CH630230A5 - Fungicidal composition - Google Patents

Description

The present invention relates to a fungicidal agent which contains 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) -y-butyrolactone or 3- (N-chloroacetyl-N-2,6-dimethylamino) as an active ingredient. Contains 5-methyl-y-butyrolactone. The agents are particularly effective, for example, for preventing and eradicating false mildew and rotting diseases on crowns and roots by phytophthora.

U.S. Patent Nos. 3,933,860 and 4,012,519 describe the use of a large class of 3- (N-acyl-N-arylamino) lactones and 3- (N-acyl-N-arylamino) lactams as protective fungicides. Nothing is said in these patents about a curative or eradicating fungicidal activity for any of the 3- (N-acyl-N-arylamino) lactones or -lactams of these patents.

British Patent 1,445,387 and US Patent 4,015,648 describe the use of N- (methoxycarbonylethyl) -N-haloacetylanilines as preventive and curative fungicides. However, comparative trials have determined that an active compound of the present invention is significantly more potent than eradicating or healing fungicide than the fungicides of these patents.

DE-OS 2 643 403 and 2 643 445 describe the use of N- (alkylthiocarbonylethyl) acetanilides for combating fungi, in particular those of the class Phycomycetes.

NL-OS 152 849 describes the use of N- (alkoxymethyl) acetanilides as fungicides.

According to the present invention, it was found that fungicidal agents containing 3- (N-chloroacetyl-N-2,6-dimethyl

5ch-r

40 wherein R represents a hydrogen atom or the methyl group contains as at least one active component.

The fungicidal agent according to the invention can be used to control false mildew infections caused by the fungal family of the Peronosporaceae and by putrefactive diseases on crowns and roots caused by fungi of the Phytophthora family that live in the ground.

The compounds of formula (I) are described in U.S. Patent 3,933,860.

The fungicidal compositions of the present invention are typically effective in combating false mildew diseases caused by fungi of the Peronosporaceae family and putrefactive diseases on crowns and roots caused by soil-dwelling fungi of the Phytophthora species .

Downy mildew is a widespread group of diseases in plants that grow, for example, in the cold, humid areas of the world. Downy mildew diseases generally include downy mildew on lettuce caused by the Bremia lactucae species; downy mildew on spinach caused by the species Peronospora effusa; downy mildew on 65 onions caused by the P. destructor species; downy mildew on soybeans caused by the P. manshurica urica species; downy mildew on cauliflower caused by the P. parasitica species

becomes; downy mildew on cabbage, which is caused by the species P. parasi-tica ssp. brassicae is evoked; downy mildew on tobacco plants caused by the species P. tabacina; downy mildew on Lucerne caused by the P. tri-foliorum species; downy beet powdery mildew caused by P. schactii; downy mildew on lima beans caused by the species Phytophthora phaseoli; downy mildew on grapevines caused by the Plasmopara viticola species; downy mildew on watermelons, cucumbers, pumpkins and related plants caused by the species Pseudo-peronospora cubensis; and downy mildew on hops caused by the species Pseudoplasmopara humuli.

Fungi of the genus Phytophtora, which live in the ground or are in the ground, generally cause various putrefactive diseases on the crowns and roots of the plants. They are usually extremely difficult to control with the help of fungicides because the location of the fungus is the soil. Soil treatment to control the fungus is generally not effective because many fungicides are not effectively distributed in the soil and / or are detoxified in the soil. Fungi that inhabit the soil can be exposed to systemic fungicides, i.e. a fungicide that moves down to the roots of the plant after application of the fungicide to the foliage of the plant. For example, many fungicides that are effective in controlling Phytophthora do not have a downward systemic activity. For example, the fungicidal agents of the present invention are systemically active upward from the roots to the foliage and downward from the foliage to the roots. The fungicidal compositions according to the invention are also preferably not detoxified by the soil and are rapidly absorbed by the roots of the plants. Thus, for example, the fungicidal compositions of the present invention are highly effective in controlling soil-dwelling fungi of the Phytophthora genus.

The types of Phytophthora that cause putrefaction on the crowns and roots of plants include, for example, Phytophthora cactorum (crown rot from walnut trees, root rot from sweet clover [sweet-oves], root cancer from avocato pear trees, collar rot from apple and pear trees); P. cambivora (citrus ink disease); P. capsici (root rot of pepper); P. cinnamoni (pineapple heart rot, Avocatos phytophthora root rot, citrus root rot); P. citricola (brown rot gummosis); P. citrophthora (root rot of citrus trees); P. cryptogea (crown and root rot of tomatoes, safflower and tobacco); P. dreschleri (root rot of safflower); P. erythrosytica (red rot of the potato); P. fragariae (red root rot of the strawberry); P. megosperma (rotten roots of cherries, peaches and walnuts); P. nicotianae (tobacco seedling disease); P. palmivora (root rot of citrus trees, bud rot of the coconut tree, cocoa cancer); P. parasitica (root rot of watermelons, root rot of citrus trees); and P. syringae (root rot of citrus trees).

The fungicidal compositions of the present invention are generally particularly useful fungicides because they cure pre-existing fungal infections. This enables, for example, an economical use of the fungicidal compositions according to the invention, since they only have to be applied to the plants when fungal infections have actually occurred. There is therefore usually no need for a preventive program of using fungicides against possible fungal infections.

