Sulfenylated carbamic esters and their use in pesticides

Novel substituted 2-phenoxyphenoxyethylcarbamic esters of the formula I ##STR1## where R.sub.1 is C.sub.1 -C.sub.4 alkyl or C.sub.3 -C.sub.4 alkenyl, R.sub.2 is C.sub.1 -C.sub.4 alkyl or a radical of the formula ##STR2## --C(CH.sub.3).sub.2 --CN or --N(R.sub.9)--COO--C.sub.1 -C.sub.4 alkyl, R.sub.3 and R.sub.4 independently of one another are hydrogen or methyl, R.sub.5 is fluorine or chlorine, R.sub.6 is either identical to the substituents given in the case of R.sub.5 or is hydrogen, R.sub.7 and R.sub.8 independently of one another are hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or nitro, R.sub.9 is C.sub.1 -C.sub.4 alkyl and n is zero, one or two, their preparation, their use in pest control, and pesticides containing these carbamic esters as active substance, are described. The preferred field of application is the control of pests on animals and plants, in partcular of eggs and larvae of phytophagous harmful insects and harmful mites.

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 formula I 
##STR3## 
where R.sub.1 is C.sub.1 -C.sub.4 alkyl or C.sub.3 -C.sub.4 alkenyl, 
R.sub.2 is C.sub.1 -C.sub.4 alkyl or a radical of the formula 
##STR4## 
--C(CH.sub.3).sub.2 --CN or --N(R.sub.9)--COO--C.sub.1 -C.sub.4 alkyl, 
R.sub.3 and R.sub.4 independently of one another are hydrogen or methyl, 
R.sub.5 is fluorine or chlorine, R.sub.6 is either identical to the 
substituents given in the case of R.sub.5 or is hydrogen, R.sub.7 and 
R.sub.8 independently of one another are hydrogen, halogen, C.sub.1 
-C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or nitro, R.sub.9 is C.sub.1 
-C.sub.4 alkyl and n is zero, one or two. 
Halogen in the definition of R.sub.7 and R.sub.8 is to be understood as 
meaning fluorine, chlorine, bromine or iodine, but preferably chlorine. 
C.sub.1 -C.sub.4 Alkyl groups can be straight-chain or branched. Examples 
of such radicals which may be mentioned are methyl, ethyl, propyl, 
isopropyl or butyl and its isomers. The preferred alkyl group is ethyl. 
C.sub.1 -C.sub.4 Alkenyl groups have the double bond preferably in the 
2-position, as is the case in allyl, methallyl or 2-butenyl. The preferred 
alkenyl group is allyl. 
Within the scope of the present invention, C.sub.1 -C.sub.4 alkoxy radicals 
of the definition of R.sub.7 and R.sub.8 are methoxy, ethoxy, propoxy, 
isopropoxy or the four butoxy isomers. Methoxy is preferred. 
If the radical R.sub.6 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.sub.6 is the same halogen atom as R.sub.5. 
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 U.S. Pat. Nos. 4,080,470, 4,215,139, 
4,413,010, 4,555,405, 4,608,389 and 4,745,128 and the German 
Offenlegungsschriften DE-OS 3,320,534, 3,334,983 and 3,706,082. There is 
therefore still a demand for active substances of this substance class 
which have improved properties. 
It has now been found that the compounds of the formula I according to the 
invention are valuable active substances in pest control while the 
tolerance by homothermals, fish and plants is favourable. The use of the 
active substances according to the invention relates to arthropods in 
particular insects and arachnids which are encountered in crop 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 
and/or a lower hatching rate. The abovementioned pests include: 
from the order of the Lepidoptera, for example Acleris spp., Adoxophyes 
spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., 
Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., 
Busseola fusca, Cadra cautella, Carposina nipponensis, 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 lycopersicella Leucoptera 
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 Trogoderma spp.; 
from the order of the Orthoptera, for example Blatta spp., Blattella spp., 
Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and 
Schistocerca spp.; 
from the order of the Isoptera, for example Reticulitermes 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., Thrips 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, Erythroneura 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 erytreae and Unaspis citri; 
from 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, 
Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia 
spp., Culex spp., Culerebra spp., Dacus spp., Drosophila melanogaster, 
Fannia 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., Rhagoletis 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 spp., Boophilus spp., 
Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., 
Dermanyssus 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 example Lepisma saccharina. 
