DK142077B - Plant fungicidal halogenacylanilides. - Google Patents

Description

(11) Petition 142077 DENMARK <»<> ι« .α · c 07 c 103 / «A Ot N 37/22 § (21) Note No. 156l ^ 5 rö ^ 26. tnar. 1975 (24, Race day 2β * Mar · 1975 (44) The application presented and.

the disclosure notice published on

DIRECTORATE OF

PATENT AND TRADEMARKET SYSTEM (30) 4509/74 CH

Feb 15 1975, 1785/75, CH

(71) CIBA-GREIGT AG, 4002 Basel, CH.

(72) Inventor: Adolf Hubele, Im Egg, 4465 Magden, CH.

(74) Plenipotentiary in the proceedings:

Dansk Patent Kontor ApS.

(64) Plant fungicidal haloacyl anilides.

The present invention relates to novel plant fungicidal haloacyl anilides which are characterized in that they have the general formula γη 0Ηλ CH 3 j 3 / CH-COOCH,

<T> -H

z> = r xco-z2 (i) p wherein Z is hydrogen or methyl, Z "*" is methyl or ethyl, and

ISLAND

Z is a C 1 -C 4 -alkyl group substituted with a chloro, bromo or iodo atom.

2 142077

By a C 2 -C 4 alkyl group is meant ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s.

German Patent Specification No. 2,212,268 discloses in general form that N-haloacylated anilinoalkanecarboxylic acid esters have selective herbicidal activity. However, only some N-haloacetylated 2, β-dialkylanilinoacetic acids and their esters are mentioned by name, and only their effect as herbicides is documented. There are no references to microbicide, especially piante fungicide action.

In the description of DK patent application no. 5552/73, furthermore, 2,6-dialkylanilinoacetic acid esters are also described, which are also N-halogenacetylated. They have microbicide, especially plant fungicide, effect.

The group of N- (1'-methoxycarbonyl-ethyl) -N-haloacyl-2,6-dialkyl-anilines of formula I has hitherto not been described in the literature, and thus they are novel. Surprisingly, in contrast to the anilinoacetic acids and acetic acid esters described in German Publication No. 2,212,268, this group has strong plant fungicidal properties.

Thus, the compounds of Formula I have both preventive and curative effects against five topogenic fungi in cultural plants, such as cereals, corn, rice, vegetables, sugar beets, soy, peanuts, fruit trees, ornamental plants, but above all in vines, hops, cucumber plants (cucumbers, pumpkins) , melons) and solanas, such as potatoes, tobacco and tomatoes, as well as banana, cocoa and cautery juice plants.

With these active substances, fungi that occur in plants or parts of the plant (fruits, flowers, foliage, stems, tubers, roots) can be inhibited or destroyed, so that later growing parts of the plant will also be spared from such fungi. The active substances are effective against phytopathogenic fungi belonging to the following classes: Asco-mycetes (Erysiphaceae); Basidiomycetes, such as, above all, rust fungi; Fungi imperfecti (such as Moniliales); but especially against those of the class of Phycomycetes belonging to Phycomycetes, such as Phytophthora, Peronospora, Pseudoperonospora, Pythium or Plasmopara. In addition, the compounds of formula I act systemically.

3 142077

They can also be used as seed dressings for the treatment of seed material (fruits, tubers, grains) and plant cuttings for protection against fungal infections as well as against phytopathogenic fungi that occur in the soil.

When extended or modified spectrum of action is desired, the active substances of formula I may be mixed with other known fungicides, bactericides, fungistatics, bacteriostatics, but also with insecticides, acaricides, herbicides, and because of their systemic effect permitting a soil application , also with nematodicides, molluscicides or rodenticides, thereby partly achieving synergistically enhanced effects.

As can be seen from Example 4, the compounds of this invention are advantageous over the related compounds described in application No. 5552/73 by providing greater safety against plant poisoning by accidental overdose. .

A microbicidal preferred group of compounds are those of Formula I wherein is methyl. These are referred to as connecting group 1a.

