DE2232730A1 - SUBSTITUTED CYCLOHEXANE-2,6-Dione-1CARBONIC ANILIDES AND THIOANILIDES, METHOD FOR THEIR MANUFACTURING AND USE AS INSECTICIDES, ACARICIDES AND FUNGICIDES - Google Patents

Description

Rt-Hg Ia

-i "JuI11972

Substituted cyclohexane-2,6-dione-1-carboxylic acid anilides. and thioanilides, processes for their preparation and their use as insecticides, acaricides and fungicides

The present invention relates to new substituted cyclohexane-2,6-dione-1-carboxylic acid anilides and thioanilides, a process for their preparation and their use as Insecticides, acaricides and fungicides.

3s it has already become known that 3,5-disubstituted 2-hydroxybenzoic anilides have an insecticidal and acaricidal activity, in particular 5,4'-dichloro-2-hydroxy-3-4 '' - chlorophenyl-benzoic anilide and the 5.2 ^! , 4 ' ₅ 5'-tetrachloro-2-hydroxy-3-4''- chlorophenylbenzoic acid anilide (see US Patents 3,216,896, 3,249,637, 3,454,638, 3,525,766; German Auslegeschriften 1 3oo 926 and 1 542 944). However, the effectiveness of these compounds, in particular against Tetranychus and Plutella species, is not always entirely satisfactory at low application concentrations. It has also become known that the unsubstituted cyclohexane-2,6-dione-carboxylic acid anilide has pharmacological properties and anti-tumor effects (compare Chem. Pharm. Bull.

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309884 / 1A7B

(Tokyo) 8, 1oi6-2o (196o)). A pesticidal effectiveness of this However, connections are not known.

It has been found that the new substituted cyclohexane-2,6-dione-1-carboxylic acid anilides and thioanilides of the formula

,1

in which

R ¹ , R ² , R ^{5 and} R represent hydrogen, halogen, alkyl and / or

and

and

ϊ8

Le A14 496

Carbalkoxy stand,

for alkyl, alkenyl, cycloalkyl and / or

optionally substituted phenyl,

also stand for hydrogen, under the preceding

12 5 exposure that of the residues R, R, R and

R is halogen, alkyl or carbalkoxy,

is hydrogen, with the proviso that one of the radicals R, R, R and R is halogen, alkyl or carbalkoxy or Β? stands for furyl,

together stand for an alkylene bridge with a maximum of 5 members, those with the adjacent Carbon atom forms a spiro bond, for halogen, nitro, cyano, alkyl, haloalkyl, Alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxycarbonyl, alkylsulfonyl, Alkylsulfoxyl and optionally substituted aroxy,

for hydrogen, halogen, nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, Haloalkylthio, alkoxycarbonyl and alkylsulfonyl stands,

09884 / U7Ö

η stands for integers from 1 to 4 and

7 8
R and R together, provided that

they are in ortho position to each other and η stands for 1, for a condensed aromatic or heteroaromatic ring system, which is optionally substituted can be, X. represents oxygen or sulfur

have very good insecticidal, acaricidal and fungicidal properties.

It has also been found that cyclohexane-2,6-dione-1-carboxylic acid anilides and thioanilides of the formula (I) are obtained when cyclohexane-1,3-diones of the formula

in which

R ¹ , R ² , R ⁵ , R ⁴ , R ⁵ , and R ^{6 have} the meaning given above

have and

M ■ for hydrogen or an equi

valent of a cation,

with isocyanates or isothiocyanates of the formula

^{v y}

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223273Ü

in which

7 s
R "« R -. X and η have the o ^ basi indicated beaeutimg,

optionally in the presence of acidic agents and solvent or thinners.

