Combination of active substances exhibiting insecticidal and acaricidal properties

Combination of active substances with insecticidal and acaricidal properties

Technical field

The invention relates to novel active substance combinations which consist of both known cyclic ketoenol and known insecticidal active substances and which have very good insecticidal and acaricidal properties.

BACKGROUND OF THE INVENTION

It is already known that certain cyclic ketoenols can be used to control animal pests such as insects and unwanted acarides (see EP-A-528 156). The efficacy of these substances is good, but in many cases does not meet the requirements at low application rates.

It is further known that nicotinic acetylcholine receptor agonists and antagonists can be used to combat insects.

SUMMARY OF THE INVENTION

It has now been found that mixtures of cyclic ketoenols of formula I

<img file="CZ20021184A3_D0001.tif" />

in which

X 'represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 3 carbon atoms,

Y 'represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 3 carbon atoms,

Z 'represents an alkyl group having 1 to 6 carbon atoms, a halogen atom or an alkoxy group having 1 to 6 carbon atoms, n being a number from 0 to 3,

A 'and B' are the same or different and denote a hydrogen atom or an optionally halogenated alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an alkynyl group having 3 to 8 carbon atoms, an alkoxyalkyl group having 1 to 10 carbon atoms carbon atoms in alkoxy and 2 to 8 carbon atoms in alkyl, polyalkoxyalkyl of 1 to 8 carbon atoms in polyalkoxy and 2 to 8 carbon atoms in alkyl, alkylthioalkyl of 1 to 10 ···· · ·· ···

4 C 4 -C 8 alkylthio and C 2 -C 8 alkyl, C 3 -C 8 cycloalkyl which may be interrupted by oxygen and / or sulfur and optionally halogen, C 1 -C 6 alkyl, haloalkyl 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy having 1 to 6 carbon atoms or nitro substituted phenyl or phenylalkyl having 1 to 6 carbon atoms in alkyl, or

A 'and B' together with the carbon atom to which they are attached, saturated or unsaturated, optionally oxygen and / or sulfur interrupted and optionally halogen, optionally C1-C6 alkyl, C1-C6 alkoxy, haloalkyl, (C 1 -C 4), (C 1 -C 4) haloalkoxy, (C 1 -C 4) alkylthio or optionally substituted phenyl substituted or optionally benzo-fused 3- to 8-membered ring; and

G 'represents a hydrogen atom (a) or groups b to f —CO-R¹ (b)

<img file="CZ20021184A3_D0002.tif" />

(C).

-SO₂-R³ (d)

-P

II

R⁴

R⁵ or

<img file="CZ20021184A3_D0003.tif" />

(0

99·· ·· 9··* • 9

<img file="CZ20021184A3_D0004.tif" />

9 9999 in which

R⁴ denotes optionally halogen-substituted alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkoxyalkyl of 1 to 8 carbon atoms in alkoxy and 2 to 8 carbon atoms in alkyl, alkylthioalkyl of 1 to 8 carbon atoms in an alkylthio group having 2 to 8 carbon atoms in the alkyl, a C 1 -C 8 polyalkoxyalkyl group having 2 to 8 carbon atoms in the alkyl group or a C 3 -C 8 cycloalkyl group which may be interrupted by oxygen and / or sulfur atoms, optionally halogen, nitro, C 1 -C 8 alkyl groups (C 6 -C 6), (C 1 -C 6) alkoxy, (C 1 -C 6) haloalkyl or (C 1 -C 6) haloalkoxy substituted by phenyl or halogenam, (C 1 -C 6) alkyl, (C 1 -C 6) alkoxy, (C 1 -C 6) haloalkyl or (C 1 -C 6) haloalkoxy substituted by C 1 -C 6 -alkyl, optionally halogen and / or or a (C 1 -C 6) alkyl group substituted with pyridyl, pyrimidyl, a thiazolyl and pyrazolyl group or, optionally, a halogen and / or an alkyl group having 1 to 4;

The phenoxyalkyl group having from 1 to 6 carbon atoms, optionally substituted by halogen, denotes an optionally substituted halogen: (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 1 -C 8) alkoxyalkyl (C 2 -C 8) alkyl and (C 1 -C 8) polyalkoxyalkyl group (s); 2 to 8 carbon atoms in the alkyl or optionally halogen, nitro, alkyl of 1 to 6 carbon atoms, (C 1 -C 6) alkoxy and (C 1 -C 6) haloalkyl substituted by phenyl or benzyl;⁴ and r 5 ​​is independently C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 8 alkylamino, C 1 -C 8 dialkylamino, C 1 -C 8 alkylthio. (C 2 -C 5) alkenylthio, (C 2 -C 5) alkynylthio, (C 3 -C 7) cycloalkylthio, optionally halogen, nitro, cyano, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 1 -C 4 alkyl and C 1 -C 4 haloalkyl Phenyl, Phenoxyl, Phenoxy, Phenoxy, Phenoxy, Phenoxy, Phenoxy, Phenoxy, Phenoxy, Phenoxy. Or a phenylthio group and fc. H

R ° and R 'are each independently halogen-substituted alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, alkenyl of 2 to 8 carbon atoms, alkoxyalkyl of 1 to 20 carbon atoms in alkyl and alkoxy optionally halogen, C 1 -C 20 haloalkyl, C 1 -C 20 alkyl or C 1 -C 20 alkoxy substituted phenyl or halogen, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl or C 1 -C 20 alkoxy substituted by a benzyl group or together denote an optionally oxygen-interrupted C 2 -C 6 alkylene ring and at least one agonist or antagonist The acetylcholine receptors of formula (II) are synergistically active and are useful for controlling animal pests.

Due to this synergism, considerably lower amounts of active ingredients can be used, i.e. the effect of the mixture is higher than that of the individual components.

