CA2014481A1 - Sulfenylated carbamic esters - Google Patents

Abstract

PS/5-17551/+

Sulfenylated carbamic esters Abstract Novel substituted 2-phenoxyphenoxyethylcarbamic esters of the formula I

(I) where R1 is C1-C4alkyl or C3-C4alkenyl, R2 is C1-C4alkyl or a radical of the formula ,

Description

44~.

PS/5-1755 1/+

Sulfenvlated carbamic esters The present invention relates to novel substituted 2-phenoxyphenoxyethylcarbamic esters, to their preparation, to their use in pest control, and to pesticides containing these carbamic esters as active substance.

The carbamic esters according to the invention are those of the forrnula I

--~3 0--CH--CH--N (I) R4 R3 S()n R2 where R1 is Cl-C4alkyl or C3-C4alkenyl, R2 is Cl-C4alkyl or a radical of the formula ~ , CH2 ~ ~ -C(CH3)2-CN or-N(Rg)-COO-Cl-C4alkyl, R8 ' R8 R3 and R4 independently of one another are hydrogen or methyl, R5 is fluorine or chlorine, R6 is either identical to the substituents given in the case of R5 or is hydrogen, R7 and R8 independently o~ one another are hydrogen, halogen, Cl-C4aL~cyl, C1-C4aL~oxy or nitro, R9 is Cl-C4alkyl and n is zero, one or two.

Halogen in the definition of R7 and R8 is to be understood as meaning fluorine, chlorine, bromine or iodine, but preferably chloline.

C1-C4Alkyl groups can be straight-chain or branched. Fxamples of such radicals which may be mentioned are methyl, ethyl, propyl, isopropyl or butyl and its isomers. The preferred alkyl group is ethyl. C3-C4Alkenyl groups have the double bond preferably in the 2-position, as is the case in allyl, methallyl or 2-butenyl. The preferred alkenyl group .

- 2 - ~ 8~

iS ~lllyl.

Within the scope of the present invention, Cl-C4alkoxy radicals of the definition of R7 and R8 are methoxy, ethoxy, propoxy, isopropoxy or the four butoxy isomers. Methoxy is preferred.

If the radical R6 has a meaning other than hydrogen, i.e. if it is fluorine or chlorine, then the meaning within the scope of this invention is that R~ is the same halogen atom as R5.

Pesticidal ethyl carbamic acid derivatives have already been disclosed in various publications, but these substances are not satisfactory with regard to the spectrum of action obtained, or only in some cases. Examples of such compounds are disclosed in US
Patents 4,080,470, 4,215,139, ~,413,010, 4,555,405, 4,60~,389 and 4,74~,128 and the German Offenlegungsschlifterl DE-OS 3,320,534, 3,334,983 and 3,706,082. There istherefore still a demand for active substances of this substance class which have improved properties.

It has now been found thal the compounds of the formula [ according to the invention are valuable active substances in pest control while the tolerarlce by homothermals, fish and plants is favourable . The use of the active substances according to the invention particularly relates to insects and arachnids which are encountered in ClOp plants and ornamental plants in agriculture, in particular in plantations of cotton, vegetables and fruit, in forests, in the protection of stored goods and materials, and in the hygiene field, in particular on domestic animals and livestock. They are active against all or individual development stages of normally-sensitive but also resistant species~ Their action can be demonstrated by an immediate, or somewhat delayed, destruction of the pests, for example during ecdysis or by a lower number of eggs deposited andlor a lower hatching rate~ The abovementioned pests include:
from the order of the Lepidoptera, for example Acleris spp~, Adoxophyes spp~, Aegeria spp., Agrotis spp., Alabarna argillaceae, Amylois spp~, Anticarsia gemmatalis, Archips spp~, Argyrotaenia spp~, Autographa spp~, Busseola fusca, Cadra cautella, Carposina nippon~.nsis, Chilo spp~, Choristoneura spp~, Clysia ambiguella, Cnaphalocrocis spp~, Cnephasia spp~, Cochylis spp~, Coleophora spp~, Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp~, Diatraea spp~, Diparopsis castanea, Earias spp~, Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp~, Hellula undalis, Hyphantria cunea, Keiferia Iycopersicella, Lel~coptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;
from the order of the Coleoptera, for example Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp. Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogodenna spp.;
from the order of the Orthoptera, for example Blatta spp., Blattella spp., Gryllotalpa spp., Le~lcophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.;
from the order of the Isoptera, for example Reti.~ulitermes spp.;
from the order of the Psocoptera, for example Liposcelis spp.;
from the order of the Anoplura, for example Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. und Phylloxera spp.;
from the order of the Mallophaga, for example Damalinea spp. and Trichodectes spp.;
from the order of the Thysanoptera, for example Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Th}ips palmi, Thrips tabaci und Scirtothrips aurantii;
from the order of the Heteroptera, for example Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;
from the order of the Homoptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum~ Empoasca spp., Eriosoma larigerum, 2~

Elythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp..
Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza ery :reae and Unaspis citri;
frorn the order of the Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp.
and Vespa spp.;
from the order of the Diptera, for example Aedes spp., Antherigona soccata, ~ibio hortulanus, Calliphora erythrocephala, ~eratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fam~ia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagole~is pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;
from the order of the Siphonaptera, for example Ceratophyllus spp., Xenopsylla cheopis, from the order of the Acarina, for example Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas sl~p., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitlimerus spp., Chorioptes spp., ~)ermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.;
and from the order of the Thysanura, for e~ample Lepisma saccharina.

Particularly important in the case of the compounds according to the invention is the use in the control of rice cicadas, for example from ~he families Delphacidae and Cicadellidae, such as Nilaparvata lugens, Laodelphax striatellus and Nepholettix cincticeps. The active substances of the formula I also have an excellent action against the so-called "whi~efly", which is difficult to combat, of the family Aleyrodidae, genera Bemisia and Trialeurodes, such as Bemisia tabaci or Trialeurodes vaporarium. The compounds of the formula I have : ~ .
~, .

an excellent action against pests of fruit trees, of the Tortricidae and Olethreutidae families, with the genera Cydia, Adoxophyes and Lobesia, for example Cydia pomonella, Adoxophyes orana and Lobesia botrana.

The compounds of the formula I essentially cause an inhibition of growth in the various development stages in the target groups of pests, so that the lower infestation with pests can be accounted for by disruptions in the development of the pests, in particular by a chemosterilizing and ovicidal effect.

Compounds of the formula I which should be emphasized because of their advantageous action are those in which a) R2 is a radical of the forrnula , --CH2 ~ or-C(CH3)2-CN and Ra .

each Rs and R6 radical is either fluorine or chlorine, or b) R2 is a radical of the formula ~ or-C(CH3)-CN, . .
R3 and R4 independently of one another are hydrogen or methyl, R5 and R6 are fluorine or chlorine, and R7 is hydrogen, halogen, Cl- '4alkyl, methoxy or nitro, or c) R~ is the radical _~ R7 \

R3 and R4 are hydrogen, R5 and R6 are fluorine or chlorine, R7 is hydrogen, chlorine, 2~
- G -bromine or Cl-C4alkyl, and n is zero or two, or d) Rl is Cl-C3alkyl, R2 is ~R7 R3 and R4 are hydrogen, R7 is hydrogen, chlorine or methyl, and n is zero.

