Pesticidal Mixtures

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Feb 24, 2011 ... compounds may be found in The Pesticide Manual, 13th. Edition, British Crop ..... Hg are preferred, compounds Ha, Hd, He are more preferred.
US 20110046123A1

(19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0046123 A1 Jamet et al. 54

(43) Pub. Date:

PESTICIDAL MIXTURES

Inventors:

Willi Laurent Gerhard, Jamet’ Dexheim Lyon (DE);

Dirk Voeste, Limburgerhof (DE)

Foreig nAPP lication Priority Data

4,

Publication . . . . . . Classi?cation . . . . . . . . . . . . . . . . . . . . . . . . . . ..

(51) Int‘ Cl‘

Correspondence Address: BRINKS, HOFER, GILSON & LIONE

A01N 43/88 A01N 43/40 A01N 43/78

(2006.01) (200601) (200601)

PO. BOX 110285 RESEARCH TRIANGLE PARK, NC 27709 (US)

A01N 43/56 A01N 43/54

(2006.01) (2006.01)

A01P 7/04

(2006.01)

‘401p 3/00

(200601)

(73) Assignee:

(21) APPI' NO‘: (22)

30

Feb. 24, 2011

PCT Filed:

(86) PCT NO;

BASF SE, LudWigshafen (DE) (52)

US. Cl. .................... .. 514/229.2; 514/357; 514/365;

(57)

514/341; 514/406; 514/407; 514/269 ABSTRACT

12/865,897 Feb- 41 2009

PCT/EP09/51260

The present invention relates to synergistic mixtures compris ing, as active components, an insecticidal compound (I) selected from following nicotinic receptor agonists/antago nists compounds, an amide compound one or tWo further

§ 371 (0X1), (2), (4) Date;

Nov, 10, 2010

fungicidal compound(s) and/or an insecticidal compound selected from the group consisting of ?pronil and ethiprole.

Feb. 24, 2011

US 2011/0046123 A1

PESTICIDAL MIXTURES

[0019] In one embodiment, the present invention provides methods for the control of animal pests (such as insects,

[0001] The present invention relates to synergistic mixtures comprising, as active components, [0002] 1) an insecticidal compound I selected from folloW

ing nicotinic receptor agonists/antagonists compounds: acetamiprid, clothianidin, dinotefuran, imidacloprid, thia methoxam and nitenpyram; and [0003] 2) an amide compound II having the formula II

breeding grounds or their locus With a pesticidally effective amount of the inventive mixtures (except for the binary mix

tures). [0020]

O

Which the plant is groWing, With a pesticidally effective amount of the inventive mixture (except for the binary mix

tures). [0021] N

N\//N I

Moreover, in another embodiment the present

invention also relates to a method of protecting plants from attack or infestation by animal pests (insects, acarids or nema todes) comprising contacting the plant, or the soil or Water in II

R4

acarids or nematodes) comprising contacting the animal pest (the insect, acarid or nematode) or their food supply, habitat,

|

R5 H

Q\ R1,

H3C

Additionally, the present invention also comprises a

method for protection of plant propagation material (prefer ably seed) from harmful pests, such as fungi or insects, arach nids or nematodes comprising contacting the plant propaga tion materials (preferably seeds) With an inventive mixture (except or the binary mixtures) in pesticidally effective amounts

[0004]

in Which the substituents are as de?ned beloW:

phenyl ring is substituted or not substituted With a ?uo

[0022] The term “plant propagation material” is to be understood to denote 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 multiplica tion of the plant. This includes seeds, roots, fruits, tubers,

rine atom;

bulbs, rhiZomes, shoots, sprouts and other parts of plants,

[0005] R4 is methyl, di?uoromethyl, or tri?uoromethyl; [0006] [0007]

[0008]

R5 is hydrogen or ?uorine. M is a thienyl ring or a phenyl ring, Wherein the

Q s a direct bond, a cyclopropylene or an anel

lated bicyclo[2.2.1]heptane ring; [0009] R1 is cyclopropyl, 1,3-dimethylbutyl, isopropyl,

including seedlings and young plants, Which are to be trans planted after germination or after emergence from soil. These

young plants may also be protected before transplantation by

phenyl substituted With tWo or three halogen atoms or a

a total or partial treatment by immersion or pouring. In a

tri?uoromethylthio radical; and

particular preferred embodiment, the term propagation mate

3) one or tWo further fungicidal compound(s) III selected from the group consisting of thiophanate-methyl,

rial denotes seeds.

procloraZ, orysastrobin, pyraclostrobin, tri?oxystrobin and

method for protection of plant propagation material (prefer ably seed) from harmful fungi comprising contacting the plant propagation materials (preferably seeds) With the binary

[0010]

aZoxylstrobin; and/or [0011] 4) compound IV selected from the group consisting of ?pronil and ethiprole as compound IV; in synergistic effective amounts. [0012] The invention furthermore relates to binary mix tures comprising, as active components, [0013] 1) an insecticidal compound I selected from folloW

[0023]

Additionally, the present invention also comprises a

mixture in pesticidally effective amounts [0024]

Moreover, the invention relates to a method for con

ing nicotinic receptor agonists/antagonists compounds: acetamiprid, clothianidin, dinotefuran, imidacloprid, thia methoxam, nitenpyram; and

trolling harmful fungi using the inventive mixtures and to the use of the compoundI and the compound II and compound(s) III and/or compound IV (or compound I and II as de?ned above) for preparing such mixtures, and also to compositions comprising such mixtures. [0025] The present invention further relates to plant-pro

[0014] 2) N-(3',4',5'-tri?uorobiphenyl-2-yl)-3-di?uorom

tecting active ingredient mixtures having synergistically

ethyl-1-methyl-1H-pyraZole-4-carboxamide as compound II in synergistic effective amounts. [0015] These binary mixtures (herein after referred as

“binary mixture”) only exhibit fungicidal synergistic effects and/ or plant health synergistic effects. [0016]

The above-referred mixtures are hereinbeloW also

referred as “inventive mixtures”. [0017] Moreover, the invention relates to a method for con

trolling pests, this refers to includes animal pests and harmful fungi, using the inventive mixtures and to the use of com

pound I and the compound II and compound(s) III and/or compound IV for preparing such mixtures, and also to com

enhanced action of improving the health of plants and to a method of applying such inventive mixtures to the plants. [0026] The active ingredients II are knoWn as fungicides (cf., for example, EP-A 545 099, EP-A 589 301, EP-A 737682, EP-A 824099, WO 99/09013, WO 03/010149, WO 03/070705, WO 03/074491, WO 2004/005242, WO 2004/ 035589, WO 2004/067515, WO 06/087343), or they can be prepared in the manner described therein. [0027] The compounds of formula I, III and IV as Well as their pesticidal action and methods for producing them are

generally knoWn. For instance, the commercially available

positions comprising such mixtures.

compounds may be found in The Pesticide Manual, 13th Edition, British Crop Protection Council (2003) among other

[0018]

publications.

Moreover, the invention relates to a method for con

trolling harmful fungi, using the inventive mixtures of com poundI and II and to the use of compound I and the compound II as de?ned above for preparing such mixtures, and also to

compositions comprising such mixtures.

[0028]

EP application No. 081520595, EP application No.

081558819, EP application No. 071198584 and PCT/ EP2008/051955 disclose binary mixtures comprising a speci ?ed amide of formula I, epoxiconaZole or metconaZole,

Feb. 24, 2011

US 2011/0046123 A1

Which may comprise a further commercial pesticide. Suitable

imaZaquin or dimethenamid-P, in particular glyphosate, sul phosate, gluphosinate or dimethenamid-P, ?pronil, imidaclo

[0041] Another dif?culty 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, that means animal pests, and harmful fungi, 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.

prid, acetamiprid, nitenpyram, carbofuran, carbosulfan, ben furacarb, dinotefuran, thiacloprid, thiamethoxam, clothianidin, di?ubenZuron, ?ufenoxuron, te?ubenZuron,

is the desire for compositions that improve plants, a process Which is commonly and hereinafter referred to as “plant

alpha-cypermethrin and meta?umiZone, in particular

health”.

?pronil, imidacloprid, acetamiprid, carbofuran, thia methoxam, clothianidin, ?ufenoxuron, te?ubenZuron, alpha

improvements of plants that are not connected to the control

ternary mixing partners mentioned therein are glyphosate,

sulphosate, gluphosinate, te?uthrin, terbufos, chlorpyrifos, chloroethoxyfos, tebupirimfos, phenoxycarb, diofenolan, pymetroZine, imaZethapyr, imaZamox, imaZapyr, imaZapic,

cypermethrin and meta?umiZone. [0029] Combinations comprising a speci?c amide of for mula I and orysastrobin and combinations amide of formula I, a strobilurine and thiophanate-methyl are disclosed in WO

[0042] Another problem underlying the present invention

[0043]

The term plant health comprises various sorts of

of pests. For example, advantageous properties that may be mentioned are improved crop characteristics including: emergence, crop yields, protein content, oil content, starch content, more developed root system (improved root groWth),

[0030] Combinations of speci?c amides of formula I together With neonicotinoids and fungicides are disclosed in

improved stress tolerance (e.g. against drought, heat, salt, UV, Water, cold), reduced ethylene (reduced production and/or inhibition of reception), tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic

WO 08/000,377.

activity, less input needed (such as fertilizers or Water), less

[0031] General disclosure about an amide of formula I together With a large fungicides or several insecticides are set

seeds needed, more productive tillers, earlier ?owering, early grain maturity, less plant verse (lodging), increased shoot

forth in WO 07/128,756. [0032] WO 06/069654, WO06/089876 and WO 06/23899

groWth, enhanced plant vigor, increased plant stand and early

07/017,416. Combinations comprising amide compound of formula II and thiophanate-methyl are disclosed in PCT/ EP2008/051331 and in PCT/EP2008/051375.

disclose mixtures of neonicotinoids and strobilurins. WO

06/23899 also discloses mixtures of imidacloprid and other

fungicides. [0033] EP 806895A, WO 97/24032, WO06/100227, WO97/40692 and WO 00/230202 all disclose combinations

of ?pronil and several, selected neonicotinoids. [0034] WO 08/006,541 discloses penthiopyrad mixtures With fungicides, Which optionally may comprise an insecti cide. [0035]

WO 97/22254 discloses mixtures of thiamethoxam With aZoles such as triticonaZole, pyrimethanil and prochlo raZ. W0 06/ 128655 disclosed mixtures of neonicotinoids With several aZoles as Well as mixtures of a huge number of

insecticides that can be combined With several fungicides. WO 06/24333 describes a neonicotinoid formulation, Which may, as second component comprise at least one further fun

gicide. [0036]

HoWever, the speci?c mixtures of the present inven

tion, Which are based on a compound I and compound II and compound(s) III and/ or compounds IV are not explicitly dis closed therein. In addition, the speci?c combinations of com poundI and II as de?ned above, is also not mentioned therein.

