DD298908A5 - 2-halo-3-phenoxy-1,4-naphthoquinone DERIVATIVES - Google Patents

Abstract

The invention relates to new * of the formula * in which R1-R5 and X have the meaning given in the description, their use for controlling pests and novel intermediates. The novel compounds of formula (I) can be prepared by analogy methods, e.g. B. by reacting suitable phenols with 2,3-Dihalogennaphthochinonen or suitable * halogenated. The * are also new and represented by the formula (IV) and can also be prepared by analogy methods, for. B. from suitable phenols and * formula (I)

Description

in which

R'-R ⁵ independently of an anane donor is hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylthio, alkylsulfonyl, alkylsulfinyl, Halogonalkylthio. Aryloxy, arylthio, haloalkylsulfinyl or haloalkylsulfonyl

and

X is halogen,

excluding the precursors in which the Rosto R ', R ¹ , R ⁴ and R * are hydrogen and R ^{3 is} hydrogen, chlorine,

Nitro, methyl or methoxy and the precursor in which R 'and R ^{5 are} methyl and R ² , R ³ and R ^{4 are} hydrogen

and X jowoils stands for Halogon, found.

Furthermore, it has been found that dio the new 2-halo-3-phenoxy-1,4-naphthoquinone derivative of the general

Formol (I)

(D

in which

R'-R ⁵ independently of one another represent hydrogen, halogon, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylthio, alkylsulfonyl, alkylsulfinyl, haloalkylthio, aryloxy, arylthio, haloalkylsulfinyl or haloalkylsulfonyl

and

X is halogen,

excluding the compounds in which the grids R ¹ , R ¹ , R ⁴ and R ^{5 are} hydrogen and R ^{3 is} hydrogen, chlorine,

Nitro, methyl or methoxy and the compound in which R 'and R ^{s are} mothyl and R ² , R ³ and R ^{4 are} hydrogen

and X is each halogen, when one obtains

(a) Phenol derivatives of the general formula (II)

R ¹ R ²

(II)

in which

R'-R ^{5 have} the meaning given above, ausgonommon the compounds in which dio Rosto R ¹ , H ² , R ⁴ and R ⁵ for Are hydrogen and R ³ is hydrogen, chlorine, nitro, mothyl or methoxy and the compound in which R 'and R ⁵ represents Methyl and R ² , R ³ and R ^{4 are} hydrogen,

with 2,3-dihalo-1,4-naphthoquinones of the general formula (III)

(III)

in which

X (Ho obon angogebono Bodoutung has and

X ^I stands for Hnlogon,

gogobononfalls in Gogonwart oinos Vordünnungsmittols and gogobononfalls in Gogenwart oincs basischon Roktionshilfsmittols umsotzt, odor (b) 2-Phonoxy-1,4nophthochlnonDorivato dor universolnon formula (IV)

(IV)

inwolchor

R'-R ⁵ dio obon angogebone have meaning

excluding the preconnon, in donon the termo R ', R ¹ , R ⁴ and R ^{5 is} hydrogen and R ^{1 is} hydrogen, chlorine, nitro, mothyl or mothoxy and the compound in which R ¹ and R ^{5 are} both methyl and R ', R ³ and R ⁴ for hydrogen stohone, with halogonone (X ₂ ) optionally spilled in Gogonwart einos Vordünnungsmittols and then gogobonenfalls in the presence einos Vordünnungsmittols and gogebononfalls in Gogonwart oinos basischon Roaktionshilfsmittols hydrogen halide (HX) eliminated.

Finally, it has been found that the new 2-halo-3-phonoxy-1,4-naphthoquinone-dorivato of general formula (I) show such good activity against pests.

The invention also relates to the orphaned 2-halo-3-phonoxy-1,4-naphthoquinone derivatives of the general formula (I), with the exception of the excluded compounds, orophobic fungicidal and acaricidal activity as the prior art 1,4-naphthoquinone Derivatives such as 2-chloro-3- (4-methylphonoxy) -1,4-naphthoquinone or 2-chloro-3- (4-methoxyphenoxy) -1,4-naphthoquinone, are chemically and functionally obvious compounds.

The 2-halo-3-phonoxy-1,4-naphthoquinone-dorivato according to the invention are defined by the formula (I) in general. The phenoxy ring in compounds of the formula (I) can be monosubstituted to disubstituted by identical or different substituents, preference being given to monosubstituted to trisubstituted and, more preferably, monosubstituted or diborohedral substitution

 Preferred are Vorbindungon dor Formol (I), at wolchon

R'-R ^{5 is} independently of Halogon odor goradkottigos odor vorzweigtos alkyl having 1 to 3 carbon atoms or

R'-R * represents a combination of hydrogen and 1 to 3, same or different of the following substituents: halogen, cyano, nitro, straight or branched alkyl of 1 to 4 carbon atoms, goradkottigos or branched haloalkyl of 1 to 3 carbon atoms and 1 to 7 same or different halogen atoms, cycloalkoxy or branched alkoxy or haloalkoxy having 1 to 3 carbon atoms and optionally 1 to 7 same or different halogen atoms, straight or branched alkylthio, haloalkylthio or haloalkylsulfonyl each having 1 to 3 carbon atoms and if desired 1 to 7 the same or different halogen atoms, phenoxy or phenylthio, the order of the substituent being beliobic, and

X for halogen bumps,

excluding the precursors in which the radicals R ¹ , R ¹ , R ⁴ and R ^{5 are} hydrogen and R ^{3 is} hydrogen, chlorine, nitro, methyl or methoxy and the compound in which R ¹ and R ^{5 is} methyl and R ', R ³ and R ^{4 are} hydrogen and X is each halogen.

