# Patent

## Title
Pesticidal active mixtures comprising aminothiazoline compounds

## Abstract

Pesticidal mixtures comprising aminothiazoline compounds The present invention relates to pesticidal mixtures comprising as active compounds 1) at least one aminothiazoline compound I of the Formula (I) wherein R1, R2, R3, R4, R5 and R6 are defined in the description; and 2) at least one active compound II selected from a group A comprising acetylcholine esterase inhibitors, GABA-gated chloride channel antagonists, sodium channel modulators, nicotinic acetylcholine receptor agonists/antagonists, chloride channel activators, juvenile hormone mimics, compounds affecting the oxidative phosphorylation, inhibitors of the chitin biosynthesis, moulting disruptors, inhibitors of the MET, voltage-dependent sodium channel blockers, inhibitors of the lipidsynthesis and other compounds as defined in the description, in synergistically effective amounts. The invention relates further to methods and use of these mixtures for combating insects, arachnids or nematodes in and on plants, and for protecting such plants being infested with pests, especially also for protecting seeds.

## Background
This application is a National Stage application of International Application No. PCT/EP2008/052158 filed Feb. 22, 2008, which claims the benefit of U.S. Provisional Application No. 60/892,365, filed Mar. 1, 2007, the entire contents of which is hereby incorporated herein by reference.


The present invention relates to pesticidal mixtures comprising as active compounds
1) at least one aminothiazoline compound I of formula I:




    
    
        wherein
        R1 is selected from hydrogen, COCH3, COCH2OCH3, COCH2CH3 or COCH2C(CH3)3;
        R2 is selected from fluoro, chloro, bromo, CF3, CH3 or CH3O,
        R3 is selected from hydrogen, fluoro, chloro, bromo, CF3 or CH3,
        or
        R2 and R3 form together with —OCF2O— or —O—CH2—O— a 5-membered fused heterocyclic ring;
        R4 is selected from hydrogen, fluoro, chloro, bromo, CF3, CH3O or CH3;
        R5, R6 are selected from hydrogen, chloro, fluoro, bromo, CH3, CH3O or CF3, wherein at least one of R5 or R6 is not hydrogen;

or the tautomers, enantiomers, diastereomers or salts thereof,

and

2) at least one active compound II selected from group A consisting of

A.1 Acetylcholine esterase inhibitors selected from triazemate or from the class of carbamates consisting of aldicarb, alanycarb, benfuracarb, carbaryl, carbofuran, carbosulfan, methiocarb, methomyl, oxamyl, primicarb, propoxur and thiodicarb or from the class of organophosphates consisting of acephate, azinphos-ethyl, azinphos-methyl, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidaphos, methidathion, mevinphos, monocrotophos, oxymethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, pirimiphos-methyl, quinalphos, terbufos, tetrachlorvinphos, triazophos and trichlorfon;

A.2 GABA-gated chloride channel antagonists selected from the cyclodiene organochlorine endosulfan, from N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon or N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon or from the class of phenylpyrazoles consisting of acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, vaniliprole and the phenylpyrazole compound II.A2.1:

    
    






A.3 Sodium channel modulators selected from the class of pyrethroids consisting of allethrin, bifenthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, tau-fluvalinate, permethrin, silafluofen and tralomethrin;

A.4 Nicotinic acetylcholine receptor agonists/antagonists selected from nicotin, cartap hydrochloride or thiocyclam or selected from the class of neonicotinoids consisting of acteamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam and AKD-1022; or selected from the allosteric nicotinic acetylcholine receptor agonist spinosad;

A.5 Chloride channel activators selected from abamectin, emamectin benzoate, lepimectin or milbemectin;

A.6 Juvenile hormone mimics selected from hydroprene, kinoprene, fenoxycarb or pyriproxyfen;

A.7 Compounds affecting the oxidative phosphorylation selected from diafenthiuron, fenbutatin oxide, propargite or chlorfenapyr;

A.8 Inhibitors of the chitin biosynthesis selected from buprofezin or from the class of benzylureas consisting of bistrifluoron, diflubenzuron, flufenoxuron, hexaflumuron, lufenuron, novaluron or teflubenzuron;

A.9 Moulting disruptors selected from cyromazine or from the class of ecdysone agonists consisting of methoxyfenozide, tebufenozide and azadirachtin;

A.10 Mitochondrial electron transport inhibitors selected from pyridaben, tolfenpyrad or flufenerim.

A.11 Voltage-dependent sodium channel blockers selected from indoxacarb or metaflumizone.

A.12 Inhibitors of the lipid synthesis selected from spirodiclofen, spiromesifen or spirotetramat.

A.13 A group of various compounds consisting of amidoflumet, amitraz, bifenazate, clofentezine, cyenopyrafen, cyflumetofen, etoxazole, flonicamid, flubendiamine, flupyrazophos, hexythiazox, piperonyl butoxide, pymetrozine, pyridalyl, pyrifluquinazon, chlorantraniliprole and the anthranilamid compound II.A13.1:





and the sulfoximine compounds II.A13.2





in synergistically effective amounts.

The present invention also provides methods for the control of insects, acarids or nematodes comprising contacting the insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with a pesticidally effective amount of mixtures of the active compound I with at least one active compound II.
Moreover, the present invention also relates to a method of protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or the soil or water in which the plant is growing, with a pesticidally effective amount of a mixture of the active compound I with at least one active compound II.
The invention also provides a method for the protection of seeds from soil insects and of the seedlings' roots and shoots from soil and foliar insects which comprises contacting the seeds before sowing and/or after pregermination with a pesticidally effective amount of a mixture of the active compound I with at least one active compound II.
The invention also relates to the use of a mixture of the active compound I with at least one compound II for combating insects, arachnids or nematodes.
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 know-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.
It was therefore an object of the present invention to provide pesticidal mixtures which solves at least one of the discussed problems as reducing the dosage rate, enhancing the spectrum of activity or combining know-down activity with prolonged control or as to resistance management.
We have found that this object is in part or in whole achieved by the combination of active compounds defined at the outset. Moreover, we have found that simultaneous, that is joint or separate, application of an active compound I and one or more compounds II or successive application of an active compound I and one or more compounds II allows enhanced control of pests compared to the control rates that are possible with the individual compounds.
Compounds I of the formula I, their preparation and their action against insect and acarid pests have been described generically in WO 2005/63724.
The prior art does not disclose pesticidal mixtures comprising selective aminothiazoline compounds according to the present invention showing unexpected and synergistic effects in combination with other pesticidically active compounds.
The commercially available compounds of the group A may be found in The Pesticide Manual, 13th Edition, British Crop Protection Council (2003) among other publications. Thiamides derivatives in analogy of formula II.A2.1 and their preparation have been described in WO 98/28279. Lepimectin is known from Agro Project, PJB Publications Ltd, November 2004. Methidathion and Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Acetoprole and its preparation have been described in WO 98/28277. Metaflumizone and its preparation have been described in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p. 237-243 and in U.S. Pat. No. 4,822,779. Pyrafluprole and its preparation have been described in JP-A 2002-193709 and in WO 01/00614. Pyriprole and its preparation have been described in WO 98/45274 and in U.S. Pat. No. 6,335,357. Amidoflumet and its preparation have been described in U.S. Pat. No. 6,221,890 and in JP-A 21010907. Flufenerim and its preparation have been described in WO 03/007717 and in WO 03/007718. Cyflumetofen and its preparation have been described in WO 04/080180. Preparation methods for neonicotinoids similar to AKD-1022 have been described by Zhang, A. et al. in J. Neurochemistry, 75(3), 2000. Anthranilamides derivatives in analogy of formula II.A13.1 and their preparation have been described in WO 01/70671; WO 02/48137; WO 03/24222, WO 03/15518, WO 04/67528; WO 04/33468 and WO 05/118552. Sulfoximine derivatives of and in analogy of formulae II.A13.2, II.A13.3 or II.A13.4 and their preparations have been described in WO 2006/060029.
Preferences
Preferred Compounds I of Formula I
With regard to their use in the pesticidal mixtures of the present invention, compounds I of formula I are preferred, wherein
R1 is hydrogen or COCH3;
R2 is selected from fluoro, chloro or CH3;
R3, R4 are selected independently from one another from hydrogen, fluoro, chloro, CF3 or CH3;
R5, R6 are selected from hydrogen or CH3, wherein at least one of R5 or R6 is not hydrogen.
Especially preferred are compounds I of formula I having the following meanings:
R1 is hydrogen;
R2, R3 are CH3;
R4 is hydrogen;
R5, R6 are CH3,
or
R1 is hydrogen;
R2, R3 are chloro;
R4 is hydrogen;
R5, R6 are CH3.
Further preferred are compounds I of formula I having the following meanings:
R1 is COCH3;
R2, R3 are CH3;
R4 is hydrogen;
R5, R6 are CH3,
or
R1 is COCH3;
R2, R3 are chloro;
R4 is hydrogen;
R5, R6 are CH3.
In cases wherein R1 is hydrogen, active compounds I of formula I can also be represented by the following tautomers of formula I-H1a and I-H1b:




Preferred compound I examples of aminothiazoline compounds of formula I are given in the following table C.I:













TABLE C.I:





