CS252814B2 - Insecticide and acaricide and method of its efficient componenent production - Google Patents

Abstract

The invention relates to novel substituted 1-phenyl-3-benzoyl- (thio)ureas of the formula (I) <IMAGE> in which X represents oxygen or sulphur, R<1> represents hydrogen, halogen, nitro, alkyl or alkylthio, R<2>, R<4> and R<5> are identical or different and represent hydrogen or halogen, R<3> represents hydrogen, halogen or nitro, R<6> and R<7> are identical or different and represent hydrogen, halogen or alkyl, R<8> and R<9> are identical or different and represent hydrogen or halogen and R<10> represents haloalkylthio or haloalkoxy, where (1) when X represents oxygen and R<2>, R<3>, R<4>, R<6>, R<8> and R<9> represent hydrogen and R<7> represents hydrogen or halogen and (a) R<1> and R<5> both represent halogen or (b) R<1> represents halogen, nitro or alkyl and R<5> represents hydrogen, in these cases the radical R<10> also represents haloalkylthio, and where (2) when X represents oxygen or sulphur and R<6> represents chlorine and R<8> represents hydrogen or chlorine and R<9> represents hydrogen and R<10> represents haloalkylthio or haloalkoxy and (a) R<1> and R<3> represent halogen and R<2>, R<4> and R<5> represent hydrogen or (b) R<5> and R<3> represent halogen and R<1>, R<2> and R<4> represent hydrogen or (c) R<1> and R<4> represent halogen and R<2>, R<3> and R<5> represent hydrogen or (d) R<2> and R<5> represent halogen and R<1>, R<3> and ... Original abstract incomplete.

Description

The present invention relates to insecticidal and acaricidal [. The active ingredient of the novel substituted 1-phenyl-3-benzoyl (thio) urea is the active ingredient. The invention further relates to a process for the preparation of these novel substituted 1-phenyl-3-benzoyl (thio) ureas and their use in the control of insects and mites.

It is already known that certain benzoyl ureas have insecticidal properties (cf., for example, European Patent Specification 0 057 888).

We have now found novel substituted 1-phenyl-3-benzoyl (thio) ureas of the formula I

(I) in which:

X represents a sulfur atom or an oxygen atom,

R is hydrogen ·· · i, a halogen atom - ^^ ntros nu or unnecessary ^to the shank formed of an alkyl group having 1 to 6 AT - we jlkylthύoskupinou atoms and having 1 to 6 carbon atoms,

R ^2, R ^t and R ^{5 with the sum} j ^é tejn NETA different ^e znjmeeaj and ^even atoms in ^. ^ík u neto atom ^^ оп ^

R ³ is hydrogen, halogen or nitro _R

R ^t and R? j ^{sum to} tejn ^s not a different ^{e b} and walk znamennaí hydrogen atom, · ft ^ l & gnnu Neto ^{o l} y ^ u ^ vuu group having 1 to 6 carbon atoms,

R @ 1 and R @ 2 are stationary or different and are hydrogen or halogen;

R ¹⁰ of ⁿ ame ⁿ g ^ halogenalkylthioskup US ^{1 and} 4 atoms of carbon or Logen ^ ^ ^ ox topino having 1 to 4 carbon atoms with 1-4 halogen atoms, preferably chlurdifluureethylthiuskup.inu, trfftuorenthylthUosktpint, chlordilUuoreethoxysktpint or trifluormethoxyykupinu, 'wherein ( 1) if X is oxygen and

R ^2, R ^3, R ^4, R ^6, R ⁸ and R ^{9 to} hydrogen and znammenaí

R is hydrogen or halogen; and

5 · (a) R and R znamennaí both halogen or (b) R ^{1 Zn} AME ⁿ and halogeno, nitro-ins or JL ^alkyl ^ ovut sbpm s is ^{from 1 to 6} carbon uhHto and R ⁵ represents hydrogen, in these cases the radical

R ¹ represents in ® ^from D ^{y g} halo enal ^to ylthiostopnu ^{«1 and 4} carbon uhHto and wherein (2) when X is oxygen or sulfur and

R is denoted by a

R ⁸ R ^{9 R 1} ° is hydrogen or chlorine and represents hydrogen, A is ^a Gene -yl ^^ ^TH iosku ^p yne with ¹ to ⁴ carbon atoms, ^{Y is} not a halo ^{b y g} enalkox SKU ^p yne with 1 to 4 carbon atoms and ( and)

R ^3, and 4 znameenaí halogen. _z >

R is hydrogen or (b)

3

R and R are halogen;

R, R and R are hydrogen or (c)

4

R and R are halogen and

R ^2, R ³ and R ⁵ znameeaaí hydrogen or (d)

5

R and R are halogen and

4

R, R and R are hydrogen, then a residue in these cases

R is in each case hydrogen ‘or an alkyl group having 1 to 6 carbon atoms.

These novel compounds have potent properties which make them suitable for use as biological, especially insecticidal and acaricidal, active ingredients of insecticidal and acaricidal compositions.

The present invention relates to an insecticidal and acaricidal composition, characterized in that it contains, as active ingredient, at least one substituted 1-phenyl-3-benzoyl (thoo) urea of the aforementioned general formula (I).

According to the present invention, the novel substituted 1-phenyl-3-benzoyl (thio) ureas of formula I are prepared by treating the substituted anilines of formula II

in which

R ⁶ , R ⁷ , R ⁸ , 9 10 R and R has:! the above meanings, in response with benzo-iso (thio) cyanates of formula III

R 2 R ¹

(IXI) in which

^X, R ^3, R ^2, R ^3, R ⁴ and ^{R 5} mmjí uvndnné above meanings or the ^p řítomnosti diluent.

