CH664562A5 - ZINC AND COPPER COMPLEX SALTS OF THE AETHYLENE-B-DITHIOKARBAMID ACID AND N- (BENZIMIDAZOLYL-2) CARBAMID ACID METHYL ESTER, METHOD FOR THE PRODUCTION AND USE THEREOF. - Google Patents

Description

DESCRIPTION

The present invention relates to new chemical compounds, namely zinc and copper complex salts of ethylene-bis-dithiocarbamic acid and N- (benz-40-imidazolyl-2) -carbamic acid methyl ester, a process for their preparation and their use as fungicides in in agriculture and as antiseptics for non-metallic materials.

It is known that benzimidazole derivatives are highly effective preparations for combating Erysiphales fungi in different cultures, but are not effective against Perono-sporales fungi (US Pat. No. 3,657,443, Cl. 424-273).

It is also known that fungicides from the class of 50 dithiocarbamates are active against fungi Peronosporales, but on the fungi Erysiphales (NN Melnikow. Chemistry and technology of pesticides, Moscow, publisher "Chi-mija", 1974. NN Melnikov, Khimiya » , i tekhnologiya pe-stitsidov, Moskva, izdatelstvo «Khimiya», 1974) do not kill 55.

Also known are complex salts of alkyl esters of N- (benzimidazolyl-2) -carbamic acid of the general formula

60

MX

1 2.

65

wherein R stands for a lower alkyl, M for zinc, copper, X for chlorine, bromine, acetate, propionate (DE-PS No. 1 957 712, Cl. C07 F, published 1970).

664 562

The specified compounds have an insufficient antifungal activity.

The proposed new compounds, zinc and copper complex salts of ethylene-bis-dithiocarbamic acid and N- (benzimidazolyl-2) -carbamic acid methyl ester have been newly developed and are not described in the specialist literature.

The invention has for its object to provide such new compounds, zinc and copper complex salts of ethylene

<T //,

c '//,

xK // - c

/ VA / - c bis-dithiocarbamic acid and the N- (benzimidazolyl-2) carbamic acid methyl ester, which have a stronger fungicidal activity and a broader spectrum of activity.

This object is achieved in that, according to the invention, new substances, zinc and copper complex salts of ethylene-bis-dithiocarbamic acid and of N- (benzimidazo-ethyl-2) -carbamic acid methyl ester of the general formula

10th

A / HCOC & 2

be proposed in which M stands for zinc, when n = 1 or 2 or for copper when n = 1.

According to the invention, the following compounds are specifically proposed:

[N- (Benzimidazolyl-2) -0-methylkarbamato] zinc-ethylene-bis-dithiocarbamate (Compound 1) of the formula

C O C H,

20 [N- (Benzimidazolyl-2) -0-methylkamamato) copper (II) ethylene bis-dithiocarbamate (compound 2) of the formula

25th

30th

35

40

Di [N- (benzimidazolyl) -2) -0-methyl carbamato) zinc ethylene bis-dithiocarbamate (compound 3) of the formula

<T / A - <V / - / - C

c a / -, sv <* /

sì / MCOC / S ,,

II ß .o

AS // CO CM-,

According to the invention is also a process for the preparation of the above compounds by reacting copper chloride or Zinkchlo.rid with the methyl ester of N- (benzimidazolyl-2) -carbamic acid at a temperature between 20 and 90 C in an aqueous medium and then adding the aqueous solution of sodium ethylene bis-dithiocarbamate and isolating the final product.

According to the invention, a fungicidal mixture is further proposed which contains zinc and copper complex salts of ethylene-bis-dithiocarbamic acid and N- (benzimidazolyl-2) -carbamic acid methyl ester as the active ingredient with the following ratio between the above-mentioned constituents in mass%:

55 active ingredient 0.01 ... 99.5

Filler up to 100.0 The new compounds are powdery substances that are insoluble in water and organic solvents and disintegrate at a temperature exceeding 200 ° C. 60 The structure of the new substances has been verified by elemental analysis, using the methods of UR spectroscopy and X-ray electron spectroscopy.

