Note: Descriptions are shown in the official language in which they were submitted.
~2542~Z7
This application is a division of Canadian Application
Serial No. 306,758, filed July 4, 1978.
T}~e present invention relates to certain new su~-
stituted phenoxyben~.yloxyc~rbonyl derivatives, to a pro-
ces~ for theiI~ preparation, and to their use as insecticides
an~ acaricides.
It is already known that certain phenoxybenzyl acetates
or carboxylates, for example 3'-phenoxybenzyl ~-isopropyl-
(3,4-dimethoxy-phenyl)-acetate, ~-chloro-~iperonyl 2,2-
dimethyl-3-(2,2-dimethyl-vinyl)-cyclopropanecarboxylate and
3'-phenoxybenzyl 2l2-dimethyl-3-indenyl-cyclopropane-
carboxylate, possess insecticidal and acaricidal properties
~see Cerman Offenlegungsschriften (German Published
Specifications) 2,335,347 and 2,605,828 and U.S. Patent
2,857,3Q9)-
Ihe invention of the above parent application originally
provided, as new compounds, the substituted phenoxybenzyloxy-
carbonyl derivatives of the general formula
~ ~ CH-0-C ~ CH=C (I)
in which
R, Rl and R2, which need not be identical, each re-
present hydroEen or halo~en,
R3 represents phenyl or phenylthio, and in either
case the phenyl ring may optionally carry one or
more substituents selected independently from alkyl
%5 ~roups and halogen atoms,
Y represents hydrogen or nitrile,
n represents l, 2, 3, 4 or 5 and
m represents l, 2, 3 or 4.
~Z542:~7
These new compounds sre distinguished by powerful
insecticidal and acaricidal properties.
Preferably,R and Rl each represent hydrogen or
fluorine, n2 represents hydrogen, chlorine or bromine,
R3 represents phenyl, phenylthio, halogenophenyl (pre-
ferred halogens bein~ chlorine or rluorine) or alkylphenyl,
the alkyl radical Or which has 1 to 6 (especially 1 to 4)
carbon atoms and Y represents hydrogen or
nitrile.
The general formula (I) here encompasses the various
possible stereoisomers, the optical isomers and mixtures Or
these components.
The parent invention also oriF~inally provided a process for
the preparation Or a substituted phenoxybenzyloxycarbonyl
derivative (I~,in which
(a) a phenoxybenzyl alcohol Or the Eeneral formula
~ ~ CH (II),
in which
R, Rl, Y, n and m have the above-mentioned meanings,
2C is reacted with a cyclopropanecarboxylic acid derivative Or
the general ~ormula
R ~ ~ CH=c\
R (III),
H3C ~CH
-- ~254227
in which
R2 and R3 have the above-mentioned meanings and
R4 represents halogen, pre:~erably chlorine, or Cl_
alkoxy, preferably methoxy or ethoxy,
ir appropriate in the presence of an acid acceptor and, i~
appropriate, in the presence of a diluent, or
(b) a phenoxybenzyl halide of the general rormula
CH-Hal (IV),
Rn 1m
in which
R, Rl, Y, n and m have the above-mentioned meanings
and
Hal represents halogen, preferably chlorine or
bromine,
is reacted, if appropriate in the presence of a diluent,
15 with acyclopropanecarboxylic acid derivative of the formula
H0-OC ~ CH=C/ 3 (V),
H3C CH3
in which
R2 and R3 have the above-mentioned meanings,
the latter being en.ployed either in the form of an alkali
metal salt, alkaline earth metal salt or ammonium salt or
as such in the presence o~ an acid acceptor.
Surprisingly, the substituted phenoxybenzyloxy-
~2542267
carbonyl derivatives according to the parent invention exhibit a
better insecticidal and acaricidal action than the corres-
ponding previously known products of analogous structure
and of the same type of action. The products according to
the parent invention thus represent a ~enuine enrichment
of the art.
If, for example, 3-(4-fluorophenoxy)-benzyl alcohol
and 2,2-dimethyl-3-(2-phenylvinyl)-cyclopropanecarboxylic
acid chloride are used as starting materials in process
variant (a) and the sodium salt of 2,2-dimethyl-3-(2-
phenylthiovinyl)-cyclopropanecarboxylic acid and 3-phenoxy-
~-cyano-benzyl bromide are used as starting materials in
process variant (b), the course of the reactions can be
represented by the following equations:
+ acid
a) ~ ~_~ acceptor
F ~ ~ CH2-OH ~ Cl-OC ~ H~CH ~ ~_
O H3 CH3
~ ~ CH2-O-C ~ CH~CH
H3C CH3
(b) CN
CH-~r + MaO-C ~ CH=CH-S ~ - NaBr
H3C CH3
CN
CH-O-C ~ H=CH-S
H3C CH3
~254~Z~
The phenoxybenzyl alcohols (II) to be used as starting
compounds are known in the majority of cases; they can all
be prepared in accordance with generally customary processe~
described in the literature (see German Offenlegungsschrift
(German Published Specification) 2,547,534).