630 230

Protective or preventive fungicidal agents and eradicating fungicidal agents generally react in completely different ways. For example, protective or preventive fungicides generally prevent fungal infection by preventing spore formation and / or infection, while eradicating fungicides cure fungal diseases after the host is already infected. Therefore, for example, it is highly surprising that the fungicidal agents of the present invention act both as protective and as eradicating fungicidal agents.

The fungicidal compositions according to the invention are preferably applied in fungicidally effective amounts to the fungi and / or their sites, e.g. vegetative host plants and their growth medium or environment, applied. The amount used will, of course, generally depend on various factors, e.g. the host, the type of fungus and the particular composition of the agent according to the invention. The fungicidal compositions of the present invention generally contain conventional, biologically inert extenders or carriers which are commonly used to facilitate the dispersion of the active fungicidal ingredient, it being understood that the formulation and mode of application can affect the effectiveness of the fungicide . Thus, the fungicidal compositions of the present invention can be granules, powdered dust preparations, wettable powders, emulsifiable concentrates, solutions or one of various other known types of formulations, depending on the desired type of application.

Wettable powders are usually in the form of finely divided particles that are easily dispersed in water or other dispersing agents. These agents generally contain about 5 to 80% of the fungicidal active ingredient, the remainder being inert material, which includes dispersants, emulsifiers and wetting agents. The powder can be applied to the floor in the form of a dry dust or, preferably, as a suspension in water. Typical carriers include fuller earth, kaolin clays, silica and other highly absorbent, wettable, inorganic diluents. Typical wetting, dispersing or emulsifying agents include e.g. the aryl and alkylaryl sulfonates and their sodium salts, the alkylamide sulfonates including the fatty acid methyl taurides; the alkylaryl polyether alcohols, sulfated higher alcohols and polyvinyl alcohols; Polyethylene oxides, sulfonated animal and vegetable oils; sulfonated petroleum products; Fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long chain mercaptans and ethylene oxide. Many other types of useful surfactants are commercially available. The surfactant, when used, usually makes up 1 to 15% by weight of the fungicidal agent.

Dust preparations are preferably free-flowing mixtures of the active fungicidal component with finely divided solids, e.g. Talc, natural clays, diatomaceous earth, pyrophyllite, chalk, diatomaceous earth, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours and other organic and inorganic solids, which serve as dispersants and carriers for the fungicidal active ingredient. These finely divided solids, for example, have an average particle size below approximately 50 μm. A typical dust preparation which can be used in the context of the present invention contains, for example, 75% of silica and 25% of the fungicidal active ingredient.

3rd

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

630 230

The usable liquid concentrates generally include the emulsifiable concentrates, which consist of homogeneous liquid or pasty compositions which are easily dispersed in water or other dispersants and which can consist exclusively of the fungicidal active ingredient and a liquid or solid emulsifier, or else a liquid carrier , such as Xylene, heavy aromatic hydrocarbons, isophorone and other non-volatile organic solvents. For use, these concentrates are normally dispersed in water or another liquid carrier and then usually applied in the form of a spray to the area to be treated.

Other useful formulations for fungicidal use forms include, for example, simple solutions of the fungicidal active ingredient in a dispersant in which it is completely soluble in the desired concentration, such as e.g. Acetone, alkylated naphthalenes, xylene or other organic solvents. Granulated formulations in which the fungicidal active ingredient is carried on relatively coarse particles are usually of particular utility for distribution from the air or for penetration of a cover of a protective fruit (cover crop canopy). Spray mist under pressure, e.g. Aerosols in which the active ingredient is in a particulate form as a result of evaporation of a low boiling dispersing solvent such as e.g. the freons being dispersed can also be used. All of these techniques for formulating and applying fungicides are normally known.

The amount of the fungicidal active ingredient in percent by weight can vary, depending on the manner in which the agent is used and the particular type of formulation, but in general an amount of 0.5 to 95% by weight of the fungicidal Active ingredient, based on the fungicidal agent, is used.

The fungicidal compositions can be formulated and used with other active ingredients including other fungicides, insecticides, nematocides, bactericides, plant growth regulators, fertilizers, etc.

The preparation, formulation and use of the fungicidal compositions according to the invention are explained in more detail in the examples below.

Example I

Preparation of 3- (N-chloroacetyl-N-2,6-dimethyl-phenylamino) -y-butyrolactone (Compound A)

A solution of 410 g (2 moles) of N-2,6-dimethylphenylamino-y-butyrolactone (mp. 85 to 86.5 ° C) and 197.5 g (2.5 moles) of pyridine in 2 liters of benzene was added heated to reflux temperature. This solution was then added dropwise over the course of 40 minutes with 260 g (2.3 mol) of chloroacetyl chloride. The reaction mixture was refluxed for a further 20 minutes, cooled and filtered to remove a precipitate from pyridine hydrochloride. The filtrate was washed with water, dried over magnesium sulfate and evaporated under reduced pressure to give a colorless white solid. The solid was slurried in isopropanol, filtered and dried to give 501 g of the product as a colorless solid with a melting point of 145.5 to 147 ° C.

The product had an oral LD50 of> 1000 mg / kg and a dermal LDS0 of> 2000 mg / kg in rats.

