CH636093A5 - MICROBICIDAL AGENTS. - Google Patents

Description

The present invention relates to compounds of the formula I.

0 = -

wherein

R Cj-Cj-alkyl, CrC4-alkoxy or halogen,

Rj is hydrogen, Ci-C3-alkyl, CrC4 alkoxy or halogen, R2 is hydrogen, C1-C3-alkyl, or halogen, and R3 are hydrogen or methyl, the total number of C atoms of the substituents R, R1 (R2 and R3 im Phenyl ring does not exceed 8, while R4 and R5 are independently hydrogen or methyl,

Process for the preparation of these compounds and agents which contain these compounds as active compounds, and the use of these active compounds as microbicides in crop protection.

Depending on the number of carbon atoms specified, alkyl or an alkyl part of an alkoxy group means the following groups: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. Butyl or tert. Butyl.

Halogen is 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 are derived from the structure of benzoyl, alkanoyl or haloalkanoyl (especially haloacetyl) derive from anilides. Anilides of this type are very widely described in the literature as herbicides, e.g. U.S. Patent 3,403,994, U.S. Patent 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.

It is therefore not surprising that the compounds mentioned in US Pat. No. 3,933,860 are suitable for the plants to be protected against fungal attack with those necessary for practical use

Application rates in part cause undesirable phytotoxicity.

It has now surprisingly been found that compounds with the structure of the formula I have a microbicide spectrum for protection which is very favorable for practical needs

(IV)

of crops without adversely affecting them through undesirable side effects. In the context of the present invention, crop plants are, for example, cereals, maize, rice, vegetables, sugar beets, soybeans, peanuts, fruit trees, ornamental plants, but above all vines, hops, cucumber plants (cucumbers, pumpkins, melons), Solanaceae such as potatoes, tobacco and tomatoes, as well as banana, cocoa and natural rubber plants. With the active ingredients of the formula I, the fungi which occur on plants 15 or parts of plants (fruits, flowers, leaves, stems, tubers, roots) of these and related crops can be contained or destroyed, with growing parts of the plants being spared by such fungi. The active substances are effective against the phytopathogenic fungi belonging to the following 20 classes: Ascomycetes (e.g. Erysiphaceae); Basidiomycetes such as especially rust fungi; Fungi imperfecti (e.g. Moniliales); then especially against the Oomycetes belonging to the class of the Phycomyce-tes such as Phytophthora, Peronospora, Pseudoperonospora, Pythium or Plasmopara. In addition, the compounds of the formula I have a systemic action. They can also be used as dressings for the treatment of seeds (fruits, tubers, grains) and plant cuttings to protect against fungal infections and against phytopathogenic fungi occurring in the soil.

Preferred plant fungicides are compounds of the formula I in which R is methyl, Rt is methyl, ethyl or chlorine, R2 is hydrogen, halogen or methyl and R3 is hydrogen (I) or methyl, while R4 and R5 have the meaning given for formula I 35.

Important individual compounds are, for example: 3- [N- (hydroxyacetyl) -N- (2,3,6-trimethylphenyl)] - amino - tetrahydro-2-furanone

3 - [N- (Hydroxy acetyl) -N- (2,6-dimethyl-3-chlorophenyl)] -40-amino-tetrahydro-2-furanone

3- [N- (Hydroxyacetyl) -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

45

50

55

0

0

NH—

R,

(Ii)

60

with a compound of formula III

Shark'-CO-CH-O-CO-R6

I.

R,

(III)

and mild alcoholysis, if appropriate, of alcoholate at room or slightly elevated temperature, where R6 is a never-65 aliphatic radical, preferably methyl or ethyl, or

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

636093

N

CO-CH shark

R

2nd

R

3rd

and exchange of the halogen atom Shark "for the acid residue of an acid HOCO-Rs 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.

In formulas II, III and IV, R to R5 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; 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, but advantageously the acid anhydrides or the acid halides, can be used. The acid chlorides or acid bromides are preferred as acid halides.

The reaction temperatures are between 0 ° and 120 ° C, preferably between 0 ° and 50 °. 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 on the preparation of intermediates of the formula II are known from US Pat. No. 3,933,860.

The compounds of formula I have a (*) in the lactone radical and a second (**) center of asymmetry in the case of R4 = CH3 and can be cleaved into optical antipodes in the usual way (e.g. fractional crystallization or chromatographic separation). The different configurations have different levels of microbicidal activity.