The following are specific examples: 3-phenoxy-benzyl
alcohol, 3-(4-fluorophenoxy)-benzyl alcohol, 3-(3-fluoro-
phenoxy)-benzyl alcohol, 3-(2-fluorophenoxy)-benzyl
alcohol, 3-phenoxy-4-f`luoro-benzyl alcohol, 3-(4-fluoro-
phenoxy)-4-fluoro-ben7yl alcohol, 3-(3-fluorophenoxy)-4-
fluoro-benzyl alcohol, 3-(2-fluorophenoxy)-4-fluoro-benzyl
alcohol, 3-phenoxy-~-cyano-benzyl alcohol, 3-(4-fluoro-
phenoxy)-~-cyano-benzyl alcohol, 3-(3-fluorophenoxy)-~-
cyano-benzyl alcohol, 3-(2-rluorophenoxy)-a-cyanobenzyl
alcohol, 3-phenoxy-4-~luoro--cyano-benzyl alcohol, 3-(4-
fluorophenoxy)-4-fluoro-~-cyano-benzyl alcohol, 3-(3-fluoro-
phenoxy)-4-fluoro-a-cyano -benzyl alcohol, 3-(2-(fluoro-
phenoxy)-4-fluoro-~-cyano-benzyl alcohol, 3-phenoxy-6-
fluoro-~-cyano-benzylalcohol, 3-(4-fluorophenoxy)-6-fluoro
~-cyano-benzyl alcohol, 3-(3-fluorophenoxy)-6-fluoro-~-
cyano-benzyl alcohol and 3-(2-~luorophenoxy)-6-fluoro-~-
cyano-benzyl alcohol.
The cyclopropanecarboxylic acid derivatives (V) also
to be used as starting compounds can be prepared from the
cyclopropane-carboxylic acid ethyl esters, some of which
are known (see Tetrahedron Letters 1976, 48, pages 4,359-
4,362), by acid or alkaline saponification. The free acids
are converted in accordance with known processes into the
corresponding salts or acid halides (III) and (V). The
ethyl esters, some Or which are known, can in turn be prepared
- ~ 254Z27
in accordance with processes known from the literature,
for exa~.ple rrom 2,2-dimethyl-3-formylcyclopropanecarboxylic acid
ethyl ester and O,O-diethylmethanephosphonic acid diester
derivatives in accordance with the following equation:
N C~
~ ~
O
O =P~ O =~
N N
-
o
N
-~:ZS42~
The followin~ may be mentioned as specific examples
of the cyclopropanecarboxylic acid derivatives (I~)and
(V): 3-[2-phenyl-vinyl]-, 3-[2-(2-chlorophenyl)-vinyl]-,
3-[2-(4-chlorophenyl)-vinyl]-, 3-~2-(3,4-dichlorophenyl)-
vinyl]-, 3-[2-(4-fluorophenyl)-vinyl]-, 3-[2-pentachloro-
phenyl-vinyl]-, 3-~2-pentafluorophenyl-vinyl]-, 3-[2-
phenylthio-vinyl]-, 3-[2-(2-chlorophenylthio)-vinyl]-,
3-[2-(4-chlorophenylthio)-vinyl]-, 3-[2-(3,4-dichlorophenyl-
thio)-vinyl]-, 3-[2-(4-fluorophbnylthio)-vinyl]-, 3-[2-
pentachlorophenylthio-vinyl]-, 3-t2-pentaf`luorophenylthio-
vinyl]- and 3-[2-(4-tert.-butylphenyl)-vinyl]-2,2-dimethyl-
cyclopropanecarboxylic acid and -2,2-dimethylcyclopro-
panecarboxylic acid chloride, as well as 3-[2-phenyl-2-
chlorovinyl]-,3-[2-(2-chlorophenyl)-2-chloro-vinyl]-,
15 3-[2-(4-chlorophenyl)-2-chloro-vinyl]-, 3-[2-(3,4-dichloro-
phenyl)-2-chlorovinyl]-, 3-[2-(4-fluorophenyl)-2-chloro-
vinyl]-, 3-[2-pentachlorophenyl)-2-chloro-vinyl]-, 3-(2-
pentafluorophenyl-2-chlorovinyl)-, 3-[2-phenylthio-2-chloro-
vinyl]-, 3-[2-(2-chlorophenylthio)-2-chloro-vinyl]-,
20 3-[2-(4-chlorophenylthio)-2-chlorovinyl]-, 3-[2-(3,4-
dichlorophenylthio)-2-chloro-vinyl]-, 3-[2-(4-fluorophenyl-
thio)-2-chloro-vinyl]-, 3-[2-pentachlorophenylthio-2-chloro-
vinyl]-, 3-[2-pentaf`luorophenylthio-2-chloro-vinyl]- and
3-[2-(4-tert.-butylphenyl)-2-chlo~-vinyl]-2,2-dimethyl-
cyclopropanecarboxylic acid and -2,2-dimethylcyclopropane-
carboxylic acid chloride, and also 3-[2-phenyl-2-bromo-
vinyl~-, 3-[2-(2-chlorophenyl)-2-bromo-vinyl]-, 3-[2-(4-
chlorophenyl)-2-bromovinyl]-, 3-[2-(3,4-dichlorophenyl)-
2-bromo-vinyl]-, 3-[2-(4-fluorophenyl)-2-bromo-vinyl]-,
3-[2-pentachlorophenyl-2-bromovinyl]-, 3-(2-pentafluoro-
phenyl-2-bromo vinyl~-, 3-[2-phenylthio-2-bromo-vinyl]-,
~2542;2~
3-[2-(2-chlorophenylthio)-2-bromo-vinyl]-, 3-[2 (4-chloro-
phenylthio)-2-bromo-vinyl]^, 3-[2-(3,4-dichlorophenylthio)-
2-bromo-vinyl]-, 3-[2-(4-fluorophenylthio)-2-bromovinyl]-,
3-[2-pentachlorophenylthio-2-bromo-vinyl]-, 3-[2-penta-
fluorophenylthio-2-bromo-vinyl]- and 3-~2-(4-tert.-butyl-
phenyl)-2-bromo-vinyl]-2,2-dimethylcyclopropanecarboxylic
acid and -2,2-dimethylcyclopropanecarboxylic acid chloride.
