DE19622190A1 - Pesticide based on cyclic polysiloxanes - Google Patents

Abstract

The invention concerns pesticides based on cyclic polysiloxanes and arthropodicidal active substances.

Description

The present invention relates to pesticides based on cyclic polysiloxanes mixed with arthropodicidal agents.

It was known that cyclic polysiloxanes with 4 and 5 siloxane units are insecticidal. It was also known to use polysiloxanes Can kill insects by spraying (US-P 4,654,328). These active ingredients however, do not show a lasting effect.

The invention therefore relates to the following mixtures and agents:

• 1. Pesticides based on cyclic polysiloxanes of the formula (I) in which
  R represents identical or different radicals from the group methyl, ethyl, propyl,
  n stands for integers from 3 to 6,
  in a mixture with arthropodicidal agents.
• 2. Means according to 1 (above), characterized in that it is predominantly as Part of the formula (I) contains compounds in which the index n = 5 is.
• 3. Agent according to 1 (above), characterized in that in the cyclic polysiloxanes of the formula (I) in which
  R represents identical or different radicals from the group methyl, ethyl, propyl
  n stands for integers from 3 to 6,
  the constituents of the formula (I) with the indices 4 and 5 in the ratio by weight = 4 <85% (weight)
  n = 5 <15% (weight).
• 4. Mixture according to 3 (above), characterized in that the constituents of the formula (I) with the indices 4 and 5 in the weight ratio n = 4 75% by weight
  n = 5 25% by weight.

Preferred arthropodicidal active ingredients for the agents according to the invention are Insecticides, especially parasiticides for use on animals. To the Insecticides include agonists or antagonists of the nicotinergic acetylcholine insect receptors, ivermectins and avermectins, and phosphorus-containing ver bonds such as phosphoric or phosphonic acid esters, natural and synthetic Pyrethroids, carbamates, amidines, juvenile hormones and juvenoid synthetic Active ingredients.

The agonists or antagonists of the nicotinergic acetylcholine receptors of insects include the compounds known from the following publications:
European Patent Application Nos. 464 830, 428 941, 425 978, 386 565, 383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600, 192 060, 163 855, 154 178, 136 636, 303 570, 302 833, 306 696, 189 972, 455 000, 135 956, 471 372, 302 389; German Offenlegungsschriften No. 3 639 877, 3 712 307; Japanese Patent Laid-Open No. 03 220 176, 02 207 083, 63 307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255 072; U.S. Patent Nos. 5,034,524, 4,948,798, 4,918,086, 5,039,686, 5,034,404; PCT applications No. WO 91/17 659, 91/4965; French Application No. 2 611 114; Brazilian application No. 88 03 621.

The methods, procedures, formulas and methods described in these publications Definitions and the individual preparations and ver Binding is hereby expressly referred to.

These compounds can preferably be represented by the general formula (II) play

in which
R represents hydrogen, optionally substituted radicals from the group acyl, alkyl, aryl, aralkyl, heteroaryl or heteroarylalkyl;
A represents a monofunctional group from the series hydrogen, acyl, alkyl, aryl or represents a bifunctional group which is linked to the radical Z;
E represents an electron withdrawing group;
X stands for the radicals -CH = or = N-, where the radical -CH = can be linked to the radical Z instead of an H atom;
Z for a monofunctional group from the series alkyl, -OR, -SR,

stands for a bifunctional group with the Radical A or the radical X is linked.

Compounds of the formula (II) in which the radicals fol have the following meaning:

R represents hydrogen and also optionally substituted radicals from the Series acyl, alkyl, aryl, aralkyl, heteroaryl, heteroarylalkyl.

Formyl, alkylcarbonyl, arylcarbonyl and alkyl may be mentioned as acyl radicals sulfonyl, arylsulfonyl, (alkyl -) - (aryl -) - phosphoryl, which in turn sub stitu can be.

Examples of alkyl which may be mentioned are C _1-10 -alkyl, in particular C₁₄-alkyl, in particular methyl, ethyl, i-propyl, sec.- or t.-butyl, which in turn can be substituted.

