SE430414B - Fungicidal compounds - Google Patents

Abstract

The invention relates to a fungicidal complex with the formula <IMAGE> (where M is a divalent metal cation, R<1> is an alkyl group, R2 is a benzyl group or a phenoxyalkyl group, which may be optionally substituted in the benzene ring, n has the value of 2 or 4, and A is a monovalent anion). The invention also relates to an analogous process for the preparation of these compounds and to a fungicidal composition comprising such an active substance, as well as excipients. The invention also covers a process for controlling phytopathogenic moulds by the application of such an active substance to seeds, plants or their growth centres.

Description

Wherein R 1 represents alkyl having 3-4 carbon atoms and R 2 represents benzyl or phenoxyethyl, the benzyl and phenoxyethyl groups being optionally methyl or halogen substituted in the phenyl ring, and a metal salt, preferably of formula MA 2, wherein M is a divalent metal cation and A is an anion Cl, Br or NO 3. Examples of suitable metal ions in the divalent state include copper, manganese, nickel and iron, with copper and manganese being the most preferred forms.

These compounds have fungicidal activity against a large number of fungi which attack agricultural crops. For example, they can be used to control powdery mildew (Erysiphe graminis) and blight (Septoria nodorum) on crops such as wheat, barley and oats and other mold diseases on cereal crops, such as the leaf spot disease (Pyrenophora avenae) on oats, "leaf stripe" (Pxrenophora) (Pxrenop). ) on barley, snow mold (Fusarium nivale) on rye and "blast" (Pxricularia orzzae) on rice.

Many horticultural crops can also be treated with the compounds of the invention, for example to protect fruit crops against Botrzis cinerea, powdery mildew (Podosphaera leucotricha) and scabies (Venturia inaegualis) on apple trees, powdery mildew (Sphaerotheca pannosa) on roses, powdery mildew (Sphaerotheca fuliginea) on cucurbita and various mold diseases on vegetables such as beans, soybeans and peanuts. The treatment can take place by direct application of the active compound to the crop, to the soil surrounding the crop or to the control of seed-borne diseases by seed treatment.

In addition to use in the treatment of agricultural crops, the compounds can in many cases be used as general fungicides, for example in industry, where materials such as paints, pulp and paper products often need to be protected against mold infestation. They are particularly valuable if the use or preparation involves mixing the compound with a powdered carrier. The compounds of formula I preferably have the following structure "\ za Ya ~ 1, / R ---- N-coN / \ M | / \ (CH2) 20 ~ - fi- 2A? III Zb II wherein R1 represents alkyl with 3-4 carbon atoms, X represents - (CH 2) 2 O-, Y represents halogen, a represents 2-3, Z represents methyl, b represents 0 or 1, M represents copper, manganese, nickel or iron, A represents Cl, Br or NO 3 and n represents 2 or 4. As mentioned above, the symbol n is preferably 2 and M is preferably copper or manganese.

In formula III above, R 1 may be propyl, isopropyl, butyl, isobutyl or tert-butyl, Y may be, for example, chlorine, bromine or iodine, although the Y groups, if more than one, need not be identical.

When X is - (CH 2) 2 O- as in formula III, there are preferably three substituents on the ring, wherein Y is chlorine and Z is methyl.

The most preferred complexes are those derived from the compound 1- [N-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoyl] imidazole- having the structure 7809660-9, / Pr I -CON, (cH2) 20 c1 The anion includes chloride, bromide and nitrate ions, especially the IV chloride ion. The complementary metal ion is selected from copper, manganese, nickel and iron, with the copper (II) and manganese (II) ions being the most preferred.

A preferred example of the compounds of the invention is the complex formed by reaction between copper (II) or manganese (II) chlorides and the compound of formula IV, which can be illustrated in the following manner Cl.U.

, / Pr --- -coN \ 'l 9.

