NL8001099A - 3- (N-ACYL-N-ARYLAMINO) - AND 3- (N-THIONOACYL-N- -ARYLAMINO) -GAMMA-BUTYROLACTONES AND GAMMA -THIOBUTYROLACTONES, AND FUNGICIDE PREPARATIONS CONTAINING THESE COMPOUNDS. - Google Patents

Description

5 5. 28,793 3 ((acyacyi-N-arylainino) - and 3 - (bhionoacyi-N-arylamino) - - - butyroctones and J-thiobutyrolactones, as well as fungicidal phenarates containing these compounds.

In U.S. Patents 3,933 * 360? 4,012,519, 4,107,323 and 4,141,989, discloses the use of a large group of 3- (N-acyl-ii-arylamino) ractones and 3- (N-acyl-IT-arylamino) lactases as protective fungicides,

In U.S. patent no. 054 ·. 108 and 4,015,648 disclose the use of 1-(ethoxycarbonyl-ethyl) -T-haloacetylanilines as preventive and curative fungicides.

German patents 2,643 * 4-05 and 2.c4p.445 disclose the use of 2- (alkylthiocarbonyl-ethyl) acetanilides to combat fungi, especially those of the class Phycomycetes.

Dutch patent 152,849 describes the use of N- (alkoxymethyl) acetanilides as fungicides.

Belgian patent 867,556 discloses 3 - (> cyclooroylcarbonyl-2T-ar3 (amino)) - - butyroctones.

Belgian patent 863,615 describes fungicide 3- (N-acyl-N-arylamino) -) - butyrolactones.

It has been found that 3- (N-acyl-N-arylamino) - and 3_ (N_PkionOaCyl-N-arylamino) -y-but 7rolactones and butythiolactones are effective in combating fungi, in particular fungicidal infections by false powdery mildew caused by schismel crypts of the da Peronosporaceae family and fungicidal potato blight infection caused by Phytochtho ra infestans.

In particular, new fungicidal compounds have been found in which the N-acyl group is alkenylcarbonyl, alkyloxide carbonyl and cycloalkylcarbonyl. New fungicide N-thionoacyl compounds have also been found. Some of the compounds of the invention are effective both as protective fungicides, that is, they occur or protect against fungicidal infections, and as effluent fungicides, i.e. they eliminate and cure. infections.

The compounds of the invention are particularly preferred for controlling false flour dew in grapes.

The compounds of the invention are represented by formula 1, wherein Ar phenyi, naphthyl, or phenyi or naphthyl substituted with 1 to 4 the same or different substituent and selected from fluorine, chlorine, bromine, alkyl of 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms, 1R alkenyl of 2 to 6 carbon atoms, alkenyloxide of 2 to 6 carbon atoms or alkenyl of 2 to 6 carbon atoms substituted with halogen or alkoxy of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, 15 cycloalkyl of 3 to 6 carbon atoms substituted with 1 to 4 of the same or different substituents selected from alkyl of 1 to 4 carbon atoms, fluorine, chlorine, bromine, 2 hydroxy or alkoxy of 1 to 4 carbon atoms, R is hydrogen, chlorine, bromine, alkyl of 1 to 6 carbon atoms, phenyi or phenyi substituted with 1 or 2 the same or different substituents selected from fluorine, chlorine, bromine and alkyl of 1 to 6 carbon atoms, Y is 0, S or -YR-, wherein R is water is a substance or alkyl of 1 to 4 carbon atoms, 77 is 0 or S and X is 0 or S, provided that when W is 25, R is in addition to the aforementioned groups hydroxymethyl, halomethyl having 1 to 3 equal or various halogens selected from fluorine, chlorine or bromine, alkoxy alkyl of 2 to 6 carbon atoms, alkylthioalkyl of 2 to 6 carbon atoms, phenylthioalkyl of 7 to 10 carbon atoms, phenoxyalkyl of 7 to 10 carbon atoms, phenylthioalkyl or phenoxyalkyl of 7 to 10 carbon atoms substituted in the phenyl ring with 1 or 2 the same or different substituents selected from fluorine, chlorine, bromine, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, with the proviso that when Ar is phenyl or η is suostituated phenyi, 77 is 0 and R is cyclpropyl, Y is not 0.

Representative substituted phenyl groups that Ar may represent are 2-fluoroferyl, 2,4-dichlorophenyl, -0-3,5-dibromophenyl, -methyifsryl, 2,5-diethylphenyl, 4-metho-80 0 1 0 S3 3-xyphenyl, 4- nitrophenyl, 2,6-dimethyl-4-chlorophenyl, 2,3-6-trimethylphenyl and 2,3,5-S-tetranethyiphenyl.

Preferred substituted phenyl Ar groups are phenyl substituted with 1 or 2 the same or 3 different substituents selected from chlorine, bromine, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms. Most preferred substituted phenyl Ar groups are 2,6-dialkylphenyl, especially 2,6-dimethylphenyl.

Representative substituted naphthyl Ar groups are 1-naphthyl, 2-naphthyl, 1-methyl-2-naphthyl, 4-methyl-2-naphthyl, A-methyl-1-naphthyl, 2-chloro-1-naphthyl, 2- methoxy-1-naphthyl, 2,1-dimethyl-1-naphthyl and 2,7-dimethyl-1-naphthyl. Preferred substituted naphthyl Ar groups are 2-alkyl-1-naphthyl groups, especially 2-methyl-1-naphthyl.

Λ

Representative halomethyl groups that R 'may represent are fluoromethyl, chloromethyl, bromomethyl, dichloromethyl, tribrooamethyl and fluoro dichlocrmethyl. The preferred haloethyl R 'group is chloronethyl, si

Representative cycloalkyl R groups are cyciopropyl, cyclooutyl, cyclopentyl, cyclohexyl and 4-methylcyclohexyl.

Representative alkoxyalkyl x 1 groups are methoxymethyl, ethoxymethyl, isopropoxymethyl and n-pentoxymethyl.