Example 2

Preparation of 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) -5-methyl-y-butyrolactone (Compound B) A 500 ml round bottom flask equipped with a two-way cock was charged with 24.2 g ( 0.2 mol) of 2,6-dimethyl-aniline and 19.0 g (0.106 mol) of a-bromo-y-valerolactone. The flask was evacuated to 20 mm Hg and then slowly heated to 100 ° C, periodically evacuated using a water jet pump to maintain the pressure at about 17 to 40 mm Hg. After the reaction mixture was heated to about 100 ° C at 27 to 40 mm Hg for 22 hours, it was cooled and diluted with 300 ml of ethyl ether. A solid precipitate of 2,6-dimethylaniline hydrobromide was removed by filtration. The filtrate was washed first with a 5% aqueous hydrochloric acid solution and then with water, dried over magnesium sulfate and evaporated under reduced pressure, 19.2 g of 3- (N-2,6-dimethylphenylamino) -5-methyl -y-butyrolactone were obtained in the form of a viscous oil.

A sample of 10.9 g (0.096 mol) of chloroacetyl chloride slowly became a solution of 19.2 g (0.088 mol) of 3- (N-2,6-dimethylphenylamino) -5-methyl-y-butyrolactone and 7.6 g (0.096 mol) of pyridine in 250 ml of ethyl acetate. An exothermic reaction occurred and a precipitate formed. After the reaction mixture was stirred at about 20 ° C for 16 hours, it was washed first with water, then with a saturated aqueous sodium bicarbonate solution, and then again with water, dried over magnesium sulfate, and evaporated under reduced pressure to give a thick oil which crystallized from ethyl ether and gave a yellow solid. The yellow solid was washed with a cold mixture of ethyl ether and petroleum ether and air-dried, with 15.8 g of 3- (N-chloroacetyl-N-2,6-dimethyl-phenylamino) -5-methyl-y-butyrolactone a melting point of 128 to 131 ° C were obtained.

Example 3

Formulation of a wettable powder A wettable powder containing 50% by weight of the active ingredient was prepared by adding 52.1 parts by weight of 3- (N-chloroacetyl-N-2,6-dimethyl-phenylamino) -y-butyrolactone (Purity 96%), 42.9 parts by weight of attapulgite clay and 5 parts by weight of a mixture of anionic surfactants, lignosulphonates and sodium stearate.

Example 4

Formulation of an Aqueous Flowable Preparation A flowable formulation containing the active ingredient at 0.41 kg / liter was prepared by adding 44.22 parts by weight of 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) -y -butyrolactone (purity 96%), 43.43 parts by weight of water, 1.42 parts by weight of a foam inhibitor made of polyvinyl acetate and polyvinyl alcohol, 9.73 parts by weight of propylene glycol, 0.20 parts by weight of a thickening agent based on polysaccharide and 1 part by weight of a nonionic surface-active agent mingled.

Example 5

Preventing downy mildew on wine

The compounds A and B and various other structurally related compounds were tested for combating downy mildew on wine, caused by the organism Plasmopara viticola. Seven week old vine plants from

4th

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

5

630 230

Vitis vinifera, variety Emperor, namely their picked leaves with a diameter of 70 to 85 mm. The leaves were sprayed with a solution of the test compound in acetone. The sprayed leaves were dried, inoculated with a spore suspension of the organism, placed in a humid chamber and incubated at a temperature of 18 to 22 ° C and a relative humidity of about 100%. The extent of the control of the disease was determined 7 to 9 days after the inoculation. The percentage control of the disease achieved with the aid of a given test compound was determined on the basis of the reduction in the disease in percent, based on untreated test plants. The test compounds, test concentrations and results are summarized in Table I below.

Example 6

Eradicating downy mildew on wine Compounds A and B and various structurally related compounds were tested for eradicating downy mildew on wine caused by the organism Plasmopara viticola. Picked leaves with a diameter of 70 to 85 mm from 7-week-old wine plants Vitis vinifera, variety Emperor, were also used as host plants. The leaves were inoculated with the organism and placed in a humid chamber where they were incubated for two days at 18 to 22 ° C and a relative humidity of about 100%. The leaves were then sprayed with a solution of the test compound in acetone. The sprayed leaves were then kept at 18 to 22 ° C and a relative humidity of about 100%. The extent of the control of the disease was determined 7 to 9 days after the inoculation. The 15 percent disease control achieved by a given test compound was determined based on the percent reduction in disease based on untreated plants. The test compounds, test concentrations and results are summarized in Table I below.

