Note: Descriptions are shown in the official language in which they were submitted.
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Pesticidal mixture comprising a carboxamide compound and a biopesticide
Description
The present invention relates to mixtures of pesticidal active compounds
having synergistically
enhanced action and to methods and uses comprising applying said mixtures.
One typical problem arising in the field of pest control lies in the need to
reduce the dosage
rates of the active ingredient in order to reduce or avoid unfavorable
environmental or
toxicological effects whilst still allowing effective pest control.
Another problem encountered concerns the need to have available pest control
agents which
are effective against a broad spectrum of pests.
There also exists the need for pest control agents that combine knock-down
activity with
prolonged control, that is, fast action with long lasting action.
Another difficulty in relation to the use of pesticides is that the repeated
and exclusive
application of an individual pesticidal compound leads in many cases to a
rapid selection of
pests which have developed natural or adapted resistance against the active
compound in
question.
Therefore there is a need for pest control agents that help prevent or
overcome resistance
induced by pesticides.
Furthermore, there is a desire for pesticide compounds or combinations of
compounds, which
- when applied - improve plants and which may result in "plant health",
"vitality of plant
propagation material" or "increased plant yield".
It is therefore an object of the present invention to provide pesticidal
mixtures, which solve one
or more than one of the discussed problems suche as
- reducing the dosage rate,
- enhancing the spectrum of activity,
- combining knock-down activity with prolonged control,
- improving resistance management,
- improving plant health,
- improving vitality of plant propagation material, also termed seed
vitality,
- increasing plant yield.
It has been found that this object is in part or in whole achieved by the
combination of active
compounds defined below.
The present invention relates to pesticidal mixtures comprising as active
components
1) at least one pesticidal active carboxamide compound I selected from
i) compound i) of formula (I):
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CF3
CH F 0B r< CF3
I 3
0 CF3
(I)
ii) compound ii) of formula (la)
CF3
Br
PSI0 CF3
0 CF3
(la)
iii) mixtures comprising i) and ii)
or the tautomers, enantiomers, diastereomers or salts thereof,
and
2) at least one biopesticide II selected from the groups L1 to L5:
L1) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant
defense activator
activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans,
Bacillus
altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensi:s, B. mycoides,
B. pumllus,
B. simplex, B. sollsalsi; B. subtill:s, B. subtfli:s var. amyloliquefaciens,
Candida oleophila,
C. salloana, Clavibacter michiganensi:s (bacteriophages), Coniothyrium
min/tans,
Cryphonectria parasitica, Cryptococcus albidus, Dflophosphora alopecuri,
Fusarium
oxysporum, Clonostachys rosea f. catenulate (also named Gliocladium
catenulatum),
Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia
fructicola,
Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus,
Paerilbacillus
alvei; Paenibacillus polymyxa, Pantoea vagans, Pen/c//Hum bilaiae, P.steckii;
Phlebiopsis
gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma tIocculosa,
Pichia
anomala, Pythium oligano'rum, Sphaerodes mycoparasitica, Streptomyces
griseovirio'is,
S. lyo'icus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides,
T
asperellum, T atroviride, T fertile, T garnsii T harmatum, T. harzianum, T
polysporum,
I stromaticum, I virens, I viride, Typhula phacorrhiza, Ulocladium oudemansi4
Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or
plant defense
activator activity: harpin protein, Reynoutria sachalinensis extract;
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L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or
nematicidal activity:
Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B.
thuringiensis
ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp.
kurstaki, B. t. ssp.
tenebrionr:s, Beauveda bass/aria, B. brongniartg Burkholder/9 sp.,
Chrornobacteriurn
subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta
granulovirus
(CrleGV), Flavobacterium sp., Helicoverpa armigera nucleopolyhedrovirus
(HearNPV),
Helicoverpa zea nucleopolyhedrovirus (HzNPV), Helicoverpa zea single capsid
nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, lsaria
fumosorosea,
Lecanicillium longisporum, L. muscarium, Metarhizium anisop&e, Metarhizium
anisopliae var. anisopliae, M. anisopliae var. acndum, Nornuraea n7eyi,
Paecriomyces
fumosoroseus, P. Illacinus, Paenrbacillus popil&e, Pasteuria sp., P.
nishizawae, P.
penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens,
Spocloptera
nucleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, S. feltiae, S.
kraussei, Streptomyces galbus, S. microflavus;
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal,
pheromone and/or
nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1-ylacetate,
ethyl formate,
(E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,11,13-hexadecatrienal,
heptyl
butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1-
butanol,
methyl eugenol, methyl jasmonate, jasmonic acid or salts or derivatives
thereof, (E,Z)-
2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadien-1-ol acetate, (E,Z)-3,13-
octadecadien-
1-01, R-1-octen-3-ol, pentatermanone, (E,Z,Z)-3,8,11-tetradecatrienyl acetate,
(Z,E)-9,12-tetradecadien-1-y1 acetate, Z-7-tetradecen-2-one, Z-9-tetradecen-1-
y1
acetate, Z-11-tetradecenal, Z-11-tetradecen-1-ol, extract of Chenopodium
ambrosiodes,
Neem oil, Quillay extract;
L5) Microbial pesticides with plant stress reducing, plant growth regulator,
plant growth
promoting and/or yield enhancing activity: A. lipoferum, A. irakense, A.
halopraeferens,
B. 149oningense, B. lupin!, Delftia acidovorans, Glornus intraradkes,
Mesorhizobium sp.,
Rhizobium legurninosarum by. phaseoli, R. I. by. trifolii, R. I. by. viciae,
Sinorhizobium
in synergistically effective amounts.
In a preferred embodiment of this invention compound I is compound i) of
formula (I).
CF3
CH F 0 Br C F3
I 3
0 C F3
(I)
Compound i) of formula (I) is also named Compound I of formula (I).
Moreover, it has been found that simultaneous, that is joint or separate,
application of one
active carboxamide compound (I) and one or more biopesticide(s) II or
successive application
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(that is immediately one after another and thereby creating the mixture "in-
situ" on the desired
location, as e.g. the plant) of one active carboxamide compound I and one or
more
biopesticide(s) II allows enhanced control of pests compared to the control
rates that are
possible with the individual compounds. Therefore, the term "mixture" as used
herein is
intended to include also combinations.
The present invention also relates to a seed treatment composition comprising
a mixture of the
active carboxamide compound I and at least one biopesticide II as defined
above as well as at
least one auxiliary.
The present invention also relates to the use of the mixture of the active
carboxamide
compound I and at least one biopesticide II for protecting a plant, plant
propagation material, or
soil or water, in which the plants are growing, against the attack or
infestation by invertebrate
pests. In particular, the present invention relates to the use of the mixture
of the active
carboxamide compound I and at least one biopesticide II for protecting plant
propagation
material, preferably seeds, from soil insects and the seedlings' roots and
shoots from soil and
foliar insects, wherein the plant progagation material as e.g. the seeds are
contacted with a
pesticidally effective amount of the mixture before sowing and/or after
pregermination.
The present invention further relates to a method for controlling invertebrate
pests, which
method comprises contacting the plant or the plant propagation material or the
soil; the pests or
their food supply, habitat or breeding grounds, with a pesticidally effective
amount of the mixture
of the active carboxamide compound I and at least one biopesticide II.
The present invention further relates to a method for controlling nematodes,
which method
comprises contacting the plant or the plant propagation material, such as the
seeds, or the soil;
the pests or their food supply, habitat or breeding grounds, with a
pesticidally effective amount
of the mixture of the active carboxamide compound I and at least one
biopesticide II with
nematicidal activity.
The invention also provides seeds comprising the mixture of at least one
active compound I
and at least one biopesticide II.
The mixture(s) of at least one active compound selected from compound i) of
formula I,
compound ii) of formula la or mixtures comprising i) and ii) with at least one
biopesticide II are
herein referred to as "mixture(s) according to the invention" or "mixture(s)
of the invention",
wherein the compounds selected from compound i) of formula I, compound ii) of
formula la or
mixtures comprising i) and ii) are understood to include their stereoisomers,
salts, tautomers or
N-oxides, or a polymorphic crystalline form, a co-crystal or a solvate of a
compound or a
stereoisomer, salt, tautomer or N-oxide thereof.
In a specific embodiment, the mixture according to the invention is a mixture
of one active
compound selected from compound i) of formula I, compound ii) of formula la or
mixtures
comprising i) and ii), preferably compound i) of formula I with one
biopesticide ll (binary
mixture).
In another embodiment, the mixture according to the invention is a mixture of
one active
compound selected from compound i) of formula I, compound ii) of formula la or
mixtures
comprising i) and ii), preferably compound i) of formula I with at least one
biopesticide II.
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In yet another embodiment, the mixture according to the invention is a mixture
of one active
compound selected from compound i) of formula I, compound ii) of formula la or
mixtures
comprising i) and ii), preferably compound i) of formula I with one
biopesticide II and another
insecticidal active compound III (ternary mixture).
In yet another embodiment, the mixture according to the invention is a mixture
of one active
compound selected from compound i) of formula I, compound ii) of formula la or
mixtures
comprising i) and ii), preferably compound i) of formula I with one
biopesticide II and one
fungicidal active compound III (ternary mixture).
The term "composition(s) according to the invention" or "composition(s) of the
present
.. invention" encompasses composition(s) comprising the mixtures of the
invention, i.e. mixtures
of the compounds selected from compound i) of formula I, compound ii) of
formula la or
mixtures comprising i) and ii), preferably compound i) of formula I with at
least one biopesticide
II for being used and/or applied in methods according to the invention as
defined herein,
wherein the compounds selected from compound i) of formula I, compound ii) of
formula la or
mixtures comprising i) and ii), preferably compound i) of formula I are
understood to include
their stereoisomers, salts, tautomers or N-oxides, or a polymorphic
crystalline form, a co-crystal
or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide
thereof.
Compound I
Carboxamide derivatives showing generally pesticidal activity have been
described
previously. W0200573165 and W02010018714 describe carboxamide compounds, their
preparation and their use as pest control agents. W02007013150, JP2011-157294,
JP2011-
157295 and JP2011-157296 describe mixtures of carboxamides with other active
ingredients.
Preparation of the carboxamide compound of formula I can further be
accomplished
according to standard methods of organic chemistry, e.g. by the methods or
working examples
described in WO 2010/018857 without being limited to the routes given therein.
The carboxamide compound i of formula I, which has been provisionally approved
under the
common name broflanilide, has been described in combination with fungicidal
active
compounds in PCT/EP2014/072189 or with insecticidal active compounds in
PCT/EP2014/072183.
The synthesis of carboxamide compound ii of formula la, which is also known
under the name
desmethyl-broflanilide, and/or similar compounds has been described in
US8686044 (inter alia
columns 75 to 76) and EP1714958A1.
However, individual mixtures of the carboxamide compound I of formula I with
selected
biopesticides have not been described previously.
The prior art does not disclose pesticidal mixtures comprising such selected
carboxamide
compound according to the present invention showing unexpected and synergistic
effects in
combination with biopestiocides.
The compound selected from compound i) of formula I, compound ii) of formula
la or mixtures
comprising i) and ii), preferably compound i) of formula I includes its
tautomers, racemic
mixtures, individual pure enantiomers and diasteroemers and the optically
active mixtures.
The term "compound of formula l" or "compound I according to the invention" or
"component
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1" comprises the compound as defined herein as well as a stereoisomer, salt,
tautomer or N-
oxide thereof. The term "compound of the present invention" is to be
understood as equivalent
to the term "compound according to the invention", therefore also comprising a
stereoisomer,
salt, tautomer or possibly N-oxide thereof.
Compounds II
Biopesticides have been defined as a form of pesticides based on micro-
organisms (bacteria,
fungi, viruses, nematodes, etc.) or natural products (compounds, such as
metabolites, proteins,
or extracts from biological or other natural sources) (U.S. Environmental
Protection Agency:
http://wvvvv.epa.gov/pesticides/biopesticides/). Biopesticides fall into two
major classes,
microbial and biochemical pesticides:
(1) Microbial pesticides consist of bacteria, fungi or viruses (and often
include the metabolites
that bacteria and fungi produce). Entomopathogenic nematodes are also
classified as microbial
pesticides, even though they are multi-cellular.
(2) Biochemical pesticides are naturally occurring substances or or
structurally-similar and
functionally identical to a naturally-occurring substance and extracts from
biological sources that
control pests or provide other crop protection uses as defined below, but have
non-toxic mode
of actions (such as growth or developmental regulation, attractents,
repellents or defence
activators (e.g. induced resistance) and are relatively non-toxic to mammals.
The biopesticides from group L1) and/or L2) may also have insecticidal,
acaricidal,
molluscidal, pheromone, nematicidal, plant stress reducing, plant growth
regulator, plant growth
promoting and/or yield enhancing activity. The biopesticides from group L3)
and/or L4) may also
have fungicidal, bactericidal, viricidal, plant defense activator, plant
stress reducing, plant
growth regulator, plant growth promoting and/or yield enhancing activity. The
biopesticides from
group L5) may also have fungicidal, bactericidal, viricidal, plant defense
activator, insecticidal,
acaricidal, molluscidal, pheromone and/or nematicidal activity.
Many of these biopesticides have been deposited under deposition numbers
mentioned herein
(the prefices such as ATCC or DSM refer to the acronym of the respective
culture collection, for
details see e. g. here: http://www. wfcc.infoiccinfo/collection/by_acronymi),
are referred to in
literature, registered and/or are commercially available: mixtures of
Aureobasidium pullulans
DSM 14940 and DSM 14941 isolated in 1989 in Konstanz, Germany (e. g.
blastospores in
Blossom Protect from bio-ferm GmbH, Austria), Bacillus amyloliquefaciens
strain AP-188
(NRRL B-50615 and B-50331; US 8,445,255); B. amyloliquefaciensspp. plantarum
D747
isolated from air in Kikugawa-shi, Japan (US 20130236522 Al; FERM BP-8234; e.
g. Double
Nickel TM 55 WDG from Certis LLC, USA), B. amyloliquefaciensspp. plantarum
FZB24 isolated
from soil in Brandenburg, Germany (also called 5B3615; DSM 96-2; J. Plant Dis.
Prot. 105,
181-197, 1998; e.g. Taegro from Novozyme Biologicals, Inc., USA), B.
amyloliquefaciens
ssp. plantarum FZB42 isolated from soil in Brandenburg, Germany (DSM 23117; J.
Plant Dis.
Prot. 105, 181-197, 1998; e.g. RhizoVital 42 from AbiTEP GmbH, Germany), B.
amyloliquefaciensssp. plantarum MBI600 isolated from faba bean in Sutton
Bonington,
Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRL B-50595;
US 2012/0149571 Al; e. g. Integral from BASF Corp., USA), B.
amyloliquefaciensspp.
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plantarum QST-713 isolated from peach orchard in 1995 in California, U.S.A.
(NRRL B-21661;
e. g. Serenade MAX from Bayer Crop Science LP, USA), B. amyloliquefaciensspp.
plantarum
TJ1000 isolated in 1992 in South Dakoda, U.S.A. (also called 1BE; ATCC BAA-
390; CA
2471555 Al; e.g. QuickRoots TM from TJ Technologies, Watertown, SD, USA), B.
firrnus CNCM
1-1582, a variant of parental strain EIP-N1 (CNCM 1-1556) isolated from soil
of central plain area
of Israel (WO 2009/126473, US 6,406,690; e. g. Votivo0 from Bayer CropScience
LP, USA), B.
pumilus GHA 180 isolated from apple tree rhizosphere in Mexico (IDAC 260707-
01; e. g. PRO-
MIX BX from Premier Horticulture, Quebec, Canada), B. purnilus INR-7
otherwise referred to
as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by
Erwinia
tracheiphlla (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumllusKFP9F
isolated from
the rhizosphere of grasses in South Africa at least before 2008 (NRRL B-50754;
WO 2014/029697; e. g. BAC-UP or FUSION-P from BASF Agricultural Specialities
(Pty) Ltd.,
South Africa), B. pumilus CIST 2808 was isolated from soil collected in
Pohnpei, Federated
States of Micronesia, in 1998 (NRRL B-30087; e. g. Sonata or Ballade Plus
from Bayer Crop
Science LP, USA), B. simplex ABU 288 (NRRL B-50304; US 8,445,255), B. subtilis
FB17 also
called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC
PTA-11857;
System. Appl. Microbial. 27, 372-379, 2004; US 2010/0260735; WO 2011/109395);
B. thurin-
ssp. aizawaiABTS-1857 isolated from soil taken from a lawn in Ephraim,
Wisconsin,
U.S.A., in 1987 (also called ABG-6346; ATCC SD-1372; e. g. XenTari from BioFa
AG,
Miinsingen, Germany), B. t ssp. kurstaki ABTS-351 identical to HD-1 isolated
in 1967 from
diseased Pink Bollworm black larvae in Brownsville, Texas, U.S.A. (ATCC SD-
1275; e. g.
Dipel DF from Valent BioSciences, IL, USA), B. t. ssp. kurstak iSB4 isolated
from E
saccharine larval cadavers (NRRL B-50753; e. g. Beta Pro from BASF
Agricultural Specialities
(Pty) Ltd., South Africa), B. t. ssp. tenebrionis NB-176-1, a mutant of strain
NB-125, a wild type
strain isolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM
5480; EP 585 215
BI; e. g. Novodore from Valent BioSciences, Switzerland), Beauveria bassiana
GHA (ATCC
74250; e. g. BotaniGarde 22WGP from Laverlam Int. Corp., USA), B. bassiana JW-
1 (ATCC
74040; e. g. Naturalis0 from CBC (Europe) S.r.I., Italy), B. bassiana PPRI
5339 isolated from
the larva of the tortoise beetle Conchyloctenia punctata (NRRL 50757; e. g.
BroadBand from
BASF Agricultural Specialities (Pty) Ltd., South Africa), Burkhokieria sp.
A396 isolated from soil
in Nikko, Japan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio
Innovations, Inc.,
USA), Coniothyrium minitans CON/M/91-08 isolated from oilseed rape (WO
1996/021358; DSM
9660; e. g. Contans WG, Intercept WG from Bayer CropScience AG, Germany),
harpin
(alpha-beta) protein (Science 257, 85-88, 1992; e. g. MessengerTM or HARP-N-
Tek from Plant
Health Care plc, U.K.), Helicoverpa armigera nucleopolyhedrovirus (HearNPV)
(J. Invertebrate
Pathol, 107, 112-126, 2011; e.g. Helicovex from Adermatt Biocontrol,
Switzerland;
Diplomata from Koppert, Brazil; Vivus Max from AgBiTech Pty Ltd.,
Queensland, Australia),
Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (e.g. Gemstar
from Certis
LLC, USA), Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e. g. Heligen from
AgBiTech
Pty Ltd., Queensland, Australia), Heterorhabditis bacteribphora (e. g. Nemasys
G from BASF
Agricultural Specialities Limited, UK), lsaria fumosorosea Apopka-97 isolated
from mealy bug
on gynura in Apopka, Florida, U.S.A. (ATCC 20874; Biocontrol Science Technol.
22(7), 747-
761, 2012; e.g. PFR-97TM or PreFeRal from Certis LLC, USA), Metarhizium
aniSopliae var.
am:sopliae F52 also called 275 or V275 isolated from codling moth in Austria
(DSM 3884, ATCC
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90448; e. g. Met520 Novozymes Biologicals BioAg Group, Canada), Metschnikowia
fructicola
277 isolated from grapes in the central part of Israel (US 6,994,849; NRRL Y-
30752; e. g.
formerly Shemer0 from Agrogreen, Israel), Paecilomyces fiacinus 251 isolated
from infected
nematode eggs in the Philippines (AGAL 89/030550; W01991/02051; Crop
Protection 27, 352-
361, 2008; e. g. BioActefrom Bayer CropScience AG, Germany and MeloCon from
Certis,
USA), Paembacillus alveiNAS6G6 isolated from the rhizosphere of grasses in
South Africa at
least before 2008 (WO 2014/029697; NRRL B-50755; e.g. BAC-UP from BASF
Agricultural
Specialities (Pty) Ltd., South Africa), Pasteuria nishizawae Pnl isolated from
a soybean field in
the mid-2000s in Illinois, U.S.A. (ATCC SD-5833; Federal Register 76(22),
5808, February 2,
2011; e.g. ClarivaTM PN from Syngenta Crop Protection, LLC, USA), Pen/cilium
bilaiae (also
called P. &lab) strains ATCC 18309 (= ATCC 74319), ATCC 20851 and/or ATCC
22348 (=
ATCC 74318) originally isolated from soil in Alberta, Canada (Fertilizer Res.
39, 97-103, 1994;
Can. J. Plant Sci. 78(1), 91-102, 1998; US 5,026,417, WO 1995/017806; e. g.
Jump Start ,
Provide from Novozymes Biologicals BioAg Group, Canada), Reynoutria
sachalinensis extract
(EP 0307510 BI; e.g. Regalia SC from Marrone Biolnnovations, Davis, CA, USA
or Milsana
from BioFa AG, Germany), Steinemema carpocapsae (e. g. Millenium from BASF
Agricultural
Specialities Limited, UK), S. feltiae (e. g. Nemashield from BioWorks, Inc.,
USA; Nemasys
from BASF Agricultural Specialities Limited, UK), Streptomyces microfiavus
NRRL B-50550
(WO 2014/124369; Bayer CropScience, Germany), Trichocterma asperelloides JM41R
isolated
in South Africa (NRRL 50759; also referred to as T fertile; e. g. Trichoplus
from BASF
Agricultural Specialities (Pty) Ltd., South Africa), T harzianum T-22 also
called KRL-AG2
(ATCC 20847; BioControl 57, 687-696, 2012; e. g. Plantshield from BioWorks
Inc., USA or
SabrExTM from Advanced Biological Marketing Inc., Van Wert, OH, USA).
Preferred biopesticides, which have been deposited under deposition numbers
mentioned
herein (the prefices such as ATCC or DSM refer to the acronym of the
respective culture
collection, for details see e. g. here: http://www.
wfcc.info/ccinfo/collection/by_acronym/), are
referred to in literature, registered and/or are commercially available:
mixtures of Aureobasidium
pullulans DSM 14940 and DSM 14941 isolated in 1989 in Konstanz, Germany (e.g.
blastospores in BlossomProtect from bio-ferm GmbH, Austria), Bacillus
amyloliquefaciens
strain AP-188 (NRRL B-50615 and B-50331; US 8,445,255); B.
amyloliquefaciensspp.
plantarum D747 isolated from air in Kikugawa-shi, Japan (US 20130236522 Al;
FERM
BP-8234; e. g. Double NickelTM 55 WDG from Certis LLC, USA), B.
amyloliquefaciensspp.
plantarum FZB24 isolated from soil in Brandenburg, Germany (also called
5B3615; DSM 96-2;
J. Plant Dis. Prot. 105, 181-197, 1998; e.g. Taegro from Novozyme
Biologicals, Inc., USA), B.
amyloliquefaciensssp. plantarum FZB42 isolated from soil in Brandenburg,
Germany (DSM
23117; J. Plant Dis. Prot. 105, 181-197, 1998; e.g. RhizoVital 42 from AbiTEP
GmbH,
Germany), B. amyloliquefaciensssp. plantarum MBI600 isolated from faba bean in
Sutton
Bonington, Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRL
B-50595;
US 2012/0149571 Al; e.g. Integral from BASF Corp., USA), B.
amyloliquefaciensspp.
plantarum QST-713 isolated from peach orchard in 1995 in California, U.S.A.
(NRRL B-21661;
e. g. Serenade MAX from Bayer Crop Science LP, USA), B. amyloliquefaciensspp.
plantarum
TJ1000 isolated in 1992 in South Dakoda, U.S.A. (also called 1BE; ATCC BAA-
390; CA
2471555 Al; e.g. QuickRoots TM from TJ Technologies, Watertown, SD, USA), B.
firmus CNCM
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1-1582, a variant of parental strain EIP-N1 (CNCM 1-1556) isolated from soil
of central plain area
of Israel (WO 2009/126473, US 6,406,690; e. g. Votivo from Bayer CropScience
LP, USA), B.
pumilus GHA 180 isolated from apple tree rhizosphere in Mexico (IDAC 260707-
01; e. g. PRO-
MIX BX from Premier Horticulture, Quebec, Canada), B. pumllus INR-7 otherwise
referred to
as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by
Erwima
trachelphlla(NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumllus QST 2808
was
isolated from soil collected in Pohnpei, Federated States of Micronesia, in
1998 (NRRL
B-30087; e. g. Sonata or Ballad Plus from Bayer Crop Science LP, USA), B.
simplex ABU
288 (NRRL B-50304; US 8,445,255), B. subtllis FB17 also called UD 1022 or UD10-
22 isolated
from red beet roots in North America (ATCC PTA-11857; System. Appl. Microbiol.
27, 372-379,
2004; US 2010/0260735; WO 2011/109395); B. thuringlensisssp. aizawai ABTS-1857
isolated
from soil taken from a lawn in Ephraim, Wisconsin, U.S.A., in 1987 (also
called ABG-6346;
ATCC SD-1372; e.g. XenTari from BioFa AG, Munsingen, Germany), B. t. ssp.
kurstaki
ABTS-351 identical to HD-1 isolated in 1967 from diseased Pink Bollworm black
larvae in
Brownsville, Texas, U.S.A. (ATCC SD-1275; e. g. Dipel DF from Valent
BioSciences, IL,
USA), B. t. ssp. tenebrionhs NB-176-1, a mutant of strain NB-125, a wild type
strain isolated in
1982 from a dead pupa of the beetle Tenebrio molitor (DSM 5480; EP 585 215 BI;
e. g.
Novodor from Valent BioSciences, Switzerland), Beauvena bassiana GHA (ATCC
74250; e. g.
BotaniGarde 22WGP from Laverlam Int. Corp., USA), B. bassiana JW-1 (ATCC
74040; e. g.
Naturalis from CBC (Europe) S.r.I., Italy), Burkholderia sp. A396 isolated
from soil in Nikko,
Japan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc.,
USA),
Coniothyrium min/tans CON/M/91-08 isolated from oilseed rape (WO 1996/021358;
DSM 9660;
e. g. Contans WG, Intercept WG from Bayer CropScience AG, Germany), harpin
(alpha-
beta) protein (Science 257, 85-88, 1992; e. g. MessengerTM or HARP-N-Tek from
Plant Health
Care plc, U.K.), Hetkoverpa armigera nucleopolyhedrovirus (HearNPV) (J.
Invertebrate Pathol.
107, 112-126, 2011; e. g. Helicovex from Adermatt Biocontrol, Switzerland;
Diplomata from
Koppert, Brazil; Vivus Max from AgBiTech Pty Ltd., Queensland, Australia),
Helkoverpa zea
single capsid nucleopolyhedrovirus (HzSNPV) (e. g. Gemstar0 from Certis LLC,
USA),
Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e. g. Heligen from AgBiTech
Pty Ltd.,
Queensland, Australia), Heterorhabdigs bacteriophora (e. g. Nemasys G from
BASF
Agricultural Specialities Limited, UK), lsaria fumosorosea Apopka-97 isolated
from mealy bug
on gynura in Apopka, Florida, U.S.A. (ATCC 20874; Biocontrol Science Technol.
