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(21)Application Number: KE/P/2004/ 000372

(22) Filing Date: 20/11/2004

(30)    Priority data: 103 56551.5  04/12/2003  DE  and 102004021566.9  03/05/2004  DE

(86)  PCT data PCTIEP04/013198 20/11/2004 W0/2005/053405 16/06/2005

(72) Inventor: FISCHER,  Nelly-Sachs-Strasse 23, 40789 Monheim,Germany; FISCHER, RUDIGER, Zu den Fussfallen 23, 50259 Pulheim Germany; FUNKE, Christian, Rothenberg 75a, 42799 Leichlingen, Germany; HUNGENBERG, Heike, Louveciennesstr. 2A, 40764 Langenfeld, Germany; ANDERSCH, Wolfram, Schlodderdicher Weg 77, 51468 Bergisch Gladbach, Germany; THIELERT, Wolfgang, Buschweg 69,51519 Odenthal, Germany and KRAUS, Anton Bremersheide 15,42799 Leichlingen, Germany,

(74)    Agent/address for correspondence: Kaplan & Stratton Advocates, P.O. Box 40111-00100, Nairobi

(51)    Int.Cl.7: AOIN43/00

(54)    Title: ACTIVE SUBSTANCE COMBINATION HAVING INSECTICIDAL AND ACARICIDAL PROPERTIES

(57)    Abstract: The invention relates to novel active substance combinations comprising cyclic keto-enols or other insecticides and additional insecticides from the group of anthranilic acid amines. Said active substance combinations are very suitable for controlling animal pests such as insects and undesired mites.
 
Active comoound combinations baving insecticidal and acaricidal pro~

The present invention relates to novel active compound combinations comprising, fLrstly, known cyclic ketoenols and, secondly, further known insecticidally active compounds which combinations are highly suitable for controlling animal pests, such as insects and unwanted acarides.

It  is  already  known  that  certain  cyclic  ketoenols  have  herbicidal,  insecticidal  and  acaricidal properties. The activity ofthese compounds is good; however, at low application rates it is sometimes unsatisfactory.

Unsubstituted bicyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A 0 355 599 and EP-A 0 4!5 211)

and  substituted  monocyclic  3-arylpyrrolidine-2,4-dione  derivatives  (EP-A  0 377 893  and  EP-A

0 442 077) having herbicidal, insecticidal or acaricidal action are known.

15    Also known are polycyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A 0 442 073) and lH-arylpyrrolidinedione derivatives (EP-A 0 456 063, EP-A 0 521 334, EP-A 0 596 298, EP-A 0 613 884, EP-A 0 613 885, WO 94/01 997, WO 95126 954, WO 95/20 572, EP-A 0 668 267, WO 96/25395, WO 96135664, WO 97/01535, WO 97/02243, WO 97136868, WO 97/43275, WO 98/05638, WO 98106721, WO 98125928, WO 99/16748, WO 99/24437, WO 99/43649, WO

20    99/48869 and WO 99/55673, WO 01123354, WO Oin4770). The activity of these componnds is good; however, at low application rates it is sometimes unsatisfactory.

It is also known that mixb.ues of phthalamides and further bioactive compounds have insecticidal and/or acaricidal action (WO 02/087334). However, the activity ofthis mixture is not always optimal
25

Furthermore, it is already know that numerous heterocycles, organotin compounds, benzoylureas and pyrethroids have insecticidal and acaricidal properties (cf. WO 93/22297, WO 93/10083, DE-A 26 41343, EP-A 0 347 488, EP-A 2!0 487, US 3,364,177 and EP-A 234 045). However, the activity of these compounds is likewise not always satisfactory.

30

It has now been found that mixtures of compounds of the formula (I) (group 1)

G\_

A~y
o''-{  'J--Yz    (I)   
       
ow'       

in which
 
-2-

X    represents halogen, alkyl, alkoxy, haloalkyl, haloalkoxy or cyano,

W1,  Y and Z independently of one another represent hydrogen, halogen, alkyl, alkoxy, haloalkyl,

    haloalk.oxy or cyano,
A3    represents  hydrogen,  in  each  case  optiolllllly  halogen-substituted  alkyl,  alkoxyalkyl,
    saturated, optionaJly substituted cycloalkyl in which  optionally at least one ring  atom  is
    replaced by a heteroatom,
A4    represents hydrogen or alkyl,
A3 and A4 furthermore together with the carbon atom to which they are attached represent a saturated
    or  unsaturated,  unsubstituted  or substituted  cycle  which  optiona1ly contains  at  least one
10    heteroatom,
D    represents hydrogen or an optiolllllly substituted radical from the group coosisting of alkyl,
    alkeny~ alkoxyalkyl. saturated cycloalkyl in which optionally one or more ring members are
    replaced by heteroatoms,

A 3 and D together with the atoms to which they are attached represent a saturated or unsaturated

15    cycle which is unsubstituted or substituted in the A3,D moiety and optionally contains at least one heteroatom,
    G1    represents hydrogen (a) or represents one of the groups   
        )lR" {b),    (d),
        E  (f)  or   
    E    represents a metal ioo or an ammocimn ion.   
        represents oxygen or sulfur,   
    M1    represents oxygen or sulfur,   
    R"    represents   in  each   case   optionally  halogen-substituted   alkyl,   alkenyl,   alkoxyalky~
        alkylthioalky~ polyalkoxyalkyl or optiolllllly halogen-, alkyl- or alkoxy-substituted cycloalkyl
        which may be interrupted by at least one heteroatom,  in each case optionally substituted
25        phenyl, phenylalky~ hetary~ phenoxyalkyl or hetaryloxyalkyl,
    R21    represents   in  each   case   optionally  halogen~substituted alkyl,   alkenyl,   alk:oxyalky~
        polyalkoxyalkyl  or  represents  in  each  case  optionally  substituted  cycloalkyl,  phenyl  or
        benzyl,   
    R22    represents optionally halogen-substituted alkyl or optiolllllly substituted phenyl,
30    R23 and R24 independently of one another represent in each case optionally halogen-substituted alkyl,
        alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio or represent in each
        case optionally substituted phenyl, benzyl, phenoxy or phenylthio and

R25  and R26  independently of one another represent hydrogen,  in each  case optionally  halogen-

substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent optionally substituted

phenyl, represent optionally substituted benzyl or together with the nitrogen atom to which

they are attached represent an optionally substituted ring which is optionally interrupted by

oxygen or sulfur,

Q[ an insecticidally active compound (groop2), preferably

(2-1)   amitraz(known from DE-A 20 61 132)

CH3    CH3
~N-~_..k_;:::.N~
H CJU    H    C~CH    3   
3    3           
10    and/or

(2-2)   buprofezin (known from DE-A 28 24 126)
H,c
~ 1  s    X:cH,
"=f} - rN CH,

o    }-cH3
H,C

and/or
15

and/or

(2-4)   pymetrozine (known from EP-A 0 314 615)
H,CI('7-N,\  r=t

N,NkO ~{{ H

and/or

20    (2-5)   pyriproxifen (known from EP-A 0 128 648)


and/or
 -4-

(2-6)    flonicamid (known from EP-A 0 580 374)
1'Jl
fl.J -~~CN

N

and/or

(2-7)    pirimicarb(knownfromGB 1181657) and at least one active compound from the group of the anthranilamides of the formula (II). are syner-gistically effective and have very good insecticidal and acaricidal properties.

Surprisingly,  the  insecticidal  and/or  acaricidal  activity  of  the  active  compound  combinations

10    according to the invention is higher than the sum of the activities of the individual active compounds.

Thus, an unforeseeable true synergistic effect is present. and not just an addition of activities.

In addition to at least one active compound of the fonnula (I) or one active compound of group 2

(compounds (2-1) to (2-7)), the active compound combinations according to the invention comprise at least one active compound of the formula (ll).

15

    Preference is given to active compound combinations comprising compounds of the formula (I) in
    which   
    W1    represents hydrogen, C1-C4-alkyl, CrC4-alkoxy, chlorine, bromine or fluorine,
    X    represents Cx-C4-alkyl, C1-C4-alkoxy, Cr.C4-haloalkyl, fluorine, chlorine or bromine,
20    Y and Z independently of one another represent hydrogen, C1-C4-alkyl, halogen, C1-C4-alkoxy or C1-
        C4-baloalkyl,
    A3    represents  hydrogen or in each case optionally halogen-substituted C1-4-alkyl or C3-C8-
        cycloalkyl,
    A 4    represents hydrogen, methyl or ethyl,
25    A3 and A4 furthermore together with the carbon atom to which they are attached represent saturated
        C3-C6-cycloalkyl in which optionally one ring member is replaced by oxygen or sulfur and
        which is optionally mono- or disubstituted by C1-C4-alkyl, trifluoromethyl or C 1-4-alkoxy,
    D    represents hydrogen, in each case optionally fluorine- or chlorine-substituted C1-Ct,-alkyl, C3-
        C4-alkenyl or C3-C,-cycloalkyl,
 
-5-

A3  and D together represent optionally methyl-substituted C3-C4-alkanediy1 in which optionally one

methylene group is replaced by sulfur,

G1    represents hydrogen (a) or represents one of the groups       
    0                   
    )lR" (b),            /SO;-R22       
                (d),       
        \    R"           
            /           
    E  (f)  or    L1rN, R"    (g), in particular (a), (b), (c)    or (g)   
E    represents a metal ion or an ammonium ion,       
L 1    represents oxygen or sulfur,           
M 1    represents oxygen or sulfur,           
R20    represents in each case optionally halogen-substituted c,-CIO-alkyl, CrCwalkenyl, c.-e..-   
    alk.oxy-C,-C.. -alkyl,  C1-C4-alkylthio-C1-C4-alkyl  or  optionally  fluorine-,  chlorine-,  C1-C4-   
l 0    alkyl- or c,-C,..allroxy-substituted c,-C,-cycloalkyl,       

represents  optionally  fluorine-,  chlorine-,  bromine-,  cyano-,  nitro-,  C1-C4-alkyl-,  C1-C4-

alkoxy-, trifluoromethyl- or trifluoromethoxy-substituted phenyl,

represents in each case optionally chlorine- or methyl-substituted pyridyl or thienyl,

- R21    represents  in each  case  optionally fluorine-  or chlorine-substituted  C1-C1o-alkyl,  CrCto-

15    oikenyL c,-e,-alkoxy-C,-C,-alkyL

represents optionally methyl- or methoxy-substituted ~-C6-cycloalkyl or

represents in each case optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-,

C 1-C4-alkoxy-, trifluoromethyl- or trifluoromethoxy-substituted phenyl or benzyl,

R22    represents  optionally  fluorine-substituted  C1-C4-alkyl  or  represents  optionally  fluorine-,

20    chlorine-, bromine-, cl-e.-a!kyl-, c~~-alkoxy-, trifluoromethyl-, trifluoromethoxy-, cyano-or nitro-substituted phenyl,
R23    represents in each case optionaUy fluorine- or chlorine-substituted C1-C4-alkyl, C1-C4-alkoxy,
    C1-C4-alkylamino, C1-C4-alkylthio or represents in each case optionally fluorine-, chlorine-,
    bromine-,   nitro-,   cyano-,   C1-C4-alkoxy-,   trifluoromethoxy-,   C1-C4-alkylthio-,   C1~-
25    haloalkylthio-, C1-C4-alkyl- or trifluoromethyl-substituted phenyl, phenoxy or phenylthio,
R24    represents C1-C4-alkoxy or Ct-C.-alkylthio,
R25    represents C1-4-alky~ C3-C6-cycloalkyl, C1-4-alk.oxy, CJ-4-alkenyl, Cl-C4-alkoxy-Ct-C•-
    alkyl,
R"    represents C1-C,;-alkyl, C,-C,-alkenyl or C1-C,-a!koxy-C1-C4-alkyl,