In addition, the phenoxybenzyl halides (IV), which can
also be prepared in accordance with processes known from the
literature, are used as starting compounds. The following
may be mentioned as specific examples of these: 3-phenoxy-
benzyl chloride and -benzyl bromide, 3-(4-fluorophenoxy)-
benzyl chloride and -benzyl bromide3 3-(3-fluorophenoxy)-
benzyl chloride and -benzyl bromide, 3-(2-fluorophenoxy)-
benzyl chloride and -benzyl bromide, 3-phenoxy-4-fluoro-
benzyl chloride and -benzyl bromide, 3-(4-fluorophenoxy)-
4-fluoro-benzyl chloride and -benzyl bromide, 3-(3-fluoro-
phenoxy)-4-fluoro-benzyl chloride and -benzyl bromide,
3-(2-fluorophenoxy)-4-fluoro-benzyl chloride and -benzyl
bromide, 3-phenoxy-~-cyano-benzyl chloride and -benzyl
bromide, 3-(4-fluorophenoxy)-~-cyano-benzyl chloride and
-benzyl bromide, 3-(3-fluorophenoxy)-~-cyano-benzyl chloride
and -benzyl bromide, 3-(2-fluorophenoxy)--cyano-benzyl
chloride and -benzyl bromide, 3-phenoxy-4-fluoro-Q-cyano-
benzyl chlorlde and -benzyl bromide, 3-(4-fluorophenoxy)-
4-fluoro-~-cyano-benzyl chloride and -benzyl bromide,
3-(3-fluorophenoxy)-4-rluoro-~-cyano-benzyl chloride and
-benzyl brom:ide, 3-(2-fluorophenoxy)-4-fluoro-~-cyano-
benzyl chlor:ide and -benzyl bromide, 3-phenoxy-6-fluoro-~-
cyano-benzyl chloride and -benzyl bromide, 3-(4-fluoro-
125~227
phenoxy)-~-fluoro--cyano-benzyl chloride and -benzyl
bromide, 3 (3-fluorophenoxy)-6-fluoro-~-cyano-benzyl
chloride and -benzyl bromide and 3-(2-fluorophenoxy)-6-
fluoro--cyano-benzyl chloride and -benzyl bromide.
The present invention is conce~ned with compounds of the general
formula (I) wherein R and R can each separately be hydrogen or halogen,
but both cannot be hydrogen, as well as with methods for the~r preparation.
The parent application is now directe~ to those compounds of the general
formula (I) wherein R and R are each hydrogen only.
All customary acid-binding agents can be used as acid
acceptors. Alkali metal carbonates and alkali metal
alcoholates, such as sodium carbonate, potassium carbonate,
sodium methylate, sodium ethylate, potassium methylate and
potassium ethylate have proved particularly suitable, as
have aliphatic, aromatic or heterocyclic am.ines, for
example trievhylamine, trimethylamine, dimethylaniline,
dimethylbenzylamine and pyridine.
The reaction temperature can be varied within a sub-
stantial range. In general, the reaction is carried out
at between 0 and 150C, preferably at from 10 to 40C in
process variant (a) and at from 100 to 130C in process
variant (b).
The reaction is in general allowed to take place under
normal pressure.
Process variants (a) and (b) for the preparation of the
compounds according to the invention are preferably carried
out in the presence Or a suitable diluent. Virtually all
inert organic solvents can be used ror this purpose,
especially aliphatic and aromatic, optionally chlorinated,
hydrocarbons, such as benzene, toluene, xylene, benzine,
methylene chloride, chloroform~ carbon tetrachloride and
chlorobenzene; ethers, for example diethyl ether, dibutyl
-- 10 --
~25~LZ~'7
ether and dioxan; ketones, Por example acetone, methyl
ethyl ketone, methyl isopropyl ketone and methyl isobutyl
ketone; nitriles, such as acetonitrile and propionitrile;
and formamides, for example dimethylformamide.
To carry out process variant (a), the starting materials
are preferably employed in equin;olar amounts. An excess
of one or other reactant produces no signiPicant advantages.
In most cases, the reactants are brought together in one Or
the stated solvents and are stirred in the presence of an
acid acceptor, in most cases at an elevated temperat~re,
for one or more hours. The reaction mixture is then
worked up by pouring it intc water, separating off the organic
phase and then workin~ up the latter in the usual manner
by washing, drying and distilling off the solvent.
In the case of the transesterification according to
process variant (a), the procedure followed in the usual
manner is to take the methyl ester or ethyl ester of the
cyclopropanecarboxylic acid, if appropriate in a suitable
solvent, together with 10-30% excess oP the alcohol of the
formula (II), and heat the mixture with addition of alkali
metal methylate or alkali n-.etal ethylate. The lower-
boiling alcohol produced is at the same time distilled
oPf continuously.