Alkyl groups which ^R3, R ^R and ^R7 and alkylthio groups in the meaning of ^Y with MboI ^r3 obsaliují in the ^alkyl portion ^P RIMO or branched ^alkyl nominal al quick match with 1-6 carbon atoms, especially 1-4 carbon atoms. Examples which may be mentioned are methyl, ethyl, n-propyl, itipripyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tethultuosaupiau, ethylthio, n-propylthio, n-butyl, n-butylthio isobutylthio, sec.butylthio and Uercutbutthio.

^Ha ogee ^and kylt ^at iostat ^pi n ^y and ^h alogtaal ^to OXYS ^to upia ^y = S ^y MboI ^R10 contain ^from D ^y alkyl CAAT straight or branched alkyl group having 1 to 4 carbon atoms, in particular 1 or 2 carbon The halogen atoms are the same or different and preferably halogen atoms are fluorine, chlorine or bromine atoms, in particular fluorine.

Examples include tofuiurmmethyHliiosk UPIN cUlordiljuortetUykthooskupinu, trijlooeeUh ^y kUhioatopiau, chlortrffjioeeUhytUhίsskupinu, tetrafjioreth ^y tUhioskupiau, tofltoormeehoxyskupinu, dilloormethoxyskupiau, tetraljurteUhox stopiau ^{y, y} chkortrffjureeUhox - and brorntrifjuoreUhoxyskupiau.

Halogen means, unless otherwise indicated, a fluorine, chlorine, bromine and iodine atom, preferably a fluorine, chlorine and bromine atom.

X is preferably oxygen.

The novel compounds of the formula I have properties which make them useful as pest control agents, in particular they are distinguished by their high purity and acaicidal activity.

Halogen is fluorine, chlorine, bromine and / or iodine, preferably fluorine, chlorine and / or bromine.

Particularly preferred are compounds of formula I wherein

X is oxygen or sulfur,

R ³ we know him ^afloat, these fluo ^ ^ bromo aitios ^к by ^{p iau,} meíthylovou quick match etykovou group, n-propyl, isopropoxy ^s age group, n-butyl, isobufylovou group, sec-butyl, tert-butyl, teetuktUioskupinu, ttUylthOostopiaj, n propyltUiostopiau, isopropoxy ltUOoskupiau ^y, n buutythioskupinu, isobutyltboostopinu, sek.butylthOostopiau or terc.butylUhOoakupiau,

R ^2, R ⁴ and R ^{5 are} public or ríizn ^ ^é ^ ing a lower hydrogen fluorine, or bromine ^chkor,

R ³ represents hydrogen fluo-chloro, bromo or aitrostop ^{i au,}

R ⁶ and R ^{7 are not} Stoute bo r ^{s of the} Zn and known NAI ^ ^ hydrogen atom cliloru fluorine, bromine, methyl quick match, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec R ⁸ and R ⁹ are the same or different and represent a hydrogen, fluorine, chlorine or bromine atom;

^R10 or gametes trijluormttllylUhioakupiau ^t ri ^j Ίuoree ^U HOX ^y hundred ^pi and p ^ eemž (1) if X represents oxygen and

R ² , R ³ , R ⁴ , R ⁶ , R ⁸ and R ⁹ are hydrogen and

R ⁷ is hydrogen, fluoro, chloro or bromo and (a) R ¹ and R ⁵ are both fluoro, chloro and / or bromo, or (b) R ¹ is fluoro, chloro, bromo, nitro or the above alkyl radicals; and

r5 is hydrogen then a residue in these cases

R ¹⁸ is in each case trifluoromethylthio wherein (2) if X

R ⁸ is g

R is

Q

R is

R ¹⁸ is trifluoromethylthio or is oxygen or sulfur and chlorine and hydrogen or chlorine and hydrogen and trifluoromethoxy; and

(and) R ¹ and R ³ signify fluorine, chlorine or bromine and R ² (b) R ⁵ and R ³ signify fluorine, chlorine or bromine and R ¹ (C) R ¹ and R ⁴ signify fluorine, chlorine or bromine. , and R ‘ (d) R ² and R ⁵ signify fluorine, chlorine or bromine and R ^first

4

R and R are hydrogen,

4, R and R are hydrogen or

5, R and R are hydrogen or

R @ 5 and R @ 5 are hydrogen or, in these cases, a residue

R is in each case hydrogen or the above-mentioned alkyl groups.

Particularly preferred are compounds of formula I wherein

X is oxygen,

R ¹ represents hydrogen, fluorine, chlorine, bromine, nitro, methyl or methylthio,

4 5

R, R and R are hydrogen, fluoro, chloro or bromo,

R ³ represents hydrogen, fluorine, chlorine or nitro,

R ⁸ and R? are the same or different and are hydrogen, chlorine or methyl,

9

R and R are the same or different and are hydrogen, fluoro or chloro, and.

R ¹⁸ is trifluoromethylthio or trifluoromethoxy, wherein (1) when R ² , R ³ , R ⁴ , R ⁸ , R ⁸ and R ⁹ are hydrogen and

R is hydrogen or chlorine; and (a) R ¹ and r ⁵ are both fluoro, chloro and / or bromo; is fluoro, chloro, bromo, nitro or methyl;

R 5 is hydrogen, then in these cases the radical

^R10 is ^plated in ^ZDY tr ^fl lorrmet ylthiosku ^{h pi} nu, and wherein ⁽²⁾ if R @ ⁶ represents ^H, C ^s and lor

O

R is hydrogen or chlorine; and g

R represents hydrogen and ^R1 represents ® ^{á t} rί. ^ll ime ^th y ^l ^ ^l ^ ^{l i} (^ l ^) ^ upi ^ nl net> o ^ if ^ orme-thoxys ^ Lupdnu and

(and) r1 a or R ³ signify fluorine, chlorine or / a bromine and R ² » R ⁴ a r5 znaromnaí hydrogen (b) R ⁵ and or r ³ meaning fluorine, chlorine or / a bromine and R ^1, R ² a r4 znamnaí river (C) R ¹ or or R ⁴ meaning fluorine. chlorine or / a bromine and R2, R ³ a r5 signify hydrogen (d) R ² a R5 meaning fluorine, chlorine or / a bromine and r \ R ³ a R ⁴ znaInrnnjí hydrogen

then in these cases the rest

R is in each case hydrogen or methyl.

