Active ingredient combination having insecticidal and acaricidal characteristics

FIELD OF THE INVENTION

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 INVENTION

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.

DETAILED DESCRIPTION OF THE INVENTION

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.

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 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

-halogenoalkyl,

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

2

0

-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

and/or

2. chlorpyrifos

and/or

3. diazinon

and/or

4. dimethoate

and/or

5. disulfoton

and/or

6. ethion

and/or

7. fenitrothion

and/or

8. fenthion

and/or

9. isoxathion

and/or

10. malathion

and/or

11. methidathion

and/or

12. oxydemeton-methyl

and/or

13. parathion

and/or

14. parathion-methyl

and/or

15. phenthoate

and/or

16. phorate

and/or

17. phosalone

and/or

18. phosmet

and/or

19. phoxim

and/or

20. pirimiphos-methyl

and/or

21. profenophos

and/or

22. prothiophos

and/or

23. tebupirimphos

and/or

24. triazophos

and/or

25. chlorfenvinphos

and/or

26. dichlorphos

and/or

27. dicrotophos

and/or

28. mevinphos

and/or

29. monocrotophos

and/or

30. phosphamidon

and/or

31. acephate

and/or

32. methamidophos

and/or

33. trichlorfon

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

and/or

37. cyhalothrin

and/or

38. cypermethrin

and/or

39. deltamethrin

and/or

40. esfenvalerate

and/or

41. etofenprox

and/or

42. fenpropathrin

and/or

43. fenvalerate

and/or

44. flucythrinate

and/or

45. lambda-cyhalothrin

and/or

46. permethrin

and/or

47. tau-fluvalinate

and/or

48. tralomethrin

and/or

49. zeta-cypermethrin

and/or

C) carbamates, preferably

50. carbaryl

and/or

51. fenoxycarb

and/or

52. formetanate

and/or

53. formetanate hydrochloride

disclosed in DE-A-1 169 194

and/or

54. methiocarb

and/or

55. methomyl

and/or

56. oxamyl

and/or

57. pirimicarb

and/or

58. propoxur

and/or

59. thiodicarb

and/or

D) benzoylureas, preferably

60. chlorfluazuron

and/or

61. diflubenzuron

and/or

62. lufenuron

and/or

63. teflubenzuron

and/or

64. triflumuron

and/or

E) macrolides, preferably

65. ivermectin

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

and/or

69. tebufenozide

and/or

G) halogenocycloalkanes, preferably

70. endosulfan

and/or

71 gamma-HCH

and/or

H) acaricides, preferably

72. fenazaquin

and/or

73. tebufenpyrad

and/or

74. pyrimidifen

and/or

75. triarathene

and/or

76. tetradifon

and/or

77. propargite

and/or

78. hexythiazox

and/or

79. bromopropylate

and/or

80. 2-(acetyloxy)-3-dodecyl-1,

4

-naphthalenedione

and/or

81. dicofol

and/or

I) other compounds such as

82. amitraz

and/or

83. azadirachtin

known from The Pesticide Manual, 11th Edition, 1997, p. 59

84. buprofezin

and/or

85. quinomethionate

and/or

86. thiocyclam hydrogen oxalate

and/or

87. triazamate

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

and/or

91. cyromazine

and/or

92. pymetrozin

93. diofenolan

and/or

94. indoxacarb

and/or

95. pyriproxyfen

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

Preferred

Especially

mixing

preferred mixing

Other component

ratio

ratio

2-(Acetyloxy)-3-dodecyl-1,4-

10:1 to 1:10

5:1 to 1:5

naphthalini-done

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

10:1 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., Ornithodorus 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.-butylamino4-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, tetrame-thylthiuram disulfide and 2,4,6-trichlorophenylmaleiimide.