Surprisingly, the srf iriciiaigsgemäiSen substituted cycloiiexane-2,6-dio.n-1-carboxylic acid sanilides and thioanilides have a considerably higher insecticidal, alcaricidal and fungicidal effect than the 3,5-di-substituted known from the prior art en 2-Hydrox, j? benzoic acid ailide (5? 4 '-Dichlor-2-hydroxy ™ 3-4' ⁵ -chlorpbeny 1-benzoic acid anilide baw. 5 j 2 '■, 4', 5 'Tetrachlor-2-hydroxj - "3-4 ^?: -Ohlorphen ^ / lb ^ ri ^ oesäureanilid) and cyclohexane-2,6-dione-1'-c: arbcnsäureanilia, which are the chemically closest active ingredients of the same type of activity. The substances according to the invention thus represent an enrichment ¹ of technology,

If 4-phenyl-cyclohexane ~ 2,6 - äic: i and 3 ₃ 4-dichlorophenyl isocyanate are used as starting materials, the reaction sequence can be represented by the following formula:

■ LT

Vt /

/ Ά , ΛΓ "'Τ // ^ιλ _Γ ^! 1 TTρ-'"

"L ^ -T /

The starting materials 3ΪΏ.ά by the Fo ^ -jb ... (11 * irid (III) generally defined. In d.sr- Foruel (II) 3 ^i: 5hsn.?. ', R "", R and R ^u Torsussweise for Viaasstoff, -.Γϊιχ · ^ sra-ük & ttiges or

Le A U 435

branched alkyl with up to 4 carbon atoms, especially methyl, for carbalkoxy with up to 4 carbon atoms in the alkyl part and for halogen, especially chlorine or bromine. R and R preferably stand for straight-chain or branched alkyl or alkenyl with up to 4 carbon atoms, for cycloalkyl with 5 to 7 carbon atoms or for optionally substituted phenyl. Preferred substituents are: nitro, halogen, especially chlorine or fluorine, straight-chain or branched alkyl and alkoxy with up to 4 carbon atoms, especially methyl and methoxy, haloalkyl with 1 to 2 carbon atoms and 2 to 5 halogen atoms, especially fluorine. Furthermore, R ^ and R preferably stand for hydrogen, but only on condition that a radical of the above-mentioned radicals R ^! , R, R and R have a different meaning

4 ^

than has hydrogen. Furthermore, R stands for hydrogen, Pl for furyl; furthermore, R and R ^{r can} jointly represent an alkylene bridge with preferably 5 members which shares a spiro bond with the adjacent carbon atom. M in the formula (II) preferably represents hydrogen or an equivalent of a cation, in particular an alkali metal cation, for example sodium.

Examples of the substituted cyclohexane-1,3-diones of the formula (II) which can be used according to the invention are in detail called:

Dimedon

5,5-diphenyl-cyclohexane-1,3-dione 4-phenyl-cyclohexane-1,3-dione 5-phenyl-cyclohexane-1,3-dione 5-p-chlorophenyl-cyclohexane-1,3-dione 5-p-methylphenyl-cyclohexan-i, 3- ^ dione 6-bromo-5,5-dimethyl-cyclohexane-1,3-dione 4-Cyclohexyl-cyclohexane-i, 3-dione 4-methyl-cyclohexane-1,3-dione 5-methyl-cyclohexane-1,3-dione 5-isopropyl-cyclohexane-i, 3-dione 4,6-I) ibromo-5 »5-dimethyl-cyclohexane-1,3-dione 5-methyl-6-ethoxycarbonyl-cyclohexane-1,3-dione Le A 14 496 ■ - 5 -

309884 / U7Ö

5-furyl- (2 j-cyclohexane-i, 3-dione 5,5-apiro-cyclohexylfcyclohexanol, 3-dione

The substituted cyclohexane-1,3-aiones of the formula (II) used as starting materials are largely known (compare J, Cliem. Sog. 193I ₅ 814-818; J. Am. Gh em. Soc. 68 (1946) S, 566 -570) or can be produced in the usual way by known processes.

7 R

In the ϊοχίβθ! (III) R and R preferably represent halogen, in particular chlorine and fluorine nitro; Cyano; straight-chain or mixed-chain alkyl, alkoxy and alleythio with up to 4 carbon atoms, in particular methyl, isopropyl, tertiary butyl, iitricxy 5 methylthio; furthermore for haloalkyl, haloalkosqr and haloalkylthio with 1 to 2 carbon atoms and 2 to 5 halogen atoms, in particular chlorine and / or fluorine. In addition, R and R preferably represent alkoxy carbonyl and alkylsulfonyl with up to 4 carbon atoms