Another microbicide important group of compounds of formula I is

1 2 wherein Z is hydrogen and Z is methyl or ethyl, while Z

-CH-R

is a group wherein R is methyl or ethyl and Y is chloro or

Y

smiles of bromine. These are referred to as connecting group Ib.

The compounds of formula I have an asymmetric carbon atom in the propion ester side chain. Compounds of formula I, Ia and Ib in the D configuration have the strongest microbicidal effect and are therefore preferred.

2 In the haloalkyl side chain Z, a second asymmetric carbon atom may be present for some of the compounds. If optically active starting materials are not used in the manufacture, a diastereomer is necessarily obtained. Unless otherwise noted in the following, by the mention of one of the active substances of formula I is always meant the diastereomer mixture.

The compounds of the invention are prepared, for example, by first reacting an aniline of the formula ch3 ^ p> -NH2 (II) Z I η z1 4 142077 with the desired α-halo gene propionic acid methyl ester of the formula CHo in 3

Hal-CH-C00CH3 (III) and then reacting the obtained compound of the formula CH-j ρ, ττ, _I 3 | H3 </ V -UH-CH-C00CH3 (IV) (lzp with the desired balo gene alkane moiety o xylic acid H00C -Z or its reactive acid, or anhydride, acid anhydride, ester or amide, preferably with the halide or anhydride of the chlorine, bromine or iodoalkanecarboxylic acid involved.

In the above formulas, Z, Z and Z have the meanings given under formula I, while Hal in formula III is halogen, preferably chlorine or bromine. As acid halides, the acid chlorides or acid bromides are preferred.

The reactions may be carried out in the presence or absence of solvents or diluents which are inactive against the reaction participants. For example, aliphatic or aromatic hydrocarbons such as benzene, toluene, xylenes and petroleum ether may be used; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride and chloroform; ethers and ether-like compounds such as dialkyl ethers, dioxane and tetrahydrofuran; nitriles such as acetonitrile; H, H-di-alkylated amides such as dimethylformamide; anhydrous acetic acid, dimethyl sulfoxide, ketones such as methyl ethyl ketone, and mixtures of such solvents.

The reaction temperatures are between 0 and 180 ° C, preferably between 20 and 120 ° C. In many cases, especially using haloacyl halides, the α-haloacylation is carried out in the presence of an acid-binding agent or condensing agent. Tertiary amines such as tri alkyl amines (e.g. triethyl amine), pyridine and pyridine bases, or inorganic bases such as oxides and hydroxides, hydrogen carbonates and alkali and alkaline earth metal carbonates, and sodium acetate may be used. In addition, an excess of the relevant aniline derivative of formula II can be used as an acid binding agent.

5 142077

The reaction can also be carried out without an acid-binding agent, and it is then appropriate in some cases to pass nitrogen to remove the hydro-halo genide formed. If the reaction is carried out without acid binding agents, the dime thylph ormamide usually acts as a catalyst.

Details of the preparation of the intermediates of formula IV can be deduced from the methods generally disclosed for the preparation of anilinoalkanoic acid esters in the following publication bodies: J.Org.Chem. 30, 4101 (1965), Tetrahedron 1967, 487, Tetrahedron 1967, 493 ·

For the preparation of the pure optical forms of formula I, e.g. from the aniline of formula II and the α-halo propionic acid, e.g. the α-bromopropionic acid, the corresponding racemic anilinopropionic acid of formula f3 CH3 ^ V-NH-CH-C00H (V) Z '1 zr, and reacting it in a manner known per se with an H-containing optically active base. By fractional crystallization of the salt obtained and subsequent release of the optical D antipode, optionally also repeating the reaction with the optically active base, one of the enantiomeric forms of the corresponding compound of formula V. is obtained. way, e.g. in the presence of HCl or H2SO4, with methanol forming the optically active ester IV. Similarly, for the formation of the anilides of formula I, the haloalkanecarboxylic acids of formula H00C-Z, if they have an asymmetric carbon atom, can also be transferred to one of the two enantiomeric forms by means of an N-containing optically active base. which in turn can be reacted with an optically active ester of formula IV. Thus, it is convenient to prepare the various diastereomers of formula I.