For example, [N- (benzimidazolyl-2) -0-methyl-carbamato] - zinc-ethylene-bis-dithiocarbamate is a yellow substance with a decomposition temperature of over 230 ° C. [N- (Benzimidazolyl-2) -0 -methylkarbamato] copper (II) ethylene bis-dithiocarbamate is a brown substance with a decomposition temperature of over 200 ° C.

664 562

4th

Di- [N- (benzimidazolyl-2) -0-methyl-carbamato] zinc-ethylene-bis-dithiocarbamate is a light yellow substance with a decomposition temperature of over 280 C.

The specified connections are made as follows.

The aqueous zinc or copper chloride solution and the aqueous suspension of the N- (benzimidazolyl-2) -carbamic acid methyl ester are introduced into a reaction flask. The reaction mixture is mixed at a temperature between 20 and 90 ° C. within 10 to 60 minutes.

After the reaction mixture has cooled, the aqueous solution of sodium ethylene bis-dithiocarbamate, prepared from the aqueous solution of ethylenediamine, carbon disulfide and sodium hydroxide solution, is then gradually added. The reaction takes place with thorough stirring at room temperature within 20 to 60 minutes. The end product is isolated in a manner known per se.

The above compounds belong to the class of weakly toxic substances. When administered orally, LD50 exceeds 2000 mg / kg for rats.

The fungicidal properties of the compounds according to the invention were tested under different climatic conditions on vegetable, technical, melon, fruit and cereal crops (on 20 agricultural crops against 40 pathogens).

The compounds 1 to 3, taken in a dose of 0.3 to 0.6 kg ha, have a high effectiveness and complex action against pathogens Erysiphales (of the genus Sphaerotheca, Uncinula, Erysiphe), the family Peronosporaceae (of the genus Peronospora, Plasmopara) , Pseudoperonospora) and the Phytophthoraceae family, as well as against Puccinia graminis, Septoria graminum, Psudope-ziza trachiphila, Coniothyrium diplodiella and Botrytis cinerea for grapes, Fusarium oxysporum for squash plants, Monilia, Polystigma lumachumumumcultymium bacteria, and coccomyymans bacteria. Fusarium oxysporum, Erysiphe in melon cultures, Bacterium Vesicatorium and Phytophthora infestans in tomatoes.

The fungicides according to the invention come primarily as solutions. Suspensions and wetting powder are used. The active substance concentration of the mixtures is between 0.01 and 99.5 mass%. The mixture is prepared by a conventional method by mixing or grinding the complex salts according to the invention with a carrier, for example with water, acetone, ethanol, white-russ. Kaolin manufactured. To produce the wetting powder, the compounds according to the invention, a mixture of polyethylene glycol acrylic esters, sulfite waste liquor, white carbon black and kaolin are mixed. For the preparation of suspensions, the compounds according to the invention are mixed with a suitable solvent, such as water, acetone, ethanol.

For a better understanding of the present invention, the following examples are given to practice the same.

example 1

An aqueous solution of 6.8 g (0.05 mol) of zinc chloride is introduced into a reaction flask equipped with a stirrer, and 9.55 g (0.05 mol) of methyl N- (benzimidazolyl-2) -carbamic acid as an aqueous suspension are intimately added Stir to. The reaction mixture is mixed within 10 to 20 minutes and then an aqueous solution of sodium ethylene bis-dithiocarbamate, prepared from 4.3 g (0.05 mol) of 70% ethylene diamine solution, 7.62 g (0.1 mol) of carbon disulfide and Gradually add 4 g (0.1 mol) caustic soda in the form of a 10% water solution. A light yellow precipitate forms. Mixing is continued within 20 to 30 minutes until a uniformly colored suspension is formed. The precipitate is filtered off, washed with chlorine ions and dried. 21.3 g (91% of theory) of [N- (benzimidazolyl-2) -0-methylkarbamato] -zinc-ethylene-bis-dithiocarbamate with a decomposition temperature of over 230 ° C. are obtained.