22(7), 747-
761, 2012; e.g. PFR-97TM or PreFeRal from Certis LLC, USA), Metarhizium
am:sopliae var.
anisopliae F52 also called 275 or V275 isolated from codling moth in Austria
(DSM 3884, ATCC
90448; e. g. Met520 Novozymes Biologicals BioAg Group, Canada), Metschnikowla
fructicola
277 isolated from grapes in the central part of Israel (US 6,994,849; NRRL Y-
30752; e. g.
formerly Shemer from Agrogreen, Israel), Paecllomyces llacinus 251 isolated
from infected
nematode eggs in the Philippines (AGAL 89/030550; W01991/02051; Crop
Protection 27, 352-
361, 2008; e. g. BioAct0from Bayer CropScience AG, Germany and MeloCon0 from
Certis,
USA), Pasteuna nishizawae Pnl isolated from a soybean field in the mid-2000s
in Illinois,
U.S.A. (ATCC SD-5833; Federal Register 76(22), 5808, February 2, 2011; e.g.
Clariva TM PN
from Syngenta Crop Protection, LLC, USA), Pen/all//urn bilaiae (also called P.
Wail) strains
ATCC 18309 (= ATCC 74319), ATCC 20851 and/or ATCC 22348 (= ATCC 74318)
originally
isolated from soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can.
J. Plant Sci. 78(1),
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91-102, 1998; US 5,026,417, WO 1995/017806; e.g. Jump Start , Provide from
Novozymes
Biologicals BioAg Group, Canada), Reynoutria sachalinensis extract (EP 0307510
B1; e. g.
Regalia SC from Marrone Biolnnovations, Davis, CA, USA or Milsana from BioFa
AG,
Germany), Steinernema carpocapsae (e. g. Millenium from BASF Agricultural
Specialities
Limited, UK), S. feltiae (e.g. Nemashield from BioWorks, Inc., USA; Nemasys
from BASF
Agricultural Specialities Limited, UK), Streptomyces microtlavus NRRL B-50550
(WO 2014/124369; Bayer CropScience, Germany), T harzianum T-22 also called KRL-
AG2
(ATCC 20847; BioControl 57, 687-696, 2012; e. g. Plantshield from BioWorks
Inc., USA or
SabrExTM from Advanced Biological Marketing Inc., Van Wert, OH, USA).
Preferred biopesticides on strain level are selected from the following groups
L1) to L5):
L1) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant
defense activator
activity: Aureobasidium pullulans DSM 14940 and DSM 14941 (L1.1), Bacillus
amyloliquefaciens AP-188 (L.1.2), B. amyloliquefaciens ssp. plantarum D747
(L.1.3), B.
amyloliquefaciensssp. plantarum FZB24 (L.1.4), B. amyloliquefaciensssp.
plantarum
FZB42 (L.1.5), B. amyloliquefaciensssp. plantarum MBI600 (L.1.6), B.
amyloliquefaciensssp. plantarum QST-713 (L.1.7), B. amyloliquefaciensssp.
plantarum
TJ1000 (L.1.8), B. pumilus GB34 (L.1.9), B. pumflus GHA 180 (L.1.10), B.
pumflus INR-7
(L.1.11), B. pumflus KFP9F (L.1.12), B. pumflus QST 2808 (L.1.13), B. simplex
ABU 288
(L.1.14), B. subtilis FB17 (L.1.15), Coniothyrium minitans CON/M/91-08
(L.1.16),
Metschnikowia fructicola NRRL Y-30752 (L.1.17), Paembacillus alvei NAS6G6
(L.1.18),
Penicillium bflaiae ATCC 22348 (L.1.19), P. bilaiae ATCC 20851 (L.1.20),
Penicfflium
bilaiae ATCC 18309 (L.1.21), Streptomyces microflavus NRRL B-50550 (L.1.22),
Trichoderma asperelloides JM41R (L.1.23), T harzianum T-22 (L.1.24);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or
plant defense
activator activity: harpin protein (L.2.1), Reynoutria sachalinensi:s extract
(L.2.2);
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or
nematicidal activity:
Bacillus firmusl-1582 (L.3.1); B. thuringiensisssp. aizawai ABTS-1857 (L.3.2),
B. t. ssp.
kurstaki ABTS-351 (L.3.3), B. t. ssp. kurstakiSB4 (L.3.4), B. t. ssp.
tenebrionis NB-176-1
(L.3.5), Beauveria bassiana GHA (L.3.6), B. bassiana JW-1 (L.3.7), B. bassiana
PPRI
5339 (L.3.8), Burkholderia sp. A396 (L.3.9), Helicoverpa armIgera
nucleopolyhedrovirus
(HearNPV) (L.3.10), Helicoverpa zea nucleopolyhedrovirus (HzNPV) ABA-NPV-U
(L.3.11), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV)
(L.3.12),
Heterohabditis bacteriophora (L.3.13), Isaria fumosorosea Apopka-97 (L.3.14),
Metarhizium anisopliae var. anisopliae F52 (L.3.15), Paecilomyces Iflacinus
251 (L.3.16),
Pasteuria nishizawae Pnl (L.3.17), Steinernema carpocapsae (L.3.18), S.
feltiae
(L.3.19);
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal,
pheromone and/or
nematicidal activity: cis-jasmone (L.4.1), methyl jasmonate (L.4.2), Quillay
extract
(L.4.3);
L5) Microbial pesticides with plant stress reducing, plant growth regulator,
plant growth
promoting and/or yield enhancing activity
in particular from
L1) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant
defense activator
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activity: Aureobasidium pullulans DSM 14940 and DSM 14941 (L1.1), Bacillus
amyloliquefaciens AP-188 (L.1.2), B. amyloliquefaciensssp. plantarum D747
(L.1.3), B.
amyloliquefaciensssp. plantarum FZB24 (L.1.4), B. amyloliquefaciensssp.
plantarum
FZB42 (L.1.5), B. amyloliquefaciensssp. plantarum MB1600 (L.1.6), B.
amyloliquefaciensssp. plantarum QST-713 (L.1.7), B. amyloliquefaciensssp.
plantarum
TJ1000 (L.1.8), B. pumilus GB34 (L.1.9), B. pumilus GHA 180 (L.1.10), B.
pumilus INR-7
(L.1.11), B. pumllus QST 2808 (L.1.13), B. simplex ABU 288 (L.1.14), B.
subtllis FB17
(L.1.15), Coniothyrium min/tans CON/M/91-08 (L.1.16), Metschnikowia fructicola
NRRL
Y-30752 (L.1.17), Penicillium bllaiae ATCC 22348 (L.1.19), P. bllaiae ATCC
20851
(L.1.20), Penicillium bllaiae ATCC 18309 (L.1.21), Streptomyces microtlavus
NRRL B-
50550 (L.1.22), T harzianum T-22 (L.1.24);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or
plant defense
activator activity: harpin protein (L.2.1), Reynoutria sachalinensis extract
(L.2.2);
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or
nematicidal activity:
Bacillus firmusl-1582 (L.3.1); B. thuringiensi:sssp. aizawai ABTS-1857
(L.3.2), B. t. ssp.
kurstaki ABTS-351 (L.3.3), B. t. ssp. tenebrioni:s NB-176-1 (L.3.5), Beauveria
bassiana
GHA (L.3.6), B. bassiana JW-1 (L.3.7), Burkholderia sp. A396 (L.3.9),
Helicoverpa
armigera nucleopolyhedrovirus (HearNPV) (L.3.10), Helicoverpa zea
nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.11), Helicoverpa zea single capsid
nucleopolyhedrovirus (HzSNPV) (L.3.12), Heterohabditis bacteriophora (L.3.13),
lsaria
fumosorosea Apopka-97 (L.3.14), Metarhizium anisopliae var. anisopliae F52
(L.3.15),
Paecllomyces lilacinus 251 (L.3.16), Pasteuria nishizawae Pn1 (L.3.17),
Steinernema
carpocapsae (L.3.18), S. feltiae (L.3.19);
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal,
pheromone and/or
nematicidal activity: cis-jasmone (L.4.1), methyl jasmonate (L.4.2), Quillay
extract
(L.4.3).
Preference is also given to mixtures comprising as pesticide!! (component 2) a
biopesticide
selected from the groups L1), L3) and L5), preferably selected from strains
denoted above as
(L.1.2), (L.1.3), (L.1.4), (L.1.5), (L.1.6), (L.1.7), (L.1.8), (L.1.10),
(L.1.11), (L.1.12), (L.1.13),
(L.1.14), (L.1.15), (L.1.17), (L.1.18), (L.1.19), (L.1.20), (L.1.21), (L.3.1);
(L.3.9), (L.3.16),
(L.3.17), (L.5.1), (L.5.2), (L.5.3), (L.5.4), (L.5.5), (L.5.6), (L.5.7),
(L.5.8); (L.4.2), and (L.4.1);
even more preferably selected from (L.1.2), (L.1.6), (L.1.7), (L.1.8),
(L.1.11), (L.1.12), (L.1.13),
(L.1.14), (L.1.15), (L.1.18), (L.1.19), (L.1.20), (L.1.21), (L.3.1); (L.3.9),
(L.3.16), (L.3.17), (L.5.1),
(L.5.2), (L.5.5), (L.5.6), (L.4.2), and (L.4.1). Preference is also fiven to
mixtures comprising as
pesticide 11 (component 2) a biopesticide selected from strains (L.1.2),
(L.1.3), (L.1.4), (L.1.5),
(L.1.6), (L.1.7), (L.1.8), (L.1.10), (L.1.11), (L.1.13), (L.1.14), (L.1.15),
(L.1.17), (L.1.19), (L.1.20),
(L.1.21), (L.3.1); (L.3.9), (L.3.16), (L.3.17), (L.4.2), and (L.4.1); even
more preferably selected
from (L.1.2), (L.1.6), (L.1.7), (L.1.8), (L.1.11), (L.1.13), (L.1.14),
(L.1.15), (L.1.19), (L.1.20),
(L.1.21), (L.3.1); (L.3.9), (L.3.16), (L.3.17), (L.4.2), and (L.4.1). These
mixtures are particularly
suitable for treatment of propagation mateials, i. e. seed treatment purposes
and likewise for
soil treatment. These seed treatment mixtures are particularly suitable for
crops such as
cereals, corn and leguminous plants such as soybean.
Preference is also given to mixtures comprising as pesticide!! (component 2) a
biopesticide
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selected from the groups L1), L3) and L5), preferably selected from strains
denoted above as
(L1.1), (L.1.2), (L.1.3), (L.1.6), (L.1.7), (L.1.9), (L.1.11), (L.1.12),
(L.1.13), (L.1.14), (L.1.15),
(L.1.17), (L.1.18), (L.1.22), (L.1.23), (L.1.24), (L2.2); (L3.2), (L3.3),
(L3.4), (L3.5), (L3.6),
(L.3.7), (L.3.8), (L.3.10), (L.3.11), (L.3.12), (L.3.13), (L.3.14), (L.3.15),
(L.3.18), (L.3.19); (L.4.2),
even more preferably selected from (L.1.2), (L.1.7), (L.1.11), (L.1.13),
(L.1.14), (L.1.15),
(L.1.18), (L.1.23), (L.3.3), (L.3.4), (L.3.6), (L.3.7), (L.3.8), (L.3.10),
(L.3.11), (L.3.12), (L.3.15),
and (L.4.2). Preference is also fiven to mixtures comprising as pesticide II
(component 2) a
biopesticide selected from strains (L1.1), (L.1.2), (L.1.3), (L.1.6), (L.1.7),
(L.1.9), (L.1.11),
(L.1.13), (L.1.14), (L.1.15), (L.1.17), (L.1.22), (L.1.24), (L.2.2); (L.3.2),
(L.3.3), (L.3.5), (L.3.6),
(L3.7), (L.3.10), (L.3.11), (L.3.12), (L.3.13), (L.3.14), (L.3.15), (L.3.18),
(L.3.19); (L.4.2), even
more preferably selected from (L.1.2), (L.1.7), (L.1.11), (L.1.13), (L.1.14),
(L.1.15), (L.3.3),
(L.3.6), (L.3.7), (L.3.10), (L.3.11), (L.3.12), (L.3.15), and (L.4.2).These
mixtures are particularly
suitable for foliar treatment. These mixtures for foliar treatment are
particularly suitable for
vegetables, fruits, vines, cereals, corn, leguminous crops such as soybeans.
For biopesticides II selected from groups L1, L3, and L5, the mixtures of the
invention
embrace not only the isolated, pure cultures of the respective microorganisms
as defined
herein, but also its cell-free extract having pesticidal activity, preferably
a ketone-based extract,
its suspensions in a whole broth culture or as a metabolite-containing
supernatant or a purified
metabolite obtained from a whole broth culture of the microorganism or
microorganism strain.
"Whole broth culture" refers to a liquid culture containing both cells and
media.
"Supernatant" or "culture medium" refers to the liquid broth remaining when
cells grown in
broth are removed by centrifugation, filtration, sedimentation, or other means
well known in the
art.
The term "metabolite" refers to any compound, substance or byproduct
(including but not
limited to small molecule secondary metabolites, polyketides, fatty acid
synthase products, non-
ribosomal peptides, ribosomal peptides, proteins and enzymes) produced by a
microorganism
(such as fungi and bacteria) that has pesticidal activity or improves plant
growth, water use
efficiency of the plant, plant health, plant appearance, or the population of
beneficial
microorganisms in the soil around the plant activity.
The term "mutant" refers to a microorganism, obtained by direct mutant
selection but also
includes microorganisms that have been further mutagenized or otherwise
manipulated (e. g.,
via the introduction of a plasmid). Accordingly, embodiments include mutants,
variants, and or
derivatives of the respective microorganism, both naturally occurring and
artificially induced
mutants. For example, mutants may be induced by subjecting the microorganism
to known
mutagens, such as N-methyl-nitrosoguanidine, using conventional methods.
Preferably such
mutants retain the pesticidal activity of the respective microorganism.
Preferences
In addition to the above defined compound selected from compound i) of formula
I, compound
ii) of formula la or mixtures comprising i) and ii), preferably compound i) of
formula I, the
pesticidal mixtures of the invention comprise a component 2), which is a
biopesticide II, which is
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selected from the groups L1 to L5 as defined above. Preferred biopesticides II
are defined
hereinafter.
The preferred embodiments regarding biopesticides II, which may be selected as
component
2) of the mixtures of the invention, are to be understood as preferred on
their own as well as
preferably in combination with the preferred embodiments of the compounds of
formula I, i.e.
component 1) of the mixture of the invention, and, where applicable, as well
as concerning the
uses and methods according to the invention and the compositions according to
the invention.
Preference is given to mixtures comprising as biopesticide II (component 2) a
biopesticide
selected from group L1, preferably selected from Bacillus
amyloliquefaciensherein even more
preferably from strains AP-136, AP-188, AP-218, AP-219, AP-295, IN937a, IT-45;
B.
amyloliquefaciensssp. plantarum (formerly called B. subtllis or B.
subtllisspp.
amyloliquefaciens) herein even more preferably from strains MBI600, D747,
FZB24, FZB42,
GB03, QST-713 and TJ1000; B. mojavensis AP-209; B. pumilus herein even more
preferably
from strains GHA 180, INR-7, KFP9F and QST 2808; B. simplex herein more
preferably strain
ABU 288; B. solisalsi herein more preferably strain AP-217; B. subtigs herein
even more
preferably selected from strains CX-9060, FBI 7 and GB07; Muscootor albus
herein more
preferably strains QST 20799 and SA-13; Paembacillus alvei herein more
preferably strain
NAS6G6, Paenibacfflus polymyxa herein more preferably strain PKB1, Pen/cu//urn
bilaiae
herein more preferably strains ATCC 22348, ATCC 20581 and ATCC 18309;
Pseudomonas
fluorescens herein more preferably strain A506; Sphaerodes mycoparasitica
herein more
preferably strain SMCD2220; Trichoderma fertile herein more preferably strain
JM41R; Tricho-
derma harzianum herein more preferably strain T-22; Trkhoderma virens herein
more
preferably strais GI-3 and G-41.
Preference is also given to mixtures comprising as biopesticide 11 (component
2) a biopesticide
selected from group L1, even more preferably selected from B.
amyloliquefaciens AP-188, B.
amyloliquefaciensssp. plantarum MBI600, B. amyloliquefaciens ssp. plantarum
QST-713, B.
pumllus IN R-7, B. pumllusQST 2808, B. simplex ABU 288, B. subtllis FB17,
Paenibacillus alvei
NAS6G6 and Trichoderma fertile JM41R.
According to one embodiment of the inventive mixtures, the at least one
biopesticide II is
Bacillus amyloliquefaciensssp. plantarum MBI600. These mixtures are
particularly suitable in
soybean.
According to another embodiment of the inventive mixtures, the at least one
biopesticide II is
B. pumllus INR-7. These mixtures are particularly suitable in soybean and
corn.
According to a further embodiment, the at least one biopesticide II is
Bacillus simplex,
preferably B. simplex ABU 288. These mixtures are particularly suitable in
soybean and corn.
According to a further embodiment, the at least one biopesticide II is
Bacillus subtllis,
preferably B. subtilis strain FB17.
According to one embodiment of the inventive mixtures, the at least one
biopesticide II is
selected from Bacillus amyloliquefaciens AP-136, B. amyloliquefaciens AP-188,
B.
amyloliquefaciens AP-218, B. amyloliquefaciens AP-219, B. amyloliquefaciens AP-
295, B.
amyloliquefaciensspp. plantarum FZB24, B. amyloliquefaciens ssp. plantarum
FZB42, B.
amyloliquefaciensssp. plantarum TJ1000, B. amyloliquefaciens ssp. plantarum
D747, B.
amyloliquefaciensssp. plantarum MBI600, B. amyloliquefaciens spp. plantarum
GB03, B.
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amyloliquefaciensspp. plantarum QST-713, B. mojavensi:s AP-209, B. pumllus
GB34, B.
pumilus IN R-7, B. pumllus KFP9F, B. pumllus QST 2808, B. pumllus GHA 180, B.
simplex ABU
288, B. solisalsi AP-217, B. subtllis CX-9060, B. subtllis FB17 and B.
subtilis GB07. These
mixtures are particularly suitable in soybean and corn, in particular for seed
treatment.
According to a further embodiment, the at least one pesticide!! is selected
from Streptomyces
spp., preferably from S. griseoviridis, S. lydicus and S. violaceusniger, in
particular from strains
S. griseoviridis K61, S. lyo'icusWYEC 108, S. violaceusnigerXL-2 and S.
violaceusnigerYCED-
9.
According to one embodiment of the inventive mixtures, the at least one
biopesticide 11 is
selected from the following fungi Coniothyrium minitans CON/M/91-08,
Trichoderma fertile
JM41R, T. harzianum T-22, T virens GI-3, T virens GL-21, T virens G-41. These
mixtures are
particularly suitable for seed and/or soil treatment.
According to a further embodiment, the at least one biopesticide 11 is
selected from Pseudo-
monas spp., preferably selected from P. chloraphis herein more preferably
strain MA 342 and
Pseudomonas sp. DSM 13134; P. tluorescens herein more preferably selected from
strains
A506, WCS 374 and Pf-5; and P. putida herein more preferably strain ATCC
202153.
The present invention also relates to mixtures wherein the at least one
biopesticide 11 is
selected from the fungal genus Trichoderma, preferably from the strains T
asperellum T34, T
asperellum SKT-1, T asperellum ICC 012, T. asperellumTV1, I atrovkide L052, T
atrovkide
CNCM 1-1237, T. fertile JM41R, I gamsllICC 080, T. harmatumTH 382, T.
harzianum T-22, T.
harzianum T-35, T. harzianum T-39, T. harzianum T-315; mixture of T. harzianum
I CC012 and
T gamsiil CC080; mixture of T. polysporum and T. harzianum; I stromaticum, I
vkens GI-3,
vkens GL-21, I vkens G-41 and; in particular T. fertile JM41R.
The present invention also relates to mixtures wherein the at least one
biopesticide 11 is
selected from the fungal species Muscodor albus preferably from the strains SA-
13 and QST
20799, which are particularly suiable for soil and seed treatment against soil-
borne pathogens
and/or nematodes.
Preference is given to mixtures comprising as biopesticide 11 (component 2) a
biopesticide
selected from group L3), preferably selected from Bacillus firmus herein
preferably strain 1-1582,
Beauveria bassiana herein preferably selected from strains GHA, H123, DSM
12256 and PPRI
5339; Burkholderia sp. and herein preferably strain A396, Metarhizium
an/sop/lee var. acridum
herein preferably strain IMI 330189, M. an/sop/lee herein preferably selected
from strains Fl-
985, Fl-1045, F52 and ICIPE 69; Paecliomyces lilacinus herein preferably
selected from strains
251, DSM 15169 and BCP2, Paenibacillus popilliae herein preferably selected
from strains
Dutky-1940, KLN 3 and Dutky 1; Pasteuria nishazawa and herein preferably
strain Pn1.
Preference is also given to mixtures comprising as biopesticide 11 (component
2) a biopesticide
selected from group L3), even more preferably from B. bassiana DSM 12256, B.
bassiana PPRI
5339, Metarhizium anisopliae var. acridum I MI 330189, M. anisopliae Fl-985,
M. anisopliae Fl-
1045, Paecilomyces lilacinus DSM 15169, P. Illacinus BCP2, P. lilacinus 251,
Paembacillus
pop//flee Dutky-1940, P. pop//flee KLN 3 and P. popilliae Dutky I.
According to a further embodiment, the at least one biopesticide Ills
Beauveria brongniartii.
According to a further embodiment, the at least one biopesticide Ills
Metarhizium an/sop/lee or
/14. an/sop/lee var. acrid/urn, preferably selected from M. an/sop/lee Fl-
1045, M. an/sop/lee F52,
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/14. anZsopliaevar. acridum strains Fl-985 and IM1330189; in particular strain
1M1330189. These
mixtures are particularly suitable for control of arthropod pests in soybean
and corn.
According to a further embodiment, the at least one biopesticide Ills
Paecllomyces fumoso-
roseus, preferably strain FE 9901 especially for white fly control.
According to a further embodiment, the at least one biopesticide Ills selected
from Nomuraea
rileyi, preferably strains SA86101, GU87401, SR86151, CG128 and VA9101; and P.
lilacinus,
preferably strains 251, DSM 15169 or BCP2, in particular BCP2, which strains
especially control
the growth of plant-pathogenic nematodes.
According to a further embodiment, the at least one biopesticide Ills Bacillus
firmus, preferably
spores of strain CNCM 1-1582, preferably useful for seed treatment of cereals,
soybean, cotton,
sugarbeets and corn against nematodes and insects.
According to a further embodiment, the at least one biopesticide Ills
Pasteuria nishizawae,
preferably spores of strain Pn1, preferably useful for seed treatment of
cereals, soybean, cotton,
sugarbeets and corn against nematodes and insects.
According to a further embodiment, the at least one biopesticide Ills
Flavobacterium sp.,
preferably spores of strain H492, preferably useful for seed treatment of
cereals, soybean,
cotton, sugarbeets and corn against nematodes and insects.
According to a further embodiment, the at least one biopesticide Ills Bacillus
cereus,
preferably spores of CNCM 1-1562, preferably useful for seed treatment of
soybean, cotton,
cereals, and corn against nematodes and insects.
According to a further embodiment, the at least one biopesticide Ills
Burkholder/asp,,
preferably strain A396, preferably useful for seed treatment of soybean,
cotton, cereals, and
corn.
According to a further embodiment, the at least one biopesticide Ills
Paecilomyces Illacinus
251, preferably useful for seed treatment of soybean, cotton, cereals, and
corn.
According to a further embodiment, the at least one biopesticide Ills a
mixture of spores of B.
firmus and B. cereus, preferably mixtures spores of above mentioned strains
CNCM 1-1582 and
CNCM 1-1562, preferably useful for seed treatment of soybean, cotton, cereals,
and corn
against nematodes and insects.
According to one preferred embodiment of the inventive mixtures, the at least
one pesticide II
is selected from Bacillus firmus CNCM 1-1582, Paecllomyces Nacinus 251,
Pasteuria nishizawa
Pn1 and Burkholdenj sp. A396 having nematicidal, acaricidal and/or
insecticidal activity. These
mixtures are particularly suitable in soybean, cotton, cereals, and corn, in
particular for seed
treatment.
Preference is also given to mixtures comprising as biopesticide II (component
2) a biopesticide
selected from group L4), preferably methyl jasmonate.
Preference is also given to mixtures comprising as biopesticide II (component
2) a biopesticide
selected from group L5), preferably selected from A. lipoferum, A. irakense,
A. halopraeferens,
Paenibacillus alvei; Penicillium bilaiae, Rhizobium leguminosarum by.
phaseoli, R. I. by. trifolii,
R. I. by. viciae, and Sinorhizobium meliloti.
Preference is also given to mixtures comprising as biopesticide II (component
2) a biopesticide
selected from group L5) selected from B. japonicum TA-11, Paenibacillus
alveiNAS6G6,
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Pen/cull/urn bilaiae strains ATCC 18309, ATCC 20851 and ATCC 22348; Rhizobium
leguminosarum by. phaseoliRG-B10, R. I. by. viciae P1NP3Cst, R. I. by. viciae
RG-P2, R. I. by.
trifolii RP113-7, R. I. by. viciae SU303, R. I. by. viciaeWSM1455, and
Sinorhizobium rneliIoti
The present invention also relates to mixtures, wherein the at least one
biopesticide II is
selected from A. lipoferum, A. irakense and A. halopraeferens, These mixtures
are particularly
suitable in soybean, especially as seed treatment.
In one embodiment, component 2), i.e. the biopesticide II, of the mixtures of
the invention is
selected from Azospirillum lipoferum, Azospirillum irakense, Azospialum
halopraeferens,
Bradyrhizobium spp., Bradyrhizobium sp. (Arachis), Bradyrhizobium sp. (Vigna),
Bradyrhizobium liaoningense, Bradyrhizobium lupini, Defflia acidovorans,
Glomus intraradices,
Mesorhizobium sp., Mesorhizobium Mesorhizobium huakg Mesorhizobium
loti,
Rhizobium leguminosarum by. phaseoli, Rhizobium leguminosarum by. trifolil,
Rhizobium
leguminosarum by. viciae, Sinorhizobium meliloti, Bacillus altitudinis,
Bacillus
amyloliquefaciens, Bacillus amyloliquefaciensssp. plantarum, Bacillus firmus,
Bacillus
megaterium, Bacillus mojavensis, Bacillus mycoides, Bacillus pumilus, Bacillus
simplex, Bacillus
solisalsi, Bacillus subtilis, Burkholderia sp., Coniothyrium min/tans,
Paecilomyces lilacinus,
Paenibacillus alver: Paenibacillus polymyxa, Paenibacillus pop/floe, Pasteuria
nishizawae,
Pasteuria usgae, Penicillium bilaiae, Pseudomonas chloraphis, Pseudomonas
fluorescens,
Pseudomonas put/do, abscisic acid, harpin protein (alpha-beta), jasmonic acid
or salts or
derivatives thereof, cis-jasmone, methyl jasmonate.
In a preferred embodiment, component 2), i.e. the biopesticide II, of the
mixtures of the
invention is selected from Bradyrhizobium sp. (Arachis) CB1015, Bradyrhizobium
sp. (Arachis)
SEMIA 6144, Bradyrhizobium sp. (Arachis) SEMIA 6462, Bradyrhizobium sp.
