CS253747B2 - Fungicide and process for preparing active compound - Google Patents

Abstract

Die Erfindung betrifft neue Nicotinamide der Formel worin R¹, R², R³, m und n die in der Beschreibung angegebenen Bedeutungen besitzen, und ihre Säureadditionssalze, Verfahren zu deren Herstellung, fungizide Mittel, die diese Verbindungen als Wirkstoffe enthalten, sowie die Verwendung solcher Verbindungen bzw. Mittel zur Bekämpfung von Fungi in der Landwirtschaft und im Gartenbau.

Description

(54) A fungicidal composition and a process for the manufacture of an active ingredient

The fungicidal composition is characterized in that the coating is an effective amount of at least one nicotinamide of the formula I

Cn O-CH ₂ -CH ₂ -O ^^ ^r2 '0 ~ ^{(R3, n.} (I) in which R ^x represents a halogen atom in position and / or 6-position of the pyridyl group,

R represents an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to carbon atoms in the alkoxy moiety having 1 to 4 carbon atoms in the alkyl moiety, a cyanoalkyl group having 1 to 4 carbon atoms in the alkyl moiety, an alkynyl group having 3 to 6 atoms carbon or optionally benzene ring with a mono-, di- or trisubstituted benzyl group, the optionally present substituents being 1 to 3 halogen atoms and / or 1 or 2 alkyl groups having 1 to 3 carbon atoms and / or 1 or 2 alkoxy groups having 1 R 3 is halogen, C 1 -C 3 alkyl or nitro, m is 1 or 2 and n is 1, 2 or 3, or addition salts thereof with acid.

The present invention relates to a fungicidal composition comprising, as an active ingredient, a heterocyclic compound, namely the nicotinamides of the general formula (I) below and further defined.

It has been found that the heterocyclic compounds, namely the iicotinamides of formula I

in which, ^r! represents talogenu in ol.oze ^P 5 and / or 6-pytoctylové sJcujDin

R represents a (C1-C6) alkyl group, ⁽ C1-C4) alkoxyalkyl, (C1-C4) cyanoalkyl, (C3 ^- C6) alkynyl or optionally benzene ring, mono-, or di- or trSuubstiUloaanou benzyl, optionally present přčeemž subssituenty are represented by 1 to 3 halogen atoms and / or 1 or 2 alkyl groups having 1 to 3 carbon atoms and / or 1 or 2 ^p alktxytku INAO 1 -C R3 is halogen, alkyl of 1 to 3 carbon atoms or nito, m is 1 or 2 and n is 1, 2 or 3, as well as addition salts of these compounds with acids have fungicidal properties and are therefore suitable as fungicidally active substances, in particular for offering in the wall. and in rewarding.

Accordingly, the present invention provides a fungicidal composition which comprises an effective amount of at least one compound of the above-defined and defined general formula (I) or an acid addition salt of such a compound, as well as excipients used in such. means.

The present invention further relates to a process for the preparation of a compound of formula I and their acid addition salts. ’

In the above formula I the term halogen includes fluorine, chlorine, bromine and iodine. The alkyl groups and the aikinyl groups may be straight or branched chain, and this also applies to the alkyl portion of the alkoxyalkyl groups, the alkoxy group and the cyanonyl groups. In tuované l-pyridyl or rituSttitoované trtsubttitoíaané or phenyl group, ^m o n ^{u tubsSituent?} R ^{1 p} R lean ^p ACLE ^J identical or rozdtoné. Thus ^é ^ i ^^ E, K, ^R Y ^Z

R is a di- or tri-substituted benzyl group, the subsites may be the same or different from each other.

The presence of at least one amino atom in the compounds of formula I results in the compounds being present in optically isomeric forms. Irrespective of this, atropisometry also occurs in certain cases. Formula I is intended to include all these possible forms of the form.

SOU compounds of formula I with k1se · ^y inimdj coming! consider f1ziρ1fюН. These preferably include these compounds with inorganic and organic such as hydrochloric acid, nitric acid, phosphoric acid, double carboxylic acid. iyselinl-and ^p ah droxyklr5ox 1pvými kyselinl ^p-i, acid, sorbic acid and

1,5-naphthalenesulfonic acid.

As affinity gels tolerant to cpsellins, with monohydrates and with acetic acid, mellipipine, amber ellipsis, film beauty, grapevine by new acid, salt ^of fp1

with a lactic acid, and with sulfonic ipseliils with n, the following must be mentioned:

para-positions of the pheny1 stopii. Preferably, the radical is a ^C 1-6 alkyl group having 1 to 6 carbon atoms in the 1 to 4 carbon moiety containing from 1 to 4 carbon atoms substituted by a benzo group, as defined in greater detail below. ^J means

Regarding preferred význlmp -1iolů ^ R, R, R, m where n is R is llipχyllkylpvP1 kylnalkylovo1 group or a group, then this group is preferably 21meehox ^p pe ^p 1ovS group optionally kylnImf ^p lovS quick match. (R ¹⁾ _m is preferably jfUniO ^y Ivy halogen atom in the 5-position ^R oy idylpvé StopIN. Rpvněi preferably located subbSit1fitp · R in the ortho- and / or ц-Ьь R @ ¹ preferably ^represents fluorine, chlorine atoms, ^Y verifies l1koxp group having 1 or llkylpvé or in ^and on, in particular with ^the UPIN ^{ethyl, i-1p} up ^PY1 ovp1 quick match no ^b ^ n of tulle quick match R 'is preferably a halogen atom or a quick match l1kylpvou 1 3 ai ^ рт1 atoms, especially chlorine or mee pvpu ^pyridine radical, m is preferably a number lil is preferably 2 or 3. More especially výhodným- The R 1 -substituted-i-group (s) (R 3) are the 2,4,6-brichloro-trichloro group, the 2,4-di-6-methyl-phenyl group and the 1,6-di-phenyl-phenyl group.

Particularly preferred compounds of formula I are:

5-fluoro-N- ^(n-propyl) -N- ^[- - ² 4 O-trichlorophenoxy) ethyl] nicotinamide. c-Choro-N- (n-l ^ Poo) -i- ² 2- ^{(2, 4,} ог тхр et ^pl ^ j ^ ni.tottoaei

5 ^ γοιπ --- (n-propyny) ---! 2- (2,4, 6 for ^ x1 ^ t11] nicotinamide, 5 "Pκ ^ (^ - ^ ^{[2 '(2,} 6-diisopropyl ^h LPU fiPxy ^f) e ^ l] - ^- - (i- ^about rpop ^l) iίko ⁱⁱ lam ^id and 5-orern --- [2- ^(4, 6 ^{h d} iih chloro-p · tp ^LP lpχ ^p) ft ^{PLJ (N- (n-op} l) Niko-AAM ^.

Further representatives of the compounds of formula I are the smoking compounds:

5-f fuρrlN- ^(IH C ^{fU 5rbinyyl)} -N- [2- ^{(2, 4,} o ^ ^ et ENOX ^p) T | n ^ i-PtíiamiU cPUl) -lH ^{'(4-chlorobenzyl)} - · - N - (2 4, O-t ^ s ^ r ^ ^ηοχ ρ) etpLj Lito-to-id-5 Prrm - ^ (- ^(if hhfr5fenz Γ ^{p (r} l-22- ^(2, 4> ^h stiff б-lpr eipχ ^{f p)} -ethyl] nitotwamid

5-f ^ ρ - Ν- ^(2, 4 ^{(d: l} thereof ou ^ ^ ^b ^ em: ^Y i ^{L) -} · [- ^{(2, 4,} for ¹ ENOX) eth yl ^j ni.tot ^ amino ^ C-COO - N- ^{(2, 4 h} -dii lpr ⁵ ENI ^py) -N- ^([2- (24-б ⁱ ch the ^l PR eifx ^{f p) p} l ft] iitot ^AEI-d ,