Found in%: C 33.59; H 3.34; N 14.99; Zn 15.3; C ^ H ^ NsO- ^ Zn 'Calculated in%: C 33.41; H 3.24; N 14.99; Zn 13.99.

Example 2

A solution of 17 g (0.1 mol) of CuCl2 • H20 in 20 ml of water and a suspension of 19.1 g (0.1 mol) of N are placed in a reaction flask equipped with a stirrer, a reflux condenser and a thermometer - (Benzimidazolyl-2) -carbamic acid methyl ester in 60 ml of water. The reaction mixture is stirred at a temperature of 50 C for 1 hour. After the reaction mixture has cooled to a temperature of 30 ° C., an aqueous solution of sodium ethylenebisdithiocarbamate, prepared from 8.6 g (0.1 mol) of 70% ethylenediamine solution, 8 g (0.2 mol) of caustic soda, is then added 50 ml of water and 15.2 g (0.2 mol) of carbon disulfide. The dark brown reaction mixture is mixed for 40 minutes at room temperature. The precipitate is filtered off, washed with water and 33 g (71.1% of theory) of [N- (benzimidazolyl-2) -0-methylkarbamato] copper (II) ethylene-bis-dithiocarbamai are obtained. The decomposition temperature exceeds 200 C.

Found in%: C 34.01; H 3.01; N 15.26; Cu 14.12; C | 3H15CuN50, S4.

Calculated in%: 33.57; H 3.26; N 15.06; Cu 13.66.

Example 3

In a reaction flask equipped with a reflux condenser, an agitator and a thermometer,

a solution of 5.5 g (0.04 mol) of zinc chloride is introduced into 50 ml of water and mixed with heating (90 to 95 ° C.) within 2 hours with 11.5 g (0.06 mol) of N-benzimidazolyl 2-carbamic acid methyl ester (BMK). The reaction mixture is then cooled and filtered off. The precipitate is washed carefully with water, dried and recrystallized from acetonitrile. A complex compound of the composition (BMK) 2 ZnCl2 of white color is obtained in a yield of 15 g (96.3% of theory) and with a melting point of 226 C.

The aqueous suspension of 10.4 g (0.02 mol) of the complex compound obtained is stirred with stirring the aqueous solution of sodium ethylene bis-dithiocarbamate, prepared in the reaction of 1.7 g (0.02 mol) of 70% aqueous A solution of ethylenediamine, 3 g (0.04 mol) of carbon disulfide and 1.6 g (0.04 mol) of caustic soda in the form of a 10% strength aqueous solution were added. The reaction mixture is mixed at room temperature for 1 hour. The pale yellow precipitate obtained is filtered off, washed with water and dried. This gives 12.7 g (96.2% of theory) of compound, di-N- (benzimidazolyi-2) -0-methylcarbamato-zinc-ethylene-bis-dithiocarbamate with a decomposition temperature of 280 ° C.

Found in %. C 40.18; H 3.49; N 17.18; S 19.59; Zn 10.27; C-H ^ NiAÄZn

Calculated in%. C 40.15; H 3.68; N, 17.02; S 19.48; Zn 9.93.

Example 4

Effect of the compounds on the mycelium of the fungus genera Fusarium moniliforme, Aspergillus niger, Rhizoctonia solani.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

5

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The compounds are mixed with acetone and, in compounds, melted glucose-potato agar (the temperature of the medium is between 50 and 60 ° C.) is introduced into the petri dishes under sterile conditions before filling.