Table I

Fighting downy mildew on wine with compounds of the formula:

CH CH2

O = C

, CH-R2

Rx R1 R2 Y Preventing eradication of downy mildew on wine

%

(ppm)

ED50 / 90 »

%

(ppm)

ED50 / 90

A

2,6- (ch3) 2

ch2c1

h o

97

M))

1.2 / 4.4

99

(6.4)

1/3

B

2,6- (ch3) 2

ch2ci ch3

0

80

(100)

8/100

99

(100)

7/28

95

(40)

1

3,4-Cl2

ch2ch3

h o

0

(100)

-

5

(40)

-

2nd

2,6- (ch3) 2

3,4-Cl2- $

H

0

-

-

29

(100)

-

3rd

2-CH30

ch2ci

H

0

0

(100)

-

12th

(100)

-

4th

2,6- (CH3) 2

ch2ci

H

nch3

-

-

3rd

(100)

-

5

H

ch2ci

H

0

-

-

0

(100)

-

6

2,6- (C2H5) 2

ch2ci

H

0

0

(100)

-

39

(100)

-

7

2-iC3H7

ch2ci

H

O

3rd

(100)

-

17th

(16)

-

8th

2-C2H5

ch2ci

H

O

0

(100)

0

(100)

-

9

2,6-Cl2

ch2ci

H

0

0

(100)

95 67

(100) (40)

35/70

10th

3,4-Cl2

ch2ci

H

0

89

(100)

66 107

39

(100)

-

11

3,5-Cl2

ch2ci

H

0

45

(100)

-

54

(100)

-

12th

2,6- (C2H5) 2

ch2ci ch3

0

-

-

87

(100)

38/100

13

2-CH3-6-C2H5

ch2ci

H

O

0

(100)

-

87

(100)

_

14

2-CH3-6-C2H5

ch2ci ch3

O

-

-

29

(100)

_

15

2,6- (CH3) 2

CH2Br h

0

-

-

54

(100)

84 / -

16

2,6- (CH30) 2

CH2C1

H

O

-

67

(100)

17th

2,6- (CH3) 2

ch2ch2ci

H

0

-

50

(100)

117/7

18th

2,6- (CH3) 2

ch2ci

H

NCH (CH3) 2

15

(100)

-

37

(100)

_

19th

2,6- (CH3) 2

CC1 = CC12

H

0

-

-

15

(100)

_

20th

2,6- (CH3) 2

CH2C1

H

nch2ch = ch2

-

-

0

(100)

21st

2,6- (CH3) 2

ch2ci

H

NH

-

-

0

(100)

_

22

2,6- (CH3) 2

ch2ci

H

N (3-CH3-4-Cl) -0

-

-

32

(100)

_

23

2,6- (CH3) 2

4-C1-0

nch3

nch3

-

-

0

(100)

-

24th

2,4,6- (CH3) 3

ch2ci

H

0

-

-

0

(100)

25th

2-CH3-6-t-C4H9

ch2ci

H

0

-

-

0

(100)

-

630230

Table I (continued)

No. R.

R2

Fighting downy mildew on wine

preventive

exterminating

%

(ppm)

ED5O / 9O *

%

(ppm) ED50 / 90

12th

(100)

_

87

(100)

78

(100)

32/152

96

(100)

84

(40)

22/54

74

(200) 100/310

100

(40)

2/13

100

(4 °) 5/19

92

(16)

86

(16)

H

O

26 3,4- (CH3) 2 CH2C1

27 open chain esters **

28 Captafol ***

29 Bordeaux mixture (water as solvent)

* ED50 (ppm of spray applied for 50% control) ® phenyl

ED90 (ppm of spray applied for 90% control) ** N- (l-methoxycarbonylethyl-Na-chloroacetyl-2,6-dimethylaniline (GB-PS 1445 387) *** cis-N- (l, l, 2 , 2-tetrachloroethylthio) -4-cyclohexene-l, 2-dicarboximide

Example 7

Preventing downy mildew on wine

A comparative test was carried out to evaluate the effectiveness of 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) -y-butyrolactone in combating downy mildew on wine, caused by Plasmopara viticola, with the effectiveness of two available fungicides. N- (Tri-chloromethylthio) phthalimide (Folpet) and cis-N- (1,1,2,2-tetrachloroethylthio) -4-cyclohexene-1,2-dicarboximide (Captafol) were used as commercial fungicides. The test was carried out as follows.

Picked leaves from three-month-old Cabernet Sauvignon vine plants were used as host plants. Four leaves were used in each test. The leaves were sprayed with a solution of the test compound in a solution of 1% acetone and 99% water containing 40 ppm of a nonionic surfactant. The sprayed leaves were dried and inoculated with 25 drops of a spore suspension of the organism (400,000 conidia / milliliter water). After inoculation, the leaves were kept in a very humid chamber. The extent of the control of the disease was determined after 10 days. The percent disease control achieved by the test compound was determined from the percent reduction in disease compared to untreated leaves. The test compound, test concentration and percent control are summarized in Table II below.

Tables

Preventing downy mildew on wine

20 ■

Test compound percentage control

40 ppm 16 ppm 6.4 ppm

Compound A 100 100

25 Folpet 97.7 98.8

Captafol 96.5 98.8

100 80.1 95.3

Example 8 Fermentation Test 30 To determine the influence of 3- (N-chloroacetyl-N-2,6-dimethyl-phenylamino) -y-butyrolactone (Compound A) on yeasts which are responsible for the alcoholic fermentation of wine performed in vitro test as follows:

35 Erlenmeyer flasks with a capacity of 500 cm3 were filled with 200 cm3 of grape juice (density 1.07 g / cm3), which had been extracted from grapes from Madeleine Angevine grapes. The test compound was added to the grape juice and then the extent of the fermentation was determined by determining the cumulative weight loss due to the volatilization of carbon dioxide. For comparison purposes, the test was carried out on an untreated sample and with a commercially available fungicide. The concentration of the 45 test compound and the results from the first 8 days of fermentation are summarized in Table III below.

