CA2146822A1

CA2146822A1 - Insecticidal mixtures

Info

Publication number: CA2146822A1
Application number: CA002146822A
Authority: CA
Inventors: Hans-Jurgen Schnorbach
Original assignee: Individual
Current assignee: Bayer AG
Priority date: 1994-04-14
Filing date: 1995-04-11
Publication date: 1995-10-15
Also published as: DE4412834A1; CN1112392A; EP0677247A1; BR9501569A; KR950030812A; ZA953065B; JPH07285818A

Abstract

Insecticidal mixtures Abstract The present invention relates to insecticidal mixtures of Bacillus spp. preparations, Bacillus spp. endotoxin containing preparations as well as transkonjugates and recombinant Bacillus spp. preparations and agonists or antagonists of the nicotinergic acetylcholine receptors of insects, and to their use.

Description

2i~68~2 The ~re~ent invention relates to insecticiaal mixtures of Bacillus 8~. pre~aration3 ana a~oni~ts or antagonists of the nicotinergic acetylcholine rece~tors of insects, and to their use.

Baeillus thuringiensis pre~arations and their use a~
inseetici.des are known (for example from (Chemical Abstract~ references) CA 71/122 392; CA 80/129 289 ~;
CA 86/1701 d; CA 118/100 539 f; as well a8 DE-OS (German Published S~ecification) 2 146 165; EP-OS (Euro~ean Published S~eeification) 63 949; EP-OS (Euro~ean Published 8~ecification) 93 062; EP-OS (Euro~ean Published S~ecifie~tion) 142 92~; EP-PS (Euro~ean Patent S~ecification) 153 166; PCT-08 (PCT Published 8~eeifiea-tion) WO 86/01 536; EP-08 (Euro~ean Published S~eeifiea-tion) 178 151; EP-08 (Euro~ean Published S~ecifieation) 200 344; BP-Og (Euro~ean Published S~ecification) 216 481; DB-OS (German Published Specifieation) 3 541 893;
PCT-Og (PCT Published 8pecifieAtion) WO 88/06 631; EP-OS
(Euro~ean Published S~ecification) 308 199 PCT-OS (PCT
Publishea 8~ecification) WO 88 08877; PCT-OS (PCT Pub-lishea 8~ecification) WO 91/09 133; EP-OS (Euro~ean Published S~eeificat~on) 500 311 x.).

A~onists or anta~onist~ of the nicotiner~ic acetyleholine reee~tors of inseets are known, for example from the follow~n~ ~ublicAtions~

Le A 30 271 .; , .:

~-` 21~822 Euro~ean Of~enlegung~schrift (European Publi~hed S~ecification) 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 Offenlegung~schrift (German Published S~ecification) Nos. 3 639 877, 3 712 307;
Ja~anese Offenle~un~schrift (Ja~ane~e Published S~ecification) Nos. 03 220 176, 02 207 083, 63 307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255 072;
US Patent Nos. 5 034 524, 4 948 798, 4 918 086, 5 039 686, 5 034 404; PCT A~lication NOB. WO 91/17 659, 91/4965; French Ap~lication No. 2 611 114; Brazilian A~lication No. 88 03 621.

Reference i8 hereby made ex~res~ly to the methods, ~roce~es, formulae ana definitions aescribed in these ~ublications and to the indiviaual ~re~arations and com~ounas described therein.

Nixtures of Bacillus thuringiensis pre~arations with insect~cide~ of various classe~ of active compouna are known (Chemical Abstracts reference CA 117/247 152 n;
113/226 446 ~; 107/54 201 n; JP Patent 1 576 352; DE-OS
(German Published S~e¢ification) 2 250 085).

However, mixtures of B~cillus S~. ~re~arations with agoniffts or antagonists of the nicotinergic acetylcholine rece~tors of insects have not been aisclosed to date.

Le A 30 271 - 2 - -The l?resent invention relates to:

1. In~3ecticidal con~ositionSt, characterize~ in that they contain a mixture o$ Bacillus 81?~-pre~arations, Bacillus 8~. enaotoxin containing pre~arations as well a~ transkonjugate~ and recombinant BRcillus 8~?~. ~rel?aration~ ana agonists or antagonists of the nicotinergic acetylcholine rece~tors of insects.

