CH633677A5 - Microbicidal composition, process for the preparation of the active compound and its use for the control of phytopathogenic fungi - Google Patents

Abstract

There are described microbicidal compositions which as active component contain at least one compound of the herein defined formula I <IMAGE> they have useful microbicidal properties and can be used for the control of microorganisms which are injurious to plants. Thus, the compounds of the formula I have, for practical needs, a very favourable curative, preventive and systemic action for the protection of crop plants, without affecting these by undesired side-effects.

Description

The present invention relates to a microbicidal agent which, as at least one active component, is a compound of the formula I.

(I)

contains what

R C1-C4-alkyl, C1-C4-alkoxy or halogen,

Rj Cj-Ca-alkyl, Ci-C4-alkoxy or halobes,

R2 is hydrogen, Cj-Q-alkyl, Q-C ^ alkoxy or halogen,

R3 are hydrogen or methyl, the total number of carbon atoms of the substituents R, Rj, R2 and R3 in the phenyl ring not exceeding 8,

R4 is hydrogen or methyl.

The invention further relates to the preparation of the compounds of the formula I and the use of these active compounds as microbicides in crop protection. The compounds of formula I are new.

Alkyl or as an alkyl part of an alkylthio or alkoxy group means the following groups, depending on the number of carbon atoms indicated: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. Butyl or tert. Butyl.

Halogen is to be understood as fluorine, chlorine, bromine or iodine.

In US Pat. No. 3,933,860, 3- (N-acyl-N-arylamino) lactones and lactams are described as fungicides which result from the structure of benzoyl-, alkanoyl- or haloalkanoyl- (especially haloacetyl-) anilides derive. Anilides of this type are very widely described in the literature as herbicides, e.g. U.S. Patent Nos. 3,403,994, 3,442,945, 3,547,620, 3,637,847, 3,598,859 or 3,946,045.

It is therefore not surprising that the compounds mentioned in US Pat. No. 3,933,860 in the plants to be protected against fungal attack sometimes have the application rates necessary for practical use. cause undesirable phytotoxicity.

It has been found that pyrazolylmethyl derivatives of the formula I have a microbicide spectrum which is very favorable for practical needs for the protection of crop plants, without adversely affecting them by undesirable side effects. Cultivated plants are, for example, cereals, corn, rice,

Vegetables, sugar beets, soybeans, peanuts, fruit trees, ornamental plants, but especially vines, hops, cucumber plants (cucumbers, pumpkin, melons), Solanaceae such as potatoes, tobacco and tomatoes, as well as banana, cocoa and natural rubber plants .

With the active ingredients of formula I on plants or parts of plants (fruits, flowers, foliage, stems, tubers, roots) of these and related crops, the fungi that occur can be contained or destroyed, and plant parts that grow later are spared from such fungi. The active substances are active against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Erysiphaceae); Basidiomycetes such as especially rust fungi; Fungi imperfect (e.g. Moniliales); 30 but especially against the pathogens belonging to the Oomycetes class Phytophthora, Peronospora, Pseudo-peronospora, Pythium or Plasmopara. In addition, the compounds of the formula I have a systemic action. They can also be used as dressing agents for the treatment of seeds (fruits, 35 tubers, grains) and plant cuttings for the protection of fungal infections and against phyto-pathogenic fungi occurring in the soil.

Preferred plant fungicides are compounds of the formula I in which R is methyl, Rx is methyl, ethyl, chlorine or 40 bromine, R2 is hydrogen, halogen or methyl and R3 is hydrogen or methyl, while R4 has the meaning given for formula I.

These are to be called connection group I '. The particularly effective microbicides include the following active compounds of the formula I: 3- [N- (1,2-pyrazol-1-ylacetyl) -N- (2,3,6-trimethylphenyl)] -

amino-tetrahydro-2-furanone,

3- [N-1,2-pyrazol-1-ylacetyl) -N- (2,6-dimethylphenyl)] - ami-no-tetrahydro-2-furanone, so 3- [N- (1,2-pyrazole- l-ylacetyl) -N- (2,3,5,6-tetramethylphenyl)] - amino-tetrahydro-2-furanone.

The compounds of formula I are according to the invention

A. by acylation of a compound of formula II «R

R,

60

0: NH-

-0

R /

(II)

R

1

with a compound of formula III

65

Shark '-cch2n; O

(in)

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manufactured, or

B. by initial monohaloacetylation of a compound of formula II to a compound of formula IV

0 = r

R,

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

The following example serves to explain the invention in more detail without restricting it. The temperature specifications relate to degrees Celsius.

