Imidazoyl and 1,2,4-triazoly fungicides

PATENT DESCRIPTION

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Additional patent to patent no. - Patent pending: 05.08.77 (P. 200093)

Priority: 07.08.76 Federal Republic

OFFICE

PATENT

PRL

German

The application was announced: 10.04.78

Patent description published: 10.10.1980

Int. Cl.^{and 2 *}

A01N 9/22 C07D233 / 54 C07D 249/08

Inventor: Patent holder: Bayer Atotiengesellschaft, Leverbusen (Federal Republic of Germany)

Fungicide and

The present invention relates to a fungicide containing the new azolyl carboxixylic acid derivatives as active substance.

It is known that especially substituted in the fenckisyl part 1- (imidisolyl) -1 / 3.3^j^ l-dimethyl phenyl ₅noixin-butanes and oily and 3,3-dimethyl -1 - £ enokis y -ίΐ - / 1, 2,4-l iaisoliiio-yl / -taultainadinate or salts have good fungicidal properties (German DOS patent specifications No. 2 325 15i5,

333 354 and 2 201 063 or 2 324 010). Action₁₀ however, especially at lower doses and ^r ribs, it is not always satisfactory.

It has been found that the strong fungicidal properties exhibit new azole-fcarboxylic acid derivatives of the formula 1 in which R is 15 -CO-OR⁸, group -CO-NR⁴R^{5 * *} or a cyano group, wherein R⁸ is an alkyl rodinoide, R⁴ is a hydrogen atom, an alkyl radical or an optionally substituted phenyl radical, and R⁵ is a hydrogen atom, an alkyl radical or · together with R⁴ they form a methylene moiety - &lt;CH₂)_m- Secondary may contain a further heteroatom, m is an integer

2-7, R.¹ and R² they may be the same or different and represent an alkyl radical or an optionally substituted phenyl radical, or together form a carbocyclic ring, A represents a keto group or a CHi (OH) group, Y represents a CH group or a nitrogen atom, Z represents a halogen atom, an alkyl radical, an alkenyl radical , chloroalkyl, cycloalkyl, alkoxy, alkylthio, alkoxycarbonyl, optionally substituted phenyl and phenoxy, optionally substituted phenylalkyl, amino, cyano or nitro, and n is an integer of 0-5, as well as their physiologically acceptable salts.

Compounds of formula 1 in which A is an OH (OH) group have two asymmetric carbon atoms and may therefore exist as geometrical isomers (erythro and threo), which may occur in different quantitative ratios. In both cases, they exist in the form of optical isomers, with vaginal isomers falling within the scope of the invention.

The new derivatives of azolylcarboxylic acid of formula 1 are obtained in such a way that the derivatives of chromo-1-ketocarbolyl acid of formula II, in which R, R¹, R², Z and n are as defined above, are reacted with azoles of formula 3 in which Y is as defined above, in the presence of a diluent and an acid-binding agent, and the resulting derivatives of aisolyl-keto-carboxysilic acid are optionally subjected to reduction. with comprehensive borohydrides, optionally in the presence of a diluent.

The resulting azolylcarboxylic acid derivatives can then be converted into salts by reaction with acids

Surprisingly, the new active substances show a significantly higher fungicidal activity, especially in cereal diseases, than the known 1- / imidazolyl 103 472

SVMW k YWOTflSt

-1 / -3,3-dW'umetyIo-łl-fienolcsy-buitann2-ones or -ole, which are the compounds most similar in terms of the structure and direction of action. Therefore, new Nactive substances enrich the state of the art;

When using 4-bromo-4- / 4-chloro-phenoxy / -2,2-dihydrate as ethyl ester starting materials^andmethyl H | -keto-butanoate and 1,2,4 ^ triazole, the course of the reaction can be represented by scheme 1 / i. By using ethyl ester · acid

4- / 4 - &lt;'hl or ofeittoks y / -2.2 -dimethyl yl-3 Mket o-4 - / 1,2,4 * -itriazolyl41 / * toutane and sodium borohydride as starting compounds, the course of the reaction can be represented in with scheme 2.

The bromoiketaicarboxylic acid derivatives used as the starting compounds are generally defined by formula 2. In this formula, preferably R is a cyano group and -OO-OK® and • COCON NRW, R³ is a straight or branched alkyl radical with 1-6 carbon atoms, R⁴ preferably, it is a hydrogen atom, a straight or branched alkyl radical with 1 to 4 carbon atoms and an optionally substituted phenyl radical, with substituents being preferably halide, especially fluoro, chloro or bromo, alkyl radicals having 1 or 2 carbon atoms and haloalkyl radicals with 1 or 2 carbon atoms and 1-5 halogen atoms, especially fluorine or chlorine, for example the trifluoromethyl group, R⁵preferably it is a hydrogen atom, a straight or branched alkyl radical with 1-4 carbon atoms or with R⁴ form a 5- or 6-membered ring optionally containing a further heteroatom, especially oxygen or nitrogen, for example a pyrrolidine, piperidine, piperazine and morpholine group, R¹ and R² are the same or different and are preferably an alkyl radical of 1-4 carbon atoms, optionally. substituted phenyl radical, with substituent groups preferably d and R being present as substituents⁴, or together form a 5- or 6-carbine cyclic carbocyclic ring.

The symbol 2 is preferably a halogen atom, a straight or branched alkyl radical with 1-4 carbon atoms, an alkenyl radical with 2-4 carbon atoms, a cycloallkHoiwy radical with 5-7 carbon atoms, in particular a diglychexyl radical, an alkyl radical with 1-2 carbon atoms and 1-5 halogen atoms, especially fluorine and chlorine, for example¹ The trifluoromethyl group, furthermore preferably denotes an alkoxy group and an alkylthio group of 1 or 2 carbon atoms and an alkoxycarbonyl group swirling in total 1-5 carbon atoms, moreover an amino, cyano and nitro group. In addition, Z is preferably an optionally substituted phenyl and phenofxyl group, with halogen, amino, cyano, nitro or alkyl radicals having 1-12 carbon atoms being preferably substituents, and furthermore preferably is an optionally substituted phenylalkyl radical with 1 or 2 carbon atoms alkyl part, wherein an alkyl part substituent is preferably an alkylcarbonyl group containing up to 3 total

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speak coal, and as .poAsita ^ H ^ W¹Preferably, halogen atoms, especially fluorine, chlorine, bromine, nitro and cyano groups are preferably present. The symbol n means preferred₅ not an integer 0-3.

