NZ613711B2 - Pesticidal compositions and processes related thereto - Google Patents

Abstract

The disclosure relates to pesticidal compositions comprising phenyl-triazol-phenyl-cyclopropyl-urea derivatives represented by "Formula One" to "Formula Four", wherein the variables are as defined in the specification. These compounds are useful for treating crops and fruit plants for controlling pests such as beer army worm (BAW), corn ear worm (CAW) and green peach aphid (GPA). Typical examples of these compounds include: 1-(2-{4-[1-(4-Trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}-cyclopropyl)-3- (2,4,6-trimethylphenyl)thiourea; Methyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl-carbamate; and 1-Mesityl-3-(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)- cyclopropyl)urea. sts such as beer army worm (BAW), corn ear worm (CAW) and green peach aphid (GPA). Typical examples of these compounds include: 1-(2-{4-[1-(4-Trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}-cyclopropyl)-3- (2,4,6-trimethylphenyl)thiourea; Methyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl-carbamate; and 1-Mesityl-3-(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)- cyclopropyl)urea.

Description

PESTICIDAL COMPOSITIONS AND PROCESSES RELATED THERETO REFERENCE TO RELATED APPLICATIONS This Application claims priority from U.S. provisional application 61/440,910 filed on February 9, 2011. The entire content of this provisional application is hereby incorporated by reference into this Application.

FIELD OF THE INVENTION The invention disclosed in this document is related to the field of processes to produce molecules that are useful as pesticides (e.g., ides, insecticides, molluscicides, and nematicides), such molecules, and processes of using such molecules to l pests.

BACKGROUND OF THE INVENTION Pests cause millions of human deaths around the world each year. Furthermore, there are more than ten thousand species of pests that cause losses in agriculture. The worldwide ltural losses amount to billions of US. dollars each year.

Termites cause damage to all kinds of private and public structures. The world—wide termite damage losses amount to ns of US. s each year.

Stored food pests eat and adulterate stored food. The world-wide stored food losses amount to billions of US. dollars each year, but more importantly, deprive people of needed food.

There is an acute need for new pesticides. Certain pests are developing resistance to pesticides in t use. Hundreds of pest species are resistant to one or more pesticides. The development of resistance to some of the older pesticides, such as DDT, the carbamates, and the organophosphates, is well known. But resistance has even developed to some of the newer pesticides.

Therefore, for many reasons, including the above reasons, a need exists for new pesticides.

DEFINITIONS The es given in the definitions are generally non-exhaustive and must not be construed as limiting the invention disclosed in this document. It is understood that a PCT/U82012/02421 7 substituent should comply with chemical bonding rules and steric compatibility constraints in relation to the particular le to which it is attached. cide Group" is defined under the heading "ACARICIDES".

"AI Group" is defined after the place in this document where the "Herbicide Group" is defined.

"Alkenyl" means an acyclic, unsaturated (at least one carbon-carbon double bond), branched or unbranched, substituent consisting of carbon and hydrogen, for example, vinyl, allyl, butenyl, pentenyl, and hexenyl.

"Alkenyloxy" means an alkenyl further consisting of a carbon—oxygen single bond, for example, allyloxy, butenyloxy, pentenyloxy, hexenyloxy.

"Alkoxy" means an alkyl further consisting of a -oxygen single bond, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and tert-butoxy.

"Alkyl" means an acyclic, saturated, branched or unbranched, substituent consisting of carbon and hydrogen, for example, methyl, ethyl, propyl, isoprOpyl, butyl, and terz—butyl.

"Alkynyl" means an c, unsaturated (at least one carbon—carbon triple bond), branched or unbranched, substituent consisting of carbon and hydrogen, for example, ethynyl, propargyl, butynyl, and pentynyl.

"Alkynyloxy" means an alkynyl further consisting of a carbon-oxygen single bond, for example, pentynyloxy, hexynyloxy, heptynyloxy, and octynyloxy.

"Aryl" means a cyclic, aromatic tuent consisting of hydrogen and carbon, for example, phenyl, naphthyl, and biphenyl.

"Cycloalkenyl" means a clic or polycyclic, rated (at least one carbon— carbon double bond) substituent consisting of carbon and hydrogen, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornenyl, bicyclo[2.2.2]octeny1, tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.

"Cycloalkenyloxy" means a lkenyl further consisting of a carbon-oxygen single bond, for example, cyclobutenyloxy, cyclopentenyloxy, nenyloxy, and bicyclo[2.2.2]octenyloxy.

"Cycloalkyl" means a monocyclic or polycyclic, saturated substituent ting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, o[2.2.2]octyl, and decahydronaphthyl.

"Cycloalkoxy" means a cycloalkyl further consisting of a carbon-oxygen single bond, for example, cyclopropyloxy, utyloxy, cyclopentyloxy, norbornyloxy, and bicyclo[2.2.2]octyloxy. l00063 823673.d0cx 1 7 JUL 201i "Fungicide Group" is defined under the heading "FUNGICIDES." "Halo" means fluoro, chloro, bromo, and iodo.

"Haloalkoxy" means an alkoxy further consisting of, from one to the maximum possible number of identical or different, halos, for example, fluoromethoxy, trifluoromethoxy, fluoropropoxy, chloromethoxy, trichloromethoxy, l,1,2,2- tetrafluoroethoxy, and pentafluoroethoxy.

"Haloalkyl" means an alkyl further ting of, from one to the maximum possible number of, identical or different, halos, for example, fluoromethyl, trifluoromethyl, 2,2- difluoropropyl, chloromethyl, trichloromethyl, and 2-tetrafluoroethyl.

"Herbicide Group" is defined under the heading "HERBICIDES." "Heterocyclyl" means a cyclic tuent that may be fully saturated, partially unsaturated, or fully rated, where the cyclic structure contains at least one carbon and at least one atom, where said atom is nitrogen, , or oxygen. Examples of aromatic heterocyclyls include, but are not limited to, benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl inyl, furanyl, indazolyl, l, olyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, inyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl, and triazolyl. Examples of fully saturated heterocyclyls include, but are not limited to, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl, tetrahydrofuranyl, and ydropyranyl. Examples of partially unsaturated heterocyclyls include, but are not limited to, l,2,3,4—tetrahydr0-quinolinyl, 4,5—dihydro—oxazolyl, 4,5—dihydro~lH—pyrazolyl, 4,5—dihydro-isoxazolyl, and 2,3—dihydro-[1,3,4]-oxadiazolyl.

"Insecticide Group" is defined under the heading "INSECTICIDES." "Nematicide Group" is defined under the heading "NEMATICIDES" "Synergist Group" is defined under the heading "SYNERGISTIC MIXTURES AND SYNERGISTS" As used herein, the term "comprise" and variations of the term, such as "comprising", "comprises" and "comprised", are not intended to exclude other additives, components, integers or steps.

Reference to any prior art in the specification is not, and should not be taken as, an ledgment, or any form of suggestion, that this prior art forms part of the common general knowledge in New Zealand or any other jurisdiction or that this prior art could ! 7JUL 8236j3.docx 2012‘» reasonably be expected to be ascertained, understood and regarded as relevant by a person skilled in the art.