Com-








pound I
R1
R2
R3
R4
R5
R6







C.I-1
H
Cl
Cl
H
H
CH3


C.I-2
H
Cl
Cl
H
H
Cl


C.I-3
H
Cl
Cl
H
H
CF3


C.I-4
H
Cl
Cl
H
H
Br


C.I-5
H
Cl
Cl
H
H
OCH3


C.I-6
H
Cl
Cl
H
H
F


C.I-7
H
Cl
Cl
H
CH3
CH3


C.I-8
H
Cl
Cl
H
Cl
Cl


C.I-9
H
Cl
Cl
H
CF3
CF3


C.I-10
H
Cl
Cl
H
OCH3
OCH3


C.I-11
H
CH3
CH3
H
H
CH3


C.I-12
H
CH3
CH3
H
H
Cl


C.I-13
H
CH3
CH3
H
H
CF3


C.I-14
H
CH3
CH3
H
H
Br


C.I-15
H
CH3
CH3
H
H
OCH3


C.I-16
H
CH3
CH3
H
H
F


C.I-17
H
CH3
CH3
H
CH3
CH3


C.I-18
H
CH3
CH3
H
Cl
Cl


C.I-19
H
CH3
CH3
H
CF3
CF3


C.I-20
H
CH3
CH3
H
OCH3
OCH3


C.I-21
H
CH3
CF3
H
H
CH3


C.I-22
H
CH3
CF3
H
H
Cl


C.I-23
H
CH3
CF3
H
H
CF3


C.I-24
H
CH3
CF3
H
H
Br


C.I-25
H
CH3
CF3
H
H
OCH3


C.I-26
H
CH3
CF3
H
H
F


C.I-27
H
CH3
CF3
H
CH3
CH3


C.I-28
H
CH3
CF3
H
Cl
Cl


C.I-29
H
CH3
CF3
H
CF3
CF3


C.I-30
H
CH3
CF3
H
OCH3
OCH3


C.I-31
H
CF3
CH3
H
H
CH3


C.I-32
H
CF3
CH3
H
H
Cl


C.I-33
H
CF3
CH3
H
H
CF3


C.I-34
H
CF3
CH3
H
H
Br


C.I-35
H
CF3
CH3
H
H
OCH3


C.I-36
H
CF3
CH3
H
H
F


C.I-37
H
CF3
CH3
H
CH3
CH3


C.I-38
H
CF3
CH3
H
Cl
Cl


C.I-39
H
CF3
CH3
H
CF3
CF3


C.I-40
H
CF3
CH3
H
OCH3
OCH3


C.I-41
H
F
CF3
H
H
CH3


C.I-42
H
F
CF3
H
H
Cl


C.I-43
H
F
CF3
H
H
CF3


C.I-44
H
F
CF3
H
H
Br


C.I-45
H
F
CF3
H
H
OCH3


C.I-46
H
F
CF3
H
H
F


C.I-47
H
F
CF3
H
CH3
CH3


C.I-48
H
F
CF3
H
Cl
Cl


C.I-49
H
F
CF3
H
CF3
CF3


C.I-50
H
F
CF3
H
OCH3
OCH3


C.I-51
H
Cl
CF3
H
H
CH3


C.I-52
H
Cl
CF3
H
H
Cl


C.I-53
H
Cl
CF3
H
H
CF3


C.I-54
H
Cl
CF3
H
H
Br


C.I-55
H
Cl
CF3
H
H
OCH3


C.I-56
H
Cl
CF3
H
H
F


C.I-57
H
Cl
CF3
H
CH3
CH3


C.I-58
H
Cl
CF3
H
Cl
Cl


C.I-59
H
Cl
CF3
H
CF3
CF3


C.I-60
H
Cl
CF3
H
OCH3
OCH3


C.I-61
H
CH3
Cl
H
H
CH3


C.I-62
H
CH3
Cl
H
H
Cl


C.I-63
H
CH3
Cl
H
H
CF3


C.I-64
H
CH3
Cl
H
H
Br


C.I-65
H
CH3
Cl
H
H
OCH3


C.I-66
H
CH3
Cl
H
H
F


C.I-67
H
CH3
Cl
H
CH3
CH3


C.I-68
H
CH3
Cl
H
Cl
Cl


C.I-69
H
CH3
Cl
H
CF3
CF3


C.I-70
H
CH3
Cl
H
OCH3
OCH3


C.I-71
H
Cl
CH3
H
H
CH3


C.I-72
H
Cl
CH3
H
H
Cl


C.I-73
H
Cl
CH3
H
H
CF3


C.I-74
H
Cl
CH3
H
H
Br


C.I-75
H
Cl
CH3
H
H
OCH3


C.I-76
H
Cl
CH3
H
H
F


C.I-77
H
Cl
CH3
H
CH3
CH3


C.I-78
H
Cl
CH3
H
Cl
Cl


C.I-79
H
Cl
CH3
H
CF3
CF3


C.I-80
H
Cl
CH3
H
OCH3
OCH3


C.I-81
H
Cl
H
Cl
H
CH3


C.I-82
H
Cl
H
Cl
H
Cl


C.I-83
H
Cl
H
Cl
H
CF3


C.I-84
H
Cl
H
Cl
H
Br


C.I-85
H
Cl
H
Cl
H
OCH3


C.I-86
H
Cl
H
Cl
H
F


C.I-87
H
Cl
H
Cl
CH3
CH3


C.I-88
H
Cl
H
Cl
Cl
Cl


C.I-89
H
Cl
H
Cl
CF3
CF3


C.I-90
H
Cl
H
Cl
OCH3
OCH3


C.I-91
H
F
H
F
H
CH3


C.I-92
H
F
H
F
H
Cl


C.I-93
H
F
H
F
H
CF3


C.I-94
H
F
H
F
H
Br


C.I-95
H
F
H
F
H
OCH3


C.I-96
H
F
H
F
H
F


C.I-97
H
F
H
F
CH3
CH3


C.I-98
H
F
H
F
Cl
Cl


C.I-99
H
F
H
F
CF3
CF3


C.I-100
H
F
H
F
OCH3
OCH3


C.I-101
H
CH3
H
CH3
H
CH3


C.I-102
H
CH3
H
CH3
H
Cl


C.I-103
H
CH3
H
CH3
H
CF3


C.I-104
H
CH3
H
CH3
H
Br


C.I-105
H
CH3
H
CH3
H
OCH3


C.I-106
H
CH3
H
CH3
H
F


C.I-107
H
CH3
H
CH3
CH3
CH3


C.I-108
H
CH3
H
CH3
Cl
Cl


C.I-109
H
CH3
H
CH3
CF3
CF3


C.I-110
H
CH3
H
CH3
OCH3
OCH3


C.I-111
H
F
H
CH3
H
CH3


C.I-112
H
F
H
CH3
H
Cl


C.I-113
H
F
H
CH3
H
CF3


C.I-114
H
F
H
CH3
H
Br


C.I-115
H
F
H
CH3
H
OCH3


C.I-116
H
F
H
CH3
H
F


C.I-117
H
F
H
CH3
CH3
CH3


C.I-118
H
F
H
CH3
Cl
Cl


C.I-119
H
F
H
CH3
CF3
CF3


C.I-120
H
F
H
CH3
OCH3
OCH3


C.I-121
H
F
H
CF3
H
CH3


C.I-122
H
F
H
CF3
H
Cl


C.I-123
H
F
H
CF3
H
CF3


C.I-124
H
F
H
CF3
H
Br


C.I-125
H
F
H
CF3
H
OCH3


C.I-126
H
F
H
CF3
H
F


C.I-127
H
F
H
CF3
CH3
CH3


C.I-128
H
F
H
CF3
Cl
Cl


C.I-129
H
F
H
CF3
CF3
CF3


C.I-130
H
F
H
CF3
OCH3
OCH3


C.I-131
H
F
H
OCH3
H
CH3


C.I-132
H
F
H
OCH3
H
Cl


C.I-133
H
F
H
OCH3
H
CF3


C.I-134
H
F
H
OCH3
H
Br


C.I-135
H
F
H
OCH3
H
OCH3


C.I-136
H
F
H
OCH3
H
F


C.I-137
H
F
H
OCH3
CH3
CH3


C.I-138
H
F
H
OCH3
Cl
Cl


C.I-139
H
F
H
OCH3
CF3
CF3


C.I-140
H
F
H
OCH3
OCH3
OCH3


C.I-141
H
F
H
Br
H
CH3


C.I-142
H
F
H
Br
H
Cl


C.I-143
H
F
H
Br
H
CF3


C.I-144
H
F
H
Br
H
Br


C.I-145
H
F
H
Br
H
OCH3


C.I-146
H
F
H
Br
H
F


C.I-147
H
F
H
Br
CH3
CH3


C.I-148
H
F
H
Br
Cl
Cl


C.I-149
H
F
H
Br
CF3
CF3


C.I-150
H
F
H
Br
OCH3
OCH3


C.I-151
H
Br
H
F
H
CH3


C.I-152
H
Br
H
F
H
Cl


C.I-153
H
Br
H
F
H
CF3


C.I-154
H
Br
H
F
H
Br


C.I-155
H
Br
H
F
H
OCH3


C.I-156
H
Br
H
F
H
F


C.I-157
H
Br
H
F
CH3
CH3


C.I-158
H
Br
H
F
Cl
Cl


C.I-159
H
Br
H
F
CF3
CF3


C.I-160
H
Br
H
F
OCH3
OCH3


C.I-161
H
CH3
H
F
H
CH3


C.I-162
H
CH3
H
F
H
Cl


C.I-163
H
CH3
H
F
H
CF3


C.I-164
H
CH3
H
F
H
Br


C.I-165
H
CH3
H
F
H
OCH3


C.I-166
H
CH3
H
F
H
F


C.I-167
H
CH3
H
F
CH3
CH3


C.I-168
H
CH3
H
F
Cl
Cl


C.I-169
H
CH3
H
F
CF3
CF3


C.I-170
H
CH3
H
F
OCH3
OCH3


C.I-171
H
OCH3
H
F
H
CH3


C.I-172
H
OCH3
H
F
H
Cl


C.I-173
H
OCH3
H
F
H
CF3


C.I-174
H
OCH3
H
F
H
Br


C.I-175
H
OCH3
H
F
H
OCH3


C.I-176
H
OCH3
H
F
H
F


C.I-177
H
OCH3
H
F
CH3
CH3


C.I-178
H
OCH3
H
F
Cl
Cl


C.I-179
H
OCH3
H
F
CF3
CF3


C.I-180
H
OCH3
H
F
OCH3
OCH3


C.I-181
H
CH3
H
Cl
H
CH3


C.I-182
H
CH3
H
Cl
H
Cl


C.I-183
H
CH3
H
Cl
H
CF3


C.I-184
H
CH3
H
Cl
H
Br


C.I-185
H
CH3
H
Cl
H
OCH3


C.I-186
H
CH3
H
Cl
H
F


C.I-187
H
CH3
H
Cl
CH3
CH3


C.I-188
H
CH3
H
Cl
Cl
Cl


C.I-189
H
CH3
H
Cl
CF3
CF3


C.I-190
H
CH3
H
Cl
OCH3
OCH3


C.I-191
H
Cl
H
CH3
H
CH3


C.I-192
H
Cl
H
CH3
H
Cl


C.I-193
H
Cl
H
CH3
H
CF3


C.I-194
H
Cl
H
CH3
H
Br


C.I-195
H
Cl
H
CH3
H
OCH3


C.I-196
H
Cl
H
CH3
H
F


C.I-197
H
Cl
H
CH3
CH3
CH3


C.I-198
H
Cl
H
CH3
Cl
Cl


C.I-199
H
Cl
H
CH3
CF3
CF3


C.I-200
H
Cl
H
CH3
OCH3
OCH3


C.I-201
COCH3
Cl
Cl
H
H
CH3


C.I-202
COCH3
Cl
Cl
H
H
Cl


C.I-203
COCH3
Cl
Cl
H
H
CF3


C.I-204
COCH3
Cl
Cl
H
H
Br


C.I-205
COCH3
Cl
Cl
H
H
OCH3


C.I-206
COCH3
Cl
Cl
H
H
F


C.I-207
COCH3
Cl
Cl
H
CH3
CH3


C.I-208
COCH3
Cl
Cl
H
Cl
Cl


C.I-209
COCH3
Cl
Cl
H
CF3
CF3


C.I-210
COCH3
Cl
Cl
H
OCH3
OCH3


C.I-211
COCH3
CH3
CH3
H
H
CH3


C.I-212
COCH3
CH3
CH3
H
H
Cl


C.I-213
COCH3
CH3
CH3
H
H
CF3


C.I-214
COCH3
CH3
CH3
H
H
Br


C.I-215
COCH3
CH3
CH3
H
H
OCH3


C.I-216
COCH3
CH3
CH3
H
H
F


C.I-217
COCH3
CH3
CH3
H
CH3
CH3


C.I-218
COCH3
CH3
CH3
H
Cl
Cl


C.I-219
COCH3
CH3
CH3
H
CF3
CF3


C.I-220
COCH3
CH3
CH3
H
OCH3
OCH3


C.I-221
COCH3
CH3
CF3
H
H
CH3


C.I-222
COCH3
CH3
CF3
H
H
Cl


C.I-223
COCH3
CH3
CF3
H
H
CF3


C.I-224
COCH3
CH3
CF3
H
H
Br


C.I-225
COCH3
CH3
CF3
H
H
OCH3


C.I-226
COCH3
CH3
CF3
H
H
F


C.I-227
COCH3
CH3
CF3
H
CH3
CH3


C.I-228
COCH3
CH3
CF3
H
Cl
Cl


C.I-229
COCH3
CH3
CF3
H
CF3
CF3


C.I-230
COCH3
CH3
CF3
H
OCH3
OCH3


C.I-231
COCH3
CF3
CH3
H
H
CH3


C.I-232
COCH3
CF3
CH3
H
H
Cl


C.I-233
COCH3
CF3
CH3
H
H
CF3


C.I-234
COCH3
CF3
CH3
H
H
Br


C.I-235
COCH3
CF3
CH3
H
H
OCH3


C.I-236
COCH3
CF3
CH3
H
H
F


C.I-237
COCH3
CF3
CH3
H
CH3
CH3


C.I-238
COCH3
CF3
CH3
H
Cl
Cl


C.I-239
COCH3
CF3
CH3
H
CF3
CF3


C.I-240
COCH3
CF3
CH3
H
OCH3
OCH3


C.I-241
COCH3
F
CF3
H
H
CH3


C.I-242
COCH3
F
CF3
H
H
Cl


C.I-243
COCH3
F
CF3
H
H
CF3


C.I-244
COCH3
F
CF3
H
H
Br


C.I-245
COCH3
F
CF3
H
H
OCH3


C.I-246
COCH3
F
CF3
H
H
F


C.I-247
COCH3
F
CF3
H
CH3
CH3


C.I-248
COCH3
F
CF3
H
Cl
Cl


C.I-249
COCH3
F
CF3
H
CF3
CF3


C.I-250
COCH3
F
CF3
H
OCH3
OCH3


C.I-251
COCH3
Cl
CF3
H
H
CH3


C.I-252
COCH3
Cl
CF3
H
H
Cl


C.I-253
COCH3
Cl
CF3
H
H
CF3


C.I-254
COCH3
Cl
CF3
H
H
Br


C.I-255
COCH3
Cl
CF3
H
H
OCH3


C.I-256
COCH3
Cl
CF3
H
H
F


C.I-257
COCH3
Cl
CF3
H
CH3
CH3


C.I-258
COCH3
Cl
CF3
H
Cl
Cl


C.I-259
COCH3
Cl
CF3
H
CF3
CF3


C.I-260
COCH3
Cl
CF3
H
OCH3
OCH3


C.I-261
COCH3
CH3
Cl
H
H
CH3


C.I-262
COCH3
CH3
Cl
H
H
Cl


C.I-263
COCH3
CH3
Cl
H
H
CF3


C.I-264
COCH3
CH3
Cl
H
H
Br


C.I-265
COCH3
CH3
Cl
H
H
OCH3


C.I-266
COCH3
CH3
Cl
H
H
F


C.I-267
COCH3
CH3
Cl
H
CH3
CH3


C.I-268
COCH3
CH3
Cl
H
Cl
Cl


C.I-269
COCH3
CH3
Cl
H
CF3
CF3


C.I-270
COCH3
CH3
Cl
H
OCH3
OCH3


C.I-271
COCH3
Cl
CH3
H
H
CH3


C.I-272
COCH3
Cl
CH3
H
H
Cl


C.I-273
COCH3
Cl
CH3
H
H
CF3


C.I-274
COCH3
Cl
CH3
H
H
Br


C.I-275
COCH3
Cl
CH3
H
H
OCH3


C.I-276
COCH3
Cl
CH3
H
H
F


C.I-277
COCH3
Cl
CH3
H
CH3
CH3


C.I-278
COCH3
Cl
CH3
H
Cl
Cl


C.I-279
COCH3
Cl
CH3
H
CF3
CF3


C.I-280
COCH3
Cl
CH3
H
OCH3
OCH3


C.I-281
COCH3
Cl
H
Cl
H
CH3


C.I-282
COCH3
Cl
H
Cl
H
Cl


C.I-283
COCH3
Cl
H
Cl
H
CF3


C.I-284
COCH3
Cl
H
Cl
H
Br


C.I-285
COCH3
Cl
H
Cl
H
OCH3


C.I-286
COCH3
Cl
H
Cl
H
F


C.I-287
COCH3
Cl
H
Cl
CH3
CH3


C.I-288
COCH3
Cl
H
Cl
Cl
Cl


C.I-289
COCH3
Cl
H
Cl
CF3
CF3


C.I-290
COCH3
Cl
H
Cl
OCH3
OCH3


C.I-291
COCH3
F
H
F
H
CH3


C.I-292
COCH3
F
H
F
H
Cl


C.I-293
COCH3
F
H
F
H
CF3


C.I-294
COCH3
F
H
F
H
Br


C.I-295
COCH3
F
H
F
H
OCH3


C.I-296
COCH3
F
H
F
H
F


C.I-297
COCH3
F
H
F
CH3
CH3


C.I-298
COCH3
F
H
F
Cl
Cl


C.I-299
COCH3
F
H
F
CF3
CF3


C.I-300
COCH3
F
H
F
OCH3
OCH3


C.I-301
COCH3
CH3
H
CH3
H
CH3


C.I-302
COCH3
CH3
H
CH3
H
Cl


C.I-303
COCH3
CH3
H
CH3
H
CF3


C.I-304
COCH3
CH3
H
CH3
H
Br


C.I-305
COCH3
CH3
H
CH3
H
OCH3


C.I-306
COCH3
CH3
H
CH3
H
F


C.I-307
COCH3
CH3
H
CH3
CH3
CH3


C.I-308
COCH3
CH3
H
CH3
Cl
Cl


C.I-309
COCH3
CH3
H
CH3
CF3
CF3


C.I-310
COCH3
CH3
H
CH3
OCH3
OCH3


C.I-311
COCH3
F
H
CH3
H
CH3


C.I-312
COCH3
F
H
CH3
H
Cl


C.I-313
COCH3
F
H
CH3
H
CF3


C.I-314
COCH3
F
H
CH3
H
Br


C.I-315
COCH3
F
H
CH3
H
OCH3


C.I-316
COCH3
F
H
CH3
H
F


C.I-317
COCH3
F
H
CH3
CH3
CH3


C.I-318
COCH3
F
H
CH3
Cl
Cl


C.I-319
COCH3
F
H
CH3
CF3
CF3


C.I-320
COCH3
F
H
CH3
OCH3
OCH3


C.I-321
COCH3
F
H
CF3
H
CH3


C.I-322
COCH3
F
H
CF3
H
Cl


C.I-323
COCH3
F
H
CF3
H
CF3


C.I-324
COCH3
F
H
CF3
H
Br


C.I-325
COCH3
F
H
CF3
H
OCH3


C.I-326
COCH3
F
H
CF3
H
F


C.I-327
COCH3
F
H
CF3
CH3
CH3


C.I-328
COCH3
F
H
CF3
Cl
Cl


C.I-329
COCH3
F
H
CF3
CF3
CF3


C.I-330
COCH3
F
H
CF3
OCH3
OCH3


C.I-331
COCH3
F
H
OCH3
H
CH3


C.I-332
COCH3
F
H
OCH3
H
Cl


C.I-333
COCH3
F
H
OCH3
H
CF3


C.I-334
COCH3
F
H
OCH3
H
Br


C.I-335
COCH3
F
H
OCH3
H
OCH3


C.I-336
COCH3
F
H
OCH3
H
F


C.I-337
COCH3
F
H
OCH3
CH3
CH3


C.I-338
COCH3
F
H
OCH3
Cl
Cl


C.I-339
COCH3
F
H
OCH3
CF3
CF3


C.I-340
COCH3
F
H
OCH3
OCH3
OCH3


C.I-341
COCH3
F
H
Br
H
CH3


C.I-342
COCH3
F
H
Br
H
Cl


C.I-343
COCH3
F
H
Br
H
CF3


C.I-344
COCH3
F
H
Br
H
Br


C.I-345
COCH3
F
H
Br
H
OCH3


C.I-346
COCH3
F
H
Br
H
F