Starting materials of the formula II are, for example, 4-phosphoromo-4- (4-chloro-phenoxy) -2-ethyl ethyl ester_s2-di-ethyl-tert-butanoate, ethyl ester of '4-Ubromo = 4- / 2.44-dimethyl] -oxyphenyl / 42, 2-di-dimethyl] -tetra-tetanbultanoic acid, 4-bromo-i- / 4- (fluorophenoxy / ^ 2, ethyl ethyl ester. 2-dimethyl-3-keto-butanoic acid, 4-bromo-4-i [-4-bromophenoxy // - 2,2-dimethyl-3-keto-butanoic acid ethyl ester, ethyl ester₁₅ 4-bromo-4- / 2-4,5-trichloro-oxenic acid (-2.2-dimethyl-3-keto-butanoic acid, 4-bromo * 4- / 3,4-divinylmethylene] oxy / - ( 2^l2-idifviumethyl-3-keto-buitanoic acid, 44-bromo-4- (2-methylphenoxy) -2,2-dimethyl-3-keto ethyl ester₂₀ -butanoic acid 4-bromo-4- (3,4-dimethylphenoxy) -2,2-dimethyl-3-keto-butanoic acid ethyl ester, 4-bromo-4- / 4-chloro-3,5-dimethylphenoxy / -2,2- dimethyl-3-keto-butonic acid, 4-bromo-4- / 2-cyclohe acid ethyl ester₂₅ xylphenoxy / -2,2-dimethy-3-keto-butanoate, 4-bromo-4- / 4-methoxyphenoxy / -2,2-dimethyl-3-keito-butanoic acid ethyl ester, 4-bromo-4 ethyl ester - / 3-trifluoromethylphenoxy / -2,2-dimethyl-3-keto-butanoic acid, ethyl ester_3θ su 4-bromo-4- (2-phenylphenoxy) 2,2-dimethyl-3-keto-butanoate, 4-bromo-4- (4-phenylphenoxy) -2,2-dimethyl-3-keto-butanoic acid ethyl ester, ester ethyl 4-bromo-4- {4- (4'-chlorophenoxy) -phenoxy] -2,2-dimethyl-3-keto-butanoic acid, _3g 4-bromo-4- (4- / 4'-chlorobenzyl-phenoxy] -2,2-dimethyl-3-keto-butanoic acid ethyl ester, 4Htaroimo acid ethyl ester^J4- / 4-cyanophenolyl / -2,2-dimethyl-3-ketO'-fouitanoic acid ', 4-bromo-4-(4/4-nitroxyphenoxy) ethyl ester / ^ 2,2-idumeume 4θ -3-ketonbutane ·, 4-bromo-4 * [4- (4'-chlorophenyl / phenoxy] d2 $ -dimethyl ^ 3-keito-butanoic acid ethyl ester, 4-toromo-4- / i2Hmethyl ethyl ester^lLO? 5-nitrofienoiksy / -2^l, 2H-dimethyl-3-fluoro-butanoic acid, 4nbro45 mo ^ 4- / 4-chloro-phenoxy / H2 acid methyl ester, 2-d-Di-ethyl-3-keto-butanoic acid, 4-bromo-4- / 4-chloro-phenoxyoxy / H2 propyl ester , 2-di-dimethio-h3-Iket o-butane, isopropyl ester of 44> romo-4- (4-chloro-phenoxy) ^ 2,2-dimethyl-3-keto-butanoic acid, 4-bromo-4- tertiary butyl acid / 4 ^ chlorophenoxy / H2 ^ H-dimethyl-3-keto 4> utanoic, 4-bromo²4- / 4-chlorine of 2 -benzene / H2, i2H-dimethyl-3-keto-butanoic acid, 4-bromo-4- / 4-chloro-phenoxy acid methylamide / -2,4, i-2-dimethyl-3-ketone ₅₅ -butanoic, dimethyl 4-bromo-4- (4-chloro-phenoxy) -I, 2,2-dimethylH3-iketo-butanoic acid, 443-chromo-4- (4-chloro-phenoxy) / -2, 2-dimethyl-3-4-keto- butanoic, 44xromo-4- / 4-chlorophenoxy / οθ -2,2-dimethyl-3H-keto-butanoic acid, 4-halophenylamide, 4-bromo-4- / 4-chloro-tofenofcsy / -2,2-dimethio-3H-keto-buitanoic acid morpholide , 2-ethyl-4-bromo-4- / 4-chlorophenoxy / -3-keto * 2 * methyl-butanoic acid ethyl ester, 4-bromo-4- / 4-chloro ethyl ester₆₅ phenoxy / -3-oxo-2-mfetyło-2-propyl-butanoic acid,

103 472 4H-bromo-4- (4-chloro-phenoxy) -ethyl ethyl ester -2-propyl-3-methylbutanoic acid, 4-bromo-ethyl ethyl ester^j4- / 4-chloro-phenoxy / ^ 3-keto-2,2-pentenyl butane, ethyl ester 443-mono-4- (4-chlorophene) -3-keto-2-methyl &lt;phenyl-2-phenyl butanoic acid ethyl ester -, 4-bromo acid ethyl ester^j4- / 4 thereof) lorofenoksy /^J2- (4-chloro-phenyl) -3-oxo-42-methylbufthanoic acid, 4-bromo ^ 4- / 4-chloroteinoxy / ^ 2- / 2,4-idevicyl chlorophenyl / -3-ketyl 42-methyl 4 -benzene.

The bromolketo-carboxylic acid derivatives of the formula II used as starting compounds are new. However, they can be prepared by known methods, for example in that the phenols of formula 4 in which Z and n are as defined above are reacted with bromoketones of formula 5 in which R, R^L and R² have the meaning given above. The remaining active hydrogen atom is then exchanged for bromine.

