GB1602871A - Fungicide - Google Patents

Abstract

The fungicide contains, as active substance, a compound of the formula <IMAGE> in which R1 and R2 are alkyl having 1 to 4 carbon atoms, R3 having 1 to 4 carbon atoms or cyclohexyl and R4 having 1 to 18 carbon atoms or R2 and R3 together with the nitrogen atom to which they are bonded form a ring of the formula <IMAGE> in which U and Y are hydrogen or methyl and Z is a hydrogen atom, or Y and Z together denote an oxygen atom and W denotes an oxygen atom, the methylene group or a radical of the formula <IMAGE> in which R1 and R4 are as defined above, X denotes a chloride, bromide, iodide or methylsulphate cation, and n is 1 or 2. The fungicide can be used for controlling Alternaria and Phytophthora.

Description

(54) A FUNGICIDE (71) We, INSTYTUT PRZEMYSLU ORGANICZNEGO, a State Enterprise recognised under the laws of Poland of Annopol Street 6, Warszawa, Poland, and POLITECHNIKA WROCLAWSKA, a State Enterprise recognised under the laws of Poland of Wybrzeze Wyspianskiego Street, 27, Wroclaw, Poland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following state- ment: This invention relates to new quaternary ammonium salts which have fungicidal properties.

For control of pathogenic fungi of the Alternana and especially of the Phyto- phthcra genera, the use of agents containing such active substances as dithiocarbamates, copper compounds, organo-tin compounds and others, has been proposed.

Among the above, most frequently used is mankozeb (a complex of ethylene-his- dithiocarbamic acid manganese salt with zinc ions), copper oxychloride and triphenyltin acetate.

The above agents control fungi of the Pkytophthora and Alternana general; however, neither of them is a systemic agent.

Preventive use of copper oxychioride requires application of very high doses (abcut 8 kg/ha). Triphenyltin acetate, as all organotin fungicides are highly toxic to all mammals; zineb and mankczeb have relatively short protective activity. The above mentioned fungicides are also not soluble in water. Water solubility is another important factor, as spore germination takes place in water. Also, as the above compounds are not systemic agents, they do not prevent infection of leaves newly developed after fungicides application.

According to the present invention there is provided a method of eradicating fungal growth in plants comprising applying to the locus -of the fungal growth a compound having the general formula 1,

in which X is a halide or methyl sulphate ion and " n " is 1 or 2; R1 and R2 are alkyl groups having from 1 to 4 carbon atoms; R3 is an alkyl group having from 1 to 4 carbon atoms or a cyclohexyl group; and R4 is an alkyl group having from 1 to 18 carbon atoms; or R2 and R3 together with the nitrogen atom to which they are attached, represent a ring structure of formula 2,

in which W is an oxygen atom, a methylene group or a group of formula 3,

where R1 and R are as defined above; U and Y are hydrogen atoms or methyl groups; and Z is a hydrogen atom, or Y and Z together represent an oxygen atom.

The compounds of formula 1 above have strong, and also systemic, action towards fungi, especially of the Altemmia and Phytophthora genera.

Preferably the compound of formula I above is applied in the form of a fungicidal preparation which contains as an active substance a compound of the general formula 1 in admixture with a solid or liquid carrier, and may also contain known additives such as mineral or organic carriers, thinners or solvents, surface-active substances, buffers and adherents.

The effectiveness of the agents according to the present invention has been tested during biological studies in vitro on the following fungi: Alternaria tennis, Botrytis cinerea and Aspergillus niger. Results are given in Table 1.

TABLE 1 Effectiveness of agents with the general formula 1 in which R1 is -CHa, X is Cl, n is 1 and R2, R, and R4 are given as below

Concentration inhibiting No. R, Ra R4 Concentration linear inhibiting spore mycelia germination growth (in ppm) (in ppm) Afternaria Botrytis As pergillus tenuis Cinerea niger 1 -CH, -CH, -C2H5 1000 1000 200 2 -CH, -CH3 -C3H7 1000 1000 20 3 -CH3 -CH, -C4Hg 1000 1000 20 4 -CH, -CH, -C6H1, 1000 1000 200 5 -CH3 -CH, -C7H15 1000 1000 200 6 -CH, -CH3 -C8Hl7 1000 1000 +20 7 -CH, -CH3 -CgHl9 1000 1000 20 8 -CH3 -CH3 -C10H21 100 100 20 9 -CH, -CH, -C12H25 10 +10 20 10 -CH, -CyC6 -C18H37 100 100 2000 11 -CH2CH2OCH2CH2- -Cl6H33 +10 10 +2000 12 -CH2CH2OCH2CH2- -C18H37 100 100 2000 13 -CH,(CH2),CH2 -cl2H2s 10 10 2000 14 -CH2(CH2),CH2- -C18H37 +10 10 2000 Known reference fungicide zineb 100 100 200 mankozeb +10 100 200 -CYC6 means cyclohexyl Example I.

50 parts by weight of dodecyloxymethyl-trimethyl ammonium chloride, 40 parts by weight of mineral carrier (kieselguhr), 2 parts by weight of wetting agent + 8 parts by weight of dispersing agent (waste calcium sulphite liquor).

