PL171529B1 - Fungicide and herbicide containing phenoxy-1,3-diketones as active substance - Google Patents

Abstract

An agent with a fungal and herbicidal effect containing known auxiliaries, characterized it contains a new compound as an active ingredient with the general formula presented in the figure, in wherein R1 are halogen atoms, simple alkyls, branched or cyclic structure up to 6 atoms carbon is found in any combination of a variety the benzene ring positions, R21 R "may be identical or different and represent hydrogen atoms, groups alkyl of 1 to 6 carbon atoms, phenyl or the phenoxy of RJ and R4 may be the same or different and represent hydrogen, halogen, substituents mono- or dialkylamino, wherein the alkyl is 1 to 6 mono and diphenylamine substituted carbon atoms in the benzene ring with halogen atoms, trichloromethyl, alkyl groups of 1 up to 3 carbon atoms, carbonylamide unsubstituted or having an alkyl group on the nitrogen atom from 1 to 4 carbon atoms or a phenyl ring substituted with a halogen atom, a trihalogenomethyl group, hydroxyimmune group or alkoxycarbonyl groups, and r5 are a substituent tert-butyl or phenyl optionally substituted halogen atoms, hydroxyl groups or amines at various positions

Description

The subject of the invention is an agent having fungicidal and herbicidal action containing as active ingredient a new compound of the general formula shown in the figure.

The novel compounds of the general formula, which are the active ingredient of the agent according to the invention, constitute a group of linear phenoxy-1,3-diketone derivatives not described in the literature with regard to their biological activity and chemical properties.

Compounds embraced by the formula in which R ¹ are halogen, straight, branched or cyclic atoms up to 6 carbon atoms in any combination at different positions on the benzene ring, R ² and R ⁶ may be the same or different and represent hydrogen atoms , alkyls of 1 to 6 carbon atoms, phenyl or phenoxy group, R ' ³ and R 4 may be the same or different and represent hydrogen, halogen, mono- or dialkylamino substituents in which the alkyl has 1 to 6 carbon atoms, mono- and diphenylamino groups substituted in the benzene ring with halogen atoms, trihalomethyl groups, alkyl groups with 1 to 3 carbon atoms, carbonylamide groups unsubstituted or containing an alkyl group at the nitrogen atom with 1 to 4 carbon atoms or a phenyl ring substituted with a halogen atom, trihalomethyl group, hydroxyimino group or alkoxycarbonyl groups R ^y is a tert-butyl or phenyl substituent optionally substituted with halogen atoms, with hydroxyl or amino groups at various positions, are obtained from methyl or ethyl esters of alkylphenoxycarboxylic acids and tert-butylmethylketone or acetophenol derivatives during Claisen ester condensation, and the products obtained can be further processed by halogenation and nucleophilic substitution. Properties of a number of obtained derivatives are summarized in Table 1.

The agent according to the invention was tested for fungicidal activity on the following test fungi: Rizoctonia solani, Fusarium culmorum and Phytophtora cactorum according to the method of inhibiting linear mycelium growth by adding specific concentrations (200 and 20 ppm) of the active substance to the potato agar medium, followed by point contamination of the nutrient medium suitable test mushroom. After the incubation period of 3 to 6 days, depending on the mycelium development, linear measurements of the mycelial growth zone were made in the control sample. For the evaluation of fungicidal activity, the principle was adopted that the total inhibition of linear growth of mycelium at 20 ppm determines the very good effect, the total inhibition between the concentrations of 20 and 200 ppm determines the good effect, the complete inhibition at the concentration of

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200 ppm indicates average performance and no complete inhibition at 200 ppm indicates no action.

The phytocidal activity was studied in greenhouse conditions on 10 bioindicator plants, namely:

- monocotyledons: ryegrass, oats, corn

- dicotyledons: white mustard, peas, beans, cucumber, flax, beetroot and buckwheat.