Preference is given to mixtures comprising compounds of formula I in which

X 'represents an alkyl group having 1 to 4 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms,

- or a haloalkyl group having 1 to 2 carbon atoms, - or a haloalkyl group having 1 to 2 carbon atoms,

Y 'represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 2 carbon atoms,

Z 'represents an alkyl group having from 1 to 4 carbon atoms, a halogen atom or an alkoxy group having from 1 to 4 carbon atoms, n being a number of 0 or 1,

A 'and B' together with the carbon atom to which they are attached form a saturated, optionally C 1 -C 4 alkyl or C 1 -C 4 alkoxy substituted five- to six-membered ring,

G 'represents a hydrogen atom (a) or groups b to c

O — CO — R¹ (b) R² in which

R @ 1 - represents an optionally halogen-substituted alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms in alkoxy and 2 to 6 carbon atoms in an alkyl or cycloalkyl group. 3 to 7 ring atoms, which may be interrupted by 1 to 99

9999 9 9 999

999 999

9 99 9 ···· f · · 9 · 9

999 999 99 999 99 9999 to 2 oxygen and / or sulfur atoms, optionally halogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 3 haloalkyl or C 1 -C 3 haloalkoxy Phenyl substituted with 3 carbon atoms; and

O

R represents an optionally substituted halogen: (C 1 -C 16) alkyl, (C 2 -C 16) alkenyl or (C 1 -C 6) alkoxyalkyl (C 2 -C 6) alkyl, or optionally halogen, nitro, (C 1 -C 4) alkyl a phenyl or benzyl group substituted by a carbon atom, a C1-C4 alkoxy group and a C1-C4 haloalkyl group, and at least one agonist, optionally an acetylcholine receptor antagonist of formula II.

Particularly preferred are mixtures comprising a dihydrofuranone derivative of the formula Ia

<img file="CZ20021184A3_D0005.tif" />

About «

and at least one agonist or antagonist of the acetylcholine receptors of the formula II.

Nicotinic acetylcholine receptor agonists and antagonists are known compounds and are known from the following publications:

<td>European</td><td>unloading</td><td>sp:</td><td>Ísy č</td>

<td> 386 565,</td><td> 383 091,</td><td> 375</td><td> 907,</td>

<td> 254 859,</td><td> 235 725,</td><td> 212</td><td> 600,</td>

<td> 136 636,</td><td> 136 686,</td><td> 303</td><td> 570,</td>

<td> 455 000,</td><td> 135 956,</td><td> 471</td><td> 372,</td>

<td> 493 369,</td><td> 580 553,</td><td> 649</td><td> 845,</td>

464 830, 428 941, 425 978,

<td> 364</td><td> 844,</td><td> 315</td><td> 826,</td><td> 259</td><td> 738,</td>

<td> 192</td><td> 060,</td><td> 163</td><td> 855,</td><td> 154</td><td> 178,</td>

<td> 302</td><td> 833,</td><td> 306</td><td> 696,</td><td> 189</td><td> 972,</td>

<td> 302</td><td> 389,</td><td> 428</td><td> 941,</td><td> 376</td><td> 279,</td>

<td> 685</td><td> 477,</td><td> 483</td><td> 055</td><td>and 580</td><td> 553</td>

German unloading documents no.

639 877 and 3,712,307;

Japanese unloading 63 307 857, 63 287 03 255 072, 05 178

U.S. Pat

<td>writings</td><td>C.</td><td> . 03</td><td> 220</td>

<td> 764,</td><td> 03</td><td> 246</td><td> 283</td>

<td> 833,</td><td> 07</td><td> 173</td><td> 157</td>

No. 5,034,524, 4

176, 02 207 083,

9371, 03 279 359, and 08 291 171;

948 798, 4 918 086,

039 686, 5,034,404 and 5,532,365;

PCT Application Nos. WO 91/17 659 and WO 91/4 965;

French Application No. 2,611,114;

Brazilian Application No. 88 03 621

The generic formulas and definitions described in these publications, as well as the individual compounds described therein, are expressly considered.

<img file="CZ20021184A3_D0006.tif" />

These methylenes, compounds are partially summarized as nitronitroimines and related compounds.

These compounds can advantageously be summarized under formula II

RN (A)

Y^(OF) (Π)

XE in which

R represents a hydrogen atom and an optionally substituted acyl, alkyl, aryl, arylalkyl, heterocyclyl, heteroaryl or heteroarylalkyl group,

A denotes a monofunctional group selected from the group consisting of a hydrogen atom, an acyl group, an alkyl group and an aryl group or denotes a bifunctional group which is linked to the radical Z,

E denotes electrons attracting the rest,

X is -CH = or = N-, wherein the -CH = group may be attached to the radical Z instead of a hydrogen atom;

Z denotes a monofunctional group selected from the group consisting of alkyl and the groups -O-R, -SR, and the radicals R may be be the same or different and are as defined above, or denote a bifunctional moiety that is linked to moiety A or moiety X.

Particularly preferred are compounds of formula II in which the substituents have the following meanings:

R represents a hydrogen atom, as well as optionally substituted radicals from the group consisting of acyl, alkyl, aryl, arylalkyl, heterocyclylalkyl, heteroarylocyl and heteroarylalkyl.

Acyl radicals include a formyl group, an alkylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, and an alkyl-aryl-phosphoryl group which may themselves be substituted.

As the alkyl group there may be mentioned an alkyl group having 1 to 10 carbon atoms, in particular an alkyl group having 1 to 4 carbon atoms and, in particular, a methyl, ethyl, i-propyl, s-butyl or t-butyl group which may themselves be substituted.

An aryl group includes phenyl and naphthyl, especially phenyl.

An arylalkyl group includes phenylmethyl or phenylethyl;

A heterocyclylalkyl group is a radical of formula

CH—

A heteroaryl group is a heteroaryl group having up to 10 ring atoms and with nitrogen, oxygen and sulfur, especially with nitrogen as heteroatoms. Individuals include thienyl, furyl, thiazolyl, imidazolyl, pyridyl, benzothiazolyl and pyridazinyl.

A heteroarylalkyl group includes heteroarylmethyl and heteroarylethyl of up to 6 ring atoms and with nitrogen, oxygen and sulfur, especially nitrogen as heteroatoms, in particular an optionally substituted heteroaryl group as defined above under the term heteroaryl.