If 4- (2-chloro-4-trifluoromethyl-3-methylphenyl) -3-methyl-phenyl-2,6-diphenylbenzylisocyanate is used as starting material in the process of the invention, the reaction scheme may be illustrated as follows:

F

CO-NCO 4 F h ₂ n

Whose

Examples of compounds of formula II include those listed in Table I below.

II (II)

Table I

6 7 Я '9 Yeah R R R R R Η H H H OCF ₃ Cl H H H ^0CF 3 Cl Cl H H OCF ₃ H Cl Cl H ^0CF 3 H H Cl Cl ^0CF 3 Cl H H Cl OCF ₃ H H Cl H ° CF ₃ H H H Cl OCF ₃ Cl Cl Cl H OCF ₃ Cl Cl H Cl ^0CF 3 Cl H Cl Cl OCF, Cl Cl Cl Cl ^0CF 3 ^CH 3 H H H OCF ₃ ^CH 3 Cl H H ^0CF 3 ^CH 3 H Cl H OCF ₃ ^CH 3 H H Cl OCF ₃ ^CH 3 H Cl Cl ° CF ₃ ^CH 3 Cl Cl H ° CF ₃ CH ₃ Cl H Cl OCF ₃ CH ₃ Cl Cl Cl ^0CF 3 ^CH 3 ^CH 3 H H OCF ₃ ^CH 3 CH ₃ Cl H ^0CF 3 ^CH 3 CH ₃ H Cl OCF ₃

continuation Table I г.6 _7 _8 9 10 R R R R R ^сн з ^CH 3 Cl Cl OCF ₃ Η H IF H scr ₃ Cl H H H SCF ₃ Cl Cl H H SCF ₃ Η Cl Cl H ^SCF 3 Η H Cl Cl SCF ₃ Cl H H Cl SCF ₃ Cl H Cl H ^SCF 3 Η H Cl H SCF ₃ Η H H Cl SCF ^ Cl Cl Cl H ^SCF 3 Cl Cl H Whose SCF ₇ Cl H Cl Cl SCF, Cl Cl Whose Cl SCF, ^CH 3 H H H ^SCF 3 CH ₃ Cl H H SCF3 ^CH 3 H Cl H SCF ₃ ^CH 3 H H Cl SCF ₃ CH ₃ H Cl Cl SCF ₃ CH 2 Cl Cl SCF-, 3 ^CH 3 Cl H Cl SCF ₃ ^CH 3 Cl Cl Cl SCF ₃ ^CH 3 ^CH 3 H H SCF ^ ^CH 3 CH ₃ Cl H ^SCF 3 CH ₃ CH ₃ H CL SCF ₃ CH ₃ ^CH 3 C l Cl Τ'v “3

The substituted anilines of the formula II which are used as starting materials are known and / or can be prepared by processes and methods known from the literature (cf. DE-OS 32 17 619, DE-OS 32 17 620, European patent 00) 57 588).

Examples of compounds of formula III include: 2-fluoro, 2-chloro, 2-bromo,

2-nitro-, 2-methoh-, 2-meeththio-, 2,6-difluoro-, 2,6-dichloro-, 2-chloo-6-fluoro, 2-chloro-4-nitro-, 3,4 - difluoro-, 3,4-dichloro-, 2,3,6-trichloro-, 4-fluoro-, 4-chloro-, 4-bromo- and 4-nitrobizrylisocyanate or -bizoyl isothiocyanate.

The starting compounds of the formula III are known.

Virtually all inert organic solvents are suitable as diluents.

These include, in particular, aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, pyrrole, benzene, toluene, xylene, ethylene chloride, ethylene oxide, chloroform, carbon tetrachloride, chlorobenzene and o-diillorbeize, ethers, such as ethyl ether and dibutyl ether, glycol dimethyl ethers and diglycol dimethyl ethers, tetraldehyde and dioxane, ketones such as acetone, ethyl ether ethyl ketone, methyl isopropyl ketone and methylhexyl isobutyl ketones; for example dimethylacetamide and N-methylpyrrolidone as well as tetramethylene sulfone.

The reaction temperature can be varied within a wide range. In general, the process according to the finding mmzi ^{y 2} 0 and 1.80 ° C, preferably between 40 and 1 ° ² ° C. Post ^{PP characterized} in compliance with finding ^and di- ^p rov ^generally at atmospheric pressure.

In carrying out the process according to the invention, the starting materials are usually in approximately equimolar amounts. Excess of one or the other reactant does not bring any significant advantages.

Treatment of the reaction products is accomplished by conventional methods, for example by filtering off the precipitated product or by dissolving undesired by-products from the reaction mixture. The melting point is used to characterize the reaction products.

