ~u~los - ~FUo~oozl~N ~ ~1 mnu~a,~,~oa mn~oFI~o~allo;
a~ Fu ~n}~I~sn,~
mn.IoF~o~alos ~FuF~
nlo~no m~ ~sn,a 31 ~ N 11 ~ ~ 'punodmoo al~F~ ,~
+~ o uoF~ uaouo"
o~ z;~ Z51 .IP~ ~ =o l Le A 16 091 -18-1066~88 OBZA~O SBUOmO~T~UBX
~ F~BB~B
BFI~In~llaa 8 'FIBn ~ aBU~ sFIn ~uë,ll.
lI~n.IO~OBO
BlO~ dO~ a B~OO~Bn~l alas~dsoo~
mnau~ms Od~o~uF~l aH N
6ua~sa~Iaulo BlOl~olsF~a aBZLIO
sF~ n~F~F
lIml~BOqlB
~nn~ F~al~
~alauFo Eil~ SF~o~
SnU-BaqB~I~
snl-oqoFI~oo~ ~1 ~n~F~In mnF~A;a I~BIOS
BFUo~oOZF~
mnusa,~,~E
mn~o~l~o~allo~
els~Fu mnFIssn,~
mnlo-~o,Ialos BFUF~OIalo$ u~
mn.IoT~no mnFIssn,~ u~
d~ n ' punotI~oo a~F~os l ,~o UoF~B~uaouo~
o ~lo ~
Le A 16 091 1~)66~88 Exam~le 2 Shoot treatment test/powdery mildew of cereal/protective (leaf-destru~tive mycosi~) To produce a suitable preparation of active compound, 0.25 g part by weight o~ active compound was taken up in ?5 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether emulsifier and 975 parts by weight of water were added. The concentrate was diluted with water to the desired final concentration of the spray liquor.
To test for protective activity, ~ingle-leaved young barley plants of the Amsel variety were sprayed with the preparation of active compound until dew-moist. After drying, the barley plants were dusted with spores of Ervsi~he r~minis var. hordei.
After 6 days' dwell time of the plants at a temperature of 21-22C and 80-90~o atmospheric humidity the occurrence of mildew pustules on the plants was evaluated. ~he degree of ~fection is expressed as a percentage of the infection of the untreated control plants. 0% denotes no infection and lOO~o denotes the same degree of infection as in the case of the untreated control. The more active the compound, the lower is the degree of mildew infection.
~he active compounds, active compound concentrations in the spray liquor and degrees of infection can be seen from thetable which follows.
Le A 16 091 20 1066181E~
Table 2 Shoot treatment test/powdery mildew o~ cereal/
protective Active Active com- In~ection compounds pound concen- .n % f in % bg weight treated .
untreated - 100 0.01 50.0 .N~ ((kcn)wn) 0.001 68.8 N ~
Cl ~ 0-ICH-C0-C(CH3)~ 0 001 317 5 L~ (14) Cl Br ~ 0-CIH-CO-C(CH~)~ 0.01 16.
~N (7) 0 ~ 0-ICH-C0-C(CH3)~ 0.01 16.3 . (8a) 0-CH-C0-C(CH~)~ 6.3 ~`11 (10) Le A 16 091 -21-106618~3 Table 2 (continued) Shoot treatment te~t/powdery mildew of cereal/
protective Active Acti~e com- Infection compound~ pound con- in % of the centration in untreated the spray liquor control in ~ by weight H ~ 3 0-CH-CH-CtCH~), OCH~ N OH 0.01 0.0 0.00132.5 ~ 13) Cl Cl ~ O-CH-CO-C(CH~)~
N 0,01 0.0 ~ ~ (4) 0-00133.8 am~le 3 Erysiphe test/~ystemic Solvent: 4,7 part~ by weight of acetone Dispersing agent: 0.3 part by weight of alkylaryl polyglycol 15ether Water: 95 parts by weight The amount of active compound required to give the desired concentration Or active compound in the watering liquid wa~ mixed with the stated amount of solvent and the concentrate wa~ diluted with the stated amount of water which contained the stated additi~es.
