Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02616852 2008-01-31
30584-125E
- 1 -
Pesticidal Composition Comprising Thiamethoxam and
Diafenthiuron, Fluazuron or Lufenuron
This is a divisional application of Canadian Patent
Application No. 2,251,877, filed April 17, 1997.
The present invention relates to a composition which
comprises a pesticidal active compound combination, a method
of controlling pests with this composition, a process for
the preparation of the composition, its use and plant
propagation material treated with it, and the use of a
compound of the following formula (A) for the preparation of
the composition.
The subject matter of the parent application has been
restricted to a composition comprising thiamethoxam and a
= compound selected from a list of fifteen organophosphorous
insecticides, and methods of using the composition.
The subject matter of this divisional application has been
restricted to a composition comprising thiamethoxam and
diafenthiuron, fluazuron or lufenuron, and methods of using
= the composition. However, the expression "the invention" as
used herein, encompasses the subject matter of both the
parent and this divisional application.
Certain mixtures of active compounds are proposed for pest
control in the literature. However, the biological
properties of these mixtures of known compounds are not
completely satisfactory in the field of pest control, and
for this reason there is a need to provide further mixtures
having synergistic pest control properties, in particular
for controlling of insects and representatives of the order
= Acarina. This object is achieved according to the invention
by providing the present composition.
CA 02616852 2008-01-31
30584-125E
- 2 -
The invention accordingly relates to a composition for
controlling insects or representatives of the order Acarina,
which comprises a combination of variable amounts of one or
more compounds of the formula
0
A r N R (A),
X
in which
A is an unsubstituted or, depending on the possibility of
substitution on the ring system, mono- to tetrasubstituted,
aromatic or non-aromatic monocyclic or bicyclic heterocyclic
radical, in which the substituents of A are chosen from the
group consisting of C1-C3alkyl, C1-C3alkoxy, halogen,
halo-C1-C3alkyl, cyclopropyl, halocyclopropyl, 02-C3alkenyl,
C2-C3alkynyl, halo-C2-C3alkenyl, halo-02-C3alkynyl,
halo-01-C3alkoxy, C1-C3alkylthio, halo-C1-C3alkylthio,
allyloxy, propargyloxy, allylthio, propargylthio,
haloallyloxy, haloallylthio, cyano and nitro;
R is hydrogen, C1-C6alkyl, phenyl-Ci-C4alkyl, C3-C6cycloalkyl,
02-C6alkenyl or C2-C6alkynyl; and
X is N-NO2 or N-ON,
in the free form or in salt form, if appropriate tautomers,
in the free form or salt form, and one or more of the
compounds:
CA 02616852 2008-01-31
30584-125E
- 2a -
(I) azamethiphos; (XVIII) methidathion;
(II) chlorfenvinphos; (XIX) monocrotophos;
(III) cypermethrin, cypermethrin (XX) phosphamidon;
high-cis; (XXI) profenofos;
(IV) cyromazin; (XXII) diofenolan;
(V) diafenthiuron; (XXIII) a substance
(VI) diazinon; obtainable from the
(VII) dichlorvos; Bacillus thuringiensis
(VIII) dicrotophos; strain GC91 or from
(IX) dicyclanil; NCTC11821;
(X) fenoxycarb; (XXIV) pymetrozine;
(XI) fluazuron; (XXV) bromopropylate;
(XII) furathiocarb; (XXVI) methoprene;
(XIII) isazofos; (XXVII) disulfuton;
(XIV) jodfenphos; (XXVIII) quinalphos;
(XV) kinoprene; (XXIX) tau-fluvalinate;
(XVI) lufenuron; (XXX) thiocyclam; or
(XVII) methacriphos; (XXXI) thiometon;
and at least one auxiliary.
According to one aspect of the present divisional
application, there is provided a composition for controlling
= insects or representatives of the order Acarina, which
CA 02616852 2010-08-11
30584-125E
- 2b -
comprises a synergistic combination of (a) a compound of the
formula A
NO2
C H3
Cl KN 0,J
(A),
and (h) a compound selected from: diafenthiuron, fluazuron
or lufenuron and (c) at least one auxiliary.
According to another aspect of the invention and the present
divisional application, there is provided a composition as
described herein wherein component (b) is diafenthiuron.
According to another aspect of the invention and the present
divisional application, there is provided a composition as
described herein wherein component (b) is fluazuron.
According to another aspect of the invention and the present
divisional application, there is provided a composition as
described herein wherein component (b) is lufenuron.
According to another aspect of the invention of the present
divisional application, there is provided a method of
controlling pests which are insects or representatives of
the order Acarina, which comprises applying a composition as
described herein to the said pests or their environment.
According to yet another aspect of the invention of the
present divisional application, there is provided a method
of protecting plant propagation material from pests which
are insects or representatives of the order Acarina which
Mk 02616852 2010-08-11
30584-125E
- 2c -
comprises treating the plant propagation material or a site
where the plant propagation material is brought out with a
composition as described herein.
The compounds of the formula (A) are described in
EP-A-580553.