Stocks

Effective and useful in protecting normally sensitive stages of pests. It has good plant snowiness and favorable toxicity to heat, pests, especially insects, spider mites in forestry, forestry and maatphials, as well as hygiene. The substances mentioned are effective against even resistant species as well as against all or only individual developmental pests mentioned above:

order of the Thinopterans ^^ sub, for example, Common Woodpecker Common Woodpecker (Aamediil · idžue vulgaaee, (РртЛ ^ scebe);

(Diplopodd), for example, the Blaniulus gnutulatuss;

centipedes (CCilopodda, for example, earthworm (Gee> hus carpophaguu)), scarecrow (Scnuigera spec.);

from the class of the Centipede (SymehhУt), for example Sccuigerella ie'neaužtaa;

row of scales (Thhltnnua), such as dommc! Lepisma tacchlaiia;

from the order of the Collembola, for example OnycCiurus arm ^ ti ^ s ^;

of the order Orthoptera, such as the cockroach (Blatta orirnnalis), the cockroach ((θ ^ ρΙ ^^ americaanaa, madegar, Russian domestic (Β131 ± ι11ι germany), cricket (Achett dorneeticus), European mole cricket (Grr. Locusta eiggatoria elggatooioidrs, Melanoplus differmnaalis, Warty locust (Schistocerca gr ^ gařa);

from the order of the speckles (DegmetPtra), for example the speckle (FooficsLt tusrcuSatia);

from the order of the Isoptega, for example Rericsltrrrmrs sper.

from the order of the lice (Annuuuaa, for example, the ball (Р ^ С ^ хт valtaltrx), duSilkt (Pemppigus spee.), louse (Peeicslss humanus coopoo), Haemetopiyus spec.,

Linogntthss spěn .;

from the order of the lice (MaHophagaa, for example, the lice (Tg ^ chodrctrs spee.),

Dametiyet spec .;

from the order of the thrips (ThysstnpPeea), for example, HerrCnothgips freooatis, Thrushweed (Tl ^ irips Ιι ^ ι.);

from the order of the Nereropera, for example Eugygaatrr spec, Dysdegcus integmedius, Beetle (Pirsma quatgata), Bedbug (Cimex LrctuLa ^: Lu ^), Rhodnius řgplixss, TgiaPema spec .;

of the order Homepteer, for example, edicm cabbage (Aleugodes brassicae),

TabθιηϊβΙι tabacc, edicm Greenhouse (Tgiareugodrs vapopat? Iprsm), Cotton Beetle (Apřiis goosscíí), Cabbage Aphid (Bgevicpgyye Ogtssictr), Currant Aphid (Crcptomyzus ribis), Peacock Thistle, Dorus Bloodwort (Eriosoma lanigrrsí), Ball (Hyaloptrrustrisndiyis),

MMcrosiphuni avrnam,

Myzus sprc. · Hop aphids (Phorodon humuli), Bird cherry aphids (Rhopalosiphum padi) _f Tufted pea (Emmposca spec.), Pea (EesscIís bilobatus)

NeePhteetix cincticeps,

Lecanium corni, Saissetia oleae,

Laodelphax striatellus,

Nilaparvata lugans,

Acondiella auuranti, Asppdiotus hederae, Psesdococcus spec., Psylla spec.

from the order of the methyls (LLpPdiettPtea), for example

Pectinophora gossyppella, Dark-spot Adder (Bupalss piniarius), Cheimatobia brumaaa, Apple Lapse (Lithotctletis blanccadeeia), Apple Mole (Hyponomeuta pade) la), Field Pitch (PluSella macSl) ^ E Maacoso ^ ma neasstra), Muscovy (Eespíocís chrpsorrhoea), Muscovy (Ly ^ ani-ia spec.),

BusccSaarix thsrbeereeia, pleated plume (Plhlloonnitis citrella), duck (Asgrois spec.), Duck (Euxoa spec.),

Feltia spec.,

Earias insulana, Hcelothis spec., Lapiygma exigsa, Mame-sra brassicae, Panoois flammeaa,

Prodenia litsra, apodoptera spec.,

TrichopaSsia ni,

Carpocapsa poi ^ oonela, White (Pieris spec.),

CChlo spec., Pyransta nuSillHs, Moth moth (EpPhatit leather), Wax moth (Ga ^ eria meelonoela),

Tineola bi sscaliella

Tinaa pelli-oneHa

HofmoaoopPilt pseEddoppeateia, carnation (Cccoecia filed,

Capsa ratinulana, ^ n ^ stones ^ fumiferana

Clysia тЫсди) ^,

Homona mmgnainima, Tootrix vir-idana;

RADS from beetles (Co ^ e ^ Teal such ^IKL and ^d striped worm (Anobdsm {/ unctttsitil, korovoik (Rhizopprtht domidOcca,

Bruchidius obtectus, Accnthoosceides obtectus, Hylotrupes bajulus, Agelantic nlni, Potato mantle (LcePionotnrsn decemlintena), Cress oilseed (Dsp. Csp. Dsp.

EpilncOnn varivestis, Gryllum spec., OrylaeppOlus suiinnoeetSs, Anthonomus spec., Sitoppilus spec. postio, skinhead (DDrmmetes spec.), 'rrogoderin spec., towel (AnnPrenus spec.), skinhead (Attngenus spec.), OrboOlnv (Lyctus spec.), rapeseed (МеНде ^^ ιι ™) ^, spider (Ptinus spec.) .), Grasshopper (Niptus Oololiucuus, Gibbium psylloides, Darkling beetle (Tribolum spec.), Darkling beetle (Tenebrio iooííoo), Beetle (Aggiotes spec.),