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, Ornithodorus 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

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 - \frac{X \cdot 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)

0.32

0

known

Betacyfluthrin

0.32

75

known

Ex. (I-b-1) + betacyfluthrin (1:1) according to the invention

0.32 + 0.32

\frac{{found}^{*}}{100} \frac{calc .^{**}}{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)

0.32

0

known

Betacyfluthrin

0.32

50

known

Ex. (I-b-1) + betacyfluthrin (1:1) according to the invention

0.32 + 0.32

\frac{{found}^{*}}{85} \frac{calc .^{**}}{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)

1.6

0

known

Betacyfluthrin

1.6

80

known

Ex. (I-b-1) + betacyfluthrin (1:1) according to the invention

1.6 + 1.6

\frac{{found}^{*}}{100} \frac{calc .^{**}}{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)

8

0

known

Betacyfluthrin

8

90

known

Ex. (I-b-1) + betacyfluthrin (1:1) according to the invention

8 + 8

\frac{{found}^{*}}{100} \frac{calc .^{**}}{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)

0.32

0

known

Methamidophos

0.32

0

known

Ex. (I-b-1) + methamidophos (1:1) according to the invention

0.32 + 0.32

\frac{{found}^{*}}{90} \frac{calc .^{**}}{0}

*found = found action

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

Number	Name	Date	Kind
2494283	Cassaday et al.	Jan 1950	A
2502258	Hay et al.	Mar 1950	A
2578652	Cassaday	Dec 1951	A
2586655	Hook et al.	Feb 1952	A
2685552	Stiles	Aug 1954	A
2701225	Lorenz	Feb 1955	A
2754243	Gysin et al.	Jul 1956	A
2758115	Lorenz	Aug 1956	A
2767194	Fancher	Oct 1956	A
2812280	Wison et al	Nov 1957	A
2812281	Meltzer et al.	Nov 1957	A
2873228	Williard et al.	Feb 1959	A
2903478	Lambrech	Sep 1959	A
2908605	Beriger et al.	Oct 1959	A
2956073	Whetstone et al.	Oct 1960	A
3244586	Rigternik	Apr 1966	A
3264177	Kenaga	Aug 1966	A
3272854	Covey et al.	Sep 1966	A
3309266	Magee	Mar 1967	A
3530220	Buchanan	Sep 1970	A
3591662	Lorenz et al.	Jul 1971	A
3632694	Pearson et al.	Jan 1972	A
3639620	Donninger et al.	Feb 1972	A
3689648	Lorenz et al.	Sep 1972	A
3711477	Schelling et al.	Jan 1973	A
3716600	Magee	Feb 1973	A
3729565	Harrison et al.	Apr 1973	A
3748356	Wellinga et al.	Jul 1973	A
3759941	Sampei et al.	Sep 1973	A
3763143	Buchanan	Oct 1973	A
3781355	Harrison et al.	Dec 1973	A
3784696	Gubler	Jan 1974	A
3801680	Magee	Apr 1974	A
3825634	Magee	Jul 1974	A
3825636	Kishino et al.	Jul 1974	A
3835176	Matsuo et al.	Sep 1974	A
3845172	Magee	Oct 1974	A
3868449	Magee	Feb 1975	A
3884968	Harrison et al.	May 1975	A
3885032	Magee	May 1975	A
3898334	Kishino et al.	Aug 1975	A
3914417	Magee	Oct 1975	A
3922281	Sauli	Nov 1975	A
3922533	Royal	Nov 1975	A
3933908	Wellinga et al.	Jan 1976	A
3947529	Kishino et al.	Mar 1976	A
3989842	Wellinga et al.	Nov 1976	A
3996244	Fujimoto et al.	Dec 1976	A
4004031	Drabek	Jan 1977	A
4013717	Wellinga et al.	Mar 1977	A
4013793	Kishino et al.	Mar 1977	A
4016179	Fujimoto et al.	Apr 1977	A
4024163	Elliott et al.	May 1977	A
4031235	Fujimoto et al.	Jun 1977	A
4035378	Staubli et al.	Jul 1977	A
4039680	Fujimoto et al.	Aug 1977	A
4049679	Magee	Sep 1977	A
4053634	Bellina et al.	Oct 1977	A
4055661	Bellina et al.	Oct 1977	A
4058622	Fujimoto et al.	Nov 1977	A
4062968	Fujimoto et al.	Dec 1977	A
4082848	Bellina et al.	Apr 1978	A
4097581	Farooq et al.	Jun 1978	A
4110443	Magee	Aug 1978	A
4110469	Wellinga et al.	Aug 1978	A
4115584	Bellina et al.	Sep 1978	A
4125139	Guertin et al.	Nov 1978	A
4139636	Sirrenberg et al.	Feb 1979	A
4143157	Bellina et al.	Mar 1979	A
4148918	Bellina et al.	Apr 1979	A
4159328	Ikeda et al.	Jun 1979	A