[0037]

One typical problem arising in the ?eld of pest con

trol lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environ mental or toxicological effects Whilst still alloWing effective

pest control. [0038] In regard to the instant invention the term pests embrace animal pests, and harmful fungi.

and better germination; or any other advantages familiar to a person skilled in the art. [0044] It Was therefore an object of the present invention to

provide pesticidal mixtures Which solve the problems of reducing the dosage rate and/or enhancing the spectrum of activity and/or combining knock-down activity With pro longed control and/or to resistance management and/ or pro

moting the health of plants. [0045]

We have found that this object is in part or in Whole

achieved by the mixtures comprising the active compounds de?ned in the outset.

[0046] Especially, it has been found that the mixtures as de?ned in the outset shoW markedly enhanced action against pests compared to the control rates that are possible With the individual compounds and/or is suitable for improving the

health of plants When applied to plants, parts of plants, seeds, or at their locus of groWth.

[0047]

It has been found that the action of the inventive

mixtures goes far beyond the fungicidal and/or insecticidal and/or plant health improving action of the active compounds present in the mixture alone. [0048] Moreover, We have found that simultaneous, that is joint or separate, application of the compound I and the com pound II and compound(s) III and/or compound IV or suc

cessive application of the compound I and the compound II and compound(s) III and/or compound IV alloWs enhanced control of pests, that means animal pests, and harmful fungi, compared to the control rates that are possible With the indi

vidual compounds (synergistic mixtures).

[0039] Another problem encountered concerns the need to have available pest control agents Which are effective against a broad spectrum of pests, e.g. both animal pests and harmful

[0049] Moreover, We have found that simultaneous, that is joint or separate, application of the compound I and the com pound II or successive application of the compound I and the compound II alloWs enhanced control of pests, that means harmful fungi, compared to the control rates that are possible

fungi.

With the individual compounds (synergistic mixtures).

[0040]

There also exists the need forpest control agents that

combine knock-down activity With prolonged control, that is, fast action With long lasting action.

[0050] Moreover, We have found that simultaneous, that is joint or separate, application of the compound I and the com pound II and compound(s) III and/ or compound IV (or com

Feb. 24, 2011

US 2011/0046123 A1

pound I and II as de?ned above) or successive application of

the compound I and the compound II and compound(s) III and/ or compound IV (or compound I and II as de?ned above) provides enhanced plant health effects compared to the plant

Which is N-(3',4'-dichloro-5-?uorobiphenyl-2-yl)-3-di?uo romethyl-1-methylpyraZole-4-carboxamide (common name bixafen), herein after referred to as “IIc.

health effects that are possible With the individual com

[0055]

pounds.

according to the invention comprise as compound II the com

[0051]

Preferably, the binary, ternary, quarternary or ?ve

In another preferred embodiment, the mixtures

pound of the formula IId

fold mixtures according to the present invention comprise as compound I clothianidin, imidacloprid, thiamethoxam or acetamiprid, more preferably clothianidin, imidacloprid or thiamethoxam. The most preferred compound I is clothiani din.

[0052]

Hd 0

H30

In another preferred embodiment, the ternary, quar

ternary or ?vefold mixtures comprise as compound II the compound of the formula 11a

H

F

/

H0

0H(0H3)3,

3

H30

o

/

N

|

\N

11 3.

N

/

N

N

l

\

Which is N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5

H

N

?uoro-1H-pyraZole-4-carboxamide, herein after referred to

/

as “IId”.

H30 F

[0056]

F,

In another preferred embodiment, the mixtures

according to the invention comprise as compound II the com pound of the formula He

P

which is N-(3',4',5'-tri?uorobiphenyl-2-yl)-3-di?uorom ethyl-1-methyl-1H-pyraZole-4-carboxamide, herein after

He

referred to as “11a”.

[0053]

0

In another preferred embodiment, the mixtures

F3H0

according to the invention comprise as compound II the com

pound of the formula 11b

/ N

H

/

0

F3H0

N

N\ |

IIb

H30

N

,

N

l

H

N

Which is N-(2-bicyclopropyl-2-yl-phenyl)-3 -di?uoromethyl

H30

1 -methyl-1H-pyraZole-4-carboxamide

(common

name:

sedaxane). [0057]

In another preferred embodiment, the mixtures

according to the invention comprise as compound II the com

Which is N-[2-(4'-tri?uoromethylthio)-biphenyl]-3-di?uo

romethyl-1 -methyl- 1 H-pyraZole-4 -carboxamide,

pound of the formula IIf

herein

after referred to as “IIb”.

[0054]

In another preferred embodiment, the mixtures

IIf

CH(CH3)2,

according to the invention comprise as compound II the com pound of the formula IIc

O

F3H0

IIc

N

N/ |

F O

FZHC

\N /

N\ | N

/ H30

N

H F

H

/ H3C

Which C1,

is

N-[1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4

methanonaphthalen-5 -yl] -3-(di?uoromethyl)-1 -methyl-1H pyraZole-4-carboxamide (common name: isopyraZam) herein after referred to as “IIf.

Feb. 24, 2011

US 2011/0046123 A1

[0058]

In another preferred embodiment, the mixtures

according to the invention comprise as compound II the com

pound of the formula Hg

quaternary mixtures containing ?pronil as compound IV. Pre ferred are the inventive ?vefold mixtures containing ?pronil as compound IV. [0071] Preferred are the inventive quaternary mixtures con

taining orysatrobin and thiophanate-methyl as compound III. Preferred are the inventive ?vefold mixtures containing ory satrobin and thiophanate-methyl as compound III. [0072] Preferred are the inventive quaternary mixtures con

taining ?pronil and thiophanate-methyl as compound III. Pre ferred are the inventive ?vefold mixtures containing ?pronil and thiophanate-methyl as compound III. [0073]

Preferred are the inventive quaternary mixtures con

taining orysatrobin and ?pronil as compound III. Preferred Which is N-[2-(1,3-dimethylbutyl)-3-thienyl]-1-methyl-3

(tri?uoromethyl)-1H-pyraZole-4-carboxamide

(common

are the inventive ?vefold mixtures containing orysatrobin and ?pronil as compound III.

name: penthiopyrad), herein after referred to as “Hg”.

[0074]

[0059] Within the subset of compounds consisting of Ha, Hb, Hc, Hd, He, Hf and Hg, compounds Ha, Hc, Hd, He, Hf and

taining orysatrobin, thiophanate-methyl and ?pronil as com pound III and IV.

Hg are preferred, compounds Ha, Hd, He are more preferred.

Most preferred compound II is compound Ha. [0060] Preferred compounds III are orysatrobin, pyraclos

trobin, prochloraZ and thiophanate-methyl. [0061] Preferred compound IV is ?pronil. [0062] Preferred are the inventive tertiary mixtures con taining clothianidin as compound I. Preferred are the inven tive quaternary mixtures containing clothianidin as com pound I. Preferred are the inventive ?vefold mixtures

containing clothianidin as compound I. [0063] Preferred are the inventive tertiary mixtures con taining Ha as compound II. Preferred are the inventive qua ternary mixtures containing Ha as compound II. Preferred are the inventive ?vefold mixtures containing Ha as compound II. [0064] Preferred are the inventive tertiary mixtures con taining Hd as compound II. Preferred are the inventive qua ternary mixtures containing Hd as compound II. Preferred are the inventive ?vefold mixtures containing Hd as compound H. [0065] Preferred are the inventive tertiary mixtures con taining He as compound H. Preferred are the inventive qua ternary mixtures containing Ha as compound II. Preferred are the inventive ?vefold mixtures containing He as compound II. [0066] Preferred are the inventive tertiary mixtures con taining thiophanate-methyl as compound III. Preferred are

the inventive quaternary mixtures containing thiophanate methyl as compound III. Preferred are the inventive ?vefold

mixtures containing thiophanate-methyl as compound III. [0067] Preferred are the inventive tertiary mixtures con taining procloraZ as compound III. Preferred are the inventive

quaternary mixtures containing procloraZ as compound III. Preferred are the inventive ?vefold mixtures containing pro cloraZ as compound III. [0068] Preferred are the inventive tertiary mixtures con taining orysatrobin as compound III. Preferred are the inven

tive quaternary mixtures containing orysatrobin as compound III. Preferred are the inventive quaternary mixtures contain

ing orysatrobin as compound III. [0069] Preferred are the inventive tertiary mixtures con taining pyraclostrobin as compound III. Preferred are the inventive quaternary mixtures containing pyraclostrobin as compound III. Preferred are the inventive quaternary mix tures containing pyraclostrobin as compound III. [0070] Preferred are the inventive tertiary mixtures con taining ?pronil as compound IV. Preferred are the inventive

[0075]

Preferred are the inventive ?vefold mixtures con

Preferred are the inventive quaternary mixtures con

taining orysatrobin and procloraZ as compound III. [0076]

Preferred are the inventive ?vefold mixtures con

taining orysatrobin and procloraZ as compound III. [0077]

Preferred are the inventive quaternary mixtures con

taining ?pronil and procloraZ as compound III. Preferred are the inventive ?vefold mixtures containing ?pronil and pro cloraZ as compound III. [0078] Preferred are the inventive quaternary mixtures con

taining orysatrobin and ?pronil as compound III. Preferred are the inventive ?vefold mixtures containing orysatrobin and ?pronil as compound III. [0079]

Preferred are the inventive ?vefold mixtures con

taining orysatrobin, procloraZ and ?pronil as compound III and IV. [0080] Preferred are the inventive tertiary mixtures con

taining Ha as compound II and pyraclostrobin as compound III.