The following individual compounds according to the present invention must be mentioned as being preferred:

~3 0~0--CH2--CH2-~CI

~0 ~3 0--CH2-CH2-N/ ~3 Cl ~0~0--CHrCH2'N

~30~30--CH2--CH2-N/ _,~

F ~ ~ --CH2--CH2- N~

F
COOC2Hs > ~ ~3 --CH2--CH2- N
-' ~3 52 (~ Cl ~ O ~=~ O--CH2--CH2- N~

Cl S02~

CoocH2-cH=cH2 ~, ~o~ o--CH2--CH2-N h~
Cl~ S~

L~

~ ~ COOC2H5 F~ C--CH2--CH2-N ~CI

~ ~3 --CH2--CH2- ~3 ~3 ~3 --CH2- CH2- N\ and F S ~3 CH3 ~3 0--CH2--CH2- N ~3 The compounds of the formula I according to the invention can be prepared by methods known per se. For example, the compounds of the forrnula I can be obtained either when a) a phenoxyphenol of thc formula II

Rs ~ 0 ~3OH (II) where R5 and R6 are as defined under formula I is reacted, in the presence of a base, with an ethylcarbamic acid derivative of the formula III

" , L--CH CH--N (111) where Rl, R2, R3 and R4 are as defined under formula I and L is a leaving group, for example halogen, preferably chlorine or bromine, or a sulfonyloxy group, for example methylsulfonyloxy, trifluoromethylsulfonyloxy, phenylsulfonyloxy or tolylsulfonylo~cy, and the resulting product of the forrnula Ia ~_ o~ ~O--CH--CH--N/ (1~) ~vhere Rl, R2, R3, R4, Rs and R6 are as defined under formula I, may be oxidized to give the compollnds of the formula I where n is one or two; or when b) an ethylcarbamic acid derivative of the formula IV

~ O ~ O--CH--CH--NH--COOR, (IV) where Rl, R3, R4, Rs and R6 are as defined under formula I, is reacted, in the presence of a base, with a sulfenyl halide of the formula V

Hal-S-R2 (V) where R2 is as defined under forrnula I and Hal is halogen, preferably chlorine, and the resulting product of the'formula Ia may be oxidized to give the compounds of the formula I where n is one or two; or when c) an ethylcarbamic acid derivative of the formula IV is reacted, in the presence of a base, with a sulfinyl halide o~ the folmula VI

Hal-SO-P~2 (Vl) where R2 is as defined under formula I and Hal is halogen, preferably chlorine, and the resulting product of the formula Ib ~ o ~3 o CH~ CH--N/ (Ib) where R~, R2, R3, R4, R5 and R6 are as defined under formula I may be oxidized to give the compounds of the forrnula I where n is two; or when d) an ethylc.arbamic acid derivative of the formula IV is reacted, in the presence of a base, with a ~ulfonyl halide of the formula VII
Hal-SO2-R2 (VII) where R2 is as defined under forrnula I and Hal is halogen, preferably chlorine, to give a compound of the formula Ic ~ o ~ O--CH--CH--N (Ic~

where R1, R2, R3, R4, R5 and R6 are as defined under formula I; or when e) an ethylamine derivative of the formula VIII

O ~ O--CH--CH--NH2 (VIII) ~ ~ .
. ;- ~ ~ .
:

where R3, R4, R5 and R6 are as defined under fonnula I is acylated, in the presence of a base, with a haloformic acid derivative of the formula IX
Hal-COOR~

where Rl is as defined under formula I and Hal is halogen, preferably chlorine, and the resulting intermediate of the formula I~ is sulfenylated with a sulfenic acid halide of the formula V in the presence of a base, and the resulting product of the formula Ia may be oxidized to give the compounds of the formula I where n is one or ~wo; or when f) an ethylamine deriva~ive of ~he formula VIII is sulfenated with a sulfenic acid halide of the forrnula V in the presence of a base and ~he resul~ing in~ermediate of the forrnula X

~ O ~ ~ O--CH--CH--NH--S - R2 (~) R , R4 R3 where R2, R3, R4, Rs and R6 are as defined under formula I is acylated with a haloformic acid derivative of the formula IX in the presence of a base, and the resulting product of the formula Ia may be oxidized to give the compounds of the formula I where n is one or ~wo;
or when g) an alkali metal salt of the sulfonamide of the formula Xa is reacted with a haloforrnic acid derivative of the formula IX, Rl to R6 being as defined under formula I and Me~
being an alkali metal cation:

Rs O ~=,~ O ~- CH--CH--N - SO2-R2 (IX~
>=/ R4 R3 Me~3 R6 (Xa) .

~0~0--CH--CH--N
=/ R4 R3 SO2-R2 R6 (Ic) The abovementioned processes a), b), c), d), e), f) and g) can preferably be carried out under atmospheric pressure and in the presence of an inert organic solvent or diluent.
Examples of suitable solvents or diluents are, depending on the type of the reaction, ether and ether-like compounds, such as dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and ~etrahydrofuran; N,N-dialkylated carboxamides, such as N,N-dimethylfonnamide, aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, ~ylene, chloroforrn, methylene chloride, carbon tetrachloride and chlorobenzene; dime~hyl sulfoxidel sulfolane, and also ketones, for example ace~one" methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone.

The reaction temperatures in these processes ale generally between -20C and the boiling point of the reaction mixture. It is preferred not to exceed an upper temperature of +100C. Preferred temperature ranges are those between 0 and ~50C, but particularly those between 0 and +40C.

Suitable bases for process a) are aLkali metal hydrides or aLIcaline earth metal hydrides, such as lithium hydride, sodium hydride or calcium hydride; alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide; alkali rnetal carbonates, such as sodium carbonate or potassium carbonate; alcoholates, such as sodium ethylate, sodium methylate, potassium ethylate, potassium methylate or potassium tert-butylate. Tertiary amines, for exarnple triethylamine, pyridine or diisopropylethylamine, are likewise suitable as bases. The etherification reaction can be carried out under milder conditions when the leaving group L is selected from the series of the sulfonic acid derivatives, such - . ~ :

~ . . .
:

as methanesulfonic acid or toluenesulfonic acid, or when, in the event that L is fluorine, chlorine or bromine, catalytic amounts of alkali metal iodide are added, for example potassium iodide.

Bases in processes b), c), d), e) and f) which are preferably suitable are tertiary amines such as trialkylamines, pyridines or N,N-dialkylanilines, for example triethylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, dimethylaniline or diethylaniline.

In the case of liquid tertiaty amines, these can be simultaneously employed in the reaction as solvents.

If it is desired to alter the oxidation level of the sulfur atoms in the compounds obtained by process a), b~, c), d), e) or f), this can be effected by oxidation reactions known per se.
Suitable reagents are customary oxidants under customary reaction conditions. The following may be mentioned as examples of oxidants: peracids, such as peracetic acid, performic acid, perbenzoic acid, 3-chloroperbenzoic acid or monoperphthalic acid, hydrogen peroxide, periodic acid, sodium petiodate NaIO4, and also alkali metal chromates. While, in typical reactions, or~anic peracids are reacted in chlorinated hydrocarbons, such as methylene chlotide, chlorofotm or ethylene chloride, the solvents suitable for inorganic oxidants contain water and/or are miscible with water, such as acetone, acetic acid or fortnic acid. It is preferred to prepare performic acid in situ, for example by adding H22 to formic acid. The reaction temperatures of the oxidation mixtures are between -20C and +60C.

