NO864807L

NO864807L - PESTICIDE 1- (4-PHENYLOXYPHENYL) -3-BENZOYL URINE COMPOUNDS AND A PROCEDURE FOR THEIR PREPARATION.

Info

Publication number: NO864807L
Application number: NO864807A
Authority: NO
Inventors: David Teh-Wei Chou; Paul Alfred Cain
Original assignee: Union Carbide Corp
Priority date: 1985-03-29
Filing date: 1986-11-28
Publication date: 1986-11-28
Also published as: NO864807D0; DK573686A; DK573686D0

Description

Foreliggende oppfinnelse angår nye urinstofforbindelser som er brukbare som aktivt giftig stoff i pesticide forbindelser. Oppfinnelsen angår også The present invention relates to new urea compounds which are usable as active toxic substances in pesticide compounds. The invention also concerns

en fremgangsmåte for fremstilling av de nye l-(4-fenoksyfenyl)-3-benzoyl urinstofforbindelser. Oppfinnelsen angår videre pesticide preparater og en fremgangsmåte for forbindelsenes anvendelse. a process for the preparation of the new 1-(4-phenoxyphenyl)-3-benzoyl urea compounds. The invention further relates to pesticide preparations and a method for the use of the compounds.

Oppfinnelsen angår videre pesticide preparater og en fremgangsmåte for forbindelsenes anvendelse. The invention further relates to pesticide preparations and a method for the use of the compounds.

I de senere år er et antall benzoylurinstofforbindelser angitt i littera-turen som besiddende pesticidaktivitet. F.eks. er benzoylureidodifenyl-etere og deres bruk beskrevet i US-PS4.005.223, 4.041.177 og 4.068.002. Videre er N-benzoyl-N'-fenoksyfenylurinstofforbindelser og deres bruk som insekticider beskrevet i US-PS 4.399.152, JP-søknad 5.5038 357, 5 6092 857 og 7002 258. In recent years, a number of benzoylurea compounds have been indicated in the literature as possessing pesticidal activity. E.g. are benzoylureidodiphenyl ethers and their use described in US-PS 4,005,223, 4,041,177 and 4,068,002. Furthermore, N-benzoyl-N'-phenoxyphenylurea compounds and their use as insecticides are described in US-PS 4,399,152, JP application 5,5038,357, 5,6092,857 and 7,002,258.

N-benzoyl-N'-fenoksypyridyl urinstofforbindelser er beskrevet i EP-PS 0069288. N-benzoyl-N'-phenoxypyridyl urea compounds are described in EP-PS 0069288.

I henhold til dette vil en eller flere av de følgende gjenstander oppnås ved gjennomføring av oppfinnelsen. En gjenstand for oppfinnelsen er å tilveiebringe ny l-(4-fenoksyfenyl)-3-benzoyl urinstofforbindelser. En annen gjenstand for oppfinnelsen er å tilveiebringe visse l-(4-fenoksyfe-nyl)-3-benzoyl urinstofforbindelser som viser udmerket insekticid aktivitet. Ytterligere en gjenstand for oppfinnelsen er å tilveiebringe nye benzoylurinstofforbindelser slik som According to this, one or more of the following objects will be achieved by implementing the invention. An object of the invention is to provide new 1-(4-phenoxyphenyl)-3-benzoyl urea compounds. Another object of the invention is to provide certain 1-(4-phenoxyphenyl)-3-benzoyl urea compounds which exhibit excellent insecticidal activity. A further object of the invention is to provide new benzoylurea compounds such as

1 - [2,3-diklor-4- (2,4-dik lorfenok sy) -6-metylfenyl] -3-(2,6-difluorbenzoyl) - urinstoff, 1- [2,3-diklor-4-(2-brom-4-klorfenoksy)-6-metylfenyl] -3-(2,6-difluorbenzo-yl)urinstoff, 1 - [4-(2,4-diklorfenoksy)-2,3,6-trimetylfenyl] -3-(2,6-difluorbenzoyl)urinstof f etc. Ytterligere en gjenstand er å tilveiebringe fremgangsmåter for fremstilling av de nye benzoylurinstofforbindelser. En ytterligere gjenstand er å tilveiebringe nye pesticide preparater inneholdende de nye benzoylurinstofforbindelser som aktiv bestanddel. Ytterligere en gjenstand for oppfinnelsen er å tilveiebringe en fremgangsmåte for å kontrollere pest ved anvendelse av de nye pesticide preparater. Disse og andre gjenstander vil lett bli tydelige for fagmannen i lys av det nedenfor følgende. 1 - [2,3-dichloro-4-(2,4-dichlorophenoxy)-6-methylphenyl]-3-(2,6-difluorobenzoyl)-urea, 1- [2,3-dichloro-4-( 2-bromo-4-chlorophenoxy)-6-methylphenyl]-3-(2,6-difluorobenzo-yl)urea, 1 - [4-(2,4-dichlorophenoxy)-2,3,6-trimethylphenyl]-3 -(2,6-difluorobenzoyl)urea etc. A further object is to provide methods for the preparation of the new benzoylurea compounds. A further object is to provide new pesticide preparations containing the new benzoylurea compounds as active ingredient. A further object of the invention is to provide a method for controlling plague using the new pesticide preparations. These and other objects will be readily apparent to the person skilled in the art in light of the following.

I sitt generelle aspekt angår foreliggende oppfinnelse nye l-(4-fenoksy-fenyl)-3-benzoyl urinstofforbindelser, pesticide preparater inneholdende disse samt fremgangsmåter for deres fremstilling. Benzoylurinstof-forbindelsene ifølge oppfinnelsen kan representeres ved formelen: In its general aspect, the present invention relates to new 1-(4-phenoxy-phenyl)-3-benzoyl urea compounds, pesticidal preparations containing these and methods for their production. The benzoylurea compounds according to the invention can be represented by the formula:

hvori: in which:

X betyr halogen; X means halogen;

X' betyr hydrogen eller halogen; X' means hydrogen or halogen;

X" betyr fluor eller hydrogen forutsatt at når X' er halogen er X" hydrogen; X" means fluorine or hydrogen provided that when X' is halogen, X" is hydrogen;

R]_, R2og R3uavhengig er metyl, klor eller brom forutsatt at en av R\og R3er forskjellig fra klor eller borm; R1_, R2 and R3 are independently methyl, chlorine or bromine provided that one of R1 and R3 is different from chlorine or bromine;

R betyr metyl, klor, fluor eller brom; ogR means methyl, chlorine, fluorine or bromine; and

R', R" og R'" uavhengig er hydrogen, metyl, klor, fluor eller brom forutsatt at minst en av R', R" og R'" er forskjellig fra hydrogen. R', R" and R'" independently are hydrogen, methyl, chlorine, fluorine or bromine provided that at least one of R', R" and R'" is different from hydrogen.

Som angitt ovenfor angår oppfinnelsen nye l-(4-fenoksyfenyl)-3-benzoyl urinstofforbindelser, pesticide preparater inneholdende disse og fremgangsmåter for deres fremstilling og bruk. As indicated above, the invention relates to new 1-(4-phenoxyphenyl)-3-benzoyl urea compounds, pesticidal preparations containing these and methods for their production and use.

Foretrukne benzoylurinstofforbindelser ifølge den generelle formel 1 er de som har formlene: Preferred benzoylurea compounds according to the general formula 1 are those having the formulas:

der X, X', Pq, R2, R3, R, R', R" og R"' er som angitt ovenfor. where X, X', Pq, R2, R3, R, R', R" and R"' are as indicated above.

Spesielt foretrukne benzoylurinstofforbindelser er de med formelen: der X, X', Rj, R2, R3, R og R" er som angitt ovenfor; og Particularly preferred benzoylurea compounds are those of the formula: wherein X, X', Rj, R2, R3, R and R" are as indicated above; and

der X, X', R og R" er som angitt ovenfor. where X, X', R and R" are as indicated above.

De følgende benzoylurinstofforbindelser angitt i tabellene A til G er illustrerende for de som omfattes av de ovenfor angitte formler og som kan fremstilles ved oppfinnelsens gjennomføring. The following benzoylurea compounds indicated in tables A to G are illustrative of those which are covered by the formulas given above and which can be produced by carrying out the invention.

De nye benzoylurinstofforbindelser ifølge oppfinnelsen kan hensiktsmessig fremstilles ved en eller flere metoder. F.eks. kan forbindelsene ifølge oppfinnelsen fremstilles ved omsetning av et substituert fenoksyanelin 2 med et benzoylisocyanat 3 i henhold til skjema I The new benzoylurea compounds according to the invention can conveniently be prepared by one or more methods. E.g. the compounds according to the invention can be prepared by reacting a substituted phenoxyaniline 2 with a benzoisocyanate 3 according to scheme I

hvori X, X', X", R1(<R>2, R3, R, R', R" og R'" ;har den betydning som er gitt i formel 1. wherein X, X', X", R1(<R>2, R3, R, R', R" and R'" have the meaning given in formula 1.

Alternativt kan de nye forbindelser fremstilles ved omsetning av et fenoksyfenylisocyanat 4 med et benzamid 5 ifølge skjema II som følger: Alternatively, the new compounds can be prepared by reacting a phenoxyphenyl isocyanate 4 with a benzamide 5 according to scheme II as follows:

hvori X, X', X", Rj, R2, R3, R, R', R" og R'" har den betydning som er gitt for formel 1. wherein X, X', X", Rj, R2, R3, R, R', R" and R'" have the meaning given for formula 1.