[0081] The ratios by Weight for the respective tertiary mix tures comprising nicotinic receptor agonists/ antagonists compound I, an anilid of formula II and one further fungicide III are from 1:100:100 to 100:1:1, preferably from 50:1:1 to 1:50:50, more preferably from 1:20:20 to 20:1:1.

[0082] The ratios by Weight for the respective quarternary mixtures comprising nicotinic receptor agonists/antagonists compound I, an anilid of formula II and tWo further fungi cides III are from 1:100:100: 100 to 100:1:1:1, preferably from 50:1:1:1 to 1:50:50:50, more preferably from 1:20:20: 20 to 20:1:1:1.

[0083] The ratios by Weight for the respective quarternary mixtures comprising nicotinic receptor agonists/antagonists compound I, an anilid of formula II and one fungicide III and an insecticide IV are from 1:100: 100:100 to 100:1 :1 :1, pref erably from 50:1 : 1:1 to 1:50:50:50, more preferably from 1:20:20:20 to 20:1:1:1.

[0084] The ratios by Weight for the respective ?vefold mix tures comprising nicotinic receptor agonists/ antagonists compound I, an anilid of formula II and tWo fungicides III and an insecticide IV are from 1 :100:100:100:100 to 100: 1: 1 :1 :1,

preferably 50:1:1:1:1 to 1:50:50:50:50, more preferably 1:20: 20:20:20 to 20:1:1:1:1.

US 2011/0046123 A1

[0085]

Feb. 24, 2011

The ratios by Weight for the binary mixtures com

prising, as active components, [0086] 1) an insecticidal compound I selected from folloW ing nicotinic receptor agonists/antagonists compounds: acetamiprid, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram; and

[0087]

2) compound 11a; in synergistically effective

amounts ’

TABLE 1-continued NO

I

H

111(1)

111(2)

IV

R_24

A

Ha

D

I

i

R-25

A

IIa

F

I

i

R'26

A

113

i

I

I

R-27

A

IIa

D

I

J

R-28

A

IIa

F

I

J

are from 1:100 to 100: 1, preferably from 50:1 to 1:50, more

R_29

A

m

D

i

i

preferably from 1:20 to 20.

R-30

A

IId

F

i

i

[0088] With respect to their intended use, the following . . _ . . . binary mixtures are preferred. 11a and cloth1amd1n, 11a and imidacloprid, 11a and thiamethoxam, 11a and acetamiprid, more preferably 11a and clothianidin, 11a and imidacloprid

R'31 R63 R_34 R-35

A A A A

m M M IId

i D F D F

E E i i

i 1 J

and 11a and thiamethoxam. The most preferred mixture is

R'36

A

H:

i

E

1

compound 11a and clothianidin.

53;

i

d

PD

5

i

[0089] With respect to their intended use, the following tertiary, quaternary and ?vefold mixtures of compound I,

R_39 R-40 R'41

A A A

m IId m

i D P

G G

i

R-42

A

IId

i

i I 1

R-32

A

IId

E

*

compound II, one or tWo compound III and/ or compound IV listed 1n the table 1 beloW are more preferred. These are

R43

A

M

D

G G G

mixtures, Wherein compound I is clothianidin, imidacloprid or thiamethoxam, compound II is 11a, 11b, 11c, IId, IIf, Hg or

R_44 R-45

A A

11d IId

1: i

G H

J

He and compound III is selected from thiophanate-methyl, . . . prochloraZ, orysastrob1n, aZoxystrobm, pyraclostrob1n or tn-

R'46 R-47 R48

A A A

m IId M

D F i

H H H

i * J

?oxystrobin and compound IV is selected from ?pronil. [0090] In addition to the abbreviations of table 1, the fol-

R49 R-50

A A

M IId

D F

H H

J J

loWing abbreviations are used herein:

R'51

A

M

i

1

R-52 R-53 R-54

A A A

IId IId IId

D F i

I I I

i i J

I is compound I

H = azoxystrobin

R-55 R56

A A

IId 11d

D 1:

I I

J 1

II is compound II III (1) is compound III

I = tri?oxystrobin I = Fipronil

R_57 R58

A A

H6 116

D 1:

i i

i i

III (2) is the second compound III IV is compound IV A is clothianidin B is imidacloprid

IIa is comopound IIa IIb is comopound IIb

R59 R_60

A A

116 H6

i D

E E

He is comopound IIc IId is comopound IIc

R_61 R_62

A A

H6 116

1; D

E i

i i J

C = thiamethoxaln D = thiophanate-methyl

He is comopound IIe IIf is comopound IIf

R_63 R_64

A A

116 H6

1: i

i E

J J

E = orysastrobin

Hg is comopound IIg

R_65

A

116

D

E

J

F = PTOClOmZ

R-66

A

He

F

E

J

G = pyraclostrobin

R_67

A

116

i

G

R-68 R-69 R-70

A A A

He He He

D F i

G G G

TABLE 1

i i I

R-71

A

He

D

G

J

A A

He 116

F i

G H

J

III (2)

IV

R-72 R-73 R-74

A

He

D

H

i

i

i

R-75

A

He

F

H

i

F

i

i

R-76

A

He

i

H

J

i D

E E

i

R-77 R-78

A A

He He

D F

H H

J J

E i i E

i

R-79

A

He

i

I

J J J

R-80 R-81 R-82

A A A

He He He

D F i

I I I

i i J

D F

E E

J J

R-83 R-84

A A

He He

D F

I I

J J

IIa

i

G

R-85

B

IIa

D

i

i

IIa

D

G

i

R-86

B

IIa

F

i

i

A A

IIa IIa

F i

G G

i J

R-87 R-88

B B

IIa IIa

i D

E E

i

R-15 R-16

A A

IIa IIa

D F

G G

J J

R-89 R-90

B B

IIa IIa

F D

E i

i J

R-17 R-18

A A

IIa IIa

i D

H H

i

R-91 R-92

B B

IIa IIa

F i

i E

J J

R-19 R-20 R-21 R-22 R-23

A A A A A

IIa IIa IIa IIa Ha

F i D F

H H H H I

R-93 R-94 R-95 R-96 R-97

B B B B B

IIa IIa IIa IIa IIa

D F i D F

E E G G G

J J

No

I

11

R-l

A

IIa

III (1)

R-2

A

IIa

R-3 R-4

A A

IIa IIa

R-5

A

IIa

F

R-6 R-7 R-8

A A A

IIa IIa IIa

D F i

R-9 R-10

A A

IIa IIa

R-ll

A

R-12

A

R-13 R-14

i J J J

i i

Feb. 24, 2011

US 2011/0046123 A1

III (1)

III (2)

IV

hydrocarbons, e. g. toluene, xylene, paraf?n, tetrahydronaph thalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohex anol, glycols, ketones such as cyclohexanone and gamma

He

F

H

J

butyrolactone, fatty acid dimethylamides, fatty acids and

He

4

I

TABLE 1-continued No

I

II

R-246

C

R-247

C

fatty acid esters and strongly polar solvents, e.g. amines such

R-248

C

He

D

I

R-249 R-250

C C

He He

F 4

I I

i J

as N-methylpyrrolidone. [0097] Solid carriers are mineral earths such as silicates,

R-251 R-252

C C

He He

D F

I I

J J

clays, dolomite, diatomaceous earth, calcium sulfate, magne

silica gels, talc, kaolins, limestone, lime, chalk, bole, loess,

sium sulfate, magnesium oxide, ground synthetic materials, [0091]

Within these mixtures, the following mixtures are

especially preferred: R-l, R-2, R-3, R-4, R-5, R-6, R-7, R-8, R-9, R-10, R-11, R-12, R-13, R-14,R-15, R-16,R-17, R-18,R-19, R-20, R-21, R-22, R-23, R-24, R-25, R-26, R-27, R-28, R-31, R-32, R-33, R-34, R-35, R-36, R-37, R-38, R-39, R-40, R-41, R-42, R-43, R-44, R-67, R-68, R-69, R-70, R-71, R-72, R-59, R-60, R-61, R-62, R-63, R-64, R-65 and R-66. Within this subset, the

following mixtures are preferred: R-l, R-2, R-3, R-4, R-5, R-6, R-7, R-8, R-9, R-10, R-11, R-12, R-13, R-14, R-15, R-16, R-31, R-32, R-33, R-34, R-35, R-36, R-37, R-38, R-59, R-60, R-61, R-62, R-63, R-64, R-65, R-66, R-39, R-40, R-41, R-42, R-43, R-44, R-67, R-68, R-69, R-70, R-71, R-72, the

fertilizers, such as, e.g., ammonium sulfate, ammonium phos phate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

[0098]

Suitable surfactants (adjuvants, wetters, tacki?ers,

dispersants or emulsi?ers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as

ligninsoulfonic acid (Borresperse® types, Borregard, Nor

way) phenolsulfonic acid, naphthalenesulfonic acid (Mor wet® types, AkZo Nobel, U.S.A.), dibutylnaphthalene-sul fonic acid (Nekal® types, BASF, Germany), and fatty acids,

alkylsulfonates, alkyl-arylsulfonates, alkyl sulfates, lau

following mixtures are more preferred: R-3, R-4, R-5, R-6,

rylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol

R-7, R-8, R-9, R-10, R-11, R-12, R-13, R-14, R-15, R-16 R-36, R-37, R-38, R-64, R-65, R-66, R-42, R-43, R-44, R-70,

thalenesulfonic acid with phenol and formaldehyde, poly

R-71, R-72. [0092]

