TREA

Active ingredient combination having insecticidal and acaricidal characteristics

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Information

  • Patent Grant
  • 6818670
  • Patent Number
    6,818,670
  • Date Filed
    Friday, April 11, 2003
    21 years ago
  • Date Issued
    Tuesday, November 16, 2004
    20 years ago
Information
Abstract
The invention relates to novel active compound combinations having very good insecticidal and acaricidal properties and containing(a) cyclic ketoenols having the formula in which the groups W, X, Y, Z, A, B, D, and G have the meanings given in the disclosure, and(b) active compounds listed in the disclosure.
Description




The present invention relates to new active compound combinations composed of known cyclic ketoenols on the one hand and of other known insecticidal active compounds on the other hand and which are highly suitable for controlling animal pests such as insects and undesired acarids.




BACKGROUND OF THE INVENTIONS




The fact that certain cyclic ketoenols have insecticidal and acaricidal properties has already been disclosed (EP-A-528 156). While the activity of these substances is good, it leaves something to be desired in some cases when applied at low rates.




Furthermore, the fact that a large number of heterocycles, organotin compounds, benzoylureas and pyrethroids have insecticidal and acaricidal properties has already been disclosed (cf. WO 93-22 297, WO 93-10 083, DE-A 2 641 343, EP-A-347 488, EP-A-210 487, U.S. Pat. No. 3,264,177 and EP-A-234 045). Again, the action of these substances is not always satisfactory when applied at low rates.











DETAILED DESCRIPTION OF THE INVENTION




It has now been found that compounds of the formula (I)











in which




X represents C


1


-C


6


-alkyl, halogen, C


1


-C


6


-alkoxy or C


1


-C


3


-halogenoalkyl,




Y represents hydrogen, C


1


-C


6


-alkyl, halogen, C


1


-C


6


-alkoxy or C


1


-C


3


-halogenoalkyl,




Z represents C


1


-C


6


-alkyl, halogen or C


1


-C


6


-alkoxy,




n represents an integer from 0-3,




A and B are identical or different and represent hydrogen or optionally halogen-substituted straight-chain or branched C


1


-C


12


-alkyl, C


3


-C


8


-alkenyl, C


3


-C


8


-alkinyl, C


1


-C


10


-alkoxy-C


2


-C


8


-alkyl, C


1


-C


8


-polyalkoxy-C


2


-C


8


-alkyl, C


1


-C


10


-alkylthio-C


2


-C


8


-alkyl, cycloalkyl having 3-8 ring atoms which can be interrupted by oxygen and/or sulphur, and phenyl or phenyl-C


1


-C


6


-alkyl, each of which is optionally substituted by halogen, C


1


-C


6


-alkyl, C


1


-C


6


-halogenoalkyl, C


1


-C


6


-alkoxy, C


1


-C


6


-halogenoalkoxy or nitro,




or in which




A and B together with the carbon atom to which they are bonded form a saturated or unsaturated, 3- to 8-membered ring which is optionally interrupted by oxygen and/or sulphur and optionally substituted by halogen, C


1


-C


6


-alkyl, C


1


-C


6


-alkoxy, C


1


-C


4


-halogenoalkyl, C


1


-C


4


-halogenoalkoxy, C


1


-C


4


-alkylthio or optionally substituted phenyl optionally benzo-fused,




G represents hydrogen (a) or the groups











in which




R


1


represents optionally halogen-substituted C


1


-C


20


-alkyl, C


2


-C


20


-alkenyl, C


1


-C


8


-alkoxy-C


2


-C


8


-alkyl, C


1


-C


8


-alkylthio-C


2


-C


8


-alkyl, C


1


-C


8


-polyalkoxy-C


2


-C


8


-alkyl


8


-alkyl or cycloalkyl having 3-8 ring atoms which can be interrupted by oxygen and/or sulphur atoms,




phenyl which is optionally substituted by halogen, nitro, C


1


-C


6


-alkyl, C


1


-C


6


-alkoxy, C


1


-C


6


-halogenoalkyl or C


1


-C


6


-halogenoalkoxy;




phenyl-C


1


-C


6


-alkyl which is optionally substituted by halogen, C


1


-C


6


-alkyl, C


1


-C


6


-alkoxy, C


1


-C


6


-halogenoalkyl or C


1


-C


6


-halogenoalkoxy,




pyridyl, pyrimidyl, thiazolyl and pyrazolyl, each of which is optionally substituted by halogen and/or C


1


-C


6


-alkyl,




phenoxy-C


1


-C


6


-alkyl which is optionally substituted by halogen and/or C


1


-C


6


-alkyl,




R


2


represents optionally halogen-substituted C


1


-C


20


-alkyl, C


2


-C


20


-alkenyl, C


1


-C


8


-alkoxy-C


2


-C


8


-alkyl or C


1


-C


8


-polyalkoxy-C


2


-C


8


-alkyl,




phenyl or benzyl, each of which is optionally substituted by halogen, nitro, C


1


-C


6


-alkyl, C


1


-C


6


-alkoxy or C


1


-C


6


-halogenoalkyl,




R


3


, R


4


and R


5


independently of one another represent optionally halogen-substituted C


1


-C


8


-alkyl, C


1


-C


8


-alkoxy, C


1


-C


8


-alkylamino, di-(C


1


-C


8


)-alkylamino, C


1


-C


8


-alkylthio, C


2


-C


5


-alkenylthio, C


2


-C


5


-alkinylthio or C


3


-C


7


-cycloalkylthio, or represent phenyl, phenoxy or phenylthio, each of which is optionally substituted by halogen, nitro, cyano, C


1


-C


4


-alkoxy, C


1


-C


4


-halogenoalkoxy, C


1


-C


4


-alkylthio, C


1


-C


4


-halogenoalkylthio, C


1


-C


4


-alkyl or C


1


-C


4


-halogeno-alkyl,




R


6


and R


7


independently of one another represent optionally halogen-substituted C


1


-C


20


-alkyl, C


1


-C


20


-alkoxy, C


2


-C


8


-alkenyl or C


1


-C


20


-alkoxy-C


1


-C


20


-alkyl, or represent phenyl which is optionally substituted by halogen, C


1


-C


20


-halogenoalkyl, C


1


-C


20


-alkyl or C


1


-C


20


-alkoxy, or represent benzyl which is optionally substituted by halogen, C


1


-C


20


-alkyl, C


1


-C


20


-halogenoalkyl or C


1


-C


20


-alkoxy, or together represent a C


2


-C


6


-alkylene ring which is optionally interrupted by oxygen,




and



















A)




