DK141168B - Fungicidal anilide compounds for use in plant protection. - Google Patents

Description

(11) FKEMUE86ELSESSKBIFT 1 ^ + 1 168 denmark "> ** <* · *% v ;;; ·;" (21) Annotation No. 1358/75 (22) Contained March 26, 1975 (23) Uncovered 26. Mar 1975 (44) The note presented and

funilumgtltBtttolfw olhmHqgiartdan Jan. 28 I98O

DIRECTORATE FOR _ -...

THE PATENT AND TRADE MARKET PWori «bagewa * M cftn

Apr 2 197 * 1, 4572/74, CH

Feb 10 1975 # 1591/75, GH

(71) £ IBA-GEIGY AG, 4002 Basel, GH

(72) Inventor: Adolf Bubele, Im. Egg # 4465 Magden, GH.

(74) The clerk omits the proceedings:

English: Patent Kontor ApS .__ i5 *) Fungicidal anilide compounds for use in plant protection.

The present invention relates to fungicidal anilide dressings.

for use in plant protection, and these compounds are peculiar in that they bear the formula: 'CH,' v '' '- · ^ :: | 3? ? H3 CH-C00CH ,; 1; i., ·: W 0 -0 CH 3, NT wherein R is hydrogen or methyl. . : will - / 2 141168

Bacterial and fungal diseases of livestock plants are favored by two factors. The first is the aim of plant breeding work, first and foremost to increase yield and quality improvement. Frequently, however, part of the plant's natural resistance to parasites is lost. On the other, experience has shown that bacteria and harmful fungi over the years have developed resistance to the known pesticides on a larger scale.

Therefore, there is an intrusive habitat for microbicides that are tolerated by culture plants and which destroy their direct parasites.

Cultural plants are e.g. cereals, corn, rice, vegetables, sugar beet, soy, peanuts, fruit trees, ornamental plants, but above all vine plants, hops, cucumber (cucumbers, pumpkins, melons), solanas such as potatoes, tobacco and tomatoes, as well as banana, cocoa, and natural rubber wash t.

German German Patent Specification No. 1,768,686 and German Patent Publication No. 2,006,471 are known to have anilides having similar structure to the compounds of Formula I. In the "Specimens 1" and "Specimens 2" listed below, such known compounds showed no or hardly sufficient action as fungicides for plant protection. In the experiments, on the other hand, it was surprisingly found that the compounds of formula I show a strong fungicidal effect.

With the compounds of formula I, fungi appearing on plants or parts of the plant (fruits, flowers, foliage, stems, tubers, roots) of these and other crops can thus be inhibited or destroyed, thereby also further increasing plant parts from such fungi. . The pore linkages are effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (eg Erysiphaceae); Basidiomycetes, such as, above all, rust fungi; Pungi imperfect !; but especially against those belonging to the class of Phycomycetes Oomycetes, such as Phytophthora, Peronospora, Pseudoperono- spora, 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 plantings for protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.

The N- (Subst. Phenyl) -K-furanoyl-alanine methyl esters of Formula I constitute a novel class of novel microbicidal active substances which are clearly superior in their field of application to the usual commercial preparations.

The compounds of formula I are prepared, for example, by acylating a compound of formula R CH, rrf

II3 f3 X-RH-CH-COOCH3 (II) CH3 with furan (2) -carboxylic acid, its acid content o genide, acid anhydride or esters, in a single case also with a furan (2) carboxylic acid amide (re-amidation) .

According to another method, the compounds of formula I can also be prepared by the fact that an acyl anilide of the formula R CH3 <zSt ° 'U (in)

I H

ch 3 with butyl lithium or Ha hydride is transferred to the corresponding alkali metal salt, whereupon with an α-halo propionic acid methyl ester it is transferred to the desired final product or the acyl anilide can be reacted with the α-halogen propionic acid methyl ester in the presence of an alkali metal carbonate such as K as a proton acceptor, preferably with the addition of catalytic amounts of alkali metal iodide, e.g. KJ.

In formulas II and III, R is hydrogen or methyl, the term acid halide preferably means acid chloride or acid bromide, and the halogen atom of the α-halo propionic acid methyl ester is preferably chlorine or bromine. The reactions may be carried out in the presence or absence of solvents or diluents which are inactive against the reaction moieties. Examples include the following: aliphatic or aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halo-generated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform; ethers and ether-like compounds such as diethyl ethers, dioxane, tetrahydrofuran; nitriles such as acetonitrile; Η, Η-dialkylated amides such as dimethylformamide; anhydrous acetic acid, dimethyl sulfoxide, ketones such as methyl ethyl ketone, and mixtures of such solvents among themselves.