The inventive mixtures can further contain one or

more insecticides, fungicides, herbicides. [0093] For use according to the present invention, the mix tures according to the invention can be converted into the

customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a ?ne and even distribution of the

mixtures according to the present invention. The formulations are prepared in a known manner (cf. US. Pat. No. 3,060,084,

EP-A 707 445 (for liquid concentrates), Browning: “Agglom eration”, Chemical Engineering, Dec. 4, 1967, 147-48, Per ry’s Chemical Engineer’s Handbook, 4th Ed., McGraw-Hill, NewYork, 1963, S. 8-57 and ff. WO 91/13546, US. Pat. No. 4,172,714, US. Pat. No. 4,144,050, US. Pat. No. 3,920,442, US. Pat. No. 5,180,587, US. Pat. No. 5,232,701, US. Pat. No. 5,208,030, GB 2,095,558, US. Pat. No. 3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, New York, 1961), Hance et al.: Weed Control Handbook (8th Ed.,

Blackwell Scienti?c, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation technology (Wiley VCH Ver

lag, Weinheim, 2001). [0094]

The agrochemical formulations may also comprise

auxiliaries which are customary in agrochemical formula tions. The auxiliaries used depend on the particular applica

tion form and active substance, respectively. [0095] Examples for suitable auxiliaries are solvents, solid

ethers, furthermore condensates of naphthalene or of naph

oxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ ethylene oxide condensates, ethoxylated castor oil, polyoxy

ethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sul?te waste liquors and proteins, denatured proteins, polysaccha rides (e.g. methylcellulose), hydrophobically modi?ed starches, polyvinyl alcohols (Mowiol® types, Clariant, Swit Zerland), polycarboxylates (Sokolan® types, BASF, Ger

many), polyalkoxylates, polyvinylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers thereof.

[0099] Examples for thickeners (i.e. compounds that impart a modi?ed ?owability to formulations, i.e. high vis

cosity under static conditions and low viscosity during agita tion) are polysaccharides and organic and anorganic clays such as Xanthan gum (KelZan®, CP Kelco, U.S.A.),

Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA). [0100] Bactericides may be added for preservation and sta biliZation of the formulation. Examples for suitable bacteri cides are those based on dichlorophene and benZylalcohol hemi formal (Proxel® from 1C1 or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothia Zolinone derivatives such as alkylisothiaZolinones and ben

carriers, dispersants or emulsi?ers (such as further solubiliZ

ZisothiaZolinones (Acticide® MBS from Thor Chemie). [0101] Examples for suitable anti-freeZing agents are eth

ers, protective colloids, surfactants and adhesion agents),

ylene glycol, propylene glycol, urea and glycerin.

organic and anorganic thickeners, bactericides, anti-freeZing

[0102]

agents, anti-foaming agents, if appropriate colorants and

emulsions (such as eg Silikon® SRE, Wacker, Germany or

tacki?ers or binders (eg for seed treatment formulations). [0096] Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of

vegetable or animal origin, aliphatic, cyclic and aromatic

Examples for anti-foaming agents are silicone

Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, ?uoroorganic compounds and mix tures thereof.

[0103]

Suitable colorants are pigments of low water solu

bility and water-soluble dyes. Examples to be mentioned and

Feb. 24, 2011

US 2011/0046123 Al

the designations rhodamin B, C. I. pigment red 112, C. I. solvent red 1, pigment blue 15 :4, pigment blue 15 :3, pigment

neous emulsion. Dilution With Water gives an emulsion. The

blue 15:2, pigment blue 15:1, pigment blue 80, pigment yel loW 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pig ment orange 43, pigment orange 34, pigment orange 5, pig ment green 36, pigment green 7, pigment White 6, pigment

Weight.

broWn 25, basic violet 10, basic violet 49, acid red 51, acidred 52, acid red 14, acid blue 9, acid yelloW 23, basic red 10, basic red 108. [0104] Examples for tacki?ers or binders are polyvinylpyr

rolidones, polyvinylacetates, polyvinyl alcohols and cellu lose ethers (Tylose®, Shin-Etsu, Japan). [0105]

PoWders, materials for spreading and dusts can be

prepared by mixing or concomitantly grinding the com pounds I and/or II and, if appropriate, further active sub stances, With at least one solid carrier.

[0106] Granules, e.g. coated granules, impregnated gran ules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc,

kaolin, attaclay, limestone, lime, chalk, bole, loess, clay,

composition has an active substance content of 25% by

v) Suspensions (SC, OD, FS) [0111]

In an agitated ball mill, 20 parts by Weight of com

pounds of the inventive mixtures are comminuted With addi

tion of 10 parts by Weight of dispersants and Wetting agents and 70 parts by Weight of Water or an organic solvent to give a ?ne active substance suspension. Dilution With Water gives a stable suspension of the active substance. The active sub stance content in the composition is 20% by Weight.

vi) Water-Dispersible Granules and Water-Soluble Granules

(WG, SG) [0112] 50 parts by Weight of compounds of the inventive mixtures are ground ?nely With addition of 50 parts by Weight of dispersants and Wetting agents and prepared as Water dispersible or Water-soluble granules by means of technical

appliances (e.g. extrusion, spray toWer, ?uidized bed). Dilu tion With Water gives a stable dispersion or solution of the active substance. The composition has an active substance

sulfate, magnesium oxide, ground synthetic materials, fertil

content of 50% by Weight. vii) Water-Dispersible PoWders and Water-Soluble PoWders

iZers, such as, e.g., ammonium sulfate, ammonium phos phate, ammonium nitrate, ureas, and products of vegetable

75 parts by Weight of compounds of the inventive mixtures

dolomite, diatomaceous earth, calcium sulfate, magnesium

(WP, SP, SS, WS)

origin, such as cereal meal, tree bark meal, Wood meal and

are ground in a rotor-stator mill With addition of 25 parts by

nutshell meal, cellulose poWders and other solid carriers.

Weight of dispersants, Wetting agents and silica gel. Dilution

[01 07] Examples for formulation types are: 1. Composition Types for Dilution With Water

With Water gives a stable dispersion or solution of the active substance. The active substance content of the composition is

i) Water-Soluble Concentrates (SL, LS)

75% by Weight. viii) Gel (GF)

[0108]

10 parts by Weight of compounds of the inventive

the inventive mixtures are comminuted With addition of 10

mixtures are dissolved in 90 parts by Weight of Water or in a Water-soluble solvent. As an alternative, Wetting agents or other auxiliaries are added. The active substance dissolves upon dilution With Water. In this Way, a formulation having a

parts by Weight of dispersants, 1 part by Weight of a gelling

content of 10% by Weight of active substance is obtained.

In an agitated ball mill, 20 parts by Weight of compounds of agent Wetters and 70 parts by Weight of Water or of an organic solvent to give a ?ne suspension of the active substance. Dilution With Water gives a stable suspension of the active

substance, Whereby a composition With 20% (W/W) of active substance is obtained.

ii) Dispersible Concentrates (DC) [0109]

20 parts by Weight of compounds of the inventive

mixtures are dissolved in 70 parts by Weight of cyclohex anone With addition of 10 parts by Weight of a dispersant, e.g. polyvinylpyrrolidone. Dilution With Water gives a dispersion. The active substance content is 20% by Weight.

iii) Emulsi?able Concentrates (EC) 15 parts by Weight of compounds of the inventive mixtures are dissolved in 75 parts by Weight of xylene With addition of calcium dodecylbenZenesulfonate and castor oil ethoxylate (in each case 5 parts by Weight). Dilution With Water gives an emulsion. The composition has an active substance content of

15% by Weight.

2. Composition Types to be Applied Undiluted

ix) Dustable PoWders (DP, DS) [0113]

5 parts by Weight of compounds of the inventive

mixtures are ground ?nely and mixed intimately With 95 parts by Weight of ?nely divided kaolin. This gives a dustable composition having an active substance content of 5% by

Weight. x) Granules (GR, FG, GG, MG) [0114] 0.5 parts by Weight of compounds of the inventive mixtures is ground ?nely and associated With 99.5 parts by Weight of carriers. Current methods are extrusion, spray

iv) Emulsions (EW, EO, ES) [0110]

25 parts by Weight of compounds of the inventive

mixtures are dissolved in 35 parts by Weight of xylene With addition of calcium dodecylbenZenesulfonate and castor oil ethoxylate (in each case 5 parts by Weight). This mixture is introduced into 30 parts by Weight of Water by means of an emulsifying machine (Ultraturrax) and made into a homo ge

drying or the ?uidized bed. This gives granules to be applied undiluted having an active substance content of 0.5% by

Weight. xi) ULV Solutions (UL) [0115]

10 parts by Weight of compounds of the inventive

mixtures are dissolved in 90 parts by Weight of an organic

Feb. 24, 2011

US 2011/0046123 A1

solvent, e.g. xylene. This gives a composition to be applied

animal pests such as insects, arachnids or nematodes to be

undiluted having an active substance content of 10% by

Weight.

controlled (for the binary mixtures harmful fungi) or their habitats such as infected plants, plant propagation materials,

[0116] The agrochemical formulations generally comprise

particularly seeds, surfaces, materials or the soil as Well as

betWeen 0.01 and 95%, preferably betWeen 0.1 and 90%, most preferably betWeen 0.5 and 90%, by Weight of active

plants, plant propagation materials, particularly seeds, soil,

substances. The compounds of the inventive mixtures are

employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). [0117] The compounds of the inventive mixtures can be used as such or in the form of their compositions, eg in the

form of directly sprayable solutions, poWders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable prod ucts, materials for spreading, or granules, by means of spray

ing, atomiZing, dusting, spreading, brushing, immersing or pouring. The application forms depend entirely on the intended purposes; it is intended to ensure in each case the

?nest possible distribution of the compounds present in the inventive mixtures.