✓1 *

The preferred alkoxyalkyl R 'group is methoxymethyl

Representative alkylthioalkyl R 'groups are methylthiomethyl, n-nronylthiomethyl and n-nentylthiomethyl,

Representative cycloalkyl R groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 4-methylcyclohexyl,

Representative substituted phenylthioalkyl and substituted phenoxyalkyl R 'groups are 4-chlorophenylthiomethyl, 4-methylphenoxyrethyl, 2'-dichloro-oxymethyl, ^ * γΊ ^ V> - * r **% -i ^ ^ O ^ ... ss' • 'η ώ "' λ ^ ~ S * y -i-— tj u- J -J - w C. ^ w» ^ rr Λ TD ^ ^ s ^ Δ vj ct'a 3 "* V * a vn -r-ï-iv-i "- ** - * ^ ---» '- - - -,' ί> · wwa * - i —— / »- Λ .- —4 w - VV / - ^ y —'i — u -1 - »urn i / üt- zm./-, - me -. mj ^, λ — j-, _so—? <η (\ ί yh! o

V v V 3 V

-r-propenyl, butenyl, 3-methoxy-prop-1-en-1-yl, 3-chloroprop-1-en-1-yl. Preferred 3rd alkenyl groups are vinyl, 2-ethyl vinyl and 2,2-dimethyl vinyl.

Representative R 1 alkenyloxide groups are oxiranyl, 5 l-methyloxiran-1-yl, 2,2-dimethyloxiran-1-yl, and 2-methyl-oxiran-1-yl.

P

Representative alkyl H "groups are methyl, ethyl, isopropyl and η-hexyl. Representative substituted phenyl R2 groups are 2-chlorophenyl, 2,4-dichlorophenyl, 4-methylphenyl and 2,3-dimethylphenyl.

Preferably Ar is phenyl substituted with 1 or 2 the same or different substituents selected from fluorine, chlorine, bromine or alkyl with 1 or 2 carbon atoms or 2-alkyl-1-naphthyl. Most preferred 3rd Ar groups are 2,6-dimethylphenyl and 2-methyl-1-naphthyl.

Preferably R 1 vinyl, 2-methyl vinyl, 2,2-dimethyl vinyl, alkoxymethyl of 1 to 6 carbon atoms, chloromethyl or bromomethyl. Most preferably R is methyl, allyl, 2-methylvinyl, 1,2-epoxypropyl, methoxymethyl or chloromethyl.

Ί

When R is cycioalkyl of 3 to 6 carbon atoms, then R 'is preferably cyclopropyl. when Y = S and cyclopentyl when Y = 0.

Representative X and W are both oxygen. When W

η 25 is sulfur, R is preferably methoxymethyl, preferably R is hydrogen or methyl.

A preferred group of R-phenylamino- and N-substituted phenyl-aminolactones is the group accelerated by formula 2, wherein R is alkenyl with 2 to 6 carbon atoms or aikenyl oxide with 2 to 6 carbon atoms, R2 hydrogen or methyl, and R 1 each represents methyl or ethyl and Y 0 or S. Particularly preferred compounds of formula 2 are those wherein R represents vinyl, 2-methylvinyl, 1,2-ethoxypronyl or 2,2-dimethylvinyl, R represents hydrogen and r 'and R / methyl, 3rd 3- (R-thionoacyl -2T-arylamino) lactones and thiolactones of the invention can be represented by formula 3, wherein Ar is phenyl, naphthyl or substituted phenyl or

W Ί O

naphthyl is as defined above, and R ', If, Y and R ~

4.0 99 ili.ΘΓΤΟ 32? Vθ2ΓΓΠ.91, CL 0 00119 ^ 29 ^ 2.339 ^ 09Ζ2. ”1ΐβΠ * 3.9Γ1 g2CO0" O

3 ή η 1 η ο ο ν ν ν ·. preferred 5- (N-thionoacyl-'7-arylamino) lactones are the greens represented by formula 4-, wherein Ί 2 R alkyloxyalkyl of 2 to 6 carbon atoms, R hydrogen or

) \ C

methyl and S 'and P each represent methyl or ethyl. Preferred compounds of formula n are 2/1-y where R represents methoxymethyl, R represents hydrogen and re and R represents methyl.

Representative compounds of formula 1 zign: 3- (R-acryloyl-li-2,6-dimetkylienylamin.o) -) / - butyrolactone, 10 3- (N-3-methylcrotonyl -}! - 2,6-dimethylphenylamino) -) - butyro-lactone, 3- (N-crotonyl-h-2,6-dinethylphenylamino) - / - butyrolactone, 3- (N-acryloyl-h-2,6-dimethylphenylamino) - / - thiobutyrolactone, 3- (N-2-methylhydrylyl) ~ 2i-2-methyl-6-ethylphenylamino) -7-but-15 tyrolactone, 3- (3-methyl-2,3-epoxy-butanoyl-2T-2,5-dimethylphenylamino) - / - butyrolactone, 3- (H- 2-methyl-2,3-eoxy-propanoyl-iT-2,5-dimethyl-phenylamino) -y-butyrolactone, 20 3- (N-met hxythi ono ace ty 1-27-2. Β-dime thylamino) -Yb ut yr o lactone, 3- (R-methoxythionoacetyl-h-2,6-dimethylphenylamino) -7-thio-butyrolactone.

A preferred group of h-cycloalkylicarbonyl-phenylaminothiolactones is the green represented by formula 5 wherein R cycloalkyl is 5 to 6 carbon atoms, 2-5 S hydrogen or methyl and R and v each represent methyl or ethyl. A particularly preferred compound of formula 5 is that wherein R 1 represents cyclopropyl, 30 I hydrogen and R 1 and R 5 methyl.

The 2T-cycloalkylcarbonyl-phenylaminolactones according to the invention can be represented by formula 6, wherein Ar is phenyl or substituted phenyl as defined above, R has the meanings indicated above and 3 'cycloalkyl with 3 Por 6 carbon aromas represents *. In the preferred group of 27-phenylamino- and E-subsuited phenylaminolactones, the green one is represented by formula 7, wherein R 'is cycloalkyl with - to δ carbon atoms,

O _ ƒ k -S

R 3 warersrop or methyl and m and R y each methyl or ethyl 3027030220 ^ 2377 323.223: 3022 2303 2327111212; '220 2.0 O2? Hl5'2.2? ft Λ A ·! h. 7 Λ c U v i v -

^ P

earn, are those in which 3 'cyclopentyi, 3 hydrogen and) I <- «3' and 37 methyl vc esters,

The Y-cycloalkyliccarbyl-phenylaninolactones and thiolac tones of the invention can be represented by formula 3, wherein Ar is naphthyl or substituted naphthyl and

P _P

wherein 3 ', n and f possess the previously described characteristics, A preferred group of Y-naphthianinolactones and thiolactones is the green represented by formula 9, λ 3 7 / ain 3' cycloalkyl with 5-6 carbon atoms, 3 represents hydrogen 10 or alkyl with 1-3 carbon atoms and I oxygen or sulfur. More preferred compounds of formula 95 are those wherein 3 cycloprcpyl, z

Ry methyl and Y represent oxygen.