Salts of compounds of formula I are considered to include salts of physiologically acceptable acids such as hydrohalic acids, e.g. hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, phosphoric acid, nitric acid, mono- and difunctional carboxylic and hydroxycarboxylic acids, for example) acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, salicylic acid, citric acid, sorting acid, lactic acid, 1,5-naphthalene disulfonic acid.

Preferred diluents for the reaction are inert organic solvents such as ketones, e.g. diethyl ketone, especially acetone and methyl ethyl ketone, nitriles, e.g. priopionitrile, especially acetonitrile, alcohols, e.g. ethanol or isopropanol, ethers, e.g. tetrahydrofuran or dioxane, benzene , formamides, especially dimethylformamide, as well as halogenated hydrocarbons, for example methylene chloride, carbon tetrachloride or chloroform.

The reaction is carried out in the presence of an acid binding agent. As acid-binding agents, all commonly used non-limiting and organic acid acceptors, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or lower tertiary alkylaamines, cycloalkylamines or aralkylamines, for example triethylamine, Ν, Ν- dimethylcyclohexylamine, dicyclylmethylamine, N ^ N-di-dimethylbenzylamine, pyridine and diazobicyclooctane An appropriate excess of nitrogen may also be used.

· The reaction temperature may vary widely. In general, the reaction is carried out at a temperature of about 20-150 ° C, preferably 60-120 ° C. Preferably, the reaction is carried out at the reflux temperature of the solvent in the presence of a solvent.

Preferably, 1-2 moles of nitrogen and 1-2 moles of an acid-binding agent are introduced into the reaction per 1 mole of the compound of formula (II). To isolate the compound of formula 1 ', the solvent is distilled off, the residue is taken up in an organic solvent and washed with water. The organic phase is dried over sodium sulfate and freed of the solvent under reduced pressure. The residue is purified by distillation or recrystallization.

Diluents for selective reduction are polar organic solvents such as alcohols, e.g. methanol, ethanol, butanol, isopropanol, and ethers, e.g. ethyl ether or tetrahydrofuran. The reaction is generally carried out at a temperature of 0-30 ° C, preferably

6-20 ° C. About 1 mole of borohydride, such as sodium borohydride, is introduced into the reaction per 1 mole of the compound of formula II. In order to isolate the compounds of formula I, the residue is taken up, for example, in dilute hydrochloric acid, then basified and extracted with an organic solvent, or only mixed with water and shaken with an organic solvent.

The further test is carried out in a known manner.

As examples of particularly preferred representatives of the new active substances, mention may be made of the compounds given in the examples 4- (4-chiorophenoxy) ethyl ester / H3-keto42-methyl-2-phenyl -4- / 1,2,4-triazolyl-yl / -butane 2-ethyl-4- (4-chloro-phenoxy) -3-keto-2-methyl-4- (1,2,4-triazol-1- (4-butanoic acid) ethyl ester, 2-ethyl-4- (4-4-chlorophenoxy) ethyl ester ^ - / imildaziolyl-yl / -3-ket-2-imethyl-foutanoic acid, 4- (4-chloro-phenoxy) -acetic acid ethyl ester, 4- (4-chlorophenoxy) ethyl ester ^ 2 ^ 2-methylO-2-propyl ^ 1-¹, 2,4-triazolyl- 1/4-butane-isopropyl-3-keto-2-methyl-4- / 1,2,4-triazolyl-1-butanoic acid, 4- / 4-chlorophenol ethyl ester^andoxy / 42-isopropyl-4- / imidazol-yl /? 3-oxo^j2-methyl butyrate, 4- / 4-chloro-ethoxy / T2,2-diethyl-34-keto ethyl ester^j4- (lA44-triazolyl-butanoic acid *, ethyl ester - '4- / 4 <± 10'-phenoxy / ^ 2,2-diethyl ^ 4- (imidazoyl) 41--3-keto-butanoic acid, ethyl ester 2- tertbutyl^j4- / 4-ichlo) rofeinoikisy / ^ 3-ikie^andto H 2 -methyl-4- (1,2,4-triazothilyl) -1-buitanoic acid, ethyl ester 24> utyl-4- (4-chloro-phenoxy) -4- (imidazazolyl-yl) -3- keto-2-methyl-foultain, 4- (4-H) -phenoxy / -34keito acid ethyl ester.^J2,2-pięciomęty^|leno-4- (yl, 2,4-triazolyl-yl) -butanoic, 4- (4-chloroifeinylamide) 4- / 4-chloro-chlorofe, noxy / ^ 2.2 <1-methylmeth H 3 -keto-4 - / [1,2,4-triiazolyl- 2-butane-4- (4-chloro-phenoxyl) -2-isopropyl-3H-keto-4- (1,2,4-triazoyl-1-butanoic acid phenylamide, 2-butyl-4-phenylamide - / 4-Chloro-phenoxy / -4- / - imidazolyl-1 / -2-isopropyl-3-keto-butanoic acid, 4- (4-chloro-phenoxy) -methyl dimethyl amide / ^ 2,2- (dimethyl-3H-keto-4- / 1,2 , 4-triazoylonl / ^ bulta, new, 44bdfenylyloxy acid ethyl ester ^ 2_s2-di-triethyl-3-keto-4- (1,2,4-friazolyl-1-foutanoic acid, ethyl ester of 4-foifenic acid ii 1 oxy -2.2 -dimethyl yl -4- / imiidazole ii o-yl (3-ikeit) -butanoic acid, [4- (4'-chilorophenyl) -pheniciki] -2,2-dimethyl-3-keo-4- / 1-ethyl ethyl ester_s2,4-triazolyl-1 / H-butanoic acid, [4- (4'-chlorophenyl) -phenoxy] -2,2 <l-dimethyl-4- (imidazolyl 41) -3-keto-foutanoic acid, ethyl ester 2,2 -idwumetylo-3-iketo-4- / 4-initrofe^andNoxy / -4 - / - 4- / 1,2,4-triaz'Oloyl-4 / H-butanoic acid, 2,2-dimethyl-4- (imidazolyl-1 / -3-ket o-4- / 4Hni ethyl acid ester ) trofenok'Sy / 4-butaine, 4- (4-) acid ethyl ester Chloro-2H-methylifeinaxa / 2, 2-dimethyl-3103 472