[0118] Aqueous application forms can be prepared from emulsion concentrates, pastes or Wettable poWders (spray able poWders, oil dispersions) by adding Water. To prepare

surfaces, materials or rooms to be protected from fungal attack) in a effective amount.

[0125] This can be obtained by applying the compound I and II and compound (s) III and/or IV (or compound I and II as de?ned above) simultaneously, either jointly (e. g. as tank mix) or separately, or in succession, Wherein the time interval betWeen the individual applications is selected to ensure that the active substance applied ?rst still occurs at the site of action in a su?icient amount at the time of application of the

further active substance(s). The order of application is not essential for Working of the present invention. [0126] In binary, ternary and quaternary mixture of the

present invention, the Weight ratio of the compounds gener ally depends from the properties of the compounds of the inventive mixtures. [0127] The compounds of the inventive mixtures can be

emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogeniZed in Water by means of a Wetter, tacki?er, dispersant or emulsi?er. Alterna

used individually or already partially or completely mixed

tively, it is possible to prepare concentrates composed of active substance, Wetter, tacki?er, dispersant or emulsi?er

further as combination composition such as a kit of parts.

and, if appropriate, solvent or oil, and such concentrates are suitable for dilution With Water.

[0119]

The active substance concentrations in the ready-to

With one another to prepare the composition according to the invention. It is also possible for them to be packaged and used

[0128] In one embodiment of the invention, the kits may include one or more, including all, components that may be

used to prepare a subject agrochemical composition. E.g., kits may include the compound I and II and compound (s) III

use preparations can be varied Within relatively Wide ranges.

and/or IV (or compound I and II as de?ned above) and/ or an

In general, they are from 0.0001 to 10%, preferably from 0.001 to 1% by Weight of compounds of the inventive mix

adjuvant component and/or a further pesticidal compound

[0121] Various types of oils, Wetters, adjuvants, herbicides,

(eg insecticide or herbicide) and/ or a groWth regulator com ponent). One or more of the components may already be combined together or pre-formulated. In those embodiments Where more than tWo components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister. In other embodiments, tWo or more components of a kit may be packaged separately, i.e., not

fungicides, other pesticides, or bactericides may be added to

pre-formulated. As such, kits may include one or more sepa

the active compounds, if appropriate not until immediately

rate containers such as vials, cans, bottles, pouches, bags or

prior to use (tank mix). These agents can be admixed With the compounds of the inventive mixtures in a Weight ratio of 1:100 to 100:1, preferably 1:10to 10:1. [0122] Compositions of this invention may also contain fertilizers such as ammonium nitrate, urea, potash, and super

canisters, each container containing a separate component for an agrochemical composition. In both forms, a component of the kit may be applied separately from or together With the

tures.

[0120] The compounds of the inventive mixtures may also be used successfully in the ultra-loW-volume process (ULV), it being possible to apply compositions comprising over 95% by Weight of active substance, or even to apply the active substance Without additives.

phosphate, phytotoxicants and plant groWth regulators and safeners. These may be used sequentially or in combination

With the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed With a composition of this inven

further components or as a component of a combination com

position according to the invention for preparing the compo sition according to the invention. [0129] The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank or a spray plane. Here, the agrochemical composition is made up With Water and/or buffer to the

desired application concentration, it being possible, if appro

tion either before or after being treated With the fertilizers. [0123] The compounds contained in the mixtures as de?ned above can be applied simultaneously, that is jointly or separately, or in succession, the sequence, in the case of

priate, to add further auxiliaries, and the ready-to-use spray liquor or the agrochemical composition according to the

separate application, generally not having any effect on the

ready-to-use spray liquor are applied per hectare of agricul

result of the control measures.

tural useful area, preferably 100 to 400 liters. [0130] According to one embodiment, individual com pounds of the inventive mixtures formulated as composition (or formulation) such as parts of a kit or parts of a binary or ternary or quaternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added,

[0124] According to this invention, applying the compound I and II and compound (s) III and/or IV (or compound I and II as de?ned above) is to be understood to denote, that at least

the compound I and II and compound (s) III and/or IV (or compound I and II as de?ned above) occur simultaneously at the site of action (i.e. the pests, such as harmful fungi and

invention is thus obtained. Usually, 50 to 500 liters of the

if appropriate (tank mix).

US 2011/0046123 A1

Feb. 24, 2011

pounds of the inventive mixtures formulated as composition

necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drech

or partially premixed components, e.g. components compris ing the compound I and II and compound (s) III and/or IV (or

phora) spp. on corn, cereals, such as barley (e.g. D. teres,

compound I and II as de?ned above) may be mixed by the user in a spray tank and further auxiliaries and additives may be

net blotch) and Wheat (e.g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused

[0131]

In a further embodiment, either individual com

added, if appropriate (tank mix). [0132] In a further embodiment, either individual compo nents of the composition according to the invention or par

tially premixed components, e. g. components comprising the compound I and II and compound (s) III and/or IV (or com pound I and II as de?ned above), can be applied jointly (e.g. after tank mix) or consecutively. [0133] As said above, the present invention comprises a method for controlling pests, that means animal pests and/or

harmful fungi, Wherein the pest, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or plant propagation material (preferably seed) are treated With an pesticidally effective amount of a mixture.

[0134]

Advantageously, the inventive mixtures are suitable

for controlling the folloWing fungal plant diseases: [0135] Albugo spp. (White rust) on ornamentals, veg

slera (syn. Helminthosporium, teleomorph: Pyreno

by Formitiporia (syn. Phellinus) punctata, F. mediterra nea, Phaeomoniella chlamydospora (earlier Phaeoacre monium chlamydosporum), Phaeoacremonium aleo philum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose)

and vines (E. ampelina: anthracnose); Entyloma oryZae (leaf smut) on rice; Epicoccum spp. (black mold) on Wheat; Erysiphe spp. (poWdery mildeW) on sugar beets (E. betae), vegetables (e.g. E. pisi), such as cucurbits (e.g. E. cichoracearum), cabbages, rape (e.g. E. crucifer arum); 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. turci

cum); Fusarium (teleomorph: Gibberella) spp. (Wilt, root or stem rot) on various plants, such as F.

etables (e.g. A. candida) and sun?owers (e.g. A. trago pogonis); Alternaria spp. (Alternaria leaf spot) on veg etables, rape (A. brassicola or brassicae), sugar beets (A.

graminearum or F. culmorum (root rot, scab or head blight) on cereals (e.g. Wheat or barley), F. oxysporum

tenuis), fruits, rice, soybeans, potatoes (e.g. A. solani or

on corn; Gaeumannomyces graminis (takeall) on cereals

A. alternata), tomatoes (e.g. A. solani or A. alternata) and Wheat; Aphanomyces spp. on sugar beets and veg

etables; Ascochyta spp. on cereals and vegetables, e.g. A. tritici (anthracno se) on Wheat andA. hordei on barley;

Bipolaris and Drechslera spp. (teleomorph: Cochliobo lus spp.) on corn (e.g. D. maydis), cereals (e.g. B. soro

on tomatoes, F. solani on soybeans and F. verticillioides (e.g. Wheat or barley) and corn; Gibberella spp. on cere

als (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; Guignardia bidWellii (black rot) on

kiniana: spot blotch), rice (e.g. B. oryZae) and turfs;

vines; Gymnosporangium spp. on rosaceous plants and junipers, e.g. G. sabinae (rust) on pears; Helminthospo

Blumeria (formerly Erysiphe) graminis (poWdery mil

rium spp. (syn. Drechslera, teleomorph: Cochliobolus)

deW) on cereals (e.g. on Wheat or barley); Botrytis

on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix

cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e.g. straWberries), vegetables (e.g. lettuce, carrots, celery and cabbages), rape, ?oWers, vines, forestry plants and Wheat; Bremia lactucae (doWny mildeW) on lettuce; Ceratocystis (syn. Ophios

(coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseo lina (syn. phaseoli) (root and stem rot) on soybeans and

cotton; Microdochium (syn. Fusarium) nivale (pink snoW mold) on cereals (e.g. Wheat or barley);

toma) spp. (rot or Wilt) on broad-leaved trees and ever

Microsphaera diffusa (poWdery mildeW) on soybeans;

greens, e.g. C. ulmi (Dutch elm disease) on elms; Cer cospora spp. (Cercospora leaf spots) on corn, rice, sugar

tigena (bloom and tWig blight, broWn rot) on stone fruits

Monilinia spp., e.g. M. laxa, M. fructicola and M. fruc

beets (e.g. C. beticola), sugar cane, vegetables, coffee, soybeans (e.g. C. sojina or C. kikuchii) and rice; Cla

and other rosaceous plants; Mycosphaerella spp. on

dosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e.g. C. herbarum (black ear) on Wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus

M. graminicola (anamorph: Septoria tritici, Septoria

(anamorph: Helminthosporium of Bipolaris) spp. (leaf

cereals, bananas, soft fruits and ground nuts, such as e.g.

blotch) on Wheat or M. ?jiensis (black Sigatoka disease) on bananas; Peronospora spp. (doWny mildeW) on cab

anamorph: H. oryZae); Colletotrichum (teleomorph:

bage (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. mei bomiae (soybean rust) on soybeans; Phialophora spp.

Glomerella) spp. (anthracnose) on cotton (e.g. C. gos

e.g. on vines (e.g. P. tracheiphila and P. tetraspora) and

spots) on corn (C. carbonum), cereals (e.g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus,

soybeans (e.g. P. gregata: stem rot); Phoma lingam (root

sypii), corn (e.g. C. graminicola), soft fruits, potatoes (e.g. C. coccodes: black dot), beans (e.g. C. lindemuth ianum) and soybeans (e.g. C. truncatum or C. gloeospo rioides); Corticium spp., e.g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e.g. C. oleaginum

morph: Diaporthe phaseolorum); Physoderma maydis

on olive trees; Cylindrocarpon spp. (e.g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonec

leaf, fruit and stem root) on various plants, such as

tria spp.) on fruit trees, vines (e.g. C. liriodendri, teleo morph: Neonectria liriodendri: Black Foot Disease) and

ornamentals; Dematophora (teleomorph: Rosellinia)

and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sun?owers, vines (e.g. P. viticola: can and leaf

spot) and soybeans (e.g. stem rot: P. phaseoli, teleo

(broWn spots) on corn; Phytophthora spp. (Wilt, root,

paprika and cucurbits (e.g. P. capsici), soybeans (e.g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e.g. P. infestans: late blight) and broad-leaved trees (e.g. P.