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 examples serve to explain the invention in more detail without restricting it. The temperature specifications relate to degrees Celsius.

example 1

a) Preparation of the intermediate

3- [N- (Acetoxyacetyl) -N- (2,3,6-trimethylphenyl)] amino - tetrahydro-2-furanone

59.1 g of 3- [N- (chloroacetyl) -N- (2,3,6-trimethylphenyl)] - amino-tetrahydro-2-furanone were treated with 37.7 g of sodium acetate in 150 ml of abs. Dimethylformamide heated to 110 ° for 48 hours. It was then cooled, poured onto ice water, taken up in methylene chloride and separated. The aqueous phase was extracted three more times with methylene chloride, the combined extracts washed three times with water, dried over sodium sulfate and evaporated. Then the last traces of dimethylformamide were removed at 90 ° in a high vacuum and ether and petroleum ether were added to the brown oil, crystallization taking place. Recrystallized from isopropanol with the aid of activated carbon, the product obtained as a mixture of diastereomers melted at 100-102 °.

b) Production of the final product

3- [N- (Hydroxyacetyl) -N- (2,3,6-trimethylphenyl)] - amino - tetrahydro-2-furanone [Verb. 2]

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

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

4th

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

5

636093

produced:

R3

R1

• c

II 0

-CH-OH

i

R

5

Verb.No.

R

Ri

R2

Rs

R4

Rs

Physical. Data

1

ch3

oh3

h h

h h

M.p. 169-170 °

2nd

ch3

ch3

3-ch3

H

h h

M.p. 151-154 °

3rd

ch3

oh3

3-ch3

5-ch3

h h

M.p. 125-130 °

4th

ch3

ch3

3-c1

H

h h

M.p. 125-130 °

5

ch3

oh3

h h

ch3

H

M.p. 140-145 °

6

ch3

ch3

h h

ch3

ch3

M.p. 128-133 °

7

ch3

C2hs h

H

h h

Mp 153-157 °

8th

ch3

ch3

4-cl h

h h

Mp 179-183 °

9

ch3

ch3

4-Br h

h h

M.p. 192-201 °

10th

ch3

cl h

H

h h

Mp 153-155 °

11

ch3

och3

h h

h h

Mp 179-180 °

12

ch3

ch3

3-ch,

H

ch3

H

M.p. 127-131 °

13

ch3

ch3

3-ch3

5-ch3

ch3

H

M.p. 116-119 °

14

C3H, (i)

C3H, (i)

H

H

H

H

resin

15

ch3

Br

4-Br

H

H

H

viscos

16

ch3

ch3

3-cl

H

ch3

H

M.p. 157-160 °

17th

ch3

ch3

3-ch3

H

H

ch3

M.p. 120-122 °

The compounds of formula I can be used alone or 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 or fertilizers.

The active substance content in commercially available agents is between 0.1 and 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):

Solid processing forms: dusts and scattering agents (up to 10%) granules, coating granules, impregnation granules and homogeneous granules (1 to 80%);

Liquid processing forms:

a) Active ingredient concentrates dispersible in water:

Wettable powders and pastes (25-90% in retail packaging, 0.01 to 15% in ready-to-use solution);

so 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: 60 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.

65

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

636093

6

Granules:

The following substances are used to produce 5% granules:

5 parts of active ingredient 0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol and 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 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 prepare a) 70% b) 40% c) and d) 25% e) 10% wettable powder:

a)

70

Parts

Active ingredient

5

Parts

Sodium atrium dibutylnaphthyl sulfonate,

3rd

Parts

Naphthalenesulfonic acids-phenolsulfonic acids-

Formaldehyde condensate 3: 2: 1,

10th

Parts

Kaolin,

12

Parts

Champagne chalk;

b)

40

Parts

Active ingredient

5

Parts

Lignin sulfonic acid sodium salt,

1

part

Dibutylnaphthalenesulfonic acid sodium salt,

54

Parts

Silica;

c)

25th

Parts

Active ingredient

4.5

Parts

Calcium lignin sulfonate,

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)

25th

Parts

Active ingredient

2.5

Parts

Isooctylphenoxy-polyoxyethylene-ethanol,

1.7

Parts

Champagne chalk / hydroxyethyl cellulose

Mixture (1: 1),

8.3

Parts

Sodium aluminum silicate,

16.5

Parts

Diatomaceous earth,

46

Parts

Kaolin;

e)

10th

Parts

Active ingredient

3rd

Parts

Mixture of saturated sodium salts

Fatty alcohol sulfates,

5

Parts

Naphthalenesulfonic acid / formaldehyde con

densat,

82

Parts

Kaolin;

The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. This gives wettable powders of excellent wettability and suspension, which can be diluted with water to form suspensions of any desired concentration and can be used in particular 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 alkyl aryl sulfonate / fatty alcohol polyglycol

colether mixture,

5 parts of dimethylformamide,

57.5 parts xylene.

This concentrate can be used to prepare emulsions of any desired concentration by dilution with water, 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

Ia) Residual preventive effect

After three weeks of cultivation, tomato plants of the "Red Gnome" variety are sprayed with a broth containing 0.06% active ingredient (made from the active ingredient made up into a wettable powder) and dried with a zoospore suspension of Phytophthora infestans. They then remain in a climatic chamber at 18 to 20 ° and high humidity for 6 days, which is generated by means of an artificial spray. After this time, typical leaf spots appear. Their number and size are the benchmark for the tested substance.

Ib) 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%. 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.

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 waiting three days, 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.

