CS212719B2

CS212719B2 - Fungicide

Info

Publication number: CS212719B2
Application number: CS804467A
Authority: CS
Inventors: Bernd Zeeh; Eberhard Ammermann; Hubert Sauter; Ernst-Heinrich Pommer
Original assignee: Basf Ag
Priority date: 1979-06-28
Filing date: 1980-06-24
Publication date: 1982-03-26
Also published as: JPS568371A; IL60277A0; EP0021327A1; PL225239A2; DK278280A; AU5967280A; ZA803855B; DE2926096A1

Abstract

The beta -triazolyl ethers have the formula <IMAGE> in which R<1> denotes C1-6-alkyl or optionally halogen-substituted benzyl, R<2> denotes C1-6-alkyl, R<3> denotes hydrogen, C1-6-alkyl, C2-6-alkenyl, C2-6-alkynyl or optionally halogen-substituted benzyl and R<4> denotes a C1-6-alkyl radical, C3-6-alkenyl radical, C3-6-alkynyl radical, or an optionally halogen-substituted benzyl radical.

Description

ČESKOSLOVENSKÁ SOCIALISTICKÁCZECHOSLOVAK SOCIALIST

REPUBLIKA (19)REPUBLIC (19)

POPIS VYNALEZUDESCRIPTION OF THE INVENTION

K PATENTU 212719 (li) (M)TO PATENT 212719 (li) (M)

ÚŘAD PRO VYNÁLEZYA O3JEVY (5.1) Int. Cl.3 A 01 N 43/48 (22) Přihlášeno 24 OB 80 (21) (PV 4467-80) (32) (31) (33) Právo přednosti od 28 03 79(P 29 26 096.6) Německá spolková republika (40) Zveřejněno 31 07 81(45) Vydáno 15 07 84 (72)THE OFFICE FOR INVENTION AND SCOPE (5.1) Int. Cl.3 A 01 N 43/48 (22) Registered 24 OB 80 (21) (PV 4467-80) (32) (31) (33) Priority right from 28 03 79 (P 29 26 096.6) Federal Republic of Germany ( 40) Posted on 07 07 81 (45) Published 15 07 84 (72)

Autor vynálezu ZEEH BERND dr., AMMERMANN EBERHARD dr., LUDWIGSHAFEN,SAUTER HUBERT dr., MANNHEIM, POMMER ERNST-HEINRICH dr.,LIMBURGERHOF (NSR) (73)Author of the invention ZEEH BERND dr., AMMERMANN EBERHARD dr., LUDWIGSHAFEN, SAUTER HUBERT dr., MANNHEIM, POMMER ERNST-HEINRICH dr., LIMBURGERHOF (NSR) (73)

Majitel patentu BASF AKTIENGESELLSCHAFT, LUDWIGSHAFEN (NSR) (54) Fungicidní prostředek iProprietor of the BASF AKTIENGESELLSCHAFT, LUDWIGSHAFEN (NSR) patent (54)

Vynález se týká fungicidního prostřed-ku, který obsahuje jako účinnou složku no-vé /J-triazolylethery. Dále se vynález týkázpůsobu výroby těchto nových /3-trlazolyl-etherů, jejich použití jako fungicidů, fun-gicidních směsí, které tyto účinné látky ob-sahují, způsobu výroby takovýchto fungi-cidních směsí, jakož i způsobu potíráníškodlivých hub těmito fungicidy nebo fun-gicidními směsmi, které tyto sloučeniny ob-sahují.The present invention relates to a fungicidal composition comprising the novel β-triazolylether as the active ingredient. The invention furthermore relates to a process for the preparation of these novel [beta] -trlazolyl ethers, to their use as fungicides, to fungicidal compositions containing the active compounds, to a process for the production of such fungicidal compositions, and to a method for controlling harmful fungi by these fungicides or fungicides. gicidal mixtures containing these compounds.

Je známo, že /l-imidazolylethery, jako na-příklad 1- [ 2’-2”,4”-dichJ.orfenyl) -2’- (2”--propenyioxy)ethyl]-lH-imidazol (DOS 2 063857), jsou fungicidně účinné. Jejich účinek,zejména proti houbám typu padlí a rzí naobilovinách, je však nedostačující. Dále jsouznámy β-triazolylalkoholy (z DOS 2 737 489).Avšak ani jejich účinek, zejména proti hou-bám typu padlí a rzí v obilovinách, nenízejména při nízkých aplikovaných množ-stvích, dostačující. Proto jsou tyto slouče-niny málo vhodné k potírání škodlivýchhub při ochraně rostlin a materiálů. Předmětem vynálezu jsou fungicidní pro-středky, které obsahují pevnou nebo kapal-nou nosnou látku a jako účinnou složkualespoň jeden /3-triazolylether obecnéhovzorce I, R-CH-C-O-R* I 1 ' (I) v němž znamená R1 alkylovou skupinu s 1 až 6 atomy uhlí-ku nebo popřípadě halogenem substituo-vanou benzylovou skupinu, R2 alkylovou skupinu s 1 až 6 atomyuhlíku, R3 vodík, alkylovou skupinu s 1 až 6atomy uhlíku, alkenylovou skupinu s 2 až6 atomy uhlíku, alkinylovou skupinu s 2 až6 atomy uhlíku nebo popřípadě halogenemsubstituovanou benzylovou skupinu a R4 alkylovou skupinu s 1 až 6 atomyuhlíku, alkenylovou skupinu se 3 až 6 ato-my uhlíku, alkinylovou skupinu se 3 až 6atomy uhlíku nebo popřípadě halogenemsubstituovanou benzylovou skupinu, nebojeho rostlinami snášenou sůl nebo jehokomplex s kovem. 212 719 212713 V obecném vzorci I znamená symbol R1výhodně alkylovou skupinu s 1 až 5 atomyuhlíku, která může mít řetězec přímý, ja-ko například methylovou, ethylovou, n-pro-pylovou, n-butylovou nebo n-pentylovouskupinu, nebo řetězec rozvětvený, jako na-příklad isopropylovou nebo isobutylovouskupinu. Dále znamená symbol R1 nesub-stituovaný nebo halogenem, výhodně chlo-rem, mono- nebo disubstituovaný benzylo-vý zbytek. R2 znamená výhodně alkylovou skupinus 1 až 4 atomy uhlíku, která může být ne-rozvětvena, jako například methylovou, e-thylovou, n-propylovou nebo n-butylovouskupinu, nebo rozvětvena, jako napříkladisopropylovou nebo terc.butylovou skupi-nu. R3 znamená výhodně vodík nebo neroz-větvenou alkylovou skupinu s 1 až 6 ato-my uhlíku, jako například methylovou, e-thylovou, propylovou, butylovou nebo pen-tylovou skupinu, rozvětvenou alkylovou sku-pinu se 3 až 6 atomy uhlíku, jako isopro-pylovou nebo isobutylovou skupinu, alke-nylovou skupinu nebo alkinylovou skupinus 2 až Θ atomy uhlíku, jako vinylovou, e-thinylovou, prop-2-en-l-ylovou, prop-2-in-l--ylovou nebo 3-methylbut-2-en-l-ylovou sku-pinu, nebo popřípadě halogenem, výhodněchlorem, mono- nebo disubstituovanou ben-zylovou skupinu. R4 znamená výhodně methylovou, ethy-lovou, n-propylovou nebo n-butylovou, iso-propylovou, 2-methyl-l-propylovou neboterc.butylovou, prop-2-en-l-ylovou, prop-2--in-l-ylovou, cykloperitylovou, cyklohex-2--en-l-ylovou nebo cyklohexylovou skupinu,dále znamená popřípadě fluorem nebo chlo-rem mono- nebo disubstituovanou benzylo-vou skupinu.It is known that 1-imidazolyl ethers such as 1- [2'-2 ', 4'-dichlorophenyl) -2'- (2'-propenyioxy) ethyl] -1H-imidazole (DOS 2 063857) ) are fungicidally effective. However, their effect, in particular against powdery mildew and rust on automobile oils, is insufficient. Furthermore, β-triazolyl alcohols (from DOS 2,737,489) are known. However, their effect, in particular against mildew and rust fungi in cereals, is not sufficient, especially at low application rates. Therefore, these compounds are poorly suited for combating harmful fungi in protecting plants and materials. The present invention provides fungicidal compositions which contain a solid or liquid carrier and, as an active ingredient, at least one β-triazolyl ether of the general formula I, R-CH-COR * I 1 '(I) wherein R 1 represents an alkyl group having 1 to 3 C 6 or optionally halogen-substituted benzyl, R 2 is C 1 -C 6 alkyl, R 3 hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or an optionally halo-substituted benzyl and R 4 alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, or an optionally halo-substituted benzyl group, or a plant-tolerated salt or metal complex thereof. 212 719 212713 In the general formula (I), R @ 1 is preferably a C1 -C5 alkyl group which may have a straight chain such as methyl, ethyl, n-propyl, n-butyl or n-pentyl, or a branched chain, such as isopropyl or isobutyl. Further, R @ 1 is unsubstituted or halogen, preferably chlorine, a mono- or disubstituted benzyl radical. R @ 2 is preferably C1 -C4 alkyl which may be unbranched, such as methyl, ethyl, n-propyl or n-butyl, or branched, such as isopropyl or tert-butyl. Preferably R3 is hydrogen or a straight chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl or pentyl, a branched alkyl group having 3 to 6 carbon atoms, such as isopropyl -polyl or isobutyl, alkenyl or alkynyl of 2 to 6 carbon atoms such as vinyl, ethynyl, prop-2-en-1-yl, prop-2-yn-1-yl or 3-methylbutyl; A 2-en-1-yl group, or optionally a halogen, preferably chloro, a mono- or disubstituted benzyl group. R4 is preferably methyl, ethyl, n-propyl or n-butyl, isopropyl, 2-methyl-1-propyl or tert-butyl, prop-2-en-1-yl, prop-2-in-1 an aryl, cycloperityl, cyclohex-2-en-1-yl or cyclohexyl group, furthermore optionally being a fluoro or chloro mono- or disubstituted benzyl group.