(Arachis) SEMIA
6464, Brao'yrhizobium sp. (Vigna) PNL1, Mesorhizobium sp. WSM1497, Rhizobium
leguminosarum by. phaseoliRG-B10, Rhizobium leguminosarum by. trifoN095,
Rhizobium
leguminosarum by. trifolii CB782, Rhizobium leguminosarum by. trifolii CC1099,
Rhizobium
leguminosarum by. trifolii CC275e, Rhizobium leguminosarum by. trifolii
CC283b, Rhizobium
leguminosarum by. trifoliiRP113-7, Rhizobium leguminosarum by. trifoNTA1,
Rhizobium
leguminosarum by. trifoNWSM1325, Rhizobium leguminosarum by. trifoNWSM2304,
Rhizobium leguminosarum by. viciae P1NP3Cst also referred to as 1435,
Rhizobium
leguminosarum by. viciae RG-P2 also called P2, Rhizobium leguminosarum by.
viciaeSU303,
Rhizobium leguminosarum by. viciaeWSM1455, Sil7orhizobium meliloti NRG185,
Sinorhizobium meNotiRCR2011 also called 2011 or SU47, Sinorhizobium meNoti,
RRI128,
Bacillus altitudinis41KF2b, Bacillus amyloliquefaciens AP-136, Bacillus
amyloliquefaciens AP-
188, Bacillus amyloliquefaciens AP-218, Bacillus amyloliquefaciens AP-219,
Bacillus
amyloliquefaciens AP-295, Bacillus amyloliquefaciensssp. plantarum D747,
Bacillus
amyloliquefaciensssp. plantarum FZB24 also called SB3651, Bacillus
amyloliquefaciens ssp.
plantarum FZB42, Bacillus amyloliquefaciensssp. plantarum GB03 also called
GB03 formerly
B. subtilis, Bacillus amyloliquefaciensssp. plantarum MBI600 also referred to
as 1430, formerly
B. subtilis, Bacillus amyloliquefaciensssp. plantarum QST-713, formerly B.
subtiks, Bacillus
amyloliquefaciensssp. plantarumTJ1000, also called 1BE, Bacillus firmus CNCM 1-
1582,
Bacillus megaterium H491, Bacillus megaterium J142, Bacillus megaterium M018,
Bacillus
mojavensi:s AP-209, Bacillus mojavensi:s SR11, Bacillus mycoides AQ726,
Bacillus mycoides J
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also called BmJ, Bacillus pumllus GB34, Bacillus pumllus GHA 180, Bacillus
pumllus INR-7
otherwise referred to as BU F22 and BU-F33, Bacillus pumllus KFP9F, Bacillus
pumilus QST
2808, Bacillus simplex ABU 288, Bacillus subtilis CX-9060, Bacillus subtllis
FB17, Bacillus
subtilis GB07, Burkholderia sp. A396, Coniothyrium minitans CON/M/91-08,
Paecllomyces
Illacinus 251, Paecilomyces Illacinus BC P2, Paenibacillus alvei NAS6G6,
Paenibaclllus
polymyxa PKB1, Paenibacillus popilliae14F-D80 also called K14F-0080,
Paenibacillus popllliae
KLN 3, Pasteuria nishizawae Pn1, Pasteuria sp. Ph3, Pasteuria sp. Pr3,
Pasteuria sp. ATCC
PTA-9643, Pasteuria usage BL1, Penicillium bilaiae (also called P. bilaii)
NRRL 50162,
Penicillium bilaiae (also called P. bilaii) NRRL 50169, Pen/cu//urn bilaiae
(also called P. bitaii)
ATCC 18309 (= ATCC 74319), Penicillium bilaiae (also called P. bilaii) ATCC
20851, Penicillium
bilaiae (also called P. bilaii) ATCC 22348 (=ATCC 74318), Pseudomonas
fluorescens A506,
Pseudomonas fluorescens ATCC 13525, Pseudomonas fluorescens CHAO, Pseudomonas
fluorescens CL 145A, Pseudomonas fluorescens NCIB 12089, Pseudomonas
fluorescens Pf-5,
Pseudomonas fluorescens WCS374, Pseudomonas putida ATCC 202153.
In one embodiment, component 2), i.e. the biopesticide II, of the mixtures of
the invention is
selected from
L1) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant
defense activator
activity: Ampelomyces quisqualiS, Aspergillus t7avus, Aureobasidium pullulans,
Bacillus
altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensiS, B. mycoides,
B. pumllus,
B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens,
Candida oleophila,
C. saitoana, Clawbacter michiganensis (bacteriophages), Coniothyrium min/tans,
Cryphonectria parasitica, Ciyptococcus albidus, Dllophosphora alopecuri,
Fusarium
oxysporum, Clonostachys roseaf. catenulate (also named Gliocladium
catenulatum),
Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia
fructicola,
Microdochhim o'imerum, Microsphaeropsis ochracea, Muscodor albus, Paembacfflus
alvei, Paenibacillus polymyxa, Pantoea vagans, Penicillium bllaiae, P.steckii;
Phlebiopsis
gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa,
Pichia
anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces
griseovkidis,
S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides,
T
asperellum, I atroviride, I fertile, I gamsii, I harmatum, T. harzianum, I
polysporum,
T stromaticum, T wrens, T. vinde, Typhula phacorrhiza, Ulocladium oudemansg
Verticillium dahlia;
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or
plant defense
activator activity: harpin protein, Reynoutria sachalinensis extract;
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or
nematicidal activity:
Agrobacterium radiobacter, Bacillus cereus, B. firmus, Burkholderia sp.,
Chromobacterium subtsugae, Flavobacterium sp., Paecilomyces fumosoroseus, P.
lilacinus, Paenibacillus popilliae, Pasteuna sp., P. nishizawae, P. penetrans,
P. ramosa,
P. thornea, P. usgae, Pseudomonas fluorescens, Streptomyces galbus, S.
microflavus-,
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal,
pheromone and/or
nematicidal activity: cis-jasmone, methyl jasmonate, jasmonic acid or salts or
derivatives
thereof;
L5) Microbial pesticides with plant stress reducing, plant growth regulator,
plant growth
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PCT/EP2016/055105
promoting and/or yield enhancing activity: A. lipoferum, A. irakense, A.
halopraeferens,
Bradyrhizobium sp., B. liaoningense, B. lupini, Delftia acidovorans, Glomus
intraradices,
Mesorhizobium sp., Rhizobium leguminosarum by. ,ohaseoli, R. I. by. trifolii,
R. I. by.
Sinorhizobiurn /millet':
In a preferred embodiment, component 2), i.e. the biopesticide II, of the
mixtures of the
invention is selected from the group L1, i.e. microbial pesticides with
fungicidal, bactericidal,
viricidal and/or plant defense activator activity: Arnpelornyces qui:squags,
Aspergillus ilavus,
Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B.
megateriurn, B.
mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B.
subtilis var.
amyloliquefaciens, Candicla oleophlla, C. saitoana, Clavibacter michiganensis
(bacteriophages),
Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus,
Dllophosphora
alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulate (also named
Gliocladium
catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes,
Metschnikowia
fructicola, Microdochiurn dirnerum, Wrosphaeropshs ochracea, Muscodor albus,
Paernbacillus
alvei, Paenibacillus polymyxa, Pantoea vagans, Penicillium bilaiae, P.steckg
Phlebiopsis
gigantea, Pseudomonas sp., Pseudomonas chlora,ohis, Pseudozyma flocculosa,
Pichia
anomala, Pythium ollgandrum, Sphaerocles mycoparasitica, Streptomyces
griseoviridis, S.
lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T
asperellum, T
atroviride, T fertile, T gamsii, T harmatum, T harzianum, T polysporurn, T
stromaticum, T
virens, T viride, Typhula phacorrhiza, (.1locladium oudemansii, Verticillium
dahlia.
In a more preferred embodiment, component 2), i.e. the biopesticide II, of the
mixtures of the
invention is selected from Bacillus amyloliquefaciens, Bacillus pumilus,
Bacillus simplex, and
Bacillus SUbliliS, in particular from the strains Bacillus amyloliquefaciens
MBI600, B.
amyloliquefaciens AP-188, Bacillus pumilus IN R-7 (otherwise referred to as BU-
F22 and BU-
F33), Bacillus simplex ABU 288, and Bacillus subtigs FB17 (also called UD 1022
or UD10-22).
According to one particularly preferred embodiment, the biopesticide II of the
mixtures of the
invention is Bacillus pumilus, preferably spores of strain INR-7.
According to another particularly preferred embodiment, the biopesticide II of
the mixtures of
the invention is Bacillus simplex, preferably spores of strain ABU 288.
According to another particularly preferred embodiment, the biopesticide II of
the mixtures of
the invention is Bacillus subtills, preferably spores of strain FBI 7,
In a further preferred embodiment, component 2), i.e. the biopesticide II, of
the mixture of the
invention is Pen/cilium steckfi; preferably Pen/cilium steckllstrain IBWF104-
06 as deposited
with DSMZ under the deposit number DSM 27859. Strain IBWF104-06 was determined
to have
potent antifungal activity, in particular, against infestion with plant
pathogens including
Phytophthora infestans, Botrytis cinerea and Alternaria solani
(PCT/EP2014/074165).
In another preferred embodiment, component 2), i.e. the biopesticide II, of
the mixtures of the
invention is selected from the group L2, i.e. biochemical pesticides with
fungicidal, bactericidal,
viricidal and/or plant defense activator activity: harpin protein, Reynoutria
sachalinensis extract.
According to one particularly preferred embodiment, the biopesticide II of the
mixture of the
invention is harpin protein (alpha-beta).
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In another preferred embodiment, component 2), i.e. the biopesticide II, of
the mixtures of the
invention is selected from the group L4, i.e. biochemical pesticides with
insecticidal, acaricidal,
moll uscidal, pheromone and/or nematicidal activity: cis-jasmone, methyl
jasmonate, jasmonic
acid or salts or derivatives thereof.
According to one particularly preferred embodiment, the biopesticide 11 of the
mixtures of the
invention is cis-jasmone.
According to another particularly preferred embodiment, the biopesticide 11 of
the mixture of
the invention is methyl jasmonate.
According to another particularly preferred embodiment, the biopesticide 11 of
the mixture of
the invention is jasmonic acid or a salt or derivative thereof.
In a particularly preferred embodiment, component 2), i.e. the biopesticide
II, of the mixtures of
the invention is selected from the group L3, i.e. microbial pesticides with
insecticidal, acaricidal,
molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus
cereus, B. firmus,
.. Burkholderia sp., Chromobacterium subtsugae, Flavobacterium sp.,
Paecilomyces
fumosoroseus, P. Nacinus, Paembacillus popllliae, Pasteuria sp., P.
nishizawae, P. penetrans,
P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Streptomyces galbus,
S.
microfiavus.
In a more preferred embodiment, component 2), i.e. the biopesticide 11, of the
mixtures of the
invention is selected from Bacillus firmus, Pasteuria nishazawa sp.,
Flavobacterium sp.,
Paecllomyces lilacinus, and Burkholderia sp, in particular from the strains
Burkholderia sp.
A396, Paecllomyces Illacinus 251, Bacillus firmus CNCM 1-1582, Pasteuria
nishizawae Pn1,
and Flavobacterium sp. H492.
In an even more preferred embodiment, component 2), i.e. the biopesticide II,
of the mixtures
of the invention is selected from Bacillus firmus, Pasteuria nishizawa, and
Flavobacterium sp.,
in particular from the strains Bacillus firmus CNCM 1-1582, Pasteuria
ni:shizawae Pn1, and
Flavobacterium sp. H492.
According to one particularly preferred embodiment, the biopesticide II of the
mixtures of the
invention is Bacillus cereus, preferably spores of strain CNCM 1-1562.
According to another particularly preferred embodiment, the biopesticide 11 of
the mixtures of
the invention is Burkholder/asp., preferably strain A396.
According to another particularly preferred embodiment, the biopesticide 11 of
the mixtures of
the invention is Paecllomyces Illacinus, preferably strain 251, DSM 15169 or
BCP2, particularly
preferably strain 251.
With regard to one embodiment of the present invention, which is the use of
mixtures
according to the present invention for the control of nematodes, the compound
1 is preferably
combined with biopesticides 11 having a nematicidal activity.
According to another particularly preferred embodiment, the biopesticide 11 of
the mixtures of
the invention is Bacillus firmus, preferably spores of strain CNCM 1-1582;
e.g. VOTR/00 from
Bayer CropScience LP, USA, which is suitable for nematode control.
According to another particularly preferred embodiment, the biopesticide 11 of
the mixtures of
the invention is Pasteuria ni:shizawae, preferably spores of strain Pn1, e.g.
Clariva PN from
Syngenta Crop Protection, LLC, USA, which is suitable for nematode control.
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According to yet another particularly preferred embodiment, the biopesticide
II of the mixtures
of the invention is Flavobacterium sp., preferably spores of strain H492, e.g.
MB1-302 from
Marrone Bio Innovations, USA, which is suitable for nematode control.
In summary, particularly preferred biopesticides 11 may be selected from the
following
biopesticides 11-1 toll-14 in accordance with each row of table II, of which
biopesticides 11-12, II-
13, and 11-14 are particularly preferred.
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Table!!
No biopesticide No biopesticide
11-1 Bacillus amyloliquefaciens 11-9
jasmonic acid or a salt or
11-2 Bacillus pumllus derivative
thereof
11-3 Bacillus simplex 11-10
Burkholderia sp.
11-4 Bacillus subtllis 11-11
Paecllomyces Illacinus
11-5 Penicillium stock/ 11-12 Bacillus fiiMUS
11-6 harpin protein (alpha-beta) 11-13 Pasteuria
nishizawae
11-7 cis-jasmone 11-14
Flavobacterium sp.
11-8 methyl jasmonate
Furthermore, particularly preferred strains of biopesticides 11 may be
selected from the
following biopesticide strains Ila-1 to Ila-11 in accordance with each row of
table Ila, of which
the biopesticide strains Ila-9, Ila-10, and Ila-11 are particularly preferred.
Table Ila
No biopesticide No biopesticide
Bacillus amyloliquefaciens II a-6
Pen/cu//urn stock//I BWF104-06
Ila-1
MBI600 Ila-7 Burkholderia sp. A396
Bacillus amyloliquefaciens AP- Ila-8
Paecllomyces lilacinus 251
Ila-2
188 Ila-9
Bacillus finnus CNCM 1-1582
Ila-3 Bacillus pumllus INR-7 Ila-10
Pasteuria nishizawae Pnl
Ila-4 Bacillus simplex ABU 288 Ila-11
Flavobacterium sp. H492
Ila-5 Bacillus SUMAS FB17
Particular embodiments of the present invention
In the context of the present invention, the following mixtures of compounds
I, preferably
compound i of formula 1, and biopesticides 11 as in Table A are preferred and
represent
embodiments of the invention:
Table A
No.
Compound Compound 11 No.
Compound Compound 11
1
A-1 1 11-1 A-8 I 11-
8
A-2 I 11-2 A-9 I 11-
9
A-3 1 11-3 A-10 I 11-10
A-4 1 11-4 A-11 I 11-11
A-5 1 11-5 A-12 I 11-12
A-6 1 11-6 A-13 I 11-13
A-7 1 11-7 A-14 I 11-14
The mixtures A-1 to A-14 as presented in table A represents binary mixtures
according to the
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WO 2016/142456 22 PCT/EP2016/055105
present invention.
Furthermore, the following mixtures of compound I, preferably compound i of
formula I, and
biopesticide strains Ila, as in Table B are preferred and represent
embodiments of the invention:
Table B
No Compound Compound II No.
Compound Compound II
.
B-1 I Ila-1 B-7 I
Ila-7
B-2 I Ila-2 B-8 I
Ila-8
B-3 I Ila-3 B-9 I
Ila-9
B-4 I Ila-4 B-b I
Ila-10
B-5 I Ila-5 B-11 I I
la-11
B-6 I Ila-6
The mixtures B-1 to B-11 as presented in table B represents binary mixtures
according to the
present invention.
According to the invention, the solid material (dry matter) of the
biopesticides (with the
exception of oils such as Neem oil) are considered as active components (e. g.
to be obtained
after drying or evaporation of the extraction or suspension medium in case of
liquid formulations
of the microbial pesticides).
In accordance with the present invention, the weight ratios and percentages
used herein for a
biological extract such as QuiIlay extract are based on the total weight of
the dry content (solid
material) of the respective extract(s).
The total weight ratios of compositions comprising at least one microbial
pesticide in the form
of viable microbial cells including dormant forms, can be determined using the
amount of CFU
of the respective microorganism to calclulate the total weight of the
respective active component
with the following equation that 1 x 101 CFU equals one gram of total weight
of the respective
active component. Colony forming unit is measure of viable microbial cells, in
particular fungal
and bacterial cells. In addition, here "CFU" may also be understood as the
number of (juvenile)
individual nematodes in case of (entomopathogenic) nematode biopesticides,
such as
Steinernema feltiae.
As already indicated above, component 1), preferably compound i of formula I,
and component
2) of the mixtures of the invention are present in synergistically effective
amounts.
In one embodiment, component 1), preferably compound i of formula I, and
component 2) of
the mixtures of the invention are present in a total weight ratio of from
100:1 to 1:100, wherein
the total weight of component 2) is based on the amount of the solid material
(dry meter) of
component 2).
In the binary mixtures and compositions according to the invention the weight
ratio of the
component 1), preferably compound i of formula I, and the component 2)
generally depends
from the properties of the active components used, usually it is in the range
of from 1:10,000 to
10,000:1, often it is in the range of from 1:100 to 100:1, regularly in the
range of from 1:50 to
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50:1, preferably in the range of from 1:20 to 20:1, more preferably in the
range of from 1:10 to
10:1, even more preferably in the range of from 1:4 to 4:1 and in particular
in the range of from
1:2 to 2:1.
According to further embodiments of the binary mixtures and compositions, the
weight ratio of
the component 1), preferably compound i of formula I, and the component 2)
usually is in the
range of from 1000:1 to 1:1, often in the range of from 100: Ito 1:1,
regularly in the range of
from 50:1 to 1:1, preferably in the range of from 20:1 to 1:1, more preferably
in the range of from
10:1 to 1:1, even more preferably in the range of from 4:1 to 1:1 and in
particular in the range of
from 2:1 to 1:1.
According to further embodiments of the mixtures and compositions, the weight
ratio of the
component 1) , preferably compound i of formula I, and the component 2)
usually is in the range
of from 20,000:1 to 1:10, often in the range of from 10,000:1 to 1:1,
regularly in the range of
from 5,000:1 to 5:1, preferably in the range of from 5,000:1 to 10:1, more
preferably in the range
of from 2,000:1 to 30:1, even more preferably in the range of from 2,000:1 to
100:1 and in
particular in the range of from 1,000:1 to 100:1.
According to a further embodiments of the binary mixtures and compositions,
the weight ratio
of the component 1) , preferably compound i of formula I, and the component 2)
usually is in the
range of from 1:1 to 1:1000, often in the range of from 1:1 to 1:100,
regularly in the range of
from 1:1 to 1:50, preferably in the range of from 1:1 to 1:20, more preferably
in the range of from
1:1 to 1:10, even more preferably in the range of from 1:1 to 1:4 and in
particular in the range of
from 1:1 to 1:2.
According to further embodiments of the mixtures and compositions, the weight
ratio of the
component 1) , preferably compound i of formula I, and the component 2)
usually is in the range
of from 10:1 to 1:20,000, often in the range of from 1:1 to 1:10,000,
regularly in the range of
from 1:5 to 1:5,000, preferably in the range of from 1:10 to 1:5,000, more
preferably in the range
of from 1:30 to 1:2,000, even more preferably in the range of from 1:100 to
1:2,000 to and in
particular in the range of from 1:100 to 1:1,000.
In the ternary mixtures, i.e. compositions according to the invention
comprising the component
1) , preferably compound i of formula I, and component 2) and a compound III
(component 3),
the weight ratio of component 1) , preferably compound i of formula I, and
component 2)
depends from the properties of the active substances used, usually it is in
the range of from
1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the
range of from 1:20
to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular
in the range of from
1:4 to 4:1, and the weight ratio of component 1) , preferably compound i of
formula I, and
component 3) usually it is in the range of from 1:100 to 100:1, regularly in
the range of from 1:50
to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the
range of from 1:10 to
10:1 and in particular in the range of from 1:4 to 4:1.
Any further active components are, if desired, added in a ratio of from 20:1
to 1:20 to the
component 1) , preferably compound i of formula I.
These ratios are also suitable for inventive mixtures applied by seed
treatment.
When mixtures comprising microbial pesticides are employed in crop protection,
the
application rates preferably range from about 1 x 106 to 5 x 1015 (or more)
CFU/ha, preferably
from about 1 x 106 to about 1 x 1013 CFU/ha, and even more preferably from
about 1 x 109 to
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about 1 x 1012 CFU/ha. In the case of (entomopathogenic) nematodes as
microbial pesticides
(e. g. Steinernema feltiae), the application rates preferably range inform
about 1 x 105 to 1 x
1012 (or more), more preferably from 1 x 108 to 1 x 1011, even more preferably
from 5 x 108 to 1
x 1010 individuals (e. g. in the form of eggs, juvenile or any other live
stages, preferably in an
.. infetive juvenile stage) per ha.
When mixtures comprising microbial pesticides are employed in seed treatment,
the
application rates with respect to plant propagation material preferably range
from about 1 x 106
to 1 x 1012 (or more) CFU/seed. Preferably, the concentration is about 1 x 106
to about 1 x 109
CFU/seed. In the case of the microbial pesticides II, the application rates
with respect to plant
.. propagation material also preferably range from about 1 x 107 to 1 x 1014
(or more) CFU per 100
kg of seed, preferably from 1 x 10 to about 1 x 1012 CFU per 100 kg of seed.
Further embodiments of the present invention
Binary mixtures have been described above as one embodiment of the present
invention.
Ternary or higher mixtures represent another embodiment of the present
invention.
In one embodiment, the mixtures of the invention, in particular the mixtures A-
1 to A-14 or B-1
to B-11, further comprise as active component 3) a further active compound
III, which is
.. selected from insecticides or fungicides.
The insecticides, which are hereinafter described by common names, are
commercially
available and may be found in The Pesticide Manual, 16th Edition, C. MacBean,
British Crop
Protection Council (2013) among other publications. The online Pesticide
Manual is updated
.. regularly and is accessible through http://bcpcdata.com/pesticide-
manual.html. Another online
data base for pesticides providing the ISO common names is
http://www.alanwood.net/pesticides.
The fungicides, which are hereinafter described by common names, are
commercially
available and may be found in the database
http://vvwvv.alanwood.net/pesticides.
In one embodiment, the mixtures of the invention further comprise as active
component 3) a
further active compound III, which is an insecticide, wherein said insecticide
is selected from the
group consisting of fipronil, clothianidin, thiamethoxam, acetamiprid,
dinotefuran, imidacloprid,
thiacloprid, sulfoxaflor, meth iocarb, tefluthrin, bifenthrin, cypermethrin,
alphacypermethrin,
.. spinosad, cyantraniliprole, chlorantraniliprole, triflumezopyrim,
flupyradifurone, abamectin,
thiodicarb, tetraniliprole and tioxazafen.
In another embodiment, the mixtures of the invention further comprise as
active component 3)
a further active compound III, which is a fungicide, wherein said fungicide is
selected from the
group consisting of azoxstrobin, trifloxystrobin, picoxystrobin,
pyraclostrobin, sedaxane,
penthiopyrad, penflufen, fluopyram, fluxapyroxad, boscalid, oxathiapiprolin,
metalaxyl,
metalaxyl-M, ethaboxam, dimethomorph, cyproconazole, difenoconazole,
prothioconazole,
flutriafol, thiabendazole, ipconazole, tebuconazole, triadimenol, prochloraz,
fluquinconazole,
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triticonazole, fludioxonil, carboxin, silthiofarm, ziram, thiram, carbendazim,
thiophanate methyl,
fenamidone, hymexazol and fluazinam.
If the active compound III is an insecticide, said insecticide is preferably
selected from the
insecticides as defined in the following table Illa. The insecticides as
listed in table IIla are in the
following referred to as insecticides IIla-1 toffla-22.
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Table Illa
No insecticide No insecticide No
insecticide
IIla-1 fipronil IIla-9 methiocarb Illa-16
chlorantraniliprole
Illa-2 clothianidin IIla-10 tefluthrin Illa-17
triflumezopyrim
II la-3 thiamethoxam IIla-11 bifenthrin IIla-18
flupyradifurone
Illa-4 acetamiprid Illa-12 cypermethrin IIla-19
abamectin
11la-5 dinotefuran IIla-13 alphacypermethri IIla-20
thiodicarb
IIla-6 imidacloprid n Ilia-21
tetraniliprole
IIla-7 thiacloprid IIla-14 spinosad IIla-22
tioxazafen
IIla-8 sulfoxaflor IIla-15 cyantraniliprole
If the active compound III is a fungicide, said fungicide is preferably
selected from the
fungicides as defined in the following table 111b. The fungicides as listed in
table IIlb are in the
following referred to as fungicides IIlb-1 to IIlb-36.
Table IIlb
No fungicide No fungicide No
fungicide
Illb-1 azoxstrobin IIlb-14 ethaboxam IIlb-27
fludioxonil
111b-2 trifloxystrobin IIlb-15 dimethomorph IIlb-28
carboxin
IIlb-3 picoxystrobin Illb-16 cyproconazole IIlb-29
silthiofarm
111b-4 pyraclostrobin Illb-17 difenoconazole III b-30
ziram
111b-5 sedaxane Illb-18 prothioconazole IIlb-31
thiram
Illb-6 penthiopyrad IIlb-19 flutriafol Illb-32
carbendazim
IIlb-7 penflufen Illb-20 thiabendazole IIlb-33
thiophanate
IIlb-8 fluopyram Illb-21 ipconazole
methyl
111b-9 fluxapyroxad III b-22 tebuconazole
111b-34 fenamidone
IIlb-10 boscalid IIlb-23 triadimenol Illb-35
hymexazol
Illb-11 oxathiapiprolin Illb-24 prochloraz IIlb-36
fluazinam
111b-12 metalaxyl II lb-25 fluquinconazole
111b-13 metalaxyl-M Ill b-26 triticonazole
In one embodiment, the present invention relates to ternary mixtures, which
comprise
at least the carboxamide compound of formula 1 as component I), preferably
compound i of
formula 1, and at least one biopesticide II, which is preferably selected from
the biopesticides II-
I toll-14, and
at least one further active compound III, which may be preferably selected
from the
insecticides Illa-1 to Illa-22 or the fungicides Illb-1 to Illb-36.
Such mixtures are preferably ternary mixture comprising the carboxamide
compound of
formula 1 as component 1) , preferably compound i of formula 1õ and one
biopesticide 11, which
is selected from the biopesticides1I-1 toll-14, in particular from the
biopesticide strains Ila-1 to
Ila-11, and one further active compound III, which may be selected from the
insecticides Illa-1
to Illa-22.
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Such mixtures are preferably ternary mixture comprising the carboxamide
compound of
formula I as component 1) , preferably compound i of formula 1, and one
biopesticide 11, which is
selected from the biopesticides 11-1 toll-14, in particular from the
biopesticide strains Ila-1 to !ta-
ll, and one further active compound III, which may be selected from the
fungicides Illb-1 to Illb-
36.
In another embodiment, the present invention relates to ternary mixtures,
which comprise
at least the carboxamide compound of formula 1 as component 1) , preferably
compound i of
formula I, and
at least one biopesticide 11 with nematicidal activity, and
at least one further nematicidal active compound III, preferably selected from
abamectin or
tioxazafen.
With regard to the use of mixtures according to the present invention for the
control of
nematodes, especially for their nematicidal activity in seed treatment, the
nematicidal mixtures
may comprise the carboxamide compound of formula las component 1) , preferably
compound
I of formula 1, combined with one biopesticide II with nematicidal activity
or, alternatively, with a
non-biopesticide with nematicidal activity, such as abamectin or tioxazafen.