CO-CH2-Hal "(XV)

and further reaction with 1,2-pyrazole or its metal salts, preferably its alkali or alkaline earth salt.

In the formulas II, III and IV, R to R4 have the meaning given for formula I, while sharks' and shark "mean halogen, preferably chlorine or bromine.

The reactions can be carried out in the presence or absence of solvents or diluents which are inert to the reactants. 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; Ether and ethereal compounds such as dialkyl ether, dioxane, tetrahydrofuran; Nitriles such as acetonitrile; N, N-dialkylated amides such as dimethylformamide; Dimethylsiüfoxid, ketones such as methyl ethyl ketone and mixtures of such solvents with each other.

The corresponding carboxylic acid itself and its esters, but advantageously the acid anhydride or, as indicated for formula III, one of the acid halides, preferably the acid chloride or acid bromide, can be used for acylation according to method A or for monohaloacetylation according to method B.

The reaction temperatures are between 0 and 180 ° C, preferably between 20 and 120 ° C. In some cases, the use of acid-binding agents or condensing agents is advantageous. Tertiary amines such as trialkylamines (e.g. triethylamine), pyridine and pyridine bases, or inorganic bases such as the oxides and hydroxides, bicarbonates and carbonates of alkali and alkaline earth metals and sodium acetate are suitable as such.

The production process A starting from compounds of the formula II and the acylation step leading to compounds of the formula IV can also be carried out without acid-binding agents, in some cases the passage of nitrogen to expel the hydrogen halide formed is indicated. In other cases, the addition of dimethylformamide as a reaction catalyst is very advantageous.

Details of the preparation of starting materials of the formula II are known.

The compounds of formula I have in the lactone radical io production of

example 1

20th

one (*) and in the case R4 = CH3 a second (**) center of asymmetry and can be split into optical antipodes in the usual way (e.g. fractional crystallization or chromatographic separation). The different configurations have different microbiocidal effects.

3- [N- (1,2-pyrazol-l-yl-acetyl) -N- (2,3,6-trimethylphenyl)] -

amino-tetrahydro-2-furanone. (Verb, k)

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a) Preparation of 2- (l-pyrazolyl) acetic acid

Under a nitrogen atmosphere, 38.7 g of sodium hydride in 100 ml of abs. Tetrahydrofuran with stirring and cooling at 20-30 ° C within 1 h 50 g pyrazole in 250 ml 30 abs. Tetrahydrofuran added dropwise. It is stirred for a further 3 hours at 40 °, cooled to 5 ° and with good cooling at 0-10 ° within 1 hour. 160.7 g of ethyl bromoacetate in 100 ml of abs. Tetrahydrofuran added dropwise. The mixture is stirred at room temperature overnight, then 150 ml of ethanol are added dropwise, the mixture is stirred for 1 hour and the suspension is evaporated. The residue is mixed with a solution of 74 g of NaOH cookies in 600 ml of 60 percent water. Methanol (aqueous) was added and the mixture was refluxed for 40 minutes. Then it is cooled and the solution is washed twice with 200 ml of ether. The aqueous phase is cooled at 5 ° with conc. Hydrochloric acid Congo acid (approx. PH 2) and the solution extracted continuously with methylene chloride for 24 hours. The extract is evaporated and recrystallized from ether tetrahydrofuran. The crystals melt 45 at 167-169 °.

b) 135 g of 2,3,6-trimethylaniline and 106 g of sodium carbonate in 750 ml of dimethylformamide are slowly mixed with 165 g of 2-bromo-4-butyrolactone at 10 ° C. and then for 16 hours at 70 ° and 24 hours. stirred at 100 °. After the

50 cool to 4-10 ° are added 1200 ml of ice water while cooling. Stirring is continued at 10 ° for 2 hours, the precipitate is filtered off and washed with water and petroleum ether: 3- [N- (2,3,6-trimethylphenyl)] - amino-tetrahydro-2-furanone, mp. 108-110 ° .

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c) 6.3 g of 2- (l-pyrazolyl) acetic acid are placed in 200 ml of toluene, 6.2 g of thionyl chloride are added and the mixture is boiled under reflux for 1 hour. The mixture is then cooled to 20 ° and with 11 g of the intermediate product obtained in b) and 5.8 g

60 soda added. After stirring at room temperature overnight, ice water is added and the mixture is extracted with methylene chloride; the extracts are washed with water, dried over sodium sulfate and evaporated. The remaining resin is cleaned over a silica gel and finally frozen out of ether at -50 °. The glassy mixture of diastereomers of 3- [N- (1,2-pyrazol-l-ylacetyl) -N- (2,3,6-trimethylphenyl)] - amino-tetrahydro-2-furanone melts at 50-60 °.