Phenyl, naphthyl, in particular phenyl, may be mentioned as aryl.

Phenylmethyl and phenethyl may be mentioned as aralkyl.

Heteroaryl with up to 10 ring atoms and N, O, S especially N as heteroatoms. In particular, Thio phenyl, furyl, thiazolyl, imidazolyl, pyridyl, benzthiazolyl.

Heteroarylmethyl, heteroarylethyl may be mentioned as heteroarylalkyl up to 6 ring atoms and N, O, S, especially N as heteroatoms.

Examples of preferred substituents are: Alkyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, i- and t-butyl; Alkoxy with before preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, Ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy; Alkylthio with before preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methyl  thio, ethylthio, n- and i-propylthio and n-, i- and t-butylthio; Haloalkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, the Halogen atoms are the same or different and as halogen atoms preferably fluorine, chlorine or bromine, especially fluorine, such as tri fluoromethyl; Hydroxy; Halogen, preferably fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine; Cyano; Nitro; Amino; Monoalkyl and dialkylamino with preferably 1 to 4, in particular 1 or 2, coals Substance atoms per alkyl group, such as methylamino, methyl-ethyl-amino, n- and i-propylamino and methyl-n-butylamino; Carboxyl; Carbalkoxy with before preferably 2 to 4, in particular 2 or 3, carbon atoms, such as carbo methoxy and carboethoxy; Sulfo (-SO₃H); Preferably alkylsulfonyl 1 to 4, in particular 1 or 2 carbon atoms, such as methylsulfonyl and Ethylsulfonyl; Arylsulfonyl with preferably 6 or 10 aryl carbon atoms, such as phenylsulfonyl and heteroarylamino and heteroarylalkyl amino such as chloropyridylamino and chloropyridylmethylamino.

A particularly preferably represents hydrogen and optionally sub substituted radicals from the series acyl, alkyl, aryl, which preferably those at R have the meanings given. A also stands for a bifunctional Group. Optionally substituted alkylene with 1-4, in particular special 1-2 carbon atoms, the substituents listed above ten substituents are mentioned and wherein the alkylene groups through Heteroatoms from the series N, O, S can be interrupted.

A and Z together with the atoms to which they are attached can form one form saturated or unsaturated heterocyclic ring. The straight Cyclic ring can be 1 or 2 identical or different hetero contain atoms and / or hetero groups. As heteroatoms are preferred wise oxygen, sulfur or nitrogen and as hetero groups N-alkyl, where alkyl of the N-alkyl group is preferably 1 to 4, in particular 1 or contains 2 carbon atoms. Alkyl, methyl, ethyl, n- and i- Propyl and n-, i- and t-butyl called. The heterocyclic ring contains 5 up to 7, preferably 5 or 6 ring members.  

Examples of the heterocyclic ring are pyrrolidine, piperidine, Piperazine, hexamethyleneimine, hexahydro-1,3,5-triazine, called morpholine, which may optionally be substituted by methyl.

E stands for an electron-withdrawing radical, in particular NO₂, CN, haloalkylcarbonyl such as 1,5-halo-C _1-4 -carbonyl, in particular COCF₃.

X stands for -CH = or -N =

Z stands for optionally substituted radicals alkyl, -OR, -SR, -NRR, where

R and the substituents preferably have the meaning given above.

In addition to the ring mentioned above, Z can be attached together with the atom which it is bound and the rest

X is a saturated or unsaturated heterocyclic Form a ring. The heterocyclic ring can be another 1 or 2 identical or contain different heteroatoms and / or hetero groups. As a straight atoms are preferably oxygen, sulfur or nitrogen and as Hetero groups N-alkyl, the alkyl or N-alkyl group being preferred contains 1 to 4, in particular 1 or 2, carbon atoms. As alkyl may be mentioned methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. Of the heterocyclic ring contains 5 to 7, preferably 5 or 6 ring members.