Representative compounds of the formula I include: 3- (h-cyciobutylocarbonyl-2I-phenyinoin) - // - butyrothiolactone, 3- (-T-cyclohexylcarbonyl-1-4-chlorophenyl amino) -7- butyrothio-lactone, 3- (7-cyclohexylcarconyl-27-α-methoxyphenyianino) / - butyrothiolactone, 20 3- (cyc-cyclopropyl ony 1-.T-2,6-dinethylphenyianino) -3-me- thyl-1-butyrothiolactone, 3- (1-cyciopentylcarbethyl-22-2,5-dimethylf enyianino 2 -7-buty-rothiolactone, 3- (3-cyciopropylcarbryl-3-3.m-dimethylphenyianino) - / - buty-2p rothiolactone, 3- (h-cyclobutylcarconyl-hn-methylphenyianino) -5-chloro - / - butyrothiolactone, 3- (Y-cyclopropylcarbonyl-2-methoxyphenyianino) - / - butyro-lactone, 3- (Y-cytlohexylcarbonyl-3-) 2-ethylnaphth-1-ylanino) -5-phenyl-7-butyrothioiactone, 3- (-T-cyclobutylcarbonyl-27-2-ethylnaphth-1-yianino) - / - buty-rothiolactone, 5- (3- (2 -chlcorcyclopropyicarbethyl-3-2-neahylnaphth-1-ylino) -35-butyrolactone and __ I (O rr '^ * r * Vi "» * - λ * 1 r \ -rv .1 "" O ^ ^ ^ ^ - »·"; v *. <-> '"' 'Ttt __ ^ \" W - J .7 - -: 7 - nc) - / - bue7rolacroii and

7 _ -n - ~ * r \. -> ™ · ’y-“ ^^ ^ - ’ηη, R 'o ^ ty w * ^ Q

4- - · * · << - \ ·· »v ·.

7 ^ -j Cf ^ 'w <a - * / 7 Q 3 “^ y. n. -j - - ^ —1 ^ ^ ^ ^ ^ ~ ^ "'-oλ ^ ^ VO" * O "^ m r ay 3" ^ 3Λ

-¾ f »n 1« 1 O C

-J -7 7 '1 V -V * 7 7

U.S. Patent Application 13,356 of February 22, 1979 by alkylation of an aniline (of Formula 1C) with an α-halo-γ-butyrolactone or α-halo-γ-thiobutyrolactone (of Formula 11) and subsequent acylation of the 5α- (7-arylamino) - * γ-butyrolactone or -thiobutyrolactone (formula 12) with an acyl halide (formula lp) to obtain the 3- (H-acyl-H-ar; nLamino) y-butyroiactor or -thiobutyrolactone- product (Formula 1A), as represented by the reaction equations to Figures 1 and 2, wherein 10 Ar, R, S and Y have the aforementioned meanings and X represents chlorine or bromine,

The alkylation reaction (Fig. 1) is carried out in the presence of a base. Suitable bases are inorganic alkali metal carbonates such as sodium carbonate or potassium carbonate or organic amines such as trialkylamines, for example triethylamine, or pyridine compounds, for example pyridine or 2,6-dimethylpyridine. Generally, mainly ecololar amounts of the reagents (10) and (11) and the base are used. In a modification of the reaction, a molar excess of the aniline reagent (10) is used as the base and no additional base is used. The reaction is performed in inert organic solvents, eg non-polar diprotic solvents such as dimethyiformamide and acetonitrile and aromatic hydrocarbons such as benzene and toluene, at reaction temperatures ranging from 25 ° C to 150 ° C, preferably from 50 ° C to 150 ° C. Water can be used as a cosolvent. The reaction pressure can be atmospheric, above-atmospheric or below-atmospheric. However, conveniently the reaction is carried out at atmospheric pressure. The reaction time will of course vary depending on. the reagents and the reaction temperature. In general, the reaction time is 0.25 to 2x hours. The product (12) is generally purified by conventional methods, for example extraction, distillation or crystallization, before use in the acylation reaction (Fig. 2).

Preferred alkylation reaction conditions, i and 6 Ti z ^ ^ ^ "* βθθ2.c. in them Arne2? Ilcs.3.ii3e oc ~ · XV ate w · * · 4 V» · Si »V, I v / '. V - »W tr -. χ té • bo _e acy.ermgs reaction .fig, x, ·' wc rut vc-gens sweater .- * 5- Λ Λ .J f \ ρ p Ά \ i ü i Any methods carried out The reactants (12) and (13) are generally contacted in substantially equimolar amounts in an inert organic solvent at a temperature of 0 ° to 100 ° C. any suitable inert organic solvents include ethyl acetate, dichloromethane, dimethoxyethane, benzene, etc. The product is isolated and purified by conventional methods such as extraction, distillation, chromatography, crystallization, etc.

When a butyrolactone product (compounds of formula 1, wherein W, X and Y are oxygen) is prepared, an organic amine such as a trialkylamine or a pyridine compound can be used as an acid binding agent. However, when a butyrothiolactone product (compounds of formula 1, wherein W and X represent oxygen and Y sulfur), an organic amine should not be used.

Preferred acylation reaction conditions are reported in more detail in U.S. Patent Application No. 84-7,504 of November 1, 1977.