C.I-347
COCH3
F
H
Br
CH3
CH3


C.I-348
COCH3
F
H
Br
Cl
Cl


C.I-349
COCH3
F
H
Br
CF3
CF3


C.I-350
COCH3
F
H
Br
OCH3
OCH3


C.I-351
COCH3
Br
H
F
H
CH3


C.I-352
COCH3
Br
H
F
H
Cl


C.I-353
COCH3
Br
H
F
H
CF3


C.I-354
COCH3
Br
H
F
H
Br


C.I-355
COCH3
Br
H
F
H
OCH3


C.I-356
COCH3
Br
H
F
H
F


C.I-357
COCH3
Br
H
F
CH3
CH3


C.I-358
COCH3
Br
H
F
Cl
Cl


C.I-359
COCH3
Br
H
F
CF3
CF3


C.I-360
COCH3
Br
H
F
OCH3
OCH3


C.I-361
COCH3
CH3
H
F
H
CH3


C.I-362
COCH3
CH3
H
F
H
Cl


C.I-363
COCH3
CH3
H
F
H
CF3


C.I-364
COCH3
CH3
H
F
H
Br


C.I-365
COCH3
CH3
H
F
H
OCH3


C.I-366
COCH3
CH3
H
F
H
F


C.I-367
COCH3
CH3
H
F
CH3
CH3


C.I-368
COCH3
CH3
H
F
Cl
Cl


C.I-369
COCH3
CH3
H
F
CF3
CF3


C.I-370
COCH3
CH3
H
F
OCH3
OCH3


C.I-371
COCH3
OCH3
H
F
H
CH3


C.I-372
COCH3
OCH3
H
F
H
Cl


C.I-373
COCH3
OCH3
H
F
H
CF3


C.I-374
COCH3
OCH3
H
F
H
Br


C.I-375
COCH3
OCH3
H
F
H
OCH3


C.I-376
COCH3
OCH3
H
F
H
F


C.I-377
COCH3
OCH3
H
F
CH3
CH3


C.I-378
COCH3
OCH3
H
F
Cl
Cl


C.I-379
COCH3
OCH3
H
F
CF3
CF3


C.I-380
COCH3
OCH3
H
F
OCH3
OCH3


C.I-381
COCH3
CH3
H
Cl
H
CH3


C.I-382
COCH3
CH3
H
Cl
H
Cl


C.I-383
COCH3
CH3
H
Cl
H
CF3


C.I-384
COCH3
CH3
H
Cl
H
Br


C.I-385
COCH3
CH3
H
Cl
H
OCH3


C.I-386
COCH3
CH3
H
Cl
H
F


C.I-387
COCH3
CH3
H
Cl
CH3
CH3


C.I-388
COCH3
CH3
H
Cl
Cl
Cl


C.I-389
COCH3
CH3
H
Cl
CF3
CF3


C.I-390
COCH3
CH3
H
Cl
OCH3
OCH3


C.I-391
COCH3
Cl
H
CH3
H
CH3


C.I-392
COCH3
Cl
H
CH3
H
Cl


C.I-393
COCH3
Cl
H
CH3
H
CF3


C.I-394
COCH3
Cl
H
CH3
H
Br


C.I-395
COCH3
Cl
H
CH3
H
OCH3


C.I-396
COCH3
Cl
H
CH3
H
F


C.I-397
COCH3
Cl
H
CH3
CH3
CH3


C.I-398
COCH3
Cl
H
CH3
Cl
Cl


C.I-399
COCH3
Cl
H
CH3
CF3
CF3


C.I-400
COCH3
Cl
H
CH3
OCH3
OCH3


C.I-401
COCH2OCH3
Cl
Cl
H
H
CH3


C.I-402
COCH2OCH3
Cl
Cl
H
H
Cl


C.I-403
COCH2OCH3
Cl
Cl
H
H
CF3


C.I-404
COCH2OCH3
Cl
Cl
H
H
Br


C.I-405
COCH2OCH3
Cl
Cl
H
H
OCH3


C.I-406
COCH2OCH3
Cl
Cl
H
H
F


C.I-407
COCH2OCH3
Cl
Cl
H
CH3
CH3


C.I-408
COCH2OCH3
Cl
Cl
H
Cl
Cl


C.I-409
COCH2OCH3
Cl
Cl
H
CF3
CF3


C.I-410
COCH2OCH3
Cl
Cl
H
OCH3
OCH3


C.I-411
COCH2OCH3
CH3
CH3
H
H
CH3


C.I-412
COCH2OCH3
CH3
CH3
H
H
Cl


C.I-413
COCH2OCH3
CH3
CH3
H
H
CF3


C.I-414
COCH2OCH3
CH3
CH3
H
H
Br


C.I-415
COCH2OCH3
CH3
CH3
H
H
OCH3


C.I-416
COCH2OCH3
CH3
CH3
H
H
F


C.I-417
COCH2OCH3
CH3
CH3
H
CH3
CH3


C.I-418
COCH2OCH3
CH3
CH3
H
Cl
Cl


C.I-419
COCH2OCH3
CH3
CH3
H
CF3
CF3


C.I-420
COCH2OCH3
CH3
CH3
H
OCH3
OCH3


C.I-421
COCH2OCH3
CH3
CF3
H
H
CH3


C.I-422
COCH2OCH3
CH3
CF3
H
H
Cl


C.I-423
COCH2OCH3
CH3
CF3
H
H
CF3


C.I-424
COCH2OCH3
CH3
CF3
H
H
Br


C.I-425
COCH2OCH3
CH3
CF3
H
H
OCH3


C.I-426
COCH2OCH3
CH3
CF3
H
H
F


C.I-427
COCH2OCH3
CH3
CF3
H
CH3
CH3


C.I-428
COCH2OCH3
CH3
CF3
H
Cl
Cl


C.I-429
COCH2OCH3
CH3
CF3
H
CF3
CF3


C.I-430
COCH2OCH3
CH3
CF3
H
OCH3
OCH3


C.I-431
COCH2OCH3
CF3
CH3
H
H
CH3


C.I-432
COCH2OCH3
CF3
CH3
H
H
Cl


C.I-433
COCH2OCH3
CF3
CH3
H
H
CF3


C.I-434
COCH2OCH3
CF3
CH3
H
H
Br


C.I-435
COCH2OCH3
CF3
CH3
H
H
OCH3


C.I-436
COCH2OCH3
CF3
CH3
H
H
F


C.I-437
COCH2OCH3
CF3
CH3
H
CH3
CH3


C.I-438
COCH2OCH3
CF3
CH3
H
Cl
Cl


C.I-439
COCH2OCH3
CF3
CH3
H
CF3
CF3


C.I-440
COCH2OCH3
CF3
CH3
H
OCH3
OCH3


C.I-441
COCH2OCH3
F
CF3
H
H
CH3


C.I-442
COCH2OCH3
F
CF3
H
H
Cl


C.I-443
COCH2OCH3
F
CF3
H
H
CF3


C.I-444
COCH2OCH3
F
CF3
H
H
Br


C.I-445
COCH2OCH3
F
CF3
H
H
OCH3


C.I-446
COCH2OCH3
F
CF3
H
H
F


C.I-447
COCH2OCH3
F
CF3
H
CH3
CH3


C.I-448
COCH2OCH3
F
CF3
H
Cl
Cl


C.I-449
COCH2OCH3
F
CF3
H
CF3
CF3


C.I-450
COCH2OCH3
F
CF3
H
OCH3
OCH3


C.I-451
COCH2OCH3
Cl
CF3
H
H
CH3


C.I-452
COCH2OCH3
Cl
CF3
H
H
Cl


C.I-453
COCH2OCH3
Cl
CF3
H
H
CF3


C.I-454
COCH2OCH3
Cl
CF3
H
H
Br


C.I-455
COCH2OCH3
Cl
CF3
H
H
OCH3


C.I-456
COCH2OCH3
Cl
CF3
H
H
F


C.I-457
COCH2OCH3
Cl
CF3
H
CH3
CH3


C.I-458
COCH2OCH3
Cl
CF3
H
Cl
Cl


C.I-459
COCH2OCH3
Cl
CF3
H
CF3
CF3


C.I-460
COCH2OCH3
Cl
CF3
H
OCH3
OCH3


C.I-461
COCH2OCH3
CH3
Cl
H
H
CH3


C.I-462
COCH2OCH3
CH3
Cl
H
H
Cl


C.I-463
COCH2OCH3
CH3
Cl
H
H
CF3


C.I-464
COCH2OCH3
CH3
Cl
H
H
Br


C.I-465
COCH2OCH3
CH3
Cl
H
H
OCH3


C.I-466
COCH2OCH3
CH3
Cl
H
H
F


C.I-467
COCH2OCH3
CH3
Cl
H
CH3
CH3


C.I-468
COCH2OCH3
CH3
Cl
H
Cl
Cl


C.I-469
COCH2OCH3
CH3
Cl
H
CF3
CF3


C.I-470
COCH2OCH3
CH3
Cl
H
OCH3
OCH3


C.I-471
COCH2OCH3
Cl
CH3
H
H
CH3


C.I-472
COCH2OCH3
Cl
CH3
H
H
Cl


C.I-473
COCH2OCH3
Cl
CH3
H
H
CF3


C.I-474
COCH2OCH3
Cl
CH3
H
H
Br


C.I-475
COCH2OCH3
Cl
CH3
H
H
OCH3


C.I-476
COCH2OCH3
Cl
CH3
H
H
F


C.I-477
COCH2OCH3
Cl
CH3
H
CH3
CH3


C.I-478
COCH2OCH3
Cl
CH3
H
Cl
Cl


C.I-479
COCH2OCH3
Cl
CH3
H
CF3
CF3


C.I-480
COCH2OCH3
Cl
CH3
H
OCH3
OCH3


C.I-481
COCH2OCH3
Cl
H
Cl
H
CH3


C.I-482
COCH2OCH3
Cl
H
Cl
H
Cl


C.I-483
COCH2OCH3
Cl
H
Cl
H
CF3


C.I-484
COCH2OCH3
Cl
H
Cl
H
Br


C.I-485
COCH2OCH3
Cl
H
Cl
H
OCH3


C.I-486
COCH2OCH3
Cl
H
Cl
H
F


C.I-487
COCH2OCH3
Cl
H
Cl
CH3
CH3


C.I-488
COCH2OCH3
Cl
H
Cl
Cl
Cl


C.I-489
COCH2OCH3
Cl
H
Cl
CF3
CF3


C.I-490
COCH2OCH3
Cl
H
Cl
OCH3
OCH3


C.I-491
COCH2OCH3
F
H
F
H
CH3


C.I-492
COCH2OCH3
F
H
F
H
Cl


C.I-493
COCH2OCH3
F
H
F
H
CF3


C.I-494
COCH2OCH3
F
H
F
H
Br


C.I-495
COCH2OCH3
F
H
F
H
OCH3


C.I-496
COCH2OCH3
F
H
F
H
F


C.I-497
COCH2OCH3
F
H
F
CH3
CH3


C.I-498
COCH2OCH3
F
H
F
Cl
Cl


C.I-499
COCH2OCH3
F
H
F
CF3
CF3


C.I-500
COCH2OCH3
F
H
F
OCH3
OCH3


C.I-501
COCH2OCH3
CH3
H
CH3
H
CH3


C.I-502
COCH2OCH3
CH3
H
CH3
H
Cl


C.I-503
COCH2OCH3
CH3
H
CH3
H
CF3


C.I-504
COCH2OCH3
CH3
H
CH3
H
Br


C.I-505
COCH2OCH3
CH3
H
CH3
H
OCH3


C.I-506
COCH2OCH3
CH3
H
CH3
H
F


C.I-507
COCH2OCH3
CH3
H
CH3
CH3
CH3


C.I-508
COCH2OCH3
CH3
H
CH3
Cl
Cl


C.I-509
COCH2OCH3
CH3
H
CH3
CF3
CF3


C.I-510
COCH2OCH3
CH3
H
CH3
OCH3
OCH3


C.I-511
COCH2OCH3
F
H
CH3
H
CH3


C.I-512
COCH2OCH3
F
H
CH3
H
Cl


C.I-513
COCH2OCH3
F
H
CH3
H
CF3


C.I-514
COCH2OCH3
F
H
CH3
H
Br


C.I-515
COCH2OCH3
F
H
CH3
H
OCH3


C.I-516
COCH2OCH3
F
H
CH3
H
F


C.I-517
COCH2OCH3
F
H
CH3
CH3
CH3


C.I-518
COCH2OCH3
F
H
CH3
Cl
Cl


C.I-519
COCH2OCH3
F
H
CH3
CF3
CF3


C.I-520
COCH2OCH3
F
H
CH3
OCH3
OCH3


C.I-521
COCH2OCH3
F
H
CF3
H
CH3


C.I-522
COCH2OCH3
F
H
CF3
H
Cl


C.I-523
COCH2OCH3
F
H
CF3
H
CF3


C.I-524
COCH2OCH3
F
H
CF3
H
Br


C.I-525
COCH2OCH3
F
H
CF3
H
OCH3


C.I-526
COCH2OCH3
F
H
CF3
H
F


C.I-527
COCH2OCH3
F
H
CF3
CH3
CH3


C.I-528
COCH2OCH3
F
H
CF3
Cl
Cl


C.I-529
COCH2OCH3
F
H
CF3
CF3
CF3


C.I-530
COCH2OCH3
F
H
CF3
OCH3
OCH3


C.I-531
COCH2OCH3
F
H
OCH3
H
CH3


C.I-532
COCH2OCH3
F
H
OCH3
H
Cl


C.I-533
COCH2OCH3
F
H
OCH3
H
CF3


C.I-534
COCH2OCH3
F
H
OCH3
H
Br


C.I-535
COCH2OCH3
F
H
OCH3
H
OCH3


C.I-536
COCH2OCH3
F
H
OCH3
H
F


C.I-537
COCH2OCH3
F
H
OCH3
CH3
CH3


C.I-538
COCH2OCH3
F
H
OCH3
Cl
Cl


C.I-539
COCH2OCH3
F
H
OCH3
CF3
CF3


C.I-540
COCH2OCH3
F
H
OCH3
OCH3
OCH3


C.I-541
COCH2OCH3
F
H
Br
H
CH3


C.I-542
COCH2OCH3
F
H
Br
H
Cl


C.I-543
COCH2OCH3
F
H
Br
H
CF3


C.I-544
COCH2OCH3
F
H
Br
H
Br


C.I-545
COCH2OCH3
F
H
Br
H
OCH3


C.I-546
COCH2OCH3
F
H
Br
H
F


C.I-547
COCH2OCH3
F
H
Br
CH3
CH3


C.I-548
COCH2OCH3
F
H
Br
Cl
Cl


C.I-549
COCH2OCH3
F
H
Br
CF3
CF3


C.I-550
COCH2OCH3
F
H
Br
OCH3
OCH3


C.I-551
COCH2OCH3
Br
H
F
H
CH3


C.I-552
COCH2OCH3
Br
H
F
H
Cl


C.I-553
COCH2OCH3
Br
H
F
H
CF3


C.I-554
COCH2OCH3
Br
H
F
H
Br


C.I-555
COCH2OCH3
Br
H
F
H
OCH3


C.I-556
COCH2OCH3
Br
H
F
H
F


C.I-557
COCH2OCH3
Br
H
F
CH3
CH3


C.I-558
COCH2OCH3
Br
H
F
Cl
Cl


C.I-559
COCH2OCH3
Br
H
F
CF3
CF3


C.I-560
COCH2OCH3
Br
H
F
OCH3
OCH3


C.I-561
COCH2OCH3
CH3
H
F
H
CH3


C.I-562
COCH2OCH3
CH3
H
F
H
Cl


C.I-563
COCH2OCH3
CH3
H
F
H
CF3


C.I-564
COCH2OCH3
CH3
H
F
H
Br


C.I-565
COCH2OCH3
CH3
H
F
H
OCH3


C.I-566
COCH2OCH3
CH3
H
F
H
F


C.I-567
COCH2OCH3
CH3
H
F
CH3
CH3


C.I-568
COCH2OCH3
CH3
H
F
Cl
Cl


C.I-569
COCH2OCH3
CH3
H
F
CF3
CF3


C.I-570
COCH2OCH3
CH3
H
F
OCH3
OCH3


C.I-571
COCH2OCH3
OCH3
H
F
H
CH3


C.I-572
COCH2OCH3
OCH3
H
F
H
Cl


C.I-573
COCH2OCH3
OCH3
H
F
H
CF3


C.I-574
COCH2OCH3
OCH3
H
F
H
Br


C.I-575
COCH2OCH3
OCH3
H
F
H
OCH3


C.I-576
COCH2OCH3
OCH3
H
F
H
F


C.I-577
COCH2OCH3
OCH3
H
F
CH3
CH3


C.I-578
COCH2OCH3
OCH3
H
F
Cl
Cl


C.I-579
COCH2OCH3
OCH3
H
F
CF3
CF3


C.I-580
COCH2OCH3
OCH3
H
F
OCH3
OCH3


C.I-581
COCH2OCH3
CH3
H
Cl
H
CH3


C.I-582
COCH2OCH3
CH3
H
Cl
H
Cl


C.I-583
COCH2OCH3
CH3
H
Cl
H
CF3


C.I-584
COCH2OCH3
CH3
H
Cl
H
Br


C.I-585
COCH2OCH3
CH3
H
Cl
H
OCH3


C.I-586
COCH2OCH3
CH3
H
Cl
H
F


C.I-587
COCH2OCH3
CH3
H
Cl
CH3
CH3


C.I-588
COCH2OCH3
CH3
H
Cl
Cl
Cl


C.I-589
COCH2OCH3
CH3
H
Cl
CF3
CF3


C.I-590
COCH2OCH3
CH3
H
Cl
OCH3
OCH3


C.I-591
COCH2OCH3
Cl
H
CH3
H
CH3


C.I-592
COCH2OCH3
Cl
H
CH3
H
Cl


C.I-593
COCH2OCH3
Cl
H
CH3
H
CF3


C.I-594
COCH2OCH3
Cl
H
CH3
H
Br


C.I-595
COCH2OCH3
Cl
H
CH3
H
OCH3


C.I-596
COCH2OCH3
Cl
H
CH3
H
F


C.I-597
COCH2OCH3
Cl
H
CH3
CH3
CH3


C.I-598
COCH2OCH3
Cl
H
CH3
Cl
Cl


C.I-599
COCH2OCH3
Cl
H
CH3
CF3
CF3


C.I-600
COCH2OCH3
Cl
H
CH3
OCH3
OCH3


C.I-601
COCH2CH3
Cl
Cl
H
H
CH3


C.I-602
COCH2CH3
Cl
Cl
H
H
Cl


C.I-603
COCH2CH3
Cl
Cl
H
H
CF3


C.I-604
COCH2CH3
Cl
Cl
H
H
Br


C.I-605
COCH2CH3
Cl
Cl
H
H
OCH3


C.I-606
COCH2CH3
Cl
Cl
H
H
F


C.I-607
COCH2CH3
Cl
Cl
H
CH3
CH3


C.I-608
COCH2CH3
Cl
Cl
H
Cl
Cl


C.I-609
COCH2CH3
Cl
Cl
H
CF3
CF3


C.I-610
COCH2CH3
Cl
Cl
H
OCH3
OCH3


C.I-611
COCH2CH3
CH3
CH3
H
H
CH3


C.I-612
COCH2CH3
CH3
CH3
H
H
Cl


C.I-613
COCH2CH3
CH3
CH3
H
H
CF3


C.I-614
COCH2CH3
CH3
CH3
H
H
Br


C.I-615
COCH2CH3
CH3
CH3
H
H
OCH3


C.I-616
COCH2CH3
CH3
CH3
H
H
F


C.I-617
COCH2CH3
CH3
CH3
H
CH3
CH3


C.I-618
COCH2CH3
CH3
CH3
H
Cl
Cl


C.I-619
COCH2CH3
CH3
CH3
H
CF3
CF3


C.I-620
COCH2CH3
CH3
CH3
H
OCH3
OCH3


C.I-621
COCH2CH3
CH3
CF3
H
H
CH3


C.I-622
COCH2CH3
CH3
CF3
H
H
Cl


C.I-623
COCH2CH3
CH3
CF3
H
H
CF3


C.I-624
COCH2CH3
CH3
CF3
H
H
Br


C.I-625
COCH2CH3
CH3
CF3
H
H
OCH3


C.I-626
COCH2CH3
CH3
CF3
H
H
F


C.I-627
COCH2CH3
CH3
CF3
H
CH3
CH3


C.I-628
COCH2CH3
CH3
CF3
H
Cl
Cl


C.I-629
COCH2CH3
CH3
CF3
H
CF3
CF3


C.I-630
COCH2CH3
CH3
CF3
H
OCH3
OCH3


C.I-631
COCH2CH3
CF3
CH3
H
H
CH3


C.I-632
COCH2CH3
CF3
CH3
H
H
Cl


C.I-633
COCH2CH3
CF3
CH3
H
H
CF3


C.I-634
COCH2CH3
CF3
CH3
H
H
Br


C.I-635
COCH2CH3
CF3
CH3
H
H