2. The use o$ the insecticiaal activity of Bacillus 81?~- ~re~arations, Bacillus 81?~- endotoxin containing ~re~ar~tions as well aE~ transkonjuslates ana reC~mbin nt B~cillus 8~ pre~arations, characterizea in that a5ronist~ or antagonists of the nicotinerSIic acetylcholine receptors in insects are lS aadea to them.

3. The use of mixtures of Bacillus El~. ~re~arations, Bacillus spp. enaotoxin containing ~re~aration~ a~
well as transkonju51ates and recoml~inant Bacillus 8~?~. ~reparation8 ana aSroniElts or antagonists of the niCotinerSric acetylcholine roce~tors in insects for combatin5r insects.

4. A method of comb~ttinçr insects, characterizea in that a mixture of Bacillus 8~. ~re~arations, Bacillus 8~. enaotoxin containin5J~?re~arations as well a8 transkonju5rates and recombinant Bacillus s~p. preparations ana aSIonists or antagonists of the nicotinerSric acetylcholine rece~tors in insects are allowea to act on insec:ts ana/or their environment.
:: : :-:

5. A ~roce~s for the ~reparation of in~ecticid l co~ositions, characterized in that Bacillu~ 8~.
~re~arations, Bacillus s~D. enaotoxin containin~
~re~arations as well as tranEIkonjus~ates and rec~mbinant Bacillus 8~. ~reparations ana a5~onists or ~taSIonists of the nicotiner~Jic acetylcholine rece~tors of insects are mixed with extenaers ana/or ailuents and surfactants.

..

. .
Le A 30 271 - 3 ~

. . . : : : . . :. , :: .. :

21~6822 It was sur~rising that the activity of Bacillus 8~.
~reparations could be increased by combining th~m with agoni~ts or antagonists of the nicotinergic acetylcholine rece~tors of insects. Bacillus ~p~. ~re~arations are ~referably sacillu~ thuringiensis ~repArations, their enaotoxins and recombinantly produced strains.

Agonists or anta~onists of the nicotinergic acetylcholine receptors of insects come in some cases under the term nitromethylenes and compounds related thereto.

These com~ounde can ~referably be represented by the general formula (I) /
C
Il , X--E
in which ~-: ' ', R represents hydro~en, o~tionally substituted radicals of the ~rou~ consistin~ of acyl, alkyl, aryl, aralkyl, heteroaryl or heteroarylalkyl;

A re~resents a monofunctional ~rou~ from the series consistin~ of hydro~en, acyl, alkyl, aryl, or a bifunctional grou~, linked to the radical Z;

E re~resents an electron-attracting radical;

~:

Le A 30 271 - 4 -~ 21~6~22 X repre~ent~ the radicals -CH= or 'N-, it being possible for the radical -CH= to be linked to the radical Z instead of an ~ atom;
Z represents a monofunctional group from the ~eries consisting of alkyl, -0-R, -S-R or ,R : :~
N~
R -or a bifunctional group, linked to the radical A or the radical X.

Partiaularly preferred compounds of the formula I are those in which the radicals have the following meaning~

10 R represents hydrogen and optionally substituted radicals from the series consisting of acyl, alkyl, -aryl, aralkyl, heteroaryl and heteroarylalkyl.

Acyl radicals which may be mentioned are formyl, alkylcarbonyl, arylcarbonyl, alkylsulphonyl, aryl~
sulphonyl, (alkyl-)-(aryl-)phosphoryl, each of which can, in turn, be substituted.

Alkyl radicals which may be mentioned are Cl10-alkyl, in particular Cl4-alkyl radicals, specifically, methyl, ethyl, i-propyl and sec- or t-butyl, each of which can, in turn, be substituted.

Aryl radicals which may be mentioned are phenyl and .'.:,`:. :-'~.
'- '"''''''''"' Le A 30 271 - 5 -',.~ . "".'.,.:.

2~822 naphthyl, in particular phenyl.

Aralkyl radicals which may be mentioned are phenyl-methyl and phenylethyl.