Thus for the control of nematodes, the carboxamide compound of formula I may
be combined
with abamectin, independently of the presence of a biopestide.
Thus for the control of nematodes, the carboxamide compound of formula I may
be combined
with tioxazafen, independently of the presence of a biopestide.
Thus the binary nematicidal mixture may comprise the carboxamide compound of
formula 1
and tioxazafen.
Thus the binary nematicidal mixture may comprise the carboxamide compound of
formula 1
and abamectin.
In view of the ternary mixtures described herein above, preference is given to
the pesticidal
mixtures compiled in the tables below.
Table 1
Pesticidal mixtures, which comprise carboxamide compound of formual las
component 1) ,
preferably compound i of formula!, and in which the combination of components
2) and 3)
corresponds in each case to the combination of a biopesticide 11 or
biopesticide strain Ila with an
active compound III according to one row of Table M said pesticidal mixtures
being referred to
as pesticidal mixtures 1-M-1 to 1-M-1453
Table M
No. 11/1Ia Ill No. 11/1Ia Ill No.
11/1Ia Ill
M-1 11-1 Illa-1 M-7 11-7 Illa-1 M-13 11-
13 Illa-1
M-2 11-2 Illa-1 M-8 11-8 Illa-1 M-14 11-
14 Illa-1
M-3 11-3 Illa-1 M-9 11-9 Illa-1 M-15 11-1
Ilia-2
M-4 11-4 Illa-1 M-10 11-10 Illa-1 M-16 11-2
Illa-2
M-5 11-5 Illa-1 M-11 11-11 Illa-1 M-17 11-3
Illa-2
M-6 11-6 Illa-1 M-12 11-12 Illa-1 M-18 11-4
Illa-2
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No. 11/1Ia III No. 11/1Ia III No. 11/1Ia III
M-19 11-5 IIla-2 M-61 11-5 IIla-5 M-103 11-5
IIla-8
M-20 11-6 IIla-2 M-62 11-6 IIla-5 M-104 11-6
IIla-8
M-21 11-7 IIla-2 M-63 11-7 IIla-5 M-105 11-7
IIla-8
M-22 11-8 IIla-2 M-64 11-8 IIla-5 M-106 11-8
IIla-8
M-23 11-9 IIla-2 M-65 11-9 IIla-5 M-107 11-9
IIla-8
M-24 11-10 IIla-2 M-66 11-10 IIla-5 M-108 11-10 IIla-8
M-25 11-11 IIla-2 M-67 11-11 IIla-5 M-109 11-11 IIla-8
M-26 11-12 IIla-2 M-68 11-12 IIla-5 M-110 11-12 IIla-8
M-27 11-13 IIla-2 M-69 11-13 IIla-5 M-111 11-13
IIla-8
M-28 11-14 IIla-2 M-70 11-14 _ IIla-5 M-112 11-14
IIla-8
M-29 11-1 IIla-3 M-71 11-1 IIla-6 M-113 11-1
IIla-9
M-30 11-2 IIla-3 M-72 11-2 IIla-6 M-114 11-2
IIla-9
M-31 11-3 IIla-3 M-73 11-3 IIla-6 M-115 11-3
IIla-9
M-32 11-4 IIla-3 M-74 11-4 IIla-6 M-116 11-4
IIla-9
M-33 11-5 IIla-3 M-75 11-5 IIla-6 M-117 11-5
IIla-9
M-34 11-6 IIla-3 M-76 11-6 IIla-6 M-118 11-6
IIla-9
M-35 11-7 IIla-3 M-77 11-7 IIla-6 M-119 11-7
IIla-9
M-36 11-8 IIla-3 M-78 11-8 IIla-6 M-120 11-8
IIla-9
M-37 11-9 IIla-3 M-79 11-9 IIla-6 M-121 11-9
IIla-9
M-38 11-10 IIla-3 M-80 11-10 IIla-6 M-122 11-10 IIla-9
M-39 11-11 IIla-3 M-81 11-11 IIla-6 M-123 11-11 IIla-9
M-40 11-12 IIla-3 M-82 11-12 IIla-6 M-124 11-12 IIla-9
M-41 11-13 IIla-3 M-83 11-13 IIla-6 M-125 11-13 IIla-9
M-42 11-14 IIla-3 M-84 11-14 IIla-6 M-126 11-14 IIla-9
M-43 11-1 IIla-4 M-85 11-1 IIla-7 M-127 11-1
IIla-10
M-44 11-2 IIla-4 M-86 11-2 IIla-7 M-128 11-2
IIla-10
M-45 11-3 IIla-4 M-87 11-3 IIla-7 M-129 11-3
IIla-10
M-46 11-4 IIla-4 M-88 11-4 IIla-7 M-130 11-4
IIla-10
M-47 11-5 IIla-4 M-89 11-5 IIla-7 M-131 11-5
IIla-10
M-48 11-6 IIla-4 M-90 11-6 IIla-7 M-132 11-6
IIla-10
M-49 11-7 IIla-4 M-91 11-7 IIla-7 M-133 11-7
IIla-10
M-50 11-8 IIla-4 M-92 11-8 _ IIla-7 M-134 11-8
IIla-10
M-51 11-9 IIla-4 M-93 11-9 IIla-7 M-135 11-9
IIla-10
M-52 II-10 IIla-4 M-94 11-10 IIla-7 M-136 , 11-10
IIla-10
M-53 11-11 IIla-4 M-95 11-11 IIla-7 M-137 11-11 IIla-10
M-54 11-12 IIla-4 M-96 11-12 IIla-7 M-138 11-12 IIla-10
M-55 11-13 IIla-4 M-97 11-13 IIla-7 M-139 11-13 IIla-10
M-56 11-14 IIla-4 M-98 11-14 IIla-7 M-140 11-14 IIla-10
M-57 11-1 IIla-5 M-99 11-1 IIla-8 M-141 11-1
IIla-11
M-58 11-2 IIla-5 M-100 11-2 IIla-8 M-142 11-2
IIla-11
M-59 11-3 IIla-5 M-101 11-3 IIla-8 M-143 11-3
IIla-11
M-60 11-4 IIla-5 M-102 11-4 IIla-8 M-144 11-4
IIla-11
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M-145 11-5 IIla-11 M-187 11-5 IIla-14 M-229 11-5
IIla-17
M-146 11-6 IIla-11 M-188 11-6 IIla-14 M-230 11-6
IIla-17
M-147 11-7 IIla-11 M-189 11-7 IIla-14 M-231 11-7
IIla-17
M-148 11-8 IIla-11 M-190 11-8 IIla-14 M-232 11-8
IIla-17
M-149 11-9 IIla-11 M-191 11-9 IIla-14 M-233 11-9
IIla-17
M-150 11-10 IIla-11 M-192 11-10 IIla-14 M-234 11-10 IIla-17
M-151 11-11 IIla-11 M-193 11-11 IIla-14 M-235 11-11 IIla-17
M-152 11-12 IIla-11 M-194 11-12 IIla-14 M-236 11-12 IIla-17
M-153 11-13 IIla-11 M-195 11-13 IIla-14 M-237 11-13 IIla-17
M-154 11-14 IIla-11 M-196 11-14 _ IIla-14 M-238 11-14
IIla-17
M-155 11-1 IIla-12 M-197 11-1 IIla-15 M-239 11-1
IIla-18
M-156 11-2 IIla-12 M-198 11-2 IIla-15 M-240 11-2
IIla-18
M-157 11-3 IIla-12 M-199 11-3 IIla-15 M-241 11-3
IIla-18
M-158 11-4 IIla-12 M-200 11-4 IIla-15 M-242 11-4
IIla-18
M-159 11-5 IIla-12 M-201 11-5 IIla-15 M-243 11-5
IIla-18
M-160 11-6 IIla-12 M-202 11-6 IIla-15 M-244 11-6
IIla-18
M-161 11-7 IIla-12 M-203 11-7 IIla-15 M-245 11-7
IIla-18
M-162 11-8 IIla-12 M-204 11-8 IIla-15 M-246 11-8
IIla-18
M-163 11-9 IIla-12 M-205 11-9 IIla-15 M-247 11-9
IIla-18
M-164 11-10 IIla-12 M-206 11-10 IIla-15 M-248 11-10 IIla-18
M-165 11-11 IIla-12 M-207 11-11 IIla-15 M-249 11-11 IIla-18
M-166 11-12 IIla-12 M-208 11-12 IIla-15 M-250 11-12 IIla-18
M-167 11-13 IIla-12 M-209 11-13 IIla-15 M-251 11-13 IIla-18
M-168 11-14 IIla-12 M-210 11-14 IIla-15 M-252 11-14 IIla-18
M-169 11-1 IIla-13 M-211 11-1 IIla-16 M-253 11-1
IIla-19
M-170 11-2 IIla-13 M-212 11-2 IIla-16 M-254 11-2
IIla-19
M-171 11-3 IIla-13 M-213 11-3 IIla-16 M-255 11-3
IIla-19
M-172 11-4 IIla-13 M-214 11-4 IIla-16 M-256 11-4
IIla-19
M-173 11-5 IIla-13 M-215 11-5 IIla-16 M-257 11-5
IIla-19
M-174 11-6 IIla-13 M-216 11-6 IIla-16 M-258 11-6
IIla-19
M-175 11-7 IIla-13 M-217 11-7 IIla-16 M-259 11-7
IIla-19
M-176 11-8 IIla-13 M-218 11-8 _ IIla-16 M-260 11-8
IIla-19
M-177 11-9 IIla-13 M-219 11-9 IIla-16 M-261 11-9
IIla-19
M-178 11-10 IIla-13 M-220 11-10 IIla-16 M-262 , 11-10
IIla-19
M-179 11-11 IIla-13 M-221 11-11 IIla-16 M-263 11-11 IIla-19
M-180 11-12 IIla-13 M-222 11-12 IIla-16 M-264 11-12 IIla-19
M-181 11-13 IIla-13 M-223 11-13 IIla-16 M-265 11-13 IIla-19
M-182 11-14 IIla-13 M-224 11-14 IIla-16 M-266 11-14 IIla-19
M-183 11-1 IIla-14 M-225 11-1 IIla-17 M-267 11-1
Illa-20
M-184 11-2 IIla-14 M-226 11-2 IIla-17 M-268 11-2
IIla-20
M-185 11-3 IIla-14 M-227 11-3 IIla-17 M-269 11-3
IIla-20
M-186 11-4 IIla-14 M-228 11-4 IIla-17 M-270 11-4
IIla-20
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M-271 11-5 IIla-20 M-313 11-4 IIlb-1 M-355 11-4
IIlb-4
M-272 11-6 IIla-20 M-314 11-5 IIlb-1 M-356 11-5
IIlb-4
M-273 11-7 IIla-20 M-315 11-6 IIlb-1 M-357 11-6
IIlb-4
M-274 11-8 IIla-20 M-316 11-7 IIlb-1 M-358 11-7
IIlb-4
M-275 11-9 Illa-20 M-317 11-8 IIlb-1 M-359 11-8
IIlb-4
M-276 11-10 IIla-20 M-318 11-9 IIlb-1 M-360 11-9 IIlb-4
M-277 11-11 IIla-20 M-319 11-10 IIlb-1 M-361 11-10 IIlb-4
M-278 11-12 IIla-20 M-320 11-11 IIlb-1 M-362 11-11 IIlb-4
M-279 11-13 IIla-20 M-321 11-12 IIlb-1 M-363 11-12 IIlb-4
M-280 11-14 IIla-20 M-322 11-13 , IIlb-1 M-364 11-13
IIlb-4
M-281 11-1 IIla-21 M-323 11-14 IIlb-1 M-365 11-14 IIlb-4
M-282 11-2 IIla-21 M-324 11-1 IIlb-2 M-366 11-1
IIlb-5
M-283 11-3 IIla-21 M-325 11-2 IIlb-2 M-367 11-2
IIlb-5
M-284 11-4 IIla-21 M-326 11-3 IIlb-2 M-368 11-3
IIlb-5
M-285 11-5 IIla-21 M-327 11-4 IIlb-2 M-369 11-4
IIlb-5
M-286 11-6 IIla-21 M-328 11-5 IIlb-2 M-370 11-5
IIlb-5
M-287 11-7 IIla-21 M-329 11-6 IIlb-2 M-371 11-6
IIlb-5
M-288 11-8 IIla-21 M-330 11-7 IIlb-2 M-372 11-7
IIlb-5
M-289 11-9 IIla-21 M-331 11-8 IIlb-2 M-373 11-8
IIlb-5
M-290 11-10 IIla-21 M-332 11-9 IIlb-2 M-374 11-9 IIlb-5
M-291 11-11 IIla-21 M-333 11-10 IIlb-2 M-375 11-10 IIlb-5
M-292 11-12 IIla-21 M-334 11-11 IIlb-2 M-376 11-11 IIlb-5
M-293 11-13 IIla-21 M-335 11-12 IIlb-2 M-377 11-12 IIlb-5
M-294 11-14 IIla-21 M-336 11-13 IIlb-2 M-378 11-13 IIlb-5
M-295 11-1 IIla-22 M-337 11-14 IIlb-2 M-379 11-14 IIlb-5
M-296 11-2 IIla-22 M-338 11-1 IIlb-3 M-380 11-1
IIlb-6
M-297 11-3 Illa-22 M-339 11-2 IIlb-3 M-381 11-2
IIlb-6
M-298 11-4 Illa-22 M-340 11-3 IIlb-3 M-382 11-3
IIlb-6
M-299 11-5 Illa-22 M-341 11-4 IIlb-3 M-383 11-4
IIlb-6
M-300 11-6 IIla-22 M-342 11-5 IIlb-3 M-384 11-5
IIlb-6
M-301 11-7 IIla-22 M-343 11-6 IIlb-3 M-385 11-6
IIlb-6
M-302 11-8 Illa-22 M-344 11-7 , IIlb-3 M-386 11-7
IIlb-6
M-303 11-9 IIla-22 M-345 11-8 IIlb-3 M-387 11-8
IIlb-6
M-304 11-10 IIla-22 M-346 11-9 IIlb-3 M-388 , 11-9
Illb-6
M-305 11-11 Illa-22 M-347 11-10 Illb-3 M-389 11-10 Illb-6
M-306 11-12 Illa-22 M-348 11-11 Illb-3 M-390 11-11 Illb-6
M-307 11-13 Illa-22 M-349 11-12 Illb-3 M-391 11-12 Illb-6
M-308 11-14 Illa-22 M-350 11-13 Illb-3 M-392 11-13 Illb-6
M-309 M-351 11-14 Illb-3 M-393 11-14 Illb-6
M-310 11-1 Illb-1 M-352 11-1 Illb-4 M-394 11-1
Illb-7
M-311 11-2 Illb-1 M-353 11-2 Illb-4 M-395 11-2
Illb-7
M-312 11-3 Illb-1 M-354 11-3 Illb-4 M-396 11-3
Illb-7
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M-397 11-4 IIlb-7 M-439 11-4 IIlb-10 M-481 11-4
IIlb-13
M-398 11-5 IIlb-7 M-440 11-5 IIlb-10 M-482 11-5
IIlb-13
M-399 11-6 IIlb-7 M-441 11-6 IIlb-10 M-483 11-6
IIlb-13
M-400 11-7 IIlb-7 M-442 11-7 IIlb-10 M-484 11-7
IIlb-13
M-401 11-8 IIlb-7 M-443 11-8 IIlb-10 M-485 11-8
IIlb-13
M-402 11-9 IIlb-7 M-444 11-9 IIlb-10 M-486 11-9
IIlb-13
M-403 11-10 IIlb-7 M-445 11-10 IIlb-10 M-487 11-10 IIlb-13
M-404 11-11 IIlb-7 M-446 11-11 IIlb-10 M-488 11-11 IIlb-13
M-405 11-12 IIlb-7 M-447 11-12 IIlb-10 M-489 11-12 IIlb-13
M-406 11-13 IIlb-7 M-448 11-13 , IIlb-10 M-490 11-13
IIlb-13
M-407 11-14 IIlb-7 M-449 11-14 IIlb-10 M-491 11-14 IIlb-13
M-408 11-1 IIlb-8 M-450 11-1 IIlb-11 M-492 11-1
IIlb-14
M-409 11-2 IIlb-8 M-451 11-2 IIlb-11 M-493 11-2
IIlb-14
M-410 11-3 IIlb-8 M-452 11-3 IIlb-11 M-494 11-3
IIlb-14
M-411 11-4 IIlb-8 M-453 11-4 IIlb-11 M-495 11-4
IIlb-14
M-412 11-5 IIlb-8 M-454 11-5 IIlb-11 M-496 11-5
IIlb-14
M-413 11-6 IIlb-8 M-455 11-6 IIlb-11 M-497 11-6
IIlb-14
M-414 11-7 IIlb-8 M-456 11-7 IIlb-11 M-498 11-7
IIlb-14
M-415 11-8 IIlb-8 M-457 11-8 IIlb-11 M-499 11-8
IIlb-14
M-416 11-9 IIlb-8 M-458 11-9 IIlb-11 M-500 11-9
IIlb-14
M-417 11-10 IIlb-8 M-459 11-10 IIlb-11 M-501 11-10 IIlb-14
M-418 11-11 IIlb-8 M-460 11-11 IIlb-11 M-502 11-11 IIlb-14
M-419 11-12 IIlb-8 M-461 11-12 IIlb-11 M-503 11-12 IIlb-14
M-420 11-13 IIlb-8 M-462 11-13 IIlb-11 M-504 11-13 IIlb-14
M-421 11-14 IIlb-8 M-463 11-14 IIlb-11 M-505 11-14 IIlb-14
M-422 11-1 IIlb-9 M-464 11-1 IIlb-12 M-506 11-1
IIlb-15
M-423 11-2 IIlb-9 M-465 11-2 IIlb-12 M-507 11-2
IIlb-15
M-424 11-3 IIlb-9 M-466 11-3 IIlb-12 M-508 11-3
IIlb-15
M-425 11-4 IIlb-9 M-467 11-4 IIlb-12 M-509 11-4
IIlb-15
M-426 11-5 IIlb-9 M-468 11-5 IIlb-12 M-510 11-5
IIlb-15
M-427 11-6 IIlb-9 M-469 11-6 IIlb-12 M-511 11-6
IIlb-15
M-428 11-7 IIlb-9 M-470 11-7 , IIlb-12 M-512 11-7
IIlb-15
M-429 11-8 IIlb-9 M-471 11-8 IIlb-12 M-513 11-8
IIlb-15
M-430 11-9 IIlb-9 M-472 11-9 IIlb-12 M-514 , 11-9
Illb-15
M-431 11-10 Illb-9 M-473 11-10 Illb-12 M-515 11-10 Illb-15
M-432 11-11 Illb-9 M-474 11-11 Illb-12 M-516 11-11 Illb-15
M-433 11-12 Illb-9 M-475 11-12 Illb-12 M-517 11-12 Illb-15
M-434 11-13 Illb-9 M-476 11-13 Illb-12 M-518 11-13 Illb-15
M-435 11-14 Illb-9 M-477 11-14 Illb-12 M-519 11-14 Illb-15
M-436 11-1 Illb-10 M-478 11-1 Illb-13 M-520 11-1
Illb-16
M-437 11-2 Illb-10 M-479 11-2 Illb-13 M-521 11-2
Illb-16
M-438 11-3 Illb-10 M-480 11-3 Illb-13 M-522 11-3
Illb-16
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M-523 11-4 IIlb-16 M-565 11-4 IIlb-19 M-607 11-4
IIlb-22
M-524 11-5 IIlb-16 M-566 11-5 IIlb-19 M-608 11-5
IIlb-22
M-525 11-6 IIlb-16 M-567 11-6 IIlb-19 M-609 11-6
IIlb-22
M-526 11-7 IIlb-16 M-568 11-7 IIlb-19 M-610 11-7
IIlb-22
M-527 11-8 IIlb-16 M-569 11-8 IIlb-19 M-611 11-8
IIlb-22
M-528 11-9 IIlb-16 M-570 11-9 IIlb-19 M-612 11-9
IIlb-22
M-529 11-10 IIlb-16 M-571 11-10 IIlb-19 M-613 11-10 IIlb-22
M-530 11-11 IIlb-16 M-572 11-11 IIlb-19 M-614 11-11 IIlb-22
M-531 11-12 IIlb-16 M-573 11-12 IIlb-19 M-615 11-12 IIlb-22
M-532 11-13 IIlb-16 M-574 11-13 _ IIlb-19 M-616 11-13
IIlb-22
M-533 11-14 IIlb-16 M-575 11-14 IIlb-19 M-617 11-14 IIlb-22
M-534 11-1 IIlb-17 M-576 11-1 IIlb-20 M-618 11-1
IIlb-23
M-535 11-2 IIlb-17 M-577 11-2 IIlb-20 M-619 11-2
IIlb-23
M-536 11-3 IIlb-17 M-578 11-3 IIlb-20 M-620 11-3
IIlb-23
M-537 11-4 IIlb-17 M-579 11-4 IIlb-20 M-621 11-4
IIlb-23
M-538 11-5 IIlb-17 M-580 11-5 IIlb-20 M-622 11-5
IIlb-23
M-539 11-6 IIlb-17 M-581 11-6 IIlb-20 M-623 11-6
IIlb-23
M-540 11-7 IIlb-17 M-582 11-7 IIlb-20 M-624 11-7
IIlb-23
M-541 11-8 IIlb-17 M-583 11-8 IIlb-20 M-625 11-8
IIlb-23
M-542 11-9 IIlb-17 M-584 11-9 IIlb-20 M-626 11-9
IIlb-23
M-543 11-10 IIlb-17 M-585 11-10 IIlb-20 M-627 11-10 IIlb-23
M-544 11-11 IIlb-17 M-586 11-11 IIlb-20 M-628 11-11 IIlb-23
M-545 11-12 IIlb-17 M-587 11-12 IIlb-20 M-629 11-12 IIlb-23
M-546 11-13 IIlb-17 M-588 11-13 IIlb-20 M-630 11-13 IIlb-23
M-547 11-14 IIlb-17 M-589 11-14 IIlb-20 M-631 11-14 IIlb-23
M-548 11-1 IIlb-18 M-590 11-1 IIlb-21 M-632 11-1
IIlb-24
M-549 11-2 IIlb-18 M-591 11-2 IIlb-21 M-633 11-2
IIlb-24
M-550 11-3 IIlb-18 M-592 11-3 IIlb-21 M-634 11-3
IIlb-24
M-551 11-4 IIlb-18 M-593 11-4 IIlb-21 M-635 11-4
IIlb-24
M-552 11-5 IIlb-18 M-594 11-5 IIlb-21 M-636 11-5
IIlb-24
M-553 11-6 IIlb-18 M-595 11-6 IIlb-21 M-637 11-6
IIlb-24
M-554 11-7 IIlb-18 M-596 11-7 _ IIlb-21 M-638 11-7
IIlb-24
M-555 11-8 IIlb-18 M-597 11-8 IIlb-21 M-639 11-8
IIlb-24
M-556 11-9 IIlb-18 M-598 11-9 IIlb-21 M-640 , 11-9
IIlb-24
M-557 11-10 IIlb-18 M-599 11-10 IIlb-21 M-641 11-10 IIlb-24
M-558 11-11 IIlb-18 M-600 11-11 IIlb-21 M-642 11-11 IIlb-24
M-559 11-12 IIlb-18 M-601 11-12 IIlb-21 M-643 11-12 IIlb-24
M-560 11-13 IIlb-18 M-602 11-13 IIlb-21 M-644 11-13 IIlb-24
M-561 11-14 IIlb-18 M-603 11-14 IIlb-21 M-645 11-14 IIlb-24
M-562 11-1 IIlb-19 M-604 11-1 IIlb-22 M-646 11-1
IIlb-25
M-563 11-2 IIlb-19 M-605 11-2 IIlb-22 M-647 11-2
IIlb-25
M-564 11-3 IIlb-19 M-606 11-3 IIlb-22 M-648 11-3
IIlb-25
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M-649 11-4 IIlb-25 M-691 11-4 IIlb-28 M-733 11-4
IIlb-31
M-650 11-5 IIlb-25 M-692 11-5 IIlb-28 M-734 11-5
IIlb-31
M-651 11-6 IIlb-25 M-693 11-6 IIlb-28 M-735 11-6
IIlb-31
M-652 11-7 IIlb-25 M-694 11-7 IIlb-28 M-736 11-7
IIlb-31
M-653 11-8 IIlb-25 M-695 11-8 IIlb-28 M-737 11-8
IIlb-31
M-654 11-9 IIlb-25 M-696 11-9 IIlb-28 M-738 11-9
IIlb-31
M-655 11-10 IIlb-25 M-697 11-10 IIlb-28 M-739 11-10 IIlb-31
M-656 11-11 IIlb-25 M-698 11-11 IIlb-28 M-740 11-11 IIlb-31
M-657 11-12 IIlb-25 M-699 11-12 IIlb-28 M-741 11-12 IIlb-31
M-658 11-13 IIlb-25 M-700 11-13 , IIlb-28 M-742 11-13
IIlb-31
M-659 11-14 IIlb-25 M-701 11-14 IIlb-28 M-743 11-14 IIlb-31
M-660 11-1 IIlb-26 M-702 11-1 IIlb-29 M-744 11-1
IIlb-32
M-661 11-2 IIlb-26 M-703 11-2 IIlb-29 M-745 11-2
IIlb-32
M-662 11-3 IIlb-26 M-704 11-3 IIlb-29 M-746 11-3
IIlb-32
M-663 11-4 IIlb-26 M-705 11-4 IIlb-29 M-747 11-4
IIlb-32
M-664 11-5 IIlb-26 M-706 11-5 IIlb-29 M-748 11-5
IIlb-32
M-665 11-6 IIlb-26 M-707 11-6 IIlb-29 M-749 11-6
IIlb-32
M-666 11-7 IIlb-26 M-708 11-7 IIlb-29 M-750 11-7
IIlb-32
M-667 11-8 IIlb-26 M-709 11-8 IIlb-29 M-751 11-8
IIlb-32
M-668 11-9 IIlb-26 M-710 11-9 IIlb-29 M-752 11-9
IIlb-32
M-669 11-10 IIlb-26 M-711 11-10 IIlb-29 M-753 11-10 IIlb-32
M-670 11-11 IIlb-26 M-712 11-11 IIlb-29 M-754 11-11 IIlb-32
M-671 11-12 IIlb-26 M-713 11-12 IIlb-29 M-755 11-12 IIlb-32
M-672 11-13 IIlb-26 M-714 11-13 IIlb-29 M-756 11-13 IIlb-32
M-673 11-14 IIlb-26 M-715 11-14 IIlb-29 M-757 11-14 IIlb-32
M-674 11-1 IIlb-27 M-716 11-1 IIlb-30 M-758 11-1
IIlb-33
M-675 11-2 IIlb-27 M-717 11-2 IIlb-30 M-759 11-2
IIlb-33
M-676 11-3 IIlb-27 M-718 11-3 IIlb-30 M-760 11-3
IIlb-33