is -L-4- / yl, and 4-tiriazo^andyl-fl / HBU^,of tartaric acid, 4- and 4-chLoro-2Hme * tylophenoxy ethyl ether^j2,2- <twumethyl-4 - / 'imidazolyl -1 / -, 3-ketin-h itanowee ·, 4- (2,4-H-dichlorophenoxy) ethyl ester / ^ 2,2-dimethyl- * 3-keto -4- / yl, 4-triazolyl-1-butanoic acid 4- 4- (1,4,4-dichlorophenoxy) ethyl ester_and2 • D-dimethyl-4- (imidazolyl) ^jl -J34-keto-butanes, 4- (4-bromophenoxy) -ethyl 2,2-dimethyl -3-keto-4- (1,12,4-triazolyl-3-butanoic acid ethyl ester, 4-ethyl ethyl ester - / 44> no <mofenaksy / ^ 2,2-dimethyl-4- / im^|idaaolilo-^|, 1 / -3-keto-butanoic acid, 2 ^ 2-dimethyl-4- / 4-fluorophenoxy / ^ - keto-4- (1, 2,4-triazolyl-1-foutanoic acid ethyl ester, 2-ethyl ester , 2-dimethyl4- (4-flucrophenoxy) -4- (iimidazolyl-yl) H 3 H -keto-butane ester, tI-ester. 4- (4-chloro-phenoxy) -H-2-dimethyl-34-keto-4- (1, 2,4-itriazoyl-yl) -butanoic acid butyl acid, an tertiary ester. 4- (4-chloro-phenoxy-2-dimethyl-4- (imidazolyl-yl) -3-keto-butanoic acid butyl acid, 2-butyl-4- (4-chloro-phenoxy) -2-isopropyl 3-fcet-4- (11,2,4) Tinazolyl-11 H -buitanoic acid, 2-butyl-4- (4-chloro-phenoxy) -4-ethyl / imidazolyl ^ -1 / -2-isopropyl-3 -, keto-bultanoic acid, 2-ethyl ^ 2-butyl-4 .- / 4-chlorophexyl / -3 ^ keto-4- (1- ^, 4-triazzolyl-1-butanoic acid ethyl ester, 2-ethyl-2-buityl-4- (4-chlorophenoxy) -4- (imidazolyl) -1-3-ethobutanoic acid ethyl ester.

The new active substances have a strong fungitoxic and phototherapeutic effect, but they do not damage crop plants in the concentrations used to control fungi and bacteria. For these reasons, they are suitable as plant protection products for * controlling fungi and bacteria. Fungitoxic agents in the field of plant protection are used to control Plasmodioipihoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes.

The new active substances have a wide range of activity and can be used against parasitic fungi infesting aerial parts of plants or attacking plants from soil, as well as against seed-borne pathogens.

They are particularly effective against parasitic fungi on the aerial parts of plants, such as the genera Erysiphe, Uromyces and Venturia, and also the genera Pyricullaria and Pełlicularia. Good effects are observed against Fusicladiuim dendriticum, Uromyces phaseoli and Erysdphe cichoriacearium and against Pełlicularia sasakiik

The new compounds also show excellent activity against cereal diseases, such as powdery mildew, cereal rust and barley pollen blade. It should be particularly noted that the new active substances act not only preventively, but also cure, that is after the infection. Furthermore, it is advantageous that the new substances have a systematic effect, so that plants can be protected against attack by fungi if the active substance is fed via soil and roots or through seeds to the aerial parts of the plants.

As plant protection products, new substances can be used for soil treatment, for seed treatment and for the treatment of aerial parts of plants.

The new active substances can be converted into known preparations such as solutions, emulsions, suspensions, powders, pastes and granules. They are prepared in a known manner, for example by mixing the active substance with diluents, i.e. liquid solvents under pressure, liquefied gases and / or solid carriers, optionally using surfactants, such as emulsifiers and / or dispersants and / loose foaming agents. When using water as the diluent, organic solvents can, for example, also be used as solubilizers. As liquid solvents, aromatic compounds such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, taffeta like cyclohexane or paraffins, e.g. petroleum, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methylisofoutyl ketone or cyclohexanone, highly polar solvents such as dimethyl formamide and dimethyesulfoxide and water.

Liquefied gaseous diluents or carriers are liquids which are gases at normal temperature and pressure, for example aerosol forming gases such as dichloradifluoromethane or trichlorofluoromethane. Natural rock powders such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth as well as synthetic non-organic powders such as high-grade silicic acid, alumina and silicates are used as solid carriers. As emulsifiers, non-ionic and anionic emulsifiers are used, such as potassiumoxyethylene fatty acid esters, polyoxyethylene ethers and fatty alcohols, for example α-alkyl aryl polyglycol ether, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. As dispersants, for example, lignin, sulphate lyes and methyl cellulose are used.

New active substances may be present in the preparation in a mixture with other active substances such as fungicides, insecticides, acaricides, nematocides, herbicides, bird repellents, growth substances, fertilizers and soil conditioners.

The formulations generally contain 0.1-95% by weight of active compound, preferably 0.5-90%.

The active substances can be used alone, in the form of kenitraites or prepared from them by further dilution of the use forms such as solutions, emulsions, suspensions, powders, pastes and granules. The agents are applied in a known manner, for example by watering, spraying, nebulization, dusting, sprinkling, dry, wet, wet, slurry or encrusting.

103 472

When used as fungicides on the list, the active substance concentrations can vary widely. In general, this concentration is 0.1-0.00001% by weight, preferably 0.05-0.0001% by weight.

In general, 0.01 to 50 g of active substance per kg of seed, preferably 0.01 to 10 g, are used for seed treatment.

For soil treatment, 1 to 1000 g of active substance are used per m2 of soil, preferably 10 to 1000 g.

At the appropriate doses, the new active substances also have a growth regulating effect.