Particularly important in the case of the compounds according to the 
invention is the use in the control of ectoparasites which damage plants. 
The compounds of formula I are active against rice cicadas, for example 
from the families Delphacidae and Cicadellidae, such as Nilaparvata 
lugens, Laodelphax striatellus and Nephotettix cincticeps. The active 
substances of the formula I also have an excellent action against the 
so-called "whitefly", 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) R.sub.2 is a radical of the formula 
##STR5## 
or --C(CH.sub.3).sub.2 --CN and each R.sub.5 and R.sub.6 radical is either 
fluorine or chlorine, or 
b) R.sub.2 is a radical of the formula 
##STR6## 
or --C(CH.sub.3)--CN, R.sub.3 and R.sub.4 independently of one another are 
hydrogen or methyl, R.sub.5 and R.sub.6 are fluorine or chlorine, and 
R.sub.7 is hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, methoxy or nitro, or 
c) R.sub.2 is the radical 
##STR7## 
R.sub.3 and R.sub.4 are hydrogen, R.sub.5 and R.sub.6 are fluorine or 
chlorine, R.sub.7 is hydrogen, chlorine, bromine or C.sub.1 -C.sub.4 
alkyl, and n is zero or two, or 
d) R.sub.1 is C.sub.1 -C.sub.3 alkyl, R.sub.2 is 
##STR8## 
R.sub.3 and R.sub.4 are hydrogen, R.sub.7 is hydrogen, chlorine or methyl, 
and n is zero. 
In a preferred embodiment of present invention the group of preferred 
compounds of formula I consists of the compounds of the narrower formula 
Ia 
##STR9## 
where R.sub.1 is C.sub.1 -C.sub.4 alkyl or C.sub.3 -C.sub.4 alkenyl, 
R.sub.2 is C.sub.1 -C.sub.4 alkyl or a radical of the formula 
##STR10## 
--C(CH.sub.3).sub.2 --CN or --N(R.sub.9)--COO--C.sub.1 -C.sub.4 alkyl, 
R.sub.3 and R.sub.4 independently of one another are hydrogen or methyl, 
R.sub.5 is fluorine or chlorine, R.sub.6 is fluorine when R.sub.5 is 
fluorine or is hydrogen when R.sub.5 is chlorine, R.sub.7 and R.sub.8 
independently of one another are hydrogen, halogen, C.sub.1 -C.sub.4 
alkyl, C.sub.1 -C.sub.4 alkoxy or nitro, R.sub.9 is C.sub.1 -C.sub.4 alkyl 
and n is zero, one or two. 
In said narrower formula Ia the following subgroups are preferred, in which 
a) R.sub.2 is a radical of the formula 
##STR11## 
or --C(CH.sub.3).sub.2 --CN and R.sub.5 and R.sub.6 are fluorine, or 
b) R.sub.2 is a radical of the formula 
##STR12## 
or --C(CH.sub.3)--CN, R.sub.3 and R.sub.4 independently of one another are 
hydrogen or methyl, R.sub.5 and R.sub.6 are fluorine and R.sub.7 is 
hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, methoxy or nitro, or 
c) R.sub.2 is the radical 
##STR13## 
R.sub.3 and R.sub.4 are hydrogen, R.sub.5 and R.sub.6 are fluorine, 
R.sub.7 is hydrogen, chlorine, bromine or C.sub.1 -C.sub.4 alkyl, and n is 
zero or two, or 
d) R.sub.1 is C.sub.1 -C.sub.3 alkyl, R.sub.2 is 
##STR14## 
R.sub.3 and R.sub.4 are hydrogen, R.sub.7 is hydrogen, chlorine or methyl, 
and n is zero. 