M u / (CHQ 2 O C - 2 ”- N Cl wherein M represents copper or manganese and n is 2 or 4. These compounds, which may also be called bis-fl-fN-propyl + N-2- (2,4,6 trichlorophenoxy) ethylcarbamoyl} imidazole] copper (II) or manganese (II) chloride complexes are prepared in solid crystalline form and can be easily purified. The compounds of formula I above are known and are included in mixtures as described, for example, in the British The compounds of the invention are distinct chemical compounds having physical properties which differ from the free imidazole compounds of formula I. The latter are mainly liquid or semi-solid. compounds, while the compounds of the invention are well-defined solids usually with melting points above 8 ° C and often above 100 ° C.

A difficulty with the original imidazole compounds of formula I is that they are difficult to handle and especially to prepare with a solid powdered carrier. In general, they must first be absorbed on a carrier before a powder can be prepared. This contributes to lowering the fungicidal activity and providing an additional step of production. Since large amounts of solid carriers need to be used, the compounds of formula I cannot be conveniently prepared in highly concentrated form.

However, the compounds of the invention are easier to handle and are more readily prepared with a solid carrier, especially as a concentrate, than the parent compounds without any loss or significant loss of fungicidal activity.

It is especially valuable that they can be easily prepared as powder compositions, as this is often the most suitable form for use as a powder, seed treatment agent or as a dispersible powder for addition to water before application to the crop.

It has now been discovered that the compounds according to the invention, in particular for example the compounds of formula V, have advantages when applied to broadleaf crops. It has been observed that in some cases the original imidazole compound of formula I easily damages such crops, which is not desirable to any small extent. The compounds according to the invention surprisingly do not have this phytotoxic effect and are completely safe on sensitive crops. Cultivations where special benefits are achieved include fruit trees (especially deciduous fruit trees (eg apples, cherries and peaches), vines, legumes (eg peanuts and soybeans) and cucurbita (eg cucumbers, 7809660-9 melons and "courgettes"). Preferred crops are fruit trees, peanuts and cucurbita.

The compounds of the invention can be readily prepared by reacting an imidazole of formula I with a suitable metal agent in a medium containing an organic solvent, for example an alcoholic aqueous solution or dichloromethane. Suitably the reactants are mixed in stoichiometric or approximately stoichiometric amounts, i.e. in a molar ratio of 2: 1 or 4: 1 (imidazole compound to metal salt) depending on whether it is desired to prepare the complex with two resp. four ligands. The reaction temperature is suitably selected in the range from 50 ° to 40 ° C, for example from 20 ° to 50 ° C.

A further aspect of the present invention relates to the use of a compound of the invention together with a carrier. The active compound can be used in a variety of formulations, for example, an aqueous dispersion, a dispersible powder, a seed treatment agent, granules or a powdering agent.

As a dispersion, the composition contains an active compound together with a dispersant dispersed in a liquid medium, preferably water. It may be in the form of a concentrated primary composition which must be diluted with an appropriate amount of water or other diluent prior to application. Such primary compositions are suitable for the consumer and a preferred example is a dispersible powder. A dispersible powder comprises an active compound, a dispersant and a solid carrier. The latter may be, for example, kaolin, talc or diatomaceous earth, and in addition the dispersible powder may contain a wetting agent.

Other formulations include seed treatment agents, granules or powdering agents, in which the active compound is present in association with a solid carrier and which are intended for direct application. They can be manufactured according to methods well known in the art. Preferably, all compositions are made comprising a solid carrier by mixing the active compound in particulate form with a particulate carrier.

The concentration of the active compound in the composition according to the invention can vary greatly. In the case of a primary composition, it preferably constitutes from 15 to 95% by weight, most preferably from 50 to 80% by weight. A composition intended for direct use on a crop preferably comprises from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight of the active compound, although compositions with a higher concentration, e.g. up to 30% by weight, can preferably be chosen when you intend to aerial spray the harvest.

With the compounds of the present invention, phytopathogenic molds are controlled by applying a compound of the invention to the seeds, plants or their habitat.

For convenience as well as efficacy, the active compound is preferably applied in the form of a composition as described above.