Nové /3-triazolylethery mají na atomuuhlíku, na který je vázán triazolylový zby-tek, a v případě, že R2 a R3 jsou vzájemněrozdílné, na atomu uhlíku karbinolové sku-piny dva středy asymetrie. Podle strukturyzbytku R4 mohou se vyskytovat popřípadědalší středy asymetrie. Pomocí obvyklýchdělicích metod se mohou sloučeniny získatve formě jednotných diastereomerů. V pra-xi lze používat jak jednotných diastreome-rů, tak i směsí, které obvykle vznikají přisyntéze. /3-triazolylethery vzorce I se dají vyrobittak, že se alkoholy obecného vzorce II,The novel β-triazolyl ethers have two centers of asymmetry on the carbon atom of the carbinol group on the carbon atom to which the triazolyl residue is bound, and when R2 and R3 are mutually different. Depending on the structure of the residue R4, other asymmetric centers may optionally exist. By conventional separation methods, the compounds can be obtained in the form of uniform diastereomers. In practice, it is possible to use both uniform diastereomers as well as mixtures which usually result from synthesis. The (3-triazolyl ethers) of formula (I) may be prepared by the use of alcohols of formula (II),

R-CH-C-OH Λ *'R-CH-C-OH Λ * '

•N lil) v němž R1, R2 a R3 mají shora uvedené významy, nebo jejich soli s alkalickými kovy nebo je-jich kvartérní amoniové soli uvádějí v re-akci s alkylačním činidlem obecného vzor-ce III, L-R4 (III) v němž R4 má shora uvedený význam a L znamená nukleofilně odštěpitelnou sku-pinu, popřípadě v přítomnosti rozpouštěd-la nebo ředidla, popřípadě v přítomnostianorganických nebo organických bází ne-bo/a urychlovače reakce při teplotách me-zi 0 a 100 °C.N (III) in which R 1, R 2 and R 3 are as defined above, or their alkali metal salts or quaternary ammonium salts thereof, react with an alkylating agent of formula III, L-R4 (III) in wherein R 4 is as defined above and L is a nucleophilically cleavable group, optionally in the presence of a solvent or diluent, optionally in the presence of inorganic or organic bases or a reaction accelerator at temperatures between 0 and 100 ° C.

Jako nukleofilně odštěpitelnou skupinu Lpro shora uvedený postup lze uvést napří-klad: halogen, výhodně chlor, brom nebojod; alkylsulfátovou skupinu, výhodně me-thylsulfátovou, popřípadě substituované al-kylsulfonyloxyskupiny, výhodně methansul-fonyloxyskupinu nebo trifluormethansulfo-nyloxyskupinu; nebo arylsulfonyloxyskupi-ny, výhodně tosylátovou skupinu.As the nucleophilically cleavable group L for the above process, for example: halogen, preferably chlorine, bromine or iodine; an alkylsulfate group, preferably a methylsulfate group, an optionally substituted alkylsulfonyloxy group, preferably a methanesulfonyloxy group or a trifluoromethanesulfonyloxy group; or arylsulfonyloxy groups, preferably a tosylate group.

Vhodnými anorganickými nebo organic-kými bázemi, které se mohou při reakcipoužívat popřípadě také jako činidla vá-zající kyselinu lze uvést například hydro-xidy alkalických kovů a kovů alkalickýchzemin, jako hydroxid sodný, draselný, vá-penatý, uhličitany alkalických kovů, jakouhličitan sodný nebo draselný, hydrídy al-kalických kovů, jako hydrid sodnýt alkoxi-dy alkalických kovů nebo kovů alkalickýchzemin, jako methoxid sodný, methoxid ho-řečnatý nebo isopropoxid sodný, nebo ter-ciární aminy, jako trimethylamin, triethyl-amin, Ν,Ν-dimethylanilin, N,N-dimethylcyk-lohexylamin, N-methylpiperidin nebo pyri-din. Používat se mohou také další obvyklébáze.Suitable inorganic or organic bases which may be used in the reaction, if appropriate also as acid-binding agents, include, for example, alkali metal hydroxides and alkaline earth metal hydroxides such as sodium, potassium, calcium, alkali metal carbonates, sodium carbonate; potassium, alkali metal hydrides such as sodium hydride, alkali metal or alkaline earth metal alkoxides such as sodium methoxide, magnesium methoxide or sodium isopropoxide, or tertiary amines such as trimethylamine, triethylamine,,, Ν-dimethylaniline , N, N-dimethylcyclohexylamine, N-methylpiperidine or pyridine. Other conventional bases can also be used.

Za použití vhodných bází, jako napříkladhydridu alkalického kovu, jako hydridu sod-ného, nebo alkyllithných sloučenin, jakobutyllithia nebo alkoxidů alkalických kovůnebo kovů alkalických zemin, jako metho-xidu sodného, se mohou alkoholy vzorce IItaké v předchozím stupni převést nejprvena své soli, tj. alkoxidy, a jako takové po-tom používat k reakci. K výhodným rozpouštědlům, popřípaděředidlům náleží halogenované uhlovodíky,jako například methylenchlorid, chloroform, 1,2-dichlorethan, chlorbenzen; alifatické ne-bo aromatické uhlovodíky, jako cyklohe-xan, petrolether, benzen, toluen nebo xy-leny, estery, jako ethylacetát, amidy, jakodimethylformamid, nitrily, jako acetonitril,sulfoxidy, jako dimethylsulfoxid, ketony ja-ko aceton nebo methylethylketon, ethery,jako diethylether, tetrahydrofuran nebodioxan nebo odpovídající směsi.Using suitable bases such as an alkali metal hydride such as sodium hydride or alkyllithium compounds such as butyllithium or an alkali metal or alkaline earth metal alkoxide such as sodium methoxide, the alcohols of the formula II can also be converted in the first step into their salts, i. alkoxides and used as such for the reaction. Preferred solvents or diluents include halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene; aliphatic or aromatic hydrocarbons such as cyclohexane, petroleum ether, benzene, toluene or xylene, esters such as ethyl acetate, amides such as dimethylformamide, nitriles such as acetonitrile, sulfoxides such as dimethylsulfoxide, ketones such as acetone or methyl ethyl ketone, ethers , such as diethyl ether, tetrahydrofuran or dioxane or the corresponding mixtures.

Jako urychlovače reakce přicházejí v ú-vahu výhodně halogenidy kovů, jako jodiddraselný, korunové ethery, kvartérní amo- 212719 niové sloučeniny, jako tetrabutylamonium-jodid nebo kyseliny, nebo kombinace těch-to urychlovačů reakce.Suitable reaction accelerators are preferably metal halides, such as potassium iodide, crown ethers, quaternary ammonium compounds, such as tetrabutylammonium iodide or acids, or combinations of these reaction accelerators.

Reakce podle vynálezu se provádějí o-becně při teplotách mezi 0 a 150 °C po do-bu 1 až 60 íhodin, ža atmosférického tlakunebo za tlaku, kontinuálně nebo diskonti-nuálně.The reactions of the invention are generally carried out at temperatures between 0 and 150 ° C for 1 to 60 hours, at atmospheric pressure or under pressure, continuously or discontinuously.

Za účelem izolace sloučenin vzorce I sepostupuje obvyklými metodami. Obecně ne-vyžadují vznikající produkty žádné dalšíčištění, mohou se však dále čistit podleznámých metod, jako překrystalováním, ex-trakcí, destilací nebo chromatografií.In order to isolate the compounds of formula I, it proceeds by conventional methods. Generally, the resulting products require no further purification, but can be further purified according to known methods such as recrystallization, extraction, distillation or chromatography.

Pokud je to žádoucí, mohou se /3-triazo-lylethery vzorce I převádět také na soli sanorganickými nebo organickými kyselina-mi, jako například na soli chlorovodíkové,bromovodíkové, dusičné, šťavelové, octové,sírové, fosforečné nebo dodecylbenzensui-fonové kyseliny. Účinnost solí je dána ka-tiontem, takže volba aniontu může být li-bovolná. Dále se dají β-triazolylethery vzorce Ipřevádět podle známých metod na komple-xy kovů. To lze provádět reakcí těchto e-therů s vhodnými solemi kovů, jako napří-klad s chloridem měďnatým, chloridem zi-nečnatým, chloridem železitým, dusična-nem měďnatým, chloridem manganatým ne-bo bromidem nikelnatým.If desired, the β-triazolyl ethers of the formula I can also be converted into salts with inorganic or organic acids, such as, for example, hydrochloric, hydrobromic, nitric, oxalic, acetic, sulfuric, phosphoric or dodecylbenzenesulfonic acids. The activity of the salts is determined by the cation, so that the choice of anion can be arbitrary. Furthermore, the β-triazolyl ethers of the formula I can be converted into metal complexes according to known methods. This can be done by reacting these ethers with suitable metal salts, such as copper (II) chloride, zinc (II) chloride, iron (III) chloride, copper (I) nitrate, manganese (II) chloride or nickel (II) bromide.