The following individual compounds according to the present invention must 
be mentioned as being preferred: 
##STR15## 
The compounds of the formula I according to the invention can be prepared 
by methods known per se. For example, the compounds of the formula I can 
be obtained either when 
a) a phenoxyphenol of the formula II 
##STR16## 
where R.sub.5 and R.sub.6 are as defined under formula I is reacted, in 
the presence of a base, with an ethylcarbamic acid derivative of the 
formula III 
##STR17## 
where R.sub.1, R.sub.2, R.sub.3 and R.sub.4 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 tolylsulfonyloxy, and the 
resulting product of the formula Ia 
##STR18## 
where R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are as 
defined under formula I, may be oxidized to give the compounds of the 
formula I where n is one or two; or when 
b) an ethylcarbamic acid derivative of the formula IV 
##STR19## 
where R.sub.1, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are as defined under 
formula I, is reacted, in the presence of a base, with a sulfenyl halide 
of the formula V 
EQU Hal-S--R.sub.2 (V) 
where R.sub.2 is as defined under formula 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 of the formula VI 
EQU Hal-SO--R.sub.2 (VI) 
where R.sub.2 is as defined under formula I and Hal is halogen, preferably 
chlorine, and the resulting product of the formula Ib 
##STR20## 
where R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are as 
defined under formula I may be oxidized to give the compounds of the 
formula I where n is two; or when 
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 
EQU Hal-SO.sub.2 --R.sub.2 (VII) 
where R.sub.2 is as defined under formula I and Hal is halogen, preferably 
chlorine, to give a compound of the formula Ic 
##STR21## 
where R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are as 
defined under formula I; or when 
e) an ethylamine derivative of the formula VIII 
##STR22## 
where R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are as defined under formula I 
is acylated, in the presence of a base, with a haloformic acid derivative 
of the formula IX 
EQU Hal-COOR.sub.1 (IX) 
where R.sub.1 is as defined under formula I and Hal is halogen, preferably 
chlorine, 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 when 
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 intermediate of the formula X 
##STR23## 
where R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 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 when 
g) an alkali metal salt of the sulfonamide of the formula Xa is reacted 
with a haloformic acid derivative of the formula IX, R.sub.1 to R.sub.6 
being as defined under formula I and Me.sup..sym. being an alkali metal 
cation: 
##STR24## 
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 
tetrahydrofuran; N,N-dialkylated carboxamides, such as 
N,N-dimethylformamide, aliphatic, aromatic and halogenated hydrocarbons, 
in particular benzene, toluene, xylene, chloroform, methylene chloride, 
carbon tetrachloride and chlorobenzene; dimethyl sulfoxide, sulfolane, and 
also ketones, for example acetone, methyl ethyl ketone, methyl isopropyl 
ketone and methyl isobutyl ketone. 
The reaction temperatures in these processes are generally between 
-20.degree. C. and the boiling point of the reaction mixture. It is 
preferred not to exceed an upper temperature of +100.degree. C. Preferred 
temperature ranges are those between 0.degree. and +50.degree. C., but 
particularly those between 0.degree. and +40.degree. C. 
Suitable bases for process a) are alkali metal hydrides or alkaline earth 
metal hydrides, such as lithium hydride, sodium hydride or calcium 
hydride; alkali metal hydroxides, such as sodium hydroxide or potassium 
hydroxide; alkali metal 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 example 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 tertiary 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 periodate 
NaIO.sub.4, and also alkali metal chromates. While, in typical reactions, 
organic peracids are reacted in chlorinated hydrocarbons, such as 
methylene chloride, chloroform or ethylene chloride, the solvents suitable 
for inorganic oxidants contain water and/or are miscible with water, such 
as acetone, acetic acid or formic acid. It is preferred to prepare 
performic acid in situ, for example by adding H.sub.2 O.sub.2 to formic 
acid. The reaction temperatures of the oxidation mixtures are between 
-20.degree. C. and +60.degree. C. 
The intermediates of the formulae II, IV, V, VI, VII and IX are known or 
can be prepared by methods known per se. 