Cucumber plants grown in standard 80il, in the 1-2 leaf ~tage, were watered three times within one week with 10 ml of the watering liquid, o~ the stated concentration of actiYe compound, per 100 cc Or ~oil.
The plants treated in this way were inoculated, after treatment, with conidia of the rungus Erlvci~he cichoracearum.
Le A 16 091 -22-The plants were then get up in a greenhouga at 2~-24C and 70% relative atmospheric humidity After 12 days, the infection of the cucumber plants was determined as a per-centage of the untreated, but also inoculated, control plants.
0~0 denotes no infection and 100% denotes that the infection was exactly as great as in the case of the control plants.
The active compounds, active compound concentrations and re~ult~ can be seen from the table which follows.
Table 3 Erysiphe test/systemic Active Infection in ~ of the compound infection of the un-treated control at an active compound con-centration of 100 ppm 25 ppm 1~1 100 ~3c,~
.N~
L~ (known) (B) Cl ~ 0-1CH-C0-C(CH~)~ 25 ~ ~ (14) _xamPle 4 Fusicladium test (apple scab) (Protective) Solvent: 4.7 parts by weight of acetone Emulsiiier:0.~ part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount oi active compound required ior the Le A 16 091 -23-~06618~
desired concentration oi the active compound in the spray liquid wa~ mixed with the gtated amount of solvent, and the concentrate wa~ diluted with the 8tated amount oi water which contained the stated additions.
Young apple seedling~ in the 4-6 leaf stage were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20C and àt a relative atmospheric humidity of 70~0. They were then inoculated with an aqueous conidium suspension of the apple scab causative organism (Fusicladium dendriticum) and incubated for 18 hour~ in a humidity chamber at 18-20C
and at a relative atmospheric humidity of 100%.
The plants then again were put in the greenhouse for 14 days, 15 day3 after inoculation, the infection of the seed-lings was determined as a percentage oi the untreated but also inoculated control plants.
O~o means no infection; 100% means that the infection was exactly as great as in the case of the control plants.
The active compound~, the concentrations of the active compounds and the results can be seen from the ~ollowing table:
Table4 ~usicladium test/protective Active compound Infection in % of the iniection oi the un-treated control at an active compound con-centration (in ~o) of 0.002~
. ~
C ~ (known) 66 ~ (B) Le A 16 091 -24-1066~88 ~able 4(continued) Fu~icladium test/protective Active compound Infection in % of the infection of the un-treated control at an : active compound con-centration (in Yo) of 0.0025 Cl ~ 0-CH-C0-C(CH~)~ 35 ~ (14) NO2 ~ 0-~H-C0-C(CH~)~
~ ~ . HCl 29 ~xample 5 Fusicladium test (apple scab) [Curative]
Solvent: 4.7 parts by weight of acetone Emulsifier: 0.~ part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the ~tated additions.
Young apple seedling~ in the 4-6 leaf stage were in-oculated with an aqueous conidium suspen~ion of the apple ~cab cau~ati~e organi~m (Fusicladium dendriticum ) and incubated for 18 hour3 in a humidity chamber at 18-20C
and at a relative atmospheric humidity o~ lOO~o. The plants then were wt in a greenhouse and were allowed to dry.
After standing for-a suitable period of time, the plants were sprayed dripping wet with the spray liquid prepared in Le A 16 091 -25-~06618~3 the manner described above. The plants then again were put ;n the ~reenhouse.
15 days after inoculation, the infection of the ap~e ~eedlings wa~ determined a~ a percentage o~ the un-treated but also inoculated control plant~.
O~o means no infection; 100% means that the infection was exactly as great as in the case of the control plantæ.