The reaction temperatures 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 carbonates of alkali and alkaline earth metals, and sodium acetate are considered. In addition, an excess of the relevant aniline derivative of formula II can be used as an acid binding agent.

The preparation method based on compounds of formula II can also be carried out without acid-binding agents, whereby it may in some cases be in place with the passage of nitrogen to displace the hydrogen halide formed. In other cases, the addition of dimethyl f imimide as a reaction catalyst is very advantageous.

Details of the preparation of the intermediates of formula II can be deduced from the methods generally disclosed for the preparation of anilino-alkanoic acid esters in the following publication bodies: J.Org. Chem.

30, 4101 (1965), Tetrahedron 1967, 487, and Tetrahedron 1967, 493 ·

The compounds of formula I have in the propionic acid ester chain 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.

Therefore, compounds of formula I having D-configuration are preferred. These D forms have a negative angle of rotation in ethanol or acetone.

For the preparation of the pure optical D antipodes, e.g. the racemic compound of the formula: H CH, ηπ II 3 f 3 X-NH-CH-COOH (IV) CH 3 (R * H or CH 3) and this is then reacted in a manner known per se with an N-containing optical active base to the corresponding salt. By fractional crystallization of the salt and subsequent release of the acid enriched with the optical B-antibody of Formula IV and optionally repeating (also several times repeating) the salt formation, crystallization and release. of the α-anilinopropionic acid of formula IV, the pure D form is gradually obtained. Of this, then, in the usual way, e.g. in the presence of HCl or ED₂SO ^, with methanol the optical D configuration of the ester of formula II is obtained. As an optically active organic base, e.g. alpha-phenyl ethyl amine on speech.

Instead of by fractional crystallization, the enantiomeric D form of formula IV can also be obtained by exchanging the hydroxyl group in the naturally occurring 1 (+) lactic acid with halogen and further resizing this product under configuration reversal with the desired 2,6-dimethylaniline. or 2,3,6-trimethylaniline.

In addition to the optical isomerism, in the case of R »CH₂, with the furanoylation of compound II (or with reaction of compound III with α-halogenopropionic acid methyl ester), an atropisomerization of the phenyl-N-axis occurs, subject to the steric hindrance of the two The N atom of the trimethyl aniline extra introduced groups. If no targeted synthesis is performed to isolate pure isomers, the following compound # 2 is obtained in the preparation as a mixture of 4 isomers.

However, the more favorable fungicidal effect of the enantiomeric D form (as compared to the D, L form or L form) remains and is not appreciably affected by the atropisomer.

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

Example 1.

Preparation of 141168 6 CH, I 3 CH, CH-COOCH, H, \ Jl 3 11 Vo / O (Compound No. 1) N- (1'-me tho xyc arbonyl-ethyl) -N- (furan- (2 (2-carbonyl) -2,6-dimethyl-aniline.

To 18.2 g of H- (1-ethoxycarbonyl-ethyl) -2,6-dimethylaniline in 10 ml of anhydrous toluene and 0.2 ml of dimethyl formamide are added dropwise with 12.6 g of furan-2-carboxylic acid chloride. After the slightly exothermic reaction is quenched, heat for 5 hours under reflux and the hydrogen chloride formed is completely removed by passing through nitrogen. After removal of the solvent is distilled in vacuo; kp. 166-168 ° C / 0.06 mm Hg. The solidified final product melts after recrystallization from toluene / petroleum ether at 81-84 ° C. X-ray powder diagrams show that the compound is polymorphic. One of the two modifications melts at 85 ° C.

The enantiomeric D configuration and its precursors have the following physical data:? H3 CH3 (D) form Λ -m- * CH-COOH = +10.7 * V- / C = 1.56 $ g / v in ethanol CH3

CH

In CH3 (D) form J V-m- * CH-C00CH3 [a] + = + 29.8 ± 0.5 °; C = 1.52 $ g / v in methanol CH.

i ψ

CH

(Eorb. No. 1a)? H3 * CH-C00CH (D) form m.p. 102-103 ° C

/ - \ - Έ 'π3 [«] f - -47.0 ± 0.7 ·! V = / \ Co-l [} C = 1 * 7 & s / v in acetone CH3 0 141168 7

Example 2.

Preparation of CH, I 3? H3? H3 CH-COOCH.