Particular preference is given to compounds of the formula (I) in which R'-R ⁵ independently of one another are fluorine, chlorine, bromine, mothyl or ethyl or

R'-R ^{5 is} a combination of hydrogen and 1 or 2, the same or different of the following substituents: fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, η-odor i-propyl, trifluoromethyl, 2,2, 2-trifluoroethyl, mothoxy, ethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio or 2,2,2-trifluorothylthio, wherein the order of the substituents is beliobig and

X is fluorine, chlorine or bromine,

excluding the compounds in which the radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen and R ^{3 is} hydrogen, chlorine, nitro, methyl or methoxy and the compound in which R 'and R ^{5 are} methyl and R ² , R ³ and R ^{4 are} hydrogen and X is each halogen.

If, for example, 2,3-dichloro-1,4-naphthoquinone and 3-fluorophonol old starting material are used, the course of the oxyacetylene precursor process (a) can be determined by the (olgondo Formolschoma dnrstollon:

HCl

Preliminary note, boisispiolswoiso 2- (3-fluorophenoxy) -1,4-naphthoquinone and chlorine as starting material, the course of action of the preform (I)) can be explained by the following formula:

1) Cl

2) -HCl

Dio in the case of the ancestor of the present invention (a) for the fulness of compounds of formol (I) as starting materials

using 2,3-dihalo-1,4-naphthoquinone-dorivate are dofiniort by the formol (III) allgomoin.

In formula (III) X has preferential or particularly those Bodeutungon, which already obon in connection with dor DESCRIPTION OF PREFERRED PREFERRED TONNONES OF THE FORMULA (I) Preferably or as particularly preferred for X.

angogebon were.

X ¹ is halogen, in particular fluorine, chlorine or bromine.

2,3-Dihalogon-1,4-naphthoquinone-dorivato of formol (III) are allgomoin known Vorbindungon dor organic chemistry (see, for example, Horst, WP et al., Ind. Eng., Chem., 35, 125251943 ).

Dio boim ancestor (a) according to the invention for the preparation of Vorbindungon dor formula (I) as Ausgangsstoffo to

using phonol-dorivato are dofiniort by the formol (II) allgomoin.

In formol (II), R ¹ , R ² , R ³ , R ⁴ and R * are preferably or in particular dioic monobutene, dio boroites, in the In connection with the description of the invention, compounds of formol (I) preferably or as

particularly preferred for R ¹ , R ² , R ³ , R ⁴ and R ^{s were} angegoben.

Phonol Dorivato dor formula (II) are allgomoin bokannto Vorbindungon the organic Chomio and könnon after general

well-known ancestors made wordon (see, for example, Boilstein, "Handbuch der organischen Chomio", vol. VI, 4th supplementary work, for example p.770,810, 1940, etc.).

Dio in the process according to the invention (b) for the preparation of Vorbindungon the formula (I) as starting materials

using 2-phenoxy-1,4-naphthoquinone derivative 9 are allgomein defniert by the formol (IV).

In formula (IV) R ', R ² , R ³ , R ⁴ and R ⁵ preferably or in particular have those meanings, dio already above in In connection with the Bosch friction of the Vorbindungon invention dor formula (I) vorzugswoiso or as

in particular, preferably R ¹ , R ² , R ³ , R ⁴ and R ^s were added.

The 2-phenoxy-1,4-naphthoquinone derivatives of the formula (IV) are new. The novel compounds of the formula (IV) are obtained,

in which

R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the abovementioned meaning when using Phonol Dorivato dor Formol (II)

Vr3 ("I

R ⁴

In wolcher

R ', R ¹ , R ¹ , R ⁴ and R ^{5 are} the same meaning as angongebono, with 2-halo-1,4-naphthoquinone dor allgomolnone Formot (V)

(V)

in wolkhor

X 'for halogen, insbosondoro for chlorine or bromine,

gobobononfalls in Gogonwart oinos diluent wio boisplolswoiso Bonzol odor toluene and gobobononfalls in

Gogonwart one of Baso wio potassium carbonate or sodium carbonate boi tomporaturone between O ⁹ C and 90 ° C. The 2-halo-1,4-naphthoquinones of the formula (V) are known ebonso wio the phonol-Dorlvato of the formula (II) in general Compounds of organic chemistry and after allgomoln bokonnton ancestor horstollbar. As a diluent for carrying the origenungsgomäßon ancestor (a) kommon vorzugswoiso inorto organic Solvent in question. For this gohoron insbosondoro aliphatic, alicyclischo odor oromatischo, gogobononfalls hologoniorto hydrocarbons, wio

boispiolswoise Bonzin, Ligroir ;, Bonzole, Toluene, Xylene, Chlorobonzole, Potrolothor, Ponton, Hoxan, Hoptan, Cyclohoxan,