The active compounds, the concentrations of the active compounds, the period of time between inoculation and ~praying ~lnd the results obtained can be seen from the following table:
Table S
Fu~icladium test/curative Active Dwell Infection in % of the compound time in infection of the un-hours treated control at an active compound 42 concentration (in ~) of -?~ 0.0062 _ ~' ~C~3 100 ~=) N (known) - ~ ~ (B) C1 ~ 0-CH-C0-C(CH~)~ _ 21 - L~ (14) Example _6 Uromyces test (bean rus~/ protective Solvent: 4.7 part~ by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight Le A 16 091 -26-~066188 The amount oi active compound required ior the deelred concentratlon of active compound in the spray liquor was mixed with the stated ~mount oi the solvent and the con-centrate was diluted with the stated amount of water which contained the stated additives.
The y~ung bean plant~, which were in the 2-leaf stage, were sprayed with the spray liquor until dripping wet. The plants remained in a greenhouse for 24 hours at 20-22C and a relative atmospheric humidity of 70% in order to dry. They were then inoculated with an aqueous uredospore suspension of the causative organi~m of bean rust (Uro~vces R aseoli ) and lncubated rOr 24 hour~ in a dark humidlty chamber at 20-22C and 100% relative atmospheric humidity.
The plants were then set up in a greenhouse under intensive illumination for 9 days at 20-22C and a relative atmospheric humidity of 70-80%.
10 days after the inoculation, the infection of the plants was determined in ~ of the untreated but also in-oculated control plants.
0~O denote~ no infection and 100% denotes that the infection was just as high as in the case of the c~ntrol plants.
The active compounds, active compound concentrations and results can be seen from the table which follows:
~able 6 Uromyces test/protective Active compound Infection in % of the in-fection of the untreated control at an active compound concentration (in%) of 0.00156 Cl ~ 0-CH-C0-C(CH~)~ 91 ~ ~ (known) (A) Le A 16 091 -27-Table 6 (continued) Uromyce~ te~t/protective Active compound Infection in % of the in~ection of the untreated control at an active com-pound concentration (in ~o) _ _ _ 0.001~6 Cl ~ O-CH-CO-C(CH3 )3 10 ~ ~ (14) Cl ~ O-cH-lcH-c(cH~ )3 34 ,N~ OH
~ I (11) CH~ ~ O-ICH-CO-C(CH~)~ 70 ~ ~ (6) Br ~ O-CH-CO-C(CH~)~
L~
SO~ ~ O-CH-CH-C(CH~)I 75 ~N~ OH
(2) CH2 ~ 0-CH-ICH-C(CH~)~ 70 N~ OH
~ 1 (12) Cl Br ~ O-CH-CO-C(CH~ )3 70 Cl ~ (5) .
Le A 16 091 -28-: 1066188 ~able 6 (continued) Uromyces test/protective Active compound Iniection in ~ o~ the inrection of the un-tre~ted control at an active compound concen-tration ~in %) Or 0.00156 o~ o-cH-co-C(CH~), ~ ~ (8) Cl Cl ~ 0-CH-C0-C(CH~)~ 0 ~ ~ (4) Exam~le 7 ~ S2 ~ 0-CH2-C0-C(C~ ) S2 ~ 0-fH-C0-C(CH3)3 Br ~ S2 ~ f-cH-co-c(cH3)3 ~1 (1) N
(preparation according to method (a)) 44 g (0.107 mole)of 1-bromo-1-(4'-phenylsulfn~1~
phenoxy)- 3,3-dimethylbutan-2-one in 500 ml o~ absolute acetonitrile were heated with 34 g (0.5 mole)of imidazole ior 26 hour~ under re~lux. The solvent wa~ then distilled Oir in a water pump vacuum and the residue wa~ taken up in Le A 16 091 -29-100 ml of water, The re~ulting precipitate was wa~hed with twice 100 ml of water and recrystallized irom benzene. 26 g (66~ of theory) of 1-[lmidazolyl-(1)]-1-[4'-(phenylsul fonyl)-phenoxy]-3,~-dimethylbutan-2-one of melting point 146C were obtained, Intermediate product:
S2 ~ 0-fH-C0-C(CH3)3 Br 49 g of bromine were added dropwise at room temperature to 99.6g(0.3 mol~ ~f 1-(4~-phenyl~ulfonyl-phen-oxy)-3,~-dimethylbutan-2-one suspended in 600 ml of c~rbon tetrachloride. After the mixture had lo~t its cOlcr, the resulting precipitate wa~ filtered off, washed with petroleum ether and recrystallized ~rom benzene, 89 g (72~o of theory) of l-bromo-1-(4'-phenyl~ulfonyl--phenoxy)-3,3-dimethylbutan-2-one of melting point 157-162C were obtained.