The compounds of the invention are applied to seeds, plants or their plant site. Thus, the active compound can be applied directly to the plant by, for example, spraying or powdering either when the mold has begun to appear on the plant or before the emergence of mold as a protective measure. In both cases, the preferred method of application is foliar spraying. It is generally important to achieve good control of mold at an early stage of growth, as this is the time when the plant can be most severely damaged. For cereal crops, such as wheat, barley and oats, it is often desirable to spray the plant at or before growth stage 5 (Feekeks Scale), although further treatments by spraying when the plant is more developed may increase the resistance to growth or spread of mold. In some cases, it is practical to treat the roots of the plant before or during planting, for example by dipping the roots in a suitable liquid or solid composition. When the active compound is applied directly to the plant, a suitable application rate is from 0.01 to 10 kilograms per 7809660-9 hectares, preferably from 0.05 to 5 kilograms per hectare.

Alternatively, the compound can be applied directly to the soil simultaneously with the seed, so that the presence of active compound in the soil controls the growth of mold that attacks the seeds. When the soil is treated directly, the active compound can be applied in any way that allows it to be intimately mixed with the soil by applying the active ingredient at the same time as sowing by introducing it into the same seed drill as the seeds.

A suitable application rate is from 0.1 to 10 kilograms per hectare.

According to a further method, the active compound of the invention can be applied to the seeds as a treatment agent to combat seed-borne diseases. This method is particularly useful for the treatment of cereals against infestations of, for example, leaf spot disease on oats and “leaf stripe” on barley. When the cereals are stored in storage spaces or containers, the storage space or container may be treated with the active compound instead of or in addition to treatment of the cereals themselves. A suitable amount of application for seed treatment is from 0.05 to 5 grams per kilogram, for example from 0.1 to 1 gram per kilogram.

A more special way according to the invention is to control mold diseases on cereals, such as for example wheat, barley, oats or rye, by applying a compound according to the invention to the crop. For each individual compound, it is necessary to select the most effective method from those described above with the appropriate amount of application to ensure mold control.

The invention is further illustrated by the following examples. 7809660-9 Example 1 This example illustrates the preparation of the compounds of the invention. (1) min a solution of 35.13 g of 1- [N-propyl-u-2- (2,4,6-trichlorophenoxy) ethylcarbamoyl] imidazole in 267 ml of ethanol was added dropwise over 25 minutes a solution of 11,3 g of copper (II) chloride (CuCl2.2H2O) in 30 ml of water. At the end of the addition, the reaction mixture was stirred at room temperature for a further Zå hours.

The solid product was isolated, washed with water and then with ether. After drying under vacuum, it was dissolved in a minimal amount of dry dichloromethane at room temperature, charcoal treated and filtered by gravity. At least the same volume of dry ether was added to the filtered solution. After seed treatment and standing, a solid was deposited. It was collected and dried under vacuum at room temperature to give bis-le- {§-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoylsimidazo} copper (II) chloride complex, as a green-blue crystalline solid, m.p. 142-144 ° C. (2) The 1- [β-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoyl] imidazole used in the above reaction was prepared as follows.

A mixture of 197.5 g of 2,4,6-trichlorophenol, 107.8 ml of 1,2-dibromomethane and 500 ml of water was stirred under reflux while sodium hydroxide solution (63 ml of caustic soda, density 1.5 and 61 ml water) was added slowly. heated under reflux for 16 hours and then the reaction mixture was removed from the excess dibromoethane as an azeotropic substance, originally To this mixture was then added 85 ml of toluene and the temperature was maintained at about 50 ° C. and washed with dilute aqueous sodium hydroxide. at atmospheric pressure and then under reduced pressure.

The organic layer was separated. To this organic layer were added 85 ml of toluene, 137 ml of sodium hydroxide (density 1.5), 137 ml of water and 134 ml of propylamine.

The reactants were stirred at 50-60 ° C for 8 hours and then left at room temperature for 60 hours. The aqueous layer was separated and the organic layer was distilled at atmospheric pressure and then under reduced pressure. D The distillate was slowly added to 39.7 g of phosgene dissolved in 370 ml of ice-cold toluene maintained at a temperature below 15 ° C. The mixture was then heated to 70 ° C and more phosgene was introduced until a clear solution formed. The toluene was removed under reduced pressure and the remaining solution was cooled in ice.