ή

The compounds of formula 1A, wherein E represents alkylthioalkyl, phenylthioalkyl or substituted phenylthioalkyl, may be prepared from the corresponding ή compound, wherein E represents haloalkyl, by reacting the corresponding haloalkyl compound with an alkali metal mercaptide as proposed in the reaction comparison with Fig. 3, in the case where E is alkylthiomethyl, in which Fig. Ar, p S, X and Y have the aforementioned meanings, M 30 represent an alkali metal and R alkyl, phenyl or substituted phenyl. In the reaction equation to Fig. 3, Y is preferably oxygen,

The compounds of formula 1A, wherein E represents hydroxymethyl and Y oxygen, can be prepared by __ η

Treatment of the corresponding compound, wherein E

halomethyl, with an inorganic alkali metal hydroxide, such as aqueous sodium hydroxide, The

bonds of formula 1A, wherein E is hydroxymethyl and Y

oxygen or sulfur can be prepared by 4-0 hydrolysis of the corresponding compound, wherein R "80 0 1 0 93 9 represents alkanoylmethyl.

Ί

Compounds of formula 1A, wherein R represents alkenyloxide, are prepared by oxidation of the corresponding compound, wherein R represents alkenyl, with an oxidizing agent such as 3-chloroperbenzoic acid, in the presence of an inorganic base, such as potassium hydrogen phosphate.

2

The compounds of formula 1A, wherein R represents chlorine or bromine, are generally prepared by chlorination or bromination of the corresponding compound, wherein R represents hydrogen, with a chlorinating or brominating agent such as R-bromosuccinimide or R-chlorosuccinimide by conventional methods, as represented in the reaction equation to Figure 4, wherein Ar, R, I and X have the aforementioned meanings.

The 3- (bT-thionoacyl-R-arylamino) butyrol acetones and thiobutyrolactones are prepared from the corresponding 3- (N-acyl-N-arylamino) butyrolactones and thiobutyrolactones of formula 2 according to the reaction equation of Fig. 5.

This reaction is carried out at the temperature at which a 20 "refluxed fret solvent, preferably xylene, with a molar ratio of the compound of formula 2A to phosphorus pentasulfide of about 4: 1 in the presence of a trace of a base, such as pyridine. The product of formula 14 can be isolated by conventional chromatography methods.

The thiolactone compounds of the invention can be prepared by cleaving the corresponding lactone compound of formula 1 with an alkyl mercaptide salt followed by formation of the thiolactone using a halogenating agent such as phosphorus trichloride, phosphorus pentachloride, thionyl chloride or oxalyl chloride as represented by the reaction equations with the FIGS. 6 and 7 in which R, R and Ar have the above meanings.

The compounds according to the invention are suitable for combating fungi, in particular fungal infections in plants. However, some fungicidal compositions of the invention may be more fungicidal than others against particular fungi. For example, the activity of the preferred compounds of the invention in 6ΠΑ 1 schimmel 00 is highly specific for certain fungal diseases such as downy mildew, for example Plasmopara viticola (grapes) and Peronospora parasitica (cabbage), potato diseases, for example Phytophthora infestans (tomatoes and potatoes) ) 5 and crown and root rot, for example Phytophthora.

The compounds of the invention are particularly useful fungicides because they cure established infections. This allows an economical use of the fungicides of the invention because they do not need to be applied to plan-10 unless a fungicidal infection actually occurs. Therefore, a preventive program for applying fungicides against a potential fungal infection is not necessary.

When used as fungicides, the compounds of the invention are applied in fungicidally effective amounts to fungi and / or the places where they occur, such as vegetative hosts and non-vegetative hosts, for example animal products. The amount used will of course depend on various factors such as the host, the type of fungus and the particular compound according to the invention. As with most pesticidal compounds, the fungicides of the invention are not usually used in full strength, but are generally mixed with conventional biologically inert extenders or carriers, which are normally used to disperse the active fungicidal compounds. facilitate, taking into account that the formulation and method of application may affect the activity of the fungicide. Therefore, the fungicides of the invention can be formulated and used as granules, as dusting powders, as wettable powders, as emulsifiable concentrates, as solutions, or as any of the various other types of formulations, depending on the desired mode of application.

Spray powders are in the form of finely divided particles, which readily disperse in water or other dispersant. These preparations usually contain about 5 to 80% fungicide and residual inert material, such as dispersants, emulsifiers and wetting agents. The powder can be applied to the soil as 80 0 1 0 99 11 as a dry dusting agent, or preferably as a suspension in water. Common carriers include fullers earth, kaolin clays, silica compounds, and other highly absorbent, wettable, inorganic diluents. Common wetting, dispersing, or emulsifying agents include, for example, the aryl and alkyl aryl sulfonates and their sodium salts, alkyl amide sulfonates, including fatty acid methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols and polyvinyl alcohols; polyethylene oxide, sulfonated animal and vegetable oils; sulfonated petroleum oils, fatty acid esters of polyhydric alcohols and the epoxyethane addition products of such esters and the addition products of long chain mercaptans and epoxyethane. Many other types of conventional surfactants are commercially available. The surfactant, when used, usually represents 1 to 15% by weight of the fungicidal composition.

Dusts are free flowing mixtures of the active fungicide with finely divided solids such as talc, natural clays, kieselguhr, pyrophyllite, chalk, diatomaceous earth, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, ground products and other organic and inorganic solids which serve as dispersants and carriers for the toxic agent.

These finely divided solids have an average particle size of less than about 50 µm. A conventional dusting formulation contains 75% silicon dioxide and 25% of the toxic agent.

Emulsifiable concentrates belonging to conventional liquid concentrates, which are homogeneous liquid or paste-like preparations, which are readily dispersed in water or another dispersant, and which may consist entirely of the fungicide with a liquid or, may be, solid emulsifier, or a liquid carrier such as xylene, heavy aromatic naphthas, isophoran and other non-volatile organic solvents. For use, these concentrates are dispersed in water or another liquid carrier and are usually used as a spraying agent on the area to be treated.

a o 010 99

Other common formulations for fungicidal applications include simple solutions of the active fungicide in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene or other organic solvents. Granular formulations, in which the fungicide is applied to relatively coarse particles, are of particular use for air distribution or penetration of a canopy covering the crop. Pressurized sprays, usually aerosols, in which the active ingredient is dispersed in finely divided form due to evaporation of a low boiling dispersant solvent carrier, such as the Freons, can also be used. All these techniques for formulating and applying fungicides are known.

The weight percentages of the fungi may vary depending on the manner in which the composition is used and the particular formulation type, but is generally between 0.5 and 95% by weight of the toxic agent of the fungicidal composition.

The fungicidal compositions can be formulated and used with other active ingredients such as fungicides, insecticides, nematocides, bactericides, plant growth control agents, fertilizers, etc.