The substituents are preferably:

Alkyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl; alkoxy having preferably 1 to 4, in particular 1 or 2, carbon atoms such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy and t-butoxy; alkylthio having preferably 1 to 4, in particular 1 or 2, carbon atoms such as methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio and t-butylthio; a haloalkyl group having preferably 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, and a carbon atom. And preferably with 1 to 5, in particular 1 to 3, halogen atoms, wherein the halogen atoms are the same or different and the halogen atom preferably denotes fluorine, chlorine or bromine, in particular fluorine, such as a trifluoromethyl group; hydroxy; a halogen atom, preferably fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine; cyano; nitro; amino; alkylamino and dialkylamino having preferably 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms in each alkyl, such as methylamino, methylethylamino, n-propylamino, i-propylamino and methyl-n-butylamino; carboxyl, carbalkoxy having preferably 2 to 4 carbon atoms, in particular 2 or 3 carbon atoms, such as carbomethoxy and carboethoxy; sulfo (-SO 4 H); alkylsulfonyl having preferably 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, such as methylsulfonyl and ethylsulfonyl; arylsulfonyl having preferably 6 or 10 aryl carbon atoms such as phenylsulfonyl as well as heteroarylamino and heteroarylalkylamino such as chloropyridylamino and chloropyridylmethylamino.

A represents a hydrogen atom or an optionally substituted radical from the group consisting of acyl, alkyl and aryl, which preferably have the meanings given for R, and furthermore represents a bifunctional group. For example, a substituted alkylene group having 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms, may be mentioned, the substituents mentioned above being mentioned, the alkylene groups being interrupted by heteroatoms selected from nitrogen, oxygen and sulfur.

A and Z can form saturated with the atoms to which they are bonded

<img file="CZ20021184A3_D0007.tif" />

• ·

<img file="CZ20021184A3_D0008.tif" />

or an unsaturated heterocyclic ring. The heterocyclic ring may contain an additional 1 or 2 identical or different heteroatoms and / or hetero groups. The heteroatoms are preferably oxygen, sulfur or nitrogen and the hetero group is an N-alkyl group, wherein the alkyl group in the N-alkyl group contains 1 to 4, especially 1 or 2, carbon atoms. Alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl. The heterocyclic ring contains 5 to 7, preferably 5 or 6 ring members.

Examples of compounds of formula (II) in which A and Z together with the atoms to which they are attached form a ring include:

R @ 1 = NH or CH3

R-bk / NH

<img file="CZ20021184A3_D0009.tif" />

<img file="CZ20021184A3_D0010.tif" />

• to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to ·

<img file="CZ20021184A3_D0011.tif" />

or CH-j

<img file="CZ20021184A3_D0012.tif" />

RN S

T

XE in which E, R and X are as defined below.

E is an electron-withdrawing radical, with particular mention being made of nitro, cyano, haloalkylcarbonyl, such as C1-C4haloalkylcarbonyl, for example COCF4, alkylsulfonyl, for example SO4-CH2 and haloalkylsulfonyl, for example SC ^CF ^ and very particularly nitro or cyano.

X is -CH = or -N =.

Z represents an optionally substituted radical from the group consisting of an alkyl group and the groups -OR, -SR and NRR, wherein R and substituents preferably have the meanings given above.

Z can form together with ato outside of the above circle together with ato · ···· fe · ···· ·· ·· · · · · · · ♦ · · ·

9 99 9 9 9 99 9 9 ·

9 · 9 9 9 9 9 · ·

9 9 9 9 9 9 9

999 999 99 999 99 9999 mem to which it is attached and the remainder = C in place of X a saturated or unsaturated heterocyclic ring. The heterocyclic ring may contain additional 1 or 2 identical or different heteroatoms and / or hetero groups. The heteroatoms are preferably oxygen, sulfur or nitrogen and the hetero group is an N-alkyl group, wherein the alkyl group in the N-alkyl group contains 1 to 4, especially 1 or 2, carbon atoms.

Alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl. The heterocyclic ring contains 5 to 7, preferably 5 or 6 ring members. Examples of heterocyclic rings include pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine and N-methylpiperazine.

Particularly preferably, the nicotinic acetylcholine receptor agonists and antagonists are compounds of formula II wherein:

Subst. y = \ (CH₂)_n

N— denotes

Subst. * - il

S (CH₂)_n or or

<img file="CZ20021184A3_D0013.tif" />

CH₂)_n

Wherein O is 0 or 2, preferably 1 and

Subst. denotes one of the abovementioned substituents, advantages 9 99 999 9

9999 99999 9 9 9

9 9 9 9 9 · · 9 9

999 9 · 9 9

999 999 99 999 99 9999 halogen atom, especially chlorine and

A, Z, X and E are as defined above.

<img file="CZ20021184A3_D0014.tif" />

N denotes in particular f) CH₂- or

Cl

<img file="CZ20021184A3_D0015.tif" />

CH, or

<img file="CZ20021184A3_D0016.tif" />

CH,

The following compounds are individually named:

<img file="CZ20021184A3_D0017.tif" />

- 18 Cl n^:

<img file="CZ20021184A3_D0018.tif" />

AND

CH₂ —N NH

Y

N-NO,

Cl

Cl

ΛΛ

N^:

CH₂ —N NH

Y

Cl

CN

Cl

Yl^:

CH₂ —N. .WITH

Cl

CN

Cl

ΥΊ

Cl

Cl • 4 · 4 · 44 · 4 · 44 · 4 · 44 4

4 4 4 4 9 4

444 44 444 44 4444^:

<img file="CZ20021184A3_D0019.tif" />

O

N^:

CH₂ —N NH

Y

CH

NO,

CH-NH

AND

CH

NO,

CH,

Cl

Cl

<img file="CZ20021184A3_D0020.tif" />

CH₂-NC-ch₃

II

N.

CN

ΎCH₂ - N. .NH

Y

N-NO,

<img file="CZ20021184A3_D0021.tif" />

CH₂-Ν, NHCH₃

O

N^:

N^:

<img file="CZ20021184A3_D0022.tif" />

CH₂-N. .WITH

<img file="CZ20021184A3_D0023.tif" />

N

N^:

<img file="CZ20021184A3_D0024.tif" />

C₂h₅

N-NO, τ

N-NO,

<img file="CZ20021184A3_D0025.tif" />

CH — NO,

CH, |

_Ch₂-NN (CH₃)₂

Ϊ

N-NO,

CH,

Y

N.