The following examples explain the invention in more detail.

Example I. Test for the treatment of shoots (powdery mildew) - ringworm damaging to Usti - preventive and curative treatment.

To obtain a preferred preparation of the active substance, 0.25 parts by weight of the active substance are dissolved in 25 parts by weight of dimethylformamide and 0.06 parts by weight of alkylaryl polyglycol ether and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration in the spray liquid.

In order to test the preventive effect, young barley plants of the Amiłów species in the one-leaf stage are sprayed into the reflux with the preparation of the active substance. After drying, the barley plants are dusted with spores of Erysiphe mówisis var. hondei.

Table I

Shoot treatment - powdery mildew (preventive and curative)

<td rowspan="2">The active substance</td><td rowspan="2">SS^s ll O o q hl and n. 3 '£ 3 £ rt ω G £</td><td colspan="2">Infection rate in% relative to iniI treated control</td>

<td>prevention gawczo</td><td>therapeutic forehead</td>

<td>untreated trial</td><td> _</td><td> 100,0</td><td> 100,0</td>

<td>compound of formula 6</td><td></td><td></td><td></td>

<td>(known)</td><td> 0,01</td><td> 21,3</td><td> 45,0</td>

<td>compound of formula 7</td><td></td><td></td><td></td>

<td>(known)</td><td> 0,01</td><td> 26,3</td><td> :—</td>

<td>compound of formula 8</td><td></td><td></td><td></td>

<td>(known)</td><td> 0,01</td><td> —</td><td> 33,8</td>

<td>compound of formula 9</td><td></td><td></td><td></td>

<td>(Zinainy)</td><td> 0,01</td><td> 20,0</td><td> —</td>

<td>compound of formula 10</td><td> 0,01</td><td> 0,0</td><td> 0,0</td>

<td>compound of formula 11</td><td> 0,01</td><td> 0,0</td><td> 0,0</td>

<td>compound of formula 12</td><td> 0,01</td><td> 0,0</td><td> ' —</td>

<td>compound of formula 13</td><td> 0,01</td><td>o, o</td><td> —</td>

<td>compound of Formula 14</td><td> 0,01</td><td> 0,0</td><td> —</td>

<td>compound of formula 15</td><td> 0,01</td><td> 0,0</td><td> —</td>

In order to examine the therapeutic effect, the procedure is similar but in the reverse order. Treatment of young barley plants at the one-leaf stage with the active substance preparation is carried out 48 hours after inoculation, when the infection is already visible.

The plants are stored for 6 days at a temperature of 21-22 ° C at a visual humidity of 80-90%, after which the degree of plant infection with the blister bubbles is determined. The degree of infection is determined as a percentage of the treated control, where 0% means no infection and 100% means the degree of attack equal to the untreated control. The active substance is the more active the lower the degree of attack with powdery mildew.

Table I lists the active substances to be tested, the concentration of the active substance in the spray liquid and the degree of infection.

Example II Testing of barley powdery mildew (Ery.sipłhe graminis var. Hordei - tinea sprouts) - systemic effect.

The active substance is used as a powder for seed treatment. This agent is prepared in such a way that the active substance is mixed with a mixture of equal parts by weight of talc and diatomaceous earth to obtain a finely powdered mixture with the desired concentration of active substance.

To treat the seed, the active substance prepared in the manner described above is shaken with barley grains in a closed glass bottle. Seed is sown using 3X112 grains into pots at a depth of 2 cm to a mixture of 1 part by volume of Erustorfer standard soil and 1 part by volume of quartz sand. Germination and growth are carried out in favorable greenhouse conditions. 7 days after sowing, when the barley plants develop their first leaf, they are dusted with fresh spores of Erysiphe graminis var. hordei and keep growing at temperature

21-20 ° C at 80-90% relative humidity and 16 hours exposure. Within 6 days, typical powdery mildew vesicles form on the leaves.

The infection rate is determined as a percentage of untreated control plants, where 0% means no attack and 100% means the degree of infection equal to the untreated control. The active substance is the more active, the lower the degree of mildew infection,

Table II gives the active substances tested, the concentration of the substance. active in the seed treatment agent, the dose of this agent and the percentage of mildew infection.

103 472

Table II

Testing of mildew of barley (Erysiphe gramlinis var. Horde i) syistemic effect

<td>The active substance</td><td>Substance concentration open inside dressing in wt.</td><td>Dose of measure in g / kg of seeds</td><td>Degree of infection in%</td><td>relative to untreated trial control</td>

<td>untreated trial</td><td> . _</td><td> _</td><td></td><td> 100,0</td>

<td>compound of formula 16</td><td></td><td></td><td></td><td></td>

<td>(known)</td><td> 25</td><td> 10</td><td></td><td> 100,0</td>

<td>compound of formula 9</td><td></td><td></td><td></td><td></td>

<td>((known)</td><td> 25</td><td> 10</td><td></td><td> 100,0</td>

<td>compound of formula 10</td><td> 25</td><td> 10</td><td></td><td> 0,0</td>

<td>compound of formula 13</td><td> 25</td><td> 10</td><td></td><td> 8,8</td>

<td>compound of formula 14</td><td> 25</td><td> 10</td><td></td><td> 33,8</td>

<td>compound of formula 15</td><td> 25</td><td> 10</td><td></td><td> 0,0</td>

Example III. Shoot testing - cereal rust (mycosis damaging leaves) - preventive action.

To obtain a preferred preparation of the active substance, 0.25 parts by weight of the active substance are dissolved in 25 parts by weight of dimethylformamide and 0.6 parts by weight of alkylaryl polyglycotyl ether and the diode consumes 975 parts by weight of water. The concentrate is diluted with water to the desired final concentration in the spray liquid.

To investigate the preventive effect, young leaf plants of the Michigan Amfoer species are infected on the one-leaf stage with a suspension of Puccinia recondita uredospores in 0.1% water agar. After drying the spore suspension, the wheat plants are sprayed with the preparation of the active substance until refluxed and left to incubate in a greenhouse for 24 hours at 20 ° C and a relative humidity of 100%. After 10 days of keeping the plants at a temperature of 20 ° C and a relative humidity of 80-90%, the degree of attack of plants by rust bubbles is determined. The degree of infection is determined as a percentage of the untreated control, with 0% indicating no infection and 100% representing the level of infection equal to the untreated control. The active substance is the more active the smaller the rust infection.

