Pesticidal compositions comprise synergistic mixtures of active compounds 1R-(-)-[(pentafluorophenyl)-methyl]-3S-3-(2,2-dichloroethenyl)-2,2-dimethy lcyclopropanecarboxylate and O,O-dimethyl O-2,2-dichlorovinyl phosphate (dichlorvos) and, if appropriate, O-isopropoxyphenyl N-methylcarbamate (propoxur). These compositions may be used for combating arthropods.

The present invention relates to new arthropodicidal synergistic 
combinations of the known active compounds 
1R-(-)-[(pentafluorophenyl)-methyl]-3S-3-(2,2-dichloroethenyl)-2,2-dimethy 
lcyclopropanecarboxylate and O,O-dimethyl O-2,2-dichlorovinyl phosphate 
(dichlorvos) and, optionally, of O-isopropoxyphenyl N-methylcarbamate 
(propoxur). 
The invention also relates to formulations (compositions) containing these 
active compound combinations, their preparation and use for combating 
arthropods. 
It is already known that propoxur and dichlorvos have a good action against 
insects and arachnids. These active compounds have therefore been employed 
with great success for many years for combating pests, particularly for 
combating domestic vermin. However, owing to the emergence of resistance, 
they suffer, like all insecticides hitherto which are in practical use, 
from certain losses in effect during the course of time, and these losses 
can, in certain cases, limit their suitability for use. The consequence of 
this is that, in order to combat resistant pests, the required use 
concentrations and use quantities have constantly to be increased in order 
still to obtain a satisfactory action, until, finally, the limit is 
reached at which the use is no longer meaningful or possible, especially 
for economic and application-technological reasons. The formation of 
resistant insect populations is particularly problematic in that their 
resistance is not only directed against a particular insecticide, but 
includes, as a rule, all active compounds of the same active-compound 
class, or even of several active-compound classes which are similar in 
their action. 
The solution of the problem of developing suitable agents for combating 
resistant pests is therefore of particularly great importance. 
The present invention now provides an arthropodicidal composition 
containing as active ingredients (1) 
1R-(-)-[(pentafluorophenyl)-methyl]-3S-3-(2,2-dichloroethenyl)-2,2-dimethy 
lcyclopropanecarboxylate, of the formula 
##STR1## 
(II) O,O-dimethyl O-(2,2-dichlorovinyl) phosphate (common name: 
dichlorvos), of the formula 
##STR2## 
and, optionally, (III)2-isopropoxy-phenyl N-methylcarbamate (common name: 
propoxur), of the formula 
##STR3## 
alone or in admixture with a solid or liquid or liquefied gaseous diluent 
or carrier. 
The active-compound combinations according to this invention have a 
particularly powerful action against arthropods, particularly against 
insects and arachnids. 
Accordingly, the invention also provides a method of combating arthropods 
(especially insects or arachnids) which comprises applying to the 
arthropods, or to a habitat thereof, a composition according to the 
present invention. 
The active compounds (II) and (III) are active compounds of known 
commercial products, and the active compound (I) is known from German 
Offenlegungsschrift (German Published Specification) No. 2,658,074. 
The activity of the active compound combination, according to the 
invention, of the two active compounds (I) and (II), or of the three 
active compounds (I), (II) and (III), is, surprisingly, substantially 
greater than the sum of the activities of the individual compounds. A 
genuine synergistic effect is thus present in the case of the combinations 
according to the invention. 
The relative proportions of the active compounds can vary within relatively 
wide ranges in the active compound mixtures of pest-combating agents 
according to the invention. The proportions (parts by weight) of the two 
components (I) and (II) are preferably between 1:100 and 1:1, especially 
between 1:100 and 1:10, and those of the three components (I), (II) and 
(III) are preferably between 1:100:100 and 1:1:1, especially between 
1:50:50 and 1:10:10. In these mixtures, the relative proportions of the 
components (II) and (III) can also vary within the limits given. Of 
course, these proportions do not have to correspond to integers. 
Particularly preferred active compound mixtures or pest-combating agents 
are those in which the proportions (parts by weight) of the active 
compounds (I) and (II) are about 1:10, about 1:25 or about 1:50, and those 
of the active compounds (I), (II) and (III) are about 1:10:25, about 
1:25:25, about 1:25:50 or about 1:50:100. 
