DE2328728A1 - SYSTEMIC FUNGICIDALS - Google Patents

Description

Bayer Aktiengesellschaft 2328728

Central area of patents, trademarks and licenses

Sir / Hs ⁵ ^ Leverkusen, Bayerwerk

^{11 a} June 5, 1973

Systemic fungicides

The present invention relates to the use of new N-fluorophenyl-N'-acyl-trichloroacetaldehyde aminals as System fungicides.

It is already known that acylated trichloroacetaldehyde aminals have a considerable fungicidal effect (cf. the German Offenlegungsschrift 1 543 6o4 and the corresponding US patent 3 52ο 927). ' In particular, the N-formyl-N'-S ^ -dichlorophenyl-trichloroacetaldehyde aminal gained importance in practice as a protective agent against powdery mildew diseases (cf. R. Wegler, "Chemistry of Plant Protection and Pest Control Agents", Volume 2, page 97, Springer-Verlag Heidelberg (197o)). However, its relatively weak systemic fungicidal properties are not entirely satisfactory Effect.

It has now been found that from the above-mentioned class of compounds, specifically the new N-fluorophenyl-lf'-acyl-trichloroacetaldehyde aminals the formula

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-NH-CH-NH-CO-R (I)

Γ ³

CN

in which

R for hydrogen and alkyl with 1 to 6 carbon atoms stands,

have strong systemic fungicidal properties.

Surprisingly, the N-fluoropheny1-N'-acy 1-trichloroacetaldehyde aminals which can be used according to the invention show a significantly higher systemic fungicidal effect than the known N-formy1-N ¹ -5,4-dichloropheny 1-trichloroacetaldehyde, which is the chemically closest active ingredient. The substances according to the invention thus represent an enrichment of technology.

Those which can be used according to the invention as system fungicides Substances are defined by the general formula I. In this formula, R preferably represents, in particular, hydrogen, also for methyl, ethyl, isopropyl, η-butyl, tert-butyl and n-amyl. The following have proven to be particularly effective proven new substances:

F-p-Fluorpheny 1-N '-f ormy 1-trichloroacetaldehy daminal, S-m-Fluorpheny 1-N '-f ormy 1-tr ichloracetald ehy daminal, F-o-fluorophenyl-N'-formy 1-trichloroacetaldehy daminal.

The substances which can be used according to the invention are new, but they can be easily prepared by known processes getting produced. So you get them z. B. if you

a) fluorinated isocyanates of the formula Le A 15 o81 - 2 -

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-N = C = O (II)

with N- (2,2,2-! Erichlor-1-hydroxyäthyl) -säureamiden der formula

HO-CH-NH-GO-R (Hl) in which
R has the meaning given in formula I,

expediently in the presence of a diluent and a catalytically effective amount of an organic one Base implements (see German Offenlegungsschrift 1 543 6o4 or US Patent 3 52o 927);

or if you

b) fluorinated anilines of the formula

\ (IV)

with N- (1,2,2,2-Ietraehloräthy1) -säureamiden of the formula CCI ₅ -CHCl-NH-CO-R (V)

in which

R has the meaning given above,

in the presence of a diluent and at least one equivalent amount of acid binding agent (cf. Ber. dtsch. former Ges. 47, 1180 (1914)).

If, according to route a), p-fluorophenyl isocyanate and N- (2,2,2-trichloro-1-hydroxyethylformamide) are used as starting materials, so can

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the course of the reaction is shown by the following equation will:

IH

F-Λ X-N = C = O + CCl ^ -CH-NH-CHO

CCl

? - / \ -NH-CH-NH-

F- / X-NH-CH-NH-CHO + CO ₂

If, according to route b), p-fluoroaniline and N- (1,2,2,2-Tetracliloräthy 1) -formamide are used as starting materials, the course of the reaction can be represented by the following formula.

F- / / - ^ ⁺ CClj-CHCl-NH-CHO

F- / \ -NH-CH-NH-CHO + HCl *

The isocyanates given under the formula II are to be understood as o-, m- or p-fluorophenyl isocyanate. These isocyanates are known (cf., for example, Zh. Obshch. Khim. YJ_, 1796 (1967), Chem. Abstr. 68, 21618 b).

The N- (2,2,2-trichloro-1-hydroxyethyl) acid amides given under formula III are partly known, they can

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otherwise from chloral and the corresponding acid amides can be obtained in a simple addition reaction (v «l. Ber. German former Ges. 45, 945, 956 (1912)). As examples for compounds of the formula III the following may be mentioned: N- (2,2,2-trichloro-1-hydroxyethyl) formamide, N- (2,2,2-trichloro-1-hydroxyethyl) acetamide, N- (2,2,2-trichloro-1-hydroxyethyl) propionamide, N- (2,2,2-trichloro-i-hydroxyethyl) isobutyramide, N- (2,2,2-trichloro-i-hydroxyethyl) valeramide, N- (2,2,2-trichior-1-hydroxy äthy1) -pivalamid, N- (2,2,2-trichloro-1-hydroxyethyl) capronamide.