(I) S-6-chloro-2,3-dihydro-2-oxo-1,3-oxazolo[4,5-b]pyridin-
3-ylmethyl 0,0-dimethyl phosphorothioate (azamethiphos) is
known from The Pesticide Manual, 9th Edition (1991),
The British Crop Protection Council, London, page 44;
(II) 2-chloro-1-(2,4-dichlorophenyl)vinyl diethyl phosphate
(chlorfenvinphos) is known from The Pesticide Manual,
10th Edition (1994), The British Crop Protection Council,
London, page 174;
(III) (RS)-a-cyano-3-phenoxybenzyl (1RS)-cis-trans-3-
(2,2-dichlorviny1)-1,1-dimethylcyclopropanecarboxylate
(cypermethrin, cypermethrin high-cis) is known from
The Pesticide Manual, 9th Edition (1991), The British Crop
Protection Council, London, page 208;
(IV) N-cyclopropy1-1,3,5-triazine-2,4,6-triamine (cyromazin)
is known from The Pesticide Manual, 9th Edition (1991),
The British Crop Protection Council, London, page 217;
CA 02616852 2008-01-31
30584-125E
- 3 -
(V) 1-tert-buty1-3-(2,6-diisopropy1-4-phenoxyphenyl)thiourea (diafenthiuron)
is known from
The Pesticide Manual, 10th Edition (1994), The British Crop Protection
Council, London,
page 294;
(VI) 0,0-diethyl 0-2-isopropyl-6-methylpyrimidin-4-yl-phosphorothioate
(diazinon) is known
from The Pesticide Manual, 9th Edition (1991), The British Crop Protection
Council,
London, page 243;
(VII) 2,2-dichlorovinyl dimethyl phosphate (dichlorvos), is known from The
Pesticide Manual,
9th Edition (1991), The British Crop Protection Council, London, page 259;
(VIII) (E)-2-dimethylcarbamoy1-1-methylvinyl dimethyl phosphate (dicrotophos)
is known
from The Pesticide Manual, 10th Edition (1994), The British Crop Protection
Council,
London, page 322;
(IX) 5-cyano-2-cyclopropylamino-4,6-diaminopyrimidine (dicyclanil) is known
from EP-A-
244360;
(X) ethyl 2-(4-phenoxyphenoxy)ethylcarbamate (fenoxycarb) is known from The
Pesticide
Manual, 9th Edition (1991), The British Crop Protection Council, London, page
375;
(XI) 144-chloro-3-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenylj-3-(2,6-
difluorobenzoy1)-
urea (fluazuron) is known from The Pesticide Manual, 10th Edition (1994), The
British
Crop Protection Council, London, page 475;
(XII) butyl 2,3-dihydro-2,2-dimethylbenzofuran-7-yIN,N'-dimethyl-N,N1-
thiodicarbamate
(furathiocarb) is known from The Pesticide Manual, 9th Edition (1991), The
British Crop
Protection Council, London, page 448;
(XIII) 0-5-chloro-1-isopropy1-1H-1,2,4-triazol-3-y10,0-diethyl
phosphorothioate (isazofos) is
known from The Pesticide Manual, 9th Edition (1991), The British Crop
Protection
Council, London, page 502;
(XIV) 0-2,5-dichloro-4-iodophenyl 0,0-dimethylphosphorothioate (jodfenphos) is
known
from The Pesticide Manual, 10th Edition (1994), The British Crop Protection
Council,
London, page 1102;
(XV) prop-2-ynyl ( ) (E,E)-3,7,11-trimethyldodeca-2,4-dienoate (kinoprene) is
known from
The Pesticide Manual, 10th Edition (1994), The British Crop Protection
Council, London,
page 1102;
(XVI) (R,S)-1-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)pheny1]-3-(2,6-
difluorobenzoy1)-
urea (lufenuron) is known from The Pesticide Manual, 10th Edition (1994), The
British
Crop Protection Council, London, page 628;
CA 02616852 2008-01-31
30584-125E
- 4 -
(XVII) methyl (E)-3-(dimethoxyphosphinothioyloxy)-2-methylacrylate
(methacriphos) is
known from The Pesticide Manual, 9th Edition (1991), The British Crop
Protection
Council, London, page 562;
(XVIII) S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl 0,0-dimethyl
phosphorodithioate (methidathion) is known from The Pesticide Manual, 9th
Edition
(1991), The British Crop Protection Council, London, page 567;
(XIX) dimethyl (E)-1-methyl-2-(methylcarbamoyl)vinyl phosphate (monocrotophos)
is known
from The Pesticide Manual, 9th Edition (1991), The British Crop Protection
Council,
London, page 597;
(XX) 2-chloro-2-diethylcarbamoy1-1-methylvinyl dimethyl phosphate
(phosphamidon) is
known from The Pesticide Manual, 9th Edition (1991), The British Crop
Protection
Council, London, page 679;
(XXI) 0-4-bromo-2-chlorophenyl 0-ethyl S-propyl phosphorothioate (profenofos)
is known
from The Pesticide Manual, 9th Edition (1991), The British Crop Protection
Council,
London, page 705;
(XXII) a mixture of 50 to 80 % of (2RS,4SR)-4-(2-ethyl-1,3-dioxolan-4-
ylmethoxy)phenyl
phenyl ether and 50 to 20 % of (2RS,4RS)-4-(2-ethyl-1,3-dioxolan-4-
ylmethoxy)phenyl
phenyl ether (diofenolan) is known from The Pesticide Manual, 10th Edition
(1994), The
British Crop Protection Council, London, page 363;
()0011) a substance obtainable from the Bacillus thuringiensis strain GC91 or
a substance
obtainable from the Bacillus thuringiensis strain NCTC11821 is known from The
Pesticide Manual, 10th Edition (1994), The British Crop Protection Council,
London, page
62;
(XXIV) 2,3,4,5-tetrahydro-3-oxo-4-[(pyridin-3-yI)-methyleneamino]-6-methyl-
1,2,4-triazine
(pymetrozine) is known from The Pesticide Manual, 10th Edition (1994), The
British Crop
Protection Council, London, page 868; and
(XXV) isopropyl 4,4'-dibromobenzilate (bromopropylate) is known from The
Pesticide
Manual, 9m Edition (1991), The British Crop Protection Council, London, page
99,
(XXVI) isopropyl (E,E)-(R,S)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoate
(methoprene)
is known from The Pesticide Manual, 10th Edition (1994), The British Crop
Protection
Council, London, page 680;
(XXVII) 0,0-diethyl S-2-ethylthioethyl phosphorodithioate (disulfuton) is
known from The
Pesticide Manual, le Edition (1994), The British Crop Protection Council,
London,
page 372;
CA 02616852 2008-01-31
30584-125E
- 5 -
(XXVIII) 0,0-diethyl 0-quinoxalin-2-ylphosphorothioate (quinalphos) is known
from The
Pesticide Manual, 10th Edition (1994), The British Crop Protection Council,
London,
page 890, and
(0(1X) (RS)-a-cyano-3-phenoxybenzyl N-(2-chloro-a,cc,ot-trifluoro-p-tolyI)-D-
valinate (tau-
fluvalinate) is known from The Pesticide Manual, 9th Edition (1991), The
British Crop
Protection Council, London, page 428.
(XXX) N,N-dimethy1-1,2,3-trithian-5-yl-amine (thiocyclam) is known from The
Pesticide
Manual, 9"' Edition (1991), The British Crop Protection Council, London, page
816; and
(XXXI) S-2-ethylthioethyl 0,0-dimethyl phosphorodithioate (thiometon) is known
from The
Pesticide Manual, 9th Edition (1991), The British Crop Protection Council,
London,
page 819.
The compounds of the formula (A) can in some cases be in the form of
tautomers. For
example, if R is hydrogen, corresponding compounds of the formula (A), i.e.
those having a
3-H-4-imino-perhydro-1,3,5-oxadiazine partial structure, can be in equilibrium
with the
respective tautomers which contain a 4-amino-1,2,5,6-tetrahydro-1,3,5-
oxadiazine partial
structure. Compounds of the formula (A) above and below are accordingly also
to be
understood as meaning, where appropriate, corresponding tautomers, even if the
latter are
not mentioned specifically in each case.