(thio)phosphates, preferably







1.




azinphos-methyl


























disclosed in U.S. 2 758 115














and/or






2.




chlorpyrifos


























disclosed in U.S. 3 244 586














and/or






3.




diazinon


























disclosed in U.S. 2 754 243














and/or






4.




dimethoate


























disclosed in U.S. 2 494 283














and/or






5.




disulfoton


























disclosed in DE-A-917 668














and/or






6.




ethion


























disclosed in U.S. 2 873 228














and/or






7.




fenitrothion


























disclosed in BE-A-594 669














and/or






8.




fenthion


























disclosed in DE-A-1 116 656














and/or






9.




isoxathion


























disclosed in DE-A-1 567 137














and/or






10.




malathion


























disclosed in U.S. 2 578 562














and/or






11.




methidathion


























disclosed in DE-A-1 645 982














and/or






12.




oxydemeton-methyl


























disclosed in DE-A-947 368














and/or






13.




parathion


























disclosed in DE-A-814 152














and/or






14.




parathion-methyl


























disclosed in DE-A-814 142














and/or






15.




phenthoate


























disclosed in GB-A-834 814














and/or






16.




phorate


























disclosed in U.S. 2 586 655














and/or






17.




phosalone


























disclosed in DE-A-2 431 192














and/or






18.




phosmet


























disclosed in U.S. 2 767 194







and/or






19.




phoxim


























disclosed in DE-A-1 238 902














and/or






20.




pirimiphos-methyl


























disclosed in DE-A-1 445 949














and/or






21.




profenophos


























disclosed in DE-A-2 249 462







and/or






22.




prothiophos


























disclosed in DE-A-2 111 414














and/or






23.




tebupirimphos


























disclosed in DE-A-3 317 824














and/or






24.




triazophos


























disclosed in DE-A-1 299 924














and/or






25.




chlorfenvinphos


























disclosed in U.S.-2 956 073







and/or






26.




dichlorphos


























disclosed in GB-A-775 085














and/or






27.




dicrotophos


























disclosed in BE-A-55 22 84














and/or






28.




mevinphos


























disclosed in U.S.-2 685 552














and/or






29.




monocrotophos


























disclosed in DE-A-1 964 535














and/or






30.




phosphamidon


























disclosed in U.S. 2 908 605














and/or






31.




acephate


























disclosed in DE-A-2 014 027














and/or






32.




methamidophos


























disclosed in U.S.-3 309 266














and/or






33.




trichlorfon


























disclosed in U.S.-2 701 225














and/or






B)




pyrethroids, preferably






34.




acrinathrin



































disclosed in EP-A-048 186







and/or






35.




alpha-cypermethrin



































disclosed in EP-A-067 461







and/or






36.




betacyfluthrin


























disclosed in EP-A-206 149














and/or






37.




cyhalothrin


























disclosed in DE-A-2 802 962














and/or






38.




cypermethrin


























disclosed in DE-A-2 326 077














and/or






39.




deltamethrin


























disclosed in DE-A-2 326 077














and/or






40.




esfenvalerate


























disclosed in DE-A-2 737 297














and/or






41.




etofenprox


























disclosed in DE-A-3 117 510














and/or






42.




fenpropathrin



































disclosed in DE-A-2 231 312







and/or






43.




fenvalerate



































disclosed in DE-A-2 335 347







and/or






44.




flucythrinate



































disclosed in DE-A-2 757 066







and/or






45.




lambda-cyhalothrin


























disclosed in EP-A-106 469














and/or






46.




permethrin


























disclosed in DE-A-2 326 077














and/or






47.




tau-fluvalinate



































disclosed in EP-A-038 617







and/or






48.




tralomethrin



































disclosed in DE-A-2 742 546







and/or






49.




zeta-cypermethrin


























disclosed in EP-A-026 542














and/or






C)




carbamates, preferably






50.




carbaryl


























disclosed in U.S.-2 903 478














and/or






51.




fenoxycarb


























disclosed in EP-A-004 334














and/or






52.




formetanate


























disclosed in DE-A-1 169 194














and/or






53.




formetanate hydrochloride







disclosed in DE-A-1 169 194







and/or






54.




methiocarb


























disclosed in DE-A-1 162 352














and/or






55.




methomyl


























disclosed in U.S.-3 639 620














and/or






56.




oxamyl


























disclosed in DE-A-1 768 623














and/or






57.




pirimicarb


























disclosed in GB-A-1 181 657














and/or






58.




propoxur


























disclosed in DE-A-1 108 202














and/or






59.




thiodicarb


























disclosed in DE-A-2 530 439














and/or






D)




benzoylureas, preferably






60.




chlorfluazuron




































disclosed in DE-A-2 818 830







and/or






61.




diflubenzuron


























disclosed in DE-A 2 123 236














and/or






62.




lufenuron


























disclosed in EP-A-179 022














and/or






63.




teflubenzuron


























disclosed in EP-A-052 833














and/or






64.




triflumuron


























disclosed in DE-A-2 601 780














and/or






E)




macrolides, preferably






65.




ivermectin







disclosed in EP-A-001 689







and/or






66.




emamectin







disclosed in EP-A-089 202







and/or






67.




milbemectin







known from The Pesticide







Manual, 11th Edition,







1997, p. 846







and/or






F)




diacylhydrazines,







preferably






68.




methoxyfenozide


























disclosed in EP-A-639 559














and/or






69.




tebufenozide


























disclosed in EP-A-339 854














and/or






G)




halogenocycloalkanes,







preferably






70.




endosulfan


























disclosed in DE-A-1 015 797














and/or






71.




gamma-HCH


























disclosed in U.S. 2,502,258














and/or






H)




acaricides, preferably






72.




fenazaquin




































disclosed in EP-A-326 329







and/or






73.




tebufenpyrad




































disclosed in EP-A-289 879







and/or






74.




pyrimidifen




































disclosed in EP-A-196 524







and/or






75.




triarathene


























disclosed in DE-A-2 724 494














and/or






76.




tetradifon


























disclosed in U.S. 2 812 281














and/or






77.




propargite


























disclosed in U.S. 3 272 854














and/or






78.




hexythiazox


























disclosed in DE-A-3 037 105














and/or






79.




bromopropylate


























disclosed in U.S. 3 784 696














and/or






80.