M-677 11-4 IIlb-27 M-719 11-4 IIlb-30 M-761 11-4
IIlb-33
M-678 11-5 IIlb-27 M-720 11-5 IIlb-30 M-762 11-5
IIlb-33
M-679 11-6 IIlb-27 M-721 11-6 IIlb-30 M-763 11-6
IIlb-33
M-680 11-7 IIlb-27 M-722 11-7 , IIlb-30 M-764 11-7
IIlb-33
M-681 11-8 IIlb-27 M-723 11-8 IIlb-30 M-765 11-8
IIlb-33
M-682 11-9 IIlb-27 M-724 11-9 IIlb-30 M-766 , 11-9
Illb-33
M-683 11-10 Illb-27 M-725 11-10 Illb-30 M-767 11-10 Illb-33
M-684 11-11 Illb-27 M-726 11-11 Illb-30 M-768 11-11 Illb-33
M-685 11-12 Illb-27 M-727 11-12 Illb-30 M-769 11-12 Illb-33
M-686 11-13 Illb-27 M-728 11-13 Illb-30 M-770 11-13 Illb-33
M-687 11-14 Illb-27 M-729 11-14 Illb-30 M-771 11-14 Illb-33
M-688 11-1 Illb-28 M-730 11-1 Illb-31 M-772 11-1
Illb-34
M-689 11-2 Illb-28 M-731 11-2 Illb-31 M-773 11-2
Illb-34
M-690 11-3 Illb-28 M-732 11-3 Illb-31 M-774 11-3
Illb-34
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M-775 11-4 IIlb-34 M-817 Ila-3 IIla-1 M-859 ha-1 IIla-5
M-776 11-5 IIlb-34 M-818 Ila-4 IIla-1 M-860 Ila-2 IIla-5
M-777 11-6 IIlb-34 M-819 Ila-5 IIla-1 M-861 Ila-3 IIla-5
M-778 11-7 IIlb-34 M-820 Ila-6 IIla-1 M-862 Ila-4 IIla-5
M-779 11-8 IIlb-34 M-821 Ila-7 IIla-1 M-863 Ila-5 IIla-5
M-780 11-9 IIlb-34 M-822 Ila-8 IIla-1 M-864 Ila-6 IIla-5
M-781 11-10 IIlb-34 M-823 Ila-9 IIla-1 M-865 Ila-7 IIla-5
M-782 11-11 IIlb-34 M-824 Ila-10 IIla-1 M-866 Ila-8 IIla-5
M-783 11-12 IIlb-34 M-825 Ila-11 IIla-1 M-867 Ila-9 IIla-5
M-784 11-13 IIlb-34 M-826 Ila-1 _ IIla-2 M-868 Ila-10
IIla-5
M-785 11-14 IIlb-34 M-827 Ila-2 Ilia-2 M-869 Ila-11 IIla-5
M-786 11-1 IIlb-35 M-828 Ila-3 IIla-2 M-870 ha-1 IIla-6
M-787 11-2 IIlb-35 M-829 Ila-4 IIla-2 M-871 Ila-2 IIla-6
M-788 11-3 IIlb-35 M-830 Ila-5 IIla-2 M-872 Ila-3 IIla-6
M-789 11-4 IIlb-35 M-831 Ila-6 IIla-2 M-873 Ila-4 IIla-6
M-790 11-5 IIlb-35 M-832 Ila-7 IIla-2 M-874 Ila-5 IIla-6
M-791 11-6 IIlb-35 M-833 Ila-8 IIla-2 M-875 Ila-6 IIla-6
M-792 11-7 IIlb-35 M-834 Ila-9 IIla-2 M-876 Ila-7 IIla-6
M-793 11-8 IIlb-35 M-835 Ila-10 IIla-2 M-877 Ila-8 IIla-6
M-794 11-9 IIlb-35 M-836 Ila-11 IIla-2 M-878 Ila-9 IIla-6
M-795 11-10 IIlb-35 M-837 Ila-1 IIla-3 M-879 Ila-10 IIla-6
M-796 11-11 IIlb-35 M-838 Ila-2 IIla-3 M-880 Ila-11 IIla-6
M-797 11-12 IIlb-35 M-839 Ila-3 IIla-3 M-881 ha-1 IIla-7
M-798 11-13 IIlb-35 M-840 Ila-4 IIla-3 M-882 Ila-2 IIla-7
M-799 11-14 IIlb-35 M-841 Ila-5 IIla-3 M-883 Ila-3 IIla-7
M-800 11-1 IIlb-36 M-842 Ila-6 IIla-3 M-884 Ila-4 IIla-7
M-801 11-2 IIlb-36 M-843 Ila-7 IIla-3 M-885 Ila-5 IIla-7
M-802 11-3 IIlb-36 M-844 Ila-8 Ilia-3 M-886 Ila-6 IIla-7
M-803 11-4 IIlb-36 M-845 Ila-9 IIla-3 M-887 Ila-7 IIla-7
M-804 11-5 IIlb-36 M-846 Ila-10 IIla-3 M-888 Ila-8 IIla-7
M-805 11-6 IIlb-36 M-847 Ila-11 IIla-3 M-889 Ila-9 IIla-7
M-806 11-7 IIlb-36 M-848 Ila-1 _ IIla-4 M-890 Ila-10
IIla-7
M-807 11-8 IIlb-36 M-849 Ila-2 IIla-4 M-891 Ila-11 IIla-7
M-808 11-9 IIlb-36 M-850 Ila-3 IIla-4 M-892 , ha-1
IIla-8
M-809 11-10 IIlb-36 M-851 Ila-4 IIla-4 M-893 Ila-2 IIla-8
M-810 11-11 IIlb-36 M-852 Ila-5 IIla-4 M-894 Ila-3 IIla-8
M-811 11-12 IIlb-36 M-853 Ila-6 IIla-4 M-895 Ila-4 IIla-8
M-812 11-13 IIlb-36 M-854 Ila-7 IIla-4 M-896 Ila-5 IIla-8
M-813 11-14 IIlb-36 M-855 Ila-8 IIla-4 M-897 Ila-6 IIla-8
M-814 M-856 Ila-9 IIla-4 M-898 Ila-7 IIla-8
M-815 Ila-1 IIla-1 M-857 Ila-10 IIla-4 M-899 Ila-8 IIla-8
M-816 Ila-2 IIla-1 M-858 Ila-11 IIla-4 M-900 Ila-9 IIla-8
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M-901 Ila-10 IIla-8 M-943 Ila-8 IIla-12 M-985 Ila-6 IIla-16
M-902 Ila-11 IIla-8 M-944 Ila-9 IIla-12 M-986 Ila-7 IIla-16
M-903 ha-1 IIla-9 M-945 Ila-10 IIla-12 M-987 Ila-8 IIla-16
M-904 Ila-2 IIla-9 M-946 Ila-11 IIla-12 M-988 Ila-9 IIla-16
M-905 Ila-3 IIla-9 M-947 ha-1 IIla-13 M-989 Ila-10 IIla-16
M-906 Ila-4 IIla-9 M-948 Ila-2 ilia-13 M-990 Ila-11 IIla-16
M-907 Ila-5 IIla-9 M-949 Ila-3 IIla-13 M-991 ha-1 IIla-17
M-908 Ila-6 IIla-9 M-950 Ila-4 IIla-13 M-992 Ila-2 IIla-17
M-909 Ila-7 IIla-9 M-951 Ila-5 IIla-13 M-993 Ila-3 IIla-17
M-910 Ila-8 IIla-9 M-952 Ila-6 _ IIla-13 M-994
Ila-4 IIla-17
M-911 Ila-9 IIla-9 M-953 Ila-7 IIla-13 M-995 Ila-5 IIla-17
M-912 Ila-10 IIla-9 M-954 Ila-8 IIla-13 M-996 Ila-6 IIla-17
M-913 Ila-11 IIla-9 M-955 Ila-9 IIla-13 M-997 Ila-7 IIla-17
M-914 ha-1 IIla-10 M-956 Ila-10 IIla-13 M-998 Ila-8 IIla-17
M-915 Ila-2 IIla-10 M-957 Ila-11 IIla-13 M-999 Ila-9 IIla-17
M-916 Ila-3 IIla-10 M-958 ha-1 IIla-14 M-1000 Ila-10
IIla-17
M-917 Ila-4 IIla-10 M-959 Ila-2 IIla-14 M-1001 Ila-11
IIla-17
M-918 Ila-5 IIla-10 M-960 Ila-3 IIla-14 M-1002 ha-1
IIla-18
M-919 Ila-6 IIla-10 M-961 Ila-4 IIla-14 M-1003 Ila-2
IIla-18
M-920 Ila-7 IIla-10 M-962 Ila-5 IIla-14 M-1004, Ila-3
IIla-18
M-921 Ila-8 IIla-10 M-963 Ila-6 IIla-14 M-1005 Ila-4
IIla-18
M-922 Ila-9 IIla-10 M-964 Ila-7 IIla-14 M-1006 Ila-5
IIla-18
M-923 Ila-10 IIla-10 M-965 Ila-8 IIla-14 M-1007 Ila-6
IIla-18
M-924 Ila-11 IIla-10 M-966 Ila-9 IIla-14 M-1008 Ila-7
IIla-18
M-925 la-1 IIla-11 M-967 Ila-10 IIla-14 M-1009 Ila-8
IIla-18
M-926 Ila-2 IIla-11 M-968 Ila-11 ilia-14 M-1010 Ila-9
IIla-18
M-927 Ila-3 IIla-11 M-969 Ila-1 IIla-15 M-1011 Ila-10
IIla-18
M-928 Ila-4 IIla-11 M-970 Ila-2 IIla-15 M-1012 Ila-11
IIla-18
M-929 Ila-5 IIla-11 M-971 Ila-3 IIla-15 M-1013 ha-1
IIla-19
M-930 Ila-6 IIla-11 M-972 Ila-4 ilia-15 M-1014 Ila-2
IIla-19
M-931 Ila-7 IIla-11 M-973 Ila-5 IIla-15 M-1015 Ila-3
IIla-19
M-932 Ila-8 IIla-11 M-974 Ila-6 _ IIla-15 M-
1016 Ila-4 IIla-19
M-933 Ila-9 IIla-11 M-975 Ila-7 IIla-15 M-1017 Ila-5
IIla-19
M-934 Ila-10 IIla-11 M-976 Ila-8 IIla-15 M-1018, Ila-6
IIla-19
M-935 Ila-11 IIla-11 M-977 Ila-9 IIla-15 M-1019 Ila-7
IIla-19
M-936 Ila-1 IIla-12 M-978 Ila-10 IIla-15 M-1020 Ila-8
IIla-19
M-937 Ila-2 IIla-12 M-979 Ila-11 IIla-15 M-1021 Ila-9 IIla-19
M-938 Ila-3 IIla-12 M-980 Ila-1 IIla-16 M-1022 Ila-10
IIla-19
M-939 Ila-4 IIla-12 M-981 Ila-2 IIla-16 M-1023 Ila-11
IIla-19
M-940 Ila-5 IIla-12 M-982 Ila-3 IIla-16 M-1024 ha-1
IIla-20
M-941 Ila-6 IIla-12 M-983 Ila-4 IIla-16 M-1025 Ila-2
IIla-20
M-942 Ila-7 IIla-12 M-984 Ila-5 IIla-16 M-1026 Ila-3
IIla-20
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M-1027 Ila-4 IIla-20 M-1069 ha-1 IIlb-2 M-1111 Ila-10
IIlb-5
M-1028 Ila-5 IIla-20 M-1070 Ila-2 IIlb-2 M-1112 Ila-11
IIlb-5
M-1029 Ila-6 IIla-20 M-1071 Ila-3 IIlb-2 M-1113 ha-1
IIlb-6
M-1030 Ila-7 IIla-20 M-1072 Ila-4 IIlb-2 M-1114 Ila-2
IIlb-6
M-1031 Ila-8 IIla-20 M-1073 Ila-5 IIlb-2 M-1115 Ila-3
IIlb-6
M-1032 Ila-9 IIla-20 M-1074 Ila-6 IIlb-2 M-1116 Ila-4
IIlb-6
M-1033 Ila-10 IIla-20 M-1075 Ila-7 IIlb-2 M-1117 Ila-5
IIlb-6
M-1034 Ila-11 IIla-20 M-1076 Ila-8 IIlb-2 M-1118 Ila-6
IIlb-6
M-1035 ha-1 IIla-21 M-1077 Ila-9 IIlb-2 M-1119 Ila-7
IIlb-6
M-1036 Ila-2 IIla-21 M-1078 Ila-10 _ IIlb-2 M-1120 Ila-8
IIlb-6
M-1037 Ila-3 IIla-21 M-1079 Ila-11 IIlb-2 M-1121 Ila-9
IIlb-6
M-1038 Ila-4 IIla-21 M-1080 ha-1 IIlb-3 M-1122 Ila-10
IIlb-6
M-1039 Ila-5 IIla-21 M-1081 Ila-2 IIlb-3 M-1123 Ila-11
IIlb-6
M-1040 Ila-6 IIla-21 M-1082 Ila-3 IIlb-3 M-1124 ha-1
IIlb-7
M-1041 Ila-7 IIla-21 M-1083 Ila-4 IIlb-3 M-1125 Ila-2
IIlb-7
M-1042 Ila-8 IIla-21 M-1084 Ila-5 IIlb-3 M-1126 Ila-3
IIlb-7
M-1043 Ila-9 IIla-21 M-1085 Ila-6 IIlb-3 M-1127 Ila-4
IIlb-7
M-1044 Ila-10 IIla-21 M-1086 Ila-7 IIlb-3 M-1128 Ila-5
IIlb-7
M-1045 Ila-11 IIla-21 M-1087 Ila-8 IIlb-3 M-1129 Ila-6
IIlb-7
M-1046 ha-1 IIla-22 M-1088 Ila-9 IIlb-3 M-1130 Ila-7
IIlb-7
M-1047 Ila-2 IIla-22 M-1089 Ila-10 IIlb-3 M-1131 Ila-8
IIlb-7
M-1048 Ila-3 IIla-22 M-1090 Ila-11 IIlb-3 M-1132 Ila-9
IIlb-7
M-1049 Ila-4 IIla-22 M-1091 Ila-1 IIlb-4 M-1133 Ila-10
IIlb-7
M-1050 Ila-5 IIla-22 M-1092 Ila-2 IIlb-4 M-1134 Ila-11
IIlb-7
M-1051 Ila-6 IIla-22 M-1093 Ila-3 IIlb-4 M-1135 ha-1
IIlb-8
M-1052 Ila-7 IIla-22 M-1094 Ila-4 IIlb-4 M-1136 Ila-2
IIlb-8
M-1053 Ila-8 IIla-22 M-1095 Ila-5 IIlb-4 M-1137 Ila-3
IIlb-8
M-1054 Ila-9 IIla-22 M-1096 Ila-6 IIlb-4 M-1138 Ila-4
IIlb-8
M-1055 Ila-10 IIla-22 M-1097 Ila-7 IIlb-4 M-1139 Ila-5
IIlb-8
M-1056 Ila-11 IIla-22 M-1098 Ila-8 IIlb-4 M-1140 Ila-6
IIlb-8
M-1057 M-1099 Ila-9 IIlb-4 M-1141 Ila-7
IIlb-8
M-1058 Ila-1 IIlb-1 M-1100 Ila-10 _ IIlb-4 M-1142 Ila-8
IIlb-8
M-1059 Ila-2 IIlb-1 M-1101 Ila-11 IIlb-4 M-1143 Ila-9
IIlb-8
M-1060 Ila-3 IIlb-1 M-1102 Ila-1 IIlb-5 M-1144 Ila-10
IIlb-8
M-1061 Ila-4 IIlb-1 M-1103 Ila-2 IIlb-5 M-1145 Ila-11
IIlb-8
M-1062 Ila-5 IIlb-1 M-1104 Ila-3 IIlb-5 M-1146 Ila-1
IIlb-9
M-1063 Ila-6 IIlb-1 M-1105 Ila-4 IIlb-5 M-1147 Ila-2
IIlb-9
M-1064 Ila-7 IIlb-1 M-1106 Ila-5 IIlb-5 M-1148 Ila-3
IIlb-9
M-1065 Ila-8 IIlb-1 M-1107 Ila-6 IIlb-5 M-1149 Ila-4
IIlb-9
M-1066 Ila-9 IIlb-1 M-1108 Ila-7 IIlb-5 M-1150 Ila-5
IIlb-9
M-1067 Ila-10 IIlb-1 M-1109 Ila-8 IIlb-5 M-1151 Ila-6
IIlb-9
M-1068 Ila-11 IIlb-1 M-1110 Ila-9 IIlb-5 M-1152 Ila-7
IIlb-9
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M-1153 Ila-8 IIlb-9 M-1195 Ila-6 IIlb-13 M-1237 Ila-4
IIlb-17
M-1154 Ila-9 IIlb-9 M-1196 Ila-7 IIlb-13 M-1238 Ila-5
IIlb-17
M-1155 Ila-10 IIlb-9 M-1197 Ila-8 IIlb-13 M-1239 Ila-6
IIlb-17
M-1156 Ila-11 IIlb-9 M-1198 Ila-9 IIlb-13 M-1240 Ila-7
IIlb-17
M-1157 ha-1 IIlb-10 M-1199 Ila-10 IIlb-13 M-1241 Ila-8
IIlb-17
M-1158 Ila-2 IIlb-10 M-1200 Ila-11 IIlb-13 M-1242 Ila-9
IIlb-17
M-1159 Ila-3 IIlb-10 M-1201 ha-1 IIlb-14 M-1243 Ila-10
IIlb-17
M-1160 Ila-4 IIlb-10 M-1202 Ila-2 IIlb-14 M-1244 Ila-11
IIlb-17
M-1161 Ila-5 IIlb-10 M-1203 Ila-3 IIlb-14 M-1245 ha-1
IIlb-18
M-1162 Ila-6 IIlb-10 M-1204 Ila-4 _ IIlb-14 M-1246 Ila-2
IIlb-18
M-1163 Ila-7 IIlb-10 M-1205 Ila-5 IIlb-14 M-1247 Ila-3
IIlb-18
M-1164 Ila-8 IIlb-10 M-1206 Ila-6 IIlb-14 M-1248 Ila-4
IIlb-18
M-1165 Ila-9 IIlb-10 M-1207 Ila-7 IIlb-14 M-1249 Ila-5
IIlb-18
M-1166 Ila-10 IIlb-10 M-1208 Ila-8 IIlb-14 M-1250 Ila-6
IIlb-18
M-1167 Ila-11 IIlb-10 M-1209 Ila-9 IIlb-14 M-1251 Ila-7
IIlb-18
M-1168 ha-1 IIlb-11 M-1210 Ila-10 IIlb-14 M-1252 Ila-8
IIlb-18
M-1169 Ila-2 IIlb-11 M-1211 Ila-11 IIlb-14 M-1253 Ila-9
IIlb-18
M-1170 Ila-3 IIlb-11 M-1212 ha-1 IIlb-15 M-1254 Ila-10
IIlb-18
M-1171 Ila-4 IIlb-11 M-1213 Ila-2 IIlb-15 M-1255 Ila-11
IIlb-18
M-1172 Ila-5 IIlb-11 M-1214 Ila-3 IIlb-15 M-1256, ha-1
IIlb-19
M-1173 Ila-6 IIlb-11 M-1215 Ila-4 IIlb-15 M-1257 Ila-2
IIlb-19
M-1174 Ila-7 IIlb-11 M-1216 Ila-5 IIlb-15 M-1258 Ila-3
IIlb-19
M-1175 Ila-8 IIlb-11 M-1217 Ila-6 IIlb-15 M-1259 Ila-4
IIlb-19
M-1176 Ila-9 IIlb-11 M-1218 Ila-7 IIlb-15 M-1260 Ila-5
IIlb-19
M-1177 Ila-10 IIlb-11 M-1219 Ila-8 IIlb-15 M-1261 Ila-6
IIlb-19
M-1178 Ila-11 IIlb-11 M-1220 Ila-9 IIlb-15 M-1262 Ila-7
IIlb-19
M-1179 Ila-1 IIlb-12 M-1221 Ila-10 IIlb-15 M-1263 Ila-8
IIlb-19
M-1180 Ila-2 IIlb-12 M-1222 Ila-11 IIlb-15 M-1264 Ila-9
IIlb-19
M-1181 Ila-3 IIlb-12 M-1223 Ila-1 IIlb-16 M-1265 Ila-10
IIlb-19
M-1182 Ila-4 IIlb-12 M-1224 Ila-2 IIlb-16 M-1266 Ila-11
IIlb-19
M-1183 Ila-5 IIlb-12 M-1225 Ila-3 IIlb-16 M-1267 Ila-1
IIlb-20
M-1184 Ila-6 IIlb-12 M-1226 Ila-4 _ IIlb-16 M-1268 Ila-2
IIlb-20
M-1185 Ila-7 IIlb-12 M-1227 Ila-5 IIlb-16 M-1269 Ila-3
IIlb-20
M-1186 Ila-8 IIlb-12 M-1228 Ila-6 IIlb-16 M-1270, Ila-4
IIlb-20
M-1187 Ila-9 IIlb-12 M-1229 Ila-7 IIlb-16 M-1271 Ila-5
IIlb-20
M-1188 Ila-10 IIlb-12 M-1230 Ila-8 IIlb-16 M-1272 Ila-6
IIlb-20
M-1189 Ila-11 IIlb-12 M-1231 Ila-9 IIlb-16 M-1273 Ila-7
IIlb-20
M-1190 Ila-1 IIlb-13 M-1232 Ila-10 IIlb-16 M-1274 Ila-8
IIlb-20
M-1191 Ila-2 IIlb-13 M-1233 Ila-11 IIlb-16 M-1275 Ila-9
IIlb-20
M-1192 Ila-3 IIlb-13 M-1234 Ila-1 IIlb-17 M-1276 Ila-10
IIlb-20
M-1193 Ila-4 IIlb-13 M-1235 Ila-2 IIlb-17 M-1277 Ila-11
IIlb-20
M-1194 Ila-5 IIlb-13 M-1236 Ila-3 IIlb-17 M-1278 Ila-1
IIlb-21
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M-1279 Ila-2 IIlb-21 M-1321 Ila-11 IIlb-24 M-1363 Ila-9
IIlb-28
M-1280 Ila-3 IIlb-21 M-1322 ha-1 IIlb-25 M-1364 Ila-10
IIlb-28
M-1281 Ila-4 IIlb-21 M-1323 Ila-2 IIlb-25 M-1365 Ila-11
IIlb-28
M-1282 Ila-5 IIlb-21 M-1324 Ila-3 IIlb-25 M-1366 ha-1
IIlb-29
M-1283 Ila-6 IIlb-21 M-1325 Ila-4 IIlb-25 M-1367 Ila-2
IIlb-29
M-1284 Ila-7 IIlb-21 M-1326 Ila-5 IIlb-25 M-1368 Ila-3
IIlb-29
M-1285 Ila-8 IIlb-21 M-1327 Ila-6 IIlb-25 M-1369 Ila-4
IIlb-29
M-1286 Ila-9 IIlb-21 M-1328 Ila-7 IIlb-25 M-1370 Ila-5
IIlb-29
M-1287 Ila-10 IIlb-21 M-1329 Ila-8 IIlb-25 M-1371 Ila-6
IIlb-29
M-1288 Ila-11 IIlb-21 M-1330 Ila-9 _ IIlb-25 M-1372 Ila-7
IIlb-29
M-1289 ha-1 IIlb-22 M-1331 Ila-10 IIlb-25 M-1373 Ila-8
IIlb-29
M-1290 Ila-2 IIlb-22 M-1332 Ila-11 IIlb-25 M-1374 Ila-9
IIlb-29
M-1291 Ila-3 IIlb-22 M-1333 ha-1 IIlb-26 M-1375 Ila-10
IIlb-29
M-1292 Ila-4 IIlb-22 M-1334 Ila-2 IIlb-26 M-1376 Ila-11
IIlb-29
M-1293 Ila-5 IIlb-22 M-1335 Ila-3 IIlb-26 M-1377 ha-1
IIlb-30
M-1294 Ila-6 IIlb-22 M-1336 Ila-4 IIlb-26 M-1378 Ila-2
IIlb-30
M-1295 Ila-7 IIlb-22 M-1337 Ila-5 IIlb-26 M-1379 Ila-3
IIlb-30
M-1296 Ila-8 IIlb-22 M-1338 Ila-6 IIlb-26 M-1380 Ila-4
IIlb-30
M-1297 Ila-9 IIlb-22 M-1339 Ila-7 IIlb-26 M-1381 Ila-5
IIlb-30
M-1298 Ila-10 IIlb-22 M-1340 Ila-8 IIlb-26 M-1382 Ila-6
IIlb-30
M-1299 Ila-11 IIlb-22 M-1341 Ila-9 IIlb-26 M-1383 Ila-7
IIlb-30
M-1300 ha-1 IIlb-23 M-1342 Ila-10 IIlb-26 M-1384 Ila-8
IIlb-30
M-1301 Ila-2 IIlb-23 M-1343 Ila-11 IIlb-26 M-1385 Ila-9
IIlb-30
M-1302 Ila-3 IIlb-23 M-1344 ha-1 IIlb-27 M-1386 Ila-10
IIlb-30
M-1303 Ila-4 IIlb-23 M-1345 Ila-2 IIlb-27 M-1387 Ila-11
IIlb-30
M-1304 Ila-5 IIlb-23 M-1346 Ila-3 IIlb-27 M-1388 ha-1
IIlb-31
M-1305 Ila-6 IIlb-23 M-1347 Ila-4 IIlb-27 M-1389 Ila-2
IIlb-31
M-1306 Ila-7 IIlb-23 M-1348 Ila-5 IIlb-27 M-1390 Ila-3
IIlb-31
M-1307 Ila-8 IIlb-23 M-1349 Ila-6 IIlb-27 M-1391 Ila-4
IIlb-31
M-1308 Ila-9 IIlb-23 M-1350 Ila-7 IIlb-27 M-1392 Ila-5
IIlb-31
M-1309 Ila-10 IIlb-23 M-1351 Ila-8 IIlb-27 M-1393 Ila-6
IIlb-31
M-1310 Ila-11 IIlb-23 M-1352 Ila-9 _ IIlb-27 M-1394 Ila-7
IIlb-31
M-1311 Ila-1 IIlb-24 M-1353 Ila-10 IIlb-27 M-1395 Ila-8
IIlb-31
M-1312 Ila-2 IIlb-24 M-1354 Ila-11 IIlb-27 M-1396 Ila-9
IIlb-31
M-1313 Ila-3 IIlb-24 M-1355 Ila-1 IIlb-28 M-1397 Ila-10
IIlb-31
M-1314 Ila-4 IIlb-24 M-1356 Ila-2 IIlb-28 M-1398 Ila-11
IIlb-31
M-1315 Ila-5 IIlb-24 M-1357 Ila-3 IIlb-28 M-1399 Ila-1
IIlb-32
M-1316 Ila-6 IIlb-24 M-1358 Ila-4 IIlb-28 M-1400 Ila-2
IIlb-32
M-1317 Ila-7 IIlb-24 M-1359 Ila-5 IIlb-28 M-1401 Ila-3
IIlb-32
M-1318 Ila-8 IIlb-24 M-1360 Ila-6 IIlb-28 M-1402 Ila-4
IIlb-32
M-1319 Ila-9 IIlb-24 M-1361 Ila-7 IIlb-28 M-1403 Ila-5
IIlb-32
M-1320 Ila-10 IIlb-24 M-1362 Ila-8 IIlb-28 M-1404 Ila-6
IIlb-32
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III
M-1405 Ila-7 IIlb-32 M-1422 Ila-2 IIlb-34 M-1439 Ila-8
IIlb-35
M-1406 Ila-8 IIlb-32 M-1423 Ila-3 IIlb-34 M-1440 Ila-9
IIlb-35
M-1407 Ila-9 IIlb-32 M-1424 Ila-4 IIlb-34 M-1441 Ila-10
IIlb-35
M-1408 Ila-10 IIlb-32 M-1425 Ila-5 IIlb-34 M-1442 Ila-11
IIlb-35
M-1409 Ila-11 IIlb-32 M-1426 Ila-6 IIlb-34 M-1443 ha-1
IIlb-36
M-1410 ha-1 IIlb-33 M-1427 Ila-7 IIlb-34 M-1444 Ila-2
IIlb-36
M-1411 Ila-2 IIlb-33 M-1428 Ila-8 IIlb-34 M-1445 Ila-3
IIlb-36
M-1412 Ila-3 IIlb-33 M-1429 Ila-9 IIlb-34 M-1446 Ila-4
IIlb-36
M-1413 Ila-4 IIlb-33 M-1430 Ila-10 IIlb-34 M-1447 Ila-5
IIlb-36
M-1414 Ila-5 IIlb-33 M-1431 Ila-11 IIlb-34 M-1448 Ila-6
IIlb-36
M-1415 Ila-6 IIlb-33 M-1432 ha-1 IIlb-35 M-1449 Ila-7
IIlb-36
M-1416 Ila-7 IIlb-33 M-1433 Ila-2 IIlb-35 M-1450 Ila-8
IIlb-36
M-1417 Ila-8 IIlb-33 M-1434 Ila-3 IIlb-35 M-1451 Ila-9
IIlb-36
M-1418 Ila-9 IIlb-33 M-1435 Ila-4 IIlb-35 M-1452 Ila-10
IIlb-36
M-1419 Ila-10 IIlb-33 M-1436 Ila-5 IIlb-35 M-1453 Ila-11
IIlb-36
M-1420 Ila-11 IIlb-33 M-1437 Ila-6 IIlb-35
M-1421 ha-1 IIlb-34 M-1438 Ila-7 IIlb-35
For illustration of a ternary mixture according to the present invention and
described in table
M, the combination of the carboxamide compound of formula I with the
biopesticide Pasteuria
nishizawae Pn1 (coded as Ila-10) and with chemical pesticide tioxazafen (coded
as Illa-22) is
represented in table M by the mixture M-1055.