DETAILED DESCRIPTION OF THE INVENTION This document discloses molecules having the following formulas: 0782g2.docx T3 R4 Het 4/N N Ar1/ \Arz \H/ \RS "Formula One" Het A/N 0 AH/ \Ar2 \H/ \RG "Formula Two" "Formula Three" R3 R3 R1 Het /<1/N N Het Ar1/ / \Arz \H/ Ar2 \AI'1 X1 R2 "Formula Four" PCT/U82012/024217 wherein: (a) Ar] is (each independently) (1) furanyl, phenyl, pyridazinyl, pyridyl, dinyl, thienyl, or (2) substituted furanyl, substituted phenyl, substituted zinyl, substituted pyridyl, Substituted pyrimidinyl, or substituted thienyl, wherein said substituted furanyl, substituted , substituted pyridazinyl, tuted pyridyl, substituted pyrimidinyl, and substituted thienyl, have one or selected from H, F, Cl, Br, more substituents independently I, CN, N02, C1-C6 alkyl, C1—C6 haloalkyl, C3-C6 Cycloalkyl, C3—C6 halocycloalkyl, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C1-C5 alkoxy, C1-C6 koxy, C2-C6 alkenyl, C2-C6 alkynyl, S(=O)n(C1- C6 alkyl), S(=O)n(C1-C6 haloalkyl), OSOz(C1—C6 alkyl), OSOZ(C1—C6 haloalkyl), C(:0)NRny, (cyc6 alky1)NRny, C(zoxcl-CG alkyI), C(=0>O(cl-c6 alkyl), (c1-c6 alkyl), C(=0)(Cl-cs haloalkyl), C(=O)O(C1-C6 haloalkyl), C(=O)(C3-C6 cycloalkyl), C(=O)O(C3-C6 cycloalkyl), C(=O)(C1-C6 haloalkyl), C(=O)(C2-C6 alkenyl), C(=O)O(C2-C6 alkenyl), (C1-C6 alky1)O(C1- C6 alkyl), (C1-C6 alkyl)S(C1—C6 alkyl), C(=O)(C1-C6 alkyl)C(=O)O(C1—C6 alkyl), phenyl, phenoxy); (d) R3 is H, CN, F, Cl, Br, I, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C1—C6 alkoxy, C2—C6 alkenyl, C2-C6 alkynyl, S(:O)n(C1—C6 alkyl), OSOz(C1—C6 alkyl), 1-C6 haloalkyl), C(=O)NRXRy, (C1-C6 alkyl)NRny, C(=0)(C1~C6 alkyl), C(=O)O(C1- C6 alkyl), C(=O)(C1—C6 haloalkyl), C(ZO)O(C1—C6 haloalkyl), C(ZO)(C3—C6 lkyl), C(zO)O(C3—C6 cycloalkyl), C(ZO)(C2—C6 l), C(=O)O(C2—C6 alkenyl), (C 1—C6 alky1)O(C1-C6 alkyl), (C1—C6 alkyl)S(C1—C6 alkyl), C(=O)(C1—C6 alkyl)C(=O)O(C1-C6 , phenyl, and phenoxy, wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl, alkynyl, phenyl, and phenoxy are optionally substituted with one or more substituents independently selected from OH, F, Cl, Br, 1, CN, N02, oxo, C1-C6 alkyl, C1—C6 haloalkyl, C1-C6 hydroxyalkyl, C3— C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 hydroxycycloalkyl, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C3-C6 hydroxycycloalkoxy, C1-C6 alkoxy, C1—C6 haloalkoxy, C2-C6 alkenyl, C2-C5 alkynyl, S(=O)n(C1-C6 alkyl), S(=O)n(C1-C6 haloalkyl), 1-C6 alkyl), OSOZ(C1- C6 kyl), C(=O)NRnya (C1-C6 NRnya C(=0)(C1-C6 , C(=O)O(Ci-Cs alkyl), C(=O)(C1-C6 haloalkyl), (C1-C6 haloalkyl), C(=O)(C3-C6 cycloalkyl), C(=O)O(C3-C6 cycloalkyl), C(=O)(C2-C6 alkenyl), C(=O)O(C2-C6 alkenyl), (C1-C6 alkyl)O(C1-C6 alkyl), (C1—C6 alkyl)S(C1-C6 alkyl), C(=O)(C1-C6 C(=O)O(C1-C6 alkyl), phenyl, and phenoxy; 100075078272d0cx (6) R4 is H, CN, F, Cl, Br, I, C1—C6 alkyl, C3~C6 cycloalkyl, C3—C6 cycloalkoxy, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, S(:O)n(C1—C6 alkyl), OSOg(C1-C6 alkyl), OSOZ(C1-C6 haloalkyl), C(=O)NRny, (C1-C6 alkyl)NRny, C(=O)(C1-C6 alkyl), C(=O)O(C1- C6 alkyl), C(=O)(C1-C6 haloalkyl), C(=O)O(C1-C6 haloalkyl), C(=O)(C3-C6 cycloalkyl), (C3-C6 lkyl), C(=O)(C2—C6 alkenyl), C(=O)O(C2-C6 alkenyl), (C1—C6 a1kyl)O(C1-C6 alkyl), (C1-C6 alkyl)S(C1—C6 alkyl), C(=O)(C1-C6 alkyl)C(=O)O(C1-C6 alkyl), phenyl, and phenoxy, wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl, alkynyl, phenyl, selected and phenoxy are optionally substituted with one or more substituents independently from OH, F, Cl, Br, 1, CN, N02, oxo, C1-C(> alkyl, C1-C6 haloalkyl, C1-C5 yalkyl, C3— C6 cycloalkyl, C3—C6 halocycloalkyl, C3-C6 ycycloalkyl, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C3-C6 hydroxycycloalkoxy, C1-C6 alkoxy, C1—C6 haloalkoxy, C2-C6 alkenyl, C2-C6 alkynyl, S(=O)n(C1—C6 alkyl), S(=O)n(C1—C6 haloalkyl), OSOZ(C1—C6 , 0802(C1- C6 haloalkyl), C(=O)NRny, (C1-C6 alkyl)NRny, C(=O)(C1—C6 alkyl), C(:O)O(C1-C6 alkyl), C(=0)(C1—C6 kyl), (C1—C6 haloalkyl), C3—C6 cycloalkyl), C(=O)O(C3-C6 cycloalkyl), C(ZOXCz-CG alkenyl), C(=O)O(C2-C6 alkenyl), (C1—C6 alkyl)O(C1—C6 alkyl), and phenoxy; (C1—C6 alkyl)S(C1—C6 alkyl), C(:O)(C1'C6 alkyl)C(:O)O(C1—C5 alkyl), phenyl, (1‘) R5 is H, CN, F, Cl, Br, I, C1—C6 alkyl, C3—C6 cycloalkyl, C3-C6 cycloalkoxy, C1—C6 alkoxy, C2—C5 l, C2—C5 alkynyl, S(=O)n(C1—C6 alkyl), OSOZ(C1—C6 alkyl), 0802(C1‘C6 haloalkyl), C(IO)NRXRy, (C1-C6 alkyl)NRny, C(:O)(C1-C6 alkyl), C(=O)O(C1- C6 , C(=O)(C1-Ce kyl), C(=O)O(C1—C6 haloalkyl), C(=O)(C3-C6 cycloalkyl), C(=O)O(C3-C6 lkyl), C2-C6 alkenyl), C(=O)O(C2-C6 alkenyl), (C1-C6 alkyl)O(C1-C6 alkyl), (C1-C6 alkyl)S(C1-C6 alkyl), C(=O)(C1-C6 alky1)C(=O)O(C1-C6 alkyl), Het, phenyl, and phenoxy, n each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl, alkynyl, Het, phenyl, and phenoxy are optionally substituted with one or more substituents independently selected from OH, F, Cl, Br, I, CN, N02, 0X0, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 hydroxyalkyl, C3—C6 lkyl, C3-C6 halocycloalkyl, C3—C6 hydroxycycloalkyl, (33,.(36 cycloalkoxy, C3-C6 halocycloalkoxy, C3-C5 hydroxycycloalkoxy, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyl, C2—C6 alkynyl, S(=O)n(C1-C6 alkyl), S(=O)n(C1-C6 kyl), OSOg(C1-C6 alkyl), OSOz(C1-C6 haloalkyl), C(=O)NRXRy, (C1-C6 alkyl)NRny, C(=O)(C1-C6 alkyl), C(:O)O(C1'C6 alkyl), C(=O)(C1-C6 haloalkyl), C(=O)O(C1-C6 haloalkyl), C(=O)(C3- C6 cycloalkyl), C(ZO)O(C3—C6 cycloalkyl), C(=O)(C2—C6 alkenyl), (C2—C6 alkenyl), lOOO750782_2.d0cx (C1-C6 alkyl)O(C1—C6 alkyl), (C1-C6 alkyl)S(C1—C6 alkyl), C(=O)(C1~C6 alkyl)C(=O)O(C1—C6 alkyl), NRXRy, phenyl, and phenoxy; (g) R6 is H, CN, F, Cl, Br, I, C1—C6 alkyl, C3—C6 cycloalkyl, C3-C6 lkoxy, C1-C6 alkoxy, C2—C6 alkenyl, C2—C5 alkynyl, S(=O)n(C1-C6 alkyl), OSOZ(C1‘C6 alkyl), OSOz(C1—C6 haloalkyl), C(=O)NRny, (C1-C6 alkyl)NRny, C(=O)(C1-C6 alkyl), C(=O)O(C1— C6 , C(=O)(C1-C5 haloalkyl), C(=O)O(C1-C(, haloalkyl), C(=O)(C3-C6 cycloalkyl), C(=O)O(C3-C6 cycloalkyl), C(=O)(C2-C5 alkenyl), C(=O)O(C2-C6 alkenyl), (C1-C6 O(C1-C6 a1ky1>, (cl-c6 alky1>SO(cl-ca alkyl), phenyl, and phenoxy, wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl, alkynyl, phenyl, selected and phenoxy are optionally substituted with one or more substituents independently from OH, F, Cl, Br, 1, CN, N02, oxo, C1~C6 alkyl, C1-C6 haloalkyl, C1-C6 hydroxyalkyl, C3— C6 lkyl, C3—C6 halocycloalkyl, C3-C6 hydroxycycloalkyl, C3—C5 cycloalkoxy, C3—C6 halocycloalkoxy, C3—C6 hydroxycycloalkoxy, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 l, C2—C6 alkynyl, (C1—C6 alkyl), S(=O)n(C1—C6 haloalkyl), OSOz(C1-C6 alkyl), OSOz(C1- C6 haloalkyl), C(=O)NRXRy, (C1-C6 NRny, C(=O)(C1—C6 alkyl), C(=O)O(C1-C6 alkyl), C1—C6 haloalkyl), C(=O)O(C1-C5 haloalkyl), C(=O)(C3—C6 cycloalkyl), (C3-C6 lkyl), C(=O)(C2—C6 alkenyl), C(=O)O(C2—C6 l), (C1—C6 alkyl)O(C1-C6 alkyl), (C1—C6 alkyl)S(C1—C6 alkyl), C(=O)(C1—C6 alkyl)C(:O)O(C1—C5 alkyl), Het, phenyl, phenoxy; (h) R7 is H, CN, F, Cl, Br, I, C1-C6 alkyl, C3—C6 cycloalkyl, C3—C6 cycloalkoxy, C1-C6 alkoxy, C2'C6 alkenyla C2-C6 alkynyl, S(=O)n(C1-C6 alkyl), 0802(C1-C6 alkyl), osoz(cl—c6 haloalkyl), C(=O)NRny, (CI'C6 alky1)NRny, C(=O)(C1'C6 alkyl), C(:O)O(Cl' C6 , C(=O)(C1-C6 haloalkyl), C(=O)O(C1-C6 haloalkyl), C(=O)(C3-C6 lkyl), C(=O)O(C3-C6 cycloalkyl), C(=O)(C2-C6 alkenyl), C(=O)O(C2-C6 alkenyl), (C1-C6 alky1)O(C1'C6 alkylla (CI'C6 a1ky1)0C(=0)(C1-C6 alkyl), (Cl'Cé a1ky1)S(C1-C6 , C(=0)(C1-C6 a1ky1)C(=O)O(C1-C6 alkyl), , and phenoxy, wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl, alkynyl, phenyl, selected and phenoxy are optionally substituted with one or more substituents independently from OH, F, Cl, Br, 1, CN, N02, oxo, C1-C6 alkyl, C1-C6 kyl, C1-C6 hydroxyalkyl, C3- C6 lkyl, C3-C6 halocycloalkyl, C3—C6 hydroxycycloalkyl, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C3—C6 hydroxycycloalkoxy, C1-C6 alkoxy, C1-C6 haloalkoxy, C2—C6 alkenyl, l000750782#2.docx C2—C6 alkynyl, (C1—C6 alkyl), S(=O)n(C1—C6 haloalkyl), OSOz(C1—C6 alkyl), OSOZ(C1— C6 haloalkyl), C(=O)NRny7 (C1-C6 alky1)NRny, C(=O)(C1-C6 alkyl), C(ZOXXCI-Cs alkyl), C(=O)(C1-C6 haloalkyl), C(=O)O(C1-C6 haloalkyl), C(=O)(C3-C6 lkyl), C(=O)O(C3—C6 cycloalkyl), C(=O)(C2-C6 l), C(=O)O(C2—C6 alkenyl), (C1-C6 a1kyl)O(C1-C6 alkyl), and phenoxy; (C1-C6 alkyl)S(C1-C6 alkyl), C(=O)(C1-C6 alkyl)C(=O)O(C1-C6 alkyl), phenyl, (i) X1 is S or 0; (j) 11: 0, 1, or 2 (each independentlY); and (k) RK and Ry are independently ed from H, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 hydroxyalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3—C6 hydroxycycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, S(=O)n(C1—C6 alkyl), S(:O)n(C1-C6 kyl), OSOg(Cl—C6 alkyl), OSOZ(C1—C6 haloalkyl), C(=O)H, C1-C6 , C(:0)0(C1—C6 alkyl), C(=O)(C1—C6 haloalkyl), C(=O)O(C1-C6 haloalkyl), C(=O)(C3—C6 cycloalkyl), C(=O)O(C3-C6 cycloalkyl), C(ZOXCz-Cs alkenyl), (C2—C6 alkenyl), (C1—C6 alkyl)O(C1—C6 alkyl), (C1—C6 alky1)S(C1—C6 , C(=O)(C1-C6 alkyl)C(=O)O(C1—C6 alkyl), and phenyl.

In another embodiment An is a substituted phenyl wherein said substituted phenyl, has one or more tuents independently selected from C1—C6 haloalkoxy.

In another embodiment Het is a triazolyl. In another embodiment Het is a 1,2,4— triazolyl. In another embodiment Het is a 1,2,4-triazolyl with one ring nitrogen atom bonded to A12. to Ar} and one ring carbon bonded In another embodiment Al‘z is a phenyl.

In another embodiment R3 is H. 0782#2.docx In another embodiment R4 is H. In another embodiment R4 is a phenyl optionally substituted with one or more substituents independently selected from C1-C6 alkyl.

PCT/U82012/024217 In another embodiment R5 is Het or phenyl wherein each are optionally substituted with one or more substituents independently selected from F, Cl, C1-C6 alkyl, C1-C5 haloalkyl, C1-C6 alkoxy, or NRny, In another ment R6 is C1-C6 alkyl or phenyl wherein each are optionally substituted with one or more substituents independently selected from F, Cl, C1-C6 alkyl, C1- C5 haloalkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, Het, or .

In another ment R7 is (C1-C5 alky1)OC(=O)(C1-C6 alkyl).

While these embodiments have been expressed, other embodiments and combinations of these expressed embodiments and other embodiments are possible.

The molecules of Formula One, Two, Three, and Four will generally have a molecular mass of about 100 Daltons to about 1200 Daltons. However, it is generally preferred if the molecular mass is from about 120 Daltons to about 900 s, and it is even more generally preferred if the molecular mass is from about 140 Daltons to about 600 Daltons.

EXAMPLES The examples are for illustration purposes and are not to be construed as limiting the invention disclosed in this document to only the embodiments disclosed in these examples.

Starting materials, reagents, and solvents that were obtained from commercial sources were used without r purification unless otherwise stated. Anhydrous solvents were purchased as Sure/SealTM from h and were used as ed. Melting points were obtained on a Thomas Hoover t capillary melting point apparatus or an OptiMelt Automated Melting Point System from Stanford ch Systems and are uncorrected.

Molecules are given their known names, named according to naming programs Within ISIS Draw, ChemDraw or ACD Name Pro. If such programs are unable to name a molecule, the molecule is named using conventional naming ruleS. 1H NMR spectral data are in ppm (5) and were recorded at 300, 400 or 600 MHz, and 13C NMR spectral data are in ppm (5) and were recorded at 75, 100 or 150 MHz, unless otherwise stated.

Compounds of this ion can be ed by making a triaryl intermediate, Ar;— Het—Arg, and then linking it to the desired intermediate to form the desired compound. A wide variety of triaryl intermediates can be used to prepare compounds of this invention, ed that such triaryl intermediates contain a le functional group on Arz to which the rest of the desired intermediate can be ed. Suitable functional groups include an oxoalkyl or a formyl group. These triaryl intermediates can be prepared by methods previously described in the chemical literature, including Crouse et a1. PCT Int. Appl. Publ. W02009/102736 A1.