Alkyltsil. Furthermore, κ preferably stands for alkyl sulfox ^ / l with up to 4 carbon atoms . - ^ !. 1 ..- / It, ..-. '.! and for Gegeberi-3Ki £ lls by Halcgsi ·; iiisbaeonäers: jlii3r _s straight-chain cc! sr branched alkyl and alkoxy with up to 3 carbon atoms difcon, substituted ^ GS arozy _s iiisbssuGdsre phenoxy; η preferably stands for i iiuu 2 «means η ale 2ahl 1 and if R 'and R are adjacent is? ortlio-Stellimg »so they can together in advance stand for a - (CK) ^ - group, the. given-ii-f = .. lls through Hetsroatoiae wio oxygen, sulfur, nitrogen ^: broken up i-ei ^ can «in a hurry ait; the adjacent Iiolil ";.". ätoffatomen äs ;: ^; ? 'iCE7lrings eir'e-ii aromatic or het ^ i'O ^:' - c - j ..- s .- ':: ical ring MXd-t. Diesar lra ^ p- gr get at most Ii Hv-tle; <^ -: i, iiisbesoiAG '^ rv; üL.lor ₅ οάοϊ gv-? x "iüL'2tt: · ^; es or v / 6L .- ^"';> l ·: i-lkyl with hi: y. · -. ^1st 4 I: oh Ic- ^ .wtcc'f ^ tojL an. .:; nsbeson ~ the ^ i-ii ^"l." '"" .- substitutability -'. u- R "':::'; s i ^v: cc: ^-:: ί ': ΐ? · '' Left just vcr-

Le ... ■ '

3-chlorophenyl isocyanate 4-chlorophenyl isocyanate 3 j 4-dieh.lorophenyl isocyanate 3-trifluoromethylphenyl isocyanate 4-trifluoromethylphenyl isocyanate 4-trifluoromethylphenyl isocyanate 3,4-bis-trifluoromethoxyphenyl isocyanate 2,4-bis -trifluoromethylphenyl isocyanate 3-methylphenyl isocyanate 4-methylthiophenyl isothiocyanate 4-chloro-3-aifluoromethyl isothiocyanate 4-chloro-3-difluoromethyl isocyanate 4-chloro-3-trifluoromethyl isocyanate 3-chloro-4-trifluoromethyl isocyanate 2-chloro-4-trifluoromethyl isocyanate 2-chloro-4-trifluoromethyl isocyanate 3-chloro-4-difluoromethylthiophenyl isocyanate 3-methyl-4-chlorophenyl isocyanate 2-methyl-4-chlorophenyl isocyanate 4-i "luorFheny 1 is ο cy anat 4-nitrophenyl isocyanate 4-nitrophenyl isothiocyanate 2,5-dichloro-4-trifluoromethylplienyl isocyanate 2,6- Dichloro-4-trifluoromethylphenyl isocyanate • 2,3-dichloro-4-trifluorometaylphenyl isocyanate 3,5 ^ dichloro-4-trifluoromethylphenyl isocyanate cc -naphthyl isocyanate ß-naphthyl isothiocyanate 1-quinoline iso cyanate 2-IBO quinoline isocyanate 4-tert-butylphenyl isocyanate 2,6-diisopropylphenyl isocyanate 2,6-dimethylphenyl isocyanate 4-p-chlorophenoxyphenyl isocyanate

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3,4-5-trichlorophenyl isocyanate 3,4,6-trichlorophenyl isocyanate 4-ethoxyphenyl isocyanate, 4-methylthiophenyl isocyanate 4-methylthiophenyl isothio gyanate, 2-isopropyl-5-nitrophenyl isocyanate 2,6-diosopropyl-3-nitrophenyl isocyanate, 2-isopropyl-4-bromophenyl isocyanate 2-isopropyl-4-chlorophenyl isocyanate, 2,6-diethyl-4-bromophenyl isocyanate 2-ethyl-4-bromophenyl isocyanate 2,6-diisopropyl-4-bromophenyl isocyanate 2,6-diethyl-3-nitrophenyl isocyanate, 2-ethyl-5-nitrophenyl isocyanate, 2,6-diethyl-3,5-dinitrophenyl isocyanate

The substituted isocyanates used as starting materials and isothiocyanates are known or can be prepared by customary methods. As a diluent come for that reaction according to the invention all inert organic solvents in question. These preferably include hydrocarbons such as benzene, toluene or xylene; Halogenated hydrocarbons such as chloroform or carbon tetrachloride; Ether like Tetrahydrofuran and dioxane; Amides such as dimethylformamide; Nitriles such as acetonitrile and benzonitrile. Implementation of the Salts are preferably found in the presence of polar organic solvents or diluents such as ketones, e.g. B. acetone, Ethers, e.g. B. tetrahydrofuran, nitriles, e.g. B. acetonitrile, amides, e.g. B. dimethylformamide instead.