The intermediates of the formula III can alternatively be obtained in 
accordance with one of the following diagrams: 
##STR25## 
The intermediates of the formula VIII can be prepared from the 
corresponding carbonyl compounds by "reductive amination": 
##STR26## 
After the imine has been formed from XVII with ammonia, other reducing 
reagents can also be used in place of the reduction system H.sub.2 
/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 adapted to given 
circumstances by adding other insecticides and/or 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 form or, 
preferably, together with agrochemically acceptable auxiliaries 
conventionally used in the art of formulation, and they are therefore 
processed in a 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 formulations, i.e. the agents, preparations or compositions containing 
the active substance 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 C.sub.8 -C.sub.12, for example 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 natural minerals, such as calcite, talc, 
kaolin, montmorillonite or attapulgite. To improve 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 bentonite, 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 communicated 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 unsubstituted ammonium salts of higher fatty acids 
(C.sub.10 -C.sub.22), such as the sodium salts or potassium salts of oleic 
or stearic acid, or of natural mixtures 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 fatty 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 sulfate 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 acid/formaldehyde condensation product. Other suitable 
compounds are the corresponding phosphates, such as the salts of the 
phosphoric ester of a p-nonylphenol/(4-14)-ethylene oxide adduct. 
Suitable non-ionic surfactants are mainly polyglycol ether derivatives of 
aliphatic or cycloaliphatic alcohols, 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 1 to 10 carbon atoms in the alkyl 
chain and which contain 20 to 250 ethylene glycol ether groups and 10 to 
100 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 ammonium 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 form of halides, methylsulfates or ethylsulfates, for example 
stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium 
bromide. 
The surfactants customary in the art of formulation are described, inter 
alia, in the following publications: 
"1985 International McCutcheon's Emulsifiers & Detergents", Glen Rock NJ 
USA, 1985", 
H. Stache, "Tensid-Taschenbuch [Surfactant Guide]", 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 rule, 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 
between 0.1 and 500 ppm. The application rates per hectare are generally 
10 to 1,000 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 10% 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 1% 
Solid carrier: 
99.9 to 90%, 
preferably 99.9 to 99% 
Suspension 
concentrates: 
Active ingredient: 
5 to 75%, preferably 10 to 50% 
Water: 94 to 24%, preferably 88 to 30% 
Surface-active agent: 
1 to 40%, preferably 2 to 30% 
Wettable powders: 
Active ingredient: 
0.5 to 90%, 
preferably 1 to 80% 
Surface-active agent: 
0.5 to 20%, 
preferably 1 to 15% 
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% 
______________________________________ 
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. 
EXAMPLE H1 
Ethyl N-phenylthio-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate 
##STR27## 
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 dimethylformamide. 18.2 g of 
ethyl 2-chloroethylcarbamate are furthermore added dropwise, and the 
reaction mixture is heated for 16 hours at +95.degree. C., 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.degree.-56.degree. C., which solidifies in crystalline 
form; yield: 92% of theory. 
b) 5.7 g of freshly distilled phenylsulfenyl chloride in 10 ml of toluene 
are added dropwise at 0.degree. to +5.degree. C. 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 mixture is stirred for 4 more hours at 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, 20:1), which gives pure ethyl 
N-phenylthio-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate, 
n.sub.D.sup.20 : 1.5700. 
EXAMPLE H2 
Ethyl 
N-(4-chlorophenylthio)-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate 
##STR28## 
7.6 g of freshly distilled 4-chlorophenylsulfenyl chloride is added 
dropwise at 0.degree. to +5.degree. C. 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 mixture 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 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, 9:1), which gives pure ethyl 
N-(4-chlorophenylthio)-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate, 
n.sub.D.sup.20 1.5763. 