In carrying out process variant (b), the cyclopropane-
carboxylic acid derivative is preferably employed in the
~orm of an alkali metal salt. This salt, in one of the
stated solvents, is heated with the benzyl halide deriva-
tive to 80-140C. An excess Or one or other reactant
produces no aclvantages. APter completion of the reaction,
the solvent is distilled orf, the residue is taken up in
nethylene chloride and the organic phase is worked up as
described above.
~2~;4~
The new compounds are obtained in the form of oils~
which in most cases cannot be distilled without decom-
position but are freed rrom the last volatile constituentsby so-called "incipient distillation", that is to say by
prolonged heating under reduced pressure to moderately
elevated temperatures, and are purified in this manner.
They are characterised by the refractive index or the
boiling point.
The substituted phenoxybenzyloxycarbonyl derivatives
according to the invention are not only active against
plant pests, pests harmful to health and pests of stored
products, but also, i~ the veterinary medicine field,
against animal parasites ~ectoparasites), such as para-
sitic fly larvae and ticks.
15The active compounds are well tolerated by plants,
have a favourable level of toxicity to warm-blooded
animals, and can be used for combating arthropod pests,
especially insects and acarids, which are encountered in
agriculture, in forestry, in the protection of stored
products and of materials, and in the hygiene field. They
are active against normally sensitive and resistant species
and against all or some stages of development. The above-
mentioned pests include:
from the class of the Isopoda, for example Oniscus
5 asellus, Armadillidium vul~are and Porcellio scaber;
from the class of the Diplopoda, for example
Blaniulus guttulatus;
from the class of the Chilopoda, for example Geophilus
carpophaæus and Scutigera spec.;
30from the class of the Symphyla, for example Scuti-
gerella immacula,ta;
from the order o~ the Thysanura, for example Lepisma
- 12 -
12~i422~
saccharina;
from the order Or the Co'llembola, for example
Onychiurus armatus;
from the order of the Orthoptera, ~or example
Blatta orientalis, PerIpl'a'n'eta americana, Le'ucoph'~ea
maderae, Blattella germanica, Acheta domesticus, ~
talpa spp.~ Locusta mi~'rat'oria migratorioides, Me'l'an'oplus
differentialis and Schi'stocerca gre~aria;
from the order of the Dermaptera, for example
10 Forficula auriculaFia;
. from the order of the Isoptera, for example
Reticulitermes spp.;
from the order of the Anoplura, for example
Phylloxera vastatrix, Pemphigus spp., Pediculus humanus
corporis, Haematopinus spp. and Lino~nathus spp.;
_ . _
from the order Or the Mallophaga, for example
Trichodectes spp. and Damalinea spp.;
rrom the order of the Thysanoptera, for example
Hercinothrips femoralis and Thrips tabaci;
20from the order of the Heteroptera, ~or example
Eury~aster spp., Dysdercus intermedius, Piesma quadrata,
Cimex lectularius, Rhodnius prolixus and Triatoma spp.;
from the order of the Homoptera, for example
Aleurodes brassicae, Bemisia tabaci, Trialeurodes
vaporariorum, Aphis gossypii, Brevicoryne brassicae,
Cryptomyzus ribis, Doralis ~abae, Doralis ~ , Eriosoma
lani~erum, Hyalo~terus arundinis, Macrosiphum avenae,
Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca
spp., Euscelis bilobatus, Nephotettix cincticeps,
Lecanium corni, Saissetia oleae, Laodelphax striatellus,
.
Nilaparvata lugens, Aonidi'e'lla au'rantii, 'Aspidio't'us
hederae, Pseudococcus spp. and PYY11a ~PP .;
- 13 -
~25422~
~ rom the order Or the Lepidoptera~ for example
Pectinophora gossypiella~ Bupalus ~ , Cheimatobia
brumata, Lithocolletis blancardella, Xyponomeuta padella,
Plutella maculipennis, Malacosom neustria, Euproctis
5 chrysorrhoea, Lymantr:;a spp., Bucculatrix thurberiella,
Phyllocnistis citrella, A~rotis spp., Euxoa spp., Feltia
spp., Earias insulana~ Heliothis spp., Laphy~ma exigua,
Mamestra brassicae, Ptmolis ~lammea, Prodenia litura,
Spodoptera spp., Trichoplusia n:L, Carpocapsa pomonella,
Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia
kuehniella, Galleria mellonella, Cacoecia podana, Capua
reticulana, Choristoneura fumi~erana, ~ ambiguella,
Homona magnanima and Tortrix viridana;
from the order o~ the Coleoptera, for example
Anobium punctatum, Rhizopertha dominica, Bruchidius
obtectus, Acanthoscelides obtectus, Hylotrupes bajulus,
Agelastica alni, Leptinotarsa decemlineata, Phaedon
cochleariae, Diabrotica spp., Psylliodes chrysocephala,
Epilachna varivestis, Atomaria spp., Oryzaephilus
surinamensis, Anthonomus spp., Sitophilus spp.,
Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorr-
hynchus assimilis, Hypera postica, Dermestes spp., Trogo-
derma spp., Anthrenus spp., Attagenus spp., Lyctus spp.,
Meligethes aeneus, Ptinus spp., Niptus hololeucus,
Gibbium psylloides, Tribolium spp., Tenebrio molitor,
Agriotes spp., Conoderus spp., Melolontha melolontha,
Amphimallon solstitiali_ and Costelytra zealandica;
from the order Or the Hymenoptera, ~or example
Diprion spp.~ Hoploc~ampa spp., Lasius spp., Mon~omo~ium
0 pharaonis anct Ve's'pa spp.;
from the order Or the Diptera, ror example- Aedes spp.,
Anopheles spp., Culex spp., Drosophila me'l'an-ogaster, Musca
- 14 -
~254227
spp., Fannia spp., Calliphora erythroce~hala, Lucilia spp.,
Chrysomy~_ spp., Cuterebra spp., Gastrophilus spp.,
_ _
Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma
spp., Tabanus spp., Tannia spp., Bibio hortulanus 3 Oscinella
frit~ Phorbia spp., Pegom~ia hyoscyami, Ceratitis capitata,
Dacus oleae and Tipula paludosa;
from the order of the Siphonaptera, ror example
Xenopsylla cheopis and Ceratophyllus spp.;
from the class Or the Arachnida, for example Scorpio
0 maurus and Latrodectus mactans;
from the order Or the Acarina, ror example Acarus
siro, Argas spp., Ornithodoros spp., Dermanyssus ~allinae,
Eriophyes ribis, Phylloco~truta oleivora, ~ spp.,
Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes
spp., Psoroptes spp. J Chorioptes spp. 9 Sarco~tes spp.,
Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and
Tetranychus spp..
