DE2022494A1 - Fungicides - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKU S EN ■ Bayerwerk Patent department

Fungi ζ id e middle 1

The present invention relates to the use of partially known 3-aryl ~ 5-alkylidene-oxazolidinedione- (2,4) as fungicides,. ■

It is already known that 3-aryl-5,5-dialkyl-ox = azolidinedione- (2,4), e.g. B. 3- (3 ', 5'-dichlorophenyl) -5,5-dimethyl-oxazolidinedione- (2,4), have fungicidal properties (cf. German Offenlegungsschrift 1 811 843). These compounds are phytopathogenic, but only against a few Mushrooms effective. '

It has now been found that the partially known 3-aryl-5-alkylidene-oxazolidinediones (2 _f 4) of the formula

T-aryl

in which '

R and R 'represent halogen and optionally substituted alkyl having 1 to 6 carbon atoms stand and

"Aryl" for optionally by halogen, nitro groups, Alkyl, alkoxy, carbalkoxyalkenyl and / or (optionally in the aryl part .sub-

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109847/1942

2022484

substituted) aryloxy-substituted aryl radicals stands,

have strong fungicidal properties.

Surprisingly, those which can be used according to the invention show 3-Aryl-5-alkylidene-oxazolidinedione- (2,4) of constitution (I) a considerably better fungicidal effect, especially against Phycomycetes (Phytophtora, Peronospora), as the 3-aryl-5,5-dialkyl-oxazolidinedione- (2,4) known from the prior art, which are the chemically closest active ingredients of the same P type of action. The substances to be used according to the invention thus represent a real asset to technology.

The products in question are generally defined by the formula (I). In formula (I), E and R ¹ preferably represent chlorine and alkyl radicals having 1 to 3 carbon atoms; they can be substituted by chlorine atoms. "Aryl" preferably stands for phenyl, which can be substituted by chlorine, nitro, alkyl and alkoxy having 1 to 3 carbon atoms, furthermore by carbalk = oxyvinyl and / or (optionally substituted) phenoxy; in addition, "aryl" still stands for naphthyl.

w As examples of the use in this invention which may be mentioned specifically:

3- (2'-chlorophenyl) -S-dichloromethylene-oxazolidinedione (2.4) of 3- (3 '-chlorophenyl) -5-dic hlormethylen-oxazolidinedione (2.4) of 3- (4 ^t -.Chlorphenyl) -5-dichloromethylene-oxazolidinedione- (2,4) 3-phenyl-5-dichloromethylene-oxazolidinedione- (2,4) 3- (2'-nitrophenyl) -5-dichloromethylene-oxazolidinedione- (2,4) 3_ (3 -Ni trophenyl) -5-dichlonaethylene-oxazolidinedione- (2,4) 3- (4-nitrophenyl) -5-dichloromethylene-oxazolidinedione- (2,4)

Le A 12 991 - 2

1093A7 / 1942

3- (2 '-MethylphenylJ-S-dichloromethylene-oxazolidinedione-2,4) 3- (3' -Methylphenyl) -5-dichloromethylene-oxazolidinedione- (2,4) 3_ (4 "_ -methylpIienyl) -5-dichloromethylene- oxazolidinedione- (2,4) 3- (4'-ethylphenyl) -5-dichloromethylene-oxa25olidinedione- (2,4) 3- (4'-isopropylphenyl) -5-dichloromethylene-oxazolidinedione- (2,4) 3 - (4'-Methoxyphenyl) -5-dichloromethylene-oxazolidinedione- (2,4) 3- (4- '-ethoxyphenyl) -5-dichloromethylene-oxazolidinedione- (2,4) 3- (4' -phenoxyphenyl) -5 -dichlormethylen-oxazolidinedione - (2,4) of 3- (4 '~ p-Chlorphenoxyphenyl) -5-dichloromethylene-oxazolidinedione ^{_■:.:: Λ} ■■■■■ .; ■ '-, -.'■,; ■ (2,4) -;

3_ (4'_p_H'itrophenoxyphenyl) -5-dichloromethylene-oxazolidindiori- '

(2,4) 3_ (4 »-p-methylphenoxyphenyl) -S-dichloromethylene-oxazolidinedione ^

; : ■ ■ '■ ".. [: ■: -, ■'. -. ■■■■; ■ (2,4):

3- (3 ^l -Carbäthoxyvinylph.enyl) -5-dichloromethylene-oxazolidinediori- '

. :. -; ■■■■: ■ ^: (2,4) "

3_ ■ '(41 -Carbathoxyviny! Phenyl) -5-di-chloromethylene-oxazolidinedione-: ■ - ■.'. ■: ■■ '■■■. -.- ■■■■ ■ '■ - ■ ⁽² » ⁴⁾ ■