30 R25 and Rl<i furthermore together represent an optionally methyl- or ethyl-substituted C3-4-alkylene radical in which optionally one carbon atom is replaced by oxygen or sulfur  and at least one active compound of the formula (ll).
    In the halogen radicals in the preferred ranges, halogen preferably represents chlorine and fluorine. Particular preference  is given to  active compound  combinations comprising compounds of the
    formula (I) in which   W1    represents hydrogen, methyl, ethyl, chlorine, bromine or methoxy,
    X    represents  chlorine,  bromine,  methyl,  ethyl,  propyl,  isopropyl,  methoxy,  ethoxy  or
        trifluoromethyl,
10    Y and Z independently of one another represent hydrogen, fluorine, chlorine, bromine. methyl, ethyl,
        propyl, isopropyl, trifluoromethyl or methoxy,
    A'    represents methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-buty~ tert-buty~ cyclopropy~
        cyclopentyl or cyc!ohexyl,
    A 4    represents hydrogen, methyl or ethyl,
15    A3 and A4 furthermore together with the carbon atom to which they are attached represent saturated
        Cc;-cycloa.Jkyl in which optionally one ring member is replaced by oxygen and which is
        optionally monosubstituted by methyl, ethyl, rnethoxy, ethoxy, propoxy nr butoxy,
•-    D    represents  hydrogen,  represents  methy~ ethyl,  propy~ isopropy~ butyl,  isobuty~ ally~
        cyc!opropy~ cyclopentyl or cyclohexy~
20    A3 Wld D together represent optionally methyl-substituted C,-C4-alkanediyl,
    G1    i-epresents hydrogen (a) or represents one of the groups

        (g)
    L 1    represents oxygen or sulfur,
    M 1    represents oxygen or sulfur,
25    R"    represents  C 1-C,-alkyl,  C2-C4-alkenyl,  methoxymethyl,  ethoxymethy~ ethylthiomethyl,
        cyclopropyl, cyc!opentyl or cyc!ohexy~
        represents phenyl which is optionally mono- to disubstituted by fluorine, chlorine, bromine,
        cyano, nitro, methyl, ethyl, methoxy, trifluoromethyl or trifluoromethoxy,
        represents pyridyl or thieny~ each of which is optionally mono- to disubstituted by chlorine
30        ormethyl,
    R21    represents  C1-C,-alky~ C2-C4-alkenyl,  methoxyethyl, ethoxyethyl  nr  represents  phenyl or
        benzyl,
    R25  and R26  independently of one another represent methyl, ethyl or together with the nitrogen atom
        to which they are attached represent morpholino, and at least one active compound of the formula (D).

Very particular preference is given to active compound combinations comprising compounds of the

formula (I) in which W1    represents hydrogen or methyl,

X    represents chlorine. bromine or methyl,

Y    and Z independently of one another represent hydrogen, chlorine, bromine or methyl,

A3 and A4 furthermore together with the carbon atom to which they are attached represent saturated C6-cycloa\kyl in which optionally ooe ring member is replaced hy oxygen and is optionally

10    monosubstituted by methyl, methoxy, ethoxy, propoxy or butoxy, represents hydrogen.
represents hydrogen (a) or represents one of the groups

    0    h'    R"           
    )lR20 (b),                   
        _,A--M,_...    (c)    or    (g)   
L 1    represents oxygen or sulfur,               
    represents oxygen or sulfur,               
R"    represents  C1-C8-alkyl,  C,-C4-alkenyl,  methoxymethyl,    ethoxymetbyl,  ethylmethylthio,   
    cyclopropyl, cyclopentyl, cyclohexyl,           

represents phenyl which is optionally monosubstituted by fluorine, chlorine, bromine. methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,

20    represents pyridyl or thieny~ each of which is optiona.Uy monosubstituted by chlorine or methyl,
R21    represents C1-C,..olkyl, C,.C4-olkenyl, methoxyethyl, ethoxyethyl, phenyl or benzyl,

R2S and R26  independently of one another represent metby~ ethyl or together with the nitrogen atom

to w'hich they are attached represent morpholino,

25    and at least one active compound of the fonnu1a (TI).

Especially preferred are active compound combinations comprising at least one of the following compounds of the formula (1-a)

R-o~G~X,y     (1-a)

,N    I\   ;
H    5
ow
Example    w'    X    y    z    R"    G'    m.p.("C)       
No.                                   
                                   
                               
I-a-1    H    Br5-CH3    H    OCH3    CO-i-c,H7    122       
1-a-2    H    Br5-CH3    H    om,    C0,-C,H5    140-142       
1-a-3    H    CH,    5-m,    H    OCH,    H    >220       
1-a-4    H    CH,    5-CH,    H    om,    CO,.C,H,    128       
I-a-5    m,    CH,    3-Br    H    OCH3    H    >220       
1-a-6    CH,    CH33-C1    H    OCH3    H    219       
1-a-7    H    Br4-CH3    5-CH,    om,    CO-i-C,H7    217       
1-a-8    H    CH,    4-CI    5-CH,    OCH3    CO,C2H5    162       
1-a-9    H    CH,    4-CH,    5-m,    om,    1\    oil       
                        CO-N\__/           
1-a-10    m,    CH,    3-CH,    4-CH,    OCH3    H    >220       
1-a-11    H    CH,    5-CH,    H    OC,H,    1\    oil       
                        co-\__/           
1-a-12    CH,    CH,    3-Br    H    Oc,Hs    CO-i-C,H7    212-214       
1-a-13    H    CH,    4-CH,    5-CH,    OC,Hs    CO-n-Pr    134       
1-a-14    H    CH,    4-CH,    5-CH,    OC,H,    CO-i-Pr    108       
1-a-15    H    CH,    4-CH,    5-m,    OC,Hs    CO-c-Pr    163       

and at least one active compound of the formula (ll}.

Especially preferred are active compound combinations comprising the compound of the formula (I-

a-4)

H,C~o

(1-a-4)


and at least one active compound of the fonnula (ll}.

Depending inter alia on the nature of the substituents, the compounds of the formula (I) can be

I 0 present as geometrical and/or optical isomers or isomer mixtures of varying composition which, if desired, may be separated in a custom8J)' manner. The present invention provides both the pure

isomers and the isomer mixtures, their preparation and use and also compositions comprising them. However, hereinbelow, for the sake of simplicity, only compounds of the formula (I) are referred to, although what is meant are both pure compounds and, if appropriate, also mixtures having varying proportions of isomeric compounds.

Especially preferred are active compound combinations comprising a compound selected from the compounds (2-l) to (2-7) of group 2 and at least one active compound of the fonnula (11).

The anthranilamides of the fonnula {IT) are likewise known compounds which are known from the following publications or embraced by them:
wo oin0671, wo 03/0I55I8, wo 03/0I55I9, wo 03/016284, wo 03/016282, wo 03/0I6283, I 0 WO 03/024222, WO 03/062226.

The generic fonnulae and definitions described in these publications and the individual compounds described therein are expressly incorporated herein by way of reference.

(II)

in which

A 1 and A2 independently of one another represent oxygen or sulfur,

X1    represents Nor CR10,

20    R1    represents  hydrogen  or  represents  C1.C.-alkyl,  C2-C6-alkenyl,  C,..C.-alkyoyl  or  C3-C6-

cycloalkyl, each of which is optionally mono- or polysubstituted. where the substituents

independently of one another may be selected from the group consisting of R6,  halogen,

cyano, nitro, hydroxyl, C 1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C,-C4-alkylsulfonyl, C2-C4;!lkoxycarbonyl, C1-C4-alkylamino, C,-C,-<liallcylamino, C3.C.-

25    cycloallcylamino, (C1-C4-allcyl)-C3.C.-cycloalkylamino and R11 ,

R' represents hydrogen, c,-C.-alkyl, C,-C,-alkenyl, C,-C,-alkyoyl, c,-C,-cycloallcyl, c,-e,-alkoxy, C,-C.-allcylamino, C,-C,-diallcylamino, C,-C6-cycloalkylamino, C,-C.-alkoxycarbonyl or C,-C6-allcylcarbonyl,
 
R'    represenls  hydrogen,  Rn  or  represenls  C 1-C,;-alkyl,  C,..C,-alkenyl,  C,..C6-alkynyl,  C3-C6-

cycJoalkyl, each of which is optiona1ly monoM or polysubstituted., where the substituents

independently of one another may be selected from the group consisting of R6,  ha1ogen,

cyano, nitro, hydroxyl, c,-c,-alkoxy, c,-e,-haloalkoxy, c,-C,-alkylthio, c,-C,-alkylsulfmyl,
C1-C4-alkylsulfonyl,  C,..C6-alkoxycarbonyl,  C,-C,;-alkylcarbonyl,  C,.C.-trialkylsilyl,  Rn,

phenyl, phenoxy and a 5- or 6-membered heteroaromatic ring, where each phenyl, phenoxy and 5- or 6-membererd heteroaromatic ring may optionally be substituted and where the substituents independently of one another may be selected from one to three radicals W or
one or more radicals R12, or

10    R2 and R3 may be attached to one another and form the ring M.

R4 represenls hydrogen, C1-C6-alky~ C,-C6-alkeny~ C2-C,-alkyny~ C,-C,;-cycloalkyl, C1-C.-haloalky~ C,..C.-haloalkeny~ C,-C,;-haloalkyny~ C,-C.-halncycloalkyl, halogen, cyano, nitro, hydroxyl, c,-C,-alkoxy, c,-<;,-haloalkoxy, c,-C,-alkylthio, c,-C,-alkylsulfinyl, c,-e,-alkylsnlfony~ C 1-C4-haloalkylthio, C1-C4-haloalkylsulfmy~ C1-C4-haloalkylsulfonyl, C1-C4-

15    alkylamino, C,-C8-dialkylamino, C,-C,;-cycloalkylamino, C,-C6-trialkylsilyl or represenls phenyl, benzyl or phenoxy, each of which is optionally mooo- or polysubstituted, where the substituents independently of one another may be selected from the group consisting of C1-
C4-alkyl, c,-e,-alkeny~ c,-e,-alkyny~ C3-C.-cycloalkyl, C1-C,-haloalkyl, C,..C4-haloalkeny~

C,-C,-haloalkyny~ C,-C.-halncycloalky~ halogen,  cyano,  .nitro,  c,-C,-alkoxy,  c,-e,-

20    haloalkoxy, c,-C,-alkylthio, c,-C,-alkylsulfiny~ c,-C,-alkylsulfony~ c,-C,-alkylamino, C,-

C,..dialkylamino, C,-C,;-cycloalkylamino, C3-C,;-{alkyl)cycloalkylamino, C,-C4-alkylcaroony~

C2-C,;-alkoxycarltony~ C2-C,;-alkylaminocarbony~ C3-C8-<IialkylaminoCIIJbonyl  and  C3-C...

trialkylsily~

R5 and R8 in each case independently of one another represent hydrogen. halogen or represent in each

25    case optionally substituted C1-C4-alkyl, c,-C4-haloalky~ R12, G, J, -DJ, .00, -S(O),-J, -S(O),-G, -S(O),-phenyl, where the substituents independently of one another mxy he selected from one to three radicals W or from the group consisting of R12, CrCw-alkyl, CrC6-alkeny~ ~­

C.-alkynyl, c,-C,-alkoxy and c,-C,-alkythio, where each substituent may he substituted by one or more substituents independent1y of one another selected from the group consisting of
30    G, J, R', halogen, cyano, nitro, amino, bydroayl, C 1-C,-alkoxy, C 1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulfinyl, c,-C,-haloalkylsulfonyl, c,-C,-alkylamino, C,-c,-<lislkylamino, c,-c.-trialkylsilyl, phenyl and phenoxy, where each phenyl or phenoxy ring mxy optionally he substituted and where the substituents independently of one another may be selected from