Starting material:
~ S2 ~ 0-CH2-C0-C(CH3)3 280 g (2 moles) of powdered pota~ium hydroxide were ~uspended in 2 liters of methyl ethyl ketone. 467 g (2 moles)of 4-phenylsulfonyl -phenol were added and the mixture wa~ heated to the boil, Thereafter 269 g (2 moles) of ~-chloropinacolone were added dropwi~e over the course of 1 hour and the mixture was heated for 15 hour~ under reflux, After cooling, the ~olid re~idue was filtered ~f, washed and recry~ta~iæed from ligroin. 687 g (85% of theory) of 1-(4'-phenyl~ulfonyl -phenoxy)-3,3-dimethylbutan-2-one o~
melting point 105-108C were obtained, Le A 16 091 -30-. _ ~
~066~8 ~xamPle 8 2~ 0-TH-~H-C(CH3)3 ~ (2) (preparation according to method (b)(3)) 1.6 g to.o42 mol~ of sodium borohydride were added in portions to 11 g (0.028 mol~ of 1-[imidazolyl-(1)]-1-[4'-(phenylsulfonyl) -phenoxy~-3,3-dimethylbutan-2-one suspended in 100 ml of methanol, at a temperature of -5C. The re-~ction mixture was stirred for 17 hours at room temperature, 6.5 m] of concentrated hydrochloric acid were then added and the mixture was again stirred ior 17 hour~ at room temperature.
It was then extracted by shaking with three times 200 ml oi methylene chloride. The combined organic phases were drl~d over sodium sulfate. The solvent was di~tilled ofi in a water pump vacuum. 50 ml oi n-pentane was added to the residue and the crystals were iiltered off. 10 g (90~o bi theory) oi l-[imidazolyl-(1)]-1-[4'-(phenylsul-fonyl) -phenoxy]-3,3-dimethylbutan-2-ol of melting point 198C were obtained.
ExamPle 9 fH3 (A) Cl ~ ~ o-fH- ,C_c ( CH3)3 ~' l 20(preparation according to method (c)) 2.4 g (0.1 mol~ of magnesium filings were suspended in 30 ml oi ether. A solution oi 14.2 g (0.1 mol~ o~ methyl Le A 16 091 -31-10661~8 iodide in 50 ml o~ absolute ether was added drapwise thereto.
After 2 hours, a solution o~ 18.4 g (0.05 mol) of 1-[4'-(4"-chlorophenyl)-phenoxy]~ midazolyl~ -3~3-dimethylbutan-2-one in 100 ml of absolute tetrahydrofurane was added drop-wise at 10C and the mixture was stirred for a further 15 hours at room temperature. Thereafter, the reaction mixture was stirred, at oC, into a solution of 10 g of ammonium chloride in 500 ml of water and the mixture was left to stand overnight. The ether phase was separated off, washed with twice 100 ml of water and dried over sodium sulfate, and the solvent was distilled off in a water pump vacuum. An oil remained, which crystallized on trituration with hot petroleum ether. It was recrystall~ ed ~rom 40 ml of ethyl acetate. 16.6 g (86% o~ theory) of 1-[4'-(4"-chlorophenyl)-phenoxy]-1-[imidazolyl-(1)]-2-methyl-3,3-dimethylbutan-2-ol of melting point 177C were obtained.
(B) ~ 0-CH-C-C(CH~)~
L ~ OH . HCl (3a) (preparation oi a salt1 5 g (0.013 mol~ of 1-[4'-(4"-chlorophenyl)-phenoxy]-l-[imidazolyl-(1)]-2-methyl-3,3-dimethylbutan-2-ol were dissolved in 25 ml of acetone and 25 ml of methylene chloride.