2-(acetyloxy)-3-dodecyl-







1,4-naphthalenedione




































disclosed in DE-A-2 641 343







and/or






81.




dicofol


























disclosed in U.S. 2 812 280














and/or






I)




other compounds such as






82.




amitraz



































disclosed in DE-A-2 061 132







and/or






83.




azadirachtin







known from The Pesticide







Manual, 11th Edition,







1997, p. 59






84.




buprofezin


























disclosed in DE-A-2 824 126














and/or






85.




quinomethionate


























disclosed in DE-A-1 100 372














and/or






86.




thiocyclam hydrogen







oxalate


























disclosed in DE-A-2 039 666














and/or






87.




triazamate


























disclosed in EP-A-213 718














and/or













88.




Trichogramma spp.







known from The Pesticide







Manual, 11th Edition,







1997, p. 1236






89.




Verticiliium lecanii







known from The Pesticide







Manual, 11th Edition,







1997, p. 1266






90.




fipronil


























disclosed in EP-A-295 117














and/or






91.




cyromazine


























disclosed in DE-A-2 736 876














and/or






92.




pymetrozin


























disclosed in EP-A-314 615













93.




diofenolan




































disclosed in DE-A 2 655 910







and/or






94.




indoxacarb




































disclosed in WO 92/11249







and/or






95.




pyriproxyfen





























disclosed in EP-A-128 648














have very good insecticidal and acaricidal properties.




Preferred active compound combinations are those comprising compounds of the formula (I)




in which




X represents C


1


-C


4


-alkyl, halogen, C


1


-C


4


-alkoxy or C


1


-C


2


-halogenoalkyl,




Y represents hydrogen, C


1


-C


4


-alkyl, halogen, C


1


-C


4


-alkoxy or C


1


-C


2


-halogenoalkyl,




Z represents C


1


-C


4


-alkyl, halogen or C


1


-C


4


-alkoxy,




n represents 0 or 1,




A and B together with the carbon atom to which they are bonded form a saturated 5- to 6-membered ring which is optionally substituted by C


1


-C


4


-alkyl or C


1


-C


4


-alkoxy,




G represents hydrogen (a) or the groups











in which




R


1


represents optionally halogen-substituted C


1


-C


16


-alkyl, C


2


-C


16


-alkenyl, C


1


-C


6


-alkoxy-C


2


-C


6


-alkyl or cycloalkyl having 3-7 ring atoms which can be interrupted by 1 or 2 oxygen and/or sulphur atoms,




phenyl which is optionally substituted by halogen, nitro, C


1


-C


4


-alkyl, C


1


-C


4


-alkoxy, C


1


-C


3


-halogenoalkyl or C


1


-C


3


-halogenoalkoxy,




R


2


represents optionally halogen-substituted C


1


-C


16


-alkyl, C


2


-C


16


-alkenyl or C


1


-C


6


-alkoxy-C


2


-C


6


-alkyl,




phenyl or benzyl, each of which is optionally substituted by halogen, nitro, C


1


-C


4


-alkyl, C


1


-C


4


-alkoxy or C


1


-C


4


-halogenoalkyl,




and at least one active compound of compounds 1 to 95.




Surprisingly, the insecticidal and acaricidal action of the active compound combination according to the invention considerably exceeds the total of the actions of the individual active compounds. A true synergistic effect which could not have been predicted exists, not just a complementation of action.




The active compound combinations according to the invention comprise at least one active compound of compounds 1 to 95, in addition to at least one active compound of the formula (I).




Especially preferred active compound combinations are those comprising the dihydrofuranone derivative of the formula (I-b-1)











and at least one active compound of compounds 1 to 95.




In addition, the active compound combinations may also comprise other fungicidally, acaricidally or insecticidally active components which may be admixed.




If the active compounds are present in the active compound combinations according to the invention in certain weight ratios, the synergistic effect is particularly pronounced. However, the weight ratios of the active compounds in the active compound combinations may be varied within a relatively large range. In general, the combinations according to the invention comprise active compounds of the formula (I) and the other component in the mixing ratios indicated in the table hereinbelow as being preferred and especially preferred.




the mixing ratios are based on weight ratios. The ratio is to be understood as meaning active compound of the formula (I): other component






















Especially








Preferred




preferred







Other component




mixing ratio




mixing ratio













2-(Acetyloxy)-3-dodecyl-




10:1 to 1:10




5:1 to 1:5







1,4-naphthalinidone







Acephate




10:1 to 1:10




5:1 to 1:5







Acrinathrin




20:1 to 1:50




10:1 to 1:1 







Alpha-cypermethrin




50:1 to 1:5 




10:1 to 1:1 







Amitraz




 5:1 to 1:20




 1:1 to 1:10







Azadirachtin




50:1 to 1:5 




10:1 to 1:1 







Azinphos-methyl




10:1 to 1:10




5:1 to 1:5







Betacyfluthrin




50:1 to 1:5 




10:1 to 1:1 







Bromopropylate




10:1 to 1:10




5:1 to 1:5







Buprofezin




10:1 to 1:10




5:1 to 1:5







Carbaryl




10:1 to 1:10




5:1 to 1:5







Quinomethionate




10:1 to 1:10




5:1 to 1:5







Chlorfenvinphos




10:1 to 1:10




5:1 to 1:5







Chlorfluazuron




10:1 to 1:10




5:1 to 1:5







Chlorpyrifos




10:1 to 1:10




5:1 to 1:5







Cyhalothrin




50:1 to 1:5 




10:1 to 1:1 







Cypermethrin




50:1 to 1:5 




10:1 to 1:1 







Cyromazine




10:1 to 1:10




5:1 to 1:5







Deltamethrin




50:1 to 1:5 




10:1 to 1:1 







Diazinon




10:1 to 1:10




5:1 to 1:5







Dichlorphos




10:1 to 1:10




5:1 to 1:5







Dicofol




10:1 to 1:10




5:1 to 1:5







Dicrotophos




10:1 to 1:10




5:1 to 1:5







Diflubenzuron




10:1 to 1:10




5:1 to 1:5







Dimethoate




10:1 to 1:10




5:1 to 1:5







Diofenolan




100:1 to 1:2 




20:1 to 1:1 







Disulfoton




10:1 to 1:10




5:1 to 1:5







Emamectin




50:1 to 1:5 




10:1 to 1:1 







Endosulfan




10:1 to 1:10




5:1 to 1:5







Esfenvalerate




50:1 to 1:5 




10:1 to 1:1 







Ethion




10:1 to 1:10




5:1 to 1:5







Etofenprox




10:1 to 1:10




5:1 to 1:5







Fenazaquin




10:1 to 1:10




5:1 to 1:5







Fenitrothion




10:1 to 1:10




5:1 to 1:5







Fenoxycarb




10:1 to 1:10




5:1 to 1:5







Fenpropathrin




10:1 to 1:10




5:1 to 1:5







Fenpyrad (tebufenpyrad)