PREPARATION OF CYCLOPROPYL-LINKED COMPOUNDS Cyclopropyl-linked compounds of Formula One can be prepared from the corresponding aryl aldehydes via reaction with t-butyl diethylphosphonoacetate and a base, such as sodium hydride (NaH), in tetrahydrofuran (THF), at 0 CC. The rated ester is converted to the cyclopropyl ester with trimethylsulfoxonium iodide in dimethyl sulfoxide (DMSO) at ambient temperature. The cyclopropyl acyl azide A can be prepared from the uni/4 {rm/\\ 'n PIVcursor ester in two We"Q Q 1 v i r\ (\an1‘ UUUYU J A u ILAUULUIJK/V {ZULU \11 n} 111 dichloromethane (CHgClg) at temperatures from 0 to 25 °C and then with diphenylphosphorylazide (DPPA) and a base, such as triethylamine, in toluene at ambient temperature. The acyl azide A is ted via Curtius rearrangement with utyl alcohol (t-BuOH) in toluene at 90 °C to the tert—butyl carbamate. The t-butyl carbamate is removed using TFA in dichloromethane at temperatures from 0 to 25 °C to provide the trifluoroacetate salt of the amine B. The thioureas can be ed from the salt B with an appropriately substituted isothiocyanate (RS—NCXl, wherein X1 = S) in the presence of a base, such as triethylamine, in THF at 80 °C, or in a two-step process, by first reacting the salt B with osgene to generate an isothiocyanate, which is d to react with an appropriately substituted amine (R4R5NH) Likewise, ureas can be generated with an appropriately substituted isocyanate (R5-NCX1, wherein X1 = O) in the presence of a base, such as l\) U1 triethylamine, in THF at 80 °C. 2012/024217 ('3 0 QB. QL O + _ Het\ A0 OEt’ Messol O-t-BU AT1/ Arz A/Het\ Mo/k NaH, THF, 0 to 25 C NaH, DMSO, 25 °C 1. TFA, CHZCIZ, Oto 25 Cc )k0JV O Het Het Ar1/ Ar1/ \Ar/Q/l2 2. DPPA, Et3N, PhCH3, 25 °C Na t-BuOH, PhCH3. 90 °c Ar/HekAr/(LHTO TFA, CHZCIQ, o to 25 °c 1 2 o >( Ht R5—NCX1EtNTHF80 c° e\ = = R4 . 3 . . _ Het\ / /Het\ 4/4 (R6)OH, PhCH3, 100 °c —————-—> mewa Two H t (R6)OC(O)C| CH Cl2 2’ Et N 4 DMAP 25 °c ‘ 3 ' ' Ar1/ e\Ar2’ PCT/U82012/024217 [F23 A/N R4 alkylhalide (R7) CHCI 100 "C IR3 ' 3' A /Het\A /Het\ A/N r1 r2 N —‘——‘_———> Ar1 Arz \ >¢N\ X1 R5 R7/X1 R4 Formula One Formula Three Compounds of Formula Four can be generated by reaction of the cyclopropyl carboxylic acid DPPA and a base, such as triethylamine, in t-BuOH at 90 °C.

R3 R3 DPPA, Et3N. t-BuOH, 90 °C Al l /Het\A MOH —-—_—_—> Het‘Al’ 1K A Ar1 r2 / 2 Ar2\Het Ar1 \ Formula Four Ar1 Example 1: Preparation of (E){4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol—3— yl]phenyl}acrylic acid tert-butyl ester \ o’k\ i=7:coN\f-N Sodium hydride (NaH, 60% sion in mineral oil; 440 milligrams (mg), 11.0 millimoles (mmol)) was suspended in THF (20 milliliters (mL)), and the mixture was cooled t0 0 OC. t—Butyl diethylphophonoacetate (2.57 mL; 11.0 mmol) was added over 2 minutes (min). The e was stirred at 0 °C for another 15 min, during which time the grey slurry turned clear within 5 min. 4—[1-(4-T1ifluoromethoxyphenyl)-lH—[l,2,4]triazol~3-yl}- benzaldehyde (3.04 grams (g); 9.13 mmol) was suspended in THF (20 mL) and then added dropwise Via cannula to the solution above. The mixture was then warmed to 25 °C, poured into saturated (satd) aqueous (aq) ammonium chloride (NH4C1; 200 mL), and extracted with 50% ethyl acetate (EtOAc)/hexanes (3 x100 mL). The combined c extracts were then dried over sodium e (Na2804) and concentrated in vacuo. The yellow solid residue was dissolved in dichloromethane (CH2C12; 10 mL) and y d as hexanes (100 mL) was added dropwise over 30 min. The light yellow crystals were collected on a Buchner funnel and dried in vacuo to afford the title compound ((2.93 g, 74%). The filtrate was concentrated in vacuo and purified by chromatography on silica gel (gradient elution with 15% to 40% to 80% EtOAc in hexanes) to afford additional product (0.215 g, 5%): mp 167—169 °C; 1H NMR (400 MHz, CDC13) 5 8.58 (s, 1H), 8.20 (d, J: 8.3 Hz, 2H), 7.80 (d, J = 8.9 Hz, 2H), 7.63 (d, J = 15.8 Hz, 1H), 7.62 (d, J = 8.5 Hz, 2H), 7.39 (d, J = 8.6 Hz, 2H), 6.44 (d, J = 16.0 Hz, 1H), 1.54 (s, 9H); HRMS—ESI (m/z) [M]+ calcd for C22H20F3N303,431.146; found, 431.1457.

Example 2: Preparation of 2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol nyl}cyclopropanecarboxylic acid tert-butyl ester NaH (60% suspension in mineral oil; 400 mg, 10.1 mmol) and tn'methylsulfoxonium iodide (2.22 g, 10 mmol) were charged into a round bottom flask with a stir bar and placed in an ice bath. DMSO (20 mL) was added over a period of 10 min with us stirring, then the resulting grey slurry was warmed to 25 °C and stirred for l h, during which time the slurry became clear. The enoate from e 1 was dissolved in DMSO (20 mL) and added transfer to the above solution via cannula over a period of 30 min. DMSO (5 mL) was used to the flask. The resulting -orange solution was stirred at 25 any remaining material from °C for 2 h, then warmed to 50 oC and stirred for 3 h. The solution was then cooled back down to 25 0C, stirred for another 12 h, and poured into ice water (300 mL). The mixture was extracted with 50% EtOAC/hexanes (3 x150 mL), and the combined organic extracts were washed with brine, dried over NaQSO4, and concentrated in vacuo to give a pale orange solid.

Purification by silica gel chromatography (gradient elution with 15% to 40% to 80% EtOAc in hexanes) afforded the t (2.19 g, 73%) as a light pink solid: mp 100—101 °C; 1H NMR (300 MHz, CDC13) 5 8.55 (s, 1H), 8.10 (d, J = 8.4 Hz, 2H), 7.79 (d, J = 9.1 Hz, 2H), 7.38 (dd, J = 9.0, 0.8 Hz, 2H), 7.19 (d, J = 8.3 Hz, 2H), 2.49 (ddd, J = 9.2, 6.4, 4.2 Hz, 1H), 1.90 (ddd, J = 8.4, 5.4, 4.2 Hz, 1H), 1.57 (ddd, J = 9.9, 9.2, 4.6 Hz, 1H), 1.48 (s, 9H), 1.29 (ddd, J = 8.4, 6.4, 4.5 Hz, 1H); ESIMS m/z 446 (M+H).

Example 3: Preparation of 2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol yl]phenyl}cyclopropanecarbonyl azide Step 1. To a solution of the tert-butyl ester from Example 2 (0.562 g; 1.26 mmol) in CH2C12 (8.0 mL) at 25 °C was added trifluoroacetic acid (TFA; 4.0 mL). The on was stirred at 25 °C for 18 h and was then concentrated in vacuo to afford the carboxylic acid TFA salt (665 mg) as a light pink solid.

Step 2. Without further purification, a portion of this solid (558 mg, 1.11 mmol) was slurried in toluene (PhCH3; 3.2 mL). Triethylamine (Eth; 0.368 mL, 2.66 mmol) was added, and the slurry clarified to give a yellow solution. Diphenylphosphoryl azide (DPPA; 0.287 mL, 1.33 mmol) was then added in one portion. The mixture was stirred for 2 h at 25 °C at which point analysis of an aliquot by liquid chromatography-mass spectrometry (LC—MS) showed complete conversion to the product. The crude on mixture was directly applied to a silica gel column and purified (gradient elution with 15% to 30% EtOAC in hexanes) to afford the product (0.356 g, 78%) as a white solid: 1H NMR (300 MHZ, CDC13) 5 8.54 (s, 1H), 8.10 (d, J = 8.3 Hz, 2H), 7.78 (d, J: 9.0 Hz, 2H), 7.37 (d, J = 8.6 Hz, 2H), 7.18 (d, J = 8.2 Hz, 2H), 2.68 (ddd, J = 9.4, 6.8, 4.1 Hz, 1H), 2.03-1.90 (m, 1H), 1.83—1.70 (m, 1H), 1.52 (ddd, J = 8.3, 6.8, 4.7 Hz, 1H); ESIMS m/z 387 (M+H). e 4: Preparation of (2-{4-[1-(4-triflu0rometh0xyphenyl)~1H-[1,2,4]triazol yl]phenyl}cycl0propyl)carbamic acid tert-butyl ester 2—{4—[1—(4-trifluoromethoxyphenyl)- lH-[1,2,4]triazol-3 - yl]pheny1}cyclopropanecarbonyl azide (0.301 g, 0.727 mmol) was slurried in PhCH3 (2.0 mL). utyl alcohol (t-BuOH; 0.250 mL, 2.64 mmol) was added, and the resulting mixture was heated at 90 °C for 24 h. During this time the slurry became homogenous to give a yellow solution. The mixture was cooled to 25 °C , and an ite precipitate was ed to form. The slurry was diluted with hexanes (3 mL) and filtered on a Bijchner WO 09292 PCT/U82012/024217 funnel to afford the product (0.252 g, 75%) as an off-white solid. The filtrate was concentrated in vacuo and purified by silica gel chromatography (gradient elution with 15% to 40% to 80% EtOAc in hexanes) to afford onal product (0.0154 g, 5%): mp 169—172 0C; 1H NMR (300 MHz, CDC13) 8 8.54 (s, 1H), 8.07 (d, J: 8.1 Hz, 2H), 7.78 (d, J = 8.9 Hz, 2H), 7.37 (d, J = 8.6 Hz, 2H), 7.21 (d, J = 8.1 Hz, 2H), 4.91 (s, J = 0.9 Hz, 1H), 2.86-2.72 (m, 1H), 2.15-2.03 (m, 1H), 1.46 (s, 9H), 1.29-1.15 (m, 2H); ESIMS m/z 461 (M+H).

Example 5: Preparation of 2-{4—[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol yl]phenyl}cyclopropylamine fiOQN‘NvQ/Q FF \sN The carbamate from Example 4 (0.249 g, 0.541 mmol) was slurried in CHzClg (3.5 mL) at 25 °C, and TFA (1.5 mL) was added. The solids dissolved to give an orange solution.

The mixture was stirred at 25 °C for 2 h and was then concentrated in vacuo to afford an orange oil. This material was carried forward Without further purification. An analytical sample was prepared by ving ca. 20 mg of the oil in CH2C12 (0.4 mL) and adding Et3N (0.007 mL, 0.05 mmol). After 1 h, a white precipitate was ed to form. The solid was collected on a Biichner funnel and dried in vacuo to afford the pure amine in se form (105 mg) as a white solid: mp 149—152 "C; 1H NMR (300 MHZ, methanol—d4) 5 9.15 (s, 1H), 8.09 (d, J = 8.4 Hz, 2H), 8.02 (d, J: 9.2 Hz, 2H), 7.50 (dd, J = 9.1, 0.8 Hz, 2H), 7.30 (d, J = 8.3 Hz, 2H), 2.93 (ddd, J = 7.9, 4.5, 3.6 Hz, 1H), 2.43 (ddd, J = 10.1, 6.7, 3.6 Hz, 1H), 1.54- 1.34 (m, 2H); ESIMS m/z 361 (M+H).

