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(19).    1:430111111
Kenya intlustrial Property Institute.    (11) Patent Number: 359
(45) Date of grant: 01/12/2009

(12) PATENT
(51) Int.CI.7: A 01N 31/14, 37/44, 43/36, 43/38, 53/00
 
(21)Application    KE/P/2001/00204
Number:
(22) Filing Date:    18/06/2001
(31) Priority Number: 10031765.0 and 10036896.4
(84) WO No. WO 02/00025 Al
03/01/2002
(32) Date: 29/06/2000 and 28/07/2000 (33) Country: DE
 
(73)    Owner(s): Bayer CropScience AG of Alfred-Nobel-Strasse 50, 40789 Monheim, Germany
(72) Inventor(s)    FISCHER, Reiner and ERDELEN, Christoph
(74)    Agent/address for correspondence: Kaplan & Stratton Advocates, P.O. Box 40111-00100, Nairobi
(54) Title:    COMBINATIONS OF ACTIVE INGREDIENTS, WHICH EXHIBIT
INSECTICIDAL AND ACARICIDAL PROPERTIES
(57) Abstract: The invention relates to novel active-ingredient combinations consisting of specific cyclic ketoenoles and the active ingredients (1) to (23), mentioned in the description. Said combinations have excellent insecticidal and acaricidal properties.
 
-1-
Active compound combinations having insecticidal and acaricidal properties
The present invention relates to novel active compound combinations comprising
known cyclic ketoenols on the one hand and other known insecticidally active
5        compounds on the other hand, which combinations are highly suitable for controlling
animal pests such as insects and undesired acarids.
It is already known that certain cyclic ketoenols have herbicidal, insecticidal and acaricidal properties. The activity of these substances is good; however, at low 10    application rates it is sometimes unsatisfactory.
Bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A-355 599 and EP-A-415 211) and substituted monocyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A-442 077) with herbicidal, insecticidal or acaricidal action are known.
15
Also known are polycyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-442 073) and 1H-arylpyrrolidine-dione derivatives (EP-A-456 063, EP-A-521 334, EP-A¬596 298, EP-A-613 884, EP-A-613 885, WO 94/01 997, WO 95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395, WO 96/35 664, WO 97/01 535,
20 WO 97/02 243, WO 97/36 868, WO 97/ 43 275, WO 98/05 638, WO 98/06 721, WO 98/25 928, WO 99/16 748, WO 99/24 437, WO 99/43 649, WO 99/48 869 and WO 99/55 673).
Furthermore, it is already known that numerous heterocycles, organotin compounds,
25 benzoylureas and pyrethroids have insecticidal and acaricidal properties (cf. WO 93/22 297, WO 93/10 083, DE-A-2 641 343, EP-A-347 488, EP-A-210 487, US 3,364,177 and EP-A-234 045). However, the activity of these substances is not always satisfactory.
30    It has now been found that mixtures of compounds of the formula (I)
 
-2-
 

 
in which
X    represents halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy or cyano,
5
W, Y and Z independently of one another each represent hydrogen, halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy or cyano,
A    represents hydrogen, in each case optionally halogen-substituted alkyl,
10    alkoxyalkyl, saturated, optionally substituted cycloalkyl, in which optionally
at least one ring atom is replaced by a heteroatom,
B    represents hydrogen or alkyl,
15    A and B together with the carbon atom to which they are attached represent a
saturated or unsaturated, unsubstituted or substituted cycle which optionally contains at least one heteroatom,
D    represents hydrogen or an optionally substituted radical selected from the 20    group consisting of alkyl, alkenyl, alkoxyalkyl, saturated cycloalkyl in which
optionally one or more ring members are replaced by heteroatoms,
A and D together with the atoms to which they are attached represent a saturated or unsaturated cycle which is unsubstituted or substituted in the A,D moiety and 25    optionally contains at least one heteroatom,
G    represents hydrogen (a) or represents one of the groups
 
-3-
 

 
in which
5    E    represents a metal ion or an ammonium ion,
L    represents oxygen or sulphur,
M    represents oxygen or sulphur,
10
R1    represents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionally halogen-,
alkyl- or alkoxy-substituted cycloalkyl which may be interrupted by at
least one heteroatom, in each case optionally substituted phenyl,
15    phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
R2    represents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl, polyalkoxyalkyl or represents in each case optionally substituted cycloalkyl, phenyl or benzyl,
20
R3    represents optionally halogen-substituted alkyl or optionally
substituted phenyl,
R4 and R5 independently of one another each represent in each case 25    optionally    halogen-substituted    alkyl,    alkoxy,    alkylamino,
dialkylamino, alkylthio, alkenylthio, cycloalkylthio or represent in
 
-4-
each case optionally substituted phenyl, benzyl, phenoxy or phenylthio and
R6 and R7 independently of one another each represent hydrogen, in each
5 case optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represents optionally substituted phenyl, represent optionally substituted benzyl or together with the N atom to which they are attached represent an optionally substituted ring which is optionally interrupted by oxygen or sulphur
10
and
pyrethroids, preferably
15    1.    acrinathrin
 
known from EP-A-048 186 and/or
 
and/or
3.    betacyfluthrin
 

 
and/or
10    4.    cyhalothrin   
     known from DE-A-2 802 962
and/or   
 

5    and/or
6.    deltamethrin
Br H C CH, 0
\    CN   
             known from DE-A-2 326 077