The intermediates of the formulae II, IV, V, VI, VII and IX are known or can be prepared by methods known per se.

The intelmediates of the formula III can alternatively be obtained in accordance with one of the following diagrams:

~4~

Di~ram l:

HO-CHR4-CHR3-NH2 + Hal-COOR1 (IX) (Xl) ~¦ base Ho-cHR4-cHR3-NH-co~R1 (Xll) `¦, A-SO2CI
A-SO2-O-CHR4-CHR3-NH-COOR1 (Xlll) ~¦~ Hal-S-R2 ,COOR1 A-SO2-O-CHR4-CHR3-N~ (Illa) TJ \S-R2 Hal: halogen, preferably chlorine, A: organic radical, preferably CH3,.CF3, phenyl or tolyl, L: leaving group, Rl, rc2, R3, R4, Y, Z: defined as under forrnula I, or .
~: Diag~m 2:

Hal-CHR4-CHR3-N=C=O + H-O-R
(XIV) ~I (XV) Hal-CHR4-CHR3-NH-CC)OR1 (XVI) - ~¦, Hal-S-R2 /COOR, H4-CHR4-CHR3-N (lllb) Hal: halogen, preferably chlorine, . ~ - : . . .
-:: : :; ...

~ .. .. ~ . ;.

A: organic radical, preferably CH3, CF3, phenyl, tolyl, L: leaving group, Rl, R2, R3, R4: defined as under formula I.

The intermediates of the formula VIII can be prepared from the corresponding carbonyl compounds by "reductive amination":

Dia~ram 3.

~,~ O ~ O--CHR4--C-O (XVI l) R5 \ NH3/H2/ca~alyst R~3 ~--CHR,,--CllR3--NIl2 (Vlll) Cntalyst: conventional hydrogenation catalysts, such as palladium, platinum, in particular Raney nickel, R3, R4, Rs, R6: de~med as under formula I.

After the imine has been forrned from XVII with ammonia, other reducing reagents can also be used in place of the reduction system H2/catalyst, such as complex hydrides, for example sodium borohydride.

The reagents employed in diagrams 1, 2 and 3 are mostly known, commercially available or they can be prepared from known products by simple methods. The reaction conditions correspond to those of analogous reactions which are known.

The action of the compounds according to the invention, or of the agents containing them, can be considerably broadened and adapîed to given circumstances by adding otherinsecticides andlor acaricides. Suitable as such additions are, for example, organophosphorus compounds, nitrophenols and their derivatives, formamidines, ureas, ~ ' :

~ ' carbamates, pyrethroids, chlorinated hydrocarbons and preparations of Bacillus thuringiensis.

It is particularly advantageous to combine the compounds of the formula I with substances which bring about a more powerful pesticidal effect. Examples of such compounds are, inter alia: piperonyl butoxide, propynyl ether, propynyl oximes, propynyl carbamates and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane or S,S,S-tributyl phosphorotrithioate.

The compounds of the formula I are employed in unaltered fo1m or, preferably, together with the auxiliaries conventionally used in the art of forrnulation, and they are therefore processed in 1 known manner to give, for example, emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations, for example in polymeric substances. The application methods, such as spraying, misting, atomizing, scattering or pouring, as well as the agents are selected to suit the intended aims and the prevailing circumstances.

The fonnulations, i.e. the agents, preparations or compositions containing the active subs~ance of the formula I or combinations of these active substances, insecticides or acaricides, and, if desired, a solid or liquid additive, are prepared in a known manner, for example by intimately mixing and/or grinding the active substances with extenders, for example with solvents, solid carriers, and, if desired, surface-active compounds(surfactants).

The following are possible as solvents: aromatic hydrocarbons, preferably the fractions C8 CI2, for exarnple xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane, paraffins, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and also epoxidized or unepoxidized vegetable oils, such as epoxidized coconut oil or soya oil, or water.

Solid carriers which are generally used, for example for dusts and dispersible powders, are ground ~atural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. To impro~e the physical properties, it is also possible to add highly-disperse silicas or highly-disperse absorptive polymers.

Possible particulate, adsorptive carriers for granules are either porous types, for example pumice, brick grit, sepiolite or hentonite, and also non-sorptive carrier materials, such as calcite or sand. Moreover, a large number of pregranulated materials of inorganic or organic nature can be used, such as, in particular, dolomite or comminuted plant residues.

Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties, depending on the nature of the active substance of the formula I to be formulated or on the combination of these active substances and other insecticides or acaricides. Surfactants are also to be understood as meaning mixtures of surfactants.

Anionic surfactants which are suitable can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or substituted or unsllbstituted ammonium salts of higher fatty acids (Cl0-c22)~ such as the sodium salts or potassium salts of oleic or stealic acid, or of natural mixtl~res of fatty acids which can be obtained, for example, from coconut or tallow oil. Mention must also be made of the fatty acid methyltaurinates.

However~ so-called surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or aLkylarylsulfonates.

The fat~y sulfonates or fatty sulfates are generally in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts, and generally have an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the Na or calcium salt of ligninsulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sul~ate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and one fatty acid radical having about 8-22 C atoms. Examples of arylalkylsulfonates are the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acidlforrnaldehyde condensation product. Other suitable compounds are the corresponding phosphates, such as the salts of the phosphoric ester of a %~ ,æ~, p-nonylphenol/(4-14)-ethylene oxide adduct.

Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols7 saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the aLkyl radical of the alkylphenols.
Other non-ionic surfactants which are suitable are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol which have I to 10 carbon atoms in the aLlcyl chain and which contain 20 to 250 ethylene glycol ether 4TOUpS and 10 to ioo propylene glycol ether groups. The abovementioned compounds customarily contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of non-ionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Other suitable substances are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan trioleate.

The cationic surfactants are mainly quaternary arnmonium salts, which contain at least one alkyl radical having 8 to 22 C atoms as N-substituent and which have lower halogenated or free alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are preferably in the folTn of halides, methylsulfates or ethylsulfates, for examplestearyltrimethylammonium chloride or ben2yldi(2-chloroethyl)ethylammonium brornide.

The surfactants customary in the art of formulation are described, inter alia, in the following publications:

"1985 International McCutcheon's Emulsifiers & Detergents", ~len Rock NJ USA, 1985", H. Stache, "Tensid-Taschenbuch [Surfactant ~uide]", 2nd edition, C. Hanser Verlag Munich, Vienna 1981, M. and J. Ash. "Encyclopedia of Surfactants", vol. I-III, Chemical Publishing Co., New York, 1980-1981.

~ . . .

As a rulel the pesticidal preparations contain 0.1 to 99 %, in particular 0.1 to 95 %, of the active substance of the formula I or combinations of this active substance with other insecticides or acaricides,1 to 99.9 % of a solid or liquid additive and 0 to 25 %, in particular 0.1 to 20 %, of a surfactant. While concentrated agents are often preferred as commercially available goods, the end user generally uses dilute preparations containing considerably lower concentrations of active substance. Typical application concentrations are between 0.1 and 1,000 ppm, preferably bet~veen 0.1 and 500 ppm. The application rates per hectare are generally 10 to l,000 g of active substance per hectare, preferably 25 to 250 g/ha.