Concentrated cumulative weight loss (in g) added by C02 volatilization after Table III fermentation test

Product ppm

1 day

2 days

3 days

4 days

7 days

8 days

Compound A

1

0.9

5.0

10.5

11.3

14.2

14.5

2nd

0.8

5.2

10.4

11.1

13.4

13.7

4th

1.0

5.2

10.4

11.1

13.1

13.3

8th

1.0

5.4

11.0

11.8

14.5

15.2

commercially available

1

0.4

0.5

2.8

3.6

8.9

10.1

fungicide

2nd

0.2

0.4

1.3

1.8

4.7

5.6

4th

0.4

0.4

0.7

0.8

2.1

3.1

8th

0.3

0.4

0.7

0.7

1.2

1.5

none

-

0.9

5.4

11.1

11.6

14.2

14.5

Example 9 butyrolactone (Compound A) and various commercially

Eradicating control of downy mildew Available fungicides have been put on their eradicating control

3- (N-chloroacetyl-N-2,6-dimethylphenylamino) yung of downy mildew (caused by plasmopa-

ra viticola) tested on vine leaves. The following commercially available fungicides were used: cis-N- (1,1,2,2-tetrachloroethylthio) -4-cyclohexene-1,2-dicarboximide (Captafol); Triphenyltin acetate (fentin acetate); 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil); and copper (II) sulfate.

Picked leaves from vine plants of the Carignane and Emperor varieties were used as host plants. The leaves were inoculated with the organism and placed in a humid chamber where they were left for 1 to 3 days (1 to 2 days for Emperor leaves, 3 days for Carignane leaves) at 18 to 22 ° C and relative humidity of about 100% were incubated. The leaves were then sprayed with a solution of the test compound in acetone. The sprayed leaves were then kept at 18 to 22 C and a relative humidity of about 100%. The extent of the control of the disease was determined 8 to 9 days after the inoculation. The percent disease control achieved with a given test compound was determined as the percentage reduction in disease compared to untreated control sheets. The test compound, the variety of the vine leaf, the duration of the treatment with the test compound (days after inoculation) and the results as ED50 values (ppm of spray applied for 50% control) and ED90 values (ppm of spray applied for 90 % control) are summarized in Table IV below:

Table IV

Eradicating control of downy mildew on wine

Test connection eradication ED50 / ED90

Emperor's leaves

Leaves of

Carignane

1 day

2 days

3 days

Compound A

9.3 / 58

27/99

20.7 / 113

Captafol

55/145

64/168

206/670

Fentin acetate

47/171

88/219

254/562

Chlorothalonil

128/293

410/1000 *

313/992

Copper (II) sulfate *

118/289

204/445

380/610

* Water as a solvent

Example 10

Eradicating control of downy mildew A preparation of 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) -y-butyrolactone in attapulgite clay consisting of a wettable powder was tested for the eradication control of downy mildew on vine leaves. Three-month-old Cabernet Sauvignon single-bud seedlings (grown in gravel) each containing 6 to 10 leaves were used as host plants. The undersides of the leaves were sprayed with a spore suspension of Plasmopara viticola, which contained 510,000 conidia per milliliter of water. The inoculated seedlings were placed in a cloud chamber. At four different times after the time of inoculation, an aqueous suspension containing 62.5 ppm of the test compound was sprayed onto the seedlings in an amount of about 3.5 ml per 100 cm 2 of leaf area. The extent of the control of the disease was determined 10 to 11 days after the inoculation. The percent disease control achieved by the test compound was determined as the percentage reduction in disease relative to untreated control seedlings. The results are summarized in Table V below.

630 230

Table V

Eradicating control of downy mildew on wine

Period between conc, at infected control

Inoculation and fungicide of leaf- the disease

Fungicide treatment (ppm) area (%) (%)

lung (in days)

1

0

21st

-

1

62.5

0.51

97.6

2nd

0

14.3

-

2nd

62.5

0.55

96.2

3rd

0

27.14

-

3rd

61.5

4.15

84.7

5

0

29.84

-

5

62.5

2.5

91.6

EXAMPLE 11 Remaining Preventive Control of Bottled Mildew on Wine A preparation of 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) -y-butyrolactone in attapulgite clay consisting of a wettable powder was tested for its remaining preventive control of downy mildew tested on vine leaves. Three-month-old Cabernet Sauvignon single-bud seedlings (grown in gravel) each containing 5 to 8 leaves were used as host plants. The seedlings were sprayed with an aqueous suspension containing 160 ppm of the test compound in an amount of about 4 ml per 100 cm 2 of leaf area. The seedlings were then placed in a humid chamber with a relative humidity of 90 to 95%. Three days after the fungicide treatment, the undersides of the leaves were sprayed with a spore suspension of Plasmopara viticola. The inoculated seedlings were then placed in a cloud chamber. The extent of the control of the disease was determined 8 to 10 days after the inoculation. The percent disease control achieved by the test compound was determined from the percent reduction in disease compared to untreated control seedlings. The results are summarized in Table VI.