Compounds of the formula (A) which contain at least one basic centre can form,
for
example, acid addition salts. These are formed, for example, with strong
inorganic acids
such as mineral acids, for example perchloric acid, sulfuric acid, nitric
acid, nitrous acid, a
phosphoric acid or a hydrogen halide acid, with strong organic carboxylic
acids, such as
C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for
example by
halogen, for example acetic acid, such as dicarboxylic acids which are
saturated or
unsaturated, for example oxalic, malonic, succinic, maleic, fumaric or
phthalic acid, such as
hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or
citric acid, or such as
benzoic acid, or with organic sulfonic acids, such as C1-C4alkane- or
arylsulfonic acids
which are unsubstituted or substituted, for example by halogen, for example
methane- or p-
toluenesulfonic acid. Compounds of the formula (A) with at least one acid
group can
furthermore form salts with bases. Suitable salts with bases are, for example,
metal salts,
such as alkali metal or alkaline earth metal salts, for example sodium,
potassium or
magnesium salts, or salts with ammonia or an organic amine, such as
morpholine,
CA 02616852 2008-01-31
30584-125E
-6 -
piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example
ethyl-, diethyl-,
triethyl- or dimethyl-propyl-amine, or a mono-, di- or trihydroxy-lower
alkylamine, for
example mono-, di- or triethanolamine. If appropriate, corresponding inner
salts can
furthermore be formed. Agrochemically advantageous salts are preferred in the
context of
the invention. As a result of the close relationship between the compounds of
the formula
(A) in the free form and in the form of their salts, the free compounds of the
formula (A) and
their salts above and below are also appropriately and expediently to be
understood as
meaning, where appropriate, the corresponding salts and the free compounds of
the
formula (A). The same applies correspondingly to tautomers of compounds of the
formula
(A) and salts thereof. In each case the free form is in general preferred.
Compositions which comprise the compound of the formula (A) in the free form
are
preferred in the context of the present invention.
The general terms used above and below have the meanings given below, unless
defined
otherwise.
Heteroatoms in the cyclic base structure of the heterocyclic radical R are all
elements of the
Periodic Table which can form at least two covalent bonds. N and S are
preferred.
Halogen - as a group per se and as a structural element of other groups and
compounds,
such as of haloalkyl, haloalkylthio, haloalkoxy, halocyclopropyl, haloalkenyl,
haloalkynyl,
haloallyloxy and haloallylthio - is fluorine, chlorine, bromine or iodine, in
particular fluorine,
chlorine or bromine, especially fluorine or chlorine, in particular chlorine.
Unless defined otherwise, carbon-containing groups and compounds in each case
contain 1
up to and including 6, preferably 1 up to and including 3, in particular 1 or
2, carbon atoms.
Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably
cyclopropyl.
Alkyl - as a group per se and as a structural element of other groups and
compounds, such
as of phenylalkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio -
is, in each case
taking into due consideration the number of carbon atoms contained from case
to case in
the corresponding group or compound, either straight-chain, i.e. methyl,
ethyl, propyl, butyl,
pentyl or hexyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-
butyl, isopentyl,
neopentyl or isohexyl.
CA 02616852 2008-01-31
30584-125E
' -7-
Alkenyl, haloalkenyl, alkynyl and haloalkynyl are straight-chain or branched
and in each
case contain two or preferably one unsaturated carbon-carbon bond(s). The
double or triple
bonds of these substituents are preferably separated from the remaining part
of the
compound of the formula (A) by at least one saturated carbon atom. Examples
are allyl,
methallyl, but-2-enyl, but-3-enyl, propargyl, but-2-ynyl and but-3-ynyl.
Halogen-substituted carbon-containing groups and compounds, such as haloalkyl,
haloalkylthio, haloalkoxy, halocyclopropyl, haloalkenyl, haloalkynyl,
haloallyloxy and
haloallylthio, can be partly halogenated or perhalogenated, and in the case of
multiple
halogenation, the halogen substituents can be identical or different. Examples
of haloalkyl -
as a group per se and as a structural element of other groups and compounds,
such as of
haloalkylthio and haloalkoxy - are methyl which is mono- to trisubstituted by
fluorine,
chlorine and/or bromine, such as CHF2 or CF3; ethyl which is mono- to
pentasubstituted by
fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCI3, CF2CHCl2,
CF2CHF2,
CF2CFCI2, CF2CHBr2, CF2CHCIF, CF2CHBrF or CCIFCHCIF; propyi or isopropyl which
is
mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as
CH2CHBrCH2Br,
CF2CHFCF3, CH2CF2CF3, CF2CF2CF3 or CH(CF3)2; and butyl or one of its isomers
which is
mono- to nonasubstituted by fluorine, chlorine and/or bromine, such as
CF(CF3)CHFCF3,
CF2(CF2)2CF3 or CH2(CF2)2CF3. Examples of haloalkenyl are 2,2-difluoroethen-1-
yl, 2,2-
dichloroethen-1-yl, 2-chloroprop-1-en-3-yl, 2,3-dichloroprop-1-en-3-y1 and 2,3-
dibromoprop-
1-en-3-yl. Examples of haloalkynyl are 2-chloroprop-1-yn-3-yl, 2,3-
dichloroprop-1-yn-3-y1
and 2,3-dibromoprop-1-yn-3-yl. Examples of halocyclopropyl are 2-
chlorocyclopropyl, 2,2-
difluorocyclopropyl and 2-chloro-2-fluoro-cyclopropyl. Examples of
haloallyloxy are 2-
chloroprop-1-en-3-yloxy, 2,3-dichloroprop-1-en-3-yloxy and 2,3-dibromoprop-1-
en-3-yloxy.
Examples of haloallylthio are 2-chloroprop-1-en-3-ylthio, 2,3-dichloroprop-1-
en-3-ylthio and
2,3-dibromoprop-1-en-3-ylthio.
In phenylalkyl, an alkyl group bonded to the remaining part of the compound of
the formula
(A) is substituted by a phenyl group, the alkyl group preferably being
straight-chain and the
phenyl group preferably being bonded to the alkyl group in a position higher
than the
a-position, in particular in the Q-position; examples are benzyl, 2-
phenylethyl and
4-phenylbutyl.
