DK146026B - BETA-AZOLYLKETONS WITH FUNGICIDE EFFECT - Google Patents

Description

. SSP

<i9) DENMARK

§ (, 2) SUBMISSION WRITING mil46026 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Patent Application No: 3421/77 (51) Lnt.CI.3: C 07 D 249/08 C 07 D 405/06 (22) Filing Date: 29 Jul 1977 A 01 N 43/64 (41) Aim. available: 01 Feb 1978 (44) Submitted: 30 May 1983 (86) International Application No: - (30) Priority: 31 Jul 1976 OE 2634511 (71) Applicant: 'BASF AKTIENGESELLSCHAFT; 6700 Ludwigshafen, DE.

(72) Inventor: Costln Rentzea; DE, Emst-Helnrich 'Pomerania; DE, Bernd 'Zeeh; THE.

(74) Plaintiff: Hofman-Bang & Boutard Patent Office ____________ (54) Fungicidal beta-azolyl ketones

The invention relates to novel, valuable β-azolyl ketones with fungicidal action for use in plant protection.

It is known that 1,2,4-triazole derivatives, e.g. 1- [1,2,4-Triazolyl- (1)] - 2- (4'-chlorophenoxy) -4,4-dimethyl-pentan-3-one exhibits good fungicidal activity (German published application no.

23 35 020). The effect of these substances is not satisfactory at low φ levels and concentrations. In addition, fung their fungitoxic effect is associated with a high phytotoxicity, so that the concentrations needed to control rust fungi also damage the culture plants. For these T reasons, they are not always suitable and not suitable in conjunction with all cereals and species for use as plant-

Q

2 146026 fungicides.

It has been found that the novel β-azolyl ketones of the formula R 2 CO-CBL-CH-R 2 (I), which are characterized by the characteristics of salts thereof, and salts thereof, have good activity. against harmful fungi, especially from the class of ascomycetes and basidiomycetes.

R · means, for example, tert-butyl or neopentyl.

2 R means, for example, phenyl, m- or p-chlorophenyl, p-bromophenyl, 2,4-dichlorophenyl or 3,4-dichlorophenyl.

One can prepare β-azolyl ketones of formula (i) or salts thereof when reacting α, β-unsaturated ketones of formula: R1-CO-CH = CH-R2 (II) wherein R 2 and R have the meaning given above. , with 1,2,4-triazole, optionally, in the presence of a basic catalyst and optionally in the presence of a diluent. This method is preferred. The compounds can also be prepared when reacting β-halogen ketones of the formula R1-CO-CH9-CH-R2 (III)

X

wherein R 2 and R are as defined above, and X is halogen, with 1,2,4-triazole, optionally in the presence of an acid binding agent and optionally in the presence of a diluent. Finally, the compounds are obtained when reacting ketones of formula R1-CO-CH3 (iy) and aldehydes of formula OCH-R2 (Y) wherein R and R are as defined above with 1,2,4-triazole , optionally in the presence of a basic catalyst and optionally in the presence of a diluent. From the compounds prepared by this method, the salts can be prepared with acids.

The reaction of α, β-unsaturated ketones with 1,2,4-triazole according to the method described above is conveniently carried out without diluent or in an inert diluent, e.g. methanol, ethanol, isopropanol, n-butanol, tetrahydrofuran, dioxane, toluene, xylene or dimethylformamide, at temperatures of ca. 0 to 100 ° C, preferably +20 to + 50 ° C.

It is thereby convenient to add an alkaline compound, e.g. sodium hydroxide, potassium hydroxide, triethylamine or N, N-dimethyl-cyclohexylamine, in catalytic amount.

The compounds II used as starting materials are known from the literature and can be prepared according to conventional methods by ketones of formula IV and aldehydes of formula V. By adding the required amount of triazole, the active substances of formula I according to the invention are obtained directly in one step. invention.

This reaction is carried out, for example, in alcohols such as methanol or ethanol or isopropanol or in amides, e.g. dimethylformamide, at temperatures of approx. 0 to 100 ° C, preferably +20 to + 50 ° C and in the presence of a basic, water-dissolved catalyst, e.g. sodium hydroxide or potassium hydroxide.

the compounds of the invention of formula I are colorless crystalline products, readily soluble in vinegar ester, acetone, ethanol, tetrahydrofuran, methylene chloride, chloroform, dimethylsulfoxide, dimethylformamide and N-methylpyrrolidone.

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The new β-azolyl ketones and their salts exhibit a "significantly" wider fungicidal effect and superior plant compatibility in comparison with the known 1- [1,2,4-triazolyl- (1)] - 2- (4 '- chloro-phenoxy) -4,4-dimethyl-pentan-5-one.

The new active substances can also be used in the form of their salts, e.g. hydrochlorides, oxalates or nitrates.