Feb. 24, 2011

US 2011/0046123 A1 11 ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants;

Plasmopara spp., e.g. P. viticola (grapevine downy mil

tis spp., e.g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e.g. U. appen diculatus, syn. U. phaseoli) and sugar beets (e.g. U.

dew) on vines and P. halstedii on sun?owers;

betae); Ustilago spp. (loose smut) on cereals (e.g. U.

Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e.g. P. leucotricha on apples; Polymyxa spp., eg on cereals, such as barley

nuda and U. avaenae), corn (e.g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e.g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and omamentals, vines, soft fruits, vegetables and ?eld crops, e.g. V. dahliae on strawberries, rape, potatoes and tomatoes.

and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella

herpotrichoides (eyespot, teleomorph: Tapesia yallun dae) on cereals, e.g. wheat or barley; Pseudoperono spora (downy mildew) on various plants, e.g. P. cubensis on cucurbits or P. humili on hop; PseudopeZicula trache

iphila (red ?re disease or, rotbrenner’, anamorph: Phi alophora) on vines; Puccinia spp. (rusts) on various plants, e.g. P. triticina (brown or leaf rust), P. striiforrnis

(stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or blackrust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, and asparagus

(e.g. P. asparagi); 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. grisea on turf and cereals; Pythium spp. (damping-off) on turf,

rice, corn, wheat, cotton, rape, sun?owers, soybeans, sugar beets, vegetables and various other plants (e.g. P.

[0136]

The inventive mixtures are also suitable for control

ling harmful fungi in the protection of materials (eg wood, paper, paint dispersions, ?ber or fabrics) and in the protection of stored products. As to the protection of wood and construc

tion materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Cera tocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp.,

Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Tri chorrna spp., Altemaria spp., Paecilomyces spp. and Zygo mycetes such as Mucor spp., and in addition in the protection

of stored products the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.

ultimum or P. aphanidermatum); Ramularia spp., e. g. R.

[0137]

collo-cygni (Ramularia leaf spots, Physiological leaf

multitude of fungi on various cultivated plants, such as

spots) on barley and R. beticola on sugar beets; RhiZoc tonia spp. on cotton, rice, potatoes, turf, corn, rape,

They are particularly important for controlling a

bananas, cotton, vegetable species (for example cucumbers, beans and cucurbits), cereals such as wheat, rye, barley, rice, oats; grass coffee, potatoes, corn, fruit species, soya, toma

potatoes, sugar beets, vegetables and various other plants, e.g. R. solani (root and stem rot) on soybeans, R.

toes, grapevines, ornamental plants, sugar cane and also on a

solani (sheath blight) on rice or R. cerealis (RhiZoctonia spring blight) on wheat or barley; RhiZopus stolonifer

tive mixtures are used in soya (soybean), cereals and com.

(black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryZae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem

large number of seeds. In a preferred embodiment, the inven

[0138] The inventive mixtures (except the binary mixture) exhibit also outstanding action against animal pests from the

following orders: insects from the order of the lepidopterans (Lepidoptera), for

rot or white mold) on vegetables and ?eld crops, such as

example Agrotis ypsilon, Agrotis segetum, Alabama argilla

rape, sun?owers (e.g. S. sclerotiorum) and soybeans

cea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Chematobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta,

(e.g. S. rolfsii or S. sclerotiorum); Septoria spp. on vari ous plants, e. g. S. glycines (brown spot) on soybeans, S.

tritici (Septoria blotch) on wheat and S. (syn. Stagono spora) nodorum (Stagonospora blotch) on cereals;

Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp.

Cydia pomonella, Dendrolimus pini, Diaphania nitidalis,

porium turcicum) and turf; Sphacelotheca spp. (smut)

Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens,

(leaf blight) on corn (e.g. S. turcicum, syn. Helminthos on corn, (e.g. S. reiliana: head smut), sorghum and sugar

Heliothis

cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases;

Hyphantria cunea, Hyponomeuta malinellus, Keiferia lyco tera coffeella, Leucoptera scitella, Lithocolletis blancardella,

Stagonospora spp. on cereals, e.g. S. nodorum (Stagono

Lobesia botrana, Loxostege sticticalis, Lymantria dispar,

spora blotch, teleomorph:

Lymantria monacha, Lyonetia clerkella, Malacosoma neus tria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis ?ammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea opercule lla, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frus

Leptosphaeria

[syn.

Phaeosphaeria] nodorum) on wheat; Synchytrium endo bioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and

T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables,

Zea,

Hellula undalis,

Hibernia defoliaria,

persicella, Lambdiva ?scellaria, Laphygma exigua, Leucop

on cereals, such as eg T. tritici (syn. T. caries, wheat

trana, Scrobipalpula absoluta, Sitotroga cerealella, Spargan othis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viri

bunt) and T. controversa (dwarf bunt) on wheat; Typhula

dana, Trichoplusia ni and Zeiraphera canadensis, beetles (Co

incarnata (grey snow mold) on barley or wheat; Urocys

leoptera), for example Agrilus sinuatus, Agriotes lineatus,

soybeans and cotton, e.g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut)

Feb. 24, 2011

US 2011/0046123 A1

Agriotes obscurus, Amphimallus solstitialis, Anisandrus dis

true bugs (Hemiptera), e.g. Acrosternum hilare, Blissus leu

par, Anthonomus grandis, Anthonomus pomorum, Aphthona

copterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysder

euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus ru? manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae,

tiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus

Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata,

Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetoc

cus interrnedius, Eurygaster integriceps, Euschistus impic pratensis, NeZara Viridula, Piesma quadrata, Solubea insu

laris, Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum,

nema tibialis, Conoderus Vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicomis, Diabrotica semipunc tata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica

Aulacorthum solani, Bemisia argentifolii, Brachycaudus car

Virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobo thrus brasiliensis, Hylobius abietis, Hypera brunneipennis,

rus homi, Cerosipha gossypii, Chaetosiphon fragaefolii,

Hypera postica, lps typographus, Lema bilineata, Lema mel anopus, Leptinotarsa decemlineata, Limonius califomicus, Lissorhoptrus oryZophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryZae, Ortiorrhynchus sulcatus, Otior

rhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyl lotreta chrysocephala, Phyllophaga sp., Phyllopertha horti

cola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria, ?ies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albop ictus, Aedes Vexans, Anastrepha ludens, Anopheles macu

lipennis, Anopheles crucians, Anopheles albimanus, Anoph eles gambiae, Anopheles freebomi, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora Vicina, Ceratitis capitata, Chrysomya beZZiana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia homini vorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassi cae, Delia antique, Delia coarctata, Delia platura, Delia radi cum, Dermatobia hominis, Fannia canicularis, GeomyZa

Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides,

Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops tor rens, LiriomyZa sativae, LiriomyZa trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Manso nia titillanus, Mayetiola destructor, Musca domestica, Mus cina stabulans, Oestrus oVis, OpomyZa ?orum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium

mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sar

dui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitopho CryptomyZus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hya lopterus pruni, HyperomyZus lactucae, Macrosiphum ave nae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura

Viciae, Melanaphis pyrarius, Metopolophium dirhodum, MyZus persicae, MyZus ascalonicus, MyZus cerasi, MyZus Varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphi gus bursarius, Perkinsiella saccharicida, Phorodon humuli,

Psylla mali, Psylla pin, RhopalomyZus ascalonicus, Rhopalo siphum maidis, Rhopalosiphum padi, Rhopalosiphum inser tum, Sappaphis mala, Sappaphis mali, SchiZaphis graminum, SchiZoneura lanuginosa, Sitobion avenae, Trialeurodes Vapo

rariorum, Toxoptera aurantiiand, Viteus Vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus.

ants, bees, Wasps, saW?ies (Hymenoptera), e.g.Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevi gata, Atta robusta, Atta sexdens, Atta texana, Crematogaster

spp., Hoplocampa minuta, Hoplocampa testudinea, Mono

morium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex bar batus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp. Vespula squamosa,

Paravespula Vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus ?oridanus, and

Linepithema humile, crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Mel

anoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schis tocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, ZonoZerus Variegatus,

cophaga haemorrhoidalis, Sarcophaga sp., Simulium Vit tatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atra tus, Tabanus lineola, and Tabanus similis, Tipula oleracea,

mus italicus, Chortoicetes terminifera, and Locustana par

and Tipula paludosa thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichro

Arachnoidea, such as arachnids (Acarina), e.g. of the families

mothrips ssp, Frankliniella fusca, Frankliniella occidentalis,

Hieroglyphus daganensis, Kraussaria angulifera, Callipta dalina, Argasidae, lxodidae and Sarcoptidae, such as Amblyomma

americanum, Amblyomma Variegatum, Ambryomma macu

Frankliniella tritici, Scirtothrips citri, Thrips oryZae, Thrips palmi and Thrips tabaci,

latum, Argas persicus, Boophilus annulatus, Boophilus

termites (lsoptera), e.g. Caloterrnes ?avicollis, Leucoterrnes ?avipes, Heterotermes aureus, Reticulitermes ?avipes, Reti culitermes Virginicus, Reticuliterrnes lucifugus, Termes