Forbindelsene kan videre fremstilles ved omsetning av et benzoylklorid 6 med et substitert urinstoff 7 ifølge skjema III som følger: The compounds can further be prepared by reacting a benzoyl chloride 6 with a substituted urea 7 according to scheme III as follows:

hvori X, X', X", RltR2, R3, R, R', R" og R"' har den betydning som er gitt for formel 1. wherein X, X', X", RltR2, R3, R, R', R" and R"' have the meaning given for formula 1.

Generelt kan de reaksjoner som er vist i reaksjonsskjema I, II og III gjennomføres i organiske oppløsningsmidler slik som aromatiske hydrokarboner, halogenerte hydrokarboner, etere o.l. Oppløsningsmidler slik som toluen, 1,2-dikloretan, diklormetan og p-dioksan er foretrukket. Disse reaksjoner skjer ved temperaturer fra omgivelsestemperatur til 150° C. In general, the reactions shown in reaction schemes I, II and III can be carried out in organic solvents such as aromatic hydrocarbons, halogenated hydrocarbons, ethers and the like. Solvents such as toluene, 1,2-dichloroethane, dichloromethane and p-dioxane are preferred. These reactions take place at temperatures from ambient to 150°C.

Mellomproduktene som er vist i skjema I, II og III kan fremstilles i henhold til gjenerelt aksepterte prosedyrer. Således kan det substituerte benzoyl isocyanat 3 fremstilles ut fra det tilsvarende benzamid 5 ifølge den generelle prosedyre ifølge J. Org. Chem. 27, 3742 (1962) som følger: The intermediates shown in Schemes I, II and III can be prepared according to generally accepted procedures. Thus, the substituted benzoyl isocyanate 3 can be prepared from the corresponding benzamide 5 according to the general procedure according to J. Org. Chem. 27, 3742 (1962) as follows:

hvori X, X' og X" har den betydning som er gitt i formel 1. wherein X, X' and X" have the meaning given in formula 1.

De substituerte fenoksyaniliner 2 der Pq og R3; ikke er klor eller brom kan fremstilles i henhold til skjema V med omsetning av et substituert fenol 9 med et klornitrobenzen 8 som følger: The substituted phenoxyanilines 2 where Pq and R3; is not chlorine or bromine can be prepared according to scheme V by reacting a substituted phenol 9 with a chloronitrobenzene 8 as follows:

hvori Pq, R2, R3, R, R'. R" og R'" har den betydning som er gitt i formel 1 forutsatt at Rj og R3ikke er klor eller brom. Omsetningen av et substitert fenol 9 med et klornitrobenzen 8 for å oppnå nitroeteren 10 skjer i nærvær av en base i et inert oppløsningsmiddel ved forhøyet temperatur. Baser egnet for denne reaksjon er kaliumkarbonat, natrium-hydrid, kaliumhydroksyd og natriumhydroksyd. Egnede oppløsningsmidler er toluen, dimetylformamid og dimetylsulfonoksyd. Den ovenfor angitte transformering kan skje i et difasereaksjonsmedium i nærvær av en faseoverføringskatalysator. wherein Pq, R2, R3, R, R'. R" and R'" have the meaning given in formula 1 provided that Rj and R3 are not chlorine or bromine. The reaction of a substituted phenol 9 with a chloronitrobenzene 8 to obtain the nitroether 10 takes place in the presence of a base in an inert solvent at elevated temperature. Bases suitable for this reaction are potassium carbonate, sodium hydride, potassium hydroxide and sodium hydroxide. Suitable solvents are toluene, dimethylformamide and dimethylsulphonic oxide. The above-mentioned transformation can take place in a diphase reaction medium in the presence of a phase transfer catalyst.

Reduksjonen av nitroeter 10 til fenoksyanilin 2 kan oppnås ved hydro-genering ved bruk av en katalytisk mengde av platina eller palladium på karbon eller Raney nikkelkatalysator under en hydrogenatmosfære ved et trykk fra 40-200 psi ved omgivelsestemperatur. Egnede oppløsningsmidler for hydrogeneringen inkluderer aromatiske hydrokarboner eller alkoholer. Reduksjonen kan også oppnås ved en kjemisk metode ved bruk av hydrazin og en metallkatalysator som beskrevet i Chem. Rev., Vol. 65, s. 51-68 (1965). The reduction of nitroether 10 to phenoxyaniline 2 can be accomplished by hydrogenation using a catalytic amount of platinum or palladium on carbon or Raney nickel catalyst under a hydrogen atmosphere at a pressure of 40-200 psi at ambient temperature. Suitable solvents for the hydrogenation include aromatic hydrocarbons or alcohols. The reduction can also be achieved by a chemical method using hydrazine and a metal catalyst as described in Chem. Rev., Vol. 65, pp. 51-68 (1965).

Isocyanat 4 kan oppnås ved omsetning av det substituerte anilin 2 med fosgen. Urinstoffet 7 kan oppnås via omsetning av isocyanat 4 med ammoniumhydroksyd eller gassformig ammoniakk. Disse reaksjoner er vist i skjema 6 nedenfor som følger: Isocyanate 4 can be obtained by reacting the substituted aniline 2 with phosgene. Urea 7 can be obtained via reaction of isocyanate 4 with ammonium hydroxide or gaseous ammonia. These reactions are shown in Scheme 6 below as follows:

hvori Rj, R2, R3, R, R', R" og R"' har den betydning som er gitt i formel 1. wherein Rj, R2, R3, R, R', R" and R"' have the meaning given in formula 1.

De substituerte fenoksyaniliner 2 for hvilke Rj eller R3er klor eller brom oppnås ved halogenering av 4-fenoksyaniliner 11 og 12 som angitt i skjema 7 nedenfor som følger: The substituted phenoxyanilines 2 for which Rj or R3 are chlorine or bromine are obtained by halogenation of 4-phenoxyanilines 11 and 12 as indicated in Scheme 7 below as follows:

hvori R3= X = klor eller brom og Rj, R2, R, R', R" og R'" har den betydning som er gitt i formel 1 for omdanning av 11 til 2 og der R\= X = klor eller brom og R2, R3, R, R', R" og R'" har den betydning som er gitt i formel 1 for omdanning av 12 til 2. Egnede oppløsningsmidler for disse transformeringer inkluderer aromatiske hydrokarboner slik som benzen, eller polarprotiske oppløsningsmidler slik som eddiksyre. Halo- wherein R 3 = X = chlorine or bromine and Rj, R 2 , R, R', R" and R'" have the meanings given in formula 1 for the conversion of 11 to 2 and where R\= X = chlorine or bromine and R2, R3, R, R', R" and R'" have the meaning given in formula 1 for the conversion of 12 to 2. Suitable solvents for these transformations include aromatic hydrocarbons such as benzene, or polar protic solvents such as acetic acid. Hello-

genering av aniliner 11 og 12 kan gjennomføres ved eksponering til klor eller brom i et egnet oppløsningsmiddel ved lav temperatur eller for-trinnsvis behandling med et N-halogensuksinimid i benzen eller eddiksyre. Temperaturene som er krevet for omsetningen varierer i henhold til identiteten av substituentene R2, Rj og R3ligger generelt innen området 20 til 80 °C. generation of anilines 11 and 12 can be carried out by exposure to chlorine or bromine in a suitable solvent at low temperature or preferably treatment with an N-halosuccinimide in benzene or acetic acid. The temperatures required for the reaction vary according to the identity of the substituents R 2 , R 1 and R 3 and are generally in the range of 20 to 80 °C.

Fenoksyaniliner av typene 11 og 12 fremstilles ved den metode som er angitt i skjema 5 ovenfor men der Rj og R3individuelt kan representere hydrogen eller metyl. Phenoxyanilines of types 11 and 12 are prepared by the method indicated in scheme 5 above, but where Rj and R3 can individually represent hydrogen or methyl.

4-klor-l-nitrobenzenene som er nødvendige i skjema V og skjema VII er enten kommersielt tilgjengelige eller kan fremstilles ved enten en Sandmeyer-reaksjon (Miller et. al., J, Med. Chem. 1980, 23, 1083) ut fra kjente 4-nitro aniliner 13 eller via en nitrering av kjente klorbenzener 14 som angitt i skjema VIII nedenfor som følger: The 4-chloro-1-nitrobenzenes required in Scheme V and Scheme VII are either commercially available or can be prepared by either a Sandmeyer reaction (Miller et. al., J, Med. Chem. 1980, 23, 1083) from known 4-nitro anilines 13 or via a nitration of known chlorobenzenes 14 as indicated in Scheme VIII below as follows:

En alternativ vei til fenoksyaniliner med formel 2, spesielt fenomsyanilin 19, er angitt i skjema IX nedenfor som følger: An alternative route to phenoxyanilines of formula 2, particularly phenomcyaniline 19, is set forth in Scheme IX below as follows:

hvori Rj, R2, R3, R og R" har den betydning som er gitt i formel 1 og R" er klor eller brom. Denne reaksjon involverer kobling av et aminofenol 15 med et 4-klornitrobenzen 16 i nærvær av en base for derved å gi 4-nitrofenoksyanilin 17 som beskrevet av Schramm et al., Ann., 740, 169 wherein Rj, R2, R3, R and R" have the meaning given in formula 1 and R" is chlorine or bromine. This reaction involves the coupling of an aminophenol 15 with a 4-chloronitrobenzene 16 in the presence of a base to give 4-nitrophenoxyaniline 17 as described by Schramm et al., Ann., 740, 169

(1970). Omsetningen av aminogruppen i 17 med trifluoreddiksyre gir amidet 18. Nitrogruppereduksjon, Sandmeyer-halogenering og beskyttel-sesfjerning av aminofunksjonen gir anilinet 19. Detaljene ved disse transformeringer er gitt i den eksperimentelle del nedenfor. (1970). The reaction of the amino group in 17 with trifluoroacetic acid gives the amide 18. Nitro group reduction, Sandmeyer halogenation and deprotection of the amino function gives the aniline 19. The details of these transformations are given in the experimental section below.