Table VI

Remaining preventive control of downy mildew on wine

Period between conc, at infected control

Inoculation and fungicide of leaf- the disease

Fungicide treatment (ppm) area (%) (%)

lung (in days)

3 0 12.81

3 160 0.03 99.8

Example 12

Control of leaf infections with downy mildew by absorption by the roots A preparation of 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) -y-butyrolactone in attapulgite clay with an active substance content of 40% was made from a wettable powder the control of leaf infections with downy mildew on wine tested by absorption by the roots. Three-month-old Cabernet Sauvignon single-bud seedlings (grown in gravel) each containing 9 to 12 leaves were used as host plants. The roots of the seedlings were immersed in an aqueous suspension containing 50 ppm of the test compound for 6 hours. The seedlings were then re-planted in gravel and placed in a cloud chamber. At four different times after root canal treatment

7

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

630 230

8th

sprayed the undersides of the leaves with a spore suspension of Plasmopara viticola. The inoculated seedlings were brought into the cloud chamber to stimulate the development of the disease. The extent of the control of the disease was determined 10 to 12 days after the inoculation. The percent disease control achieved by the test compound was determined from the percent reduction in disease compared to untreated control seedlings. The results are summarized in Table VII.

Table VII

Fighting downy mildew on wine through absorption by the roots

Period between

Conc, to infected

Combat

Root canal treatment

fungicide

Leaf disease and inoculation

(ppm)

area (%)

(%)

(in days)

1

0

10.82

_

1

50

6.26

33.5

5

0

17.51

5

50

0.32

98

9

0

10.11

-

9

160

0.19

99

16

0

39.35

-

16

160

22.43

43

Example 13

Fighting down mildew on lettuce

A preparation of 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) -y-butyro-5 lactone in attapulgite clay with an active substance content of 50%, present as a wettable powder, was caused to combat downy mildew on lettuce tested by the organism Bremia lac-tucae.

Salad seeds (Marty variety) were sown in plastic boxes filled with a mixture of two thirds compost and one third sandy soil. The boxes were placed in a greenhouse at 17 to 24 ° C. 6 days after sowing, the salad seedlings (cotyledon 15 step) were sprayed with an aqueous suspension of the test compound in different test concentrations (1 box per concentration). One day after the application of the fungicide, the seedlings were sprayed with a spore suspension which contained 140,000 conidia of the organism per milliliter of 20 water. The seedlings were placed in a moist chamber at 12 to 14 ° C, which was kept under artificial light for 12 hours a day. Eight days after inoculation, the extent of the disease control was determined by counting the number of surviving seedlings per box. The results for the test compound, two commercially available preparations and two untreated control tests are summarized in Table VIII.

Table VIII Control of Downy Mildew on Salads

fungicide

Application ratio g active ingredient / hl

Total number of seedlings per box killed

Seedlings (%)

Control (%)

Test connection 25

Test connection 50

Test connection 100

Captafol 160

Maneb * 160

Control attempt without treatment - (not contaminated)

Control attempt without treatment - (contaminated)

* Manganese salt of ethylene bisdithiocarbamate Example 14

Preventive and curative control of downy mildew on cabbage

A preparation consisting of a wettable powder of 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) -y-butyrolactone in attapulgite clay with an active substance concentration of 50% was used to combat downy mildew on cabbage caused by the organism Pe-ronospora parasitica ssp. brassicae, tested.

Preventive control Cabbage seeds (Milan hatif d'Aubervilliers variety) were sown in flat plastic boxes containing a mixture of three parts compost and one part sandy soil. The seeded boxes were kept in a very humid greenhouse. 7 days after sowing, three boxes of cabbage seedlings were sprayed with an aqueous suspension of the test compound in various concentrations until the overflow. Two days after application of the fungicide, the boxes with the cabbage seedlings were washed with an aqueous suspension of the conidia (approx

689

5.9

75.8

780

1.1

90.6

780

2.3

95.5

614

3.6

85.2

422

14.5

40.6

363

1.9

-

427

24.4

-

300,000 per ml) of the organism sprayed. Eleven days after inoculation, the extent of the control of the disease was determined by counting the number of 50 sick seedlings covered with a white mycelium at the single-leaf stage. The results for boxes treated with the test compound, those treated with a commercially available preparation, and control boxes are shown in Table IX.

Healing treatment Cabbage seeds (Milan hatif d'Aubervilliers variety) 60 were sown in flat plastic boxes, each containing a mixture of three parts compost and one part sandy soil. The seeded boxes were kept in a very humid environment. 9 days after sowing, three boxes of cabbage seedlings were sprayed with an aqueous suspension of the conidia (about 300,000 per ml) of the organism. 4 days after the inoculation, the boxes were sprayed with 65 of an aqueous suspension of the test compound in various concentrations until it overflowed. The extent of the control of the disease was determined 7 days after application of the fungicide by

9

630 230

one counted the number of sick seedlings which were covered with a white mycelium at the single-leaf stage. The results for the test compound treated boxes, for boxes treated with a commercial product, and for control boxes are shown in Table IX below.

Table IX

Fighting downy mildew on cabbage

fungicide

Use ratio g active ingredient / hl preventive Total number of seedlings killed (%)

Combat * (%)

Connection A Connection A Connection A Captafol none / inoculates none / not inoculates

80 40 20 160

231 138 171 161 175 177

1.5 2.2 1.8 59.6 97.6 1.7

98.5 97.7 98.2 38.9

fungicide

Application ratio g active substance / hl healing total number of seedlings killed (%)

Combat * (%)

Connection A Connection A Connection A Captafol none / inoculates none / not inoculates

80 40 20 160

155 203 165 148

0.6 1.0 1.8 65.5

99.4 99.0 98.2 32.9

* Reduced disease compared to the control box that was not treated with fungicide.