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The following compounds of the formula are used in an analogous manner

(R ^ = 6-position)

produced:

Verb.

R

rI

r2

r3

R4

Physics. Constant a

ch3

ch3

h h

H

M.p. 131-132 °

b ch3 '

cl h

h ch3

c ch3

c2h5

h h

H

d ch3

cl h

h h

M.p. 107-111 °

e ch3

ch3

3-ch3

5-ch3

H

M.p. 128-130 °

f ch3

c2h5

h h

ch3

g ch3

ch3

h h

ch3

h ch3

ch3

3-ch3

5-ch3

ch3

i ch3

ch3

3-c1

h h

M.p. 113-118 °

j ch3

ch3

3-Br h

ch3

k ch3

ch3

3-ch3

h h

Mp 50-60 °

1

ch3

ch3

3-c1

h ch3

m ch3

ch3

3-Br h

H

n ch3

ch3

4-c1

h ch3

M.p. 112-118 °

0

ch3

ch3

3-ch3

h ch3

P

ch3

ch3

4-c1

h h

q ch3

Br

4-c1

h h

r ch3o ch3

h h

H

s ch3o

Cl h

h h

The compounds of formula I are used together with suitable carriers and / or other additives. Suitable carriers and additives can be solid or liquid and correspond to the substances commonly used in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants,

Wetting agents, adhesives, thickeners, binders and fertilizers.

The content of active ingredient in commercial agents is between 0.1 to 90%.

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

Fixed processing forms:

Dusts and scattering agents (up to 10%) granules, coating granules, impregnation granules and homogeneous granules (1 to 80%);

Liquid processing forms:

a) Water-dispersible active ingredient concentrates: wettable powders and pastes (25-90% in the retail pack, 0.01 to 15% in a ready-to-use solution);

Emulsion and solution concentrates (10 to 50%; 0.01 to 15% in ready-to-use solution);

b) solutions (0.1 to 20%);

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

Dusts:

The following substances are used to produce a) 5% and b) 2% dust:

a) 5 parts of active ingredient,

95 parts talc;

b) 2 parts of active ingredient,

1 part of highly disperse silica,

97 parts talc;

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

Granules:

The following substances are used to produce 5% granules:

5 parts of active ingredient,

0.25 parts of epoxidized vegetable oil,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (grain size 0.3-0.8 mm). The active substance is mixed with epoxidized vegetable oil and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin, and the acetone is then evaporated off in vacuo. Such microgranules are particularly suitable for soil application.

Spray powder:

The following constituents are used to produce a) 70%, b) 40%, c) and d) 25%, a) 10% wettable powder:

a) 70 parts of active ingredient,

5 parts of sodium dibutylnaphthyl sulfonate,

3 parts of naphthalenesulfonic acids-phenolsulfonic acids-

Formaldehyde condensate 3: 2: 1,

10 parts of kaolin,

12 parts of champagne chalk;

b) 40 parts of active ingredient,

5 parts of sodium lignosulfonic acid,

1 part of dibutylnaphthalenesulfonic acid sodium salt,

54 parts of silica;

c) 25 parts of active ingredient,

4.5 parts of calcium lignin sulfonate,

1.9 parts champagne chalk / hydroxyethyl cellulose

Mixture (1: 1),

1.5 parts of sodium dibutyl naphthalenesulfonate, 19.5 parts of silica,

19.5 parts of champagne chalk,

28.1 parts kaolin;

d) 25 parts of active ingredient,

2.5 parts isooctylphenoxy polyoxyethylene ethanol, 1.7 parts champagne chalk / hydroxyethyl cellulose

Mixture (1: 1),

8.3 parts of sodium aluminum silicate,

16.5 parts of diatomaceous earth,

46 parts of kaolin;

e) 10 parts of active ingredient,

3 parts mixture of saturated sodium salts

Fatty alcohol sulfates,

5 parts naphthalenesulfonic acid / formaldehyde con-

densat,

82 parts of kaolin;

The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. Spray powder of excellent wettability and suspension is obtained, which can be combined with water to form suspensions of any desired concentration

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2S

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40

45

50

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60

65

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Dilute the concentration and have it used especially for leaf 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 xylene.