10:1 to 1:10




5:1 to 1:5







Fenthion




20:1 to 1:10




5:1 to 1:5







Fenvalerate




20:1 to 1:5 




10:1 to 1:1 







Fipronil




10:1 to 1:10




5:1 to 1:5







Flucythrinate




50:1 to 1:5 




10:1 to 1:1 







Formetanate




10:1 to 1:10




5:1 to 1:5







Hexyhiazox




20:1 to 1:5 




10:1 to 1:2 







Indoxacarb




50:1 to 1:5 




20:1 to 1:2 







Isoxathion




10:1 to 1:10




5:1 to 1:5







Ivermectin




50:1 to 1:5 




10:1 to 1:1 







Lambda-cyhalothrin




50:1 to 1:5 




10:1 to 1:1 







Lindane (gamma-HCH)




10:1 to 1:10




5:1 to 1:5







Lufenuron




20:1 to 1:5 




10:1 to 1:2 







Malathion




10:1 to 1:10




5:1 to 1:5







Methamidophos




10:1 to 1:10




5:1 to 1:5







Methidathion




10:1 to 1:10




5:1 to 1:5







Methiocarb




10:1 to 1:10




5:1 to 1:5







Methomyl




10:1 to 1:10




5:1 to 1:5







Methoxyfenozide




10:1 to 1:10




5:1 to 1:5







Mevinphos




10:1 to 1:10




5:1 to 1:5







Milbemectin




50:1 to 1:5 




10:1 to 1:1 







Monocrotophos




10:1 to 1:10




5:1 to 1:5







Oxamyl




 5:1 to 1:100




 1:1 to 1:20







Oxydemeton-methyl




10:1 to 1:10




5:1 to 1:5







Parathion




10:1 to 1:10




5:1 to 1:5







Parathion-methyl




10:1 to 1:10




5:1 to 1:5







Permethrin




10:1 to 1:10




5:1 to 1:5







Phenthoate




10:1 to 1:10




5:1 to 1:5







Phorate




10:1 to 1:10




5:1 to 1:5







Phosalone




10:1 to 1:10




5:1 to 1:5







Phosmet




10:1 to 1:10




5:1 to 1:5







Phosphamidon




10:1 to 1:10




5:1 to 1:5







Phoxim




10:1 to 1:10




5:1 to 1:5







Pirimicarb




40:1 to 1:10




5:1 to 1:5







Pirimiphos-methyl




10:1 to 1:10




5:1 to 1:5







Profenophos




10:1 to 1:10




5:1 to 1:5







Propargite




10:1 to 1:10




5:1 to 1:5







Propoxur




10:1 to 1:10




5:1 to 1:5







Prothiophos




10:1 to 1:10




5:1 to 1:5







Pymetrozin




10:1 to 1:10




5:1 to 1:5







Pyrimidifen




50:1 to 1:5 




10:1 to 1:1 







Pyriproxyfen




10:1 to 1:10




5:1 to 1:5







Tau-fluvalinate




20:1 to 1:5 




10:1 to 1:2 







Tebufenozide




10:1 to 1:10




5:1 to 1:5







Tebupirimphos




10:1 to 1:10




5:1 to 1:5







Teflubenzuron




20:1 to 1:5 




10:1 to 1:2 







Tetradifon




10:1 to 1:10




5:1 to 1:5







Thiocyclam




 5:1 to 1:20




 1:1 to 1:10







Thiodicarb




 5:1 to 1:20




 1:1 to 1:10







Tralomethrin




50:1 to 1:5 




10:1 to 1:1 







Triarathene




 5:1 to 1:20




 1:1 to 1:10







Triazamate




10:1 to 1:10




5:1 to 1:5







Triazophos




 5:1 to 1:20




 1:1 to 1:10







Trichlorfon




10:1 to 1:10




5:1 to 1:5







Trichogramma spp.







Triflumuron




10:1 to 1:10




5:1 to 1:5







Verticillium lecanii







Zeta-cypermethrin




50:1 to 1:5 




10:1 to 1:2 















The active compound combinations according to the invention are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids found in agriculture, in afforestations, in the protection of stored product and materials and in the hygiene sector. They are active against normally sensitive and resistant species, and against all or individual developmental stages. The abovementioned pests include:




From the order of the


Isopoda


, for example,


Oniscus asellus, Armadillidium vulgare, Porcellio scaber.






From the order of the


Diplopoda


, for example,


Blaniulus guttulatus.






From the order of the


Chilopoda


, for example,


Geophilus carpophagus, Scutigera


spp.




From the order of the


Symphyla


, for example,


Scutigerella immaculata.






From the order of the


Thysanura


, for example,


Lepisma saccharina.






From the order of the


Collembola


, for example,


Onychiurus armatus.






From the order of the


Orthoptera


, for example,


Acheta domesticus, Gryllotalpa


spp., Locusta migratoria migratorioides,


Melanoplus


spp.,


Schistocerca gregaria.






From the order of the


Blattaria


, for example,


Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica.






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


Phthiraptera


, for example,


Pediculus humanus corporis, Haematopinus


spp.,


Linognathus


spp.,


Trichodectes


spp.,


Damalinia


spp.




From the order of the


Thysanoptera


, for example,


Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.






From the order of the


Heteroptera


, for example,


Eurygaster


spp.,


Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma


spp.




From the order of the


Homoptera


, for example,


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 cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus


spp.,


Psylla


spp.




From the order of the


Lepidoptera


, for example,


Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria


spp.,


Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis


spp.,


Euxoa


spp.,


Feltia


spp.,


Earias insulana, Heliothis


spp.,


Mamestra brassicae, Panolis flammea, Spodoptera


spp.,


Trichoplusia ni, Carpocapsa pomonella, Pieris


spp.,


Chilo


spp.,


Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus


spp.,


Oulema oryzae.






From the order of 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, 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 zealandica, Lissorhoptrus oryzophilus.






From the order of the


Hymenoptera


, for example,


Diprion


spp.,


Hoplocampa


spp.,


Lasius


spp.,


Monomorium pharaonis, 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.,


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, Hylemyia


spp.,


Liriomyza


spp.




From the order of the


Siphonaptera


, for example,


Xenopsylla cheopis, Ceratophyllus


spp.