As an optically active organic base, e.g. α-phenylethylamine is used.

Instead of by fractional crystallization, the enantiomeric D-precursors of formula IV can also be prepared by diazotizing the amino group in naturally occurring 1-alanine in the presence of e.g. HCl or HBr, and thus during N2 decomposition and during retention of the L-conjugation, yields with halogen, then esterifies with methanol and then reacts with the aniline of formula II, whereby inversion to the D configurations of formula IV (predominantly) occurs ( j.Am.Chem.

Soc. 76, 6056).

The preparation of the active substances of formula I is illustrated by the following Examples 1 and 2.

Example 1.

Preparation of CHt? H3 1 3 I J CH-C00CH.

<1> - <N -FNCO-CH-CH3 CH3 Cl E- (1'-methoxycarhonyl-ethyl) -H-a-chloropropionyl-2,6-dimethylaniline (D, I).

a) Preparation of the intermediate α- (2,6-dimethylanilino) -propionic acid methyl ester.

67 g of 2,6-dimethylaniline, 125 g of α-bromopropionic acid methyl ester and 53 g of NaHCO 3 are stirred at an oil bath temperature of 140 ° C for 17 hours and diluted after cooling with 300 ml of ether. After washing twice with water, the ether extract is dried over sodium sulfate and filtered. After distilling off the ether and the excess α-bromopropionic acid methyl ester in water jet vacuum, the crude product is distilled; kp. 98 ° C / 0.8 mm Hg.

(fa) 51.8 g of the propionic acid ester prepared in (a) and 35 g of a-ehloropropionic acid chloride are combined in 300 ml of chlorobenzene with stirring, raising the temperature of the reaction mixture to 40 ° C.

After the addition of 2 ml of dimethylformamide, it is heated under reflux for 2 hours and the chlorobenzene is distilled off in vacuo. By tearing with petroleum ether, the crude product is crystallized.

After recrystallization in toluene, the diastereomer mixture, which is present in the recrystallized sample of NMR spectrum in a ratio of 2: 3, melts at 108-110 ° C (Compound No. 1).

7 142077

Example 2.

Preparation of CH-, CH, I 3 IJ CH-COOCH, No. ^ C-CH ^ CH ^ Cl ch3 II 2 2 -5 o N- (11-Methoxycarbonyl-ethyl) -] - (1-mp-chloroethyl-carbonyl) -2,6 -dimethyl-aniline (compound # 13).

To 74 g of N- (1-ethoxy carbonyl-ethyl) -2,6-dimethyl aniline in 300 ml of chlorobenzene are dropped 57 g of 3-chlorobropionic acid chloride in 200 ml of chlorobenzene. After the slightly exothermic reaction was quenched, 2 ml of dimethyl formamide was added and the mixture was heated for 4 hours to reflux. After cooling, the reaction mixture is washed twice with dilute sodium carbonate solution and twice with water, dried over sodium sulfate, filtered and the solvent is distilled off in rotary evaporator. After recrystallization of petroleum ether, the compound has a m.p. at 6g-71 ° C.

In an analogous manner to Example 1a) the following propionic acid methyl esters are also prepared as intermediates: α- (2-ethyl-6-methylanilino) -, b.p. 88-90 ° C / O, Gl mm Hg, α- (2-ethyl-3,6-dimethylanilino) -, b.p. 96-99 ° 0 / 0.03 mm Hg, α- (2,3,6-trimethylanilino) ~, bp. 83-85 ° C / 0.03 mm Hg; kp. 144-146 ° C / 9 mm Hg, α- (2,4,6-trimethylanilino) -, bp. 88-90 ° C / 0.04 with Hg, q- (2-ethyl-5,6-dimethyl anilino) -, b.p. 87-90 ° C / 0.04 mm Hg.