Heteroaryl radicals which may be mentioned are heteroaryl radicals having up to 10 ring atoms and N, O or S, in particular N, as hetero atoms.
Thiophenyl, furyl, thiazolyl, imidazolyl, pyridyl and benzthiazolyl may be mentioned individually.

Heteroarylalkyl radicals which may be mentioned are heteroarylmethyl and heteroarylethyl radicals having up to 6 ring atoms and N, O or S, in particular N, as hetero atoms.

The following substituents may be mentioned by way of example and as being preferred:
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 having 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 having preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methylthio, ethylthio, n- and i-propylthio and n-, i- and t-butylthio; halogenoalkyl having 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 being ::
.. .

' .:"~
Le A 30 271 - 6 ~

21~682~

identical or different and preferably fluorine, chlorine or bromine, in particular fluorine, ~uch as trifluoromethyl; hydroxyl; halogen, preferably fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromi~e; cyano;
ntiro; amino; monoalkyl- and dialkylamino having preferably 1 to 4, in particular 1 or 2, carbon atoms per alkyl group, such a~ methylamino, methyl-ethyl-amino, n- and i-propylamino and methyl~
n-butylamino; carboxyl; carbalkoxy having preferably 2 to 4, in particular 2 or 3, carbon atoms, such as carbomethyoxy and carboethoxy; sulpho (-S03H);
alkylsulphonyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl-sulphonyl and ethylsulphonyl; arylsulphonyl having preferably 6 or 10 aryl carbon atoms, such as phenylsulphonyl, and also heteroarylamino and heteroarylalkylamino, such as chloropyridylamino and chloropyridyl~ethylamino.

20 A particularly preferably represents hydrogen and optionally substituted radicals from the series consisting of acyl, alkyl, aryl, all of which preferably have the meanings given in the case of R.
A furthermore represents a bifunctional group.
Mention may be made of optionally substituted alkylene having 1-4, in particular 1-2, C atoms, suitable substituents being the substituents enumerated further above, it being possible for the alkylene groups to be interrupted by hetero atoms ` "'~'' ' .''','"""'"-,"`"".'-'.'''' Le A 30 271 - 7 - -from the ~erie~ consisting of N, O and S.

A and Z together with the atoms to which they are bonded can form a ~aturated or un6aturated heterocyclic ring. The heterocyclic ring can contain one or two further identical or different hetero atoms and~or hetero group~. Hetero atoms are preferably oxygen, sulphur or nitrogen, and hetero group~ N-alkyl, alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms. Alkyl radicals which may be mentioned are methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. The heterocyclic ring contains 5 to 7, preferably 5 or 6, ring members.

Examples which may be mentioned of the heterocyclic ring are pyrrolidine, piperidine, piperazin~, hexa-methyleneimine, hexahydro-1,3,5-triazine and mor~
pholine, each of which can optionally be substituted, preferably by methyl.

E represents an electron-attracting radical, par-ticular mention being made of NO~, CN and halogeno-alkylcarbonyl, such as 1,5-halogeno-C,,-carbonyl, in particular COCF3.

X represents -CH- or -N-Z represents optionally substituted radicals alkyl, -OR, -SR or NRR, R and the substituents preferably :-.,'"'~,'-.''':", ' Le A 30 271 - 8 -,;' ,;~ ~ .

--- 2146~2 having the abovementioned meaning.

Z can, in addition to the abovementioned ring, together with the atom to which it i8 bonded and the radical .

in the place of X
form a saturated or unsaturated heterocyclic rinq.
The heterocyclic ring can contain 1 or 2 further identical or different hetero atoms and/or hetero groups. ~etero atoms are preferably oxygen, sulphur -~;
or nitrogen, and heterogroups N-alkyl, the alkyl or N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms. Alkyl radicals which may be mentioned are methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. The heterocyclic ring contains 5 to 7, preferably 5 or 6, ring members.
~ :' Examples of the heterocylic ring which may be mentioned are pyrrolidine, piperidine, piperazine, hexamethylene~;ne, morpholine and N-methyl- -~
piperazine.