Aminofenoler av typen 15 er lett tilgjengelige og kan fremstilles som vist ved opparbeidingen av aminofenol 23 via nitrering av en 3,5-disubstituert fenol 20 fulgt av halogenering og nitrogruppereduksjon som angitt i skjema 10 nedenfor som følger: Aminophenols of type 15 are readily available and can be prepared as shown by the work-up of aminophenol 23 via nitration of a 3,5-disubstituted phenol 20 followed by halogenation and nitro group reduction as indicated in Scheme 10 below as follows:

der Rj og R3har den betydning som er gitt i formel 1 og Y er brom eller klor. Denne tilnærming til mellomproduktene 21 og 22 reflekterer det som er beskrevet av Albert og Sears. J. Am. Chem. Soc., 76, 4979 where Rj and R3 have the meaning given in formula 1 and Y is bromine or chlorine. This approach to intermediates 21 and 22 reflects that described by Albert and Sears. J. Am. Chem. Soc., 76, 4979

(1954). (1954).

En alternativ og komplimentær rute til aminofenoler 15 er detaljert i skiema 11 som fol p-er: An alternative and complementary route to aminophenols 15 is detailed in scheme 11 as follows:

hvori Pq, R2og R3har den betydning som er gitt i formel 1. Dette involverer omsetning av et trisubstituert fenol 24 med et diazoniumsalt fremstilt fra sulfanilsyre for å oppnå den mellomliggende diazoforbindelse 25 som reduseres for å gi aminofenol 15. Syntesemetodologien som benyttes for å komme til aminofenoler 15 er det som beskrives i US-PS 3.752.838. wherein Pq, R2 and R3 have the meanings given in formula 1. This involves the reaction of a trisubstituted phenol 24 with a diazonium salt prepared from sulfanilic acid to obtain the intermediate diazo compound 25 which is reduced to give aminophenol 15. The synthetic methodology used to arrive at aminophenols 15 are those described in US-PS 3,752,838.

Forbindelsene ifølge oppfinnelsen kan benyttes som insekticider ifølge velkjente metoder for fagmannen. Presticide preparater inneholdende forbindelsene som aktiv toksikant vil vanligvis omfatte en bærer og/eller et fortynningsmiddel, enten fast eller flytende. The compounds according to the invention can be used as insecticides according to methods well known to the person skilled in the art. Presticidal preparations containing the compounds as active toxicant will usually comprise a carrier and/or a diluent, either solid or liquid.

Egnede flytende fortynningsmidler eller bærere inkluderer vann, petro-leumdestillater eller andre flytende bærere med eller uten overflateaktive midler. Flytende konsentrater kan fremstilles ved å oppløse en av disse forbindelser med et ikke-fytotoksisk oppløsningsmiddel slik som aceton, xylen, nitrobenzen, cykloheksanon eller dimetylformamid og å dispergere toksikantene i vann ved hjelp av egnede overflateaktive emulgerings- og dispergeringsmidler. Suitable liquid diluents or carriers include water, petroleum distillates or other liquid carriers with or without surfactants. Liquid concentrates can be prepared by dissolving one of these compounds with a non-phytotoxic solvent such as acetone, xylene, nitrobenzene, cyclohexanone or dimethylformamide and dispersing the toxicants in water using suitable surface-active emulsifying and dispersing agents.

Valget av dispergerings- og emulgeringsmidler og mengdene som benyttes dikteres av arten av preparatet og evnen til midlet til å lette disperger-ingen av toksikanten. Generelt er det ønskelig å bruke så lite som mulig av midlet, konsistent med den ønskede dispersjon av toksikanten i sprayen slik at reng ikke reemulgerer toksikanten efter at den er påført på planten og vasker den av denne. Ikke-ioniske, anioniske eller kation-iske dispergerings- og emulgeringsmidler kan benyttes, f.eks. kondensa-sjonsproduktene av alkylenoksyder med fenol og organiske syrer, alkylarylsulfonater, komplekse eteralkoholer kvaternære ammoniumforbind-elser o.l. The choice of dispersing and emulsifying agents and the amounts used are dictated by the nature of the preparation and the ability of the agent to facilitate the dispersion of the toxicant. In general, it is desirable to use as little of the agent as possible, consistent with the desired dispersion of the toxicant in the spray so that reng does not reemulsify the toxicant after it has been applied to the plant and washes it off. Non-ionic, anionic or cationic dispersing and emulsifying agents can be used, e.g. the condensation products of alkylene oxides with phenol and organic acids, alkylaryl sulphonates, complex ether alcohols, quaternary ammonium compounds, etc.

Ved fremstilling av fuktbare pulvere eller støv eller granulerte preparater, blir den aktive bestanddel dispergert i og på en egnet oppdelt fast bærer slik som leire, talkum, bentonitt, diatomejord, fullersjord o.l. Ved formulering av de fuktbare pulvere kan de ovenfor angitte dispergeringsmidler såvel som lignosulfonater inkluderes. In the production of wettable powders or dusts or granulated preparations, the active ingredient is dispersed in and on a suitable divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fuller's earth and the like. When formulating the wettable powders, the above-mentioned dispersants as well as lignosulfonates can be included.

Den nødvendige mengde toksikant som her benyttes kan påføres pr. 4 mål behandlet i fra 1 til 200 gallon eller mere væskebærer og/eller fortynningsmiddel eller i fra 5 til 500 pund inert faststoffbærer og/eller fortynningsmiddel. Konsentrasjon i det flytende konsentrat vil vanligvis variere fra ca. 10 til 95 vekt-% og i de faste formuleringer fra ca. 0,5 til ca. 90 vekt-%. Tilfredsstillende spray, støv eller granulat for generell bruk inneholder fra ca. 1/4 til 15 pund aktiv toksikant pr- ca. 4 mål. The necessary amount of toxicant used here can be applied per 4 measures treated in from 1 to 200 gallons or more of liquid carrier and/or diluent or in from 5 to 500 pounds of inert solid carrier and/or diluent. Concentration in the liquid concentrate will usually vary from approx. 10 to 95% by weight and in the solid formulations from approx. 0.5 to approx. 90% by weight. Satisfactory sprays, dusts or granules for general use contain from approx. 1/4 to 15 pounds of active toxicant pr- approx. 4 goals.

De her beskrevne pesticider forhindrer angrep av insekter på planter og annet materialer på hvilke pesticidene påføres, og de kan ha relativt høy resttoksisitet. Med henblikk på planter har den høye sikkerhetsmargin idet at når de brukes i en tilstrekkelig mengde til å avlive eller å avvise insekter vil de hverken brenne eller skade planten, og de motstår en klimapåvirkning som inkluderer avvaskin på grunn av regn, dekomponering på grunn av ultravilett lys, oksydasjjon eller hydrolyse i nærvær av fuktighet, eller, ikke minst, slik dekomponering, oksydasjon eller hydrolyse som vesentlig vil redusere de ønskede pesticide karakteristika for ttoksikantene eller gi disse uønskede karakteristika, f.eks. fytotoksisitet. Toksikantene er så kjemisk inerte at de nu er kompatible med i det vesentlige enhver annen bestanddel i sprayspekteret, og de kan benyttes i jord, på frø, eller på planterøtter uten å skade hverken frø eller røtter av planter. Blandinger av aktive bestanddeler kan benyttes hvis dette er ønskelig såvel som kombinasjoner av aktive forbindelser ifølge oppfinnelsen med andre biologiske aktive forbindelser eller bestanddeler. The pesticides described here prevent attacks by insects on plants and other materials to which the pesticides are applied, and they can have relatively high residual toxicity. For plants, it has a high margin of safety in that when used in sufficient quantity to kill or repel insects, they will neither burn nor harm the plant, and they resist a climate impact that includes wash-off due to rain, decomposition due to ultraviolet light, oxidation or hydrolysis in the presence of moisture, or, not least, such decomposition, oxidation or hydrolysis which will significantly reduce the desired pesticidal characteristics of the toxicants or give these undesirable characteristics, e.g. phytotoxicity. The toxicants are so chemically inert that they are now compatible with essentially any other component in the spray spectrum, and they can be used in soil, on seeds or on plant roots without damaging either the seeds or the roots of plants. Mixtures of active ingredients can be used if this is desired as well as combinations of active compounds according to the invention with other biologically active compounds or ingredients.

De følgende eksempler er illustrerende for de metoder som benyttes ved fremstilling av mellomprodukter og forbindelser ifølge oppfinnelsen. For v NMR-spektroskopisk analyse er de kjemiske skift angitt i ppm nedstrøms den indre standard, tetrametylsilan. The following examples are illustrative of the methods used in the production of intermediate products and compounds according to the invention. For v NMR spectroscopic analysis, the chemical shifts are given in ppm downstream of the internal standard, tetramethylsilane.