^5-fluoro-1 --Ν- ^[2 - (2,4, s ^ here: ^ (^ ^H) ^ f ^ I ^ ^ff if ^χ ^)) ^ t: ^t ^]. ^] (^ ^- l-4 tufflpurrft ^{pl. 5} fnzy ^s) iitot ^ ^d AEI. 5-0111 (^ ---- ^[2- (2,4, ^x ^ e IOX ey ^first Iou --- - e ^ lleizy ¹ ) litotJLnu — id,

Five-br ^o m-1l- ^[- 2- (2,4,6-stiff lfuffifxyle ^h ^ l. ^- - ⁽⁴ - ^t r ^f1 LPU) rmft ^p5 bfiz ^P1) i ^{i i} lar Cpt ^id 5- 1f1upr-N- ⁽¹ -mfthpχ ^Y5 Enz ^py) - ^R1o 2- ^(2, 4-phenoxy) -ethyl-5-nitotdnami CK1 ^of u ^ (^ - i, 4 ^- ethpχyb5ei УL ^yl) -N- [2- (-4, ^{6 h} -tuic lpr eipχ ^{f y), P} l ^j et Nitot Lnamid-5-bromo-N- (4-mrehho УenfnZ ^yl) -1--22 (2,4, or ^ ηοχρ) ^ρ ^ 1 niOoilnr aa-id

5-rl ^1p u - 1 (MEF-4 ^{P 5} L ^yy EEI) -N- [2- ^(2,4,6 -tuic ^hy eipχ fc ^{f p)} et ^py ^ J Nitot ínam.И 5- ^ 1 1 ^ --- (4--6 vltanny ^ ¹⁾ - · - N - (2,4, ^{6 h} -tuic LFR eiPxy ^f) e ^{f j} iitottoaei- 5-5γό yl ^- - 4-m ^ ^ beei ^) --- [ ^2- (2,4, 4-trichloro-ethoxy) -ethoxy] -idene, 5-11 ^^ - (3 ^, ^ (Uichtor ⁵ ©!! ^ ¹ ) -1--2- (-4 ^^^^ р ^ еих ¹ ^ t ^p1) j

5-chloro · ^ρ r-- ^{- (3, 4} ~ ⁵ pu diih ^{y yy ENI) -} --- [- (2 4 e IOX ^y ^^ Ι] ^ iitot aeid,

5-5 ^uo- -N- ^(3, 4- ^d iih ^y Pu ⁵ ENI ^yy) - ^- -1 2- ^(2, 4, ^{6 and} ch -TU ^fp eiPxp ^{f r)} ftplJn ^IPP laei ^U t ^i, 5 -11 --- ^ 1 ^ H-nitoobenz: ¹ :)) --- ^ ² - (4 ⁴ o ^ ^^ silence ENOX ¹⁾ iitot-amide,

5-chloro ^yp r1 - ^(4-py 5fnz iitp ^P) 1-1 ^{[2- (2,} 4, ^{6 and} -TU C ^H L ^{P f} r eipχp) FT11] nito-benzenesulfonamide Б-Ьгот -! - ( 4-n ⁱ trob5ei ^yy) -N- ^[2 - ^(2, 4, ^{6 and} c -TU ^HFP eipχ r ^{f p)} f-1] N ^ ot ^ by amino-5 --- SPD (nib51yУ) --- -2- (2,4-6 tuichf rfeiPX1 ^p) f t11] ^ nk ^ Oin -id, jod-- · 5 - - - ^J 2- ^(2,4,6 -triene ⁱ ch ^l or ^f inpχ ^p ) e ^ 1 ^] nitito namide

5 ^j-p-ef dr ^y --- 1 ^{2 1} - ^(4-6-P ro dichh it ^^ x ^ ¹ et 1] and nitotwaeid

5 SLM --- 1! F ^t ^ - ^ 2- ^(2,6 - ^{d] j} i ^h iPr. ^F EIO) yУef ^ \ dJ iitottoaeid ^l.

The process for the preparation of the compounds of the formula I and their acid addition salts according to the invention consists in reacting a nicotinic acid derivative of the formula II with a reactive derivative.

COOH

in which

R ¹ and m have the same meaning as above, with 2-phenoxyethylamine of formula III

in which

3 *

R, R and n are as defined above, and optionally the compound of the formula thus obtained

It is converted by reaction with an acid to the corresponding acid addition salt.

In the process according to the invention, the nicotinic acid derivatives of the formula serve as reactive derivatives

III is preferably a cyanogen chloride, in particular a cyanogen bromide or a cyanogen bromide or an imidazole. In both cases, the reaction is expediently carried out in the presence of a substantially anhydrous, inert diluent, in particular an organic solvent, such as an alkyl or cyclic ether, for example 1,2-dimethoxyethanol, trifluoromethylphenol. tc, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene or toluene; an alkali halogenated hydrocarbon, baked adelenesilide or chloroform; or dj ^ m ^ Ethyl ^^ ^ and ODM-bromide, or with such diluents Smee te ^ ^ rotates between ^about-20 ° C and about ⁵ l 0 ° C. ^V ^ for planks ^ ožitíí ^h alo ^g Enid ^to yseliny with ^ acuje above ^h ODN ^{e p} s te ^ rotation-mei ° C and te ^ Otto boiling rea ^ her he ^{m IEI,} particularly bowtie above ^h o ^{n e p} s temperature between approximately rOOM ^ i, and in case of ingestion of the imidazolide reaction is preferably carried out at temperatures mei room temperature ^and about ¹² 0 ° C, particularly preferably ^{of p} s boiling temperature between approximately reatóní sráíěi ^p Z ^ ^ what sLex chilled.

In addition, the reaction of the acid halide with 2-phenoxyethylamine is conveniently carried out in an organic or inorganic acid-binding agent. Suitable acid-forming agents are, in particular, tertiary amines, such as triethylamine and pyridine, as well as alkali metal and alkali metal hydrogencarbonates, such as sodium carbonate and potassium carbonate and sodium hydrogencarbonate and potassium lydrogen carbonate.

In the desert of imidazolide, iiidazolide is preferably produced in situ by reacting nicotinic acid of formula (II) with carbonyldiimidazole in a substantially anhydrous inert diluent, in particular one of the abovementioned organic solvents, and at elevated temperature, in particular boiling point. Under reflux. The reactants are used for the reaction preferably in a substantially equimolar manner. Thereafter, optionally after cooling the reaction mixture to the temperature of the mixture, 2-phenoxyethylamine of the formula III is added to the mixture, although also preferably in an equimolar amount, and the reaction of the imidazolide produced in situ with the amine is then carried out as described above in the same reaction medium. . Iidazolid, however, can first be isolated in the usual manner and then reacted with the amine in a new diluent.

The acid addition salts of the compounds of formula I are prepared by reacting the compounds of formula I with the desired acids in a conventional manner.

methods known per se

The isolation and purification of the compounds of the formula I thus prepared and the acid addition salts thereof can be carried out by methods known per se. In addition, the optional isomers of the isomers of these compounds can be separated by isomers.

The starting materials, i.e., the cicotinic acids of the formula i, 2-phthylamines of the formula III are either known or

II and its reactive derivatives, as can be prepared by methods known per se.

The compounds of the formula I and their acid addition compounds have a fungicidal action and can accordingly be used for combating fungi in agriculture and in agriculture. They are particularly suitable for inhibiting the growth or destruction of phytopathogenic fungi on parts of rossiins, for example on lice, stems, roots, tubers, fruits or flowers and on seeds, as well as in soils, and are particularly effective in combating weed bites and fungi Ceecotpoteela herpoOricUnidmt (cereal stalk breakers), rapeseed (Alternaria brassicae and Aletrnaria braessciccoa), and cucumber Erysiphe cichoraceauum, and harmful fungi of the genera Poducarium, Unicomium, Podosphaeralaera Rhhzoctonia, Cercospora, Helminthosporium, Veericilluum, Bootytis, Pecicluluum, VemCuuij, ScCeeotinia and Rhynchosporium.

In addition, the more sophisticated representatives of the compounds produced according to the invention have a marked action against wood-destroying fungi such as, for example, Coniophora puteana, Gloeophyllum trabeum, Aumobasidium pullulans and Sclerophoma pithytphrla.