On well-developed seedlings of bioindicator plants, acetone-water solutions of biologically active substances in the amount of 5 kg / ha were applied with a special sprayer. The evaluation of the activity of compounds was carried out after 2 weeks, grading according to the scale:

- no action

- very poor performance

- weak performance

- medium action

- good action - (complete destruction of plants)

Compounds that in a given class of plants destroy them to a degree of at least 3.5 are qualified for further research.

Table 2 lists selected compounds covered by the formula shown in the figure by way of example, and their biological activity was determined in accordance with the above-mentioned methodology. Compound No. 3 showed very good activity against Rhizoctonia solani and Fusarium culmorum and good against Phytophtora cactorum. At the same time, in the studies on the phytocidal effect at the dose of 5 kg / ha of the active substance, it had a phytotoxic effect to a less than average degree on plants from the dicotyledonous class, while it showed a very weak phytotoxic effect on monocotyledons. Hence, it can be considered as a potential fungicide to protect cereals against fungal diseases.

Compounds Nos. 5, 7, 8 and 9 showed a strong phytocidal effect on dicotyledonous species with no effect (compound No. 5) or very little (remaining three compounds) on monocotyledonous plants. This clearly selective action of these compounds predisposes them to use in cereals and other monocotyledonous crops.

The selected four compounds covered by the formula shown in Figs. 5, 7, 8 and 9 (Table 3) were tested on three species of monocotyledonous weeds and several species of dicotyledonous weeds in comparison to the known herbicide MCPA. All the tested compounds had no or weak effect on weed species of the monocot class, while MCPA, especially at higher doses, visibly damaged monocotyledons. In contrast, many species of dicotyledonous weeds were completely destroyed by the compounds of the formula shown in the figure even at lower doses, especially compound 5.

The compounds covered by the formula presented in the figure belong to a new group of fungicides and therefore can be effectively used even in those cases where, after using fungicides from other known chemical groups, individual species of parasitic fungi, especially from the genera Fusarium, Rizoctonia and Phytophtora, have become resistant to them. . Moreover, they are moderately toxic to higher animals and therefore pose no risk when used. The following examples illustrate the preparation method and the formulations in which the agent according to the invention can be used.

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Table 1.

Physicochemical properties of compounds covered by the general formula presented in the figure

No related Chemical structure of the compound mp.Ł ° C Analysis calculated% found R ¹ R2 R3 R ⁴ R ⁵ R6 C. H. N 1 2,4-Cl ₂ H. H. H. c ₆ h _p H. 116-117 59.4 3.7 - 59.3 3.7 - 2 2,4-Cl ₂ H. Cl Cl c ₆ h _p H. 87-88 48.9 2.6 - 48.9 2.9 - 3 4-Cl ch ₃ Cl H. c ₆ h ₅ H. 110-111 60.5 4.2 - 60.5 4.2 - 4 2-CH - 4-CI H. 1,2,4-triazol-1-yl H. WH3 H. 70-72 51.9 3.2 9.6 51.7 3.4 9.5 5 2,4-Cl ₂ H. Cl H. 4-BrC ₆ H5 H. 107-108 44 2.3 - 44.1 2.6 - 6 4-Cl ch ₃ h H. c ₆ h _s 1 ch ₃ Oil 68.2 5.4 - 68.3 5.4 - 7 2-CH - 4-Cl H. Cl CL c ₆ h ₅ H | 119-121 54.9 3.5 - 54.7 3.4 - 8 2.4 <l ₂ ch ₃ Cl Cl 2,4-Cl2C ₆ H3 H. 105-107 43 2.1 - 43 2.1 - 9 2,4-Cl, ch ₃ = N-O-CH3 2,4-Cl ₃ C ₆ H3 H. 134-135 48.1 2.9 3.1 48.2 2.9 3.2 10 2-C ₂ H ₅ H Br Br 4-ClC ₆ H4 H. 129-130 45.6 3.2 - 45.8 3.3 - 11 4-CH - H. 4-NO ₂ CH <| H. 4-CHjOCW H. 50-52 68.7 5 3.3 68.7 4.8 3.6 12 2-CH - 4-Cl H NHC ₆ H ₄ Br-4 NHC ₆ H ₄ Br-4 C..H. H. 114-116 54.2 3.6 4.4 54 3.9 4.2 13 2-CH ₃ -4-Cl H. CONC H. C _Ć H _S | H. 76-78 62.5 4.6 4.1 62.2 4.4 4.4 14 4-Cl ch ₃ 3.5 - ^^ 3 HIC ₆ H _s H. 108-109 56.7 3.4 2.6 56.4 3.1 2.5 15 2,4-Cl ₂ ch ₃ 1,2,4-triazol-1-yl H. 2,4-Cl2C ₆ H3 H. 182-184 52 3.2 9.6 52.2 3.33 9.5 16 4-Cl ch ₃ H. F. c ₆ h ₅ H. 92-93 63.7 4.4 - 63.8 4.5 ' -