35    one to three radicals Worone or more radicals R12,
 -II-

G    in each case independently of one another represent a 5- or 6-membered non-aromatic carbocyclic or heterocyclic ring which may optionally contain one or two ring members from the group consisting of C(=O), SO and S(=O), and which may optiooally he substituted by one to four substituents independently of one another selected from the group consisting of
C1-Cralkyl, halogen, cyano, nitro and C1~-alkoxy, or independently of one another represent C,C.-alkeny~ C2-C,-alkynyl, C3-Crcycloalkyl, (cyano)-C3-C,-cycloalky~ (C1-C4-alkyl)-C3-C,-cycloalkyl, (C3-C,-cycloalkyl)-C1-C4-alky~ where each cycloalky~
 
R'

15

R'
 

(alkyl)cycloalkyl and (cycloalkyl)alkyl may optionally he substituted by one or more halogen

atoms,

in each case independently of one another represent an optionally substituted 5- or 6-membered heteroaromatic ring, where the substituents independently of one another may be selected from one to three radicals W or one or more radicals R12,
independently    of   one   another   represent   -C(=E1)R19,    -LC(=E1)R19,    -C(=E1)LR19,

-LC(~E1)LR19, -OP(=Q)(OR1'), -SO,LR18 or -LSO,LR19, where each E1 independently of one another represent. 0, S, N-R", N-OR", N-N(R1'),,N-S=O, N-CN orN-NO,,

represent. hydrogen, C1-C4-alkyl, C1-C4-haloalky~ halogen, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C,-alkylsulfony~ C1-C4-haloalkylthio, C1-C4-

haloalkylsulfiny~ c,-C,-haloalkylsulfony~
 

    R'    represent. c,-C,-haloalky~ c,-C,-haloalkoxy, c,-C,-haloalkylsulfmyl or halogen,       
20    R"    represent. hydrogen, c,-C,-alkyl, c,-C,-haloalky~ halogen, cyano or c,-C,-haloalkoxy,   
    R"    in each case independently of one another represents in each case optionally mono- to   
        trisubstituted    C1-C6-alkylthio,    C1-C6-a!kylsulfeny~    CrC.-haloalkythio,    C1-C,-   
        haloalkylsulfeny~ phenylthio or phenylsulfeny~ where the substituent. independently of one   
        another  may  he  selected  from  the  list  W,  -S(O),N(R    16    -C(=O)R    13        14   
            ),,        ,    -L(C=O)R  ,   

25    -S(C=O)LR14, -C(=O)LR13, -S(O),NR13C(=O)R13, -S(O),NR13C(=O)LR14 -S(O),NR13 S{0)2LR14,

L    in each case independently of one another represents 0, NR18 or S,
R12    in each case independently of one another represents -B(OR17)2, amino, SH, 1hiocyanato, C3-
    C,-trialkylsilyloxy,  C1-C4-alkyl  disulfide,  -SF,,  -C(~E1)R19, -LC(~E1)R19, -C(~E1)LR19,
30    -LC(~E')LR19, -OP(:QXOR''),, -So,LR19 or -LSo,LR19 ,
Q    represent. 0 or S,
R13    in each case independently of one another represent hydrogen or represent in each case
    optionally  mono-  or polysubstituted c,-C,-a!ky~ C,-C,-alkenyl,  C,-C,-alkynyl  or  C,-C,-
    cycloalkyl, where the substituents independently of one another may be selected from the
35    group consisting of R', halogen, cyano, nitro, hydroxyl, C1-C4-alkoxy, C1-C4-alkylsulfiny~
 
C1-C.-alkylsulfony~ C1-C.-alkylamino, CrC.-<lialkyiamino, c,-c,-cycloalkylamino or (C1-

C4-alkyi)-C3-C.-cycloalkylamino,

R14    in each case  independently of one another represent in each case optionally mono- or

polysubstituted C1-C20-alkyl, CrC20-alkenyl, C,-C,.-alkynyl or C3-C,-cycloalkyl, where the

substituents independently of one another may be selected from the group consisting of R6,

halogen, cyano, nitro, hydroxyl, C -C -alkoxy,    C    1    -C    4    -alkylsulfmy~ C -C -alkylsulfonyl,    C -   
1    4                    1    4    1   
C4-alkylamino,   C,-C,..dialkylamino,   C3-C6-cycloalkylarnino   and   (C1-C,-alkyi)-C3-C6-

cycloalkylamino  or  represent  optionally  substituted  phenyl,  where  the  substituents

independently of one another may be selected from one to three radicals W or one or more

10    radicalsR12,                                   
R15    in each case independently of one another represent hydrogen or represent in each case
    optiooally mono- or polysubstituted CrC.-haloalkyl or C1-C,-alkyl, where the suhstituents
    independently of one another may be selected from the group consisting of cyano, nitro,
    hydroxy~ C -C -alkoxy,  C -C -haloalkoxy,  C -C -alkylthio,    C    -C -alkylsulfiny~ C -C -
    1    4    1    4    1    4    1    4    1    4
15    alkylsulfooyl, c,-C,-haloalkylthio, c,-C,-ha!oalkylsulfinyl, c,-C,-haloalkylsulfonyl, c,-C,-alkylsmino, c,-c,-dialkylsmino, CrC..alkoxycarbony~ C,-C.-alkylcarbony~ c,-e.-1rinlkylsilyl and optionally substituted phenyl, where the substituents independently of one another may be selected from one to three radicals W or one or more radicals R12, or N(R15)2

represents a cycle which forms the ring M,

20    R"    represents C1-C1:r<ill<yl or C1-C1,-haloalky~ or N(R1'),  represents a cycle which forms the

iingM,

R" in each case independently of one another represent hydrogen or C1-C4-aJkyl, or B(OR17h represents a ring in which the two oxygen atoms are attached via a chain having two to three carbon atoms which are optionally substituted by one or two substituents independently of
25    one another selected from the group consisting of methyl and CrC6-alkoxycarbonyl,

R" in each case independently of one another represent hydrogen, Cr-4-alkyl or "C1-C6-haloalky~ or N(R13)(R18) represents a cycle which forms the ring M,

R"    in each case independently of one another represent hydrogen or represent in each case optionally mono- or polysubstituted Cr4-alkyl, where the substi:blents independently of one

30    another may be selected from the group consisting of cyano, nitro, hydroxyl. C1-C4-alkoxy, c,-C,-haloalkoxy, c,-C,-alkylthio, c,-C,-alkylsulfmyl, c,-C,-alkylsulfony~ c,-e,-haloalkylthio, C1-C4-haloalkylsulfmy~ C1-C4-haloalkylsulfony~ C1-C,-alkylamino, c,-c,-dialkylarnino, CO,H, CrC.-alkoxycarbonyl, C2-C.-alkylcarbony~ C3-C6-trialkylsilyl and

optionally substibrted phenyl, where the substituents independently of one another may be

35    selected from one to three radicals w, c,-C,-haloalkyl, c,-C,-cycloalkyl or phenyl or pyridyl, each of which is optionally mono- to trisubstituted by W,

M    in each case represents an optionally mono- to tetrasubstituted ring which, in addition to the nitrogen atom attached to the substituent pair R13 and R18, (R15h or (R11z, contains two to six carbon atoms and optionally additionally a further nitrogen. sulfur or oxygen atom, where the substituents independently of one another may be selected from the group consisting of Cr
Cz-alky~ halogen, cyano, nitro and C1-CraJkoxy,

W    in each case independently of one another represent C1-C4-alkyl, ~-C4-alkenyl, ~-C4-alkyny~ C,-C.-cycloalkyl, C 1-C.-haloalkyl, C,..C4-haloalkenyl, C,..C4-haloalkynyl, C,..C6-
halocycloalky~ halogen, cyano, nitro, C1-C4-alkoxy, C1-C,-haloalkoxy, C1-C4-allcylthio, C1-

C4-alkylsulfmyl,   C1-C4-allcylsulfonyl,   C 1-C,-alkylanrino,   CrC,-dialkylamino,   C,-C,;-

10    cycloalkylamino, (C1-C4-allcyl)-c,-C6-cycloalkylanrino, C,..C4-allcylcarbony~ C,-C,-alkoxycarbony~ CO,H, C2-C6-alkylanrinocarbony~ C3-C,-dialkylaminocarbonyl or C3-C6-

ttialkylsily~

in each case independently of one another represent 0 or 1,

p    in each case independently of one another represent 0, 1 or 2,

15

where,  if (a)  R'  represents  hydrogen,  C1-c,-alky~ CrC.-haloalky~ C,..C.-haloalkenyl,  C,..C.-
haloalkynyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio or halogen and (b) R' represents hydrogen, C1-C,;-
alkyl, C1-C,;-haloalky~ C2-C.,haloalkeny~ C,..C6-haloalkyny~ C1-C4-haloalkoxy, C1-C4-haloalkylthio, halogen, C,..C4-allcylcarbony~ C2-C.-aikoxycarbooy~ c,-C.-aikYlaminocarbonyl or C3-C8
20    dialkylaminocarbony~ (c) at least one sobstituent selected from the group consisting ofR6,  R 11 and

R12 is ~and (d) ifR12 is not present, at least one of the radicals R6 andR11 is different from Cr

C,-allcylcarl>ony~ C2-C,; alkoxycarl>onyl, C2-C6-alkylamioocarbonyl and C3-C,-dialkylaminocarbonyl.

The compounds of the general formula (ll) comprise N-oxides and salts.

25

Depending inter alia on the nature of the substituents, the compounds of the formula (ll) 'canbe

present as geometrical and/or optical isomers or isomer mixtures of varying composition which, if desired, may be separated in a customacy manner. The present invention provides both the pure isomers and the isomer mixtures, their preparation and use and also compositions comprising them.
30    However, hereinbelow, for the sake of simplicity, only compounds of the formula (II) are referred to, although what is meant are both pure compounds and, if appropriate, also mixtures having varying proportions of isomeric compounds.

Prefermce is given to active compound combinations comprising compounds of the formula (Il-l)

(Il-l)


in which

R'    represents hydrogen or c,-C,..alkyl,

R'    represents C1-C6-alkyl which is optionally substituted by one R6,

R'    represents C1-C4-alkyl, C1-C2-halnalkyl, C1-C,-haloalkoxy or halogen,

R'    represents hydrogen, C1-C4-alkyl, C1-C,-halnalkyl, C1-C,-haloalkoxy or halogen,

R'    2    19    2    19    2    19    19    2   
    represents  -C(-E )R ,    -LC(-E )R ,    -C(-E )LR        or  -LC(-E')LR,    where  each  E   
independently  of one  another represents  0,  S, N-R1s,  N-OR15,  N-N(R15)2,  and each L

independently of one another represents 0 or NR18,

10    R' represents C1-C4-haloalkyl or halogen.

R' represeots C1-C,-halnalkyl, C1-C,-haloalkoxy, S(O),-C1-C,-halnalkyl or halogen,

R" in each case independently of one another represent hydrogen or represent in each case

R''

R''

p

20
 

optionally substituted Cr•C.-halnalkyl or CrC.-alkyl, where the substituents independently of

one another may be selected from the group consisting of•cyano, C1-C4-alkoxy,  C1-C4-

haloalknxy,  C1-C4-alkylthio,  C1-C4-alkylsulfinyl, _C1-C,-a!kylsulfonyl,  C1-C,-halnalkyhhio,

C1-C4-halnalkylsulfinyl and C1-C4-halnalkylsulfonyl,

in each case represents hydrogen or Cr.C4-alky~

in each case independently of one another represeot hydrogen or C1-C,-alky!,

independently of one another represent 0, I, 2.
 

In the radical definitions mentioned as being preferred, halogen represents fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.

Particular preference  is given to active compound  combinations  comprising compounds  of the

25    formula (11-1) in which
    R2    represents hydrogen or methyl,
    R3    represents C1-C4-alkyl (in particular methyl, ethyl, n-, isopropyl, n-, iso-, sec-, tert-butyl),
    R4    represents methyl, trifluoromethyl, trifluoromethoxy, fluorine, chlorine, bromine or iodine,
    R5    represents hydrogen, fluorine, chlorine, bromine, iodine, tri:fluoromethyl or tri:fluoroethoxy,
30    R7    represents chlorine or bromine,
    R!1    represents trifluoromethyl, chlorine, bromine, difluoromethoxy or trifluoroethoxy.
 