W '\ Π I C-l * i (compound # 2)

CH, 11 XK

0 N- (11-methoxycarbonyl-ethyl) -N- (furan- (2 ") carbonyl) -2,3,6-trimethyl-aniline.

a) A suspension of 51.5 g (0.382 mol) of 2,3,6-trimethylaniline, 35.3 g of NaHCO 3 and 126 ml (1.15 mol) of 2-bromopropionic acid methyl ester is stirred for 6 hours at a bath temperature of 130 ° C. ; then cooled, the salt filtered off and the mixture distilled: 67.3 g of α- (2,3,6-trimethylanilino) -propionic acid methyl ester, b.p. 144-146 ° C / 9 mm Hg.

b) To a suspension of 33.5 g (0.152 mol) of the ester obtained in (a) and 18 g (0.17 mol) of sodium carbonate in 200 ml of absolute benzene is added dropwise 16.7 ml (0.17 mol) of furan. 2-carboxylic acid chloride at 60-70 ° C and this temperature is kept for 4 hours. After cooling, filtration and evaporation of the filtrate, the final product crystallizes from isopropyl ether; mp. 98-102 ° C.

Acylating the D form of α- (2,3,6-trimethylanilino) propionic acid methyl ester with furan (2) carboxylic acid or one of its reactive derivatives gives the D form of compound 2 as a mixture of atropisomers (compound # 2a). The percent of each of these isomers obtained depends on the conditions of manufacture.

The compounds of formula I may be used to extend their spectrum of action with other 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 the art in the formulation technique, 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 $).

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: a) 5 parts active substance # 2 95 parts talc; b) 2 parts active substance No. 1 1 part high-dispersion silicic acid 97 parts talc.

141168 9

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

granules;

For the preparation of a 5 # 1 granule, the following substances are used; 5 parts of active substance # 1 0.25 parts of epichlorohydrin 0.25 parts of cetyl polyglycol ether 3.50 parts of polyethyl englycol 91 parts of 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 micro granule is advantageously used to control soil fungi.

Sorøjtepulver:

For preparing an a) 70 µs, b) 40 µs, c) and d) 25 µs, e) 10 µ syringes, the following ingredients are used: a) 70 parts of N- (11-methoxycarbonyl) ethyl) -N- [furan (2 ") carbonyl] - 2,6-dimethylaniline, active substance # 1a (D-form) 5 parts sodium dibutylnaphthylsulfonate 3 parts naphthalenesulfonic acid phenolsulfonic acid formaldehyde condensate 3: 2: 1 10 parts kaolin 12 parts Champagne chalk; b) 40 parts active ingredient No. 2 5 parts lignin sulfonic acid sodium salt 1 part dibutylnaphthalenesulphonic acid e-sodium salt 54 parts silicic acid; c) 25 parts active substance No. 2a (D form) 4.5 parts of calcium lignin sulfonate 1.9 parts Champagne chalk / hydroxyethyl cellulose mixture (1: 1) 1.5 parts sodium dibutyl naphthalene sulfonate 19.5 parts silicic acid 19.5 parts Champagne chalk 28.1 parts kaolin; 10 U1TS8 d) 25 parts active substance No. 2 2, 5 parts isooctylphenoxy-polyoxyethylene ethanol 1.7 parts Champagne chalk / hydroxyethyl cellulose mixture (1: 1) 8.3 parts sodium aluminum silicon at 16.5 parts diatomaceous earth 46 parts kaolin; e) 10 parts active substance No. 1a (D-form) 3 parts mixture of sodium salts of saturated fatty alcohol sulphates 5 parts naphtha! ensulfonic 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.

Emulsifiable concentrates:

For the preparation of a 25 $ emulsifiable concentrate, the following substances are used: 25 parts of active ingredient # 1 2.5 parts of epoxidized vegetable oil 10 parts of an alkyl aryl sulphonate / fatty tallow with 1 po 1 y gly co 1 e th er 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.

141168 11

Experiment 1.

Effect against phytophthora infestans on tomatoes.

The following known compounds were used as comparators:

Compound A (DE Publication No. 2,006,471? S · 13 and 18): CH3 V-eh-co -._ Π

CH

CH3 ^

Compound B (DE Publication No. 2,006,471? S · 13): CH, __i3 V-KH-CO -,

^ = 1 P

0H3

Compound C (DE Publication No. 2,006,471? 3. 13): ch3 P V-HH-C0 -._ Π

Aq / ch3

Compound D (German Patent Specification No. 1,768,686, Example 1): -iffl-CO-p

Compound E (DE Publication No. 2,006,471? S · 19? Fourth Compound): CH 2 0 0H3 141168 12

If a fungal attack exceeding $ 50 is found when using a test substance, this substance is considered ineffective for practical purposes.