Example 15

Fighting down mildew on cucumbers by treating the foliage

Compound A was tested for control of downy mildew on cucumbers, caused by the organism Pseudoperonospora cubensis, by applying a spray to the foliage.

A three-week-old cucumber plant (Marketeer variety) was sprayed with a solution of the test compound in a suspension of 1% acetone in 99% water containing 40 ppm of a nonionic surfactant. Four leaves were picked from the plant, dried and inoculated with a spore suspension of the organism by spraying. After inoculation, the leaves were kept in a very humid chamber at 20 to 25 ° C. The extent of the disease was determined after 6 days. The percent disease control achieved by the test compound was determined from the percent reduction in disease compared to untreated control sheets. The test compound, test concentration and percent control are summarized in Table X.

Table X

Fighting down mildew on cucumbers by spraying the foliage

Test connection

Conc, (ppm)

Control (%)

Connection A Connection A Connection A Maneb Maneb Maneb

100 40 16 100 40 16

100 88 63 98.3 90 80

Example 16

Control of crown and root rot on snapdragons Compound A was tested to determine its activity against crown and root rot on the snapdragon plants (variety Antirrhinum), caused by the organism Phytophthora cryptogea. The known preparations Captafol and Mancozeb were subjected to the same test for comparison purposes.

Soil irrigation treatment Four pots filled with young plants were transplanted into 13 cm soil infected with the organism. 40 ml of an aqueous solution of the test 45 compound containing 100 ppm of the test compound was poured into the pots. The plants were then kept in a greenhouse to develop the disease. 5 days after the treatment, the plants were assessed for leaf necrosis and withering and crown rot. The percent disease control achieved by the test compound was determined from the reduction in disease compared to untreated control plants. The results are summarized in Table XI.

55 Control by spraying the foliage

Young plants were transplanted into four 13 cm diameter pots filled with soil infected with the organism. The bottom was covered with a plastic film, and the foliage of the 60 plant was sprayed until an overflow with an aqueous suspension of the test compound containing 100 ppm of the test compound. The plants were then taken to a greenhouse where the disease could develop. 5 days after treatment 65, the plants were assessed for leaf necrosis and withering and crown rot. The percent disease control achieved by the test compound was compared to the reduction in disease

630 230

10th

untreated control plants determined. The results are summarized in Table XI.

Table XI

Control of crown and root rot on snapdragon

connection

Control (%) soil treatment

Spraying the foliage

A

Captafol Mancozeb *

100 0 0

97 0 0

* Mixture of manganese (II- [N, N'-ethylenebis (dithiocarbamate)] and zinc [N, N'-ethylenebis (dithiocarbamate)]

Example 17

Systemic treatment of the foliage to combat crown and root rot on safflower Compound A was tested to determine its systemic activity against crown and root rot, caused by the organism Phytophthora cryptogea, when applied to the foliage.

Two week old safflower seedlings were used as host plants. Pots containing the seedlings 5 were sprayed with an aqueous solution of the test compound at different test concentrations. A day after the treatment, a fungal culture of the organism was poured onto the soil surface in the pots. The mushroom culture was prepared by growing the organism in a mixture of oatmeal, potato dextrose and soil. The inoculated seedlings were then kept in a greenhouse where the temperature was 20 to 25 ° C during the day and 15 to 20 ° C at night. Three to four weeks after the inoculation, the plant roots 15 and crowns were assessed for pathological symptoms. The percentage disease control achieved by the test compound was determined from the percentage reduction in disease compared to untreated control plants. The test concentration and 20 percent disease control are summarized in Table XII.

Table XII

Control of crown and root rot on safflower by spraying the foliage

connection

Conc, ppm

Control (%)

Compound A

, ch:

0

M

ff \

ch-

"CCHaCl

■ chco2ch3 «

ch3

5-ethoxy-3-trichloromethyl-l, 2,4-thiadiazole **

** known from U.S. Patent 3,260,588 and 3,260,725 Example 18

Control of crown and root rot on safflower by systemic treatment using soil irrigation

Compound A was tested to determine its systemic activity against crown and root rot, caused by the organisms Phytophthora cryptogea and P. parasitica, when applied via soil irrigation.

Two week old safflower seedlings were used as host plants. Pots containing the seedlings were treated with an aqueous suspension of the test compound at various test concentrations (4 pots per concentration) by watering the soil. A day after the treatment, a fungal culture of the organism was poured onto the surface of the soil in the pots. The mushroom culture was prepared by growing the organism in a mixture of oatmeal, potato dextrose and soil. The inoculated seedlings were then kept in a greenhouse in which the temperature was 20 to 25 ° C. during the day and 15 to 20 ° C. at night. Three to four weeks after the inoculation, the plant roots and crowns were assessed for pathological symptoms. The percentage control of the disease achieved by the test compound was derived from the percentage reduction in

100 40 16

100 40 16

100 40 16

100 97 92

10 0 0

61 1 0

Disease determined in comparison to untreated control plants. The test concentrations and percent control of the disease are summarized in Table XIII.