10    and/or
7.    esfenvalerate
 

 
15    and/or
 
- 7 -
8.    ethofenprox
10    known from DE-A-2 231 312
and/or
9.    fenvalerate 15
CI     

known from DE-A-2 335 347
and/or
20
 
8
11.    flucythrinate
 
known from DE-A-2 757 066
and/or
12.    lambda-cyhalothrin
 

 
and/or
 
13.    permethrin
 

 
and/or
 
14.    taufluvalinate
CI    O    CN
F3C    H3C    CH,
known from EP-A-038 617
and/or
15.    tralomethrin
and/or
 
16.    zeta-cypermethrin
 
and/or
18.    bifenthrin
 
known from EP-A-026 542
known from DE-A-27 09 264
 

     known from EP-A-049 977

15    and/or
 
19.    cycloprothrin
 

 
known from DE-A-2653189
5    and/or
20.    eflusilanate
 

 
known from DE-A-36 04 781
10
and/or
21.    fubfenprox
 
15    known from DE-A-37 08 231
 
R = -CH3 or -CO2CH3
R1 = -CH=CH2 or -CH3 or -CH2CH3
known from The Pesticide Manual, 1997, 11th edition, p. 1056 and/or
23.    resmethrin
 
15    known from GB-A-1 168 797
have very good insecticidal and acaricidal properties.
Surprisingly, the insecticidal and acaricidal activity of the active compound
20 combinations according to the invention is considerably higher than the sum of the activities of the individual active compounds. Thus, an unforeseeable real synergistic effect is present, and not just an addition of activities.
 
- 13 -
In addition to at least one active compound of the formula (I), the active compound combinations according to the invention comprise at least one active compound from among the compounds 1 to 23.
5    Preference is given to active compound combinations comprising compounds of the
formula (I) in which the radicals are as defined below:
W    preferably represents hydrogen, C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine
or fluorine,
10
X    preferably represents C1-C4-alkyl, C1-C4-alkoxy, C1-C4-halogenoalkyl,
fluorine, chlorine or bromine,
Y and Z independently of one another each represent hydrogen, C1-C4-alkyl, 15    halogen, C1-C4-alkoxy or C1-C4-halogenoalkyl,
A    represents hydrogen or in each case optionally halogen-substituted C 1-C6-
alkyl or C3-C8-cycloalkyl,
20    B    preferably represents hydrogen, methyl or ethyl,
A, B and the carbon atom to which they are attached represent saturated C3-C6- cycloalkyl in which optionally one ring member is replaced by oxygen or sulphur and which is optionally mono- or disubstituted by CI-Ca-alkyl,
25    trifluoromethyl or Ci-C4-alkoxy,
D    preferably represents hydrogen, in each case optionally fluorine- or chlorine-
substituted Ci-C6-alkyl, C3-C4-alkenyl or C3-C6-cycloalkyl,
 
-14-
A and D together preferably represent in each case optionally methyl-substituted C3- C4-alkanediy1 in which optionally one methylene group is replaced by sulphur.
5    G    preferably represents hydrogen (a) or represents one of the groups
0    L    R4
 2
R1 (b),    R (c),    SOT— R3 (d), — P , 5
L."    (e),
(e),
R6
E (0or    N.    (g) in particular represents (a), (b), (c) or
L(g)
in which
10    E    represents a metal ion or an ammonium ion,
L    represents oxygen or sulphur and
M    represents oxygen or sulphur,
15
R'    preferably represents in each case optionally halogen-substituted C i-Cio-alkyl,
C2-C10-alkenyl, C1-C4-alkoxy-Ci-C4-alkyl, C1-C4-alkylthio-Ci-C4-alkyl or optionally fluorine-, chlorine-, C i-C4-alkyl or C1-C2-alkoxy-substituted C3- Cs-cycloalkyl,
20
represents optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4- alkyl-, C1-C4-alkoxy-, trifluoromethyl- or trifluoromethoxy-substituted phenyl,
25    represents in each case optionally chlorine- or methyl-substituted pyridyl or
thienyl,
 
-15-
R2    preferably represents in each case optionally fluorine- or chlorine-substituted
C2-Cio-alkenyl, C i-Ca-alkoxy-C2-Ca-alkyl,
represents optionally methyl- or methoxy-substituted C5-C6-cycloalkyl or
5
represents in each case optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl, C1-Ca-alkoxy, trifluoromethyl- or trifluoromethoxy¬substituted phenyl or benzyl,
10    R3    preferably represents optionally fluorine-substituted C1-C4-alkyl or represents
optionally fluorine-, chlorine-, bromine-, C1-Ca-alkyl, C -C4-alkoxY, trifluoromethyl, trifluoromethoxy, cyano or nitro-substituted phenyl,
R4    preferably represents in each case optionally fluorine- or chlorine-substituted
15    CI-Ca-alkyl, C1-C4-alkoxy, C i-Ca-alkylamino, C1-Ca-alkylthio or represents in
each case optionally fluorine-, chlorine-, bromine-, nitro-, cyano-, C 1-C4- alkoxy-, trifluoromethoxy-, CI-Ca-alkylthio-, C1-Ca-halogenoalkylthio-, CI-Ca-alkyl- or trifluoromethyl-substituted phenyl, phenoxy or phenylthio,
20    R5    preferably represents Ci-C4-alkoxy or C1-Ca-thioalkyl,
R6    preferably represents CI-C6-alkyl, C3-C6-cycloalkyl, Ci-C6-alkoxy, C3-C6-
alkenyl, C1-Ca-alkoxy-Ci-Ca-alkyl,
25    R7    preferably represents CI-C6-alkyl, C3-C6-alkenyl or C1-C4-alkoxy-C1-C4-alkyl,
R6 and R7 together preferably represent an optionally methyl- or ethyl-substituted C3- C6-alkylene radical in which optionally one carbon atom is replaced by oxygen or sulphur,
30
 