Dichloromethane, chloroform, carbon tetrachloride; Ethor, wio diethyl ether, dioxane, tetrahydrofuran odor Ethyl glycol glycol or diethyl ether; Kotono, such as Acoton or Butanone; Nitriles wio acetonitrile or propionitrile; amides,

wio dimethylformamide, dimethylacotamide, N-mothylformanllid, N-Mothylpyrrolidon or Hoxamothylphosphorsäurotriamid;

Estor, acetic acid thylate or Bason, wio pyridine. The process (a) according to the invention is carried out in gogobonon gogon-oinos bosischon Roaktionshilfsmittels. As such, all common inorganic or organic bases in Frago come wio boisplolswoiso alkali hydroxides Alkali metal carbonates, tertiary amines, triethylamine wio, Ν, Ν-dimothylaniline, pyridine, Ν, Ν-dimothylaminopyridine, diazabicyclooctane

(DABCO), diazabicyclononene (DBN) or diazabicycloundocon (DBU). Preferably, the alkali metal carbonates are prewired, for example sodium carbonate or potassium carbonate.

The Reaktionstomperaturen in carrying out the erfindungsgomäßon process (a) in a wider range

be varied. In general, one works at temperatures between +50 ⁰ C and + 16O ⁰ C, preferably boi Tomporaturon between + GO ⁰ C and + 90 ^c C.

The process (a) according to the invention is usually carried out under atmospheric pressure. However, it is also possible under

increased pressure to work.

To carry out the process (a) according to the invention, the mixture is sorbed per mole of 2,3-dihalonaphthoquinone of the formula (III) 1

to 5 mol, preferably 1 to 2 moles of phenol derivative of formol (II) and gegobonenfalls 0.5 to ι mol of basic

Reactive Helmet - Medium. Dio Reaction, workup and isolation of the reaction products is carried out in analogy to

well-known ancestor.

As a diluent for carrying out dos according to the invention Vorfahrons (b) kommon ebonfalls inert organic Solvent in Frago. It is preferable to co-disperse the diluent mentioned in Verfahron (a), but it may not

also organic acids such. For example, acetic acid has been vorwondot.

The erfindungsgomäßo process (b) is carried out gobobononfalls in the presence of a basic reaction auxiliaries. As solcho come all the usual inorganic or organic Bason in Frago, such as boispiolswoise alkali and Alkaline earth hydroxides, alkali carbonates, alkali acetato, tertiary amines, such as triethylamine, Ν, Ν-dimothylaniline, pyridine, N ₁ N- Dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononone (DBN) or diazabicycloundecene (DBU '

it is used alkali acetates, such as sodium acetate.

The reaction temperatures can boi the implementation of the erfindungsgemäonon process (b) in a larger Boreich

has been varied. In general, one works at temperatures between + 8O ⁰ C and + 14O ⁰ C, preferably at temperatures between + 10O ⁰ C and +120 ⁰ C.

The ancestor (b) according to the invention is usually carried out under atmospheric pressure. However, it is also possible under

increased pressure to work.

To carry out process (h) according to the invention, the amount of 2-phenoxy-1,4-naphthoquinone derivative used is 1 to 2 mol per mole Formula (IV) 1 to 5 mol, preferably 1 to 2 moles of halogen and optionally 1 to 2 moles of basic reaction auxiliary

on. The reaction is carried out in analogy to generalized ancestors.

The active compounds according to the invention have a strong microbicidal action and can be used to combat unwanted microorganisms Microorganisms are used practically. The active substances are suitable for use as pesticides. Fungicides in crop protection are used to combat Plasmodiophoromycotos, Oomycotes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes. Bactericidal agents are used in crop protection for the control of Pseudomonadacoao, Rhizobiaceae, Entorobacteriacoae, Corynebactoriaceae and Streptomycetaceae used. Belepleiha. * But not interfering with some pathogens of pilillchon and bacteriollon disorders, which are among the above

fall ongoiflhlton OborbogrKfo, called:

Xanthomonas arton, for example, Xanthomonas campostris pv. Ory / no; Psoudomonas species, wlo bolsplolswoiso Peeudomonas syrlngao pv. Lacluymons; EcwinloAfton, wlo boispiolswolso Erwinla amylovora; Pythlum-Arton, wlo boispiolswolso Pythium ultimum; Phytophthora arton, wio bolsplolswoiso Phytophthoro infostons; Pseudoporonospora arton, such as boispiolsolso Psoudoporonospora humuli or Psoudoporonospora cubonsis; Plasmopara artery, wio bolsplolswoiso Plasmopara viticola; Poronospora arlon, wio for example Poronosporo plsi odor P. brasslcao; Erysipho-Arton, wio boispiolswolso Eiysipho gromlnls; Sphaorothoco-Arton, wio boispiolswolso Sphaorothoco (ullglnoa; Podosphaora-Arton, wlo bolsplolswoiso Podosphaoro loucot.'lcha; Vonturia-Arton, wio bolsplolswoiso Vonturio inaoqualis; Pyrenophora Arton, wio boispiolswoiso Pyrcnophorus toros odor P. gromlnoa