EKSEMPELAEXAMPLE

Fremstilling av 4- amino- 2, 3, 5- trimetylfenolPreparation of 4-amino-2,3,5-trimethylphenol

Til en oppløsning av sulfanilinsyre 49,4 g, 258 mol, i 258 ml vann, inneholdt i en rundkolbe utstyrt med røreverk, termometer og isbad ved 15° C, ble det tilsatt fast Na2C03(13,68 g, 129 mmol) fulgt av en oppløsning av NaN02(19,38 g, 280 mmol) i 53 ml vann. Til en separat rundkolbe utstyrt med røreverk, termometer, isbad og 240 g is ble det chargert 46 ml konsentrert HC1 og oppløsningen av diazoniumsalter fremstilt ovenfor. Denne blanding ble omrørt ved 15°C i 45 min. I mollomtiden ble en tredje kolbe utstyrt med kondensator, nitrogeninnløp, termometer, tilsetningstrakt og mekanisk rører, chargert med vann (258 ml), NaOH (56,8 g, 142 mmol) og 2,3,5-trimetylfenol (35,3 g, 259 mmol). Denne blanding ble avkjølt til 0°C ved hjelp av et is-saltbad og diazoniumsalt -HC1-blandingen fremstilt ovenfor ble tilsatt dråpevis mens man holdt temperaturen under 5°C. Ef ter tilsetning av diazoniumsalt-HC1-blandingen ble reaksjonsblandingen oppvarmet til 52 °C og fast Na2S20"4 (11,9 g, 68,3 mmol) tilsatt. Omrøringen ble fortsatt og blandingen oppvarmet til 80"C hvorefter Na2S204b(107,l g, 615,13 mol) ble tilsatt i tre like andeler (35,7 g, 205,04 mmol) med 5 minutters inter-valler. Blandingen ble så omrørt ved 80"C i 20 minutter, avkjølt til romtemperatur og filtrert for derved å gi et råprodukt som ble oppløst i etylacetat og tørket over natriumsulfat. Denne oppløsning ble konsentrert under redusert trykk og ga urent 4-amino-2,3,5-trimetylfenol. NMR spektroskopisk anlayse antydet: H'-NMR (CDC13): 2,1 (S, 9H) 4,6 (S. 2H), 6,49 (S. 1H). To a solution of sulfanilic acid 49.4 g, 258 mol, in 258 ml of water, contained in a round-bottomed flask equipped with a stirrer, thermometer and ice bath at 15° C, was added solid Na 2 CO 3 (13.68 g, 129 mmol) followed by a solution of NaNO 2 (19.38 g, 280 mmol) in 53 mL of water. To a separate round bottom flask equipped with a stirrer, thermometer, ice bath and 240 g of ice was charged 46 ml of concentrated HC1 and the solution of diazonium salts prepared above. This mixture was stirred at 15°C for 45 min. In the molar period, a third flask equipped with a condenser, nitrogen inlet, thermometer, addition funnel and mechanical stirrer was charged with water (258 ml), NaOH (56.8 g, 142 mmol) and 2,3,5-trimethylphenol (35.3 g , 259 mmol). This mixture was cooled to 0°C using an ice-salt bath and the diazonium salt-HCl mixture prepared above was added dropwise while maintaining the temperature below 5°C. After addition of the diazonium salt-HCl mixture, the reaction mixture was heated to 52 °C and solid Na2S20"4 (11.9 g, 68.3 mmol) was added. Stirring was continued and the mixture was heated to 80"C after which Na2S204b (107.1 g , 615.13 mol) was added in three equal portions (35.7 g, 205.04 mmol) at 5 minute intervals. The mixture was then stirred at 80°C for 20 minutes, cooled to room temperature and filtered to give a crude product which was dissolved in ethyl acetate and dried over sodium sulfate. This solution was concentrated under reduced pressure to give impure 4-amino-2,3 ,5-trimethylphenol NMR spectroscopic analysis indicated: H'-NMR (CDCl 3 ): 2.1 (S, 9H) 4.6 (S. 2H), 6.49 (S. 1H).

Eksempel BExample B

Fremstilling av 4-( 2- klor- 4- nitrofenoksy)- 2, 3, 6- trimetylanilinPreparation of 4-(2-chloro-4-nitrophenoxy)-2,3,6-trimethylaniline

Til en 500 ml rundkolbe utstyrt med magnetisk rører og nitrogeninnløp ble det chargert 4-amino-2,3,5-trimetylfenol (30,0 g, 175 mmol) fremstilt ifølge eksempel A, dimetylsulfoksyd (110 ml). 3,4-diklornitrobenzen (28,0 g, 146 mmol) og potassium t-butoksyd (18,1 g, 161 mmol). Reaksjonsblandingen ble omrørt ved romtemperatur overnatt og så fortynnet med toluen. Det organiske sjikt ble vasket med 1,5 1 vann, 200 ml mettet NH4CI og 2,5%-ig NaOH inntil det vandige sjikt forble så og si farveløst. Det organiske sjikt ble så vasket med saltoppløsning, tørket over Na2SO"4, og konsentrert under redusert trykk for derved å gi et råprodukt av 4-(2-klor-4-nitrofenoksy)-2,3,6-trimetylanilin som en brun olje (11,5 g). NMR-spektroskopisk analyse antydet:H'-NMR (CDCI3): 8,36 (d.J = 2 Hz. 1H). 8,0 (d.d: J = 2,9 Hz; 1H). 6,73 (S. 1H), 6,63 (d. J = 9 Hz. 1H), 3,66 (brS. 2H), 2,50, 2,47, 2,36 (3-S.9H). To a 500 mL round bottom flask equipped with a magnetic stirrer and nitrogen inlet was charged 4-amino-2,3,5-trimethylphenol (30.0 g, 175 mmol) prepared according to Example A, dimethyl sulfoxide (110 mL). 3,4-dichloronitrobenzene (28.0 g, 146 mmol) and potassium t-butoxide (18.1 g, 161 mmol). The reaction mixture was stirred at room temperature overnight and then diluted with toluene. The organic layer was washed with 1.5 L of water, 200 ml of saturated NH 4 Cl and 2.5% NaOH until the aqueous layer remained virtually colorless. The organic layer was then washed with brine, dried over Na 2 SO 4 , and concentrated under reduced pressure to give a crude product of 4-(2-chloro-4-nitrophenoxy)-2,3,6-trimethylaniline as a brown oil (11.5 g). NMR spectroscopic analysis indicated: H'-NMR (CDCl 3 ): 8.36 (d.J = 2 Hz. 1H). 8.0 (d.d: J = 2.9 Hz; 1H). 6 .73 (S. 1H), 6.63 (d. J = 9 Hz. 1H), 3.66 (brS. 2H), 2.50, 2.47, 2.36 (3-S.9H).

EKSEMPEL CEXAMPLE C

Fremstilling av 4-( 2- klor- 4- nitrofenoksy)- 2, 3, 6- trimetyl- N- trifluor-acetanilid Preparation of 4-(2-chloro-4-nitrophenoxy)-2,3,6-trimethyl-N-trifluoroacetanilide

Til en magnetisk omrørt oppløsning av 4-(2-klor-4-nitrofenoksy)-2,3,6-trimetylanilin (10,50 g, 34,23 mmol) fremstilt i eksempel B, og 50 ml toluen, ble det tilsatt ren trifluoreddiksyre anhydrid (74,35 g, 353,9 mmol). Reaksjonsblandingen ble omrørt ved romtemperatur overnatt i løpet av hvilket tidsrom utfellingen av produktet skjedde. Blandingen ble filtrert på en frittet skive og vasket med heksan. Dette ga rent 4-(2-klor-4-nitro-fenoksy)-2,3,6-trimetyl-N-trifluoravetanilid (2,9 g, 7,2 mmol, 27,6%) som et off-white-pulver. NMR-spektroskopisk analyse antydet: H'-NMR (CDCI3) 8,37 (d, J = 2Hz, 1H), 8,05 (d.d; J = 2,9 Hz, 1H), 7,71 (br.S. 1H), 6,77 (s. 1H). 6,70 (s. 1H). To a magnetically stirred solution of 4-(2-chloro-4-nitrophenoxy)-2,3,6-trimethylaniline (10.50 g, 34.23 mmol) prepared in Example B, and 50 ml of toluene, was added pure trifluoroacetic anhydride (74.35 g, 353.9 mmol). The reaction mixture was stirred at room temperature overnight during which time precipitation of the product occurred. The mixture was filtered on a fritted disc and washed with hexane. This gave pure 4-(2-chloro-4-nitro-phenoxy)-2,3,6-trimethyl-N-trifluorovetanilide (2.9 g, 7.2 mmol, 27.6%) as an off-white powder. NMR spectroscopic analysis indicated: H'-NMR (CDCl 3 ) 8.37 (d, J = 2Hz, 1H), 8.05 (d.d; J = 2.9 Hz, 1H), 7.71 (br.S. 1H), 6.77 (p. 1H). 6.70 (p. 1H).

EKSEMPEL DEXAMPLE D

Fremstilling av 4-( 4- amino- 2- klorfénoksy)- 2, 3, 6- trimetyl- N- trifluor-acetanilid Preparation of 4-(4-amino-2-chlorophenoxy)-2,3,6-trimethyl-N-trifluoroacetanilide

Til en 250 ml Parr-kolbe ble det chargert 4-(2-klor-4-nitrofenoksy)-2,3,6-trimetyl-N-trifluoravetanilid (2,82 g, 7,56 mmol) fremstilt i eksempel C samt 50 ml etylacetat. Kolben ble- spylt med nitrogen og 280 mg 5%-ig platina på karbon ble tilsatt. Reaksjonsblandingen ble hydrogenert i 45 minutter på en Parr-vugge hydrogenator ved 40-50 psi hydrogentrykk og ved romtemperatur. Katalysatoren ble fjernet ved filtrering gjennom celitt og filtratet ble konsentrert under redusert trykk hvorved man oppnådde rent 4-(4-amin-2-klorfenoksy) -2,3,6-tirmetyl-N-trifluoracetanilid (2,32 g, 6,22 mmol, 82%) som et off-white-pulver. NMR spektroskopisk analyse antydet: H'-NMR(CDC13) 10,23 (br s. 1H), 6,40-6,86 (m. 3H), 6,32 (s. 1H), 4,41 (br s. 2H), 2,29 (s. 3H), 2,20 (s. 1H) 2,10 (s. 1H). To a 250 ml Parr flask was charged 4-(2-chloro-4-nitrophenoxy)-2,3,6-trimethyl-N-trifluorovetanilide (2.82 g, 7.56 mmol) prepared in Example C as well as 50 ml of ethyl acetate. The flask was flushed with nitrogen and 280 mg of 5% platinum on carbon was added. The reaction mixture was hydrogenated for 45 minutes on a Parr cradle hydrogenator at 40-50 psi hydrogen pressure and at room temperature. The catalyst was removed by filtration through celite and the filtrate was concentrated under reduced pressure to give pure 4-(4-amino-2-chlorophenoxy)-2,3,6-tirmethyl-N-trifluoroacetanilide (2.32 g, 6.22 mmol, 82%) as an off-white powder. NMR spectroscopic analysis suggested: H'-NMR(CDCl 3 ) 10.23 (br p. 1H), 6.40-6.86 (m. 3H), 6.32 (p. 1H), 4.41 (br p . 2H), 2.29 (p. 3H), 2.20 (p. 1H) 2.10 (p. 1H).