In these three experiments, the compounds of the formula I show good foliar fungicidal activity. With the compounds No. 1, 2, 3, 4, 5, 11, 12, 13 and 16, the fungal attack is completely prevented.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

7

636 093

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 (0.02% active ingredient) prepared from the active ingredient formulated as 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 substances tested.

b) Curative effect

“Chasselas” vine cuttings were grown in the greenhouse and infected in 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 the formula I showed good foliar fungicidal effects in these two experiments. The vine plants looked healthy.

In experiment a) the compounds Nos. 2 and 12 both showed 0.02%. as in 0.006%. Concentration a complete prevention of fungal infection.

Example 4

Action against Pythium debaryanum on Beta vulgaris (sugar beet)

5 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 a 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.

20 Treatment with compound

% healthy plants

1

85%

25 3

80%

4th

100%

5

85%

30th

80%

16

100%

b) Effect after pickling application 35 The fungus 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 dressed 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 one of the active ingredients Nos. 1 to 17 of the formula I, more than 80% of the sugar beet plants emerged and had a healthy appearance.

40

45

V

Claims (16)

636093 2. Compounds of formula I according to claim 1, in which R is methyl, Rj is methyl, ethyl or chlorine, R2 is hydrogen, halogen or methyl and R3 is hydrogen or methyl, while R4 and R5 are independently hydrogen or methyl. 2nd PATENT CLAIMS 1. Compounds of the formula 0 =, 0 (I) R2 is hydrogen, C1-C3-alkyl, or halogen, and R3 is hydrogen or methyl, the total number of C atoms of the substituents R, R1: R2 and R3 in the phenyl ring not exceeding 8, while 5 are R4 and R5 are independently hydrogen or methyl, characterized by acylation of a compound of formula II R, R 3rd 636 »93 and exchange of the halogen atom Shark "for the acid residue of an acid HOCO-R6 with the aid of the acid itself or one of its salts, and subsequent mild alcoholysis in the presence of alcoholate at room temperature or slightly elevated temperature, the formulas II and IV being R to R5 have meanings given for formula I, while shark "stands for halogen. 3. 3- [N- (Hydroxyacetyl) -N- (2,3,6-trimethylphenyl)] - amino-tetrahydro-2-furanone as a compound according to claim 1. 4. 3- [N- (Hydroxyacetyl) -N- (2,6-dimethyl-3-chlorophenyl)] - amino-tetrahydro-2-furanone as a compound according to claim 1. 5. Plant microbicidal agent, characterized in that it contains as active component a compound of formula I according to claim 1 together with suitable carriers. 6. Composition according to claim 5, containing as the active component a compound according to claim 2. 7. Composition according to claim 5, containing as the active component a compound according to claim 3. 8. Composition according to claim 5, containing as the active component a compound according to claim 4. 9. A method for combating phytopathogenic fungi, characterized by application of a compound of formula I of claim 1. 10. The method according to claim 9, characterized by application of a compound according to claim 2. 10th where R, R CrC4-alkyl, Cj-Q-alkoxy or halogen, 15 R is hydrogen, CrC3-alkyl, Q-C4-alkoxy or halogen, R2 is hydrogen, CrC3-alkyl, or halogen, and R3 is hydrogen or methyl, the total number of C atoms of the substituents R, R1; R2 and R3 in phenyl ring does not exceed 8, while R4 and R5 are independently hydrogen or methyl. 11. The method according to claim 9, characterized by application of a compound according to claim 3. 50 12. The method according to claim 9, characterized by application of a compound according to claim 4. 13. Process for the preparation of a compound of formula I. NH-1 R, (Ii) with a compound of formula III 20 sharks'-CO-CH-O-CO-R6 I. R5 (III) and mild alcoholysis in the presence of alcoholate at room temperature or slightly elevated temperature, where R6 is a lower aliphatic radical and the substituents R to R5 in the formulas II and III have the meanings indicated under formula I, while Hai 'is halogen. 30th 14. The method according to claim 13, characterized in that a compound of the formula III is used in which R6 is methyl or ethyl, R5 is as defined under formula I and Hai 'is chlorine or bromine. 15. Process for the preparation of a compound of formula 35 40 45 (I) 55 worm R C1-C4-alkyl, Cj-Q-alkoxy or halogen, Rj is hydrogen, Cj-C3-alkyl, C1-C4-allcoxy or halogen, R2 is hydrogen, C1-C3 alkyl, or halogen, and R3 are hydrogen or methyl, the total number of C atoms of the substituents R, R1; R2 and R3 do not exceed 8, while R4 and R5 are independently hydrogen or methyl, characterized by initial monohaloacylation of a compound of formula II (I) 60 65 wherein R CrC4-alkyl, Q-Q-alkoxy or halogen, Rj hydrogen, Cj-co-alkyl, CrC4-alkoxy or halogen, (II) to a compound of formula IV 16. The method according to claim 15, characterized in that one starts from a compound of formula IV, wherein R to R5 are as defined under formula I and shark "chlorine or bromine.