(Konldion Foriiv Drochslora, Syn: Holminthosporium);

Cochliobolus arton, wio boispiolswoiso Cochllobolus sativus

(Conidium form: Drochslorn, Syn: Holminthosporium);

Uromycos species, wio boispiolswoiso Uromycos appondlculatus; Puccinia-arton, wio boispiolswolso Puccinio rocondita; Tillotia-Arton, wio, for example, Tillotia caries; Ustilogo-Arton, wio boiusswoiso Ustilago nuda odor Ustilago avonao; Pollicularia-arton, wio boispiolswolso Pollicularia sasakii; Pyricularia arton, wio boispiolswoiso Pyriculario oryzao; Fusarium-Arton, as boispiolswoiso Fusnrium culmorum; Bolrytis-Arton, wio boispiolswoiso Dotrytis cinoroa; Soptoria-Arton, wio boispiolswoiso Soptoria nodorum; Loptosphaoria-Arton, wio boispiolswoiso Loptosphaorla nodorum; Corcospora arton, wio boispiolswoiso Corcospora canoscons; Altornaria-Arton, wio boispiolswoiso Altornaria brassicao; Psoudocercosporolla-Arton, wio boispiolsweiso Psoudocorcosporolla horpotrichoidos. The guto plant tolerates the active ingredients in don for Bokiimpfung of Pflanzonkrankhoiton notwondigon Konzontrationon

allows oino treatment of Oborii Jischon planting stock, of planting and seed, and the Bodons.

In particular, active ingredients have olno potenti fungicidal activity, eg gogon don errogor of rot Tomatoes (Phytophthora), oino protoktivo effect gogon don Apfolschorforrogor (Vonturia inaoquolis), out of gogon Plasmopara en vines, gogon botrytis and sclerotiniapilzo, and gogon Pyricularia and pollicularia on rice. The active compounds are also suitable for controlling animal pest, preferably arthropodone and nematodes,

in particular, spider animals found in agriculture, in Forston, in stockpile and material protection, and in dom-hygienic fields. They are gogen normal sensitive and rosistonto ar tone sowio effective against all odor individual development stadium.

To the obon mentioned pests gohöron: From the order of Isopoda z. B. Oniscus asollus, Armadillidium vulgaris, Porcollio scabor. From the order of diplopoda e.g. Blaniulus guttulatus. From the order of Chilopoda z. Goophilus cerpophagus, Scutigora spoc. From the order of Symphyla z. B. Scutigorolln immaculate. From the order dor Thysanura z. B. Lopisma saccharine. From the order of Collombola z. 8. Onychiurus armatus. From the order of Orthoptora z. 8. Biatta oriontalis, Poriplanota americana, Leucophaoa maderae, Biettolle gormanica, Achota

domesticus, Gryllotelpa spp., Locusta migratoria mlgratorloldos, Molonoplus differentialis, Schistocorca grogaria.

From the order of the Dormaptora e.g. Forficula auricularia. From the order of Isoptera z. B. Roticulitormes spp. From the order of Anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Rhodiculus humanus corporis, Haomatopinus spp., Linognathusspp. From the order of Mallophaga z. B. Trichodoctos spp., Damalinoa spp. From the order of Thysanoptora z. B. Horcinothrips form ilis, Thrips tabaci. From the order of the Hotoroptora e.g. Eurygastor spp., Dysdorcus intormodius, Piosma quadrata, Cimox lectularius, Rhodnius

prolixus, Triatoma spp.

From the order of Homoptora z. Aleurodos brassicao, Bomlsia tabaci, Trialourndos vaporariorum. Aphis gossypii, Brevicoryne brassicao, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigorum, Hyaloptorus arundinis, Macrosiphum

avonao, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Ernpoasca spp., Euscolis bilobatus, Nephotettix cincticeps,

Lecanium corni, Saissotia oloae, Laodolphax striatollus, Nilaparvata lugons, Aonidiella aurantii, Aspidiotus hodora, Pseudococcus spp. Psylla spp. From the order of Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Choimatobia brumata, Lithocolletis

blancardella, Hyponomouta padella, Plutella maculiponnis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.

Bucculatrix thurberiotla, Phyllocnistis citrella, Arjrotis spp., Euxoa spp., Feltia spp., Earias insulana, Holiothis spp., Spodoptora

exigua, Mamestra brassicae, Panolis flammoa, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonolla, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuohniolla, Galleria mellonella, Tineola bisselliolla, Tinea pellionolla,

Hofmannophila psoudosprotella, Cacoecia podana, Capua reticulana, Choristonoura fumiferana, Clysia ambiguella, Homona

magnanima, Tortrix viridana.

From the order of the Coloopters i. B. Anobium punctatum, Rhlzoportha dominice, Acanthoscolidos obtoctue, Hylotrupos

bajulus, Agolastico alni, Loptinotarsn docomllnoatn, Phaodon cochloariao, Diabrotlca spp., Psylliodos chrysocophala, Epilaclmavarivostis, Atomaria spp., Oryzaophilus surlnamonsls, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcetus, Coemopolitos dordidus, Choulhorrhynchut assimllls, Mypora pottlca, Dormestes spp ,, Trogodorma spp., Anthronus spp., Attagenus spp.,

Lyctus spp., Moligothos aoneus, Ptnnus spp., Niptus hololoucus, Qibblum psylloidos, Tribollum spp., Tonobrlo molitor, Agriotos

Spp., Conodofus spp., Mololontha mololontha, Amphlmallon solstitialis, Costotytra zoalandica.

