DE2205871C3 - Fungicidal agent for crop protection - Google Patents

Description

C == S

contains, in which X is a hydrogen or halogen atom and R is an alkyl radical having 1 to 4 carbon atoms or denotes an alkenyl, aryl or substituted aryl radical.

2. Fungicidal agent according to claim 1 for combating the pathogens of real and fake Powdery mildew, leaf spot diseases and gray rot, characterized in that it

an alkyl radical with '. to 4 carbon atoms or an alkenyl, aryl or substituted aryl radical. Examples of active ingredients of the structure mentioned which have a fungicidal effect are given in Table 1.

Table 1

COOC ₂ H ₅

C = S

contains.

The present invention relates to chemical agents for controlling fungal diseases of green plants.

Most of the fungicides that are used on plants in the growing season are only against tine limited number of fungal diseases effective. This creates certain difficulties in protecting plants. In order to combat a whole complex of diseases in a single culture, one often uses several fungicides. One turns to one because of the incompatibility of tinctorial fungicides with one another

{separated plant treatment to what the protective cost elevated.

Many fungicides have different effectiveness against such diseases as real and downy mildew and spot diseases (copper compounds, zineb, ziram and others), real ones Powdery mildew and gray rot (captan and others) etc. Therefore, the search for fungicides loses with one

Large fungicidal range of activity by no means their meaning.

The aim of the present invention is to expand the range of fungicides for green plants, including those «with a wider range of fungicidal effects against the types of diseases mentioned than the mentioned copper compounds, Zineb and others.

In contrast, the invention relates to a fungicidal agent for combating fungal diseases green plants, including powdery mildew and downy mildew, spot disease and gray rot, with a grade on esters of benzoxazolinethione carboxylic acid of the general formula

number χ R. Melting temperature the ver binding I C) 1 H CH ₃ 141-1.5 number X R. Fp. the ver binding 2 H C ₂ H ₅ 92 3 H CH ₂ -CH-CH ₂ 75-76 4th 6-Cl C ₂ H ₅ 134-135.0 5 6-Cl C ₃ H ₇ -n 96-97 6th H C ₃ H ₇ -ISo 96-97 7th 6-Cl C ₃ H ₇ -ISo 112-112.5 8th 6-Br C ₃ H ₇ -ISO 119-120 9 6-Cl C ₄ H "-n 62-63 .0 6-Br C ₄ H ₉ -n 94-95 11th H C ₆ H ₄ -CH ₃ -m 111-112 12th 6-Br C ₆ H ₄ - CH ₃ -m 160-160.5

x-4-

-N-COOR

C = S

6s

in which X is a hydrogen or halogen atom and R The active ingredients contained according to the invention are obtained by reacting the benzoxazoline thiones with chlorocarbonic acid esters in the presence of an acceptor for hydrogen chloride. The structure of the compounds, which are derivatives of the lactam form, is confirmed by their IR spectra, which are characterized by an intense absorption band of the bond C = S in the area 1380 cm " ¹ and a band belonging to surface vibrations Λ CH in the area 1483 cm " ¹ .

Compounds of the formula are in concentration of 0.1% effective against single or several types of fungal diseases of green plants, namely against real cucumber powdery mildew (Erysiphe cichoracearum D. C), downy potato powdery mildew or late blight (Phytophthora infestans D. B.), against wheat rust (Puccinia graminis f. Tritici Erikss. Et Hcnn.), Spot diseases such as corn helminthosporiosis (HeI-minthosporium turcicum Pass), rice pyriculariosis (Piricularia oryzae Br. et Cav.) or grape mold (Botrytis cinerea Pers), as well as against spores of the phytopathogen fungi Alternaria solani, Botrytis cinerea. Fusarium oxysporum and Verticillium dahliae.

Depending on the degree of effectiveness against some of the diseases mentioned, those according to the invention are available Agents do not follow the known fungicides and are also economically interesting.

A number of these remedies are used against a fungal disease complex, real and downy mildew Leaf spot diseases and gray rot are effective in trapping. Connection 4 is the most promising It can fight such diseases as powdery mildew (E. cichoracearum). downy mildew (Ph. infestans) Spot diseases (H. furcicum), gray rot (B. cinerea) and others are used. The said compound is in concentrations of 0.025 * to 0.1 "/ c

effective, has a long period of fungicidal action, healing properties, is in the concentrations mentioned not phytotoxic and not very toxic for warm-blooded animals.

example 1

Determination of the fungicidal effectiveness of the
links

IO

To determine the fungicidal activity, compounds of the formula I were geaen on plants tested a number of fungal diseases.