The agar plate is inoculated 18 to 20 hours after the medium has been filled. After the appropriate holding at a temperature of 25 to 26 ° C, the diameter of fungal colonies is measured. The preparation is tested on the mycelium of the fungi at a concentration of 0.003% tetramethyl active ingredient using TMTD (Te 10 thiuramid-tramethylthiuramidsulfid) as an etalon. The experiment was repeated three times in sulfide. (Etalon)

The inhibition of growth of mycelium is

nk-nt

Active substance inhibition in%

fertilize

Fusarium

Asper

Rhizoc tion in%

moniliform

gillus-

tonia so-

me niger lani

1

0.003

100

100

100

2nd

0.003

100

100

100

3rd

0.003

100

100

100

0.003

100

100

100

melvonAbbotT

H.:

100% determined where

T means the growth inhibition of the culture in%, nk the diameter of colonies in the control culture, no the diameter of culture colonies in the embodiment with the use of the preparation.

The test results are shown in Table 1.

Table 1

Results obtained when testing the connections on the mycelium.

15

20th

Example 5

Effect of the compounds in relation to the antiseptic activity on the mycelium of pure fungal cultures, which cause the destruction of non-metallic materials, namely Aspergillus niger, Chaetomium globosum, Paecilomuces va-rioti, Pénicillium cyclopium.

The methodology for determining the antiseptic activity of compounds 1 to 3 is similar to that of the experiment described above. Pentachlorophenol serves as an etalon. The test results are given in Table 2.

Table 2

Results obtained when testing compounds for antiseptic activity

Compound inhibition of mycelium growth in%

gene concentration

Aspergil

Chaeto

Paecilo

Péni

tion in%

lus niger mium muces cillium

globosum varioti cyclo

pium

1 2

3rd

4th

5

6

1 0.003

100

100

100

100

2 0.003

100

100

100

100

3 0.003

100

100

100

100

Pentachlor

phenol

100

(Etalon) 0.003

98

100

97

Table 3

preparations

Active ingredient

Disease inhibition in%

45

concentra

Erysiphe

Erysiphe

tion in%

cichora graminis

cearum

Example 6

1

2nd

3rd

4th

Investigation of the activity of connections related

connection

0.05

100

100

on Erysiphe of cucumber and wheat

50

0.025

100

97.5

The tests of the connections are in a Ge

0.012

98.0

.96.0

carried out greenhouse. The plants of cucumber or

0.006

95.0

90.0

Wheat is tested with aqueous suspensions of

0.003

94.0

the compounds in different active ingredient concentrations

0.0015

90.0

and sprayed the control plants with water. After 55

After drying, the plants are artificially infected with the

Connection 2

0.05

100

100

aqueous suspension of conidia Erysiphe cichoracearum

Connection 3

0.05

99

-

and Erysiphe graminis (200,000 each 1 cm3 water). The plant

N- (benzimide-

0.05

100

zen are in the greenhouse at a temperature of 20

azolyI-2) -

0.025

97.0

kept up to 25 C. The spread of the disease in the 60th

-carbamide-

treated with preparations and control plants is 10

acid methyl

Estimated days after fungal attack. The wheat ester

0.012

97.0

The variety is red-grain wheat («Krasnosernaja»), the cucumber

(Etalon)

0.006

90.0

variety «Mnogoplodny VSChV» (BCXB). The reproducers

Zinc ethylene

The trials are triple.

65

bis-dithio-

0.05

30.0

The test results are summarized in Table 3

carbamate

sums up.