3_ (3 · -Carbmethoxyvinylphenyl) -5-dichloromethylene-oxazolidine =

■ dion »(2,4)

3_ (3 ", 4 ^r -Dichlorophenyl) -5-dichloromethylene-oxazolidinedione- (2,4) 3- (3 ', 5'-dichlorophenyl) -5-dichloromethylene-oxazolidinedione- (2,4) 3- (2' , 4 ', 5'-irichlorophenyl) -5-dichloromethylene-oxazolidine =

dione (2.4)

3-naphthyl-5-dichloromethylene-oxazolidinedione (2.4) 3_ (4 "-chlorophenyl) -5- (1 _'t 2 ^t -dichlorpropyliden) oxazolidin =

■■■■ · ■ dione- (2,4)

3-phenyl-5- (1 ^r _l 2- ^l -dichlone-ropyilden) -oxazolidindidn-C2,4) '3-naphthyl-5- (1 *, 2 ^l -diehlorpropylidene) -oxazolidinedione- (2,4) 3 - (4'-Ethoxyphenyl) -5- (1 · ^ '- dichloropropylideni-oxazolidine =

dione (2.4)

3- (4 "-p-chlorophenoxyphenyl) -5- (1" 2'-dichloropropylide ^ -oxazo =

lidindione (2.4)

3-phenyl-5-isopropylidene-oxazolidinedione- (2,4) 3- (4-chlorophenyl) -5-i3opropylidene-oxazolidinedione- (2,4)

Le A 12 991 - 3 -

1093 ^ 7/194?

One of the substances to be used according to the present invention is known from the literature, namely 3-phenyl-5-dichloromethylene-oxazolidinedione- (2,4) (cf. Bull. Soc. Chim. (1898) J ^ _x 779-785 ), but its structure was not corrected until 1940 (cf. J. Chem. Soc. 1940. 1512-1513). The other products have not yet been described, but they can be obtained in a simple manner by customary methods. So the products are z. B. obtained when Ot-hydroxy-ß-haloalkanecarboxylic acid ester with aryl isocyanates at temperatures between 0 and 50 ⁰ C in the presence of an inert organic diluent or solvent, such as. B. toluene, benzene, chloroform or methylene chloride, and acid acceptors, e.g. B. triethylamine, or carbanilides of the <X-Hydroxy-ßhalogencarbonsäureester treated under the conditions given above with an acid acceptor. Here, in the above process, are conveniently the reactants at the stated temperatures in the presence of a solvent together and then added to this mixture with stirring the acid acceptor added, the reaction mixture is maintained by external cooling preferably 10 to 2O ⁰ C internal temperature. After stirring for two hours at about 20 ^° C., to isolate the reaction product, the precipitate formed is filtered off, washed with cold chloroform and dried in the air.

The active ingredients according to the invention are highly fungitoxic Effect on. Because of their low toxicity to warm blooded animals, they are used to combat unwanted fungal growth suitable. Their very good tolerance for higher plants allows them to be used as a pesticide against fungal infections Plant diseases.

The active ingredients are particularly suitable for combating phytopathogenic fungi on above-ground parts of plants,

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109847/1942

as well as against phytopathogenic fungi that affect the plants from the soil attack or damage seeds.

The active ingredients have a "particularly high fungicidal potency against economically important plant-damaging fungi from the group of Phycomycetes. These include B. Phytophthora infestans and Plasmopara viticola. Also Venturia inaequalis (= Fusieladium dendriticum), the causative agent of apple scab, is combated by compounds according to the invention. However, the active ingredients can also be used to combat it with good success still further phytopathogenic pilae are used *, e.g., against fungi that cause diseases in rice, such as piricularia oryzae, Pellicularia sasakii and Cochliobolus miyabeanus.

The active ingredients are very effective in very low concentrations and are highly tolerated by plants the end. Accidental overdoses can therefore be accepted without further ado.

The active ingredients according to the invention can be converted into the customary formulations, such as solutions, emulsions, Suspensions, powders, pastes and granulates. These are made in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally.under Use of surface-active agents, that is to say emulsifiers and / or dispersants. In the event of the use of water as an extender can, for. B. also used organic solvents as auxiliary solvents will. The main liquid solvents that can be used are: aromatics, such as xylene and benzene, chlorinated aromatics such as chlorobenzenes, paraffins such as petroleum fractions, alcohols such as methanol and butanol, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; as feate carrier materials:

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108847/1942

natural minerals such as kaolins, clays, talc and chalk, and synthetic minerals such as highly dispersed ones Silicic acid and silicates; as emulsifiers: nonionic and anionic emulsifiers, such as polyoxy = ethylene fatty acid ester, polyoxyethylene fatty alcohol ether, z. B. alkylaryl polyglycol ethers, alkyl sulfonates and aryl = sulfonates; as a dispersant! z. B. lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be used in the formulations as a mixture with other inorganic and organic see fungicides and / or insecticides present.