OCH3


C.I-636
COCH2CH3
CF3
CH3
H
H
F


C.I-637
COCH2CH3
CF3
CH3
H
CH3
CH3


C.I-638
COCH2CH3
CF3
CH3
H
Cl
Cl


C.I-639
COCH2CH3
CF3
CH3
H
CF3
CF3


C.I-640
COCH2CH3
CF3
CH3
H
OCH3
OCH3


C.I-641
COCH2CH3
F
CF3
H
H
CH3


C.I-642
COCH2CH3
F
CF3
H
H
Cl


C.I-643
COCH2CH3
F
CF3
H
H
CF3


C.I-644
COCH2CH3
F
CF3
H
H
Br


C.I-645
COCH2CH3
F
CF3
H
H
OCH3


C.I-646
COCH2CH3
F
CF3
H
H
F


C.I-647
COCH2CH3
F
CF3
H
CH3
CH3


C.I-648
COCH2CH3
F
CF3
H
Cl
Cl


C.I-649
COCH2CH3
F
CF3
H
CF3
CF3


C.I-650
COCH2CH3
F
CF3
H
OCH3
OCH3


C.I-651
COCH2CH3
Cl
CF3
H
H
CH3


C.I-652
COCH2CH3
Cl
CF3
H
H
Cl


C.I-653
COCH2CH3
Cl
CF3
H
H
CF3


C.I-654
COCH2CH3
Cl
CF3
H
H
Br


C.I-655
COCH2CH3
Cl
CF3
H
H
OCH3


C.I-656
COCH2CH3
Cl
CF3
H
H
F


C.I-657
COCH2CH3
Cl
CF3
H
CH3
CH3


C.I-658
COCH2CH3
Cl
CF3
H
Cl
Cl


C.I-659
COCH2CH3
Cl
CF3
H
CF3
CF3


C.I-660
COCH2CH3
Cl
CF3
H
OCH3
OCH3


C.I-661
COCH2CH3
CH3
Cl
H
H
CH3


C.I-662
COCH2CH3
CH3
Cl
H
H
Cl


C.I-663
COCH2CH3
CH3
Cl
H
H
CF3


C.I-664
COCH2CH3
CH3
Cl
H
H
Br


C.I-665
COCH2CH3
CH3
Cl
H
H
OCH3


C.I-666
COCH2CH3
CH3
Cl
H
H
F


C.I-667
COCH2CH3
CH3
Cl
H
CH3
CH3


C.I-668
COCH2CH3
CH3
Cl
H
Cl
Cl


C.I-669
COCH2CH3
CH3
Cl
H
CF3
CF3


C.I-670
COCH2CH3
CH3
Cl
H
OCH3
OCH3


C.I-671
COCH2CH3
Cl
CH3
H
H
CH3


C.I-672
COCH2CH3
Cl
CH3
H
H
Cl


C.I-673
COCH2CH3
Cl
CH3
H
H
CF3


C.I-674
COCH2CH3
Cl
CH3
H
H
Br


C.I-675
COCH2CH3
Cl
CH3
H
H
OCH3


C.I-676
COCH2CH3
Cl
CH3
H
H
F


C.I-677
COCH2CH3
Cl
CH3
H
CH3
CH3


C.I-678
COCH2CH3
Cl
CH3
H
Cl
Cl


C.I-679
COCH2CH3
Cl
CH3
H
CF3
CF3


C.I-680
COCH2CH3
Cl
CH3
H
OCH3
OCH3


C.I-681
COCH2CH3
Cl
H
Cl
H
CH3


C.I-682
COCH2CH3
Cl
H
Cl
H
Cl


C.I-683
COCH2CH3
Cl
H
Cl
H
CF3


C.I-684
COCH2CH3
Cl
H
Cl
H
Br


C.I-685
COCH2CH3
Cl
H
Cl
H
OCH3


C.I-686
COCH2CH3
Cl
H
Cl
H
F


C.I-687
COCH2CH3
Cl
H
Cl
CH3
CH3


C.I-688
COCH2CH3
Cl
H
Cl
Cl
Cl


C.I-689
COCH2CH3
Cl
H
Cl
CF3
CF3


C.I-690
COCH2CH3
Cl
H
Cl
OCH3
OCH3


C.I-691
COCH2CH3
F
H
F
H
CH3


C.I-692
COCH2CH3
F
H
F
H
Cl


C.I-693
COCH2CH3
F
H
F
H
CF3


C.I-694
COCH2CH3
F
H
F
H
Br


C.I-695
COCH2CH3
F
H
F
H
OCH3


C.I-696
COCH2CH3
F
H
F
H
F


C.I-697
COCH2CH3
F
H
F
CH3
CH3


C.I-698
COCH2CH3
F
H
F
Cl
Cl


C.I-699
COCH2CH3
F
H
F
CF3
CF3


C.I-700
COCH2CH3
F
H
F
OCH3
OCH3


C.I-701
COCH2CH3
CH3
H
CH3
H
CH3


C.I-702
COCH2CH3
CH3
H
CH3
H
Cl


C.I-703
COCH2CH3
CH3
H
CH3
H
CF3


C.I-704
COCH2CH3
CH3
H
CH3
H
Br


C.I-705
COCH2CH3
CH3
H
CH3
H
OCH3


C.I-706
COCH2CH3
CH3
H
CH3
H
F


C.I-707
COCH2CH3
CH3
H
CH3
CH3
CH3


C.I-708
COCH2CH3
CH3
H
CH3
Cl
Cl


C.I-709
COCH2CH3
CH3
H
CH3
CF3
CF3


C.I-710
COCH2CH3
CH3
H
CH3
OCH3
OCH3


C.I-711
COCH2CH3
F
H
CH3
H
CH3


C.I-712
COCH2CH3
F
H
CH3
H
Cl


C.I-713
COCH2CH3
F
H
CH3
H
CF3


C.I-714
COCH2CH3
F
H
CH3
H
Br


C.I-715
COCH2CH3
F
H
CH3
H
OCH3


C.I-716
COCH2CH3
F
H
CH3
H
F


C.I-717
COCH2CH3
F
H
CH3
CH3
CH3


C.I-718
COCH2CH3
F
H
CH3
Cl
Cl


C.I-719
COCH2CH3
F
H
CH3
CF3
CF3


C.I-720
COCH2CH3
F
H
CH3
OCH3
OCH3


C.I-721
COCH2CH3
F
H
CF3
H
CH3


C.I-722
COCH2CH3
F
H
CF3
H
Cl


C.I-723
COCH2CH3
F
H
CF3
H
CF3


C.I-724
COCH2CH3
F
H
CF3
H
Br


C.I-725
COCH2CH3
F
H
CF3
H
OCH3


C.I-726
COCH2CH3
F
H
CF3
H
F


C.I-727
COCH2CH3
F
H
CF3
CH3
CH3


C.I-728
COCH2CH3
F
H
CF3
Cl
Cl


C.I-729
COCH2CH3
F
H
CF3
CF3
CF3


C.I-730
COCH2CH3
F
H
CF3
OCH3
OCH3


C.I-731
COCH2CH3
F
H
OCH3
H
CH3


C.I-732
COCH2CH3
F
H
OCH3
H
Cl


C.I-733
COCH2CH3
F
H
OCH3
H
CF3


C.I-734
COCH2CH3
F
H
OCH3
H
Br


C.I-735
COCH2CH3
F
H
OCH3
H
OCH3


C.I-736
COCH2CH3
F
H
OCH3
H
F


C.I-737
COCH2CH3
F
H
OCH3
CH3
CH3


C.I-738
COCH2CH3
F
H
OCH3
Cl
Cl


C.I-739
COCH2CH3
F
H
OCH3
CF3
CF3


C.I-740
COCH2CH3
F
H
OCH3
OCH3
OCH3


C.I-741
COCH2CH3
F
H
Br
H
CH3


C.I-742
COCH2CH3
F
H
Br
H
Cl


C.I-743
COCH2CH3
F
H
Br
H
CF3


C.I-744
COCH2CH3
F
H
Br
H
Br


C.I-745
COCH2CH3
F
H
Br
H
OCH3


C.I-746
COCH2CH3
F
H
Br
H
F


C.I-747
COCH2CH3
F
H
Br
CH3
CH3


C.I-748
COCH2CH3
F
H
Br
Cl
Cl


C.I-749
COCH2CH3
F
H
Br
CF3
CF3


C.I-750
COCH2CH3
F
H
Br
OCH3
OCH3


C.I-751
COCH2CH3
Br
H
F
H
CH3


C.I-752
COCH2CH3
Br
H
F
H
Cl


C.I-753
COCH2CH3
Br
H
F
H
CF3


C.I-754
COCH2CH3
Br
H
F
H
Br


C.I-755
COCH2CH3
Br
H
F
H
OCH3


C.I-756
COCH2CH3
Br
H
F
H
F


C.I-757
COCH2CH3
Br
H
F
CH3
CH3


C.I-758
COCH2CH3
Br
H
F
Cl
Cl


C.I-759
COCH2CH3
Br
H
F
CF3
CF3


C.I-760
COCH2CH3
Br
H
F
OCH3
OCH3


C.I-761
COCH2CH3
CH3
H
F
H
CH3


C.I-762
COCH2CH3
CH3
H
F
H
Cl


C.I-763
COCH2CH3
CH3
H
F
H
CF3


C.I-764
COCH2CH3
CH3
H
F
H
Br


C.I-765
COCH2CH3
CH3
H
F
H
OCH3


C.I-766
COCH2CH3
CH3
H
F
H
F


C.I-767
COCH2CH3
CH3
H
F
CH3
CH3


C.I-768
COCH2CH3
CH3
H
F
Cl
Cl


C.I-769
COCH2CH3
CH3
H
F
CF3
CF3


C.I-770
COCH2CH3
CH3
H
F
OCH3
OCH3


C.I-771
COCH2CH3
OCH3
H
F
H
CH3


C.I-772
COCH2CH3
OCH3
H
F
H
Cl


C.I-773
COCH2CH3
OCH3
H
F
H
CF3


C.I-774
COCH2CH3
OCH3
H
F
H
Br


C.I-775
COCH2CH3
OCH3
H
F
H
OCH3


C.I-776
COCH2CH3
OCH3
H
F
H
F


C.I-777
COCH2CH3
OCH3
H
F
CH3
CH3


C.I-778
COCH2CH3
OCH3
H
F
Cl
Cl


C.I-779
COCH2CH3
OCH3
H
F
CF3
CF3


C.I-780
COCH2CH3
OCH3
H
F
OCH3
OCH3


C.I-781
COCH2CH3
CH3
H
Cl
H
CH3


C.I-782
COCH2CH3
CH3
H
Cl
H
Cl


C.I-783
COCH2CH3
CH3
H
Cl
H
CF3


C.I-784
COCH2CH3
CH3
H
Cl
H
Br


C.I-785
COCH2CH3
CH3
H
Cl
H
OCH3


C.I-786
COCH2CH3
CH3
H
Cl
H
F


C.I-787
COCH2CH3
CH3
H
Cl
CH3
CH3


C.I-788
COCH2CH3
CH3
H
Cl
Cl
Cl


C.I-789
COCH2CH3
CH3
H
Cl
CF3
CF3


C.I-790
COCH2CH3
CH3
H
Cl
OCH3
OCH3


C.I-791
COCH2CH3
Cl
H
CH3
H
CH3


C.I-792
COCH2CH3
Cl
H
CH3
H
Cl


C.I-793
COCH2CH3
Cl
H
CH3
H
CF3


C.I-794
COCH2CH3
Cl
H
CH3
H
Br


C.I-795
COCH2CH3
Cl
H
CH3
H
OCH3


C.I-796
COCH2CH3
Cl
H
CH3
H
F


C.I-797
COCH2CH3
Cl
H
CH3
CH3
CH3


C.I-798
COCH2CH3
Cl
H
CH3
Cl
Cl


C.I-799
COCH2CH3
Cl
H
CH3
CF3
CF3


C.I-800
COCH2CH3
Cl
H
CH3
OCH3
OCH3


C.I-801
COCH2C(CH3)3
Cl
Cl
H
H
CH3


C.I-802
COCH2C(CH3)3
Cl
Cl
H
H
Cl


C.I-803
COCH2C(CH3)3
Cl
Cl
H
H
CF3


C.I-804
COCH2C(CH3)3
Cl
Cl
H
H
Br


C.I-805
COCH2C(CH3)3
Cl
Cl
H
H
OCH3


C.I-806
COCH2C(CH3)3
Cl
Cl
H
H
F


C.I-807
COCH2C(CH3)3
Cl
Cl
H
CH3
CH3


C.I-808
COCH2C(CH3)3
Cl
Cl
H
Cl
Cl


C.I-809
COCH2C(CH3)3
Cl
Cl
H
CF3
CF3


C.I-810
COCH2C(CH3)3
Cl
Cl
H
OCH3
OCH3


C.I-811
COCH2C(CH3)3
CH3
CH3
H
H
CH3


C.I-812
COCH2C(CH3)3
CH3
CH3
H
H
Cl


C.I-813
COCH2C(CH3)3
CH3
CH3
H
H
CF3


C.I-814
COCH2C(CH3)3
CH3
CH3
H
H
Br


C.I-815
COCH2C(CH3)3
CH3
CH3
H
H
OCH3


C.I-816
COCH2C(CH3)3
CH3
CH3
H
H
F


C.I-817
COCH2C(CH3)3
CH3
CH3
H
CH3
CH3


C.I-818
COCH2C(CH3)3
CH3
CH3
H
Cl
Cl


C.I-819
COCH2C(CH3)3
CH3
CH3
H
CF3
CF3


C.I-820
COCH2C(CH3)3
CH3
CH3
H
OCH3
OCH3


C.I-821
COCH2C(CH3)3
CH3
CF3
H
H
CH3


C.I-822
COCH2C(CH3)3
CH3
CF3
H
H
Cl


C.I-823
COCH2C(CH3)3
CH3
CF3
H
H
CF3


C.I-824
COCH2C(CH3)3
CH3
CF3
H
H
Br


C.I-825
COCH2C(CH3)3
CH3
CF3
H
H
OCH3


C.I-826
COCH2C(CH3)3
CH3
CF3
H
H
F


C.I-827
COCH2C(CH3)3
CH3
CF3
H
CH3
CH3


C.I-828
COCH2C(CH3)3
CH3
CF3
H
Cl
Cl


C.I-829
COCH2C(CH3)3
CH3
CF3
H
CF3
CF3


C.I-830
COCH2C(CH3)3
CH3
CF3
H
OCH3
OCH3


C.I-831
COCH2C(CH3)3
CF3
CH3
H
H
CH3


C.I-832
COCH2C(CH3)3
CF3
CH3
H
H
Cl


C.I-833
COCH2C(CH3)3
CF3
CH3
H
H
CF3


C.I-834
COCH2C(CH3)3
CF3
CH3
H
H
Br


C.I-835
COCH2C(CH3)3
CF3
CH3
H
H
OCH3


C.I-836
COCH2C(CH3)3
CF3
CH3
H
H
F


C.I-837
COCH2C(CH3)3
CF3
CH3
H
CH3
CH3


C.I-838
COCH2C(CH3)3
CF3
CH3
H
Cl
Cl


C.I-839
COCH2C(CH3)3
CF3
CH3
H
CF3
CF3


C.I-840
COCH2C(CH3)3
CF3
CH3
H
OCH3
OCH3


C.I-841
COCH2C(CH3)3
F
CF3
H
H
CH3


C.I-842
COCH2C(CH3)3
F
CF3
H
H
Cl


C.I-843
COCH2C(CH3)3
F
CF3
H
H
CF3


C.I-844
COCH2C(CH3)3
F
CF3
H
H
Br


C.I-845
COCH2C(CH3)3
F
CF3
H
H
OCH3


C.I-846
COCH2C(CH3)3
F
CF3
H
H
F


C.I-847
COCH2C(CH3)3
F
CF3
H
CH3
CH3


C.I-848
COCH2C(CH3)3
F
CF3
H
Cl
Cl


C.I-849
COCH2C(CH3)3
F
CF3
H
CF3
CF3


C.I-850
COCH2C(CH3)3
F
CF3
H
OCH3
OCH3


C.I-851
COCH2C(CH3)3
Cl
CF3
H
H
CH3


C.I-852
COCH2C(CH3)3
Cl
CF3
H
H
Cl


C.I-853
COCH2C(CH3)3
Cl
CF3
H
H
CF3


C.I-854
COCH2C(CH3)3
Cl
CF3
H
H
Br


C.I-855
COCH2C(CH3)3
Cl
CF3
H
H
OCH3


C.I-856
COCH2C(CH3)3
Cl
CF3
H
H
F


C.I-857
COCH2C(CH3)3
Cl
CF3
H
CH3
CH3


C.I-858
COCH2C(CH3)3
Cl
CF3
H
Cl
Cl


C.I-859
COCH2C(CH3)3
Cl
CF3
H
CF3
CF3


C.I-860
COCH2C(CH3)3
Cl
CF3
H
OCH3
OCH3


C.I-861
COCH2C(CH3)3
CH3
Cl
H
H
CH3


C.I-862
COCH2C(CH3)3
CH3
Cl
H
H
Cl


C.I-863
COCH2C(CH3)3
CH3
Cl
H
H
CF3


C.I-864
COCH2C(CH3)3
CH3
Cl
H
H
Br


C.I-865
COCH2C(CH3)3
CH3
Cl
H
H
OCH3


C.I-866
COCH2C(CH3)3
CH3
Cl
H
H
F


C.I-867
COCH2C(CH3)3
CH3
Cl
H
CH3
CH3


C.I-868
COCH2C(CH3)3
CH3
Cl
H
Cl
Cl


C.I-869
COCH2C(CH3)3
CH3
Cl
H
CF3
CF3


C.I-870
COCH2C(CH3)3
CH3
Cl
H
OCH3
OCH3


C.I-871
COCH2C(CH3)3
Cl
CH3
H
H
CH3


C.I-872
COCH2C(CH3)3
Cl
CH3
H
H
Cl


C.I-873
COCH2C(CH3)3
Cl
CH3
H
H
CF3


C.I-874
COCH2C(CH3)3
Cl
CH3
H
H
Br


C.I-875
COCH2C(CH3)3
Cl
CH3
H
H
OCH3


C.I-876
COCH2C(CH3)3
Cl
CH3
H
H
F


C.I-877
COCH2C(CH3)3
Cl
CH3
H
CH3
CH3


C.I-878
COCH2C(CH3)3
Cl
CH3
H
Cl
Cl


C.I-879
COCH2C(CH3)3
Cl
CH3
H
CF3
CF3


C.I-880
COCH2C(CH3)3
Cl
CH3
H
OCH3
OCH3


C.I-881
COCH2C(CH3)3
Cl
H
Cl
H
CH3


C.I-882
COCH2C(CH3)3
Cl
H
Cl
H
Cl


C.I-883
COCH2C(CH3)3
Cl
H
Cl
H
CF3


C.I-884
COCH2C(CH3)3
Cl
H
Cl
H
Br


C.I-885
COCH2C(CH3)3
Cl
H
Cl
H
OCH3


C.I-886
COCH2C(CH3)3
Cl
H
Cl
H
F


C.I-887
COCH2C(CH3)3
Cl
H
Cl
CH3
CH3


C.I-888
COCH2C(CH3)3
Cl
H
Cl
Cl
Cl


C.I-889
COCH2C(CH3)3
Cl
H
Cl
CF3
CF3


C.I-890
COCH2C(CH3)3
Cl
H
Cl
OCH3
OCH3


C.I-891
COCH2C(CH3)3
F
H
F
H
CH3


C.I-892
COCH2C(CH3)3
F
H
F
H
Cl


C.I-893
COCH2C(CH3)3
F
H
F
H
CF3


C.I-894
COCH2C(CH3)3
F
H
F
H
Br


C.I-895
COCH2C(CH3)3
F
H
F
H
OCH3


C.I-896
COCH2C(CH3)3
F
H
F
H
F


C.I-897
COCH2C(CH3)3
F
H
F
CH3
CH3


C.I-898
COCH2C(CH3)3
F
H
F
Cl
Cl


C.I-899
COCH2C(CH3)3
F
H
F
CF3
CF3


C.I-900
COCH2C(CH3)3
F
H
F
OCH3
OCH3


C.I-901
COCH2C(CH3)3
CH3
H
CH3
H
CH3


C.I-902
COCH2C(CH3)3
CH3
H
CH3
H
Cl


C.I-903
COCH2C(CH3)3
CH3
H
CH3
H
CF3


C.I-904
COCH2C(CH3)3
CH3
H
CH3
H
Br


C.I-905
COCH2C(CH3)3
CH3
H
CH3
H
OCH3


C.I-906
COCH2C(CH3)3
CH3
H
CH3
H
F


C.I-907
COCH2C(CH3)3
CH3
H
CH3
CH3
CH3


C.I-908
COCH2C(CH3)3
CH3
H
CH3
Cl
Cl


C.I-909
COCH2C(CH3)3
CH3
H
CH3
CF3
CF3


C.I-910
COCH2C(CH3)3
CH3
H
CH3
OCH3
OCH3


C.I-911
COCH2C(CH3)3
F
H
CH3
H
CH3


C.I-912
COCH2C(CH3)3
F
H
CH3
H
Cl


C.I-913