(Etalon)

0.012

0.0

0.006

0.0

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6

Table 3 (continued)

Disease inhibition in% concentration- Erysiphe erysiphe tion in%

cichora-cearum graminis heterogeneous mixture of methyl N- (benzimide-azolyl-2) -carbamic acid with zinc-ethylene-bis-dithiocarbamate at a ratio of 1: 1

2: 1

2,4-dinitro-6- (sec.-octyl-2) phenyl crotonate (etalon)

0.003

0.0015

0.05

0.05 0.025 0.012 0.006

92.0 72.0 85.0

98.0 94.0 86.0 76.0

Botrytis cinerea in beans

N, N-dimethyl

N'-dichlorofluoro-

methylmerkapto-

N'-phenylsulfamide

(Etalon)

The spread of the disease in the control plants

0.05

97.0

39.0

79.0

10th

Example 7

Investigation of the effectiveness of compound 1 during the control of various fungi

The compound 1 against pathogens of the gray rot Botrytis cinerea is investigated at 0.05% active ingredient concentration under warm house conditions on beans (variety Russische Schwarze Russkije Chernyje) and grapes.

The plants are grown until 7 to 10 leaves are formed.

The infection is carried out using the spore suspension of the fungus Botrytis cinerea grown on the carrot agar. The suspension density is 150 to 200,000 conidia / cm3. When examining the protective effect, the infection is carried out after 1 to 1.5 hours after the treatment of the plants with the compounds to be tested.

The infected plants are kept in a humidification chamber within 24 hours at a temperature of 26 C and 100% relative humidity. The fungal attack on the plants is estimated on the 5th to 7th day after being infected. The test results are shown in Table 4.

Table 4

Fungicidal activity of the compounds against gray rot (botrytis cinerea) of beans and grape preparations active ingredient. Disease inhibition in%

concentration in%

Example 8

Investigation of the effectiveness of compound 1 against tomato powdery mildew (Phytophthora infestans)

The effectiveness of compound 1 against tomato powdery mildew is investigated under warm house conditions on the «Gribovskije» tomato variety. The infection is carried out using the spore suspension of the fungus Phytophthora infestans grown on potato slices.

When examining the protective effect, the infection is carried out after 1.5 to 2 hours. The infected plants are kept in a humidification chamber for 24 hours at a temperature of 18 C and 100% relative humidity.

The fungus count on the plants is estimated on the 4th and 5th day after 25 of infection.

The test results are shown in Table 5.

Table 5

The effectiveness of compound 1 against tomato flour-30 tau (Phytophthora infestans)

preparations

35

40

Connection 1

Zinc-N, N'-ethylene-bis - dithiocarbamate (etalon) N- (benzimidazolyl-2) -carbamic acid methyl ester (etalon)

Spread of the disease in the control plants

Drug concentration in% 0.015 0.0075

0.015

0.015

31 to 33%

Disease inhibition in%

93.0 91.0

76.0

0.0

45

50

Botrytis cinerea on grape

1 2 3

Compound 1 0.05 98.0

heterogeneous

Mixture of

N- (benzimide-

azolyl-2) -carbamide-

acid methyl

ester with zinc

ethylene-bis-dithio-

carbamate at

Ratio 1: 1 0.05 78

4th

98.0

80

Example 9

Investigation of the effectiveness of compound 2 in combating tomato mildew (Phytophthora infestans).

The effectiveness of compound 2 is examined on plants of tomatoes of the «Gribovskii» variety. The plants are treated with the preparation and then artificially infected with the aqueous suspension of conidia spores of the fungus Phytophthora infestans. The spore concentration of the suspension is 50,000 per 1 ml of water. The conidia suspension is held at 10 C for 40 minutes before inoculation to exit 55 zoospores. After inoculation, the plants are placed in a humidification chamber at a temperature between 20 and 22 ° C for 24 hours. After 6 days, leaf disease is determined. The assessment is based on a sense of proportion in the five-point procedure. The reproducibility of the tests is threefold. Zineb, N, N'-zinc-ethylene-bis-dithiocabamate serves as the etalon. The test results are given in Table 6.

When testing the preparation for controlling tomato mildew in a field trial (Moscow region), the plants are treated twice with compound 2 during the growing season. The first spraying of plants with the preparation is before the onset of the disease

60

65

7

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and the second after 14 days. Polycarbazine, double salt of zinc N, N'-ethylene-bis-dithiocarbamate and ethylene-bis- (thiocarbamo-

yl) disulfide. The reproducibility of the tests is threefold. The test results are shown in Table 6.