- 16-
W    particularly preferably represents hydrogen, methyl, ethyl, chlorine, bromine
or methoxy,
X    particularly preferably represents chlorine, bromine, methyl, ethyl, propyl, i-
    5    propyl, methoxy, ethoxy or trifluoromethyl,
Y and Z independently of one another each represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, trifluoromethyl or methoxy,
    10    A    particularly preferably represents methyl, ethyl, propyl, i-propyl, butyl, i-
butyl, sec-butyl, tert-butyl, cyclopropyl, cyclopentyl or cyclohexyl,
B    particularly preferably represents hydrogen, methyl or ethyl,
    15    A, B and the carbon atom to which they are attached particularly preferably represent
saturated C6-cycloalkyl in which optionally one ring member is replaced by oxygen and which is optionally monosubstituted by methyl, ethyl, methoxy, ethoxy, propoxy or butoxy,
    20    D    particularly preferably represents hydrogen, represents methyl, ethyl, propyl,
i-propyl, butyl, i-butyl, allyl, cyclopropyl, cyclopentyl or cyclohexyl,
A and D together particularly preferably represent optionally methyl-substituted C3- C4-alkanediyi,
25
G    particularly preferably represents hydrogen (a) or represents one of the groups
0    0    R6
R1 (b),    R2 (c), or    0    FZ7 (g),
 
- 17 -
in which
M    represents oxygen or sulphur,
5    RI    particularly preferably represents C1-Cs-alkyl, C2-C4-alkenyl, methoxymethyl,
ethoxymethyl, ethylthiomethyl, cyclopropyl, cyclopentyl or cyclohexyl,
represents optionally fluorine-, chlorine-, bromine-, cyan-, nitro-, methyl-, ethyl-, methoxy-, trifluoromethyl- or trifluoromethoxy-substituted phenyl,
10
represents in each case optionally chlorine- or methyl-substituted pyridyl or thienyl,
R2    particularly preferably represents C1-C8-alkyl, C2-C4-alkenyl, methoxyethyl,
15    ethoxyethyl or represents phenyl or benzyl,
R6 and R7 independently of one another particularly preferably represent methyl or ethyl or together represent a C5-alkylene radical in which the C3-methylene group is replaced by oxygen.
20
W    very particularly preferably represents hydrogen or methyl,
X    very particularly preferably represents chlorine, bromine or methyl,
25    Y and Z independently of one another each very particularly preferably represent
hydrogen, chlorine, bromine or methyl,
A, B and the carbon atom to which they are attached very particularly preferably represent saturated C6-cycloalkyl in which optionally one ring member is
30        replaced by oxygen and which is optionally monosubstituted by methyl,
methoxy, ethoxy, propoxy or butoxy,
 
- 18 -
D    very particularly preferably represents hydrogen,
G    very particularly preferably represents hydrogen (a) or represents one of the
5    groups
0    0
.R2    or
(b),    M(c),    R6
)
0

in which
10
M    represents oxygen or sulphur,
R1    very particularly preferably represents CI-Cs-alkyl, C2-C4-alkenyl,
methoxymethyl, ethoxymethyl, ethylmethylthio, cyclopropyl, cyclopentyl, 15    cyclohexyl or
represents optionally fluorine-, chlorine-, bromine-, methyl-, methoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- or nitro-substituted phenyl,
20    represents in each case optionally chlorine- or methyl-substituted pyridyl or
thienyl,
very particularly preferably represents CI    C2-C4-alkenyl,
methoxyethyl, ethoxyethyl, phenyl or benzyl,
25
R6 and R7 independently of one another each very particularly preferably represent methyl, ethyl or together represent a C5-alkylene radical in which the C3-methylene group is replaced by oxygen.
 

Example No.    w    x    Y    Z    R    G    m.p.°C
I-1    H    Br    5-CH3    H    OCH3    CO-i-C3H7    122
1-2    H    Br    5-CH3    H    OCH3    CO2-C2H5    140 - 142
1-3    H    CH3    5-CH3    H    OCH3    H    > 220
1-4    H    CH3    5-CH3    H    OCH3    CO2-C2H5    128
1-5    CH3    CH3    3-Br    H    OCH3    H    > 220
1-6    CH3    CH3    3-C1    H    OCH3    H    219
1-7    H    Br    4-CH3    5-CH3    OCH3    CO-i-C3H7    217
I-8    H    CH3    4-Cl    5-CH3    OCH3    CO2C2H5    162
1-9    H    CH3    4-CH3    5-CH3    OCH3        oil
                        —
CO—N    0   
                           
1-10    0-13    CH3    3-CH3    4-CH3    OCH3    H    >220
I-11    H    CH3    5-CH3    H    0C2H5    /---\ CO—N    0    oil
                           
1-12    CH3    CH3    3-Br    H    0C2H5    CO-i-C3H7    212 -214
1-13    H    CH3    4-CH3    5-CH3    0C2H5    CO-n-Pr    134
1-14    H    CH3    4-CH3    5-CH3    0C2H5    CO-i-Pr    108
I-15    H    CH3    4-CH3    5-CH3    0C2H5    CO-c-Pr    163

and at least one active compound from among the compounds 1 to 23.
In addition, the active compound combinations may comprise further fungicidally, 5    acaricidally or insecticidally active mixing components.
 