Dermacentor andersoni, Dermacentor Variabilis, Hyalomma

natalensis, and Coptotermes formosanus,

decoloratus, Boophilus microplus, Dermacentor silvarum, truncatum, lxodes ricinus, lxodes rubicundus, lxodes scapu

laris, lxodes holocyclus, lxodes paci?cus, Omithodorus moubata, Omithodorus hermsi, Omithodorus turicata, Orni

japonica, Periplaneta brunnea, Periplaneta fuligginosa,

thonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes oVis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and

Periplaneta australasiae, and Blatta orientalis,

Eriophyidae spp. such as Aculus schlechtendali, Phyllocop

cockroaches (Blattaria-Blattodea), e.g. Blattella germanica,

Blattella asahinae, Periplaneta americana, Periplaneta

Feb. 24, 2011

US 2011/0046123 A1

lus species; dagger nematodes, Xiphinema americanum,

trata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tet

Xiphinema index, Xiphinema diversicaudatum and other Xiphinema species; and other plant parasitic nematode spe

ranychidae spp. such as Tetranychus cinnabarinus, Tetrany

cies.

chus kanZaWai, Tetranychus paci?cus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri,

[0139] The mixtures according to the invention can be applied to any and all developmental stages of pests, such as egg, larva, pupa, and adult. The pests may be controlled by

and Oligonychus pratensis; Araneida, e.g. Latrodectus mac tans, and Loxosceles reclusa, ?eas (Siphonaptera), e. g. Ctenocephalides felis, Ctenocepha

lides canis, Xenopsylla cheopis, Pulex irritans, Tunga pen etrans, and Nosopsyllus fasciatus, silver?sh, ?rebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica,

centipedes (Chilopoda), e.g. Scutigera coleoptrata,

contacting the target pest, its food supply, habitat, breeding ground or its locus With a pesticidally effective amount of the

inventive mixtures or of compositions comprising the mix tures.

[0140] “Locus” means a plant, plant propagation material (preferably seed), soil, area, material or environment in Which a pest is groWing or may groW.

millipedes (Diplopoda), e.g. Narceus spp.,

[0141]

EarWigs (Dermaptera), e.g. for?cula auricularia, lice (Phthiraptera), e. g. Pediculus humanus capitis, Pediculus

the amount of the inventive mixtures or of compositions com prising the mixtures needed to achieve an observable effect on

humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes

prevention, and removal, destruction, or otherWise diminish ing the occurrence and activity of the target organism. The

capillatus, plant parasitic nematodes such as root-knot nematodes,

Meloidogyne arenaria, Meloidogyne chitWoodi, Meloid ogyne exigua, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica and other Meloidogyne species; cyst nematodes, Globodera rostochiensis, Globodera pallida, Glo bodera tabacum and other Globodera species, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Het erodera trifolii, and other Heterodera species; seed gall nema

todes, Anguina funesta, Anguina tritici and other Anguina species; stem and foliar nematodes, Aphelenchoides besseyi, Aphelenchoides fragariae, Aphelenchoides ritZemabosi and other Aphelenchoides species; sting nematodes, Belonolai mus longicaudatus and other Belonolaimus species; pine

nematodes, Bursaphelenchus xylophilus and other Bursaph elenchus species; ring nematodes, Criconema species, Cri conemella species, Criconemoides species, and Mesocri conema species; stem and bulb nematodes, Ditylenchus

destructor, Ditylenchus dipsaci, Ditylenchus myceliophagus and other Ditylenchus species; aWl nematodes, Dolichodorus

In general, “pesticidally effective amount” means

groWth, including the effects of necrosis, death, retardation, pesticidally effective amount can vary for the various mix

tures/compo sitions used in the invention. A pesticidally effec tive amount of the mixtures/compositions Will also vary according to the prevailing conditions such as desired pesti

cidal effect and duration, Weather, target species, locus, mode of application, and the like. [0142] As said above, the present invention comprises a method for improving the health of plants, Wherein the plant, the locus Where the plant is groWing or is expected to groW or

plant propagation material, from Which the plant groWs, is treated With an plant health effective amount of an inventive

mixture. [0143] The term “plant effective amount” denotes an amount of the inventive mixtures, Which is su?icient for achieving plant health effects as de?ned hereinbeloW. More

exemplary information about amounts, Ways of application and suitable ratios to be used is given beloW. AnyWay, the skilled artisan is Well aWare of the fact that such an amount can vary in a broad range and is dependent on various factors, eg the treated cultivated plant or material and the climatic

species; spiral nematodes, Helicotylenchus dihystera, Heli

conditions.

cotylenchus multicinctus and other Helicotylenchus species, Rotylenchus robustus and other Rotylenchus species; sheath nematodes, Hemicycliophora species and Hemicri

employ the pure active compounds, to Which further active

conemoides species; Hirshmanniella species; lance nema

todes, Hoplolaimus columbus, Hoplolaimus galeatus and other Hoplolaimus species; false root-knot nematodes, Nacobbus aberrans and other Nacobbus species; needle

nematodes, Longidorus elongates and other Longidorus spe cies; pin nematodes, Paratylenchus species; lesion nema

todes, Pratylenchus brachyurus, Pratylenchus coffeae, Praty lenchus curvitatus, Pratylenchus goodeyi, Pratylencus neglectus, Pratylenchus penetrans, Pratylenchus scribneri,

[0144]

When preparing the mixtures, it is preferred to

compounds against pests, such as insecticides, herbicides, fungicides or else herbicidal or groWth-regulating active compounds or fertilizers can be added as further active com

ponents according to need. [0145] The inventive mixtures are employed by treating the

fungi or the plants, plant propagation materials (preferably seeds), materials or soil to be protected from fungal attack With a pesticidally effective amount of the active compounds. The application can be carried out both before and after the

infection of the materials, plants or plant propagation mate

Pratylenchus vulnus, Pratylenchus Zeae and other Pratylen chus species; Radinaphelenchus cocophilus and other Radi

rials (preferably seeds) by the pests. [0146] In the method of combating harmful fungi depend

naphelenchus species; burrowing nematodes, Radopholus

ing on the type of compound and the desired effect, the application rates of the mixtures according to the invention are from 0.3 g/ha to 2000 g/ha, preferably 5 g/ha to 2000 g/ha, more preferably from 50 to 900 g/ha, in particular from 50 to

similis and other Radopholus species; reniforrn nematodes, Rotylenchulus reniformis and other Rotylenchulus species; Scutellonema species; stubby root nematodes, Trichodorus primitivus and other Trichodorus species; Paratrichodorus minor and other Paratrichodorus species; stunt nematodes,

750 g/ha. [0147] In the method of combating animal pests (insects,

Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species and Merlinius species; citrus nematodes, Tylenchulus semipenetrans and other Tylenchu

acarids or nematodes) depending on the type of compound and the desired effect, the application rates of the mixtures according to the invention are from 0.3 g/ha to 2000 g/ha,

Feb. 24, 2011

US 2011/0046123 A1

preferably 5 g/ha to 2000 g/ha, more preferably from 50 to 900 g/ha, in particular from 50 to 750 g/ha. [0148] The inventive mixtures or compositions of these mixtures can also be employed for protecting plants from attack or infestation by animal pests (insects, acarids or nema todes) comprising contacting a plant, or soil or Water in Which

the plant is groWing. [0149]

In the context of the present invention, the term plant

refers to an entire plant, a part of the plant or the propagation

Weight, preferably from 0.1 to 40% by Weight, in the ready to-use preparations. Application can be carried out before or

during soWing. Methods for applying or treating agrochemi cal compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are knoWn in the

art, and include dressing, coating, pelleting, dusting and soak ing application methods of the propagation material (and also in furroW treatment). In a preferred embodiment, the com

pounds or the compositions thereof, respectively, are applied

material of the plant.

on to the plant propagation material by a method such that

[0150] Plants and as Well as the propagation material of said plants, Which can be treated With the inventive mixtures

germination is not induced, eg by seed dressing, pelleting,

coating and dusting.

include all genetically modi?ed plants or transgenic plants,

[0159]

e.g. crops Which tolerate the action of herbicides or fungi

erably seed), the application rates of the inventive mixture are

cides or insecticides oWing to breeding, including genetic engineering methods, or plants Which have modi?ed charac teristics in comparison With existing plants, Which can be

generally for the formulated product (Which usually com prises from 10 to 750 g/l of the active(s)). [0160] The invention also relates to the propagation prod ucts of plants, and especially the seed comprising, that is,

generated for example by traditional breeding methods and/ or the generation of mutants, or by recombinant procedures.

[0151]

For example, mixtures according to the present

invention can be applied (as seed treatment, spray treatment, in furroW or by any other means) also to plants Which have

been modi?ed by breeding, mutagenesis or genetic engineer ing including but not limiting to agricultural biotech products on the market or in development (cf. http://WWW.bio.org/

speeches/pubs/er/agri_products.asp). Genetically modi?ed plants are plants, Which genetic material has been so modi?ed by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more

genes have been integrated into the genetic material of a

genetically modi?ed plant in order to improve certain prop erties of the plant. Such genetic modi?cations also include but

In the treatment of plant propagation material (pref

coated With and/ or containing, a mixture as de?ned above or a composition containing the mixture of tWo or more active ingredients or a mixture of tWo or more compositions each

providing one of the active ingredients. The plant propagation material (preferably seed) comprises the inventive mixtures in an amount of from 0.01 g to 10 kg per 100 kg of plant

propagation material (preferably seed). [0161] For example, the ratio by Weight of compound I is herein preferably betWeen 0.1-200 g/100 kg plant propaga tion material (preferably seed), more preferred 1 to 200 g/100

kg plant propagation material (preferably seed) and most preferred 1 to 100 g/100 kg plant propagation material (pref

erably seed). [0162]

For example, the ratio by Weight for compound II is

are not limited to targeted post-transitional modi?cation of

herein preferably betWeen 1-200 g/100 kg plant propagation

protein(s), oligo- or polypeptides eg by glycosylation or polymer additions such as prenylated, acetylated or famesy

material (preferably seed), more preferred 5 to 200 g/100 kg plant propagation material (preferably seed), and most pre ferred 5 to 100 g/100 kg plant propagation material (prefer

lated moieties or PEG moieties.