Preparative forms of the compounds in the form of wettable powders were used for the experiments the following composition prepared in percent by weight.

20th

1. Compound of formula I
Active ingredient - 50
Filler:

2. Kaolin -45

3. Surfactant OP-7 (alkylphenol polyethylene glycol ether) - 2.5

4. Stabilizer (calcium lignosulfonate) -2.5 z ₅

When testing for plants, aqueous suspensions of these wettable powders were found in concentration 0.1% (based on active ingredient) used. In the "control" variant, an aqueous emulsion of OP-7 in the concentration 0.1%, in the variant "Eichsubs'.anz" a well-known fungicide preparation is used.

Planting of cucumbers in leaf stage 2, of potatoes in leaf stages 4-6, of wheat and maize in the Leaf stage 1, of rice in leaf stage 4 have been treated with the prepared agents until they are fully wetted splashed under greenhouse conditions. After 24 hours, the sprayed cucumber plants were inoculated with the powdery mildew suspension (E. cichoracearum) of over 50,000 spores / ml density; Potato plants with a conidia suspension of late blight (Ph infestans) with a density of 50,000 spores / ml; Wheat plants with rust summer spores (P.graminis f.trifici) mixed with talc under the calculation of 30 mg Spores per 30 plants; Maize plants with a conidia suspension of helminthosporiosis (H. turcicum) of over 50,000 spores / ml density; Rice plants with a conidia suspension of pyriculariosis (p.oryzae) of over 100,000 spores / ml.

Thereafter, the plants were left in an atmosphere for 20 to 24 hours to develop the infection brought by 100% moisture. According to the symptoms was the degree of development of powdery mildew, late blight and helminthosporiosis in percent evaluated according to a scale ranging from 1 to 4, the grade 1 being the disease infestation of 5%, 2 the infestation of 25%, 3 the infestation of 50% and 4 the infestation of 75% and more percent leaf area is equivalent to; the number of rusty summer pustules per 1 wheat leaf and the number were also determined of pyriculariosis spots per 1 rice plant. The degree of disease suppression was calculated in Percent, based on the "control".

In each comparative experiment, 6 cucumber, 6 potato, 30 wheat, 10 corn and 20 rice plants were used used. The experiments were repeated 2 to 5 times.

The test results are shown in Table 2. Thereafter, the agents according to the invention at a concentration of 0.1% suppressed the development of cucumber powdery mildew by 76 to 100% , that of late blight by 48 to 81%, that of wheat rust by 75 to 100%, that of Maize helminthosporiosis 79 to 100%, that of rice pyriculariosis 55 to 100%, which for some compounds is close to, equals or even exceeds the effectiveness of the reference agents: such as dichlone, zineb, kitazin.

Drugs Nos. 3, 4, 5 and 6 suppressed one whole complex of diseases, including cucumber powdery mildew, late blight, leaf spot diseases - Corn helminthosporiosis and rice pyriculariosis. Active ingredient no. 4 was shown to be effective against some diseases of this complex, which ranged from 81 to 100%.

Example 2

Active ingredient No. 4 was in the form of aqueous suspensions of a wettable powder in concentrations of 0.1, 0.05, 0.025, 0.0125 and 0.00625% (calculated on the active ingredient) against cucumber powdery mildew and Late blight used in greenhouse conditions compared to known fungicides. Otherwise, the course of the test is the same as the test described in Example 1.

Test results are shown in Table 3. Thereafter, drug No. 4 suppressed in concentrations from 0.025 to 0.1% cucumber powdery mildew as well as the fungicide morestan; after the effectiveness against late blight the compound was close to the zineb and superior to the ziram.

Example 3

The fungicidal permanent action was for active ingredient No. 4 on cucumber plants under warm house conditions definitely.

Leaf stage 2 cucumber plants were washed with aqueous suspensions of the wettable powder containing them Active ingredient no. 4 sprayed at a concentration of 0.05% (based on active ingredient). The splashed Plants were inoculated with powdery mildew suspension (E. cichoracearum) after 14 days. Otherwise led the experiment is carried out analogously to Example 1.