EKSEMPEL EEXAMPLE E

Fremstilling av 4-( 2, 4- diklorfenoksy)- 2, 3, 6- trimetylanilinPreparation of 4-(2,4-dichlorophenoxy)-2,3,6-trimethylaniline

Til en iskjølt, magnetisk omrørt oppløsning av NaN02(453 mg, 6,57 mmol)To an ice-cooled, magnetically stirred solution of NaN02 (453 mg, 6.57 mmol)

i 3,2 ml konsentrert svovelsyre ble det dråpevis tilsatt en oppløsning av 4-(4-amino-2-klorfenoksy)-2,3,6-trimetyl-N-trifluoracetanilid (2,25 g, 6,036 mmol) fremstilt i eksempel D, i 14,7 ml eddiksyre. REaksjonstemperaturen ble holdt under 15 °C. Efter tilsetning bvle reaksjonsblandingen omrørt i 2 timer ved romtemperatur. I løpet av dette tidsrom ble det fremstilt en oppløsning av kobberlklorid som følger: til en oppløsning av CUSO4(H20)5(5,26 g, 21,07 mmol), NaCl (899 mg, 15,39 mmol) og vann (23,7 ml) ble det under nitrogen tilsatt en oppløsning av NaHSC>3 (841,6 mg, 8,088 mmol). NaCH (485,2 mg, 12,13 mmol) og vann (3,96 ml). Blandingen ble omrørt og ga et hvitt bunnfall. Supernatanten ble dekantert og presipitatet vasket en gang med vann. 14 ml konsentrert HCl ble tilsatt, noe som ga en grønnsort oppløsning. Til denne .oppløsning ble det dråpevis med omrøring tilsatt det ovenfor fremstilte diazoniumsalt i eddiksyre/- H2Sq4, og blandingen ble omrørt i 30 minutter ved romtemperatur. Reaksjonsblandingen ble fortynnet med etylacetat, vasket tre ganger med H20, en gang med saltoppløsning og tørket over natriumsulfat. Konsentrering under redusert trykk ga 2,0 g urent 4-(2,4-diklorfenoksy)-2,3,6-trimetyl-N-trifluoracetanilid som en orange olje. Til dette produkt ble -det tilsatt 20 ml metanol fulgt av 30 ml NH2NH2'H20. Reaksjonsblandingen ble kokt under tilbakeløp og omrørt i 5,5 timer, tillatt avkjøling, fortynnet med vann og så ekstrahert med toluen. Det organiske sjikt ble vasket to ganger med mettet NH4CI; en gang med H20, en gang med saltoppløsning og tørket over natriumsulfat. Konsentrering under redusert trykk ga 1,49 g urent 4-(2,4-diklorfenoksy)-2,3,6-trimetylanilin som en olje. Reaksjonsblandingen ble renset ved flashkolonnekromatografi, 70:1 fyllingsforhold, 3:1 heksan:etylacetat, hvorved man oppnådde rent 4-(2,4-diklorfenoksy)-2,3,6-trimetylanilin (810 mg, 2,73 mmol, 45% utbytte) som offwhitekrystaller med et smeltepunkt på 80,5 "C - 84 "C. NMR-spektroskopisk analyse antydet følgende:H'-NMR (CDCI3): 7,27 (d. J= 2Hz, 1H), 6,93 (d.d: J = 2,9Hz, 1H), 6,57 (s. 1H), 6,42 (d. J=9Hz, 1H), 3,36 (br. s. 2H), 2,06 (s. 6H), 1,96 (s. 3H). in 3.2 ml of concentrated sulfuric acid was added dropwise a solution of 4-(4-amino-2-chlorophenoxy)-2,3,6-trimethyl-N-trifluoroacetanilide (2.25 g, 6.036 mmol) prepared in Example D , in 14.7 ml of acetic acid. The reaction temperature was kept below 15 °C. After addition, the reaction mixture was stirred for 2 hours at room temperature. During this time, a solution of copper chloride was prepared as follows: to a solution of CUSO 4 (H 2 O) 5 (5.26 g, 21.07 mmol), NaCl (899 mg, 15.39 mmol) and water (23 .7 ml) a solution of NaHSC>3 (841.6 mg, 8.088 mmol) was added under nitrogen. NaCH (485.2 mg, 12.13 mmol) and water (3.96 mL). The mixture was stirred and gave a white precipitate. The supernatant was decanted and the precipitate washed once with water. 14 mL of concentrated HCl was added, giving a greenish-black solution. To this solution, the above-prepared diazonium salt in acetic acid/H 2 Sq 4 was added dropwise with stirring, and the mixture was stirred for 30 minutes at room temperature. The reaction mixture was diluted with ethyl acetate, washed three times with H 2 O, once with brine and dried over sodium sulfate. Concentration under reduced pressure gave 2.0 g of crude 4-(2,4-dichlorophenoxy)-2,3,6-trimethyl-N-trifluoroacetanilide as an orange oil. To this product was added 20 ml of methanol followed by 30 ml of NH 2 NH 2 'H 2 O. The reaction mixture was refluxed and stirred for 5.5 hours, allowed to cool, diluted with water and then extracted with toluene. The organic layer was washed twice with saturated NH 4 Cl; once with H 2 O, once with brine and dried over sodium sulfate. Concentration under reduced pressure gave 1.49 g of impure 4-(2,4-dichlorophenoxy)-2,3,6-trimethylaniline as an oil. The reaction mixture was purified by flash column chromatography, 70:1 loading ratio, 3:1 hexane:ethyl acetate, affording pure 4-(2,4-dichlorophenoxy)-2,3,6-trimethylaniline (810 mg, 2.73 mmol, 45% yield) as off-white crystals with a melting point of 80.5 "C - 84 "C. NMR spectroscopic analysis indicated the following: H'-NMR (CDCl3): 7.27 (d. J= 2Hz, 1H), 6.93 (d.d: J = 2.9Hz, 1H), 6.57 (s. 1H ), 6.42 (d. J=9Hz, 1H), 3.36 (br. p. 2H), 2.06 (p. 6H), 1.96 (p. 3H).

EKSEMPEL 1EXAMPLE 1

Fremstilling av 1- [ 2, 3- diklor- 4-( 2, 4- diklorfenoksy)- 6- metylfenyl] - 3-( 2, 6- difluorbenzoyl) urinstoff Preparation of 1-[2,3-dichloro-4-(2,4-dichlorophenoxy)-6-methylphenyl]-3-(2,6-difluorobenzoyl)urea

Del A: Fremstilling av 3- klor- 4-( 2, 4- diklor- fenoksy)- 6- metylnitrobenzen Til en enliters trehalsrundkolbe utstyrt med magnetisk røreverk, tilbake-løpskondensator, termometer og nitrogen innløp ble det chargert 36,4 g (176,7 mmol) 4,5-diklor-2-metylnitrobenzen, 35,9 g (220,2 mmol) 2,4-diklorfenol, 21,1 g (152,5 mmol) kaliumkarbonat og 350 ml dimetylformamid. Reaksjonsblandingen ble omrørt og kokt under tilbakeløp i 2 timer, filtrert varm og så avkjølt til romtemperatur og konsentrert under redusert trykk. Resten ble fortynnet med metylenklorid og de organiske sjikt ble vasket med saltoppløsning, tørket over vannfri Na2S04og konsentrert under redusert trykk for derved å gi et råprodukt som en mørkebrun viskøs væske. Tilsetningen av heksan og toluen ga et lysebrunt faststoff som ble underkastet flashkolonnekromatografi (4:1-2:1 hek-samtoluen) hvorved man oppnådde rent 3-klor-4-(2,4-diklorfenoksy)-6-metyl-nitrobenzen (24,5 g, 73,7 mmol, 42%) NMR spektroskopisk analyse antydet: H'-NMR (CDC13):8,26 (br S. 1H), 7,60 (d. J=2Hz, 1H), 7,35 (d.d: 2.9 Hz: 1H), 7,06 (d. J=9Hz, 1H), 6,59 (S. 1H), 2,53 (S. 3H). Part A: Preparation of 3-chloro-4-(2,4-dichloro-phenoxy)-6- methylnitrobenzene Into a one-liter three-neck round-bottomed flask equipped with a magnetic stirrer, reflux condenser, thermometer and nitrogen inlet was charged 36.4 g (176 .7 mmol) of 4,5-dichloro-2-methylnitrobenzene, 35.9 g (220.2 mmol) of 2,4-dichlorophenol, 21.1 g (152.5 mmol) of potassium carbonate and 350 ml of dimethylformamide. The reaction mixture was stirred and refluxed for 2 hours, filtered hot and then cooled to room temperature and concentrated under reduced pressure. The residue was diluted with methylene chloride and the organic layers were washed with brine, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure to give a crude product as a dark brown viscous liquid. The addition of hexane and toluene gave a light brown solid which was subjected to flash column chromatography (4:1-2:1 hec-cotoluene) to give pure 3-chloro-4-(2,4-dichlorophenoxy)-6-methyl-nitrobenzene (24 .5 g, 73.7 mmol, 42%) NMR spectroscopic analysis indicated: H'-NMR (CDCl 3 ): 8.26 (br S. 1H), 7.60 (d. J=2Hz, 1H), 7, 35 (d.d: 2.9 Hz: 1H), 7.06 (d. J=9Hz, 1H), 6.59 (S. 1H), 2.53 (S. 3H).