Agricultural compositions
In a further embodiment, the present invention relates to agricultural
compositions comprising
a mixture of the invention, in particular any one of the mixtures A-1 to A-14
or B-1 to B-11 or I-
M-1 to I-M-1453.
The user applies the composition according to the invention usually from a
predosage device,
a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
Usually, the
agrochemical composition is made up with water, buffer, and/or further
auxiliaries to the desired
application concentration and the ready-to-use spray liquor or the
agrochemical composition
according to the invention is thus obtained. Usually, 20 to 2000 liters,
preferably 50 to 400 liters,
of the ready-to-use spray liquor are applied per hectare of agricultural
useful area.
Preferences regarding suitable formulations and auxiliaries, which may be
present in such
agricultural compositions are defined below.
According to one embodiment, individual components of the composition
according to the
invention such as parts of a kit or parts of a binary or ternary mixture may
be mixed by the user
himself in a spray tank or any other kind of vessel used for applications (e.
g. seed treater
drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may
be added, if
appropriate.
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When living microorganisms, such as microbial pesticides from groups L1), L3)
and L5), form
part of such kit, it must be taken care that choice and amounts of the
components (e. g.
chemical pesticides) and of the further auxiliaries should not influence the
viability of the
microbial pesticides in the composition mixed by the user. Especially for
bactericides and
solvents, compatibility with the respective microbial pesticide has to be
taken into account.
Consequently, one embodiment of the invention is a kit for preparing a usable
pesticidal
composition, the kit comprising a) a composition comprising component 1) ,
preferably
compound i of formula I as defined herein and at least one auxiliary; and b) a
composition
comprising component 2) as defined herein and at least one auxiliary; and
optionally c) a
composition comprising at least one auxiliary and optionally a further active
component 3) as
defined herein.
In a further embodiment, the present invention relates to a seed treatment
composition
comprising an auxiliary and a mixture of the invention, preferably any one of
the mixtures A-1 to
A-14 or B-1 to B-11 or I-M-1 to I-M-1453, wherein the auxiliary is preferably
selected from the
group consisting of surfactants, antifreezing agents, binders, and pigments,
and is particularly
preferably a surfactant or a binder.
In a preferred embodiment, the seed treatment composition is in the form of a
flowable
concentrate FS, a solution LS, a powder for dry treatment DS, a water
dispersible powder for
slurry treatment WS, a water-soluble powder SS, an emulsion ES or EC, or a gel
formulation,
and is preferably in the form of a flowable concentrate.
Further preferences regarding seed treatment compositions of the invention are
defined below.
In one embodiment, the present invention relates to the use of a mixture of
the invention, in
particular a mixture selected from the mixtures A-1 to A-14 or B-1 to B-11 or
I-M-1 to I-M-1453,
or a seed treatment composition as defined above, for protecting a plant,
plant propagation
material, or soil or water, in which the plants are growing, against the
attack or infestation by
invertebrate pests.
In another embodiment, the present invention relates to a method for
controlling invertebrate
pests, which method comprises contacting the plant or the plant propagation
material or the soil;
the pests or their food supply, habitat or breeding grounds, with a
pesticidally effective amount
of a mixture of the invention, in particular a mixture selected from the
mixtures A-1 to A-14 or B-
1 to B-11, or a seed treatment composition as defined above.
Preferences regarding plants, pests and application methods are defined below.
In one embodiment, the present invention relates to seeds comprising the
mixture of the
invention, in particular a mixture selected from the mixtures A-1 to A-14 or B-
1 to B-11 or I-M-1
to I-M-1453, or a seed treatment composition as defined above in an amount of
from 0.01 g to
10000 g per 100 kg of seeds.
It is noted that the amount per 100 kg seeds is based on the weight of the
pesticidal mixture
irrespective of whether it is referred to the mixture as such or the seed
treatment composition
thereof.
Preferred seeds are seeds selected from wheat, maize, barley, oat, rye, rice,
soybean, cotton,
sugarbeet, rapeseed, and potato.
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With regard to all the mixtures of the invention as defined herein, the
following embodiments are
additionally preferred.
Additional mixing partners
The mixtures of the present invention may be combined and applied in
agriculture in mixture
with other active ingredients, for example with other pesticides,
insecticides, nematicides,
fungicides, herbicides, safeners, fertilizers such as ammonium nitrate, urea,
potash, and
superphosphate, phytotoxicants and plant growth regulators.
These additional ingredients may be used sequentially or in combination with
the mixtures of
the invention, if appropriate also added only immediately prior to use (tank
mix). For example,
the plant(s) may be sprayed with a mixture of this invention either before or
after being treated
with other active ingredients.
Formulations
The invention also relates to agrochemical compositions comprising an
auxiliary and at least
one mixture of the present invention.
An agrochemical composition comprises a pesticidally effective amount of a
mixture of the
present invention. The term "pesticidally effective amount" is defined below.
The mixtures of the present invention can be converted into customary types of
agro-chemical
compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes,
granules,
pressings, capsules, and mixtures thereof. Examples for composition types are
suspensions
(e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW,
EO, ES, ME),
capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP,
SP, WS, DP,
DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG),
insecticidal
articles (e.g. LN), as well as gel formulations for the treatment of plant
propagation materials
such as seeds (e.g. GF). These and further compositions types are defined in
the "Catalogue of
pesticide formulation types and international coding system", Technical Mono-
graph No. 2, 6th
Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet
and Grube-
mann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New
developments in
crop protection product formulation, Agrow Reports DS243, T&F lnforma, London,
2005.
Examples for suitable auxiliaries are solvents, liquid carriers, solid
carriers or fillers, surfac-
tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration
enhancers, protec-
five colloids, adhesion agents, thickeners, humectants, repellents,
attractants, feeding stimu-
lants, compatibilizers, bactericides, anti-freezing agents, anti-foaming
agents, colorants, tackifi-
ers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as
mineral oil frac-
tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of
vegetable or animal origin;
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aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin,
tetrahydronaphthalene, al-
kylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol,
benzylalcohol, cyclo-thexanol;
glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates,
fatty acid esters,
gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-
methylpyrrolidone,
fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica
gels, talc, kaolins,
limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite,
calcium sulfate,
magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose,
starch;
fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate,
ureas; products of
vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal,
and mixtures
thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic,
nonionic and
amphoteric surfactants, block polymers, polyelectrolytes, and mixtures
thereof. Such surfactants
can be used as emusifier, dispersant, solubilizer, wetter, penetration
enhancer, protective
colloid, or adjuvant. Examples of surfactants are listed in IV1cCutcheon's,
Vol.1: Emulsifiers &
Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed.
or North
American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of
sulfonates, sul-
fates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates
are alkylaryl-
sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates,
sulfonates of fatty
acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of
alkoxylated arylphenols,
sulfonates of condensed naphthalenes, sulfonates of dodecyl- and
tridecylbenzenes, sulfonates
of naphthalenes and alkyl-'naphthalenes, sulfosuccinates or sulfosuccinamates.
Examples of
sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of
alcohols, of ethox-
ylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate
esters. Exam-
ples of carboxylates are alkyl carboxylates, and carboxylated alcohol or
alkylphenol eth-
oxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides,
amine oxides,
esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
Examples of
alkoxylates are compounds such as alcohols, alkylphenols, amines, amides,
arylphenols, fatty
acids or fatty acid esters which have been alkoxylated with 1 to 50
equivalents. Ethylene oxide
and/or propylene oxide may be employed for the alkoxylation, preferably
ethylene oxide. Exam-
ples of N-subsititued fatty acid amides are fatty acid glucamides or fatty
acid alkanolamides.
Examples of esters are fatty acid esters, glycerol esters or monoglycerides.
Examples of sugar-
based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose
esters or
alkylpolyglucosides. Examples of polymeric surfactants are homo- or copolymers
of
vinylpyrrolidone, vinylalcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example
quaternary ammonium
compounds with one or two hydrophobic groups, or salts of long-chain primary
amines. Suitable
amphoteric surfactants are alkylbetains and imidazolines. Suitable block
polymers are block
polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and
polypropylene
oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and
polypropylene oxide.
Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids
are alkali salts of
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polyacrylic acid or polyacid comb polymers. Examples of polybases are
polyvinylamines or
polyethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no
pesticidal activity
themselves, and which improve the biological performance of the mixtures of
the present
invention on the target. Examples are surfactants, mineral or vegetable oils,
and other
auxilaries. Further examples are listed by Knowles, Adjuvants and additives,
Agrow Reports
D5256, T&F lnforma UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum,
carboxymethylcellulose),
anorganic clays (organically modified or unmodified), polycarboxylates, and
silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as
alkylisothiazoli-
nones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and
glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of
fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water
solubility and water-
soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide,
iron hexacyanofer-
rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine
colorants).
Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates,
polyvinyl alcohols,
polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of the mixture according to the invention and 5-15 wt% wetting agent
(e.g. alcohol
alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g.
alcohols) up to 100
wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of the mixture according to the invention and 1-10 wt% dispersant (e.
g. polyvi-
nylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g.
cyclohexanone). Dilution
with water gives a dispersion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of the mixture according to the invention and 5-10 wt% emulsifiers
(e.g. calcium
dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100
wt% water-
insoluble organic solvent (e.g. aromatic hydrocarbon). Dilution with water
gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of the mixture according to the invention and 1-10 wt% emulsifiers
(e.g. calcium
dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt%
water-insoluble
organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into
up to 100 wt% water
by means of an emulsifying machine and made into a homogeneous emulsion.
Dilution with
water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of the mixture according to the invention
are comminuted
with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium
lignosulfonate and
alcohol ethoxylate), 0,1-2 wt% thickener (e.g. xanthan gum) and up to 100 wt%
water to give a
fine active substance suspension. Dilution with water gives a stable
suspension of the active
sub-stance. For FS type composition up to 40 wt% binder (e.g.
polyvinylalcohol) is added.
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vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of the mixture according to the invention are ground finely with
addition of up to 100
wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol
ethoxylate) and
prepared as water-dispersible or water-soluble granules by means of technical
appliances (e. g.
extrusion, spray tower, fluidized bed). Dilution with water gives a stable
dispersion or solution of
the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of the mixture according to the invention are ground in a rotor-
stator mill with ad-
dition of 1-5 wt% dispersants (e.g. sodium lignosulfonate), 1-3 wt% wetting
agents (e.g. alcohol
ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with
water gives a stable dis-
persion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of the mixture according to the invention
are comminuted
with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1-5 wt%
thickener (e.g. car-
boxymethylcellulose) and up to 100 wt% water to give a fine suspension of the
active sub-
stance. Dilution with water gives a stable suspension of the active substance.
ix) Microemulsion (ME)
5-20 wt% of the mixture according to the invention are added to 5-30 wt%
organic solvent
blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant
blend (e.g.
alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This
mixture is stirred for
1 h to produce spontaneously a thermodynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of the mixture according to the invention, 0-
40 wt% water
insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic
monomers (e.g.
methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed
into an aqueous
solution of a protective colloid (e.g. polyvinyl alcohol). Radical
polymerization initiated by a radi-
cal initiator results in the formation of poly(meth)acrylate microcapsules.
Alternatively, an oil
phase comprising 5-50 wt% of the mixture according to the invention, 0-40 wt%
water insolu-ble
organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g.
diphenylme-
thene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a
protective colloid (e.g.
polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine)
results in the for-
mation of a polyurea microcapsule. The monomers amount to 1-10 wt%. The wt%
relate to the
total CS composition.
xi) Dustable powders (DP, DS)
1-10 wt% of a the mixture according to the invention are ground finely and
mixed intimately
with up to 100 wt% solid carrier, e.g. finely divided kaolin.
xii) Granules (GR, FG)
0.5-30 wt% of the mixture according to the invention is ground finely and
associated with up to
100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion,
spray-drying or the
fluidized bed.
xiii) Ultra-low volume liquids (UL)
1-50 wt% of the mixture according to the invention are dissolved in up to 100
wt% organic
solvent, e.g. aromatic hydrocarbon.
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The compositions types i) to xi) may optionally comprise further auxiliaries,
such as 0.1-1 wt%
bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents,
and 0.1-1 wt% col-
orants.
The agrochemical compositions generally comprise between 0.01 and 95%,
preferably be-
tween 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of
active substance.
The active substances are employed in a purity of from 90% to 100%, preferably
from 95% to
100% (according to NMR spectrum).
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and
other pesticides (e.g.
herbicides, insecticides, fungicides, growth regulators, safeners) may be
added to the active
.. substances or the compositions com-prising them as premix or, if
appropriate not until
immediately prior to use (tank mix). These agents can be admixed with the
compositions
according to the invention in a weight ratio of 1:100 to 100:1, preferably
1:10 to 10:1.
The user applies the composition according to the invention usually from a
predosage de-vice,
a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
Usually, the
agrochemical composition is made up with water, buffer, and/or further
auxiliaries to the desired
application concentration and the ready-to-use spray liquor or the
agrochemical composition
according to the invention is thus obtained. Usually, 20 to 2000 liters,
preferably 50 to 400 liters,
of the ready-to-use spray liquor are applied per hectare of agricultural
useful area.
According to one embodiment, individual components of the composition
according to the in-
vention such as parts of a kit or parts of a binary or ternary mixture may be
mixed by the user
himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the composition
according to the in-
vention or partially premixed components, e.g. components comprising mixtures
of the present
.. invention, may be mixed by the user in a spray tank and further auxiliaries
and additives may be
added, if appropriate.
In a further embodiment, either individual components of the composition
according to the in-
vention or partially premixed components, e. g. components comprising mixtures
of the present
invention, can be applied jointly (e.g. after tank mix) or consecutively.
Application methods
The mixtures of the present invention are suitable for use in protecting
crops, plants, plant
propagation materials, such as seeds, or soil or water, in which the plants
are growing, from
attack or infestation by animal pests. Therefore, the present invention also
relates to a plant
protection method, which comprises contacting crops, plants, plant propagation
materials, such
as seeds, or soil or water, in which the plants are growing, to be protected
from attack or
infestation by animal pests, with a pesticidally effective amount of a mixture
of the present
invention.
The mixtures of the present invention are also suitable for use in combating
or controlling
animal pests. Therefore, the present invention also relates to a method of
combating or
controlling animal pests, which comprises contacting the animal pests, their
habitat, breeding
ground, or food supply, or the crops, plants, plant propagation materials,
such as seeds, or soil,
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or the area, material or environment in which the animal pests are growing or
may grow, with a
pesticidally effective amount of a mixture of the present invention.
The mixtures of the present invention are effective through both contact and
ingestion.
Furthermore, the mixtures of the present invention can be applied to any and
all developmental
stages, such as egg, larva, pupa, and adult.
The mixtures of the present invention can be applied as such or in form of
compositions
comprising them as defined above. Furthermore, the mixtures of the present
invention can be
applied together with a mixing partner as defined above or in form of
compositions comprising
said mixtures as defined above. The components of said mixture can be applied
simultaneously, jointly or separately, or in succession, that is immediately
one after another and
thereby creating the mixture "in situ" on the desired location, e.g. the
plant, the sequence, in the
case of separate application, generally not having any effect on the result of
the control
measures.
The application can be carried out both before and after the infestation of
the crops, plants,
plant propagation materials, such as seeds, soil, or the area, material or
environment by the
pests.
Suitable application methods include inter alia soil treatment, seed
treatment, in furrow
application, and foliar application. Soil treatment methods include drenching
the soil, drip
irrigation (drip application onto the soil), dipping roots, tubers or bulbs,
or soil injection. Seed
treatment techniques include seed dressing, seed coating, seed dusting, seed
soaking, and
seed pelleting. In furrow applications typically include the steps of making a
furrow in cultivated
land, seeding the furrow with seeds, applying the pesticidally active mixture
to the furrow, and
closing the furrow. Foliar application refers to the application of the
pesticidally active mixture to
plant foliage, e.g. through spray equipment. For foliar applications, it can
be advantageous to
modify the behavior of the pests by use of pheromones in combination with the
mixtures of the
present invention. Suitable pheromones for specific crops and pests are known
to a skilled
person and publicly available from databases of pheromones and semiochemicals,
such as
http://www.pherobase.com.
As used herein, the term "contacting" includes both direct contact (applying
the
mixtures/compositions directly on the animal pest or plant - typically to the
foliage, stem or roots
of the plant) and indirect contact (applying the mixtures/compositions to the
locus, i.e. habitat,
breeding ground, plant, seed, soil, area, material or environment in which a
pest is growing or
may grow, of the animal pest or plant).
The term "animal pest" includes arthropods, gastropods, and nematodes.
Preferred animal
pests according to the invention are arthropods, preferably insects and
arachnids, in particular
insects. Insects, which are of particular relevance for crops, are typically
referred to as crop
insect pests.
The term "crop" refers to both, growing and harvested crops.
The term "plant" includes cereals, e.g. durum and other wheat, rye, barley,
triticale, oats, rice,
or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g.
sugar beet or fodder
beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears,
plums, peaches,
nectarines, almonds, cherries, papayas, strawberries, raspberries,
blackberries or gooseberries;
leguminous plants, such as beans, lentils, peas, alfalfa or soybeans; oil
plants, such as
rapeseed (oilseed rape), turnip rape, mustard, olives, sunflowers, coconut,
cocoa beans, castor
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oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes,
pumpkins,
cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus
fruit, such as
oranges, lemons, grapefruits or mandarins; vegetables, such as eggplant,
spinach, lettuce (e.g.
iceberg lettuce), chicory, cabbage, asparagus, cabbages, carrots, onions,
garlic, leeks,
tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, such as
avocados,
cinnamon or camphor; energy and raw material plants, such as corn, soybean,
rapeseed, sugar
cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea;
bananas; vines (table
grapes and grape juice grape vines); hop; sweet leaf (also called Stevia);
natural rubber plants
or ornamental and forestry plants, such as flowers (e.g. carnation, petunias,
geranium/pelargoniums, pansies and impatiens), shrubs, broad-leaved trees
(e.g. poplar) or
evergreens, e.g. conifers; eucalyptus; turf; lawn; grass such as grass for
animal feed or
ornamental uses. Preferred plants include potatoes sugar beets, tobacco,
wheat, rye, barley,
oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or
sugar cane; fruits;
vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or
squashes.
The term "plant" is to be understood as including wild type plants and plants,
which have been
modified by either conventional breeding, or mutagenesis or genetic
engineering, or by a
combination thereof.
Plants, which have been modified by mutagenesis or genetic engineering, and
are of particular
commercial importance, include alfalfa, rapeseed (e.g. oilseed rape), bean,
carnation, chicory,
cotton, eggplant, eucalyptus, flax, lentil, maize, melon, papaya, petunia,
plum, poplar, potato,
rice, soybean, squash, sugar beet, sugarcane, sunflower, sweet pepper,
tobacco, tomato, and
cereals (e.g. wheat), in particular maize, soybean, cotton, wheat, and rice.
In plants, which have
been modified by mutagenesis or genetic engineering, one or more genes have
been
mutagenized or integrated into the genetic material of the plant. The one or
more mutagenized
or integrated genes are preferably selected from pat, epsps, cry1Ab, bar,
cry1Fa2, cry1Ac,
cry34Ab1, cry35AB1, cry3A, cryF, cry1F, mcry3a, cry2Ab2, cry3Bb1, cry1A.105,
dfr, barnase,
vip3Aa20, barstar, als, bxn, bp40, asn1, and ppo5. The mutagenesis or
integration of the one or
more genes is performed in order to improve certain properties of the plant.
Such properties,
also known as traits, include abiotic stress tolerance, altered growth/yield,
disease resistance,
herbicide tolerance, insect resistance, modified product quality, and
pollination control. Of these
properties, herbicide tolerance, e.g. imidazolinone tolerance, glyphosate
tolerance, or
glufosinate tolerance, is of particular importance. Several plants have been
rendered tolerant to
herbicides by mutagenesis, for example Clearfield oilseed rape being tolerant
to
imidazolinones, e.g. imazamox. Alternatively, genetic engineering methods have
been used to
render plants, such as soybean, cotton, corn, beets and oil seed rape,
tolerant to herbicides,
such as glyphosate and glufosinate, some of which are commercially available
under the trade
names RoundupReady (glyphosate) and LibertyLink (glufosinate). Furthermore,
insect
resistance is of importance, in particular lepidopteran insect resistance and
coleopteran insect
resistance. Insect resistance is typically achieved by modifying plants by
integrating cry and/or
vip genes, which were isolated from Bacillus thuringiensis (Bt), and code for
the respective Bt
toxins. Genetically modified plants with insect resistance are commercially
available under trade
names including WideStrike , Bollgard , Agrisure0, Herculex , YieldGard ,
Genuity0, and
Intacta . Plants may be modified by mutagenesis or genetic engineering either
in terms of one
property (singular traits) or in terms of a combination of properties (stacked
traits). Stacked
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traits, e.g. the combination of herbicide tolerance and insect resistance, are
of increasing
importance. In general, all relevant modified plants in connection with
singular or stacked traits
as well as detailed information as to the mutagenized or integrated genes and
the respective
events are available from websites of the organizations "International Service
for the Acquisition
of Agri-biotech Applications (ISAAA)"
(http://www.isaaa.org/gmapprovaldatabase) and "Center
for Environmental Risk Assessment (CE RA)" (http://cera-
gmc.org/GMCropDatabase).
The term "plant propagation material" refers to all the generative parts of
the plant such as
seeds and vegetative plant material such as cuttings and tubers (e.g.
potatoes), which can be
used for the multiplication of the plant. This includes seeds, roots, fruits,
tubers, bulbs,
rhizomes, shoots, sprouts and other parts of plants. Seedlings and young
plants, which are to
be transplanted after germination or after emergence from soil, may also be
included. These
plant propagation materials may be treated prophylactically with a plant
protection mixture either
at or before planting or transplanting.
The term "seed" embraces seeds and plant propagules of all kinds including but
not limited to
true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains,
cuttings, cut shoots and the
like, and means in a preferred embodiment true seeds.
In general, "pesticidally effective amount" means the amount of active
ingredient needed to
achieve an observable effect on growth, including the effects of necrosis,
death, retardation,
prevention, and removal, destruction, or otherwise diminishing the occurrence
and activity of the
target organism. The pesticidally effective amount can vary for the various
mixtures/compositions used in the invention. A pesticidally effective amount
of the compositions
will also vary according to the prevailing conditions such as desired
pesticidal effect and
duration, weather, target species, locus, mode of application, and the like.
In the case of soil treatment, in furrow application or of application to the
pests dwelling place
or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100
m2, preferably
from 0.001 to 20 g per 100 m2.
For use in treating crop plants, e.g. by foliar application, the rate of
application of the active
ingredients of this invention may be in the range of 0.0001 g to 4000 g per
hectare, e.g. from 1 g
to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to
100 g per hectare,
more desirably from 10 g to 50 g per hectare, e.g., 10 to 20 g per hectare, 20
to 30 g per
hectare, 30 to 40 g per hectare, or 40 to 50 g per hectare.
The mixtures of the present invention are particularly suitable for use in the
treatment of seeds
in order to protect the seeds from insect pests, in particular from soil-
living insect pests, and the
resulting seedling's roots and shoots against soil pests and foliar insects.
The present invention
therefore also relates to a method for the protection of seeds from insects,
in particular from soil
insects, and of the seedling's roots and shoots from insects, in particular
from soil and foliar
insects, said method comprising treating the seeds before sowing and/or after
pregermination
with a mixture of the present invention. The protection of the seedling's
roots and shoots is
preferred. More preferred is the protection of seedling's shoots from piercing
and sucking
insects, chewing insects and nematodes.
The term "seed treatment" comprises all suitable seed treatment techniques
known in the art,
such as seed dressing, seed coating, seed dusting, seed soaking, seed
pelleting, and in-furrow
application methods. Preferably, the seed treatment application of the active
mixture is carried
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out by spraying or by dusting the seeds before sowing of the plants and before
emergence of
the plants.
The present invention also comprises seeds coated with or containing the
active mixture. The
term "coated with and/or containing" generally signifies that the active
ingredient is for the most
part on the surface of the propagation product at the time of application,
although a greater or
lesser part of the ingredient may penetrate into the propagation product,
depending on the
method of application. When the said propagation product is (re)planted, it
may absorb the
active ingredient.
Suitable seed is for example seed of cereals, root crops, oil crops,
vegetables, spices,
ornamentals, for example seed of durum and other wheat, barley, oats, rye,
maize (fodder
maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers,
cotton,
sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet,
eggplants,
potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash,
cabbage, iceberg
lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas,
garlic, onions,
carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes,
petunias,
geranium/pelargoniums, pansies and impatiens.
In addition, the active mixture may also be used for the treatment of seeds
from plants, which
have been modified by mutagenisis or genetic engineering, and which e.g.
tolerate the action of
herbicides or fungicides or insecticides. Such modified plants have been
described in detail
above.
Conventional seed treatment formulations include for example flowable
concentrates FS,
solutions LS, suspoemulsions (SE), powders for dry treatment DS, water
dispersible powders
for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and
gel
formulation GE. These formulations can be applied to the seed diluted or
undiluted. Application
to the seeds is carried out before sowing, either directly on the seeds or
after having
pregerminated the latter. Preferably, the formulations are applied such that
germination is not
included.
The active substance concentrations in ready-to-use formulations, which may be
obtained
after two-to-tenfold dilution, are preferably from 0.01 to 60% by weight, more
preferably from 0.1
to 40 % by weight.