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Table 2

Fungicidal and phytocidal activity of selected compounds

Relationship no Complete inhibition of test fungus mycelium ppm Phytocidal action, scale 0-4 plants Rizoctonia solani Fusarium culmorum Phytophthora cactorum monocots dicots 1 > 200 > 200 > 200 0 2.3 2 200 200 200 1 3.1 3 twenty twenty > 20 1.3 2.9 4 > 200 > 200 > 200 0 3 5 > 200 > 200 > 200 0 3.9 6 > 200 > 200 > 200 0.3 0.1 7 200 200 200 1.3 3.7 8 200 200 200 1 3.5 9 > 200 > 200 > 200 1 3.7 10 > 200 > 200 > 200 0 0 11 > 200 > 200 > 200 0 0.1 12 > 200 > 200 > 200 0 0 13 > 200 > 200 > 200 1 1.3 14 200 200 200 0 0.8 15 > 200 > 200 > 200 0 2.5 16 > 200 > 200 > 200 0 0.4

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Table 3, the herbicidal activity of compounds falling within the general formula shown in the figure tested on several species of monocotyledonous weeds and dicotyledonous weeds

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EXAMPLE I To a solution of 0.1 mole of methyl 2,4-dichlorofenoksyoctanu and 0.1 mol of acetophenone in 50 cm ³ of methanol is added 0.1 mole of sodium methoxide. The mixture was heated to reflux for 1 hour and then the solvent was distilled off under reduced pressure. The reddish brown oily residue is acidified with 5% hydrochloric acid, extracted with methylene chloride, and then the organic layer is re-extracted with aqueous sodium bicarbonate to remove 2,4-dichlorophenoxyacetic acid byproduct. The crude product is obtained from the organic layer after distilling off methylene chloride under reduced pressure. After crystallization from methanol, 1-phenyl-4- (2,4-dichlorophenesky) -1,3-butanedione (compound No. 1 of Table 1) was obtained in 89.7% yield, m.p. 116-117 ° C.

Elemental analysis:

calculated for the formula CcHhC2COo C59.4, H3.7 Found: C 59.3, H 3.7

Example II. The process was carried out in the same way as described in Example 1, using 0.03 mol of methyl 4-chloro-2-methylphenoxyacetate, 0.03 mol of 1- (2,4-dichlorobenzoylmethyl) 1,2,4-triazole, 0.03 mol of sodium methoxide and 30 cm 3 of methanol. The reaction was carried out under reflux for a period of 2 hours. The obtained crude product was crystallized from methanol, yielding a 68.4% yield of a crystalline product with a melting point of 70-72 ° C, being 1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl). 4 (4'-ChloiO-2-inethyliniioxy-11,3-butnedione (compound No. 4 of Table 1).

Elemental analysis:

Calculated for the formula C19H14Cl3N3O3: C 51.9, H 3.2, N 9.6 Found: C51.7, H3.4, N 9.5

Example III. The process was carried out in the same manner as described in Example 1, using 0.07 mole of methyl 2- (4-chlorophenoxy) -2-methyltopionate, 0.07 mole of acetophinobium, 0.07 mole of sodium methoxide and 50 cm3 of methanol. The reaction was carried out at reflux for 2.5 hours. The crude product was obtained which was further purified from aceionenone by steam distillation. 1-Onyl-4- (4-chloro-enoxy) -4-methyl-1,3-peotanedio (compound No. 6 in Table 1) was obtained in 55.0% yield in the form of a sparingly crystallizing oil.