-IS-

Very particular preference  is given to active compound combinations comprising the fol1owing

compounds of the formula (ll-1):
            f    Q-R7               
                H    N -N        (ll-1)           
        ~£.                       
            ~~ N~R'               
        R5::::-...,    R-40                       
                                       
    Example    R'    R'    R'    R'    R'    R'    m.p.("C)   
    No.                                   
11-1-1    H    Me    Me    Cl    Cl    CF,    185-186       
11-1-2    H    Me    Me    Cl    Cl    OCH,CF3    207-208       
11-1-3    H    Me    Me    Cl    Cl    Cl    225-226       
11-1-4    H    Me    Me    Cl    Cl    Br    162-164       
11-1-5    H    Me    Cl    Cl    Cl    CF,    155-157       
11-1-6    H    Me    Cl    Cl    Cl    OCH2CF3    192-195       
11-1-7    H    Me    Cl    Cl    Cl    Cl    205-206       
11-1-8    H    Me    Cl    Cl    Cl    Br    245-246       
11-1-9    H    iMPr    Me    Cl    Cl    CF,    195-196       
11-1-10    H    i-Pr    Me    Cl    Cl    OCH2CF3    217-218       
11-1-11    H    i-Pr    Me    Cl    Cl    Cl    173-175       
11-1-12    H    i-Pr    Me    Cl    Cl    Br    159-161       
• 11-1-13    H    i-Pr    Cl    Cl    Cl    CF3    200-201       
11-1-14    H    i-Pr    Cl    Cl    Cl    oCH,CF3    232-235       
11-1-15    H    i-Pr    Cl    Cl    Cl    Cl    197-199       
11-1-16    H    i-Pr    Cl    Cl    Cl    Br    188-190       
11-1-17    H    Et    Me    Cl    Cl    CF3    163-164       
11-1-18    H    Et    Me    Cl    Cl    OCH;,CF,    205-207       
11-1-19    H    Et    Me    Cl    Cl    Cl    199-200       
11-1-20    H    Et    Me    Cl    Cl    Br    194-195       
11-1-21    H    Et    Cl    Cl    Cl    CF3    201-202       
11-1-22    H    Et    Cl    Cl    Cl    Cl    206-208       
11-1-23    H    Et    Cl    Cl    Cl    Br    214-215       
11-1-24    H    t-Bu    Me    Cl    Cl    CF3    223-225       
11-1-25    H    t-Bu    Me    Cl    Cl    Cl    163-165       
11-1-26    H    t-Bu    Me    Cl    Cl    Br    159-161       
11-1-27    H    t-Bu    C1    Cl    Cl    CF3    170-172       
11-1-28    H    t-Bu    Cl    Cl    Cl    Cl    172-173       
11-1-29    H    t-Bu    Cl    Cl    Cl    Br    179-180       
11-1-30    H    Me    Me    Br    C1    CF,    222-223       
11-1-31    H    Et    Me    Br    Cl    CF,    192-193       
11-1-32    H    i-Pr    Me    Br    Cl    CF,    197-198       
11-1-33    H    t-Bu    Me    Br    Cl    CF,    247-248       
11-1-34    H    Me    Me    Br    Cl    Cl    140-141       
    11-1-35    H    Et    Me    Br    Cl    Cl    192-194       
          
                                   
    Example    R'    R'    R'    R'    R'    R'    m.p.("C)   
    No.                               
11-1-36    H    i-Pr    Me    Br    Cl    Cl    152-153   
11-1-37    H    t-Bu    Me    Br    Cl    Cl    224-225   
11-1-38    H    Me    Me    Br    Cl    Br    147-149   
11-1-39    H    Et    Me    Br    Cl    Br    194-196   
11-1-40    H    i-Pr    Me    Br    Cl    Br    185-187   
11-1-41    H    t-Bu    Me    Br    Cl    Br    215-221   
11-1-42    H    Me    Me    I    Cl    CF3    199-200   
11-1-43    H    Et    Me        Cl    CF,    199-200   
11-1-44    H    i-Pr    Me        Cl    CF3    188-189   
11-1-45    H    t-Bu    Me        Cl    CF,    242-243   
11-1-46    H    Me    Me        Cl    Cl    233-234   
11-1-47    H    Et    Me        Cl    Cl    196-197   
11-1-48    H    i-Pr    Me        Cl    Cl    189-190   
11-1-49    H    t-Bu    Me        Cl    Cl    228-229   
11-1-50    H    Me    Me        Cl    Br    229-230   
11-1-51    H    iPr    Me        Cl    Br    191-192   
11-1-52    H    Me    Br    Br    Cl    CF3    162-163   
11-1-53    H    Et    Br    Br    Cl    CF,    188-189   
11-1-54    H    i-Pr    Br    Br    Cl    CF3    192-193   
11-1-55    H    t-Bu    Br    Br    Cl    CF,    246-247   
..  11-1-56    H    Me    Br    Br    Cl    Cl    188-190   
11-1-57    H    Et    Br    Br    Cl    Cl    . -192-194   
• 11-1-58    H    i-Pr    Br    Br    Cl    Cl    197-199   
11-1-59    H    t-Bu    Br    Br    Cl    "Cl    210-212   
11-1-60    H    Me    Br    Br    Cl    Br    166-168   
11-1-61    H    Et    Br    Br    Cl    Br    196-197   
11-1-02    H    i-Pr    Br    Br    Cl    Br    162-163   
11-1-03    H    t-Bu    Br    Br    Cl    Br    194-196   
11-1-04    H    t-Bu    Cl    Br    Cl    CF,    143-145   
11-1-05    Me    Me    Br    Br    Cl    Cl    153-155   
11-1-06    Me    Me    Me    Br    Cl    CF,    207-208   
11-1-07    Me    Me    Cl    Cl    Cl    Cl    231-232   
11-1-08    Me    Me    Br    Br    Cl    Br    189-190   
11-1-09    Me    Me    Cl    Cl    Cl    Br    216-218   
11-1-70    Me    Me    Cl    Cl    Cl    CF3    225-227   
11-1-71    Me    Me    Br    Br    Cl    CF,    228-229   
    11-1-72    H    i-Pr    Me    H    Cl    CF,    237-239   

and also an active compound of the formula (I) (group 1) or of group 2 selected from the compotmds

(2-1)to(2-7).

Especially preferred are active compound combinations comprising a compcnmd of the following

foiDlulae
 
H,C,NH

Cly¢I"'o
H,;O~NHQ
Cl
.;;N

CF,

(11-1-1)

"~I"' o Q
H;'O~NH     Cl

.;;N

Br

(11-1-4)

~"I."' Q
Cl O~NH    Cl
.;;N

Cl

(11-1-7)
J:'
-I~ o Q

H;'O~NH     Cl

.;;N

Cl

(11-1-ll)
 
HsC'NH
Clu;¢I"'o  Q
H;0~NH~
,    Cl
.;;N

o............... cF3

(11-1-2)

H,C'NH
Cly¢I"'o  Q

:    O~NH.;;N    Cl

CF,

(11-1-5)
•~I"'o  Q-

:    O~NH.;;N    Cl

Br

(11-1-8)

H,CJ~H
Cl~I"'o
~
H;'0~NH1
.;;N    c1

Br

(11-1-12)
 
H3C'NH
CI'Q¢I"'oQ

H;'o~NH~  Cl
.;;N

Cl

(11-1-3)
~I"'o  Q

:    O~~NH     Cl

YN

o.........,.....cF3

(11-1-6)
J:'
-I"'~o
H,;•~NHQ
.;;N    0

F,

(11-1-9)

H:l
~I"'o  Q
:    O~NH     Cl

.;;N

CF,

(11-1-13)
 



;:•
~I:"0NHo q
1:; Cl
...:N

Cl

(11-1-15)
•y;¢I"o
0
:    1:;NHNQ
Cl
...:N

CF3

(11-1-21)
H c:J:3
-I•"'~ o
H;.'1tNHNQ
.;:N    0

F,

(11-1-24)

H C
~~;l3_NH

Cl~I"'o
:    0NH   NQ
1:; Cl
.;:N

Br

(11-1-29)
 



-18-
J:•
~I:0NHo q
1:; Cl
.;:N

Br

(11-1-16)
-I"'~ o q
:    0NH
1:; Cl
...:N

Cl

(11-1-22)

H,c
~:~NH
Cl~I"'o q
H;01:;NH
3

Cl
.;:N

Br

(11-1-26)

H3C'NH
Bry¢Io q
H;0~NH~.  Cl
'
.;:N

CF3

(11-1-30)
 


-I"~o q
H;0~NH~  Cl
3
...:N

Cl

(11-1-19)
•~I"o
:    NH   NQ

O):;    Cl
...:N

Br

(11-1-23)

H,c
H,~
'~q
I  ~    Cl
.;:N

CF3

(11-1-27)
-I"~o  q
H;0~NH~  Cl
'
...:N

CF3

(11-1-31)
 




H,Cl~H
Br~I"oQ

H;'O~NH     Cl

-<N

CF,

(11-1-32)
-I"~ oq

H;'O~NH Cl Br-<N
(11-1-39)

•~I" oq
H;    NH
' 01r;'j~  Cl
.<N

CF,

(11-1-43)
J:'
~I"o
H;    NH   Q
' 01r;'j~  Cl
Br-<N
(11-1-51)
 


-19-

HcJ.':.'
-I"~ oq

H;.'1tNH,.<N0

F,

(11-1-33)
J:•
-I"~ oq

H;'O~NH Cl Br.<N
(11-1-40)
J:•
•~I" oq
H;    NH
' 01r;'j~  Cl
.<N

CF,

(11-1-44)

H3C'NH
Br1f¢0
I":   NH    q
O~ Ci
.<N

CF,

(11-1-52)
 





H3C'NH
Br1f¢0
~: NH   Q
' o1qI~  Cl
Br.<N
(11-1-38)

H3C'NH
I "    o
ly¢    Q
H;    NH
' o1q'j~  Cl
.<N

CF,

(11-1-42)

H3C'NH
11f¢I"oq

H;'O~NH Cl Br,<N
(11-1-50)
-I"~oq

:    O~NH     Cl

.<N

CF,

(11-1-53)
 



J:•
•1;¢Io q
:    NH
O~ Cl
.<N

CF3

(ll-1-54)
-I~o

: O~NHNQ Cl

.<N

Cl

(ll-1-57)
-I"'~ o q

:    NH
O~ Cl
Br.<N
(ll-1-61)
-I"'~oq

:    '?NH.<N


0

I

(ll-1-65)
 



-20-

HcJ:'
~I"' o q
:    NH
O~ Cl
.<N

CF3

(ll-1-55)
J:'
-I"'~o  q
:    NH
O~ Cl
.<N

Cl

(ll-1-58)
H3CJ~H
Br'i(¢
I "'  o  q
:    NH
O~ Cl
Br.<N
(ll-1-62)

H C,N,....CH
Bry¢3     3
I "'  o p
H,; NH

O\\    Cl

.<N

CF3

(ll-1-66)
 





H3C'NH
Br'Q¢
I "'  o q
:    NH
O~ Cl
.<N

Cl

(ll-1-56)
-I"'~o q

:    '?NH.r<N0




(ll-1-60)

H3C
~~NH
Br'¢¢
I "'  o  q

: NH ~0.<N
F,

(ll-1-64)
0~I"'oq

:    •qNH.<N 0

I

(ll-1-67)
 



                    -21-                   
    H,C....N_.-CH,        H,C,N_.-CH,        H3C,N.,...CH3   
Bry¢Io    Q    Cly¢I--..,o    Q    I--..,o       
                Cl'((¢   
:    NH        :    NH        :NH    q   
    O\~;.N    Cl        O~.<N    Cl    O~.<N    Cl   
    Br            Br            CF,   
    (11-1~8)                (11-1~9)            (11-J-70)       
    ~C,N.,...CH3            J:•                   
Bry¢Io    Q    ~0~               
:    0 NH        H,C 0    Q           
    ~;.N    0    ~.<N        0           
        F,            F,                   
    (11-1-71)                (11-1-72)                   

•-  and also an active compound of the formula (I) (group 1) or ofgroup2 selected from the compounds

(2-J)to(2-7).