The anilines given under the formula IV are to be understood as o-, m- and p-fluoroaniline. These substances are known (cf. the relevant manuals, e.g. "Beilstein's Handbook of Organic Chemistry" Volume 1_2, 3rd supplementary work, Pages 1273 - 1277).

In the compounds of the formula V, R is preferably in particular for hydrogen, also for methyl, ethyl, isopropyl, η-butyl, tert-butyl and n-amyl. These N- (1,2,2,2-tetrachloroethyl) acid amides are known in part, they can also be obtained from the above-mentioned N- (2,2,2-trichloro-1-hydroxyethyl) acid amides synthesized with the help of inorganic acid chlorides (cf.ber. dtsch. former Ges.-47, 118o, (1914)).

The reactions can be carried out in the presence of inert solvents. These preferably include aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene and gasoline, chlorinated hydrocarbons such as chlorobenzene, Chloroform or carbon tetrachloride, ethers such as diethyl ether, dioxane or tetrahydrofuran, or nitriles,

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such as acetonitrile, also esters such as methyl acetate, and ketones such as acetone.

Basic auxiliaries can e.g. as catalysts in process a) and as an acid binder in process b) in particular organic tertiary amines, such as triethylamine, dialkylamines, pyridine or quinoline can also be used.

The reaction temperatures can be varied over a wide range; generally preferably carried out between 0 C and 15o ° C, between 10 ⁰ C and 100 ° C.

When carrying out the method according to the invention, sets one has approximately equimolecular amounts of the reaction partner. After the reaction has ended, the end product is isolated in the usual way Way by removing any salts present with water, removing the solvent and any Purification of the product by recrystallization.

The active ingredients according to the invention have a strong fungitoxic effect. Fungitoxic agents in crop protection are used to control fungi from various classes of fungi, such as Archimycetes, Phycomycetes, Axomycetes, Basidiomycetes and i * ungi imperfecti.

The active ingredients according to the invention not only have the good properties of excellent commercial preparations, but also also have considerable advantages. These are primarily in the ability of the substances according to the invention, to penetrate the plant, to be guided systemically and away from the place of application for the fungitoxic effect get. They can be absorbed from the seed surface, from the roots and also from above ground Plant organs after external application. Also own

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they have the beneficial ability to act locosystemically to come d. H. to exert a deep effect in the eplant tissue and in doing so, eliminating fungal pathogens that have already invaded the tissue of the host plant.

The active compounds according to the invention can be used as crop protection agents for the treatment of above-ground parts of plants, for Soil and seed treatment can be used. They are particularly effective against powdery mildew fungi (Erysiphaceae), z. B. against Erysphe, Podosphaera, Sphaerotheca and Micro sphaera species.

The substances according to the invention are well tolerated by plants. They have only a low level of toxicity to warm blooded animals and are not uncomfortable to handle because of their low odor and their good tolerance for human skin.

Active ingredients according to the invention can be used in the usual Formulations are transferred, such as solutions, emulsions, suspensions, powders, pastes and granules. These are in produced in a known manner, e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In case of Use of water as an extender can be, for. B. also used organic solvents as auxiliary solvents will. The main liquid solvents are: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or Methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones, such as

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Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl isulfoxide, and water; with -liquefied gaseous Extenders or carriers are liquids which are meant, which at normal temperature and below Normal pressure are gaseous, e.g. B. aerosol propellants such as halogenated hydrocarbons, e.g. B. Freon; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorilloaite and Diatomaceous earth, and synthetic minerals such as finely divided silica, aluminum oxide and silicates; as Emulsifiers and / or foam-generating agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as a dispersant: e.g. B. Lignin, Sulphite liquors and methyl cellulose.

The active ingredients according to the invention can be present in the formulations as a mixture with other known active ingredients, such as Fungicides, insecticides, acaricides, nematicides, herbicides, Protective substances against bird damage, growth substances, plant nutrients and soil conditioners.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 9o 5i.

The active ingredients can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, Powders, pastes and granules can be used. It is used in the usual way, for. B. by pouring, spraying, Spraying, dusting, scattering, dry pickling, moist pickling, wet pickling, slurry pickling or encrusting.

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When used as exfoliating fungicides, the active compound concentrations in the use forms can be varied over a wide range. They are generally between 0.5 and 0.05 percent by weight, preferably between 0.2 and 0.010 .

The active ingredients according to the invention also have one micro-static effect.

The various possible uses are shown in the following examples:

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Example A. .Λ

Erysiphe test / systemic

Solvent: 4.7 parts by weight acetone Dispersant: 0.3 parts by weight alkyl-aryl-polyglycol

ether

Water: 95 parts by weight

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

Cucumber plants grown in standard soil are in the 1-2 leaf stage three times within a week with 2o ecm the Pouring liquid in the specified concentration of active ingredient, based on 1oo ecm of soil.