25 Examples

The preparation and fungicidal activity of the compounds of the invention are illustrated by the following examples.

Example I

50 Preparation of 3- (N-methoxyacetyl-H-2,6-dimethylphenylamino) -7-thiobutyrolactone

A solution of 1.46 g (0.0135 mol) of methoxyacetyl chloride in 10 ml of dichloromethane was added dropwise to a reflux solution of 3 g (0.0135 mol) of 3 ~ (N-2,6-dimethylphenylamino) - / -thio-butyrolactone in 200 ml of toluene. The reaction mixture was refluxed for 3 hours and evaporated to give a solid. The solid was recrystallized from a solvent mixture of ether: benzene-40-se: hexane in the ratio 10: 1: 10, 1.8 g of 80 0 1 o 99 13 of the product as a tan solid with a melting point 86-87 ° C were obtained. The infrared spectrum of the product showed two strong carbonyl absorption bands at 5 85 µm and 6.03 µm.

Example II

Preparation of 3- (N-acetoxyacetyl-N-2,6-dimethylphenylainino) -7-butyrolactone

A sample of 13 7 S (0.1 mole) acetoxyacetyl chloride was added dropwise to a solution of 10 20.5 g (0.1 mole) N-2,6-dimethylphenylamino-7-butyrolactone and 7.9 g (0 1 mol) pyridine in 150 ml benzene. After completion of the addition, the reaction mixture was stirred at about 25 ° C for 4 hours, then washed with water, dried with magnesium sulfate and evaporated under reduced pressure to give an oily residue.

The residue was crystallized from ethyl ether / hexane to obtain 27.5 g of product, mp 90 DEG-91 DEG.

3- (N-cyclopropylcarbonyl-N-2,6-dimethylphenylamino) -20 7-butyrolactone can be prepared in an analogous manner using cyclopropylcarbonyl chloride and N-2,6-dimethylphenylamino-7-butyrolactone as starting products. Example III

Preparation of N-hydroxyacetyl-N-2,6-dimethylphenylamino-γ-butyrolactone

A solution of 50 g (0.18 mol) 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) - / - butyrolactone, 14.5 g (0.36 mol) sodium hydroxide dissolved in 50 ml water and 4-50 ml of dimethoxyethane were stirred at about 25 ° C for 16 hours. The resulting reaction mixture was filtered and diluted with 500 ml of dichloromethane. Hydrogen chloride gas was bubbled into the reaction mixture for 1 hour. The reaction mixture was filtered, dried over magnesium sulfate and evaporated under reduced pressure. The residue was washed with 10% 55 ethyl ether / 90% hexane, filtered and air dried to give 36.5 g of the product as a white crystalline solid, mp 175-174 ° C.

80 0 1 0 99

Example IV

Preparation of N-ethoxyacetyl-N-2,6-dimethylphen; ylamino - / - butyrolactone

A sample of 6.2 g (0.05 mol) of ethoxyacetyl chloride 5 was added dropwise to a refluxing solution of 10.3 g (0.05 mol) 3- (N-2,6-dimethylphenylamino) -) butyrolactone in 150 ml of toluene. The reaction mixture was then refluxed for 2 hours. After cooling, the reaction mixture was washed with water, washed with a saturated solution of sodium hydrogen carbonate, washed with water, dried with magnesium sulfate and evaporated to give 11.2 g of 3- (H-ethoxyacetyl-N-2,6-dimethylphenylamino) -) / - butyrolactone, mp 75-75 ° C.

Example V

Preparation of N-methylthioacetyl-N-2,6-dimethylphenylamino) -7-butyrolactone

A sample of 22 g (0.3 mole) of sodium methyl mercaptide was added in small amounts to a solution of 25.5 g (0.08 mole) of N-bromoacetyl-N-2,6-dimethylphenyl-amino) -7-butyrolactone, melting point 116-117 ° C, in 200 ml dimethyl sulfoxide. A weak exotherm-developed. The reaction mixture was stirred at about 25 ° C for about 16 hours. Then, the reaction mixture was heated to about 150 ° C under a reduced pressure, generated with the water jet pump, to remove part of the dimethyl sulfoxide solvent. The residue was diluted with water and the aqueous layer was separated.

The organic part was dissolved in 350 ml of dichloromethane, washed with water, dried with magnesium sulfate and evaporated under reduced pressure to yield an oil. The oil was chromatographed through a silica gel column (20% acetone / 80% petroleum ether elution) to give 11 g of the product, which after crystallization from ethyl ether / acetone at 77-78 ° C melted.

Example VI

Preparation of 3- (N-methoxyacetyl-N-2-methylnaphth-1-ylamino-7-butyrolactone 40) A sample of 2.4 g (0.022 mol) of methoxyacetyl chloride was added dropwise to a solution of 5.5 g (0.022 mol) 3- (N-2-methylnaphth-1-ylamino) -) - butyro-lactone and 1.7 g (0.022 mol) pyridine in 100 ml dichloromethane. The reaction mixture was stirred at about 25 ° C for 1 hour and then refluxed for 6 hours. After cooling overnight, the reaction mixture was washed successively with water, a saturated solution of sodium hydrogen carbonate and water, dried with magnesium sulfate and evaporated under reduced pressure. The residue was subjected to a chromatographic treatment through a silica gel column. Elution with 25% acetone / 75% petroleum ether gave 4.3 g of product with a melting point of 42 - 46 ° C.

Example VII

Preparation of 3- (N-methoxythionoacetyl-N-2'-6-dimethyldenyl-15 amino) -y-thiobutyrolactone

A suspension of 6.0 g of phosphorus pentasulfide in 300 ml of xylene was heated under a Dean-Stark water separator to azeotropically remove any water. After cooling to 100 ° C, 2 ml of pyridine was added, followed by 33.3 g of 3 - (“-ethoxyacetyl-3-N-2,6-dimethylphenylamino) -y-butyrolactone. The stirred suspension was heated to 150 ° C. After about 45 minutes, the phosphorus pentasulfide dissolved and the mixture was kept at 150 ° C for a weekend.

The mixture was diluted with an equal volume of dichloromethane and washed with 200 ml of saturated sodium hydrogen carbonate and 200 ml of water and dried with magnesium sulfate.