The fungicide prepared as above was tested in concentrations of the active compound 0,1% and 0,01% and its effectiveness compared to a known fungicide (man kozeb). Investigations were carried out on tomato seedlings in the 5-6 leaves phase, spraying plants with the tested substance and infecting afterwards with a suspension of Phytophthora infestans spores. The percent of infected plants were then evaluated in comparison to unsprayed plants (check) after 6 days. Results are given in Table 2.

TABLE 2 Effectiveness of the agent obtained in example I against potato blight (Phytophthora infestans).

Fungicide Concentration in % Percent of infected plants Agent as in 0.01 25.8 example I 0.1 0 mankozeb 0.01 34.1 0.1 9.0 Check (without - 100.0 the fungicide) Example II.

10 parts by weight of dodecyloxymethyl trimethylammonium chloride, 0,3 parts by weight of alkylarylpolyglycol ether, 89,7 parts by weight of distilled water.

The fungicide prepared as above was studied for systemic activity in comparison to a known systemic fungicide carbendazime 2 - benzimidazole carbamic acid methyl ester and a known preventive agent-mankozeb.

The agent in the example and reference fungicide were diluted with distilled water to concentrations of 1.0 0.1 and 0.01%. Roots of bean seedlings were submerged in the solutions for 24 hours. Next, the sprouts were cut into 1 cm fragments. The fragments in groups of five, were next placed in Petri dishes with an agar-potato nutrient infected with Aspergillus niger spores. Mycelia growth inhibition zone around the fragments was measured after 4 days. Results are given in table 3.

TABLE 3 Systemic activity of the agent with general formula 1.

Diameter of Aspergillus niger mycelia growth concentration inhibition zone around tested agent in % the fragment in mm Average zone of growth inhibition 123 1 2 3 4 5 in mm in mm -Agent as in 1.0 7 9 5 7 9 7.4 example II 0.1 6 0 5 5 0 3.2 0.01 0 0 0 0 0 0 Carbendazime 1.0 6 5 9 5 7 6.4 0.1 6 5 5 0 6 4.4 0.01 0 0 0 0 0 - 0 Mankozeb 1.0 0 0 0 0 0 0 0.1 0 0 0 0 0 0 0.01 0 0 0 O O O Check with water O 0 0 O - O O

The results obtained show that the agent used in the present invention, penetrates through the roots to the bean sprouts, in a manner similar to the known systemic fungicides-carbendazime. Thus the systemic action of the agent has been confirmed.

An advantage of the agent used in the present invention in addition to its high effectiveness is its systemic activity, is its hitherto unknown ability to control fungi of the Altentarta and Phytophdiora genera. Also an important advantage of the product used in the present invention is its low toxicity to mammals and its good solubility in water, which simplifies application.

Compounds of general formula I are quaternary ammonium salts and are prepared by known quaternization techniques.

WHAT WE CLAIM IS: 1. A method of eradicating fungal growth in plants, comprising applying to the locus of the fungal growth a compound having the general formula 1,

in which X is a halide or methyl sulphate ion and " " is 1 or 2; R1 and Ra are alkyl groups having from 1 to 4 carbon atoms; R9 is an alkyl group having from 1 to 4 carbon atoms or a cyclohexyl group; and R4 is an alkyl group having from 1 to 18 carbon atoms; or R2 and RS together with the nitrogen atom to which they are attached, represent a ring structure of formula 2,

in which W is an oxygen atom, a methylene group or a group of formula 3,

wherein R1 and R4 are as defined above; U and Y are hydrogen atoms or methyl group; and Z is a hydrogen atom, or Y and Z together represent an oxygen atom.

2. A method according to claim 1 in which the compound of general formula 1 defined in claim 1 is applied in admixture with a solid or liquid carrier.

3. A method according to claim 2 in which the compound of general formula I is applied as a fungicidal preparation as described in Example I or Example II hereinbefore.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (3)

**WARNING** start of CLMS field may overlap end of DESC **. The results obtained show that the agent used in the present invention, penetrates through the roots to the bean sprouts, in a manner similar to the known systemic fungicides-carbendazime. Thus the systemic action of the agent has been confirmed. An advantage of the agent used in the present invention in addition to its high effectiveness is its systemic activity, is its hitherto unknown ability to control fungi of the Altentarta and Phytophdiora genera. Also an important advantage of the product used in the present invention is its low toxicity to mammals and its good solubility in water, which simplifies application. Compounds of general formula I are quaternary ammonium salts and are prepared by known quaternization techniques. WHAT WE CLAIM IS:

1. A method of eradicating fungal growth in plants, comprising applying to the locus of the fungal growth a compound having the general formula 1,

in which X is a halide or methyl sulphate ion and " " is 1 or 2; R1 and Ra are alkyl groups having from 1 to 4 carbon atoms; R9 is an alkyl group having from 1 to 4 carbon atoms or a cyclohexyl group; and R4 is an alkyl group having from 1 to 18 carbon atoms; or R2 and RS together with the nitrogen atom to which they are attached, represent a ring structure of formula 2,

in which W is an oxygen atom, a methylene group or a group of formula 3,

wherein R1 and R4 are as defined above; U and Y are hydrogen atoms or methyl group; and Z is a hydrogen atom, or Y and Z together represent an oxygen atom.

2. A method according to claim 1 in which the compound of general formula 1 defined in claim 1 is applied in admixture with a solid or liquid carrier.

3. A method according to claim 2 in which the compound of general formula I is applied as a fungicidal preparation as described in Example I or Example II hereinbefore.