Particularly preferred compounds of the formula (A) are those in which
CA 02616852 2008-01-31
30584-125E
- 8 -
(1) R is hydrogen, C1-C4alkyl, C3-C6cycloalkyl, C2-C6alkenyl or C2-C6alkynyl,
in particular H
or CH3;
(2) the cyclic base skeleton of A contains 2 to 4, preferably conjugated,
double bonds,
preferably contains 2, preferably conjugated, double bonds,
and in particular has aromatic character,
(3) the cyclic base skeleton of A contains 1 up to and including 4, in
particular 1 up to and
including 3, especially 1 or 2, heteroatoms, particularly preferably 2
heteroatoms;
(4) the cyclic base skeleton of A contains 1, 2 or 3 heteroatoms chosen from
the group
consisting of oxygen, sulfur and nitrogen, not more than one of the
heteroatoms contained
in the cyclic base skeleton being an oxygen or sulfur atom,
preferably at least one nitrogen atom;
(5) a compound of the formula (A) in which A is mono- or disubstituted by
substituents
chosen from the group consisting of halogen and C1-C3alkyl, in particular by
halogen,
especially by chlorine;
(6) a compound of the formula (A) in which the cyclic base skeleton of A is a
pyridyl,
1-oxidopyridinio or thiazolyl group,
preferably the cyclic base skeleton of A is a pyrid-3-y1-, 1-oxido-3-pyridinio
or thiazol-5-y1
group,
in particular A is a pyrid-3-yl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-C1-
C3alkylpyrid-5-yl,
1-oxido-3-pyridinio, 2-halo-1-oxido-5-pyridinio, 2,3-dihalo-1-oxido-5-
pyridinio or 2-
halothiazol-5-y1 group,
A is especially a pyrid-3-yl, 2-halopyrid-5-yl, 2-halo-1-oxido-5-pyridinio or
2-halothiazol-5-y1
group,
preferably A is a 2-chloropyrid-5-yl, 2-methylpyrid-5-yl, 1-oxido-3-pyridinio,
2-chloro-1-oxido-
5-pyridinio, 2,3-dichloro-1-oxido-5-pyridinio or 2-chlorothiazol-5-y1 group,
A is especially a pyrid-3-yl, 2-chloropyrid-5-yl, 2-chloro-1-oxido-5-pyridinio
or 2-chlorothiazol-
5-y1 group,
in particular A is a 2-chloropyrid-5-y1 or, preferably, 2-chlorothiazol-5-y1
group;
(7) a compound of the formula (A), in which X is N-NO2;
CA 02616852 2008-01-31
3058 4-1 2 5E
- 9 -
(8) a compound of the formula (A), in which A is a 2-chlorothiazol-5-y1 or 2-
chloropyrid-5-y1
group, R is C1-C4alkyl and X is N-NO2.
Compounds of the formula (A) which are named as preferred in the context of
the invention
are
(A.1) 5-(2-chloropyrid-5-ylmethyl)-3-methyl-4-nitroimino-perhydro-1,3,5-
oxadiazine;
(A.2) 5-(2-chlorothiazol-5-ylmethyl)-3-ethyl-4-nitroimino-perhydro-1,3,5-
oxadiazine;
(A.3) 3-methyl-4-nitroimino-5-(1-oxido-3-pyridiniomethyl)-perhydro-1,3,5-
oxadiazine;
(A.4) 5-(2-chloro-1-oxido-5-pyridiniomethyI)-3-methyl-4-nitroimino-perhydro-
113,5-
oxadiazine;
(A.5) 5-(2-chlorothiazol-5-ylmethyl)-3-methyl-4-nitroimino-petydro-1,3,5-
oxadiazIne;
(A.6) 3-methyl-5-(2-methylpyrid-5-ylmethyl)-4-nitroimino-perbydro-1,3,5-
oxadiazine;
(A.7) 3-(2-chloropyrid-5-ylmethyl)-4-nitroimino-perhydro-1,3,5-oxadiazine; and
(A.8) 3-(2-chlorothiazol-5-ylmethyl)-4-nitroimino-perhydro-1,3,5-oxadiazine.
A composition which, in addition to the compound of the formula (A), comprises
only one
other pesticidally active compound (I) to (XXXI) is also preferred. A
composition which
comprises the compound 5- (2-chiorothiazol-5-ylmethyl)-3-methyl-4-nitroimino-
perhydro-
1,3,5-oxadiazine as active component (A) is likewise preferred. Compositions
which, in
addition to a compound of the formula (A), comprise azamethiphos,
cypermethrin, cypermethrin
high-cis, fenoxycarb, diofenolan, profenofos or pymetrozine are furthermore
preferred.
The active .compound combination according to the invention preferably
comprises the
active compound of the formula (A) and one of the active compounds (I) to
(XXXI) in a
mixing ratio of 100:1 to 1:6000, in particular 1:50 to 50:1, in particular in
a ratio of between
1:20 and 20:1, in particular between 10:1 and 1:10, especially between 5:1 and
1:5,
particularly preferably between 2:1 and 1:2, and also preferably between 4:1
and 2:1,
especially in the ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or
4:2, or 4:3, or 3:1, or 3:2,
or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2;4, or 3:4, or 1:3, or
2:3, or 1:2, or, 1:600, or
1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or
1:6000, or 1:3000, or
1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. These
ratios are
understood as meaning weight ratios on the one hand, but also molar ratios on
the other
hand.
CA 02616852 2008-01-31
30584-125E
- 10 -
-
It has now been found, surprisingly, that the combination of the active
compound of the
formula (A) or of one of its salts with one of the active compounds (I) to
(XXXI) not only
causes an additive increase in the action spectrum on the pests to be
controlled, which is to
be expected in principle, but also achieves a synergistic effect which extends
the action
limits of both preparations under two aspects:
On the one hand, the rates of application of the compound of the formula (A)
and of the
individual compounds (I) to (XXXI) are lowered for the same good action. On
the other
hand, the combined mixture also still has a high degree of pest control where
the two
individual substances have become completely inactive in the range of low
rates of
application. This allows on the one hand a considerable extension to the
spectrum of pests
which can be controlled, and on the other hand an increase in application
reliability.
In addition to the actual synergistic action in respect of pesticidal
activity, however, the
compositions according to the invention also additionally have further
surprising advantages
which can likewise be described as synergistic in a broadened sense: thus, for
example, it
is possible to control pests which cannot be controlled or sufficiently
effectively controlled
with the individual compounds(A) or (I) to (XXXI), and the compositions
according to the
invention have a better toleration by plants, i.e. a reduced phytotoxicity,
than the individual
compounds (A) and (I) to (XXXI). The insects can furthermore be controlled in
their various
stages of development, which is not always the case with the individual
compounds (A) and
(I) to (XXXI), since these compounds can be used, for example, only as
adulticides or only
as larvicides against quite specific larval stages. In addition, combinations
of the compound
(A) with certain compounds (I) to (XXXI) show more favourable properties
during grinding,
mixing, storage and also spraying.
The compositions according to the invention are already valuable preventively
and/or
curatively at low rates of concentration in the field of pest control, while
being tolerated by
warm-blooded animals, fishes and plants, and have a very favourable biocidal
spectrum.
The compositions according to the invention are active against all or
individual stages of
development of normally sensitive and also resistant animal pests, such as
insects and
representatives of the order Acarina. The insecticidal and/or acaricidal
action of the
compositions according to the invention can manifest itself here directly,
i.e. in a destruction
of the pests, which occurs immediately or only after some time, for example
during
CA 02616852 2008-01-31
30584-125E
- 11 -
moulting, or indirectly, for example in a reduced oviposition and/or hatching
rate, the good
action corresponding to a rate of destruction (mortality) of at least 50 to 60
cYo.