From the order of Hymonoptera e.g. Diprlon spp., Hoplocampa spp., Laslus spp., Monomorium pharaonis, Vospa spp. For the order dor Diptora e.g. Aodos spp., Anopholos spp., Culox spp., Drosophita molanogostor, Musen spp., Fannia spp., Calliphora orythrocophala, Lucilia spp., Chrysomyla spp., Cutorobra spp., Gastrophlus spp., Hyppobosca spp., Slomoxys spp., Oostrus spp., Hypodorma spp., Tabnnus spp., Tannia spp., Biblo tiortulanus, Oscinolla frit, Phorbia spp., Pogomyia hyoscyami, Coratitis capitate, Dacus oloao, Tipula paludoso. For the order dor Slphonaptora e.g. Xonopsylla choopls, Corotophyllus spp. From the order of the arachnid e.g. Scorpio maurus, Latrodoctus mactans. From the order dor Acurina z. Acornus siro, Argas spp., Ornithodoros spp., Dormnnyssus gollinao, Eriophyos ribis, Phyllocoptruta oloivoro, Boophiius spp., Rhiplcophalus spp., Amblyomma spp., Hyolommn spp., Ixodos spp., Psoroptos spp., Chorioptos spp., Sarcoptos spp., Tarsonomus spp., Bryobla praotlosa °; .. onychus spp., Totranychus spp. Go to don plantcnparasiilWon Nomatodon go Pratylonus spp., Radopholus slmilis, Dilylnnchus dipsoci, Tyloncliulus

somiponotrans, Hotorodora spp., Moloidogyno spp., Apholoncholdos spp., Longidorus spp., Xiphinomn spp., Trichodorus spp.

The orogenungsgomäßon active ingredients zoigon insbosondoro horvorrogondo akarizido effect, also gogon rosistonto spider mite,

vvio e.g. Totranychus urticao, wolcho nutipflanzon, vvio e.g. Bohnon harmful.

The active compounds can be converted into conventional, depending on their respective physical and / or choric properties Formulations are carried out, wio solutions, emulsions, susponsionone, pulvor, foams, pastes, granules Aoroso'o, Active ingredient-impregnated nature · and synthotischo Stoffo, Foinstvorkapsolungon in polymoron fabrics and in Hüllmasson for Seeds, further in formulations with a distillate, wio hauchorpatronon, -doses, -spiral, etc., as well as ULV-KaIt- and Wormnobol-Formulierungon. These formulations are known in the art, e.g. by Vermischon dor Wirkstoffo with Strockmitteln, ie

liquid solvents, under pressure stohondon vorsonlgton Gason and / or foston Trägerstoffon, gobobononfalls untor

Prevention of surface active agents, ie emulsifiers and / or dispergents and / or foaming agents Means. In the case of using water as an extender, e.g. also organic solvents as Hilfslösungsmittcl

used. As liquid solvents come in wosontlichon in Frogo: Aromaton, wio xylene, toluene, odor

Alkylnaphthalenes, chlorinated aromatics odor chloriorto aliphatico Kohlonwassorstoffo, wio chlorobonzolo, chlorothylono or Mothylon chloride, aliphatic hydrocarbons wio cyclohoxone or paraffin, e.g. Petroleum fraction, alcohol, wio butanol

odor glycol and dioron ether and ester, kotono, wio acoton, Mothylothylkoton, Mothylisobutylkoton odor cyclohexanone, strong polar solvents, wio dimethylformamide and Dimothylsulfoxid, sowio water; with liquefied gaseous solid styrene carrier are such liquids gomoint, welclio boi normal temperature and under atmospheric pressure gaseous,

z. Eg, aorosol-troibgaso, wio halogoncarbon-butoxy-butane, butane, propane, nitrogen and carbon dioxide; as fosto Tragorstoffekommon in Frago: z. Natural gostoinsmohlo, wio kaolins, tonordon, talc, kroido, quartz, attopulgite, montmorillonite odor

Diatomoonordo and synthotischo Gestoinsmohlo, wio hochdisporsu kiosolsäuro, alumina and silikato; as solid Trägorstoffo for granules kommon in question: e.g. cracked and fractioniorto natural gostoino wio calcite, marble, pumice, Sopiolith, dolomite and synthetic granules of inorganic and organic Mohlon sowio Granulato of organic Material such as sawdust, coconut shell, corncob and Tobakstongol; as emulsifier and / or foaumorzougondo means

come into question: z. B. nichtionogono and anionic emulsifiers, wio Polyoxyolliylon l ^: otisäuro-Estor, Polyoxyothylon-

Fottalcohol ether, e.g. Alkylarylpolyglycol ethor, alkylsulfonates, alkylsulfato, arylsulfonato, and, in some cases, hydrolyzate; when Dispersant kommon in Frago: e.g. Lignin sulphite blebone and Mothylcolluloso. It can in the formulations adhesives wio carboxymethylcellulose, natural and synthetic powdery, körnigo odor

polymoro, wio gum arabic, polyvinyl alcohol, polyvinyl acetate, sowio natural

Phospholipids, such as cephalins and lecithin, and syntheto phospholipid. Woitoro Additivo can be mineral and

vegetabiloÖlesoin.