Del B: Fremstilling av 3- klor- 4-( 2, 4- diklorfenoksy)- 6- metylanilinPart B: Preparation of 3-chloro-4-(2,4-dichlorophenoxy)-6-methylaniline

Til en 250 ml Parr-kolbe ble det chargert 24,44 g (73,48 mmol) 3-klor-4-(2,4-diklorfenoksy)-6-metylnitrobenzen som fremstilt i del A samt 150 ml toluen. Kolben ble spylt med nitrogen og 3,7 g fast 5%-ig platina på karbon ble tilsatt. Reaksjonsblandingen ble så hydrogenert i 1 time ved 40-50 psi hydrogenog romtemperatur på en Parr vuggehydrogenator. Katalysatoren ble fjernet ved filtrering gjennom selitt og filtratet ble konsentrert under redusert trykk for derved å gi produktet som en tykk gul olje. Tilsetningen av heksan ga rent 3-klor-4-(2,4-diklorfenoksy)-6-metylanilin (20,41 g, 67,5 mmol, 92%) som et lysebrunt faststoff. NMR spektroskopisk analyse antydet: H'-NMR (CDCI3): 7,41 (d. J=2Hz, 1H), 7.10 (d,d; J=2,9 Hz; 1H), 6,78 (s. 1H), 6,72 (s. 1H), 6,55 (d. J=9Hz, 1H), 3,59 (br. s. 2H), 2,10 (s. 3H). To a 250 ml Parr flask was charged 24.44 g (73.48 mmol) of 3-chloro-4-(2,4-dichlorophenoxy)-6-methylnitrobenzene as prepared in part A and 150 ml of toluene. The flask was flushed with nitrogen and 3.7 g of solid 5% platinum on carbon was added. The reaction mixture was then hydrogenated for 1 hour at 40-50 psi hydrogen and room temperature on a Parr cradle hydrogenator. The catalyst was removed by filtration through celite and the filtrate was concentrated under reduced pressure to give the product as a thick yellow oil. The addition of hexane gave pure 3-chloro-4-(2,4-dichlorophenoxy)-6-methylaniline (20.41 g, 67.5 mmol, 92%) as a light brown solid. NMR spectroscopic analysis suggested: H'-NMR (CDCl 3 ): 7.41 (d. J=2Hz, 1H), 7.10 (d,d; J=2.9 Hz; 1H), 6.78 (s. 1H) , 6.72 (p. 1H), 6.55 (d. J=9Hz, 1H), 3.59 (br. p. 2H), 2.10 (p. 3H).

Del C: Fremstilling av 2, 3- diklor- 4-( 2, 4- diklorfenoksy)- 6- metylanilinPart C: Preparation of 2, 3- dichloro- 4-( 2, 4- dichlorophenoxy)- 6- methylaniline

Til en 100 ml rundkolbe utstyrt med magnetisk røreverk og nitrogeninnløp ble det chargert 9,41 g (31,10 mmol) 3-klor-4-(2,4-diklorfenoksy)-6- metylanilin fremstilt under C, 62 ml eddiksyre og 4,6 g (34,21 mmol) N-klorsuksinimid. Blandingen ble omrørt ved omgivelsestemperatur i 45 min. og fortynnet med toluen og mettet med Na2SC>3oppløsning. Toluensjiktet ble vasket med mettet Na2SC>3oppløsning tre ganger, med vann tre ganger, med 5%-ig NaOH oppløsning tre ganger, med vann en gang og med saltoppløsning; tørket over Na§04og konsentrert under redusert trykk for derved å gi et råprodukt som en tykk brun olje. Flashkolonnekromatografi med et fyllingsforhold på 100:1 og med 3:1 heksametylacetat ga 2,3-diklor-4-(2,4-diklorfenoksy)-6-metylanilin (1,47 g, 4,36 mmol, 14%). NMR-spektroskopisk analyse viste: H'-NMR (CDCI3) 7,43 (d._ J2Hz, 1H), 7,30 (d.d; J=2, 9Hz, 1H), 6,74 (s. 1H), 6,56 (d. J=9Hz, 1H), 4,08 (br. s. 2H), 2,18 (s. 3H). 9.41 g (31.10 mmol) of 3-chloro-4-(2,4-dichlorophenoxy)-6-methylaniline prepared under C, 62 ml of acetic acid and 4 .6 g (34.21 mmol) of N-chlorosuccinimide. The mixture was stirred at ambient temperature for 45 min. and diluted with toluene and saturated with Na2SC>3 solution. The toluene layer was washed with saturated Na2SO3 solution three times, with water three times, with 5% NaOH solution three times, with water once and with saline; dried over Na 2 O 4 and concentrated under reduced pressure to give a crude product as a thick brown oil. Flash column chromatography with a packing ratio of 100:1 and with 3:1 hexamethylacetate gave 2,3-dichloro-4-(2,4-dichlorophenoxy)-6-methylaniline (1.47 g, 4.36 mmol, 14%). NMR spectroscopic analysis showed: H'-NMR (CDCl3) 7.43 (d._ J2Hz, 1H), 7.30 (d.d; J=2, 9Hz, 1H), 6.74 (s. 1H), 6 .56 (d. J=9Hz, 1H), 4.08 (br. p. 2H), 2.18 (p. 3H).

Del D: Fremstilling av 1-[ 2, 3- diklor- 4-( 2, 4- diklorfenoksy)- 6- metylfenyl] - 3-( 2, 6- difluorbenzoyl) urinstoff Part D: Preparation of 1-[ 2, 3- dichloro- 4-( 2, 4- dichlorophenoxy)- 6- methylphenyl] - 3-( 2, 6- difluorobenzoyl) urea

Til en magnetisk opprørt oppløsning av 2,3-diklor-4-(2,4-diklorfenoksy)-6-metylanilin (1,43 g,x.4,24 mmol) fremstilt under del C i toluen (4 ml) og heksan (4 ml) under nitrogenatmosfære ble det tilsatt ren 2,6-difluorben-zoylisocyanat (780 mg, 4,24 mmol) og blandingen ble omrørt overnatt ved romtemperatur. Det resulterende presipitat ble samlet ved filtrering, vasket med heksan og tørket hvorved man oppnådde rent 1-[2,3-diklor-4-(2,4-diklorfenoksy)-6-metylfenyln-3-(2,6-difluorbenzoyl) urinstoff (670 mg, 1,29 mmol, 28%) som et hvitt faststoff med et smeltepunkt på 196-100° C. Elementanalyse for det hvite faststoff antydet følgende: To a magnetically stirred solution of 2,3-dichloro-4-(2,4-dichlorophenoxy)-6-methylaniline (1.43 g, x 4.24 mmol) prepared under part C in toluene (4 mL) and hexane (4 mL) under a nitrogen atmosphere was added pure 2,6-difluorobenzoyl isocyanate (780 mg, 4.24 mmol) and the mixture was stirred overnight at room temperature. The resulting precipitate was collected by filtration, washed with hexane and dried to obtain pure 1-[2,3-dichloro-4-(2,4-dichlorophenoxy)-6-methylphenyln-3-(2,6-difluorobenzoyl)urea (670 mg, 1.29 mmol, 28%) as a white solid, mp 196-100° C. Elemental analysis of the white solid suggested the following:

Analyse: C21H12CI4<F>2N2O3Analysis: C21H12Cl4<F>2N2O3

Beregnet: C, 48,49; H, 2,33, N, 5,39.Calculated: C, 48.49; H, 2.33, N, 5.39.

Funnet: C, 48,18; H, 2,43; N, 5,34. Found: C, 48.18; H, 2.43; N, 5.34.

EKSEMPLENE 2 OG 3EXAMPLES 2 AND 3

På en måte tilsvarende det somb le vist i de foregående eksempler og vedIn a way similar to what was shown in the previous examples and by

å benytte et av de tidligere beskrevne synteseskjemaer, ble andre urinstofforbindelser fremstilt. Identiteten for substituentene i den generiske formel og de analytiske data er angitt i tabell I nedenfor: using one of the previously described synthesis schemes, other urea compounds were prepared. The identities of the substituents in the generic formula and the analytical data are set out in Table I below:

Visse representative eksempler på de nye forbindelser ble bedømt for å bestemme deres pesticide aktivitet mot visse insekter inkludert en larve og en bille. De nye forbindelser ble også prøvet på fytotoksisitet på viktige økonomiske avlinger inkludert prydbønner, agurk og henna. De nye forbindelser ble videre bedømt med henblikk på pattedyrtoksisitet. Certain representative examples of the new compounds were evaluated to determine their pesticidal activity against certain insects including a caterpillar and a beetle. The new compounds were also tested for phytotoxicity on important economic crops including ornamental beans, cucumber and henna. The new compounds were further assessed for mammalian toxicity.