Emphasis is given to active compound combinations comprising the compound of the formula (II-•

1-9) and the stated active compound of the formula (I) (group I) or of group 2:

10    a) Active compound combinations comprising (11-1-9) and (1-a-4).

b)    Active compound combinations comprising (11-1-9) and (2-2) buprofezin.

c)    Active compound combinations comprising (11-1-9) and (2~) flonicamid.

d)    Active compound combinations comprising (11-1-9) and (2-7) pirimicarb.

15    Emphasis is given to the following specifically stated active compound combinations (2-com.ponent mixtures) comprising one compound of the formula (I) and one compound of the formula (II-1) or of group 2:

No.    Active compound combination    No.    Active compound combination   
    comprising        comprising   
               
Ia)    (1-a-4) and (11-J-1)    28a)    (1-a-4) and (11-1-39)   
!b)    (2-2) buprofezin and (11-1-1)    28b)    (2-2) buprofezin and (11-1-39)   
!c)    (2~) flonicamid and (11-1-1)    28c)    (2~) flonicamid and (11-1-39)   
!d)    (2-7) pirimica:rb and (11-1-1)    28d)    (2-7) pirirnicarb and (11-1-39)   
2a)    (1-a-4) and (11-1-2)    29a)    (1-a-4) and (11-1-40)   
 



-22-

    No.    Active compmmd combination    No.    Active compound combination   
        comprising        comprising   
                   
    2b)    (2-2) buprofezin and (11-1-2)    29b)    (2-2) buprofezin and (11-1-40)   
    2c)    (2-6) flonicamid and (11-1-2)    29c)    (2-{i) flonicamid and (11-1-40)   
    2d)    (2-7) pirimicarb and (11-1-2)    29d)    (2-7) pirimicarb and (11-1-40)   
    3a)    (1-a-4) and (11-1-3)    30a)    (1-a-4) and (11-1-42)   
    3b)    (2-2) buprofezin and (11-1-3)    30b)    (2-2) buprofezin and (11-1-42)   
    3c)    (2-{i) flonicamid and (11-1-3)    30c)    (2-6) flonicamid and (11-1-42)   
                   
    3d)    (2-7) pirimicarll and (11-1-3)    30d)    (2-7) pirimicarb and (11-1-42)   
    4a)    (1-a-4) and (11-1-4)    31a)    (1-a-4) and (11-1-43)   
    4b)    (2-2) buprofezin and (11-1-4)    31b)    (2-2)buprofezin and (11-1-43)   
    4c)    (2-0)flonicamid and (11-1-4)    31c)    (2-6) flonicamid and (11-1-43)   
    4d)    (2-7) pirimicarll and (11-1-4)    31d)    (2-7) pirimicarll and (11-1-43)   
    Sa)    (1-a-4) and (11-1-5)    32a)    (1-a-4) and (11-1-44)   
    Sb)    (2-2) buprofezin and (11-1-5)    32b)    (2-2) buprofezin and (11-1-44)   
    Sc)    (2-6) flonicamid and (11-1-5)    32c)    (2-6) flonicamid and (11-1-44)   
    Sd)    (2-7) pirimicarll and (11-1-5)    32d)    (2-7) pirimicarb and (11-1-44)   
    6a)    (1-a-4) and (11-l.{i)    33a)    (1-a-4) and (11-1-50)   
    6b)    (2-2) buprofezin and (11-1-{i)    33b)    (2-2) buprofezin and (11-1-50)   
    6c)    (2-6) flonicamid and (11-l.{i)    33c)    (2-{i) flonicamid and (11-1-50)   
    6d)    (2-7) pirimicarll and (11-J.{i)    33d)    (2-7) pirimicarb and (11-1-50)   
    7a)    (1-a-4) and (11-1-7)    34a)    (l-a-4)and(II-l-51)   
                   
    7b)    (2-2) buprofezin and (11-1-7)    34b)    (2-2) buprofezin and (11-1-51)   
    7c)    (2-{i) flonicamid and (11-1-7)    34c)    (U) flonicamid and (11-1-51)   
    7d)    (2-7) pirimicarb and (11-1-7)    34d)    (2-7) pirimicarb and (11-1-51)   
    8a).    (1-a-4) and (11-1-8)    35a)    (1-a-4) and (11-1-52)   
    8b)    (2-2) buprofezin and (11-1-8)    35b)    (2-2) buprofezin and (11-1-52)   
    Be)    (U) flonicamid and (11-1-8)    35c)    (2-6) flonicamid and (11-1-52)   
    8d)    (2-7) pirimicarll and (11-1-8)    35d)    (2-7)pirimicarll and (11-1-52)   
    9a)    (1-a-4) and (11-1-9)    36a)    (1-a-4) and (11-1-53)   
    9b)    (2-2) buprofezin and (11-1-9)    36b)    (2-2) buprofezin and (11-1-53)   
    9c)    (2-6) llonicamid and (11-1-9)    36c)    (2-6) llonicamid and (11-1-53)   
    9d)    (2-7) pirimicarll and (11-1-9)    36d)    (2-7) pirimicarll and (11-1-53)   
    lOa)    (1-a-4) and (11-1-ll)    37a)    (1-a-4) and (11-1-54)   
    lOb)    (2-2) buprofezin and (II-1-11)    37b)    (2-2) buprofezin and (11-1-54)   
    JOe)    (2-0)flonicamid and(II-1-11)    37c)    (2.{;) flonicamidand (11-1-54)   
    !Od)    (2-7) pirimicarll and (11-1-11)    37d)    (2-7) pirimicarb and (11-1-54)   
    lla)    (1-a-4) and (11-1-12)    38a)    (1-a-4) and (11-1-55)   
    lib)    (2-2) baprofezin and (II-1-12)    38b)    (2-2) buprofezin and (11-1-55)   
                   
    lie)    (2-6) flonicarnid and (II-1-12)    38c)    (2-6)1lonicamid and (11-1-55)   
    lid)    (2-7) pirimicarb and (11-l-12)    38d)    (2-7)pirimicarll and (11-1-55)   
    !2a)    (l-a-4)and(II-1-13)    39a)    (1-a-4) and (11-1-56)   
    12b)    (2-2) buprofezin and (11-1-13)    39b)    (2-2) buprofezin and (11-1-56)   
    12c)    (2-{i) llonicamid and (11-1-13)    39c)    (2-{i) flonicamid and (11-1-56)   
    12d)    (2-7) pirimicarll and (11-1-13)    39d)    (2-7) pirimicarll and (11-1-56)   
    13a)    (1-a-4) and (II-1-15)    40a)    (1-a-4) and (11-1-57)   
    13b)    (2-2) buprofezin and (11-1-15)    40b)    (2-2) buprofezin and (11-1-57)   
                   
 



-23-

    No.    Active compound combination    No.    Active compound combination   
        comprising        comprising   
                   
    13c)    (2-6) flooicamid and (Il-l-IS)    40c)    (2-6) flonicamid and (ll-l-S7)   
    !3d)    (2-7) pirimicarb and (Il-l-IS)    40d)    (2-7) pirimicarb and(ll-l-S7)   
    !4a)    (l-a-4)and(ll-l-16)    4Ja)    (1-a-4) and (ll-l-S8)   
    !4b)    (2-2) buprofezin and (ll-1-16)    4lb)    (2-2) buprofezin and (ll-i-S8)   
    14c)    (2-6) flonicamid and (ll-1-16)    4ic)    (2-6) flonicamid and (ll-i-S8)   
    14d)    (2-7) pirimicarb and (li-I-I6)    4Id)    (2-7) pirimicarb and (li-I-S8)   
                   
    !Sa)    (1-a-4) and(ll-1-19)    42a)    (l-a-4)and(li-I-60)   
                   
    !Sb)    (2-2) buprofezin and (ll-i-I9)    42b)    (2-2) buprofezin and (ll-1-60)   
    !Sc)    (2-6) flooicamid and (ll-l-I9)    42c)    (2-6) flonicamid and (ll-1-60)   
    !Sd)    (2-7) pirimicarb and (ll-1-19)    42d)    (2-7) pirimicarb and (li-I-60)   
    16a)    (1-a-4) and (ll-i-2I)    43a)    (1-a-4) and (ll-1-61)   
    16b)    (2-2) buprofezin and (ll-1-21)    43b)    (2-2) buprofezin and (ll-l-6I)   
    16c)    (2-6) flonicamidand (li-I-21)    43c)    (2-6) flonicamid and(ll-l-6I)   
    16d)    (2-7) pirimicarb and (ll-1-21)    43d)    (2-7) pirimicarb and (li-I-61)   
    17a)    (1-a-4) and(ll-1-22)    44a)    (1-a-4) and (ll-1-62)   
    17b)    (2-2) buprofezin and (ll-1-22)    44b)    (2-2) buprofezin and (li-I-62)   
    17c)    (2-6) flonicamid and (ll-1-22)    44c)    (2-6) flonicamid and (ll-1-62)   
    17d)    (2-7)pirimicarb and (ll-1-22)    44d)    (2-7) pirimicarb and (li-I-62)   
    !Sa)    (1-<>-4) and(li-I-23)    4Sa)    (1-a-4) and (ll-1-64)   
    18b)    (2-2) buprofezin and (ll-1-23)    4Sb)    (2-2) buprofezin and (ll-1-64)   
    18c)    (2-6) flonicamid and (ll-1-23)    4Sc)    (2-6)flonicamid and (ll-1-64)   
    !8d)    (2-7) pirimicarb and (ll-1-23)    4Sd)    (2-7) pirimicarb and (li-I-64)   
    19a)    (1-a-4) and (ll-1-24)    46a)    (1-a-4) and (ll-l-6S)   
    !9b)    (2-2) buprofezin and (ll-1-24)    46b)-    (2-2) buprofezin and (ll-l-6S)   
    19c)    (2-6) flonicamid and(ll-1-24)    46c)    (2-6) flonicamid and (ll-l-6S)   
    19d)    (2-7) pirimicarb and (ll-1-24)    46d)    (2-7) pirimicarb and (li-I-6S)   
    20a)    (1-a-4) and (ll-1-26)    47a)    (1-<>-4) and (ll-1-66)   
    20b)    (2-2) buprofezin and (ll-!-26)    47b)    (2-2) buprofezin and (ll-1-66)   
    20c)    (2-6) flonicamid and (ll-1-26)    47c)    (2-6) flonicamid and (ll-1-66)   
    20d)    (2-7) pirimicarb and (ll-1-26)    47d)    (2-7) pirimicarb and (II-I-66)   
    2la)    (1-a-4) and(ll-1-27)    48a)    (1-a-4) and (ll-1-67)   
    2Ib)    (2-2) buprofezin and (ll-1-27)    48b)    (2-2) buprofezin and (ll-1-67)   
    2Ic)    (2-6) flonicamid and(ll-1-27)    48c)    (2-6) flonicamid and (ll-1-67)   
    2ld)    (2-7) pirimicarb and (li-I-27)    48d)    (2-7) pirimicarb and (ll-1-67)   
    22a)    (1-a-4) and (li-I-29)    49a)    (l-a-4)and(ll-l-68)   
    22b)    (2-2) buprofezin and (ll-1-29)    49b)    (2-2) buprofezin and (ll-1-68)   
    22c)    (2-6) flonicamid and (ll-1-29)    49c)    (2-6) flonicamid and (li-I-68)   
    22d)    (2-7) pirimicarb and (li-I-29)    49d)    (2-7) pirimicarb and (ll-1-68)   
    23a)    (1-a-4) and (ll-1-30)    SOa)    (1-a-4) and (li-I-69)   
    23b)    (2-2) buprofezin and (li-I-30)    SOb)    (2-2) buprofezin and (ll-1-69)   
    23c)    (2-6) flonicamid and (ll-1-30)    SOc)    (2-6) flonicamid and (li-I-69)   
    23d)    (2-7) pirimicarb and (li-I-30)    SOd)    (2-7) pirimicarb and (ll-1-69)   
    24a)    (1-a-4) and (ll-1-31)    Sia)    (1-a-4) and (ll-1-70)   
    24b)    (2-2) buprofezin and (ll-l-3I)    Sib)    (2-2) buprofezin and (ll-1-70)   
    24c)    (2-6) flonicamid and (li-I-3I)    Sic)    (2-6) flonicamid and (U-I-70)   
 
