DE2902861A1 - MICROBICIDAL AGENTS - Google Patents

Description

Dr. F. Zumsiein sen. - Dr. E. Assmann - Dr. R. Koenicjsberger Dipl.-Phys. R. Holzbauer - Dipl .-! Ng. F. [CJIstgs.3is.er. - Dr. F. Zumstein jun.

PATEMTA ν 'Λ'Λ LT E

80OO Munich 2 · Bräuhausstrasse 4 Telephone Sammei-Nr 22 53 41 · Telegrams Zumpat ■ Telex ^^ | ⁷ Q 2

• 5-

Gases 5-11

CIBA-GEIGY AG, CH-4002 Basel / Switzerland

Microbicidal agents

The present invention relates to compounds of the Formula I.

R ^R

^R 2. r- ~ \ J ^> - R ₄

(D

C-CH-CH

wherein

RC ₁ -C ^ -alkyl, C ₁ -C ₄ -AIkOXy or halogen,

R _{1 is} hydrogen, C 1 -C, -alkyl, C ₁ -C ₇ -alkyl or halogen, L Lj Lh

R _{2 is} hydrogen, C ₁ -C ₃ -AUCyI, or halogen, and R _{3 is} hydrogen or methyl, the total number of carbon atoms of the substituents R, R ₁ , R ₂ and R ₃ in the phenyl ring not exceeding 8, while

R, and R- independently of one another are hydrogen or methyl are.

Process for the preparation of these compounds as well as agents which contain these compounds as active ingredients, and the use of these active ingredients as microbicides im

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Plant protection.

Under alkyl or as an alkyl part of a Alkoxy groups are to be understood as meaning the following groups, depending on the number of carbon atoms specified: methyl, ethyl, Propyl, isopropyl, butyl, isobutyl, sec. Butyl or tert. Butyl.

Halogen is fluorine, chlorine, bromine or iodine.

In US-PS 3,933,860 3- [N-acyl-N-arylamino) lactones and -lactams are described as fungicides, which derive from the structure of benzoyl, alkanoyl or haloalkanoyl (especially haloacetyl) anilides. Anilide this Type are described very numerous in the literature as herbicides, e.g. US-PS 3,403,994, US-PS 3,442,945, U.S. Patent 3,547,620, U.S. Patent 3,637,847, U.S. Patent 3,598,859, or U.S. Patent 3,946,045.

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It is therefore not surprising that the compounds mentioned in US Pat. No. 3,933,860 are among those to be protected from fungal attack Plants can cause undesirable phytotoxicity with the application rates necessary for practice.

It has now surprisingly been found that compounds with the structure of the formula I are a practical Needs a very affordable range of microbicides for the shooter of cultivated plants without adversely affecting them by undesired side effects. Crops be in the context of the present invention, for example, grain, corn, rice, vegetables, sugar beet, soy, peanuts, Fruit trees, ornamental plants, but above all vines, hops, Cucumber plants (cucumbers, squash, melons), Solanaceae such as Potatoes, tobacco and tomatoes, as well as banana, cocoa and natural rubber plants.

With the active ingredients of formula I can on plants or Plant parts (fruits, flowers, foliage, stems, tubers, roots) of this and related crops occurring fungi are contained or destroyed, with later overgrown plant parts of such Fungi spared «The active ingredients are against the phytopathogenic fungi belonging to the following classes effective: Ascomycetes (e.g. Erysiphaceae); Basidiomycetes, especially rust fungi; Fungi imperfect! (e.g. Moniliales); but then especially against the Oomycetes belonging to the class of Phycomycetes such as Phytophthora "Peronospora, Pseudoperonospora, Pythium or Plasmopara. In addition, the compounds of the formula I have a systemic effect. she can also be used as a dressing agent for the treatment of seeds (fruits, tubers, grains) and plant cuttings Protection against fungal infections and against phytopathogenic fungi occurring in the soil are used.

909831 / 07AS

«SsiWA INSPECTED

Preferred plant fungicides are compounds of the formula I in which R is methyl, R, methyl, ethyl or chlorine, R 1 is hydrogen, halogen or methyl and R _{3 is} hydrogen or methyl, while R 1 and R 1 are as defined for formula I.

Important individual connections are, for example:

3- [N- (Hydroxyacetyl) -N- (2,3,6-triethylphenyl)] -aminotetrahydrο -2 -furanone

3- [N- (Hydroxyacetyl) -N- (2,6-dimethyl-3-chlorophenyl)] -atninote tr ahydr ο-2-for anon

3- [N- (Hydroxyacetyl) -N- (2,3,5,6-tetramethyl-phenyl)] -amino-tetrahydro-2-furanone.