All customary acid binders can be used as acid binders. Particularly suitable are: alkali metal hydroxides such as potassium hydroxide or sodium hydroxide, alkyl alcoholate such as sodium ethylate, alkali metal carbonates such as sodium carbonate or potassium carbonate, alkaline earth metal carbonates such as barium carbonate, tertiary organic bases such as trimethylamine or pyridine.
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The process according to the invention can be carried out within a relatively wide temperature range. In general, between ⁰ ° C. and 100 ° C., preferably between 10 ° and 60 ° C., are used.

When carrying out the process according to the invention, 1 to 1.1 mol is used for 1 mol of the compound of the formula (II) the compound of the formula (III) and 0.1 to 1 mol of acid binder. ''

Any excess isocyanate is used for isolation Hydrolysis destroyed, the reaction mixture acidified and the active ingredient according to the invention by extraction with organic Solvents, distilling off the solvents and optionally further cleaning (recrystallization) obtained.

The active compounds according to the invention have an excellent insecticidal and acaricidal activity. You will be in crop protection successfully used to control harmful sucking and biting insects and harmful mites.

The sucking insects mainly include aphids (Aphidae) such as the green peach aphid (Myzus persicae), the black bean (Doralis fabae), oat (Rhopalosiphum padl), peas (Macrosiphum pisi) and potatoes (Macrosiphum solanifolii), furthermore the currant gall (Cryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black cherry aphid (Myzus cerasi), as well as scale and mealybugs (Coccina), e.g. the ivy scale (Aspidiotus hederae) and cup scale (tecanium hesperidum) and the mealybug (Pseudococcus maritimus); Bladder feet (Thysanoptera) such as Hercinothrips femoralis and Bed bugs, for example beet bugs (Piesma quadrata), cotton bugs (Dysdercus intermedius), bed bugs (Cimex lectularius), predatory bugs (Rhodnius prolixus) and chagas bugs (Triatoma infestans), also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

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The most biting insects are caterpillars (Lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantrla dispar), gold juicer (Euproctis chrysorrhoea) and ring moth (Maläcosoma neustria), furthermore the cabbage (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small frostworm (Cheimatobia brumata), oak moth (Tortrix viridana), the army (Laphygma frugiperda) and Egyptian Cotton worm (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kühniella) and large wax moth (Galleria mellonella),

Furthermore, the biting insects include beetles (Coleoptera) e.g. grain (Sitophilus granarius = Calandra granaria), Potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosus), table bean (Bruchidius = Acanthoscelides obtectus), Bacon (Dermestes frischl), khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeamais), bread (Stegobium paniceum), common flour (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground, e.g. B. Wireworms (Agriotes spec.) and grubs (Melolontha melolontha); Cockroaches like the German (BlattteHa germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia maderae), Oriental (Blatta orientalis), Giant (Blaberus giganteus) and giant black cockroach (Blaberus fuscus) and Henschoutedenia flexivitta; furthermore orthoptera e.g. the cricket (Acheta domesticus); Termites such as the terrestrial termites (Reticul'itermes flavipes) and Hymenoptera such as ants, for example the Meadow ant (Lasius niger).

The Diptera essentially comprise flies like the Tau (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small room (Fannia canicularis), glossy fly (Phormia regina) and blowfly

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(Calliphora erythrocephala) and the Wadenstech'er (Storaoxys calcitrans); also mosquitoes, e.g. mosquitoes such as the yellow fever (Aedes aegypti), house mosquito (Culex pipiens) and malaria mosquito (Anopheles stephensi) _etc.