The pest-combating agents according to the invention have an excellent 
knock-down action and fatal action against the most diverse destructive 
insects and arachnids, particularly insects. In this context, the rapid 
knock-down action is of great importance particularly in combating 
domestic vermin, since the user lays particular value on a rapid 
elimination of the annoyance, especially for reasons of hygiene. The 
pest-combating agents of this invention are much more active against the 
pests which are resistant to carbamates, phosphoric (phosphonic) acid 
esters and pyrethroids, and can therefore be employed in much smaller 
quantities or concentrations, and with better success, than pest-combating 
agents which contain only 
1R-(-)-[(pentafluorophenyl)-methyl]-3S-3-(2,2-dichloroethenyl)-2,2-dimethy 
lcyclopropanecarboxylate or dichlorvos or propoxur. 
The abovementioned pests include, for example, the following pests: 
from the order of the Thysanura, for example Lepisma saccharina; 
from the order of the Orthoptera, for example Blatta orientalis, 
Periplaneta americana, Leucophaea maderae, Blattella germanica and Acheta 
domesticus; 
from the order of the Dermaptera, for example Forficula auricularia; 
from the order of the Isoptera, for example Reticulitermes spp.; 
from the order of the Heteroptera, for example Cimex lectularius, Rhodnius 
prolixus and Triatoma spp.; 
from the order of the Lepidoptera, for example Ephestia kuehniella and 
Galleria mellonella; 
from the order of the Coleoptera, for example Anobium punctatum, 
Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, 
Hylotrupes bajulus, Oryzaephilus surinamensis, Sitophilus spp., Dermestes 
spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Ptinus 
spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., and Tenebro 
molitor; 
from the order of the Hymenoptera, for example Lasius spp., Monomorium 
pharaonis and Vespa spp.; 
from the order of the Diptera, for example Aedes spp., Anopheles spp., 
Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora 
erythrocephala, Lucilia spp., Chrysomyia spp., Stomoxys spp., and Tabanus 
spp.; 
from the order of the Siphonaptera, for example Xenopsylla cheopis and 
Ceratophyllus spp.; 
from the class of the Arachnida, for example Scorpio maurus and Latrodectus 
mactans; 
from the order of the Acarina, for example Acarus siro, Argas spp., 
Ornithodoros spp., Dermanyssus gallinae, Boophilus spp.; Rhicephalus spp., 
Amblyomma spp., Hyalomma spp., and Ixodes spp. 
The active compound combinations can be converted into the customary 
formulations, such as solutions, emulsions, wettable powders, suspensions, 
powders, dusting agents, pastes, soluble powders, aerosols, 
suspension/emulsion concentrates, natural and synthetic materials 
impregnated with active compound, very fine capsules in polymeric 
substances, and formulations used with burning equipment, such as 
fumigating cartridges, fumigating cans, and fumigating coils, as well as 
ULV cold mist and hot mist formulations. 
These formulations may be produced in known manner, for 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 
surface-active agents, that is to say emulsifying agents and/or dispersing 
agents and/or foam-forming agents. In the case of the use of water as an 
extender, organic solvents can, for example, also be used as auxiliary 
solvents. 
As liquid 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 paraffins, 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 normal pressure, for 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, clays, 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 as synthetic 
granules of inorganic and organic meals, and granules of organic material 
such as sawdust, coconut shells, corn cobs and tobacco stalks. 
As emulsifying and/or foam-forming agents there may be used non-ionic and 
anionic emulsifiers, such as polyoxyethylene-fatty acid esters, 
polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol 
ethers, 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 of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, can be used in the formulations. 
For use in baits, the formulations can contain the customary lures and 
baits, for example pheromones, attractive colorants, carbohydrates and 
proteins. 
Aerosols, oil sprays and emulsion concentrates are particularly preferred 
formulations. 
The formulations contain, in general, between 0.5 and 100% by weight of the 
active-compound combinations, preferably between 0.5 and 60% by weight. 
The active compound combinations 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. 
The active compound content of the use forms prepared from the formulations 
of the types that are commercially available can vary within wide ranges. 
The active compound concentration of the use form can be from 0.01 to 100% 
by weight of total active compounds, preferably between 0.1 to 10% by 
weight. 
The compounds may be employed in a customary manner appropriate for the use 
forms. 
Because of their particular properties, the active compound mixtures 
according to the invention, or their formulations, can be employed in many 
areas for combating arthropods. Preferred areas of use are commercial and 
private hygiene (for example in schools, hospitals, foodstuff-processing 
factories and households), commercial and private protection of stored 
products (for example in foodstuff stores) and use in agriculture and 
animal husbandry (for example for combating stable flies).