The compounds of the formula I are distinguished by their preventive and curative activity as well as their high tolerance to plants.

Compounds of formula I under greenhouse conditions already at concentrations of 1 mg to 500 mg of active ingredient per liter of spray suspension. In field trials, concentrations of from 50 g to 1.5 kg of active compound of the formula I per ha are preferably applied. To control the fungi which attack the seeds or which are in the soil, 1.5 g of the active compound of the formula I per kg of seeds are preferably used, in the case of pickling, preferably from 0.05 to possibly soil.

The compounds of formula I and their acid addition salts can be formulated into various compositions, such as solutions, suspensions, emulsions, emulsifiable citrates, and powder formulations. The fungicidal compositions according to the invention are characterized in that they contain an effective amount of at least one compound of the formula I or an acid addition salt of such a compound as well as auxiliaries which are used in such preparations. The compositions preferably comprise at least one of the following excipients:

Solid carriers; solvents or dispersants; surfactants (surfactants and modifiers); dispersants (non-tactide) and stabilizers.

The following are essentially solid carriers in Uvah:

naturally occurring (substances such as cation, clays, diatomaceous earth, calcium, benzene, chalk, for example, quartz, dolomite, highly dispersed cdulose, starch, such float chalk, magnesium, limestone, and diatomide; Bleaching agents such as aluminum and hens and, for example, silicates, organic substances such as fertilizers, such as phosphates and nitrates, in the form of granules or powders.

attapuugite, monCmirorlon-silicic acid, urea oxide and synthetic gums may be present

Suitable solvents or dispersants are essentially:

aromatic hydrocarbons such as toluene, xylenes, benzene and alkylnaphthalenes; chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes and meeylene chloride; aliphatic hydrocarbons such as cyclohexane and paraffins, for example petroleum fractions; alcohols such as butanol and glycol as well as their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutylktton and cyclohexanone; and strongly polar solvents or dispersants such as dimethylformamide, N-methylpololidone and dimeepysulfoxide, such solvents or dispersants preferably having a flash point of at least 30 ° C and a boiling point of at least 50 ° C and water. Possible solvents or dispersants are also so-called. liquefied gaseous carriers or fillers which are products which are gaseous substances at room temperature and at atmospheric pressure.

Examples of such products are, in particular, aerosol propellants, such as halogenated hydrocarbons, for example dichlorodifluoromethane. If water is used as a solvent, for example, organic solvents can also be used as co-solvents.

The surfactants (wetting agents and emulsifiers) may be non-inogenic compounds, such as fatty acid, fatty alcohol condensation products or fatty substance condensation products. fat phenols with ethylene oxide. Also contemplated are fatty acid esters and ethers with sugars or polyhydric alcohols as well as products obtained from sugars or polyhydric alcohols by condensation with ethylene oxide. Further, ethylene oxide and propylene oxide block polymers may be used as surfactants or alkyldimethylamine oxides may be used.

Anionic compounds such as a soap may also be used as surfactants; sulfated fatty acid esters, for example dodetyl sodium sulfate; alkyl sulfonates, and fatty and aromatic sulfonates such as alkylbenzenesulfonates, for example dodecylbenzenesulfonic acid calcium salt with butylnaphthalene sulfonates; as well as complex fatty sulfonates; for example, the amide condensation products of oleic acid and N-mpeyltaurine with sodium sulfonate dioctylsuinate.

Finally, the surfactants may also be represented by cationic compounds such as alkyldipetylbenzylammoniumchloids, dialkyldimethylammoniumchlooids, alkyltriphenylsuphonium chlorides with ethoxylated quaternary ammonium chloride.

Suitable surfactants (without surfactant effect) are in particular: lignin, sodium ammonium salts of ligninsuioonic acid, sodium salts of polymers of mmleic anhydride and Siitobutlene, sodium and ammonium salts of sulfonated polycondensation products of naphthalene and aldehyde, and sulfite waste liquors.

Examples of suitable disintegrants which are particularly suitable as thickeners and / or as anti-settling agents include, but are not limited to, cellulose, carboxymethyl cellulose, hydroxyl cellulose, polyvinyl alcohol, alginates, caseinates with blood albumin.

Examples of suitable stabilizers include acid binding agents, for example epichlorbydrin, phenolcedethetra and epoxidized soybean oil products; antioxidants such as gallic acid esters and butylated hydroxytoluene; UV absorbers, for example, unsubstituted benzotenols, Siftnylacrylnitrile esters with cinnamic acid esters; with deactivators, for example, poly (ethylenediamine tetraacetic acid) salts with polyols.

In addition to the active compounds of the formula I, the fungicidal compositions according to the invention may also contain other active compounds, for example fungicides of another type, insecticidal and acaric. prosteeds, bactericides, plant growth regulators with fertilizers. Such combinations are useful for broadening the spectrum of activity or for specifically affecting plant growth.

In general, the fungicidal compositions according to the invention contain, depending on their type, between 0,001 and 85% by weight of the compound according to the invention or the compounds according to the invention as active compound (s). These compositions may be present in a form suitable for storage and transport. In such forms, for example in emulsifiable concentrates, the concentration of the active ingredient is usually in the higher range of the above concentration ranges. These forms can then be diluted with the same or auxiliary substances used in such compositions up to the concentrations of the active ingredient which are suitable for practical use, and such concentrations are usually in the lower range of the aforementioned concentration range. Emulsifiable concentrates generally contain 5 to 85% by weight, preferably 25 to 75% by weight, of the compound or compounds of formula I. Suitable dosage forms are, inter alia, directly applicable solutions, emulsions and suspensions which are suitable, for example, as spray suspensions. In such spray compositions, the active compound concentrations may be between 0,001 and 20% by weight. In the UVL (Ultra-Low-Volume) procedures, spray supernatants may be formulated so that the concentration of the active ingredient in these compositions is 0.5 to 20% by weight, while the spray suspensions formulated for the purposes of the Low-Volume and High-Volume procedures preferably a concentration of active compound of 0.02 to 1.0, or 0.002 to 1.0% by weight.

The fungicidal compositions according to the invention can be prepared by mixing at least one compound of the formula I or an acid addition salt of such a compound with the excipients used in the compositions.

The preparation of the compositions can be carried out in a manner known per se, for example by mixing the active compound with solid carriers, dissolving or suspending in suitable solvents or dispersants, optionally using surfactants as wetting or emulsifying agents or using dispersing agents, diluting previously prepared emulsifiable concentrates with solvents or dispersing agents, etc.

In the case of powder formulations, the active ingredient can be mixed with a solid carrier, for example by co-milling. In addition, the solid carrier can be impregnated with a solution or suspension of the active ingredient and then the solvent or dispersant is removed by evaporation, heating or suction under reduced pressure. By the addition of surfactants or dispersants, such powder compositions can be made readily compatible with water so that they can be converted into aqueous suspensions which are suitable, for example, as spray compositions.

The active ingredients may also be mixed with a surfactant and a solid carrier to form a wettable powder which is dispersible in water or may be mixed with a solid pre-granulated carrier to give the product in granular form.

If desired, the active ingredient can be dissolved in a water-miscible solvent, such as an alicyclic ketone, which conveniently contains an emulsifier in the dissolved state, so that the water-added solution acts self-emulsifying. On the other hand, the active ingredient can be mixed with an emulsifier and the resulting mixture is then diluted with water to the desired concentration. In addition, the active ingredient can be dissolved in a solvent and then mixed with an emulsifier. Such a mixture can also be diluted with water to the desired concentration. In this way, emulsifiable concentrates or ready-to-use emulsions are obtained.

The compositions according to the invention can be used according to the application methods customary in plant protection or in agriculture. The method of combating fungi consists in treating the products to be protected, for example plants, plant parts or seeds, with an effective amount of a compound produced according to the invention or a composition according to the invention.

The following examples illustrate the invention in more detail without limiting its scope.