Elemental analysis:

calcd for the formula C 19 H 19 Cl 2: C 68.2, H 5.4 Found: C 68.3, H 5.4

Example IV. 0.1 mole of 1- (43brorenleoylo) -4 - (/ 2,4 - dlcCloroί'enoxyy-1,3-butanedione 1 0.1 mole of sulfuryl chloride with the addition of a few crystals of benzoyl peroxide as the initiator of the reaction was heated in a solution of 50 cm ³ Carbon dioxide tntachlate until gas evolution ceases. The reaction mixture is washed with water, dried and the solvent is distilled off under reduced pressure. The crude product is crystallized from n-hexane and obtained in 77.9% yield 1- (4-bromo-nyl) -2-chloro-4 - (2,4-dichloro-enoxy) -1,3-butanndione (compound No. 5 from Table 1) with a melting point of 107-108 ° C. The structure of the product was confirmed by elemental analysis and spectroscopy.

Elemental analysis:

calculated for the formula C16HiOBrCl3O3: C 44.0, H 2.3 Found: C44.1, H 2.6

Example 5 The process was carried out in the same manner as described in Example 4 using 0.1 mol of 1-phenyl-4- (2,4-dichlorophynoxy) -1,3-butanedio and 0.2 mol of sulfuryl chloride in a 50 cm3 solution. carbon tetrachloride with a small amount of benzoyl peroxide as the initiator. The reaction was carried out at reflux for 8 hours. A crystalline product with a yield of 82.9%, m.p. 87-88 ° C (from chloroform) was obtained, being pure 1-phnyl-2,2-dichloro-4- (2,4-dichinrophenoxy) -1,3-butanedione (compound 2 from table 1). Elemental analysis:

Calculation for the formula C16H1oCl4O3: C 48.9, H 2.6 Found: C 48.9, H 2.9

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Example VI. 250 g of the compound listed in Table 1 under the number 3.80 g of emulsifier P3, 20 g of Ronacet R-40, 100 g of cyclohexanone are dissolved in xylene to 100% to give a 25% emulsifiable concentrate fungicide.

Example VII. 500 g of the compound listed in Table 1 under number 7, 350 g of kaolin, 50 g of NNO dispersant, 15 g of Rokafenol N-8 and 85 g of Aresil were prepared in such a way that the abovementioned amounts of Rokafenol N-8 were applied to Aresil for absorption. and then mixed in a fluid bed mixer with the remaining components and micronized in an air-jet mill. The milled product was homogenized in a fluid bed mixer to give a 50% herbicidal wettable powder.

Publishing Department of the UP RP. Circulation of 90 copies. Price PLN 2.00

Claims (1)

Patent claim An agent with fungicidal and herbicidal action containing known auxiliaries, characterized in that the active ingredient is a new compound of the general formula shown in the figure, in which R 'is halogen atoms, straight alkyls, branched or cyclic atoms up to 6 carbon atoms present in any combination in the various positions of the benzene ring, R ² and R ⁶ may be the same or different and represent hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, phenyl or phenoxy, R ³ and R ⁴ may be the same or different and represent hydrogen, halogen, mono- or dialkylamino substituents in which the alkyl has 1 to 6 carbon atoms, mono- and diphenylamino, substituted in the benzene ring with halogen atoms, trihalomethyl groups, alkyl groups with 1 to 3 carbon atoms, carbonylamide groups unsubstituted or containing at the nitrogen atom an alkyl group from 1 to 4 carbon atoms or a phenyl ring substituted with a halogen atom, a trihalomethyl group, a group hydroxyimino or alkoxycarbonyl groups, and R ^s is a tert-butyl or phenyl substituent optionally substituted with halogen, hydroxyl or amino groups at various positions.