The compounds of formula I are according to the invention A) by acylation of a compound of formula II

(ID

with a compound of the formula III

Hal ¹ -CO-CH-O-CO-R, (III)

1 ⁶

^R 5

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and mild alcoholysis in the presence of alcoholate at room or slightly elevated temperature, where R ^ a

represents lower aliphatic radical, preferably methyl or ethyl, or

B) by initial monohaloacylation of a compound of formula II to give a compound of formula IV

(IV)

CO-CH -shark "

and exchange of the halogen atom Hai "for the acid residue an acid HOCO-Rg with the help of the acid itself or one of its salts, preferably its alkali or alkaline earth salt, and subsequent mild alcoholysis in the presence of alcoholate at room temperature or slightly higher Temperature.

In formulas II, III and IV, R to R _{5 have} the meaning given for formula I, while Hal ¹ and Hal "denote halogen, preferably chlorine or bromine.

The reactions can be carried out in the presence or absence of a solution or solution which is inert towards the reactants

909831/0745

ORiGIiSlAL SMSPECTEO

■ ΛΌ-

Diluents are carried out. For example, the following are possible: aliphatic ^ or aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, Methylene chloride, ethylene chloride, chloroform; Ethers and ethereal compounds such as dialkyl ethers, Dioxane, tetrahydrofuran; Nitriles such as acetonitrile; Ν, Ν-dialkylated amides such as dimethylformamide; Dimethyl sulfoxide, Ketones such as methyl ethyl ketone and mixtures of such solvents with one another.

For the monohaloacetylation according to variant B, the corresponding carboxylic acids themselves and their esters, however, it is advantageous to use the acid anhydrides or the acid halides. As acid halides are the Acid chlorides or acid bromides are preferred.

The reaction temperatures are between 0 ° and 120 ° C, preferably between 0 ° and 50 °. In some cases the use of acid binding agents or Condensate JLonsmit te In advantageous. Tertiary amines such as trialkylamines (e.g. triethylamine), Pyridine and pyridine bases, or inorganic bases such as the oxides and hydroxides, hydrogen carbonates and carbonates of alkali and alkaline earth metals as well as sodium acetate into consideration.

The preparation starting from compounds of the formula II process A and the acylation step leading to compounds of the formula IV can also be carried out without acid-binding Means are carried out, in some cases the bubbling of nitrogen to drive off the formed Hydrogen halide is indicated. In other cases it is

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an addition of dimethylformamide as a reaction catalyst is very advantageous.

Details on the preparation of intermediates / Formula II are from US Pat. No. 3,933,860 known.

The compounds of the formula I have a lactone radical

a (*) and, in the case of R, = CH _3, a second (**) asymmetry center and can be split into optical antipodes in the usual way (eg fractional crystallization or chromatographic separation). The different configurations have microbicidal effects of different strengths.

Unless a specific synthesis for the isolation of pure isomers of the formula I or of the butyrolactone used, a product is normally obtained as a mixture of isomers.

The following examples serve to explain the invention in more detail without restricting the same. The temperature information relate to degrees Celsius.

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ORIGINAL

/ i

example 1

CH ₃ CH ₃

Production of

3- [N- <Hydroxyacetyl) -N- (2,3,6-trimethylphenyl)] -aminotetrahydro-2-furanone [Verb. 2]

0.5 g of sodium were in 10 ml of abs. Dissolved methanol. A solution of 21.4 g of 3- [N- (acetoxyacetyl) -N- (2,3,6-trimethylphenyl)] -amino-tetrahydro-2-furanone was added in 60 ml abs. Methanol was added dropwise at 20-25 ° with stirring. Then the stirring was continued overnight at room temperature, evaporated on a rotary evaporator and mixed with 500 ml of ice water offset. The suspension then became Congo acidic with 1% hydrochloric acid with ice cooling set (pH 2), suction filtered and washed neutral with water. The one obtained as a mixture of drastereomers After recrystallization from isopropanol, the product had a melting point of 151-155 °.