The mites (Acari) include especially the spider mites (letranychidae) such as the bean (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the fruit tree spider mite (Paratetranychus pilosus = Panonychus ulmi), Gall mites, e.g. B. the currant mite (Eriophyes ribis) and tarsonemids, such as the shoot tip mite (Hemitarsonemus latus) and cyclamen mite (Tarsonemus pallidus); finally ticks, such as the leather tick (Ornithodorus moubata).

The active ingredients according to the invention have a strong fungitoxic effect against phytopathogenic fungi. Your good tolerance for warm-blooded animals and for higher plants allows their use as pesticides against fungal diseases. They do not damage cultivated plants in the concentrations necessary to combat the fungi. You practice on that Skin and mucous membranes in the fungitoxic concentrations do not cause irritation.

Fungitoxic agents in crop protection are used to control fungi from the most varied classes of fungi, such as Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi imperfecti.

The active ingredients according to the invention have a very broad spectrum of activity, e.g. they are effective against parasitic fungi on above-ground parts of plants, causing tracheomycosis Fungi that attack the plant from the ground, seed-borne fungi and soil-dwelling fungi.

The active ingredients against powdery mildew fungi from the Erysiphacean family, e.g. against fungi of the genus Erysiphe, Oidium and Podosphaera and against fungi of the genus Fusicladium. The active ingredients can Le A 14 496 - 11 -

■ J09884M47G

but also with good success for combating other phytopathogenic Fungi are used, e.g. against fungi that cause diseases in rice or other crops. the Active ingredients show good action against Piricularia oryzae, Pellicularia sasakii and Chochliobolus miyabeanus, three Pathogens that occur in rice plants and against Collitotrichum coffeanum in coffee, Mycosphaerella musicola in bananas, Cercospora species and Altermaria species.

In addition, some of the compounds according to the invention show a good action against seed-transferable fungi, phytopathogens Soil and sprout mushrooms.

The microbistatic effect of the active ingredients according to the invention should also be mentioned.

The active compounds according to the invention can be converted into the customary 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 using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-producing agents. In the case of use of water as an extender can be, for. B. organic solvents can also be used as auxiliary solvents. The main liquid solvents that can be used are: aromatics, such as xylene, toluene, benzene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, z. B. petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar

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Solvents such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, e.g. B. aerosol propellants such as halogenated hydrocarbons, e.g. B. Freon; as solid carrier substances: natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite, or diatomaceous earth, and synthetic minerals such as finely divided silica, aluminum oxide and silicates; as emulsifiers and / or foaming agents: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as a dispersant: e.g. B. lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be used in the formulations present in a mixture with other known active ingredients.

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

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use Solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts ■ medium and granules are used. It is used in the usual way, for. B. by spraying, 'spraying, misting, Dusting, scattering, smoking, gasifying, pouring, pickling or encrusting.

The active ingredient concentrations in the ready-to-use Preparations can be varied over a wide range. Generally they are between ο, οοοΐ and 1o $, preferably between o, o1 and $ 1.

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a-

The active ingredients can also be used successfully in ultra-low volume (ULY) to be used where it is possible, formulations up to $ 95 or even the 100 ^ igen active ingredient to apply alone.

Example A.

Phaedon larvae test

Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount Solvent containing the specified amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

Cabbage leaves (Brassica oleracea) are sprayed to runoff with the preparation of the active compound and are populated with mustard beetle larvae (Phaedon cochleariae).

After the specified times, the degree of destruction is determined in $> . $ 100 means that all beetle larvae have been killed. O # means that no beetle larvae were killed.

Active ingredients, active ingredient concentrations, times of evaluation and results are shown in the table below:

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A "

Table A (Plant Damaging Insects) Phaedon Larvae Test

Active ingredients Active ingredient concentration in

Degree of destruction in accordance

^0H V ^ oo.si

^0Η ί ^ - \

CH. CH

vy-ci 0.1

0.1 0.01

0.1 0.01

0.1 0.01

20th

100 70

100 60

100 100

CH CH

CO-NH

0.1 0.01

100 100

CH CH

0.1 0.01

100 80

CH.

