Note: Descriptions are shown in the official language in which they were submitted.
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
R5
--~3 0--CH--CH--N (I)
R4 R3 S()n R2
R6
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
COOC2H5
~0 ~3 0--CH2-CH2-N/ ~3
Cl
~0~0--CHrCH2'N
~30~30--CH2--CH2-N/ _,~
F ~ ~ --CH2--CH2- N~
F
COOC2Hs
CH3
> ~ ~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)
R6
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
" ,
COOR1
L--CH CH--N (111)
R4 R3 S-R2
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~)
R4 R3 S-R2
R6
~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
R5
~ O ~ O--CH--CH--NH--COOR, (IV)
R6
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
- 10-
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
R5
~ o ~3 o CH~ CH--N/ (Ib)
R6 R4 R3 SO-R2
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
R5
~ o ~ O--CH--CH--N (Ic~
R6
where R1, R2, R3, R4, R5 and R6 are as defined under formula I; or when
e) an ethylamine derivative of the formula VIII
R5
O ~ O--CH--CH--NH2 (VIII)
R4 R3
R6
~ ~ .
. ;- ~ ~ .
:
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
R5
~ 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:
- 12-
Rs
O ~=,~ O ~- CH--CH--N - SO2-R2 (IX~
>=/ R4 R3 Me~3
R6 (Xa)
.
R5
~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
- . ~ :
~ . . .
:
- 13-
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.
R5
~,~ O ~ O--CHR4--C-O (XVI l)
R6
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,
~ ' :
~ '
- 16-
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
- 17-
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~,
- 18-
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.
~ . . .
- 19-
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 ~
- 20 -
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~
- 21 -
~-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
,
- 22-
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
,: : :: . ~ ~ :
- 23 -
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~
- 24 -
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
, .... : .:
` ~
: : .
:
. .. , . : ..
- 25 -
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~.
- 26 -
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.
-
:' : ' ~'', ~ ~
- 27 -
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:
,
- 28 -
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
.. - : ,
-. ,
: : : .: ; - .: . . :
- 29 -
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~
- 30-
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.
- 32 -
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~
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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
,
:
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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 %.