Suspensjoner av prøveforbindelsene ble fremstilt ved å oppløse 100 mg forbindelse i 1,5 ml dimetylformamid og så å tilsette 8,5 ml acetonopp-løsning inneholdende 0,25% av et alkylfenoksypolyetoksyetanoloverflate-aktivt middel som emulgerings- eller dispergeringsmiddel. Den resulterende oppløsning ble blandet til 30 ml vann for å gi grovt 40 ml av en suspensjon inneholdende forbindelsen i findelt form. Den således fremstilte utgangssuspensjon inneholdt 2,5 vekt-% forbindelse. Prøvekon-sentrajsonene i ppm på vektbasis benyttet i de nedenfor beskrevne prøver ble oppnådd ved egnede fortynninger av utgangssuspensjonen med vann. Sonikering ble benyttet der dette var nødvendig for å oppnå en homogen suspensjon. Prøveprosedyrene var som følger: Suspensions of the test compounds were prepared by dissolving 100 mg of compound in 1.5 ml of dimethylformamide and then adding 8.5 ml of acetone solution containing 0.25% of an alkylphenoxypolyethoxyethanol surfactant as an emulsifier or dispersant. The resulting solution was mixed with 30 ml of water to give roughly 40 ml of a suspension containing the compound in finely divided form. The starting suspension thus produced contained 2.5% by weight of compound. The sample concentrations in ppm on a weight basis used in the samples described below were obtained by suitable dilutions of the starting suspension with water. Sonication was used where this was necessary to achieve a homogeneous suspension. The test procedures were as follows:

Southern hærmyggbladsprayprøveSouthern army mosquito leaf spray sample

Larver av southern hærmygg (Spodoptera eridania, (Cram.)) beitende på Tendergreenbønneplanter ved en temperatur av 80±5°F og en relativ fuktighet på 50 ± 5% utgjorde prøveinsektene. Larvae of the southern armyworm (Spodoptera eridania, (Cram.)) feeding on tender green bean plants at a temperature of 80 ± 5°F and a relative humidity of 50 ± 5% constituted the test insects.

Prøveforbindelsene ble formulert ved å fortynne utgangssuspensjonene med vann for derved å oppnå en suspensjon inneholdende prøveforbind-elsen i de konsentrasjoner i deler prøveforbindelse pr. milliondeler sluttformulering som angitt i tabellene nedenfor. Pottesatt prydbønneplan-ter av standard høyde og alder ble anbragt på et dreiebord og besprøytet med 100 ml prøveforbindelse ved bruk av DeVilbiss sprøytepistol under 40 psig lufttrykk. Denne påføring som varte i 25 sek. var tilstrekkelig til å fukte platene til avdrypping. Som kontroll ble 100 ml av en vann-aceton-emulgeringsmiddeloppløsning uten prøveforbindelser også sprøytet på infiserte planter. Efter tørking ble de parrede blad separert og hvert ble anbragt i en 9 cm Petriskål utforet med fuktet filterpapir. Fem tilfeldig valgte larver ble innført i hver skål og skålene lukket. De lukkede skåler ble merket og holdt ved 80-85° C i fem dager. Selv om larvene lett kunne konsumere hele bladet i løpet av 24 timer, ble de ikke gitt mere næring. Larvene som ikke var istand til å bevege seg i kroppslengden, selv efter stimulering med stikking, ble ansett døde. Den prosentuale mortalitet ble notert for hvert konsentrasjonsnivå. The test compounds were formulated by diluting the starting suspensions with water to thereby obtain a suspension containing the test compound in the concentrations in parts test compound per parts per million final formulation as indicated in the tables below. Potted ornamental bean plants of standard height and age were placed on a turntable and sprayed with 100 ml of test compound using a DeVilbiss spray gun under 40 psig air pressure. This application, which lasted for 25 sec. was sufficient to wet the plates for draining. As a control, 100 ml of a water-acetone emulsifier solution without test compounds was also sprayed on infected plants. After drying, the paired leaves were separated and each was placed in a 9 cm Petri dish lined with moistened filter paper. Five randomly selected larvae were introduced into each dish and the dishes closed. The closed dishes were labeled and kept at 80-85°C for five days. Although the larvae could easily consume the entire leaf within 24 hours, they were not given more food. Larvae that were unable to move their body length, even after stimulation with stinging, were considered dead. The percentage mortality was noted for each concentration level.

Meksikanske bønnebillebladssprayprøveMexican Bean Beetle Leaf Spray Sample

Tredje stadiums larver av den meksikanske bønnebille (Ephilachna varivestis, Muls.), beitende på Tendergreen bønneplante ved en temperatur av 80 5°F, og 50 ± 5 prosent relativ fuktighet, var prøveinsektene. Third instar larvae of the Mexican bean beetle (Ephilachna varivestis, Muls.), feeding on Tendergreen bean plant at a temperature of 80 5°F, and 50 ± 5 percent relative humidity, were the test insects.

Prøveforbindelsene ble formulert ved å fortynne utgangssuspensjonene med vann for derved å oppnå en suspensjon inneholdende prøveforbind-elsen i de konsentrasjoner i deler prøveforbindelse pr. milliondeler sluttformulering som angitt i tabellene nedenfor. Pottesatt prydbønneplan-ter av standard høyde og alder ble anbragt på et dreiebord og besprøytet med 100 ml prøveforbindelse ved bruk av DeVilbiss sprøytepistol under 40 psig lufttrykk. Denne påføring som varte i 25 sek. var tilstrekkelig til å fukte platene til avdrypping. Som kontroll ble 100 ml av en vann-aceton-emulgeringsmiddeloppløsning uten prøveforbindelser også sprøytet på infiserte planter. Efter tørking ble de parrede blad separert og hvert ble anbragt i en 9 cm Petriskål utforet med fuktet filterpapir. Fem tilfeldig valgte larver ble innført i hver skål og skålene lukket. De lukkede skåler ble merket og holdt ved en temperatur av 80 ± 5"F i fem dager. SElv om larvene lett kunne forbruke bladet i løpet av 24 til 28 timer ble de ikke gitt mere næring. Larver som ikke kunne bevege kroppslengden, selv ved stimulering, ble ansett døde. The test compounds were formulated by diluting the starting suspensions with water to thereby obtain a suspension containing the test compound in the concentrations in parts test compound per parts per million final formulation as indicated in the tables below. Potted ornamental bean plants of standard height and age were placed on a turntable and sprayed with 100 ml of test compound using a DeVilbiss spray gun under 40 psig air pressure. This application, which lasted for 25 sec. was sufficient to wet the plates for draining. As a control, 100 ml of a water-acetone emulsifier solution without test compounds was also sprayed on infected plants. After drying, the paired leaves were separated and each was placed in a 9 cm Petri dish lined with moistened filter paper. Five randomly selected larvae were introduced into each dish and the dishes closed. The closed dishes were labeled and kept at a temperature of 80 ± 5"F for five days. Although the larvae could readily consume the leaf within 24 to 28 hours, they were not given additional food. Larvae that could not move their body length, even at stimulation, were considered dead.

Tobakk " Budworm" og bomull " Bollworm" bladssprayåteprøveTobacco "Budworm" and cotton "Bollworm" foliar spray feeding trial

Annet stadiums larver av tobakk budworm med kroppsvekt ca. 2,5 mg (Heliothis virescens, F.) samt bomulls bollworm med en kroppsvekt ca. 2,5 mg (Heliothis zea. (Boddie)), oppnådd kommersielt og dyrket på kunstig diet ved en temperatur av 80 ± 5°F og en relativ fuktighet på 50 ± 5%, utgjorde prøveinsektene. Second-stage tobacco budworm larvae with a body weight of approx. 2.5 mg (Heliothis virescens, F.) and cotton bollworm with a body weight of approx. 2.5 mg (Heliothis zea. (Boddie)), obtained commercially and reared on artificial diet at a temperature of 80 ± 5°F and a relative humidity of 50 ± 5%, constituted the test insects.

Ved bruk av en prosedyre tilsvarende den ovenfor anførte men ved å benytte bomullsplanter istedet for prydbønner, ble behandlede og tørkede bomullsblad innført i 9 cm Petriskåler som ble organisert i sett på 10 skåler. En tilfeldig valgt larve ble innført i hver skål i et tiskålsett og skålen ble lukket. De lukkede skåler ble merket og holdt ved 80 ± 5°F i fem dager. Larver som ikke kunne bevege kroppslengden, selv ved stim.ulering, ble ansett døde. Dødelighetsprosenten ble notert for for-skjellige konsentrasjonshensyn. Using a procedure similar to that stated above but using cotton plants instead of ornamental beans, treated and dried cotton leaves were introduced into 9 cm Petri dishes which were organized into sets of 10 dishes. A randomly selected larva was introduced into each dish in a tea dish set and the dish was closed. The closed dishes were labeled and held at 80 ± 5°F for five days. Larvae that could not move their body length, even when stimulated, were considered dead. The mortality rate was noted for various concentration considerations.

De biologiske egenskaper for visse representative eksempler av forbindelsene ifølge oppfinnelsen er angitt i tabellene II, III og IV nedenfor. The biological properties for certain representative examples of the compounds according to the invention are indicated in Tables II, III and IV below.