I. Examples illustrating the preparation of the active compounds of the formula I

Example 1

To a solution of 2.4 g (8.5 ml) of 5-bromo-cotinic acid chloride in 20 ml of anhydrous methylene chloride is added dropwise a solution of 2.4 g (8.5 ml) of N- [2- (2,4, ml)]. 6-trichlorophenoxy) ethyl] -n-propylamine and 0.85 g (8.5 mol) of triethylamine in 10 ml of methylene chloride are added and the reaction mixture is further stirred at room temperature for 1 hour. The mixture was washed with water and dried over anhydrous sodium sulfate. After removal of the solvent, the remaining dark brown oil is chromatographed on silica gel using chloroform as eluent. In this way it is obtained

3.7 g (93% of theory) of 5-broa-N- (n-propyl) -N- [2- (2,4,6-trichorphoroxy) ethyl] isotilamide as a yellowish oil.

The following compounds are obtained in an analogous manner:

from 5-bromotinic acid chloride and N- [η 2 (4,6-eichlsr-s-tolyloxy) ethyl] in-psopylaine,

5-Baam-N- [2- (4,6-dichloro-s-cyclohexyloxy) ethyl] -N-propylinicoilane as a brown oil;

starting from 4-bromo-4-thienoic acid chloride and N- [η 2 (-, 4,6-tri-chlorophenethoxy) phthyl] ethylamine

5-Oram-N-naphthyl-N-22- (2,4,6-triohalo-ethoxy) -phthyl] -amide, m.p. 84-86 ° C;

from 5-bromotrotinic acid chloride with N- [η 2 (2,4,6-triephosphenoxy) phthyl] --- Uutllaain

5-oma-N-en-uuty-N - [- (-, 4,6-tri-chlorophenesxy) phthyl] nicotinamide as a colorless oil;

starting from 5-bromoicotinic acid chloride and N- (2,4,6-trichlorophenoxy) ethyl] -n-pentylaine

5-Oram-N-in-pentyl) -N-2- (2,4,6-trichlorophenethoxy) phthyl] nicotilane as a colorless oil;

starting from 5-bromotrotinic acid chloride and N-2- (2,4,6-triohorsulfoxy) ethyl] --- exoxylalamine

5-broa-N- (n-hexyl) -N-Q2 - (-, 4,6-tri-chlorophinesxy) phthyl] nicotilane as a colorless oil;

starting from 5-chloricstinic acid chloride and N- [4- (2,4,6-trichlorophenesxy) phthyl] ethylamine

5-chloro-N-ethyl-N - ['2- (2,4,6-trichloffensxy) phthyl] nicotinamide, m.p. 85-188 ° C;

from 5-chloronicstinic acid chloride and N- [E - (4,6-dichloro-s-tslylsxy) phthyl] -n-poopylamine

5-chloro-N- (1-propyl) -N- [4- (4,6-diohlsr-s-tslylsxy) phenyl] nicotinamide as a brown oil;

starting from 5-chloronicotinic acid chloride and N- [2- (2,4,6-triohsophenoxy) ethyl] -in-psoyylaine,

5-chloro-N- (n-propyl) -N '(2' - (-, 4,6-tri-phosphenesxy) ethyl] nicotilmia as a brown oil;

from 5-chloronicotinic acid chloride ky ^ i ^ ^ ya LLiL N- [£ - (- 4,6-triohlorfensxy) ftyl] -N-but ^yl laainu gave

5-chloro-N- (n-butyl) -N- (-, 4,6-tri-chlorophenethoxy) phenyl] nicotinamide as a brown oil; starting from 5-chloronicctinic acid chloride and N- [η 2 (-, 4,6-trichlorophenoxy) phthyl] -1-enylaluminum to give

5-chloro-N- (1-propyl) -N- [eta] < 2 >-( 2,4,6-triohorphinoxy) ethyl] nicotinamide as a brown oil; starting from 5-chloronicstinic acid chloride and N- [E - (-, 6-dichlorophenyl) ethyl] -pyrrolidine,

5-chltr S- ^[2 - ^(2, 6-dichlorfentxy) ethyl] -S- (n-propyl) nikoiiaamid in a form of an brown oil;

^5-oh chloride of ^{d-i-totonové KY ei} - and ^y - ^ A ^ -triLchtoftenoxyletyl] ethyl-U was obtained

5 ^- iodo-N-eeyl N - ^. 2- (2> 4,6-trtohtof ^ et ^ nox ^t l ^- n ^to the laěi ^{s i-,} s-th pulse of 92 to 94 ^DEG from cMorito ^ jo ^ i ^ totonové βοΙ ^- .- ¹ and ^Q 2 N ^{2 (4, 6--diihlor} pTol = ^tl Px ^t) th ^y l] ^- - ^-p RP-u ^pt laěi gave ^5-N -jpd ^([2 - ^{(4,6--diihlpr} ρ ^- tPly ^{of l} Ox) 2-- ^^ ^- (- ^ ro ^ l) · -itotonamid in from ^of a brown oil of ^ · ^ ⁱ ^ l.prί ^5-oh sa ^'d -itotonové ^to yseli- ^y and ^- - [J2 ^{(-, 4, 6} ^' ^t r ⁱ c ^ ¹ LOLF ^No ^ - ^ pχ ^t) Th ^l lj ^- -ρ ^r Prp ^yl AEI -u obtained ⁵ -JP ^I - ^- - ^{(n - prlL} for N -2 ^{- (-} 4, ⁶ -tric LPF ^{1 No} erюxyto ^ l] ^ -itotonam -ažloutléto in the form ^of an oil;

chloride ^ ^ jo itotonové kyseli.- ¹ and N- ^[2 - ^{(- 6 - d 1} II ^No LPF enpχ ^t) ι ^ 1] - ^ ro ^ nu lamination gave

5-β-N- [2 - (-, 6-trifluoro-p-1) -ethyl] -N- (- propyl) -? - amide as a brown oil;

of cMortau ^ toomúkotinové tyseH- ¹ and ^N - [2-U ^^ - Tenox trtohtof ¹⁾ th ^l l ^- N ^{(- 1} -ěčt Pxyetyl) amine gave ^{5 «b} rom-N- ^(- -ěečhOP ^χ · tc ^{yl) -N-} ^ ² · ^- (2 ^ 4 trtohtoftenox ¹⁾ e ^ l] -ito ^t- NaeI ^te ^ OTA th -d 86 ° C;

chloride from ^5,6 - ^d i ^ lor-itotonové Jeyseli.- ¹ and ^N - ^[- - (2 ^4,6 'thirtieth lpr ^{No. 1} e-pχ ^y) e ^ey lLj-R' (- ^r rp ^ry laminates are gains

^{5, 6} cP ^{r 1} -i O - N (R-OR ^<py l) -N-Q2- (2 4-phenyl-tricřilof oxyletyl] -itotonémid, ^and 72 ° C.

melting point

Example 2 ml of meeylene mixing is added dropwise

To a suspension of 5-bromotinic acid chloride (22.0 g, 0.1 mol) in 200 chloride was added sodium hydrogencarbonate (9.2 g, 0.11 mol). · Then, 8.3 g of ² N - ^[[22 (2,4,6-Tric ^1] Of ENOX ^{l s)} · l ^the l ^{- n-} PPE ^yl am ⁱ -u so that the temperature μ ^ Smě £ π ^{- the level of the} mix did not exceed ³⁵ ° C. The reaction mixture, i.e. ^b ^ su The colorless E from with stirring on ^with frodi g ^3-yl when ^p te lot ^of místnoosi. The suspension is then poured onto 200 ml of water and the mixture is shaken while the solids are dissolved. The pH was adjusted to about 7.5 by the addition of a small amount of saturated sodium-urea solution. The aqueous phase is extracted twice with 50 ml of meetlene chloride each time, the combined organic phases are dried over anhydrous sodium sulphate and evaporated under reduced pressure. The residue is taken up in 50 ml of toluene, the solution is evaporated and the new residue is mixed with 100 ml of diisopropyl acetate and crystallized with stirring.

this Hila m ^ nze is stirred for 1 hour ^{Ste p} s temperature between approximately O ° C. The crystalline powder was washed twice with 20 ml of cold isopropyl alcohol each time.