Example 6: Preparation of 1-phenyl(2-{4-[1-(4-trifluoromethoxyphenyl)-1H- [1,2,4]triazolyl]phenyl}cyclopropyl)thiourea (Compound 1) 2012/024217 The amine trifluoroacetate salt from Example 5 (0.064 g, 0.135 mmol) was dissolved in THF (0.5 mL). Et3N (0.037 mL, 0.27 mmol) was added, followed by phenyl isothiocyanate (0.020 mL, 0.15 mmol). The resulting dark yellow solution was heated to 80 °C and stirred for 4 h. The solution was cooled to 25 °C , loaded directly onto a silica gel column and purified (gradient n with 15% to 40% to 80% EtOAc in hexanes) to afford the product (0.0222 g, 33%) as a yellow oil: IR vmax 3380, 3218 (br), 1617, 1598, 1518, 1497, 1448, 1356, 1326, 1264, 1221, 1168, 1111, 1065, 986, 910, 851, 756, 732, 694 cm]; 1H NMR (300 MHz, CDC13) 8 8.56 (s, 1H), 8.11 (d, J = 8.3 Hz, 2H), 7.90 (br s, 1H), 7.78 (d, J = 9.0 Hz, 2H), 7.46 — 7.32 (m, 5H), 7.31 — 7.21 (m, 5H), 3.10 (br s, 1H), 2.25 (br s, 1H), 1.51 — 1.30 (in, 2H); HRMS—ESI (m/z) [M]+ calcd for C25H20F3N50S, 495.134; found, 495.1341.

The following compounds were sized in accordance with Example 6 above. 1~(2,6—Dichlorophenyl)—3-(2-{4-[1 -’4-triflu0r0meth0xyphenyl)-1H-[1,2,4]triazol yl]phenyl}cyclopr0pyl)thi0urea (Compound 2) The product was ed as a yellow solid (0.021 g, 28%): mp 118-123 0C; 1H NMR (300 MHz, CDC13) 6 8.56 (s, 1H), 8.10 (d, J = 8.3 Hz, 2H), 7.78 (d, J = 9.1 Hz, 2H), 7.47 — 7.33 (m, 5H), 7.29 — 7.16 (m, 4H), 3.00 (br s, 1H), 2.42 (br s, 1H), 1.57 - 1.42 (m, 2H); HRMS—ESI (m/z) [M]+ calcd for C25H13C12F3N508, 563.056; found, 563.0562. 1-(4-Methoxymethylphenyl)~3-(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol- 3-yl]phenyl}cyc‘.0propyl)thiourea (Compound 3) PCTfUS2012/024217 The product was isolated as a yellow solid (0.013 g, 18%): IR Vmax 3377, 3220 (br), 2928, 2854, 1612, 1517, 1446, 1247, 1162, 1113, 1047, 986, 909, 850, 731 cm"; ‘H NMR (300 MHz, CDC13) 5 8.55 (s, 1H), 8.09 (d, J: 8.3 Hz, 2H), 7.79 (d, J = 9.1 Hz, 2H), 7.44 (b1 J = 8.6, 2.7 Hz, 3, 1H), 7.38 (m, 2H), 7.28 (br s, 2H), 7.17 (br s, 1H), 6.81 (br s, 1H), 6.78 (d, 1H), 5.80 (br s, 1H), 3.81 (s, 3H), 3.20 (br s, 1H), 2.25 (s, 3H), 2.17 (br s, 1H), 1.29 — 1.22 (m, 2H); SI (m/z) [M]+ calcd for C27H24F3N5028, 0; found, 539.1602. 1-(4-Chloromethylphenyl)(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol yl]phenyl}cyclopropyl)thiourea (Compound 4) F‘KOON’Nfi/Q/Q" "<9‘11"S c: FF N The product was isolated as an off-white oily foam (53.4 mg, 82%): IR vmx 3210 (br), 3029, 2978, 1728, 1518, 1492, 1446, 1354, 1327, 1264 cm’lg 1H NMR (300 MHz, CDClg) 8 8.55 (s, 1H), 8.11 (d, J = 8.3 Hz, 2H), 7.78 (d, J = 9.0 Hz, 2H), 7.51 (br s, 1H), 7.42 — 7.35 (m, 2H), 7.30 — 7.08 (m, 6H), 3.10 (br s, 1H), 2.38 — 2.09 (app s, 4H), 1.55 — 1.29 (m, 2H); HRMS—ESI (m/z) [M]+ calcd for C26H21C1F3N5OS, 543.1107; found, 09. 1-(2-Chlorophenyl)—3-(2-{4-[1—(4—trifluoromethoxyphenyl)~1H—[1,2,4]triazol yl]phenyl}cyclopropyl)thiourea (Compound 5) The product was isolated as a white solid (49.0 mg, 78%): mp 176—179 °C; 1H NMR (300 MHz, CDCl3) 5 8.56 (s, 1H), 8.12 (d, J: 8.3 Hz, 2H), 8.02 (br s, 1H), 7.79 (d, J = 9.0 Hz, 2H), 7.43 - 7.35 (m, 3H), 7.31 (td, J: 7.9, 1.4 Hz, 1H), 7.25 — 7.10 (m, 4H), 6.81 (br s, 1H), 3.04 (br s, 1H), 2.49 — 2.28 (m, 1H), 1.62 ~ 1.39 (m, 2H); HRMS—ESI (m/z) [M]+ calcd for C25H19C1F3N508, 529.0951; found, 529.0950.

PCT/U32012/024217 1-(2,6-Diethylphenyl)(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol yl]phenyl}cyclopropyl)thiourea (Compound 6) FfioQNCTQ/Q Ys The product was isolated as a light yellow oil (24.5 mg, 36%): IR vmax 3375, 3180 (br), 2971, 2937, 2876, 1518, 1326, 1264, 1168, 1111, 1064, 986, 910, 851, 731 our]; 1H , NMR (400 MHz, CDC13) 5 8.55 (s, 1H), 8.09 (d, J = 8.2 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.41 — 7.36 (m, 2H), 7.35-7.28 (m, 3H), 7.24 — 7.12 (m, 3H), 5.55 (s, 1H), 3.29 — 3.22 (m, 1H), 2.73 — 2.52 (In, 4H), 2.13 ~ 2.05 (m, 1H), 1.41 ~ 1.09 (In, 8H); HRMS—ESI (m/z) [M]+ calcd for C29H23F3N508, 551.197; found, 551.1967. 1-(4-Dimethylaminophenyl)(2-{4-[l-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol yl]phenyl}cyclopropyl)thiourea (Compound 7) H H N N 17gOQN,N\ \=N I The product was isolated as a yellow-orange solid (47.8 mg, 75%): mp 925 °C; 1H NMR (300 MHZ, CDCl3) 8 8.54 (s, 1H), 8.09 (d, J: 8.3 Hz, 2H), 7.79 (d, J = 9.0 Hz, l\)C) 2H), 7.58 (s, 1H), 7.37 (d, J = 9.0 Hz, 2H), 7.27 (d, J = 9.4 Hz, 2H), 7.10 (br d, J = 7.5 Hz, 2H), 6.70 (d, J: 9.0 Hz, 2H), 6.10 (br s, 1H), 3.30 — 3.10 (m, 1H), 2.98 (s, 6H), 2.25 — 2.12 (m, 1H), 1.47 — 1.18 (m, 2H); HRMS—ESI (m/Z) [M]+ calcd for C27H25F3NGOS, 538.1763; found, 538.1754. 4-[1-(4-Trifluoromethoxyphenyl)-1H-[1,2,4]triazolyl]phenyl}-cyclopropyl)(4- trifluoromethylphenyl)thiourea (Compound 8) PCT/U82012/024217 The product was ed as a white foam (50.5 mg, 73%): IR Vmax 3377, 3217 (br), 3027, 1617, 1518, 1446, 1417, 1327, 1267, 1223,1167, 1126, 1067, 1018, 987, 909, 841, 732 cm"; 1H NMR (300 MHz, CDC13) 8 8.57 (s, 1H), 8.15 (d, J = 8.3 Hz, 2H), 7.94 (br s, 1H), 7.79 (d, J = 9.0 Hz, 2H), 7.67 — 7.56 (m, 4H), 7.39 (d, J = 8.5 Hz, 2H), 7.24 (d, J = 9.5 Hz, 2H), 6.82 (br s, 1H), 2.98 (br s, 1H), 2.41 — 2.25 (m, 1H), 1.70 — 1.39 (m, 2H); HRMS—ESI (m/z) [M]+ calcd for C26H19F5NsOS, 563.122; found, 563.1217. 1-(2-{4-[1-(4-Trifluoromethoxyphenyl)-1H—[1,2,4]triazolyl]phenyl}-cyclopropyl)-3— (2,4,6-trimethylphenyl)thiourea (Compound 9) The product was isolated as a white foam (55.0 mg, 78%): IR vmX 3373, 3205 (br), 3025, 2922, 1616, 1517, 1492, 1262, 1221, 1166, 986, 910, 852, 731 an]; 1H NMR (300 MHz, CDC13) 5 8.54 (s, 1H), 8.09 (d, J = 7.8 Hz, 2H), 7.78 (d, J 2 9.0 Hz, 2H), 7.37 (d, J = 8.5 Hz, 2H), 7.33 ~ 7.27 (m, 2H), 7.24 ~ 7.13 (m, 1H), 6.96 (app 8, 2H), 5.59 (s, 1H), 3.26 (br s, 1H), 2.30 (s, 3H), 2.22 (s, 6H), 2.17 — 2.06 (m, 1H), 1.42 — 1.04 (m, 2H); HRMS—ESI (m/z) [M]+ calcd for C28H26F3NsOS, 537.181; found, 12. 1-(2,4—Dimethoxyphenyl)(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triaz0l yl]phenyl}cyclopropyl)thi0urea (Compound 10) H H N N Y 1:1 FE: \sN l PCT/U82012/024217 The product was ed as a light yellow foam (58.2 mg, 69%): IR Vmax 3357, 3204 (br), 2976, 2838, 1619, 1549, 1517, 1495, 1460, 1262, 1208, 1182, 1159, 1047, 1031, 985 cm']; 1H NMR (400 MHZ, CDC13) 5 8.56 (s, 1H), 8.50-7.60 (br, 2H), 8.11 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 9.1 Hz, 2H), 7.38 (d, J: 8.9 Hz, 2H), 7.24 (d, J = 7.8 Hz, 1H), 6.40 — 6.90 (br m, 2H), 6.50 (dd, J = 8.8, 2.6 Hz, 1H), 6.44 (s, 1H), 3.79 (s, 3H), 3.62 (br s, 3H), 3.05 (br s, 1H), 2.29 (br s, 1H), 1.50 — 1.35 (m, 2H); HRMS—ESI (m/Z) [M]+ calcd for C27H34F3N503S, 555.1552; found, 555.156.

Example 7: Preparation of 3-(4-(2-isothioeyanatoeyclopropyl)phenyl)(4- oromethoxy)phenyl)-1H-1,2,4-triazole o / MNz-zs/ | \ ,N\ \- 2:om Thiophosgene (0.173 mL, 2.256 mmol) was added to a rapidly stirred mixture of CH2C12 (11 mL) and satd aq NaHC03 (11 mL) at 25 °C. The amine trifluoroacetate salt from Example 5 (1.07 g, 2.256 mmol) was then added, and stirring was continued for 10 min, during which time the solids completely dissolved. The layers were separated, the aqueous phase was extracted with , and the combined organic extracts were concentrated to afford the isothiocyanate as a yellow solid (0.86 g, 95%): mp 99—104 0C; 1H NMR (400 MHZ, CDC13) 5 8.55 (s, 1H), 8.12 (d, J : 8.4 Hz, 2H), 7.79 (d, J : 9.1 Hz, 2H), 7.38 (dd, J = 9.0, 0.7 Hz, 2H), 7.16 (d, J = 8.2 Hz, 2H), 3.05 (ddd, J = 7.5, 4.3, 3.3 Hz, 1H), 2.49 (ddd, J = .1, 7.0, 3.2 Hz, 1H), 1.56 (ddd, J = 10.0, 6.3, 4.3 Hz, 1H), 1.47 - 1.37 (m, 1H); ESIMS m/z 403 (M+H).