When calculating the effectiveness, the suspension of active ingredient no. 4 was sprayed on Plants demonstrated complete absence of powdery mildew and 100% infestation of the control plants. The received Results show that the agent according to the invention has a longer fungicidal properties Maintains time (over 15 days).

Example 4

The presence of the healing properties was determined on the basis of active ingredient no. 4 with regard to the Cucumber powdery mildew.

The cucumber plants in leaf stage 2 were inoculated with the powdery mildew suspension (E. cichoracearum). On the 5th day after the inoculation, the plants were sprayed with aqueous suspensions of the wettable Powder of compound no. 4 in concentrations of 0.1 and 0.05%, based on active ingredient.

Otherwise, the experiment was carried out analogously to Example 1.

22nd

When calculating the effectiveness, the suspensions of active ingredient no. 4 were sprayed on Plants demonstrated complete absence of powdery mildew and 100% infestation of the control plants. From the The results obtained, it can be concluded that Active Ingredient No. 4 has medicinal properties against powdery mildew fungi owns.

Example 5

Determination of the phytotoxicity of the compounds

The bytotoxicity of the agents according to the invention was determined in the tests for fungicidal activity. The tests were carried out analogously to Example 1. Before calculating the fungicidal Effect, the presence of damage on plants was established by treatment caused with aqueous suspensions of the wettable powders of the compounds of formula 1 became. The degree of damage was determined for each plant according to the scale

the grade 0 corruption is missing

the grade 1 damage up

5% leaf area the grade 2 damage from 5 to

25% leaf area the grade 3 damage of over

25% leaf area

The average damage value was calculated by rounding it up to a whole Number.

The results of the calculation of the phytotoxicity of the agents are given in the description below attached table 4.

According to the information in Table 4, individual active ingredients of the formula I are on some types of crops phytotoxic.

Compounds Nos. 6 and 10 have remarkable ones Phytotoxicity on cucumber. The other compounds were not or only slightly phytotoxic.

Example 6

Determination of the fungicidal effect on spores of the phytopathogenic fungi

The fungicidal activity was determined for compounds No. 1, 2, 3 and 5 on spores of the fungi Alternaria solani and Botrytis cinerea and for compound no. 4 on spores of the fungi A. solani, 3. cinerea, Fusarium oxysporum and Verticillium dahliae detected.

Spores of each type of fungus were placed on microscope slides in the drops as described in Example 1 prepared aqueous suspensions of the wettable powders of the compounds in concentrations of " 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 10, 50, 100 and 150 mg / 1, based on active ingredient, brought. At the same time, the Spores of the same species of fungus in the drops of an aqueous emulsion of OP-7 upon concentration 150 mg / l ("control") and of aqueous suspensions of the known preparations Zineb and Morestan at the concentrations mentioned for the compounds (based on active ingredient).

871 Ψ

¹ 6

After 24 hours, the presence of the germination and the concentration of the active ingredient were established in which no spore germination was observed. . .

The test results are in the description Table 5 attached below.

According to the information in Table 5, Compounds No. 1, 2, 3, 4 and 5 completely suppressed this Germination of the spores of the above-mentioned fungi at concentrations of 0.5 to 100 mg / l. Dip fungicides Zineb and Morestan suppressed spore germination of the same fungi in concentrations of 3 to 100 mg / 1.

The information obtained has shown that the agents according to the invention act on the spores of phytopathogenic fungi have a fungicidal effect in the same way as the known fungicides.

Example 7

The effectiveness of compound no. 4 against grape mold was tested under field conditions (E. cinerea).

The compound was in the form of suspensions of the wettable powder described in Example 1 used in a concentration of 0.1%, based on the active ingredient. The untreated were used as controls Grape vines. As a comparison fungicide, the antibiotic griseofulvin was used in the concentration of 0.05% used.

Each experiment was carried out on 20 sticks (5 sticks each in 4 repetitions).

Grape plants of the "Terbasch" variety were sprayed every 13 to 20 days on 4 dates. The effectiveness became consistent by counting the number of diseased handles and the degree of their damage with a scale from 1 to 5 with the following calculation of the degree of Disease development, expressed as a percentage, determined. The data processing was carried out according to the Dispersion analysis method.