After 16 hours the suspension is filtered, the ether and while rye ^{3 l, h} 0 ^g tezvarvýc crystals of the d. ⁵⁰ and ⁵² ° C. The mother liquor was concentrated to obtain another product, the residue was subjected to column chromatography with 400 g of silica gel for 1: 2 ethyl acetate: n-hexane.

V as an elucid or sensors. (Pure fractions were combined and -echcaí to crystallize from 10 mL dřiropropyletteru. ^ Of this row, detects -cis ^ ^{1 3.4. GB} EZ arvýc ^hk feature ^{b t l} s and a temperature ^of-50 s ^{and 52} ° C . výtože tilt ^this anniversary> ^b ^ en ^Star it frrorn ^ Hn ^ i ^ Trp-N - ^ - ^^^ - ^ ORFE Tric-oxirtoerJ Itota-C-amide and 34.4 g (73.7% of theory yield).

Example g (15 mol) of 5-bromo-nicotinic acid and 2.43 g (15 ranoO) of 1,1'-carbonate are heated under reflux in 50 ml of tetrahydrofuran for 2.5 hours. ^{3.39 g (15} mml ^) ^q 2 N-P ^ -dichlorfenoxy) ^ey e lj-n-butylamine in ²⁰ ml of tetrahydrofuran,

The mixture was then 3.03 diimidazole to ^{give p} s at místnoosi tetrahydrofurane and the reaction mixture in Fromm resulting solution was heated for another 3 hours under reflux.

The reaction mixture was evaporated, the residue was taken up in ethyl acetate and washed twice with saturated sodium chloride solution. The organic phase is dried over sodium sulphate, evaporated and crystallized from a mixture of ethyl ether and n-hexane. 2.8 g (43% teoretCckého in ^YT EZ ^to u) of 5-bromo- ^- - (n ^{- u} yl) -N- ^{[2 '(2,} 6-dichlro ^phenoxy) e ^e yl her ^to otiaamidu the ^f orm ^of colorless crystals, mp 62-63 ° C.

The following compounds are obtained in an analogous manner:

^ ^Z ^ fluoronicotinic new С ^! ^ ^{«^])} Д ^ - ^ ^у and N 2 ² ^^^" tr ^ CH ^^ - ARX ¹⁾ et.fll-and-poop-amine of ⁵ kA ^ - ^(fluoro-N- (- ^{l and} oil) ^{((N- [2} - (2,4, ⁶ - ^t y ^{C t} Chofu erюx ^l) et ^II] n oi ^{Ck -} aam ^even the ^p ture t ^and -I ^from 69 and 68 ° ^C, from 5-fluoronicotinoyl aové tyseH- ^{N 1} and N - ^ - ^^ - ^ ichlorfe of ^χ-yl) ethyl ^l l] ^- - ^AP r ^{p i} -u ylamine z ^ tert ^{5-fluoro-N- ([2} - ^{(2, 6} - ^(f T ^{dichloro-oxy) t} yl] ^(N - (- ^(· ro ^{and al} l) -i ^to rt ^- us ^d in ^f orm ^with colorless oil.

Example 4

In a similar manner to that described in Example 1, 2 or 3, the following may also be prepared. compounds:

chloride 5-bromo-nicotinic ^ Sehne optionally from 5-bromaikotinové acid and 2 - [- (4-e ^ o-belly trlilony) ethyl] ^ Liam-nu give ⁵ - ^{(bromo-N-ethyl-N- l} -2 ^{2 _(4/6} dichloro-o-tol ^y lox ^y) ethyl] -i ^to rt ^{- benzenesulfonamide,} TE ^p lota t ^ i 73, and ^{75 DEG} from chloride RRM ^b ^^ ^-) ^ (^ TTJ Ilrv ^ ^é ^ J ^ ¹ seH- opřípacté of ^{5 "b n} romňi cyanonicotinic ^s tyselin NQH- and ^1, 6-Cicrlor rχyχy) ethyl] ylmethyl-u was obtained rom ^ ^ ^ Wi--fh loHenox ^ et ^{yl] -} 2-methyl ^{TT1 to} otiaamid ^ai, t ^ T, ^and the Lot 56-57 ° ^{C; chloride,} hypobromous ^ ^ ^ Otín tysehny ^ when ^ ^ roímkotinoiré reads out the ^y sowed and ^ny 2 - ^ - (44 t ^ cr χοΗ -ί onix ^s) etyij MMT ^y Camino obtained от ^ ^^ ^ ¹ -те ^-2 - · ^ ^- ^ 4 ^^^ 1 ^ 0 ^ -1rox ^s) etyrjnMcot ^ amide molds viscous oil;

cliloriclu of ⁵ - Rome ^{II b} ^ ⁽ⁱ ^ tt ^ ^newly Selin ^ky ^ ^y ^ when reading from hypobromous ^ ^ ^ ^ otinr Selin ¹ and 2 - N - ^(4-d ic ^h lor ^- o ^- tol ^yO oN ^y) ^ ^у 1] meth ^yl l.aminu of ^{s and} SK

5-bromo--Jjž-U ^ -cHcl ^ or-o-tol ^yl lon ^y) tt ^yl] -2-meth ^yl -ikot AAM ^{id n} in ^f orm ^{v i c} ^ l ^ ^I axis it oil; chloride ⁵ - ^b romňi ^also otinov tyseHny ^é ^ when ^^ ^b of 5- Rome ^- kotiiov ^é tyseli- ^one and 2- (2 · - (- ^{4 /} t-cr 100111-0X0X1) 1 ^ 1] ^y beaz ethylamine gave ⁵ - ^(bromo-N Beti ^2-yl) - ² - ^{[-2 (- / 4/62} CH ^C tr ^r or ^f eaon ^l) eth ^yl] -i ^{c TI} nlmid ^te ^ OTA Tani ⁸ 2 and ⁸³ ° ^C, from petroleum jelly chloride ^ ^ ^ Z ^ eventually brrmn otinr ^ ^ ^ Semnyi ¹ and ² - ^{[2- (4-6-} IC ^ o ^ oo ^ lon ^{1-t yl]} ^ to ^ amine ZIS ^{ca. 5-bromo-2} 'Beti ^yl - ² - ^{([2 2 (4, 6-dichloro -} r ^y that he ^lyo) eth ^yl] II ^{C and} rt naeid ^/ te ^ t OTA ^and -I ⁷ 1 to 7 ° ^C, from 5-bromeikotinové chloride to ^gamma-SEEI and optionally from 5-bromonicotinic C SEEI ^y-y and 2 ^ 2 - (- 6--10-1-0X1) 1 ^ 1] bienzylaminu the z- ^ ^ bromo-benzoimidazole ^y1 - ² -Q ² - ^{(- 6} - ^d ic ^{1 e} lor ^phenoxy) eth ^yl] nitotňam- in Forer ^ o colorless oil;

of broniJ ^^ ^ i ^ rti ^ i ^ ew C ^y-y or the salts of chloride of 5-bromo-nicotinic acid and 2 - ^ - (- 6-i-e-lo-one ^yl) eth ^{yl] nn ar} OAP ^yl amine CIS ^Ca

5 ^-b rom-2- ^[2- (2, ^6--άί 1ο-enoxy ^y in ^f orm ^of teztanrého oil;

from ⁵ clilor ^ u ro ^e ^^ ^- ^ J (t ^ ^r ^^ ⁱ b ^s ^ C ^ eMny popřípa of ⁵ - ^B Roma ^-k otinov Selin ^{s ky} and ^y 2 - ^ - (- 6-cicriorfoxix ^yl) ethyl] ethyl ^ C ^ minutes gave ⁵ -broJΓ- ² -Et ^Y1 2- ^£ 2- ⁽² ', ⁶ - ^d ox ^ic1lorft-yl) eth ^yl] ot n ^{ic and} nlmid ^pulse Ota-t ^and -I 7 ^8-80 ° ^C, from 5- ctilrridu ^b rom ^ ^-] ^ <^ t ^j ^ i ^ s ^ ^s ^ ¹ sel- přípacté of -omn ^ ^ ^ Otín kyše- ¹ and 2-- ^ - ^{(4,6-2'-dLc1lrr} trCylrny) TTYL] n ^-but-ylamine gave