Examples of the heterocyclic ring are pyrrolidine, piperidine, Piperazine, hexamethyleneimine, morpholine and N-methylpiperazine called.

Compounds which can be used according to the invention are very particularly preferred Compounds of the general formulas (III) and (IV) called:

in which
n represents 1 or 2,
Subst. Stands for one of the substituents listed above, in particular for halogen, very particularly for chlorine,
A, Z, X and E have the meanings given above,
The following connections are specifically mentioned:

The phosphoric or phosphoric acid esters include:
0-ethyl-0- (8-quinolyl) phenylthiophosphate (Quintiofos),
0.0-diethyl-0- (3-chloro-4-methyl-7-coumarinyl) thiophosphate (Coumaphos),
0.0-diethyl-0-phenylglyoxylonitrile oxime thiophosphate (phoxime),
0,0-diethyl-0-cyanochlorobenzaldoxime thiophosphate (chlorophoxime),
0,0-diethyl-0- (4-bromo-2,5-dichlorophenyl) phosphorothionate (bromophos-ethyl),
0,0,0 ′, 0′-tetraethyl-S, S′-methylene-di (phosphorodithionate) (ethion),
2,3-p-dioxanedithiol-S, S-bis (0,0-diethylphosphorodithionate,
2-chloro-1- (2) 4-dichlorophenyl) vinyl diethyl phosphate (chlorfenvinphos),
0.0-Dimethyl-0- (3-methyl-4-methylthiophenyl) thionophosphoric acid ester (fenthion).

The carbamates include:
2-isopropoxyphenylmethyl carbamate (propoxur),
1-naphthyl-N-methyl carbamate (carbaryl).

The synthetic pyrethroids include compounds of the formula V.

in which
R¹ and R² represent halogen, optionally halogen-substituted alkyl, optionally halogen-substituted phenyl,
R³ represents hydrogen or CN,
R⁴ represents hydrogen or halogen,
R⁵ represents hydrogen or halogen,
Synthetic pyrethroids of the formula V in which are preferred
R¹ represents halogen, in particular fluorine, chlorine, bromine,
R² represents halogen, in particular fluorine, chlorine, bromine, trihalomethyl, phenyl, chlorophenyl,
R³ represents hydrogen or CN,
R⁴ represents hydrogen or fluorine,
R⁵ stands for hydrogen.

Synthetic pyrethroids of the formula V in which are particularly preferred
R¹ represents chlorine,
R² represents chlorine, trifluoromethyl, p-chlorophenyl,
R³ stands for CN,
R⁴ represents hydrogen or fluorine,
R⁵ stands for hydrogen.

Compounds of the formula V may be mentioned in particular
R¹ represents chlorine,
R² represents chlorine or p-chlorophenyl,
R³ stands for CN,
R⁴ represents fluorine in the 4-position,
R⁵ stands for hydrogen.

The following may be mentioned in detail:
3- [2- (4-chlorophenyl) -2-chlorovinyl] -2,2-dimethyl-cyclo-propanecarboxylic acid [(α-cyano-4-fluoro-3-phenoxy) benzyl] ester (flumethrin),
2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid-α-cyano (4-fluoro-3-phenoxy) -benzyl ester (cyfluthrin) and its enantiomers and stereoisomers,
α-cyano-3-phenoxybenzyl (±) -cis, trans-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate (deltamethrin),
2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid-α-cyano-3-phenoxybenzyl ester (cypermethrin),
3-phenoxybenzyl (±) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane carboxylate (permethrin),
α- (p-Cl-phenyl) -isovaleric acid-α-cyano-3-phenoxy-benzyl ester (fenvalerate),
2-Cyano-3-phenoxybenzyl-2- (2-chloro-α, α, α-trifluoro-p-toluidino) -3-methylbutyrate (fluvalinate).