EXAMPLE H3 
Ethyl N-phenylthio-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate 
##STR29## 
a) 60 g of methanesulfonyl chloride are metered over approximately 30 
minutes at 0.degree. to +5.degree. C. to a solution of 66.5 g of ethyl 
2-hydroxyethylcarbamate, 43.5 g of pyridine and 1.9 g of 
4-dimethylaminopyridine in 150 ml of methylene chloride, with stirring, 
and the mixture is stirred for 2 more hours at +5.degree. C. 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 completely by distillation in vacuo, which gives ethyl 
2-methylsulfonyloxyethylcarbamate, n.sub.D.sup.20 1.4450. 
b) 21.1 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 phenylsulfenyl chloride in 15 ml of 
toluene are added dropwise in the course of 20 minutes at 0.degree. to 
+5.degree. C., with stirring. The mixture is stirred at this temperature 
for 4 more 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-phenylthio-2-methylsulfonyloxyethylcarbamate, n.sub.D.sup.20 : 
1.5390. 
c) A solution of the sodium salt of 4-(3,5-difluorophenoxy)phenol (prepared 
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 +25.degree. C. in the course of 5 hours to a 
solution of 6.5 g of ethyl N-phenylthio-2-methylsulfonyloxyethylcarbamate 
and 0.1 g of hydroquinone in 20 ml of anhydrons 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), 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, 
n.sub.D.sup.20 : 1.5700. 
EXAMPLE H4 
Ethyl N-phenylthio-2[4-(3,5-fluorophenoxy)phenoxy]ethylcarbamate 
##STR30## 
A solution of the potassium salt of 4-(4-fluorophenoxy)phenol (prepared 
from 4.3 g of 4-(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 +25.degree. C. in the course of 5 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, 
n.sub.D.sup.20 : 1.5700. 
EXAMPLE H5 
Ethyl N-phenylthio-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate 
##STR31## 
A solution of 4.3 g of 4-(3,5-difluorophenoxy)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 +25.degree. C. in the course of 5 hours to a 
solution of 6.4 g of ethyl N-phenylthio-2-methylsulfonyloxyethylcarbamate 
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 
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, 
n.sub.D.sup.20 1.5700. 
EXAMPLE H6 
Ethyl N-phenylsulfinyl-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate 
##STR32## 
A solution of 8.1 g of 55% 3-chloroperbenzoic acid in 50 ml of 
dichloromethane is added dropwise at 0.degree. to +5.degree. C. 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, with stirring. After the reaction mixture has been 
stirred for 2 hours at +20.degree. to +22.degree. C., 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 n.sub.D.sup.20 :1.5645. 
EXAMPLE H7 
Ethyl N-phenylsulfonyl-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate 
##STR33## 
A solution of 4.0 g of 55% 3-chloroperhenzoic acid in 30 ml of 
dichloromethane is added dropwise at about +5.degree. C. in the course of 
10 minutes to a solution of 4.8 g of ethyl 
N-phenylsulfinyl-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate in 30 ml 
of dichloromethane, with stirring. The reaction mixture is stirred 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 distilled 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)phenoxy]ethylcarbamate is 
isolated as a colourless resinous substance, n.sub.D.sup.20 : 1,5610. 
EXAMPLE H8 
Ethyl N-methylsulfonyl-2-[4-(3-chlorophenoxy)phenoxy]ethylcarbanate 
##STR34## 
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.degree.-46.degree. C.; prepared from 4-(3-chlorophenoxy)phenol 
and ethyl 2-chloroethylcarbamate in dimethylformamide analogously to 
Example H1a) in 30 ml of tetrahydrofuran is added dropwise at room 
temperature to this suspension with stirring, and the mixture is stirred 
for about 5 hours 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.degree.-5.degree. C. 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 and extracted repeatedly 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 silica gel (eluent: n-hexane/diethyl ether, 5:1), by 
which process ethyl 
N-methylsulfonyl-2-[4-(3-chlorophenoxy)phenoxy]ethylcarbamate is obtained 
as a colourless, viscous oil, n.sub.D.sup.21 : 1.5573. 
Analogously, 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, n.sub.D.sup.20 : 
1.5790. 