Alkoholy obecného vzorce II rLch-c-ohAlcohols of general formula (II-C-OH)

(II) v němž R1, R2 a R3 mají shora uvedené významy,které se používají k syntéze ^-triazolylethe-rů vzorce I podle vynálezu, jsou částečněznámé (DOS 2 737 489) nebo se mohou vy-rábět podle známých metod z vhodnýchα-triazolylketonů, například redukcí keto-nů komplexními hydridy nebo reakcí keto-nů s Grignardovými činidly. Výrobu sloučenin vzorce I podle vynále-zu blíže objasňují následující příklady. Přikladl K suspenzi 1,6 g hydridu sodného v 80 mltetrahydrofuranu se pod atmosférou dusí- ku přikape roztok 16,4 g l-(2,4-dichlorfe-nyl) -2- (1,2,4-triazol-l-yl) -4,4-dimethylpen-tan-3-olu v 70 ml tetrahydrofuranu a po-tom se reakční směs dále míchá 2 hodinypři teplotě varu pod zpětným chladičem.Potom se při teplotě místnosti přikape 5,2ml allylbromidu. Po míchání přes noc senadbytečný hydrid sodný rozloží přidáním150 ml vody. Vodná fáze se třikrát extra-huje vždy 100 ml diethyletheru, spojenéorganická fáze se třikrát promyje 50 ml vo-dy, vysuší se a zahustí.(II) wherein R 1, R 2 and R 3 have the meanings given above, which are used for the synthesis of the β-triazolylethers of the formula I according to the invention, are partially known (DOS 2,737,489) or can be produced from suitable α triazolyl ketones, for example by reduction of ketones with complex hydrides, or by reaction of ketones with Grignard reagents. The following examples illustrate the preparation of the compounds of the formula I according to the invention. EXAMPLE 1 A solution of 16.4 g of 1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) was added dropwise under a nitrogen atmosphere to a suspension of 1.6 g of sodium hydride in 80 ml of tetrahydrofuran. -4,4-Dimethyl-pentan-3-ol in 70 ml of tetrahydrofuran, and the reaction mixture was further stirred at reflux for 2 hours. 5.2 ml of allyl bromide were then added dropwise at room temperature. After stirring overnight, the excess sodium hydride is decomposed by addition of 150 ml of water. The aqueous phase is extracted three times with 100 ml of diethyl ether each time, the combined organic phase is washed three times with 50 ml of water, dried and concentrated.

Zbyde 16,5 g krystalického l-(2,4-dí·chlorfenyl) -2- (1,2,4-triazol-l-yl) -4-4-dime-thylpentyl-3-allyletheru o teplotě tání 90až 95 °C.16.5 g of crystalline 1- (2,4-di-chlorophenyl) -2- (1,2,4-triazol-1-yl) -4-4-dimethylpentyl-3-allyl ether, m.p. Deň: 32 ° C.

Analýza: vypočteno: C 58,7 %, H 6,3 %, N 11,4 %, Cl 19,3 %?nalezeno: C 58,6 %, H 6,3 %, N 11,3 %, Cl 19,2 %.Příklad 2 K suspenzi 1,6 g hydridu sodného ve 100ml tetrahydrofuranu se přikape roztok 15,4 g l-(4-chlorfenyl)-2-(l,2,4-triazol-l--yl)-3,4,4-trimethylpentan-3-olu ve 100 mltetrahydrofuranu. Potom se směs míchá 2hodiny při teplotě varu pod zpětným chla-dičem. Po ochlazení na teplotu místnostise přidá 3,7 ml methyljodidu, přičemž tep-lota stoupne na 30° C. Po 5 hodinách mí-chání při teplotě varu pod zpětným chla-dičem se přidá 200 ml vody. Reakční směsse třikrát extrahuje vždy 100 ml diethyl-etheru, spojené etherické fáze se třikrátpromyjí vždy 50 ml vody, vysuší se a za-hustí. Z petroletheru vykrystaluje 9,5 g 1--(4-chlorfenyl )-2-( 1,2,4-triazol-l-yl j-3,4,4--trimethylpentyl-3-methyletheru o teplotětání 125 až 127 °C.Analysis: Calculated: C 58.7%, H 6.3%, N 11.4%, Cl 19.3% Found: C 58.6%, H 6.3%, N 11.3%, Cl 19 EXAMPLE 2 A solution of 15.4 g of 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -3 is added dropwise to a suspension of 1.6 g of sodium hydride in 100 ml of tetrahydrofuran. 4,4-trimethylpentan-3-ol in 100 ml of tetrahydrofuran. The mixture was then stirred at reflux for 2 hours. After cooling to room temperature, 3.7 ml of methyl iodide are added, the temperature rising to 30 DEG C. After stirring for 5 hours at reflux, 200 ml of water are added. The reaction mixture is extracted three times with 100 ml of diethyl ether each time, the combined ether phases are washed three times with 50 ml of water each, dried and concentrated. 9.5 g of 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -3,4,4-trimethylpentyl-3-methyl ether crystallized from petroleum ether, m.p. 125 DEG-127 DEG. C.

Analýza: vypočteno: C 63,4 %, H 7,5 %, N 13,1 nalezeno: C 62,2 %, H 7,4 O/o, N 12,8 %.Analysis: Calculated: C 63.4%, H 7.5%, N 13.1 Found: C 62.2%, H 7.4 O / o, N 12.8%.

Analogickým způsobem se vyrobí násle-dující sloučeniny vzorce I: 212719 7 a ipříklad č. R1 R2 R3 R4 teplota tání(°C) 3 4-C1—CeH4—CHz terc.-C4H9 H C2H5 106—108 4 4-C1—CeHá—CH2 terc.-C4H9 H CH2—CH=CH2 105—107 5 4-C1—CeHd—CH2 terc.-C4H9 H CH2—C=CH 98—100 Θ 4-C1—CeH4—CH2 terc.-C4H9 H CHz—4—C1—C6H4 75—77 7 2,4-02—C6H3—CH2 terc.-C4H9 H C2H5 102-104 8 2,4-Cl2—C8H3—CH2 terc.-C4H9 H CH2—C6H5 96—98 9 2,4-02—C6H3—CH2 terc.-C4Hg H CH2— 4—Cl—CeH4 125—127 10 2,4-Cl2-C6H3—CH2 terc.-C4H9 CH=CH2 CH3 11 2,4-Clz—GeHs—CH2 terc.-CiHo CH3 GH2—CH=CH2 12 2,4-Cl2-C6H3—CH2 terc.-C4Ho CH=CH2 C2H5 13 2,4-02—CeH3—CH2 terc.-C4H9 CH3 CHz—4—Cl—CeH4 14 2,4-02—CgH3—CH2 terc.-C4H9 CH=GH2 CH2—C6H5 15 n-C3H7 C2H5 H CHs 16 U-C3H7 C2H5 H CH2— CH=CH2 17 n-C3H7 C2H5 H CHz—CeHs nD20 = 1,5130 18 11-C3H7 C2H5 H CH2—2,4—CI2—C6H3 olej 19 n-C3H7 C2H5 CH3 C2H5 20 C6H5—CHa terc.-C4H9 H C2H5 79—81 21 4-0—C6H4— CH2 terc.-C4H9 H CH2—C&H5 73—75 22 C6H5—CH2 terc.-C4H9 H CH2—CH=CH2 64—65 23, C6H5—CH2 terc.-C4H9 H CH3 24 C6H5—ch2 terc.-C4H9 H 2,4-02—C6H3—CH2 25 4-O-C6H4.-CH2 terc.-C4H9 CH3 CH2— CH=CH2 olej 26 2,4-Cl2-C6H5-CH2 terc.-C4H9 H CHz—CsCH 70—72The following compounds of formula I are prepared in an analogous manner: 212719 7 and for example No. R1 R2 R3 R4 Melting point (° C) 3 4-C1-CeH4-CH2 t-C4H9H C2H5 106-108 4-C1-CeHa —CH2 tert-C4H9H CH2 — CH = CH2 105-107 5 4-C1 — CeHd — CH2 tert-C4H9H CH2 — C = CH 98–100 Θ 4-C1 — CeH4 — CH2 tert-C4H9 H CH2 —4 — C1 — C6H4 75—77 7 2.4-02 — C6H3 — CH2 t-C4H9H C2H5 102-104 8 2,4-Cl2 — C8H3 — CH2 t-C4H9H CH2 — C6H5 96—98 9 2,4-02-C6H3 — CH2 tert-C4Hg H CH2-4 — Cl — CeH4 125–127 10 2,4-Cl2-C6H3 — CH2 t-C4H9 CH = CH2 CH3 11 2,4-Clz-GeHs —CH2 t-C1Ho CH3 GH2 — CH = CH2 12 2,4-Cl2-C6H3 — CH2 t-C4Ho CH = CH2 C2H5 13 2,4-02 — CeH3 — CH2 t-C4H9 CH3 CH2-4 — Cl —CeH4 14 2,4-02 — CgH3 — CH2 t-C4H9 CH = GH2 CH2 — C6H5 15 n-C3H7 C2H5 H CHs 16 U-C3H7 C2H5 H CH2 — CH = CH2 17 n-C3H7 C2H5 H CH2 — CeH5 nD20 = 1.5130 18 11-C3H7 C2H5H CH2-2.4-Cl2-C6H3 oil 19 n-C3H7 C2H5 CH3 C2H5 20 C6H5-CHa tert-C4H9H C2H5 79-81 21 4-0-C6H4-CH2 tert. -C4H9H CH2 — C & H5 73-75 22 C6H5 — CH2 tert-C4H9H CH2 — CH = CH2 64–65 23, C6H5 — CH2 tert-C4H9 H CH3 24 C6H5 — ch2 tert-C4H9 H 2, 4-02 — C6H3 — CH2 25 4-O-C6H4.-CH2 tert-C4H9 CH3 CH2-CH = CH2 oil 26 2,4-Cl2-C6H5-CH2 tert-C4H9 H CH2 — CsCH 70–72

Sloučeniny podle vynálezu, jejich soli ajejich komplexní sloučeniny s kovy se vy-značují výnikající účinností vůči širokémuspektru fytopatogenních hub, zejména zetřídy Ascomycetes a Basidiomycetes. Tytosloučeniny jsou zčásti účinné také syste-micky a mohou se používat jako listové apůdní fungicidy.The compounds according to the invention, their salts and their complex compounds with metals are distinguished by their excellent activity against a broad spectrum of phytopathogenic fungi, in particular of the classes Ascomycetes and Basidiomycetes. These compounds are also partially systemically active and can be used as foliar and soil fungicides.