The active compounds can be converted into the
customary formulations, such as solutions, emulsions,
wettable powders, suspensions, powders, dusting agents,
foams, pastes, soluble powders, granules, aerosols,
suspension-emulsion concentrates, seed-treatment powders,
natural and synthetic materials impregr.ated with active
compound, very fine capsules in polymeric substances,
coating compositions for use on seed, and formulations
used with burning equipment, such as ~umigating cartridges,
fumigating cans and fumigating coils, as well as ULV
cold mist and warm mist formulations.
These formulations may be produced in known manner,
ror example by mixing the active compounds with extenders,
that is to say liquid or liquefied gaseous or solid
diluents or carriers, optionally with the use of surrace-
~LZ542~7
active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-rorming agents. In
the case Or the use Or water as an extender, organic
solvents can, rOr example, also be used as auxiliary
solvents.
As liquid solvents diluents or carriers, especially
solvents, there are suitable in the main, aromatic
hydrocarbons, such as xylene, toluene or alkyl naphthalenes,
chlorinated aromatic or chlorinated aliphatic hydrocarbons,
such as chlorobenzenes, chloroethylenes or methylene
chloride, aliphatic or alicyclic hydrocarbons, such
as cyclohexane or parafrins, for example mineral oil
fractions, alcohols, such as butanol or glycol as well
as their ethers and esters, ketones, such as acetone,
methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,
or strongly polar solvents, such as dimethylformamide
and dimethylsulphoxide, as well as water.
By liquefied gaseous diluents or carriers are
meant liquids which would be gaseous at normal temperature
and under norr;al pressure, ~or example aerosol propellants,
such as halogenated hydrocarbons as well as butane,
propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural
minerals, such as kaolins, claysJ talc, chalk, quartz,
attapulgite, montmorillonite or diatomaceous earth,
and ground synthetic minerals, such as highly-dispersed
silicic acid, alumina and silicates. As solid carriers
for granules there may be used crushed and fractionated
natural rocks such as calcite, marble, pumice, sepiolite
and dolomite, as well aq synthetic granules of inorganic
and organic meals, and granules Or organic material
such aq sawdust, coconut shells, maize cobs and tobacco
~:254227
stalks.
As emulsifying and/or foam-forming agents there
may be used non-ionic and anionic emulsiriers, such
as polyoxyethylene-fat'y acid esters, polyoxyethylene-
fatty alcohol ethers, ror example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates
as well as albumin hydrolysis products. Dispersing
agents include, for example, lignin sulphite waste
liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and
natural and synthetic polymers in the form Or powders,
granules or latices, such as gum arabic, polyvinyl
alcohol and polyvinyl acetate, can be used in the formula-
tions.
It is possible to use colorants such as inorganic
pigments, for example iron oxide, titanium oxide and
Prussian Blue, and organic dyestuffs, such as alizarin
dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs,
and trace nutrients, such as salts of iron, manganese,
boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from O.l to
95 per cent by weight Or active compound~ preferably
from 0.5 to 9O per cent by weight.
The active compounds according to the invention
may be used in the form of their formulations of the
types that are commercially available or in the use
forms prepared from these formulations
~ he active compound content of the use forms pre-
pared from the formulations of the types that are
commerciall~ available can vary within wide ranges.
The active compound concentration of the use forms can
be from O.OOOOC)Ol to lOOg by weight of active compound,
~Z54ZZ7
preferably from C.01 to 10% by weight.
The compounds may be employed in a customary manner
appropriate for the particular use forms.
When used against pests harmful to health and pests
of stored products, the active compounds are distinguished
by an excellent residual activity on wood and clay as
well as a good stability to alkali on limed substrates.
In the veterinary field, the active compounds accord-
ing to the invention may be used in a known manner,
such as orally in the form of, for example, tablets,
capsules, drenches and granules; dermally by means
of, for example, dipping, spraying, pouring-on, spotting-
on and powdering; and parenterally, for example by means
of injections.
The present invention also provides an arthropodicidal
composition containing 2S active ingredient a compound
of the present invention in admixture with a solid or
liquefied gaseous diluent or carrier or in admixture
with a liquid diluent or carrier containing a surface-
active agent.