4166124	Wellinga et al.	Aug 1979	A
4174405	Relyea et al.	Nov 1979	A
4178460	Berkelhammer et al.	Dec 1979	A
4179575	Martel et al.	Dec 1979	A
4183948	Huff	Jan 1980	A
4199569	Chabala et al.	Apr 1980	A
4199595	Berkelhammer et al.	Apr 1980	A
4215139	Fischer et al.	Jul 1980	A
4224227	Martel et al.	Sep 1980	A
4225598	Brechbuhler et al.	Sep 1980	A
4231932	Martel et al.	Nov 1980	A
4239777	Berkelhammer et al.	Dec 1980	A
4254050	Baum	Mar 1981	A
4254051	Baum	Mar 1981	A
4254052	Baum	Mar 1981	A
4257978	Martel et al.	Mar 1981	A
4260633	Anderson et al.	Apr 1981	A
4266074	Fujimoto et al.	May 1981	A
4279835	Martel et al.	Jul 1981	A
4310542	Martel et al.	Jan 1982	A
4322534	Baum	Mar 1982	A
4322535	Baum	Mar 1982	A
4323685	Baum	Apr 1982	A
4330675	Huff	May 1982	A
4378316	Huff	Mar 1983	A
4397864	Nakatani et al.	Aug 1983	A
4409150	Wood	Oct 1983	A
4427663	Mrozik	Jan 1984	A
4431814	Iwataki et al.	Feb 1984	A
4442116	Iwataki et al.	Apr 1984	A
4457943	Becher et al.	Jul 1984	A
4503071	Hirano et al.	Mar 1985	A
4510098	Crosby	Apr 1985	A
4510160	Robson	Apr 1985	A
4511350	Romanauskas	Apr 1985	A
4531002	Harris	Jul 1985	A
4531008	Fujimoto et al.	Jul 1985	A
4570005	Nakatani et al.	Feb 1986	A
4590272	Shiokawa et al.	May 1986	A
4606862	Harris	Aug 1986	A
4607044	Wellinga et al.	Aug 1986	A
4622337	Elliott et al.	Nov 1986	A
4622340	Becher et al.	Nov 1986	A
4666894	Maurer et al.	May 1987	A
4687845	Hollowood et al.	Aug 1987	A
4690947	Zeck et al.	Sep 1987	A
4732903	Martel et al.	Mar 1988	A
4742072	Jacobson et al.	May 1988	A
4751225	Nishida et al.	Jun 1988	A
4782174	Fuchs et al.	Nov 1988	A
4798837	Drabek et al.	Jan 1989	A
4833151	Wellinga et al.	May 1989	A
4843068	Hamaguchi et al.	Jun 1989	A
4845097	Matsumoto et al.	Jul 1989	A
4879292	Nishida et al.	Nov 1989	A
4883806	Martel et al.	Nov 1989	A
4918086	Gsell	Apr 1990	A
4918088	Gsell	Apr 1990	A
4920135	Wellinga et al.	Apr 1990	A
4931439	Kristinsson	Jun 1990	A
4948798	Gsell	Aug 1990	A
4950668	Okada et al.	Aug 1990	A
4962126	Drabek	Oct 1990	A
4963572	Gsell	Oct 1990	A
4963574	Bachmann et al.	Oct 1990	A
4970222	Nishida et al.	Nov 1990	A
4970330	Huff	Nov 1990	A
4980506	Drabek et al.	Dec 1990	A
4996325	Kristinsson	Feb 1991	A
5004822	Elliott et al.	Apr 1991	A
5010098	Brown et al.	Apr 1991	A
5034404	Uneme et al.	Jul 1991	A
5049571	Gsell	Sep 1991	A
5063236	Gsell	Nov 1991	A
5107017	Drabek et al.	Apr 1992	A
5110986	Kelly	May 1992	A
5142064	Wellinga et al.	Aug 1992	A
5153224	Drabek et al.	Oct 1992	A
5175301	Minamida et al.	Dec 1992	A
5192778	Kodaka et al.	Mar 1993	A
5214152	Minamida et al.	May 1993	A
5232940	Hatton et al.	Aug 1993	A
5245071	Wellinga et al.	Sep 1993	A
5256679	Minamida et al.	Oct 1993	A
5262383	Fischer et al.	Nov 1993	A
5264584	Kodaka et al.	Nov 1993	A
5310938	Brown et al.	May 1994	A
5319092	Jacobson et al.	Jun 1994	A
5342958	Wellinga et al.	Aug 1994	A
5367093	Dekeyser et al.	Nov 1994	A
5411963	Dreikorn et al.	May 1995	A
5434181	Kodaka et al.	Jul 1995	A
5438123	Dekeyser et al.	Aug 1995	A
5455263	Doscher et al.	Oct 1995	A
5462938	Annus et al.	Oct 1995	A
5470984	Jacobson et al.	Nov 1995	A
5478855	Suzuki et al.	Dec 1995	A
5489603	Uneme et al.	Feb 1996	A
5532365	Kodaka et al.	Jul 1996	A
5536746	Dekeyser et al.	Jul 1996	A
5547974	Hatton et al.	Aug 1996	A
5595915	Geysen	Jan 1997	A
5608077	Hatton et al.	Mar 1997	A
5614527	Kinoshita et al.	Mar 1997	A
5633375	Uneme et al.	May 1997	A
5696256	Kando et al.	Dec 1997	A
5708170	Annis et al.	Jan 1998	A
5714191	Hatton et al.	Feb 1998	A
5849768	Minamida et al.	Dec 1998	A
5852012	Maienfisch et al.	Dec 1998	A
5916618	Hatton et al.	Jun 1999	A
6022871	Maienfisch et al.	Feb 2000	A
6022967	Shiokawa et al.	Feb 2000	A
6124297	Minamida et al.	Sep 2000	A