In this way or by any of the methods set forth above, the following compounds of formula I are prepared, having as iodine fungicides and / or dressing agents particularly suitable iodine-containing compounds, e.g. can be prepared from the chlorine-containing compounds by halogen exchange with alkali metal iodide (Z + = 6 position): 8 142077

Compound Z Z ^ Z ^ Physical No. Contant

_ ° C

1 Ξ CH 3 -CH-CH 2 Mp.108-110 °

Cl 2 Ξ CH, -CH-OH, Kp. 148-152 ° /? 0.05 mm Hg 5 H CH, -CH-CHp-CH, Kp. 143-145 ° / 5 σι 0.1131111 Hs 4 H- CH, -CH-CHp-CH, bp 140-142 ° / 5 gr 5 0.1 mm Hg 5 H CpHt- -CH-CH, Kp. 127-130 ° / 5 Cl 0.03 111111 Hs 6 H CX -CH-CH, bp 149-155 ° / ir 3 0.0? Mm Hg 7 H COHc -CH-CHo-OH, bp 140 -142 ° / 25 01 0.1 mm Hg 8 HC XX -CH-CHO-CH, bp 147-149 ° / 25 ir 0.1 mm Hg 9 H CH, -CHo-CHo-CHo-01 bp 150 -152 ° / 3 2 2 2 * o, 03 mm Hg 10 3-0¾ CH-, -CH₂ -CH₂ -CH₂-C1 bp 158-162 ° / 3 3 2 2 2 * 0.03 mm Hg 11 Ξ C 2 H 5 -CH 2 -CH 2 -CH 2 -C1 viscose 12 3-CH 2 C 2 H 5 -CH 2 -CH 2 -CH 2 -C1 viscose 13 H CH 2 -CH 2 -CH 2 -C1 mp 69-71 ° 14 3-CH 2 CH 3 - CH2-CH2-C1 Mp 85-89 ° H ^ 2 ^ 5 -CH2-CH2-C1 Calc crystalline 16 3-OH, C XX-OH-CHo-Cl viscose 3 2 5 2 2 17 4 — CH, CH, -CHo-OH-Cl mp 99-100 ° 5 5 2 2 18 H CH 2 -CH 2 -CH 2 -Br viscose 19 3-0¾ 0¾ -CHo-OH-Br viscose 5 5 2 2 20 H CH, -CH- CH, bp 156-159 ° / 0 5 0.02 mm Hg 21 3-OH, OH, -CH-CH, bp 162-164 ° / 5 0.01 mm Hg 22 5-CH. OH .CH-CH CHP 171-175 ° / 5 5 j 5 * 0.02 mm Hg U20 77 9

Compound Z T? Physical No. constant and 23 H CH, -CH-CHO-CH, viscous 3 t 2 5

J

24 3-CH, CH, -CH-CH 2 -CH, semi-crystalline 2 3 t 2 2

J

H CH5 -CH-CH (CH5) 2 oil, n + ° =

Cl 1.5275 26 3-CH, CH, -CH-CH (CH,), viscous 3 3 in 3 4

Cl 27 H Cg H 2 - -CH-CH (CH 2) 2 viscose

Cl 28 3-CH 2 C 2 -CH-CH (CH 5) 2 semi-crystalline

Cl 29 4-CH, CH, -GH-CH (CH,) D b.p. 172-174 ° / 2 ° 5 £ 0.08 ra Hg 4-CH, GÅ, - -CH-CH (CH 152-154 ° / 5 ^ -7 ^ 5 2 0.04 Ran Hg 31 H CH 2 -CH 2 -CH-CH 2 -CH 5 semi-crystalline

Cl 32 3-CH, CH, -CHO-CH-CH - GH, bp. 161-163 ° / 5 d Q, 2 0.02 mm Hg 33 H C 2 -CH 2 -CH 2 -CH 2 -CH 2 viscose

Cl

CH

34 H CH2 -C5 Mp. 67-69 ° C70H3 4-CH, CH, -CHCH, m.p. 120-122 ° j 0 * o

Cl 36 4-CH, CH, -CHOCHOCHOCl1 Kp. 158-164 ° / 5 5 2 2 2 0.03 yyyy Hh 37 3-CH, COH, -CHCH, Kp. 137-139 ° / 525 £ 5 0.04 mm Hg 38 3-CH 3 C 2 H 5 -CHCH 2 viscose 39 5-CH 3 C 2 H 5 -CHCH 3 viscose

Cl 40 5-CH, CÆ -CHCH, Kp. 155-157 ° / 5 2 2 .2 0.03 mm Hg cl 142077 ίο

The compounds of formula I can be used to extend their spectrum of action with other suitable pesticides or plant growth promoting agents.