Table XIII

Control of crown and root rot on safflower by soil irrigation

Concentration ppm. Control (%)

P. Cryptogea P. Parasitica

Compound A

5-ethoxy-3-tri-chloromethyl-1,2,4-60 thiadiazole **

** U.S. Patent 3,260,588 and 3,260,725

100 *

100

100

40

97

99

16

92

94

100

78

80

40

12th

21st

16

0

0

Tl2

65 Example 19

Control of crown and root rot on tobacco plants by systemic soil treatment Compound A has been tested for its systemic

11

630 230

Determine effectiveness against crown and root rot caused by the organisms Phytophthora parasitica and P. Cryptogea when applied to the soil by soil irrigation.

10 week old tobacco seedlings (variety Glurk) were used as host plants. Pots containing the seedlings were treated with an aqueous solution of the test compound at various test concentrations (4 pots per concentration) by soil irrigation. A day after the treatment, a fungal culture of the organism was poured onto the surface of the soil in the pots. The mushroom culture was prepared by growing the organism in a mixture of oatmeal, potato dextrose and soil. The inoculated seedlings were then kept in a greenhouse by the day temperature being 20 to 25 ° C and the night temperature 15 to 20 ° C. Three to four weeks after the inoculation, the plant roots and crowns were assessed for pathological symptoms. The percent disease control achieved by the test compound was determined from the percent reduction in disease compared to untreated control plants. The test concentration and percent control of the disease are summarized in Table XIV.

Table XIV Control of crown and root rot on tobacco plants by soil irrigation

Connection conc, ppm control (%)

P. Cryptogea P. Parasitica

Compound A

100 *

100

100

Compound A

40

99.8

99.1

Compound A

16

96

96

5-ethoxy-3-tri-

100

80

52

chloromethyl-1,2,4-

40

48

30th

thiadiazole **

16

9

0

* 100 ppm = 50 ng / cm2

** U.S. Patent 3,260,588 and 3,260,725

Example 20 Control of Root Fire on Pepper (Sweet Peppers)

A preparation of 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) -Y-butyrolactone in attapulgite clay in the form of a wettable powder with an active substance content of 50% was used to combat root burns on goat pepper ( Sweet Peppers), caused by the soil-living organism Phytophthora capsici ge-lo tested.

Goat pepper seedlings (Doux de Valence variety) in the four-leaf stage were planted in pots filled with a sterilized mixture of part compost and part sand soil. The pots were then inoculated with the organism by spreading a layer of oat grains contaminated with the organism Phytophthora capsici on the soil surface and covering this layer with a 1 cm high layer of the sterilized soil mixture. The goat's pepper was then sprayed with goat pepper until it overflowed with an aqueous suspension of the test compound in different concentrations (12 pots per concentration). The extent of the disease control was determined by counting the number of 25 plants killed. The percent disease control achieved by the test compound was determined from the percentage reduction in disease compared to untreated control seedlings. The results are summarized in Table XV.

30th

Table XV Control of root burn on pepper

Conc, to living

Combat damaged

35 fungicide

Seedlings

(%)

Leaf surface g / hl

(%)

(%)

100

50

25th

0

200

100

100

1.3

4o 400

100

100

1.63

0

33.3

-

0

Claims (6)

630230 PATENT CLAIMS 1. Fungicidal agent, characterized in that it is a compound of the formula 5ch-r wherein R represents a hydrogen atom or the methyl group as at least one active component. 2. Fungicidal composition according to claim 1, characterized in that it contains a compound of formula I, wherein R represents a hydrogen atom. 3. Use of the fungicidal composition according to claim 1 for combating false mildew infections on plants which have been caused by the fungal family of the Peronosporaceae and of putrefactive diseases on crowns and roots which have been caused by soil-dwelling fungi of the Phytophthora family. 4. Use according to claim 3, characterized in that vines are treated as plants. 5. Use according to claim 3, characterized in that the plants are treated with lettuce or cabbage. 6. Use according to claim 3, characterized in that tobacco, snapdragon, safflower or pepper are treated as plants. phenylamino) -Y-butyrolactone or 3- (N-chloroacetyl-N-2,6-dimethylphenylamino) -5-methyl-y-butyrolactone, are effective for combating downy mildew and rotting diseases on crowns and roots caused by phytophthora. The fungicidal compositions according to the invention are generally effective both as protective fungicides, i.e. they prevent fungal infections or protect against fungal infections, as well as eradicating fungicides, i.e. they eliminate and cure infections that have already occurred. As will be explained in more detail below, the eradicating activity of the fungicidal compositions of the present invention is usually a particular advantage. The fungicidal compositions according to the invention are generally particularly advantageous for combating downy mildew on wine, since it has been found that they do Fermentation of grapes harvested from vines that have been treated with the active compounds according to the invention do not inhibit. Furthermore, it was found that the fungicidal compositions according to the invention usually have a surprisingly high activity for eradicating downy mildew on vines, and that downy mildew fungi on vines apparently do not develop any resistance to the fungicidal compositions according to the invention. The fungicidal composition according to the invention is characterized in that it is a compound of the formula I. ceH2ci 25th