The amidines include:
3-methyl-2-t2,4-dimethylphenylimino] thiazoline
2- (4-chloro-2-methylphenylimino) -3-methylthiazolidine
2- (4-chloro-2-methylphenylimino) -3- (isobutyl-1-enyl) thiazolidine
1,5-bis (2,4-dimethylphenyl) -3-methyl-1,3,5-triazapenta-1,4-diene (Amitraz).

Juvenile hormones or juvenile hormone-like substances include substitutes ized diaryl ethers, benzoyl ureas and triazine derivatives. To the juvenile hormones and juvenile hormone-like substances belong in particular to compounds of following formulas:

The substituted diaryl ethers include, in particular, substituted ones Alkoxydiphenyl ether or diphenylmethane of the general formula VI

in which
R¹ represents hydrogen, halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, dioxyalkylene, dioxyhalogenalkylene, CN, NO₂, alkenyl, alkynyl, alkoxyalkyl, alkoxyalkoxy, hydroxyalkoxy,
R² represents the radicals indicated at R ′,
R³ represents the radicals indicated at R ′,
R⁴ represents hydrogen, alkyl, haloalkyl or halogen,
R⁵ represents the radicals specified for R⁴,
Het represents optionally substituted heteroaryl which is not bound to the rest of the radical via the heteroatom,
X, Y independently of one another represent -O-, -S-
Z represents -O-, -S-, -CH₂-, -CHCH₃-, -C (CH₃) ₂-,
m and n independently of one another represent 0, 1, 2, 3 but their sum is equal to or greater than 2.

Compounds of the formula VI are particularly preferred
in which
R1 is hydrogen-methyl, trifluoromethyl, methoxy, trifluoromethoxy, chlorine, fluorine
R² represents hydrogen,
R³ represents hydrogen, fluorine, chlorine, methyl,
R⁴ represents hydrogen or methyl,
R⁵ represents methyl, ethyl, trifluoromethyl or hydrogen,
Het is pyridyl or pyridazinyl which are optionally substituted by fluorine, chlorine, methyl, NO₂, methoxy, methylmercapto,
X stands for O,
Y stands for O,
Z represents O, CH₂ or -C (CH₃) ₂-,
m represents 1,
n stands for 1.

The following connections are specifically mentioned:

Benzoylureas include compounds of the formula VII

in which
R¹ represents halogen,
R² represents hydrogen or halogen,
R³ represents hydrogen, halogen or C _1-4 alkyl,
R⁴ for halogen, 1-5-halo-C _1-4 -alkyl, C _1-4 -alkoxy, 1-5-halo-C _1-4 alkoxy, C₁₄-alkylthio, 1-5-halo-C _-4 - alkylthio, phenoxy or pyridyloxy which may optionally be substituted by halogen, C _1-4 -alkyl, 1-5-halo-C _1-4 -alkyl, C _1-4 -alkoxy, 1-5-halo-C- _{1- 4} alkoxy, C _1-4 alkylthio, 1-5 haloC _1-4 alkylthio.

In particular, the following should be mentioned:

The triazines include compounds of the formula (VIII)

wherein
R₁ represents cyclopropyl or isopropyl;
R₂ is hydrogen halo, C₁-C₁₂ alkylcarbonyl, cyclopropylcarbonyl, C₁-C₁₂ alkylcarbamoyl, C₁-C₁₂ alkylthiocarbamoyl or C₂-C₆ alkenylcarbamoyl; and
R₃ is hydrogen, C₁-C₁₂-alkyl, cyclopropyl, C₂-C₆-alkenyl, C₁-C₁₂-alkyl carbonyl, cyclopropylcarbonyl, C₁-C₁₂-alkylcarbamoyl, C₁-C₁₂-alkylthio carbamoyl or C₂-C₆-alkenylcarbamoyl and their acid addition salts which are non-toxic to warm-blooded animals.

In particular, the following should be mentioned:

The arthropodicidal active ingredients with the comnon should be particularly emphasized names Propoxur, Cyfluthrin, Flumethrin, Pyriproxyfen, Methoprene, Diazinon, Amitraz, fenthion, imidacloprid, Ti 435, AKD 1022, Ti 304, triflumuron, Ivermectin, avermectin.