CO-NH

Cl

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- 15 -

100 30

09884/1476

Active ingredients

Continuation of the table for Phaedon larvae test, active ingredient concentration in

^S degree of destruction in% after 3 ^Ta S

GH, OH,

CO-NH

■ OP,

0.1 100 0.01 100 0.001 40

CH

CO-NH

0.1 0.01 100 100

CH

0.1 0.01

0.1

0.01

0.001

0.1 0.01 100 95

100

100

100 30

CH CH

Cl

0.1 0.01 100 100

CH CH

CO-NH

0.1 0.01 100 100

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Active ingredients

Continuation table Phaedon larva test

Active ingredient concentration in

Degree of destruction

^s in io after 3 ^Ta S

GH CE

0.1
0.01

100 70

CH CH

CO-NH

0.1
0.01

100 100

CH CH

.0.1
0.01
0.001

100 95 65

CH CH

0-NH

SCP ₂ Cl 0.1
0.01

100 90

CO-NH

-Γ 0.1
0.01

100 100

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Example B Plutella test

Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount Solvent containing the specified amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of active compound and they are populated with caterpillars the cabbage moth (Plutella maculipennis).

After the specified times, the degree of destruction is determined in $. $ 100 means that all caterpillars were killed, while O $ indicates that no caterpillars were killed.

Active ingredients, active ingredient concentrations, evaluation times and The results are shown in the table below:

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Active ingredients

Table B.
(plant-damaging insects) Plutella test

Wirkstoffkon-ζentration in Kill rate in io after 3 ^Ta £ ^s

( known )

0.1

SCP ₂ Cl

0.1

0.01

0.001

0.1 0.01

0.1

0.01

0.001

0.1 0.01

0.1

0.01

0.001

0.1 0.01

100

100

100 80

100

100

100 95

100

100

100 90

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Example C

letranychus test (resistant)

Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent that contains the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.

Bean plants (Phaseolus vulgaris) which are approximately 10 to 3o cm in height are used with the preparation of the active compound, sprayed dripping wet. These bean plants are strong with everyone Stages of development of the common spider mite or bean spider mite (Tetranychus urticae).

After the specified times, the effectiveness of the active ingredient preparation is determined by counting the dead animals. The degree of destruction obtained in this way is given in $. 100 io means that all spider mites have been killed, 0 means that none of the spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and The results are shown in the table below:

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Active ingredients

Table C (plant-damaging mites) Tetranychus - test (resistant)

Act of if concentrate ion in

Kill rate in ^s * after 2 ^Ta S

( known )

) H Cl

(known) 0.1

0.1

20th

CH, CH,

CH CH

CO-NH

0.1

0.1 0.01

100

100 45

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For tsetzu ng Table G Tetranychus test (resistant)

Agents Wirkstoffkon- Abtötungegrad concentration in% after 2 t in ^T agen

GH. GH.

Eq 0.1

90

GH, GH.

GO-NH

0.1

98

GH GH.

Eq 0.1

0.01

0.001

100 95 45

GH CH

GO-NE

GF, 0.1

100

GH CH

CH CH

GO-NH · CO-NH

Eq

0.1

0.1

100

100

Cl ₁

CH CH

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Cl 0.1

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99

Active ingredients

Continuation of Table C Tetranychus test (resisten-t)

Active ingredient concentration in $>

Degree of destruction in % after 2 days

CH

CO-NH Cl

0.1
0.01

100 40

CH CE

CO-NH

0.1

98

CE CH

0.1
0.01

100 75

O-NH

0.1
0.01

100 40

Le A 14 - 23 -

Example D
Erysiphe test

Solvent: 4.7 parts by weight. Emulsifier: 0.3 parts by weight Water: 95 parts by weight

volume

Alky laryl polyglycol ether

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 concentrate with the specified amount of water, which contains the additives mentioned contains.

Young cucumber plants with about three leaves are sprayed with the spray liquid up to the dropping point. The cucumber plants remain in the greenhouse to dry for 24 hours. They are then pollinated for inoculation with lonidia of the fungus Erysiphe eichoreacearum. The plants are subsequently at 23 - 24 ⁰ G placed and about 75 # strength relative humidity in the greenhouse.

After 12 days, the attack on the cucumber plants is determined as a percentage of the untreated, but also inoculated control plants. O fi means no «?. Infestation, 100 # means that the infestation is just as high as in the case of control plants.