-20-
If the active compounds in the active compound combinations according to the invention are present in certain weight ratios, the synergistic effect is particularly pronounced. However, the weight ratios of the active compounds in the active compound combinations can be varied within a relatively wide range. In general, the
5 combinations according to the invention comprise the active compounds of the formula (I) and the mixing partners in the preferred and particularly preferred mixing ratios stated in the table below:
The mixing ratios are based on weight ratios. The ratio is to be understood as 10    meaning active compound of the formula (I): Mixing partner
Mixing partner    Preferred mixing ratio    Particularly preferred mixing ratio
acrinathrin    20:1 to 1:50    10:1 to 1:1
alpha-cypermethrin    50:1 to 1:5    10:1 to 1:1
betacyfluthrin    50:1 to 1:5    10:1 to 1:1
cyhalothrin    50:1 to 1:5    10:1 to 1:1
cypermethrin    50:1 to 1:5    10:1 to 1:1
deltamethrin    50:1 to 1:5    10:1 to 1:1
esfenvalerate    50:1 to 1:5    10:1 to 1:1
etofenprox    10:1 to 1:10    5:1 to 1:5
fenpropathrin    10:1 to 1:10    5:1 to 1:5
fenvalerate    20:1 to 1:5    10:1 to 1:1
flucythrinate    50:1 to 1:5    10:1 to 1:1
lambda-cyhalothrin    50:1 to 1:5    10:1 to 1:1
permethrin    10:1 to 1:10    5:1 to 1:5
tau-fluvalinate    20:1 to 1:5    10:1 to 1:2
tralomethrin    50:1 to 1:5    10:1 to 1:1
zeta-cypermethrin    50:1 to 1:5    10:1 to 1:2
cyfluthrin    50:1 to 1:5    10:1 to 1:1
bifenthrin    10:1 to 1:10    10:1 to 1:1
 
- 21 -
Mixing partner    Preferred mixing ratio    Particularly preferred mixing ratio
cycloprothrin    10:1 to 1:10    5:1 to 1:5
eflusilanate    10:1 to 1:10    5:1 to 1:5
fubfenprox    10:1 to 1:10    5:1 to 1:5
pyrethrin    50:1 to 1:10    5:1 to 1:1
resmethrin    50:1 to 1:10    5:1 to 1:1

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 animal health, in forests, in the protection of
 5 stored products 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,
    10    Porcellio scacalc.
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.
    15    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,
    20    Leucophaea maderae, Blatta 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.
 
- 22 -
From the order of the Thysanoptera, for example, Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
5 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
10        cincticeps, Lecanium comi, 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.,
15 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,
20        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.,
25 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
30        molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon
solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.
 
- 23 -
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,
5 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 10    spp.
From the class of the Arachnida, for example, Scorpio maunis, 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.,
15        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
20        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,
25 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 30    active compounds with extenders, that is, liquid solvents and/or solid carriers,
 
-24-
optionally with the use of surfactants, that is, emulsifiers and/or dispersants, and/or foam formers.
If the extender used is water, it is also possible, for example, to use organic solvents
 5 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
 10 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:
    15    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
 20 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
    25    hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and
methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and
    30    polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and
 
- 25 -
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,
 5 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
    10    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,
 15 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, inter alia.
    20    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
 25 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
    30    available formulations can vary within wide limits. The active compound
 
-26-
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.
5
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 good stability to alkali on limed substrates.
10    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, head lice, bird lice and fleas. These parasites include:
15    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
20    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
25 spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Moreilia 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., 30    Xenopsylla spp., Ceratophyllus spp.
 
- 27 -
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, Blattela germanica, Supella spp.
    5    From the subclass of the Acaria (Acarida) and the orders 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.
    10    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.,
    15    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,
 20 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
    25    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
    30    example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-
through method, suppositories, by parenteral administration such as, for example, by
 
-28-
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
    5    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,
    10    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
    15    materials.
The following insects may be mentioned by way of example and with preference, but not by way of limitation:
    20    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
    25    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
 
-29-
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
Bristle-tails such as Lepisma saccharina.
5
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.
10    The material which is to be protected from insect attack is very particularly
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 15    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, chipboard, joinery, or timber products
20    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.
25
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
30    auxiliaries.
 
-30-
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.
5    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.
10
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.
15
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
20        mineral-oil-containing solvent mixtures, preferably white spirit, petroleum and/or
alkylbenzene.
Mineral oils 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 are
25    advantageously used.
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,
30    preferably a-monochloronaphthalene are used.
 