EXAMPLE H9 
Methyl N-phenylthio-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate 
##STR35## 
a) 21.3 g of potassium carbonate powder, 1.5 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 95.degree. C. The 
cooled reaction mixture 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 crude product is chromatographed on silica gel (eluent: 
n-hexane/diethyl ether, 5:1), by which process pure methyl 
2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate is obtained, 
n.sub.D.sup.21 : 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, n.sub.D.sup.21 : 1.5243 
and allyl 2-[4-(3-chlorophenoxy)phenoxy]ethylcarbamate, m.p. 
51.degree.-52.degree. C. 
b) Analogously to the procedure of Example H1b), the following active 
substances according 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, 
n.sub.D.sup.20 : 1.5750; 
isopropyl N-phenylthio-2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate, 
n.sub.D.sup.20 : 1.5638 and 
allyl N-phenylthio-2-[4-(3-chlorophenoxy)phenoxy]ethylcarbamate, 
n.sub.D.sup.20 : 1.6079. 
EXAMPLE H10 
Ethyl N-phenylthio-2-[4-(3-chlorophenoxy)phenoxy]-1-methylethylcarbamate 
##STR36## 
a) 32.5 g of anhydrous potassium carbonate powder and 2 g of finely 
pulverized 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 to 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 40.degree. C. The resulting oily 
4-(3-chlorophenoxy)phenoxypropanone, n.sub.D.sup.20 : 1.5788, analytical 
grade, is directly reacted further. 
b) In a stirred autoclave, 51 g of 4-(3-chlorophenoxy)phenoxypropanone are 
dissolved in 510 ml of methanol. 31 g of liquid ammonia are forced in, and 
the mixture is subjected to reductive amination at 40.degree.-45.degree. 
C. for 3 hours in the presence of 10 g of Raney nickel and 50 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, 5:1), by which process pure 
1-[4-(3-chlorophenoxy)phenoxy]-2-aminopropane is obtained, n.sub.D.sup.20 
: 1.5743. 
c) 13.5 g of ethyl chloroformate are added dropwise at 20.degree. C. 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 external cooling, and the mixture is 
stirred for a further 15 hours at 20.degree. C. 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 sulfate, and the solvents 
are distilled off in vacuo. The crude product is chromatographed on silica 
gel (eluent: n-hexane/diethyl ether, 5:1), by which process pure ethyl 
2-[4-(3-chlorophenoxy)phenoxy]-1-methylethylcarbamate is obtained as a 
pale yellow oil, n.sub.D.sup.21 : 1.5530. 
d) A solution of 4 g of phenylsulfenyl chloride in 10 ml of toluene is 
added dropwise at 0.degree.-5.degree. C. in the course of 20 minutes to a 
solution of 9 g of ethyl 
2-[4-(3-chlorophenoxy)phenoxy]-1-methylethylcarbamate 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 45.degree. C., 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)phenoxy]-1-methylethylcarbamate is 
obtained as a colourless oil, n.sub.D.sup.20 : 1.5810. 
The following active substances of the formula I can be obtained 
analogously: 
TABLE 1 
__________________________________________________________________________ 
##STR37## 
Comp No. 