The active substances tested, the concentration of the active substance in the spray liquid and the degree of infection are given in Table III.

Chapter IV. Seed treatment agent (barley pollen blade - mycosis from seeds).

To obtain a beneficial seed treatment agent, the active substance is mixed with a mixture of equal parts by weight of talc

Table III

Shoot treatment test (cereal rust) - preventive action

<td> 5 16</td><td>Substance c</td><td>zynna</td><td>Substance concentration active in liquid to spraying in % by weight</td><td>Degree of infection in% against untreated trial control</td>

<td></td><td colspan="2">untreated trial</td><td> —</td><td> 100,0</td>

<td> 15</td><td>compound of formula</td><td> 17</td><td> 0,025</td><td> 82,5</td>

<td></td><td>(known)</td><td></td><td> 0,011</td><td> 100,0</td>

<td></td><td>compound of formula</td><td> 18</td><td> 0,025</td><td> 100,0</td>

<td></td><td>(known)</td><td></td><td> 0,025</td><td> 100,0</td>

<td></td><td>compound of formula</td><td> 13</td><td> 0,025</td><td> 25,0</td>

<td> 20</td><td>compound of formula</td><td> 14</td><td> 0,025</td><td> 25,0</td>

<td></td><td>compound of formula</td><td> 19</td><td> 0,01</td><td> 12,5</td>

and diatomaceous earth, obtaining a finely powdered mixture with the desired concentration of substance_2g active participation.

For treatment, the barley seeds are shaken naturally infected with the barley pollen head (Usłtilago nuda) with the dressing agent in a closed bottle. The seed sows_3θ weighs 2X100 grains in boxes to a depth of 2 cm to a mixture of 1 part by volume of standard soil Frubstorfer and 1 part by volume of quartz sand. The boxes are placed in a greenhouse at a temperature of about 18^ATC ₃₅ keeps in normal humidity and irradiates daily for 16 hours. After 10-12 weeks, barley blooms and turns out to be healthy and sick ears. After the lapse of this time, sick ears are determined as a percentage of the total_4θ ears generated, where 0% means that there are no sick ears, and 100% means that all ears are sick. The active substance is the more active the less sick ears.

Table IV gives the tested active substances₄₅ ne, concentration of active substance in the treatment agent, doses of the agent and number of affected ears.

Table IV

Seed dressing agent - barley pollen blade

<td>The active substance</td><td>The concentration of active substance in the treatment agent in wt.</td><td>Product dose in g / kg of seeds</td><td>Number of sick ears in% relative to the total number of ears</td>

<td>untreated trial</td><td> —</td><td> —</td><td> 11,4</td>

<td>compound of formula 20</td><td> 25</td><td> 10</td><td> 12,3</td>

<td>compound of formula 21</td><td> 25</td><td>and</td><td> 9,2</td>

<td>compound of formula 10</td><td> 25</td><td> 10</td><td> 0,0</td>

<td>compound of formula 11</td><td> 25</td><td> 10</td><td> 0,0</td>

103 472

Example V. Fusicladium testing (apples) - preventive action.

Solvent: 4.7 parts by weight of acetone. Emulsifier: 0.3 parts by weight of alkylaryl polyglycolyl ether.

Water: 95 parts by weight

The amount of active substance needed to obtain the desired concentration of active substance in the spray liquid is mixed with the amount of solvent given and the concentrate is diluted with the amount of water containing the additives mentioned. Young apple seedlings at the 4-6 leaf stage are sprayed with liquid for spraying. The plants are left in the greenhouse for 24 hours at 20 ° C and a relative humidity of 70%. They are then infected with an aqueous suspension of Fusicladium dendriticum spores and kept in a humid chamber at 18-20 ° C at 100% relative humidity for 18 hours, whereby the plants are again transferred to a greenhouse for a period of 14 days. 15 days after infection, the degree of plant attack is determined. The values ​​obtained are converted into percentages, where 0% means no infection and 100% means that the plants are completely attacked.

Table V lists the active substances tested, the active substance concentration and the results obtained.

Table V

Test ina Fusicladium (apple tree) - preventive action

<td>The active substance</td><td>The degree of infection in% at the concentration of the active substance 0.025% 0.01% / 0.0025%</td>

<td>compound of formula 9 (known)</td><td> 43 — —</td>

<td>compound of formula 22 (known)</td><td> — 62 —</td>

<td>compound of formula 10</td><td> — 59 —</td>

<td>compound of formula 11</td><td> — 62 —</td>

<td>compound of formula 15</td><td> — — 26</td>

<td>compound of formula 19</td><td> — 10 —</td>

Example VI. Uromyces testing (bean rust) - preventive action. Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkyl aryl polyglycol ether

Water: 95 parts by weight

The active substance in the amount needed to obtain the desired concentration in the spray liquid is mixed with the amount of solvent given and the concentrate is diluted with the given amount of water containing the additives mentioned. Young bean plants at the 2-leaf stage are sprayed with a spray liquid. The plants are left to dry in a greenhouse for 24 hours at a temperature of 20-22 ° C and a relative humidity of 70%. They are then infected with an aqueous suspension of Uromyces phaseoli uredospores and kept for 24 hours in a dark moist chamber at a temperature of 20-22 ° C and a relative humidity of 100%. Then the plants are transferred to the greenhouse intensively irradiated for 9 days at a temperature of 20-22 ° C and a relative humidity of 70-80%. 10 days after infection, the degree of attack on the plants is determined. The values ​​obtained are converted into percentages, where 0% means no infestation and 100% means complete infestation.

The active substances tested, the concentration of active substances and the results obtained are given in Table VI.