(a) Curative effect

Tomato plants of the "Rot 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 wiping the plants, they are sprayed with a spray liquid containing the test substance formulated as a spray powder at one of the indicated concentrations. 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.

As a basis for assessment, infected but untreated control plants serve.

Investigated Concentration Fungus attack compound ($ active substance) ($)

Kr. 1 0.06 5-10 0.02 5-10

Kr. 2 0.06 5-10 0.02 5-20 A 0.06 20-40 0.02> 50 B 0.06 20-40 0.02 20-40 C 0.06> 50 0.02> 50 D 0.06> 50 0.02> 50 E 0.06> 50 0.02> 50 b) Preventive-systemic effect

The test substance formulated as a spray powder is applied in the form of a spray liquid to the soil surface at 3 weeks old, in pots of tomato plants of the variety "Rotary Gnom", so that in a tempering area there is an active substance concentration of 0.006 and 0.002 respectively calculated on the soil volume. . Ensure that the spray liquid does not come into contact with above-ground plant parts. After 48 hours, the treated plants are sprayed with a sporang suspension of the fungus. The assessment of the fungal attack occurs after incubation of the infected plants for 5 days at 20 ° C and saturated humidity. The number and size of the leaf spots present at this time serve as a measure of the effect of the substances studied in relation to infected but untreated control plants.

Investigated Concentration Fungus attack compound (# active substance) T $)

No. 1 0.006 5-10 0.002 5-10

No. 2 0.006 5-10 0.002 5-10 A 0.006 20-40 *) 0.002 20-40 *) B 0.006 20-40 0.002> 50 C 0.006> 50 **) 0.002> 50 *) D 0.006 20-40 0.002> 50 E 0.006> 50 0.002> 50.

*) = slight phytotoxicity **) = unacceptable phytotoxicity.

Experiment 2.

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

(a) Residual-preventive effect In greenhouses, grapevine cuttings of the variety "Chasselas" are grown. At the 10-leaf stage, 3 plants are sprayed with a test liquid prepared from a spray powder 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.

In comparison, the known compounds A-E mentioned in Experiment 1 were used.

14- U1168

Investigated ^ Concentration fungal attack compound (# active substance) (#)

Sir. 1 0.02 0-5 0.006 0-5

Sir. 2 0.02 0-5 0.006 0-5 A 0.02 20-40 0.006> 50 B 0.02 20-40 0.006> 50 C 0.02> 50 0.006> 50 D 0.02> 50 0.006> 50 E 0.02> 50 0.006> 50 b) Curative effect

Vines of the "Chasselas" variety are grown in greenhouses and infected at the 10-leaf stage with a spore suspension of ELasmopara viticola on the underside of the leaves. After a 24 hour stay in a humidifier, the plants are sprayed with an 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 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.

In these two experiments a) and b), the compounds of formula I show strong fungicidal activity at the following concentrations:

Active substance No. Concentration Fungal attack by _. _ a) and b) 1 0.05% 0-5% 0.02% 0-5% la 0.02% 0-5% 2 0.05 # 0-5 #. 0.02 to 0-5%.

2a 0.02% 0-5%

Control - 100 #

Claims (2)

Experiment 3 · Effect against ffythium debaryanum on Beta vulgaris (Swallows ro e). a) Effect after soil application The fungus is grown on sterile oatmeal and added to a soil-sand blend. The soil thus infected is filled in herb pots and sown with sugar beet seeds. Immediately after sowing, the test compositions formulated as spray powders are read as aqueous suspensions out of the soil ($ 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) Effect after pickling application The fungus is grown on sterile oatmeal and added to a soil-sand-bl breath. The soil thus infected is filled in herb pots and sown with sugar beet seeds, which are stained with the test formulas formulated as spray powders ($ 0.1 active substance based on 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. Under conditions of both test (a) and (b), after treatment with one of the active substances 1, 1a, 2 or 2a, over $ 85 beet plants grow up and have a uniform healthy appearance. In the untreated control trial, less than $ 20 plants with a partially morbid appearance grow up. PATENTHAV. 1. Fungicidal anilide compounds for use in plant protection, characterized in that they have the general formula CH, I 3? ? h3 ch-cooch3 <1 1 O) ^ f No-G ch3 λο ^ «