- 31 -
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
    5    flash point of above 30°C, preferably above 45°C, and that the 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
    10    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
 15 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
    20    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
 25 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
    30    comprises, as organochemical binders, at least one alkyd resin or modified alkyd
resin and/or a drying vegetable oil. Alkyd resins which are preferably used in
 
- 32 -
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
 5 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
 10 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.
    15    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, water, if appropriate as a mixture with one or more of the abovementioned organochemical solvents or diluents,
    20    emulsifiers and dispersants.
Particularly effective timber protection is achieved by industrial-scale impregnating processes, for example the vacuum, double-vacuum or pressure processes.
    25    The active compound combinations according to the invention can at the same time
be employed for protecting objects which come into contact with saltwater or brackish water, such as hulls, screens, nets, buildings, moorings and signalling systems, against fouling.
    30    Fouling by sessile Oligochaeta, such as Serpulidae, and by shells and species from
the Ledamorpha group (goose barnacles), such as various Lepas and Scalpellum
 
- 33 -
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 stops in the dry dock.
5
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.
10    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, allows the use
of heavy metals such as, for example, in bis(trialkyltin) sulphides, tri-n-butyltin
15 laurate, tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride, tri-n-buty1(2- pheny1-4-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,
20 bisdimethyldithiocarbamoylzinc ethylenebisthiocarbamate, zinc oxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, copper naphthenate and tributyltin halides to be dispensed with, or the concentration of these compounds substantially reduced.
25    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 30    according to the invention are:
 
-34-
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;
5
fungicides such as
benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide, dichlofluanid,
fluorfolpet, 3-iodo-2-propinyl butylcarbamate, tolylfluanid and azoles such as azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole,
10    propiconazole and tebuconazole;
molluscicides such as
fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and trimethacarb;
15    or conventional antifouling active compounds such as
4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl sulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine, 2,4,5,6-tetrachloroisophthalonitrile,
20    tetramethylthiuram disulphide 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
 
- 35 -
active compounds according to the invention, antifouling paints comprise, in particular, binders.
Examples of recognized binders are polyvinyl chloride in a solvent system,
 5 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
    10    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 insoluble in salt water. Paints may furthermore
 15 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.
20
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
    25    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,
    30    Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis,
Dermatophagoides pteronissimus, Dermatophagoides forinae.
 
-36-
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 scacalc.
5        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,
10 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.
15    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.
20 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.
25    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
30        fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula
spp., Tetramorium caespitum.
 
-37-
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.
5
They are used as aerosols, pressureless 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,
10        evaporation systems, moth papers, moth bags and moth gels, as granules or dusts, in
baits for spreading or in bait stations.
According to the invention, it is possible to treat all plants and parts of plants. Plants
are to be understood here as meaning all plants and plant populations such as desired
15 and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeder's certificates. Parts
20 of plants are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubers and rhizomes. Parts of plants also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers,
25    rhizomes, cuttings and seeds.
The treatment according to the invention of the plants and parts of plants with the
active compounds is carried out directly or by action on their environment, habitat or
storage area according to customary treatment methods, for example by dipping,
30    spraying, evaporating, atomizing, broadcasting, brushing-on and, in the case of
 
- 38 -
propagation material, in particular in the case of seeds, furthermore by one- or multi-layer coating.
As already mentioned above, it is possible to treat all plants and their parts according
5 to the invention. In a preferred embodiment, wild plant species and plant varieties, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant varieties obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts
10        thereof are treated. The terms "parts", "parts of plants" and "plant parts" have been
explained above.
Particularly preferably, plants of the plant varieties which are in each case commercially available or in use are treated according to the invention.
15
Depending on the plant species or plant varieties, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an
20 increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products,
25        better storage stability and/or processability of the harvested products are possible
which exceed the effects which were actually to be expected.
The transgenic plants or plant varieties (i.e. those obtained by genetic engineering)
which are preferred and to be treated according to the invention include all plants
30        which, in the genetic modification, received genetic material which imparts
particularly advantageous useful traits to these plants. Examples of such traits are
 
-39-
better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or
 5 processability of the harvested products. Further and particularly emphasized examples of such properties are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the
 10 important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton and oilseed rape. Traits that are particularly emphasized are the increased defence of the plants against insects by toxins formed in the plants, in particular those formed by
 15 the genetic material from Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryMA, CryMB2, Cry9c Cry2Ab, Cry3Bb and CrylF and also combinations thereof) (hereinbelow referred to as "Bt plants"). Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas,
 20 glyphosate or phosphinotricin (for example the "PAT" gene). The genes in question which impart the desired traits can also be present in combination with one another in the transgenic plants. Examples of "Bt plants" which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans),
 25 KnockOutO (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link® (tolerance to
    30    phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and
STS1D (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants
 
-40-
(plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant varieties having these or still¬to-be-developed genetic traits, which plants will be developed and/or marketed in the
    5    future.
The plants listed can be treated according to the invention in a particularly
advantageous manner with the active compound mixtures according to the invention.
The preferred ranges stated above for the mixtures also apply to the treatment of
    10    these plants. Particular emphasis is given to the treatment of plants with the mixtures
specifically mentioned in the present text.
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
    15    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
    20    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
25
X    is the kill rate, expressed as a percentage of the untreated control, when
employing active compound A at an application rate of m g/ha or in a concentration of m ppm,
 
-41
Y    is the kill rate, expressed as a percentage of the untreated control, when
employing active compound B at an application rate of n g/ha or in a concentration of n ppm and
5    E    is the kill rate, expressed as a percentage of the untreated control, 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
X -Y
10    E=X Y— 100
If the actual insecticidal kill rate exceeds the calculated value, the action of the
combination is superadditive, i.e. a synergistic effect is present. In this case, the
actually observed kill rate must exceed the value calculated using the above formula
15    for the expected kill rate (E).
After the desired period of time, the kill rate in % is determined. 100% means that all the animals have been killed; 0% means that none of the animals has been killed.
 