The present invention also provides a method o~
combating arthropods (especially insects or acarids)
which comprises applying to the arthropods , or to
a habitat thereo~, a compound of the present invention
alone or in the form of a composition containing as
active ingredient a compound of the present inmention
in admixture with a di.luent or carrier.
The present invention also provides a method of
freeing or protecting domesticated animals from ecto-
parasitical insects or acarids which comprises applyingto said animals a compound according to the present
invention, in admixture with a diluent or carrier.
- 18 -
- ~.2S422~
The present invention further provides crops protected
from damage by arthropods by being grown in areas in
which immediately prior to and/or during the time of
the growing a compound of the present invention was
applied alone or in admixture wlth a diluent or carrier.
It ~ill be seen that the usual methods of providing
a harvested crop may be improvecl by the present invention.
The present invention further provides domesticated
animals whenever freed or protected from ectoparasitical
insects or acarids by the application to said animals
of a compound according to the present invention, in
admixture with a diluent or carrier.
The insecticidal and acaricidal activity of the
compounds of this invention is illustrated by the follow-
ing biotest Examples.
In these Examples, the compounds according tothe present invention are each identified by the number
(given in brackets) of the corresponding preparative
Example, which will be found later in this specification.
The known comparison compounds are identified as
follows:
/ CH3
(A) ( ~ 1 CH ~CH CH3
3 ~ C _ CH3
(B) - ~ ~ 0 ~ CH2-0-C0~ H ~ H3
(C) = ~ CO-O-CH2~ ~
~254Z27
Example A
Phaedon larvae test
Solvent: 3 parts by weight Or dimethylformamide
Emulsifier: 1 part by weight Or alkylaryl polyglycol
ether
To produce a suitable preparation of active compound,
1 part by weight cf the active compound was mixed h~ith
the stated amour.t of solven~ containing the stated
amount Or emulsifier and the concentrate was diluted
with water to the desired concentration.
Cabbage leaves (Brassica oleracea) were sprayed
wit~. the preparation Or the active compound until dripping
wet and were then inrested with mustard beetle larvae
(Phaedon-cochleariae).
After the specified periods Or time, the degree
Or destruction was determined in %: 100% meant that
all Or the beetle larvae had been killed whereas 0%
meant that none Or the beetle larvae had been killed.
The active compounds, the concentrations Or the
active compounds, the evaluation times and the results
can be seen from the following table:
T a b 1 e A
.
(insects ~hich damage plants)
Phaedon larvae test
Active Active compound Degree o~ de-
compounds concentration in struction in
% % after 3 days
(A) 0.1 100
O.01 100
0.001 0
(~) 0.1 100
O . 01 90
0.001 0
(2) 0.1 100
0.01 100
O . 001100
( 10 ) O . 1 100
0.01 100
O.001 100
~0 (1) 0.1 100
O . 01 100
0.001 100
- 20 -
25422~7
Example B
Myzus test (contact action)
Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
To produce a suitable preparation cf active compound,
1 part by weight of the active compound was mixed with
the stated amount of solvent containing the stated amount
Or emulsifier and the concentrate was diluted with water
to the desired concentration.
Cabbage plants (Brassica oleracea) which had been
heavily infested with peach aphids (Myzus persicae)
were sprayed with the preparation of the active compound
until dripping wet.
Arter the specified periods of time, the degree
Or destruction was determined as a percentage: 100
meant that all Or the aphids were killed whereas 0
meant that none of the aphids were killed.
l`he active compounds, the concentrations of the
active cGmpounds, the evaluation times and the results
can be seen from the following table:
T a b 1 e B
(insects which da~a~e plants)
~ test
Active Active compound Degree of de-
compounds concentration in struction in
% g after 1 day
(C) 0.1 50
0.01
(2) 0.1 100
O . 01100
(7) 0.1 100
0.01 90
(10) 0.1 lOG
0.01 90
(11) 0.1 100
0.01 95
(1) O.1 100
O . 01100
(6) 0.1 100
O . 01100
- 21 -
~" ~2542Z7
Exam~le C
Tetranychus test (resistant)
Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by wei~ht Or alkylaryl polyglycol
ether
To produce a suitable preparation of active compound,
1 part by weight of the active compound was mixed with
the stated amount of solvent and the stated amount of
emulsifier and the concentrate was diluted with water
to the desired concentration.
~ ean plants (Phaseolus vul~aris) which were heavily
infested with the two-spotted spider mite ( ~
urticae) in all stages of development were sprayed with
the preparation Or the active compound until dripping
wet,
After the specified periods Or time, the degree
Or destruction was determined as a percentage: 100%
meant that all of the spider mites were killed whereas
0~ meant that none o~ the spider mites were killed.
The active compounds, the concentrations of the
active compounds, the evaluation times and the results
can be seen from the following table:
T a b 1 e C
(Mites which damage plants)
Tetranychus test
Active Active compound Degree of de-
compound concentration struction in
in % ~ after 2 davs
.,
(A) 0.1 0
tC) 0.1 0
(2) 0.1 90
- ~2 -
~25~227
T a b 1 e C (continued)
(mites which damage plants)
Tetranychus test
Active Active compound Degree of de-
5compound concentration struction in
in g % after 2 d~s
(7) 0.1 98
t4) 0.1 9B
(11) 0.1 90
(1) 0.1 98
(6) 0.1 100
Example D
Test with parasitic adult cattle ticks
Solvent: alkylaryl polyglycol ether
To produce a suitable preparation of an active compound,
that compound was mixed with the stated solvent in the ratio
of 1:2 and the concentrate thus obtained was diluted with
water to the desired concentration.