    No.    Active compound combination    No.    Active compound combination   
        comprising        comprising   
                   
    24d)    (2-7) pirimicarb and (11-1-31)    Sid)    (2-7) pirimicarb and (11-1-70)   
    25a)    (1-a-4) and (11-1-32)    52a)    (J-a-4)and (11-1-71)   
    25b)    (2-2) buprofezin and (11-1-32)    52b)    (2-2) buprofezin and (11-1-71)   
    25c)    (2-6) flonicamid and (11-1-32)    52c)    (2-6) flonicamid and (11-1-71)   
    25d)    (2-7) pirimicarb and (11-1-32)    52d)    (2-7) pirimicarb and (11-1-71)   
    26a)    (1-a-4) and (11-1-33)    53 a)    (1-a-4) and (11-1-72)   
    26b)    (2-2) buprofezin and (11-1-33)    53 b)    (2-2) buprofezin and (11-1-72)   
    26c)    (2-6) flonicamid and (11-1-33)    53c)    (2-6) flonicamid and (11-1-72)   
    26d)    (2-7) pirimicarb and (11-1-33)    53 d)    (2-7) pirimicarb and (11-1-72)   
    27a)    (1-a-4) and (11-1-38)           
    27b)    (2-2) buprofezin and (11-1-38)           
    27c)    (2-6) flonicamid and(ll-1-38)           
    27d)    (2-7) pirimicarb and (11-1-38)           

However, the  geneml  or preferred radical  definitions  or illustrations  given  above can also be

combined with one another as desired. ie. including combinations between the respective ranges and

preferred ranges.  They  apply both to the  end products and, correspondingly, to precursors and

intermediates.

Preference according to the invention is given to active compound 'Cembinations comprising the

compounds of the formula (I) or a compound of group ~ and also at least one compound of the

formula •(TI) where the individual radicals are a combination of the meanings given above as being

10    preferred (preferable).

Particular preference according to the invention is given to active compound combinations comprising the compounds of the formula (I) or a coiD.pound of group 2 and also at least one

compound of the formula (TI) where the individual radicals are a combination of the meanings given

15    above as being particularly preferred.

Very particular preference according to the invention is given to active compound combinations comprising the compounds of the formula (I) or a compound of group 2 and also at least one compound of the formula (TI) where the individual radicals are a combination of the meanings given
20    above as being very particularly preferred.

Saturated or unsaturated hydrocarbon radicals, such as alkyl or alkenyl, can in each case be straight-chain or branched as far as this is possible, including in combination with heteroatoms, such as, for example, in alkoxy.

25
 
Optionally    substituted  radicals  may  be  mono-  or  polysubstituted,  where  in  the  case  of

polysubstitution the substituen~ can be identical or different.

In additi~ the active compound combinations may also comprise further fungicidally, acaricidally or

insecticidally active co-components.

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. The mixing mtios required for fmding the synergism are not necessarily the preferred mixing ratios relevant for 100% activity.
10    However, the weight ratios of the active compounds in the active compound combinations can be varied within a relatively wide range. In general, the combinations according to the invention comprise active compounds of the formula (I) or a compound of group 2 and the mixing partner of the formula (II) in the stated prefurred and particularly preferred mixing ratios:

15    The mixing ratios are based on \\"eight ratios. The ratio is to be understood as meaning active compound of the formula (1): mixing partner
 

Mixing pm1ner

(I-a-4)

Amitrnz

Buprofezin

Pymetrozine

Pyripmxyphen

Triazamate

Flonicamid

Pirimicarb
 


Preferred mixing ratio    Particularly preferred
    mixing ratio
10:1 to 1:10    5:1 to 1:5
5:1 to 1:20    1:1 to 1:10
10:1 to 1:10    5:1 to 1:5
10:1 to 1:10    5:1 to 1:5
10:1 to 1:10    5:1 to 1:5
10:1 to 1:10    5:1 to 1:5
10:1 to 1:10    5:1 to 1:5
10:1 to 1:10    5:1 to 1:5
 

The  active  compound combinations of the  invention  are  suitable for  controlling animal  pests,

20    preferably arthropods and nematodes, in particular insects and arachnids, found in agriculture, in animal health. in forests, in gardens and leisure facilities, in the protection of stored products and materials and in the hygiene sector, while exhibiting good tolerability to plants, low toxicity to wann-
blooded species and good environmental compatibility. They are active against normally sensitive

and resistant species, and against all or individual developmental stages. The abovementioned pests

25    include:

From the order of the Isopoda, for example, Oniscus asellus, Annadillidium 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 ofth~ Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina From the order of the Coliembola, for example. Onychiurus armatus.
From  the  order of the  Orthoptera,  for  example,  Acheta  domesticus,  Gryllotalpa  spp.,  Locusts

migratoria migratorioides, Melanoplus spp., Scbistocerca gregaria.

From the order of the Blattaria, for example, Blatta orientalis, Periplaneta americana, Leucophaea.

maderae, Blattella gennanica.

10    From the order of the Dermaptera. for example, Forficula auricularia. From the order of the Isoptera, for example, Reticulitennes 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 tahac~ Thrips

15    palm~ FrankJiniella accidentalis.

From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma

quadrats, Cimex lectulariw:~, Rhodnius prolix.us, Triatoma spp.

• • From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporarioiUDl, Aphis gossypi~ Brevicoryne brassicae, Cryptomyzus ribis, Aphis faba.e, Aphis pomi.,

20    Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera yastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon hmu~ Rhopalosiphmu padi, Empoasca spp., Euscelis bilobatus, Nephotettix 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,

25    CheimatDbia brumata, Lithocolletis blancardella, Hypouomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrlloea, Lymantria spp., Bucculatria thurberiella, Phyl!cicnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana. Heliothis spp., Mamestra bmssicae, Panolis flammea, Spodoptera. spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp.,
Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella,

30    Hofmannophila pseudospretella, Cacoecia podaua, Capua reticuhma, 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, Diabroti.ca. spp., Psylliodes clrrysocephala, Epilachna varivestis,

35    Atomaria spp., OryzJ!ephilus soriuamensis, Anthonomus spp., Sitophilus spp., Otiorthyuchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dennestes spp.,
 Trogodenna  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,  Lissorhopt:Iw

oryzophilus.

From the order of the  Hymenoptern, for example, Diprion spp., Hoplocampa spp.,  Lasius  spp.,

Monomoriwn phmaonis, 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., Cluysomyia spp., Cuterebra spp., Gasb"ophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp.,

10    Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis ""Jlitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp.
From the order oftb.~ 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,  Phyllocoptnrta  oleivora,

15    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 dipsac~ Tylenchulus semipenetrans, Heterodent spp., Glooodera spp., Meloidogyne spp.,

20    Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp ..

The active compound combinations of the invention of the compounds of the formula (I) and at least one compound 1 to 15 are particularly suitable for controlling "biting'' pests. These include, in particular, the following pests:

25

From the order of the Lepidoptera for example, Pectinophom gossypiella, Bupalus piriiarius, Cheimatobia brumata, Lithocolletis blancanlella, Hypooomeuta padella, Plutella xylostella, Malacosoma neustrla, Euproctis chcysonhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Mamestra hmssicae,

30    Panolis flammea, Spodoptem spp., Trichoplusia rri, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Cspua reticulana, Choristooeura fumifurana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.
From  the  order  of the  Coleoptera,  for  example,  Anobiwn  punctatum.  Rhizopertha  dominica,

35    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.,  Otionbynchus

sulcatus,  Cosmopolites  sordidus,  Ceuthorrbynchus  assimilis,  Hypera  postica,  Dennestes  spp.,

Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbiwn psyHoides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorbopbus ocyzophilus.

The active compound combinations of the invention of the compounds of the fonnula (I) and at least

one compound 5 to 8 are additionally particularly suitable for controlling ••sucking'' pests. These

10    include, in particular, the following pests:

From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, B~coryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi,

Eriosoma  Ianigerum,  Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum

avenae, Myzus  spp., Phorodon hwnuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,

15    Nepbotettix cincticeps, Lecanium comi, Saissctia oleae, Laodelphax striatellus, Nilaparvata lugens;

Aonidiella aurantii, Aspidiotus hederae, Pseudocoocus spp., Psylla spp.

The active compound combinations of the invention have, in particular, excellent activity against

caterpillars, beetle larvae, spider mites, aphids and leaf-mining flies.

20

The  active  compound  combinations  of the  invention  can  be  converted  into  the  custon:uuy

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.

25

These formulations are pnxluced in a known manner, for example by mixing the active comjx>unds

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.

30    If the extender used is water, it is also possible, fur example, to use organic solvents 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 35    glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl
 ketone or cyclohexanone, strongly polar solvents such as dimet:hylformamide and dimethyl sulfoxide, or else water.

Suitable solid carriers are: for example anunoniwn salts and ground natural minerals such as kaolins,

clays, talc, chalk, quartz, attapulgite, montmorillonite or diatoma.coous earth. and ground S)nthetic

materials such as finely divided silica, alumina and silicates; suitable solid carriers for granules are:

for example crushed and fractionated rurtura.l 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

10    formers are: for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates, or else protein hydrolysates; suitable dispersants are: for example lignin~ sulfite waste liquors and metbylcellulose.

15    Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the fonn 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.

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

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

The active compound combinations of the invention can be present in their commercially available

formulations and in the use fonns, prepared from these formulations, as a mixture with other active

30    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 subs!Bnces produced by microorganisms, inter alia.

35    Mixtures with other knovm active compounds such as herbicides or with fertilizers and growth regulators are also possible.
 
When used as insecticides. the active compound combinations of 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 compcnmds, 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

fonnulations 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

10    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 residua] action on wood and clay as well as good stability to alkali on

limed substrates.

IS

The active compo1md combinations of 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 hBrd ticks, soft ticks, lllliiige mites, harvest mites, flies (stinging and licking),

parasitizing fly larvae, lice, head lice, bird lice and fleas. These parasites include:

20

From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp.,

Phtirus spp., Solenop- spp.

From the order of the Mallophagida and the suborders Amblycerioa and !scboocerina, fur example,

Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Wemeckiella spp., Lepikcntron spp.,

25    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., Eusim.ulium spp., Phlebotomus spp., Lutzomyia spp.,

Culicoides  spp., Cluysops spp., Hybomitra spp., Atylotus  spp., Tabanus spp., Haematopota spp.,

Philipomyia  spp.,  Braula  spp.,  Musca spp.,  Hydrotaea  spp.,  Stomoxys  spp.,  Haematobia  spp.,

30    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.

35    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, Blatte11a

gennanica, Supella spp.