From the class of the


Arachnida


, for example,


Scorpio maurus, Latrodectus mactans, 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.,


Hemitarsonemus


spp.,


Brevipalpus


spp.




The plant-parasitic nematodes include, for example,


Pratylenchus


spp.,


Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera


spp.,


Globodera


spp.,


Meloidogyne


spp.,


Aphelenchoides


spp.,


Longidorus


spp.,


Xiphinema


spp.,


Trichodorus


spp.,


Bursaphelenchus


spp.




The active compound combinations can be converted into the customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric materials.




These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents and/or solid carriers, optionally with the use of surfactants, that is, emulsifiers and/or dispersants, and/or foam formers.




In the case of the use of water as an extender, organic solvents can, for example, also be used as cosolvents. The following are essentially suitable as liquid solvents: aromatics 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, mineral and vegetable oils, alcohols such as butanol or glycol and 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, or else water.




Suitable solid carriers are:




for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic materials such as highly-disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates; suitable dispersants are: 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, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.




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




The formulations generally comprise between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.




The active compound combinations according to the invention can be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms.




Mixtures with other known active compounds such as herbicides or with fertilizers and growth regulators are also possible.




When used as insecticides, the active compound combinations according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergists. Synergists are compounds which increase the action of the active compounds, without it being necessary for the synergist added to be active itself.




The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.




The compounds are employed in a customary manner appropriate for the use forms.




When used against hygiene pests and stored-product pests, the active compound combinations are distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.




The active compound combinations according to the invention are not only active against plant pests, hygiene pests and stored-product pests, but also, in the veterinary medicine sector, against animal parasites (ectoparasites) such as hard ticks, soft ticks, mange mites, harvest mites, flies (stinging and licking), parasitizing fly larvae, lice, hair lice, bird lice and fleas. These parasites include:




From the order of the


Anoplurida


, for example,


Haematopinus


spp.,


Linognathus


spp.,


Pediculus


spp.,


Phtirus


spp.,


Solenopotes


spp.




From the order of the


Mallophagida


and the suborders


Amblycerina


and


Ischnocerina


, for example,


Trimenopon


spp.,


Menopon


spp.,


Trinoton


spp.,


Bovicola


spp.,


Werneckiella


spp.,


Lepikentron


spp.,


Damalina


spp.,


Trichodectes


spp.,


Felicola


spp.




From the order


Diptera


and the suborders


Nematocerina


and


Brachycerina


, for example,


Aedes


spp.,


Anopheles


spp.,


Culex


spp.,


Simulium


spp.,


Eusimulium


spp.,


Phlebotomus


spp.,


Lutzomyia


spp.,


Culicoides


spp.,


Chrysops


spp.,


Hybomitra


spp.,


Atylotus


spp.,


Tabanus


spp.,


Haematopota


spp.,


Philipomyia


spp.,


Braula


spp.,


Musca


spp.,


Hydrotaea


spp.,


Stomoxys


spp.,


Haematobia


spp.,


Morellia


spp.,


Fannia


spp.,


Glossina


spp.,


Calliphora


spp.,


Lucilia


spp.,


Chrysomyia


spp.,


Wohlfahrtia


spp.,


Sarcophaga


spp.,


Oestrus


spp.,


Hypoderma


spp.,


Gasterophilus


spp.,


Hippobosca


spp.,


Lipoptena


spp.,


Melophagus


spp.




From the order of the


Siphonapterida


, for example,


Pulex


spp.,


Ctenocephalides


spp.,


Xenopsylla


spp.,


Ceratophyllus


spp.




From the order of the


Heteropterida


, for example,


Cimex


spp.,


Triatoma


spp.,


Rhodnius


spp.,


Panstrongylus


spp.




From the order of the


Blattarida


, for example,


Blatta orientalis, Periplaneta americana, Blattella germanica, Supella


spp.




From the subclass of the


Acaria


(


Acarida


) and the order of the


Meta


- and


Mesostigmata


, for example,


Argas


spp.,


Omithodorus


spp.,


Otobius


spp.,


Ixodes


spp.,


Amblyomma


spp.,


Boophilus


spp.,


Dermacentor


spp.,


Haemophysalis


spp.,


Hyalomma


spp.,


Rhipicephalus


spp.,


Dermanyssus


spp.,


Raillietia


spp.,


Pneumonyssus


spp.,


Sternostoma


spp.,


Varroa


spp.




From the order of the


Actinedida


(


Prostigmata


) and


Acaridida


(


Astigmata


), for example,


Acarapis


spp.,


Cheyletiella


spp.,


Ornithocheyletia


spp.,


Myobia


spp.,


Psorergates


spp.,


Demodex


spp.,


Trombicula


spp.,


Listrophorus


spp.,


Acarus


spp.,


Tyrophagus


spp.,


Caloglyphus


spp.,


Hypodectes


spp.,


Pterolichus


spp.,


Psoroptes


spp.,


Chorioptes


spp.,


Otodectes


spp.,


Sarcoptes


spp.,


Notoedres


spp.,


Knemidocoptes


spp.,


Cytodites


spp.,


Laminosioptes


spp.




The active compound combinations according to the invention are also suitable for controlling arthropods which attack agricultural livestock such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, honey bees, other domestic animals such as, for example, dogs, cats, caged birds, aquarium fish and so-called experimental animals such as, for example, hamsters, guinea pigs, rats and mice. By controlling these arthropods, cases of death and reductions in productivity (for meat, milk, wool, hides, eggs, honey and the like) should be diminished, so that more economical and simpler animal husbandry is possible by the use of the active compound combinations according to the invention.




The active compound combinations according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration such as, for example, by injections (intramuscularly, subcutaneously, intravenously, intraperitoneally and the like), implants, by nasal administration, by dermal administration in the form of, for example, immersing or dipping, spraying, pouring-on, spotting-on, washing, dusting, and with the aid of active-compound-comprising moulded articles such as collars, ear tags, tail tags, limb bands, halters, marking devices and the like.




When used for cattle, poultry, domestic animals and the like, the active compound combinations can be applied as formulations (for example powders, emulsions, flowables) comprising the active compounds in an amount of 1 to 80% by weight, either directly or after 100- to 10,000-fold dilution, or they may be used as a chemical dip.




Moreover, it has been found that the active compound combinations according to the invention show a potent insecticidal action against insects which destroy industrial materials.




The following insects may be mentioned by way of example and with preference, but not by way of limitation:




Beetles such as






Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus


spec.,


Tryptodendron


spec.,


Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon


spec.,


Dinoderus minutus.








Dermapterans


such as






Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.