[0152] In a preferred embodiment of the invention, the inventive mixtures are used for the protection of the seed and

ably seed).

the seedlings’ roots and shoots, preferably the seeds.

methyl as compound III is herein preferably betWeen 10-200

[0153]

g/100 kg plant propagation material (preferably seed), more preferred 25 to 200 g/100 kg plant propagation material (pref erably seed) and most preferred 25 to 100 g/100 kg plant

Seed treatment can be made into the seed box before

planting into the ?eld. [0154] For seed treatment purposes, the Weight ration in the binary, ternary and quaternary mixtures of the present inven

tion generally depends from the properties of the compounds of the inventive mixtures.

[0155]

Compositions, Which are especially useful for seed

treatment are e. g.:

A Soluble concentrates (SL, LS)

D Emulsions (EW, EO, ES)

E Suspensions (SC, OD, FS) [0156] F Water-dispersible granules and Water-soluble

granules (WG, SG) G Water-dispersible poWders and Water-soluble poWders

(WP, SP, WS) H Gel-Formulations (GF)

[0157] I Dustable poWders (DP, DS) [0158] These compositions can be applied to plant propa gation materials, particularly seeds, diluted or undiluted. The

[0163] For example, the ratio by Weight for thiophanate

propagation material (preferably seed). [0164] For example, the ratio by Weight for procloraZ as compound III is herein preferably betWeen 1-200 g/100 kg plant propagation material (preferably seed), more preferred 5 to 50 g/100 kg plant propagation material (preferably seed) and most preferred 5 to 20 g/100 kg plant propagation mate

rial (preferably seed). [0165] For example, the ratio by Weight for the strobilurins as compound III, Which are aZoxystrobin, pyraclostrobin,

tri?oxystrobin or orysastrobin (in particular orysastrobin) as compound III is herein preferably betWeen 1-200 g/100 kg plant propagation material (preferably seed), more preferred 1 to 50 g/100 kg plant propagation material (preferably seed) and most preferred 1 to 20 g/100 kg plant propagation mate

rial (preferably seed). [0166] For example, the ratio by Weight for compound IV is herein preferably betWeen 0, 1-200 g/100 kg plant propaga tion material (preferably seed), more preferred 1 to 200 g/100

compositions in question give, after tWo-to-tenfold dilution,

kg plant propagation material (preferably seed) and most preferred 1 to 50 g/100 kg plant propagation material (pref

active substance concentrations of from 0.01 to 60% by

erably seed).

Feb. 24, 2011

US 2011/0046123 A1

[0167]

The separate or joint application of the compounds

of the inventive mixtures is carried out by spraying or dusting the seeds, the seedlings, the plants or the soils before or after soWing of the plants or before or after emergence of the

plants. [0168]

The inventive mixtures are effective through both

contact (via soil, glass, Wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part) and through trophallaxis and transfer. [0169] Preferred application methods are into Waterbodies, via soil, cracks and crevices, pastures, manure piles, seWers, into Water, on ?oor, Wall, or by perimeter spray application and bait. [0170] According to another preferred embodiment of the invention, for use against non crop pests such as ants, ter

mites, Wasps, ?ies, mosquitoes, crickets, locusts, or cock roaches the inventive mixtures are prepared into a bait prepa ration. [0171]

The bait can be a liquid, a solid or a semisolid

preparation (eg a gel). The bait employed in the composition

[0178] For use in spray compositions, the content of the mixture of the active ingredients is from 0.001 to 80 Weights %, preferably from 0.01 to 50 Weight % and most preferably from 0.01 to 15 Weight %.

1-15. (canceled) 16. A mixture comprising, as active components, 1) an insecticidal compound I selected from the group

consisting of nicotinic receptor agonists/antagonists

compounds: acetamiprid, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram; and 2) N-(3',4',5'-tri?uorobiphenyl-2-yl)-3-di?uoromethyl-1 methyl-1H-pyraZole-4-carboxamide as compound II in synergistic effective amounts. 17. A mixture comprising, as active components, 1) an insecticidal compound I selected from the nicotinic

receptor agonists/antagonists compounds acetamiprid, clothianidin, dinotefuran, imidacloprid, thiamethoxam and nitenpyram; and 2) an amide compound II having the formula II

is a product Which is su?iciently attractive to incite insects such as ants, termites, Wasps, ?ies, mosquitoes, crickets etc.

II

or cockroaches to eat it. This attractant may be chosen from

R4

O

feeding stimulants or para and/or sex pheromones readily knoWn in the art.

[0172]

N/ l

Methods to control infectious diseases transmitted

11]

by insects (e.g. malaria, dengue and yelloW fever, lymphatic ?lariasis, and leishmaniasis) With the inventive mixtures and

their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-?y trap or the like. Insecticidal compositions for application to ?bers, fabric, knitgoods, non-Wovens, netting material or foils and tarpau lins preferably comprise a composition including the inven tive mixtures, optionally a repellent and at least one binder. [0173] The inventive mixtures and the compositions com prising them can be used for protecting Wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materi

als, furniture, leathers, ?bers, 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 (eg when the pests invade into houses and public facilities). [0174]

In the case of soil treatment or of application to the

pests dWelling place or nest, the quantity of active ingredient

in Which the substituents are as de?ned beloW:

R4 is methyl, di?uoromethyl, or tri?uoromethyl; R5 is hydrogen or ?uorine. M is a thienyl ring or a phenyl ring, Wherein the phenyl ring is substituted or not substituted With a ?uorine

atom; Q is a direct bond, a cyclopropylene or an anellated

bicyclo[2.2.1]heptane ring; R1 is cyclopropyl, 1,3-dimethylbutyl, isopropyl, phenyl substituted With tWo or three halogen atoms or a trif

luoromethylthio radical; and 3) one or tWo further fungicidal compound(s) III selected

from the group consisting of thiophanate-methyl, pro

cloraZ, orysastrobin, pyraclostrobin, tri?oxystrobin and aZoxylstrobin; and/or

ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 20 g per 100 m2.

4) compound IV selected from the group consisting of

[0175]

in synergistic effective amounts. 18. The mixture according to claim 17, comprising

Customary application rates in the protection of

materials are, for example, from 0.01 g to 1000 g of active

compound per in2 treated material, desirably from 0.1 g to 50 g per m2. [0176] Insecticidal compositions for use in the impregna tion 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. [0177] For use in bait compositions, the typical content of

active ingredient is from 0.0001 Weight % to 15 Weight %, desirably from 0.001 Weight % to 5% Weight % of active compound. The composition used may also comprise other additives such as a solvent of the active material, a ?avoring agent, a preserving agent, a dye or a bitter agent. Its attrac

tiveness may also be enhanced by a special color, shape or texture.

?pronil and ethiprole clothianidin as compound I.

19. The mixture according to claim 17, comprising N-(3', 4', 5' -tri?uorobiphenyl -2 -yl) -3 -di?uoromethyl -1 -methyl 1H-pyraZole-4-carboxamide as compound II. 20. The mixture according to claim 17, Wherein the one or tWo further fungicidal compound(s) III are selected from the

group consisting of thiophanate-methyl, procloraZ, pyraclos trobin and orysastrobin. 21. The mixture according to claim 17, comprising ?pronil as compound IV.

22. The mixture according to claim 16, comprising com

pound clothianidin, N-(3',4',5'-tri?uorobiphenyl-2-yl)-3-dif luoromethyl-1 -methyl-1H-pyraZole-4-carboxamide, prochloraZ, orysastrobin and ?pronil.

Feb. 24, 2011

US 2011/0046123 A1

23. The mixture according to claim 17, comprising

clothianidin,

N-(3',4',5'-tri?uorobiphenyl-2-yl)-3-di?uo

romethyl-1 -methyl-1H-pyraZole-4-carboxamide,

orysas

trobin and ?pronil. 24. The mixture according to claim 17, comprising com

pound clothianidin, N-(3',4',5'-tri?uorobiphenyl-2-yl)-3-dif luoromethyl-1 -methyl-1H-pyraZole-4-carboxamide, thiophanate-methyl, orysastrobin and ?pronil. 25. A pesticidal composition, comprising a liquid or solid carrier and a mixture as de?ned in claim 16.

26. A method for controlling pests and/or improving the health of plants, Wherein (a) the pest, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or plant propagules; or (b) the plant, the locus Where the plant is groWing or is expected to groW or plant propagation material from Which the plant groWs; are treated With an effective amount of a mixture as

de?ned in 16.

27. A method for protection of plant propagation material

30. A plant propagation material, comprising the mixture as de?ned in claim 16 in an amount offrom 0.01 g to 10 kg per

100 kg of plant propagation material. 31. A method for controlling pests and/or improving the health of plants, Wherein (a) the pest, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or plant propagules; or (b) the plant, the locus Where the plant is groWing or is expected to groW or plant propagation material from Which the plant groWs; are treated With an effective amount of a mixture as

de?ned in 17.

32. A method for protection of plant propagation material

from pests comprising contacting the plant propagation mate rials With a mixture as de?ned in claim 16 in pesticidally effective amounts. 33. The method as claimed in claim 31, Wherein the mix ture is applied in an amount of from 0.01 g to 10 kg per. 100

from pests comprising contacting the plant propagation mate

kg of plant propagation materials.

rials With a mixture as de?ned in claim 16 in pesticidally effective amounts. 28. The method as claimed in claim 27, Wherein the mix ture is applied in an amount offrom 0.01 g to 10 kg per 100 kg

34. The method of claim 33, Wherein compound I and compounds 11 are applied simultaneously, that is jointly or

of plant propagation materials.

as de?ned in claim 17 in an amount offrom 0.01 g to 10 kg per

29. The method as claimed in claim 28, Wherein compound

separately, or in succession.

35. A plant propagation material, comprising the mixture

100 kg of plant propagation material.

I and compounds 11 are applied simultaneously, that is jointly or separately, or in succession.

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