From the  subclass of the  Acacia (Acarida) and  the orders  of the Meta- and  Mesostigmata, for

example, Argas spp., Ornithodoros spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dennacentor spp., Haemaphysalis spp., Hya1omma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Stemostoma spp., Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Aearapis

spp.,  Cheyletiella  spp.,  Omithocheyletia  spp.,  Myobia  spp.,  Psorergates  spp.,  Demodex  spp.,

Trombicula spp., Listrophorus spp., Acarus spp., Tymphagus spp., Caloglyphus spp., Hypodectes

10    spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

The active compound combinations of 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

15    as, for example, dogs, cats, caged birds, aquarium fish and so-called experimeotal animals such as, for example, hamsters, guinea pigs, J"8tol and mice. By controlling these arthropods, cases of death and reductions in productivity (for mea~ milk, woo~ hides, eggs, hooey aod the like) should be

--    diminished, so that more economical and simpler animal husbandry is possible by the use of the active compound combinations of the invention.
20

The acti've compmmd combinations of 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, intraveno~ly, intraperitoneally and
25    the like), implaots, by nasal adminislmtion, by dermal edministration in the form o~ for example, immersing or dipping, spraying, pouring-on, spotting-on, washing, dusting, and with the aid o:factive-compound-comprising molded articles such as collars, ear tags, tail tags, limb bands, halters, marking devices and the like.

30    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 I 0,000-fold dilution, or they may be used as a chemical dip.

Moreover, it has been found that the active compound combinations of the invention show a potent

35    insecticidal action against insects which destroy industrial materials.
 


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The fol1owing insects may be mentioned by way of example and with preference, but not by way of

limitation:

Beetles  such  as  Hylotrupes  bajulus,  Chlorophorus  pilosis,  Anobiwn  punctatwn,  Xestobium

rufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apate monacbus, Bostzychus capucins, Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus.

Dennapterans such as Sirexjuvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augw-. Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotennes indicola, Reticulitermes

10    flavipes, Reticulitennes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootennopsis nevadeosis, Coptotermes form.osanus.
Bristle-tails such as Lepisma saccharine.

Industrial materials in the present context are understood as meaning non-living materials such as,

15    preferably, polymers, adhesives, glues, puper uud board, leather, wood, timber products uud paints.

The rna1erial which is to he protected from insect attack is very particularly preferably wood uud timber products.

20    Wood and timber products which can be protected bythe_composition of the invention, or mixtures comprising it, are to be understood as meaning, for exan;tple:

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 which quite generally are used in bouse construction
25    or building joinery.

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

30    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.
 


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

0.001 to 60"/o 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 200/o 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 organochemica.l solvent or solvent mixture and/or an oily or

oil-type organochemical solvent or solvent mixture of low volatility ancl!or a polar organochemica.l

solvent or solvent mixture and/or water and, if appropriate, an emulsifier and/or wetter.

15    Organochemica.I 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, petrolemn and/or aJkylben:zene.

20

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 of250 to 350°C, petroleum and aromatics with a boiling range of 160 to 280°C, oil of turpentine, and the like are advantageously used.

25    In a preferred embodiment, liquid aliphatic hydrocarl>ons 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 •2200C and/or spindle oil and/or monochlorooaphthalene, preferably a.-monochloronaphtbalene, are used.

The organic oily or oil-type solvents of low volatility and with an evaporation nwnber of above 35

30    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 30CC, prefenbly above 450C, and that the mixture is soluble or emulsifiable in this solvent mixture.

35    In a preferred embodiment, some of the organochemical solvent or solvent mixture or an aliphatic polar organochemical solvent or solvent mixture is replaced. Aliphatic organochemical solvents
 



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which contain hydroxyl and/or ester and/or ether groups are preferably used, such as, for example,

glycol ethers, este!S 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  act)'late  resin,  a vinyl  resin,  for  example  polyvinyl  acetate,  polyester  resin,

pplycondensation  or polyaddition resin.  polyurethane resin,  alkyd  resin or modified alkyd resin.

phenol resin,  hydrocarbon  resin such as indenelcoumarone resin, silicone resin, drying  vegetable

10    and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.

The S)111hetic resin employed as binder can be employed in the fotm 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, odor-masking agents, and inhibitors or

15    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 hinders, at least one alkyd resin or modified alkyd resin and/or a drying vegetable oil.

Alkyd resins which are prefembly used in accordance with the invention are those with an oil content

20    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 300/o of the binder (based on 100% of

25    binder employed).

The plasticizers are from the chemical classes of the phthalic esters, such as dibutyl phthalate, dioctyl phthalale or benzyl butyl phthalate, phosphoric esten; such as tributyl phosphate, adipic este!S such as

di(2-ethylhexyl)adipate, stearates such as butyl stearate or amyl stearnte, oleates such as butyl oleate,

30    glycerol ethers or higher-molecular-weight glycol ethers, glycerol esters and p-toluenesulfonic esters.

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

35    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, emulsifiers and dispersants.
 



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Particularly effective timber protection is achieved by industria1-scale impregnating processes, for example the vacuwn, double-vacuum or pressure processes.

The active compound combinations of 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 signaling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells and species from the Ledamorpha

10    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 stops in the dry dock.

IS    Apart from fouling by  algae, for  exsmple Ectocorpus sp. and Ceramium sp., fouling by sessile

Entomostraka groups, which come under the generic term Cirripedia (cirriped crustaceans), is of

particular importance.

Surprisingly, it bas now been found that the active ~ound comb~tions of the invention have an

20    outstanding antifouling action.

Using the active compound combinations of the invention allows the use of heavy metals such as, for

example,  in bis(trialkyltin) sulfides, tri-n-butyltin  launrte, tri-n-butyltin chloride, copper(!) oxide,

triethyltin    chloride,   tri-n-buty1(2-phenyl-4-<:hlorophenoxy)tin,   tributyltin   oxide,   molybdenum

25    disulfide, antimony oxide, polymeric butyl titanate, phenyl(bispyridine )bismuth chloride,_ tri-n-butyltin fluoride, manganese ethylenebisthiocarbamate, zinc dimethylditbiocarbamate, zinc ethylenebisth.iocarbama.te, rinc salts and copper salts of 2-pyricUnethiol 1-oxide, bisdimethyldith.iocarbamoylzinc ethylenebisthiocarbamate, rinc oxide. copper(I) ethylene-

bisdithiocarllamate, eopper thiocyanate, copper naphthenate and tributyltin halides to be dispensed

30    with, or the concentration of these compounds to be 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.

35    Preferable suitable components in combination with the antifouling compositions according to the invention are:
 



-36-

algicides such as 2-terl-butylamino-4-<:yclopropylamino-6-methyltlrio-1,3,5-triazine, dichloropheo, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryo;

fungicides  such as benzo[ h ]thiophenecarboxylic acid  cyclohexylamide  S,S-dioxide, dichlofluanid,

fluorl'olpet,    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

I 0    trimethacarb;

or conventional antifouling active compounds such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylpanrtryl sulfone, 2-(N,N-dimethyltlriocarbamoylthio)-5-nitrothiazyl, potassi- copper, sodium and zinc salts of 2-p}Ti.dinetb.iol !-oxide, pyridine/triphenylborane, tet:rabutyldistannoxane,

IS    2,3,5,6-tetrachloro-4-{methylsulfonyl)pyridine,    2,4,5,6-tetrachloroisophthalonitrile,

tetramethylthiumm disulfide and 2,4,6-trichlorophenylma.leimide.

The antifouling compositions used comprise the active compound com~inations of the invention in a

concentration ofO.OOl to 500/o by weight. in particular 0.01 to 200/o by weight

20

Moreover, the antifouling compositions of the invention comprise the customary components such as,

fur exmnple, those described in Ungerer, Chem. Ind. 1985, 37, 730-732 and Willisms, Antifuullng

Marine Coatings, Noyes, Park Ridge, 1973.

25    Besides the algicidal, fungicidal, molluscicidal active compounds and insecticidal active com.eowtds of 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

30    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.

35    If appropriate, paints also comprise inorganic pigments, organic pigments or colorants which are prefembly insoluble in saJt water. Paints may furthennore comprise materials such as colophonium to
 



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aHow controlled release of the active compounds. Furthermore, the paints may comprise plasticizers,

modifiers  which  affect  the  rheological  properties  and  other  conventional  constituents.  The

compounds of 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,

factoty 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

10    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, Btyobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodoros moubat. Rhipicephalus sanguineus,
Trombicula    alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus,

15    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 aseUus, Porcellio scaber.

20    From th~ 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 saccharins, l..epismodes

inquilinus.

From the order of the Blattaria, for example, Blatta orientalies, Blattella germanica, Blattella asahinai,

25    Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Peri~laneta ameri.,_ 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 lsoptera, for example, Kalotermes spp., Reticulitermes spp.

30    From the order of the Psocoptera, for example, l..epinatus spp., Liposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryza.e, Necrobia spp., Ptinus spp., Rhizopertha dominies, Sitophilus granarius, Sitophilus
oryza.e, Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypt~ Aedes albopictus, Aedes taeniorhynchus,

35    Anopheles  spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus,  Culex
 



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pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica., Phlebotomus spp.,

Sarcophaga camaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.

From  the  order  of the  Lepidoptera,  for  example,  Achroia  grisella.,  Galleria mellonella,  Plodia

interpunctella, Tinea cloacella, Tinea pellionella, rmeola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex

irritans, Tunga penetrans, Xenopsylla cheopis.

From  the  order of the  Hymenop~ 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  hwnanus  capitis,  Pediculus  humanus

10    corpori~ Pluhirus pubis.

From the order of the Heteroptera, for example, Cimex bemipterus, Cimex lectularius, Rhodinus

prolixus, Triatoma infesta.ns.

They are used as aerosols. pressureless spray products, for example pump and atomizer sprays,

15    automatic fogging systems, fogg=, foams, gels, evaporator products with evaporator tablets made of cellulose or polymer, liquid evaporators, gel and membrane evaporators, prope11er-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.

20    Accordffig to the invention, it is possible to treat ali pl4nts and parts of plants. Plants are to be understood here as meaning all plants and plant populatioos such as desired and undesired wild plaots or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be ob1ained by conventional breeding and optimization methods or by biote:chnological and genetic
engineering methods or combinations of these methods, including the transgenic plants and including

25    the plant cultivars which can or cannot be protected by plant breeders' certificates. Parts of p~ are to be understood as meaoing all above-ground and below--oround parts and orgam; 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,

30    rhizomes, cuttings and seeds.

The treatment of the invention of the plants and parts of plants with 1he active compounds is carried out directly or by action on their enviroomeot, habitat or storage area according to customary

treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, brushing-

35    on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multi-layer coating.
 



-39-

As already mentioned above, it is possible to treat all plants and their parts according to the invention.

In a preferred embodiment, wild plant species and plant cultivars, or thOse obtained by conventional

biological breeding methods, such as crossing or protoplast fusio~ and parts thereof, are treated. In a

further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering,

if appropriate in combination with conventional methods (Genetically Modified Organisms), and

parts thereof are treated. The terms "parts", "parts of plants11  and "plant parts" have been explained

above.

Particularly preferably, plants of the plant cultivarS which are in each case commercially available or

10    in use are treated according to the invention.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment of the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced application mtes and/or a widening of the activity spectrum
15    and/or an increase in the activity of the substances and compositions which can be used according to the inventio~ better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering perfonnance, easier harvesting, accelerated maturation. higher harvest yields, better qualiii and/or a higher nutritional value of the harvested products, better st<rrage siability and/m processability of the harvested products
20    are possible which exceed the effects which wero actually to be expected.