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The following compounds of the formula

manufactured: R. R. 1 R. 2 H R. 3 H R, H R _p H Physically. Verb. 6-CH ₃ 3-CH ₃ H 4th H 5 H data No. CH ₃ 6-CH ₃ 3-CH ₃ 5-CH ₃ H H M.p. 169-170 ° 1 CH ₃ 6-CH ₃ 3-Cl H H H 151-154 ° 2 CH ₃ 6-CH ₃ H H CH ₃ H M.p. 125-130 ° 3 CH ₃ 6-CH ₃ H H CH ₃ M.p. 125-130 ° 4th CH ₃ 6-CH ₃ H H H H M.p. 140-145 ° 5 CH ₃ 6-C ₂ H ₅ 4-Cl H H H M.p. 128-133 ° 6th CH ₃ 6-CH ₃ 4-Br H H H 153-157 ° 7th CH ₃ 6-CH ₃ H H H H 179-183 ° 8th CH ₃ 6-Cl H H H H 192-201 ° 9 CH ₃ 6-OCH ₃ 3-CH ₃ H CH ₃ H 153-155 ° 10 CH ₃ 6-CH ₃ 3-CH ₃ 5-CH ₃ CH ₃ H M.p. 179-180 ° 11 CH ₃ 6-CH ₃ H H H H M.p. 127-131 ° 12th CH ₃ 6-C ₃ H ₇ Ci) 4-Br H H H M.p. 116-119 ° 13th C ₃ H ₇ (I) 6-Br 3-Cl H CH- H resin 14 ι CH ₃ 6-CH ₃ 3 -CH H H CH, viscos 15th CH ₃ 6 -CH 157-160 ° 16 CH ₃ M.p. 120-122 ° 17th

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The compounds of the formula I can be used alone or together with suitable carriers and / or other additives be used. Suitable carriers and additives can be solid or liquid and correspond to those used in formulation technology common substances such as natural or regenerated mineral substances, solution, dispersing, wetting, adhesive, Thickeners, binders or fertilizers.

The content of active ingredient in hand-icing products is between 0.1 to 90%.

For administration, the compounds of the formula I can be in the following working-up forms (the percentages by weight represent advantageous amounts of active ingredient in brackets):

Fixed forms of processing: dust and grit (up to

10 7o) Granules, coated granules, impregnation · granulate and homogeneous granulate late (1 to HO%);

Liquid processing forms:

a) Active substance concentrates dispersible in water:

Wettable powders and pastes (U5-90 % in the hand pack, 0.01 to 15% in ready-to-use solution); Emulsion concentrates and solution concentrates (10 to 50%; 0.01 to 15 \ in ready to use solution);

b) solutions (0.1 to 20%);

The active ingredients of the formula I of the present invention can be formulated, for example, as follows:

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INSPECTS)

Dust: The following substances are used to produce a) 5% and b) 27th dust:

a) 5 parts of active ingredient
95 parts of talc;

b) 2 parts of active ingredient

1 part of highly disperse silica, 97 parts of talc;

The active ingredients are mixed and ground with the carrier substances and can be dusted in this form for use.

Granules: The following substances are used to produce 5 x granules:

5 parts of active ingredient

0.25 part of epichlorohydrin,

0.25 parts of cetyl polyglycol ethers,

3.50 parts of polyethylene glycol

91 parts of kaolin (cortex 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 added. The solution obtained in this way is sprayed onto kaolin, and then the acetone evaporated in a vacuum. Such a microgranulate is particularly suitable for soil application.

Wettable powder: To produce a) 70% b) 40% c) and d) 25% e) 10% wettable powder, the following ingredients are used:

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a) I. I. 25th 70 parts 4, 5 parts 1, 3 parts 1, 10 parts 19th 12 parts H) 19th 40 parts 28, 5 parts 25th Part 1 2.5 54 pieces 6) 1.7 Parts 8.3 , 5 parts 16.5 , 9 parts 46 5 parts 10 5 parts 3 5 parts 5 1 parts d) 82 Parts Parts Parts Parts Parts Parts, e) Parts Parts Parts Parts

Active ingredient

Sodium dibutylnaphchylsulfonate,

Naphthalenesulfonic Acids-Phenolsulfonic Acids-

Formaldehyde condensate 3: 2: 1, Kaolin, champagne chalk;

Active ingredient ligninsulphonic acid sodium salt,

Dibutylnaphthalenesulfonic acid e-sodium salt,

Silica;

Active ingredient calcium lignin sulfonate,

Champagne chalk / hydroxyethyl cellulose

Mixture (1: 1), sodium dibutyl naphthalene sulfonate, Silica, champagne chalk, Kaolin;

Active ingredient isooctylphenoxy-polyoxyethylene-ethanol, Champagne chalk / Hydroxyä thy Ice Hulose mixture (1: 1), sodium aluminum silicate, kieselguhr, kaolin;

Active ingredient Mixture of the sodium salts of saturated fatty alcohol sulfates.