5-bromo-N "(- ^ u ^ JJ-MN-H -dichlo ^ ^ o ^ ^ he ^ RLI et ^y] ni ^ ^f orm oHaamid in teztarvého ^with oil;

chloride of S-chloro-N-o-in charging new ^ ¹ ^ ^ přípacté of hypochlorous ^ o ^ aové seli- ¹ and 2 - N - (4 from ^^

S-chloro ^ -el ^y l ^-2 - ^{[2- (4, 6-dichloro - 2 t} O ^r oles ox ^y) eth ^ i ^ AT-amide t-lota ^ ^a - ^{d 6} 2 and ⁶⁵ ° ^C ;

° C; and N- [2 ^and 89 ° ^C; of ^5-chome c ^h; Lorn ^also on ^t ^ r ^ t ^ b ^{s 1 p} yseKn OPŘ ^{IP ga} of ⁵ c ^{h nk} Lorn otinov SELT ^s ^ ¹ - [JI2 (2 todtotortooxixy ETB Lamti is from ⁱ to ^{5 ka} -οΜογ- ^- - ^ ^υ 1ι ^{ν-2- (2, 6} - ^{-d l} ic Lori: fnoxy) eth ^yl i ^nk = NR ⁿ ot ^m. te ^ o ^ T, ^and the ⁶⁵ and ⁶⁷ from 5-dchlori ^also INOV of ^{t e} ^ o ^{p p} SELT of ^{IP ga} Florida ⁵ c ^h Lorn ^also otinové sel k ^{y i} n ^y - (2,4-6 trCtoSorfnnoxy) ethyl] benzylamine · yield ^{5 -} c ^--- SR ^hL bfiz ^{yl -} - ^[2 - ^{- (-} 4, ⁶ - ^the ric ^l Llor ensx ^{f s) of the} f l] ^ n ^ te ^ Oton point ⁸⁸ rotatably chloride 5-cllorniks0insvé after ^a case-ester of 5-chlornikonioové acid --- 22 (2 todtotoor f ^ oxixtoeto BENA limtou with from ^I to ⁵ -chlsr ^{ka -} --beni ^y1 - ^ N ^- 2 ^{- (-} _/ ⁶ - DIC lorffnsxγ ^l) eth ^yl benzenesulfonamide nicotinate ^{i /} te ^ OTA point 66 and ⁶⁸ ° ^C, zc ^{H, L d} at the ori ⁵ c ^h o ⁰ Lori ^also INOV ^{s ky} o ^p Selin ^{yp at} pH of ⁵ and ^DE ^ C ^H L ^L ori ^nk about ⁰ ^^ ^e ^ o SELT ¹ and N- ^[2 - (4-d-oo-turn lotolyx ^y) y ^ ej-benamimtou the ZTO) ⁵ ---- -CLL · sr beni ^{y1 -} 1 N ^- 2 ^- ( ⁴ , ⁶ - ^d ichl · sr-s · t ^{y Ly} LSX) ft ^yl RLI ^to us ^and we ^d T, ^and the pulse of ^{7 F} 5 and 7 ^{to 8} ° ^C; from about ⁵ tolortou ^b rom ^ ⁱⁱ ^ ¢ ^ Sa ^ ⁿ new SELT ^{1 p} o ^p and ^{DE at} pH of ^{5 WPTs} rom ^ ⁱⁱ ^ (^ ^{n s} t tyselto new ^one and N- [2- (2 ^{fourth 6- RLC h} LSR eilox ^{f y)} ft ¹ l ^{Co2, 4} - ^{di hl} c or ^b enz ^ylamine with from ^{I ka}

^{5-bromo-N-r2-d} ^ a ^^ a ^ ¹ enz - ^{- [2-} (2, -4, ^6-trimethyl Lc ^ ^hL ^ SR ^ i ^ f ^ ^f ^ ^ isχУe ^yl ] nidUnamid te ^ ota to 109 to 110;

chloride 5-bromo ^ ii ^ c ^ t: -amide after ^a case-from 5-Ьromrlikotnnové acid and N- 2- (2-d ctooirtoenxytoelto] -2-totolorbenztoamtou it is ZTO)

5-bromo-N- (2-dichlorobenzyl ^{1) (2, 6} - ^d lC lorffnsxy ^h) eth ^y l ^L] · il ^to rt ^and Naml ^{d te} ^ t OTA ^ck

160 ^and from 161 ° ^C; tolortou of ⁵ - ^b romto ^to rt ^{and newly} SELT ^ ^{1 P P} A ^de Lean totoomtokottoové líyselto of ^{1 -} - [2- (2 ^6/4 - ^L Tric Llor eisx ^{f y)} f ^{o TT} - ³ - < ^lH or ^{YR e} NNZ am ⁱ Nu ztoto ^{5-bromo-N- (2з} tolorbenz ^{yl) -No} [22 ^2- (2,4 ^{-t 6} ritolsr ensx ^{f y)} f l ^j ntootoaamto ^those in ^f orm ^{of b} ez ^b arvého oil;

tolortou of 5-bromo-N ^also ot ^e ^ ⁿ IOV SELT ^{1 p} o ^p of ^IP ^ ^ga of totoomtokottoové SELT ^{1 6} d ^{l i} c ⁰ LRF oχyχ ^{f) Cy} y l] ^CLC with ^{m r} Leiben LNM ^Nu from ^í s ^ká

5-bromo-IN ^(L Ззoh chlorobenzyl ^{y1) -} - ^- 2 ^"(2 tototolorfenoxy lettojntoo t-inamto ^te ^ OTA

106 [deg.] C .;

of 5- tolortou ^b romnikoti.nov SELT ^{1 e} ^ ^{p p} o ^at pH of ⁵ and ^DE - ^{b n} ot romňi ^{also newly} tyselto ^{1 4} 0-tritolei ^with enyχ ^{e) about} FC et ^{l r m} leibynř LNM ^with nu se zto)

5-bromo-N-toorbenzyl · a) a ^- [2- (2,4 ⁶ - ^about richlor ^{phenoxy yl)} phenyl] ^kanamycin niikottoamto, this tfpoto

Mp 134-135 ° C.

and from N [2- (2, melting point 105 through N) and N- [2- (2,

Example 5

To a solution of 2. ^{0 g} (4, ³ mMol) 5-bromo-N- (N propyl ^N "N- ^{[2- (2,} 4,6-trichlorophenoxy) ethyl] nicotinamide in 10 ml ftanolu was added 10 ml of 4N hydrochloric acid and the reaction mixture are allowed to stand at room temperature for about 16 hours, then the solvent is evaporated, the residual yellow colored oil is dissolved in 10 ml of ethanol, a solution of 60 ml of diethyl ether is added to the solution. h. the resulting precipitate was oddrltruje, yromyje the diftylethefem and dried in a stream of air. this yielded 2.0 g (93% yield off teoritického ^YC u) of 5-bromo- ^- - a ^ oil ^{1) -} - [7- (24 totoichlortonox ethyl ^ Jn ^ h ^ otiammid-Roch-riclu in Orme bílýto ^r ^^ Here the phallus rozJkládaaí ^п ^ ^^ OTE ^d 'l ²⁰ ° C.

Analogously to method Z ^ of tofluortoton ^ ro ^ n - ^^ - ^ this íritolor-phenoxy et ^{yy y} l ^j ntoottoamidu and hydrochloric ^Cart o ^e k ^ i ^ (l ^ ⁱ ^ ^y N z ^{i KA 5} -f fluoro- ^{l -} - (n ^-p rs ^{ry l) -} - ^[2 - _(f ² 4, ^6-trichloro ensx ^{f y)} ft ljnikotinamid ^{y-h yd} hydrochloride as white Cr ^y centuries that decompose in interval ^of d 132 d ^at 138 ° C.