Zvláště zajímavé jsou fungicidní sloučeni-ny k potírání celé řady hub na různýchkulturních rostlinách nebo na jejich seme-nech, zejména pšenici, žitu, ječmeni, ovsu,rýži, kukuřici, bavlníku, sóji, kávovníku,cukrové třtině, ovocných rostlinách a o-krasných rostlinách v zahradnictví, jakoži na zelenině, jako jsou okurky, fazole ne-bo tykvovité rostliny.Of particular interest are fungicidal compounds for combating a variety of fungi on various cultured plants or on their seeds, in particular wheat, rye, barley, oats, rice, corn, cotton, soy, coffee, sugar cane, fruit plants and ornamental plants. horticultural plants and vegetables such as cucumbers, beans or pumpkin plants.

Nové sloučeniny jsou vhodné zejména kpotírání následujících chorob rostlin:The novel compounds are particularly suitable for controlling the following plant diseases:

Erysiphe graminis (padlí travní] na obilni-nách,Erysiphe graminis (powdery mildew) on cereals,

Erysiphe cichoracearum (padlí řepné] natykvovitých,Erysiphe cichoracearum (sugar beet)

Podosphaera leucotricha (padlí jabloňové]na jabloních,Podosphaera leucotricha (apple powdery mildew) on apple trees,

Uncinula necator (padlí révové) na révěvinné,Uncinula necator (powdery mildew) on grapevine,

Erysiphe polygoni (padlí rdesnové) na fa-zolích a bobech,Erysiphe polygoni (powdery mildew) on beans and beans,

Sphaerotheca pannosa (padlí) na růžích,druhy Puccinia (rež)1 na obilovinách,Rhizoctonia solani (kořenomorka brambo- rová) na bavlníku, druhy Helminthosporium (helminthosporió-za) na obilovinách, druhy Ustilago (prašná sněť) na obilovi-nách a třtině cukrové,Sphaerotheca pannosa (powdery mildew) on roses, Puccinia (overhead) 1 on cereals, Rhizoctonia solani on cotton, Helminthosporium (helminthosporióza) on cereals, Ustilago species on cereals and cane sugar,

Rhynchosporium secale (rhynchosporiováskvrnitost) na obilovinách,Rhynchosporium secale (rhynchosporium) on cereals,

Venturia inaegualis (strupovitost jabloní),plíseň šedá (Botrytis cinerea) na jahod- nících a vinné révě.Venturia inaegualis (apple scab), gray mold (Botrytis cinerea) on strawberry and grapevine.

Sloučeniny podle vynálezu se používajítak, že se rostliny účinnými látkami postří-kají nebo popráší nebo se účinnými látka-mi ošetří semena rostlin. Aplikace se pro-vádí před infekcí nebo po infekci rostlinnebo semen houbami. Účinné látky podle vynálezu je možnopřevádět na obvyklé prostředky, jako naroztoky, emulze, suspenze, popraše, práš-kové prostředky, pasty a granuláty. Apli-kační formy se zcela řídí účely použití, vkaždém případě však mají zajistit jemné arovnoměrné rozptýlení účinné látky. Tytoprostředky se připravují známým způsobem,například smísením účinné látky s rozpouš-tědlem nebo/a nosnými látkami, popřípaděza použití emulgátorů a dispergátorů, při-čemž v případě použití vody jako ředidlaje možno používat jako pomocná rozpouš-tědla také organická rozpouštědla. Jakonosné a pomocné látky přicházejí přitom vúvahu hlavně: rozpouštědla, jako aromáty(například xylen nebo benzen), chlorova-né aromáty (například chlorbenzeny)’, pa-rafiny (například ropné frakce), alkoholy(například methanol nebo butanol), aminy(například ethanolamin), dimethylforma-mid a voda, nosné látky, jako přírodní ka-menné moučky (například kaoliny, alumi-ny, mastek nebo křída) a syntetické ka-menné moučky (například vysoce disperzní 212719 19 kyselina křemičitá nebo křemičitany), e-mulgátory, jako neionogenní a anionickéemulgfitory (například polyoxyethylenethe-ry mastných alkoholů, alkylsulfonáty a aryl-sulfonáty) a dispergátory, jako lignin, sul-fitové odpadní louhy a methylcelulóza.The compounds according to the invention are used in that plants are sprayed or dusted with the active compounds or the plant seeds are treated with the active compounds. Administration is carried out before or after infection of the plants or seeds with fungi. The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The dosage forms depend entirely on the intended use, but in any case they are intended to ensure a gentle and uniform distribution of the active ingredient. These formulations are prepared in a manner known per se, for example by mixing the active ingredient with a solvent and / or carriers, optionally using emulsifiers and dispersants, whereby organic solvents can also be used as auxiliary solvents when water is used as a diluent. In this context, the following are particularly useful: auxiliaries such as aromatics (e.g. xylene or benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol or butanol), amines (e.g. ethanolamine), dimethylformamide and water, carriers such as natural stone flours (for example kaolins, alumina, talc or chalk) and synthetic stone flours (for example highly disperse silicic acid or silicates), e- emulsifiers such as non-ionic and anionic emulsifiers (e.g., polyoxyethylene ethers of fatty alcohols, alkylsulfonates and aryl-sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.

Fungicidní prostředky obsahují obecněmezi 0,1 a 95 % hmotnostními, výhodně me-zi 0,5 a 90 % hmotnostními účinné látky.The fungicidal compositions generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of active ingredient.

Aplikované množství se podle druhu po-žadovaného efektu pohybuje mezi 0,1 a 3kg účinné látky nebo více na 1 ha. Novésloučeniny se mohou používat také při o-chraně materiálů, kromě jiného k potírá-ní hub rozrušujících dřevo, jako jsou Co-niophora puteanea a Polystictus versico-lor. Při použití účiných látek při ochraněmateriálů, například jako fungicidů pro ná-těrové barvy a měkký polyvinylchlorid, či-ní aplikovaná množství 0,05 až 5 % hmot-nostních účinné látky, vztaženo na celko-vou hmotnost konzervovaných barev, po-případě polyvinylchloridu s mikrobicidní ú-pravou. Nové účinné látky se mohou pou-žívat také jako fungicidně účinné složkyolejových prostředků k ochraně dřeva přednapadením houbami, které způsobují zbar-vení dřeva. Aplikace se provádí tím způso-bem, že se dřevo těmito prostředky ošetří,například impregnuje nebo se natírá.Depending on the type of effect desired, the application rate is between 0.1 and 3 kg of active substance or more per ha. The novel compounds can also be used in the protection of materials, inter alia, for combating wood-destroying fungi such as Co-niophora puteanea and Polystictus versicor. When active substances are used in the protection of materials, for example as fungicides for paints and soft polyvinyl chloride, the application rates are 0.05 to 5% by weight of the active substance, based on the total weight of the tinned paints or polyvinyl chloride. microbicidal treatment. The novel active compounds can also be used as fungicidally active components of the oil-based wood preservatives by pre-infesting with fungi which cause wood coloring. The application is carried out in such a way that the wood is treated, for example impregnated or painted.

Prostředky, popřípadě přímo upotřebitel-né přípravky vyrobené z těchto prostředků,jako roztoky, emulze, suspenze, prášky, po-praše, pasty nebo granuláty, se aplikujíznámým způsobem, například postřikem,zamlžováním, poprašováním, posypem, mo-řením nebo zaléváním.The compositions or ready-to-use preparations made from these compositions, such as solutions, emulsions, suspensions, powders, powders, pastes or granules, are applied in a manner known per se, for example by spraying, fogging, dusting, sprinkling, pickling or potting.