Naphthalenesulfonic acid / formaldehyde condensate, Kaolin;

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The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate mills and rollers. Spray powder of excellent quality is obtained Wettability and suspensibility, which can be diluted with water to form suspensions of any desired concentration and especially for foliar application.

Emulsifiable concentrates: The following substances are used to produce a 25% emulsifiable concentrate:

25 parts of active ingredient

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.

This concentrate can be diluted with water to produce emulsions of any desired concentration. which are particularly suitable for foliar application.

The compounds of the formula I can, in order to adapt them to the given circumstances, to broaden their spectrum of activity with other suitable pesticides, such as fungicides, insecticides, acaricides, nematicides, rodenticides, Herbicides or affecting plant growth Active ingredients and fertilizers are used together.

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ye

Action against Phytophthora infestans on tomatoes

Ia) Residual preventive effect
Tomato plants of the "Red Gnome" variety are infected with a zoospore suspension of Phytophthora infestans after they have been grown for 3 weeks after they have been sprayed with a broth containing 0.06% active ingredient (made from the active ingredient that has been worked up into a wettable powder). You then stay for 6 days in a climatic chamber at 18 to 20 ° and high humidity, which is generated by means of an artificial spray. After this time, typical leaf spots appear. Their number and size are the assessment criteria for the tested substance.

Ib) Curative effect

After three weeks of cultivation, tomato plants of the "Red Gnome" variety are sprayed with a zoospore suspension of the fungus and incubated in a cabin at 18 to 20 ° and saturated humidity. Interruption of humidification after 24 hours. After the plants have dried, they are sprayed with a broth which contains the active substance formulated as a wettable powder in a concentration of 0.06 % . After the spray coating has dried on, the plants are placed back in the humid cabin for 4 days. The number and size of the typical leaf spots that appear after this time are the yardstick for assessing the effectiveness of the substances tested.

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II) Preventive systemic action The active substance formulated as a wettable powder is applied in a concentration of 0.006% (based on the soil volume) to the soil surface of three-week-old potted tomato plants of the "Red Gnome" variety. After a three-day waiting period, 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 ° and saturated humidity. After this time, typical leaf spots form, the number and size of which are used to assess the effectiveness of the substances tested.

In these three experiments the compounds of formula I show good leaf fungicidal effect. With compounds 1, 2, 3, 4, 5, 11, 12, 13 and 16, the fungal attack is complete prevent.

Example 3

Action against Plasraopara viticola (Bert, et Gurt.) (Berl. et DeToni) on vines

a) Residual preventive effect

Vine cuttings from the "Chasselas" sots were grown in the greenhouse. At the 10-leaf stage, 3 plants were sprayed with a broth (0.0 2 % active ingredient) prepared from the active ingredient formulated as a wettable powder. After the spray coating had dried on, the plants on the underside of the leaves were evenly infected with the spore suspension of the fungus. The plants were then kept in a humid chamber for 8 days. After this period, clear symptoms of the disease appeared on the control plants. The number and size of the infection sites on the treated plants served as an evaluation standard for the effectiveness of the substances tested.

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b) Curative effect

Vine cuttings of the "Chasselas" variety were grown in the greenhouse and infected at the 10-leaf stage with a spore suspension of Plasmopara viticola on the underside of the leaf. After a stay of 24 hours in the humid cabin, the plants were sprayed with a 0.06 active ingredient broth which had been prepared from a wettable powder of the active ingredient. The plants were then kept in the humid cabin for 7 days. After this time, the disease symptoms appeared on the control plants. The number and size of the infection points on the treated plants served as an assessment tab for the effectiveness of the substances tested.

The compounds of formula I showed good foliar fungicides Effects in these two experiments. The vines had a healthy look.

In experiment a) the compounds No. 2 and 12 showed both in 0.027% and in 0.006%. Concentration one complete prevention of fungal attack.

Example 4 Effect against Pythium debaryanum on Beta vulgaris (sugar beet)

a) Effect after application to the soil

The mushroom is cultivated on sterile oat kernels and added to a mixture of soil and sand. The earth infected in this way becomes in Flower pots filled and sown with sugar beet seeds. Immediately after sowing, they are formulated as wettable powders Test preparations poured over the soil as aqueous suspensions (20 ppm active ingredient based on the volume of the soil).