This concentrate can be used to prepare emulsions of any desired concentration, which are particularly suitable for foliar application.

In order to adapt them to the given circumstances, the compounds of the formula I can be used to broaden their activity spectrum with other suitable pesticides, such as e.g. Fungicides, insecticides, acaricides, nematicides, rodenticides, herbicides or active substances influencing plant growth and fertilizers are used together.

Example 2

Effect against Phytophthora infestans on tomatoes

I. Curative effect

After growing for three weeks, tomato plants of the “Red Gnome” variety are sprayed with a zoospores suspension of the fungus and incubated in a cabin at 18 to 20 ° and saturated air humidity. Humidification interrupted after 24 hours. After the plants have dried, they are sprayed with a broth which contains the active substance formulated as wettable powder in a concentration of 0.06 or 0.02%. After the spray coating has dried on, the plants are set up again in the wet room for 4 days. The number and size of the typical leaf spots that appear after this time are the evaluation standard for the effectiveness of the tested substances. Compounds of the formula I consistently caused a decrease in fungal infection to less than 20% at an active ingredient concentration of 0.06%. The compounds with the designations a, d, e, i, k, n and others caused an inhibition of fungal attack to 0-5% at this concentration. With an active ingredient concentration of 0.02%, i.a. also the compounds with the designation a, d, e, k inhibit fungal infection to 0-5%. No phytotoxicity was observed.

II.Preventive-systemic effect

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 plants is sprayed with a zoo spore suspension of Phytophthora infestans. They are then kept in a spray booth at 18 to 20 ° and saturated humidity for 5 days. After this time, typical leaf spots form, the number and size of which serve to evaluate the effectiveness of the substances tested.

The tomato plants treated with compounds of the formula I consistently showed less than 20% fungal attack in comparison with control plants (= 100% attack). The compounds labeled a, d, e, i, k, n and others completely or almost completely prevented fungal attack (0-5% infection).

Example 3

Action against Plasmopara viticola (Bert, et Curt.)

(Beri, et DeToni) on vines a) Residual preventive effect

"Chasselas" vine cuttings were grown in the greenhouse. In the 10-leaf stage, 3 plants were sprayed with a broth (0.06% active ingredient) prepared from active substance formulated with dermis wettable powder. After the spray coating had dried on, the plants on the underside of the leaf were evenly infected with the spore suspension of the fungus. The plants were then kept in a moist chamber for 8 days. After this time, clear disease symptoms appeared on the control plants. The number and size of the infection sites on the treated plants served as an evaluation benchmark for the effectiveness of the tested substances.

b) Curative effect

"Chasselas" vine cuttings 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 24 hours in the wet room, 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 wet room for 7 days. After this time the disease symptoms appeared on the control plants. The number and size of the infection sites on the treated plants served as a benchmark for the effectiveness of the tested substances.

The compounds of formula I showed very strong foliar fungicidal effects in these two experiments. The vine plants looked healthy. In particular, the compounds a, d, e, i, k and n inhibited the infection to less than 15% in both experiments.

Example 4

Action against Pythium debaryanum on Beta vulgaris (sugar beet)

a) Effect after floor application

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

The pots are then placed in the greenhouse at 20-24 ° C for 2-3 weeks. The earth is kept evenly moist by lightly spraying it with water. When evaluating the tests, the emergence of the sugar beet plants and the proportion of healthy and sick plants are determined.

After treatment with the active ingredients of formula I, more than 80% of the sugar beet plants emerged and had a healthy appearance. This result was also achieved with an active substance concentration in the soil of 6 ppm when using the compounds with the designations a, d, e, i, k, n and others.

6

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b) Effect after pickling application

The mushroom is cultivated on sterile oat grains and added to a soil-sand mixture. The soil infected in this way is filled into flower pots and sown with sugar beet seeds which have been stained with the test preparations formulated as mordant powder (1000 ppm of active ingredient based on the seed weight). The sown pots are placed in the greenhouse at 20-24 ° C for 2-3 weeks. 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 sick plants are determined.

After treatment with the active compounds of the formula I 5, both under test conditions a) and b), more than 80% of the sugar beet plants emerged and had a healthy appearance.