<img file="CZ20021184A3_D0026.tif" />

'NO, 4 4 4

44 • 4 • 4 4

4 444

4 «

4 AND

4*4

- 19 ····

44

4 4 4

4 4

4 4 • 4 4

4444

Cl ο

Ν^:

<img file="CZ20021184A3_D0027.tif" />

^C2^H5

AND

CH -NC-CH

II

N.

O

<img file="CZ20021184A3_D0028.tif" />

H

CH₂ —N

Cl

N^:

<img file="CZ20021184A3_D0029.tif" />

CH - NC - NHCH?₂h₅

II CH 1 CN

H

N —CH,

NO.

?^H3 CH.

'NO.

Cl

<img file="CZ20021184A3_D0030.tif" />

N ch₂-n

<img file="CZ20021184A3_D0031.tif" />

N ·

N - CH, CN

S NH Π

CH

AND

NO.

ci - &lt;\

N-

<img file="CZ20021184A3_D0032.tif" />

CH- N. N. NH

NO.

ci - &lt;\

Nn

CH-N N-CH¥

N.

'NO.

CH.-N. NH

Ύ

CH

NO.

Cl ·

<img file="CZ20021184A3_D0033.tif" />

IN ch₂-nh .NHCH₃

NO.

CH.

<img file="CZ20021184A3_D0034.tif" />

CHr-N. / N-CH

N.

NGOs.

Cl

<img file="CZ20021184A3_D0035.tif" />

- 20 «« *·*· • ·

9 99

<img file="CZ20021184A3_D0036.tif" />

<img file="CZ20021184A3_D0037.tif" />

<img file="CZ20021184A3_D0038.tif" />

Very particularly preferred nicotinic acetylcholine receptor agonists and antagonists are compounds of the formulas:

<img file="CZ20021184A3_D0039.tif" />

(face)

Cl ch₂ (Hb)

<img file="CZ20021184A3_D0040.tif" />

NHCH₃ n-no₂^xno₂

<img file="CZ20021184A3_D0041.tif" />

CN

<img file="CZ20021184A3_D0042.tif" />

to · this · to · to · to * to · to · to · to · to · to · to · ··· ·· «· * ··· Φ * this ··

CH₃ ch₂-nc-ch₃ (Ile)

CN

<img file="CZ20021184A3_D0043.tif" />

Cl

N (lig)

Cl

<img file="CZ20021184A3_D0044.tif" />

in

N

Cl ~ (\ a

N^:

<img file="CZ20021184A3_D0045.tif" />

^C2^H5

AND

CH₂-N-C-NHCH₃ (lli)

AND!

CH \

NO.

CH,

AND ⁴

AND

CH, —N ^ N - CH (Uf)

Y

N —NO,

<img file="CZ20021184A3_D0046.tif" />

N-NO.

(Hh)

N—⁷ ; 1 (11k) N-CN ° A^CH'(III)

H ₂\ A a

NO.

'CH.

S ^^ CH₂-NH 2 NHCH, ^WHOSE_AND

Mαι m)

NO.

especially a compound of the following formulas

Cl

<img file="CZ20021184A3_D0047.tif" />

N ch₂-n nh H (ila) Ν '' no.

or Cl

<img file="CZ20021184A3_D0048.tif" />

( &gt;

N^:

CH₃ ch₂-n ch₃II (Ile) Ν

CN

444« 44 444« 44 44 • · · « 4 » 4 4

444 4 4 «4« «4 4 • 4 · 4 444 4 4 • · · 4 4 4 4

444 4« »4« 44 444« ^WHOSE~(\

Or or or or or

<img file="CZ20021184A3_D0049.tif" />

(iig) or

<img file="CZ20021184A3_D0050.tif" />

N-NOCl (alcohol)

Cl? 2^H5 H

<img file="CZ20021184A3_D0051.tif" />

(II k) N-CN / ν-α-υ-Ν N

<img file="CZ20021184A3_D0052.tif" />

CH₂-NH / NHCH

N.

(lim)

CH,

NO,

NO, ♦ »0 0 0 0

0 • «·*

0 « 0 «4 • · · 00 • 0

0

000 «4

0

0 • 0

0

0 0

AND

0 4 0

Very particularly preferred are compounds of formulas IIIa, IIk and lim.

Further particularly preferred are compounds of formulas Ile, lig, alcohol, III and IIc.

A particularly preferred mixture comprises a compound of formula Ia and a compound of formula IIa;

another particularly preferred mixture comprises a compound of formula Ia and a compound of formula IIk;

furthermore particularly preferred are mixtures comprising a compound of formula Ia and a compound of formula Ia.

The active compound mixtures are suitable for good plant acceptance and good warm-blood toxicity for the control of animal pests, especially insects, arachnids and nematodes found in agriculture, forestry, for the protection of stocks and materials and in the hygiene sector. They are effective against normally sensitive and resistant species, as well as against individual developmental stages. The above mentioned pests include:

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

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

From the order of the Chilopoda, for example, Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

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

From the order of the Collembola, for example, Onychiurus armatus.

totototo

4t to ** · ···································· * «··· ** ··· ·· · * ··

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

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

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

From the order of the Thysanoptera, for example, Hercinothrips femoralis,

Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Hyalopterus arundinis, Macrosiphum avenae, Phyloxosus spp., Myzus sp. Pemphigus spp., Epocelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.

Ttt 9999

From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusiani,

Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia administered, Capua reticulana, Choristoneura fumiferana, Cistoneura fumiferana, Cistellae, Tortona.

From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa ​​decemlineata, Phaedon cochleariae, Diabrotica spp., Apt. spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Museum spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp. Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis,

Ceratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus, Latrodectus mactans.

From the order of the Acarina, for example, Acarus sulfur, Argas spp.,

Ornithodoros spp., Dermanyssus gallinae, Eriophyes spp., Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp. praetiosa, Panonychus spp., Tetranychus spp.

Nematodes parasitizing on plants include:

Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

The ratio of the compounds of the formula I to the compounds of the formula II used, as well as the total amount of the mixture, are dependent on the type and the occurrence of the pests. The optimum ratios and total dose amount can be ascertained in each test using a number of tests. In general, the ratio of the compounds of the formula I is 9.