The animal pests include, for example:
from the order Lepidoptera
Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama
argillaceae, Amylois
spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp.,
Busseola
fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp.,
Clysia
ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora
spp.,
Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp.,
Diparopsis
castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella,
Euproctis spp.,
Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula spp.,
Hyphantria
cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp.,
Lobesia botrana,
Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca
sexta,
Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis
flammea,
Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp.,
Plutella
xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp.,
Spodoptera
spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and
Yponomeuta
spp.;
from the order Coleoptera, for example
Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis,
Cosmopolites
spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus
spp.,
Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Oryzaephilus
spp.,
Otiorhynchus spp., Phlyctinus spp., Popillia spp.,.Psylliodes spp.,
Rhizopertha spp.,
Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp.
and Trogoderrna
spp.;
from the order Orthoptera, for example
Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta
spp., Periplaneta
spp. and Schistocerca spp.;
from the order lsoptera, for example
Reticulitermes spp.;
from the order Psocoptera, for example
Liposcelis spp.;
from the order Anoplura, for example
CA 02616852 2008-01-31
30584-125E
- 12 -
Haematopinus spp., Linognathus spp., Pediculus spp., Pernphigus spp. and
Phylloxera
spp.;
from the order Mallophaga, for example
Damalinea spp. and Trichodectes spp.;
from the order Thysanoptera, for example
Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi,
Thrips tabaci and
Scirtothrips aurantii;
from the order Heteroptera, for example
Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp. Eurygaster
spp.
Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella
singularis,
Scotinophara spp. and Triatoma spp.;
from the order Homoptera, for example
Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae,
Aphis spp.,
Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium,
Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma
lanigerum,
Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni,
Lepidosaphes spp.,
Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria
spp.,
Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp.,
Psylla
spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp.,
Saissetia spp.,
Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum,
Trioza
erytreae and Unaspis citri;
from the order Hymenoptera, for example
Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia
polytoma,
Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp.,
Solenopsis spp.
and Vespa spp.;
from the order Diptera, for example
Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala,
Ceratitis
spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila
melanogaster,
Fannia spp., Gastrophilus spp., Glossina spp., Hypoderrna spp., Hyppobosca
spp.,
Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp.,
Orseolia spp.,
OscineIla frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara
spp.,
Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;
from the order Siphonaptera, for example
CA 02616852 2008-01-31
30584-125E
- 13 -
Ceratophyljus spp. and Xenopsylla cheopis;
from the order Thysanura, for example
Lepisma saccharina and
from the order Acarina, for example
Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas
spp.,
Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp.,
Chorioptes spp.,
Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp.,
lxodes spp.,
Olygonychus pratensis, Omithodoros spp., Panonychus spp., Phyllocoptruta
oleivora,
Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus
spp.,
Sarcoptes spp., Tarsonemus spp. and Tetranychus spp..
Using the active compound mixtures according to the invention, in particular
pests of the
type mentioned which occur on plants, especially useful plants and omamentals
in
agriculture, in horticulture and in forestry, or on parts such as fruit,
blossom, foliage, stems,
tubers, or roots, of such plants can be controlled, i.e. checked or destroyed;
in some cases
even parts of plants which grow later are still protected from these pests.
The pesticidal mixture according to the invention can advantageously be
employed for pest
control in cereals, such as maize or sorghum; in fruit, for example pome,
stone and soft
fruit, such as apples, pears, plums, peaches, almonds, cherries or berries,
for example
strawberries, raspberries and blackberries; in leguminous plants, such as
beans, lentils,
peas or soya; in oil-bearing crops, such as oilseed rape, mustard, poppy,
olive, sunflower,
coconut, castor, cacao or groundnuts; in cucurbits, such as pumpkins,
cucumbers or
melons; in fibre plants, such as cotton, flax, hemp or jute; in citrus fruits,
such as oranges,
lemons, grapefruits or mandarins; in vegetables, such as spinach, lettuce,
asparagus,
cabbage varieties, carrots, onions, tomatoes, potatoes or capsicum; in
laurareous plants,
such as avocado, cinnamonium or camphor; or in tobacco, nuts, coffee,
aubergines, sugar
cane, tea, pepper, vines, hops, musaceous plant, natural rubber plants or
ornamentals,
in particular in maize, sorghum, pome and stone fruits, leguminous plants,
gourds, cotton,
citrus fruits, vegetables, aubergines, vines, hops or ornamentals,
especially in maize, sorghum, apples, pears, plums, peaches, beans, peas,
soya, olives,
sunflowers, coconut, cacao, groundnuts, cucumbers, pumpkins, citrus fruits,
cabbage
varieties, tomatoes, potatoes, vines or cotton,
particularly preferably in vines, citrus fruits, apples, pears, tomatoes and
cotton.
CA 02616852 2008-01-31
30584-125E
- 14 -
Other fields of use of the active compound mixtures according to the invention
are
protection of stored products and stocks and of material, and in the hygiene
sector, in
particular the protection of domestic animals and productive livestock against
pests of the
type mentioned.
Dependindon the aims to be achieved and the given circumstances, the
pesticides
according to the invention are emulsifiable concentrates, suspension
concentrates, directly
sprayable or dilutable solutions, spreadable pastes, dilute emulsions,
sprayable powders,
soluble powders, dispersible powders, wettable powders, dusts, granules or
encapsulations
in polymeric substances which comprise the compound of the formula (A) or one
of its salts
and one of the other active compounds (I) to (XXXI) according to the
invention.
The active compounds are employed in these compositions in a pure form, the
solid active
compounds, for example, being employed in a specific particle size, or,
preferably, together
with - at least - one of the auxiliaries conventionally used in the art of
formulation, such as
extenders, for example solvents or solid carriers, or such as surface-active
compounds
(surfactants).
Solvents are, for example: non-hydrogenated or partly hydrogenated aromatic
hydrocarbons, preferably fractions C8 to C12 of alkylbenzenes, such as xylene
mixtures,
alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic
hydrocarbons,
such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or
butanol, glycols
and ethers and esters thereof, such as propylene glycol, dipropylene glycol
ether, ethylene
glycol or ethylene glycol monomethyl or -ethyl ether, ketones, such as
cyclohexanone,
isophorone or diacetone alcohol, strongly polar solvents, such as N-
methylpyrrolid-2-one,
dimethyl sulfoxide or N,N-dimethylformamide, water, non-epoxidized or
epoxidized plant
oils, such as non-epoxidized or epoxidized rapeseed, castor, coconut or soya
oil, and
silicone oils.
Solid carriers, for example for dusts and dispersible powders, which are as a
rule used are
natural rock powders, such as calcite, talc, kaolin, montmorillonite or
attapulgite. Highly
disperse silicic acids or highly disperse absorbent polymers can also be added
to improve
the physical properties. Granular, adsorptive granule carriers are porous
types, such as
pumice, crushed brick, sepiolite or bentonite, and non-adsorptive carrier
materials are
CA 02616852 2008-01-31
30584-125E
- 15 -
calcite or sand. A large number of granulated materials of inorganic or
organic nature, in
particular dolomite or comminuted plant residues, can furthermore be used.
Surface-active compounds are, depending on the nature of the active compound
to be
formulated, nonionic, cationic and/or anionic surfactants or surfactant
mixtures having good
emulsifying, dissolving and wetting properties. The surfactants listed below
are to be
regarded only as examples here; many other surfactants which are
conventionally used in
the art of formulation and are suitable according to the invention are
described in the
relevant literature.