II. Examples illustrating the composition and preparation of compositions

For liquid active substances

а)

1.

lad 6

Emulsifiable concentrate:

g / liter active ingredient of the formula I ethoxylated nonylphenol (10 mol ethylene oxide) dodecylbenzenesulfonic acid calcium salt a mixture of alkylbenzenes (with 10 carbon atoms)

250

50-70 to 1 liter

The components are mixed together until a clear solution is obtained.

2. Wettable powder:

Active ingredient of the formula I Hydrated silicic acid Lignin sulphonic acid Sodium lauryl sulphate Calcium carbonate Parts by weight

100 ALIGN!

The liquid or molten active substance is applied to the silicic acid, the other components and the resulting mixture are finely ground in a suitable mill.

(b) Solid active substances

Wettable powder:

active ingredient of the formula I hydrated acid sodium lauryl sulphate sodium lignosulphate kaolin and / or clay silicone parts

100 ALIGN!

The components are mixed together and the mixture is then ground in a suitable mill.

III. Examples illustrating biological activity:

Test 1

Effect against Helminthosporium oryzae Up to 20 rice seedlings (divided into 2 pots) are thoroughly sprayed at stage 1 leaf with an aqueous dispersion of the test compound (which is generally processed into a wettable powder) and the treated plants are then grown in an air-conditioned space at temperature of 19 ° C and under 16-hour illumination daily. Two days after treatment, test plants are infected by spraying with an aqueous suspension of conditions (about 80,000 conidia / ml). Then, the rice plants are incubated at -24 to 26 ° C, under dew point conditions and under a light hour for a day. Evaluation of the experiment is carried out 2 to 5 days after infection by detecting the leaf area in% disrupted by Helminthosporium oryzae as compared to infected but untreated control plants.

Test 2

Effect against Septoria nodorum up to 40 wheat seedlings divided into 2 pots are sprayed thoroughly on both sides with an aqueous dispersion of the test compound (which is - as is generally customary - processed into a wettable powder) and treated plants at stage 1 of the leaf. are then grown in a climatized space at 15 to 17 ° C and 14 hours illumination daily. Two days after treatment, the plants are infected by spraying with an aqueous suspension of conidia (containing about 1x10 conidia / ml). Then, the wheat plants are incubated for 2 days in a conditioned chamber under dew point conditions at 24 ° C and then for 5 days in a greenhouse.

Evaluation of the experiment is carried out by detecting the area of the leaves in% agitated by the action of the weevil (Septoria nodorum as compared to the infected but untreated control plants).

Test 3

The effect against green birch (Alternaria brassicae) on the brassica of the brassica seedlings, divided into two pots, is thoroughly sprayed at the 6-leaf stage with an aqueous dispersion of the test compound (processed as usual as a wettable powder) and then grown in a conditioned space at temperature. 19 ° C and 16 day illumination daily. Two days after treatment, the plants are infected by spraying with an aqueous suspension (about 30,000 conidia / ml). Then the brassica plants are incubated at 24 to 26 ° C, under dew point conditions and under 16-hour illumination daily.

The experiment is evaluated for 2-5 days of infection by detecting the percentage of leaf area infected with cabbage (Alternaria brassicae) as compared to infected but untreated control plants.

The wettable powder mentioned in the tests contained 25% by weight of the test compound (a compound of the formula I or active ingredient known in the art) and 75% by weight of carrier mixtures, each having the following composition:

Carrier mixture A (for test compounds in solid form)

Folders:

% by weight nonylphenol ethoxylate 3 highly disperse silicic acid 6 methylhydroxyethylcellulose 1 sodium oleate 2 sodium polynaphthalenecarboxylic acid 10 hydrated aluminum silicate 78

100 ALIGN!

Carrier mixture В (for test compounds in liquid state)

Folders:

% mono-mono-nonylphenol ethoxylate 6 o-ethylhycioyl-cellulose 2 sodium oleate ´ 4 polynaphthalenecarboyylic acid sodium salt 20 precipitated silicic acid 68

100 ALIGN!

A sufficient amount of water is always added to the powdered powder to prepare a spray spray with a concentration of 16, 50, 160 or 500 mg of test compound / filter.

The results of the above tests are summarized in the following nabulct:

Table :

Test compound: active ingredient of the formula I dose (mg test compound 0 / 11tr spray) is active in Helmintosporium Septoria oryza nodorum

Alternaria brassicat

5-Bromo-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) β / 1] - 500 160 40 97 60 niconinamide 50 95 (Example 1, 1st compound I) 16 92 5-bromo-N-ethyl-N - [] 2- (2,4-tri- 500 70 70 chlorphenoyl) βP / n nicotines-d 160 97 (Example 1, 3rd Compound I) - 50 90 16 70 5-bromo-N- (n-butyl-N - ([2- (2,4,6- 500 70 40 - · trCchOofnonoУl) nthll] nicotine- 160 100 ALIGN! amid 50 90 (Example 1, 4th Compound I) 16 90 5-chloro-N- (n-propyl) - [2- (4,6- 500 90 65 95 -rnchlor-Obtollloyynyl] - 160 40 90 nnkoninamir 50 0 75 (Example 1, 8th slice I) 16 0 0 5-chloro-N - (n-propyl) --- Q> - (2,4,6- 500 90 95 Bromobenzoylthyl] niconinamide 160 20 May 100 ALIGN! 90 (Example 1, 9th Compound I) 50 0 95 85 16 0 95 80 5-fluoro --- (n-propyl) -N- 500 100 ALIGN! - [2- (2,46-trichlorenenoyl) - 160 95 90 95 tty]] оП ^ Шю-ПГ 50 80 90 95 (Example 3, 2nd compound I) 16 20 May 90 80 5-Bromo-N-ethyl-N - [] 2- (4,6-dichloro- 500 20 May 100 ALIGN! -o-tolyooyl-ttyl- 160 100 ALIGN! 80 оП ^ Шю-ПГ 50 80 60 (Example 4, 1st compound I) 16 50 50 S-bromo-N - [2- (2,6- <lichlor- 500 100 ALIGN! phthaloylthyl] --- (n-propyl) - 160 95 100 ALIGN! 100 ALIGN! nicotinamide 50 90 95 95 (Example 4, 8th Compound I) 16 40 95 85

Table continuation:

Test compound: active ingredient of formula I dose (mg test compound (liter spray suspension)

Helmintosporium Speekoria oryzae nodorum

Alternaria brassicae

5-Bromo-N-ethyl-N- [2- (2,6-di-) 500 90 90 chlorienoxylethyl nicotinamide 160 90 98 90 (Example 4, 9 Compound I) 50 60 95 80 16 0 95 0 2,4-dichloro-6- (2-chloro- 500 60 90 anniino) -1,3,5-triazine 160 70 20 May (Anilazire) Cunning 50 60 0 known from the US Patent 16 40 0 file ^no . ^{2,720 48} Q ^] bis - (4-fluorophenyl) methyl (1H-1,2,4- 500 30 40 60 ^{-triazrl-l-yl} ylmtt) tiaan 160 (FlusHazoV) known compound 50 from European patent application 16 No. 68 813) ']

tests clearly implies the transport of new compounds of the formula

From the above results

Even over the known compound Annlazine (cf. U.S. Patent No. 2,720,480) and the known compound Flusilazole (cf. European Patent Application No. 68,813) in that the new compounds have in most cases a much higher effect at the same fermentation.