- 42 -
Use Examples
Example A
    5    Aphis gossypii test
Solvent:    3 parts by weight of dimethylformamide
Emulsifier:    1 part by weight of alkylaryl polyglycol ether
    10    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 water to the desired concentrations.
Cotton leaves (Gossypium hirsutum) which are heavily infested by the cotton aphid
    15    (Aphis gossypii) are treated by being dipped into the preparation of active compound
of the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all the animals have been killed; 0% means that none of the aphids has been killed. The kill
    20    rates that are determined are calculated using Colby formula.
In this test, for example, the following active compound combination according to the present application exhibits a synergistically enhanced activity compared to the active compounds applied individually:
 
- 43 -
Table A Plant-damaging insects
Aphis gossypii test
Active compounds    Active compound concentration in ppm    Kill rates in% after 6d
Ex. I-10
Known from WO 97/36868    1.6    0   
cyfluthrin known    1.6    75   
Ex. I-10 + cyfluthrin (1:1)
according to the invention    1.6 + 1.6    found*    calc.**
        95    75

* found = activity found
**calc. = activity calculated using Colby's formula
 
- 44 -
Example B 
Myzus test
5    Solvent:    3 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 10    concentrate is diluted with water to the desired concentrations.
Cabbage leaves (Brassica oleracea) which are heavily infested by the peach aphid (Myzus persicae) are treated by being dipped into the preparation of active compound of the desired concentration.
15
After the desired period of time, the kill in % is determined. 100% means that all the animals have been killed; 0% means that none of the animals has been killed. The kill rates determined are calculated using Colby's formula.
20    In this test, for example, the following active compound combination according to
the present application exhibits a synergistically enhanced activity compared to the active compounds applied individually:
 
- 45 -
Table B  Plant-damaging insects
Myzus test
Active compounds    Active compound concentration in ppm    Kill rates in % after ld
Ex. I-10
known from WO 97/36868    1.6    0
cyfluthrin known    1.6    25
Ex. I-10 + cyfluthrin (1:1)
according to the invention    1.6 + 1.6    found*    calc.**
        65    25

* found = activity found
**calc. = activity calculated using Colby's formula
 
-46-
Example C
Critical concentration test / soil insects — treatment of transgenic plants
    5    Test insect:    Diabrotica balteata - larvae in soil
Solvent:    7 parts by weight of acetone
Emulsifier:    1 part by weight of alkylaryl polyglycol ether
    10    To produce a suitable preparation of active compound, 1 part by weight of active
compound is mixed with the stated amounts of solvent, the stated amount of emulsifiers added and the concentrate is diluted with water to the desired concentrations.
    15    The preparation of active compound is poured onto the soil. Here, the concentration
of active compound in the preparation is virtually irrelevant, only the amount by weight of active compound per volume unit of soil, which is stated in ppm (mg/1), matters. 0.25 1 pots are filled with the soil and allowed to stand at 20°C.
    20    Immediately after preparation, 5 pre-germinated maize corns of the variety
YIELD GUARD (trade mark of Monsanto Comp., USA) are placed into each pot. After 2 days, the corresponding test insects are placed into the treated soil. After a further 7 days, the efficacy of the active compound is determined by counting the maize plants that have emerged (1 plant = 20% efficacy).
 
-47-
Example D
Heliothis virescens test — treatment of transgenic plants
5    Solvent:    7 parts by weight of acetone
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 amount of solvent and the stated amount o 10    emulsifier, and the concentrate is diluted with water to the desired concentration.
Soya bean shoots (Glycine max) of the Roundup Ready variety (trade mark o
Monsanto Comp. USA) are treated by being dipped into the preparation of activ
compound of the desired concentration and are populated with the tobacco budworn
15    Heliothis virescens while the leaves are still moist.
After the desired period of time, the kill of the insects is determined.
 
-48-
Patent claims
1.    Composition, comprising mixtures of compounds of the formula (I)
G-0
 

 
in which
X    represents halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy or
cyano,
W, Y and Z independently of one another each represent hydrogen, halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy or cyano,
A    represents hydrogen, in each case optionally halogen-substituted alkyl,
15    alkoxyalkyl, saturated, optionally substituted cycloalkyl, in which
optionally at least one ring atom is replaced by a heteroatom,
B    represents hydrogen or alkyl,
20    A and B together with the carbon atom to which they are attached represent a
saturated or unsaturated, unsubstituted or substituted cycle which optionally contains at least one heteroatom,
D    represents hydrogen or an optionally substituted radical selected from
25    the group consisting of alkyl, alkenyl, alkoxyalkyl, saturated
cycloalkyl in which optionally one or more ring members are replaced by heteroatoms,
 
-49-
A and D together with the atoms to which they are attached represent a saturated or unsaturated cycle which is unsubstituted or substituted in the A,D moiety and optionally contains at least one heteroatom,
5    G    represents hydrogen (a) or represents one of the groups
 