The test results are listed in Table 6 attached to the description.

According to the information in Table 6, the compound No. 4 in the concentration 0.1% suppressed the development of grape mold such as griseofulvin. The information received gives every reason that Consider compound no. 4 an effective fungicide for combating gray rot.

Example 8

Determination of acute oral toxicity
of connections for warm-blooded animals

The acute oral toxicity of Compound No. 4 to white mice was determined. The connection was by means of a metallic probe in the stomach of the animals under the calculation of 1000, 2000 and 3000 mg per 1 kg of animal weight introduced.

No lethal outcomes were observed. The information received will enable the connection

No. 4 for
keep.

g slightly toxic (LD ₅₀ > 3000 mg / kg)

Table 2

Disease suppression in percent, based on control ¹ ), at the active ingredient concentration

No. of

Connections loud
1 table 1

Types of Diseases

Cucumber powdery mildew

76

100

100

100

Late blight

66

48 70 81 72 75 48

Wheat rust

100

100 100

- - 80 - -

Corn rice

hel- pyri-

min- cula-

thosporiosis riosis

100 -

100 -

92 -

-

-

-

20th

No. of Types of Diseases Card White Corn- Rice- Connections loud toffcl- Zen hel- pyri- Table 1 Gur- herb- rust min- cula- know- rot thospo- riose flour- riose lukewarm - 100 55 10 100 - 75 64 11th - 12th

Calibration substances
Dichlone
Standard
Zineb

100 - -

- 75- 85- 100
100 95

Kitazin - - - - 84-99

¹ I In the »control« the development of cucumber powdery mildew is 100%, that of potato cabbage 90%. that of corn helminthnsporiosis 100%, that of wheat rust 20 summer pustules per 1 leaf, that of rice pyriculariosis 25 to 50 spots per 1 plant.

Table 3

Suppression of powdery mildew of cucumber and late blight with active ingredient No. 4 and known fungicides as a percentage of the control

No. Disease sari fungicide Concentrations. % 0.05 0.025 0.0125 OX 0.1 100 100 88 70 1 Cucumber powdery mildew Active ingredient No. 4 100 100 100 100 92 T Cucumber powdery mildew Morestan *) 100 61 47 36 17th 3 Late blight Active ingredient No. 4 - 70 59 17th 12th 4th Potato leaf blight Zineb - 34 34 13th 5 Potato cabbage rotten Ziram

(In the "control" the development of cucumber powdery mildew is 100%. That of Karloffelkraut rot S7%.) ·) Moreslan contains S.S-6-methyl-quinoxalinyl- (2,3) -dithiocarbonate as an active ingredient.

Table 4

Phytotoxicity of the compounds at a concentration of 0.1%

No. of
Active ingredients
according to
Table 1 Culture
Cucumber potato wheat Corn rice 1 1 0 2 1 0 - - - 3 0 0 - 0 - 4th 0 0 0 0 - 5 0 0 - 0 - 6th 3 0 0 - 0 7th - 0 0 - 1 8th - - 0 - 0 9 0 - - - - 10 2 - - - 1 1 - ■ 0 0 12th 0 O

609 624/3

9 \ Q 10

Table 5

Minimum concentrations of the compounds in mg / 1 that ensure 1 (X)% suppression of fungal spore germination

No. of connections Allernaria Botrytis according to table I. solani dnerea 1 50 IO 2 50 10 3 50 K) 4th 100 5 S. 50 K) Calibration substance: 3 K) Morestan Calibrant: Zineb 100 100

Kusarium Verlicilliutn oxysporum dahliac

100

0.5

50

(In the "control" the germination amounts to; the spores of all types of fungus > 90%.)

Table 6

Effectiveness in combating grape mold

fungicide

Concentrated grapes% of that of Beschadi-Iration Degree of graying

Mould

affected (%) grapes (%)

1 Active ingredient No. 4 0.1 312 72 1.49 ~ t Griseofulvin 0.05 289 79 1.84 (Eichsubslanz) 3 control 331 100 12.97

Claims (1)

Claims: Al 1. Fungicidal agent for crop protection, characterized in that it is an ester the benzoxazolinethione carboxylic acid of the general formula N-COOR