Termites


such as






Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.






Bristle tails such as


Lepisma saccharina.






Industrial materials in the present context are understood as meaning non-living materials such as, preferably, polymers, adhesives, glues, paper and board, leather, wood, timber products and paints.




The material which is to be protected from insect attack is very especially preferably wood and timber products.




Wood and timber products which can be protected by the composition according to the invention, or mixtures comprising it, are to be understood as meaning, for example:




Construction timber, wooden beams, railway sleepers, bridge components, jetties, vehicles made of wood, boxes, pallets, containers, telephone poles, wood lagging, windows and doors made of wood, plywood, clipboard, joinery, or timber products which quite generally are used in house construction or building joinery.




The active compound combinations can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.




The abovementioned formulations can be prepared in a manner known per se, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant and/or binder or fixative, water repellant, if desired desiccants and UV stabilizers, and if desired colorants and pigments and other processing auxiliaries.




The insecticidal compositions or concentrates used for protecting wood and timber products comprise the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.




The amount of composition or concentrate employed depends on the species and the abundance of the insects and on the medium. The optimal quantity to be employed can be determined in each case by test series upon application. In general, however, it will suffice to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.




A suitable solvent and/or diluent is an organochemical solvent or solvent mixture and/or an oily or oil-type organochemical solvent or solvent mixture of low volatility and/or a polar organochemical solvent or solvent mixture and/or water and, if appropriate, an emulsifier and/or wetter.




Organochemical solvents which are preferably employed are oily or oil-type solvents with an evaporation number of above 35 and a flash point of above 30° C., preferably above 45° C. Such oily and oil-type solvents which are insoluble in water and of low volatility and which are used are suitable mineral oils or their aromatic fractions or mineral-oil-containing solvent mixtures, preferably white spirit, petroleum and/or alkylbenzene.




Mineral oils which are advantageously used are those with a boiling range of 170 to 220° C., white spirit with a boiling range of 170 to 220° C., spindle oil with a boiling range of 250 to 350° C., petroleum and aromatics with a boiling range of 160 to 280° C., oil of terpentine, and the like.




In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range of 180 to 210° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 220° C. and/or spindle oil and/or monochloronaphthalene, preferably α-monochloronaphthalene are used.




The organic oily or oil-type solvents of low volatility and with an evaporation number of above 35 and a flash point of above 30° C., preferably above 45° C., can be replaced in part by organochemical solvents of high or medium volatility, with the proviso that the solvent mixture also has an evaporation number of above 35 and a flash point of above 30° C., preferably above 45° C., and that the insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture.




In a preferred embodiment, some of the organochemical solvent or solvent mixture is replaced by an aliphatic polar organochemical solvent or solvent mixture. Aliphatic organochemical solvents which contain hydroxyl and/or ester and/or ether groups are preferably used, such as, for example, glycol ethers, esters or the like.




Organochemical binders used for the purposes of the present invention are the synthetic resins and/or binding drying oils which are known per se and which can be diluted in water and/or dissolved or dispersed or emulsified in the organochemical solvents employed, in particular binders composed of, or comprising, an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenol resin, hydrocarbon resin such as indene/coumarone resin, silicone resin, drying vegetable and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.




The synthetic resin employed as binder can be employed in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances may also be used as binders, in amounts of up to 10% by weight. In addition, colorants, pigments, water repellants, odour-masking agents, and inhibitors or anticorrosive agents and the like, all of which are known per se, can be employed.




In accordance with the invention, the composition or the concentrate preferably comprises, as organochemical binders, at least one alkyl resin or modified alkyl resin and/or a drying vegetable oil. Alkyd resins which are preferably used in accordance with the invention are those with an oil content of over 45% by weight, preferably 50 to 68% by weight.




Some or all of the abovementioned binder can be replaced by a fixative (mixture) or plasticizer (mixture). These additives are intended to prevent volatilization of the active compounds, and also crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of binder employed).




The plasticizers are from the chemical classes of the phthalic esters, such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate, phosphoric esters such as tributyl phosphate, adipic esters such as di-(2-ethylhexyl)-adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ethers or higher-molecular-weight glycol ethers, glycerol esters and p-toluenesulphonic esters.




Fixatives are based chemically on polyvinyl alkyl ethers such as, for example, polyvinyl methyl ether, or ketones such as benzophenone and ethylenebenzophenone.




Other suitable solvents or diluents are, in particular, also water, if appropriate as a mixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersants.




Particularly effective timber protection is achieved by industrial-scale impregnating processes, for example the vacuum, double-vacuum or pressure processes.




The active compound combinations according to the invention can also be employed for protecting objects which come into contact with saltwater or brackish water, such as hulls, screens, nets, buildings, moorings and signalling systems, from fouling.




Fouling by sessile Oligochaeta, such as Serpulidae, and by shells and species from the Ledamorpha group (goose barnacles), such as various Lepas and Scalpellum species, or by species from the Balanomorpha group (acorn barnacles), such as Balanus or Pollicipes species, increases the frictional drag of ships and, as a consequence, leads to a marked increase in operation costs owing to higher energy consumption and additionally frequent residence in the dry dock.




Apart from fouling by algae, for example Ectocarpus sp. and Ceramium sp., fouling by sessile Entomostraka groups, which come under the generic term Cirripedia (cirriped crustaceans), is of particular importance.




Surprisingly, it has now been found that the active compound combinations according to the invention have an outstanding antifouling action.




Using the active compound combinations according to the invention, the use of heavy metals such as, for example, in bis(trialkyltin) sulphides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride, tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenum disulphide, antimony oxide, polymeric butyl titanate, phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride, manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzinc ethylenebisthiocarbamate, zinc oxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, copper naphthenate and tributyltin halides can be dispensed with, or the concentration of these compounds substantially reduced.




If appropriate, the ready-to-use antifouling paints can additionally comprise other active compounds, preferably algicides, fungicides, herbicides, molluscicides, or other antifouling active compounds.




Preferably suitable components in combinations with the antifouling compositions according to the invention are:




algicides such as




2-tert.-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophen, diuron, endothal, fentine acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;




fungicides such as




benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide, dichlofluanid, fluor-folpet, 3-iodo-2-propinyl butylcarbamate, tolylfluanid and azoles such as azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and tebuconazole;




molluscicides such as fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and trimethacarb;




or conventional antifouling active compounds such as




4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl sulfone, 2-(N,N-di-methylthiocarbamoylthio)-5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4,6-trichlorophenylmaleiim




The antifouling compositions used comprise the active compound combinations according to the invention in a concentration of 0.001 to 50% by weight, in particular 0.01 to 20% by weight.