Of great interest are the fungicidal agents of the invention in connection with various culture plants, e.g. by

Ustilago scitaminea κ sugar cane rust)

Hemileia vastatrix

Uromyces fabae and appendiculatus (bean rust)

Puccinia species (grain rust)

Erysipbe graminis (corn mildew)

Botrytis cinerea by wine and strawberry Uncinula necator Sphaerotheca fuliginea Erysipbe cicboracearum Podospbaera leucotrieha.

Yed cultural plants are understood in this context especially wheat, rye, barley, oats, rice, corn, apples, cucumbers, beans ,, coffee, sugar cane, vine, strawberries and ornamental plants in garden plants.

The active substances according to the invention are systemically active. The systemic activity of these agents is of particular interest in the context of the control of internal plant diseases, e.g. grain rust or barley mildew.

The agents containing the compounds of the invention can simultaneously suppress the growth of two or more of the fungi indicated and exhibit high plant compatibility. The amount of application needed to control the phytopathogenic fungi is between 0.05 and 2 kg of active substance / ha of culture surface.

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Table 1 1 2

Conn. R R Melting point, ° C

No. Base Hydrochloric! 1 (ch3) 3c- 141-143 2 (CH3) 3C- 153-155 3 (CH3) 3C- O 69-71 156-160 4 (CH3) 2CH- Cl ^ Sy 118-120 5 (CH3) 3C-Cl ^> - 139-141 6 (ch3) 3c-ch2- ci- <0> - 110-111 7 (CH3) 3C- J5) - 146-147 8 (CH3) 3C- BrOy 142-145 9 (ch3) 3c - Cl - ^ - 154-156 (CH3) 3C- Cl-)) - 158-160 u (ch3) 3c- V®- 166-168 12 (CH3) 2CH- C1 <5V 143-145 ^ C1 13 (CH3) 3C-CH2-Cl- ^ V 164-169 C Η 14 01 ^ 126-128 6 146026

Conn. R f melting point, ° C

No. Base Hydrochloride 15 (CH3) 3C- Br-Equ 104-106 'Br 16 (CH3) 3C- Cl- ^ V 130-132 cl'ci 17; (CH3) 3C-Cl-®- 50-52 mch3 18 (CH3) 2CH-CH2- 163-166

The active substances of the invention can be transferred to the usual formulations such as solutions, emulsions, suspensions, pastes and granules. Pieces are prepared in a known manner, e.g. by mixing the active substance with solvents and / or carriers, optionally using emulsifiers and dispersants, whereby in the case of wetting with water as diluent, other organic solvents can also be used as auxiliary solvents. As auxiliaries can be essentially stated: solvents such as aromatics (e.g.

xylene, benzene), chlorinated aromatics (e.g., chlorobenzene), paraffins (e.g., petroleum fractions), alcohols (e.g., methanol, butanol), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as natural mineral flour (e.g., kaolin, clay, talc, chalk) and synthetic mineral flour (e.g., high-dispersion silicic acid, silicates); emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin, sulfite waste liquor and methyl cellulose.

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90 $.

The agents or preparations based on these ready-to-use preparations, such as solutions, emulsions, suspensions, powders, pastes or granules, are used in a manner known per se, e.g. by spraying, misting, spraying, spraying, pickling or pouring.

7 146026

The agents containing the compounds of the invention may in this application be present with other active substances, e.g. herbicides, insecticides, growth regulators and fungicides or also mixed with fertilizers.

In combating mildew and rust diseases in cereals, an effect-enhancing effect (synergism) was obtained using 1- [1,2,4-triazolyl- (1)] - 1- (4'-ehlorophenyl) -4,4-dimethylpentane -3-one or 1- [1,2,4-triazolyl- (1)] - 1- (2 ', 4'-dichlorophenyl) -4,4-dimethyl-pentan-3-one, either as bases or in form their salts in admixture with N-tridecyl-2,6-dimethylmorpholine and its salts. A particularly pronounced increase in effect is observed at the mixing ratios of 1: 2 to 1: 4 parts by weight.

The following examples illustrate the preparation of the β-azolyl ketones of the invention (Example 1) as well as the fungicidal action of the new active substances (Examples 2-4) and the preparation (Examples 5-10).

EXAMPLE 1 f1

Cl - (o) -CH-CH 2 -CO-C (CH 3) 3 O ··· 450 g (2.58 mol) 2,4-dichlorobenzaldehyde, 275 g (2.75 mol) Dissolve methylbutan-3-one and 24 g of potassium hydroxide in 1500 ml of ethanol, stir for 3 hours at 60 ° C, mix with 375 g (5> 4 moles) of 1,2,4-triazole and stir for an additional 2 days at 60 ° C.