COCH2C(CH3)3
F
H
CH3
H
CF3


C.I-914
COCH2C(CH3)3
F
H
CH3
H
Br


C.I-915
COCH2C(CH3)3
F
H
CH3
H
OCH3


C.I-916
COCH2C(CH3)3
F
H
CH3
H
F


C.I-917
COCH2C(CH3)3
F
H
CH3
CH3
CH3


C.I-918
COCH2C(CH3)3
F
H
CH3
Cl
Cl


C.I-919
COCH2C(CH3)3
F
H
CH3
CF3
CF3


C.I-920
COCH2C(CH3)3
F
H
CH3
OCH3
OCH3


C.I-921
COCH2C(CH3)3
F
H
CF3
H
CH3


C.I-922
COCH2C(CH3)3
F
H
CF3
H
Cl


C.I-923
COCH2C(CH3)3
F
H
CF3
H
CF3


C.I-924
COCH2C(CH3)3
F
H
CF3
H
Br


C.I-925
COCH2C(CH3)3
F
H
CF3
H
OCH3


C.I-926
COCH2C(CH3)3
F
H
CF3
H
F


C.I-927
COCH2C(CH3)3
F
H
CF3
CH3
CH3


C.I-928
COCH2C(CH3)3
F
H
CF3
Cl
Cl


C.I-929
COCH2C(CH3)3
F
H
CF3
CF3
CF3


C.I-930
COCH2C(CH3)3
F
H
CF3
OCH3
OCH3


C.I-931
COCH2C(CH3)3
F
H
OCH3
H
CH3


C.I-932
COCH2C(CH3)3
F
H
OCH3
H
Cl


C.I-933
COCH2C(CH3)3
F
H
OCH3
H
CF3


C.I-934
COCH2C(CH3)3
F
H
OCH3
H
Br


C.I-935
COCH2C(CH3)3
F
H
OCH3
H
OCH3


C.I-936
COCH2C(CH3)3
F
H
OCH3
H
F


C.I-937
COCH2C(CH3)3
F
H
OCH3
CH3
CH3


C.I-938
COCH2C(CH3)3
F
H
OCH3
Cl
Cl


C.I-939
COCH2C(CH3)3
F
H
OCH3
CF3
CF3


C.I-940
COCH2C(CH3)3
F
H
OCH3
OCH3
OCH3


C.I-941
COCH2C(CH3)3
F
H
Br
H
CH3


C.I-942
COCH2C(CH3)3
F
H
Br
H
Cl


C.I-943
COCH2C(CH3)3
F
H
Br
H
CF3


C.I-944
COCH2C(CH3)3
F
H
Br
H
Br


C.I-945
COCH2C(CH3)3
F
H
Br
H
OCH3


C.I-946
COCH2C(CH3)3
F
H
Br
H
F


C.I-947
COCH2C(CH3)3
F
H
Br
CH3
CH3


C.I-948
COCH2C(CH3)3
F
H
Br
Cl
Cl


C.I-949
COCH2C(CH3)3
F
H
Br
CF3
CF3


C.I-950
COCH2C(CH3)3
F
H
Br
OCH3
OCH3


C.I-951
COCH2C(CH3)3
Br
H
F
H
CH3


C.I-952
COCH2C(CH3)3
Br
H
F
H
Cl


C.I-953
COCH2C(CH3)3
Br
H
F
H
CF3


C.I-954
COCH2C(CH3)3
Br
H
F
H
Br


C.I-955
COCH2C(CH3)3
Br
H
F
H
OCH3


C.I-956
COCH2C(CH3)3
Br
H
F
H
F


C.I-957
COCH2C(CH3)3
Br
H
F
CH3
CH3


C.I-958
COCH2C(CH3)3
Br
H
F
Cl
Cl


C.I-959
COCH2C(CH3)3
Br
H
F
CF3
CF3


C.I-960
COCH2C(CH3)3
Br
H
F
OCH3
OCH3


C.I-961
COCH2C(CH3)3
CH3
H
F
H
CH3


C.I-962
COCH2C(CH3)3
CH3
H
F
H
Cl


C.I-963
COCH2C(CH3)3
CH3
H
F
H
CF3


C.I-964
COCH2C(CH3)3
CH3
H
F
H
Br


C.I-965
COCH2C(CH3)3
CH3
H
F
H
OCH3


C.I-966
COCH2C(CH3)3
CH3
H
F
H
F


C.I-967
COCH2C(CH3)3
CH3
H
F
CH3
CH3


C.I-968
COCH2C(CH3)3
CH3
H
F
Cl
Cl


C.I-969
COCH2C(CH3)3
CH3
H
F
CF3
CF3


C.I-970
COCH2C(CH3)3
CH3
H
F
OCH3
OCH3


C.I-971
COCH2C(CH3)3
OCH3
H
F
H
CH3


C.I-972
COCH2C(CH3)3
OCH3
H
F
H
Cl


C.I-973
COCH2C(CH3)3
OCH3
H
F
H
CF3


C.I-974
COCH2C(CH3)3
OCH3
H
F
H
Br


C.I-975
COCH2C(CH3)3
OCH3
H
F
H
OCH3


C.I-976
COCH2C(CH3)3
OCH3
H
F
H
F


C.I-977
COCH2C(CH3)3
OCH3
H
F
CH3
CH3


C.I-978
COCH2C(CH3)3
OCH3
H
F
Cl
Cl


C.I-979
COCH2C(CH3)3
OCH3
H
F
CF3
CF3


C.I-980
COCH2C(CH3)3
OCH3
H
F
OCH3
OCH3


C.I-981
COCH2C(CH3)3
CH3
H
Cl
H
CH3


C.I-982
COCH2C(CH3)3
CH3
H
Cl
H
Cl


C.I-983
COCH2C(CH3)3
CH3
H
Cl
H
CF3


C.I-984
COCH2C(CH3)3
CH3
H
Cl
H
Br


C.I-985
COCH2C(CH3)3
CH3
H
Cl
H
OCH3


C.I-986
COCH2C(CH3)3
CH3
H
Cl
H
F


C.I-987
COCH2C(CH3)3
CH3
H
Cl
CH3
CH3


C.I-988
COCH2C(CH3)3
CH3
H
Cl
Cl
Cl


C.I-989
COCH2C(CH3)3
CH3
H
Cl
CF3
CF3


C.I-990
COCH2C(CH3)3
CH3
H
Cl
OCH3
OCH3


C.I-991
COCH2C(CH3)3
Cl
H
CH3
H
CH3


C.I-992
COCH2C(CH3)3
Cl
H
CH3
H
Cl


C.I-993
COCH2C(CH3)3
Cl
H
CH3
H
CF3


C.I-994
COCH2C(CH3)3
Cl
H
CH3
H
Br


C.I-995
COCH2C(CH3)3
Cl
H
CH3
H
OCH3


C.I-996
COCH2C(CH3)3
Cl
H
CH3
H
F


C.I-997
COCH2C(CH3)3
Cl
H
CH3
CH3
CH3


C.I-998
COCH2C(CH3)3
Cl
H
CH3
Cl
Cl


C.I-999
COCH2C(CH3)3
Cl
H
CH3
CF3
CF3


C.I-
COCH2C(CH3)3
Cl
H
CH3
OCH3
OCH3


1000









Preferred Active Compounds II Selected from Group A

With respect to their use in the pesticidal mixtures of the present invention, particular preference is given to the compounds C.II as listed in the paragraphs below.
With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.1 as defined above is preferably triazemate or primicarb.
With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.2 as defined above is preferably endosulfan, N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole or vaniliprole or the phenylpyrazole compound II.A2.1.
More preferably the compound II is N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, acetoprole or fipronil.
With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.3 as defined above is preferably allethrin, bifenthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, etofenprox, fenpropathrin, fenvalerate, flucythrinate, taufluvalinate, silafluofen or tralomethrin.
More preferably the compound II is alpha-cypermethrin or deltamethrin.
With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.4 as defined above is preferably thiocyclam or from the class of neonicotinoids acteamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam and AKD-1022; or the allosteric nicotinic acetylcholine receptor agonist spinosad.
More preferably the compound II is clothianidine, imidacloprid or thiamethoxam.
With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.5 as defined above is preferably abamectin, emamectin benzoate, lepimectin or milbemectin.
More preferably the compound II is abamectin.
With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.7 as defined above is preferably diafenthiuron.
With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.8 as defined above is preferably buprofezin.
With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.10 as defined above is preferably pyridaben or flufenerim.
With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.11 as defined above is preferably indoxacarb or metaflumizone. More preferably the compound II is metaflumizone.
With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.12 as defined above is preferably spirodiclofen, spiromesifen or spirotetramat.
More preferably the compound II is spiromesifen or spirotetramat.
With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.13 as defined above is preferably amitraz, flonicamid, flubendiamine, pymetrozine, pyridalyl, pyrifluquinazon, chlorantraniliproler, the anthranil compound II.A13.1 or the sulfoximine compounds II.A13.2, II.A13.3 or II.A13.4.
More preferably the compound II is flonicamid, pymetrozine, pyrifluquinazon, chlorantraniliprole or the anthranil compound II.A13.1.
Especially preferred are pesticidal mixtures containing N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon as compound II.
Especially preferred are pesticidal mixtures containing N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon as compound II.
Especially preferred are pesticidal mixtures containing acetoprole as compound II.
Especially preferred are pesticidal mixtures containing fipronil as compound II.
Especially preferred are pesticidal mixtures containing alpha-cypermethrin as compound II.
Especially preferred are pesticidal mixtures containing clothianidin as compound II.
Especially preferred are pesticidal mixtures containing imidacloprid as compound II.
Especially preferred are pesticidal mixtures containing thiamethoxam as compound II.
Especially preferred are pesticidal mixtures containing pymetrozine as compound II.
Especially preferred are pesticidal mixtures containing flonicamid as compound II.
Especially preferred are pesticidal mixtures containing spiromesifen as compound II.
Especially preferred are pesticidal mixtures containing spirotetramat as compound II.
Especially preferred are pesticidal mixtures containing pyrifluquinazon as compound II.
Especially preferred are pesticidal mixtures containing chlorantraniliprole as compound II.
Especially preferred are pesticidal mixtures containing the anthranilamid compound II.A13.1




as compound II.

Especially preferred are pesticidal mixtures containing the sulfoximine compound II.A13.2




as compound II.

Especially preferred are pesticidal mixtures containing the sulfoximine compound II.A13.3




as compound II.

Especially preferred are pesticidal mixtures containing the sulfoximine compound II.A13.4




as compound II.

Preferred Mixtures According to the Invention

Especially preferred are inventive mixtures wherein the compound II of group A is acetoprol and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is fipronil and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is alpha-cypermethrin and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is deltamethrin and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is clothianidin and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is imidacloprid and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is thiamethoxam and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is abamectin and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is pymetrozine and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is flonicamid and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is diafenthiuron and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is buprofezin and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is pyridaben and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is flufenerim and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is metaflumizone and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is spiromesifen and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is spirotetramat and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is pyrifluquinazon and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is chlorantraniliprole and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is the anthranilamid compound II.A13.1 and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is the sulfoximine compound II.A13.2 and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is the sulfoximine compound II.A13.3 and the compound I of formula I is a compound of Table C.
Especially preferred are inventive mixtures wherein the compound II of group A is the sulfoximine compound II.A13.4 and the compound I of formula I is a compound of Table C.
The following table M represents preferred combinations of the active compounds I of formula I as defined in table C and the active compounds II of group A in mixtures according to the invention:












TABLE M





Mixture
Compound I
Compound-II
Mixture
Compound I
Compound II







M.1
C.I-1
acetoprole
M.113
C.I-1
diafenthiuron


M.2
C.I-7
acetoprole
M.114
C.I-7
diafenthiuron


M.3
C.I-11
acetoprole
M.115
C.I-11
diafenthiuron


M.4
C.I-17
acetoprole
M.116
C.I-17
diafenthiuron


M.5
C.I-21
acetoprole
M.117
C.I-21
diafenthiuron


M.6
C.I-27
acetoprole
M.118
C.I-27
diafenthiuron


M.7
C.I-51
acetoprole
M.119
C.I-51
diafenthiuron


M.8
C.I-57
acetoprole
M.120
C.I-57
diafenthiuron


M.9
C.I-81
acetoprole
M.121
C.I-81
diafenthiuron


M.10
C.I-87
acetoprole
M.122
C.I-87
diafenthiuron


M.11
C.I-91
acetoprole
M.123
C.I-91
diafenthiuron


M.12
C.I-97
acetoprole
M.124
C.I-97
diafenthiuron


M.13
C.I-101
acetoprole
M.125
C.I-101
diafenthiuron


M.14
C.I-107
acetoprole
M.126
C.I-107
diafenthiuron


M.15
C.I-201
acetoprole
M.127
C.I-201
diafenthiuron


M.16
C.I-207
acetoprole
M.128
C.I-207
diafenthiuron


M.17
C.I-211
acetoprole
M.129
C.I-211
diafenthiuron


M.18
C.I-217
acetoprole
M.130
C.I-217
diafenthiuron


M.19
C.I-221
acetoprole
M.131
C.I-221
diafenthiuron


M.20
C.I-227
acetoprole
M.132
C.I-227
diafenthiuron


M.21
C.I-251
acetoprole
M.133
C.I-251
diafenthiuron


M.22
C.I-257
acetoprole
M.134
C.I-257
diafenthiuron


M.23
C.I-281
acetoprole
M.135
C.I-281
diafenthiuron


M.24
C.I-287
acetoprole
M.136
C.I-287
diafenthiuron


M.25
C.I-291
acetoprole
M.137
C.I-291
diafenthiuron


M.26
C.I-297
acetoprole
M.138
C.I-297
diafenthiuron


M.27
C.I-301
acetoprole
M.139
C.I-301
diafenthiuron


M.28
C.I-307
acetoprole
M.140
C.I-307
diafenthiuron


M.29
C.I-1
fipronil
M.141
C.I-1
buprofezin


M.30
C.I-7
fipronil
M.142
C.I-7
buprofezin


M.31
C.I-11
fipronil
M.143
C.I-11
buprofezin


M.32
C.I-17
fipronil
M.144
C.I-17
buprofezin


M.33
C.I-21
fipronil
M.145
C.I-21
buprofezin


M.34
C.I-27
fipronil
M.146
C.I-27
buprofezin


M.35
C.I-51
fipronil
M.147
C.I-51
buprofezin


M.36
C.I-57
fipronil
M.148
C.I-57
buprofezin


M.37
C.I-81
fipronil
M.149
C.I-81
buprofezin


M.38
C.I-87
fipronil
M.150
C.I-87
buprofezin


M.39
C.I-91
fipronil
M.151
C.I-91
buprofezin


M.40
C.I-97
fipronil
M.152
C.I-97
buprofezin


M.41
C.I-101
fipronil
M.153
C.I-101
buprofezin


M.42
C.I-107
fipronil
M.154
C.I-107
buprofezin


M.43
C.I-201
fipronil
M.155
C.I-201
buprofezin


M.44
C.I-207
fipronil
M.156
C.I-207
buprofezin


M.45
C.I-211
fipronil
M.157
C.I-211
buprofezin


M.46
C.I-217
fipronil
M.158
C.I-217
buprofezin


M.47
C.I-221
fipronil
M.159
C.I-221
buprofezin


M.48
C.I-227
fipronil
M.160
C.I-227
buprofezin


M.49
C.I-251
fipronil
M.161
C.I-251
buprofezin


M.50
C.I-257
fipronil
M.162
C.I-257
buprofezin


M.51
C.I-281
fipronil
M.163
C.I-281
buprofezin


M.52
C.I-287
fipronil
M.164
C.I-287
buprofezin


M.53
C.I-291
fipronil
M.165
C.I-291
buprofezin


M.54
C.I-297
fipronil
M.166
C.I-297
buprofezin


M.55
C.I-301
fipronil
M.167
C.I-301
buprofezin


M.56
C.I-307
fipronil
M.168
C.I-307
buprofezin


M.57
C.I-1
imidacloprid
M.169
C.I-1
pyridaben


M.58
C.I-7
imidacloprid
M.170
C.I-7
pyridaben


M.59
C.I-11
imidacloprid
M.171
C.I-11
pyridaben


M.60
C.I-17
imidacloprid
M.172
C.I-17
pyridaben


M.61
C.I-21
imidacloprid
M.173
C.I-21
pyridaben


M.62
C.I-27
imidacloprid
M.174
C.I-27
pyridaben


M.63
C.I-51
imidacloprid
M.175
C.I-51
pyridaben


M.64
C.I-57
imidacloprid
M.176
C.I-57
pyridaben


M.65
C.I-81
imidacloprid
M.177
C.I-81
pyridaben


M.66
C.I-87
imidacloprid
M.178
C.I-87
pyridaben


M.67
C.I-91
imidacloprid
M.179
C.I-91
pyridaben


M.68
C.I-97
imidacloprid
M.180
C.I-97
pyridaben


M.69
C.I-101
imidacloprid
M.181
C.I-101
pyridaben


M.70
C.I-107
imidacloprid
M.182
C.I-107
pyridaben


M.71
C.I-201
imidacloprid
M.183
C.I-201
pyridaben


M.72
C.I-207
imidacloprid
M.184
C.I-207
pyridaben


M.73
C.I-211
imidacloprid
M.185
C.I-211
pyridaben


M.74
C.I-217
imidacloprid
M.186
C.I-217
pyridaben


M.75
C.I-221
imidacloprid
M.187
C.I-221
pyridaben


M.76
C.I-227
imidacloprid
M.188
C.I-227
pyridaben


M.77
C.I-251
imidacloprid
M.189
C.I-251
pyridaben


M.78
C.I-257
imidacloprid
M.190
C.I-257
pyridaben


M.79
C.I-281
imidacloprid
M.191
C.I-281
pyridaben


M.80
C.I-287
imidacloprid
M.192
C.I-287
pyridaben


M.81
C.I-291
imidacloprid
M.193
C.I-291
pyridaben


M.82
C.I-297
imidacloprid
M.194
C.I-297
pyridaben


M.83
C.I-301
imidacloprid
M.195
C.I-301
pyridaben


M.84
C.I-307
imidacloprid
M.196
C.I-307
pyridaben


M.85
C.I-1
abamectin
M.197
C.I-1
spiromesifen


M.86
C.I-7
abamectin
M.198
C.I-7
spiromesifen


M.87
C.I-11
abamectin
M.199
C.I-11
spiromesifen


M.88
C.I-17
abamectin
M.200
C.I-17
spiromesifen


M.89
C.I-21
abamectin
M.201
C.I-21
spiromesifen


M.90
C.I-27
abamectin
M.202
C.I-27
spiromesifen


M.91
C.I-51
abamectin
M.203
C.I-51
spiromesifen


M.92
C.I-57
abamectin
M.204
C.I-57
spiromesifen


M.93
C.I-81
abamectin
M.205
C.I-81
spiromesifen


M.94
C.I-87
abamectin
M.206
C.I-87
spiromesifen


M.95
C.I-91
abamectin
M.207
C.I-91
spiromesifen


M.96
C.I-97
abamectin
M.208
C.I-97
spiromesifen


M.97
C.I-101
abamectin
M.209
C.I-101
spiromesifen


M.98
C.I-107
abamectin
M.210
C.I-107
spiromesifen


M.99
C.I-201
abamectin
M.211
C.I-201
spiromesifen


M.100
C.I-207
abamectin
M.212
C.I-207
spiromesifen


M.101
C.I-211
abamectin
M.213
C.I-211
spiromesifen


M.102
C.I-217
abamectin
M.214
C.I-217
spiromesifen


M.103
C.I-221
abamectin
M.215
C.I-221
spiromesifen


M.104
C.I-227
abamectin
M.216
C.I-227
spiromesifen


M.105
C.I-251
abamectin
M.217
C.I-251
spiromesifen


M.106
C.I-257
abamectin
M.218
C.I-257
spiromesifen


M.107
C.I-281
abamectin
M.219
C.I-281
spiromesifen


M.108
C.I-287
abamectin
M.220
C.I-287
spiromesifen


M.109
C.I-291
abamectin
M.221
C.I-291
spiromesifen


M.110
C.I-297
abamectin
M.222
C.I-297
spiromesifen


M.111
C.I-301
abamectin
M.223
C.I-301
spiromesifen


M.112
C.I-307
abamectin
M.224
C.I-307
spiromesifen


M.113
C.I-1
anthranilamid
M.225
C.I-1
chlorantraniliprole




II.A13.1


M.114
C.I-7
anthranilamid
M.226
C.I-7
chlorantraniliprole




II.A13.1


M.115
C.I-11
anthranilamid
M.227
C.I-11
chlorantraniliprole




II.A13.1


M.116
C.I-17
anthranilamid
M.228
C.I-17
chlorantraniliprole




II.A13.1


M.117
C.I-21
anthranilamid
M.229
C.I-21
chlorantraniliprole




II.A13.1


M.118
C.I-27
anthranilamid
M.230
C.I-27
chlorantraniliprole




II.A13.1


M.119
C.I-51
anthranilamid
M.231
C.I-51
chlorantraniliprole




II.A13.1


M.120
C.I-57
anthranilamid
M.232
C.I-57
chlorantraniliprole




II.A13.1


M.121
C.I-81
anthranilamid
M.233
C.I-81
chlorantraniliprole




II.A13.1


M.122
C.I-87
anthranilamid
M.234
C.I-87
chlorantraniliprole




II.A13.1


M.123
C.I-91
anthranilamid
M.235
C.I-91
chlorantraniliprole




II.A13.1


M.124
C.I-97
anthranilamid
M.236
C.I-97
chlorantraniliprole




II.A13.1


M.125
C.I-101
anthranilamid
M.237
C.I-101
chlorantraniliprole




II.A13.1


M.126
C.I-107
anthranilamid
M.238
C.I-107
chlorantraniliprole




II.A13.1


M.127
C.I-201
anthranilamid
M.239
C.I-201
chlorantraniliprole




II.A13.1


M.128
C.I-207
anthranilamid
M.240
C.I-207
chlorantraniliprole




II.A13.1


M.129
C.I-211
anthranilamid
M.241
C.I-211
chlorantraniliprole




II.A13.1


M.130
C.I-217
anthranilamid
M.242
C.I-217
chlorantraniliprole




II.A13.1


M.131
C.I-221
anthranilamid
M.243
C.I-221
chlorantraniliprole




II.A13.1


M.132
C.I-227
anthranilamid
M.244
C.I-227
chlorantraniliprole




II.A13.1


M.133
C.I-251
anthranilamid
M.245
C.I-251
chlorantraniliprole




II.A13.1


M.134
C.I-257
anthranilamid
M.246
C.I-257
chlorantraniliprole




II.A13.1


M.135
C.I-281
anthranilamid
M.247
C.I-281
chlorantraniliprole




II.A13.1


M.136
C.I-287
anthranilamid
M.248
C.I-287
chlorantraniliprole




II.A13.1


M.137
C.I-291
anthranilamid
M.249
C.I-291
chlorantraniliprole




II.A13.1


M.138
C.I-297
anthranilamid
M.250
C.I-297
chlorantraniliprole




II.A13.1


M.139
C.I-301
anthranilamid
M.251
C.I-301
chlorantraniliprole




II.A13.1


M.140
C.I-307
anthranilamid
M.252
C.I-307
chlorantraniliprole




II.A13.1


M.141
C.I-1
deltamethrin
M.253
C.I-1
flufenerim


M.142
C.I-7
deltamethrin
M.254
C.I-7
flufenerim


M.143
C.I-11
deltamethrin
M.255
C.I-11
flufenerim


M.144
C.I-17
deltamethrin
M.256
C.I-17
flufenerim


M.145
C.I-21
deltamethrin
M.257
C.I-21
flufenerim


M.146
C.I-27
deltamethrin
M.258
C.I-27
flufenerim


M.147
C.I-51
deltamethrin
M.259
C.I-51
flufenerim


M.148
C.I-57
deltamethrin
M.260
C.I-57
flufenerim


M.149
C.I-81
deltamethrin
M.261
C.I-81
flufenerim


M.150
C.I-87
deltamethrin
M.262
C.I-87
flufenerim


M.151
C.I-91
deltamethrin
M.263
C.I-91
flufenerim


M.152
C.I-97
deltamethrin
M.264
C.I-97
flufenerim


M.153
C.I-101
deltamethrin
M.265
C.I-101
flufenerim


M.154
C.I-107
deltamethrin
M.266
C.I-107
flufenerim


M.155
C.I-201
deltamethrin
M.267
C.I-201
flufenerim


M.156
C.I-207
deltamethrin
M.268
C.I-207
flufenerim


M.157
C.I-211
deltamethrin
M.269
C.I-211
flufenerim


M.158
C.I-217
deltamethrin
M.270
C.I-217
flufenerim


M.159
C.I-221
deltamethrin
M.271
C.I-221
flufenerim


M.160
C.I-227
deltamethrin
M.272
C.I-227
flufenerim


M.161
C.I-251
deltamethrin
M.273
C.I-251
flufenerim


M.162
C.I-257
deltamethrin
M.274
C.I-257
flufenerim


M.163
C.I-281
deltamethrin
M.275
C.I-281
flufenerim


M.164
C.I-287
deltamethrin
M.276
C.I-287
flufenerim


M.165
C.I-291
deltamethrin
M.277
C.I-291
flufenerim


M.166
C.I-297
deltamethrin
M.278
C.I-297
flufenerim


M.167
C.I-301
deltamethrin
M.279
C.I-301
flufenerim


M.168
C.I-307
deltamethrin
M.280
C.I-307
flufenerim


M.169
C.I-1
metaflumizone
M.281
C.I-1
α-cypermethrin


M.170
C.I-7
metaflumizone
M.282
C.I-7
α-cypermethrin


M.171
C.I-11
metaflumizone
M.283
C.I-11
α-cypermethrin


M.172
C.I-17
metaflumizone
M.284
C.I-17
α-cypermethrin


M.173
C.I-21
metaflumizone
M.285
C.I-21
α-cypermethrin


M.174
C.I-27
metaflumizone
M.286
C.I-27
α-cypermethrin


M.175
C.I-51
metaflumizone
M.287
C.I-51
α-cypermethrin


M.176
C.I-57
metaflumizone
M.288
C.I-57
α-cypermethrin


M.177
C.I-81
metaflumizone
M.289
C.I-81
α-cypermethrin


M.178
C.I-87
metaflumizone
M.290
C.I-87
α-cypermethrin


M.179
C.I-91
metaflumizone
M.291
C.I-91
α-cypermethrin


M.180
C.I-97
metaflumizone
M.292
C.I-97
α-cypermethrin


M.181
C.I-101
metaflumizone
M.293
C.I-101
α-cypermethrin


M.182
C.I-107
metaflumizone
M.294
C.I-107
α-cypermethrin


M.183
C.I-201
metaflumizone
M.295
C.I-201
α-cypermethrin


M.184
C.I-207
metaflumizone
M.296
C.I-207
α-cypermethrin


M.185
C.I-211
metaflumizone
M.297
C.I-211
α-cypermethrin


M.186
C.I-217
metaflumizone
M.298
C.I-217
α-cypermethrin


M.187
C.I-221
metaflumizone
M.299
C.I-221
α-cypermethrin


M.188
C.I-227
metaflumizone
M.300
C.I-227
α-cypermethrin


M.189
C.I-251
metaflumizone
M.301
C.I-251
α-cypermethrin


M.190
C.I-257
metaflumizone
M.302
C.I-257
α-cypermethrin


M.191
C.I-281
metaflumizone
M.303
C.I-281
α-cypermethrin


M.192
C.I-287
metaflumizone
M.304
C.I-287
α-cypermethrin


M.193
C.I-291
metaflumizone
M.305
C.I-291
α-cypermethrin


M.194
C.I-297
metaflumizone
M.306
C.I-297
α-cypermethrin


M.195
C.I-301
metaflumizone
M.307
C.I-301
α-cypermethrin


M.196
C.I-307
metaflumizone
M.308
C.I-307
α-cypermethrin


M.197
C.I-1
clothianidine
M.309
C.I-1
thiamethoxam


M.198
C.I-7
clothianidine
M.310
C.I-7
thiamethoxam


M.199
C.I-11
clothianidine
M.311
C.I-11
thiamethoxam


M.200
C.I-17
clothianidine
M.312
C.I-17
thiamethoxam


M.201
C.I-21
clothianidine
M.313
C.I-21
thiamethoxam


M.202
C.I-27
clothianidine
M.314
C.I-27
thiamethoxam


M.203
C.I-51
clothianidine
M.315
C.I-51
thiamethoxam


M.204
C.I-57
clothianidine
M.316
C.I-57
thiamethoxam


M.205
C.I-81
clothianidine
M.317
C.I-81
thiamethoxam


M.206
C.I-87
clothianidine
M.318
C.I-87
thiamethoxam


M.207
C.I-91
clothianidine
M.319
C.I-91
thiamethoxam


M.208
C.I-97
clothianidine
M.320
C.I-97
thiamethoxam


M.209
C.I-101
clothianidine
M.321
C.I-101
thiamethoxam


M.210
C.I-107
clothianidine
M.322
C.I-107
thiamethoxam


M.211
C.I-201
clothianidine
M.323
C.I-201
thiamethoxam


M.212
C.I-207
clothianidine
M.324
C.I-207
thiamethoxam


M.213
C.I-211
clothianidine
M.325
C.I-211
thiamethoxam


M.214
C.I-217
clothianidine
M.326
C.I-217
thiamethoxam


M.215
C.I-221
clothianidine
M.327
C.I-221
thiamethoxam


M.216
C.I-227
clothianidine
M.328
C.I-227
thiamethoxam


M.217
C.I-251
clothianidine
M.329
C.I-251
thiamethoxam


M.218
C.I-257
clothianidine
M.330
C.I-257
thiamethoxam


M.219
C.I-281
clothianidine
M.331
C.I-281
thiamethoxam


M.220
C.I-287
clothianidine
M.332
C.I-287
thiamethoxam


M.221
C.I-291
clothianidine
M.333
C.I-291
thiamethoxam


M.222
C.I-297
clothianidine
M.334
C.I-297
thiamethoxam


M.223
C.I-301
clothianidine
M.335
C.I-301
thiamethoxam


M.224
C.I-307
clothianidine
M.336
C.I-307
thiamethoxam


M.225
C.I-1
flonicamid
M.337
C.I-1
spirotetramat


M.226
C.I-7
flonicamid
M.338
C.I-7
spirotetramat


M.227
C.I-11
flonicamid
M.339
C.I-11
spirotetramat


M.228
C.I-17
flonicamid
M.340
C.I-17
spirotetramat


M.229
C.I-21
flonicamid
M.341
C.I-21
spirotetramat


M.230
C.I-27
flonicamid
M.342
C.I-27
spirotetramat


M.231
C.I-51
flonicamid
M.343
C.I-51
spirotetramat


M.232
C.I-57
flonicamid
M.344
C.I-57
spirotetramat


M.233
C.I-81
flonicamid
M.345
C.I-81
spirotetramat


M.234
C.I-87
flonicamid
M.346
C.I-87
spirotetramat


M.235
C.I-91
flonicamid
M.347
C.I-91
spirotetramat


M.236
C.I-97
flonicamid
M.348
C.I-97
spirotetramat


M.237
C.I-101
flonicamid
M.349
C.I-101
spirotetramat


M.238
C.I-107
flonicamid
M.350
C.I-107
spirotetramat


M.239
C.I-201
flonicamid
M.351
C.I-201
spirotetramat


M.240
C.I-207
flonicamid
M.352
C.I-207
spirotetramat


M.241
C.I-211
flonicamid
M.353
C.I-211
spirotetramat


M.242
C.I-217
flonicamid
M.354
C.I-217
spirotetramat


M.243
C.I-221
flonicamid
M.355
C.I-221
spirotetramat


M.244
C.I-227
flonicamid
M.356
C.I-227
spirotetramat


M.245
C.I-251
flonicamid
M.357
C.I-251
spirotetramat


M.246
C.I-257
flonicamid
M.358
C.I-257
spirotetramat


M.247
C.I-281
flonicamid
M.359
C.I-281
spirotetramat


M.248
C.I-287
flonicamid
M.360
C.I-287
spirotetramat


M.249
C.I-291
flonicamid
M.361
C.I-291
spirotetramat


M.250
C.I-297
flonicamid
M.362
C.I-297
spirotetramat


M.251
C.I-301
flonicamid
M.363
C.I-301
spirotetramat


M.252
C.I-307
flonicamid
M.364
C.I-307
spirotetramat


M.253
C.I-1
pymetrozine
M.365
C.I-1
pyrifluquinazone


M.254
C.I-7
pymetrozine
M.366
C.I-7
pyrifluquinazone


M.255
C.I-11
pymetrozine
M.367
C.I-11
pyrifluquinazone


M.256
C.I-17
pymetrozine
M.368
C.I-17
pyrifluquinazone


M.257
C.I-21
pymetrozine
M.369
C.I-21
pyrifluquinazone


M.258
C.I-27
pymetrozine
M.370
C.I-27
pyrifluquinazone


M.259
C.I-51
pymetrozine
M.371
C.I-51
pyrifluquinazone


M.260
C.I-57
pymetrozine
M.372
C.I-57
pyrifluquinazone


M.261
C.I-81
pymetrozine
M.373
C.I-81
pyrifluquinazone


M.262
C.I-87
pymetrozine
M.374
C.I-87
pyrifluquinazone


M.263
C.I-91
pymetrozine
M.375
C.I-91
pyrifluquinazone


M.264
C.I-97
pymetrozine
M.376
C.I-97
pyrifluquinazone


M.265
C.I-101
pymetrozine
M.377
C.I-101
pyrifluquinazone


M.266
C.I-107
pymetrozine
M.378
C.I-107
pyrifluquinazone


M.267
C.I-201
pymetrozine
M.379
C.I-201
pyrifluquinazone


M.268
C.I-207
pymetrozine
M.380
C.I-207
pyrifluquinazone


M.269
C.I-211
pymetrozine
M.381
C.I-211
pyrifluquinazone


M.270
C.I-217
pymetrozine
M.382
C.I-217
pyrifluquinazone


M.271
C.I-221
pymetrozine
M.383
C.I-221
pyrifluquinazone


M.272
C.I-227
pymetrozine
M.384
C.I-227
pyrifluquinazone


M.273
C.I-251
pymetrozine
M.385
C.I-251
pyrifluquinazone


M.274
C.I-257
pymetrozine
M.386
C.I-257
pyrifluquinazone


M.275
C.I-281
pymetrozine
M.387
C.I-281
pyrifluquinazone


M.276
C.I-287
pymetrozine
M.388
C.I-287
pyrifluquinazone


M.277
C.I-291
pymetrozine
M.389
C.I-291
pyrifluquinazone


M.278
C.I-297
pymetrozine
M.390
C.I-297
pyrifluquinazone


M.279
C.I-301
pymetrozine
M.391
C.I-301
pyrifluquinazone


M.280
C.I-307
pymetrozine
M.392
C.I-307
pyrifluquinazone









General Preparation Methods of Compounds of Formula I

Aminothiazoline compounds of formula I of the present invention can be prepared starting from amines of the general formula II:




Amines of the general formula II can be prepared e.g. by addition of appropriately substituted anion equivalents, for examples of organometallic compounds V, to appropriately substituted C═N bond containing compounds IV (cf. for example Chem. Rev. 1998, 98, 1407-1438):
Starting imines IV can for example be prepared by methods familiar to an Organic chemist from the corresponding aldehydes III by reaction with amines in the presence of a dehydrating agent or from nitriles by reduction (e.g. J. Org. Chem. 1990, 55, 4199-4200) and are well known in the art. Starting imines IV include also chiral compounds as for example described in Tetrahedron 1999, 55, 8883-8904.




An example for the latter method is given in unpublished U.S. application U.S. 60/817,973, preparation examples 3.2 and 3.3. Another example for the addition of organometallic compounds to imines has been described in unpublished U.S. 60/817,973 for related compounds by reaction of in situ generated trimethylsilylimines with benzyl magnesium compounds (cf. example 1 in unpublished 60/817,973 and example given below).
Amines of the general formula II can also be prepared e.g. by addition of appropriately substituted organometallic compounds V to nitriles VI followed by reduction of the intermediate imines as demonstrated in the following scheme:




A further preparation of amines of the general formula II involves the addition of benzylic compounds to masked benzylamines such as the substitution reaction of benzyl halides X with e.g. substituted benzyl benzophenone imines IX in the presence of base followed be the liberation of the amine or its salt by means of e.g. acids as described for similar compounds in unpublished international application PCT/EP2006/069525, example P.I.1.b.). Substituted benzophenone imines can be obtained e.g. by condensation of amines VII with benzophenone VIII.




A further preparation of amines of the general formula II involves the Hofmann degradation of carboxamides XI as demonstrated in the following scheme:




A general method for the preparation of compounds similar to formula II by such methods has been described in U.S. Pat. No. 4,536,599.
The starting carboxamides XI can be prepared as described in the above cited publication or by conventional methods known by the person skilled in the art.
Examples are given in the following scheme:




Such nitriles XIII can for example be prepared from their corresponding halides XII by substitution reaction with cyanides such as potassium or sodium cyanide in appropriate solvents.




Amines of the general formula II can also be prepared e.g. by reductive amination of their corresponding ketones XV as outlined in the following scheme:




Reductive amination can be accomplished by several means, e.g. reaction with ammonia and hydrogen at higher pressure in an autoclave starting from either ketones XV of oximes XVI, cf. for example WO 2005/063724.
Preparation of the corresponding ketones XV are various and very well known to those skilled in the art. Examples among other methods involve e.g. the addition of benzyl organometallic compounds or anions to appropriately substituted benzoic acids or their esters. Alternatively the addition of such organometallic compounds/anions V to corresponding benzaldehydes III followed by oxidation of the resulting alcohols XVII as demonstrated below. Another route is the addition of phenylmetals XVIII to appropriately substituted phenyl acetaldehyde XIX




Preparation of such ketones XVII is also possible via the addition of benzyl halides X to masked aldehydes such as XX or XXI utilizing the umpolung reactions as demonstrated in the scheme below:




A further method involves the reaction of appropriately substituted nitromethyl benzene compounds XXII with an appropriately substituted benzaldehyde III. The corresponding nitro stilbenes XXIII can be converted to amines of the general formula II by reduction as described e.g. in Journal of Pharmaceutical Sciences 1985, 73 (11), 1548-1550. An example of this type of reaction is also given in unpublished international application PCT/EP2006/069525, see example P.I.1.a for similar compounds structures).




Aminoazolines of the general formula I can be prepared e.g. by addition of chloro-ethyliso(-thio)cyanate XXIV to amines II and subsequent cyclization of compounds XXV in the presence of base (cf. WO 2005/063724):




Aminoazolines of the general formula I can also be prepared e.g. by reaction of amines II with (thio-)phosgene or (thio-)phosgene type reagents or reaction of the corresponding iso(thio)cyanates with aminoethanol and cyclisation in the presence of acids and or dehydrating agents (cf. eg. WO 2005/063724 or unpublished international application PCT/EP2006/069525).
Likewise, aminothiazolines of the general formula I can be prepared by converting amines of the general formula I or a salt thereof to the corresponding aminothiocarbonylaminoethane compound, by reacting the amine with acetoxyethyl isothiocyanates and subsequent saponification as described e.g. in unpublished international application PCT/EP2006/069525 for the preparation of similar compounds. Acetoxyethyl isothiocyanate can be prepared according to the procedures described in Coll. Czech. Chem. Commun. 1986, 51, 112-117.
Aminothiazolines of the general formula I can also be prepared e.g. by reacting an appropriately protected benzylamino thiazoline XXVI with benzylhalides X in the presence of base and subsequent deprotection of compounds XXVII for example in the presence of mineralic of trifluoroacetic acid as outlined below or described for similar compounds in unpublished international application PCT/EP2006/069525, example P.II.1 and PII.2.