The solid formed was filtered off. This toluene solution was diluted with an additional 250 ml of toluene and stirred at 80 ° C for two hours with 47.3 g of imidazole and 96.0 g of anhydrous potassium carbonate. This mixture was allowed to cool and 386 ml of water was added. The organic layer was separated, washed with water and then dried over anhydrous magnesium sulfate. This was then concentrated under reduced pressure; was stirred with dilute hydrochloric acid and the aqueous layer was adjusted to pH 8 and ether was extracted to give 1- [D-propyl -N-2- (2,4,6-trichlorophenoxy) ethylcarbamoyljimidazole.

The following compounds were prepared according to the same method using suitable imidazole compounds and metal salts as reactants. bis-1H-N-2- (2,4-dichloro-6-methylphenoxy) ethyl-N-propylcarbamoyl imidazole manganese (II) chloride complex, m.p. 132-134 ° C. bis- [1-N-butyl-N-2- (2,4-dichloro-6-methylphenoxy) ethylcarbamoylsimidazole copper (II) chloride complex, m.p. 136-138 ° C. b1s- [1''-§-N-butyl-N-2- (4-chloro-2, a] bromophenoxy) ethylcarbamoyl; imidazo (copper (II) fl chloride complex, m.p. 168-169 ° C. bis- [α-α-propyl-N-2- [2,4,6-trichlorophenoxy) ethylcarbamoylsimidazole copper (II) bromide complex, m.p. 151-135 ° C. 78109660 "9 11 bis- [fi- {fl-2- (2-bromo-4-chlorophenoxy) ethyl-N-butylcarbamoyl imidazo fl copper (II) chloride complex, m.p. 130-132 ° C. Bis - [] - âN- propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoylimidazole] copper (II) nitrate complex, m.p. 124-12600. bis- Ü- {N-2- (2,4-dichloro-6-methylphenoxy) ethyl N-propylcarbomoyg imidazole} copper (II) chloride complex, m.p. 130-132 ° C. bis-L1-N-2- (2,4-dichloro-6-methylphenoxy) ethyl-N-propylcarbamoyl imiaazole nickel-chloride complex, m.p. 158 DEG-10 DEG C. bis- [1- {N-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoylsimidazole] ferric chloride complex, m.p. 136 DEG-138 DEG C. bis-1- (N-2-phenoxyethyl-N-propylcarbamoyl) imidazole copper (II) chlorine complex, melting point 125-127 ° C. , melting point 78-50 ° C.

Example 2 The procedure described in Example 1 was used to prepare complexes with four imidazole ligands by obtaining 7.5 g of 1- [N-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoycjimidazole in 50 ml of ethanol react with 0.85 g of copper (II) chloride in 7 ml of water.

After washing with water and ether, crude tetrakis- [1-§N-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoy] imidazo fl copper (II) chloride complex was collected. This material was further purified using dry methylene dichloride, charcoal and dry ether as described in Example 1 to give the product, m.p. 133-134 ° C. Example 3 This example relates to the preparation of bis- [J-N-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoylsimidazole] manganese (II) chloride complex.

To 79 g of manganese chloride (MnCl 2 .4H 2 O) in 600 ml of ethanol was added 300 g of 1-1N-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoyl] imidazole dissolved in 840 ml of ethanol. The reaction mixture was stirred at room temperature for 18 hours at room temperature for two days, filtered by suction filtration and then washed with water. This product was then dried under vacuum at 50 ° C to give bis- [1- [N-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoylsimidazog manganese (II) chloride complex, m.p. 137-139 ° C. Example 4 This example relates to the preparation of tetrakis-b-N-2-phenoxyethyl-N-propylcarbamoylsimidazoilmangan (II) chloride complexes.