Nonionic surfactants are, in particular, polyglycol ether derivatives of
aliphatic or
cycloaliphatic alcohols, saturated or unsaturated fatty acids and
alkylphenols, which can
contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the
(aliphatic) hydrocarbon
radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
Water-soluble
adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100
propylene glycol
ether groups, of polyethylene oxide on polypropylene glycol,
ethylenediaminopolypropylene
glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl
chain are
furthermore suitable. The compounds mentioned usually comprise 1 to 5 ethylene
glycol
units per propylene glycol unit. Examples are nonylphenol-polyethoxyethanols,
castor oil
polyglycol ether, polypropylene/polyethylene oxide adducts,
tributylphenoxypolyethoxyethanol, polyethylene glycol and
octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene-sorbitan, such as polyogethylene-sorbitan
trioleate,
are furthermore possible.
Cationic surfactants are, in particular, quaternary ammonium salts which
contain, as
substituents, at least one alkyl radical having 8 to 22 C atoms and, as
further substituents,
lower, non-halogenated or halogenated alkyl, benzyl or lower hydroxy alkyl
radicals. The
salts are preferably in the form of halides, methyl sulfates or ethyl
sulfates. Examples are
stearyltrimethylammonium chloride and benzyldi(2-chloroethyl)ethylammonium
bromide.
Suitable inorganic surfactants can be both water-soluble soaps and water-
soluble synthetic
surface-active compounds. Suitable soaps are the alkali metal, alkaline earth
metal and
substituted and unsubstituted ammonium salts of higher fatty acids (C10-C22),
such as the
sodium or potassium salts of oleic or stearic acid, or of naturally occurring
fatty acid
mixtures, which can be obtained, for example, from coconut oil or tall oil;
and furthermore
CA 02616852 2008-01-31
30584-125E
- 16 -
also the fatty acid methyltaurine salts. However, synthetic surfactants are
more frequently
used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole
derivatives or
alkylarylsulfonates. The fatty sulfonates and sulfates are as a rule in the
form of alkali
metal, alkaline earth metal or substituted or unsubstituted ammonium salts,
and in general
contain an alkyl radical having 8 to 22 C atoms, alkyl also including the
alkyl moiety of acyl
radicals; examples are the sodium or calcium salt of ligninsulfonic acid, of
dodecylsulfuric
acid ester or of a fatty alcohol sulfate mixture prepared from naturally
occurring fatty acids.
These also include the salts of sulfuric acid esters and sulfonic acids of
fatty alcohol-
ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably
contain two
sulfonic acid groups and one fatty acid radical having about 8 to 22 C atoms.
Alkylarylsulfonates are, for example, the sodium, calcium or
triethanolammonium salts of
dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a
naphthalenesulfonic acid-formaldehyde condensation product. Corresponding
phosphates,
such as salts of the phosphoric acid ester of a p-nonylphenol-(4-14)-ethylene
oxide adduct
or phospholipids, are furthermore also suitable.
The compositions as a rule comprise 0.1 to 99 %, in particular 0.1 to 95 %, of
a mixture of
the active compound of the formula (A) with one of the active compounds (I) to
(XXXI), and
1 to 99.9 %, in particular 5 to 99.9 %, of - at least - one solid or liquid
auxiliary, where as a
rule 0 to 25 %, in particular 0.1 to 20 %, of the compositions can be
surfactants ( % is in
each case per cent by weight). While concentrated compositions are rather
preferred as
commercial goods, the end user as a rule uses dilute compositions which have
considerably
lower active compound concentrations. Preferred compositions have, in
particular, the
following composition (% = per cent by weight):
Emulsifiable concentrates:
Active compound mixture 1 to 90 %, preferably
5 to 20 %
Surfactant: 1 to 30 %, preferably
10 to 20 %
Solvent: 5 to 98 %, preferably
70 to 85 %
Dusts:
Active compound mixture: 0.1 to 10 /0,
preferably 0.1 to 1 %
Solid carrier: 99.9 to 90 %,
preferably 99.9 to 99 %
=
CA 02616852 2008-01-31
30584-125E
- 17 -
Suspension concentrates:
Active compound mixture: 5 to 75 A),
preferably 10 to 50 %
Water: 94 to 24 %,
preferably 88 to 30 %
Surfactant: 1 to 40 %, preferably
2 to 30 %
Wettable powders:
Active compound mixture: 0.5 to 90 %,
preferably 1 to 80 %
Surfactant: 0.5 to 20 c/o,
preferably 1 to 15 %
Solid carrier 5 to 99 A,
preferably 15 to 98 %
Granules:
Active compound mixture: 0.5 to 30 %,
preferably 3 to 15 %
Solid carrier 99.5 to 70 %,
preferably 97 to 85 %
The compositions according to the invention can also comprise other solid or
liquid
auxiliaries such as stabilizers, for example non-epoxidized or epoxidized
plant oils (for
example epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for
example silicone
oil, preservatives, viscosity regulators, binders and/or tackifiers, as well
as fertilizers or other
active compounds for achieving specific effects, for example bactericides,
fungicides,
nematicides, molluscicides or herbicides.
The compositions according to the invention are prepared in a known manner, in
the
absence of auxiliaries, for example, by grinding, sieving and/or pressing a
solid active
compound or active compound mixture, for example to a particular particle
size, and in the
presence of at least one auxiliary, for example, by intimate mixing and/or
grinding of the
= active compound or active compound mixture with the auxiliary or
auxilaries. The invention
therefore also relates to a process for the preparation of the compositions.
Mixtures of a compound of the formula (A) with one or more of the compounds
(I) to (XXXI)
are preferably employed with the auxiliaries conventionally used in the art of
formulation,
and are therefore processed, for example, to emulsifiable concentrates,
directly sprayable
= or dilutable solutions, dilute emulsions, wettable powders, soluble
powders, dusts and
granules, and also to encapsulations in, for example, polymeric substances, in
a known
manner. The methods of application, such as spraying, atomizing, dusting,
wetting,
CA 02616852 2008-01-31
30584-125E
- 18 -
scattering or pouring are chosen, as is the nature of the composition,
according to the aims
to be achieved and the given circumstances.
The invention furthermore relates to the methods of application of the
compositions, i.e. the
methods of controlling pests of the type mentioned, such as spraying,
atomizing, dusting,
spreading, dressing, scattering or pouring, to be chosen according to the aims
to be
achieved and the given circumstances, and the use of the compositions for
controlling pests
of the type mentioned. Typical rates of concentration here are between 0.1 and
1000 ppm,
preferably between 0.1 and 500 ppm, of active compound. The rate of
application can vary
within wide limits and depends on the nature of the soil, the nature of the
application, (leaf
application; seed dressing; application in the seed furrow), the crop plant,
the pest to be
controlled, the particular climatic circumstances which prevail and other
factors determined
by the nature of the application, the time of application and the target crop.