In particular, preferred formulations have the following composition: (% = percent by weight) Emulsifiable concentrates Active ingredient:1 to 20 %,5 to lO % being preferred Surface-active agent:5 to 30 %, preferably 10 to 20 %
Liquid carrier:50 to 94 %, preferably 70 to 85 %

Dusts:
Active ingredient:0.1 to 10 %, preferably 0.1 to l %
Solid carrier:99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates:
Active ingredient:5 to 75 %, preferably 10 to S0 Water: 94 to 24 %, preferably 88 to 30 %
Surface active agent:1 to 40 %, preferably 2 to 30 %

Wettable po vders Active ingredient:0.5 to 90 %, preferably 1 ~o 80 %
Surface-active agent:0.5 to 20 %, preferably 1 to lS %
Solid carrier material: 5 to 95 %, preferably 15 to 90 %

Granules:
Active ingredient:0.5 to 30 %, preferably 3 to 15 %
Solid carrier:99.5 to 70 %, preferably 97 to 85 %

~ 4 ~

The agents can also contain further additions, such as stabilizers, defoamers, preservatives, viscosity regulators, binders, tackifiers and also fertilizers or other active substances for achieving specific effects.

The examples which follow are intended to illustrate the invention. They do not restrict the invention.

ExampleHl: EthylN-phenvlthio-2-~4-(3.5-difluorophenoxY)phenoxvlethvlcalbamate F~ O--CH2--CH2- N ~ 3 a) 27.6 g of finely pulverulent potassium carbonate and 1.0 g of pulverized potassium iodide are added to a solution of 22.2 g of 4-(3,5-difluorophenoxy)phenol in 80 ml of dimethylforrnamide. 18.2 g of ethyl 2-chloroethylcarbamate are furthermore addeddropwise, and the reaction mixture is heated for 16 hours at ~95C, with stirring. The reaction mixture is then filtered, the filtrate is poured into 400 ml of water, and the mixture is extracted three times using diethyl ether. The combined organic phases are washed with water and dried over sodium sulfate, and the solvent is distilled off. The residue is purified over silica gel (eluent: n-hexane/diethyl ether, 3:1), which gives pure ethyl 2-~4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate as a colourless solid of melting point 54-56C, which solidifies in crystalline form; yield: 92 % of theo~y.

b) 5~7 g of freshly distilled phenylsulfenyl chloride in 10 ml of toluene are added dropwise at 0 to +5C in the course of 30 minutes ~o a solution of 12 g of ethyl 2-L4-(3,5-difluorophenoxy)phenoxy]ethylcar~amate in 40 ml of pyridine, with stirring.
After this, the mixture is stirred for 4 more hours a~ room temperature. The reaction mixture is poured into 300 ml of 2N hydrochloric acid and ice, and the mixture is extracted twice using diethyl ether. The combined organic phases are washed to neutrality with water and sodium chloride solution and dried over sodium sulfate. The solvent is distilled off in vacuo, and the residue is purified by chromatography on silica gel (eluent:
hexane/diethyl ether, 2Q: 1), which gives pure ethyl ., ': ':: ' 2~ 4~

~-phenylthio-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate, nD20: 1.5700.
Example H2: Ethvl N-(4-chlorophenvlthio)-'7-~4-(3,5-difluorophenoxy)phenoxvlethylcarbamate F

F ~0--CH2--CH2-N ~3 7.6 g of freshly distilled 4-chlorophenylsulfenyl chloride is added dropwise at 0 to +5C
in the course of 30 minutes to a solution of 12 g of ethyl 2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate in 40 ml of pyridine, with stirring.
After this, the mixnlre is stirred for 16 more hours at room temperature. The reaction mixture is poured into 200 ml of 2N hydrochloric acid and ice, and the mixture is extracted twice using diethyl ether. The combined ether extracts are washed to neutrality with water and dlied over sodium sulfate. The solvent is distilled off in vacuo, and the residue is pu~ified by chromatography on silica gel (eluent: hexane/diethyl ether, 9:1), which gives pure ethyl N-(4-chlorophenylthio)-2-[4-(3,5-diQuorophenoxy)phenoxy]ethylcarbamate, nD20 1.5763.

Example H3: Ethvl N-phenvlthio-2-~4-(3,5-difluorophenoxv)phenoxylethvlcarbamate F

~o~ 30 CH CH

a) 60 g of mcthanesulfonyl chlolide are metered over approximately 30 minutes at S) to +5C to a solution of 66.5 g of elhyl 2-hydroxyethylcarbamate, 43.5 g of pyridine and 1.9 g of 4-dimethylaminopyridine in 150 ml of methylene chloride, with stining, and the mixture is stirred for 2 more hours at +5C and then for 16 hours at room temperature. The reaction mixture is filtered, the residue is washed with a small quantity of ethyl acetate, and the combined filtrates are washed with dilute hydrochloric acid and water. After the mixture has been dried over magnesium sulfate, the solvent mixture is removed , comple~ely by distillation in vacuo, which gives ethyl 2-methyls~llfonyloxyethylcarbamate, nD20 1.4450.

b) 21. I g of ethyl 2-methanesulfonyloxyethylcarbamate, obtained as above, and 0.4 g of 4-dimethylaminopyridine are dissolved in 48 g of pyridine, and 15.8 g of freshly distilled pher~vlsulfenyl chloride in 15 ml of toluene are added dropwise in the course of 20 minutes at 0 to +5C, with stirring. The mixture is stirred at this temperature for 4 mo}e hours. After this, the reaction mixture is poured into 300 g of ice and 200 ml of 2N
hydrochloric acid, and the mixture is extracted several times with ether. The combined organic phases are washed to neutrality with saturated sodium chloride solution and dried over sodium sulfate. The solvent is distilled off in vacuo. Chromatographic purification on silica gel (eluent: diethyl ether/hexane, 1:1) gives pure ethyl N-phenyl~hio-2-methylsulfonyloxyethylcarbamate, nD20: 1.5390.

c) A solution of the sodium salt of 4-(3,5-difluorophenoxy)phenol (preparecl from 4.3 g of 4-(3,5-difluorophenoxy)phenol and 0.8 g of a 55 % dispersion of sodium hydride in mineral oil in 40 ml of dry dimethyl sulfoxide) is metered at a constant rate at -~25C in the course of 5 hours to a solution of 6.5 g of ethyl N-ph~nylthio-2-methylsulfonyloxyethylcarbamate and 0.1 g of hydroquinone in 20 ml of anhydrons dimethyl sulfoxide, with stirring. The mixture is stirred for S more hours at room temperature. After this, the reaction mixture is poured into ice-water and extracted repeatedly with an ether/hexane mixture (1:4), and the combined organic phases are washed with water and dried over sodium sulfate. After the solvents have been distilled off in vacuo, the crude product is puAfied by chromatography, by which process ethyl N-phenylthio-2-[4-(3,5-di~uorophenoxy)phenoxy]ethylcarbama~e is isolated, nD20:
1.5700.