Table VI

Uromyces testing - preventive action

<td rowspan="2">The active substance</td><td colspan="2">Paralysis in% of untreated control at active substance concentration</td>

<td> 0,005%</td><td> 0,0025%</td>

<td>compound of formula 22</td><td></td><td></td>

<td>(known)</td><td> 59</td><td></td>

<td>compound of formula 10</td><td> —</td><td> 46</td>

<td>compound of formula 11</td><td> — '</td><td> 12</td>

<td>compound of formula 15</td><td> —</td><td> 54</td>

<td>compound of formula 12</td><td> —</td><td> 29</td>

Example VII. Testing · Erysdphe (cucumbers) - preventive action.

Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether Water: 95 parts by weight

The active substance in the amount needed to obtain the required concentration of active substance in the spray liquid is mixed with the indicated amount of solvent and the concentrate is diluted with the given amount of water containing the said additives. Spraying liquid - young cucumber plants with about 3 assimilation leaves are sprayed for refluxing. Cucumber plants are left in. greenhouse to dry for 24 hours. They are then dusted with spores of the Erysiphe cichoriacearum fungus, after which the plants are kept in a greenhouse at a temperature of 23-24 ° C with a relative humidity of about 75%. 12 days after infection, cucumber plant infection is determined. Obtained. the values ​​are converted into percentages, where 0% means no infestation and 100% means complete infestation.

Table VII lists the active substances tested, the concentration of active substances and the results obtained.

103 472

Taifolica VII

Testing Eryisipihe (cucumbers) - preventive action

<td rowspan="2">The active substance</td><td>Paralysis in% at the concentration of the active substance</td>

<td> 0,000.31% 10,00025%</td>

<td colspan="2">compound of formula 16 (, known) 56 - compound of formula 22 (known) ²⁹ - a compound of formula 13-19 a compound of formula 14-16</td>

Example VIII Pellicularia testing. Solvent: 11.75 parts by weight of acetone Dyspergatoir: 0.75 parts by weight of polyglycol ether

Water: 987.50 parts by weight

Other additives: - parts by weight

The amount of active substance needed to obtain the desired concentration of active substance in the spray liquid is mixed with the amount of solvent and dispersant given and the concentrate is diluted with the given amount of water. The spray liquid is sprayed to reflux 2X30 approximately

2–4 weeks of rice plants. The plants for drying · are left in the greenhouse at temperature

22-24 ° C and a relative humidity of approximately 70%. Plants are infected with malt agar culture Pellicularia sasaikii and left at 28-30 ° C and 100% relative humidity. Pellicularia sasakii paralysis on. plants are determined after 5-8 days in relation to untreated but infected control plants. The results are determined on a 1 to 9 scale, with 1 being 100%, performance, 3 being good, 5 being medium and 9 being inactivity.

Table VIII lists the active substances tested, the active substance concentration and the results obtained.

Table VIII Testing Pellicularia

<td>The active substance</td><td>Degree of infestation at active substance concentration 0.025%</td>

<td>compound of formula 23</td><td></td>

<td>(known)</td><td> 9</td>

<td>compound of formula 10</td><td> 3</td>

<td>compound of formula 12</td><td> 5</td>

<td>compound of formula 14</td><td> 3</td>

<td>compound of formula 19</td><td> 3</td>

The following examples further explain the method for producing the active ingredient of the agent according to the invention.

Example IX. Compound of formula 10.

g (0.091 mol) of 4-fororo-4- (4-chloro-phexoxy) / H-2,2-dimethyl-3-ketone-ethyl ester is dissolved in 240 ml of acetonitrile. Then 24 g (0.345 mole) 1,2,4-yttriumzol are added and the mixture is heated under reflux for 48 hours. Then the solvent is distilled off under reduced pressure, the residue is dissolved in 200 mil of methylene chloride, washed three times with portions of 50 ml of water, dried over sodium sulfate and concentrated. The oil obtained as a residue is boiled with 100 ml of petroleum ether and crystallization takes place. The solid is filtered off and dried. 24.9 g (78% of theory) of 4- / 4-trichloro-phenoxy / -2,2-dimethyl-3-keto-4- (1, 2-4-triazolyl-1) ethyl ester are obtained. butane with a melting point of 88-89 ° C.

The starting compound of Formula 24 is prepared as follows:

316 g (i2 moles) of ethyl ester · 4-bromo-2,2-idwurneltyl-3-ketO'-bU'tainic acid is added dropwise at 30 ° C to 246 g (2 mole) of 4H-phosphoroyl and 210 g of potassium carbonate in 1000 ml dimethoyl-thimma-midu. The mixture is left for 20 hours at room temperature and for 2 hours at 40 ° C, after which the mixture is transferred to 2000 m, 1 water. The aqueous phase is shaken twice with 500 ml portions of methylene chloride and the organic phase twice with 250 ml portions of water. The combined organic phases are dried, concentrated and distilled. 324 g (56% of theory) of 4- / 4HC'-4-chlorophenoxy-2,2-idimethyl-43-ikio-foutaine ethyl ester with melting point 125-135 ° C / 0.1 mm Hg.

g (0.0191 mole) of ethyl ester 4- / 4-ichllor of enokis y / -2.2-two-nitrole 3 -Ik et o-butane dissolved in 150 ml · carbon tetrachloride. At room temperature, 4.7 ml (0.091 mol) of bromine in 50 ml of carbon tetrachloride are added dropwise in talcum so that continuous consumption occurs. Then stir for 30 minutes at room temperature. After distilling off the solvent under reduced pressure, 44óromo-4- / 4-chloro-phenoxy / H2,2-! -Divumethyl-3-keto-foutanoic acid 'ethyl ester is obtained in quantitative yield, which is directly processed further.

Example X. A compound of formula 13.

145 g (0.4 mol) of 4-bromo-4-chloro-phenoxy-2-S-dimethyl-nS-4-butyl-ethanoic acid ethyl ester is dissolved in 800 ml of acetonitrile. 100 g (1.45 mol) of imiidazole are added and heated for 20 hours under reflux. Then the solvent is distilled off under reduced pressure, the residue is taken up in 500 ml of methylene chloride, washed three times with water in 200 ml portions, dried over sodium sulfate and concentrated. The oil obtained as a residue is dissolved in 800 ml of acetone and treated with 100 g (0.35 mol) of 1,6-naphthalene disulphonic acid in 300 ml of acetone. The crystalline precipitate obtained is suction filtered and dried. 122.5 g (62% of theory) of naphthalene-1,5-di-103 472 are obtained

18 4- (4-di-chlorophenokBy) -2,2-dimethyl-4- (imidazolyl- 1/3-keto-butanoic acid ethyl ester sulfonate, m.p. 194 ° C.