9999 9 · *

9 9 9 9 · *

9 9 9 9 9

9999 and compounds of formula II 1: 100 to 100: 1, preferably 1: 25 to 25: 1 and particularly preferably 1: 5 to 5: 1. These are parts by weight.

The active compound mixtures can be present in their commercial preparations as well as in the use forms made of these preparations in admixture with other active substances, such as insecticides, baiting agents, sterilants, acaricides, nematicides, fungicides, growth regulators or herbicides. Insecticides include, for example, phosphoric esters, carbamates, carboxylic esters, chlorinated hydrocarbons, phenylureas, and substances produced by microorganisms. The following insecticides and fungicides are individually mentioned as partners.

Insecticides which may optionally be admixed include, for example:

Phosphoric esters such as Azinphos-ethyl,

Azinphos-methyl, α-1- (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, Chlorpyrifos, Coumaphos,

Demeton, Demeton-S-methyl, Diazinone, Dichlorvos, Dimethoate, Ethoate, Ethoprophos, Etrimphos, Phenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothi Triazophos and Trichlorphon;

carbamates such as Aldicarb, Bendiocarb, α-2- (1-methylpropyl) phenylmethylcarbamate, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Isoprocarb, Methomyl, Oxamyl, Pirimicarb, Promecarb, Propoxur and Thiodarb;

organosilicon compounds, Advantageously · # ♦ · · # # # # # # # # # # # # # # # # # # # # # # Dimethyl (phenyl) silyl-methyl-3-phenoxybenzyl ethers such as dimethyl (4-ethoxyphenyl) -silylmethyl-3-phenoxybenzyl ether or (dimethylphenyl) -silylmethyl-2-phenoxy-6-pyridylmethyl ether such as dimethyl- ( 9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) -3- (3-phenoxyphenyl) -propyl] (dimethyl) -silane such as (4-ethoxyphenyl) - [3- (4 -fluoro-3-phenoxyphenyl-propyl] dimethylsilane, Silafluofen;

pyrethroids such as Allethrin, Alphamethrin, Bioresmethrin, Byfenthrin, Cycloprothrin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2) (trifluoromethylvinyl) cyclopropanecarboxylate, Fenpropathrin, Fenfluthrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate, Permethrin, Resmethrin and Tralomethrin;

nitroimines and nitromethylenes such as

1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1H-imidazol-2-amine (Imidacloprid),

1

N - [(6-chloro-3-pyridyl) methyl-] N -cyano-N-methylacetamide (NI-25);

Abamectin, AC 303.630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine,

Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyrethrins, Pyridaben, Pyridafenthion, Pyriproxyfen, Quinalphos, RH-7988, Rotenone, Sodium Fluoride, Sodium Hexafluorosilicate, Sulfotep, Sulfuryl Fluoride, Tar Oils, Tefosur, Tefosenz

Tetrachlorvinphos, Tetramethrin,

O-2-tert-butylpyrimidin-5-yl-o-isopropyl phosphorothioate, Thiocyclam, Thiofanox, Thiometon, Tralomethrin, Triflumuron, Trimethacarb, Vamidothion, Verticillium Lacanii, XMC, Xylylcarb, Benfuracall, Benthrinrin, Benshrinrin, Benshrin, MER S) -cyclopentenyl isomer, Bromophos, Bromophos-ethyl, Buprofezin, Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionat, Chlordane,

Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloropicrin, Chlorpyrifos, Cyanophos, Beta-Cyfluthrin, Alpha-Cypermethrin, Cyophenothrin, Cyromazine, Dazomet, DDT, Demeton-S-methylsulphon, Diafenthiuron, Dialifos, Dicrotebophos, Dicrotebophos

Diaxacarb, Disulfotone, DNOC, Empenthrin, Endosulfan, EPN,

Esfenvalerate, Ethiofencarb, Ethion, Etofenprox, Fenobucarb, Fenoxycarb, Fensulfothion, Spinosynen, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hydramethyluride, Hexaflumuride, Hexaflumuride

Isazofos, Isofenphos, Isoprothiolane, Isoxathion,

Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam, Mephospholane, Mercurous, chloride, Metam, Metarthizium, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Necrophosphate, Mevolphos, Mevolphos, Mevar, B , Omethoate, Oxydemeton-methyl, Pentachlorophenol, Petroleum oils, Phenothrin, Phenthoate, Phorate.

The further insecticides which can be added at the same time can be derived from the class of compounds of the formula I.

The fungicides which may be admixed with one another may be fc fc

<img file="CZ20021184A3_D0053.tif" />

• fc • fcfcfc preferably considers:

Triazoles such as:

Azaconazole, Propiconazole, Tebuconazole, Cyproconazole, Metconazole, Amitrole, Azocyclotin, BAS 480F, Bitertanol, Difenoconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imibenconazole, Isosobosil-cisobutane, Myclobutan, Myclobutol, Myclobutol 4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol,

Tetraconazole, Triadiraefon, Triadimenol, Triapenthenol,

Triflumizole, Triticonazole, Uniconazole, as well as their metal salts and acid adducts.

Imidazoles such as:

Imazalil, Pefurazoate, Prochloraz, Triflumizole,

2- (1-tert-butyl) -1- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) -propan-2-ol, thiazolecarboxanilides such as 2 ', 6'-dibromo- 2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide, 1-imidazolyl-1- (4'-chlorophenoxy) -3,3-dimethylbutan-2-one, and their metal salts and adducts with acids.

methyl (E) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-thioamidophenoxy)] pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2 - [2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (pyrimidin-2-yloxy) phenoxy] phenyl ] -3-methoxyacrylate,