The active substances are in the agents in concentrations of 0.1 to 20% by weight before, preferably between 1 to 10 wt .-%.

The agents according to the invention have considerable practical advantages. Your Effect on pests is immediate, d. H. the consumer sees that The control measure is carried out directly.

The agents according to the invention sometimes show considerably better tolerability compared to the use of the individual active ingredients.  

The compositions according to the invention are suitable for controlling animal pests, preferably arthropods, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:
From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda z. B. Blaniulus guttulatus.

From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerella immaculata.

From the order of the Thysanura z. B. Lepisma saccharina.

From the order of the Collembola z. B. Onychiurus armatus.

From the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schi stocerca gregaria.

From the order of the Dermaptera z. B. Auricular Forficula.

From the order of the Isoptera z. B. Reticulitermes spp.

From the order of the Anoplura z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.

From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincti cep s, Lecanium corni, S ai sseti a oleae, Laodelphax stri atellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.

From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella  maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mell onella, Tineola bisselliella, Tinea pelli onella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera z. B. 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, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma 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 solstitialis, Costelytra zeal andica.

From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.

From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.  

With favorable warm-blooded toxicity, the agents are suitable for combating animal pests such as arthropods, preferably insects, arachnids, the in animal husbandry and animal breeding in utility, breeding, zoo, laboratory, experimental and Hobby animals occur. You are against all or individual developments stages of development of the pests and against resistant and normally sensitive types of Pests effective.

The pests include:
From the order of the Anoplura z. B. Haematopinus spp., Linognathus spp., Soleno potes spp., Pediculus spp., Pthirus spp .;
from the order of the Mallophaga z. B. Trimenopon spp., Menopon spp., Eomenacanthus spp., Menacanthus spp., Trichodectes spp., Felicola spp., Damalinea spp., Bobiola spp .;
from the order of the Diptera z. B. Chrysops spp., Tabanus spp., Musca spp., Hydrotaea spp., Muscina spp. <Haematobosca spp., Haematobia spp., Stomoxys spp., Pannia spp., Glossina spp., Lucilia spp., Calliphora spp., Also Meromyia spp., Cardylobia spp., Cochiomyia spp., Chrysomyia spp., Sarcophaga spp., Wohlfartia spp., Gaserophilus spp., Oesteromyia spp., Oedemagena sp., Hypoderma spp., Oestrus spp., Rhinoestrh spp., Mpp ., Hippobosca spp.

From the order of the Siphonaptera z. B. Ctenocephalides spp., Echidnophaga spp., Ceratophyllus spp.

From the order of the metastigmata z. B. Hyalomma spp., Rhipicephalus spp., Boophilus spp., Ambyomma spp., Haemophysalis spp., Dermacentor spp., Ixodes spp., Argas spp., Ornithodorus spp., Otobius spp .;
from the order of the mesastigmata z. B. Dermanyssus spp., Ornithonyssus spp., Pneumonyssus spp.

From the order of the prostigmata z. B. Cheyletiella spp., Psorergates spp., Myobia spp., Demdex spp., Neotrombicula spp .;
Domestic and farm animals include mammals such as. B. cattle, sheep, goats, horses, pigs, dogs, cats, camels, water buffalos, donkeys, rabbits, fallow deer, reindeer, fur animals such as. B. mink, chinchilla, raccoon, birds such. B. chickens, turkeys, pheasants, geese, ducks.

Laboratory and experimental animals include e.g. B. mice, rats, guinea pigs, Golden hamster, dogs and cats.

The hobby animals include z. B. Dogs and cats.

The agents according to the invention can also be used in closed rooms such as Use apartments, halls or similar. They are particularly suitable for combating animal pests and nuisances that occur in the household.

Flies, mosquitoes, wasps, ants, cockroaches, Silverfish.

The agents according to the invention are used directly or in the form of animals of suitable preparations dermally or by treating their environment.