Conoderus spec., COroust (MelooontOn о11 ^ 1 ^ <^ пП ^ 1 ^ с ^), cOroustik summer (AnmPOmlnlon sool sitinHs), Ccoselytin aealnndicn;

and order tannokřídlocO (Η ^^ ιιο ^ <^] ^ 1 ^ € ϊ1) ^),

Orebenule (Diprion spec.), Pilnlkn (Уoplocrmpr spec.), Worm (Lasius spec.),

Monomorium pharnonis, Hornet (Vespn spec.);

and order double-winged (Diiptea), tapped chamber (Aedes spec.), motelis (AnnppOles spec.), mosquito (Culix spec.), vinegar (Drosoppol mlannpglStl), flour (Muscn spec.), sun. kn (Fattin spec.), buzzing (CallipOpil liyt0ioceppola), buzzing (Luuiiin spec.),

Chryspmyir spec.,

Cuuerebrn spec., Galus (GalSrppPluslus spec.), ΫγρροΡοεο spec., Bodalkn (St ^ o ^ moxys spc ... uncle (Ooetrus spec.), Middle (Hypoderma spec.), Horsefly (Tabanus spec.),

Tannia spec., Brassica (Bibio hortulanus), Barberry (OsscnnCla frit),

Phoobia spec., Pegomyia hyoscyami, Common Propeller (Cecatitis caaPtata),

Dacus oleae (Tipula palcdosa);

from the order of the Siphonappera, for example XenoopsUa cheoopss, Ceeaaopphllus spee.

from the order of Arachnida, for example ·

Scorpio maurus, Weaver (Latrodectus yaaianss;

from the order of the mites (Accaina), for example Acarus s.ro, Argas spee.

Ornithodoros spec., Cornflower (D ^ irm ^ r ^^ yssus gaaiinae), Currant (Eriophyes ribis),

Phhllocoptruta oleivora, Keychain (Booohilus spee.), Drinker (Rhipicepitlcs spee.), Drinker (Amblyomma spee.),

Hyalonma spec., Tick (Ixodes spee.), Psoroptes spee., Chooioptes spee.

Sarcoptes spec., Mites (Tarsonemus spee.), Currant Spider (Bryobia praetiosa), Spider Mite (Panonychus spee.), Spider Mite (Tetranychus spee.).

The active substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic substances impregnated with active substances, polymer coated particles and seed coatings, as well as flammable additives such as smoke cartridges, smoke jars, smoke sprays and the like, as well as compositions in the form of a concentrate of active substance for cold or hot fog scattering.

These compositions are prepared in a manner known per se, for example by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied with gasification gases. The composition may be applied under a solvent and / or a solid carrier, optionally using surfactants, i.e., emulsifiers and / or dispersants and / or foaming agents.

If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. Suitable liquid solvents are in particular: aromatics such as xylene, toluene or chlorine, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as cilorbeteenes, chloroethyl or chloromethyl, or aliphatic hydrocarbons, such as cyclohexane; aromatic hydrocarbons, petroleum fractions, alcohols such as butanol or glycol, as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dioetyl sulfoxide, and water. .

By liquefied gaseous fillers or carriers is meant those liquids which are gaseous at normal temperature and at atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.

Suitable solid carriers are: natural stone meal, such as kaolins, alumina, moss, chalk, quartz, attapulgite, molar molonite or quartz, and synthetic stone meal, such as highly disperse silicic acid, alumina and silicates.

Suitable solid carriers for the preparation of granulates are crushed and fractionated natural stone materials such as limestone, marble, pumice stone, sepol and dolomite, as well as synthetic granules of inorganic and organic flours, and granules of organic maize, such as sawdust, shells. coconut, corn sticks and tobacco stems.

Suitable emulsifiers and / or foaming agents are non-diphthetic and atiotic emulsions, such as polyoxyethylene fatty acid esters, polyoxyethylene bridge alcohol alcohols, e.g. lignin, sulphite waste liquors and oeehyycceulosa.

The compositions of the present invention include adhesives such as carboxy-alcohol acetate, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

Further, these compositions may contain coloring agents such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes, azo dyes and metallic dyes, as well as trace elements such as iron salts, oongan, boron, oia, cobalat, molybdenum and zinc.

The cooneenates generally contain 0.1 and 95% of the active substance, preferably

0.5 to 90% Ут ^ по ^^ о! active substance.

The active compounds according to the invention can be used in the form of commercial preparations, as well as in dosage forms prepared from these preparations in a network with other active substances such as insecticides, baits, sterile agents, acicides, nemaocides, fungicides, growth regulators or herbicides.

The insects include, for example, phosphoric acid esters, cobalt, carboxylic acid esters, chlorinated hydrocarbons, phenyloureas, substances produced by microorganisms and the like.

The active compounds according to the invention can furthermore be used in the form of preparations which are commercially available, as well as in the use forms prepared from these preparations in the form of sytergic active compounds.

Synergically active substances are those compounds which increase the effect of the active substances without the added active substance having to be active on its own.

The active compound content of the dosage forms prepared from the preparations which are commercially available can vary widely. The cooneenraet of the active ingredient in the dosage forms can be from 0.000.000 L to 95% of the active ingredient, but preferably between 0.0001 and 1% by weight.

The application is carried out in a customary manner adapted to the application forms.

When used by professional pests in the field of hygiene and against storage pests, the active compounds are distinguished by an excellent residual effect on wood and clay as well as by good stability on lime substrates.

The active compounds according to the invention are also suitable for combating ectoparasites and endoparasites in game keeping and livestock cultivation, whereby pest control can achieve better results such as higher dojivossi, increased hmoonnosi, more beautiful animal hair, longer life span. etc.

The active compounds according to the invention in these regions is effected in known manner vněěší applications napžíklad as koupplí for immersion of ^the otPikt, drenches (pour-on and spot-on) and powders, as well as oral administration nappíklad via feed or drinking water in the form of, for example, tablets, capsules, beverages and granules.

The following Examples illustrate the preparation of the compounds of formula (I).