The compounds of Form I can be used alone or together with suitable carriers and / or other additives. Suitable carriers and additives may be solid or liquid and are similar to those of the art of the formulation technique, such as natural or regenerated mineral substances, solvents, dispersants, wetting, jawing, thickening, binder or fertilizers.

The content of the active substance in the means of negotiation is between $ 0.1 and $ 90.

For application, the compounds of formula I may be in the following working forms (the percentages by weight of which are given in parentheses are advantageous amounts of active substance):

Solid forms of reprocessing: dusting agents and powders (up to $ 10), granules, wrapping granules, impregnating granules and homogeneous granules (1-80 $).

Liquid reprocessing forms: (a) water dispersible active ingredient concentrates: spray powders (wettable powders) and pastes ($ 25-90 in commercial packing, $ 0.01-15 in ready-to-use solution), emulsion and solution concentrates ($ 10-50, 0 , $ 01-15 in ready-to-use solution); b) solutions ($ 0.1-20).

For example, the active substances of formula I may be formulated as follows:

For the preparation of an a) 5 $ and b) 2 $ dust, the following substances are used: u H2077 a) 5 parts active substance 95 parts talc; b) 2 parts active substance 1 part bend dispersion silicic acid 97 parts talc.

The active substances are mixed with the carriers and can be atomized in this form for use.

granules;

For the preparation of a 5 $ granule, the following substances are used; 5 parts active substance 0.25 parts epichlorohydrin 0.25 parts cetyl polyglycol ether 3.50 parts polyethylene glycol 91 parts kaolin (grain size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; to this is added polyethyl ethyl glycol and cetyl polyglycol ether. The solution thus obtained is sprayed on kaolin and then the acetone is evaporated in vacuo. Such a micro granule is advantageously used to control soil fungi.

Injection Powder;

For the preparation of an a) 70 #, b) 40 $, c) and d) 25 $, e) 10 # spray powder, the following ingredients are used: a) 70 parts active substance 5 parts sodium dibutyl naphthalenesulfonate 3 parts napht hal ensul fo nsyr e-ph enol sul phonic acid formal ehy d condensate 3: 2: 1 10 parts kaolin 12 parts Champagne chalk; b) 40 parts active substance 5 parts lignin sulfonic acid sodium salt 1 part dibutylnaphthalenesulfonic acid sodium salt 54 parts silica; c) 25 parts active substance 4.5 parts calcium lignin sulfate 1.9 parts Champagne chalk / hydroxyethyl cellulose mixture (1: 1) 12 parts 1.5 sodium dibutyl-naphthalenesulphonate 19.5 parts silicic 19.5 parts Champagne chalk 28.1 del kaolin; d) 25 parts active substance 2.5 parts in s o o c tylpheno xy-polyo xyethylene ethanol 1.7 parts Champagne chalk / hydroxyethylcellulose bl breath (l: l) 8.3 parts sodium aluminum silicate 16.5 parts diatomaceous earth 46 parts kaolin; e) 10 parts active ingredient 3 parts mixture of sodium salts of saturated fatty alcohol sulphates 5 parts naphthalene sulfonic acid / formaldehyde condensate 82 'parts kaolin.

The active substances are thoroughly mixed in suitable mixers with the additives and ground on mills and rollers. Spray powders with excellent wettability and buoyancy are obtained, which powders can be diluted with water to suspensions of any desired concentration, and which can be used especially for leaf application.