 
R6
E    or    Nc 7 (g),
L
in which
10
E    represents a metal ion or an ammonium ion,
L    represents oxygen or sulphur,
15    M    represents oxygen or sulphur,
R1    represents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionally halogen-,
alkyl- or alkoxy-substituted cycloalkyl which may be interrupted by at
20        least one heteroatom, in each case optionally substituted phenyl,
phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
R2    represents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl, polyalkoxyalkyl or represents in each case optionally 25    substituted cycloalkyl, phenyl or benzyl,
 
-50-
R3    represents optionally halogen-substituted alkyl or optionally
substituted phenyl,
R4 and R5 independently of one another each represent in each case
5 optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio or represent in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio and
10    R6 and R7 independently of one another each represent hydrogen, in each
case optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represents optionally substituted phenyl, represent optionally substituted benzyl or together with the N atom to which they are attached represent an optionally substituted ring which is
15    optionally interrupted by oxygen or sulphur
and at least one of the compounds below
acrinathrin alpha-cypermethrin
betacyfluthrin
cyhalothrin cypermethrin deltamethrin esfenvalerate etofenprox fenpropathrin
fenvalerate flucythrinate lambda-cyhalothrin
permethrin
 
-51-
tau-fluvalinate
tralomethrin zeta-cypermethrin
cyfluthrin bifenthrin cycloprothrin eflusilanate fubfenprox pyrethrin
resmethrin.
2.    Composition according to Claim 1, comprising compounds of the formula (I)
in which
    5    W    represents hydrogen, C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or
fluorine,
X    represents C1-C4-alkyl, C1-C4-alkoxy, C1-C4-halogenoalkyl, fluorine,
chlorine or bromine,
10
Y and Z independently of one another each represent hydrogen, C1-C4-alkyl,
halogen, C1-C4-alkoxy or C1-C4-halogenoalkyl,
A    represents hydrogen or in each case optionally halogen-substituted C1-
    15    C6-alkyl or C3-C8-cycloalkyl,
B    represents hydrogen, methyl or ethyl,
A, B and the carbon atom to which they are attached represent saturated
    20    C3-C6-cycloalkyl in which optionally one ring member is replaced by
 
- 52 -
oxygen or sulphur and which is optionally mono- or disubstituted by trifluoromethyl or C1-C4-alkoxy,
D    represents hydrogen, in each case optionally fluorine- or chlorine-
5    substituted CI-C6-alkyl, C3-C4-alkenyl or C3-C6-cycloalkyl,
A and D together represent in each case optionally methyl-substituted C3-C4- alkanediy1 in which optionally one methylene group is replaced by sulphur,
10
G    represents hydrogen (a) or represents one of the groups
0
R4
ll Ri (b),    '    R    (e),
,    (0,    R3 (A    P 5
R6
E (0 or    (g)
15    in which
E    represents a metal ion or an ammonium ion,
L    represents oxygen or sulphur and
M    represents oxygen or sulphur,
represents in each case optionally halogen-substituted CI-Cio-alkyl, C2-Cio-alkenyl, C1-C4-alkoxy-Ci-C4-alkyl, C1-C4-alkylthio-C1-C4- alkyl or optionally fluorine-, chlorine-, CI-C4-alkyl or Ci-C2-alkoxy¬substituted C3-C6-cycloalkyl,
 
- 53 -
represents optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1- Ca-alkyl-, C1-C4-alkoxy-, trifluoromethyl- or trifluoromethoxy-substituted phenyl,
5    represents in each case optionally chlorine- or methyl-substituted
pyridyl or thienyl,
R2    represents in each case optionally fluorine- or chlorine-substituted
C1-Cio-alkyl, C2-C10-alkenyl, C1-C4-alkoxy-C2-C4-alkyl,
10
represents optionally methyl- or methoxy-substituted C5-C6-cycloalkyl or
represents in each case optionally fluorine-, chlorine-, bromine-, 15    cyano-, nitro-, CI-CI-alkyl, CI -C4-alkoxy, triflouromethyl- or
trifluoromethoxy-substituted phenyl or benzyl,
R3    represents optionally fluorine-substituted CI-C4-alkyl or represents
optionally fluorine-, chlorine-, bromine-, CI-CI-alkyl, C1-C4-alkoxy, 20    trifluoromethyl, trifluoromethoxy, cyano or nitro-substituted phenyl,
R4    represents in each case optionally fluorine- or chlorine-substituted
CI-C4-alkyl, C i-C4-alkoxy, CI-C4-allcylamino, Ci-C4-alkylthio or
represents in each case optionally fluorine-, chlorine-, bromine-,
25 nitro-, cyano-, CI-C4-allcoxy, trifluoromethoxy, C1-C4-alkylthio, Ci¬C4-halogenoalkylthio, C1-C4-alkyl or trifluoromethyl-substituted phenyl, phenoxy or phenylthio,
R5    represents C i-C4-alkoxy or Ci-C4-thioalkyl,
30
 