Example 8: Preparation of 1—(2,4eDimet..ylpheny1)-3=(2=(4=(1=(4= (trifluoromethoxy)phenyl)-1H-1,2,4-triazol-S-yl)phenyl)cyclopropyl)thiourea (Compound 11) The ocyanate from Example 7 (50 mg, 0.124 mmol) was dissolved in dioxane (0.35 mL) at 25 °C, and 2,4—dimethylaniline (16.6 mg, 0.137 mmol) was added in one portion. The mixture was d at 25 °C for 20 h and was then concentrated in vacuo. Silica gel chromatography (gradient elution with 10% to 50% to 100% EtOAc in hexanes) provided the title compound (43.3 mg, 67%) as a light yellow oil: IR vmx 3379, 3215, 3025, 1616, 1446, 1517, 1326, 1262, 1165, 1111, 1064, 986, 909, 850, 731 cm‘l; 1H NMR (400 MHz, CDC13) 6 8.55 (s, 1H), 8.10 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.46 (s, 1H), 7.38 (dd, J = 9.0, 0.7 Hz, 2H), 7.33 - 7.22 (m, 2H), 7.21 — 7.01 (m, 3H), 3.19 (br s, 1H), 2.34 (s, 3H), 2.24 (s, 3H), 2.20 (br s, 1H), 1.40 (br s, 1H), 1.34 - 1.21 (m, 2H); SI (m/z) [M]+ calcd for C27H24F3NsOS, 523.1654; found, 523.1653.

The following compounds were synthesized in accordance with Example 8.

-Dimethylphenyl)(2-(4-(1-(4-(trifluoromethoxy)phenyl)-lH—1,2,4-triaz0l yl)phenyl)cyclopropyl)thiourea (Compound 12) The reaction mixture was heated at 100 °C for 12 h, and the product was isolated as a tan foam (26.9 mg, 41%): IR vmax 3372, 3208, 3032, 2976, 2916, 2143, 1617, 1517, 1493. 1445, 1326, 1262, 1167, 1111, 1064 cm'l; 1H NMR (400 MHz, CDClg, data for major rotamer) 6 8.55 (s, 1H), 8.08 (d, J = 7.4 Hz, 2H), 7.78 (d, J = 9.0 Hz, 2H), 7.58 (br s, 1H), 7.37 (d, J = 8.3 Hz, 2H), 7.34 — 7.08 (m, 5H), 5.58 (br s, 1H), 3.26 (br, 1H), 2.28 (s, 6H), 2.11 (br s, 1H), 1.34 (s, 1H), 1.18 (s, 1H); HRMS—ESI (m/z) [M]+ calcd for C27H24F3N50S, 523.1654; found, 523.1653. 1-(2-Isopropylmethoxyphenyl)(2-(4-(1-(4-(triflu0romethoxy)phenyl)-1H-1,2,4- triazolyl)phenyl)cyclopr0pyl)thiourea (Compound 13) PCT/U52012/024217 Hem#3")?("O/)5 The on mixture was stirred at 25 °C for 4 h, and the product was isolated as a lavender solid via filtration of the reaction e (43 mg, 51%): mp 130—134 °C; 1H NMR (400 MHZ, CDC13) 5 8.54 (s, 1H), 8.10 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.44 — 7.34 (m, 3H), 7.28 (d, J = 7.9 Hz, 2H), 7.21 — 7.10 (m, 1H), 6.89 (d, J = 2.6 Hz, 1H), 6.78 (dd, J = 8.6, 2.9 Hz, 1H), 5.78 (br, 1H), 3.83 (s, 3H), 3.21 (br s, 1H), 3.14 — 3.03 (m, 1H), 2.16 (br 3,1H), 1.42 — 1.32 (m, 1H), 1.30 — 1.17 (m, 1H), 1.20 (d, J = 6.9 Hz, 3H), 1.19 (d, J = 6.9 Hz, 3H); HRMS—ESI (m/z) [M]+ calcd for C29H28F3N5028, 567.1916; found, 567.1928. 1-(6—Methoxy-2,4—dimethylpyridinyl)(2-(4-(1-(4-(trifluoromethoxy)—phenyl)—1H- 1,2,4-triazolyl)phenyl)cyclopropyl)thiourea (Compound 14) VGANTNH / N l O ,N S \ / F‘7< QN \ O F \sN The reaction mixture was stirred for 20 h at 25 OC, and the product was isolated as an off-white solid (59.6 mg, 72%): mp 1824188 0C; 1H NMR (400 MHz, CDC13, e of rotamers) 8 8.54 (s, 1H), 8.10 (br d, J = 6.1 Hz, 2H), 7.78 (d, J = 9.0 Hz, 2H), 7.38 (d, J = 8.3 Hz, 2H), 7.35 — 7.05 (m, 4H), 6.51 (br s, 1H), 5.57 (br s, 0.5H), 3.91 (s, 3H), 3.48 - 3.21 (m, 0.5H), 2.93 (dd, J = 8.6, 5.1 Hz, 0.5H), 2.39 (br s, 3H), 2.21 (br s, 3H), 2.12 (br, 0.5H), 1.64 — 1.46 (br, 1H), 1.43 — 1.32 (br, 0.5H), 1.25 — 1.10 (br, 0.5H); HRMS—ESI (m/z) [M]+ calcd for C27H25F3N6023, 12; found, 554.1727.

Example 9: Preparation of (Z)-(N'-(2,6-dimethylphenyl)-N-(2-(4-(1-(4- (trifluoromethoxy)phenyl)-1H-1,2,4-triazolyl)phenyl)cyclopropyl)- carbamimidoylthio)methyl isobutyrate (Compound 15) PCT/U82012/024217 To a solution of 1—(2,6-dimethylphenyl)—3-(2-(4-(1-(4-(t1ifluoromethoxy)—pheny1)—1H- 1,2,4—triazolyl)pheny1)cyclopropyl)thiourea (75 mg, 0.143 mmol) in chloroform (CHClg; 0.72 mL) was added chloromethyl isobutyrate (31.1 mg, 0.172 mmol). The mixture was heated at 100 0C for 1 h. The mixture was cooled to 25 °C, and the residue was purified by silica gel chromatography (EtOAc—hexanes gradient) to afford the title compound (17.3 mg, 19%) as a yellow oil: IR vmax 3332 (br), 3124, 2976, 2939, 1739, 1631, 1590, 1518, 1264, 1171, 986 cm"1; 1H NMR (400 MHz, CDC13) 8 8.54 (s, 1H), 8.09 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.37 (d, J = 8.3 Hz, 2H), 7.20 (d, J = 7.2 Hz, 2H), 7.02 (d, J = 7.5 Hz, 2H), 6.88 (t, J = 7.5 HZ, 1H), 5.65 (br S, 2H), 2.88 (br s, 1H), 2.68 — 2.52 (m, 1H), 2.10 (s, 6H), 1.82 — 1.46 (m, 2H), 1.46 —— 1.22 (m, 2H), 1.22 — 1.18 (m, 6H); ESIMS m/z 624 (M+H).

The following compound was sized in accordance with Example 9.

(Z)-(N'-Mesityl—N-(2-(4—(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4—triazol yl)phenyl)cyclopropyl)carbamimidoylthi0)methyl isobutyrate (Compound 16) OON'N‘YQ/Qrgr/dH /N F1 \fiN CID The product was isolated as a h-brown foam (48.3 mg, 20%): IR vmax 2974, 2921, 1739, 1612, 1515, 1298, 1205, 1163, 1053, 1025, 1006, 985, 852, 818, 755 cm'lg 1H NMR (600 MHz, DMSO—ds, 100 °C) 5 9.22 (s, 1H), 8.03 (d, J = 9.0 Hz, 2H), 7.99 (d, J = 8.2 Hz, 2H), 7.55 (d, J = 8.9 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 6.78 (s, 2H), 5.55 (s, 2H), 2.60 — 2.52 (m, 1H), 2.26 - 2.12 (m, 1H), 2.18 (s, 3H), 2.04 (s, 6H), 1.55 — 1.34 (m, 1H), 1.32—1.22 (m, 1H), 1.13 (d, J = 7.0 Hz, 3H), 1.12 (d, J = 7.0 Hz, 3H); ESIMS m/z 638 (M+H).

WO 09292 e 10: tert-Butyl 2-(4-(1-(4-(trifluorometh0xy)phenyl)-1H-1,2,4-triazol yl)phenyl)-cyclopropylcarbamate (Compound 17) 1-(4-trif1uoromethoxyphenyl)—lH-[l,2,4]triazol yl]phenyl}cyclopropanecarbonyl azide (0.301 g, 0.727 mmol) was slurried in PhCH3 (2.0 mL). tert-Butyl alcohol (t-BuOH; 0.250 mL, 2.64 mmol) was added, and the resulting mixture was heated at 90 °C for 24 h. During this time the slurry became homogenous to give a yellow solution. The mixture was cooled to 25 °C , and an off—white precipitate was Al‘nalwflfl tA ERMA rm UUDUI VW L 1 111. rue slurry was diluted with s (3 mL) and filtered on a Buchner funnel to afford the title compound (0.252 g, 75%) as an off-white solid. The filtrate was concentrated in vacuo and purified by silica gel chromatography (gradient elution with 15% to 40% to 80% EtOAc in hexanes) to afford additional product (0.0154 g, 5%): mp 169—172 °C; 1H NMR (300 MHz, CDC13) 5 8.54 (s, 1H), 8.07 (d, J : 8.1 Hz, 2H), 7.78 (d, J = 8.9 Hz, 2H), 7.37 (d, J = 8.6 Hz, 2H), 7.21 (d, J: 8.1 Hz, 2H), 4.91 (s, J = 0.9 Hz, 1H), 2.86—2.72 (m, 1H), 2.15-2.03 (m, 1H), 1.46 (s, 9H), 1.29—1.15 (m, 2H); ESIMS m/z 461 (M+H).

The ing compounds were synthesized in accordance with Example 10.

Methyl 2-(4-(1-(4-(triflu0r0methoxy)phenyl)-1H-1,2,4-triazolyl)phenyl)cyclopropyl- carbamate (Compound 18) H o Pg:OQN-"YQ/Q I\sN The product was isolated as an off-white solid (43.6 mg, 74%): mp 227—2285 °C; 1H NMR (400 MHz, DMSO-ds) 5 9.38 (s, 1H), 8.06 (d, J = 9.0 Hz, 2H), 7.99 (d, J = 8.2 Hz, 2H), 7.61 (d, J = 8.6 Hz, 2H), 7.24 (d, J = 8.3 Hz, 2H), 3.54 (s, 3H), 2.82 — 2.38 (m, 1H), PCT/U82012/024217 2.00 (td, J = 7.7, 2.5 Hz, 1H), 1.26 — 1.13 (m, 2H); HRMS—ESI (m/z) [M]Jr calcd for C20H17F3N403, 418.125; found, 418.1252. ylethyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazolyl)phenyl)- cyclopropylcarbamate (Compound 19) FflOQNi:whoO 6 The product was purified by silica gel chromatography (EtOAc~hexanes gradient) and isolated as a light yellow solid (73.7 mg, 66%): mp l25-l37 °C; 1H NMR (400 MHz, CDC13, 1:1 dr) 6 8.55 (s, 1H), 8.08 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.44 — 7.12 (m, 9H), .85 (q, J : 6.6 Hz, 1H), 5.08 (s, 1H), 2.87 A 2.77 (m, 1H), 2.20 — 2.05 (m, 1H), 1.56 (diastereomer A, d, J = 4.7 Hz, 1.5 H), 1.54 (diastereomer B, d, J = 4.7 Hz, 1.5 H), 1.41 ~ 1.15 (m, 2H); ESIMS m/z 510 . 1-(Pyridinyl)ethyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)-lH-l,2,4-triazol-3—yl)phenyl)— cyclopropylcarbamate (Compound 20) FflOONT/J‘536W)O 6‘ The product was ed by silica gel chromatography (EtOAc—hexanes gradient) and isolated as a light yellow solid (83.6 mg, 73%). mp 122-130 °C. 1H NMR (400 MHz, CDC13, 3:2 dr, data for major diastereomer) 5 8.59 (d, J = 3.4 Hz, 1H), 8.55 (s, 1H), 8.08 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 8.9 Hz, 2H), 7.67 (s, 1H), 7.43 ~ 7.35 (m, 2H), 7.35 — 7.29 (m, 1H), 7.25 — 7.13 (m, 3H), 5.88 (q, J = 6.6 Hz, 1H), 5.22 (br s, 1H), 2.84 (br s, 1H), 2.28 — 2.06 (m, 1H), 1.61 (d, J = 6.2 Hz, 3H), 1.40 —1.15(m, 2H); ESIMS m/z 511 (M+H).