10 adult cattle ticks (~oophilus microplus res.) were
dipped for 1 minute in the preparation of active compound
to be tested. After transrerring the ticks into a plastic
beaker and keeping them in a climatically controlled
chamber, the degree o~ destruction in per cent was de-
termined, with 100~ denoting that all of the ticks had been
killed and 0% denoting that no ticks had been killed.
The results are shown in the following table.
T a b 1 e D
Active Active compound Degree of de-
compound concentration struction in
in ppm __ %
(7) 10,000 100
Example E
Test with parasitic fly larvae
Emulsirier: 80 parts by weight of alkylaryl glycol ether
To produce a suitable preparation of active compound,
- 23 -
:L2542~2,7
20 parts by weight of the active compound in question
were mixed with the stated amount of the emulsifier
and the mixture thus obtained was diluted with water
to the desired concentration.
About 20 fly larvae (Lucilia cuprina) were introduced
into a test tube which contained about 3 ml of a 20%
strength suspension o~ eg~ yolk powder in water, and
which was fitted with a cottonwool plug of appropriate
size. 0.5 ml of the active compound preparation was
placed on this egg yolk powder suspension. After 24
hours, the degree Or destruction in % was determined.
lC0% meant that all of the larvae had been killed and
0% meant that none of the larvae had been killed.
The active compound, amounts used and results can
be seen from the table which follows:
T a b 1 e E
Active Active compound Destructive
compound concentration action in
in ~Dm %
(2) 1,000 100
( 10 ) 1, 000 100
Preparative Examples
Example 1:
CN
~ H3C ~C~3
7.3 ~ (0.03 mol) of 3~(4-fluorophenoxy)-~-cyanobenzyl
alcohol and 8.1 g (0.03 mol) of 2,2-dimethyl-3-(2-phenyl-2-
chlorovinyl)-cyclopropanecarboxylic acid chloride were
- 24 -
-" ~Z5422~7
dissolved in 150 ml of anhydrous toluene and 2.4 g ~0.03
mol) Or pyri~ine, dissolved in 50 ml of toluene, were added
dropwise at 25-30C, whilst stirring. Thereafter, stirring
was continued for 3 hours at 25C. The reaction mixture
was poured into 150 ml of water and the organic phase
WâS separated off and again washed, with 100 ml of water.
The toluene phase was then dried over sodium sulphate and
the solvent was distilled off uncler a water-pump vacuum.
The last remnants Or solvent were removed by brief incipient
distillation under 1 mm ~g at 60C bath temperature. 12.0 g
(~4% of theory) of 3'-(4-fluorophenoxy)-~-cyanobenzyl
2,2-dimethyl-3-(2-phenyl)-2-chlorovinyl)-cyclopropane carboxy-
late were obtained asayellow oil having a refractive index
n24 of 1.5670.
~xample_2:
0 ~ CH2-0-C0 ~ CH-C ~ (2)
3 H3
24.3 g (0.05 mol) Or the sodium salt of 2,2-dimethyl-3-
(2-phenylthio-2-chlorovinyl)-cyclopropaneCarboxyliC acid
were dissolved in 150 ml of dimethylformamide and heated
to 120C, together with 15.8 g (o.o6 mol) Or 3-phenoxy~
benzyl bromide for 4 hours. After completion of the
reaction, the dimethylformamide was distilled off in vacuo
and the residue was taken up in 200 ml o~ methylene
chloride. It was then extracted by shaking with twice
150 ml of water, the organic phase was dried over sodium
sulphate and t;he solvent was stripped O~r in vacuo. The
last remnants Or solvent were removed by brief incipient
distillation under 1 mm Hg at 60C bath temperature.
- 25 -
~L254227
15 g (53.8% o~` theory) of 3'-phenoxy-benzyl 2,2-dimethyl-3-
(2-phenylthio-2-chlorovinyl)-cyclopropane carboxylate were
obtained as a yellow oil having a re~ractive index
n23 of 1.5948~
The following compounds could be prepared analogously:
- 26 -
:ILZ5422~7
c ~o ~ ~a~ ~'~
--~ O 0 ~
~ s ~ t_ t~
Q~
.,, c~
o c~
a c~
z,:~:
o~ ~ o~ ~
r~ Z
IL2542Z7
~X o ~ ~ o
_ ~ N~ N~q N~
~ O
~ 0' U~ ,
~ ~ ~ ~
~ .
L~ ~ ~ ~ O
-- 28 --
~.2S4~ ~
a~
~ ~o ~ o
c~ ......... a~
X U~
~a ~ ~ .
a ~ a
o
Q)
~ S O~
~rl ~ ~1 ~ ~D
o U~
3 ~
E o
Z
.` 2
-~ :iL254227
Q) r-
v u~ 8
c~ N~a ~ a ~ a
o
a~
~, ~ ~ ~ o
. c~
,~
~ z u~
-- 30 --
~25~L2Z7
~ X
h ~ ~ Q
~S Cl~
:~0
~ < m~
~ o~ U ~ ~ o,
N Z ~ ~N
o~
~:z a~
1 2~;i 42d~7
a~
.~
X
~: ,
~o
o
~ Q~
.,~
V
b
X N t~J N
k~
-- 32 --
~S~227
a~
.,, ..
h ~ O
~I;
O
~ .C ~
~ O
~3 U U~a
m
o o o
~ ~ 0~
O N ~ O
-- 33 --
~LZ54ZZ7
a:~
Q~ ~D
C~ . . .`
to X
F~ ~ ..