It may be dyes wio inorganic pigments, eg. For example, iron oxide, titanium oxide, Ferrocyanblau and organic dyes », wio Alizarin, Azo and Motalt Phthalocyanine Dyes and Spur Nutrient Oils Salt of Eison, Manganese, Boron, Copper, Cobalt, Molybdenum and zinc are used. The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%. The active ingredients can be prepared in their commercial formulations as well as donated from diosone formulations Forms of use in mixture with other active substances, wio lnsoktizidon, attractant, sterilants, acaricides, Nomatizidon, Fungicides, regulate the growth of London substances or Horbicides vorliogon. To don hsoktizidon include, for example Phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylurea, by microorganisms

Fabrics u.a.

The active ingredients may further be prepared in their commercial formulations as well as in these formulations Application forms in mixture with synergists are present. Synergists are compounds through which the effect of Active ingredients is gosteigert, without that the zugeotzte synergist must be so actively active. The active ingredient content of the application formon prepared from commercial formulations may be in wide boron

vary. The active ingredient concentration of the use forms may be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.

The application is done in a manner adapted to the application forms customary manner. The biological activity of the compounds of the invention is dictated by the application example.

HeritollungtbeUplele Example 1

(Ancestor (o))

6.7 g (Ο, Οβ mol) of 3-fluorophenol and 3.8 g (0.03 mol) of potassium carbonate were heated in Bonzol for 3 hours on Wasoorabscholdor to Siodon. 11.3 g (0.05 mol) of 2,3-dichloro-1,4-naphthoquinone, dissolved in tetrahydrofuran, is refluxed for 16 hours, after cooling with water Obtaining the crude product ob. 10.5 g (69% of thoorio) of 2-chloro-3 (3-fluoro-phenoxy) -1,4-naphthoquinone of melting point 123 ° C. are obtained.

(Vorfnhron Ib))

5u (0.019 mol) of 2- (3-fluoro-phenoxy) -1,4-naphthoquinone dissolved in 100 ml Eisossig. 0oi Raumtomporntur loitot man 3g (0.043 mol) of chlorine gas oil and stir woitoro 12 Stundon boi Raumtomporntur. DorobobildotoFoststoff is orcified obfiltriort, in 100ml Eisossig suspondiort and still adding 3g (0.036 mol) sodium acotate for 20 min.

Subsequently, the roaction mixture is filtered off on Wassor gogosson and dor ousgofollono Foststoff. 4.3 g (76% dor Thoorio) of 2-chloro-3- (3-fluorophonoxy) -1,4-naphthoquinone are obtained from the molten point 123X.

In ontsprochondor Woiso, analogous to the above boschriobonon ancestor (a) and (b) and, accordingly, allgomoinon information on the follicularity, one obtains lio succession 2-halogon-3-phonoxy-1,4-nophthoquinone-dorilato dor nllgomoinone formol (I. ):

Table 1 11 o R ¹ R ⁵ R ' R ⁴ R ⁴ R ^s phys. Ex. Dnton No. H Cl R ' H H Mp. Il H H Cl 134X 2 H H H H F 146x 3 F H H H H 136x 4 H H H H H 164x 5 H H F H H 139X 6 H H F I) H 104 X 7 CH, H OCF, H H 107 ⁰ C. 8th Cl H SCF, H H 135X 9 Cl K H H H 151 X 10 H CF, Cl CF, H 189X 11 H H CF, OCH, H 158X 12 H H H H OCH, 102 X 13 H H H Cl H 141X 14 H H H H H 129x 15 H H Cl H Cl 169 X 16 CN 140X 17 OCF,

In Examples 2-17, χ is chlorine

Preparation of Auigangi Conflicts Example (IV) -I

3, Gg (0.03 mol) of 3-Fluorphonol wordon with 2.2g (0.016 mol) of potassium carbonate in BOmI benzene boiled for 3 hours on a water. Anschlioßond wordon 6.4 g (0.028 mol) of 2-chloro-1,4-naphthoquinone, golöst In Totrohydrofuran, and the grafted Clio mixture 15 Stundon refluxed. Still Zugobo of water is sucked out nosgofallono Roaktionsprudukt. It is 5.9 ". (/ 8% dor Thoorio) 2- | 3-fluorophonoxy) -1,4-naphthoquinone of melting point 109T.

Anwendungsbolsplelo

In (oon succession, applicationboispiolcn wurdon clio nachstohond aufgoführton preconnon oingosotzt as Vorgloichsubstanzon:

(A)

(B)

(Boido bokannt from Postic.Sci. 15,235-240 (1984)).