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The pots are then placed in a greenhouse at 20-24 ° C. for 2-3 weeks. The earth is thereby light Spraying with water kept evenly moist. When evaluating the tests, the emergence of the sugar beet plants and the proportion of healthy and diseased plants is determined.

treatment % healthy with connection running plants 1 85% 3 80% 4th 100% 5 85% 13th 80% 16 100% Effect after pickling application

The mushroom is cultivated on sterile oat grains and one Earth-sand mixture added. The earth infected in this way becomes in Flower pots filled and sown with sugar beet seeds, which were pickled with the experimental preparations formulated as pickling powders have been (1000 ppm active ingredient based on the weight of the seeds). The sown pots are kept in the greenhouse for 2-3 weeks 20-24 ° C. The earth is kept evenly moist by lightly spraying it with water. During the evaluation, the emergence of the sugar beet plants and the proportion of healthy and diseased plants are determined.

After treatment with one of the active ingredients No. 1 to 17 of the formula I emerged more than 80% of the sugar beet plants and had a healthy appearance.

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Claims (9)

Claims 1.- Compounds of the formula (D RC ₁ -C, -alkyl, C ₁ -C, -alkoxy or halogen, R _n hydrogen, C, -C _Q -alkyl, C ₁ -C, -alkoxy or halogen, J. IJlH- R _{9 is} hydrogen, C, -Cj-alkyl, or halogen, and R "is hydrogen or methyl, the total number of carbon atoms of the substituents R, R ₁ , R ₂ and R ₃ in the phenyl ring not exceeding 8, while R, and R ₁ . independently of one another hydrogen or methyl s ind. 2. Compounds of formula I according to claim 1, in which R is methyl, R _{1 is} methyl, ethyl or chlorine, R _{2 is} hydrogen, halogen or methyl and R _{3 is} hydrogen or methyl, while R and R are independently hydrogen or methyl. 9Π9831 / 07 4 5 ORIGINAL INSPECTED 3. 3- [N- (Hydroxyacetyl) -N- (2,3,6-trimethylphenyl)] -aminotetrahydro-2-furanone. 4. 3-] N- (Hydroxyacetyl) -N- (2,6-dimethy1-3-chlorophenyl)] amino-tetrahydro-2-furanone. 5. Plant microbicidal agent, characterized in that that there is a compound of the formula I according to claim 1 together with suitable carriers as the active component contains. 6. Agent according to claim 5, containing a compound according to claim 2 as the active component. 7. Agent according to claim 5, containing as active component a compound according to claim 3. 8. Agent according to claim 5, containing a compound according to claim 4 as the active component. 9. A method for combating phytopathogenic fungi, characterized by applying a compound of the Formula I of claim 1. 10. The method according to claim 9, characterized by application of a compound according to claim 2. 11. The method according to claim 9, characterized by applying a compound according to claim 3. 12. The method according to claim 9, characterized by Application of a compound according to claim 4. 0 09831 / 074S ORIGINAL INSPECTED 13. Process for the preparation of a compound of the formula I. R ^Oas j ° ^R 4 C-CH-OH ^R i Sr ₅ RC ₁ -C / -Alkyl, C ₁ -Cy-AlkOXy or halogen, IA L * f R is hydrogen, C, -C _o -alkyl, C ₁ -C, -alkoxy or halogen, 1 IJ I ^ R _{2 is} hydrogen, C ₁ -C ₃ -AlkYl, or halogen, and R «is hydrogen or methyl, the total number of C atoms of the substituents R, R ₁ , R ₂ and R ₃ in the phenyl ring not exceeding 8, while R 1 and R ₅ independently of one another are hydrogen or methyl are,
A) by acylation of a compound of formula II (II) with a compound of the formula III Hal ¹ -CO-CH-O-CO-R ₆ (III) re 9098 31/0745 ORIGIiMAL ISMSPECTK and mild alcoholysis in the presence of alcoholate at Rautn or slightly elevated temperature, where R ^ a represents lower aliphatic radical, preferably methyl or ethyl, or B) by initial monohaloacylation of a compound of formula II to a compound of formula IV and exchange of the halogen atom Hai "for the acid residue of an acid HOCO-Rg with the aid of the acid itself or one of its salts, preferably its alkali or alkaline earth salt, and subsequent mild alcoholysis in the presence of alcoholate at room temperature or slightly elevated temperature, with in the formulas II, III and IV R to R _{5 have} the meanings given for formula I, while Hal 'and Hal "mean halogen, preferably chlorine or bromine. 9 0 9831/07 «p _OB1G1NAL