Aminothiazolines of the general formula Ib can also be obtained by reaction of aminothiazolines Ia with e.g. acetyl chloride or acetic acid anhydride in the presence of base.




Pests

The mixtures of the active compounds I and II, or the active compounds I and II used simultaneously, that is jointly or separately, exhibit outstanding action against pests from the following orders:
Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Chematobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis, 

beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria, 

flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, 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 torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa 

thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, 

termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Termes natalensis, and Coptotermes formosanus, 

cockroaches (Blattaria—Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis, 

true bugs (Hemiptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, 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, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus. 

ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile, 

crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina, 

Arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa, 

fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, 

silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica, 

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

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

Earwigs (Dermaptera), e.g. forficula auricularia, 

lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. 

Plant parasitic nematodes such as root-knot nematodes, Meloidogyne arenaria, Meloidogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica and other Meloidogyne species; cyst nematodes, Globodera rostochiensis, Globodera pallida, Globodera tabacum and other Globodera species, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; seed gall nematodes, Anguina funesta, Anguina tritici and other Anguina species; stem and foliar nematodes, Aphelenchoides besseyi, Aphelenchoides fragariae, Aphelenchoides ritzemabosi and other Aphelenchoides species; sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; ring nematodes, Criconema species, Criconemella species, Criconemoides species, and Mesocriconema species; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus myceliophagus and other Ditylenchus species; awl nematodes, Dolichodorus species; spiral nematodes, Helicotylenchus dihystera, Helicotylenchus multicinctus and other Helicotylenchus species, Rotylenchus robustus and other Rotylenchus species; sheath nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; lance nematodes, 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 species; pin nematodes, Paratylenchus species; lesion nematodes, Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus curvitatus, Pratylenchus goodeyi, Pratylencus neglectus, Pratylenchus penetrans, Pratylenchus scribneri, Pratylenchus vulnus, Pratylenchus zeae and other Pratylenchus species; Radinaphelenchus cocophilus and other Radinaphelenchus species; burrowing nematodes, Radopholus similis and other Radopholus species; reniform 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, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species and Merlinius species; citrus nematodes, Tylenchulus semipenetrans and other Tylenchulus species; dagger nematodes, Xiphinema americanum, Xiphinema index, Xiphinema diversicaudatum and other Xiphinema species; and other plant parasitic nematode species.

Moreover, the inventive mixtures are especially useful for the control of Lepidoptera, Coleoptera, Diptera, Thysanoptera and Hymenoptera.
In particular the inventive mixtures are useful for the control of Thysanoptera and Hymenoptera, especially Hymenoptera.
Formulations
The mixtures according to the present 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 fine and even distribution of the compounds according to the invention.
The formulations are prepared in a known manner (see e.g. for review U.S. Pat. No. 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, U.S. Pat. No. 4,172,714, U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701, U.S. Pat. No. 5,208,030, GB 2,095,558, U.S. Pat. No. 3,299,566, Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001, 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active compound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, anti-foaming agents, anti-freezing agents, for seed treatment formulation also optionally gelling agents.
Examples of suitable solvents are water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP(N-methyl-pyrrolidone), NOP(N-octylpyrrolidone)), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.
Suitable emulsifiers are nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates).
Examples of dispersants are lignin-sulfite waste liquors and methylcellulose.
Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are 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 hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.
Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
A suitable preservative is e.g. dichlorophen.
An example of a gelling agent is carrageen (Satiagel®)
Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, 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.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compounds. In this case, the active compounds are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).
For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compounds by weight, preferably 0.1 to 40% by weight.
The mixtures of the present invention can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compounds according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare 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, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1% per weight.
The active compound(s) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.
The following are examples of formulations:
1. Products for dilution with water for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
A) Water-Soluble Concentrates (SL, LS)
10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolve(s) upon dilution with water, whereby a formulation with 10% (w/w) of active compound(s) is obtained.
B) Dispersible Concentrates (DC)
20 parts by weight of the active compound(s) are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compound(s) is obtained.
C) Emulsifiable Concentrates (EC)
15 parts by weight of the active compound(s) are dissolved in 7 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, whereby a formulation with 15% (w/w) of active compound(s) is obtained.
D) Emulsions (EW, EO, ES)
25 parts by weight of the active compound(s) 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 emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.
E) Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)
50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound(s), whereby a formulation with 50% (w/w) of active compound(s) is obtained.
G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, SS, WS)
75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s), whereby a formulation with 75% (w/w) of active compound(s) is obtained.
H) Gel-Formulation (GF)
In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
2. Products to be applied undiluted for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
I) Dustable Powders (DP, DS)
5 parts by weight of the active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound(s).
J) Granules (GR, FG, GG, MG)
0.5 part by weight of the active compound(s) is ground finely and associated with 95.5 parts by weight of carriers, whereby a formulation with 0.5% (w/w) of active compound(s) is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
K) ULV Solutions (UL)
10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound(s), which is applied undiluted for foliar use.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents usually are admixed with the agents according to the invention in a weight ratio of 1:10 to 10:1.
Applications
The compounds I and the one or more compound(s) II can be applied simultaneously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
The mixtures of the invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with a insecticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.
The compounds I and the one or more compound(s) II are usually applied in a weight ratio of from 500:1 to 1:100, preferably from 20:1 to 1:50, in particular from 5:1 to 1:20. Depending on the desired effect, the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 1500 g/ha, in particular from 50 to 750 g/ha.
The mixtures according to the invention are effective through both contact and ingestion.
According to a preferred embodiment of the invention, the mixtures according to the present invention are employed via soil application. Soil application is especially favorable for use against ants, termites, crickets, or cockroaches.
According to another preferred embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the mixtures according to the present invention are prepared into a bait preparation.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
Another aspect of the present invention is when preparing the mixtures, it is preferred to employ the pure active compounds I and II, to which further active compounds, e.g. against harmful fungi or having herbicidal activity, or growth-regulating agents or fertilizers can be added.
Compositions of this invention may further contain other active ingredients than those listed above. For example fungicides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These additional ingredients 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 invention either before or after being treated with other active ingredients.
The mixtures according to the invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult. The pests may be controlled by 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 mixtures.
“Locus” means a plant, seed, soil, area, material or environment in which a pest is growing or may grow.
In general, “pesticidally effective amount” means the amount of the inventive mixtures or of compositions comprising the mixtures 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 and/or compositions used in the invention. A pesticidally effective amount of the mixtures and/or 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.
The inventive mixtures or compositions of these mixtures can also be employed for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting a plant, or soil or water in which the plant is growing.
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.
Preferred application methods are into water bodies, via soil, cracks and crevices, pastures, manure piles, sewers, into water, on floor, wall, or by perimeter spray application and bait.
According to another preferred embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the inventive mixtures are prepared into a bait preparation.
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, mosquitoes, crickets etc. or cockroaches to eat it. This attractant may be chosen from feeding stimulants or para and/or sex pheromones readily known in the art.
Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, 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-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, non-wovens, netting material or foils and tarpaulins preferably comprise a composition including the inventive mixtures, optionally a repellent and at least one binder.
The inventive mixtures and the compositions comprising 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 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).
In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient(s) ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 20 g per 100 m2.
Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound(s) per m2 treated 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.
For use in bait compositions, the typical content of active ingredient(s) 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 flavoring agent, a preserving agent, a dye or a bitter agent. Its attractiveness may also be enhanced by a special color, shape or texture.
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 %.
For use in treating crop plants, the rate of application of the mixture of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
In the context of the present invention, the term plant refers to an entire plant, a part of the plant or the plant propagation material.
The mixtures of the present invention and the compositions comprising them are particularly important in the control of a multitude of insects on various cultivated plants.
Plants which can be treated with the inventive mixtures include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures.
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 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 mentioned. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
The term “cultivated plants” is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
The term “cultivated plants” is to be understood also including plants that have been rendered tolerant to applications of specific classes of herbicides, such as hydroxy-phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e.g. U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e.g. U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e.g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e.g. EP-A-0242236, EP-A-242246) or oxynil herbicides (see e.g. U.S. Pat. No. 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield® summer rape (Canola) being tolerant to imidazolinones, e.g. imazamox. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
The term “cultivated plants” is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ä-endotoxins, e.g. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are disclosed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of insects, especially to beetles (Coeloptera), two-winged insects (Diptera), and butterflies (Lepidoptera).
The term “cultivated plants” is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called “pathogenesis-related proteins” (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for example potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lyso-zym (e.g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
The term “cultivated plants” is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e.g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environ-mental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
The term “cultivated plants” is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, for example oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera® rape).
The term “cultivated plants” is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato).
Some of the inventive mixtures have systemic action and can therefore be used for the protection of the plant shoot against foliar pests as well as for the treatment of the seed and roots against soil pests.
Seed Treatment
The mixtures according to the present invention are therefore suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect pests and the resulting plant's roots and shoots against soil pests and foliar insects.
The protection of the resulting plant's roots and shoots is preferred.
More preferred is the protection of resulting plant's shoots from piercing and sucking insects.
The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedlings' roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with mixtures according to the present invention. Particularly preferred is a method, wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably a method, wherein the plants shoots are protected from aphids.
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.
The term seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
The present invention also comprises seeds coated with or containing the active compound(s). The term “coated with and/or containing” generally signifies that the active ingredient(s) are 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 are (re)planted, it may absorb the active ingredient.
Suitable seeds are seeds 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 mixtures according to the invention may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.
For example, the active mixtures can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP-A-0242236, EP-A-242246) (WO 92/00377) (EP-A-0257993, U.S. Pat. No. 5,013,659) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A-0142924, EP-A-0193259),
Furthermore, the mixtures according to the present invention can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972).
The seed treatment application of the mixtures is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
In the treatment of seeds the corresponding formulations are applied by treating the seeds with an effective amount of the mixture according to the present invention. Herein, the application rates of the active compound(s) 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, in particular from 1 g to 2.5 kg per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
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)
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)
I Dustable powders (DP, DS)
Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. 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 pre-germinated the latter
In a preferred embodiment a FS formulation is used for seed treatment. Typically, a FS formulation may comprise 1-800 g/l of active ingredient(s), 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Preferred FS formulations of compounds of formula I for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient(s), from 0.1 to 20% by weight (1 to 200 g/l) 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.
Seed Treatment formulations may additionally also comprise binders and optionally colorants.
Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are block copolymers EO/PO surfactants but also polyvinylalcohols, polyvinyl pyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, tylose and copolymers derived from these polymers.
Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 112, C.I. Solvent Red 1, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
The invention also relates to seed comprising mixtures according to the present invention. The amount of the compound I 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.
Animal Health
The mixtures of the present invention are in particular also suitable for being used for combating parasites in and on animals.
An object of the present invention is therefore also to provide new methods to control parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.
The invention also relates to compositions containing a parasiticidally effective amount of compounds of formula I or the enantiomers or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.
The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of mixture of the present invention or a composition comprising it.
The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a mixture of the present invention or a composition comprising it.
Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.
Surprisingly it has now been found that mixtures of the present invention are suitable for combating endo- and ectoparasites in and on animals.
Mixtures of the present invention and compositions comprising them are preferably used for controlling and preventing infestations and infections animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
Mixtures of the present invention and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.
Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas.
The mixtures of the present invention and compositions comprising them are suitable for systemic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
The mixtures of the present invention are especially useful for combating ectoparasites.
The mixture of the present invention are especially useful for combating parasites of the following orders and species, respectively:
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, 
cockroaches (Blattaria—Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis, 
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus argentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, 

lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. 

ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus gallinae, 

Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,

Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus, 

Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp,

Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp,

Roundworms Nematoda:

Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp,

Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,

Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus, Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus, Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioctophyma renale, 

Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi, 

Camallanida, e.g. Dracunculus medinensis (guinea worm)

Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp.a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp.,

Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracanthorhynchus hirudinaceus and Oncicola spp,

Planarians (Plathelminthes):

Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp,

Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.

The mixtures of the present invention and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
Moreover, the use of mixtures of the present invention and compositions containing them for combating mosquitoes is especially preferred.
The use of mixtures of the present invention and compositions containing them for combating flies is a further preferred embodiment of the present invention.
Furthermore, the use of the mixtures of the present invention and compositions containing them for combating fleas is especially preferred.
The use of the mixtures of the present invention and compositions containing them for combating ticks is a further preferred embodiment of the present invention.
The mixtures of the present invention also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).
Administration can be carried out both prophylactically and therapeutically.
Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
For oral administration to warm-blooded animals, the mixtures of the present invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the mixtures of the present invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the mixtures of the present invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The formula I compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the mixtures of the present invention may be formulated into an implant for subcutaneous administration. In addition the formula I compound may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the active compounds.
The mixtures of the present invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the active compounds. In addition, the active compound mixtures may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
Suitable preparations are:

    
    
        Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
        Emulsions and suspensions for oral or dermal administration; semi-solid preparations;
        Formulations in which the active compound is processed in an ointment base or in an oil-in-water or water-in-oil emulsion base;
        Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
    
    


Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile.
Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N-methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.
The active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.
Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.
Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.
Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.
Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.
Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results. The thickeners employed are the thickeners given above.
Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.
Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added.
Suitable solvents which are: water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N-methylpyrrolidone, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1,3-diox-olane and glycerol formal.
Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.
Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.
Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.
Suitable light stabilizers are, for example, novantisolic acid.
Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacrylates, natural polymers such as alginates, gelatin.
Emulsions can be administered orally, dermally or as injections.
Emulsions are either of the water-in-oil type or of the oil-in-water type.
They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances.
Suitable hydrophobic phases (oils) are:
liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length C8-C12 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the C8-C10 fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C16-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof.
Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
Suitable emulsifiers are:
non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether;
ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt;
cation-active surfactants, such as cetyltrimethylammonium chloride.
Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.
Liquid suspending agents are all homogeneous solvents and solvent mixtures.
Suitable wetting agents (dispersants) are the emulsifiers given above.
Other auxiliaries which may be mentioned are those given above.
Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
For the production of solid preparations, the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.
Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.
Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
In general, “parasiticidally 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 parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
The compositions which can be used in the invention can comprise generally from about 0.001 to 95 wt % of the active compounds of the mixtures of the present invention.
Generally it is favorable to apply the active compounds of the mixtures of the present invention in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
Ready-to-use preparations contain the active compounds of the mixtures of the present invention acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 percent by weight, preferably from 0.1 to 65 percent by weight, more preferably from 1 to 50 percent by weight, most preferably from 5 to 40 percent by weight.
Preparations which are diluted before use contain the active compounds of the mixtures of the present invention acting against ectoparasites in concentrations of 0.5 to 90 percent by weight, preferably of 1 to 50 percent by weight.
Furthermore, the preparations comprise the active compounds of the mixtures of the present invention against endoparasites in concentrations of 10 ppm to 2 percent by weight, preferably of 0.05 to 0.9 percent by weight, very particularly preferably of 0.005 to 0.25 percent by weight.
In a preferred embodiment of the present invention, the compositions comprising the mixtures of the present invention are applied dermally/topically.
In a further preferred embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
Generally it is favorable to apply solid formulations which release the active compounds of the mixtures of the present invention in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the compounds of formula I. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.


EXAMPLES
The present invention is now illustrated in further details by the following specific examples.
Some of the preferred compound examples are characterized by their physical data in the following table C. The characterization can be done by coupled High Performance Liquid Chromatography/mass spectrometry (HPLC/MS), by NMR or by their melting points.
Some compounds were characterized by 1H-NMR. The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: M=multiplett, q=quartett, t=triplett, d=doublet and s=singulett.
Alternatively the compounds were additionally or instead characterized by their melting point.
Specific compound examples of aminothiazoline compounds of formula I:










TABLE C





Compound

melting point
1H NMR (in CDCl3):


example
Structure of compound I
Fp [° C.]
δ [ppm]


















C.1




111.00-114.00


 


C.2




135.00-139.00


 


C.3




150.00-151.00


 


C.4





CDCl3: 2.2-2.35 (m), 2.85-3.0 (m), 3.2 (t), 3.9 (t), 5.05 (mc), 6.65 (s), 6.8 (s), 6.9-7.1 (m)


 


C.5





CDCl3: 2.25 (s), 2.85-3.1 (m), 3.25 (mc), 3.9 (mc), 5.15 (mc), 6.65 (s), 6.8-7.05 (m)


 


C.6




120.00-121.00


 


C.7




143.00-146.00


 


C.8





CDCl3: 2.2 (s), 3.0 (mc), 3.2 (mc), 3.7 (s), 3.8 (s), 3.9 (mc), 5.1 (mc), 6.6-6.85 (m)


 


C.9





CDCl3: 2.25 (s), 3.05 (mc), 3.25 (mc), 3.7 (s), 3.8 (s), 3.9 (mc), 5.05 (mc), 6.6-7.1 (m)


 


C.10





CDCl3: 2.25 (s), 3.0 (mc), 3.25 (mc), 3.9 (mc), 5.15 (mc), 6.65 (s), 6.85 (s), 6.95 (mc), 7.3 (mc)


 


C.11





CDCl3: 2.25 (s), 2.55-2.8 (m), 3.15 (mc), 3.65 (mc), 3.8 (s), 5.2 (mc), 6.8 (s), 6.9 (mc), 7.2-7.4 (m)


 


C.12




169.00-171.00


 


C.13





d6-DMSO: 2.3 (s), 2.6-2.9 (m), 3.1 (mc), 3.65 (mc), 3.75 (s), 5.1 (mc), 6.8 (mc), 6.95-7.2 (m), 7.45 (mc)


 


C.14





d6-DMSO: 2.3 (s), 2.65-2.85 (m), 3.1 (mc), 3.65 (mc), 3.75 (s), 5.2 (mc), 6.9-7.3 (m)


 


C.15




137.00-141.00


 


C.16




121.00-123.00


 


C.17




141.00-143.00


 


C.18




126.00-129.00


 


C.19




146.00-150.00


 


C.20




131.00-132.00


 


C.21




131.00-136.00


 


C.22




144.00-147.00


 


C.23




93.00-96.00


 


C.24





CDCl3: 2.2 (s), 2.25 (s), 2.6 (s), 2.9-3.1 (m), 3.95-4.15 (m), 4.6 (mc), 6.6 (s), 6.8 (s), 7.3 (t), 7.55 (d), 7.65 (d)


 


C.25




138.00-140.00


 


C.26





CDCl3: 1.05 (s), 2.25 (s), 2.85-3.15 (m), 4.05 (mc), 4.9 (mc), 6.75 (s), 6.85 (s), 7.2 (mc), 7.35 (mc)


 