The rates of
application per hectare are in general 1 to 2000 g of active compound per
hectare, in
particular 10 to 1000 g/ha, preferably 20 to 600 g/ha.
A preferred method of application in the field of crop protection is
application to the foliage
of the plants (foliar application), where the frequency of application and
rate of application
can be chosen according to the risk of infestation by the particular pest.
However, the active
compound can also enter the plants via the root system (systemic action) by
impregnating
the locus of the plants with a liquid composition or introducing the active
compounds in solid
form into the locus of the plants, for example into the soil, for example in
the form of
granules (soil application). In paddy rice crops, such granules can be metered
onto the
flooded rice field.
The compositions according to the invention are also suitable for the
protection of plant
propagation material, for example seeds, such as fruit, tubers, or grain, or
plant seedlings,
against animal pests. The propagation material can be treated with the
composition before
being brought out, for example seed can be dressed before sowing. The active
compounds
according to the invention can also be applied to the seed grains (coating)
either by
impregnating the grains in a liquid composition or coating them with a solid
composition.
The composition can also be applied to the site where the propagation material
is brought
out, during broadcasting, for example into the seed furrow during sowing. The
invention
furthermore relates to these treatment methods for plant propagation material
and the plant
propagation material treated in this way.
CA 02616852 2008-01-31
30584-125E
- 19 -
The following examples serve to illustrate the invention. They do not limit
the invention.
Formulation examples (% = per cent by weight, active compound ratios = weight
ratios)
Example Fl: Emulsion concentrates a) b)
c)
Active compound mixture [Compound (A) :
Compound (I) to (XXXI) = 1: 3] 25 % 40 % 50
%
Calcium dodecylbenzenesulfonate 5 % 8 %
6 %
Castor oil polyethylene glycol ether (36 mol of EO) 5 %
Tributylphenol polyethylene glycol ether (30 mol of EO) 12
% 4 %
Cyclohexanone 15
A 20 %
Xylene mixture 65 % 25 % 20
%
EO is the degree of ethoxylation of castor oil or tributylphenol.
Emulsions of any desired concentration can be prepared from such concentrates
by dilution
with water.
Example F2: Solutions a) b)
c) d)
Active compound mixture [Compound (A) :
Compound (1) to (XXXI) = 1 :10] 80% 10% 5%
95%
Ethylene glycol monomethyl ether 20
%
Polyethylene glycol molecular wt. 400 70
%
N-methyl-2-pyrrolidone 20 % -
Epoxidized coconut oil
1 % 5 A
Benzine (boiling limit 160-190 C)
94 %
The solutions are suitable for use in the form of tiny drops.
Example F3: Granules a) b)
c) d)
Active compound mixture [Compound (A) :
Compound (1) to (XXXI) = 2 : 1] 5% 10%
8% 21%
Kaolin _ 94 %
79 % 54 `)/0
Highly disperse silicic acid 1 %
13 % 7 %
Attapulgite 90
% 18 %
CA 02616852 2008-01-31
30584-125E
- 20 -
The active compounds are dissolved together in methylene chloride, the
solution is sprayed
onto the carrier and the solvent is then evaporated off in vacuo.
Example F4: Dusts a) b)
Active compound mixture [Compound (A) :
Compound (I) to (XXXI) = 1 : 1] 2 % 5 %
Highly disperse silicic acid 1 % 5 cto
Talc 97%
Kaolin 90%
Intimate mixing of the carriers with the active compounds gives ready-to-use
dusts.
Example F5: Wettable powders a) b) c)
Active compound mixture [Compound (A) :
Compound (I) to (XXXI) = 1: 75] 25 % 50 % 75 %
Sodium ligninsulfonate 5 % 5 %
Sodium lauryl sulfate 3 % 5 %
Sodium diisobutylnaphthalenesulfonate 6 % 10 To
Octylphenol polyethylene glycol ether (7-8 mol of EO) 2 % -
Highly disperse silicic acid 5 % 10 % 10 %
Kaolin 62% 27% -
The active compounds are mixed with the additives and ground thoroughly in a
suitable mill.
Wettable powders which can be diluted with water to give suspensions of any
desired
concentration are obtained.
Example F6: Emulsion concentrate
Active compound mixture [Compound (A) :
Compound (I) to (XXXI) = 1: 350] 10 %
Octylphenol polyethylene glycol ether (4-5 mol of EO) 3 %
Calcium dodecylbenzenesulfonate 3 %
Castor oil polyglycol ether (36 mol of EO) 4 %
Cyclohexanone 30 %
Xylene mixture 50 %
CA 02616852 2008-01-31
30584-125E
- 21 -
Emulsions of any desired concentration can be prepared from this concentrate
by dilution
with water.
Example F7: Dusts a) b)
Active compound mixture (2 : 3) 5% 8 clo
Talc 95% -
Kaolin 92 %
Ready-to-use dusts are obtained by mixing the active compounds with the
carrier and
grinding the mixture on a suitable mill.
Example F8: Extruded granules
Active compound mixture [Compound (A) :
Compound (I) to (XXXI) = 1 : 4] 10 %
Sodium ligninsulfonate 2 %
Carboxymethylcellulose 1 %
Kaolin 87 %
The active compounds are mixed with the additives and the mixture is ground
and
moistened with water. This mixture is extruded, granulated and then dried in a
stream of air.
Example F9: Coated granules
Active compound mixture [Compound (A) :
Compound (I) to (XXXI) = 1: 300] 3 %
Polyethylene glycol (molecular wt. 200) 3 %
Kaolin 94%
The finely ground active compounds are applied uniformly to the kaolin, which
is moistened
with polyethylene glycol, in a mixer. Dust-free coated granules are obtained
in this way.
CA 02616852 2008-01-31
30584-125E
- 22 -
Example F10: Suspension concentrate
Active compound mixture (2 : 350)
40 %
Ethylene glycol
10 %
Nonylphenol polyethylene glycol ether (15 mol of EO)
6 %
Sodium ligninsulfonate
10 %
Carboxymethylcellulose
1 %
37 % aqueous formaldehyde solution
0.2 %
Silicone oil in the form of a 75 % aqueous emulsion
0.8 `)/0
Water
32%
The finely ground active compounds are mixed intimately with the additives. A
suspension
concentrate from which suspensions of any desired concentration can be
prepared by
dilution with water is thus obtained.
It is often more practical to formulate the active compound of the formula (A)
and one of the
mixing partners (I) to (XXXI) individually and then to bring them together in
the applicator in
the desired mixing ratio as a "tank mix" in the water only shortly before
application.