4·· · 4· 4· · · · · • 4 4 4 · ·

4 · · 4

4 · ·

4 · 4 44 4444 methyl (E) -2- [2- [3- (5-methylpyrimidin-2-yloxy) -phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (phenylsulfonyloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2 -phenoxyphenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dimethylbenzoyl) pyrrol-1-yl] -3-methoxyacrylate, methyl (E) -2- [2- (3-methoxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (2-phenylethen-1-yl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dichlorophenoxy) pyridin-3-yl] -3-methoxyacrylate, methyl (E) -2- (2- (3- (1,1,2,2- Tetrafluoroethoxy) phenoxy) phenyl) -3-methoxyacrylate, methyl (E) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxyacrylate, methyl (E) -2- (2- (4 (phenoxypyridin-2-yloxy) phenyl) -3-methoxyacrylate, methyl (E) -2- [2- (3-n-propyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3 -isopropyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3-ethoxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (4-tert-butylpyridin-2-yloxy) phenyl] -3-methoxyacrylate , methyl (E) -2- [2- [3- (3-cyanophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3-methylpyridin-2-yloxymethyl) phenyl] - 3-Methoxyacrylate, methyl (E) -2- [2- [6- (2-methylphenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, this is this Methyl (E) -2- [2- (5-bromopyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-chloropyridin-3)] (E) methyl-2- [2- (5,6-dimethylpyrazin-2-ylmethyloxiininomethyl) phenyl] -3-methoxyacrylate, (E) -yloxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate; (methyl) 2- {2- [6- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, (E), (E) methyl 2- {2- (3) (methoxyphenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E) methyl 2- {2- (6- (2-azidophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, (E), (E) methyl 2- {2- [6-phenylpyrimidin-4-yl) -methyloximinomethyl] phenyl} -3-methoxyacrylate, (E), (E) methyl 2- {2 - [(4) (E) methyl 2- {2- [6- (2-n-propylphenoxy) -1,3,5-triazin-4-yloxy] phenyl} -3-chlorophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate -methoxyacrylate, (E), (E) methyl 2- {2 - [(3-nitrophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate;

Succinate dehydrogenase inhibitors such as:

Fenfuram, Furcarbanil, Cyclafluramide, Furmecyclox, Seedvax, Metsulfovax, Pyrocarbolide, Oxycarboxin, Shirlan, Mebenil (Mepronil), Benodanil, Flutolanil (Moncut);

naphthalene derivatives such as Terbinafine, Naftifine, Butenafine,

3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-yne);

sulfenamides such as Dichlofluanid, Tolylfluanid, Folpet, Fluorfolpet; Captan, Captofol;

imid benzimidazoles such as Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiophonate-methyl, Thiabendazole or salts thereof;

morpholine derivatives such as Fenpropimorph, Falimorph,

Dimethomorph, Dodemorph, Aldimorph, Fenpropidine and their salts with arylsulfonic acids such as p-toluenesulfonic acid and p-dodecylphenylsulfonic acid;

dithiocarbamates, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram;

benzthiazoles such as 2-mercaptobenzothiazole;

benzamides such as 2,6-dichloro-N-4-trifluoromethylbenzyl) benzamide;

boron compounds such as boric acid, boric acid esters, borax;

formaldehyde and formaldehyde cleaving compounds such as benzyl alcohol mono (poles) -hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylol chloroacetamide, paraformadehyde, Nitropyrin, Oxolinsaure, Tecloftalam;

Tris-N- (cyclohexyldiazeniumdioxy) aluminum,

N- (Cyclohexyldiazeniumdioxy) tributyltin, optionally K-salts, Bis-N- (cyclohexyldiazeniumdioxy) copper;

N-methylisothiazolin-3-one

5-chloro-N-methylisothiazolin-3-one,

4,5-dichloro-N-octylisothiazolin-3-one;

9 9 9 • · ·

<img file="CZ20021184A3_D0054.tif" />

φ

N-octyl-isothiazolin-3-one

4,5-trimethylene-isothiazolinones

4,5-benzisothiazolinones; N-methylol chloroacetamide;

aldehydes such as cinnamic aldehyde, formaldehyde, glutardialdehyde, β-bromo-thaldehyde;

thiocyanates such as thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate, and the like;

quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;

iodine derivatives such as diiodomethyl-p-tolylsulfone,

3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate,

2,3,3-Triiododalcohol, 3-bromo-2,3-di-2-propenyl alcohol, 3-iodo-2-propynyl-n-butylcarbamate, 3-iodo-2-propynyl-n-hexylcarbamate, 3-iodo od-2-propynylcyclohexylcarbamate,

3-iodo-2-propynylphenylcarbamate;

phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, Dichlorphen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their derivatives alkali metal and alkaline earth metal salts;

halogen-activated microbicides such as chloroacetamide, bronopol, bronidox, tectamer such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile -propionamide, 1,2-dibromo-2,4-dicyanobutane, p-bromo-p-nitrostyrol;

·» 999· • 9 99

9 9 «99

999 99 9 * 99 pyridines such as 1-hydroxy-2-pyridinethione (and its Na-, Fe-,

-Η-, Zn-salts), tetrachloro-4-methylsulfonylpyridine, Pyrimethanol, Mepanipyrim, Dipyrithione, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2 (1H) -pyridine;

metal soaps such as tin-, copper-, zinc-naphthenate, octoate, 2-thylhexanoate, -oleate, -phosphate, -benzoate;

metal salts such as copper (II) bicarbonate, potassium dichromate, sodium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate, and copper fluorosilicate, especially mixtures thereof with fixing agents;

oxides such as tributyltin oxide, Ck 2 O, CuO, ZnO;

dialkyldithiocarbamates such as Na- and Zn-salts with dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyl dithiocarbamate;

nitriles such as 2,4,5,6-tetrachloroisophate halodinitrile, disodium cyanodithioimidocarbamate;

quinolines such as 8-hydroxyquinoline and its Cu salts;

mucochloric acid, 5-hydroxy-2 (5H) -furanone;

4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone,

4,5-trimethylenedithiazolinone, 4,5-dichloro- (3H) -1,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1,3,5-thiadiazin-2-thione, N- (2-p -chlorobenzoylethyl) -hexaminium chloride, potassium-N-hydroxymethyl-N-methyl-dithiocarbamate, chloride ···· 0 · ·· *

9 9 9 9 9 9

9 999 9 9 ·

9 · 9 9 9 9 9

9 9 9 9 9

9 99 99 999 9 2-oxo-2- (4-hydroxy-phenyl) acethydroximic acid, phenyl- (2-chloro-cyano-vinyl) sulfone, phenyl- (1,2-dichloro-2-cyano-vinyl) sulfone;

Ag, Zn or Cu-containing zeolites alone or enclosed in the polymeric active ingredient, or else mixtures of the aforementioned fungicides.