The dermal application happens for. B. in the form of bathing, diving (dipping), Spraying (spraying), pouring (pour-on or spot-on), washing, shampoo rens, watering, powdering.

Suitable preparations are:
Solutions or concentrates for administration after dilution, solutions for use on the skin, infusion formulations, gels;
Emulsions and suspensions for dermal use and semi-solid preparations;
Formulations in which the active ingredients are processed in an ointment base or in an oil in water or water in oil emulsion base;
Solid preparations such as powder or dusts, also through microencapsulation of the liquid ingredients.

In addition to being used on animals, these preparations can also be used in the household, use in hygiene or agriculture.

Solutions for use on the skin are dripped on, spread on, rubbed in, sprayed on, sprayed on or by diving (dipping), bathing or Wash applied.

The solutions are prepared by the active ingredients in the cycl. Silicones and / or suitable solvents and any additives such as solutions Mediators, acids, bases, buffer salts, antioxidants, preservatives added be added.

The following may be mentioned as solvents: Physiologically compatible solvents such as Water, alcohols such as ethanol, butanol, benzyl alcohol, glycerin, hydrocarbon substances, propylene glycol, polyethylene glycols, N-methyl-pyrrolidone, and mixtures the same.

The active ingredients can, if appropriate, also be physiologically tolerated dissolve vegetable or synthetic oils.

The following may be mentioned as solubilizers: solvents which dissolve the Promote active ingredient in the main solvent or prevent its precipitation. Examples are polyvinyl pyrrolidone, polyoxyethylated castor oil, polyoxy ethylated sorbitan esters.

Preservatives are: benzyl alcohol, trichlorobutanol, p-hydroxybenzoe acid ester, n-butanol.

It may be advantageous to use thickeners in the preparation of the solutions inflict. Thickeners are: Inorganic thickeners such as Bentonite, colloidal silica, aluminum monostearate, organic Verdic agents such as cellulose derivatives, polyvinyl alcohols and their copolymers, Acrylates and metacrylates.  

Gels that are applied or spread on the skin are made by using solutions prepared as described above with so much Thickeners are added that a clear mass with ointment-like Consistency arises. The thickeners specified above are used Thickeners used.

Pour-on formulations are poured onto limited areas of the skin or sprayed on, the active ingredients being distributed on the surface of the body.

Pour-on formulations are made by combining the active ingredients in suitable Skin-compatible solvents or solvent mixtures dissolved, suspended or be emulsified. If necessary, other auxiliaries such as dyes, Antioxidants, light stabilizers, adhesives added.

The following may be mentioned as solvents: water, alkanols, glycols, polyethylene glycols, Polypropylene glycols, glycerin, aromatic alcohols such as benzyl alcohol, phenyl ethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ether such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, ketones such as acetone, methyl ethyl ketone, aromatic and / or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, Dimethylacetamide, N-methylpyrrolidone, 2-dimethyl-4-oxy-methylene-1,3-dioxole.

Dyes are all dyes approved for use on animals that are dissolved or may be suspended.

Excipients are also spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils, fatty acid esters, triglycerides, fatty alcohols.

Antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbin acid, butylated hydroxytoluene, butylated hydroxyanisole, tocopherol.

Light stabilizers are e.g. B. substances from the class of benzophenones or Novantisol acid.  

Adhesives are e.g. B. cellulose derivatives, starch derivatives, polyacrylates, natural Polymers such as alginates, gelatin.

Emulsions are either water in oil or oil in water.

They are made by placing the active ingredients in either the hydrophobic or dissolves in the hydrophilic phase and more suitable with the help Emulsifiers and optionally other auxiliaries such as dyes, resorption promotional substances, preservatives, antioxidants, light stabilizers, viscosi substances increasing the homogeneity with the solvent of the other phase.

The following may be mentioned as hydrophobic phase (oils): paraffin oils, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic / capric acid bigylceride, triglyceride mixture with vegetable fatty acids of chain length C _8-12 or other specially selected natural fatty acids, partial glyceride mixtures saturated or unsaturated, possibly also hydroxyl-containing fatty acids, mono- and diglycerides of C₈ / C₁₀ fatty acids.