The transgenic plants or plant cultiVBIS (i.e. those obtained by genetic engineering) which are preferred and to be treated according to the invention include all plants which, in the genetic modification, received genetic material which imparts particularly advantageous useful traits to these

25    plants. Examples of such traits are 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 processability of the

harvested products. Further and particularly emphasized examples of such traits are a better defense

30    of the plants against animal and microbial pests, such as against insects, mite~ phytopathogenic fung~ 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 important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, cotton, tobacco, oilseed rape and also fruit

plants (with the fruits apples, pears, citrus fruits and grapes), and particular emplmsis is given to

35    maize, soya beans, potatoes, cotton, tobacco and oilseed mpe. Traits that are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and wonns by toxins
 



-40-

fanned in the plants:, in particular those fanned in the plants by the genetic material from Bacillus

thuringionsis (for example by the genes Cry!A(a), Cry!A(b), Cry!A(c), CryllA, Cryll!A, CryiiiB2, Cry9c Cry2Ab, Cry3Bb and Cry!F and also combinations thereof) (hereinbelow referred to as "Bt
plants"). Traits that are also particularly emphasized are the increased defense of plants against fung4

bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and also

resistance  genes  and  correspondingly  expressed proteins  and  toxins.  Traits that are  furthermore

particularly  emphasized  are  the  increased  tolerance  of the  plants  to certain  herbicidally active

compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example

the  "PAT" gene).  The  genes  in question  which  impart the desired traits can  also  be  present in

10    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 pomto varieties which are sold under the tmde names YIELD GARD® (for example maize, cotton, soya beans), KnockOut®

(for example maize1 StarLink® (for example maize1 Bollgard® (cctton1 Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize

15    varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya beans), Libetty Link® (tolerance

__ to phosphinotric~ for example oilseed mpe), IMI® (tolemnce to imidazolinones) and STS® (tolerance to solfonylureas, for example maize). Herbicide-resista~.t plants (plants bred in a

~ conventional manner for herbicide tolerance) which may be mentioned include the varieties sold

20    under th~ name Clearfield® (for example maize). Of coUrse, these statements also apply to plant cultivars having these or still~to-be--developed genetic traits, which plants will be developed and/or marlreted in the future.

The plants listed can be treated according to the invention in a particularly advantageous manner with

25    the active compound mixtures of the invention. The preferred ranges stated above for the ~ also apply to the treatment of 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 of the invention can

30    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 swn of actions.

A synergistic effect in insecticides and acaricides is always present when the action of the active

compound combinatioru; exceeds  the totaJ  of the  actions  of the  active compounds  when applied

35    individually.
 



-41-

The expected action for a given combination of two active compounds can be calculated as follows,

using "Colby's fonnula" (cf. S.R. Colby, "Calculating Synergistic and Antagonistic Responses of

Herbicide Combinations", Weeds l2ll 12. 20-22):

If

X    is the kill rate, expressed as a percentage of the untreated control, when employing active compound A at an application rate of mgtha or in a concentration of mppm,

Y    is the kill rate, expressed as a percentage of the untreated control, when employing active

compound B at an application rate of D glha or in a concentration of n ppm and

10    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 glha or in a concentration of m and n

ppm,

then
X•Y
E=X+Y-   1iiQ

15

H 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 fonnula for the expected kill rate (E).
 



-42-

Use examoles



Aphis gossypii test

Solvent:    parts by weight of dimethylformamide

Emulsifier:    parts by weight of all<ylaryl 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 emulsifier-containing water to the desired concentration.

Cotton leaves (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypil)

15    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 aphids have been killed; 0% means that none of the aphids have been killed. The detenni;ned kill rates are entered into
•    Colby's furmula(seepage41).

20

In this test, for example, the following active compound combination in accordance with the present application shows a synergistically enhanced activity compared to the active compounds applied on their own:

25
 



-43-

Table AI: Plant-<larnaging insects

Aphis goosypii test

Active compounds            Concentration of active    Kill rate in % after   
                    compound in ppm        7'   
                        found*        calc. ••   
                                   
                                   
                        20           
                (11-1-9)                   
                               
    1    s  H,C).:;cH,                       
o-aNr")=N/-cH3    CH3        20               
        H,C                           
(2-2) buprofezin                           
                       
(11-1-9) + (2-2) buprofezin (1:5)        4+20    40        20   
                           
found    = activity found                       
calc.        = activity calculared using Colby's formula               
            Table A2: Plant-damaging ~rts               
                Aphis gossypii test               
                       
Active compounds            Concentration of active    Kill rate in% after   
                    compound in ppm        6d   
                        found*        calc. ••   
                                   
                                   
                    20    55           
                (11-1-9)                   
                                   
CF3    0                               
C{{'cN        20    40           
N                                   
(2-6) flonicamid                           
                       
(11-1-9) + (2-6) flonicamid (1:1)        20+20    99        73   
                           
found    = activity found                       
calc.        = activity calculared using Colby's fonnula               
 



    -44-
Myzus persicae test   
Solvent:    parts by weight of dimethylfonnamide
Emulsifier:    2    parts by weight of alkylazyl 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 emulsi:fier-

10    containing water to the desired concentratioiL

Cabbage leaves (Brassica oleracea) which are heavily infested by the green peach aphid (.Myzw persicae) are treated by being dipped into the preparation of active compound of the desired

concentration.

IS

After the desired period of time, the kill in% is detennined. 100% means that all aphids have been

killed; 0% means that none of the aphids have been killed The determined kill rates are entered into

Colby's formula (see on page 41).

20    In this ~st, for example, the follo~g active compound cOmbination in accordance with the present application shows a synergistically enhanced activity compared to the active compounds applied on their own:
 



-45-

Table B I: Plant-damaging insects

Myzus persicae test

Active compounds                Concentration of active    Kill rate in % after   
                        compound in ppm        6'   
                            found*        calc.••   
                                       
                                       
CHar-        H    N-N            4    30           
        N~                       
"'~ Q-o                           
:::-....    I    0    ~    CF,                       
cr        H3C            (ll-1-9)                   
                                       
                                   
        o--.                           
    od.._    CH,                           
                                   
H3C..,..O        o H3c                           
        ~    -    ;,        4    80           
                                       
    H'N    ~                           
                                   
        0        CH, (1-a-4)                   
                                   
                               
(ll-1-9)+(1-a-4) (1:1)                4+4    98        86   
found        ..                           
                                   
        =actiVIty found                       
calc.        =activity calculared using Colby's formula               
                Table B2: Plant-damaging insects               
                    Myzus persicae test               
                           
Active compounds                Concentration of active    Kill rate in % after   
                        compound in ppm        6'   
                            found*        calc.••   
                                       
                           
H,Cy~ Q-Cl            4    0           
        H    N-N                           
CH,c;,-        N~                       
:::-....    I    0        CF,                       
Cl        H,C            (ll-1-9)                   
                                       
                                   
    ~ ............... CN                4    40           
~N                                   
                                   
(2-6) flonicamid                               
(ll-1-9) + (2-6) flooicamid (I: I)        4+4    95        40   
                               
found        =activity found                       
calc.        =activity calculated using Colby's formula               
 



-46-


Pbaedon cochleariae larvae test

Solvent    parts by weight of dimethylfonnamide

Emulsifier:    parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compmmd is mixed

with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-

10    containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with lmvae of the mustard beetle (Phaedon cochleariae) while the leaves are still moist

15

After the desired period of time, the kill in % is determined. 100% means that all beetle larvae have

been killed; 00/o means that none of the beetle lmvae have been killed. The detennined kill rates are

entered into Colby's formula (see page 41 ).

20    In this te,st, for example, the following active compound cOmbination in accordance with the present application shows a synergistically enhanced activity compared to the active compounds applied on their own:


25
 



-47-

Table Cl: Plant-damaging insects

Phaedon cochleariae larvae test

    Active compounds        Concentration of active    Kill rate in % after   
                    compound in ppm        3'   
                        found•        calc.••   
                                   
                                   
    'Y)&CH3'/"    H    N N    0.16    5           
        N~Q-a                   
    ~ I        0    CF3                   
    Cl    H,C    (ll-1-9)                   
                                   
                                   
            H,C                       
    o-rsN)=N)    .:;:cH,                   
        CH3                   
    or"> -cH,    100    20           
                       
        H,C                       
    (2-2) buprofezin                           
                       
    (ll-1-9) + (2-2) buprofezin (1:625)    0.16+ 100    65        24   
                           
    found    = activity found                   
    calc.    =activity calculated using Colby's formula               
                Table C2: Plant-damaging insects               
                Pbaedon cochleariae larvae~test               
                       
    Active compounds        Concentration of active    Kill rate in % after   
                    compound in ppm        6d   
                        found*        calc. ••   
                                   
                                   
                    0.16               
                (ll-1-9)                   
                                   
                        15           
            0    CH, (1-a-4)                   
                           
    (ll-1-9)+(1-a-4) (1:25)        0.16+4    55        15   
                               
    found        =activity fmmd                   
    calc.        =activity calculated using Colby's formula               
 



-48-


Plutella xylostella test (resistant stnlin)

Solvent:    parts by weight of dimethylformamide

Emulsifier:    parts 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-

! 0    containing water to the desired concentration.

Cabbage leaves  (Brassica  oleracea) are treated by being dipped  into the  preparation  of active

compound of the desired concentration and are populated with caterpillars of the diamondback moth

(PluteUa rylostella, resistant strain) while the leaves are still moist.

15

After the desired period of time, the kill in% is determined. 1000/o means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed. The detemtined kill rates are entered into Colby's formula (see page 41 ).

20    In this te,st. for example, the following active compound cOmbination in accordance with the present application shows a synergistically enhanced activity compared to the active compounds applied on their own;
 


-49.

TableD: Plant-damaging insects

Plutella xyl.,.tella test (RSistaot strain)

Active compounds            Concentration of active    Kill rate in % after   
                    compound in ppm        6'   
                        found•        calc.**   
                       
'<y~ Q-o        0.0064    0           
CH,~        ~r(Jl                   
:::-....    I    0        CF3                   
cr        H3C        (ll-1-9)                   
                                   
                                   
        0--'\                           
    od....    CH,                       
H3C..,..O        0  H3C                       
        ~    -        0.16    0           
                /,                   
    ,N    ~                       
    H    0                           
                CH, (l..a-4)                   
                                   
                           
(ll-1-9) + (1-a-4)(1 :25)            0.0064 + 0.16    65        0   
                           
                           
fouruf        = activity foUPd                   
calc.        =activity calculated using Colby's formula               
 



-50-


Spodoptera frogiperda test

Solvent:    parts by weight of dimethylfonnarnide

Emulsifier:    parts 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-

10    containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the anny worm

(Spodopterafrugiperda) while lhe leaves are still moist

15

After the desired period of time, the kill in % is determined. 100% means that all caterpillars have

been killed; 0% means that none of the caterpillars have been killed. The determined kill rates are

entered into Colby's formula (see page 41).

20    In this ~st, for example, the following active compmmd combination in accordance with the present application shows a synergistically enhanced activity compared to the active compounds applied on their own:
 


-51-

Table E: Plant-damaging insects

Spodoptera frugiperda test

Active e:ompounds            Concentration of active    Kill rate in% after   
                    compound in ppm        3'   
                        found*        calc.••   
                                   
                                   
CH,""I~            0.16    45           
"Ay)&"Q:                           
Cl    ::-....    0    CFa                       
        H,C        (II-1-9)                   
                                   
                                   
CF3    0                               
if~/'-CN            100    5           
N                                   
(2-6) Flonicamid                           
                       
(11-1-9) + (2-6) f!onicamid (1 :625)        0.16+ 100    100        47.75   
                           
foond    ~ activity found                       
calc.    ~activity calculated using Colby's formula               
 







A  composition  for  controlling  animal  pests  compiising  a synergistically  effective active

compound combination of the compound of the formula (I~a-4)
d..a----.CH,
H,c'o'9fqo
~    -

H'N    ~ /,

0    CH, (1-a-4},

QI. at least one insecticidally active compound (group 2) selected from

(2~2)  buprofezin.

(2-6)   flonicamid,

(2-7)   pitimicwb,

im4 at least one active compound ti:om the group of the antbranilamides of the fmmula (IT~ 1)







in which
R2    represents hydrogen or methyl,
R3    represents Cr..C.~alkyl,
R4    represents methyl, trifluoromethyl, trifluoromethoxy, flumine,  chlorine, bromine or
    iodine,
R'    tepresents  hydrogen,   fluorine,   chlorine,  bromine,  iodine,  trifluoromethyl   or
    ttifluoromethoxy,
R7    represents chlorine 01 bromine,
R9    u:presents trifluorom.ethyl, chlorine, bromine, diflucnomethoxy 01 trifluoroeth~XL_

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