Example 1 1: Phenyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol yl)phenyl)cyclopropyl-carbamate (Compound 21) WO 09292 PCT/U52012/024217 2—{4—[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3— yl]pheny1}cyclopropanecarbonyl azide (75 mg, 0.18 mmol, 1.0 equiv) was slurried in PhCH3 (0.52 mL, 0.35 M). Phenol (18.7 mg, 0.199 mmol, 1.1 equiv) was added, and the resulting mixture was heated at 100 °C for 2 h. During this time the slurry homogenized to give a yellow solution. The mixture was then cooled to 25 °C and Et3N (32.8 uL, 0.235 mmol, 1.3 equiv) was added. An off-white precipitate was observed to form. The mixture was diluted with 20% EtOAc in s, and the product was collected by vacuum filtration to afford the title compoqu (62.9 mg, 72%) as an off—white solid: mp 171—173 "C; 1H NMR (400 MHZ, CDC13) 5 8.54 (s, 1H), 8.09 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.44 — 7.31 (m, 4H), 7.28 (d, J = 7.7 Hz, 2H), 7.21 (t, J = 7.4 Hz, 111), 7.15 (d, J = 7.9 Hz, 2H), 5.42 (s, 1H), 2.90 (s, 1H), 2.27 (ddd, J = 9.6, 6.6, 3.2 Hz, 1H), 1.27 — 1.04 (m, 2H); ESIMS m/z 480 (M+H).

The ing compounds were synthesized in accordance with Example 11. 4—Fluor0methylphenyl 2—(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazolyl)- phenyl)cyclopropylcarbamate (Compound 22) N o %OQ‘ Ny/QA/ EDI/flN'\ F FFF \sN The product was isolated as an off-white solid (58.7 mg, 63%): mp 172—175 °C; 1H NMR (400 MHz, CDC13) 5 8.55 (s, 1H), 8.09 (d, J = 8.3 Hz, 2H), 7.78 (d, J = 9.0 Hz, 2H), 7.44 — 7.35 (m, 2H), 7.35 — 7.21 (m, 2H), 7.04 (dd, J = 8.1, 5.0 Hz, 1H), 6.95 — 6.81 (m, 2H), .46 (s, 1H), 3.16 —2.67 (m, 1H), 2.28 (dd, J = 6.4, 3.2 Hz, 1H), 2.21 (s, 3H), 1.46 —— 1.23 (m, 2H); ESIMS m/z 513 (M+H). 2-Cyclopentylphenyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazolyl)phenyl)- ropylcarbamate (Compound 23) F7630"?do")?O FF \IN The product was ed by silica gel chromatography (EtOAc—hexanes gradient) and isolated as a white solid (64.9 mg, 63%): mp 9 °C; 1H NMR (400 MHZ, CDC13, data for major rotamer) 5 8.54 (s, 1H), 8.09 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.41 — 7.34 (m, 2H), 7.33 4 7.27 (m, 3H), 7.22 — 7.14 (m, 2H), 7.11 — 7.04 (m, 1H), 5.44 (br s, 1H), 3.26 — 3.10 (m, 1H), 2.91 (br s, 1H), 2.26 (ddd, J = 9.5, 6.6, 3.2 Hz, 1H), 2.01 (brs, 2H), 1.79 (br s, 2H), 1.72 — 1.53 (m, 4H), 1.41 — 1.28 (m, 2H); ESIMS m/z: 550 (M+H). 2-tert-Butylphenyl 2-(4-(1-(4-(trifluorometh0xy)phenyl)-lH-l,2,4-triazolyl)phenyl)- cyclopropylcarbamate (Compound 24) 0 .N\53780150 127: ONE".

The product was purified by silica gel chromatography (EtOAc—hexanes gradient) and isolated as a white solid (70.5 mg, 67%): mp l43.5—145.0 "C; 1H NMR (400 MHz, CDC13, data for major rotamer) 5 8.54 (s, 1H), 8.09 (d, J = 8.2 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.42 — 7.36 (m, 3H), 7.29 (d, J = 7.7 Hz, 2H), 7.23 (td, J = 7.6, 1.6 Hz, 1H), 7.15 (td, J = 7.6, 1.5 Hz, 1H), 7.09 (d, J = 7.6 Hz, 1H), 5.46 (s, 1H), 2.93 (s, 1H), 2.32 — 2.21 (m, 1H), 1.42 — 1.28 (m, 2H), 1.39 (s, 9H); ESIMS m/z 538 (M+H). 2-(Trifluoromethyl)phenyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3—yl)- phenyl)cyclopropylcarbamate (Compound 25) .3@WQKLH" The product was isolated as an off-white solid (66.9 mg, 46%). The filtrate was concentrated in vacuo and purified by silica gel tography (EtOAc—hexanes gradient) to afford additional product (26.2 mg, 20%): mp 183~187 °C; 1H NMR (400 MHz, CDCl3, data for major rotamer) 5 8.54 (s, 1H), 8.09 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.65 (d, J = 7.7 Hz, 1H),7.614 7.53 (m, 1H), 7.45 — 7.06 (m, 6H), 5.59 (s, 1H), 3.03 — 2.80 (m, 1H), 2.37 —2.21 (m, 1H), 1.43 — 1.29 (m, 2H); ESIMS m/z 549 (M+H).

Examnle 12; M . ity! 7n_1 n: o A_h-:nunl_’1_ .. . -v..,-- 2_(4_(1_{4_(§l~i"nIfll’nmofl'lnvur\n .1:"VA uvaj IFun [I‘Lll 1,14," Ellabvl J y!)phenyl)cyclopropyl-carbamate (Compound 26) Step 1. 2,4,6—trimethylphenol (272 mg, 2.00 mmol, 1.0 equiv) was dissolved in CH2C12 (3.33 mL, 0.3 M) under en (N2) and cooled to 0 °C. Triphosgene (208 mg, 0.700 mmol, 0.35 equiv) was dissolved in CHZCIZ (3.33 mL) and added dropwise, ed by pyridine (0.162 mL, 2.00 mmol, 1.0 equiv). The mixture was allowed to warm to 25 °C over 18 h, at which point the reaction was quenched with 10 mL 1 normal (N) hydrochloric acid (HCl; aq) and extracted with EtOAc. The organic layer was washed with l N HCl (aq), dried over NaZSO4, and concentrated to give mesityl chloroformate as an oil (88% purity by 1H NMR spectroscopy). The formate so prepared was used directly in the next step without further purification.

Step 2. 2—{4—[1-(4-trifiuoromethoxyphenyl)-1H-[1,2,4Jtriazol y1]pheny1]cyclopropylamine (46.0 mg, 0.13 mmol, 1.0 equiv) was dissolved in CH2C12 (0.55 mL) under N2. 4-Dimethylaminopyridine (DMAP; 0.8 mg, 0.006 mmol, 0.05 equiv) and Eth (27 uL, 0.19 mmol, 1.5 equiv) were added, followed by mesityl formate prepared above (33 mg, 0.17 mmol, 1.2 equiv). The reaction was stirred for 5 min and was then 2012/024217 quenched with NaHC03 (aq). The layers were separated, and the aqueous layer was extracted twice more with CH2C12. The combined organic extracts were trated, and the crude product was purified by silica gel chromatography (EtOAc—hexanes gradient) to afford the title compound as a white solid (53.0 mg, 79%): mp 199—202 °C; IH NMR (400 MHz, CDC13, data for major rotamer) 5 8.54 (s, 1H), 8.08 (d, J = 8.3 Hz, 2H), 7.78 (d, J = 9.0 Hz, 2H), 7.39 (d, J = 0.7 Hz, 2H), 7.32 — 7.21 (m, 2H), 6.86 (s, 2H), 5.71 — 5.36 (m, 0.7H), 5.22 — 4.82 (m, 0.3H), 3.09 — 2.81 (m, 1H), 2.26 (s, 4H), 2.17 (s, 6H), 1.43 — 1.26 (m, 2H); ESIMS m/z 523 (M+H).

The following compounds were synthesized in ance with Example 12. 4-Methoxyphenyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)—1H~1,2,4—triazolyl)phenyl)- cyclopropylcarbamate (Compound 27) rlhe product was isolated as a white solid (60.0 mg, 66%): mp 163—164 0C; 1H NMR (400 MHZ, CDC13) 5 8.54 (S, 1H), 8.09 (d, J = 8.3 HZ, 2H), 7.79 (d, J = 9.0 HZ, 2H), 7.38 (dd, J = 9.0, 0.7 Hz, 2H), 7.29 (d, J = 7.9 Hz, 2H), 7.06 (d, J = 8.9 Hz, 2H), 6.88 (d, J = 9.1 Hz, 2H), 5.35 (s, 1H), 3.80 (s, 3H), 2.89 (s, 1H), 2.27 (ddd, J = 9.6, 6.6, 3.2 Hz, 1H), 1.40 — 1.26 (m, 2H); ESIMS m/z 511 (M+H), 509 (M-H). 2,6-Dichlorophenyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)-lH-l,2,4-triazolyl)phenyl)- cyclopropylcarbamate (Compound 28) The product was isolated as a white solid (26.1 mg, 33%): mp 160—162 °C; 1H NMR (400 MHz, coca, data for major rotamer) a 8.54 (s, 1H), 8.09 (d, J = 8.3 Hz, 2H), 7.79 (d, J PCTfU52012/024217 = 9.0 Hz, 2H), 7.38 (d, J = 8.1 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 7.13 (t, J = 8.1Hz, 1H), 5.62 (s, 1H), 2.94 (s, 1H), 2.31 (S, 1H), 1.46 — 1.28 (m, 2H); ESIMS m/z 550 (M+H). 2-Isopropylphenyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)-lH-l,2,4-triazolyl)phenyl)- cyclopropylcarbamate (Compound 29) The product was isolated as 1 a. white solid (52.8 m0 6397 : p 1864 88 °C‘, u n . \ (400 MHz, CDC13, data for major rotamer) 8 8.54 (s, 1H), 8.09 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 744 ~ 7.34 (m, 2H), 7.33 —7.26 (m, 2H), 7.23 ~ 7.16 (m, 2H), 7.13 — 7.05 (m, 1H), 5.43 (br s, 1H), 3.19 2 3.07 (m, 1H), 2.91 (br s, 1H), 2.27 (ddd, J = 9.5, 6.7, 3.1 Hz, 1H), 1.42 — 1.33 (m, 2H), 1.22 (br d, J = 6.1 Hz, 3H); ESIMS m/z 523 (M+H).

Example 13: 1—Mesityl(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-S-yl)phenyl)- cyclopropyl)urea (Compound 30) H H o / 'Nfi/Q/Q | O \ F'7\( QN¥\’ F "N F 2- {4-[1-(4-trifluoromethoxyphenyl)—lH-[1,2,4]tfiazolyllpheny1}Cyclopropylamine oacetate salt (58 mg, 0.12 mmol, 1.0 equiv) was dissolved in THF (0.60 mL, 0.20 M) at 25 °C under N2. The isocyanate (22 mg, 0.13 mmol, 1.1 equiv) was added in one portion, followed by Et3N (19 pL, 0.13 mmol, 1.1 . The mixture was d at 25 °C for l h, and then methyl alcohol—water (1:1) was added. The precipitate was collected by vacuum filtration and rinsed with methyl alcohol to afford the title compound as a white solid (41.3 mg, 65%): mp 254—256 °C; 1H NMR (300 MHZ, DMSO-ds) 8 9.35 (s, 1H), 8.04 (d, J = 9.0 PCT/U52012/024217 Hz, 2H), 7.97 (d, J = 8.3 Hz, 2H), 7.59 (d, J = 8.5 Hz, 2H), 7.32 (s, 1H), 7.22 (d, J = 8.3 Hz, 2H), 6.82 (s, 2H), 6.48 (s, 1H), 2.87 — 2.73 (m, 1H), 2.19 (s, 3H), 2.10 (s, 6H), 2.06 - 1.95 (m, 1H), 1.28 — 1.11 (m, 2H); ESIMS m/z 522 (M+H).

The following compound was synthesized in accordance with e 13, 1-(2,6-Dichlorophenyl)(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol yl)phenyl)cyclopropyl)urea (Compound 31) O WO Fag \Q‘NBN CI The product was isolated as a white solid (44.6 mg, 80%): mp 215.5—2175 °C; 1H NMR (300 MHz, DMSO—ds) 5 9.35 (s, 1H), 8.05 (d, J = 9.1 Hz, 2H), 7.98 (app (1, J = 8.1 Hz, 3H), 7.61 (s, 2H), 7.47 (d, J = 8.0 Hz, 2H), 7.32 — 7.22 (m, 3H), 6.87 (d, J = 3.2 Hz, 1H), 2.88 — 2.66 (m, 1H), 2.13 — 1.96 (m, 1H), 1.31. — 1.14 (m, 2H); ESIMS m/z 549 (M+H), 547 (M—H).