U~
~ ,,
~: h
_~ O
~O ~ r~ ~
a) ~ _
~-1 ~ co J
o a~
rl ~) r~
U I ~
o ~ n U
a~ æ~
r -~ ~4
r~ ) J
x~.
-- 34 --
1254~
t`
a~
.,,U~
~,
X
a~
..
o
~h
~ O
~a~ 0 ~ ~
~ _ _ ~
a~ ~ ~D
~1 ~HL~
:~ O
E
O ~
1::, 11 11
~ X~
O
~ C z
C~ - O C~- -O ~)- -O
0~
~1
~0
XZ ~ r~
-
~542:Z7
The cyclopropanecarboxylic acids (V), or their salts
and acid chlorides (III)required as starting compounds,
could be prepared as described below:
/Cl
(a) C2~l5o-c ~ CH~C ~
H3C CH3 Cl
2~.3 g (0.1 mol) of 4-chlorobenzyl-phosphonic acid
diethyl ester were dissolved in 400 ml of absolute tetra-
hydrofuran and the solution was cooled to -70C. 0.11
nmol of n-butyl-lithiun (as a 15~ strength solution in
hexane) were added drcpwise under a counter-current of
nitrogen and whilst stirring well, and the reaction mix-
ture was then stirred ror a further 15 minutes at -70C.
Thereafter, 15.4 g (C.l mol) of carbon tetrachloride were
added dropwise at -70C, still under nitrogen; in the
course thereof, the reaction mixture assumed a red-brown
colour. After stirring for a ~urther 15 minutes, 18.6 g
(0.1 nmol) of 2,2-dimethyl-3-formyl-cyclopropanecarboxylic
acid etnyl ester were added at -65C. The reaction mix-
ture was then allowed to come to room temperature and was
stirred for a further 3 hours at 25C. The reaction batch
was then poured into 2 litres of water and extracted with
600 n;l of ether. The ether phase was dried over sodium
sulphate, the solvent was stripped off in ~acuo and the
oily residue was distilled at 150-155C/2 mm Hg. 2,2-
Dimethyl-3-~2-chloro-2-p-chlorophenyl-vinyl)-cyclopropane-
carboxylic acid ethyl ester was obtained in 54.3% yield.
The follow:ing could be prepared analogously:
- 36 -
~2542Z7
Yield Physical
(% of data (re-
Formula theory) fractive
index;
boiling
goint ~
C/mm Hg)
, _ _
Cl
C2 5 ~ ~ C/ nD3:1,5222
H3C CH3
~2H5-C ~ CH~C ~ Cl 45~4 n25:1,5621
H3C H3 Cl
C2H50-C0 ~ CH- ~ 52,7 155-160/1
H3C CH3 Cl
C2H50-C0 ~ CH~ ~ 57 n25:1,520~
C2H50-C ~ S ~ -Cl 81 nD5:1,5025
H3C H3
Cl
C2H50-C0 ~ CH2C\ 71 nD6:1,5359
H3 CH3
- 37 -
Z54227
(b) C2~5~-C ~ CH=C
H3C CH3
22.8 g (0.1 mol) of benzylphosphonic acid diethyl
ester were dissolved in 400 ml of absolute tetrahydro-
furan and the solution was cooled to -70C. 0.11 mol of
n-butyl-lithium (as a :5% strength solution in hexane)
were added dropwise under a counter-current of nitrogen
and whilst stirring we:l; the mixture was then stirred
at -70C for a further 15 minutes, and thereafter 18.6 g
(0.1 mol) of 2,2-dimethyl-3-formyl-cyclopropanecarboxylic
acid ethyl ester were added dropwise at -65C, again still
under nitrogen. The reaction mixture was then allowed to
come to room temperature and was stirred further for 3 hours
at 25C. Thereafter, the reaction batch was poured into
2 litres of water and extracted with 600 ml of ether.
The ether phase was dried over sodium sulphate and the
solvent was then stripped off in vacuo. The oily residue
was distilled 2t 145-150C/3 mm Hg. 2,2-Dimethyl-3-(2-
phenyl-vinyl)-cyclopropanecarboxylic acid ethyl ester
having a refractive index n23 of 1.5022 was obtained in
69.6~ yield.
The following could be prepared analogously:
- 38 -
- ~2~422~7
Yield (~ Yhysical
theory) data (re-
fractive
Formula index;
boilin~
point ~ C/mm
_
C2H50-C0 CH~C
H ~H ~Cl 70,2 n25:1,5584
49.6 n25:1,5o57
H3C CH3 F
H
C2H5-C~7CC~I~C~[~3 46 150-155/l
3 ~3 1
The cyclopropanecarboxylic acid ethyl esters pre-
pared according to Example (a) or (b) were subjected to
acid or alkaline saponification, in accordance with
known methods, to give the ~rrespondin~ acids. These
were converted, in accordance with methods which are
also known, into the corresponding salts (for example
alkali metal salts or ammonium salts) or acid chlorides.
- 39 -