R.sub.1 R.sub.2 n R.sub.3 
R.sub.4 
R.sub.5 
R.sub.6 
Physical data 
__________________________________________________________________________ 
1.01 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
0 H H F F n.sub.D.sup.20 : 1.5700 
1.02 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
1 H H F F n.sub.D.sup.20 : 1.5645 
1.03 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
2 H H F F n.sub.D.sup.20 : 1.5610 
1.04 C.sub.2 H.sub.5 
4-ClC.sub.6 H.sub.4 
0 H H F F n.sub.D.sup.20 : 1.5763 
1.05 C.sub.2 H.sub.5 
4-CH.sub.3C.sub.6 H.sub.4 
0 H H F F n.sub.D.sup.20 : 1.5705 
1.06 C.sub.2 H.sub.5 
3-CH.sub.3C.sub.6 H.sub.4 
0 H H F F 
1.07 C.sub.2 H.sub.5 
2-CH.sub.3C.sub.6 H.sub.4 
0 H H F F 
1.08 C.sub.2 H.sub.5 
3-ClC.sub.6 H.sub.4 
0 H H F F 
1.09 C.sub.2 H.sub.5 
3-Cl-4-ClC.sub.6 H.sub.4 
0 H H F F 
1.10 C.sub.2 H.sub.5 
4-NO.sub.2C.sub.6 H.sub.4 
0 H H F F 
1.11 C.sub.2 H.sub.5 
C.sub.6 H.sub.5CH.sub.2 
0 H H F F 
1.12 CH.sub.3 C.sub.6 H.sub.5 
0 H H F F n.sub.D.sup.20 : 1.5750 
1.13 C.sub.4 H.sub.9 -n 
C.sub.6 H.sub.5 
0 H H F F 
1.14 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
0 CH.sub.3 
H Cl 
H n.sub.D.sup.20 : 1.5810 
1.15 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
1 CH.sub.3 
H F F 
1.16 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
1 H H F F 
1.17 C.sub.2 H.sub.5 
4-CH.sub.3C.sub.6 H.sub.4 
1 H H F F 
1.18 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
0 H H F H 
1.19 C.sub.2 H.sub.5 
4-ClC.sub.6 H.sub.4 
0 H H F H 
1.20 C.sub.2 H.sub.5 
C.sub.6 H.sub.5CH.sub.2 
0 H H F H 
1.21 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
1 H H F H 
1.22 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
0 H H Cl 
H n.sub.D.sup.21 : 1.5851 
1.23 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
1 H H Cl 
H 
1.24 C.sub.2 H.sub.5 
4-ClC.sub.6 H.sub.4 
0 H H Cl 
H n.sub.D.sup.20 : 1.5879 
1.25 C.sub.2 H.sub.5 
4-CH.sub.3C.sub.6 H.sub.4 
0 H H Cl 
H n.sub.D.sup.20 : 1.5934 
1.26 C.sub.2 H.sub.5 
4-CH.sub.3C.sub.6 H.sub.4 
0 H H Cl 
Cl 
1.27 C.sub.2 H.sub.5 
4-ClC.sub.6 H.sub.4 
0 H H Cl 
Cl 
1.28 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
0 H H Cl 
Cl 
1.29 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
1 H H Cl 
Cl 
1.30 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
0 (CH.sub.2 ).sub.4 
Cl 
Cl 
1.31 C.sub.2 H.sub.5 
2-CH.sub.3 -4-CH.sub.3C.sub.6 H.sub.3 
0 H H F F n.sub.D.sup.20 : 1.5713 
1.32 C.sub.2 H.sub.5 
CH.sub.3 2 H H Cl 
H n.sub.D.sup.21 : 1.5573 
1.33 C.sub.3 H.sub.7 -i 
C.sub.6 H.sub.5 
0 H H F F n.sub.D.sup.20 : 1.5638 
1.34 C.sub.2 H.sub.5 
4-ClC.sub.6 H.sub.4 
2 H H F F n.sub.D.sup.22 : 1.5641 
1.35 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
2 H H Cl 
H n.sub.D.sup.20 : 1.5790 
1.36 CH.sub.2 CHCH.sub.2 
C.sub.6 H.sub.5 
0 H H Cl 
H n.sub.D.sup.20 : 1.6079 
1.37 C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
0 CH.sub.3 
H F F 
__________________________________________________________________________ 
FORMULATION EXAMPLES OF LIQUID ACTIVE SUBSTANCES OF THE FORMULA I 
(%=PERCENT BY WEIGHT) 
______________________________________ 
F1. Emulsion concentrates 
a) b) c) 
______________________________________ 
Active substance No. 1.01 
25% 40% 50% 
Ca dodecylbenzenesulfonate 
5% 8% 6% 
Castor oil polyethylene glycol 
5% -- -- 
ether (36 mol of EO) 
Tributylphenol polyethylene 
-- 12% 4% 
glycol ether (30 mol of EO) 
Cyclohexanone -- 15% 20% 
Xylene mixture 65% 25% 20% 
______________________________________ 
Emulsions of any desired concentration can be prepared from such 
concentrates by diluting them with water. 