Number	Date	Country
2753426	Jun 1978	DE
161 047	Sep 1984	DE
199 393 95	Apr 2000	DE
199 131 74	Sep 2000	DE
0 528 156	Feb 1993	EP
0 639 559	Oct 1997	EP
775085	Sep 1952	GB
834815	May 1960	GB
1 181 657	Feb 1970	GB
1 589 259	May 1981	GB

Active ingredient combination having insecticidal and acaricidal characteristics

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Priority Claims (1)

PCT Information

US Referenced Citations (185)

Foreign Referenced Citations (10)

Non-Patent Literature Citations (7)

Entry
Weeds 15, (month unavailable) 1967, pp. 20-22, Calculating Synergistic and Antagonistic Responses of Herbicide Combinations by S.R. Colby.
The Pesticide Manual, Eleventh Edition, Editor: C D S Tomlin, (Date Unavailable) Verticillium lecanii Biological Agent pp. 1266-1267.
The Pesticide Manual, Eleventh Edition, Editor: C.D.S. Tomlin (Date Unavailable) Azadirachtin Insecticide pp. 59-60.
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 Presticide Manual, Tenth Edition” Pesticide Manual, GB, Farnham,.
BCPC, vol. Ed. 10, Page(s) 1335-1341 XP002099499 ISBN:0-948404-79-5 the index of the active agent classes.