The following examples are intended to illustrate the preparation of the 
pest-combating agents according to the invention. 
FORMULATION EXAMPLES 
EXAMPLE 1 
______________________________________ 
Spray formulation Parts by weight 
______________________________________ 
Active compound (I) 0.01 
Active compound (II) 
1.0 
Methylene chloride 5.0 
Deodorized kerosene/mixture 
10.0 
or saturated aliphatic 
hydrocarbons 
Perfume oil 0.01 
Propellant: propane/butane 
83.98 
(15:85) 
______________________________________ 
EXAMPLE 2 
______________________________________ 
Spray formulation Parts by weight 
______________________________________ 
Active compound (I) 
0.04 
Active compound (II) 
1.0 
Methylene chloride 5.0 
Deodorized kerosene 
10.0 
Perfume oil 0.01 
Propellant: propane/butane 
83.95 
(15:85) 
______________________________________ 
EXAMPLE 3 
______________________________________ 
Spray formulation Parts by weight 
______________________________________ 
Active compound (I) 
0.04 
Active compound (II) 
1.0 
Active compound (III) 
2.0 
Methylene chloride 25.0 
Deodorized kerosene 
12.43 
Perfume oil 0.03 
Propellant: propane/butane 
59.50 
(15:85) 
______________________________________ 
EXAMPLE 4 
______________________________________ 
Oil Spray formulation 
Parts by weight 
______________________________________ 
Active compound (I) 
0.08 
Active compound (II) 
0.5 
Isopropanol 10.0 
Petroleum 89.42 
______________________________________ 
EXAMPLE 5 
______________________________________ 
Oil spray formulations 
Parts by weight 
______________________________________ 
Active compound (I) 
0.02 
Active compound (II) 
1.0 
Isopropanol 10.0 
Petroleum 88.98 
______________________________________ 
EXAMPLE 6 
______________________________________ 
Oil spray formulation 
Parts by weight 
______________________________________ 
Active compound (I) 
0.04 
Active compound (II) 
1.0 
Active compound (III) 
1.0 
Isopropanol 10.0 
Petroleum 87.96 
______________________________________ 
The following examples are intended to illustrate the activity of the 
active-compound combinations according to the invention. 
BIOLOGICAL EXAMPLES 
Spray cans or oil sprays which contained either only active compound (I) or 
active compound (II) or active compound (III), as well as spray cans or 
oil sprays which contained the active compounds (I) and (II), or the 
active compounds (I), (II) and (III) in combinations, were sprayed in 
rooms of 30 m.sup.3 capacity. 3 wire cages, each containing 20 Musca 
domestica (.male..male., strain Hans) which were strongly resistant to 
carbamates, phosphoric (phosphonic) acid esters and pyrethroids, were 
previously hung in the rooms. After the application (by spraying) of 17 g 
of the formulations, in each case, per room, the rooms were closed and the 
action on the flies was continuously monitored for up to one hour. The 
test measured after how many minutes 50% (yields: K.D. 50 values) or 95% 
(yields: K.D. 95 values) of the test animals had been knocked down. The 
values determined are contained in the following table: 
TABLE A 
______________________________________ 
Musca domestica (strain Hans, .male..male., multi-resistant) 
% (by weight) of 
active compounds 
Knock-down action in 
Active in the minutes after the application 
compounds 
formulation K.D. 50 K.D. 95 
______________________________________ 
(I) 0.01 to 0.08 none none 
(II) 0.5 none none 
1.0 30 55 
(III) 2.0 none none 
(I) 0.01 28 44 
+ + 
(II) 1.0 
(I) 0.02 21 39 
+ + 
(II) 1.0 
(I) 0.04 18 34 
+ + 
(II) 1.0 
(I) 0.03 23 51 
+ + 
(II) 0.5 
(I) 0.08 20 40 
+ + 
(II) 0.5 
(I) 0.02 18 33 
+ + 
(II) 1.0 
+ + 
(III) 2.0 
(I) 0.03 16 26 
+ + 
(II) 1.0 
+ + 
(III) 2.0 
(I) 0.04 14 21 
+ + 
(II) 1.0 
+ + 
(III) 2.0 
______________________________________ 
"None" denotes that a K.D. 50 or K.D. 95 was not achieved during the 
course of 1 hour. 
It will be understood that the specification and examples are illustrative 
but not limitative of the present invention and that other embodiments 
within the spirit and scope of the invention will suggest themselves to 
those skilled in the art.