Compounds which may be mentioned as compounds which can very particularly preferably be used according to the -~
invention are those of the general formulae (II) and (III): -. ~ . .,:
: ......

:, . .
,,.. ~, Le A 30 271 - 9 - ;

~ ;: ,' .. .. -- , .: . . .. -: . :- , .
~ - -- 21~6822 ~(C~)n N~ /~ (Il)~
N C
X--E

gb~ ~ :
S~\(C~)n 1~
li : :
X-E
in which n represents 1 or 2, subst. represent~ one of the abovementioned substi~
tuents, in particular halogen, very particularly chlorine, -~

A, Z, X and ~ have the abovementioned meanings, ,. . .
The following compounds may be mentioned individually~

a~CH~--N~NH C1~3CH~_N~NH~

NO2 N NO2 ; `
~', -".' ' :' .' ' ,~ ~ ','- ' .' '. .
. - - ~ ~ ., ,.,: ::

- - ~ ;. :, . .:
Le A 30 271 - 10 -21~822 ~CH3 CI~CI-12 N~S J~CH

O ' ~
Cl~3CH2 N~7 H--N~¦¦~OC2H
N_CN N~

Cl~3CH2 N~NH C1~3CH2 NyNHCH3 ~CN N--NO2 Cl~3CH2--N~S Cl~3CH2--N~,S
N
CN N--NO2 :~:

''`'"'~' ~'`' . .` ..~'. .
-~,,,:, ~`" :, :~ ~ : .'., , Le A 3 0 2 71 ~ , . , - ~ ~

~` 214S~22 C1~3 CH C1~
~NO2 CH--NS)2 C1~3N~NHC1~3CH2-- N~N(CH3)2 fH3 : - ~
C1~3 I H3 CH2 N N--CH

N--CN N

C1~3CH, N--11--NHCH~ C1~3CH,--N~ ~CH, , ~, ',,~'.',~,...

"'''-Le A 30 271 - 12 - ::

- 21~822 S`~HNH S~CH2 N~,NH

--S~N~NH ~S ~CH,_N~NH

N2 "
. .:

The mixtures according to the invention are suitable for combating animal pests, preferably axthropod~ and nematode~ in particular insects and arachnids, encount~red in agriculture, in forestry, in the protection of stored produ¢ts 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 abovementioned pests include~

From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus Le A 30 271 - 13 -21~B82~

carpophagu~ and scutigera 8pec.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiuru~
armatus.
... ~.~.. .
From the order of the Orthoptera, for example, Blatta -orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula aurlcu arla. ~ ~,.,.-.

From the order of the I~optera, for example, Reticulitermes spp..

From the order of the Anoplura, for example, Pedculus humanus corporis, Haematopinu~ spp. and Linognathus spp..

From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp..

From the order of the Thysanoptera, for example, Hercinothrip~ femoralis and Thrip~ tabaci.

From the order of the Heteroptera, for example, -: ' .'~' '' Le A 30 271 - 14 - ~ -:, .

t , ,~
.~-- 2~46~22 Eurygaster 8~., Dysdercus intermedius, Piesma ~uadrata, Cimex lectularius, Rhodnius ~rolixus and Triatoma sp~..