The solvent is then distilled off in vacuo, the residue is dissolved in 1500 ml of ether and the organic solution is washed three times, each time with 300 ml of water. The organic phase is then dried over sodium sulfate, filtered off and gassed with gaseous hydrogen chloride. The precipitate of 1- [1,2,4-triazolyl- (1) J-1- (2 ', 4'-dichlorophenyl) -4,4-dimethylpentan-3-one hydrochloride is sucked off and dried.

8 166026

Yield: 590 g (7490 theory) of white crystals (compound no.

9), mp 158-160 ° C. The free base melts at 78-79 ° C.

The other compounds listed in Table 1 are prepared in an analogous manner.

EXAMPLE 2

barley mildew

Leaves of barley-driven barley germ are sprayed with aqueous emulsions of 80% active substance and 20% emulsifier and sprayed after the initial drying of the spray coating with oidia (spores) of barley dust (Erysiphe graminis var. Hordei). The test plants are then set up in greenhouses at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 10 days, the extent of the development of mildew fungi is determined.

0 means no attack, escalated to 5, which means total attack.

Active substance Attack of the leaves after spraying with ..% active substance in the liquid 0.1 0.05 0.025 0.012 2 0 0 0 0 5 0 0 0 0 '0 0 0 0 10 0000 5 * 3

CH, -C-C 0 CH

CT, 15 4 5 known (German Publication No. 23 35 020)

Control (Untreated) 5 9 EXAMPLE 3 146026

Wheat

Leaves of potato-grown wheat seedlings of the species "Jubilar" were sprayed with aqueous emulsions of 80 $ (wt.%) Of active substance and 20 µm of emulsifier and powdered after the initial drying of the spray coating with oidia (spores) of Wheat Milk (Erysiphe graminis var.). The test plants are then set up in greenhouses at temperatures between 20 and 22 ° C and 75 to 80 $ relative humidity. After 10 days, the extent of mildew fungus development is ascertained. 0 means no attack, escalated to 5 meaning total attack.

Attack of the leaves after spraying with .. $ active substance in the liquid

Active substance 0.005 0.025 0.012 5 0 0 0 6 0 0 0 8 0 0 0 9 0 0 0 10 0 0 0

Clij-C-CO-Cti 2 3 5 ch3 known German Publication No. 23 35 020)

Control (untreated) 5 10 146026 EXAMPLE · 4

cucumber

Leaves of potato-cucumber seedlings are sprayed with aqueous 80 $ active ingredient and 20 $ emulsifier and powdered after the initial drying of the spray coating with oidia (spores) of cucumber mildew (Erysiphe cichoriaeearum). The soil plants are then set up in greenhouses at temperatures between 20 and 22 ° 0 and 75 to 80 $ relative humidity. After 10 days, the extent of mildew fungus development is ascertained. 0 means no attack, escalated to 5 meaning total attack.

Attack of the leaves after spraying actively; stand with. $ active substance in the liquid _0J_ 3 0 4 0 +)

Control (untreated) 5 minor leaf damage EXAMPLE · 5

90 parts by weight of compound 5 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a solution suitable for use in very small droplets is obtained.

EXAMPLE 6 20 parts by weight of compound 1 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the preparation product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of preparation products of 40 ml of ethylene oxide to 1 mole of castor oil.

By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

EXAMPLE 7 11 parts by weight of compound 2 are dissolved in a "mixture" consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the product of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 10 parts by weight of the product of 40 moles of ethylene. oxide to 1 mole of castor oil. Ted pouring and fine distribution of the solution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.02% by weight of the active substance.

EXAMPLE 8 30 parts by weight of compound 3 is thoroughly mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel.

In this way, a preparation of the active substance with good adhesiveness is obtained.

EXAMPLE 9 40 parts by weight of the active substance 5 are thoroughly mixed with 10 parts of sodium salt of a phenolic sulfonic acid urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Ted dilution with 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of active substance.

EXAMPLE 10 20 parts of the active substance 4 are thoroughly mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid urea-formaldehyde condensate and 68 parts of sodium salt of a phenol-sulfonic acid urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable, oily dispersion is obtained.

Claims (2)

12 U6026. Patent claims: 1. β-Azolyl ketones with fungicidal effect for use in plant protection, characterized in that they have the general formula: R1-CO-CH 1. R is alkyl of 3 to 5 carbon atoms and R is phenyl optionally substituted with methyl or halogen or where R is furyl and its salts. The β-azolyl ketone according to claim 1, characterized in that it has the formula: CH3 \ ch3 -c-co-ch2-ch - @ - ci CH3 ^ Λ Lj 3. The β-azolyl ketone according to claim 1, characterized in that it has the formula: Cl CH3 \ C CH3 -c-co-ch2-ch - ^ - ci Ά A, I-II 4. β-azolyl ketone according to claim 1, characterized in that it has the formula: CH3 \ CH, -b -C0-CHo-CH- (5V C1 1 i