Emulgerb are wife entr at er;

For the preparation of a 25 $ emulsifiable concentrate, the following substances are used: 25 parts of active substance 2.5 parts of epoxidized vegetable oil 10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture 5 parts of dimethylformamide 57.5 parts of xylene.

From such concentrates, by dilution with water, emulsions of any desired concentration can be prepared which are particularly suitable for leaf application.

Example 3

Effect against Rhytophthora infestans on Solanum-lyeopersieum (tomatoes). Ia) Resi dual preventive effect

Solanum lycopersicum plants of the "Rotate Gnom" variety are infected after 13 weeks of post-spray cultivation with a spray liquid containing $ 0.05 active substance (prepared from the active ingredient processed into a spray powder) and dried with a zoospore suspension of Phyto -phthora infestans. They then stay for 6 days in a climate chamber at 18 to 20 ° C and high humidity, which is produced by an artificial spray mist. After this time, typical leaf spots appear. Their number and size are the benchmark for the substance under study.

Ib) Curative effect

Tomato plants of the "Rotary Gnom" variety are sprayed after 3 weeks of cultivation with a zoospore suspension of the fungus and incubated in a cabin at 18 to 20 ° C and saturated humidity. Wetting off after 24 hours. After drying the plants, they are sprayed with a spray liquid containing the active ingredient formulated as spray powder at a concentration of 0.05 $. After drying the spray coating, the plants are put back in the damp cabin for 4 days. The number and size of the typical leaf spots occurring after this time are the benchmark for the effect of the substances studied.

II) Preventive-systemic effect

The active substance formulated as a spray powder is applied at a concentration of $ 0.05 (calculated on soil volume) on the soil surface at 3 weeks old, in pots of tomato plants of the variety "Rotate Gnom").

After · 3 days of waiting, the underside of the leaves of the plants is sprayed with a zoospore suspension of Phytophthora infestans. They are then kept for 5 days in a spray booth at 18 to 20 ° C and saturated humidity. ' After this time, typical leaf spots are formed, the number and size of which serve to judge the effect of the substances studied.

In these three experiments, the compounds of formula I show the strong leaf fungicidal activity shown in the following table.

14 142077 • Table for example 3 (average values)

Porb. No. Mushroom attack Forb. No. Fungus Percentage Percentage Percentage 1 0-5 $ 25 <20 $ 2 <20 $ 26 <20 $ 3 0-5 $ 27 <20 $ 4 <20 $ 28 <20 $ 5 <20 $ 29 <20 $ 7 20-40 $ 30 20-40 $ 9 <20 $ 31 <20 $ 11. <20 $ 32 <20 $ 12 <20 $ 34 0-5 $ 13 <20 $ 35 0-5 $ 14 <20 $ 36 < 20 $ .15 <20 $ 37 <20 $ 17 <20 $ 39 <20 $ 19 <20 $

The compound # 1 decreases in the same trials at application concentrations of only $ 0.02 fungal attack to below $ 20.

Example 4

(Comparative Experiment)

Conn. A = F-Ethoxycarbonylmethyl-N- (2,6-dimethylphenyl) chlorac et amide (Example 8 of DE Publication No. 2,212,268).

Conn. B = N-Chloroacetyl-E-2,6-dimethylphenyl-alanine methyl ester (Danish Patent Application No. 5552/73).

Conn. C = E-Bromoacetyl-N-2,6-dimethylphenyl-alanine methyllayter (Danish Patent Application No. 5552/73).

Effect against Plasmopara viticola (Bert, et Curt.) (Berl. Et DeToni) on vine plants.

a) Residual-preventive effect.

In greenhouses, grapevine cuttings of the "Chasselas" variety are grown. At the 10-leaf stage, 3 plants are sprayed with an active substance prepared from spray powder (0.05 $ active substance) formulated as a spray powder. After drying the spray coating, the plants are uniformly infected on the underside of the leaves with a spore suspension of the fungus. The plants are then kept for 8 days in a humid chamber. After this time, clear disease symptoms appear in the control plants. The number and size of infection sites in the treated plants serve as a benchmark for the efficacy of the substances studied.

b) Curative effect.

Vine cuttings of the "Chasselas" variety are grown in greenhouses and infected at the 10-leaf stage with a spore suspension of Plasmopara viticola on the underside of the leaves. After a 24 hour stay in a humidity booth, the plants are sprayed with a 0.05 $ active ingredient spray liquid made from an active ingredient spray powder. The plants are then kept for a further 7 days in a humidifier. After this time, disease symptoms appear in control plant moth. The number and size of infection sites in the treated plants serve as a benchmark for the effect of the substances studied.

In experiment a) of Example 4, the compounds of formula I show strong fungicidal activity:

Example 4 Table (Average Values)

Porb. No. Mushroom attack Porb. No. Fungus Percentage Percentage Percentage 1 0-5 $ 14 · ° "2 <20 $ 15 <20 $ 3 0-5 $ 16 <20? δ 4 <20 $ 17 <20 * 5 <20 $ 18 <20 ^ 6 <20 $ 19 <2 8 20-40 $ 20 <20 $ g 0-5 $ 21 <20 $ 10 0-5 $ 22 <20 $ 11 0-5 $ 25 20-40 $ 12 0-5 $ 26 20-40 $ 13 0-5 $ 27 <20 $ 16 142077

Table continued:

Conn. No. Mushroom attacks as a percentage 28 20-40 $ 29 <20 $ 30 20-40 $ 31 20-40 $ 32 20-40 $ 33 20-40 $ 34 0-5 $ 35 0-20 $ 36 0-5 $ 37 <20 $ 38. <20 $ 39 <20 $ A 50-100 ** B 0-5 * C 0-5 *

Compounds Nos. 1, 3, 9, 10, 13, 14 and 34 decrease in the same experiments at application concentrations of only 0.02% fungal attack to also 0-5%. The D-forms of compounds Nos. 1, 3, 9, 13 and 34 derived from the D-configuration of N- (1'-methoxyearbonyl-ethyl) -2,6-dimethylaniline decrease to 0.02% fungal attack to 0 -10%.

In experiment b) of Example 4, the compounds of formula I show strong fungicidal activity at the following concentrations:

Example 4 Table (Average Values)

Conn. No._ Wife_Sponge attack as a percentage 9 0.06 0-5 0.02 0-5 0.006 0-5 13 0.06 0-5 0.02 0-5 0.006 0-5 14 0.06 0-5 0 , 02 0-5 0.006 0-5 17 142077 A 0.06 50-100 ** B 0.06 0-5 »0.02 0-5 0.006 0-5 C 0.06 0-5» 0.02 0 -5 0.006 0-5 * Light phytotoxicity at concentrations of 0.05% or higher.

** The degree of phytotoxicity is blurred by the fungal attack.

The Comparative Compound A listed as herbicide shows no fungicidal effect at all. The sasma equation compounds B and C designated as fungicides have, at high concentrations, an undesirable, slight phytotoxicity which does not occur in the indicated concentration range of the compounds of the invention.

In the compounds of the invention no phytotoxicity occurs at the indicated concentrations. The compounds of the invention have the advantage of greater safety in case of accidental overdose over the comparative compounds B and Q.

Example 5

Effect against Pythium debaryanum on Beta vulgaris (sugar beet).

(a) Effect after soil application

The fungus is grown on sterile oatmeal and added to a soil-sand mixture. The soil thus infected is filled in herb pots and sown with sugar beet seeds. just after sowing, test formulations formulated as spray powders are poured into the soil as aqueous suspensions (0.002% active substance calculated on soil volume). The herb pots are then set up for 2-3 weeks in greenhouses at 20-24 ° C. The soil is kept uniformly moist by light spraying with water. When assessing the experiments, the growth of beet plants as well as the number of healthy and diseased plants is determined.

b) Impact after pickling application

The fungus is grown on sterile oatmeal and added to a soil-sand mixture. The soil thus infected is filled in herb pots and sown with