Belsplol A

Phytophthora Tost (Tomato) / protoktiv Solvent: 4,7 Gowichtstoilo acetone Emulsifier: 0.3 gowichtstoilo alkyl-aryl-polyglycolethor To Horstollung oinor expedient Wirkstoffwirkoreitung premixed 1 Gowichtstoil active ingredient with the specified Mongol solvent and emulsifier, and preceded the Konzontrat with water to dio gowünschto concentration. To test for protektivo effectiveness, jungo Pflanzon is sprayed with the drug delivery line until dripping wet. To Drying the sprayed coating / it wordon dio planton inoculated with oinor aqulronon sporone suspension of Phytophthora iniostans. The planton wordon in oinor incubation cabin set up with 100% rolatlvor humidity and about 20 ° C.

3 days after the inoculation, the localization takes place.

There is a clear superiority in the efficacy of an active ingredient (concentration of 10ppm over the prior art

show in this test z. B. the Vorbindungon according to donHereollungsboispiolei; 1,4, 5, 6,7 and 9.

Example B Vonturia-Tost (ApfoD / protoctive Solvent: 4,7 Gowichtstoilo acetone Emulsifier: 0.3 gowichtstoilo alkyl-aryl-Potyglykolethor To prepare a suitable Wirkstoffzuboroitung premixed 1 part by weight of active compound with the angegebonon Mengon solvent and emulsifier and vorünnt the Konzontrat with Wassor to the desired concentration. To check for protektivo efficacy, jungo Pflanzon sprays with the active ingredient to the dripping wet. To Drying of the spray coating dio plants with an aqueous conidia suspension of Apfolschorferregors (Venturia

inaoqualis) and then stay 1 day boi 20 ° C and 100% relative humidity in an incubation cabino.

-12- 298 S08

The plants were then aufgoslollt in the greenhouse at 2O ⁰ C and olnor relative humidity of about 70%.

12 days after the inoculation, the evaluation is carried out.

A Doutliche Superiority In its efficacy, olnor offered drug concentration of 6 ppm gogonübor dom state of the art

zolgon in dios tomost, for example, the preconnonon gomass don Mollingboispiolon: I ₁ Ί, 5, β, 7, 9 and 10.

Examples Totranychus-Tost (rosistent) Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight Alkylaiylpolyglykoläthur For the preparation of an appropriate Wirkstoffzuboroitung premixed 1 Gowichtsteil active ingredient with don angobobonon Amounts of solvent and emulsifier and predilutes the concentrate with water to the gowünschto concentration. Bohnon plants (Phasoolus vulgaris), dio strong of allon developmental stage, gomoinon spider mite odor Bean spider mites (Tetrnnychus urticao) are desired by Tauchon in dio drug delivery Concentration bohandolt. According to the gowünschton ZoIt the destruction is in% Daboibodoutot 100%, that ollo Spinnmilbonabgotötot were; 0%

bodoutot that koino spider mite were killed.

In this tost zoigon z. For example, the successful compounds of Preparation Bioliolo 2, 3 and 7 are transglomerates effective in goyon before

dom Stand dor Tochnik bol oin drug concentration of 0.1%.

Claims (6)