Active ingredients, active ingredient concentrations vc ^ ß The results are shown in the following table:

Le A14 496

■? O 9 3 8 4 / U 7 θ

Table D Erysiphe test

Active ingredients infestation in $ of the infestation of the untreated control an active ingredient concentration from O, O25 #

(known) 100

(known) 100

100

CH, CH,

CO-NH

CO-NH

Le A 14

- 25th

12th

309884 / U7G

Port setting table

Erysiphe test

Active ingredients infestation in # of the infestation of the untreated control an active ingredient concentration from O, O25 #

CH,

CO-NH

"" »^ TCÜ

CH ₅ ^ N £

12th

12th

CH, CH,

CO-NH

Le A 14

J <: ■ 'ό vj>

example 1

32.5 g (0.2 mol) of sodium dimedon are dissolved in 200 ml of anhydrous Dissolved dimethylformamide. This is done at 1o to 2o C under reflux and external cooling, a solution of 37.4 g (0.2 mol) of 3-trifluoromethylphenyl isocyanate in 50 ml of anhydrous Benzene dripped. The mixture is then stirred at room temperature for 12 hours and the reaction mixture is added to 1 liter. Ice water. After acidification with 15 ml of glacial acetic acid, the organic phase is extracted three times with 100 ml of chloroform each time dried over sodium sulfate and the solvent was distilled off in vacuo. The residue is made from 100 ml of petroleum ether recrystallized.

37 g (67 % of theory) of 4,4-dimethyl-cyclohexane-2,6-dione-1-carboxylic acid (3-trifluoromethyl) anilide with a melting point of 110 ° C. are obtained.

Le A 14 496 - 27 -

4/14 7

a?

Example 2

CO-NH

18.8 g (0.1 mol) of 4-phenyl-cyclohexan-i, 3-dione are in 150 ml of anhydrous benzene dissolved, to this 10 ml (0.07 mol) Triethylamine given and a solution of 11.6 g (0.1 mol) 3,4-dichlorophenyl isocyanate in 50 ml of anhydrous benzene added dropwise with reflux cooling and stirring so that the temperature does not rise above 40.degree. To complete the reaction is then heated to boiling for 2 hours. Then 10 ml of glacial acetic acid are added, the solvent distilled off in vacuo and the remaining residue is recrystallized from ethanol.

14.6 g (39 % of theory) of 4-phenyl-cyclohexane-2,6-dione-1-carboxylic acid (3,4-dichloro) anilide _{with a} melting point of 140 ° -142 ° C. are obtained.

Le A 14 496 - 28 -

09884/1476

CD CA CX)

(D

VD

T a

Hurry

tV3
VD

example
number

R ¹

3
4th
5
6th
7th
8th
9

10
11
12th

13th
14th
15th
16

17th

H H H H H H H H H H

H H H H H

y melting point

H H H H H H H H H H

H H H H H

CH

CH ₃
CH ₃
CH ₃
OH,

CH

CH

CH ₃
CH ₃
CH ₃
CH,

CH,

ch '