In a preferred embodiment a FS formulation is used for seed treatment.
Typically, a FS
formulation may comprise 1-800 g/I of active ingredient, 1-200 g/I Surfactant,
0 to 200 g/I
antifreezing agent, 0 to 400 g/I of binder, 0 to 200 g/I of a pigment and up
to 1 liter of a solvent,
preferably water.
Especially preferred FS formulations of the mixtures of the present invention
for seed
treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/I) of the
active ingredient,
from 0.1 to 20 % by weight (1 to 200 g/I) of at least one surfactant, e.g.
0.05 to 5 % by weight of
a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by
weight, e.g. from 5
to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by
weight of a pigment
and/or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a binder
(sticker /adhesion
agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a
thickener, optionally
from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a
biocide,
antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a
filler/vehicle up to
100 % by weight.
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In the treatment of seed, the application rates of the mixtures of the
invention are generally
from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg
of seed, more
preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to
200 g per 100 kg
of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.
The invention therefore also relates to seed comprising a mixture of the
present invention, or
an agriculturally useful salt thereof, as defined herein. The amount of the
mixture of the present
invention or the agriculturally useful salt thereof will in general vary from
0.1 g to 10 kg per 100
kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from
1 g to 1000 g per
100 kg of seed. For specific crops such as lettuce the rate can be higher.
The mixtures of the present invention may also be used for improving the
health of a plant.
Therefore, the present invention also relates to a method for improving plant
health by treating a
plant, plant propagation material and/or the locus where the plant is growing
or is to grow with
an effective and non-phytotoxic amount of a mixture of the present invention.
As used herein "an effective and non-phytotoxic amount" means that the mixture
is used in a
quantity which allows to obtain the desired effect but which does not give
rise to any phytotoxic
symptom on the treated plant or on the plant grown from the treated propagule
or treated soil.
The terms "plant" and "plant propagation material" are defined above.
"Plant health" is defined as a condition of the plant and/or its products
which is determined by
several aspects alone or in combination with each other such as yield (for
example increased
biomass and/or increased content of valuable ingredients), quality (for
example improved
content or composition of certain ingredients or shelf life), plant vigour
(for example improved
plant growth and/or greener leaves ("greening effect"), tolerance to abiotic
(for example drought)
and/or biotic stress (for example disease) and production efficiency (for
example, harvesting
efficiency, processability).
The above identified indicators for the health condition of a plant may be
interdependent and
may result from each other. Each indicator is defined in the art and can be
determined by
methods known to a skilled person.
The mixtures of the invention are also suitable for use against non-crop
insect pests. For use
against said non-crop pests, mixtures of the present invention can be used as
bait composition,
gel, general insect spray, aerosol, as ultra-low volume application and bed
net (impregnated or
surface applied). Furthermore, drenching and rodding methods can be used.
As used herein, the term "non-crop insect pest" refers to pests, which are
particularly relevant
for non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitos,
crickets, or
cockroaches.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The
bait employed in
the composition is a product, which is sufficiently attractive to incite
insects such as ants,
termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The
attractiveness can
be manipulated by using feeding stimulants or sex pheromones. Food stimulants
are chosen,
for example, but not exclusively, from animal and/or plant proteins (meat-,
fish- or blood meal,
insect parts, egg yolk), from fats and oils of animal and/or plant origin, or
mono-, oligo- or
polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose,
glucose, starch,
pectin or even molasses or honey. Fresh or decaying parts of fruits, crops,
plants, animals,
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insects or specific parts thereof can also serve as a feeding stimulant. Sex
pheromones are
known to be more insect specific. Specific pheromones are described in the
literature (e.g.
http://www.pherobase.com), and are known to those skilled in the art.
For use in bait compositions, the typical content of active ingredient is from
0.001 weight % to
.. 15 weight %, desirably from 0.001 weight % to 5% weight % of active
mixture.
Formulations of the mixtures of the present invention as aerosols (e.g in
spray cans), oil
sprays or pump sprays are highly suitable for the non-professional user for
controlling pests
such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are
preferably composed
of the active mixture, solvents, furthermore auxiliaries such as emulsifiers,
perfume oils, if
appropriate stabilizers, and, if required, propellants.
The oil spray formulations differ from the aerosol recipes in that no
propellants are used.
For use in spray compositions, the content of active ingredient is from 0.001
to 80 weights %,
preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight
%.
The mixtures of the present invention and its respective compositions can also
be used in
mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term
vaporizers and
also in moth papers, moth pads or other heat-independent vaporizer systems.
Methods to control infectious diseases transmitted by insects (e.g. malaria,
dengue and yellow
fever, lymphatic filariasis, and leishmaniasis) with mixtures of the present
invention and its
respective compositions also comprise treating surfaces of huts and houses,
air spraying and
.. impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap
or the like. Insecticidal
compositions for application to fibers, fabric, knitgoods, nonwovens, netting
material or foils and
tarpaulins preferably comprise a mixture including the insecticide, optionally
a repellent and at
least one binder.
The mixtures of the present invention and its compositions can be used for
protecting wooden
materials such as trees, board fences, sleepers, frames, artistic artifacts,
etc. and buildings, but
also construction materials, furniture, leathers, fibers, vinyl articles,
electric wires and cables etc.
from ants and/or termites, and for controlling ants and termites from doing
harm to crops or
human being (e.g. when the pests invade into houses and public facilities).
Customary application rates in the protection of materials are, for example,
from 0.001 g to
2000 g or from 0.01 g to 1000 g of active mixture per m2treated material,
desirably from 0.1 g to
50 g per m2.
Insecticidal compositions for use in the impregnation of materials typically
contain from 0.001
to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1
to 25 weight %
of at least one repellent and/or insecticide.
Pests
The mixtures of the the present invention are especially suitable for
efficiently combating animal
pests such as arthropods, gastropods and nematodes including but not limited
to:
insects from the order of Lepidoptera, for example Achro49 grisella, Aden's
spp. such as A.
fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta
major, Adoxophyes spp.
such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A.
exclamationis, A.
fucosa, A. ipsllon, A. orthogoma, A. segetum, A. subterranea; Alabama
argfilacea, Aleuroclicus
dispersus, Alsophila pometaria, Am,oelo,ohaga rubiginosa, Amyelois
transitella, AnacampsZs
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sarcitella, Anagasta kuehniella, Anarsia lineatella, Ani:sota sanatoria,
Antheraea pemp, Anticarsia
(=Thermesia) spp. such as A. gemmatalis; Apamea spp., Aproaerema modkella,
Archips spp.
such as A. argyrospila, A. fuscocupreanus, A. rosana, A. xyloseanus;
Argyresthia conjugella,
Argyroploce spp., Argyrotaenia spp. such as A. velutinana; Athetis mindara,
Austroasca
viridign:sea, Autographa gamma, Autographa nigrisigna, Barathra brassicae,
Bedellia spp.,
Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus
piniarius, Busseola spp.,
Cacoecia spp. such as C. murinana, C. podana; Cactoblastis cactorum, Cadra
cautella, Calingo
brazil/ens/s. Calopas theivora, Capua reticulana, Carposina spp. such as C.
niponensis, C.
sasakil; Cephusspp., Chaetocnema andula, Cheimatobia brumata, Chilospp. such
as C. Indicus,
C. suppressalis, C. partellus; Choreutt:s pariana, Choristoneura spp. such as
C. contlictana, C.
fumiferana, C. longkellana, C. murinana, C. occidental/s, C. rosaceana;
Chrysodeixis
(=Pseudoplusia) spp. such as C. eriosoma, C. includens; Cirphi:s unipuncta,
Clysia ambiguella,
Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Cochylis hospes,
Coleophora
spp., Colias eurytheme, Conopomorpha spp., Conotrachelus spp., Copitarsia
spp., Corcyra
cephalonica, Crambus caliginosellus, Crambus teterrellus, Crocidosema
(=Epinotia) aporema,
Cydalima (=Diaphania) perspectalis, Cydia (=Carpocapsa) spp. such as C.
pomonella, C.
latiferreana; Dalaca noctuides, Datana integerrima, Dasychira pin/cola,
Dendrolimus spp. such
as D. pini, D. spectabilis, D. sibfricus; Desmia funeral/s, Diaphania spp.
such as D. nit/dal/s, D.
hyalinata; Diatraea grandiose//a, Diatraea saccharalis, Diphthera festiva,
Eariasspp. such as E
insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) cur/ails,
Elasmopalpus
lignosellus, Eldana saccharina, Endopiza viteana, Ennomos subsignana, Eoreuma
loftini,
Ephestia spp. such as E. cautella, E. elutella, E. kuehniella; Epinotia
aporema, Epiphyas
postvittana, Erannis ti//aria, Erionota thrax, Etiella spp., Eulia spp.,
Eupoecilia ambiguella,
Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta
Feltia spp. such as F.
subterranean; Galleria melloneia, Gracillaria spp., Grapholita spp. such as G.
funebrana, G.
molesta, G. inopinata; Halysidota spp., Harn:sina americana, Hedylepta spp.,
Helicoverpa spp.
such as H. armigera (=Heliothis armigera), H. zea (=Heliothi:s zea); Heliothis
spp. such as H.
assulta, H. sub flexa, H. virescens; Hellula spp. such as H. undalis, H.
rogatalis; Helocoverpa
gelotopoeon, Hemlleuca
Herpetogramma licarsisalis, Hibernia defoliaria, Hofmannophfla
pseudospretella, Homoeosoma electellum, Homona magnanima, Hypena scabra,
Hyphantria
cunea, Hyponomeuta padella, Hyponomeuta
Kakivoria flavofasciata, Keiferia
lycopersicella, Lambdina fiscellaria
Lambdina fiscellaria lugubrosa, Lamprosema
indicata, Laspeyresia mole sta, Leguminivora glycinivorefla, Lerodea eufala,
Leucinodes
orbonalis, Leucoma
Leucoptera spp. such as L. coffee//a, L. scitella; Leuminivora
lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo
(=Amyna axis), Lobesia
botrana, Lophocampa spp., Loxagroti:s alb/costa, Loxostege spp. such as L.
sticticalis, L.
cereraks; Lymantria spp. such as L. dispar, L. monacha; Lyonetia clerkella,
Lyonetia
Malacosoma spp. such as M. americanurn, M. californicum, M. constrictum, M.
neustria;
Mamestra spp. such as M. brassicae, M. configurata; Mamstra brassicae, Manduca
spp. such as
M. quinquemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis,
Megalopyge
lanata, Melanchra picta, Melanitt:s leda, Mods spp. such as M. laplles, M.
repanda; MOGI:9 ',Wipes,
Monochroa fragariae, Mythimna separata, Nemapogon cloacella, Neoleucinodes
elegantalis,
Nepytia spp., Nymphula spp., Oiketicus spp., Om/odes indicata, Omphisa
anastomosalis,
Operophtera brumata, Orgyia pseudotsugata, Oria spp., Orthaga thyrisaks,
Ostrinia spp. such as
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0. nut:Walls; Oulema oryzae, Paleacrita vemata, PanolLs flammea, Parnara spp.,
Papaipema
nebri:s, Pap/i/o cresphontes, Paramyelois transitella, Paranthrene regal4s,
Paysandisia archon,
Pectinophora spp. such as P. gossypiella; Peridroma saucia, Perfleucoptera
spp., such as P.
coffee/la; Phalera bucephala, Phryganidia californica, Phthorimaea spp. such
as P. operculella;
Phyllocry:st4s citrella, Phyllonorycter spp. such as P. blancardella, P.
crataegella, P. 1:ssikk, P.
ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. nap,- Pilocrocis
tripunctata, Plathypena
scabra, Platynota spp. such as P. flavedana, P. idaeusalis, P. stultana;
Platyptilia carduidactyla,
Plebejus argus, Plodia interpunctella, Plusia spp, Plutella maculipennis,
Plutella xylostella, Pontia
protodica, Prays spp., Prodeniaspp., Proxenus leplgone, Pseudaletia spp. such
as P. sequax, P.
unipuncta; Pyrausta nubilalis, Rachiplusia nu, Richia albicosta, Rhizobius
ventralis, Rhyacionia
frustrana, Sabulodes aegrotata, Schizura con cinna, Schoenobius spp.,
Schreckensteinia
festal/el/a, Scirpophaga spp. such as S. incertulas, S. innotata; Scotia
segetum, Sesamia spp.
such as S. inferens, Seudyra subflava, Sitotroga cerealella, Sparganothis
pilleriana, Spilonota
lechriaspis, S. ocellana, Spodoptera (=Lamphygma) spp. such as S. eridania, S.
exigua, S.
frugiperda, S. lagsfascia, S. &crafts, S. litura, S. omithogalk= Stlgmella
spp., Stomopteryx
subsecivella, Strymon bazochii, Sylepta derogata, Synanthedon spp. such as S.
exitiosa, Tecia
solanivora, Telehin licus, Thaumatopoea pityocampa, Thaumatotibia
(=Cryptophlebia) leucotreta,
Thaumetopoea pi"tyocampa, Thecla spp., Theresimima ampelophaga, Thyrinteina
spp, Tfldenia
inconspicuella, Tinea spp. such as T cloacella, I pellionella; Tineola
bisselliella, Tortrivspp. such
as T. viridana; Trichophaga tapetzella, Trichoplusia spp. such as I ni,. Tuta
(=Scrobipalpula)
absoluta, (idea spp. such as U. rubigalis, U. rubigalis; Virachola spp.,
Yponomeuta padella, and
Zefraphera canadensis;
insects from the order of Coleoptera, for example Acalymma vittatum,
Acanthoscehdes
obtectus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A.
planipennis, A.
sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus;
Alphitobius ogaperinus,
Amphimallus solstitialis, Anisandrus dispar, Ani:soplia austriaca, Anobium
punctatum, Anomala
corpulenta, Anomala rufocuprea, Anoplophora spp. such as A. glabripennis;
Anthonomus spp.
such as A. eugenk, A. grand/s, A. pomorum; Anthrenus spp., Aphthona
euphoridae, Apion spp.,
Apogonia spp., Athous haemorrhoidalls, Atomaria spp. such as A. linear/s;
Attagenus spp.,
Aulacophora femoral/s, Blastophagus piniperda, Blitophaga undata, Bruchidius
obtectus,
Bruchus spp. such as B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae,
Callidiellum
rufipenne, Ca/lop/stria floridensis, Callosobruchus chinensis, Cameraria
ohridella, Cassida
nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp. such as C.
ass/mills, C.
nap,- Chaetocnema tibialis, Cleonus men dicus, Conoderus spp. such as C.
vespertinus;
Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crloceris
asparagi,
Cryptolestes ferrugineus, Cryptorhynchus lapathi, Ctenicera spp. such as C.
destructor; Curculio
spp., Cylh7drocopturus spp., Cyclocephala spp., Dactyl/spa balyi, Dectes
texanus, Dermestes
spp., Diabroticaspp. such as D. undecimpunctata, D. speciosa, D. long/corn/s.
D. semipunctata,
D. virgifera; Diaprepes abbreviates, Dichocrocisspp., Dicladispa armigera,
Diloboderus abderus,
Diocalandra frumenti (Diocalandra stlgmaticollis), Enaphalodes rufulus,
Epllachna spp. such as
E. varivestis, E. vigintioctomaculata; Epitrivc spp. such as E hinYpenni;s, E.
simllan;s; Eutheola
humilis, Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides,
Gnathocerus cornutus,
Hellula undalis, Heteronychus orator, Hylamorpha elegans, Hylobius abletis,
Hylotrupes bajulus,
Hypera spp. such as H. brunneipenn4s, H postica; Hypomeces squamosus,
Hypothenemusspp.,
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fps typogra,ohus, Lachnosterna consanguinea, Lasioderma serricorne, Lathetkus
oryzae,
Lathridius spp., Lema spp. such as L. Mineata, L. melanopus; Leptinotarsa spp.
such as L.
decemlineata; Leptispa pygmaea, Limonius californicus, Lissorhoptrus
oryzo,ohilus, LA-us spp.,
Luperodes spp., Lyctus spp. such as L. bruneus; Liogenys fuscus, Macrodactylus
spp. such as
M subspinosus; Maladera matricla, Megaplatypus mutates, IVegascelis spp.,
Melanotus
communis, Meligethes spp. such as M. aeneus; Melolontha spp. such as M.
hippocastani, M.
melolontha; Metarnasius hemipterus, Microtheca spp.,ti:gdo/us spp. such as M.
fryanus,
Monochamus spp. such as M. alternatus; Naupactus xanthographus, Niptus
hololeucus, Oberia
brevis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis,
Oryzaphagus oryzae,
Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulcatus, Oulema
melanopus,
Oulema oryzae, Oxycetonia jucunda, Phaedon spp. such as P. brassicae, P.
cochleariae;
Phoracantha recurva, Phyllobius pyri, Phyllo,oertha hart/co/a, Phyllophaga
spp. such as P. hellen;
Phyllotreta spp. such as P. chrysocephala, P nemorum, P. striolata, P.
vittula; Phyllopertha
horticola, Popillre japonica, Premnotrypes spp., Psacothea Marls, Psylliodes
chrysocephala,
Prostephanus truncates, Psylliodes spp., Ptinus spp., Pulga saltona,
Rhizopertha dominka,
Rhynchophorus spp. such as R. billineatus, R. ferrugineus, R. palmarum, R.
phoenicis, R.
vulneratus; Saperda candida, Scolytus schevyrewi, Scypho,ohorus acupunctatus,
Sitona lineatus,
SitopMus spp. such as S. granane, S. oryzae, S. zeamais; Sphenophorus spp.
such as S. !ewe;
Stegobium paniceum, Sternechus spp. such as S. subsignatus; Strophomorphus
ctenotus,
Symphyletesspp., Tanymecusspp., Tenebrio molitor, Tenebrioides rnauretanicus,
Tnboliumspp.
such as T castaneum; Trogoderma spp., Tychiusspp., Xylotrechus spp. such as X
pyrrhoderus;
and, Zabrus spp. such as Z tenebrioides;
insects from the order of Diptera for example Aedes spp. such as A. aegyptr;
A. albopictus, A.
vexans; Anastrepha ludens, Anopheles spp. such as A. alb/mantis, A. crucians,
A. freeborni, A.
garnbiae, A. leucosphyrus, A. maculipennis, A. minim us, A. quadrimaculatus,
A. sinensre;
Bactrocera invarlens, Bibio hortulanus, Calliphora erythrocephala, Calliphora
vicina, Ceratigs
capitata, Chrysomyia spp. such as C. bezziana, C. hominivorax, C. macellaria;
Chrysops
atlanticus, Chrysops dis calls, Chrysops silacea, Cochliomyia spp. such as C.
hominivorax;
Contarinia spp. such as C. sorghkola; Corrlylobre anthropophaga, Cu/ex spp.
such as C.
nr:gripalpus, C. pip/ens, C. quinquefasciatus, C. tarsaAs, C.
tritaeniorhynchus; Culicoides furens,
Cu//seta inomata, Culiseta melanura, Cuterebraspp., Dacus cucurbitae, Dacus
oleae, Dasineura
brassicae, Dasineura oxycoccana, De//a spp. such as D. antique, D. coarctata,
D. platura, D.
radicum; Dermatobia hominis, Drosophila spp. such as D. suzukir, Fannia spp.
such as F.
can/cu/ails; Gastraphllus spp. such as G. intestinal/s; Geomyza tipunctata,
Glossinaspp. such as
G. fuscipes, G. morsitans, G. pa/pails, G. tachinoides; Haematobia irritans,
Haplodi,olosis
equestne, Hippelatesspp., Hylemyia spp. such as H. platura; Hypodermaspp. such
as H. lineata;
Hyppobosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp.
such as L. sativae,
L. trifolii; Lucilia spp. such as L. caprina, L. cuprina, L. sericata; Lycoria
pectoralis, Mansonia
titillanus, Mayetiolaspp. such as M. destructor; Musca spp. such as M
autumnal/s, M. domestica;
MUSCi/78 stabulans, Oestrus spp. such as O. ovis; Opomyza forum, Oscinellaspp.
such as 0. frit;
Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. such
as P. ant/qua,
P. brassicae, P. coarctata; Phytomyza gymnostoma, Pros/mu//urn mixtum, Ps//a
rosae,
Psorophora columbiae, Psorophora discolor, Rhagoletis spp. such as R. cerasi,
R. cingulate, R.
indifferens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp.
such as S.
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haemorrhoidalis; Simulium vittatum, Sitodiplos4s mosellana, Stomoxys spp. such
as S. calcitrans;
Tabanus spp. such as T atratus, T. bovinus, I lineola, I simllis; Tannia spp.,
Thecodiplosis
japonensis, Tipula oleracea, Tipula paludosa, and Wohlfahrtia spp;
insects from the order of Thysanoptera for example, Baliothrips biformis,
Dichromothrips
corbetti, Dichromothrips ssp., EchMothrips americanus, Enneothrips flavens,
FranklMiella spp.
such as F. fusca, F. occidentalis, F tritic4. Heliothrips spp., Hercinothrips
femoralis, Kakothrips
spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips
kellyanus,
Rhipiphorothrips cruentatus, Scirtothrips spp. such as S. citri, S. dorsalis,
S. perseae;
Stenchaetothrips spp, Taeniothrips cardamon!, Taeniothrips inconsequens,
Thrips spp. such as
T imagines, T hawaliensis, T oryzae, T. palm', T. parvispinus, T tabacl,-
insects from the order of Hemiptera for example, Acizzia jamatonica,
Acrosternum spp. such as
A. h//are; Acyrthosipon spp. such as A. onobrychis, A. pi:sum; Adelges lands,
Adelges tsugae,
Adelphocoris spp., such as A. rapidus, A. superbus; Aeneolamia spp.,
Agonoscena spp.,
Aulacorthum solani, Aleurocanthus woglumi, Aleurodesspp., Aleurodicus
disperses, Aleurolobus
barodensis, Aleurothrbais spp., Amrasca spp., Anasa tn:sks, Antestiopsis spp.,
Anuraphr:s cardui,
Aonidiellaspp., Aphanoskgma pin; Aphidula nasturtk Aphis spp. such as A.
craccivora, A. fabae,
A. forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pomi, A.
sambuci, A. schneicleri, A.
spfraecola; Arboridia apical/s. An//us critatus, Asp/die//a spp., Aspidiotus
spp., Atanus spp.,
Aulacaspi:s yasumatsul, Aulacorthum solani, Bactericera cockerelli (Paratrioza
cockere119,
Bemisia spp. such as B. argent/folk B. tabaci (Aleurodes tabaci); Blissus spp.
such as B.
leucopterus; Brachycaudus spp. such as B. cardui, B. helichrysi, B. persicae,
B. prunicola;
Brachycolus spp., Brachycorynella asparagi, Brevicoryne brassicae, Cacopsylla
spp. such as C.
fulguralis, C. pyricola (Psylla pfri); Calligypona marginata, Calocon:s spp.,
Campylomma livida,
Capitophorus horn', Cameocephala fulgida, Cavelerius spp., Ceraplastes spp.,
Ceratovacuna
lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii,
Chionaspis
tegalensis, Chlorita onukii, Chromaphi:s jug/and/cola, Chrysomphalus ficus,
Cicadulina mbila,
Cimex spp. such as C. hemipterus, C. lectularius; Coccomytllus hall!, Coccus
spp. such as C.
hesperidum, C. pseudomagnoliarum; Corythucha arcuata, Creontiades dilutus,
Cryptomyzus
rib/s. Chrysomphalus aonidum, Cryptomyzus nbis, Ctenarytaina spatulata,
Cyrtopelks notatus,
Dalbulusspp., Dasynus piper/s. Dialeurodesspp. such as D. citrifolk. Dalbulus
maid/s, Diaphorina
spp. such as D. On; Diaspisspp. such as D. bromeliae; Dichelops furcatus,
Diconocoris hewetti,
Dora/is spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp.,
Dysaphis spp. such as
D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus
spp. such as D.
cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocorisspp.,
Empoasca spp. such
as E. fabae, E. solana; Epidiaspis leperk Eriosoma spp. such as E lanigerum,
E. pyricola;
Erythroneura spp., Eurygasterspp. such as E. integriceps; Euscelis bllobatus,
Euschistus spp.
such as E. heros, E. impictiventn:s, E. servus; Fioni-iia theae, Geococcus
coffeae, Glycasp:s
brimblecombei, Halyomorpha spp. such as H. halys; Heliopelks spp., Homalocksca
vitripennis
(=H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lactucae,
Icerya spp. such
as I. purchase, ldiocerus spp., Idioscopus spp., Laodelphax striatellus,
Lecanium spp.,
Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptocorisa spp.,
Leptoglossus
phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineolaris, L.
pratensis;
Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus,
Macrosiphumspp. such as
/14. rosae, M avenae, M. euphorbiae; Macrosteles quadn7ineatus, Mahanarva
fimbriolata,
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Megacopta cribraria, Megoura viciae, Melanaphi:s pyrarius, Melanaphi:s
sacchari, MelanocalliS
(=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia
costa/Is,
Monelliopsis pecan/s. Myzocallis coryli, Murgantia spp., Myzus spp. such as M.
ascalonicus, M.
cerasi, M. nicotianae, /14. persicae, M. varians; Nasonovia ribis-argri,
Neotoxoptera formosana,
Neomegalotomus spp, Nephotettix spp. such as N. malayanus, N. nigropictus, N.
parvus, N.
virescens; Nezara spp. such as N. viridula; Nilaparvata lugens, Nysius
huttoni, Oebalusspp. such
as 0. pugnax; Oncometopia spp., Orthezia praelonga, Oxycaraenus hyalinipennis,
Parabemisia
myricae, Parlatoria spp., Parthenolecanium spp. such as P. corn!, P. persicae;
Pemphigus spp.
such as P. bursar/us, P. populivenae; Peregrinus maidis, Perkinsiella
sacchariada, Phenacoccus
spp. such as P. aceris, P. gossypir,. Phloeomyzus passerinii, Phorodon humuli,
Phylloxera spp.
such as P. devastatrix, Piesma qua drata, Piezootorus spp. such as P.
guildinri,. Pinnaspi:s
aspidistrae, Planococcus spp. such as P. att.', P. ficus; Prosapia bicincta,
Protopulvinaria
pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona,
Pseudococcus
spp. such as P. comstocla,. Psylla spp. such as P. mali; Pteromalus spp.,
Pulvinaria amygdali,
Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada gigas,
Rastrococcus spp.,
Reduvius senilis, Rhizoecus amerkanus, Rho dnius spp., Rhopalomyzus
ascalonicus,
Rhopalosiphum spp. such as R. pseudobrassicas, R. insertum, R. maidis, R. pad
i; Sagatodes
spp., Sahlbergella singular/s. SaLssetia spp., Sappaphr:s ma/a, Sappaphis mak;
ScaptocoriS spp.,
Scaphoides titanus, Schizaphi:s graminum, Schizoneura lanuginosa, Scotinophora
spp.,
Selenaspidus artkulatus, Sitobion avenae, Sogata spp., Sogatella furcifera,
Solubea insularis,
Spissistllus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis
pyrioides, Stephanitis
takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis maculate,
Thyanta spp.
such as T accerra, T perditor; Tibracaspp., Tomas/Xs spp., Toxoptera spp. such
as I aurantii;
Trialeurootes spp. such as I abutilonea, I ricini, I vaporariorum; Triatoma
spp., Trioza spp.,
Typhlocyba spp., Unaspis spp. such as U. citn, U yanonensis; and Viteus
vitifolii,
Insects from the order Hymenoptera for example Acanthomyops interjectus,
Atha//a rosae, Atta
spp. such as A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A.