Moreover, the antifouling compositions according to the invention comprise the customary components such as, for example, those described in Ungerer,


Chem. Ind


. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.




Besides the algicidal, fungicidal, molluscicidal active compounds and insecticidal active compounds according to the invention, antifouling paints comprise, in particular, binders.




Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, in particular in an aqueous system, vinyl chloride/vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene/styrene/acrylonitrile rubbers, drying oils such as linseed oil, resin esters or modified hardened resins in combination with tar or bitumens, asphalt and epoxy compounds, small amounts of chlorine rubber, chlorinated polypropylene and vinyl resins.




If appropriate, paints also comprise inorganic pigments, organic pigments or colorants which are preferably soluble in salt water. Paints may furthermore comprise materials such as colophonium to allow controlled release of the active compounds. Furthermore, the paints may comprise plasticizers, modifiers which affect the rheological properties and other conventional constituents. The compounds according to the invention or the abovementioned mixtures may also be incorporated into self-polishing antifouling systems.




The active compound combinations are also suitable for controlling animal pests, in particular insects, arachnids and mites, which are found in enclosed spaces such as, for example, dwellings, factory halls, offices, vehicle cabins and the like. They can be employed in domestic insecticide products for controlling these pests. They are active against sensitive and resistant species and against all developmental stages. These pests include:




From the order of the


Scorpionidea


, for example,


Buthus occitanus.






From the order of the


Acarina


, for example,


Argas persicus, Argas reflexus, Bryobia


ssp.,


Dermanyssus gallinae, Glyciphagus domesticus, Omithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.






From the order of the


Araneae


, for example,


Aviculariidae, Araneidae.






From the order of the


Opiliones


, for example,


Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.






From the order of the


Isopoda


, for example,


Oniscus asellus, Porcellio scaber.






From the order of the


Diplopoda


, for example,


Blaniulus guttulatus, Polydesmus


spp.




From the order of the


Chilopoda


, for example,


Geophilus


spp.




From the order of the


Zygentoma


, for example,


Ctenolepisma


spp.,


Lepisma saccharina, Lepismodes inquilinus.






From the order of the


Blattaria


, for example,


Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora


spp.,


Parcoblatta


spp.,


Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.






From the order of the


Saltatoria


, for example,


Acheta domesticus.






From the order of the


Dermaptera


, for example,


Forficula auricularia.






From the order of the


Isoptera


, for example,


Kalotermes


spp.,


Reticulitermes


spp.




From the order of the


Psocoptera


, for example,


Lepinatus


spp.,


Liposcelis


spp.




From the order of the


Coleptera


, for example,


Anthrenus


spp.,


Attagenus


spp.,


Dermestes


spp.,


Latheticus oryzae, Necrobia


spp.,


Ptinus


spp.,


Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.






From the order of the


Diptera


, for example,


Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles


spp.,


Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila


spp.,


Fannia canicularis, Musca domestica, Phlebotomus


spp.,


Sarcophaga carnaria, Simulium


spp.,


Stomoxys calcitrans, Tipula paludosa.






From the order of the


Lepidoptera


, for example,


Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.






From the order of the


Siphonaptera


, for example,


Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.






From the order of the


Hymenoptera


, for example,


Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula


spp.,


Tetramorium caespitum.






From the order of the


Anoplura


, for example,


Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis.






From the order of the


Heteroptera


, for example,


Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.






They are used as aerosols, pressure-free spray products, for example pump and atomizer sprays, automatic fogging systems, foggers, foams, gels, evaporator products with evaporator tablets made of cellulose or polymer, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-free, or passive, evaporation systems, moth papers, moth bags and moth gels, as granules or dusts, in baits for spreading or in bait stations.




All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (inclusive of naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and recombinant methods or by combinations of these methods, inclusive of the transgenic plants and inclusive of the plant varieties protectable or not protectable by plant breeders' rights, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offsets and seeds.




Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on the surroundings, environment or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on and, in the case of propagation material, in particular in the case of seed, also by applying one or more coats.




The good insecticidal and acaricidal action of the active compound combinations according to the invention can be seen from the examples which follow. While the individual active compounds show weaknesses in their action, the combinations show an action which exceeds a simple sum of actions.




A synergistic effect in insecticides and acaricides is always present when the action of the active compound combinations exceeds the total of the actions of the active compounds when applied individually.




The expected action for a given combination of two active compounds can be calculated as follows, using the formula of S. R. Colby, Weeds 15 (1967), 20-22:




If




X is the efficacy when employing active compound A at an application rate of m g/ha or in a concentration of m ppm,




Y is the efficacy when employing active compound B at an application rate of n g/ha or in a concentration of n ppm and




E is the efficacy when employing active compounds A and B at application rates of m and n g/ha or in a concentration of m and n ppm,




then






E
=

X
+
Y
-


X
·
Y

100












The efficacy is determined in %. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection/infestation is observed.




If the actual action exceeds the calculated value, the action of the combination is superadditive, i.e. a synergistic effect is present. In this case, the actually observed efficacy must exceed the value calculated using the above formula for the expected efficacy (E).




USE EXAMPLES




Example A






Heliothis virescens


Test





















solvent:




7 parts by weight of dimethylformamide







emulsifier:




1 part by weight of alkylaryl polyglycol ether















To produce a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.




Soya bean shoots (


Glycine max


) are treated by immersion in the active compound preparation of the desired concentration and are populated with


Heliothis virescens


caterpillars while the leaves are still moist.




After the desired period, the destruction is determined in %. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed. The kill figures determined are calculated using Colby's formula.




In this test, a synergistically increased efficacy in comparison with the active compounds when applied individually is shown, for example, by the following active compound combination in accordance with the present application:












TABLE A











plant-injurious insects








Heliothis virescens


test














Active compound




Percentage







concentration




destruction






Active compounds




In ppm




after 3 days









Ex. (I-b-1) known




0.32




 0






Betacyfluthrin known




0.32




75














Ex. (I-b-1) + betacyfluthrin (1:1)




0.32 + 0.32




found*




calc.**






according to the invention





100




75











*found = found action










**calc. = action calculated using Colby's formula













Example B






Nephotettix


Test





















solvent:




7 parts by weight of dimethylformamide







emulsifier:




1 part by weight of alkylaryl polyglycol ether















To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.




Rice seedlings (


Oryza sativa


) are treated by immersion in the active compound preparation of the desired concentration and are populated with green rice leaf-hoppers (


Nephotettix cincticeps


) while the leaves are still moist.