Biological Examples ( /0 = per cent by weight, unless stated otherwise)
A synergistic effect is always present if the action EA of the combination of
an active
compound of the formula (A) with one of the active compounds (I) to (XXXI) is
greater than
the sum of the action of the active compounds applied individually:
EA, > X + Y (B)
However, the pesticidal action EA to be expected for a given combination of
two pesticides
can also be calculated as follows (cf. COLBY, S.R., "Calculating synergistic
and
antagonistic response of herbicide combinations", Weeds 15, Pages 20-22,
1967):
EA = X + Y ( 100 - X ) (C)
2 100
In this equation:
X = Per cent mortality on treatment with the compound of the formula (A)
at a rate of
application of p kg per hectare compared with the untreated control (= 0 %).
CA 02616852 2008-01-31
30584-125E
- 23 -
Y = Per cent mortality on treatment with a compound (I) to (XXXI) at a
rate of application
of q kg per hectare compared with the untreated control.
EA = Expected pesticidal action (per cent mortality compared with the
untreated control)
after treatment with the compound of the formula (A) and a compound (I) to
(XXXI) at a rate
of application of p + q kg of active compound per hectare.
If the action actually observed is greater than the expected value EA,
synergism exists.
Example B1: Action against Bemisia tabaci
Dwarf bean plants are placed in gauze cages and populated with adults of
Bemisia tabaci.
After oviposition has taken place, all the adults are removed. 10 days later,
the plants with
the nymphs on them are sprayed with an aqueous suspension spray liquor
comprising 50
ppm of the active compound mixture. After a further 14 days, the percentage
hatching of
the eggs is evaluated in comparison with untreated control batches.
In this test, combinations of an active compound of the formula (A) with one
of the active
compounds (I) to (XXXI) have a synergistic effect. In particular, a suspension
spray liquor
which comprises 40 ppm of the compound (A.1) and 10 ppm of the compound (II)
has an
activity of over 80%.
Example B2: Action against Spodoptera littoralis caterpillars
Young soya plants are sprayed with an aqueous emulsion spray liquor which
comprises 360
ppm of the active compound mixture. After the spray coating has dried on, the
soya plants
are populated with 10 caterpillars of the third stage of Spodoptera littoralis
and placed in a
plastic container. Evaluation takes place 3 days later. The percentage
reduction in the
population and the percentage reduction in feeding damage (% action) are
determined from
comparison of the number of dead caterpillars and of the feeding damage on the
treated
plants with those on the untreated plants.
In this test, combinations of an active compound of the formula (A) with one
of the active
compounds (I) to (XXXI) have a synergistic effect. In particular, a suspension
spray liquor
which comprises 200 ppm of the compound (A.2) and 160 ppm of the compound (11)
and a
suspension spray liquor which comprises 180 ppm of the compound (A.3) and 180
ppm of
the compound (XV) have a good action.
CA 02616852 2008-01-31
30584-125E
- 24 -
Example B3: Ovicidal action on Lobesia botrana
Lobesia botrana eggs deposited on filter paper are immersed for a short time
in an acetone-
aqueous test solution comprising 400 ppm of the active compound mixture to be
tested.
After the test solution has dried, the eggs are incubated in Petri dishes.
After 6 days, the
percentage hatching of the eggs is evaluated in comparison with untreated
Control batches
(% reduction in hatching).
In this test, combinations of an active compound of the formula (A) with one
of the active
compounds (I) to (XXXI) have a synergistic effect. In particular, a suspension
spray liquor
which comprises 300 ppm of the compound (A.5) and 100 ppm of the compound
(III) and a
suspension spray liquor which comprise 200 ppm of the compound (A.5) and 200
ppm of
the compound (XVI) have an activity of over 80%..
Example B4: Ovicidal action on Heliothis virescens
Heliothis virescens eggs deposited on filter paper are immersed for a short
time in an
acetone-aqueous test solution comprising 400 ppm of the active compound
mixture to be
tested. After the test solution has dried, the eggs are incubated in Petri
dishes. After 6 days,
the percentage hatching of the eggs is evaluated in comparison with untreated
control
batches (% reduction in hatching).
In this test, combinations of an active compound of the formula (A) with one
of the active
compounds (I) to (XXXI) have a synergistic effect. In particular, a suspension
spray liquor
which comprises 240 ppm of the compound (A.1) and 160 ppm of the compound
(XII) and a
suspension spray liquor which comprise 300 ppm of the compound (A.5) and 100
ppm of
the compound (V) have an activity of over 80%.
Example B5: Action against Plutella xylostella caterpillars
Young cabbage plants are sprayed with an aqueous emulsion spray liquor which
comprises
440 ppm of the active compound. After the spray coating has dried on, the
cabbage plants
are populated with 10 caterpillars of the third stage of Plutella xylostella
and placed in a
plastic container. Evaluation takes place 3 days later. The percentage
reduction in the
population and the percentage reduction in eating damage (% action) are
determined from
comparison of the number of dead caterpillars and of the eating damage on the
treated
plants with those on the untreated plants.
CA 02616852 2008-01-31
4 30584-125E
-25 -
In this test, combinations of an active compound of the formula (A) with one
of the active
compounds (I) to (XXXI) have a synergistic effect. In particular, a suspension
spray liquor
which comprises 400 ppm of the compound (A.5) and 40 ppm of the compound (VII)
and a
suspension spray liquor which comprises 220 ppm of the compound (Al) and 220
ppm of
the compound (IV) have an activity of over 80%.
Example B6: Action against Myzus persicae
Capsicum plants (Capsicum annuum L) 6 weeks old are sprayed with an aqueous
emulsion
spray liquor which comprises the individual compounds and mixtures according
to the
following table. The plants were placed in a greenhouse until determination of
the activity.
The activity against Myzus persicae was measured in bioassays. 2-4 hours after
application,
circles of leaf are stamped out, placed with the upper side down on agar in
Petri dishes and
infested with an M. persicae mixed population consisting of 40-50 non-
synchronous
individuals. A total of 9 circles of leaf per concentration are used. The
Petri dishes are
covered with a cotton wool filter, closed with a plastic lid and placed in a
climatically
controlled chamber for plants. One day after infestation, the circles of leaf
are cleaned of
adults, skins and nymphs, so that only 25-40 nymphs laid overnight remain per
circle of leaf.
Four days after infestation, the mortality is determined by counting the dead
and living
nymphs. The tests are carried out 3 times. The results shown in the table are
the average
values of the tests.
CA 02616852 2008-01-31
4 '
30584-125E
" - 26 -
Table: Synergistic action of pesticide mixtures : M. persicae
Compound / Mixture Conc., Action % EA, %
calc. EA2 % calc.
ppm formula (B) formula (C)
A.5 0.1 5.9 -
-
A.5 0.2 35.0 -
-
Profenofos 35 12.3 -
-
Cypermethrin high-cis 600 8.2 -
-
Pymetrozine 0.3 38.4 -
-
A.5 / profenofos 0.1 /35 31.4 18.2
17.5
A.5 / cypermethrin high-cis 0.1 /600 22.8 14.1
13.6
A.5 / cypermethrin high-cis 0.2 / 600 65.6 43.2
40.3
A.5 / pymetrozine 0.1 / 0.3 53.1 44.3
42.0
=