Example 14: Preparation of 1,3-bis(2-(4-(l-(4-(trifluoromethoxy)phenyl)-1H—1,2,4- triazolyl)phenyl)cyclopropyl)urea (Compound 32) H H Hoot 1 Wing 12N=\N N O ‘N\ O F F'7( QN O F \=N Step 2 in Example 3 was carried out using t-butyl alcohol as solvent instead of PhCH3. The e was heated at 90 °C for 3 h, cooled to 25 °C, and diluted with 1:1 t-butyl alcohol—water. The mixture was then filtered to afford the title compound (202.2 mg, 93%) as an ite solid. The intended product (the t—butyl carbamate) was not isolated: mp 232— 234 °C dec; 1H NMR (300 MHz, DMSO-dfi) 6 9.37 (s, 2H), 8.06 (d, J = 9.0 Hz, 4H), 7.99 (d, J = 8.2 Hz, 4H), 7.61 (d, J = 8.8 Hz, 4H), 7.23 (d, J: 8.3 Hz, 4H), 6.39 (d, J = 3.0 Hz, 2H), 2.89 — 2.66 (m, 2H), 2.12 — 1.89 (m, 2H), 1.25 — 1.07 (m, 4H); ESIMS m/z 747 (M+H).

Example 15: AYS ON BEET ARMYWORM ) AND CORN EARWORM ) BAW has few effective parasites, diseases, or predators to lower its population. BAW infests many weeds, trees, grasses, legumes, and field crops. In various places, it is of economic concern upon asparagus, , corn, soybeans, tobacco, alfalfa, sugar beets, peppers, tomatoes, potatoes, onions, peas, sunflowers, and citrus, among other plants. CEW is known to attack corn and tomatoes, but it also attacks artichoke, gus, cabbage, cantaloupe, collards, cowpeas, cucumbers, eggplant, lettuce, lima beans, melon, okra, peas, peppers, potatoes, pumpkin, snap beans, spinach, squash, sweet potatoes, and elon, among other plants. CEW is also known to be resistant to certain insecticides. Consequently, e of the above factors control of these pests is important. Furthermore, molecules that control these pests are useful in controlling other pests.

"Mam molecules d H‘; An "ma" "m." t aLCu against un vv"Rt/VJ nnnznat DAY" ,..,,1 flvxxr VVLLuALL ; n u d ' in uuS uuCuurcut WC1 auu pnvv using procedures described in the following examples. In the ing of the results, the "BAW & CEW Rating Table" was used (See Table Section).

BIOASSAYS ()N BAW (Spodoptera exigua) Bioassays on BAW were conducted using a l28—well diet tray assay. one to five second instar BAW larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 rig/cm2 of the test compound (dissolved in 50 uL of 90:10 acetone-water mixture) had been applied (to each of eight wells) and then d to dry. Trays were covered with a clear self—adhesive cover, and held at 25 0C, 14:10 light—dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then averaged. The results are indicated in the table NU1 entitled "Table: Bio Results" (See Table Section).

BIOASSAYS 0N CEW (Helicoverpa zea) Bioassays on CEW were conducted using a 128—well diet tray assay. one to five second instar CEW larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 pg /cm2 of the test compound (dissolved in 50 uL of 90:10 e—water mixture) had been applied (to each of eight wells) and then allowed to dry. Trays were covered with a clear self-adhesive cover, and held at 25 °C, 14:10 dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then averaged. The results are indicated in the table entitled "Table: Bio Results" (See Table Section).

Example16: BIOASSAYS 0N GREEN PEACH APHID ("GPA") (Myzus persicae).

GPA is the most significant aphid pest of peach trees, causing decreased growth, shriveling of the leaves, and the death of various tissues. It is also hazardous because it acts as a vector for the ort of plant viruses, such as potato virus Y and potato leafroll virus to members of the nightshade/potato family Solanaceae, and various mosaic viruses to many other food crops. GPA attacks such plants as broccoli, burdock, cabbage, , cauliflower, daikon, nt, green beans, lettuce, macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress, and zucchini, among other plants. GPA also s many ornamental crops such as carnation, Chrysanthemum, flowering white cabbage, poinsettia, and roses.

GPA has developed resistance to many pesticides.

Certain molecules sed in this document were tested t GPA using procedures described in the following example. In the reporting of the results, the "GPA Rating Table" was used (See Table Section).

Cabbage seedlings grown in 3—inch pots, with 2-3 small (3—5 cm) true leaves, were used as test substrate. The seedlings were ed with 20-50 GPA (Wingless adult and nymph stages) one day prior to chemical application. Four pots with individual seedlings 2O were used for each treatment. Test compounds (2 mg) were dissolved in 2 mL of acetone/methanol (1:1) solvent, forming stock solutions of 1000 ppm test compound. The stock ons were diluted 5X with 0.025% Tween 20 in H20 to obtain the solution at 200 ppm test compound. A hand—held aspirator-type sprayer was used for spraying a solution to both sides of cabbage leaves until runoff. Reference plants (solvent check) were sprayed with the diluent only ning 20% by volume of acetone/methanol (1:1) solvent. Treated plants were held in a holding room for three days at approximately 25 °C and ambient ve humidity (RH) prior to grading. Evaluation was ted by counting the number of live aphids per plant under a microscope. Percent Control was measured by using Abbott’s correction formula (W.S. , "A Method of Computing the Effectiveness of an Insecticide" J. Econ. Entomol. 18 (1925), pp.265—267) as follows.

Corrected % Control: 100 * (X - Y) / X where X = No. of live aphids on solvent check plants and Y = No. of live aphids on treated plants PCT/U32012/024217 The results are indicated in the table entitled "Table: Bio Results" (See Table PESTICIDALLY ACCEPTABLE ACID ADDITION SALTS, SALT DERIVATIVES, ES, ESTER DERIVATIVES, POLYMORPHS, ISOTOPES AND RADIONUCLIDES les of Formula One, Two, Three, and Four may be formulated into pesticidally acceptable acid on salts. By way of a non-limiting example, an amine function can form salts with hydrochloric, hydrobromic, sulfuric, phosphoric, acetic, benzoic, citric, malonic, salicylic, malic, fumaric, , succinic, tartaric, lactic, gluconic, ascorbic, maleic, aspartic, benzenesulfonic, methanesulfonic, ethanesulfonic, hydroxymethanesulfonic, and hydroxyethanesulfonic acids. Additionally, by way of a non—limiting example, an acid function can form salts including those derived from alkali or ne earth metals and those derived from ammonia and amines. Examples of preferred cations include sodium, potassium, and magnesium.

Molecules of Formula One, Two, Three, and Four may be formulated into salt derivatives. By way of a non-limiting e, a salt tive can be prepared by contacting a free base with a sufficient amount of the desired acid to produce a salt. A free base may be regenerated by treating the salt with a suitable dilute aqueous base solution such as dilute aqueous sodium hydroxide (NaOH), potassium carbonate, ammonia, and sodium bicarbonate. As an example, in many cases, a pesticide, such as 2,4-D, is made more water— soluble by converting it to its dimethylamine salt.

Molecules of Formula One, Two, Three, and Four may be formulated into stable complexes with a solvent, such that the complex remains intact after the non-complexed solvent is removed. These xes are often referred to as "solvates." However, it is particularly desirable to form stable hydrates with water as the solvent.

Molecules of Formula One, Two, Three, and Four may be made into ester tives.

These ester derivatives can then be applied in the same manner as the invention disclosed in this document is applied.

Molecules of a One, Two, Three, and Four may be made as s crystal polymorphs. Polymorphism is important in the development of agrochemicals since different crystal polymorphs or structures of the same molecule can have vastly different physical properties and ical performances.

Molecules of Formula One, Two, Three, and Four may be made with different isotopes. Of particular importance are molecules having 2H (also known as deuterium) in place of 1H. les of Formula One, Two, Three, and Four may be made with different radionuclides. Of particular importance are molecules having 14C.

STEREOISOMERS Molecules of Formula One, Two, Three, and Four may exist as one or more stereoisomers. Thus, certain molecules can be produced as racemic mixtures. It will be appreciated by those skilled in the art that one stereoisomer may be more active than the other stereoisomers. Individual isomers may be ed by known selective synthetic procedures, by conventional synthetic procedures using resolved starting materials, or by conventional resolution procedures.

INSECTICIDES Molecules of Formula One, Two, Three, and Four may also be used in combination (such as, in a compositional mixture, or a simultaneous or tial application) with one or more of the following insecticides — 1,2—dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, cypermethn'n, alpha—ecdysone, endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, ine, thion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos~methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, yfluthrin, beta-cypermethn'n, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, hos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, BYI-02960, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, yl, carbofuran, carbon disulfide, carbon hloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, econe, chlordimeform, chlordimeforrn hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, n II, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, hos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, PCT/U82012/024217 cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothfin, ethrin, cyphenole'n, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion, ion-O, demephion—S, demeton, demeton-methyl, demeton-O, demeton-O- methyl, demeton-S, demeton-S-methyl, demeton—S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, fenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, oate, dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d- limonene, DNOC, DNOC—ammonium, DNOC-potassium, DNOC—sodium, doramectin, ecdysterone, emamectin, emamectin te, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepalléthrine, esfenvalerate, etaphos, ethiofencarb, ethion, ole, ethoate-methyl, ophos, ethyl formate, ethyl-DDD, e‘iiylen" ide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthn'n, fenitrothion, fenobucarb, fenoxacrim, carb, fenpirithfin, fenpropathrin, fensulfothion, on, fenthion—ethyl, erate, fipronil, flonicamid, flubendiamide (additionally resolved s thereof), flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, nate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospiratc, fosthietan, zide, furathiocarb, furethn'n, gamma—cyhalothrin, gamma—HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, ethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidaclopn’d, imiprothrin, carb, thane, IPSP, isazofos, isobenzan, isocarbophos, isodn’n, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone HI, kelevan, kinoprene, lambda— cyhalothrin, lead arsenate, ctin, leptophos, lindane, lirimfos, lufenuron, lythidathjon, malat‘nion, malonoben, mazidox, mecarbam, mecarphon, menazon, meperfluthrin, folan, mercurous de, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methonyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene Chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, otophos, monomehypo, monosultap, thion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, PCT/U52012/024217 oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene, ion, parathion-methyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, lan, phosmet, phosnichlor, phosphamidon, phosphine, , phoxim—methyl, pirimetaphos, pirimicarb, pin'miphos-ethyl, pirimiphos-methyl, potassium arsenite, ium thiocyanate, T, prallethrin, precocene I, precocene II, precocene III, ophos, profenofos, alin, profluthrin, promacyl, arb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pymetrozine, ofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethn'ns, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos—methyl, quinothion, rafoxanide, resmethrin, ne, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron—sodium, sulfluramid, sulfotep, sulfoxaflor, yl fluoride, sulpronS, tau—fluvalinate, arb, ’l‘DE, tebufenozide, tebufenpyrad, rimfos, teflubenzuron, tefluthn'n, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiaclopn'd, thiamethoxam, fos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap—disodium, ltap—monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, ermethrin, triarathene, triazamate, niazophos, trichlorfon, tn'chlormetaphos—3, trichloronat, tn'fenofos, triflumuxon, tn'methacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta~cypermethrin, and zolaprofos (collectively these commonly named insecticides are defined as the "Insecticide Group").