EXAMPLE 1

F

Cl (0.02 mol) of 3,5-dictlor-4- (4-trlU0uormethoxyflnoxy) aaniinu in 60 ml ^{of p} s t ^ lolz ⁶ 0 ° ^C at 3 ^{gives 66 g (0.02} mol) '2 ^6-d if l ^{u s t} uoebenio ookyan ^and the mixture ^{of p} Otom MICs are ≤ ¹ hour s te ^ OTE ⁸⁰ ° C. After K ^^ ⁱ ^ izi: ^s for the triol

To a solution of 6.76 ^¹H absolute toluene here in ¹⁰ ml toluene. 20 ° C from odukt reafóní ^ ^ filtered and dried in ^y.

9 g (86.5% Пю 11) l- (2,6-difluoro-гИп у ^!) ^ - ^, 5-dichloro-4- (4-rfiuororeethoxyfenoxy) fenyljmočoviny tepJotě ^th of the ¹⁹⁴ ° C .

Example 2

Analogously to Example 1, a compound of the formula:

from ₃ Cl

5.1 g (89% Пют11) 1- (2-brombeezzoyl-3- [3,5-diimthyly4- (3 "chlorinating 4-trifluoro ^mo thoxyienox ^yl) phenyl] Urine: ooin ^y ^ ture of tx ^th the ¹⁶⁷ ° C.

The following compounds of formula I are prepared in an analogous manner

(AND)

T a b u 1 and 2 Example number R ¹ R ^{2 r3 r4 r5 r6 r7 r8 r9} R ¹⁰ X Melting point (° C)

3 Cl H H H H Cl CL H H 0CF3 0 194 4 Cl H H H F Cl CL H H OCF ₃ 0 193 5 Br H H H H Cl CL H H SCF ₃ 0 199 6 Cl H H H H Cl CL H H SCF3 0 198 7 F H ' H H F Cl CL H H SCF3 0 215 8 Cl H H H Cl Cl CL H H SCF3 0 226 9 Cl H H H F Cl Cl H H SCF3 0 226 10 F H H H F Cl Cl CL H 0CF ₃ 0 167 11 Cl H H H F CL Cl CL H 0CF3 0 154 12 Cl H H H H CL Cl CL H 0CF3 0 178 13 F H H H F cl Cl CL H ^OCF3 with 170 14 Br H H H H cl Cl CL H OCF3 with 151 15 Dec Cl H H H F CL Cl CL H OCF3 with 182 16 ^N0 2 H H H H CL Cl CL H ° ^CF 3 0 202 17 sch ₃ H H H H CL Cl CL H OCF3 0 181 18 H H Cl H H CL CL CL H OCF3 0 232 19 Dec Cl H ⁿ ° ₂ H H CL Cl CL H ^OCF3 0 230 20 May H Cl Cl H H CL Cl CL H OCF3 0 128 21 Br H H H H CL Cl CL H OCF3 0 171 22nd CH3 H H H H CL Cl CL H 0CF3 0 188 23 Cl H H H Cl CL Cl CL H 0CF3 0 203 24 CH ₃ H H H H Cl CL H H ^0CF3 0 206 25 Br H H H H CL CL H H ^OCF3 0 200 26 Cl H H H Cl CL CL H H ° CR with 194 27 Mar: Cl H H H F CL CL H H OCF3 with 152 28 F H H H F CL CL H H ^OCF ' ³ with 145 29 Cl H H H Cl H H H H OCF3 with 154 30 F H H H F H H H H 0CF3 with 139 31 Cl H H H F CL H H H 0CF3 with 121

continuation of Table 2

Example Melting point

1 _2 '3 '4 '5 r> 6 Ί '8 9 10 .0 v ClF10 R R R R R R R R R R X (C) 32 Cl H H H H H H Cl H ^0CF 3 0 154 33 F H H H F H H Cl H ° CF ₃ 0 162 34 Br H H H H H H Cl H OCF ₃ 0 167 35 Cl H H H Cl H H Cl H ^0CF 3 with 156 36 Cl H H H F H H Cl H ° ^CF 3 with 148 37 Cl H H H H Cl H Cl H ° ^CF 3 0 151 38 F H H H F Cl H Cl H OCF ₃ 0 156 39 Cl я H no Cl Cl H Cl H ^0CF 3 with 143 40 Cl H p •'-and C:. H Cl H ° CF ₃ 0 188 41 Cl H at H Cl Cl H Cl ^0CF 3 0 200 42 Cl H H H H Cl Cl Cl H ^SCF 3 0 207 43 F · H H H F Cl Cl Cl H SCF ₃ 0 216 44 - H H H F Cl Cl H Cl OCF ₃ 0 196 45 Cl 4 no H F Cl Cl Cl H ^SCF 3 with 166 46 CH ₃ H H я H Cl Cl Cl H ^SCF 3 0 207 * .47 Cl H H H F Cl Cl H Cl ^0CF 3 with 161 48 Br H H n H Cl Cl H Cl ^0CF 3 with 154 49 Br and H H H Cl Cl Cl H ^SCF 3 0 204 50, Br H H H H Cl Cl H Cl ° ^CF 3 0 180 51 ^CH 3 H H H H Cl Cl H Cl ^0CF 3 0 207 52 Cl H 4 H Cl Cl Cl Cl H ^SCF 3 0 205 53 Cl H H H Cl Cl Cl Cl H OCF ₃ 0 220 54 v.l H H Cl ^CH 3 ^CH 3 H Cl ^0CF 3 0 191-192 55 Cl H H H H CH ₃ ^CH 3 H Cl ^0CF 3 0 174-175 e < Cl H H H F ^CH 3 ^CH 3 H Cl OCF ₃ 0 172-173 - F H H H F CH ₃ CH ₃ H Cl ^0CF 3 0 182-183 5Я Cl H H H H ^CH 3 ^CH 3 Cl H OCF ₃ 0 200-206 59 C3 П H H H CH ₃ ^CH 3 H H SCF ₃ 0 201 л n H я F CH ₃ ^CH 3 Cl H ^0CF 3 0 151 61 я at - CřK □ CH ₃ H H ^SCF 3 0 200 62 г 3 Cl Cl Cl H ° GF ₃ 0 196 63 H if H 7 ~ ^: 3 CH ₃ Cl H ° ^CF 3 0 149 64 Cl. Í1 H H F CH ₃ CH ₃ Cl H ° ^CF 3 with 155 65 H H H F CH ₃ ^CH 3 Cl H ^0CF 3 with 133

The biological activity of the compositions of the invention is illustrated by the following examples. Example A.