Jako příklady takovýchto přípravků lzeuvést: I. 90 dílů hmotnostních sloučeniny z pří-kladu 1 se smísí s 10 díly hmotnostními N--methyl-ai-pyrrolidonu a získá se roztok,který je vhodný pro použití ve formě mi-nimálních kapek. II. 20 dílů hmotnostních sloučeniny z pří-kladu 2 se rozpustí ve směsi, která se sklá-dá z 80 dílů hmotnostních xylenu, 10 dílůhmotnostních adičního produktu 8 až 10mol ethylenoxidu na 1 mol N-monoetha-nolamidu olejové kyseliny, 5 dílů hmot-nostních vápenaté soli dodecylbenzensulfo-nové kyseliny a 5 dílů hmotnostních adič-ního produktu 40 mol ethylenoxidu s 1 molricinového oleje. Vylitím a jemným rozptý-lením roztoku ve 100 000 dílech hmotnost-ních vody se získá vodná disperze, kteráobsahuje 0,02 % hmotnostního účinné lát-ky. III. 20 dílů hmotnostních sloučeniny zpříkladu 3 se rozpustí ve směsi, která seskládá ze 40 dílů hmotnostních cyklohe-xanonu, 30 dílů hmotnostních isobutanolu,20 dílů hmotnostních adičního produktu 40mol ethylenoxidu s 1 mol ricinového oleje.Vylitím a jemným rozptýlením roztoku ve100 000 dílech hmotnostních vody se získá vodná disperze, která obsahuje 0,02 % hmotnostního účinné látky. IV. 20 dílů hmotnostních sloučeniny zpříkladu 4 se rozpustí ve směsi, která seskládá z 25 dílů hmotnostních cyklohexa-nolu, 65 dílů hmotnostních frakce minerál-ního oleje o teplotě varu 210 až 280 °C a10 dílů hmotnostních adičního produktu 40mol ethylenoxidu s 1 mol ricinového ole-je. Vylitím a jemným rozptýlením roztokuve 100 000 hmotnostních dílech vody se zís-ká vodná disperze, která obsahuje 0,02 °/ohmotnostního účinné látky. V. 20 dílů hmotnostních sloučeniny z pří-kladu 7 se dobře smísí se 3 díly hmotnost-ními sodné soli diisobutylnaftalen-a-sulfo-nové kyseliny, 17 díly hmotnostními sodnésoli ligninsulfonové kyseliny ze sulfitovýchodpadních louhů a 60 díly hmotnostnímipráškového silikagelu a směs se rozemelev kladivovém mlýně. Jemným rozptýlenímsměsi ve 20 000 dílech hmotnostních vodyse získá postřiková suspenze, která obsa-huje 0,1 % hmotnostního účinné látky. VI. 3 díly hmotnostní sloučeniny z pří-kladu 2 se důkladně smísí s 97 díly hmot-nostními jemně dispergovaného kaolinu.Tímto způsobem se získá popraš, obsahující3 % hmotnostní účinné látky. VII. 30 hmotnostních dílů sloučeniny zpříkladu 1 se důkladně smísí se směsí 92dílů hmotnostních práškovitého silikagelua 8 dílů hmotnostních parafinového oleje,který byl nastříkán na povrch tohoto sili-kagelu. Tímto způsobem se získá přípravekúčinné látky s dobrou adhezí. VIII. 40 dílů hmotnostních sloučeniny zpříkladu 3 se důkladně smísí s 10 díly sod-né soli kondenzačního produktu fenolsul-fonové kyseliny, močoviny a formaldehy-du, 2 díly silikagelu a 48 díly vody. Získáse stabilní vodná disperze. Zředěním tétodisperze 100 000 díly hmotnostními vody sezíská vodná disperze, která obsahuje 0,04proč. hmotnostního účinné látky. IX. 20 dílů sloučeniny z příkladu 4 sedůkladně smísí s 2 díly vápenaté soli do-decylbenzen sulfonové kyseliny, 8 díly po-lyglykoletheru mastného alkoholu, 2 dílysodné soli kondenzačního produktu fenol-sulfonové kyseliny, močoviny a formalde-hydu a 68 díly parafinického minerálníhooleje. Získá se stabilní olejová disperze.Examples of such formulations are as follows: I. 90 parts by weight of the compound of Example 1 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone to give a solution suitable for use as minimal drops. II. 20 parts by weight of the compound of Example 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide per mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonic acid salt and 5 parts by weight of an adduct of 40 moles of ethylene oxide with 1 molricin oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient. III. 20 parts by weight of the compound of Example 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mol of castor oil. to give an aqueous dispersion which contains 0.02% by weight of the active ingredient. IV. 20 parts by weight of the compound of Example 4 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction boiling at 210 DEG-280 DEG C. and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mol of castor oil. Yippee. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient. V. 20 parts by weight of the compound of Example 7 are well mixed with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of sodium ligninsulfonic acid from sulphite-east liquors and 60 parts by weight of powdered silica gel and ground with hammer. mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of the active ingredient. VI. 3 parts by weight of the compound of Example 2 are intimately mixed with 97 parts by weight of finely dispersed kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained. VII. 30 parts by weight of the compound of Example 1 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silica gel. In this way, the active substance formulation with good adhesion is obtained. VIII. 40 parts by weight of the compound of Example 3 are intimately mixed with 10 parts of the sodium salt of the condensation product of phenol sulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution of this dispersion with 100,000 parts by weight of water yields an aqueous dispersion containing 0.04% by weight. % by weight of active ingredient. IX 20 parts of the compound of Example 4 are mixed with 2 parts of calcium dodecylbenzene sulfonic acid calcium, 8 parts of fatty alcohol polyglycol ether, 2 parts of phenol-sulfonic acid, urea and formaldehyde condensation salt and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained.

Prostředky podle vynálezu se mohou vtěchto aplikačních formách vyskytovat ta-ké společně s dalšími účinnými látkami,jako například s herbicidy, insekticidy, re-gulátory růstu rostlin a fungicidy, nebo ta-ké s hnojivý, se kterými se vzájemně mísía aplikují. Při míšení s fungicidy se přitomdosáhne v mnoha případech rozšíření spek-tra fungicidního účinku. Následující přehled fungicidů, s nimižje možno sloučeniny podle vynálezu kom-binovat, blíže ilustruje tyto kombinační 11 možnosti, v žádném případě je však nikte-rak neomezuje.The compositions according to the invention may also be present in these dosage forms together with other active ingredients, such as herbicides, insecticides, plant growth regulators and fungicides, or fertilizers with which they are mixed with one another. When mixed with fungicides, in many cases the spectrum of fungicidal activity is broadened. The following list of fungicides with which the compounds of the present invention may be combined illustrates these combination possibilities, but is not intended to limit them in any way.

Fungicidy, s nimiž je možno kombinovatsloučeniny podle vynálezu, jsou napříkladsíra, dithiokarbamáty a jejich deriváty, jakodimethyldithiokarbamát železitý,dimethyldithiokarbamát zinečnatý,ethylen-bis-dithiokarbamát manganatý,ethylendiamin-bis-dithiokarbamát manga- natozinečnatý, ethylen-bis-dithiokarbamát zinečnatý,tetramethylthiuramidisulfid,amoniakální komplex N,N’-ethylen-bis-di- thiokarbamátu zinečnatého a N,N’-poly-ethylen-bis- (thiokarbamoyl) disulfidu, Ν,Ν’-propylen-bis-dithiokarbamát zinečnatý,amoniakální komplex N,N’-propylen-bis-di-thiokarbamátu zinečnatého a N,N’-poly- propylen-bis- (thiokarbamoyl j disulfidu;nitroderiváty, jako dinitro- (1-methylheptyl j f enylkr otonát,2-sek.butyl-4,6-dinitrofenyl-3,3-dimethyl- akrylát, 2-sek.butyl-4,6-dinitrofenylisopropylkarbo- nát; heterocyklické sloučeniny, jako N- (1,1,2,2-tetrachlorethy lthio j tetrahy dro-ftalimid, N-trichlormethylthio-tetrahydroftalimid,N-trichlormethylthio-ftalimid,2-heptadecyl-2-imidazolin-acetát, 2,4-dichlor-6- (o-chloranilino) -s-triazin,O,O-diethylftalimidofosfonothioát, 5-amino-l-[ bis- (dimethylamino) f osfinyl j - -3-fenyl-l,2,4-triazol, 5-ethoxy-3-trichlormethyl-l,2,4-thiadiazol, 2.3- dikyan-l,4-dithioanthrachinon,2-thio-l,3-dithio[ 4,5-b ] chinoxalin,methylester l-butylkarbamoyl-2-benzimi- dazolkarbamové kyseliny,2-methoxykarbonylaminobenzimidazol,2-thiokyanatomethylthiobenzthiazol, 4- (2-chlorfenylhydrazono)-3-methyl-5-iso-xazolon, pyridin-2-thiol-l-oxid, 8-hydroxychinolin nebo jeho měďnatá sůl, 2.3- dihydro-5-karboxanilido-6-methyl-l,4- -oxathiin-4,4-dioxid, 2.3- dihydro-5-karbonilido-6-methyl-l,4- -oxathiin, 2- (2-f uryl) benzimidazol, piperazin-l,4-diyl-bis- [ 1- (2,2,2-trichlore-thyfj^ormamid], 2- (4-thiazolyl j benzimidazol, 5- butyl-2-dimethylamino-4-hydroxy-6- -methylpyrimidin, bis- (p-chlorfenyl) -3-pyridinmethanol, 12 1,2-bis- (3-ethoxykarbonyl-2-thioureido) -benzen, 1,2-bis- (3-methoxykarbonyl-l-thioureido j -benzen; a různé fungicidy, jako dodecylguanidinacetát, 3- [ 3- (3,5-dimethyl-2-hydroxycyklohexyl) - -2-hydr oxyethyl ] glutarimid,hexachlorbenzen, N-dichlorfluormethylthio-N’,N’-dimethyl- -N-fenyldiamid kyseliny sírové, 2.5- dimethylfuran-3-karboxanilid,cyklohexylamid 2,5-dimethylfuran-3-kar- boxylové kyseliny, 2-kyan-N- {ethylaminokarbonyl) -2- [ metho-xyimino j acetamid, anilid 2-methylbenzoové kyseliny,anilid 2-jodbenzoové kyseliny, 1- (3,4-dichloranilino J-l-formylamino- -2,2,2-trichlorethan, 2.6- dimethyl-N-tridecylmorfolin a jeho soli, 2.6- dimethyl-N-cyklododecylmorfolin a je-ho soli, D,L-methyl-N- (2,6-dimethylfenyl) -N-2- -furoylalaninát, methylester D,L-N- (2,6-dimethylfenyl) -N- - (2’-methoxyacetyl ) alaninu,diisopropylester 5-nitroisoftalové kyseliny, 1- [ l’,2’,4’-triazol-l’-yl) - [ 1- (4’-chlorfeno- xy) )-3,3-dimethylbutan-2-on, 1- (r,2’,4’-triazol-l’-yl) - [ 1- (4’-chlorfeno- xy) ] -3,3-dimethylbutan-2-ol, N- (2,6-dimethylf enyl j -N-chloracetyl-D,L- -2-aminobutyrolakton, N- (n-pr opyl) -N- (2,4,6-trichlorf enoxyethyl) - -N’-imidazolylmočovina. Následující příklady A a B ilustrují bio-logický účinek nových látek. Jako srovná-vací látka slouží l-[2’-(2”,4”-dichlorfenyl)--2’- (2”-propenyloxy) ethyl ] -lH-imidazol,který je znám z DOS 2 063 857.Fungicides with which the compounds of the invention may be combined are, for example, sulfur, dithiocarbamates and derivatives thereof, such as ferric iron dimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylenebis-dithiocarbamate, ethylenediamine bis-dithiocarbamate dianthiocarbamate, manganese, zinc N, N'-ethylene-bis-di-thiocarbamate complex and zinc-N, N'-poly-ethylene-bis- (thiocarbamoyl) disulfide, Ν, Ν'-propylene-bis-dithiocarbamate zinc ammoniacal complex N, N'- zinc propylene bis-di-thiocarbamate and N, N'-poly-propylene bis- (thiocarbamoyl) disulfide; nitro derivatives such as dinitro- (1-methylheptylphenyl) cronate, 2-sec-butyl-4,6-dinitrophenyl- 3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenylisopropylcarbonate, heterocyclic compounds such as N- (1,1,2,2-tetrachloroethylthio) tetrahydro-phthalimide, N-trichloromethylthio-tetrahydrophthalimide , N-trichloromethylthiophtha limide, 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethylphthalimidophosphonothioate, 5-amino-1- [bis- (dimethylamino) phosphinyl] j-3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio [4,5-b] quinoxaline, 1-butylcarbamoyl-2-benzimidazolecarbamic acid methyl ester, 2-methoxycarbonylaminobenzimidazole, 2-thiocyanatomethylthiobenzothiazole, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridin-2 -thiol-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide, 2,3-dihydro-5-carbonilido-6- methyl-1,4-oxathiine, 2- (2-furyl) benzimidazole, piperazine-1,4-diylbis- [1- (2,2,2-trichloromethylphosphoramide)], 2- (4 -thiazolyl] benzimidazole, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis- (p-chlorophenyl) -3-pyridinmethanol, 12 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene, 1,2-bis- (3-methoxycarbonyl-1-thioureido) -benzene en; and various fungicides such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-hydroxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenyldiamide sulfuric acid, 2,5-dimethylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide, 2-cyano-N- (ethylaminocarbonyl) -2- [methoxyimino] acetamide, 2-methylbenzoic acid anilide, 2-iodo-benzoic acid anilide, 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine and its salts, 2,6-dimethyl-N-cyclododecylmorpholine and its salts D, L-methyl-N- (2,6-dimethylphenyl) -N-2-furoylalaninate, methyl ester D, LN- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine, diisopropyl ester 5 -nitroisophthalic acid, 1- [1 ', 2', 4'-triazol-1'-yl) - [1- (4'-chlorophenoxy) -3,3-dimethylbutan-2-one, 1- ( 1,2 ', 4'-triazol-1'-yl) - [1- (4'-chlorophenoxy) -3,3-dimethylbutan-2-ol, N- (2,6-dimethylphenyl) - N-chloroacetyl -D, L- -2-aminobutyrolactone, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazolylurea. The following Examples A and B illustrate the biological effect of the novel compounds. 1- [2 '- (2', 4 '-dichlorophenyl) -2' - (2 '-propenyloxy) ethyl] -1H-imidazole, which is known from DOS 2,063,857, serves as the comparative.