The content of active substances in the dosage forms prepared from commercial preparations can vary within wide limits. The concentration of active ingredients in the dosage forms may be in the range of 0.0000001 to 95% by weight of active ingredient, preferably in the range of 0.001 to 1% by weight of active ingredient.

The active compound combinations according to the invention can be converted into conventional preparations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active-impregnated natural and synthetic substances, microcapsules in polymeric substances and in seed encapsulants, flame retardant preparations such as smoke cartridges, plates, spirals and the like, as well as ULV misting preparations.

These preparations are prepared by known methods, for example by mixing the active ingredient with a filler, i.e. a liquid solvent and / or a solid carrier, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents.

In the case of using water as a diluent, for example, organic solvents can also be used as solubilizers.

· · Fe fe fe fe fe fe fe fe fe * fe fe fe * * * * * * fe fe fe t fe fe fe t t fe fe fe • · ·

1· »···

Basically suitable liquid solvents are: aromatics such as xylene, toluene and alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins such as petroleum fractions, mineral and vegetable oils, alcohols such as butyl alcohol or glycols and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide or dimethylsulfoxide, and water.

Liquefied gaseous diluents or carriers are understood to be liquids which are gaseous at normal temperature and pressure, for example aerosol carrier gases such as butane, propane, nitrogen and carbon dioxide.

Suitable solid carriers are, for example, ammonium salts and natural pulverulent rocks such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic flours such as highly disperse silicic acid, alumina and silicates. Suitable solid carriers for granulates are, for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sephiolite, dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic materials such as sawdust, coconut shells, corn cobs and tobacco stems.

Suitable emulsifiers and / or foaming agents are, for example, non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters and ethers 4 &amp; lt; tb &amp; gt; &amp; lt; tb &amp; gt; • · · 4 4 4 4

4 44 polyoxyethylene fatty alcohols, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, as well as protein hydrolysates. Suitable dispersing agents are, for example, ligninsulphite leachates and methylcellulose.

Adhesion promoters such as carboxymethylcellulose, natural and synthetic, powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids may also be used in the compositions. Other additives may be mineral and vegetable oils.

Dyes such as inorganic pigments such as iron oxides, titanium dioxide, ferrocyanate blue and organic dyes such as alizarin dyes, azo dyes and metallic phthalocyanine dyes and trace nutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain 0.1 to 95% by weight of active ingredient, preferably 0.5 to 90% by weight.

The compositions of the present invention may be applied through the leaves.

All plants and plant parts can be treated according to the present invention. Plants are understood here to mean all plants or plant populations, such as desirable and undesirable wild plants or crop plants (including naturally occurring crop plants). Cultivated plants may be plants that can be obtained. By conventional cultivation and optimization methods or by biotechnological and genetic technology methods or combinations of these methods, including transgenic plants and including plant species protected or unprotected by species protection. Plant parts are all above-ground and underground parts of plants and plant organs such as shoots, leaves, flowers and roots, for example, leaves, needles, stems, trunks, flowers, fruit bodies, fruits and seeds, as well as roots, tubers and rhizomes.

Plant parts also include harvested products as well as vegetative and generative propagation material such as seedlings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and plant parts according to the invention with the active substances is carried out directly or by action on their surroundings, the environment or the storage environment, by conventional methods of treatment such as dipping, spraying, evaporation, fogging, dusting, painting and propagation material, especially seeds, single or multilayer coating.

When using the active compound combinations according to the invention, the application rates can vary within wide limits depending on the type of application. In the treatment of plant parts, the application rate of the active compound combination is generally from 0.1 to 10 000 g / ha, preferably from 10 to 1000 g / ha.

The good insecticidal and acaricidal effect of the active compound combinations according to the present invention results from the following examples. While the individual active substances show weakness in effect, the combinations have an effect that exceeds a simple sum of the effects.

• ·

A synergistic effect occurs with insecticides and acaricides whenever the effect of the combination of active substances is greater than the sum of the effects of the individually applied active substances.

The expected effect for a given combination of two active substances can be calculated as follows (see COLBY, SR, Veeds 15: 20-22, 1967):

When

X = degree of effect when active substance A is applied at an application rate of mg / ha or at a concentration of m ppm,

Y = degree of effect when active substance B is applied at an application rate of ng / ha or at a concentration of

E = degree of effect using active substances A and B at an application rate of man g / ha or at a concentration of man ppm, then

Ε = X + Y - (X. Y / 100).

In this case, the degree of effect in% is determined. Here, it indicates that% corresponds to a degree of effect that corresponds to a control, while a degree of effect of 100% means that no attack is observed.

When the actual effect is greater than the calculated effect, it is * * ený * je »» »» »*» »» »» »» »*» »» »» » · · · · · · · · · · · · · · · · · · · · · · · · · The combination in its effect is supernatural, ie it shows a synergistic effect. In this case, the degree of effect actually observed must be greater than the value calculated from the above formula for the expected degree of effect (E).

DETAILED DESCRIPTION OF THE INVENTION

Example A

Aphis gossypii test

Solvent: 3 parts by weight of dimethylformamide, emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To prepare an effective preparation of the active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

Leaves of cotton (Gossypium hirsutum) which are heavily infected with cotton aphids (Aphis gossypii) are treated by soaking in the preparation of active substance of the desired concentration.

After the required time, the% killing is determined. 100% indicates that all aphids have been killed; 0% indicates that no aphids have been killed. The killing values ​​are recalculated according to the Colby equation.