The solution was filtered and the filtrate stripped under reduced pressure to give a dark oil which was chromatographed on 300 g of silica gel by eluting with petroleum ether, 80% petroleum ether in diethyl ether, 70% petroleum ether in diethyl ether, 60% petroleum ether in diethyl ether, 40% petroleum ether in diethyl ether and 25% petroleum ether in diethyl ether.

The oil separated from the petroleum ether: diethyl ether elutions was dissolved in dichloromethane and treated with charcoal and magnesium sulfate, filtered and stripped to give the intended product as an oil (1.8 g). The product is listed in Table 3 as Compound 10.

80 0 1 0 99

ID

Example VIII

Preparation of 5- (N-crotonyl-N-2,6-dimethylphenylamino) -7-butyrolactone 6 g Crotonic acid and 12 g thionyl chloride were refluxed for 1 hour and excess thionyl chloride removed under reduced pressure. 14 g of 3- (N-2,6-dimethylphenylamino) - / - butyrolactone were added with 150 ml of toluene and refluxed for 2 hours.

The mixture was washed with water and a saturated solution of sodium hydrogen carbonate, dried with magnesium sulfate, filtered and stripped of solvent. The product was chromatographed on 260 g of silica gel; elution with acetone / ether / petroleum ether gave 3 µg of the desired product, m.p. 122-123 ° C. The product is listed in Table A as compound 3

Example IX

Preparation of 3- (N-3-methyl-2,3-epoxybutanoyl-N-2,6-dime-20-thylphenylamino) - / - butyrolactone 3- (N-3-methyl-c-rotonyl-N-2 ♦ 6-dimethyphenylamino) - / Butyrolactone (A) was prepared as in Example VIII using 3-methylcrotonic acid as a starting product. Product A (9 g), 3-chloroperbenzoic acid (6 g) and ΚΗ2ΡO ^ 25 (4.7 g) in 75 ml of dichloromethane were refluxed for 48 hours.

The mixture was washed with water, dried with magnesium sulfate and stripped. The residue was crystallized from ether / hexane to obtain 5-4 g of the desired product, mp 100-104 ° C. The product is listed in Table A as compound 7

Example X Myc elium inhibition

Compound 2 of the present invention was evaluated for fungicidal effectiveness by a mycelium inhibition test. This test is designed to measure the fungitoxic activity of fungicidal chemicals expressed in their degree of inhibition of mycelial growth. Compound 2 was dissolved in acetone to a concentration of 40,500 ppm. Panel strips were inoculated with Pythium 80 0 * 1 0 99 17 ultimum mycelium growth by covering the paper with a potato dextrose liquid culture of mycelium suspension.

The inoculated paper strips were then applied to potato dextrose agar plates and sprayed with a fungicide solution using a micro-sprayer. The treated paper strips were incubated at 25 ° C and determinations are made after 24 hours. Fungicidal activities are measured by a zone of inhibited mycelium growth from the center of the paper strip. The effectiveness of compound 2 tested for fungicidal activity is 100% expressed as percent inhibition over Difolatan.

Example XI

Fungus disease bi, 1 tomatoes Compounds according to the invention were tested for the preventive control of the tomato fungal disease organism Phytophthora infestans. Five to six week old tomato seedlings (Bonny Best) were used. The tomato plants were sprayed with a suspension of the test compound at a concentration of 250 ppm in acetone, water and a small amount of a nonionic emulsifier. The sprayed plants were then inoculated with the organism a day later, placed in an environmental room and incubated at 19 to 20 ° C and a relative humidity of 100% for at least 16 hours. After the incubation, the plants were kept in a greenhouse for about 7 days at a relative humidity of 60-80%. The percent disease control provided by a given test compound was based on the percent disease reduction with respect to untreated control plants. The results are shown in Tables C and D. In the tables, the test concentration is 250 ppm unless otherwise indicated by numbers in parentheses.

Example XII

35 Fungus disease, including celery

Celery fungal disease tests were performed using 11-week-old celery (Utah) plants. The organism was Sentoria a-pii. The celery plants were sprayed with solutions of the toxic agent mixed with acetone, water and a non-ionic emulsion 10 99 ΙΟ

agent. The plants were then inoculated with the organism and placed in an environmental chamber and incubated for about 48 hours at 19-20 ° C and 100% relative humidity. After the incubation, the plants were dried and then maintained in a relative humidity of 60-80% for 14 days. The percent disease control provided by a given toxicant is based on the percent disease reduction with respect to untreated control plants. 10 The results are shown in Tables C and D. Example XIII

Downy mildew-bèstri.idinp; at the grape

The compounds of the invention were tested for control of the grape mildew organism Plasmopara viticola.

Loosened leaves, between 70 and 85 mm in diameter, from 7 week old grape seedlings Vitis vinifera strain Emperor were used as hosts. The leaves were sprayed with a solution of the test compound 20 in acetone. The sprayed leaves were dried, inoculated with a spore suspension of the organism, placed in a humid environmental space and incubated at 18-20 ° C and a relative humidity of about 100%.

The degree of disease control was determined 7 to 9 days after the inoculation. The percent disease control provided by a given test compound was related to the percent disease reduction with respect to untreated control plants. The results are shown in Tables 0 and D.

50 Example XIV

Alternaria disease bi.1 the tomato

Compounds of the invention were tested for control of Alternaria solani conidia in the tomato. Tomatoes (Bonny Best variety) seedlings from 6 to 7 weeks of age were used. The tomato plants were sprayed with a 250 ppm solution of the test compound in an acetone and water solution containing a small amount of a nonionic emulsifier. The sprayed plants were inoculated with the organism 1 day later, dried and kept at a relative humidity of 60-80% for about 12 days. The disease control rate was based on the disease development rate of untreated control plants. The compounds tested and the results are shown in 5 Tables C and D.

Example XV Primary mildew

The primary mildew test was done using bean seedlings (Bountiful variety) with well-developed primary leaves. The pathogen was Erysiphe nolygoni. The bean seedlings were sprayed with a 250 ppm solution of the test compound in an acetone-water mixture containing a nonionic emulsifier. The treated plants were inoculated with the pathogen 1 day after spraying and the test compound.

The plants were then stored in a greenhouse at a relative humidity of 60 - 80% and a temperature of 20 - 21 ° C. The degree of infection of the leaves was determined after about 10 days. The percent disease control provided by a given test compound was related to the disease reduction with respect to untreated control plants. The results are shown in Table D.