C.27





CDCl3: 2.25 (s), 2.8-3.1 (m), 3.5 (s), 3.95-4.2 (m), 4.55 (d), 4.7 (d), 4.85 (mc), 6.65 (s), 6.85 (s), 7.2 (t), 7.3 (d), 7.4 (d)


 


C.28




91.00-94.00


 


C.29





CDCl3: 1.05 (s), 2.2 (br s), 2.9-3.1 (m), 4.05 (mc), 4.6 (mc), 6.6 (s), 6.8 (s), 7.3 8 t), 7.55 (d), 7.7 (d)


 


C.30





CDCl3: 2.25 (s), 2.3 (s), 2.95 (mc), 3.1 (mc), 3.95-4.2 (m), 4.5-4.7 (m), 6.6 (s), 6.85 (s), 7.3 (t), 7.55 (d), 7.6 (d)


 


C.31





d6-DMSO: 2.2 (s), 2.5 (s), 2.95 (mc), 3.05 (mc), 3.8-4.0 (m), 4.4 (mc), 5.9 (s), 6.0 (s), 6.7-6.8 (m)


 


C.32





CDCl3: 1.2 (t), 2.2 (s), 2.3 (s), 2.9-3.1 (m), 3.95-4.2 (m), 4.6 (mc), 6.6 (s), 6.85 (s), 7.3 (t), 7.55 (d), 7.65 (d)


 


C.33




127.00-132.00


 


C.34




139.00-142.00


 


C.35




174.00-177.00


 


C.36




145.00-148.00


 


C.37




127.00-133.00


 


C.38




144.00-145.00


 


C.39




154.00-158.00


 


C.40




127.00-129.00


 


C.41




165.00-167.00


 


C.42




173.00-174.00


 


C.43




92.00-93.00









Specific Synthesis Examples of Compounds of Formula I
S.1 Preparation of (4,5-Dihydro-thiazol-2-yl)-[2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-amine [specific compound example C.33 of table C]
S.1.a) Preparation of Intermediate Compound 2-(3,5-dimethylphenyl)-1-(2,3-dimethylphenyl)-ethylamine
Step 1: Preparation of 3,5-dimethylbenzyl magnesium chloride: To a mixture of 12.8 g magnesium turnings in 100 ml of anhydrous THF (tetrahydrofuran) was added under nitrogen atmosphere 0.3 ml ethyl bromide as starter reagent and the reaction was heated to 50° C. A solution of 67.8 g 3,5-dimethylbenzyl chloride in 450 ml of anhydrous THF was added slowly so that the reaction proceeded without violent reaction but with clear consumption. After the addition of the total amount of chloride, the solution was heated at 50° C. overnight. This resulted in a clear, greenish solution of 3,5-dimethylbenzyl magnesium chloride. This solution was used for the next step.
Step 2: A solution of 2,3-dimethylbenzaldehyde (50.0 g) in 200 ml of THF was treated at room temperature with a solution of lithium hexamethyl disilazane (LiHMDS) in toluene (410 ml, 1.0 M-solution, 1.1 equivalent) dropwise and the stirring was continued for 1.5 hours.

    
    
        To this solution was added the solution of 3,5-dimethylbenzyl magnesium chloride prepared as described above dropwise. Stirring was continued afterwards for 2 hours at 35° C.
        The reaction was quenched by the cautious addition of 300 ml of potassium carbonate solution (5 wt % in water), extracted three times with diethyl ether and the combined organic phases were washed with water, dried over sodium sulphate and the solvent evaporated. The residue was purified on silica gel with a gradient of petrol ether/ethyl acetate and methanol/ethyl acetate. This yielded 78 g (83%) of the title compound 2-(3,5-dimethylphenyl)-1-(2,3-dimethylphenyl)-ethylamine as a yellowish oil.
    
    


S.1.b) Preparation of Intermediate Compound [2-(3,5-Dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-isothiocyanate
A solution of thiophosgene (39.5 g) in 200 ml of chloroform was treated with a solution of potassium carbonate (99 g) in water (200 ml) at room temperature. To this mixture was added a solution of 2-(3,5-dimethylphenyl)-1-(2,3-dimethylphenyl)-ethylamine (72.5 g) in chloroform (600 ml) with vigorous stirring. After completion of the reaction the mixture was poured into dichloromethane (500 ml) and washed three times with water, dried over sodium sulphate and the solvent evaporated in vacuo. This yielded the title compound [2-(3,5-Dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-isothiocyanate in form of a yellow oil (81.9 g).
S.1.c) Preparation of Intermediate compound 1-[2-(3,5-Dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-3-(2-hydroxy-ethyl)-thiourea
To a solution of [2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-isothiocyanate (81.9 g) in chloroform (1 l) was added ethanolamine (25.4 g) dropwise at room temperature. The mixture was stirred for 3 hours and the solvent evaporated, the remainder dissolved in ethyl acetate and washed 6 times with water. The solution was dried over sodium sulphate. Removal of the solvent in vacuo yielded the 1-[2-(3,5-Dimethylphenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-3-(2-hydroxy-ethyl)-thiourea (94.8 g) as an off-white powder.
S.1.d) Preparation of (4,5-Dihydro-thiazol-2-yl)-[2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-amine [specific compound example C.33 of table C]
A mixture of the above 1-[2-(3,5-Dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-3-(2-hydroxy-ethyl)-thiourea (94.7 g) and concentrated hydrochloric acid (700 ml) was heated under reflux for 2 hours. The hydrochloric acid phase was decanted carefully and the remainder dissolved in ethyl acetate and thoroughly washed three times with potassium carbonate solution (5 wt % in water), three times with water and dried over sodium sulphate. The solvent was removed by evaporation and the remainder titurated with a solution of light petrol ether/ethyl acetate (20/1), filtrated to yield the product (4,5-dihydro-thiazol-2-yl)-[2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-amine [specific compound example C.33 of table C] as an off-white solid (67.1 g)
S.2 Preparation of (4,5-Dihydro-thiazol-2-yl)-[2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-amine [specific compound example C.23 of table C]


    S.2.d) A solution of [1-(2,3-dichlorophenyl)-2-(3,5-dimethylphenyl)-ethyl]-(4,5-dihydro-thiazol-2-yl)-amine (60.1 g, prepared accordingly to the preparation described above for specific compound example C.33, using 2,3-dichlorobenzaldehyde in Step 2) in dimethyl formamide (600 ml) was treated with potassium carbonate (32.8 g) and heated up to 60° C. A solution of acetyl chloride (14.9 g) in dimethyl formamide (100 ml) was added drop by drop and stirred for 5 hours at the same temperature. Stirring was continued overnight at room temperature, dimethyl formamide removed in vacuo and the remainder dissolved in ethyl acetate, washed once with water and three times with potassium carbonate solution (5 wt % in water), again with water and the organic phase dried over sodium sulphate. Evaporation of the solvent yielded (4,5-Dihydro-thiazol-2-yl)-[2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-amine [specific compound example C.23 of table C] as a viscous oil (65.6 g) that crystallized upon standing.

Biology



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, 20-22):




  E
  =
  
    XY
    100
  




When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.
The following tests demonstrates 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 was determined using Colby's equation. Synergy was demonstrated with Compound C.33 of table C:




Test B.1

For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.
The compounds or mixtures were formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the leaf disks at 2.5 μl, using a custom built micro atomizer, at two replications.
For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.
After application, the leaf disks were air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at 23±1° C., 50±5% RH (relative humidity) for 5 days. Aphid mortality and fecundity was then visually assessed. For the mixture tested the results are listed in table B.1.











TABLE B.1









Average



Vetch Aphid
ppm
Control %









Abamectin + compound
0 + 0.8
0



C.33
0.08 + 0  
0




0.08 + 0.8  
75*



Thiamethoxam +
0 + 0.8
0



compound C.33
0.08 + 0  
0




0.08 + 0.8  
100* 



Fipronil + compound
0 + 0.8
0



C.33
2 + 0  
25 




2 + 0.8
75*







*synergistic control effect according to Colby's equation






Test B.2

For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.
The compounds or mixtures were formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures were pipetted into the aphid diet, using a custom built pipetter, at two replications.
For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.
After application, 5-8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at 23±1° C., 50±5% RH for 3 days. Aphid mortality and fecundity was then visually assessed. For the mixture tested the results are listed in table B.2.











TABLE B.2









Average



Green Peach Aphid
ppm
Control %









Pymetrozine + compound
  0 + 0.8
 0



C.33
40 + 0 
50




 40 + 0.8
 75*



Pyridaben + compound
 0 + 20
 0



C.33
40 + 0 
 0




40 + 20
100*



Abamectin + compound
0 + 4
 0



C.33
0.08 + 0  
 0




0.08 + 4  
100*



Alphacypermethrin +
0 + 4
 0



compound C.33
10 + 0 
50




10 + 4 
 75*



Chlorantraniliprole +
0 + 4
 0



compound C.33
0.4 + 0  
50




0.4 + 4  
100*



Thiamethoxam + test
 0 + 20
50



compound
0.08 + 0  
 0




0.08 + 20  
 75*



Fipronil + compound
 0 + 20
 0



C.33
0.4 + 0  
 0




0.4 + 20 
100*







*synergistic control effect according to Colby's equation






Further test systems which can be used for evaluating synergistic effects are e.g.
Test B.3
For evaluating control of boll weevil (Anthonomus grandis) the test unit consists of 24-well-microtiter plates containing an insect diet and 20-30 A. grandis eggs.
The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the insect diet at 20 μl, using a custom built micro atomizer, at two replications.
For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.
After application, microtiter plates are incubated at 23±1° C., 50±5% RH for 5 days. Egg and larval mortality is visually assessed.
Test B.4
For evaluating control of Mediterranean fruitfly (Ceratitis capitata) the test unit consists of 96-well-microtiter plates containing an insect diet and 50-80 C. capitata eggs.
The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the insect diet at 5 μl, using a custom built micro atomizer, at two replications.
For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.
After application, microtiter plates are incubated at 28±1° C., 80±5% RH for 5 days. Egg and larval mortality is visually assessed.
Test B.5
For evaluating control of tobacco budworm (Heliothis virescens) the test unit consists of 96-well-microtiter plates containing an insect diet and 15-25H. virescens eggs.
The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the insect diet at 10 μl, using a custom built micro atomizer, at two replications.
For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.
After application, microtiter plates are incubated at 28±1° C., 80±5% RH for 5 days. Egg and larval mortality is visually assessed.
Test B.6
For evaluating control of bird cherry aphid (Rhopalosiphum padi) through contact or systemic means the test unit consists of 96-well-microtiter plates containing barley leaf disks.
The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the leaf disks at 2.5 μl, using a custom built micro atomizer, at two replications.
For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.
After application, the leaf disks are air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids are then allowed to suck on the treated leaf disks and incubated at 25±1° C., 80±5% RH for 3 to 5 days. Aphid mortality and fecundity is visually assessed.

## Claims

1. A pesticidal mixture comprising,
1) at least one compound I of formula I:




wherein
R1 is hydrogen, COCH3, COCH2OCH3, COCH2CH3 or COCH2C(CH3)3;
R2 is fluoro, chloro, bromo, CF3, CH3 or CH3O,
R3 is hydrogen, fluoro, chloro, bromo, CF3 or CH3,
or
R2 and R3 form together with —OCF2O— or —O—CH2—O— a 5-membered fused heterocyclic ring;
R4 is hydrogen, fluoro, chloro, bromo, CF3, CH3O or CH3;
R5, R6 are hydrogen, chloro, fluoro, bromo, CH3, CH3O or CF3,
wherein at least one of R5 or R6 is not hydrogen;

or the tautomers, enantiomers, diastereomers or salts thereof,
and
2) at least one active compound II selected from group A consisting of
A.1 Acetylcholine esterase inhibitors triazemate or from the class of carbamates selected from the group consisting of aldicarb, alanycarb, benfuracarb, carbaryl, carbofuran, carbosulfan, methiocarb, methomyl, oxamyl, primicarb, propoxur and thiodicarb, or from the class of organophosphates selected from the group consisting of acephate, azinphos-ethyl, azinphos-methyl, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidaphos, methidathion, mevinphos, monocrotophos, oxymethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, pirimiphos-methyl, quinalphos, terbufos, tetrachlorvinphos, triazophos and trichlorfon;
A.2 GABA-gated chloride channel antagonists selected from the group consisting of cyclodiene organochlorine endosulfan, N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon and N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon or from the class of phenylpyrazoles consisting of acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, vaniliprole and the phenylpyrazole compound II.A2.1:






A.3 Sodium channel modulators selected from the class of pyrethroids consisting of allethrin, bifenthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, tau-fluvalinate, permethrin, silafluofen and tralomethrin;
A.4 Nicotinic acteylcholine receptor agonists/antagonists selected from the group consisting of nicotin, cartap hydrochloride, and thiocyclam or from the class of neonicotinoids consisting of acteamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam and AKD-1022; or the allosteric nicotinic acteylcholine receptor agonist spinosad;
A.5 Chloride channel activators abamectin, emamectin benzoate, lepimectin or milbemectin;
A.6 Juvenile hormone mimics hydroprene, kinoprene, fenoxycarb or pyriproxyfen;
A.7 Compounds affecting the oxidative phosphorylation diafenthiuron, fenbutatin oxide, propargite or chlorfenapyr;
A.8 Inhibitors of the chitin biosynthesis buprofezin or from the class of benzylureas consisting of bistrifluoron, diflubenzuron, flufenoxuron, hexaflumuron, lufenuron, novaluron and teflubenzuron;
A.9 Moulting disruptors cyromazine or from the class of ecdysone agonists selected from the group consisting of methoxyfenozide, tebufenozide and azadirachtin;
A.10 Mitochondrial electron transport inhibitors pyridaben, tolfenpyrad or flufenerim;
A.11 Voltage-dependent sodium channel blockers indoxacarb or metaflumizone;
A.12 Inhibitors of the lipid synthesis spirodiclofen, spiromesifen or spirotetramat;
A.13 group of various compounds selected from the group consisting of amidoflumet, amitraz, bifenazate, clofentezine, cyenopyrafen, cyflumetofen, etoxazole, flonicamid, flubendiamine, flupyrazophos, hexythiazox, piperonyl butoxide, pymetrozine, pyridalyl, pyrifluquinazon, chlorantraniliprole, the anthranilamid compound II.A13.1





and the sulfoximine compounds II.A13.2




in synergistically effective amounts.

2. The pesticidal mixture of claim 1, wherein in compound I of formula I,
















R1
is hydrogen or COCH3;



R2
is fluoro, chloro or CH3;



R3, R4
are independently from one another 




hydrogen, fluoro, chloro, CF3 or CH3;




and



R5, R6
are hydrogen or CH3, wherein at 




least one of R5 or R6 is not hydrogen;.









or the tautomers, enantiomers, diastereomers or salts thereof.

3. The pesticidal mixture of claim 1, wherein in compound I of formula I,
















R1
is hydrogen;



R2, R3
are CH3;



R4
is hydrogen; and



R5, R6
are CH3;.









or the tautomers, enantiomers, diastereomers or salts thereof.

4. The pesticidal mixture of claim 1, wherein in compound I of formula I,
















R1
is hydrogen;



R2, R3
are chloro;



R4
is hydrogen; and



R5, R6
are CH3;.









or the tautomers, enantiomers, diastereomers or salts thereof.

5. The pesticidal mixture of claim 1, wherein in compound I of formula I,
















R1
is COCH3;



R2, R3
are CH3;



R4
is hydrogen; and



R5, R6
are CH3;.









or the enantiomers, diastereomers or salts thereof.

6. The pesticidal mixture of claim 1, wherein in compound I of formula I,
















R1
is COCH3;



R2, R3
are chloro;



R4
is hydrogen; and



R5, R6
are CH3;.









or the enantiomers, diastereomers or salts thereof.

7. The pesticidal mixture of claim 1, wherein at least one active compound II is selected
within group A.1 from triazemate or primicarb;
within group A.2 from endosulfan, N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole or vaniliprole or the phenylpyrazole compound II.A2.1;
within group A.3 from allethrin, bifenthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, etofenprox, fenpropathrin, fenvalerate, flucythrinate, tau-fluvalinate, silafluofen or tralomethrin;
within group A.4 from thiocyclam, actamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, AKD-1022 or spinosad;
within group A.5 from abamectin, emamectin benzoate, lepimectin or milbemectin;
within group A.7 from diafenthiuron;
within group A.8 from buprofezin;
within group A.10 from pyridaben or flufenerim;
within group A.11 from indoxacarb or metaflumizone;
within group A.12 from spirodiclofen, spiromesifen or spirotetramat;
within group A.13 from amitraz, flonicamid, flubendiamine, pymetrozine, pyridalyl, pyrifluquinazon, chlorantraniliprole, the anthranil compound II.A13.1 or the sulfoximine compounds II.A13.2, II.A13.3 or II.A13.4.

8. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.2 is N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, acetoprole or fipronil.

9. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.3 is alpha-cypermethrin or deltamethrin.

10. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.4 is clothianidin, imidacloprid or thiamethoxam.

11. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.5 is abamectin.

12. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.7 is diafenthiuron.

13. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.8 is buprofezin.

14. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.10 is pyridaben or flufenerim.

15. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.11 is metaflumizone.

16. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.12 is spiromesifen or spirotetramat.

17. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.13 is flonicamid.

18. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.13 is pymetrozine or pyrifluquinazon.

19. The pesticidal mixture of claim 1, wherein at least one active compound II selected
from group A.13 is chlorantraniliprole, the anthranil compound II.A13.1 or the sulfoximine compounds II.A13.2, II.A13.3 or II.A13.4.

20. The pesticidal mixture of claim 1, comprising the active compound I of the formula I and the active compound II in a weight ratio of from 500:1 to 1:100.

21. A method for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or the soil or water in which the plant is growing, with a mixture of claim 1 in pesticidally effective amounts.

22. A method for controlling insects, arachnids or nematodes comprising contacting an insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with a mixture of claim 1 in pesticidally effective amounts.

23. The method of claim 21, wherein said mixture is applied in an amount of from 5 g/ha to 2000 g/ha.

24. A method for protection of seed comprising contacting the seeds with a mixture of claim 1 in pesticidally effective amounts.

25. The method of claim 24 wherein said mixture is applied in an amount of from 0.1 g to 10 kg per 100 kg of seeds.

26. A seed treated with the mixture of claim 1 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.

27. A method for protecting animals against infestation or infection by parasites which comprises administering to the animals a parasitically effective amount of said mixture of claim 1 to the animal in need thereof.

28. A method for treating animals infestated or infected by parasites which comprises administering to the animals a parasitically effective amount of said mixture of claim 1 to the animal in need thereof.

29. A pesticidal or parasiticidal composition, comprising a liquid or solid carrier and the mixture of claim 1.