Example H4: Ethvl N-phenylthio-2~4-(3,5-fluorophenoxY)phenoxylethvlcarbamate F
~ ,ç~ COOC2H5 ~ ~ O--CH2--CH2- N ~

A solution of the potassium salt of 4-(4-~luorophenoxy)phenol (prepared from 4.3 g of ,: : :: . ~ ~ :

1-(3,5-difluorophenoxy)phenol and 2.04 g of potassium tert-butylate in 35 ml of dry dimethyl sulfoxide) is metered at a uniform rate at +25C in the course of S hours to a solution of 5.8 g of ethyl N-phenylthio-2-chloroethylcarbamate, 0.1 g of potassium iodide and 0.2 g of hydroquinone in 20 ml of anhydrous dimethyl sulfoxide, with stirring. The mixture is stirred for 5 more hours at room temperature. After this, the reaction mixture is poured into ice-water and extracted repeatedly with an ether/hexane mixture (1:4). The combined organic phases are washed with water and dried over sodium sulfate. After the solvents have been distilled off in vacuo, the crude product is purified by chromatography, by which process ethyl N-phenylthio-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate is isolated, nD~: 1.5700.

Example HS: Ethvl N-phenvlthio-2-~4-(3,5-difluorophenoxY)phenoxvlethvlcarbamate F

~ O ~ 0--CH2- (,H2- N/ ~

A solution of 4.3 g of 4-(3,5-diflllorophenoxy)phenol and 1.58 g of pyridine or 2.58 g of ethyl diisopropylamine in 35 ml of dry dimethyl sulfoxide is metered at a constant rate at +25C in the course of S hours to a solution of 6.4 g of ethyl N-phenylthio-2-methylsulfonyloxyethylcarbamate and 0.2 g of hy~roquinone in 20 ml of anhydrous dimethyl sulfoxide, with stirring. The mixture is stirred for S more hours at room temperature. After this, the reaction mixture is poured into ice-water and extracted three times with an ether~hexane mixture (1:4), and the combined organic phases are washed with water and dried over sodium sulfate. After the solvents have been distilled off in vacuo, the crude product is purified by chromatography, by which process ethyl N-phenylthio-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate is isolated, nD20 1.5700.

Example H6- Ethyl N-phenylsulfinyl-2-~4-(3,5-difluorophenoxy~phenoxylethylcarbamate F

cooC2H5 ~~--CH2--CH2-- ~o~æ~

A solution of 8.1 g of 55 % 3-chloroperbenzoic acid in 50 ml of dichloromethane is added dropwise at 0 to ~5C in the course of 20 minutes to a solution of 11.5 g of ethyl N-phenylthio-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate in 80 ml of dichloromethane, ~vith stirring. After the reaction mixture has been stirTed for 2 hours at -~20 to +22C, it is extracted twice with a 10 % sodium carbonate solution and washed to neutrality with water. The dichloromethane phase is dried over sodium sulfate, and the solvent is distilled off in vacuo. The residue is purified by chromatography on silica gel (eluent: n-hexane/diethyl ether, 3:1), which process gives ethyl N-phenylsulfinyl-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate, colourless viscous oil nD20: 1.5645.

Example H7: Ethvl N-phenylsulfonvl-2-~4-(3.5-difluorophenoxy)phenoxylethYlcarbamate F

~ ~ o~/ \\~

A solution of 4~0 g of 55 % 3-chloroperbenzoic acid in 30 ml of dichloromethane is added dropwise at about +5C in the course of 10 minutes to a solution of 4.8 g of ethyl N-phenylsulfilnyl-2-~4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate in 30 ml of dichloromethane, with stirring. The reaction mixture is stirTed for 16 hours at room temperature and then washed twice with 10 % sodium carbonate solution and then to neutrality with water. The organic phase is dried over magnesium sulfate, and the solvent is distille~ off in vacuo. The crude product is purified further by chromatography on silica gel (eluent: n-hexane/diethyl ether, 3:1), by which process ethyl N-phenylsulfonyl-2-[4-(3,5-difluorophenoxy)phenoxylethylcarbamate is isolated as a colourless resinous substance, nD20: 1.5610.

ExampleHg: EthylN-methylsulfonvl-2-~4-(3-chlorophenoxy)phenoxylethylcarbamate ¢~ 0 ~0--CH CH N/ 2 5 >== / SO2-CH3 Cl , .... : .:
` ~

: : .

:
. .. , . : ..

1.47 g of a 55 % dispersion of sodium hydride in mineral oil are washed repeatedly with n-hexane and suspended in 30 ml of tetrahydrofuran. A solution of 11.3 g of ethyl 2-[4-(3-chlorophenoxy)phenoxy]ethylcarbamate (m.p. 45-46C; prepared from 4-(3-chlorophenoxy)phenol and ethyl 2-chloroethylcarbamate in dimethylformamide analogously to Example Hla) in 30 ml of tetrahydrofuran is added dropwise at room temperature to this suspension with stirr~ng, and the mixture is stirred for about S hollrs at room temperature until the reaction of the sodium hydride is complete. After this, a solution of 4.2 g of methanesulfonyl chloride in 10 ml of tetrahydrofuran is added dropwise at 0-5C in the course of 10 minutes, and the mixture is stirred for 15 more hours at room temperature. The reaction mixture is now poured into ice-water andextracted repeated]y with ether. The combined ether phases are washed repeatedly with 5 % sodium carbonate solution and then with water, the organic phase is dried over sodium sulfate and the solvent is distilled off. The crude product is purified further by chromatography on silic~a gel (eluent: n-hexane/diethyl ether,5:1), by which process ethyl N-methylsulfonyl-2-[4-(3-chlorophenoxy)phenoxy]ethylc:arbamate is obtained as a colourless, viscous oil, nD 1: 1.5573.

Anal(?gously, ethyl N-phenylsulfonyl-2-[4-(3-chlorophenoxy)phenoxy]ethylcarbamate is obtained from ethyl 2-[4-(3-chlorophenoxy)phenoxy]ethylcarbamate and benzenesulfonyl chloride as a colourless, viscous oil, nD20: 1.5790.

Example H9: Methvl N-phenvlthio-2-~4-(3,5-difluorophenoxY)phenoxYlethvlcarbamate F ~ COOCH3 S~o~30 CH2--CH2-N~ ~3 F

a) 21.3 g of potassium carbonate powder, l.S g of pulverized potassium iodide and 16 g of methyl 2-chloroethylcarbamate are added to a solution of 17.1 g of 4-(3,5-difluorophenoxy)phenol in 100 ml of dimethylformamide, and the reaction mixture is heated for 16 hours at 95C. The cooled reaction mixnlre is then poured into ice-water, and the mixture is extracted repeatedly with diethyl ether. The combined ether phases are washed with water and dried over sodium sulfate, and the solvent is distilled off. The `

4~.

crude product is chromatographed on silica gel (eluent: n-hexane/diethyl ether, S:1), by which process pure methyl 2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate is obtained, nD2l: 1.5394.

Analogously, the following are obtained from isopropyl 2-chloroethylcarbamate, allyl 2-chloroethylcarbamate and 4-(3,5-difluorophenoxy)phenol:
isopropyl 2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate, nD2l: 1.5243 and allyl 2-[4-(3-chlorophenoxy)phenoxy]ethylcarbamate, m.p. 51-52C.

b) Analogously to the procedure of Example Hlb), the following active substancesaccording to the invention are obtained from the carbamic esters obtained in a) by reacting -them with phenylsulfenyl chloride:

Methyl N-phenylthio-2 [4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate, nD20: 1.5750;
isopropyl N-phenylthio-2-[4-(3,5-diflllorophenoxy)phenoxy]ethylcarbamate, nD20: 1.5638 and allyl N-phenylthio-2-[4-(3-chlorophenoxy)phenoxy]ethylcarbamate, nD20: 1.6079.
ExampleH10: Ethyl ~-p'nenvlthio-2-~4-(3-chlorophenoxY)phenoxYl-l-me hylethvlcarbamate ~30~30--CH2--CH--N __~

Cl .
a) 32.5 g of anhydrous potassium carbonate powder and 2 g of finely pulveri~ed potassium iodide are added to a solution of 39.8 g of 4-(3-chlorophenoxy)phenol in 250 ml of ethyl methyl ketone, and the mixture is heated fO reflux temperature. 25 g of freshly distilled chloroacetone are now added dropwise in the course of 45 minutes, and the mixture is stirred for 2 more hours at reflux temperature. When the reaction mixture has cooled down, it is filtered, the solvent is distilled off in vacuo, and the residue is freed completely from the solvent in a high vacuum at 4ûC. The resulting oily 4-(3-chlorophenoxy)phenoxypropanone, nD20: 1.5788, analytical grade, is directly reacted further.