Example XVI 25 Leaf rust

The leaf rust test was performed using pinto beans. The pathogen was ionyces phaseoli tipica. The pinto bean plants were sprayed with a 250 ppm solution of the test compound in an acetone-30 water mixture containing a nonionic emulsifier.

The treated plants were then inoculated with the pathogen and then incubated in an environmental room for about 20 hours at a relative humidity of 90% and a temperature of 20-21 ° C. The plants were then removed from the room, dried and then stored in a greenhouse at a relative humidity of 60-80%. The infection rate of the leaves was determined after about 14 days. The percent disease control provided by a given test compound was based 40 on the disease reduction with respect to untreated 80 0 1 0 99

control plants. The results are shown in Table D. Example XVII

Preparation of 3- (N-cyclopentylcarbonyl-N-2,6-dimethylphenylamino) -X-butyrolactone 5 A sample of 5 7 g (0.045 mol) of cyclopentylcarbonyl chloride was added dropwise to a solution of 8.8 g (0.043 mol) ) N-2,6-dimethylphenylamino - / - butyrolactone in 100 ml of toluene. After completion of the addition, the reaction mixture was refluxed overnight, with water, with saturated sodium carbonate solution and again washed with water, dried with magnesium sulfate and evaporated under reduced pressure to give an oily residue . The residue was crystallized from diethyl ether to yield 6.1 g of product with a melting point of 109-113 ° C.

The product is listed in Table C as compound C1. Example XVIII

Preparation of 2- (N '-cyclopropylcarbonyl-2,6-dimethylanilino) -4-tert-butylthio) -butanoic acid To 4.2 g of t-butyl mercaptan in 100 ml of 1,2-dimethoxyethane were added 2.5 g of sodium methanolate with stirring. A sample of 11.6 g of 3- (cyclopropylcarbonyl-2,6-dimethylanilino) -butyrolactone (prepared as described in Example I) was added to the reaction mixture and stirred overnight at ambient temperature and poured into ice water.

The mixture was washed with 2 x 100 ml of toluene and the toluene was backwashed with water. The aqueous phase was brought to a pH of 1 with 12 N hydrochloric acid and then extracted twice with dichloromethane. The dichloromethane extracts were washed with water, dried with magnesium sulfate, filtered and stripped to give 10.6 g of the desired product as an oil.

35 Example XIX

Preparation of 3- (N-cyclopropylcarbonyl-2,6-dimethylanilano) -butyrothiolactone

The acid prepared in Example XVIII (10.6 g) was dissolved in 200 ml of dichloromethane in a flask equipped with a 40 condenser, cooled to -20 ° C, then 6.0 g of PCl ^ 80 0 1 0 99 21 were added dropwise. The exothermic reaction allowed the mixture to warm to 36 ° C. More dichloromethane was added and the. mixture was kept overnight at ambient temperature, after which two phases were formed.

The dichloromethane layer was collected, dried (magnesium sulfate, silica gel), filtered and stripped.

The resulting oil was crystallized from petroleum ether to give the desired product, m.p. 145-14-7 ° C.

The compounds listed in Table E were prepared according to methods similar to those of Examples XVII to XIX. The structure of each compound in the tables was confirmed by nuclear magnetic resonance spectroscopy and / or infrared spectral analysis.

15 80 0 1 0 99

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No. GDM TLB CLB TEB BR BPM

Cl 81 19 0 0 10 C2 50 19 0 0 0 C3 - 0 7 0 0 4 C4 98 71 19 0 29 4 C5A 99 6 44 21 0 0 C5B 99 13 44 56 0 23 C6 13 11 0 0 0 98 GDM = false mildew on the grape TLB = tomato, fungal disease CLB = celery, fungal disease TEB = tomato, altemaria disease BR = bean root st BPM = primary mildew on the bean 80 0 1 0 99

Claims (36)