robusta, A. sexdens, A.
texana, Bombus spp., Brachymyrmex spp., Camponotus spp. such as C. floridanus,
C.
pennsylvanicus, C. modoc; Cardiocondyla nuda, Chakbion sp, Crematogasterspp.,
Dasymutfila
occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmexspp.,
Dryocosmus kuriphllus,
Formica spp., Hoplocampa spp. such as H. minuta, H. testudri7ea; Iridomyrmex
hum//is, Lasius
spp. such as L. niger, Linepithema humile, Liometopum spp., Leptocybe invasa,
Monomorium
spp. such as /14. pharaonis, Monomorium, Nylandria fulva, Pachycondyla
chinens4s, Paratrechina
long/corn/s. Paravespula spp., such as P. germanica, P pennsylvanica, P
vulgaris; Pheickle
spp. such as P. megacephala; Pogonomyrmex spp. such as P. barbatus, P.
californicus, Polistes
rubiginosa, Prenolepr:s impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex
cyaneus,
Solenopsr:s spp. such as S gemfr7ata, Sinvicta, S. molesta, S. richteri, S.
xyloni, Sphechis
speciosus, Sphexspp., Tapinoma spp. such as I melanocephalum, I sessile;
Tetramoriumspp.
such as T caespitum, I bicarinatum, Vespa spp. such as V. crabro; Vespula spp.
such as V
squamosal; Wasmannia auropunctata, Xylocopasp;
Insects from the order Orthoptera for example Acheta domestkus, Calliptamus
italicus,
Chortoicetes terminifera, Ceuthophllus spp., Diastrammena asynamora,
Dociostaurus
maroccanus, Gryllotalpa spp. such as G. africana, G. gryllotalpa; Gryllus
spp., Hieroglyphus
daganensis, Kraussaria angulifera, Locusta spp. such as L. migratoria, L.
pardalina; Melanoplus
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spp. such as M. bivittatus, M. fernurrubrum, M. mexkanus, M. sanguinkes, M
spretus;
Nomadacris septemfasciata, Oedaleus senegalensis, Scapteriscusspp.,
Schistocercaspp. such
as S. americana, S. gregaria, Stemopelmatus spp., Tachycines asynamorus, and
Zonozerus
vanegatus;
Pests from the Class Arachnida for example Acari,e.g. of the families
Argasidae, Ixodidae and
Sarcoptidae, such as Amblyomma spp. (e.g. A. americanum, A. variegatum, A.
maculatum),
Argas spp. such as A. persku), Boophilusspp, such as B. annulatus, B.
decoloratus, B. mkroplus,
Dermacentor spp. such as Dsilvarum, D, andersoni, 12 variabllis, Hyalomma spp.
such as H.
truncatum, Ixodes spp. such as I. ricinus, I. rubicundus, I. scapular/s. I.
holocyclus, I. pacificus,
Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, 0. hermsi, 0.
turicata,
Ornithonyssus bacoti, Otoblirs megnini, Dermanyssus gallinae, Psoroptes spp.
such as P. owe,
Rhipicephalus spp. such as R. sanguineus, R. appendiculatus, Rhipicephalus
everts',
Rhizoglyphus spp., Sarcoptes spp. such asS. Scabiel, and Family Eriophyidae
including Aceria
spp. such as A. sheldoni, A. anthocoptes, Acallitus spp., Aculo,os spp. such
as A. lycopersic"; A.
pelekasst, Aculusspp. such as A. schlechtendag. Colomerus vitle,
Ep/tr/meruspyri Phyllocoptruta
oleivora; Eriophytes rib's and Eriophyes spp. such as Eriophyes sheldoni;
Family Tarsonemidae
including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus
talus,
Stenotarsonemus spp. Steneotarsonemus sp./7kt, Family Tenuipalpidae including
Brevipalpus
spp. such as B. phoenicis; Family Tetranychidae including Eotetranychus spp.,
Eutetranychus
spp., Oligonychusspp., Petrobia latens, Tetranychus spp. such as T
cinnabarinus, T vans', T
kanzawar, T, pacificus, T phaseulus, T telarius and T urticae; Bryobia
praetiosa; Panonychus
spp. such as P. ulmi, P. citrt, Metatetranychus spp. and Oligonychus spp. such
as 0. pratensts,
0. perseae, Vasates lycopersici, Raoiella indica, Family Carpoglyphidae
including Carpoglyphus
spp.; Penthaleidae spp. such as Halotydeus destructor, Family Demodicidae with
species such
as Demodex spp.; Family Trombicidea including Trombkula spp.; Family
Macronyssidae
including Ornothonyssus spp.; Family Pyemotidae including Pyemotes tritict,
Tyrophagus
putrescentlee; Family Acaridae including Acarus siro; Family Araneida
including Latrodectus
mactans, Tegenaria agrestis, Chiracanthium sp, Lycosa sp Achaearanea
tepidariorum and
Loxosceles reclusa;
Pests from the Phylum Nematoda, for example, plant parasitic nematodes such as
root-knot
nematodes, Meloidogynespp. such as M. hap/a, M. incognita, M. javanica; cyst-
forming
nematodes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H.
avenae, H.
glycines, H. schachtg H. tr/fo/il;Seed gall nematodes, Anguinaspp.; Stem and
foliar
nematodes, Aphelenchoidesspp. such as A. bessep; Sting nematodes,
Belonolaimusspp.
such as B. longicaudatus; Pine nematodes, Bursaphelenchusspp. such as B.
lignicolus, B.
xylophllus; Ring nematodes, Criconerna spp., Criconemellaspp. such as C.
xenoplaxand C.
ornata; and, Crkonemoidesspp. such as Criconemoio'es informis; Mesocriconema
spp.; Stem
and bulb nematodes, DiVenchusspp. such as D. destructor, D. dipsaa,. Awl
nematodes,
Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; Sheath and
sheathoid
nematodes, Hemicycliophora spp. and Hemicriconemoides spp.; Hirshmanniella
spp.; Lance
nematodes, Hoploaimusspp.; False rootknot nematodes, Nacobbusspp.; Needle
nematodes,
Longidorusspp. such as L. elongatus; Lesion nematodes, Pratylenchusspp. such
as P.
brachyurus, P. neglectus, P. penetrans, P. curvitatus, P. goodey"; Burrowing
nematodes,
Radopholusspp. such as R. sirnllis; Rhadopholusspp.; Rhodopholusspp.; Reniform
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nematodes, Rotylenchus spp. such as R. robustus, R. reniformis; Scutellonema
spp.; Stubby-
root nematode, Trichodorus spp. such as T obtusus, T primitivus;
Paratrichodorus spp. such
as P. minor; Stunt nematodes, Tylenchorhynchusspp. such as I claytoni, I
dub/us; Citrus
nematodes, Tylenchulusspp. such as T semipenetrans; Dagger nematodes,
Xiphinemaspp.;
and other plant parasitic nematode species;
Insects from the order lsoptera for example Calotermes fiavicollis,
Coptotermesspp. such as C.
formosanus, C. gestroi, C. acinaciformis; Cornllermes cumulans, Cryptotermes
spp. such as C.
brevis, C. cavifrons; Globitermes sulfureus, Heterotermes spp. such as H.
aureus, H. longiceps,
H. tenur:s; Leucotermes flavipes, Odontotermes spp., Incr:sitermesspp. such as
I. minor, I. Snyder,
Marginitermes hubbardi, Mastotermes spp. such as M. darwiniensis
Neocapritermes spp. such
as N. opacus, N. parvus; Neotermes spp., Procornitermes spp., Zootermopsis
spp. such as Z
angusticollis, Z nevadens4s, Reticulitermesspp. such as R. hesperus, R.
tibialis, R. speratus, R.
flavipes, R. grassei, R. lucifugus, R. santonensis, R. virginicus; Termes
natalensis,
Insects from the order Blattaria for example Blattaspp. such as B. or/entails,
B. lateralis; Blattella
spp. such as B. asahinae, B. germanka; Leucophaea maderae, Panchlora nivea,
Periplaneta
spp. such as P. americana, P. australasiae, P. brunnea, P. fuliggfr7osa, P.
japonica; Supella
long/pa/pa, Parcoblatta pennsylvanica, Eurycotis floridana, Pycnoscelus
surinamensis,
Insects from the order Siphonoptera for example Cediopsylla simples,
Ceratophyllus spp.,
Ctenocephalidesspp. such as C. fells, C. can/s, Xenopsylla cheopr:s, Pulex
irritans, Trichodectes
canis, Tunga penetrans, and Nosopsyllus fasciatus,
Insects from the order Thysanura for example Lepisma saccharina , Ctenolepisma
urbana, and
Thermobia domestica,
Pests from the class Chilopoda for example Geophflus spp., Scutigera spp. such
as Scutigera
coleoptrata;
Pests from the class Diplopoda for example Blaniulus guttulatus, Julus spp.,
Narceus spp.,
Pests from the class Symphyla for example Scutigerella immaculata,
Insects from the order Dermaptera, for example Forficula auricularia,
Insects from the order Collembola, for example Onychiurus spp., such as
Onychiurus armatus,
Pests from the order Isopoda for example, Armadilfidium vulgare, Oniscus
asellus, Porcellio
scaber,
Insects from the order Phthiraptera, for example Damalinia spp., Pediculus
spp. such as
Pediculus humanus capitis, Pediculus humanus corporis, Pediculus humanus
humanus; Ptlyrus
pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus su4s;
Linognathus
spp. such as Linognathus vituk Boy/cola bovis, Menopon gallinae, Menacanthus
stramineus and
Solenopotes capillatus, Trichodectesspp.,
Examples of further pest species which may be controlled by mixtures of the
invention include:
from the Phylum Mollusca, class Bivalvia, for example, Dreissenaspp.; class
Gastropoda, for
example, Arlon spp., Biomphalaria spp., Bulinus spp., Derocerasspp.,
Galbaspp., Lymnaea
spp., Oncomelania spp., Pomacea canalklata, Succinea spp.; from the class of
the helminths,
for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma
brazil/ens/s.
Ancylostoma spp., Ascari:s lubricoides, Ascaris spp., Brugia malayi, Brugia
timorr, Bunostomum
spp., Chabertia spp., C/onorchLs spp., Cooperia spp., Dkrocoelium spp.,
Dktyocaulus fl/aria,
Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus,
Echinococcus
multdocularis, Enterobius vermicular4s, Faciolaspp., Haemonchus spp. such as
Haemonchus
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contortus; Heteralu:sspp., Hymen lep:s nana, Hyostrongulusspp., Loa Loa,
Nernatodirusspp.,
Oesophagostomumspp., Opisthorchisspp., Onchocerca volvulus, Ostertagia spp.,
Paragonimusspp., Schistosomenspp., Strongyloides fuelleborni, Strongyloides
stercora li.s,
Stronyloidesspp., Taenia saginata, Taenks so//urn, Trkhinella spire//s,
Trkhinella native,
Trichinella britovi, Trkhinella nelsom; Trichinella pseudopsiralis,
Trichostrongulus spp., Trkhuri:s
trichuria, Wuchereria bancrofti.
Plant diseases
The mixtures of the present inventon are particularly suitable for controlling
the following
plant diseases:
Albugospp. (white rust) on ornamentals, vegetables (e. g. A. cam:tic/a) and
sunflowers (e. g. A.
tragopogonis); Alternariaspp. (Alternaria leaf spot) on vegetables, rape (A.
brass/cola or
brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g.
A. so/an/or A.
alternate), tomatoes (e. g. A. so/an/or A. alternate) and wheat;
Aphanomycesspp. on sugar
beets and vegetables; Ascochytaspp. on cereals and vegetables, e. g. A.
tritici(anthracnose)
on wheat and A. horde/ on barley; &polaris and Drechsleraspp. (teleomorph:
Cochllobo/us
spp.), e. g. Southern leaf blight (D, mayclis) or Northern leaf blight (B.
zeicola) on corn, e. g. spot
blotch (B. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs;
Blumeria (formerly
Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley);
Botrytis cinerea
(teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g.
strawberries),
vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers,
vines, forestry plants and
wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocysgs (syn.
Ophiostoma) spp. (rot or
wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease)
on elms;
Cercos,00raspp. (Cercospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-
mayclis), rice,
sugar beets (e. g. C. bet/co/a), sugar cane, vegetables, coffee, soybeans (e.
g. C. sojina or C.
kikuchii) and rice; Clao'osporium spp. on tomatoes (e. g. C. fulvum: leaf
mold) and cereals, e. g.
C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals;
Cochllobo/us
(anamorph: Helminthosporium of Bipolar/s) spp. (leaf spots) on corn (C.
carbonum), cereals
(e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. m)iabeanus,
anamorph: H.
oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton
(e. g. C.
gossypk), corn (e. g. C. graminkola:Anthracnose stalk rot), soft fruits,
potatoes (e. g. C.
coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C.
truncatum or C.
gloeosporioides); Corticiumspp., e. g. C. sasakii (sheath blight) on rice;
Corynespora cassiicola
(leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. a oleaginum
on olive trees;
Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline,
teleomorph: Nectrh9 or
Neonectriaspp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph:
Neonectria lirioclendri.
Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rose///n/a)
necatrix (root and
stem rot) on soybeans; Diaporthespp., e.g. D. phaseolorum (damping off) on
soybeans;
Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn,
cereals, such as
barley (e. g. D. teres, net blotch) and wheat (e. g. D. trilici-repentis: tan
spot), rice and turf; Esca
(dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus)
punctata, F. medllerranea,
Phaeomoniella chlamyclospora (earlier Phaeoacremonium chlamydosporurn),
Phaeoacremonium aleophkum and/or Botryosphaeria obtuse; Elsinoespp. on pome
fruits (E.
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pyn), soft fruits (E. veneta: anthracnose) and vines (E ampelina:
anthracnose); Entyloma
oryzae (leaf smut) on rice; Epicoccumspp. (black mold) on wheat; Erysiphespp.
(powdery
mildew) on sugar beets (E betae), vegetables (e. g. E. pist), such as
cucurbits (e. g. E.
cichoracearurn), cabbages, rape (e. g. E cruciferarum); Eutypa lata (Eutypa
canker or dieback,
anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines
and ornamental
woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum);
Fusarlum
(teleomorph: Obberella) spp. (wilt, root or stem rot) on various plants, such
as F. graminearum
or F culmorum (root rot, scab or head blight) on cereals (e. g. wheat or
barley), F. oxysporum
on tomatoes, F. solani (f. sp. glycines now syn. F. virgulfforme) and F
tucumaniae and F.
brasillense each causing sudden death syndrome on soybeans, and F.
verticillioldes on corn;
Gaeumannomyces gram/n& (take-all) on cereals (e. g. wheat or barley) and corn;
Obberella
spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi. Bakanae
disease); Glomerella
cingulata on vines, pome fruits and other plants and G. gossypii on cotton;
Grainstaining
complex on rice; Guignardla bidwellii(black rot) on vines; Gymnosporangiumspp.
on rosaceous
plants and junipers, e.g. G. sabinae (rust) on pears; Helminthosporiumspp.
(syn. Drechslera,
teleomorph: Cochllobo/us) on corn, cereals and rice; Hemilela sop., e. g. H.
vastatfix(coffee leaf
rust) on coffee; Isarlopsis clavispora (syn. Cladosporium WI's) on vines;
Macrophomina
phaseolina (syn. phaseok) (root and stem rot) on soybeans and cotton;
Mkrodochium (syn.
Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley);
IVIicrosphaera diffusa
.. (powdery mildew) on soybeans; Mondinia app., e.g. M. laxa, M. fructicola
and M. fructigena
(bloom and twig blight, brown rot) on stone fruits and other rosaceous plants;
Mycosphaerella
spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M.
graminkola (anamorph:
Septoria &ilia; Septoria blotch) on wheat or M "lenst:s (black Sigatoka
disease) on bananas;
Peronosporaspp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P.
parasitica),
onions (e. g. P destructor), tobacco (P. tabacina) and soybeans (e. g. P
manshurica);
Phakopsora pachyrhizi and P. melbomlae (soybean rust) on soybeans;
Phialophoraspp. e.g.
on vines (e. g. P. trachelphila and P tetraspora) and soybeans (e. g. P.
gregata: stem rot);
Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot,
leaf spot and
damping-off) on sugar beets; Phomopsisspp, on sunflowers, vines (e. g. P.
vi/cola: can and
leaf spot) and soybeans (e. g. stem rot: P. phaseok; teleomorph: Diaporthe
phaseolorum);
Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf,
fruit and stem
root) on various plants, such as paprika and cucurbits (e. g. P capsict),
soybeans (e. g. P.
megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P Infestans: late
blight) and broad-
leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae
(club root) on
cabbage, rape, radish and other plants; Plasmoparaspp., e. g. P viticola
(grapevine downy
mildew) on vines and P halstedi i on sunflowers; Podosphaeraspp. (powdery
mildew) on rosa-
ceous plants, hop, pome and soft fruits, e.g. P leucotricha on apples;
Polymyxaspp., e.g. on
cereals, such as barley and wheat (P. graminis) and sugar beets (P betae) and
thereby
transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot,
teleomorph: Tapesia
yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew)
on various
plants, e. g. P. cubenst:s on cucurbits or P hum/Hon hop; Pseudopezicula
trachelphlla (red fire
disease or ,rotbrenner', anamorph: Phialophora) on vines; Puccinia spp.
(rusts) on various
plants, e. g. P &Nana (brown or leaf rust), P strifformis (stripe or yellow
rust), P horde/(dwarf
rust), P. graminis (stem or black rust) or P recondita (brown or leaf rust) on
cereals, such as
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e. g. wheat, barley or rye, P. kuehm7(orange rust) on sugar cane and P.
asparagi on asparagus;
Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P.
teres (net blotch)
on barley; Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea,
rice blast) on rice
and P. gr/seaon turf and cereals; Pythiumspp. (damping-off) on turf, rice,
corn, wheat, cotton,
rape, sunflowers, soybeans, sugar beets, vegetables and various other plants
(e. g. P. ultimum
or P. aphanidermatum); Ramulariaspp., e. g. R. collo-cygni(Ramularia leaf
spots, Physiological
leaf spots) on barley and R. bet/cola on sugar beets; Rhizoctonla spp. on
cotton, rice, potatoes,
turf, corn, rape, potatoes, sugar beets, vegetables and various other plants,
e. g. R. so/an! (root
and stem rot) on soybeans, R. so/ani(sheath blight) on rice or R. cereaAs
(Rhizoctonia spring
blight) on wheat or barley; Rhizopus stolonifer(black mold, soft rot) on
strawberries, carrots,
cabbage, vines and tomatoes; Rhynchosporium secalls (scald) on barley, rye and
triticale;
Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp.
(stem rot or white
mold) on vegetables and field crops, such as rape, sunflowers (e. g. S.
sclerotiorum) and
soybeans (e. g. S. rolfsiior S. sclerotiorum); Septoriaspp. on various plants,
e. g. S. glycines
(brown spot) on soybeans, S. tritici(Septoria blotch) on wheat and S. (syn.
Stagonospora)
nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe)
necator(powdery mildew,
anamorph: tucker') on vines; Setospaeria spp. (leaf blight) on corn
(e. g. S. turcicum,
syn. Helminthosporium turckum) and turf; Sphacelothecaspp. (smut) on corn, (e.
g. S. reilina:
head smut), sorghum und sugar cane; Sphaerotheca fuli;ginea (powdery mildew)
on cucurbits;
Spongospora subterranea (powdery scab) on potatoes and thereby transmitted
viral diseases;
Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch,
teleomorph:
Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium enclobiotkum
on
potatoes (potato wart disease); Taphrinaspp., e. g. T deformans (leaf curl
disease) on peaches
and T pruni (plum pocket) on plums; Thielaviops4sspp. (black root rot) on
tobacco, pome fruits,
vegetables, soybeans and cotton, e.g. T baskola (syn. Chalara elegans);
(common bunt or stinking smut) on cereals, such as e. g. T tr/t/c/(syn. T
caries, wheat bunt)
and T contro versa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold)
on barley or
wheat; Urocystisspp., e.g. U. occulta (stem smut) on rye; Uromycesspp. (rust)
on vegetables,
such as beans (e. g. U. appendkulatus, syn. U. phaseoll) and sugar beets (e.
g. U. betae);
Ustllagospp. (loose smut) on cereals (e. g. U nuda and U. avaenae), corn (e.
g. U maydi:s:
corn smut) and sugar cane; Ventufiaspp. (scab) on apples (e. g. V. inaequalis)
and pears; and
Vertkillium spp. (wilt) on various plants, such as fruits and ornamentals,
vines, soft fruits,
vegetables and field crops, e. g. V cfah/49e on strawberries, rape, potatoes
and tomatoes.
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Examples
Synergism can be described as an interaction where the combined effect of two
or more
compounds is greater than the sum of the individual effects of each of the
compounds. The
presence of a synergistic effect in terms of percent control, between two
mixing partners (X and
Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating
Synergistic and
Antagonistic Responses in Herbicide Combinations, Weeds, 15, 21-22):
_ XY
E = X + 1 ¨ ¨
100
When the observed combined control effect is greater than the expected
combined control
effect (E), then the combined effect is synergistic.
Tests may demonstrate the control efficacy of compounds, mixtures or
compositions of this
invention on specific pests. However, the pest control protection afforded by
the compounds,
mixtures or compositions is not limited to these species. In certain
instances, combinations of a
compound of this invention with other invertebrate pest control compounds or
agents are found
to exhibit synergistic effects against certain important invertebrate pests.
The analysis of synergism or antagonism between the mixtures or compositions
may be
determined using Colby's equation.
Pesticides tested
The preferred Compound I, namely compound i of formula I has been
provisionally approved
under the common name broflanilide.
Formulation . Description
_ Active Ingredient
Broflanilide SC Broflanilide, GABA antagonist 10%
Beauveria bassiana, strain PPRI5339,
Broadband 1019 EC formulation
¨4X 109 CFU/ml
Bacillus thuringiensis, subsp. kurstaki, strain 54%
fermentation solids,
Dipel Pro DF ABTS-351, dry flowable formulation
spores, and toxins
Lepidopteran Efficacy
Large leaf lima bean (southern armyworm) and radish (diamondback moth) were
dipped in
treatment solution and allowed to dry. The leaves were excised and placed
individually into
square petri dishes containing two filter paper discs moistened with 0.5 ml of
reverse osmosis
water. One neonate insect per dish (total of 20 dishes per treatment, grouped
into 5 dishes per
replicate) were infested for the test with southern armyworm. Five insects per
dish (total of 5
dishes per treatment) were infested for the test with diamondback moth. The
studies were held
in an environmental chamber 14L: 10D at 30 C and 70% RH. The number of dead
and
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moribund insects were recorded (moribund was considered dead). Rate rundowns
were
conducted initially to determine sublethal rates for the combination testing.
replications with 5 insects are each conducted per treatment, insects are held
singly.
Control mortality is less than 15% and standard treatments yielded 100%
mortality.
5
Table 4. Efficacy of Broadband BB 1019 (B. bassiana) and broflanilide against
neonate
diamondback moth via radish leaf dip
Mean % Mortality @
Days after Treatment
Treatment 2 DAT
broflanilide @ 0.01 ppm 44.0
Broadband 1019 @20 u1/1 00m1 16.0
Combination 96.0
Synergy Factor 1.8
Synergy Observed (Colby's Formula) yes
The results showed that the combination of broflanilide and Broadband
displayed an obvious
synergistic effect against diamondback moth.
Table 5. Efficacy of Dipel (B. thuringiensis) + broflanilide against neonate
southern armyworm
via lima bean leaf dip
Mean % Mortality
@ Days after Treatment
Treatment 4 DAT
BAS 450 @ 0.0025 ppm 23.5
Dipel @ 25 ppm 10.3
Combination 47.1
Synergy Factor 1.5
Synergy Observed (Colby's Formula) Synergy
Efficacy of the combination of broflanilide and Dipel against southern
armyworm was numerically
higher than that of individual products, and showed a synergistic effect.
63a
In some aspects, described herein are one or more of the following items:
1. Pesticidal mixtures comprising as active components:
1) a pesticidal active carboxamide compound I of formula (I)
CF3
F
Br
CH F 0 CF3
I 3
N
N
H
0 CF3
(I);
and
2) Beauveria bassiana or Bacillus thuringiensis;
in synergistically effective amounts.
2. The mixtures according to item 1, wherein component 1) and component 2)
are present in
a total weight ratio of from 10:1 to 1:20 000 wherein the total weight of
component 2) is
based on the amount of the solid material (dry matter) of component 2).
3. The mixtures according to item 1, wherein component 1) and component 2)
are present in
a total weight ratio of from 1:1 to 1:10 000 wherein the total weight of
component 2) is
based on the amount of the solid material (dry matter) of component 2).
4. The mixtures according to any one of items 1 to 3, wherein component 2)
is Beauveria
bassiana.
5. The mixtures according to any one of items 1 to 3, wherein component 2)
is Bacillus
thuringiensis.
6. A seed treatment composition comprising an auxiliary and a mixture as
defined in any one
of items 1 to 5, wherein the auxiliary is selected from the group consisting
of surfactants,
antifreezing agents, binders, and pigments.
7. The seed treatment composition of item 6, wherein the auxiliary is a
surfactant.
8. The seed treatment composition of item 6, wherein the auxiliary is a
binder.
Date Recue/Date Received 2022-09-02
63b
9. The seed treatment composition according to any one of items 6 to 8,
which is in the form
of a flowable concentrate FS, a solution LS, a powder for dry treatment DS, a
water
dispersible powder for slurry treatment WS, a water-soluble powder SS, an
emulsion ES or
EC, or a gel formulation.
10. The seed treatment composition according to any one of items 6 to 8, which
is in the form
of a flowable concentrate.
11. Use of the mixture as defined in any one of items 1 to 5 or the seed
treatment composition
as defined in any one of items 6 to 10, for protecting a plant, a plant
propagation material,
or soil or water, in which the plants are growing, against the attack or
infestation by
invertebrate pests.
12. A method for controlling invertebrate pests, which method comprises
contacting a plant, a
plant propagation material, a seed, soil, or water; or the pests or their food
supply, habitat
or breeding grounds, with a pesticidally effective amount of the mixture as
defined in any
one of items 1 to 5 or with the seed treatment composition as defined in any
one of items 6
to 10.
13. A method for controlling nematodes, which method comprises contacting a
plant,a plant
propagation material, a seed, soil, or water, or the nematodes or their food
supply, habitat
or breeding grounds, with a pesticidally effective amount of the mixture as
defined in any
one of items 1 to 5 or with the seed treatment composition as defined in any
one of items 6
to 10.
14. Use of seeds treated with the mixture as defined in any one of items 1
to 5 or the seed
treatment composition as defined in any one of items 6 to 10, in an amount
from 0.01 g to
10000 g per 100 kg of seeds, for protecting a plant, a plant propagation
material, or soil or
water, in which the plants are growing, against the attack or infestation by
invertebrate
pests.
15. Use of the mixture as defined in any one of items 1 to 5 or the seed
treatment composition
as defined in any one of items 6 to 10, in an amount of from 0.01 g to 10000 g
per 100 kg
for treating seeds, for controlling invertebrate pests in a plant, a plant
propagation material,
soil or water.
16. The use according to item 11, 14, or 15, wherein the invertebrate pests
are nematodes.
Date Recue/Date Received 2022-09-02