Table 6

Test results obtained in the control of tomato powdery mildew (Phytophthora infestans) Preparations active ingredient

No. concentration in%

Disease inhibition in% warm house field trial

Connection 2

Zinc-N, N'-ethylene-bis-dithiocarbamate (etalon)

3rd

0.05

0.025

0.15

0.05

0.025

0.15

0.05

0.025

4th

100 100

99 97

100

3 polycarbazine (etalon)

4 copper-N, N'-ethylene-bis - dithiocarbamate

5 N- (benzimidazolyl-2)

carbamic acid methyl ester 0.05

6 Mixture of copper-N, N'- 0.05 ethylene-bis-dithiocarbamate 0.025 with methyl N- (benzimidazolyl-2) carbamate at a ratio of 1: 1

Warm house test. Spread of the disease in the control plants 71%

Field trial. Disease spread to control plants 46%.

90

93 85

0 85 80

Example 10

Tests of compound 3 on the mycelium of the fungi, pathogens of potato Fusarium sambucinum, Sphae-ropsis malorum, Rhizoctonia solani.

The methodology of the tests of compound 3 is similar to that of the experiment on the mycelium phytopathogenic fungi Fusarium moniliform, Aspergillus niger, except that the preparation 35 is not introduced into the glucose-potato medium but into the wort agar medium.

The test results are shown in Table 7.

Table 7

Results obtained when testing preparations against potato pathogens

Current No.

preparations

1.Connection 3

2nd

Tetramethyl-thiuramidsul-fid (etalon)

Drug concentration in%

0.003 0.001

% Mycelium growth inhibition as a pathogen

0.003 0.001

Fusarium sambucinum 96 86

96 57

Sphaerop-sis malorum 100 86

95 66

Aspergillus niger

99 97

Rhizoctonia solani

97

95 50

86

55

Example 11

Investigation of the effectiveness of the compounds according to the invention for combating wheat and currant diseases.

When examining the effect of the compounds for controlling wheat diseases, the plants were sprayed with fungicides twice during the growing season. The first spraying of the plants with the preparations took place during the tillering stage of the wheat and the second during the stalk formation. The reproducibility of the tests is threefold.

In the course of the action of the compounds for controlling blackcurrant diseases, the bushes of the fruiting blackcurrant were treated twice with fungicides during the growing season. The first spraying of the black currant was carried out before the flowering of the black currant and the second after the harvest 65. The reproducibility of the tests is threefold.

The test results are shown in Table 8.

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8th

Table 8

Effectiveness of the compounds against diseases of wheat and black currant

Current No.

1.

2nd

3rd

preparations

Drug concentration in%

Compound 2 Compound 3 N- (Benzimidazo-lyl-2) -carbamidic acid methyl ester (etalon) control (disease development in%

0.05 0.05

0.05

preparations

Connection 1

O.O-Diethyl-S-

benzyl thiophosphate

(Etalon)

Disease spread in control plants in%

Drug concentration in% 0.05 0.025

0.05 0.025

45 to 50

Disease inhibition in%

100.0 90.0

99.0 89.0

Example 13

Investigation of the effectiveness of compound 2 on potato plants (in a field trial).

In the course of the study of the activity of compound 2 against potato blight (Phytophthora infestans), the plants are sprayed with fungicides three times during the vegetation period. The first spraying is done before the onset of illness, and the following spraying is done after 12 to 14 days. A mixture consisting of 15% zinc ethylene bis-di-thiocarbamate and 65% copper (II) oxychloride is used as the etalon. The potato variety is called “Ogonjok”. The reproductive inhibition in% wheat

Blackcurrant

Erysiphe graminis

98.0 98.0

99

Puccinia

Sphaero

Puccinia graminis theca ribis

morsuvae

65.0

96.0

60.0

90.0

97.0

92.0

35.0

60.0

30.0

98.0

38.0

58.0

35.0

20th

Example 12

Effectiveness of the compounds according to the invention against Piricularia spot disease v rice (Piricularia oryzae).