Example XI. Compound of formula 14.

122.5 g (0.248 mol) of naphthalene, ethyl ester 5-disulfonate · 4- (4-chlorophenoxy) acid / -2.2Hd-dimethyl (1) / imidazinylH1 / 3-iketo-butanoic acid (Example X) are suspended in 500 ml of methylene chloride and mixed with 1000 ml of saturated sodium bicarbonate solution for 1/2 hour. The organic phase is separated, dried over sodium sulfate and concentrated. The residue crystallizes on heating with 200 ml of petroleum ether. 85 g (98% of theory) of 4- / 4-chlorophenoxy / -2,2-dimethyl-4- (imidazolyl-1 / -3-keto-butanoic acid ethyl ester) are obtained with a melting point of 88 ° C.

Example XII. Compound of formula 15.

17.5 g (0.05 mole) of 4- (4-chloro) enoxyl-2-yl-4- (imidazolylH1 / 3-ket-4-butanoic acid ethyl ester) (Example 11) is dissolved in 100 ml of ethanol. Then 2 g (0.05 mol) sodium borohydride are added portionwise at 0-10 ° C and stirred for a further 15 hours at room temperature. The solvent is then distilled off under reduced pressure and the residue is taken up in 100 ml of methylene chloride,

100 ml of water and 5 ml of concentrated hydrochloric acid.

The mixture is stirred for 4 hours at room temperature, neutralized with sodium bicarbonate, the organic phase separated, dried over sodium sulfate and concentrated. The oily residue is recrystallized from ether (petroleum ether to give 12.3 g (70% of theory)₅ 4-) 4-chloro-phenoxyl ethyl ester / ^ 2-dimethyl-3-hydroxy^j4- / imidazole^andyl^J1 / -butane as a mixture of isomers (erythro and threo) with a melting point of 120 ° -124 ° C.

and Example XIII. Compound of formula 25.

8.2 g (0.026 mol) 14> romOHl- / 4-chlo-phenoxy / -2-cyano-3-methyl-butanone-2-dissolved in 20 ml of acetone and slowly dropped into a boiling mixture 6.8 g (0.1 mole) imidazole in 150 ml of acetone. The mixture is heated under reflux for 2 hours, then the solvent is distilled off and the oily residue is separated in a water / methylene chloride two-phase system. The methylene chloride phase is separated off, washed several times with water, dried over sodium sulfate and concentrated. The oily residue is taken up in 50 ml of acetone and treated with an excess of naphthalene-1,5-disulphonic acid. The crystalline solid obtained is suction filtered and dried. 8 g (69% of theory) of naphthalene-1, 5-chlorophenoxonate 1- (4-chloro-phenoxy) -3-cyanoHl - / imidazolyl4 / 3-methyl-butanone-2 with melting point 245 ° C (decomposition).

By analogy with the above examples you can ³⁰ also obtain compounds of formula 1 as listed in Table IXj

Table IX

<td>Relationship Code No.</td><td>Zn</td><td>Y</td><td>AND</td><td>R^L</td><td>R "</td><td>R</td><td>Temperature MELTING (O °</td>

<td> 6</td><td>2,4-C1₂</td><td>CH</td><td>WHAT</td><td>CH »</td><td>ch.</td><td>-oox&gt; c h₅</td><td>235-237 (model 26)</td>

<td> 7</td><td>4 R Cl</td><td>N</td><td>WHAT</td><td>CH »</td><td>CH,</td><td>-CO-O-₂h₅</td><td>128-130 (x HCl)</td>

<td> 8</td><td>4 ^ -Cl</td><td>N</td><td>WHAT</td><td>CH,</td><td>CH,</td><td>^ CO-OCH</td><td> 94—95</td>

<td> 9 *</td><td>C1 ^ 4</td><td>N</td><td>WHAT</td><td>CH,</td><td>C "H,</td><td>-CO-OC₂H₅</td><td> 91—94</td>

<td> 10</td><td> 4—0</td><td>N</td><td>WHAT</td><td>CH,</td><td>iso-C "H₇</td><td>-CO-O-₂h₅</td><td>73-77 (schedule)</td>

<td> 11</td><td>designs 27</td><td>N</td><td>WHAT</td><td>CH,</td><td>CH,</td><td>-CO-O-₂h₅</td><td> 95—97</td>

<td> 12</td><td>pattern 27</td><td>N</td><td>WHAT</td><td>CH,</td><td>CH,</td><td>&lt;X) -OC ^ H₅</td><td>12 — '79 (x HCl)</td>

<td> 13</td><td>4-Cl</td><td>CH</td><td>What</td><td>CHi</td><td>iso-C H₇</td><td>-CO-OĆjHs</td><td> 84—08</td>

<td> 14</td><td> 4—^01</td><td>N</td><td>What</td><td>c * h₅</td><td></td><td>-CO-OCjH.</td><td> 83—05</td>

<td> 15</td><td>4-Cl</td><td>N</td><td>CHKOH)</td><td>CH,</td><td>c, h₅</td><td>-CO-OCaH.</td><td>98 aoe</td>

<td> 16</td><td>4-Cl</td><td>CH</td><td>WHAT</td><td>CH,</td><td>c, h₅</td><td>-CO-OC₂H₅</td><td> 86—09</td>

<td> 17</td><td>formula 27</td><td>CH</td><td>WHAT</td><td>CH,</td><td>ch.</td><td>-CO-O-₂h₅</td><td> 83—06</td>

<td> 18</td><td>4-NO₂</td><td>N</td><td>WHAT</td><td>CH,</td><td>CH,</td><td>-CO-O-₂h₅</td><td>158 (X HNO,)</td>