- 54 -
R6    represents C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C3-C6-
alkenyl, Ci-C4-alkoxy-Ci-C4-alkyl,
R7    represents CI-C6-alkyl, C3-C6-alkenyl or CI-C4-alkoxy-CI-C4-alkyl,
5
R6 and R7 together represent an optionally methyl- or ethyl-substituted C3-C6- alkylene radical in which optionally one carbon atom is replaced by oxygen or sulphur.
10    3.    Composition according to Claim 1, comprising compounds of the formula (I)
in which
W    represents hydrogen, methyl, ethyl, chlorine, bromine or methoxy,
15    X    represents chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy,
ethoxy or trifluoromethyl,
Y and Z independently of one another each represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, trifluoromethyl or 20    methoxy,
A    represents methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, tert-
butyl, cyclopropyl, cyclopentyl or cyclohexyl,
25    B    represents hydrogen, methyl or ethyl,
A, B and the carbon atom to which they are attached represent saturated C6-cycloalkyl in which optionally one ring member is replaced by oxygen and which is optionally monosubstituted by methyl, ethyl,
30    methoxy, ethoxy, propoxy or butoxy,
 
-55-
D    represents hydrogen, represents methyl, ethyl, propyl, i-propyl, butyl,
i-butyl, allyl, cyclopropyl, cyclopentyl or cyclohexyl,
A and D together represent optionally methyl-substituted C3-C4-alkanediyl,
5
G    represents hydrogen (a) or represents one of the groups
R6
p1    , R2 (0, or
(g),
(b),    m    0
10
in which
M    represents oxygen or sulphur,
15    RI    represents C1-Cs-alkyl, C2-C4-alkenyl, methoxymethyl, ethoxymethyl,
ethylthiomethyl, cyclopropyl, cyclopentyl or cyclohexyl,
represents optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, methyl-, ethyl-, methoxy-, trifluoromethyl- or trifluoromethoxy¬20    substituted phenyl,
represents in each case optionally chlorine- or methyl-substituted pyridyl or thienyl,
25    R2    represents C1-Cg-alkyl, C2-C4-alkenyl, methoxyethyl, ethoxyethyl or
represents phenyl or benzyl,
R6 and R7 independently of one another represent methyl or ethyl or together represent a C5-alkylene radical in which the C3-methylene group is 30    replaced by oxygen.
 
-56-
4.    Composition according to Claim 1, comprising compounds of the formula (I)
in which
5    W    represents hydrogen or methyl,
X    represents chlorine, bromine or methyl,
Y and Z independently of one another each represent hydrogen, chlorine, 10    bromine or methyl,
A, B and the carbon atom to which they are attached represent saturated Cs-cycloalkyl in which optionally one ring member is replaced by oxygen and which is optionally monosubstituted by methyl, methoxy,
15    ethoxy, propoxy or butoxy,
D    represents hydrogen,
G    represents hydrogen (a) or represents one of the groups
0    0R6
R, — (b),     m.R2 (c    \-- ), or    --Ni
0    IR7 (g),
in which
M    represents oxygen or sulphur,
R'    represents C i-Cralkyl, C2-C4-alkenyl, methoxymethyl, ethoxymethyl,
ethylmethylthio, cyclopropyl, cyclopentyl, cyclohexyl or
 
-57-
represents optionally fluorine-, chlorine-, bromine-, methyl-, methoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- or nitro-substituted phenyl,
5    represents in each case optionally chlorine- or methyl-substituted
pyridyl or thienyl,
R2    represents C1-Cg-alkyl, C2-C4-alkenyl, methoxyethyl, ethoxyethyl,
phenyl or benzyl,
10
R6 and R7 independently of one another each represent methyl, ethyl or together represent a C5-alkylene radical in which the C3-methylene group is replaced by oxygen.
in which
W, X, Y, Z, R and G are each as defined in the table.
W    X    Y    Z    R    G
H    Br    5-CH3    H    OCH3    CO-i-C3H7
H    Br    5-CH3    H    OCH3    CO2-C2H5
H    CH3    5-CH3    H    OCH3    H
H    CH3    5-CH3    H    OCH3    CO2-C2H5
CH3    CH3    3-Br    H    OCH3    H
CH3    CH3    3-Cl    H    OCH3    H
H    Br    4-CH3    5-CH3    OCH3    CO-i-C3H7
 
-58-
W    X    Y    Z    R    G
H    CH3    4-CI    5-CH3    OCH3    CO2C2H5
H    CH3    4-CH3    5-CH3    OCH3    /---\
CO—N\__/ 0
CH3    CH3    3-CH3    4-CH3    OCH3    H
H    CH3    5-CH3    H    0C2H5    /--\
CO—N    0
\___/
CH3    CH3    3-Br    H    0C2H5    CO-i-C3H7
H    CH3    4-CH3    5-CH3    0C2H5    CO-n-Pr
H    CH3    4-CH3    5-CH3    OC2H5    CO-i-Pr
H    CH3    4-CH3    5-CH3    OC2H5    CO-c-Pr

    6.    Use of mixtures as defined in Claim 1, 2, 3, 4 or 5 for controlling animal
pests.
5    7.    Method for controlling animal pests, characterized in that mixtures as defined
in Claim 1, 2, 3, 4 or 5 are allowed to act on animal pests and/or their habitat.
    8.    Process for preparing insecticidal and acaricidal compositions, characterized
in that mixtures as defined in Claim 1, 2, 3, 4 or 5 are mixed with extenders 10    and/or surfactants.
 
-5V-
 
Li absazumnics9!1?thaliong 11.21-inseefigidal lad nearicidnizsie3
Abstraci
The novel activc compound cumtyizotiuts of Curislin    kelOtral$ Me ale active
COMIC111:1CIS (3) t; (23) lid in the description bave very gond humid/Lai and acarizidal Frupriles.
 
indexation.Ist QC OK tags.Ist

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