The plants treated in this way are after treatment with Conidia of the fungus Erysiphe eichoracearum inoculated. Afterward the plants are placed in the greenhouse at 23 ° -24 ° C. and a relative atmospheric humidity of 70 °. After 12 days, the infestation of the cucumber plants is a percentage of the untreated, but also inoculated Control plants determined.

0 to 6 means no infestation, 100 % means that the infestation is just as high as in the case of the control plants.

Active ingredients, active ingredient concentrations and results are shown in the following table:

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Table A.

Erysiphe test / systemiscta.

Active ingredient

Infestation in i "of the infestation of the untreated Eontrolle at an active compound concentration of 25 ppm

Cl- / \ -NH-CH-

NH-CHO

(known)

. OC ₁ ,

-NH-CH-NH-CHO

^ Γ ⁵

P- / \ v -NH-CH-NH-CHO

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Podosphaera test / systemic

Solvent: .4.7 parts by weight of acetone. Dispersant: 0.3 parts by weight of alkyl aryl polyglycol ether Water: 95 parts by weight

The amount of active ingredient required for the desired active ingredient concentration in the casting liquid is mixed with the specified amount Amount of the solvent and dilute the concentrate with the specified amount of water, which the said Contains additives.

Apple seedlings grown in standard soil are at the 3-4 leaf stage within a week once with 2o ecm of the casting liquid in the specified active ingredient concentration on 1oo ecm earth, poured.

The plants treated in this way are inoculated after treatment with conidia of Podosphaera leueotricha and placed in a greenhouse with a temperature of 21-23 ° C and a relative humidity of about $ 70. 10 days after the inoculation, the seedlings are infected in Percentage of the untreated, but also inoculated control plants determined.

0 % means no infestation, 1 oo fo 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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Table B.

Podosphaera-Iest / systemic.

Active ingredient

Infestation in 96 of the infestation of the untreated control with an active ingredient concentrate ion of 5ο ppm

Cl- / A-NH-CH-CCl, Λλ // ι ■>

Cl

NH-CHO 69

(known)

CCl

3.

-NH-CH-NH-CHO 44

I ¹ CCl,

-NH-CH-NH-CHO 57

CCl,

-NH-CH-NH-CHO 17

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Production examples Example 1 :

Method a):

38.5 g (o, 2 mol) of N- (2,2,2-tricloro-1-hydroxyethyl) formamide are placed in 2oo ecm dry acetonitrile with the addition of 1 ecm triethylamine. In addition one gives under easier Cooling and stirring 27.4 g (0.2 mol) of p-fluorophenyl isocyanate in 5o ecm dry acetonitrile. The mixture is then boiled for a further 3 hours, the solvent is removed in vacuo and the residue recrystallized from a little ethyl acetate.

3o.5 g of N-p-fluorophenyl-N'-formyl-trichloroacetaldehyde aminal are obtained with a melting point of 95 - 96 ° C, that is 52%

Theory.

Method b):

655.7 g (3.1 mol) of N- (1,2,2,2-TetraehloräthyI) formamide are placed in 3 liters of dry chloroform. 345 g (3.1 mol) of p-fluoroaniline and then 713.9 g (3.1 mol) of triethylamine are stirred in dropwise at a maximum of 20 ° C. while cooling with ice. The mixture is stirred for a further 2 hours, then the solution is filtered, the filtrate is shaken out with water and the ChI or O form phase is dried with calcium chloride. After removing the solvent, the residue is digested with cyclohexane and a little ether, filtered and the solid product is boiled with water. After cooling, / bsaugen and drying, so 715 g Np-fluorophenyl-N'-formyltrichlor-acetaldehydaminal melting point of 92-95 ⁰ C, which are 81 $ of theory.

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In a similar way, the following connections can be made:

Example no. Formula Γρ. ( ⁰ C)

.-NH-CH-NHCHO

-NH-CH-NH-CHO

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Claims (1)

Claims ^ “Systemic - fungisiel @ means, keanzelehnet by one Content of I-eluophenyl-l'-aeyl-triehloroacetaldehyde aminals the Pormel ,. _#i , -MH-CH-MH-OQR in which R stands for hydrogen and alkyl with 1 to 6 carbon atoms «, 2. A method for the systemic control of fungi, characterized in that M-lluorophenyl-li'-acyl-tri chloroacetaldehyde aminals according to claim 1 are allowed to act on pilgrims or their habitat » 3 « Use of I amiaalen according to claim 1 söt syst © mischen combat «ag Mushrooms «. 4. The process for Herstelliffiig ψ on S3? St @ aisch "= fuagizidsn Hitteln" gekeaaseiclinet by ₉ äaß to ST Fluprphenyl I 'acyl trichloracetaldsb ^ daminal® claim ι with' Stffeckmitteln IMD / ODSR whether © rfläch © aaktiv © n means 5. lp-fluoropheny 1-lV = f oraj? I = IeZ ¹ I chlor®,! Formula T5 ¹ =. // \ V TiTU te TC fills Trs
\ - '-J Le A 15 081 - 16 = ■ GI 7th -NH-GH-NH-CHO Le A 15 o81 - 17 - 409882/1169