Příklad AExample A

Listy klíčních rostlin pšenice (druh „Ju-bilar”), pěstovaných v květináčích, se po-stříkají vodnými emulzemi obsahujícími vsušině 80 % hmotnostních účinné látky a20 % hmotnostních emulgátoru, a po o-schnutí povlaku naneseného postřikem sepopráší sporami (oidiemij Erysiphe grami-nis var. tritici (padlí pšeničné). Pokusnérostliny se potom uchovávají ve skleníkupři teplotě 20 až 22 °C a při 75 až 80'% re-lativní vlhkosti vzduchu.The leaves of potato sprouted wheat plants ('Ju-bilar') are sprayed with aqueous emulsions containing 80% by weight of active ingredient and 20% by weight of emulsifier, and after spray coating has dried, they are dusted with spores (oidiemij Erysiphe grami- The test plants are then stored in a greenhouse at a temperature of 20-22 ° C and at 75-80% relative air humidity.

Po 10 dnech se zjistí stupeň vývoje pad-lí. Výsledky jsou uvedeny v následující ta-bulce: 212719 13 14After 10 days, the degree of development of the mildew was determined. The results are shown in the following table: 212719 13 14

Tabulka účinná látka z příkladu napadení listů po postřiku ... % suspenzí účinné látky 0,012 0,006 10 0 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 8 0 0 9 0 0 18 0 1 20 0 1 21 0 0 22 0 1 25 0 2 srovnávací látka 3 4 kontrola (neošetřeno) 5 0 — žádné napadení houbou, odstupňováno až do 5 = celkové napadeníTable active substance from example leaf infestation ...% active substance suspensions 0.012 0.006 10 0 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 8 0 0 9 0 0 18 0 1 20 0 1 21 0 0 22 0 1 25 0 2 reference substance 3 4 control (untreated) 5 0 - no fungal attack, graded up to 5 = total infestation

Příklad BExample B

Listy klíčních rostlin pšenice (druh„Ca-ribo”) pěstovaných v květináčích se poprá-ší sporami rzi Puccinia recondita. Potom sekvětináče umístí na 24 hodin do komory svysokou vlhkostí vzduchu (90 až 95 %) přiteplotě 20 až 22 °C. Během této doby spo-ry vyklíčí a jejich klíčky pronikají tkánílistů. Infikované rostliny se potom až doorosení postříkají vodnými suspenzemi ob- účinná látka z příkladu sáhujícími 0,012 a 0,006 hmotnostního %účinné látky, přičemž tyto suspenze obsa-hují v sušině 80 % účinné látky a 20 % lig-ninsulfonátu. Po oschnutí vrstvy postřikuse pokusné rostliny umístí do skleníku přiteplotě mezi 20 a 22 °C a při relativní vlh-kosti vzduchu 65 až 70 %. Po 8 dnech sezjistí stupeň vývoje rzi na listech. Výsledky jsou uvedeny v následující ta-bulce: napadení listů po postřiku... % suspenzí účinné látky 1 3 4 5 6 7 8 21 srovnávací látkakontrola (neošetrenoj 0 0 0 0 1 0 0 1 5 0 1 0 1 2 0 0 3 5 0 — žádné napadení houbou, odstupňovánoaž do 5 = celkové napadeníThe leaves of potted wheat plants (Ca-ribo) grown in pots are dusted with spores of Puccinia recondita rust. It is then placed in the chamber for 24 hours with high humidity (90 to 95%) at 20 to 22 ° C. During this time, the savings germinate and their germs penetrate the tissue writers. The infected plants are then sprayed with aqueous suspensions of the active compound of between 0.012 and 0.006% by weight of active compound, which contain, in dry matter, 80% of active compound and 20% of lignin sulphonate. After the spray layer has dried, the test plants are placed in a greenhouse at a temperature between 20 and 22 ° C and at a relative humidity of 65 to 70%. After 8 days, they detect the degree of rust development on the leaves. The results are presented in the following table: attack of leaves after spraying ...% of active substance suspensions 1 3 4 5 6 7 8 21 comparative substancecontrol (neošetrenoj 0 0 0 0 1 0 0 1 5 0 1 0 1 2 0 0 3 5 0 - no fungal infestation, graded up to 5 = total infestation

Claims

The present invention relates to a fungicidal composition comprising, as active ingredient, novel [beta] -triethylsilyl-thiers. The invention furthermore relates to a process for the preparation of these novel (thiazolyl ethers), to their use as fungicides, to fungicidal compositions containing them, to a process for the production of such fungicidal compositions, and to a method for controlling harmful fungi by such fungicides or fungicidal compositions.

It is known that β-imidazolyl ethers such as 1- [2'-2 ", 4" -dichlorophenyl) -2 '- (2 "-propenyloxy) erlyl] triazole (DOS 2 063 857) are fungicidally effective. However, their effect, in particular against mildew and rust fungi on cereals, is insufficient. Furthermore, β-triazolyl alcohols (from DOS 2,737,489) are known. However, their effect, in particular against mildew and rust fungi in cereals, is not sufficient, especially at low application rates. Therefore, these compounds are poorly suited for combating harmful fungi in protecting plants and materials.

SUMMARY OF THE INVENTION The present invention provides fungicidal compositions which contain a solid or liquid carrier and, as an active ingredient, at least one of a (m-thiazolyl ether) of formula (I ^).

R ^b

^Both R ^and _R ¹ * ^R-CH-CO-R

I ^Ν .ι П l - _N (I) in which means

R 1 is C 1 -C 6 alkyl or optionally halogen-substituted benzyl,

R ² is alkyl having 1 to 6 carbon atoms,

R ^{3 is} hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or an optionally substituted benzyl group; and

R ^{4 is} C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, or optionally halogen-substituted benzyl, or a plant-tolerated salt or metal complex thereof.

212 719

211 7 1! I

In formula (I), R @ ^{1 is} preferably a C1 -C5 alkyl group which may have a straight chain such as methyl, ethyl, n-propyl, n-butyl or n-pentyl, or a branched chain such as for example isopropyl or isobutyl. Further, R1 represents an unsubstituted or halogenated, preferably chlorine, mono- or disubstituted benzyl radical.

R @ ² is preferably C1 -C4 alkyl which may be unbranched, such as methyl, ethyl, n-propyl or n-butyl, or branched, such as isopropyl or tert-butyl.

R ³ is preferably hydrogen or a straight-chain alkyl group having 1 to 6 carbon atoms, such as a methyl, ethyl, propyl, butyl or pentyl group, a branched alkyl group having 3 to 6 carbon atoms, such as an isopropyl or isobutyl group, alkenyl or (C 2 -C 6) alkynyl such as vinyl, ethynyl, prop-2-en-1-yl, prop-2-iii-1-yl or 3-methylbut-2-en-1-yl or optionally halogen preferably chloro, mono- or disubstituted benzyl.