From the order of the Homo~tera, for ex~mple, Phylloxera vastatrix, Pem~higus s~p., Aleurode~ brassicae, Bemisia tabaci, Trialeurodes va~orariorum, A~his ~os~y~ii, Brevicoryne brassicae, Cry~tomyzus ribi~, A~his fabae, Doralis ~omi, Eriosoma laniyerum, Hyalo~terus arundinis, ~acrosi~hum avenae, Myzus 8~., Phorodon humuli, Rho~alosi~hum ~adi, Empoasca 8~., Eu~celis bilobatuo, N~hotettix cinctice~s, Lecanium corni, Saissetia oleae, Laodel~hax striatellus, Nila~arvata lu~en~, Aonidiella aurantii, As~idiotus hederae, Pseudococcus 8~. and Psylla ~p..
~ ",: ~.',' Fro~ the order of the Le~ido~tera, for example, Pectino~hora ~ossypiella, Bu~alus ~iniarius, Cheimatobia brumata, Lithocolletis blancardella, Hy~onomeuta padella, Plutella maculipennis, malacosoma neustria, Eu~roctis chrysorrhooa, Lymantria 8~., Bucculatrix thurberiella, Phyllocn~stis citrella, A~rotis 8~., S~odo~tera exi~ua, Mamestra brassicae, Panolis flammea, Prodenia litura, 8~odo~tera 8~., Tricho~lusia ni, Carpoca~sa ~omonella, Pieris 8~., Chilo 8~., Pyrausta nubilalis, E~hestia kuehniella, Galleria mellonella, T~neola bisselliella, Tinea ~ellionella, Hofmannophila ~seudos~retella, Cacoecia ~odana, Ca~ua reticulana, Choristoneura fumiferana, Clysia ambi~uella, Homona ma~nanima and Tortrix viridana and Heliothis 8~
From the order of the Coleo~tera, for example, Anobium Le A 30 271 - 15 -,, . - , . : :

b .~ ~' . . , . - .

2~-6822 punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides obtectus, HylotrupeE bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., P~ylliodes chrysocephala, ~pilachna varivesti~, Atomaria 8pp ., Oryzaephilus surinamensis, Anthonomus pp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, ~ypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus ~pp., ~eligethes aeneus, Ptinus spp., Niptu~
hololeucus, Gibbium psylloides, Tribolium ~pp., Tenebrio molitor, Agriotes Bpp-, Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., ~oplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp..

From the order of the Diptera, for example, Aedes 8pp. ~
Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia 8pp- ~ Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobo~ca spp., Stomoxys spp., Oestrus spp., ~ypoderma spp., Tanaus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.

From the order of the Siphonaptera, for example, ~' Le A 30 271 - 16 -. ~ .

, ,,-,, . . . :

.

21~682~

Xenopsylla cheopis and Ceratophyllus spp..

From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactan~
'~
Insects which may be mentioned, in particular, are chewing biting insects, for example from the order3 Coleoptera or Lepidoptera.
,:
The mixtures according to the invention in their respec~
tive physical and/or chemical properties can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for seed, and additionally in formulation~ used with burning equipment, such as fumigating cartridge~, fumigating cans, fumigating coils and the like, as well as ULV cold mist and warm mist formulations.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that i8, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is 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 solvents, there are suitable in the main:

Le A 30 271 - 17 -21~6822 aromatic~, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic 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, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; as solid carriers for granules there are suitable: for example 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 sawdu~t, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether~, alkylsulphonates, alkyl ' ': '' ~ ' Le A 30 271 - 18 -: : :
21~82~

sulphates, aryl~ulphonate~ as well as albumen hydrolysis -~
product~; as di~persing agent~ there are ~uitable: for example lignin-~ulphite wa~te liquors and methylcellulose. ~:
;, ~ ' Adhesive~ such as carboxy-methylcellulose and natural and :~ :
synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipid~, such : ~
as cephalins and lecithins, and synthetic phospholipids, ~;
can be used in the formulations. Other additives can be : :
mineral and vegetable oil~

It is possible to use colourants such as inorganic pigments, for example iron oxide, titanium oxide and ~;
Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound mixture, preferably between 0.5 and 90 %.
:' The mixtures according to the invention can additionally contain other active compounds, such as in~ecticides, ~ ;.
attractants, ~terilizing agents, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. -The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, Le A 30 271 - 19 :
:

~i'`'~'':'`, . ' ' : - ' - ~ .

phenylurea~ and the like.

The mixtures accoraing to the invention can furthermore be ~re~ent in their commercially available formulAtions ana in the use forms, pre~ared from the~e formulations, -as a mixture with synergistic agent~. Syner~istic agents are com~ounas which increase the action of the active com~ounds, without it being necessary for the synergistic ~
a~ent aaaed to be active itself. ~- -The active compound content of the use forms ~re~ared from the commercially available formulations can vary - -within wide limits. The active com~ouna concentration of ~
agon~its or antagonists of the nicotinergic acetyl- --chlorine rece~tors of insects in the use forms can be from 0.0001 to 1 % by wei~ht of active com~ound, ~re- -~
ferably between 0.0016 and 0.1 ~ by weight. The acti~e com~ouna content in the case of ~acillu6 thuringiensi~
~re~arations of the use forms can vary from 102-101~ IU ~er 100 ml, ~referably 10'-107 s~ores/ml IU ~er 100 ml. -~
-~-.:~. :, The com~ounas are em~loyed in a customary manner a~ropriate for the use forms by s~raying, atomizing, dusting, misting or ~ouring.