20 ml of ethereal hydrochloric acid were added thereto, the solvent was distilled off in a water pump vacuum and the residue was boiled up with acetone. 4.7 g (86~ of theory) oi 1=~4'-(4"-chlorophenyl)-phenoxy]-1-[imidazolyl-(1)]-2-methyl-3,3-dimethylbutan-2-ol hydrochloride of melting point 220-224C (decomposition) were obtained.
Le A 16 091 -32-~066188 The following compounds of the general formula Z - ~ 0-~H-A-C(CH3)3 X~ Yb ~ N
were obtained analogously to ~xample~ 7 to 9:
Le A 16 091 ~066~88 -o`
h~
O O
~:
L~
L O ~ ~ ~a L~ ~ ~L~ L~) L~ ~ ~ D ,D ~ ~ p 5 Ll) L~
h ~1 O
h U
C) L~ _ _ -- ~ O ~ ~ ~
O h _ _ _ ~_ _ _ _ P~ a) O g ~ N ~ 0 Ir~ O Lr~ N
t--~I 0 1~ J ~_1 o ~ I ~ t-- 0 U~ ~1 0 0 ~1 ~ 0 1~ t-- 0 U~
r-- ~ o ¢ 8 ~ c~ ~) ~~ ~O~ ~o) ~c r~
~ ~ I v,,,,, ,o ~ JO ~U O O O O O O O O O O O
rl ~
c~
P~ I I I ~
~J N~D I h ~ I I I I I I I I I I I
N m .~ ~ 1 o ~1 o o ~1 o ~ ,~ o o v v m~ ~ m~
Le A 16 091 -34-1066~88 bD I
h O
~
h O O
~ Y
h O
P~ h ~d O
.
~ V
~ ~ m ~ . _ ~ ' ~
_ C~ ~
C) cd O O '' _ ~
-~ ~ ~ o~ P~
a~ ~ 0~ ~ o o ~ P:
.~ O ~ O ~ ~
0~ ~ C) o------a~
c~ o ~d a) o ~ o ~ ~ o ~ ~ ~ ~ U~
.,, o--_I o,1 a) ,~ ~1 O h~I t ~ 0 r- I I
IO ~ I I I ~ 0 co~,1a~ ~ o o ¢ 8 8 8 8 u 8 ~ o o o o o o o o ~ l l l l l l l l ~,~ ~
o Le A 16 091 35 1(~661~8 Other compounds which can be similarly prepared from appropriate starting materials and thereafter converted to salts, if desired, include:
Table 8 Compound X a Y b ` Z A
No.
2~4-di-cH3 2 2-F 1 _ -C(C2H5)(0H) 16 3-C3H7-i 1 2-oCH3 1 -S- -CO-17 4-NH(C2H5) 1 3-SCF3 1 -O- -CO-18 4-SCC12F ( 3)2 -CO-It will be appreciated that the instant specification and examples are set forth by way of illustrat~ n and not limitation, and that various difications and changes may be made without departing from the spirit and scope of the present inventionO
Le A 16 091
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of combating phytopathogenic fungi which comprises applying to such fungi or to a fungus habitat a fungicidally effective amount of a compound of the formula in which X and Y each independently is halogen, alkyl, alkoxy, halo-alkylthio, nitro, amino, alkylamino or dialkylamino, Z is a direct bond, oxygen, sulfur, methylene, sulfonyl, alkoxymethylene or keto, A is -CO-, -CHOH- or -(OH)-, R is alkyl, a is an integer from 1 to 3 or may be O if Z is not a direct bond, and b is an integer from O to 3, or a salt thereof.
2. The method according to claim 1 in which X and Y each inde-pendently is fluorine, chlorine, bromine, alkyl with up to 4 carbon atoms, alkoxy with up to 4 carbon atoms, haloalkylthio with up to 4 carbon atoms and up to 5 fluorine or chlorine atoms, nitro, amino, alkylamino with up to 4 carbon atoms or dialkylamino with up to 4 carbon atoms in each alkyl moiety.