A stirred solution of 10; 92 g of 1- [N-2-phenoxyethyl-N-propylcarbamoyljimidazole in 30 ml of ethanol was added dropwise at room temperature to a solution of 1.98 g of manganese chloride (MnCl 2 .4H 2 O) in 20 ml of ethanol. . After the addition was complete, the reaction mixture was stirred at room temperature for a further three hours to give a homogeneous solution. The solvent was then removed by rotary evaporation at 30 ° C and 2 mm pressure for two hours to give a syrup-like residue. This was then triturated with ether to give a cream solid. This was washed with ether and dried under vacuum at room temperature to give tetrakis-fl-fN-2-phenoxyethyl-N-propylcarbamoyl} imidazole] manganese (II) chloride complex, m.p. 86-88 ° C.

The following compound was prepared in the same manner: tetrakis- [1- {N-2,4-dichlorobenzyl-N-isopropylcarbamoyl} imidazole manganese (II) chloride complex, m.p. 167-119 ° C. 7809660-9 13 In an analogous manner, tetrakis-fl-§N-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoyl} imidazole / manganese (II) chloride complex was also prepared, m.p. 141-142 ° C.

Example 5 A wettable powder preparation was prepared by mixing the following substances bis- [1-N-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoylsimidazole] manganese (II) chloride complex 25.0% Monolone PB * 3.0% Dyapol PT ** 5.0% kaolin to 100.0% by weight * a complex ethylene oxide-propylene oxide copolymer ** a sulphated condensate of urea, cresol and formaldehyde.

Preparations similar to those mentioned above were prepared by substituting the above active compound. with the same amount of any of the compounds of the invention as described in Examples 1-4.

Example 6 A wettable powder preparation was prepared by mixing the following substances bis - [] - {N-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoylsimidazole oil manganese (II) "chloride complex 70.0% Dyapol PT 7 .5% Aerosol OTB * 1.0% kaolin to 100.0% by weight * a sodium dioctyl sulfosuccinate 78Û-9CV6Û- 9 14 Example 7 A suitable powder preparation was prepared by mixing the following substances bis «[] - {N-propyl-N-2 - (2,4,6-trichlorophenoxy) ethylcarbamoylsimidazole] copper (II) chloride complex 71.0% Reax 88B * 10.0% Aerosol OTB 1.0% kaolin 'to 100.0% by weight * a mixture of sodium lignosulphate and wetting agents.

Example Gel 8 A seed treatment agent was prepared from the following ingredients bis- [J- {N-propyl-N-2- (2,4,6-trichlorophenoxy) ethylcarbamoylsimidazole manganese (II) chloride complex _ 10.0% Lake Red Toner (dye) 1.0% light liquid paraffin 2.0% talc - to 100% by weight Similar seed treatment agents were prepared by replacing the oleophane compound with the same amount of any of the compounds of the invention as described in Examples 1-4.

Example 9 The following ingredients were used to prepare a granular preparation - bis-1-LN-2-phenoxyethyl-N-propylcarbamoyl] imidazole copper (II) chloride complexes - 5.0% - Ethylane BV * 1.0% fuller's soil f 94.0% * an alkylphenol ethoxylate Example 10 This example illustrates the fungicidal activity of the compounds of the invention for controlling powdery mildew on barley.

In one set of experiments, barley seedlings were infected with cereal powdery mildew, Erysiphe graminis, and then sprayed with a suspension of the test compound at a concentration of 1000 ppm.

In a further set of experiments, barley seedlings were first sprayed with a suspension of the test compound at 1000 ppm and then the seedlings were inoculated with powdery mildew.

Visual assessment was made of any infection and a comparison was made with untreated barley seedlings.

All of the compounds of the invention described in Examples 1 to 4 gave more than 50 percent control of powdery mildew in both of these tests.

Example 11 This example illustrates the activity of the compounds of the invention for controlling Botryis cinerea.