After the desired period, the destruction is determined in %. 100% means that all leafhoppers have been killed; 0% means that none of the leafhoppers have been killed. The kill figures determined form the basis for calculations with Colby's formula.




In this test, a synergistically increased efficacy in comparison with the active compounds when applied individually is shown, for example, by the following active compound combination in accordance with the present application:












TABLE B











plant-injurious insects






Nephotettix test














Active compound




Percentage







concentration




destruction






Active compounds




in ppm




after 6 days









Ex. (I-b-1) known




0.32




 0






Betacyfluthrin known




0.32




50














Ex. (I-b-1) + betacyfluthrin (1:1)




0.32 + 0.32




found*




calc.**






according to the invention





85




50











*found = found action










**calc. = action calculated using Colby's formula













Example C






Plutella


Test





















solvent:




7 parts by weight of dimethylformamide







emulsifier:




1 part by weight of alkylaryl polyglycol ether















To produce a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.




Cabbage leaves (


Brassica oleracea


) are treated by immersion in the active compound preparation of the desired concentration and are populated with diamond-back moth caterpillars (


Plutella xylostella


) while the leaves are still moist.




After the desired period, the destruction is determined in %. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed. The kill figures determined are calculated using Colby's formula.




In this test, a synergistically increased efficacy in comparison with the active compounds when applied individually is shown, for example, by the following active compound combination in accordance with the present application:












TABLE C











plant-injurious insects






Plutella test














Active compound




Percentage







concentration




destruction






Active compounds




in ppm




after 3 days









Ex. (I-b-1) known




1.6




 0






Betacyfluthrin known




1.6




80














Ex. (I-b-1) + betacyfluthrin (1:1)




1.6 + 1.6




found*




calc.**






according to the invention





100




80











*found = found action










**calc. = action calculated using Colby's formula













Example D






Spodoptera exigua


Test





















solvent:




7 parts by weight of dimethylformamide







emulsifier:




1 part by weight of alkylaryl polyglycol ether















To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.




Cabbage leaves (


Brassica oleracea


) are treated by immersion in the active compound preparation of the desired concentration and are populated with fall army worm caterpillars (


Spodoptera exigua


) while the leaves are still moist.




After the desired period, the destruction is determined in %. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed. The kill figures determined are calculated using Colby's formula.




In this test, a synergistically increased efficacy in comparison with the active compounds when applied individually is shown, for example, by the following active compound combination in accordance with the present application:












TABLE D











plant-injurious insects








Spodoptera exigua


test














Active compound




Percentage







concentration




destruction






Active compounds




in ppm




after 6 days









Ex. (I-b-1) known




8




 0






Betacyfluthrin known




8




90














Ex. (I-b-1) + betacyfluthrin (1:1)




8 + 8




found*




calc.**






according to the invention





100




90











*found = found action










**calc. = action calculated using Colby's formula













Example E






Tetranychus


Test




OP-resistant/spray Treatment





















solvent:




7 parts by weight of dimethylformamide







emulsifier:




1 part by weight of alkylaryl polyglycol ether















To produce a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.




Bean plants (


Phaseolus vulgaris


) which are severely infested with all stages of the common spider mite (


Tetranychus urticae


) are sprayed with an active compound preparation of the desired concentration.




After the desired period, the action is determined in %. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed. The kill figures determined are calculated using Colby's formula.




In this test, a synergistically increased efficacy in comparison with the active compounds when applied individually is shown, for example, by the following active compound combinations in accordance with the present application:












TABLE E











plant-injurious mites






Tetranychus test (OP-resistant/spray treatment)














Active compound




Percentage







concentration




destruction






Active compounds




in ppm




after 14 days









Ex. (I-b-1) known




0.32




0






Methamidophos known




0.32




0














Ex. (I-b-1) + methamidophos (1:1)




0.32 + 0.32




found*




calc.**






according to the invention





90




0











*found = found action










**calc. = action calculated using Colby's formula












Claims
  • 1. A composition consisting essentially of a mixture of(1) the compound (I-b-1) (2) at least one compound selected from the group consisting of chlorpyrifos at a weight ratio of compound (I-b-1) to chlorpyrifos of from 10:1 to 1:10, methamidophos at a weight ratio of compound (I-b-1) to methamidophos of from 10:1 to 1:10, methidathion at a weight ratio of compound (I-b-1) to methidathion of from 10:1 to 1:10, prothiophos at a weight ratio of compound (I-b-1) to prothiophos of from 10:1 to 1:10, triazophos at a weight ratio of compound (I-b-1) to triazophos of from 5:1 to 1:20, propargite at a weight ratio of compound (I-b-1) to propargite of from 10:1 to 1:10, milbemectin at a weight ratio of compound (I-b-1) to milbemectin of from 50:1 to 1:5, fenpropathrin at a weight ratio of compound (I-b-1) to fenpropathrin of from 10:1 to 1:10, tau-fluvalinate at a weight ratio of compound (I-b-1) to tau-fluvalinate of from 20:1 to 1:5, and acrinathrin at a weight ratio of compound (I-b-1) to acrinathrin of from 20:1 to 1:50.
  • 2. A method of controlling at least one animal pest comprising applying an insecticidally and/or acaricidally effective amount of the composition of claim 1 to the animal pest and/or its environment.
  • 3. A process for the preparation of an insecticidal and/or acaricidal composition comprising mixing the composition of claim 1 with at least one of extenders and surfactants.
Priority Claims (1)
Number Date Country Kind
199 53 775 Nov 1999 DE
RELATED APPLICATIONS

This application is a division of application Ser. No. 10/129,589 filed May 7, 2002, now U.S. Pat. No. 6,576,661, which is the National Stage of International Application No. PCT/E00/10620, filed Oct. 27, 2000, which is entitled to the right of priority of German Patent Application No. 199 53 775.5, filed Nov. 9, 1999.

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The Pesticide Manual, Eleventh Edition, Editor C.D.S. Tomlin (Date Unavailable) Trichogramma spp. Biological Agent pp. 1236-1237.
The Pesticide Manual, Eleventh Edition, Editor C.D.S. Tomlin (Date Unavailable) Milbemectin Acaricide, insecticide pp. 846-847.
**C Tomlin (ED): “The Presiticide Manual, Tenth Edition” Presticide Manual, GB, Farnham, BCPC, vol. Ed. 10, pp. 1335-1341 XP002099499 ISBN:0-948404-79-5 the index of the active agent classes.