3. The method according to claim 1, wherein the compound or a salt thereof with a physiologically tolerated acid is applied to a fungus of the species Erysiphe, Fusi-cladium or Uromyces.
4. The method according to claim 1, wherein said compound is 1-[imidazolyl-(1)]-1-[4'-(4"-chlorophenyl)-(2'-chlorophenoxy)]-3,3-dimethylbutan-2-one of the formula
5. The method according to claim 1, wherein said compound is 1-[imidazolyl-(1)]-1-[4'-phenoxy-phenoxy]-3,3-dimethylbutan-2-one of the formula
6. The method according to claim 1, wherein said compound is 1-[imidazolyl-(1)]-1-[4'-(4"-chlorophenyl)-phenoxy]-3,3-dimethylbutan-2-ol of the formula
7. The method according to claim 1, wherein said compound is 1-[imidazolyl-(1)]-1-[4'-(4"-chlorophenyl)-phenoxy]-3,3-dimethylbutan-2-ol sulfate of the formula . H2SO4
8. The method according to claim 1, wherein said compound is 1-[imidazolyl-(1)]-1-[4l-(4"chlorophenyl)-phenoxy]-3,3-dimethylbutan-2-ol hydrochloride of the formula HC1
9. The method according to claim 1, wherein said compound is 1-[imidazolyl-(1)]-1-[4'-(.alpha.-methoxybenzyl)-phenoxy]-3,3-dimethyl-butan-2-ol of the formula
10. The method according to claim 1, wherein said compound is 1-[imidazolyl-(1)]-1-[4'-(4"-chlorophenyl)-phenoxy]-3,3-dimethyl-butan-2-one of the formula
11. A fungicidal composition for plant protection use com-prising a diluent and a fungicidally effective amount of a compound of the formula in which X and Y each independently is halogen, alkyl, alkoxy, haloalkylthio, nitro, amino, alkylamino or dialkylamino, Z is a direct bond, oxygen, sulfur, methylene, sulfonyl, alkoxymethylene or keto, A is -CO-, -CHOH- or -OH)-, R is alkyl, and a and b each independently is an integer from O to 3, or a salt thereof.
12. The composition according to claim 1, wherein said compound is 1-[imidazolyl-(1)]-1-[4'-(4"-chlorophenyl)-(2'-chlorophenoxy)]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-phenoxy-phenoxy]-3,3-dimethylbutan-2-one, 1-[imidazolyl-(1)]-1-[4'-(4"-chlorophenyl)-phenoxy]-3,3-dimethylbutan-2-ol, 1-[imidazolyl-(1)]-1-[4'-(4"-chlorophenyl)-phenoxy]-3,3-dimethylbutan-2-ol sulfate, 1-[imidazolyl-(1)]-1-l4'-(4"-chlorophenyl)-phenoxy]-3,3-dimethylbutan-2-ol hydrochloride, 1-[imidazolyl-(1)]-1-[4'-(.alpha. -methoxybenzyl)-phenoxy]-3,3-dimethylbutan-2-ol or 1-[imidazolyl-(1)]-1-[4'-(4"-chlorophenyl)-phenoxy]-3,3-dimethylbutan-2-one or a salt thereof.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742455953 DE2455953A1 (en) | 1974-11-27 | 1974-11-27 | FUNGICIDALS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1066188A true CA1066188A (en) | 1979-11-13 |
Family
ID=5931783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA240,505A Expired CA1066188A (en) | 1974-11-27 | 1975-11-26 | Combating fungi with 1-(diaryloxy)-1-imidazol(1')yl-3,3-dimethyl-butan(2)ones and derivatives |
Country Status (21)
| Country | Link |
|---|---|
| JP (1) | JPS5176431A (en) |