R4 is preferably methyl, ethyl, n-propyl or n-butyl, isopropyl, 2-methyl-1-propyl or tert-butyl, prop-2-en-1-yl, prop-2-in-1-yl, cyclopentyl , cyclohex-2-en-1-yl or cyclohexyl, further optionally being a fluoro or chloro mono- or disubstituted benzyl group.

The new β-triazolyl ethers have two centers on the carbon atom to which the triazolyl moiety is bound and, when R 2 and R 3 are different from each other, on the carbon atom of the carbinol group. asymmetry. Depending on the structure of the radical R @ 4, other asymmetric centers may optionally exist. By conventional separation methods the compounds can be obtained in the form of uniform diastereomers. In practice, it is possible to use both uniform diastreomers and mixtures which are usually formed in the synthesis.

/ - τίβζοίγΐβ ^ β ^ · of formula I may be prepared by the addition of alcohols of formula II in which:

R1, R2 and R3 are as defined above, or their alkali metal salts or quaternary ammonium salts thereof react with an alkylating agent of formula III,

L-R4 (III) wherein

R4 is as defined above and

L is a nucleophilically cleavable group, optionally in the presence of a solvent or diluent, optionally in the presence of inorganic or organic bases and / or a reaction accelerator at temperatures between 0 and 100 ° C.

As the nucleophilically cleavable group L for the above process, for example: halogen, preferably chlorine, bromine or iodine; an alkylsulfate group, preferably a methylsulfate, optionally substituted alkylsulfonyloxy group, preferably a methanesulfonyloxy group, or a thifluoromethanesulfonyloxy group; or arylsulfonyloxy groups, preferably a tosylate group.

Suitable inorganic or organic bases which may optionally be used as acid binding agents in the reaction include, for example, alkali metal and alkaline earth metal hydroxides such as sodium, potassium, calcium, alkali metal carbonates such as sodium or potassium carbonate, alkali hydrides metals such as sodium hydride, alkali metal or alkaline earth metal alkoxides such as sodium methoxide, magnesium methoxide or sodium isopropoxide, or tertiary amines such as trimethylamine, triethylamine, Ν, Ν-dimethylaniline, N, N-dimethylcyclohexylamine, N-methylpiperidine or pyridine. Other conventional bases can also be used.

Using suitable bases, such as, for example, an alkali metal hydride such as sodium hydride or alkyllithium compounds such as butyllithium or alkali metal or alkaline earth metal alkoxides such as sodium methoxide, the alcohols of formula II can also be converted into their salts in the previous step. i.e., alkoxides, and as such used for the reaction.

Preferred solvents or diluents include halogenated hydrocarbons such as methylene chloride, chloroform,

1,2-dichloroethane, chlorobenzene; aliphatic or aromatic hydrocarbons such as cyclohexane, petroleum ether, benzene, toluene or xylenes, esters such as ethyl acetate, amides such as dimethylformamide, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, ketones such as acetone or methyl ethyl ketone, ethers such as diethyl ether, terium or dioxane or corresponding mixtures.

Suitable reaction accelerators are preferably metal halides, such as potassium iodide, crown ethers, quaternary ammonium compounds, such as tetrabutylammonium iodide or acids, or a combination of these reaction accelerators.

The reactions of the invention are generally carried out at temperatures between 0 and 150 ° C for 1 to 60 hours, at atmospheric pressure or under pressure, continuously or discontinuously.

In order to isolate the compounds of formula (I), conventional methods are employed. Generally, the resulting products require no further purification, but can be further purified according to known methods, such as recrystallization, extraction, distillation or chromatography.

If desired, the β'-triazolyl ethers of the formula I can also be converted to salts with inorganic or organic acids, such as hydrochloric, hydrobromic, nitric, oxalic, acetic, sulfuric, phosphoric or dodecylbenzenesulfonic acids. The effectiveness of the salts is determined by the-cation, so that the choice of anion can be arbitrary.

Furthermore, the β'-triazolyl ethers of the formula I can be converted into metal complexes according to known methods. This can be accomplished by reacting these ethers with suitable metal salts such as copper (II) chloride, zinc (II) chloride, iron (III) chloride, copper (II) nitrate, manganese (II) chloride or nickel (II) bromide.

Alcohols of formula II I ₄

R ^L CH-c-oh 11 wherein

R 1, R ² and R ³ have the above-mentioned meanings, which are used for the synthesis of the • triazolyl ethers of the formula I according to the invention, are partially known (DOS 2,737,489 ') or can be prepared according to known methods from suitable α-triazolyl ketones, reduction of ketones with complex hydrides or reaction of ketones with Grignard reagents.

The following examples illustrate the preparation of the compounds of formula I according to the invention.

He did

To a suspension of 1.6 g of sodium hydride in 80 ml of tetrahydrofuran under a nitrogen atmosphere is added dropwise a solution of 16.4 g of 1- (2,4-dichlorophenyl) -2- (1,3-dichlorophenyl) -4, Of 4-dimethylpentan-3-ol in 70 mL of tetrahydrofuran, and then the reaction mixture is further stirred at reflux for 2 hours. 5.2 ml of allyl bromide are then added dropwise at room temperature. After stirring overnight, the excess sodium hydride is decomposed by adding 156 ml of water. The aqueous phase is extracted three times with 100 ml of diethyl ether each time, the combined organic phase is washed three times with 50 ml of water, dried and concentrated.

16.5 g of crystalline 1- (2,44 + chlorophenyl) -2- (1,2,4-thiazol-1-yl) -4-4-dimethylpentyl-3-allyl ether, m.p. 90 DEG-95 DEG C., remains.

Analysis:

calculated:

C 58.7 - -%, H 6.3%, N 11.4%, Cl 19.3%? found *

C 58.6%, H 6.3%, N 11.3%, Cl 19.2%.

Example 2

To a suspension of 1.6 g of sodium hydride in 100 ml tetrahydrofuran was added dropwise a solution of 15.4 g of l- (4-chloro-phenyl} - (- (L ₁ 2 - triaool-yl) -3,4,4-trimethylpentane The mixture was stirred at reflux for 2 hours and after cooling to room temperature, 3.7 ml of methyl iodide was added, raising the temperature to 30 ° C. 200 ml of water are added to the reflux temperature, and the reaction mixture is extracted three times with 100 ml of diethyl ether each time, the combined ether phases are washed three times with 50 ml of water each time, dried and concentrated. 9.5 g of 1- (4-chlorophenyl) - (- (1,2,4-riazol-1-yl) -3,4,4-trimethylpentyl-3-methyl ether), m.p. 125- 127 ° C.

Analysis:

calculated:

C 63.4 -%, H 7.5%, N 13.1 found:

C 62.2%, H 7.4 O / _o , N 12.8%.

The following compounds of formula I are prepared in an analogous manner:

R2 R3 R1

21271Э

R ¹ and no.

melting point (° C

3 4-CI — СбН4 — CH2 t-C4H9 H СгНб 106—108 4 4-C1 — СбН4 — СНг t-C4H9 H СНг — СН = СНг 105—107 5 4-C1 — CgHi — СНг t-C4H9 H СНг — С ^ СН 98—100 6 4-C1-C8H4-CH2 t-C4H9 H СНг — 4 — С1 — СбН4 75—77 7 2,4-C 12 —Salz — CH2 t-C4H9 H С2Н5 102-104 8 2,4-Ch-Sn-CH2 t-C4H9 H СНг — СбНб 96—98 9 2.4-012 — СбНз — СНг t-C4H9 H СНг — 4 — С1 — СбШ 125—127 10 2.4-012 — СбНз — СНг t-C 1 H 8 СН = СНг СНз 11 2.4-012 — СбНз — СНг t-CiHo СНз СНг — СН = СНг 12 2.4-012 — СбНз — СН2 t-C4H9 СН = СНг СзНб 13 2.4-012 — СбНз — СНг t-C4H9 СНз СНг — 4 — С1 — СвН4 14 2.4-012 — СбНз — СНг t-C4H9 СН = СНг СНг — СбНб 15 Dec п-СзНг C2H5 Η СНз 16 п-СзНг C2H5 Η СНг — СН = СНг 17 п-СзН7 C2H5 Η СНг — СбНб n _D 2 = = 1.5130 18 п-СзН7 C2H5 Η СНг — 2.4 — С1г — СбНз oil 19 Dec П-С3Н7 C2H5 СНз С2Н5 20 May СбНб — СНг t-C4H9 Η СгНб 79—81 21 4-С1 — СбН4 — СНг t-C4H9 Η СНг — СбНб 73—75 2 - 2 СбНб — СНг t-C4H9 Η СНг — СН = СНг 64—65 23 .. СбНб — СНг lerc.-C4H9 Η СНз 24 СбНб — СНг t-C4H9 Η 2.4-С12- СбНз — СНг 25 4-С1 — СбН4 — СНг t-C4H9 СНз СНг — СН = СНг oil 26 2,4-С1 ₂ -С _в Н ₅ -СН t-C4H9 Η СНг — С = СН 70—72

The compounds according to the invention, their salts and their complex compounds with metals are distinguished by excellent activity against a wide range of phytopathogenic fungi, in particular from the class of Ascomycetes and Basidiomycetes. Some of these compounds are also systemically active and can be used as foliar and soil fungicides.

Of particular interest are fungicidal compounds for controlling a variety of fungi on various crop plants or on their seeds, in particular wheat, rye, barley, oats, rice, corn, cotton, soybean, coffee, sugarcane, fruit plants and ornamental plants in horticulture, as well as even on vegetables such as cucumbers, beans or pumpkin plants.

The novel compounds are particularly suitable for combating the following plant diseases:

Erysiphe graminis (powdery mildew) on cereals,

Erysiphe cichoracearum (Powdery mildew) on cucurbits,

Podosphaera leucotricha (apple powdery mildew) on apple trees,

Uncinula necator (powdery mildew) on grapevine,

Erysiphe polygoni (powdery mildew) on beans and beans,

Sphaerotheca pannosa (powdery mildew) on roses, Puccinia (chop) ¹ on cereals, Rhizoctonia solani (cotton potato), Helminthosporium species (helminthosporosis) on cereals, Ustilago species on cereals and sugar cane,

Rhynchosporium secale (rhynchosporia) on cereals,

Venturia inaegualis (apple scab), gray mold (Botrytis cinerea) on strawberry and grapevine.