When used against hygiene ~ests ana ~ests of stored ~roducts, the chemical active compounds are distinguished by an excellent resi~ual action on wooa and clay as well a~ a good stability to alkali on limed substrates. ~

Le A 30 271 - 20 - ~ :

21~6~22 In the exam~le~ which follow, the com~ound of common name imidacloprid (l-(2-chloro-5-~yridinyl-methyl)-2-nitro-iminoimidazolidine) iB e~ployed a~ a representative of an agonist or antagonist of the nicotinergic acetylcholine rece~tors of insects, ana as representative~ of sacillus ~reRaration containing Bacilllus thuringien~is, ~referably the ~trains s.t.var kurstaki, -aizawai, tenebroni~, -israelensis.

Imidaclo~rid was employed in the form of the commercially available ~re~aration ~Confidor.

Co~binations of imidacloprid with a range of concentration~ of Bacillus thuringiensis were tested biologically in laboratory tests in com~arison with the individual c~onents. To be able to determine the interactive effect of the active com~ounds on the ~nsecticidal activity of the combinations, low active com~ound concentrations were selectea which are in ~he ran~e of the threshold level and which, by them~elves, do not result in a full activity. The te~t animals usea were Phaedon cochloariae larvae and larvae of S~odo~tera fon~i~erda, Plutellaxylo stella, Heliothis armigera. The larvae were in the L2 stage. Savoy cabbage leaves (Brassica oleracea var. Sabauda) or leaves of sojbean ~lants were dip~ed into the test solutions and infected with the ~est after they had dried. The evaluation was carried out 3 and 7 days after the infection. Not oaly the insecticidal activity (mortality), but also the degree of ~rotection (feeding damage) were a~ses~ed. Eaoh of the ex~eriments were carried out in two reDlications.

Le A 30 271 - 21 --- -. - . .

!:' ` . . . ~ `. . . :

~ . ~ . . ' . .. , ' . . . .

~ 2146~22 - ~

Tabulated te~t re~ults Exam~le 1 :~
Phaedon cochleariae Combination of Imiaaclo~rid / Bacillus thurin~iensi~ ~r.
kurstaki (~Di~el 2 x, Fa.Abbott) ¦Pre~aration/ Effecti~eness ~:
combination after 3 days ¦
_ Mortality (%) ¦¦
midaclo~rid (0.008 ~O) 2 ¦
qDi~el 2x (5.0 x 105 2 ¦
IU/100 ml) l : --:~
qDi~el 2x (2.5 x ¦
lO~IU/100 ml) IU/100 ml)Imidaclo~rid 19 (0.008%) and Di~el 2x (5 x l lOsIU/100 ml) l .., Imidaclo~rid (0.008%) 65 ¦ ¦~

~Di~el 2x (2.5 x l -10CIU/lOO ml) l ~:
Control 0 ¦

~,''~'..
.,`;

Le A 30 271 - 22 - ~ ~

~i,~ ` .. ~ .: ' . ' - :

- 21~68~ :