The effectiveness of compound 1 against Piricularia spot disease of rice (Piricularia oryzae) is investigated under warm house conditions on the variety «Dubowski». The plants are grown in growing pots until the stage of forming 3 to 4 leaves.

The infection is carried out using the spore suspension of the mushroom Piricularia oryzae grown on the carrot agar. The suspension density is 150,000 to 200,000 conidia per 1 cm '. When examining the protective effect, the infection is carried out 1.5 to 2 hours after the treatment of the plants with fungicides. The infected plants are kept in a humidification chamber over a period of 24 hours at 26 C and a relative humidity of 100%. Plant infestation is estimated on the 7th to 10th day after infection.

The test data are shown in Table 9.

Table 9

Effectiveness of preparations against Piricularia spot disease in rice (Piricularia oryzae)

25th

decorability is triple. The test results are summarized in Table 10.

The table shows that compound 2 is effective with Etalonni-veau.

Table 10

Results obtained when testing compound 2 for combating potato blight (Phytophthora infestans)

30 Ldf. No.

35

40

preparations

Compound 2 Kuprosan mixture (15% zinc-ethylene-bis-dithiocarbamate + 65% copper (II) oxychloride) Spread of the disease in the control plants 25.0%

Drug concentration in% 0.2

0.2

Disease inhibition in%

100

77.0

Example 14

Investigation of the fungicidal activity of compound 3 45 on pure fungal cultures

Pure cultures of the mushrooms grown on the potato-dextrose agar as pathogens of the Pythium fruit rot in Guiken (Pythium sp.), The sugar beet root rot, the lettuce rot (Bremia sp.), The phytophthora blotch disease of tomatoes (Phytophthora infestans), The gray rot of strawberry (Botrytis cinerea), the sclerotinia rot of the sunflower (Sclerotinia sclerotiorum), the blight rot in potatoes (Phoma sp.) and the Fusarium rot in cucumbers (Fusarium sp.) were taken as test objects.

The fungicidal activity is investigated by introducing the acetone suspensions of the preparation into the agarated medium. The inhibition of growth of fungal conidia is estimated on the 6th day according to Abbott's formula.

The test results (Table 11) show that compound 3 is superior to the N- (benzimidazolyl-2) carbamic acid re-methyl ester in its activity against the test objects mentioned (the fungi belong to the class of lower fungi) and the zinc ethylene bis-dithiocarbamate is practically equivalent to 65. In addition, compound 3 comes in the activity against fungi, which are sensitive to the N- (benzimidazolyl-2) - carbamic acid methyl ester, is not the same as this preparation and is superior to individual fungi. The ge50

55

60

9

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Information obtained confirms the advantage of compound 3, which has fungicidal activity both against lower fungi

The investigation of the fungicidal activity against Erysiphe cichoracearum and Erysiphe graminis and Phytophthora infestans in tomatoes and potatoes has thus shown that the compounds according to the invention have a high fungicidal activity which is equivalent to that of etalones, namely Karathan, for combating Erysiphe cichoracearum and Zineb as a preparation against Phytophthora related to infestans. The tested compounds have a significantly broader spectrum of activity compared to etalones (zinc-ethylene-bis-dithiocarbamate, TMTD and pentachlorophenol). (The compounds are very effective against pathogen complexes in various agricultural crops, including Peronosporaceae and Erysiphales. Zinc-ethylene-bis-dithiocarbamate and TMTD are not effective and are not approved for use in agriculture against Erysiphales of various plants. Karathan is only effective against Erysiphales active and not effective against Peronosporaceae of various agricultural crops Pentachlorophenol is known as an antiseptic and is not applicable as a fungicide for combating the diseases of agricultural crops.