Field Witch Test (Plutella maccUipennis)

Solvent: 15 parts of mono-dimethyl dimethylformamide emulsifier: 1 part of mono-alkylcryl polyglycol ether

In order to obtain a suitable active agent, 1 part is mixed. of the active ingredient with said solvent and said emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by immersion in the preparation of active substance of the desired concentration and occupied, if the leaves are still moist, by the caterpillars (plutella raacUipeenC ^ S).

Percent mortality is determined after the required time. For example, mm means 100% when all caterpillars were killed, while 0% means no zhousenekebyylauoInrecna.

In this test, for example, at a concentration of 0.001%, the compound of Examples 1, 3, 4, 7, 10, 11, 12, 21, 22, 37, 38, 43, 44, 57, 58, 60, 61 and 63 after 7 days 100% ю ^ аИи.

Example B

Test for mosquito larvae

Experimental insects: mosquito (Aedes aegypti) in the 2nd larval stage solvent: 99 parts of acetone acetone emuuggore: 1 part ^ τ ^ ο ^ η! clkylarylflyglykulntCnru

To prepare a suitable effective. 2 parts of the active ingredient are dissolved in 1000 parts by volume of solvent containing the above-mentioned emulsifier. The solution thus obtained is diluted with water to the desired lower concentrations.

Aqueous active agent compositions of the desired concentration are filled into a plastic beaker and then 20 larval mosquito larvae in the second larval stage are added to each beaker. Larvae feed daily.

After 1, 8 and 21 days, the percentages are determined. 100% means that all larvae or pupae have been killed. 0% means that none of the larvae were killed at all.

In this test, a concentration of 10 ppm, for example, of the compound of Examples 38 to 63 after 100 days, showed 100% yield.

Example

Test with paaazztujici buzzer larvae (Luuilia čupřina)

Retrofoil: 35 parts of nUtUsSoRtUntiSy: nUtUtSor: 33 parts of nucylnenulpulygullyconetner

To prepare a suitable active ingredient, 30 parts of the active ingredient are mixed with the indicated amount of solvent containing the above-mentioned emulsifier, and the concentrate thus obtained is diluted with water to the desired concentration.

About 20 buzzard larvae (Lucilia scum) are transferred to tubes containing about ³ cm ^{3 of} horse muscle. About 0.5 ml of the active ingredient preparation was applied to this horse meat. After 24 hours, the percentage of mortality was determined. 100% means that all larvae were killed and 0% means that none of the larvae were killed (control).

and

In this test, for example at the active compound concentration of 1000 ppm, for example, the compounds of Examples 1 and 4 show 100% mortality.

Example D

Test for spider mite (Tetranychus urticae) - resistant strain

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

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with said amount of solvent and said amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris), strongly attacked by all developmental stages of the spider mite (Tetranychus urticae), are treated by immersion in the preparation of active substance of the desired concentration.

Percent mortality is determined after the required time. 100% means that all spider mites have been killed, while 0% means that none of the mites has been killed.

In this test, for example at a concentration of 0.1%, the compounds of Examples 2, 33, 37, 38, 43, 47, 55, 56, 57, 58, 60, 61 and 63 show 98% mortality after 10 days.

SUBJECT OF THE INVENTION

Claims (5)