An amount of agar containing 2% malt extract was sterilized in an autoclave. The material (20 ml) was dispersed in a boiling tube containing a sufficient amount of the active compound to give a concentration of 5 .mu.m, after stirring to ensure even distribution. The contents of the cooking tube were then poured into a petri dish and allowed to solidify. A spore suspension in sterile distilled water was prepared and the agar was inoculated with it. After incubating the agar for a period of one week, it was examined to assess mold growth and compared with control experiments, where the active compound was excluded from the agar medium. Measurements of the diameter of the mold growth were compared with control samples and all 7809660-9 16 listed below. compounds showed a reduction in the diameter of at least 50 å: bis- L1 - EN-propyl-NZ- (2,4,6-trichlorophenoxy) ethylcarbamoylsimidazole] copper (II) -NZ- (2,4,4-trichlorophenoxyethylcarbamoylsimidazole) manganese (II) chloride complex lex - bis- H1 - 1N-propyl-NZ- (2,4,4-G-trichlorophenoxy) ethylcarbamoyg imidazole] copper ( II) -bromide complex big- 1 1-N-butyl-N-2- (1H-chloro-z, e-abromophenoxy) ethylcarbamoyl imiaazole] copper (In-chloride complex in tetrakis--1N-propyl-NZ- (2, 4, ñ-trichlorophenoxy) ethylcarbamoylsimidazole] copper (II) chloride complex bis-1H-N-propyl-N-2- (2,4,4-trichlorophenoxy) ethylcarbamoylsimidazoleJ copper '(II) nitrate complex' bis- 1-N, N-2- (2,1-dichloro-G-methylphenoxy) ethyl-N-propylcarbamoylimidazole (II) chloride complex bis-11-N-Z- (2,4-dichloro-6-methylphenoxy) ethyl-N -propylcarbamoyl) imidazole nickel chloride complex bis- (N-Z-2,4-dichloro-6-methylphenoxy) ethyl-N-propylcarbamoylsimidazole manganese (IIT-chloro complex> bis- [j-1N-butyl-N-Z- (2,6-dichloro-G-methylphenoxy) ethylcarbamoyl] imidazole] copper (n) -coride complex bis- L1 -AN-propyl-N-Z- (2,4; β-trichlorophenoxy) ethylcarbaxnoyl imidazole (ferric chloride complex).

Claims (6)

7809660- 9 17 PATENT CLAIMS A fungicidal compound of the formula "_ z Q" i "conz RI 2.9 M _ \ XN /" Zb wherein R1 represents alkyl having 3 or 4 carbon atoms, X represents -CH2- or - (CH2) denotes halogen, a denotes 0-3, Z denotes Me, b denotes 0 or 1, M denotes Cu, Mn, Ni or Fe, A denotes Cl, Br or NO 3 and n denotes 2 or 4. A compound according to claim 1, characterized in that Y represents chlorine, Z represents methyl, n represents 2 or 4 and M represents copper. 3. A compound according to claim 1, characterized in that Y represents chlorine, Z represents methyl, n represents 2 or 4 and M represents manganese. A compound according to any one of claims 2 or 3, characterized in that A represents a chloride ion. A compound according to claim 1 having the formula 78096 60-9 18 29 Cl / C 3 H 7 N_CON \ (CH) o cl 2019 M | ä 2 2 w G where M denotes copper or manganese and n denotes 2 or 4. Use of a fungicidal compound of the formula m_- -el '' _, 2 U - _ I 2 (:) 1 - _CON \ ,, / _.- M9 M I ~ .zb. wherein R 1 represents alkyl having 3 or 4 carbon atoms, X represents -CH 2 - or - (CH 2) 2 O-, Y represents halogen, a represents 0-3, Z represents Me, b represents 0 or 1, M represents Cu, Mn, Ni or Fe, A represents Cl, Br or NO 3 and n represents 2 or '4, in a fungicidal composition in an amount of at least 15% by weight, calculated on the weight of the composition, in the form of a particulate solid, together with a solid particulate carrier. 7809660-9 SUMMARY A fungicidal complex compound of the formula pf 29 ___.__ N-coN / 2 \ RM ZAQ wherein M represents a divalent metal cation, R 1 represents alkyl, R 2 represents benzyl or phenoxyalkyl, wherein the benzyl or phenoxyalkyl groups are optionally substituted 1 phenyl ring , n represents 2 or 4 and A represents a monovalent anion, an analogous process for the preparation of the compound and a fungicidal composition comprising an active compound and a carrier, and a method for controlling phytopathogenic molds by applying an active compound to seeds, plants or their plant site. .