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

The active ingredients can be used as such, in the form of their formulations or the form of use prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granulates. The application happens in the usual way, for. B. by spraying, splashing, pouring or scattering.

h The application concentrations can fluctuate over a very wide range. Usually they are between about $ 0.00001 and $ 2, preferably between 0.0001 and 1 fo. Are the active ingredients according to special procedures, for. B. after the ultra-low volume method, applied, the concentrates have active ingredient concentrations between 10 and 80 #, preferably 'between 20 and 60 $ on.

The following examples explain the use according to the invention:

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Example A;
Phytophthora test

Solvent: 4.7 parts by weight acetone Dispersant 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight

Mix the concentration required for the desired active ingredient The amount of active ingredient required in the spray liquid with the specified amount of solvent and dilutes the concentrate ' with the specified amount of water, which the named Contains additives.

Young tomato plants (Bonny best) with 2 - 6 leaves of beer are sprayed with the spray liquid until they are dripping wet. The plants remain at 20 ^° C. and a relative temperature for 24 hours. Humidity of $ 70> in the greenhouse. The tomato plants are then inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are placed in a humid chamber with a 100 #igen humidity and a temperature of 18 - 20 ⁰ O accommodated.

After 5 days, the attack on the tomato plants is determined as a percentage of the untreated but also inoculated control plants. 0 i » means no infestation, 100 96 means that the infestation is just as high as in the control plants.

Active ingredient, active ingredient concentrations and results go out de * following table:

■ β ■■■ <·

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109847/1942

Tabel

Phytophthora test '

Active ingredient attack in $> of the attack on the untreated control at an active ingredient concentration (in i ») of

0.025 0.0062

(known)

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109847/1942

Example B;
Plasmopara test

Solvent: 4.7 parts by weight acetone Dispersant: 0.3 parts by weight of alkylaryl polyglycol ethers, water: 95 parts by weight

The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the amount indicated Amount of solvent and dilute the concentrate with. the specified amount of water, which the additives mentioned contains.

Young potted vines (variety Müller-Thurgau) with 2-6 leaves are sprayed with the spray liquid until they are dripping wet. The plants remain in the greenhouse at 20 ° C. and a relative humidity of 70 ° for 24 hours. The vine plants are then inoculated with an aqueous spore suspension of Plasmopara viticola. The plants are placed in a humid chamber with a 100 follow humidity and a temperature of 20 - 22 ⁰ C accommodated.

After 5 days, the infection of the vines is determined as a percentage of the untreated but also inoculated control plants. 0 <fo means no infestation, 100 # means that the infestation is just as high as in the control plants.

Active ingredients, active ingredient concentrations and results go from the table below:

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109847/1942

Tabel

Plaamopara test

Active ingredient infestation in fo the infestation of the untreated control at an active ingredient concentration of 0.00078 '

(known)

Cl ₂ C

S — Ν-

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109847/1942

Example 0; ·

Fusicladium test (apple scab) / Protective

Solvent: 4 _f 7 parts by weight of acetone Emulsifier: 0.3 parts by weight Alkylarylpolyglykolather Water: 95 parts by weight

Mix the concentration required for the desired active ingredient The amount of active substance required in the spray liquid with the specified Amount of solvent and dilute the concentral; · with the specified amount of water containing the additives mentioned.

Young apple seedlings that are in the 4-6 leaf stage are sprayed with the spray liquid until they are dripping wet. The plants remain for 24 hours at 2O ⁰ C and a relative humidity of 70 i "in the greenhouse. They are then inoculated with an aqueous conidia suspension of the apple scab causative organism (Fusicladium dendriticum puck.) And in a humid chamber at 18 for 18 hours - incubated 2O ⁰ C and 100 i * relative humidity.

The plants are then returned to the greenhouse for 14 days.

15 days after the inoculation, the infestation of the seedlings in i · the untreated, but also inoculated control plants is determined.

0 ί means no infestation, 100 # means that the infestation is just as high as in the control plants.

Active ingredients, active ingredient concentrations and results go from the table below:

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Tabel

Fusicladium test / protective

Active ingredient infestation in fo the infestation of the untreated control at an active ingredient concentration (in fo) of 0.025

(known)

Cl

0.