SUBJECT OF THE INVENTION Insecticidal and acaricidal composition, characterized in that it contains at least one 1-phenyl-3-benzoyl (thio) urea of the formula I as active ingredient R ⁶ CO-NH -CX-NH- / Qn-o-R ^w In r8 R (I) wherein X represents a sulfur atom or an oxygen atom; represents a hydrogen atom, a halogen atom, a nitro group or a radical selected from the group consisting of alkyl of 1 to 6 carbon atoms and alkylthio of 1 to 6 carbon atoms, 2 4 3 ^R, R and R are identical or different and are hydrogen or halogen, ^R3 is hydrogen, the gene-Neto aitroskupiau, ^RG and ^R7 are the same ^e neta different ^e and mean hydrogen in ^ík ^ j ^{u H} JLO ^g NNU ^b not on asylum group having 1 to 6 carbon atoms, 8 9 R c and R d are the same or different and are not defined. a hydrogen atom or a halogen atom; and ^R10 represents ^H ^ allogeneic yltLhioskupinu having ¹ to ⁴ carbon atom ^s Uhl ^Cart with no o ^ ^b ^^ logenalRox dialkylamino having 1 to 4 carbon atoms with 1-4 halogen atoms, straight-ieemž (1) if X represents oxygen and R ^2, R ^3, R ^4, R ^6, R ⁸ and R ⁹ is hydrogen and zaamenají R ⁷ represents hydrogen or halogen and (a) R ¹ and R ⁵ both are halogen znameeají or (b) R ¹ n considerably ^^ ^a ^ lo ^ u ^to u aitios ^p iau NETIO asylum group ^{1 of 6} atoms of carbon and ^Y r 3 is hydrogen, then in these cases the residue R ^{1 s 0} zaamea haligeaa ai ^{y j h} kylt IOT ^to upiau ^{1 and 4} of ^Y uh-ku straight-EMZ (2) when X is to ^Y oxygen or a sulfur, and ^R6 considerably ^^ n ^and chlorine AG I do know hydrogen R ^ ^b of ^the non clilor and R is hydrogen and ^R10 represents ^H aligena ^j kylt ^h ios ^to upiau ^{1 and 4} atoms in ^the carbon net alignaalkix ^{h s p} iau SKUs having 1 to 4 carbon atoms and 1 3 2 4 5 (a) R ¹ and R ³ melted! halogen and ^{R, R} and ^{R are} hydrogen net 5 3 1 2 ⁴ (b) R and R alkyleneoxy means halogen and ^{R, R} and R are hydrogen, or (c) R ¹ and R ⁴ znameeají halogen and ^{R2, R3} and ^R8 are hydrogen or (d) R ² and R ⁵ are halogen and ^{R1, R3} and ^R ^ ena Znaim 0! hydrogen, then the remainder in these cases R7 is in each case hydrogen or alkyl of 1 to 6 carbon atoms. 2. A composition according to claim 1, characterized in that it contains at least one compound of the formula I as active ingredient in which: X is oxygen or sulfur, ^One of R ^ m ^ chlorine and hydrogen fluo-bromo) nitooskupinu HJ e ^ ^{n of} nominal group ethyl group, n-prop-verifies group ^^ p ^ py ^ v ^ group, nb-yl, isiSjtzloviu, sec .Sutyloviu group terč.buffovou group eenthZthiiskupinu, ethylthio, and-pripylthiotkupiau, itipripylthiotkupinu and-Sujylthioskupinu, itiSut ^y lthioskjpiaj, tek.bujylthioskupiau or terí.Sjtzlthiotkupinu, R ^2, R ^{4 and} R ⁵ or rů.zn ^js ou ^é znhmenají hydrogen and chlorine, or ^{b rom} R is hydrogen, fluoro, chloro, bromo or nitro, and R ⁷ are identical or different and denote hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, a sec-butyl group or a tert-butyl group ·, 8 9. R and R are the same or different and are hydrogen, fluorine, chlorine or bromine and are trifluoromethylthio or trifluoromethoxy, wherein (1) when X is oxygen and, R ⁴ , R 6, Κθ and are hydrogen and R ⁷ is hydrogen, fluoro, chloro or bromo and (A) R 1 and R 2 are both fluorine, chlorine and / or bromine; or (b) R ¹ is fluorine, chlorine, bromine, nitro or the above alkyl radicals; and R is hydrogen, then in these cases the radical r10 is in each case trifluoromethylthio and wherein (2) when X is oxygen or sulfur and r6 is chlorine and R is hydrogen or chlorine; and g R is hydrogen and r 10 is trifluoromethylthio and is (a) R and R are fluoro, chloro, or bromo, and 2 45 R, R and R are hydrogen or (b) r ⁵ and R ² are fluoro, chloro or bromo and 124 R, R and R are hydrogen; or (c) R and R are fluoro, chloro or bromo; R, R and R are hydrogen or (D) R and R are fluoro, chloro or bromo; R ¹ , R ³ and R ⁴ are hydrogen, then in these cases the radical R ⁷ is in each case hydrogen or the above-mentioned alkyl groups. 3. A composition according to claim 1 or 2, characterized in that it contains at least one compound of the formula I as active ingredient in which X is oxygen and the other substituents have the meanings given in 1 or 2. 4. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula (I) wherein: X is oxygen, R ³ is hydrogen, fluoro, chloro, bromo, nitro, methyl or methylthio, 2 4 5 R, R and R are hydrogen, fluoro, chloro or bromo, R ³ represents hydrogen, fluorine, chlorine or nitro, R ⁶ and R ⁷ are the same or different and are hydrogen, chlorine or methyl, 8 9 R and R are the same or different and are hydrogen, fluoro or chloro, and R ³⁹ is trifluoromethylthio or. trifluoromethoxy, wherein (1) when R ² , R ³ , R ⁴ , R ⁶ , R ⁸ and R ⁹ are hydrogen and R ⁷ is hydrogen or chloro and (a) R ³ and R ⁵ are both fluorine, chlorine and / or bromine; or (b) R ³ is fluorine, chlorine, bromine, nitro or methyl; and R ¹¹ is hydrogen, then in these cases the residue R ³⁹ is in each case trifluoromethylthio and wherein (2) when R is chlorine and g R is hydrogen or chloro and R is hydrogen and R ³⁹ is trifluoromethylthio or trifluromethoxy and (a) r ¹ and R ³ are fluoro, chloro and / or bromo and 2 45 R, R and R are hydrogen or (b) R and R are fluorine, chlorine and / or bromine and R ³ , R ² and R ⁴ are hydrogen or (c) R and R are fluorine, chlorine and / or bromine and 2 35 R, R and R are hydrogen or (D) R and R are fluoro, chloro and / or bromo and R ^3, R ³ and R ⁴ represent hydrogen, in these cases, radical R ⁷ is hydrogen or methyl. 5. A process for the preparation of an active ingredient according to claim 1, wherein (II) wherein ^{R6f- R0} , 9 10 R and R are as defined in ^{b s} uveěen by ^EJ 1, are reacted with benzoyl iso (thio) cyanates of the general formula III -NCX (III) wherein X _f R ^1, R ^{2, r0, R9} and ^R5 mmáí výonam ^y en Uve ^{of b s} in the ^EJ 1, optionally in příOomnooSi diluent.