Eksempelene 4 og 5 og sammenligningseksempel A Examples 4 and 5 and comparative example A

For å vise den forbedrede biologiske aktivitet mot meksikansk bønnebille ble representative l-(4-fenoksyfenyl)-3-benzoyl urinstofforbindelser ifølge oppfinnelsen sammenlignet med kjente forbindelser. Resultatene er gitt i tabell III nedenfor. Fra de i tabell III angitte data er det klart at l-(4-fenoksyfenyl)-3-benzoyl urinstofforbindelsene ifølge oppfinnelsen gir forbedret biologisk aktivitet mot meksikansk bønnebille sammenlignet med kjente forbindelser. Som brukt i tabell III ble forbindelsene i sammenligningseksempel A fremstilt tilsvarende JP-søknad 5 6092 857. To demonstrate the improved biological activity against Mexican bean beetle, representative 1-(4-phenoxyphenyl)-3-benzoyl urea compounds according to the invention were compared with known compounds. The results are given in Table III below. From the data given in Table III, it is clear that the 1-(4-phenoxyphenyl)-3-benzoyl urea compounds according to the invention provide improved biological activity against the Mexican bean beetle compared to known compounds. As used in Table III, the compounds in Comparative Example A were prepared corresponding to JP application 5 6092 857.

Eksemplene 6 og 7 samt sammenligningseksempel BExamples 6 and 7 as well as comparative example B

For å vise den forbedrede biologiske aktivitet mot Heliothis spp., ble representative l-(4-fenoksyfenyl)-3-benzoyl urinstofforbindelser ifølge oppfinnelsen sammenlignet med kjente forbindelser. Resusltatene er gitt i tabell IV nedenfor. Fra de i tabell IV gitte data er det klart at l-(4-fenoksyfenyl)-3-benzoyl urinstofforbindelser ifølge oppfinnelsen gir forbedret biologisk aktivitet mot Heliothis spp. sammenlignet med kjente forbindelser. Som benyttet i tabell IV ble forbindelsene i sammenligningseksempel B fremstilt på en måte tilsvarende fremgangsmåten beskrevet i JP-søknad 5 6092 857. To show the improved biological activity against Heliothis spp., representative 1-(4-phenoxyphenyl)-3-benzoyl urea compounds according to the invention were compared with known compounds. The results are given in Table IV below. From the data given in Table IV, it is clear that 1-(4-phenoxyphenyl)-3-benzoyl urea compounds according to the invention provide improved biological activity against Heliothis spp. compared to known compounds. As used in Table IV, the compounds in comparative example B were prepared in a manner corresponding to the method described in JP application 5 6092 857.

Selv om oppfinnelsen er illustrert ved de foregående eksempler skal den ikke være begrenset av disse, modifiseringer og utførelsesformer kan gjennomføres uten å gå utenfor kravenes ånd og ramme. Although the invention is illustrated by the preceding examples, it shall not be limited by these, modifications and embodiments can be carried out without departing from the spirit and scope of the claims.

Claims

1. Compound, characterized by the formula:

in which: X means halogen; X' means hydrogen or halogen; X" means fluorine or hydrogen provided that when X' is halogen, X" is hydrogen; R1 , Pv2 and R3 independently are methyl, chlorine or bromine provided that one of R1 and R3 is different from chlorine or bromine; R means methyl, chlorine, fluorine or bromine; and R', R" and R'" independently are hydrogen, methyl, chlorine, fluorine or bromine provided that at least one of R', R" and R'" is different from hydrogen.

2. Compound according to claim 1, characterized by the formula:

wherein X, X', Rlt R2 , R3 , R, R', R" and R"' are as stated in claim 1.

3. Compound according to claim 1, characterized by the formula:

wherein X, X', Rj, <R> 2, R3 , R and R" are as stated in claim 1.

4. Compound according to claim 1, characterized by the formula:

wherein X, X', Rj_, R2 , R3 , R and R are as stated in claim 1.

5. Compound according to claim 1, characterized by the formula:

wherein X, X', Rj, <R> 2, R3 , R and R"' are as stated in claim 1..

6. Compound according to claim 1, characterized by the formula:

wherein X, X', Rj, R2 , R3 , R, R' and R" are as stated in claim 1.

7. Compound according to claim 1, characterized by the formula:

wherein X, X', Rj, R2 , R3 , R, R' and R"' are as stated in claim 1.

8. Compound according to claim 1, characterized by the formula:

wherein X, X', Rlf R2 , R3 , R, R" and R"' are as stated in claim 1.

9. Compound according to claim 1, characterized by the formula:

wherein X, Rj, R2 , R3 , R ig R" are as stated in claim 1.

10. Compound according to claim 1, characterized by the formula:

wherein X, X', R and R" are as stated in claim 1.

11. Compound according to claim 1, characterized by the formula: r

wherein X, R and R" are as set forth in claim 1.

12. Compound according to claim 3, characterized in that X' is halogen and R and R" independently are methyl, bromine or chlorine.

13. Compound according to claim 3, characterized in that X' is hydrogen and R and R" are independently methyl, bromine or chlorine.

14. Compound according to claim 3, characterized in that X and X' are fluorine and R and R" independently are methyl, bromine or chlorine.

15. Compound according to claim 5, characterized in that R and R'" independently are methyl, bromine and chlorine.

16. Compound according to claim 6, characterized in that R, R' and R" independently are methyl, bromine or chlorine.

17. Compound according to claim 8, characterized in that R, R" and R"' are independently methyl, bromine or chlorine.

18. Compound according to claim 9, characterized in that X is fluorine and that R and R" independently are methyl, bromine and chlorine.

19. Compound according to claim 10, characterized in that X and X' are fluorine and R and R" independently are methyl, bromine or chlorine.

20. Compound according to claim 10, characterized in that X and X' are fluorine, R is chlorine or bromine and R" is chlorine.

21. Compound according to claim 11, characterized in that X is fluorine and that R and R" independently are methyl, bromine or chlorine.

22. Compound according to claim 11, characterized in that X is fluorine, R is chlorine or bromine and R" is chlorine.

23. Compound according to claim 1, characterized in that it is 1-[2,3-dichloro-4-(2,4-dichlorophenoxy)-6-methyl-phenyl]-3-(2,6-difluorobenzo-yl )urea.

24. Compound according to claim 1, characterized in that it is 1-[3-chloro-4-(2,4-dichlorophenoxy)-2,6-dimethylphenyl]-3-(2,6-difluorobenzo-yl) urea.

25. Compound according to claim 1, characterized in that it is 1-[4-(2,4-dichlorophenoxy)-2,3-6-trimethylphenyl]-3-(2,6-difluorobenzoyl)urea.

26. Compound according to claim 1, characterized in that it is 1-[3-chloro-4-(2,4-dichlorophenoxy)-2,6-dimethylphenyl]-3-(2,6-difluorobenzo-yl) urea.

27. Compound according to claim 1, characterized in that it is 1-[3-chloro-4-(2-bromo-4-chlorophenoxy)-2,6-dimethylphenyl]-3-(2,6-difluorobenzo-yl)urea.

28. Compound according to claim 1, characterized in that it is 1-[2,3-dichloro-4-(2,4-dichlorophenoxy)-6-methylphenyl]-3-(2-fluorobenzoyl)urea.

29. Compound according to claim 1, characterized in that it is 1-[2,3-dichloro-4-(2-bromo-4-chlorophenoxy)-6-methylphenyl]-3-(2-fluorobenzo-yl) urea.

30. Compound according to claim 1, characterized in that it is 1-[4-(2,4-dichlorophenoxy)-2,3,6-trimethylphenyl]-3-(2-fluorobenzoyl)urea.

31. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 1.

32. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 2.

33. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 3.

34. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 4.

35. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 5.

36. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 6.

37. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 7. -

38. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 8.

39. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 9.

40. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 10.

41. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 11.

42. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 23.

43. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 24.

44. Pesticide preparation, characterized in that it comprises an acceptable carrier and a pesticide-effective amount of the compound according to claim 25.

45. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 1.

46. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 2.

47. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 3.

48. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 4.

49. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 5.

50. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 6.

51. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 7.

52. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 8.

53. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 9.

54. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 10.

55. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 11.

56. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 23.

57. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 24.

58. Method for controlling plague, characterized in that it comprises subjecting the cause of plague to a pesticidally effective amount of the compound according to claim 25.

59. Procedure for the preparation of a compound of the formula:

in which: X means hydrogen; X' means hydrogen or halogen; X" means fluorine or hydrogen provided that when X' is halogen, X" is hydrogen; R 1 , R 2 and R 3 independently are methyl, chlorine or bromine provided that one of R 1 and R 3 is different from chlorine or bromine; R means methyl, chlorine, fluorine or bromine; and R', R" and R'" independently are hydrogen, methyl, chlorine, fluorine or bromine provided that at least one of R', R" and R"' is different from hydrogen, characterized in that it comprises reacting a phenoxyaniline with the formula:

with a benzoisocyanate of the formula:

60. Procedure for the preparation of a compound of the formula:

X means halogen; X' means hydrogen or halogen; X" means fluorine or hydrogen provided that when X' is halogen, X" is hydrogen; R 1 , R 2 and R 3 independently are methyl, chlorine or bromine provided that one of R 1 and R 3 is different from chlorine or bromine; R means methyl, chlorine, fluorine or bromine; and R', R" and R'" are independently hydrogen, methyl, chlorine, fluorine or bromine provided that at least one of R', R" and R'" is different from hydrogen, characterized in that it comprises reacting a phenoxyphenyl isocyanate with the formula :

with a benzamide of the formula:

Procedure for the preparation of a compound of the formula:

in which : X means hydrogen; X' means hydrogen or halogen; X" means fluorine or hydrogen provided that when X' is halogen, X" is hydrogen; R1 , R2 and R3 independently are methyl, chlorine or bromine provided that one of R1 and R3 is different from chlorine or bromine; R means methyl, chlorine, fluorine or bromine; and R', R" and R'" independently are hydrogen, methyl, chlorine, fluorine or bromine provided that at least one of R', R" and R'" is different from hydrogen, characterized in that it comprises reacting a substituted urea with the formula:

with a benzoyl chloride of the formula: