DK141995B - Fungicide, optionally halogen-substituted furan (2) or tetrahydrofuran (2) carboanilides for use in plant protection or other technical purposes. - Google Patents

Description

Mém

In UU | IN

\ Ra / (11) PUBLICATION WRITING 1 U 1 9 95

DENMARK lnt · 01 · 5 I

A 01 N 43/08 '(21) Application No 1 359/75 (22) Filed on 2β · ΓΠ3Χ1 · 19 * 75 (23) Running day 26 Mar 1975 (44) The application presented and.

the petition published on 4 August. 1 QoO

DIRECTORATE OF, λλ4 l, PATENT AND TRADEMARKET (30) Priontet requested from the

Apr 2 1974, 4572/74, CH Feb 10 1975 * 1591/75, CH

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

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

(74) Plenipotentiary in the proceedings:

Dansk Patent Kontor ApS.

(54) Fungicide, optionally halogen-substituted furan (2) - or tetrahydro = furan (2) carboanilides for use in plant protection or other technical purposes.

The present invention relates to novel fungicidal, optionally halogen-substituted furan (2) or tetrahydrofuran (2) carboanilides for use in plant protection or other technical purposes. The compounds of the invention are peculiar in that they have the general formula R1,

R5 _I

/ -f VNC (i) 0-R4

Η2 I

2 141995 1? wherein R is C1-C ^ alkyl, C ^^ C C ^ alkoxy or halogen, R is hydrogen,.

C -, C C ^ alkyl or halogen is hydrogen, C - ^ C C alkyl or halogen, R ° is hydrogen or methyl, the total number of C atoms in the substituents R ^, R₂, R and R 2 in the phenyl ring does not exceed the number 8, X is -CH 2 - or f H 3, R 1 is -COOR 'or -COR 1 R', where R ', R "-GH-XR"' and R "1 are independent of each other is hydrogen, methyl or ethyl, and R 2 is optionally halogen-substituted 2-furanyl or 2-tetrahydro-furanyl, with the proviso that the phenyl ring contains an additional substituent when substituted in 2.6 or 2.3 , 6-position with methyl, and when at the same time R 1 is a 2-furanyl group and -XR 2 is an α-propionic acid methyl ester group.

By alkyl and as acyl part of an alkoxy group, the following groups are understood to mean the following groups: methyl, ethyl, n-propyl, isopropyl or n-, iso-, sec- or tert-butyl. As halogen, fluorine, chlorine, bromine or iodine come into play.

German Patent Publication No. 2,006,471 is known (2'-methyl-furanyl-3 ') - carbonyl-2,6-dimethylaniline and (21-methylfuranyl-3') - carbonyl-2-methyl-6-ehloroaniline as active substances with moderate action against certain fungi (Uromyces phaseoli, Altemaria solani, Rhizoctonia solani).

Surprisingly, it has now been found that compounds of the distinctly different structure of formula I have a very favorable fungicide spectrum for protecting plant plants for their practical needs. Cultural plants are here, for example, cereals, maize, rice, vegetables, sugar beet, soy, peanuts, fruit trees, ornamental plants, but above all vine plants, hops, cucumber plants (cucumbers, pumpkins, melons), solanas such as potatoes, tobacco and tomatoes, as well as banana, cocoa and natural rubber growths.

With the active substances of formula I, occurring fungi on plants or plant parts (fruits, flowers, foliage, stems, tubers, roots) of these and other crops can be inhibited or killed, as later growing plant parts remain spared from such fungi. The active substances are effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (eg Erysiphaceae), Basidiomycetes, such as, above all, rust fungi, Fungi imperfecti, but especially against those belonging to the class Fhycomycetes, such as Phytophthora, Peron Pseudoperonospora, Pythium or Plasmopara. In addition, the compounds of formula I act systemically. They can also be used as dressing agents 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.

Preferred as fungicides are compounds of formula I wherein R 2 is methyl, R is in the ortho position of the amino group and is methyl, ethyl or chloro, -X-R 3 is the grouping 9 ^ 3, while R 4, R CH-COOR 'R and R1 have the meaning given. These should be referred to as connecting group 1a.

Among these compounds 1a are highlighted those in which R 4 is an unsubstituted 2-furanyl group.

The preparation of the compounds of formula I is carried out e.g. by acylation of a compound of formula R5 J> X-R3 (id r6 / Z lp

R

with a carboxylic acid of the formula HO-CO-R4 (III) or its acid halide, acid anhydride or ester, in a single case also with one of its acid amides (rearrangement).

According to another method, the compounds of formula I can be prepared by transferring acyl anilides of formula 5

_IN

V -NH-CO-R4 (IV) 4 but with lithyl lithium or Ha-hydride to the corresponding alkali metal salt, which then has a compound of the formula

Hal-X-R 3 (V) leads to the desired final product, or by reacting the acyl anilides of formula IV with the compound of formula V in the presence of an alkali metal carbonate (such as NagCO 2 or K 2 CO 2) as proton acceptor , preferably with the addition of catalytic amounts of alkali metal iodide (such as KJ).

In formulas II, III, IV and V, R to R and X have the meaning given by formula I, while Hal is a halogen atom, preferably chlorine or bromine, or another easily leaving group. The term "acid halide" preferably refers to the acid chloride or acid bromide.

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

Reacted at our temp, the atoms are between 0 and 180 ° C, preferably between 20 and 120 ° C. In many cases, the use of acid binding agents or condensing agents is advantageous. As such, tertiary amines such as trialkylamines (e.g. triethylamine), pyridine and pyridine bases, or inorganic bases such as oxides and hydroxides, hydrogen carbonates and alkali and alkaline earth metal carbonates, and sodium acetate are considered. In addition, as an acid binding agent, an excess of the relevant aniline derivative of formula II can be used in the first process.

The process starting from compounds of formula II can also be carried out without acid-binding agents, in which case a passage of nitrogen to displace the hydrogen halide formed may be in place. In other cases, the addition of dimethylformamide as a reaction catalyst is very advantageous.

5 141996

Details of the preparation of the intermediates of Formula II can be obtained from the methods commonly used for the preparation of anilino-alkanoic acid esters, which are set forth in the following publication bodies: J.Org.Chem. 30, 4101 (1965), Tetrahedron 1967, 487, Tetrahedron 1967, 493 · CH-j

I J

The compounds of formula I having the meaning X = - * CH- have an asymmetric carbon atom (*) and can be cleaved in the usual way into optical antipodes. Hereby, the enantiomeric D form has the strongest microbicidal effect.

Accordingly, within the scope of the invention, those compounds of formula I having D-configuration are preferred. These D-forms, when measured in ethanol or acetone, generally have a negative angle of rotation.

For the preparation of the pure optical D antipodes, e.g. the racemic compound of formula R1 2 3 4 R5 [| H3 X -M-CH-C00H (VI) R4-jn per c wherein R, R, Br and R have the meaning of formula I, and this is then reacted on known in the art with an N-containing optically active base to the corresponding salt. By fractional crystallization of the salt and subsequent release of the formula VI-enriched acid of the formula VI and optionally repeating (also several times repeating) the salt formation, crystallization and release of the α-aniline propionic acid of formula VI, the pure one is gradually obtained D-form. Of this, one may, if desired, in a conventional manner, e.g. in the presence of HCl or HgSO 4, with methanol or ethanol, prepare the optical D configuration of the ester of formula II or the corresponding amine of formula HN (R ") (R, n) the amide corresponding to formula II As an optically active organic base, for example, α-phenylethylamine is considered.

instead of by fractional crystallisation, the enantiomeric D-2 form of formula VI can also be obtained by exchanging the hydroxyl group in 3 the naturally occurring L (+) lactic acid with halogen and further reaction of this product under configuration reversal with the desired 5 aniline with formula 6 141995 r5 R1 V ^ A.-nh2 (VII) R6 / XI7

R

Regardless of the optical isomer, an atropisomer of the phenyl axis is usually observed in cases where the phenyl ring is substituted at least in the 2.6 position and at the same time asymmetric to this axis (possibly also in the presence of additional substituents). This phenomenon is contingent on the steric hindrance of the further introduced by the yderligere atom in the aniline of formula VII -X-R ^, but especially by the heterocyclic group -CO-R ^. If no targeted synthesis is performed to isolate pure isomers, a product is usually obtained as a mixture of two optical isomers or two atropisomers or as a mixture of these four possible isomers. However, the more favorable fungicidal effect of the enantiomeric D form (in comparison with the D, L form or L form) remains conserved and is not appreciably affected by the atropisomer.

The following examples serve to further explain the invention. Unless otherwise indicated, by the mention of an active substance of formula I which may occur in optically active forms, the racemic mixture is always meant.

Example 1.

Manufacture of CHt CEU OH. I -3 I J I J ^ ch-cooch3 V-R (compound # 2)

VM

c2h5 | V

N- (l'-methoxycarbonyl-ethyl) -N- (furan (2 ") - carbonyl) -2,3-dimethyl-6-ethylaniline.

a) 100 g of 2,3-dimethyl-6-ethylaniline, 223 g of 2-bromopropionic acid methyl ester and 84 g of KaHCO3 are stirred for 17 hours at 140 ° C; then cooled, diluted with 300 ml of water and extracted with diethyl ether. The extract was washed with a little water, dried over sodium sulfate, filtered and the ether evaporated. After distilling off the excess 2-bromopropionic acid methyl ester, the crude product is distilled in high vacuum; kp. 88-90 ° C / 0.04 mm Hg.

b) To 17 g of the ester obtained in (a), 2 ml of dimethylformamide and 150 ml of absolute toluene are added dropwise with stirring 13 g of furan-2-carboxylic acid chloride and heated for 1 hour under reflux. After evaporation of the solvent, the crude product is crystallized by tearing with petroleum ether; mp. 110.5-126 ° C (ethyl acetate / petroleum ether). Compound # 2 is a mixture of two diastereomer pairs.

Acylating the D-form of oc- (2,3-dimethyl-6-ethylanilino) -propionic acid methyl ester with furan- (2) -carboxylic acid or with one of its reactive derivatives gives the D-forms of the two atropisomers ( compounds 2a and 2b).

Example 2.

Preparation of J OH-, ptt I * / 3 _> n3 CH2CH ^ .-. CH-j (compound # 42)

## STR13 ## N- (dimethylaminocarbonylmethyl) -N- (furan- (2 ") carbonyl) -2,6-dimethyl-aniline.

28 g of the N- (methoxycarbonylmethyl) -N- (furan- (2 ") carbonyl) -2,6-dimethylaniline, analogous to Example 1, mp 98-99 ° C, is stirred for one day with 150 ml 40% aqueous dimethylamine solution and 0.5 g of triethyl endiamine at room temperature, unreacted starting material is removed by ether extraction twice, then the aqueous phase is evaporated in rotary evaporator and the residual viscous oil is crystallized by grating with hexane.

After recrystallization of hexane / tetrahydrofuran, the final product has a m.p. at 142-145 ° C.

In one of the above methods, the following is prepared in the phenyl core tri- or tetra-substituted compound of formula (R1 = 2-position): R7 R1 ".Α <χ ·" e9 \ c.e4 R8 «R0

Conn. R · * - R7 R8 R ^ —X — R8 R ^ Physically constant ___; _ (° C) 1 CH, CH, CH, 5-CH, -CH-COOCH, _ Smo. 109-112

J J J J I J I I

“\ / O x0 2 CH CH, CH H -CH-COOCH, - I J I Stop. 110.5-12 6

οκ3 'V

3 C2H CH Cf ^ H -CH-COOCH _ Kp. 176-177 / 0.05 J I I mm Hg

^ 3 "V

4 CH, CEL Cl H -CH-COOCH, - Snp. 82-86

I II

“3 'V

03, -0- CH- Cl H -CH-COOCH-, _. Oil

III

æ3 V

6 CH, Br CH, H -CH-ODOCH,, m.p. 83-118

I J I

“3 V

9 141995

Conn. R ^ R ^ -X-R ^ R ^ Physically constant _for 7 CH H CH, 4-CH, -CH-COOCH, - Stip. 113-114 3 3 3 i 3.

'J I

cb2 y 8 CH3 C2H5 CH3 H -CH-COOCH3 -. Mp. 95-101 'j i

3 V

9 CH- CH, CH, H -CH-COOCH, __r Snp. 88-91 3 3 3 I 3 ^ CH -Ϊ 4-Br • i N0 / 10 CH, CH, CH. H -CH - COOCH- - Oil 3 3 3 2 3

-I 1 -BT

V

11 CH3 CH3 CH3 H -CH2-OTJ (CH3) 2 r- arp. 132-139 -v-- 12 CH3 CH3 CH H -CH-COOCH3 _ Kp. 171-176 / 0.2 l in mm Hg

V

13 CH3 H CH3 4-CH3 -CH-C00CH3 _ Snp. 104-107

1 I I

CH -r) -Br 0 14 CEL CH. · CH, 5-CEL -CH-COOCH, _ Oil Å in 3 3 I 3 OL -, - -Br 3 ^ 0/15 CH3 H CH3 4-C1 -CH-COOCH3 _ Snp. 106-110 '.11

3 V

Conn. R1 R7 R8 R9 -X-R3 R4 Physically constant (° C) 141995 ίο 16 CH3 H CH3 4-Br -CH-C00CH3 Mp. 113-115 L J 1

3 V

17 CEL H Cl 4-C1 -CH-COOCH Mp. 125-128

III

18 OL H Cl 4-Br -CH-COOCH- Sirp. 132-134 O] ό L .i 1

“3 V

19 OL H CH_ 4-Cl -CH-COOCH- Mp. 108-111

I I I

CH -r 1 | -fir The following are mentioned compounds which are mono- or disubstituted in the phercyl nucleus.

These include compounds of the formula

Rl 3

1 X-R

£> <„π 2 'CO-1 Ji

R X0X

n 141995 12 3

Conn. R R -X-R Physically constant (° C) 20 CH3 6-σΐ3 -CH-COO-C2H5 Snp. 90-94 ^ 3 21 CH- H -CH-COOCH, Kp. 126-148 / 0.02 I mn Hg οη3 22 CH, 3-CH, -CH-OOOCH, Kp. 151 / 0.03 3 3 I 3 nm Hg οη3 23 CH3 4-CH3 -CH-COOCH3 Mp. 89-91 0Η3 24 CH- 5-CH, -CH-OOOCH- Srp. 114-116 • J J i ά ch3 CH3 6_C2H5 -CH2-COOCH3 Mp. 91-94 26 CH3 6-C1 -CH-COOC2H5 Sip. 112-113 ch3 27 CH3 6-CH3 -CH-CO-NH2 Snp. 128-130 ch3 28 Cl 5-C1 -CH-COOCH, Snp. 110-112 I 3 ch3 29 C2H5 6-C2H5 -CH2-CO-NH2 Snp. 127-128 CH, 6-C1 -CH-COOCH, Snp. 92-93

3 I

CH3 31 AD HQ-0- H -CH-COOCH- Kp. 170-173 / 0.04 I itm Hg ^ 3 12 141995 12 3

Conn. R R -X-R Physically constant (C) 32 CH3 6-CH3 -CH-CO-NHCH3 Mp. 141-143 αί3 33 iso-C6-iso-C3H7 -CH-COOCH3 Srrp. 86-96 άί3 34 iso-C3H7 H -CH-COOCH3 Kp. 158 / 0.03 35 F H -CH-C00CH3 Kp. 150 / 0.03 I mmHg ch3 36 Cl H -CH-C00CH3 Kp. 155 / 0.05 I imi Ha CH3 37 Cl 6-Cl -CH-COOCE, m.p. 113-116 I 3 ch3 38 J H -CH-COOCET, I 3 CH Kp. 145 / 0.2 nm Hg 39 Br H -CH-COOCH3 Kp. 145 / 0.05 in Hg ΟΪ3 40 CH3 6-CH3 -CH ^ 00CH3 Mp. 98-99 41 CH3 6-CH3 -CH2-CO-NHCH3 Mp. 164-165 42 CH3 6-CH3 -CH2-CO-N (CH3) 2 Mp. 142-145 43 ai3 4-CH..0- -CH-COOCH Kp. 168 / 0.07 J I ram Hg Οί3 44 CH. 4-sec.C.H-O -CH-COOCH- Kp. 178 / 0.05 ^ 4 y * o __ j imi Kg ch3 12 3

Conn. R R -X-R Physically constant (° C) 13 C19H5 6_C2H5 -CH2-CO-N (CH3) 2 Mp. 178-181 46 C2H5 6-C2H5 -CH2-CCXXH3 Mp. 88 47 C2H5 6_C2H5 -CH2-CO-NH: 2H5 arp. 158-159

Further, the compounds of general formula X-R3

r2 / CO-R

12 3 4

Conn. R R -X-R R Physically constant _ (° C) 48 CH-, 6-CH- -CH-COOCH- Oil

3 3 I 3 H

CH3 -W

J No 49 CH_ 6-CH, -CH-COOCH- Oil

3 J! 3 H

CH-1 1-Br 3 50 CH-, 6-C1 -CH-COOCH. Oil

Ο I O

CH3 <1/0 51 Cl 6-C1 -CH-COOCH- Oil

I J H

CH3 Λ) 3 141995 12 3 4

Conn. R R -X-R R Physically constant (° C) 14 52 CH, 6-CH, -CH-COOCH, - m.p. 90-92

3 3 1 3 II

CH3 '^ 0 ^ Br 53 CH- 6-Cl -CH-COOCH, -Smp. 102-104

I II

ch3 V'Br

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

The compounds of formula 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 conventional formulation techniques, such as natural or regenerated mineral substances, solvents, dispersants, wetting, adhesives, 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 weight percentages in parentheses being advantageous amounts of active substance):

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

15 U1995

Liquid reprocessing forms: a) Water dispersible active ingredient concentrates: spray powders (wettable powders) and pastes ($ 25-90 in bundle 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).

The active substances of formula I can e.g. formulated as follows: Dust agents;

For the preparation of an a) 5 $ and b) 2 $ dust, the following substances are used: a) 5 parts active substance 95 parts talc; b) 2 parts active substance 1 part high-dispersion silica 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 cetylpolygLycol 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; then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed on kaolin and then the acetone is evaporated in vacuo. Such a microgranulate is advantageously used to control soil fungi.

16 141995 S try it epul ver:

For the preparation of an a) JOfo, 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 naphthalenesulfonic acid phenolic sulfonic acid -formaldehyde condensate 3: 2: 1 10 parts kaolin 12 parts Champagne chalk; b) 40 parts active ingredient 5 parts lignin sulfonic acid sodium salt 1 part dibut ylnaphthal ensul formic acid e-sodium total 54 parts silica; c) 25 parts active substance 4.5 parts calcium lignin sulfate 1.9 parts Champagne chalk / hydroxyethyl cellulose mixture (1: 1) 1.5 parts sodium dibutyl-naphthalenesulfonate 19.5 parts silica 19.5 parts Champagne chalk 28.1 parts kaolin; d) 25 parts active substance 2.5 parts isooctylphenoxy-polyoxyethylene ethanol 1.7 parts Champagne chalk / hydroxyethyl cellulose mixture (1: 1) 8.3 parts sodium aluminum ili c at 16.5 parts diatomaceous earth • 46 parts kaolin; e) 10 parts active substance 3 parts mixture of sodium salts of saturated fatty alcohol sulphate is 5 parts naphthalenesulfonic 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.

17 1A19 9 5

Emulsifiable concentrates;

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

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

In Example 3 ° S 4 below, a biological effect comparison has been made between the compounds of the invention and the structurally closely related known compounds.

Comparative Compounds GH ^

Conn. A -NH-CO- -. DE Publication V - [II Script No. 2,006,471 OHj ^ 19 ° g 0ΐ £ Β · 5 'fl · GH, _i3

Eorb. B LC- ^ ^ »- BH-GO -, - DE Publication- ^ X-r — I In Publication No. 2,006,471 L · H-C-l * ') (p. 19 and Ex. 5, p.

CH3 5 Nk 25) GH,

Conn. G -NH-CO-.- DE Publication X: —X I In Publication No. 2,006,471 H, C- ^ oj (p. 19)

Eorb. D -NH-CO-- DK patent specification no.

I I 123,063 V-V-0H3

Cl

Conn. E ^ "5" -NH-CO- (DE disclosure no.

5 XK No. 1,187,420 (Ex.

1, cont. 7) 18 141995

Example 3

Impact: against Phytophthora infestans on tomatoes.

Curative effect

Tomato plants of the "Rot Gnom" variety are sprayed after 3 years 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 study powder formulated as a spray powder at a concentration of $ 0.06. After drying the spray coating, the plants are placed 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. As a basis for assessment, infected but untreated control plants serve.

The compounds of formula I and the above comparison compounds showed the following effect.

Table for Example 3.

Conn. No. Mushroom attack Forb. No. Fungal attack _ in percent in percent 1 0-5 $ 26 <20 $ 2 <20 $ 27 0-5 $ 3 <20 $ 30 <20 $ 4 0-5 $ 37 <20 $ 6 <20 $ 48 <20 $ 7 <20 $ 50 <20 $ 8 0-5 $ 52 0-5 $ 9 <20 $ 53 <20 $ 12 <20 $ A 20-40 $ 14 <20 $ B 20-40 $ 20 0-5 $ C > 50 $ 22 <20 $ D> 50 $ 23 0-5 $ E> 50 $ 24 <20 $ ig U1995

Example 4

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

Residual preventive effect In greenhouses, grapevine cuttings of the variety "Chasselas" are grown. At the 10-leaf stage, 3 plants are sprayed with a spray liquid made from a 0.02 $ active ingredient 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 effect of the substances studied. As a basis for assessment, infected but untreated control plants serve.

The fungal attack is completely or almost inhibited (0-5% attack) by the active substances Nos. 1, 6, 7, 12, 15, 16, 17, 18, 40, 41, 48, 50, 52 and 53, and by the other active substances of formula I the fungal attack is less than 20%.

By comparison, however, the following results are obtained.

Active substance no fungal attack A 20-40% B 20-40% 0> 50% D> 50% E> 50%

Example 3

Effect against Erysiphe graminis on Hordeum vulgare fbvg ^.

Residual protective effect

Ca. 8 cm tall barley plants are sprayed with a spray liquid made from the active ingredient ($ 0.05 active substance). After 48 hours, the treated plants are sprayed with conidia of the fungus.

The infected barley plants are placed in a greenhouse at approx. 22 ° C and the fungal attack is evaluated after 10 days.

Part of the compounds of formula I in this experiment show a reduction of the fungal attack to below $ 20.

Example 6

Effect against lythium 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. Immediately after sowing, test formulations formulated as spray powders are poured into the soil as aqueous suspensions (20 ppm 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 sugar beet seeds, which are stained with the test preparations formulated as spray powders (1000 ppm active substance based on the seed weight). The sown herb pots are set up for 2-3 weeks in greenhouses at 20-24 ° C. The soil is kept uniformly moist by light spraying with water. The assessment determines the growth of sugar beet plants as well as the number of healthy and diseased plants.

After treatment with the active substances of formula I, both test conditions a) and b) more than $ 85 of the sugar beet plants grew up and had a healthy appearance. In the untreated control trials, less than $ 20 plants grew up with partly sickly appearance.