CH ₃

CH ₃

H H H H H H H H H H

H H H H H

H
H
H
H

3-Cl
4-01
4-F
4-NO,

H
H
H
H

H 4 -C (CH ₃ ) ₃ H.
H 4-OC ₂ H ₅ H
H

H
H
H
H

H
H
H
H

3-CH ₃ 4-Cl
3-Cl 4-CF,
3-CH ₃ H

3-Cl 4-Cl
2-CF ₃ 4-Cl
2-Cl 4-Cl
4-0-1

H 2 -CH (CH ₃ ) ₂

0
0
0
0
0
0
0
1
1
0

1
1
1
1
1

0 0 0 0 0 0 0 0 0 0

0 0 0 0 0

6-CH (CH ₃ ) 2

87

140

127-129 127-134 120-121 122-124

120

222-223 124-127 77

134

118

153-155 154-155

138

tf
CD continuation T ate lie 1 R ⁴ R ⁵ R ⁶ R ⁷ R ⁸ η X Melting point 2232730 J>
VO Example-
number R ¹ R ² R ⁵ CH ₃ H H 3-OF ₃ 4-01 1 O 140-145 18th H H CH ₃ H H 3-Cl 4-OCF ₃ 1 O 104-105 19th H • H CH ₃ / "ΊΤΤ H H 3-CF ₂ H 4-01 1 O 10y-i Ό 20th H H CH, CH ₃ H H 3-Cl 4-SCF ₂ ClI O 116-118 21st H H CH, H H 2-Cl 4-CF ₃ 1 O 130-132 22nd H H CH ₃ H H 3-01 4,5-Cl ₂ 2 O 140-142 23 H H OH ₃ CH ₃ H H 2-Cl 4,5-Cl ₂ 2 O 188-191 24 H H CH ₃ CH ₃ H H 4-CF ₃ 2,5-Cl ₂ 2 O 145 I. 25th H H OH ₃ CH, H H 4-OF '2,6-01 ₂ 2 O 143-146 V »
O 26th H H CH ₃ H H HO ^ 33H
HH O 264-265 I. 27 H H CH ₃ H H H 4-CF ₃ HO O 154-155 • 28 H H H H H 3-Cl 4-CF ₃ 1 O 147-150 29 H H Qr-

Claims (6)

Pat is subject to: R, R, R ^ and R for hydrogen, halogen, carbalkoxy R ^ and R ^ for alkyl, alkenyl, cycloalkyl and / or optionally substituted phenyl, also represent hydrogen, with the ^{proviso that one of the radicals R 1} , R ² , R ⁵ and R represents halogen, carbalkoxy or alkyl, R stands for hydrogen, -under the preceding- 12 setting that of the residues R, R, R and R one stands for halogen, alkyl or carbalkoxy or R- ^ for furyl, R ^ and R together for an alkylene bridge with there are at most 5 members that form a spiro bond with the adjacent carbon atom forms, R for halogen, nitro, cyano, alkyl, halo genalkyl, alkoxy, haloalkoxy, alkylthio, HaloalkyIthiο, alkoxy carbonyl, Alkylsulfonyl, alkylsulfoxyI and optionally substituted aroxy, Le A 14 496 _. - 31 - 309884/1476 BAD ORIGINAL R ⁷ and R ⁸ represents hydrogen, halogen, nitro, cyano, alky 1, halogen alkyl 1, alkoxy, Ha J. ν & er alkoxy, alkylthio, halogens L'üyittiio, alkoxy carbonyl and alky! sulfonyl, stands for integers from 1 to 4 and together, under the goal exposure, that they are in ortho position to one another and η stands for 1, stands for a fused aromatic or heteroaromatic ring system, which can optionally be substituted,
represents oxygen or sulfur. 2. Process for the preparation of the substituted cyclohexane-2,6-dione-1-carboxylic acid anilides and thioanilides of the formula I, characterized in that cyclohexanes, 6-diones of formula II H (II) in which R ¹ , R, R ^, R ^, R and R have the meaning given above have and M for hydrogen or an equi valent of a cation, with isocyanates or isothiocyanates of the formula (III) , 7 (III) R ¹ XCN Le A14 496 - 32 - 109884/1476 JiAD ORIGINAL in which 7 8 R, R, η and X have the meaning given above, optionally reacts in the presence of acid binders and diluents. 3. Agents for combating insects, mites and phytopathogens Mushrooms characterized by a content of substituted cyclohexane-2,6-dione-i-carboxylic acid anilides and thioanilides of the formula (I) according to Claim 1. 4. Methods of combating insects, mites and phytopathogens Mushrooms, characterized in that substituted cyclohexane-2,6-dione-1-carboxylic acid anilides and thioanilides of the formula (I) according to claim 1 on insects, mites and phytopathogenic fungi or their habitat can act. 5. Use of substituted cyclohexane-2,6-dione-1-carboxylic acid anilides and thioanilides of the formula (i) according to Claim 1 for combating insects and mites and phytopathogenic fungi. 6. Process for the production of an insecticidal, acaricidal and fungicidal agent, characterized in that one substituted cyclohexane-S.ö-dione-i-carboxylic acid anilides and thioanilides of the formula (I) according to claim 1 with extenders and / or surface-active agents -, :: .. mixes. Le A 14 496 - 33 - 309884 / U76