V-Cl

Cl,

Cl

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3 47/1942

Production examples; Example 1;

The compound and its preparation are known (cf. Bull. Soc. Chim. (1898) 19, 779-785 and J. Chem. Sog. 1940, 1512-1513); The following manufacturing method, which is not described, is also well suited:

To a solution of 332 g (1.5 mol) Trichlormilchsäureäthyl = ester in 1.2 1 of chloroform are added at 1O ⁰ C 360 g (3MoI) phenyl isocyanate and allowed to this mixture with stirring and external cooling, at an internal temperature of 10 * 20 ⁰ C 170 g of triethylamine run in. The mixture is left for 2 hours at 2O ⁰ C and react for filtered off the precipitate formed. This is washed with cold chloroform and dried in air .. is obtained in this way 277 g of 3-phenyl-S-dlchiorniethylen-oxazolidinedione-C ^, 4) as colorless crystals, mp. 202 ⁰ C. The yield is 71 " ft of theory .. '"'" -. ■ '

Furthermore, the following compounds not yet described can be prepared in a corresponding manner

Example 2; Ί

With stirring and external cooling is added dropwise at a temperature of 15 ⁰ C 27, Og Triäthylamln to a mixture

Le A 12 991 - 13 "-.

from 44.3 g (0.2 mol) of ethyl trichloro lactate, 65.0 g (0.4 mol) of 4-ethoxyphenyl isocyanate and 300 ml of chloroform. The mixture is left to stir for 75 minutes and then the precipitate formed is filtered off with suction. This is washed with chloroform and air-dried. 40 g of 3- (4'-ethoxy = phenyl) -5-dichloromethylene-oxazolidinedione- (2,4) are obtained in the form of colorless crystals with a melting point of 175 ^° C. The yield is "■" 66 % of theory.

Example 3:

^ N - / * vy_Cl

ClpC ^^ O - ^^ O

The representation takes place in the usual way. Colorless crystals with a melting point of 183 ^° C.

Example 4:

Cl

* The presentation takes place in the usual way. Colorless crystals of m.p. 187 ⁰ G.

In game 5:

The presentation is successful * in overview colorless crystals of mp. 166 ⁰ O.

Le A 12 991 - 14 -

Example 6;

O Cl

fill rttl v / il ^ - υ «- ¹

The representation takes place in the usual way, colorless crystals from Pp .. 183 ⁰ C.

Example 7:

01

CH-

Cl

The representation takes place in the usual way. Colorless crystals from pp. 180 ⁰ C.

Example 8:

The representation takes place in the usual way, colorless crystals of Pp * 150 ⁰ C.

Example 9:

It is presented in the usual way, colorless crystals with a pp. 193 ° C. '" ^L

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109847/1942

Example 10s

A \ q

CH = OH O = C-OC ₂ H ₅

The representation takes place in the usual way. Colorless crystals from Pp. 131 ⁰ G.

Example 11:

The representation takes place in the usual way. Colorless crystals with a melting point of 198 ^° C.

Example 12:

Cl

The representation takes place in the usual way. Colorless crystals, mp. 18O ⁰ C.

La A 12 991

- 1 β-

0 9847719A2

Claims (5)

Claims; 1) Fungicidal agent, characterized by a content of 3-Aryl-5-alkylidene-oxazolidinedione- (2,4) of the formula R ' in which R and R 'is halogen, and optionally substi-' i iertes alkyl having 1 to 6 carbon atoms and "Aryl" means optionally substituted by halogen, nitro groups, alkyl, alkoxy, carbalkoxyalkenyl and / or aryloxy-substituted aryl radicals (optionally substituted in the aryl part) stands. 2) A method of combating fungi, characterized in that 3-aryl-5-alkylidene-oxazolidinediones (2,4) according to claim 1 can act on fungi or their habitat. 3) Use of 3-aryl-5-alkylidene-oxazolidinedione (2,4) according to claim 1 for combating fungi. 4) Process for the preparation of fungicidal agents, characterized in that 3-aryl-5-alkylidene-oxazolidine = dione (2,4) according to claim 1 mixed with extenders and / or surface-active agents. 5) 3-Aryl-5-alkylidene-oxazolidinediones- (2,4) of the formula Le A 12 991 - 17 - 10 9 8 47/1942 R LNR "R ¹ in which R and R ^{1 represent} halogen and optionally substituted alkyl having 1 to 6 carbon atoms and R ″ stands for one or more times by halogen, nitro groups, alkyl, alkoxy, carbalkoxyalkenyl and / or aryloxy-substituted phenyl (optionally substituted in the aryl part) or represents naphthyl. Le A 12 991 - 18 - 109847/1942