(Table 11, experiment 1) as well as against imperfecti fungi (higher fungi) (Table 11, experiment 2).

in %

Phytophthora infes. 100

0

95

100 100

70

The use of the compounds according to the invention at the same time for controlling Personosporaceae and Erysiphales of different agricultural crops will therefore lead to a reduction in the number of treatments and consumption standards of the preparation and to a reduction in environmental pollution.

Example of the production of wetting powder The effectiveness of preparations is examined in combating various diseases of agricultural crops. The plants are sprayed using an aqueous suspension, prepared from a wetting powder at a working standard of between 500 and 6001 / h of working fluid.

For the preparation of the wetting powder, 50 parts by weight of the compound according to the invention, 3 parts by weight of a mixture of polyethylene glycol acrylic esters, 3 parts by weight of sulfite waste liquor, 10 parts by weight of white carbon black and 34 parts by weight of kaolin are mixed and mixed until a homogeneous mixture is obtained.

Table 11

Results obtained when testing the new compound 3 on pure cultures

Try

links

Active ingredient

Inhibition of growth of the Testobjeli series no.

concentration

of the agar

Pythium

Bremia

Aphano

in %

s.p.

s.p.

myces s.p.

I.

Compound 3 N- (benzimide

0.03.

100

100

100

azolyl-2) -

0.03

10th

0

15

carbamic acid

methyl ester

Zinc-N, N'-ethy

0.03

84

100

85

len-bis-di-

thiocarbamate

Botrytis

Sclerot.

Phoma

Fusarium

cinerea sclerot.

s.p.

s.p.

II

Compound 3 N- (benzimide

0.03

100

100

100

azolyl-2) -

0.03

100

44

70

carbamic acid

methyl ester

Zinc-N, N'-ethy

0.03

74

31

36

len-bis-dithio-

carbamate

45

c

Claims (7)

664 562 2nd PATENT CLAIMS Zinc and copper complex salts of ethylene bis-dithio karbaraidic acid and the N- (Benzimidazolyl-2) - carbamic acid remethyl ester of the general formula C / - /, - / VH— C \ S- ■ M C //, <Y / -I C ' 0 = 4 ^. / f '/ H ■ A / HCOCHj n where M stands for zinc when n = 1 or 2 or for copper when n = 1. 2. [N- (Benzimidazolyl-2) - O-methylkarbamato) - zinc-ethylene-bis-dithiocarbamate according to claim 1 of the formula Ç / 4 5. A process for the preparation of the compounds according to claim 1 to 4, characterized in that the copper-15 or zinc chloride with N- (benzimidazolyl-2) carbamic acid methyl ester in an aqueous medium at a temperature between 20 and 90 C with subsequent Add sodium ethylene bis-dithiocarbamate is reacted and the end product is isolated. 6. A fungicidal mixture which contains an active ingredient and a filler, characterized in that it contains zinc and copper complex salts of ethylene-bis-dithio-carbamic acid and N- (benzimidazolyl) -2) -carbamide-acidic methyl ester as the active ingredient as claimed in claim 1 up to 4 with the following ratio between the above-mentioned components in mass%: Active ingredient 0.01 to 99.5 filler up to 100. 7. Antiseptic mixture for non-metallic material-30 fe, characterized in that it contains zinc and copper complex salts of ethylene-bis-dithiocarbamic acid and N- (benzimidazolyl-2 -) - carbamic acid methyl ester according to claims 1 to 4 as the active ingredient. 3. [N- (Benzimidazolyl-2) -0-methyl carbamato] copper (II) ethylene bis-dithiocarbamate according to claim 1 of the formula C / Vj COCH; 4. Di- [N- (benzimidazolyl-2) -0-methyl carbamato] zinc ethylene bis-dithiocarbamate according to claim 1 of the formula C / - / 3 - ■ v / - / - c ' tf / A - y \ / s - / - C 35