10th

s

Claims (5)

633 677 2. Composition according to claim 1, characterized in that in the active compounds of the formula IR are methyl, Rx is methyl, ethyl, chlorine or bromine, R2 is hydrogen, halogen or methyl and R3 is hydrogen or methyl, while R4 is for formula I in claim 1 has the meaning given. 2nd PATENT CLAIMS 1. Microbicidal agent containing, as at least one active component, a compound of the formula I (I) contains what R Q-Q-alkyl, Cj-Q-alkoxy or halogen, Rj Ci-C3-alkyl, Cj-Q-alkoxy or halogen, R2 hydrogen, Cj-Cj-alkyl, C1-C4-alkoxy or halogen, R3 are hydrogen or methyl, the total number of carbon atoms of the substituents R, R1; R2 and R3 in the phenyl ring do not exceed 8, R4 is hydrogen or methyl. 3,633,677 22. The method according to claim 21, characterized by treating plants, parts of plants or their surroundings with a compound of the formula I according to one of claims 2 or 3. 3. Composition according to claim 1, characterized in that it contains as active ingredient at least one compound of the formula I which is selected from the series 3- [N- (1,2-pyrazol-1-ylacetyl) -N- (2, 3,6-trimethylphenyl)] - amino-tetrahydro-2-furanone, 3- [N- (1,2-pyrazol-l-ylacetyl) -N- (2,6-dimethylphenyl)] - ami- no-tetrahydro-2-furanone, 3- [N- (1,2-pyrazoI-1-ylacetyl) -N- (2,3,5,6-tetramethylphenyl)] - amino-tetrahydro-2-furanone. * 4 (II) in a temperature range from 0 to 180 ° C with a carboxylic acid of the formula / = HO-CO-CH -N XNr or its acid anhydride, its ester or acid halide of the formula III Hai1 -CCH, (III) acylated, where R, Rl5 R2, R3 and R4 have the meanings given for formula I, while Hai 'represents a halogen atom. 5. The method according to claim 4, characterized in that it is carried out in the presence of an inert, organic solvent. CO-CH2-Hal "(IV) monohaloacetylated and further reacting the latter with 1,2-pyrazole or its metal salt, where R, Rx, R2, R3 and R4 45 have the meanings given for formula I, while Hai "represents a halogen atom. 13. The method according to claim 12, characterized in that it is carried out in the presence of an inert, organic solvent. 14. Process according to claim 12 or 13, characterized in that the reaction is carried out at a temperature of 20 to 120 ° C. 15. The method according to any one of claims 12 to 14, characterized in that the introductory monohalo- 55 acetylation with the acid chloride or acid bromide of the acid HOOC-CH2-Hal ", where shark" denotes a halogen atom. 16. The method according to any one of claims 12 to 15, characterized in that the reaction in the presence 60 an acid-binding agent. 17. The method according to any one of claims 12 to 15, characterized in that one carries out the reaction in the presence of dimethylformamide. 18. The method according to any one of claims 12 to 15, characterized in that nitrogen gas is passed through the reaction mixture. 19. The method according to any one of claims 12 to 18, characterized in that introductory to a Zwi The product of the formula IV is monohaloacetylated, in which shark means chlorine or bromine. 20. The method according to any one of claims 12 to 19, characterized in that one produces a compound of formula I according to one of claims 2 or 3. 21. A method for combating phytopathogenic fungi or for preventing fungal attack, characterized by treating plants, parts of plants or their surroundings with a compound of the formula I according to claim 1. 4. A process for the preparation of compounds of formula I according to claim 1, characterized in that a compound of formula II R R 2. , 1 0 =; 0 6. The method according to claim 4 or 5, characterized in that one carries out the reaction at a temperature of 20 to 120 ° C. 7. The method according to any one of claims 4 to 6, characterized 5, that with an acid halide Formula III acylated, wherein shark 'is chlorine or bromine. 8. The method according to any one of claims 4 to 7, characterized in that one carries out the reaction in the presence of an acid-binding agent. io 9. The method according to any one of claims 4 to 7, characterized in that one carries out the reaction in the presence of dimethylformamide. 10. The method according to any one of claims 4 to 7, characterized in that nitrogen gas is passed through the rice action mixture. 11. The method according to any one of claims 4 to 10, characterized in that a compound of formula I according to one of claims 2 or 3 is prepared. 12. Process for the preparation of compounds of 2o Formula I according to claim 1, characterized in that initially a compound of formula II 25th CID 30 "1 with a halocarboxylic acid of the formula HOOC-CH2-Hal ", its ester, acid anhydride or acid halide to give an intermediate of formula IV R O NH—! 23. The method according to spoke 21, characterized in that the phytopathogenic fungi belong to the family of Ascomycetes, Fungi imperfecti, Basidiomycetes or Oomycetes.