Claims (12)

SUBJECT OF THE INVENTION What is claimed is: 1. A fungicidal composition, characterized in that it contains an effective amount. at least one compound of formula I in which denotes halo ^g ene in 5-position and / or ⁶ yr ^Ids hunting ^{S k} UPIN ^y, means an alkyl SKU ^p yne with 1-6 carbon atoms, alkoxyalkyl SKU ^p yne with 1 to carbon in the alkoxy moiety having 1 to 4 carbon atoms in the alkyl moiety, a cyanoalkyl having 1 to 4 carbon atoms in the alkyl moiety, an alkynyl group having 3 to 6 carbon atoms r4 R ² C6 or optionally the core benzeovém mono-, di- or trtiubttiiroaanri benzyl, wherein optionally present tubsSitient ^y are represented by 1 to 3 halogen atoms and / or one or 2 alkyl groups having 1 to 3 carbon atoms and / or 1 or 2 alkoxy groups having 1 to 3 carbon atoms and / or a trifluoromethyl group and / or a nitroskuein, R is halogen, alkyl having 1-3 carbon atoms or nitooskupinu ^4, m is 1 or 2 and n denotes 1, 2 or 3, or an addition Sou such a compound with an acid together with the excipients used in such compositions. 2. A composition according to claim 1, characterized in that it contains as active ingredient at least one sloučeřinu formula I wherein R ³ is fluorine, chlorine or bromine and the other symbols mmjí defined in paragraph 1, or an addition salt of such a compound with an acid . 3. A composition according to claim 1 or 2, characterized in that it contains at least one compound of the formula I in which m represents the number and the other symbols as defined in point 1 or 2, or an acid addition salt of such a compound. . 4. A composition according to claim 3, characterized in that it contains at least one compound of the formula I as active ingredient, in which the halogen atom in the meaning of the symbol r1 is in the position 5 and the other symbols have the meaning given in point 3, or an acid addition salt of such a compound. 5. A composition according to any one of Claims 1 to 4 which comprises as an active ingredient at least one compound of formula (I) wherein R is ethyl, n-propyl or n-butyl and the other symbols are as defined in or any of the acid addition salts of such a compound. 6. A composition according to any one of claims 1-5, vyznajující in that it contains as active ingredient at least one compound of formula I wherein R ³ is chlorine or a methyl radical and the other symbols maai defined in any of claims 1 to 5, or an acid addition salt of such a compound. 7. A composition according to any one of Claims 1 to 6 which comprises at least one compound of the formula I as active ingredient in which n is 2 or 3 and the other symbols have the meaning given in any one of Claims 1 to 6. 6, or an acid addition salt of such a compound. . 8. A composition according to claims 6 and 7, vyznn ^ itself by the fact that it contains as active ingredient at least one compound of formula I in which the phenyl group substituted by a residue ^(R3) _n is represented by 2,4,6-trichlorlanylovot group 2 , 4-dichloro-6-methylphenyl or 2,6-dichlorophenyl and the other symbols have the meanings given in 6 and 7, or an acid addition salt thereof. 9. The composition of clause 1, comprising an effective amount of at least one compound selected from the group consisting of: 5-methyl-N- (2- (2,4,6-trichlorophloxys) -Syanoaneaminamine), β-α-β-β-β-β-β-β-β-γ-ω-2- (2,4 6-trichlorophenyl) nicotnaamide, 5-bromo-N- (e.g. PS) -N- (2,4,4,6-trichlorolanox) ethyl] nicotaamide, 5-bromo-N- (naproopS) -N--; 2 - ((2,4,6-trichloro-zincs) -tsyl) nicotaaaea, 5-bromo-N- [2- (2,6-dichloro-zincs) ethyl (-N- (n-propyl) lowerotinamide) and 5-bromo-N- [2- (4,6-Dichloro-2-tosyloxy) -one]] - (((-Rosyl) loweroamyl amine) as well as excipients used in such formulations). 10. A composition according to claim 1 comprising an effective amount of at least one compound selected from the group consisting of: 5-broa-N-eeyS-N- [2- (2,4,6-trichophophenoxys) -silanetanamide, 5-broa-N- (nabutyS) --- [2 - ((2f 4,6-trichlorophenyl) ethyl)] nicotinamide, ‘ 5-bromo-N- (na-penyl) -N-2- (2,4,6-trichlorophenoxy) ethyl] nicothaaea, 5-bromo-N- (n-hexyl) -N- [2- (2, 2, 4 4,6-trichžOflanoxs) ETSI] niOotinamidam, ₁ 5-chloro-N-ets1 --- [2- (2,4,6-trichlorlenžXs) ^ sUnikotánamidem, 5-Chloro-N- (n-propyl) ----- 2- (4,6-dichloro-1-tosoxy) -Eyla lowerothiazine, 5-chloro-N- (n-butyl) -NQ ² (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-chloro-N- (n-pentyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] -trichlorfenoxy) -ethyl nicotinamide, 5-chloro-N- 2- (2,6-dichlorophenoxy) ethyl-N- (n-propyl) -nicotinamide, ^{5-iodo-N-ethyl-N-C2} "(2.4, 6-trichlorophenoxy) ethyl] nicotinamide, 5-iodo-N- [2- (4,6-dichloro-o-tolyloxy) ethyl] -N- (n-propyl) nicotinamide, 5-iodo-N- (n-propyl) ) -N- [2- (2,4,6-Trichlorophenoxy) ethyl] nicotinamide, 5-iodo-N - [(2- (2,6-dichlorophenoxy) ethyl] -N- (n-propyl) nicotinamide, 5-bromo) -N- (n-butyl) -N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, 5-fluoro-N- (2,6-dichlorophenoxy) ethyl] -N- (n-propyl) nicotinamide, 5-bromo-N-ethyl-N- [2- (4,6-dichloro-o-tolyloxy) ethyl] nicotinamide, 5-bromo-N- [2- (2,6-dichlorophenoxy) ethyl] -N -methyl-nicotinamide, 5-bromo-N-methyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- [2- (4,6-dichloro-o-tolyloxy) ethyl] - N-methylnicotinamide, 5-bromo-N-benzyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N-benzyl-N- [2- (4,6-dichloro- o-tolyloxy) ethyl] nicotinamide with 5-bromo-N-benzyl- N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, S-bromo-N-ethyl-N - [- (2,6-dichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (n-butyl- N- [2- (4,6-dichloro-o-tolyloxy) ethyl] nicotinamide, 5-chloro-N-ethyl- [2- (4,6-dichloro-o-tolyloxy) ethyl] nicotinamide, 5-chloro-N -ethyl-N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, 5-chloro-N-benzyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-chloro- N-benzyl-N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, 5-chloro-N-benzyl-N- [2- (4,6-dichloro-o-tolyloxy) ethyl] nicotinamide, 5- bromo-N- (2,4-dichlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, as well as excipients used in such compositions. 11. A composition according to claim 1 comprising an effective amount of at least one compound selected from the group consisting of 5-bromo-N- (2-methoxyethyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinic acid, 5,6-dichloro-N- (n-propyl-N- [2- ( 2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (2,4-dichlorobenzyl) -N- 2- (2,6-dichlorophenoxy) ethyl nicotinamide, 5-bromo-N- (3-chlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (3-chlorobenzyl) -N-] 2- (2,6-dichlorophenoxy) ethyl] nicotinamide, 5 -bromo-N- (2-chlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl nicotinamide, 5-bromo-N- (n-propyl) -N- [1 - (2,4) , 6-trichlorophenoxy) ethyl] nicotinamide hydrochloride and 5-fluoro-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide hydrochloride as well as excipients used in such compositions. A process for the preparation of compounds of formula I (R ¹ ) (i) wherein R ¹ represents a halogen atom in position 5 and / or 6 of the pyridyl group, R represents an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms in the alkoxy group and having 1 to 4 carbon atoms in the alkyl portion, a cyanoalkyl group having 1 to 4 carbon atoms in the alkyl portion, an alkynyl group having 3 to 6 carbon atoms or an optionally mono-, di- or trisubstituted benzyl group in the benzene nucleus, the optionally present substituents being 1 to 3 halogen atoms and / or 1 or 2 alkyl groups having 1 to 3 carbon atoms and / or 1 or 2 alkoxy groups having 1 to 3 carbon atoms and / or tri- (methylmethylene) and / or nitro) R3 represents a halogen atom, a (C1-C3) -alkyl or nitro group, m represents a number of 1 or 2 and n represents a number of 1, 2 or 3, as well as the acid addition salts of the compounds according to item 1, wherein the reactive nicnicinic acid derivative of the general formula II (II) in which the above-mentioned meanings are given is treated with a 2-phenoxyethyl ester of the general formula III (III) in which 2 3 R &lt; 6 &gt; has the meanings given above, and optionally the compound of formula I thus obtained is converted by treatment with an acid into the acid addition salt.