A compound of formula 16, wherein Ar is phenyl, naphthyl, or phenyl or naphthyl substituted with 1 to 4 the same or different substituents such as fluorine, chlorine, 5 bromine, alkyl of 1 to 4 carbon atoms and / or alkoxy of 1 to 4 carbon atoms, E alkenyl of 2 to 6 carbon atoms, optionally substituted with halogen or alkoxy of 1 to 4 carbon atoms, alkenyloxid% and 2 to 6 carbon atoms, E hydrogen, chlorine, bromine, alkyl of 1 to 10 carbon atoms, phenyl or phenyl substituted with 1 or 2 the same or different substituents such as fluorine, chlorine, bromine and / or alkyl of 1 to 6 carbon atoms, Y 0, S or -NE-, where E represents hydrogen or alkyl of 1 to 4 carbon atoms, W 0 or S and X represent 0 or S-15. 2. S 6 carbon atoms, R is hydrogen or methyl and R and R 'are individually methyl or ethyl. 2. A compound of the formula: wherein Ar is phenyl, naphthyl, or phenyl or naphthyl substituted with 1 to 4 the same or different substituents such as fluorine, chlorine, bromine, alkyl of 1 to 4 carbon atoms and / or alkoxy of 1 to 4 η 20 carbon atoms , E hydroxymethyl, halomethyl with 1 to 5 the same or different halogen atoms such as fluorine, chlorine and / or bromine, alkoxyalkyl with 2 to 6 carbon atoms, alkylthioalkyl with 2 to 6 carbon atoms, phenylthioalkyl with 7 to 10 carbon atoms, phenoxyalkyl 25 with 7 to 10 carbon atoms , phenylthioalkyl or phenoxyalkyl of 7 to 10 carbon atoms, substituted in the phenyl ring with 1 or 2 the same or different substituents such as fluorine, chlorine, bromine, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, cyclo-50 alkyl of 5 to 4 6 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, cycloalkyl with 3 to 6 carbon atoms substituted with 1 to 4 the same or different substituents such as alkyl with 1 to 4 carbon atoms men, fluorine, chlorine, bromine, hydroxy or alkoxy with 1 to 4 carbon atoms and E hydrogen, chlorine, bromine, alkyl with 1 to 6 carbon atoms, phenyl or phenyl substituted with 1 or 2 the same or different substituents such as fluorine, chlorine, bromine or alkyl of 1 to 6 carbon atoms, Y 0, S or -NE-, in which E represents hydrogen or alkyl of 1 to 4 carbon 40 atoms and X represents 0 or S. 80 0 1 0 99 Compound according to claim 1, characterized in that H represents alkenyl of 2 to 6 carbon atoms. 4. A compound according to claim 3, characterized in that I and X are oxygen. Compound according to claim 4, characterized in that Ar represents 2,6-dialkylphenyl, Y oxygen or p sulfur and E hydrogen. 6. A compound according to claim 5, characterized in that Ar represents 2,6-dimethylphenyl, E 2-methyl vinyl and Y oxygen. 7. A compound according to claim 5, characterized in that Ar represents 2,6-dimethylphenyl, E vinyl and Y oxygen. 8. A compound according to claim 5, characterized in that Ar represents 2,6-dimethylphenyl, E 2,2-dimethylphenyl and Y oxygen. 9. A compound according to claim 5, characterized in that Ar represents 2,6-dimethylphenyl, E vinyl and Y 20 sulfur, 10. A compound according to claim 5, characterized in that Ar represents 2,6-dimethylphenyl, E 1,2-epoxy propane and Y oxygen. 11. A compound according to claim 2, characterized in that X represents oxygen and Ar 2,6-dialkylphenyl. 12. A compound according to claim 11, characterized in that Ar represents 2,6-dimethylphenyl, E hydrogen, A E methoxymethyl and Y oxygen or sulfur. 30 Compound according to claim 12, characterized in that Y represents sulfur. 14. A method for controlling fungi, characterized in that said fungi or the places where they occur are contacted with a fungicidally effective amount of a compound of the formula according to claim 1. Method for controlling the growth of PhvtQOhthora infestans fungi, characterized in that it is applied to this fungi or to the place where it is. To prevent fungi, use a fungicidally effective amount of 80 0 1 o 99 2U a compound of formula according to claim 1. 16. Method for controlling the growth of Plasmopara viticola fungi, characterized in that a fungicidally effective amount of a compound of the formula according to claim 1 is used on this fungi or on the place where these fungi occur. A fungicidal composition, characterized by the presence of a biologically inert carrier and a fungicidally effective amount of a compound of the formula according to claim 1. 18. A method for controlling fungi, characterized in that this fungi or the site where these fungi occur is contacted with a fungicidally effective amount of a compound of the formula according to claim 2. 19. A method for controlling the growth of Phytonhthora infestans fungi, characterized in that a fungicidally effective amount of a compound of the formula according to claim 2 is used at this fungi or the place where these fungi occur. 20. Method for controlling the growth of Plasmooara viticola fungi, characterized in that a fungicidally effective amount of a compound of the formula according to claim 2 is applied to this fungi or to the place where these fungi occur. applies. A fungicidal composition, characterized by the presence of a biologically inert carrier and a fungicidally effective amount with a compound of the formula according to claim 2. A compound of formula 8, wherein Ar is phenyl, naphthyl, or phenyl or naphthyl substituted with 1 to 4 the same or different substituents such as fluorine, chlorine, bromine, alkyl of 1 to 4 carbon atoms and / or alkoxy of 1 to 4 carbon atoms, E cycloalkyl of 3 to 6 carbon atoms, 35 cycloalkyl of 3 to 6 carbon atoms substituted with 1 to 4 of the same or different substituents such as alkyl of 1 to 4 carbon atoms, fluorine, chlorine, bromine, hydroxy and / or alkoxy of 1 to 4 carbon atoms and E hydrogen, chlorine, bromine, alkyl of 1 to 6 carbon atoms, 40 phenyl or phenyl substituted with 1 or 2 the same or different substituents such as fluorine, chlorine, bromine and / or alkyl of 1 to 6 carbon atoms Y represents O, S or NE, wherein R is hydrogen or alkyl of 1 to 4 carbon atoms, with the proviso that when Ar is phenyl or substituted phenyl and E is cyclopropyl, Y is not 0. A compound according to claim 22 of formula 17, wherein Ar represents phenyl or substituted phenyl as defined 1 in claim 22 and E and R have the meanings set out in claim 22. A compound according to claim 23., characterized in that Ar phenyl substituted with 1 or 2 is the same or different substituents such as fluorine, chlorine, bromine, alkyl with 1 to 4 carbon atoms and / or alkoxy with 1 to 4 carbon atoms * 15 # Compound according to claim 24 - of formula 5 », characterized in that E cycloalkyl with 3 to 26. A compound according to claim 25, characterized in that R 1 represents cyclopropyl, R represents hydrogen and R and 5 represents R-1 methyl. A compound according to claim 22 of formula 6, characterized in that Ar represents phenyl or substituted phenyl as defined in claim 22 and R and R have the meanings set out in claim 22. 28. A compound according to claim 27 of formula 7, characterized in that R represents cycloalkyl with 4 to 45 carbon atoms, R represents hydrogen or methyl and R and separately methyl or ethyl. 29. A compound according to claim 28, characterized in that R represents cyclopentyl, R represents hydrogen and R and 5 represent methyl. A compound according to claim 22 of formula 8, 35, characterized in that Ar represents naphthyl or substituted naphthyl as defined in claim 22, 1 and R, R and Y have the meanings set out in claim 22. A compound according to claim 22 of formula 9, η 40, characterized in that R has the meanings stated in claim 22 80 0 1 0 99 7. R 1 represents hydrogen or alkyl of 1 to 3 carbon atoms and Y represents oxygen or sulfur . 32. A compound according to claim 31 characterized in that R represents cyclopropyl, R methyl and Y oxygen. 33. A method for controlling fungi, characterized in that this fungi or the place where these fungi occur is contacted with a fungicidally effective amount of a compound of the formula according to claim 22. 34 ·. Method for controlling the growth of Phttophthora infestans fungi, characterized in that a fungicidally effective amount of a compound of the formula according to claim 22 is used on this fungi or at the location where these fungi occur. Method for controlling the growth of Plasmopara viticola fungi, characterized in that a fungicidally effective amount of a compound of the formula according to claim 22 is applied to this fungi or to the place where these fungi occur. . A pungicidal composition, characterized by a biologically inert carrier and a fungicidally effective amount of a compound of the formula according to claim 22. 80 0 1 0 99