R ¹ - R ⁵ independently of one another represent hydrogen, halogon, cyano, nitro, alkyl, haloalkyl, Alkoxy, haloalkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, haloalkylthio, aryloxy, arylthio, haloalkylsulfinyl or haloalkylsulfonyl and X is halogen, excluding the compounds in which the radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen and R ^{3 is} hydrogen, chlorine, nitro, methyl or methoxy and the precursor in which R ¹ and R ^{5 are} methyl and R ² , R ³ and R ^{4 are} hydrogen and X is each halogen. A 2-halo-3-phenoxy-1,4-naphthoquinone derivative dorformol (I) according to claim 1, in which R'-R ⁵ independently of one another are halogen or straight-chain or branched alkyl having 1 to 3 carbon atoms or R'-R ^{5 represents} a combination of hydrogen and 1 to 3, the same or different the following substituents stand: Halogen, cyano, nito, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms, straight-chain or branched alkoxy or haloalkoxy having in each case 1 to 3 carbon atoms and optionally 1 to 7, identical or different Halogen atoms, straight-chain or branched alkylthio, haloalkylthio or Halogenoalkylsulfonyl each having 1 to 3 carbon atoms and optionally 1 to 7 same or different halogen atoms, phenoxy or phenylthio and X is halogen, excluding the compounds in which the radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen and R ^{3 is} hydrogen, chlorine, nitro, methyl or methoxy and the compound in which R ¹ and R ^{5 are} methyl and R ² , R ³ and R ^{4 are} hydrogen and X is each halogen. A 2-halo-3-phenoxy-1,4-naphthoquinone derivative of the formula (I) according to claim 1, in which R'-R ^s independently of one another are fluorine, chlorine, bromine, methyl or ethyl, or R'-R ⁵ for a combination of hydrogen and 1 or 2, equals or different dor the following substituents stand: Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i-propyl, trifluoromethyl, 2,2,2-trifluoroethyl, methoxy, ethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, mothylthio, ethylthio, trifluoromethylthio or 2,2,2-trifluoroethylthio and X is fluorine, chlorine or bromine, excluding the compounds in which the radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen and R ^{3 is} hydrogen, chlorine, nitro, methyl or methoxy and the compound in which R ¹ and R ^{5 are} methyl and R ² , R ³ and R ^{4 are} hydrogen and X is each halogen. 4. Ancestors for the preparation of 2-halo-3-phonoxy-1,4-naphthoquinone dorivaton of the general formula (I)
O (D in which R'-R ⁵ independently represent hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, haloalkylthio, aryloxy, arylthio, Halogoiialkylsulfinyl or haloalkylsulfonyl and X is halogen, excluding the compounds in which the grids R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen and R ^{3 is} hydrogen, chlorine, nitro, mothyl or mothoxy and the compound in which R ¹ and R ^{5 are} methyl and R ² , R ³ and R ^{4 are} hydrogen and X is in each case halogen, characterized in that (a) Phenol derivatives of the general formula (II) Ho- '' Vr ³ RR ⁴ in which R ¹ -R ^{5 have} the abovementioned meaning, except for the compounds in which dio R ¹ , R *, R ⁴ and R ^{5 are} hydrogen and R ^{3 is} hydrogen, chlorine, nitro, methyl or methoxy and the compound in which R ¹ and R ^{5 is} methyl and R ² , R ³ and R ⁴ for hydrogen stand, with 2,3-dihalo-1,4-naphthoquinones of the general formula (III) in which X has the meaning given above and X ^{I is} halogen, if appropriate in the presence of a diluent and if appropriate in the presence of a basic R 'reaction aid, or
(b) 2-phenoxy / -1,4-naphthoquinone derivatives of the general formula (IV) (IV) in which H ¹ -R ^{5 have} the meaning given above, excluding the compounds in which the radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen and R ^{3 is} hydrogen, chlorine, nitro, methyl or methoxy and the compound in which R ¹ and R ^{5 are} methyl and R ² , R ³ and R ^{4 are} hydrogen, optionally halogenated with halogens (X ₂ ) in the presence of a diluent and then optionally eliminated in the absence oinos diluent and optionally in the presence of a basic reaction auxiliary hydrogen halide (HX). 5. pest control agent, characterized by a content of at least oinom 2-halo-3-phenoxy-1,4-naphthoquinone derivative of the formula (I) according to claims 1 and 4. 6. Use of 2-halo-3-phonoxy-1,4-naphthoquinone derivatives of formol (I) according to donations 1 and 4 for combating pests. 7. ancestors for combating pests, characterized in that 2-halo-3-phenoxy-M-naphthoquinone derivative dor formula (I) according to claims 1 and 4 is allowed to act on pests and / or their habitat. 8. A process for the preparation of pesticides, characterized in that pre-mixing 2-halo-3-phonoxy-1,4-naphthoquinone derivatives of the formula (I) according to claims 1 and 4 with extenders and / or surface-active agents. 9. S-phenoxy-M-naphthoquinone derivatives of formol (IV), (IV) in which R'-R ⁵ independently represent hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, haloalkylthio, aryloxy, arylthio, haloalkylsulfinyl or haloalkylsulfonyl.
10. A process for the preparation of S-phenoxy-M-naphthoquinone derivative of the formula (IV), (IV) OR ^v in which R'-R ⁵ are each independently hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, haloalkylthio, aryloxy, arylthio, haloalkylsulfinyl or haloalkylsulfonyl, characterized in that phenol derivatives of Formula (II) ,1 R " in which R ¹ , R ³ , R ⁴ and R ^{5 have} the abovementioned meaning, with 2-halo-1,4-naphthoquinone of the general formula (V)
O (V) in which X ^{2 is} halogen, if appropriate in the presence of a diluent and if desired in Gogonwart one base at temperatures between ^{0 0} C and 9O ⁰ C reacted The invention relates to nouo 2 · ΗαΙο9θη · 3 · ρΙιοηοχγ · 1,4 · ηηρΙιΐΙιοεΙιΙηοη · ΟθΓίνη (ο, mohroro prefohr to itsor Morstolluiig and iluo Voi wall as pesticides insbosondoro as fungicides and Akarizklo. It is not known that certain 1,4-naphthoquinone dorivato, boispiolswoiso 2-chloro-3- (4-mothoxyphonoxy) -1,4- naphthoquinone, 2-chloro-3- (4-chloronoxy) -1,4-naphthoquinone, 2-chloro-3- (4-methyloxyphenoxy) -1,4-naphthoquinone, 2 Chloro-S-M-nitrophonoxyl-M-naphthoquinone 2-bromo-3-phonoxy-1,4-naphthoquinone, fungicidal eigonschaftone Bositzon (see Postic., 15,235-24011904 |). The fungizido and akarizido efficacy diosor vorbokannton compounds is not iodine in ollon application gobioton completely randomly. Woichhin, this is 2-chloro-3- (2,5-dimethyphenyl) -1,4-naphthoquinone (see CA 99 [5]: 38149 n; Zh. Org. Khim., 19 | 1 |, 158-164 (19831). Uordio physiologischo effectiveness diosor Vorbindung is, however, nothing bokonnt. Nouo2-halogon-3-phonoxy-1,4-naphthoquinone-dor-dor-allgomoinone formol (I), (I)