Fatty acid esters such as ethyl stearate, di-n-butyryl adipate, lauric acid hexyl ester, dipro pylene glycol pelargonate, ester of a branched fatty acid with medium chain length saturated fatty alcohols of chain length C₁₆-C₁₈, isopropyl myristate, isopropyl palmitate, caprylic / capric acid ester of saturated fatty alcohols of chain length C₁₂-C₁₈, isopropyl stearate, oleic acid oleyl ester, oleic acid decyl ester, ethyl oleate, milk Acid ethyl ester, waxy fatty acid esters such as dibutyl phthalate, adipic acid diiso propyl ester, the latter related ester mixtures u. a. Fatty alcohols such as Isotri decyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol.

Fatty acids such as B. oleic acid and its mixtures.

The following can be mentioned as the hydrophilic phase:
Water, alcohols such as B. propylene glycol, glycerin, sorbitol and their mixtures.

The following may be mentioned as emulsifiers: nonionic surfactants, e.g. B. polyoxyethylated castor oil, polyoxyethylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether;
ampholytic surfactants such as di-Na-N-lauryl-β-iminodipropionate or lecithin;
anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono / dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt;
cationic surfactants such as cetyltrimethylammonium chloride.

The following may be mentioned as further auxiliaries: viscosity-increasing agents and the emulsion stabilizing substances such as carboxymethyl cellulose, methyl cellulose and others Cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, Polyvinyl pyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and Maleic anhydride, polyethylene glycols, waxes, colloidal silica or Mixtures of the listed substances.

Suspensions are made by placing the active ingredients in a carrier liquid if necessary with the addition of other auxiliaries such as wetting agents, colors substances, absorption-promoting substances, preservatives, antioxidants Sunscreen suspended.

Carrier liquids are all homogeneous solvents and solutions called middle mixtures.

As surfactants (dispersants) are the surfactants specified above called.

Further additives mentioned are those mentioned above.

Semi-solid preparations for dermal administration differ from those Suspensions and emulsions described above only by their higher Viscosity.

To prepare solid preparations, the active ingredients are mixed with suitable ones Carriers optionally mixed with the addition of auxiliaries and into the brought the desired shape.  

All physiologically compatible solid inert substances may be mentioned as carriers. All of these serve inorganic and organic substances. Inorganic substances are e.g. B. table salt, carbonates such as calcium carbonate, hydrogen carbonates, aluminum oxides, silicas, clays, precipitated or colloidal silicon dioxide, Phosphates.

Excipients are preservatives, antioxidants, dyes that are already on have been listed above.

Other suitable auxiliaries are lubricants and lubricants such as. B. Magnesium stearate, stearic acid, talc, B entonite.

Ready-to-use preparations contain the active ingredients in concentrations of 1 ppm-20 weight percent, preferably from 0.01-10 weight percent.

Preparations that are diluted before use contain the active ingredients in Concentrations of 0.5-90 percent by weight, preferably from 1 to 50 Percent by weight.

In general, it has been found advantageous to use amounts from about 0.5 to about 50 mg, preferably 1 to 20 mg, of active ingredient per kg of body weight per day for education effective results.

Agents according to the invention in which the arthropodicide is particularly preferred Active ingredient is present in the cyclic polysiloxane dissolved.

Claims (3)

1. Pesticides based on cyclic polysiloxanes of the formula (I) in which
R represents identical or different radicals from the group methyl, ethyl, propyl,
n stands for integers from 3 to 6,
in a mixture with arthropodicidal agents. 2. Composition according to claim 1, characterized in that it is a component of the formula (I) contain compounds in which the index n = 5. 3. Composition according to claim 1, characterized in that the components of formula (I) with the indices 4 and 5 in the weight ratio
n = 4 85 to 50% by weight
n = 5 15 to 50% by weight
available.