-:' : ' ~'', ~ ~

b) In a stirred autoclave,51 g of 4-(3-chlorophenoxy)phenoxypropanone are dissolved in S10 ml of methanol. 31 g of liquid ammonia are forced in, and the mixture is subjected to reductive amination at ~0-45C for 3 hours in the presence of 10 g of Raney nickel and ~0 bar of hydrogen pressure. After the pressure in the autoclave has been let down, the Raney nickel is filtered off from the reaction mixture. The catalyst is washed with methanol, and the methanol is finally distilled off from the reaction mixture. The residue is chromatographed on silica gel (eluent: diethyl ether/methanol, S:l), by which process pure 1-[4-(3-chlorophenoxy)phenoxy~-2-aminopropane is obtained, nD20: 1.5743.

c) 13.5 g of ethyl chloroformate are added dropwise at 20C in the course of 30 minutes to a solution of 31.5 g of 1-[4-(3-chlorophenoxy)phenoxy]-2-aminopropane,20 g of diisopropylethylamine and 1 g of 4-dimethylaminopyridine in 120 ml of toluene, with stirring and slight ex~ernal cooling, and the mixture is stirred for a further 15 h(~urs at 20C. After this, the reaction mixture is poured into 200 ml of 2N hydrochloric acid and ice-water, and the toluene phase is separated off. The aqueous phase is re-extracted with ether, the combined organic phases are washed to neutrality with water and sodium chloride solution and dried over sodium sul~ate, and the solvents are distilled off in vacuo.
The crude product is chromatographed on silica gel (eluent: n-hexane/diethyl e~her, S:I), by which process pure ethyl 2-[4-(3-chlorophenoxy)phenoxy]-1-methylethylcarbamclte is obtained as a pale yellow oil, nD21: t.5530.

d) A solution of 4 g of phenylsulfellyl rhloride in 10 ml of toluene is added dropwise at 0-5C in the course of 20 minutes to a solution of 9 g of ethyl ~-[4-(3-chlorophenoxy)phenoxy]-1-methylethylcarbarnate in 30 ml of pyridine, with stirring, and the mixture is stirred for a further 15 hours at room temperature. Most of the pyridine and toluene is then distilled off in vacuo at a temperature of lower than 45C, and the residue is poured into 300 ml of ice~water and extracted repeatedly with ether. The combined ether phases are first washed with cold, dilute hydrochloric acid and then with water, the mixture is dried over sodium sulfate, and the solvent is distilled off completely.
The residue is purified further by chromatography on silica gel (eluent: n-hexane/diethyl ether, 19:1~, by which process ethyl N-phenylthio-2-[4-(3-chlorophenoxy)phenoxyl-1-methylethylcarbamate is ob~ained as a colourless oil, nD20: 1.5810.
The following active substances of the formula I can be obtained analogously:

, Table 1: Rs ~ o ~3 o CH--CH--N

R6 R4 R3 S()n R2 Ccmp Rl R2 n R3 R4 RS R6 Physical data 1.01 C2Hs C6Hs H H F F nD20: 1.5700 1.02 C2Hs c6~s 1 H H F F nD20: 1.5645 1.03 C2Hs C6Hs 2 H H F F n~20: 1.5610 1.04 C2Hs 4-CI-C6H4- 0 H H F F nD20: 1.5763 1.05 C2Hs 4-CH3-C6~I4- 0 H H F F nD20: 1.5705 1.06 C2Hs 3-ClI3-C~H4- O H H F F
1.07 C2Hs 2-cH3-c6H4- 0 H H F F .
1.08 C2E~s 3-CI-C6H4- O H H F F
1~09 C2Hs 3-CI-4-CI-C6H4- 0 H H F F
1.10 C2Hs 4-NO2-C6H4- 0 H H F F
1.11 C2Hs C6Hs-cH2- 0 H H F F
1.12 CH3 C6Hs H H F F nD20: 1.5750 1.13 C4Hg-n C6Hs H H F F
1.14 C2H5 C6Hs CH3 H Cl H nD20: 1.5810 1.15 C2Hs C6Hs 1 CH3 H F F
1.16 C2Hs C6Hs 1 H H F F
1.17 C2Hs 4-CH3-C6H4- 1 H H F F .
1.18 C2Hs C6H5 H H F H
1.19 C2Hs 4-Cl-C6H4- O H H }; H
1.20 C2Hs C6Hs-c~2- 0 H H F H
1.21 C2Hs C6Hs 1 H H F H

.. - : , -. , : : : .: ; - .: . . :

Table 1 (continuation) Comp _ _ R2 n RJ R4 R5 R6 Pt Y ~

1.22 C2Hs C6Hs H H Cl H nD21: 1.5851 1.23 C2Hs C6Hs 1 H H C1 H
1.24 C2Hs 4-CI-C6H4- 0 H H Cl H nD20: 1.5879 1.25 C2Hs 4-CH3-C6H4- 0 H H C1 H nD~: 1.5934 1.26 C2Hs 4-CH3-C6H4- 0 H H C1 Cl 1.27 C2H5 4-CI-C6H4- 0 H H Cl Cl 1.~ 8 C2Els C6Hs H H Cl Cl 1.29 C2Hs C6Hs 1 H H C1 Cl 130 C2Hs C6Hs (CH2)4 Cl Cl 1.31 C2Hs 2-CH3-4-CH3-C6H3- 0 H H F F nD20: 1.5713 1.32 ¦ C2Hs CH3 2 H H Cl H nD21: 1.5573 1.33 C3H7-i C6Hs H H F F nD20: 1.5638 1.34 ~2Hs 4-CI-C6H4- 2 H H F F nD22: 1.5641 135 C2Hs C6Hs 2 H H Cl H nD20: 1.5790 1.36 -CH2CH=CH2 C6H5 H H C1 H nD20: 1.6079 1~37 C2Hs --- C6Hs C~I3 H F F
Formulation examples of liquid active substances of the formula I (% = percent bv wei~Jht) Fl. Emulsionconcentrates a) b) c) Active substance No. 1.01 . 25 % 40 % S0 %
Cadodecylbenzenesulfonate 5 % 8 % 6 %
Castor oil polyethylene glycol ether (36 mol of EO) 5 %
Tributylphenol polyethylene glycol ether (30 mol of EO) - 12 % 4 %
Cyclohexanone - lS % 20 %

2~:~4~

Xylene mixture 65 % 25 % 20 %

Emulsions of any desired concentration can be prepared from such concentrates bydiluting them with water.