Example 2: Phaedon cochleariae and combination of ~, Imidacloprid / Bacil lus thuringiensis var. aizawai (RXentari, Fa. Abbott) . _ Ef fectiveness af ter Preparation / Ccxrbination 3 davs ,, (%) ~midacloprid (0,0008 %) 2 B. t. var. aizawai O
(2,0 x lOE6 I.U./100 ml) B. t. var. aizawai _ __ (1,0 x lOE7 I.U./100 ml) Imidacloprid (0,0008 %) ~nd B. t. var. 20 aizawa; (2,0 x lOE6 I.U./100 ml) Imidacloprid (0,0008 %) ~nd B. t. var. 50 aizawai (1,0 x lOE7 I.U./100 ml) L contrQl o _ Example 3: Phaedon cochlearieae and combination of I i~acloPrid- l Baçillys ~hur1~iensis va~,,,tenebrionis Novodur 2 %, Fa . Neudorf f ) . ... .
~r,eparation / CanbinationEffectiveness after ~ :' Imidacloprid (0,0008 %) 3 Imidacloprid (0,004 %) 40 - -~-B. t. var. tenebrionis (0 00012 %) , , ,.:
B. t. var. tenebrionis 23 - ~ ' ' (0,0006 %) ~, Imidacloprid (0,0008 /0) and B. t. var. 33 tenebrionis (0,00012 %) Imidacloprid (0,0008 %) and B. t. var. 47 tenebrionis (0,0006 %) In~idacloprid (0,004 %) and B. t. var. 100 t_ebrionis ~0,00012 %) Imidacloprid (0,004 %) and B. t. var. 100 tenebrionis (0,0006 %) , Control O

Le A 30 271 - 23 -.`:` ' ' ~' - . ' :
, ~ ` ' ': . . : ' ' :,, , :

-^`` 2146822 Example ~: Spodoptera frugiperda and combination of I~idacloprid / Bacillus thuringiensis var. tenebrionis ( Novodor 2 %. Fa. Neudorff) Preparation / combination ¦Effectiveness after Imidacloprid (0,004 %) 3 day (/) I -B. t. var. tenebrionis 0 l (0,0006 %) l B. t. var. ténebrionis (0,003 %) . ~.
Imidacloprid (0,004 /0) a.ld B. t. var. 1 80 ;
tenebrionis (0,0006 %) ~
Imidaclopnd (0,004 %) ~nd B. t. vllr. 90 : . :
tenebrionis (0,003 %) I .:
Control _ _ _ 7 Example 5: Spodoptera frugiperda and combination of ~ ~
IRidacloprid / Bacillus thuringiensis var. kurstaki ` ~ `
( Dipel 2 x , Fa.Abbott) ~;- ;
, _ ......... ,_ :
~reparation / ~ination 3 days (0/ess afte~
Imidacioprid(0,0008 %) 7 _ ~
B. t. var. kurstaki 18 -(2,0 x lOE6 I.U./I00 ml~ ~
Imidacloprid (0,0008 %),Lmd B. t. var. 51 I ~ ~:
kurstaki (2,0 x lOE6 I.U./100 ml) Control 0 1 . ... ,_ , - :.. ~ . . .

:', ~ ' :','', Le A 30 271 - 24 ~

; ~:,. . .

Claims

1. Insecticidal compositions, characterized in that they contain a mixture of Bacillus spp.
preparations, Bacillus spp. endotoxin containing preparations as well as transkonjugates and recombinant Bacillus spp. preparations and agonists or antagonists of the nicotinergic acetylcholine receptors of insects.

2. Improvement of the insecticidal activity of Bacillus spp. preparations, Bacillus spp. endotoxin containing preparations as well as transkonjugates and recombinant Bacillus spp. preparations, characterized in that agonists or antagonists of the nicotinergic acetylcholine receptors in insects are added to them.

3. Use of mixtures of Bacillus spp. preparations, Bacillus spp. endotoxin containing preparations as well as transkonjugates and recombinant Bacillus spp. preparations and agonists or antagonists of the nicotinergic acetylcholine receptors in insects for combatting insects.

4. Method of combatting insects, characterized in that a mixture of Bacillus spp. preparations, Bacillus spp. endotoxin containing preparations as well as transkonjugates and recombinant Bacillus spp.
preparations and agonists or antagonists of the nicotinergic acetylcholine receptors in insects are allowed to act on insects and/or their environment.

5. Process for the reparation of insecticidal compositions, characterized in that Bacillus spp.
preparations, Bacillus spp. endotoxin containing preparations as well as transkonjugates and recombinant Bacillus spp. preparations and agonists or antagonists of the nicotinergic acetylcholine receptors of insects are mixed with extenders adn/or diluents and surfactants.