In this test, for example, the following active compound combinations according to the invention exhibit synergistically enhanced activity in comparison with the individual active compounds used:

Table Al

Insect Harmful to Plants - Aphis gossypii test

<td>Active substance</td><td>Concentration effective in ppm</td><td colspan="2">Degree of killing in% after 6 days</td>

<td>Ex. Ia</td><td> 1,6</td><td> 0</td><td></td>

<td>known</td><td></td><td></td><td></td>

<td>Ex. Ila</td><td> 1,6</td><td> 85</td><td></td>

<td>known</td><td></td><td></td><td></td>

<td>Ex. Ia + Ex. Ila</td><td> 1,6 + 1,6</td><td>gef. *</td><td>ber. **</td>

<td>according to the invention</td><td></td><td> 95</td><td> 85</td>

gef. * = observed effect ber. ** = calculated effect according to Colby's equation

Table A2

Insect Harmful to Plants - Aphis gossypii test

<td>Active substance</td><td>Concentration effective in ppm</td><td colspan="2">Degree of killing in after 6 days</td>

<td>Ex. Ia</td><td> 1,6</td><td> 0</td><td></td>

<td>known</td><td></td><td></td><td></td>

<td>Ex. Ilk</td><td> 1,6</td><td> 55</td><td></td>

<td>known</td><td></td><td></td><td></td>

<td>Ex. Ia + Ex. Ilk</td><td> 1,6 + 1,6</td><td>gef. *</td><td>ber. **</td>

<td>according to the invention</td><td></td><td> 95</td><td> 55</td>

gef. * = observed effect ber. ** = calculated effect according to Colby's equation t · ··· ♦

Example B

Aphis gossypii-test / larval mortality

Solvent: 3 parts by weight of dimethylformamide, emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To prepare an effective preparation of the active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

Leaves of cotton (Gossypium hirsutum), which are heavily attacked by the developmental stages and cotton aphid larvae (Aphis gossypii), are treated by soaking in the active ingredient preparation of the desired concentration.

After the required time, the% killing is determined. 100% indicates that all larvae were killed; 0% indicates that no larvae were killed. The killing values ​​are recalculated according to the Colby equation.

In this test, for example, the following active compound combinations according to the invention exhibit synergistically enhanced activity in comparison with the individual active compounds used:

• this • it • it • it • it • it • it

• · ··&lt;

to · · toto toto to to to to to to to

Table Bl

Insect Harmful to Plants - Aphis gossypii / larval mortality test

<td>Active substance</td><td>Concentration effective in ppm</td><td colspan="2">Degree of killing in% after 6 days</td>

<td>Ex. Ia</td><td> 1,6</td><td> 0</td><td></td>

<td>known</td><td></td><td></td><td></td>

<td>Ex. Ha</td><td> 1,6</td><td> 80</td><td></td>

<td>known</td><td></td><td></td><td></td>

<td>Ex. Ia + Ex. Ha</td><td> 1,6 + 1,6</td><td>gef. *</td><td>ber. **</td>

<td>according to the invention</td><td></td><td> 95</td><td> 80</td>

gef. * - observed effect ber. ** = calculated effect according to the Colby equation

Table B2

Insect Harmful to Plants - Aphis gossypii / larval mortality test

<td>Active substance</td><td>Concentration effective in ppm</td><td colspan="2">Degree of killing in% after 6 days</td>

<td>Ex. Ia</td><td> 1,6</td><td> 0</td><td></td>

<td>known</td><td></td><td></td><td></td>

<td>Ex. Ilk</td><td> 1,6</td><td> 60</td><td></td>

<td>known</td><td></td><td></td><td></td>

<td>Ex. Ia + Ex. Ilk</td><td> 1,6 + 1,6</td><td>gef. *</td><td>ber. **</td>

<td>according to the invention</td><td></td><td> 95</td><td> 60</td>

r * * i * * ber.

= observed effect = calculated effect according to Colby's equation

9 9 9 • *

<img file="CZ20021184A3_D0055.tif" />

Example

Myzus test

Solvent emulsifier:

parts by weight of dimethylformamide, part by weight of alkyl aryl polyglycol ether.

To prepare an effective preparation of the active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea), which are heavily infected with peach aphids (Myzus persicae), are treated by soaking in the preparation of active substance of the desired concentration.

After the required time, the% killing is determined. 100% indicates that all aphids have been killed; 0% indicates that no aphids have been killed. The killing values ​​are recalculated according to the Colby equation.

In this test, for example, the following active compound combinations according to the invention exhibit synergistic enhanced potency compared to the individual active compounds used:

* * ·

4 4 4 ·

44 ·

4-4

4·· ·

4 4 4

44 444

Table C

Insects harmful to plants - Myzus test

<td>Active substance</td><td>Concentration effective in ppm</td><td colspan="2">Degree of killing in% after 6 days</td>

<td>Ex. Ia</td><td> 1,6</td><td> 0</td><td></td>

<td>known</td><td></td><td></td><td></td>

<td>Ex. Ha</td><td> 1,6</td><td> 70</td><td></td>

<td>known</td><td></td><td></td><td></td>

<td>Ex. Ia + Ex. Ha</td><td> 1,6 + 1,6</td><td>gef. *</td><td>ber. **</td>

<td>according to the invention</td><td></td><td> 98</td><td> 70</td>

gef. * - observed effect ber. * * = calculated effect according to Colby's equation

Example D

Myzus test / larval mortality

Solvent: 3 parts by weight of dimethylformamide, emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To prepare an effective preparation of the active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea), which are strongly affected by the developmental stages and the larvae of the peach aphid (Myzus persicae), are treated by soaking in the preparation of active substance of the desired concentration.

• · tttt

After the required time, the% killing is determined. 100% indicates that all larvae were killed; 0% indicates that no larvae were killed. The killing values ​​are recalculated according to the Colby equation.

In this test, for example, the following active compound combinations according to the invention exhibit synergistically enhanced activity in comparison with the individual active compounds used:

Table D

Insect-damaging plants - Myzus / larval mortality test

<td>Active substance</td><td>Concentration effective in ppm</td><td colspan="2">Degree of killing in% after 6 days</td>

<td>Ex. Ia</td><td> 0,32</td><td> 0</td><td></td>

<td>known</td><td></td><td></td><td></td>

<td>Ex. Ha</td><td> 0,32</td><td> 0</td><td></td>

<td>known</td><td></td><td> -</td><td></td>

<td>Ex. Ia + Ex. Ha</td><td> 0,32 + 0,32</td><td>gef. *</td><td>ber. **</td>

<td>according to the invention</td><td></td><td> 55</td><td> 0</td>

gef. = observed effect ber. * * = calculated effect according to Colby's equation