______________________________________ 
F2. Solutions a) b) c) d) 
______________________________________ 
Active substance No. 1.02 
80% 10% 5% 95% 
Ethylene glycol monomethyl 
20% -- -- -- 
ether 
Polyethylene glycol MW 400 
-- 70% -- -- 
N-Methyl-2-pyrrolidone 
-- 20% -- -- 
Epoxidized coconut oil 
-- -- 1% 5% 
Petroleum ether (boiling range 
-- -- 94% -- 
160-190.degree. C.) 
______________________________________ 
The solutions are suitable for use in the form of minute droplets. 
______________________________________ 
F3. Granules a) b) 
______________________________________ 
Active substance No. 1.02 
5% 10% 
Kaolin 94% -- 
Highly-disperse silica 
1% -- 
Attapulgite -- 90% 
______________________________________ 
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 
1% 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 WEIGHT) 
______________________________________ 
F5. Wettable powder 
a) b) c) 
______________________________________ 
Active substance 1.03 
25% 50% 75% 
Na ligninsulfonate 
5% 5% -- 
Na laurylsulfate 3% -- 5% 
Na diisobutylnaphthalene- 
-- 6% 10% 
sulfonate 
Octylphenol polyethylene glycol 
-- 2% -- 
ether (7-8 mol of EO) 
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 substance No. 1.03 
10% 
Octylphenol polyethylene glycol ether 
3% 
(4-5 mol of EO) 
Ca dodecylbenzenesulfonate 
3% 
Castor oil polyglycol ether 
4% 
(36 mol of EO) 
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% 8% 
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 granules 
______________________________________ 
Active substance No. 1.03 
10% 
Na ligninsulfonate 2% 
Carboxymethylcellulose 
1% 
Kaolin 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. Coated granules 
______________________________________ 
Active substance No. 1.03 
3% 
Polyethylene glycol (MW 200) 
3% 
Kaolin 94% 
______________________________________ 
In a mixer, the finely ground active substance is applied uniformly 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 
6% 
ether (15 mol of EO) 
Na ligninsulfonate 10% 
Carboxymethylcellulose 1% 
37% aqueous formaldehyde solution 
0.2% 
Silicon oil in the form of a 75% aqueous 
0.8% 
emulsion 
Water 32% 
______________________________________ 
The finely ground active substance is intimately 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 B1 
Action against 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 
terms 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 B2 
Action against Aedes aegypti 
50-100 Aedes aegypti larvae 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 this 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 Cydia 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 them 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%. 
EXAMPLE B4 
Ovicidal action on Adoxophyes reticulana 
Adoxophyes reticulana 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 them with 
untreated controls (% hatch reduction). 
In this test, compounds according to Table 1 have a good action against 
Adoxophyes reticulana. In particular the compounds 1.01, 1.05 and 1.12 
have an action of more than 80%. 
EXAMPLE B5 
Ovicidal action against 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 1 have a good action against Dermanyssus gallinae. 
In particular, 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 weeks, the potatoes are immersed in an aqueous 
emulsion spray liquor containing the active substance to be tested in a 
concentration of 400 ppm. After the treated 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 Aonidiella 
aurantii. In particular the compounds 1.01, 1.04 and 1.31 have an action 
of more than 80%. 
EXAMPLE B7 
Action against Nilaparvata 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. 
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 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 against 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 1 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 against Bemisia tabaci 
Dwarf beans are placed in gauze cages and infested with Bemisia tabaci 
adults (whitefly). After eggs have been laid, all adults are removed, and, 
10 days later, the plants together with the nymphs living on them are 
treated with a spray liquor of an aqueous emulsion of the active 
substances to be tested (concentration 400 ppm). 14 days after the active 
substance has been applied, the population is evaluated for hatch % 
compared with untreated controls. 
In this test, compounds according to Table 1 have a good action against 
Bemisia tabaci. In particular the compounds 1.01, 1.04, 1.22, 1.24 and 
1.25 have an action of more than 80%.