F2. Solutions a) b) c) d) Active substance No. 1.02 80 % 10 % 5 % 95 %
Ethylene glycol monomethyl ether 20 %
Polyethylene glycol MW 400 - 70 %
N-Methyl-2-pyrrolidone - 20 %
Epoxidizedcoconutoil - - 1% 5 %
Petroleum ether (boiling range 1 60- 1 90C) 94 %

The solutions are suitable for use in the forrn of minute droplets.

F3. Granules ~ a) b) Active substance No. 1.02 5 % 10 %
Kaoiin 94 %
Highly-disperse silica 1 %
Attapulgite go %

The active substance is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is then evaporated off in vacuo.

F4. Dusts a) b) Active substance No. 1.01 2 % 5 %
Highly-disperse silica l % 5 %
Talc 97 %
Kaolin - 90%

Ready-to-use dusts are obtained by intimately mixing the carriers with the active substance.

Formulation examples of solid active substances of the formula I ~% = percent by wei~ht) .

, ~ , . . :
. , .

FS. Wettablepowder a) b) c) Ac~ive substance 1.03 25 % 50 % 75 %
Na ligninsulfonate 5 % 5 %
Na laurylsulfate 3 % - 5 %
Na diisobutylnaphthalene-sulfonate - 6 % 10 %
Octylphenol polyethylene glycol ether (7-8 mol of EO) - 2 %
Highly-disperse silica 5 % 10 % 10 %
Kaolin 62 % 27 %

The active substance is mixed thoroughly with the additives, and the mixture is ground thoroughly in a suitable mill. Wettable powders which can be diluted with water to give suspensions of any desired concentration are obtained.

F6. Emulsion concentrate Active substallce No. 1.03 10 %
Octylphenol polyethylene glycol ether (4-5 mol of EO) 3 %
Ca dodecylbenzenesulfonate 3 %
Castor oil polyglycol ether (36 mol of EO) 4 %
Cyclohexanone 30 %
Xylene mixture 50 %

Emulsions of any desired concentration can be prepared from this concentrate by diluting it with water.

F7. Dusts a) b) Active substance No. 1.03 5 % ~ %
Talc 95 %
Kaolin - 92 %

The ready-to-use dusts are obtained by mixing the active substance with the carrier and grinding the mixture on a suitable mill.

F8. Extruder ranules Active substance No. 1.03 10 %
Na ligninsulfonate 2 %
Carboxymethylcellulose 1 %
E~aolin 87 %

The active substance is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded, granulated and then dried in a stream of air.

F9. ~oated ~ranules Active substance No. 1.03 3 %
Polyethylene glycol (MW 200) 3 %
Kaolin 94 %

In a mixer, the finely ground active substance is applied unifonnly to the kaolin which has been moistened with polyethylene glycol. In this manner, dust-free coated granules are obtained.

F10. Suspension concentrate Active substance No. 1.03 40 %
Ethylene glycol 10 %
Nonylphenol polyethylene glycol ether (15 mol of EO) 6 %
Na ligninsulfonate 10 %
(: arboxymethylcellulose 1 %
37% agueous forrnaldehyde solution 0.2 %
Silicon oil in the forrn of a 75% aqueous emulsion 0.8 %
Water 32 %

The finely ground active substance is intimalely mixed with the additives. In this manner, a suspension concentrate is obtained from which suspensions of any desired concentration can be prepared by diluting it with water.

In the biological examples which follow, a good action means that the desired effect occurs to a degree of at least 50 to 60 %.

:,.. ., . , ~ , .

- ~
.: , .
, . . . .

Example B 1: Action a~ainst Boophilus microplus Adult female ticks which have sucked themselves full are stuck onto a PVC plate and covered with a cottonwool ball. For the treatment, 10 ml of an aqueous test solution containing 125 ppm of the active substance to be tested are poured over the test animals.
The cottonwool ball is then removed, and the ticks are incubated for 4 weeks to deposit eggs. The action against Boophilus microplus is demonstrated either on the female in terrns of mortality or sterility, or on the eggs as an ovicidal action.

In this test, compounds of Table 1 have a good action against Boophilus microplus. In particular the compounds 1.01, 1.03 and 1.33 have an action of more than 80 %.

Example 132: Action a~ainst Aedes aegypti 50-100 Aedes aegypti }arvae are introduced into 200 ml of an aqueous test solution containing 400 ppm of the active substance to be tested and a very small amount of feed.
The test vessel is then sealed with a lid and incubated. The test is evaluated 14 days after it has been set up, for hatch % of the adults compared with untreated controls.

In t'nis test, compounds according to Table 1 have a good action against Aedes aegypti. In particular the compounds 1.04, 1.22, 1.24 and 1.25 have an action of more than 80 %.

Example B3: Ovicidal action on Cvdia pomonella Cydia pomonella eggs which have been deposited on paper filters are briefly immersed in an acetonic-aqueous test solution containing~ 400 ppm of the active substance to be tested.
After the test solution has dried on, the eggs are incubated in Petri dishes. After 6 days, the percentages of eggs where hatching is observed are evaluated by comparing ~hem with untreated controls (% hatch reduction).

In this test, compounds according to Table 1 have a good action against Cydia pomonella.
In particular the compounds 1.01, 1.04 and 1.05 have an action of more than 80 %.

_ample B4: Ovicidal action on Adoxophyes reticulana Adoxophyes reticulana eggs which have been deposited on paper filters are brie~ly immersed in an acetonic-aqueous test solution consaining 400 ppm of the active substance to be tested. After the test solution has dried on, the eggs are incubated in Petri dishes. After 6 days, the percentages of eggs where hatching is observed are evaluated by comparing 2~

them with untreated controls (% hatch reduction).

In this test, compounds according to Table 1 have a good action against Adoxophyes reti-culana. In particular the compounds 1.01, 1.05 and 1.12 have an action of more than 80 %.

E~cample B5: Ovicidal action a~ainst Dermanyssus gallinae About 200 mites in various development stages and 2 to 3 ml of a solution containing 10 ppm of active substance are introduced into a glass vessel which is open at the top. The container is then sealed with a cottonwool ball, shaken for 10 minutes until the mites are completely wetted, and then briefly turned over so that the remaining test solution can be absorbed by the cottonwool. After 3 days, the mortality of the mites is determined.

The compounds of Table l have a good action against Dermanyssus gallinae. In ~articuhlr, the compounds 1.01, 1.05 and 1.22 have an action of more than 80 %.

Example B6: Action against Aonidiella aurantii Potato tubers are infested with crawlers of Aonidiella aurantii (orange scale). After about 2 week~s, the potatoes are immersed in an aquet)us emulsion spray liquor containing the active substance to be tested in a concentration of 400 ppm. After the trea~ed potato tubers have dried, they are incubated in a plastic container. For evaluation after 10-12 weeks, the survival rate of the crawlers of the first consecutive generation of the treated scaly insect population is compared with that of untreated controls~

In this test, compounds according to Table 1 have a good action against Aonidiella aurantii.
In particular the compounds 1.01, 1.04 and 1.31 have an action of more than 80 %.

Example B7: Action ag~ainst Nilaealvata lugens Rice plants are treated with a spray liquor of an aqueous emulsion containing 400 ppm of the active substance. After the spray coating has dried on, the rice plants are infested with adult cicadas, which lay eggs. ~fter this, the adults are removed and the plants are incubated. The tests are evaluated after 14 days. The percentage reduction of progeny (%
action) is determined by comparing the number of hatched nymphae on the treated plants with those on the untreated plants.