| AT (1) | ATA901075A (en) |
| AU (1) | AU8701675A (en) |
| BE (1) | BE835952A (en) |
| BR (1) | BR7507854A (en) |
| CA (1) | CA1066188A (en) |
| CH (1) | CH612327A5 (en) |
| CS (1) | CS186724B2 (en) |
| DD (1) | DD124575A5 (en) |
| DE (1) | DE2455953A1 (en) |
| DK (1) | DK533175A (en) |
| FR (1) | FR2292427A1 (en) |
| GB (1) | GB1504016A (en) |
| HU (1) | HU172757B (en) |
| IE (1) | IE42758B1 (en) |
| IL (1) | IL48524A (en) |
| IT (1) | IT1050312B (en) |
| LU (1) | LU73865A1 (en) |
| PL (1) | PL95713B1 (en) |
| TR (1) | TR18552A (en) |
| ZA (1) | ZA757431B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2635663A1 (en) * | 1976-08-07 | 1978-02-09 | Bayer Ag | AZOLYL-CARBONIC ACID DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DE2635666A1 (en) * | 1976-08-07 | 1978-02-09 | Bayer Ag | 1-AZOLYL-4-HYDROXY-BUTANE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES AND BACTERICIDES |
| DE2713777C3 (en) * | 1977-03-29 | 1979-10-31 | Bayer Ag, 5090 Leverkusen | Process for the preparation of l-azolyl-33-dimethyl-l-phenoxy-butan-2-ones |
| DE2720654A1 (en) * | 1977-05-07 | 1978-11-16 | Bayer Ag | AZOLYL ALKANOCARBONIC ACID DERIVATIVES, METHOD FOR THEIR PRODUCTION AND THEIR USE AS FUNGICIDES |
| DE2720949A1 (en) * | 1977-05-10 | 1978-11-23 | Bayer Ag | AZOLYL ETHER DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| CA1329614C (en) * | 1987-05-02 | 1994-05-17 | Rainer Buerstinghaus | N-substituted azoles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2105490C3 (en) * | 1971-02-05 | 1979-06-13 | Bayer Ag, 5090 Leverkusen | 1-imidazolyl ketone derivatives |
-
1974
- 1974-11-27 DE DE19742455953 patent/DE2455953A1/en not_active Withdrawn
-
1975
- 1975-10-17 GB GB42624/75A patent/GB1504016A/en not_active Expired
- 1975-11-19 CS CS7500007824A patent/CS186724B2/en unknown
- 1975-11-24 TR TR18552A patent/TR18552A/en unknown
- 1975-11-24 CH CH1523275A patent/CH612327A5/en not_active IP Right Cessation
- 1975-11-24 IL IL48524A patent/IL48524A/en unknown
- 1975-11-25 IT IT29649/75A patent/IT1050312B/en active
- 1975-11-25 DD DD189673A patent/DD124575A5/xx unknown
- 1975-11-25 PL PL1975185008A patent/PL95713B1/en unknown
- 1975-11-25 LU LU73865A patent/LU73865A1/xx unknown
- 1975-11-26 ZA ZA00757431A patent/ZA757431B/en unknown
- 1975-11-26 HU HU75BA00003340A patent/HU172757B/en unknown
- 1975-11-26 DK DK533175A patent/DK533175A/en unknown
- 1975-11-26 BE BE162180A patent/BE835952A/en unknown
- 1975-11-26 IE IE2573/75A patent/IE42758B1/en unknown
- 1975-11-26 BR BR7507854*A patent/BR7507854A/en unknown
- 1975-11-26 CA CA240,505A patent/CA1066188A/en not_active Expired
- 1975-11-27 JP JP50141255A patent/JPS5176431A/ja active Pending
- 1975-11-27 AT AT901075A patent/ATA901075A/en not_active Application Discontinuation
- 1975-11-27 AU AU87016/75A patent/AU8701675A/en not_active Expired