The compounds according to the invention are used by spraying or dusting the plants with the active compounds or by treating the seeds of the plants with the active compounds. Application is carried out before or after infection of plants or seeds by fungi.

The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The dosage forms depend entirely on the intended use, but in any case are intended to ensure a fine and uniform distribution of the active ingredient. These compositions are prepared in a manner known per se, for example by mixing the active ingredient with a solvent and / or carriers, optionally with emulsifiers and dispersants, and in the case of water as a diluent, organic solvents can also be used as auxiliary solvents. Suitable carriers and auxiliaries are, in particular, the following: solvents such as aromatics (for example xylene or benzene), chlorinated aromatics (for example chlorobenzenes), paraffins (for example petroleum fractions), alcohols (for example methanol or butanol), amines (for example ethanolamine) , dimethylformamide and water, carriers such as natural stone meal (e.g. kaolins, alumina, talc or chalk) and synthetic stone meal (e.g. highly disperse silicic acid or silicates), emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The fungicidal compositions generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight, of the active ingredient.

Depending on the type of effect desired, the application rate is between 0.1 and 3 kg of active substance or more per ha. The novel compounds can also be used in the protection of materials, inter alia to combat wood-destroying fungi such as Coniophora puteanea and Polystictus versicolor. When active substances are used in the protection of materials, for example as fungicides for paints and soft polyvinyl chloride, the application rates are 0.05 to 5% by weight of the active substance, based on the total weight of the tinned paints or the microbicide-treated polyvinyl chloride. The novel active compounds can also be used as fungicidally effective drops of oil compositions to protect wood from attack by fungi which cause wood coloring. The application is carried out in such a way that the wood is treated, for example impregnated or painted.

The compositions or ready-to-use preparations made from these compositions, such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in a known manner, for example by spraying, fogging, dusting, spreading, pickling or potting.

Examples of such preparations are:

I. 90 parts by weight of the compound of Example 1 are mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone to give a solution which is suitable for use as minimal drops.

II. 20 parts by weight of the compound of Example 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide per mole of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid. % by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

III. 20 parts by weight of the compound of Example 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

IV. 20 parts by weight of the compound of Example 4 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction boiling at 210-280 ° C and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mol of castor oil. Pouring and finely distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

V. 20 parts by weight of the compound of Example 7 are well mixed with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of ligninsulfonic acid sodium salt from sulphite waste liquors and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

VI. 3 parts by weight of the compound of Example 2 are intimately mixed with 97 parts by weight of finely dispersed kaolin. A dust containing 3% by weight of the active ingredient is obtained.

VII. 30 parts by weight of the compound of Example 1 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silica gel. In this way, an active substance preparation with good adhesion is obtained.

VIII. 40 parts by weight of the compound of Example 3 are intimately mixed with 10 parts of sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution of this dispersion with 100,000 parts by weight of water yields an aqueous dispersion containing 0.04% by weight of active ingredient.

IX 20 parts of the compound of Example 4 are intimately mixed with 2 parts of calcium dodecylbenzene sulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of phenol sulfonic acid, urea and formaldehyde condensation product and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained.

The compositions according to the invention can also be present in these dosage forms together with other active substances, such as herbicides, insecticides, plant growth regulators and fungicides, or also with fertilizers, with which they are mixed and applied. When mixed with fungicides, in many cases a broadening of the fungicidal effect spectrum is achieved.

The following list of fungicides with which the compounds of the present invention may be combined illustrates these combination

2 1 2 7 1 ϋ possibilities, but in no way restricts them in any way.

Fungicides with which the compounds of the invention may be combined are, for example, sulfur, dithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylenebis-dithiocarbamate, ethylenediamine bis-dithiocarbamate tannate, zinc diisate, zinc diisate, zinc ammoniacal complex of N, N'-ethylene bis-dithiocarbamate and zinc N, N'-polyethylene bis- (thiocarbamoyl) disulfide, Ν, Ν'-propylene bis-dithiocarbamate zinc dithiocarbamate and N, N'-polypropylene-bis- (thiocarbamoyl disulfide);

nitro derivatives, such as dlnitro- (1-methylheptyl) phenylcronate, 2-sec-butyl-4,6-dinitrophenyl-

3,3-dimethylacrylate,

2-sec-butyl-4,6-dinitrophenylisopropyl carbonate;

heterocyclic compounds such as

N- (1,1,2,2-tetraclilorethylthio) tetrahydrophthalide,

N-1-Chloromethylthio-4-etrahydrophthalimide, N-trichloromethylthio-phthalimide, 2-heptadecyl-2-imidazoline acetate,

2,4-Dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethylphthalimidophosphonothiate, 5-amino-1- [bis- (dimethylamino) phosphinyl] -

-3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloro-methyl-1,2,4-thiadiazole,

2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio [4,5-b] quinoxaline, 1-butylcarbamoy-2-benzimidazolecarbamic acid methyl ester, 2-methoxycarbonylaminobenzimidazole, 2-thiocyanathiazolthiobenzoyl,

4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide, 8-hydroxyquinoline or its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide,

2,3-dihydro-5-carbonodo-6-methyl-1,4-oxathiin,

2- (2-furyl) benzimidazole. piperazine-l, 4-diyl-bis [1- _(2> 2,2-trichloroethoxycarbonyl thyrjTormamid]

2- (4-thiazolyl) benzimidazole,

5-Butyl-2-dimethyl-amino-4-hydroxy-6t

-methylpyrimidine, bis- (p-chlorophenyl) -4-pyridine-methanol,

1,2-bis- (3-ethoxycarbonyl-2-haloethyl) benzene,

1,2-bis- (3-methoxycarbonyl-1-thiogureidene) benzene;

and various fungicides such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-hydroxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, N-dichlorofluoromethylthio-N, N-dimethyl-N-phenyldiamide sulfuric,

2,5-dimethylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide, 2-cyano-Nt (ethylaminocarbonyl) -2- (methoxyimino) acetamide, 2-methylbenzoic acid anilide, 2-iodobenzoic acid anilide,

1- (ЗЗ ^ сЫигапШпо) ^{l -} .- foimy1amino-

-2,2,2-richloroethane, 2,6-dimethyl-N-tridecylmorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine and its salts,

D N-methyl-N- (2,6-dimethylphenyl) -N-2-furoylalaninát, D-methyl-N- _(2] 6-01теШуЬепу1) -N- (2'tmethoxyacetyl) alanine, 5-diisopropyl ester nitroisгftalové ,

1- ^(Γ'2, '4' - tiazoilt'-y1) --1- (4'-C Thor eno- xy)] -3,3-dimethyl-2tone,

1- (1 ', 2', 4'-Thiazol-4-yl) - (1- (4-chlorophenoxy)] -3,3-dimethylbutan-2-yl, N- (2,6-dimethylphenyl) -N- chloroacety - D, L-2-aminobutyrolactone,

N- (n-propyl) -N- (2,4-butylorophenylethyl) -N'-imidazoyllyngmine.

The following Examples A and B illustrate the biological effect of the novel compounds. As a comparator, it is [2 ' (2 ', 4 ' -dichlorophenyl-2 '-( 2 ' -proppenyloxy) ethyl] -1H-imidazole which is known from DOS 20 03377.

Example A

The leaves of potato sprouts of wheat (type 'Jubilar') are sprayed with aqueous emulsions containing 80% by weight of active ingredient and 20% by weight of emulsifier in the dry matter, and after spray coating has dried, they are dusted with Erysiphe graminis var. tritici (powdery mildew). The test plants are then stored in a greenhouse at 20-22 ° C and 75-80% relative humidity.

After 10 days, the degree of mildew development was determined. The results are shown in the following table:

the active ingredient of the example

Table of infestation of leaves after spraying ...% of active substance suspensions

0.012 0.006 Comparative Control (untreated)

0 o o o o o

1 o

0 = no fungal infestation, graded up to 5 = total infestation

Example В

The leaves of potted wheat plants ('Caribo') grown in pots are dusted with spores of Puccinia recondita rust. The pots were then placed in a high humidity chamber (90-95%) at 20-22 ° C for 24 hours. During this time the spores germinate and their germs penetrate the leaf tissue. Infected plants are then sprayed with aqueous suspensions containing 0.012 and 0.006% w / w of the active ingredient until dew, containing 80% active ingredient and 20% lignin sulphonate in dry matter. After the spray layer has dried, the test plants are placed in a greenhouse at a temperature between 20 and 22 ° C and a relative air humidity of 65 to 70 ° / o. After 8 days, the degree of rust development on the leaves was determined.

The results are shown in the following table:

the active ingredient of the example attacking the leaves after spraying ...% active substance suspensions 0.012 0.006 1 0 0 3 0 1 4 0 0 5 0 1 6 1 2 7 0 0 8 0 0 21 1 3 comparative substance 5 5 inspection (untreated) 5

0 = no fungal infestation, graded to 5 = total infestation

SUBJECT OF THE INVENTION

A fungicidal composition comprising, as active ingredient, at least one? -Triazolylether of the formula (I) in which:

R ¹ is alkyl having 1 to 6 carbon atoms or benzyl, which is optionally substituted by halogen,

R ² represents an alkyl group having 1 to 6 carbon atoms,

R ^{3 is} hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or benzyl optionally substituted by halogen; and

R 4 is C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or benzyl optionally substituted with halogen, its plant-tolerated salt, or its metal-tolerant plant , together with a solid or liquid carrier.