The compounds of Table 1 have a good action against Nilaparvata lugens in this test. In particular, the compounds 1.01, 1.02, 1.04, 1.22, 1.24, 1.25 and 1.31 have an action of more , :

than 80 %.

Example B8: Action aoainst Nephotettix cincticeps Rice plants are treated with a spray liquor of an aqueous emulsion containing 400 ppm of the active substance. After the spray coating has dried on, the rice plants are infested with adult cicadas, which lay eggs. After this, the adults are removed and the plants are incubated. The tests are evaluated after 14 days. The percentage reduction of progeny (%
action) is determined by comparing the number of hatched nymphae on the treated plants compared with those on the untreated plants.

The compounds of Table l have a good action against Nephotettix cincticeps in this test. In particular, the compound 1.01 has an action of more than 80 %.

Example B9: Action aoainst Bemisia tabaci Dwarf beans are placed in gauze cages and infe~ted with Bemisia tabaci adults (whitetly).
After eggs have been laid, all adults are removed, and, 1~) days later, the plants together with the nymphs living on them are treated with a spray liquor of an aqueous emulsion of the acti~e substances to be tested (concentration 400 ppm~. 14 days after the aetive substance has been applied, the population is evaluated for hateh % eompared with untreated eontrols.

In this test, eompounds according to Table 1 have a good action against Bemisia tabaei. In particular the compounds 1.01, 1.04, 1.22, 1.24 and 1.25 have an action of more than 80 %.

Claims (14)

1. A 2-phenoxyphenoxyethylcarbamic ester of the formula I

(I) where R1 is C1-C4alkyl or C3-C4alkenyl, R2 is C1-C4alkyl or a radical of the formula , ,-C(CH3)2-CN or-N(R9)-COO-C1-C4alkyl, R3 and R4 independently of one another are hydrogen or methyl, R5 is fluorine or chlorine, R6 is either identical to the substituents given in the case of R5 or is hydrogen, R7 and R8 independently of one another are hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy or nitro, R9 is C1-C4alkyl and n is zero, one or two.

2. A compound according to claim 1, wherein R2 is a radical of the formula , or-C(CH3)2-CN and each R5 and R6 radical is either fluorine or chlorine.

3. A compound according to claim 1, wherein R2 is a radical of the formula or-C(CH3)-CN, R3 and R4 independently of one another are hydrogen or methyl, R5 and R6 are fluorine or chlorine, and R7 is hydrogen, halogen, C1-C4alkyl, methoxy or nitro.

4. A compound according to claim 1, wherein R2 is the radical , R3 and R4 are hydrogen, R5 and R6 are fluorine or chlorine, R7 is hydrogen, chlorine, bromine or C1-C4alkyl, and n is zero or two.

5. A compound according to claim 1, wherein R1 is C1-C3alkyl, R2 is , R3 and R4 are hydrogen, R7 is hydrogen, chlorine or methyl, and n is zero.

6. A compound according to claim 1, selected from the group comprising , , , and

7. A process for the preparation of the compounds of the formula I according to claim 1, wherein either a) a phenoxyphenol of the formula II

(II) where R5 and R6 are as defined under formula I is reacted, in the presence of a base, with an ethylcarbamic acid derivative of the formula III

(III) where R1, R2, R3 and R4 are as defined under formula I and L is a leaving group, and the resulting product of the formula Ia (Ia) where R1, R2, R3, R4, R5 and R6 are as defined under formula I, may be oxidized to give the compounds of the formula I where n is one or two; or b) an ethylcarbamic acid derivative of the formula IV

(IV) where R1, R3, R4, R5 and R6 are as defined under formula I, is reacted, in the presence of a base, with a sulfenyl halide of the formula V

Hal-S-R2 (V) where R2 is as defined under formula I and Hal is halogen, and the resulting product of the formula Ia may be oxidized to give the compounds of the formula I where n is one or two;
or c) an ethylcarbamic acid derivative of the formula IV is reacted, in the presence of a base, with a sulfinyl halide of the formula VI

Hal-SO-R2 (VI) where R2 is as defined under formula I and Hal is halogen, and the resulting product of the formula Ib (Ib) where R1, R2, R3, R4, R5 and R6 are as defined under formula I may be oxidized to give the compounds of the formula I where n is two; or d) an ethylcarbamic acid derivative of the formula IV is reacted, in the presence of a base, with a sulfonyl halide of the formula VII
Hal-SO2-R2 (VII) where R2 is as defined under formula I and Hal is halogen, to give a compound of the formula Ic (Ic) where R1, R2, R3, R4, R5 and R6 are as defined under formula I; or e) an ethylamine derivative of the formula VIII

(VIII) where R3, R4, R5 and R6 are as defined under formula I is acylated, in the presence of a base, with a haloformic acid derivative of the formula IX

Hal-COOR1 where R1 is as defined under formula I and Hal is halogen, and the resulting intermediate of the formula IV is sulfenylated with a sulfenic acid halide of the formula V in the presence of a base, and the resulting product of the formula Ia may be oxidized to give the compounds of the formula I where n is one or two; or f) an ethylamine derivative of the formula VIII is sulfenated with a sulfenic acid halide of the formula V in the presence of a base and the resulting internediate of the formula X

(X) where R2, R3, R4, R5 and R6 are as defined under formula I is acylated with a haloformic acid derivative of the formula IX in the presence of a base, and the resulting product of the formula Ia may be oxidized to give the compounds of the formula I where n is one or two;
or g) for the preparation of a compound of the formula Ic, an alkali metal salt of a compound of the formula Xa (Xa) is reacted with a compound of the formula IX, R1 to R6 being as defined under formula I
and Me? being an alkali metal cation.

8. A pesticidal composition, containing, as the active component, at least a compound of the formula I

(I) where R1 is C1-C4alkyl or C3-C4alkenyl, R2 is C1-C4alkyl or a radical of the formula , , -C(CH3)2-CN or -N(R9)-COO-C1-C4alkyl, R3 and R4 independently of one another are hydrogen or methyl, R5 is fluorine or chlorine, R6 is either identical to the substituents given in the case of R5 or is hydrogen, R7 and R8 independently of one another are hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy or nitro, R9 is C1-C4alkyl and n is zero, one or two.

9. A composition according to claim 8, which contains additionally at least a carrier.

10. Use of a compound of the formula I

(I) where R1 is C1-C4alkyl or C3-C4alkenyl, R2 is C1-C4alkyl or a radical of the formula , , -C(CH3)2-CN or -N(R9)-COO-C1-C4alkyl, R3 and R4 independently of one another are hydrogen or methyl, R5 is fluorine or chlorine, R6 is either identical to the substituents given in the case of R5 or is hydrogen, R7 and R8 independently of one another are hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy or nitro, R9 is C1-C4alkyl and n is zero, one or two, for controlling pests on plants and animals, in the protection of stored goods, and in hygiene.

11. Use according to claim 10 for controlling arthropods, in particular insects and arachnids.

12. Use according to claim 11 for controlling larvae and eggs of phytophagous harmful insects and harmful mites.

13. Use according to claim 11 for destroying eggs of insects and ectoparasites which damage plants.

14. Use according to claim 11 for inhibiting the development of larvae of insects and ectoparasites which damage plants.

FO 7.5 CW/gb*