- 1975-11-27 FR FR7536347A patent/FR2292427A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| AU8701675A (en) | 1977-06-02 |
| CS186724B2 (en) | 1978-12-29 |
| PL95713B1 (en) | 1977-11-30 |
| HU172757B (en) | 1978-12-28 |
| IT1050312B (en) | 1981-03-10 |
| DK533175A (en) | 1976-05-28 |
| BE835952A (en) | 1976-05-26 |
| TR18552A (en) | 1977-03-24 |
| FR2292427A1 (en) | 1976-06-25 |
| LU73865A1 (en) | 1976-09-06 |
| IE42758L (en) | 1976-05-27 |
| IL48524A0 (en) | 1976-01-30 |
| JPS5176431A (en) | 1976-07-02 |
| ATA901075A (en) | 1978-06-15 |
| GB1504016A (en) | 1978-03-15 |
| IL48524A (en) | 1979-11-30 |
| IE42758B1 (en) | 1980-10-08 |
| BR7507854A (en) | 1976-08-10 |
| ZA757431B (en) | 1976-10-27 |
| FR2292427B1 (en) | 1980-02-08 |
| DE2455953A1 (en) | 1976-08-12 |
| DD124575A5 (en) | 1977-03-02 |
| CH612327A5 (en) | 1979-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3952002A (en) | Triazolyl-O,N-acetals | |
| US3912752A (en) | 1-Substituted-1,2,4-triazoles | |
| US4772623A (en) | Triazolyl-alkanones or triazolyl-alkanols | |
| US3940414A (en) | 1-Phenoxy-[imidazolyl-(1)]-2-hydroxy-alkanes | |
| US4438122A (en) | Combating fungi with 1-phenoxy-2-pyridinyl-alkanols | |
| US3940415A (en) | 1-(Imidazolyl-1)-2-aryloxy-3-hydroxy-alkanes | |
| CA1212952A (en) | 1-phenyl-2-triazolyl-ethyl ether derivatives and their use as fungicides | |
| CS199531B2 (en) | Fungicide and process for preparing effective compounds | |
| CA1092128A (en) | Combatting fungi with 1-(azol-1-yl)-4-halo-1-phenoxy- butan-2-ones and -ols | |
| US3665077A (en) | N-trityl-imidazoles as plant fungicides | |
| US3972892A (en) | 1-[1,2,4-triazolyl-(1)]-2-aryloxy-3-hydroxy-alkanes | |
| PL117293B1 (en) | Fungicide and process for preparing isonitrosotriazolylethaneszoliloehtanov | |
| CA1066188A (en) | Combating fungi with 1-(diaryloxy)-1-imidazol(1')yl-3,3-dimethyl-butan(2)ones and derivatives | |
| US4151287A (en) | Combating fungi with 1-diaryloxy-1-triazolyl-3,3-dimethyl-butan-2-ones and butan-2-ols | |
| US4102891A (en) | 1-(2-Halogeno-2-phenyl-ethyl)-triazoles | |
| US4154842A (en) | Fungicidally and bactericidally active 1-azolyl-4-hydroxy-1-phenoxy-butane derivatives | |
| CA1150279A (en) | Triazolyl-alkene derivatives, a process for their preparation and their use as fungicides | |
| US3972891A (en) | 1-Phenoxy-1-[halo-1,2,4-triazolyl-(1)]-3,3-dimethyl-butan-2-ones | |
| US4134988A (en) | 2-acyloxy-1-phenoxy-1-imidazolyl-(1)-3,3-dimethyl-butanes | |
| CA1088549A (en) | 1-acyloxy-1-phenyl-2-azolyl-ethanes, and their use as fungicides or nematocides | |
| US4073901A (en) | Metal complexes of N-trityl-azoles for combatting fungi | |
| US4921870A (en) | Fungicidal novel substituted phenethyl-triazolyl derivatives | |
| US3914427A (en) | Combating fungi with 1-ethylimidazoles | |
| US4053620A (en) | Combating fungi with 1-aryl-5-alkylidene-2,4-dioxo-imidazolidines | |
| US3835164A (en) | N-alkoxycarbonyl-n{40 -acyl-n{41 12-acylamidophenyl-guanidines |