ACARICIDES Molecules of Formula One, Two, Three, and Four may also be used in combination (such as, in a compositional mixture, or a aneous or sequential application) with one or more of the following acaricides - nocyl, amidoflumet, arsenous oxide, azobenzene, azocyclotin, benomyl, benoxafos, benzoximate, benzyl benzoate, bifenazate, binapacryl, bromopropylate, chinomethionat, enside, chlorfenethol, chlorfenson, chlorfensulphide, chlorobenzilate, chloromebuform, chloromethiuron, chloropIOpylate, clofentezine, cyenopyrafen, cyflumetofen, cyhexatin, dichlofluanid, dicofol, dienochlor, diflovidazin, dinobuton, dinocap, dinocap-4, dinocap—6, dinocton, dinopenton, dinosulfon, dinoterbon, diphenyl sulfone, disulfiram, dofenapyn, etoxazole, fenazaquin, fenbutatin oxide, 2012/024217 fenothiocarb, oximate, fenson, fentn'fanil, fluacrypyrim, fluazuron, flubenzimine, fluenetil, flumethrin, fluorbenside, hexythiazox, mesulfen, MNAF, nikkomycins, proclonol, propargite, ofos, iclofen, sulfiram, sulfur, tetradifon, tetranactin, tetrasul, and inox (collectively these commonly named acaricides are defined as the "Acaricide NEMATICIDES Molecules of Formula One, Two, Three, and Four may also be used in combination (such as, in a compositional mixture, or a simultaneous or sequential application) with one or more of the following nematicides - 1,3-dichloropropene, benclothiaz, dazomet, dazomet— sodium, DBCP, DCIP, diamidafos, fluensulfone, fosthiazate, furfural, imicyafos, ofos, isazofos, metam, metam-ammonium, metam—potassium, metam—sodium, phosphocarb, and trio—lazi-i (collectively these commonly named nematicides are defined as the "Nematicide Group") FUNGICIDES Molecules of Formula One, Two, Three, and Four may also be used in combination (such as, in a compositional mixture, or a simultaneous or sequential ation) with one or more of the ing fungicides - (3—ethoxypropyl)mercury bromide, 2— methoxyethylmercury chloride, 2—phenylphenol, oxyquinoline sulfate, 8— phenylmercurioxyquinoline, acibenzolar, zolar—S—methyl, acypetacs, acypetacs—copper, acypetacs—zinc, aldimorph, allyl alcohol, ametoctradin, amisulbrom, ampropylfos, anilazine, aureofungin, azaconazole, azithiram, azoxystrobin, barium lfide, benalaxyl, benalaxyl- M, nil, benomyl, benquinox, bentaluron, benthiavalicarb, benthiavalicarb-isopropyl, benzalkonium chloride, benzamacril, benzamacril-isobutyl, benzamorf, ydroxamic acid, bethoxazin, binapacryl, yl, bitertanol, bithionol, bixafen, blasticidin—S, Bordeaux mixture, boscalid, bromuconazole, bupin'mate, Burgundy mixture, buthiobate, butylamine, calcium polysulfide, captafol, captan, carbamorph, carbendazim, carboxin, carpropamid, carvone, Cheshunt mixture, Chinomethionat, chlobenthiazone, chloraniformethan, chloranil, enazole, chlorodinitronaphthalene, chloroneb, chloropicrin, chlorothalonil, chlorquinox, chlozolinate, climbazole, clotrimazole, copper e, copper carbonate, basic, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper silicate, copper sulfate, copper zinc chromate, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, 2012/024217 cyprodinil, dazomet, dazomet-sodium, DBCP, rb, decafentin, dehydroacetic acid, dichlofluanid, dichlone, dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomezine, diclomezine-sodium, dicloran, fencarb, diethyl pyrocarbonate, difenoconazole, diflumetorim, dimethirimol, dimethomorph, strobin, diniconazole, diniconazole-M, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, ram, ditalimfos, dithianon, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate, dodemorph benzoate, dodicin, dodicin—sodium, dodine, drazoxolon, edifenphos, epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethylmercury 2,3-dihydroxypropyl tide, ethylmercury acetate, ethylmercury bromide, ethylmercury de, ethylmercury phosphate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, amid, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, , fentin chloride, fentin hydroxide, ferbam, ferimzone, fluazinam, onil, flumetover, flumorph, fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fiuquinconazole, flusilazole, flusulfamide, flutianil, nil, flutn'afol, fluxapyroxad, , formaldehyde, fosetyl, fosetyl—aluminium, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furconazole-cis, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene, hexaconazole, hexylthiofos, hydrargaphen, hymexazol, il, imazalil nitrate, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine trialbesilate, iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, isovaledione, kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid, mepanipyrim, il, meptyldinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, ammonium, metam—potassium, sodium, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl isothiocyanate, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, metiram, nostrobin, metrafenone, metsulfovax, milneb, myclobutanil, olin, N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin, nitrostyrene, nitrothal-isopropyl, nuan'mol, OCH, octhilinone, ofurace, orysastrobin, yl, oxine—copper, nazole, oxpoconazole fumarate, oxycarboxin, zoate, penconazole, pencycuron, penflufen, pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivative of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, phosdiphen, phthalide, picoxystrobin, piperalin, polycarbamate, polyoxins, orim, polyoxorim—zinc, potassium azide, potassium polysulfide, potassium thiocyanate, probenazole, oraz, procymidone, propamocarb, propamocarb hloride, propiconazole, eb, proquinazid, prothiocarb, prothiocarb hydrochloride, prothioconazole, pyracarbolid, pyraclostrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxychlor, pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinconazole, quinoxyfen, quintozene, rabenzazole, salicylanilide, ne, silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide, sodium hlorophenoxide, sodium polysulfide, spiroxamine, streptomycin, sulfur, sultropen, TCM'I‘B, tebuconazole, quin, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, fluor, thicyofen, thifluzamide, thiochlorfenphim, thiomersal, thiophanate, thiophanate-methyl, thioquinox, thiram, tiadinil, tioxymid, fos- , tolylfluanid, tolylmercury acetate, triadimefon, triadimenol, tn'amiphos, triarimol, ti‘iazbutil, triazoxide, tributyl‘tin oxide, tn'chlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, uniconazole-P, validamycin, valifenalate, vinclozolin, zarilamid, zinc naphthenate, zineb, ziram, zoxamide (collectively these commonly named fungicides are defined as the cide Group").

HERBICIDES Molecules of a One, Two, Three, and Four may also be used in combination (such as, in a compositional mixture, or a simultaneous or sequential application) with one or more of the following herbicides - 2,3,6—TBA, 2,3,6—TBA-dimethy1amm0nium, 2,3,6—TBA— sodium, 2,4,5—T, 2,4,5—T—2—butoxypropyl, 2,4,5—T—2—ethylhexy1, 2,4,5—T—3-butoxypropy1, 2,4,5—TB, T-butometyl, 2,4,5-T-butotyl, 2,4,5-T-buty1, 2,4,5—T-isobuty1, 2,4,5-T-isocty1, 2,4,5—T-isopropyl, 2,4,5-T-methy1, 2,4,5-T-pentyl, 2,4,5-T-sodium, 2,4,5—T- triethylammonium, 2,4,5-T-trolamine, 2,4-D, 2,4-D-2—butoxypropy1, 2,4-D-2—ethylhexyl, 2,4- D—3-butoxypropy1, 2,4-D-ammonium, , 2,4—DB-buty1, 2,4-DB-dimethylammonium, 2,4-DB-isocty1, 2,4-DB-potassium, 2,4-DB-sodium, 2,4—D-butoty1, 2,4-D-buty1, 2,4-D- lammonium, 2,4-D—dimethylammonium, 2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4—DEP, 2,4-D-ethy1, 2,4—D—heptylammonium, 2,4-D-isobutyl, 2,4-D-isocty1, 2,4- D—isopropyl, isopropy1ammonium, 2,4—D-lithium, 2,4-D—mepty1, 2,4-D-methyl, 2,4-D- octyl, 2,4—D-penty1, 2,4-D-potassium, 2,4-D—propyl, 2,4-D-sodium, 2,4-D-tefuryl, 2,4-D- tetradecylammonium, 2,4-D-triethylammonium, 2,4-D-tris(2—hydroxypropyl)ammonium, 2,4- D—trolamine, 3,4-DA, 3,4-DB, 3,4-DP, 4-CPA, 4—CPB, 4-CPP, acetochlor, acifluorfen, acifluorfen-methyl, rfen-sodium, fen, acrolein, alachlor, chlor, alloxydim, PCT/U52012/024217 dim-sodium, allyl alcohol, alorac, ameuidione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminocyclopyrachlor—methyl, aminocyclopyrachlor— potassium, aminopyralid, aminopyralid—potassium, aminopyralid-tris(2- ypropyl)ammonium, amiprofos-methyl, amitrole, ammonium sulfamate, os, anisuron, asulam, asulam—potassium, asulam—sodium, atraton, ne, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, benazolin- dimethylammonium, benazolin-ethyl, benazolin-potassium, bazone, benfluralin, benfuresate, bensulfuron, bensulfuron—methyl, bensulide, bentazone, bentazone-sodium, benzadox, ox-ammonium, benzfendizone, benzipram, icyclon, benzofenap, benzofluor, benzoylprop, benzoylprop—ethyl, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, borax, bromacil, bromacil- lithium, bromacil—sodium, bromobonil, bromobutide, bromofenoxim, bromoxynil, bromoxynil butyrate, bromoxynil heptanoate, bromoxynil octanoate, bromoxynil-potassium, brompyrazon, butachlor, butafenacil, fos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, te, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, dichlor, carbasulam, carbetamide, carboxazole, carfentrazone, carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen, mben, chloramben—ammonium, chloramben-diolamine, Chloramben-methyl, chloramben—methylammonlum, chloramben— sodium, chloranocryl, chlorazifop, chlorazifop-propargyl, chlorazine, chlorbromuron, chlorbufam, turon, chlorfenac, chlorfenac—sodium, chlorfenprop, chlorfenprop—methyl, chlorflurazole, chlorflurenol, Chlorflurenol—methyl, chloridazon, Chloximuron, chlofimuron- ethyl, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorprocarb, chlorpropham, chlorsulfuron, chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, cinidon—ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, afop-propargyl, clofop, clofop-isobutyl, clomazone, clomeprop, cloprop, xydim, clopyralid, clopyralid-methyl, clopyralid-olamine, clopyralid-potassium, clopyralid-tn‘s(2-hydroxypropyl)ammonium, cloransulam, cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, ine, cresol, ron, cyanamide, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, on, cyhalofop, cyhalofop-butyl, uat, cyperquat chloride, cyprazine, cyprazole, cypromid, daimuron, dalapon, dalapon-calcium, dalapon-magnesium, dalapon—sodium, dazomet, dazomet-sodium, delachlor, desmedipham, desmetryn, di-allate, a, dicamba—dimethylammonium, dicamba-diolamine, dicamba- isopropylammonium, dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba- sodium, dicamba—trolamine, dichlobenil, ralurea, dichlormate, dichlorprop, PCT/U52012/024217 dichlorprop-Z-ethylhexyl, dichlorprop-butotyl, dichlorprop-dimethylammonium, dichlorprop- mmonium, dichlorprop—isoctyl, dichlorprop-methyl, dichlorprop—P, dichlorprop-P— dimethylammonium, dichlorprop—potassium, dichlorprop-sodium, diclofop, diclofop—methyl, diclosulam, diethamquat, diethamquat dichloride, diethatyl, diethatyl-ethyl, difenopenten, difenopenten—ethyl, difenoxuron, difenzoquat, difenzoquat metilsulfate, diflufenican, diflufenzopyr, diflufenzopyr—sodium, dimefuron, perate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, b, b acetate, dinoseb-ammom’um, dinoseb- diolamine, dinoseb-sodium, b-trolamine, dinoterb, dinoterb e, diphacinone- sodium, diphenamid, dipropetryn, diquat, diquat dibromide, disul, disul-sodium, dithiopyr, , DMPA, DNOC, DNOC-ammonium, DNOC-potassium, DNOC—sodium, DSMA, EBEP, zine, eglinazine—ethyl, endothal, endothal—diammom'um, endothal—dipotassium, nnAnH—n‘] f]:nI\rJ¢-‘ ouuuuiai-mwuium, epIOuaz, EPTC, eron, esprocarb, ethalfiuralin, ethametsulfuron, ethametsulfuron-methyl, ethidimuron, ethiolate, ethofumesate, fen, ethoxyfen-ethyl, ethoxysulfuron, etinofen, etnipromid, etobenzanjd, EXD, fenasulam, fenoprop, fenoprop propyl, fenoprop~but0metyL fenoprop—butotyl, fenoprop—butyl, fenoprop—isoctyl, fenoprop—methyl, fenoprop-potassium, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop—P-ethyl, fenoxasulfone, fenteracol, fenthiaprop, fenthiaprop-ethyl, fentrazamide, n, fenuron TCA, ferrous sulfate, flamprop, flamprop—isopropyl, flamprop-M, p— methyl, flamprop—M—isopropyl, flamprop-M-methyl, flazasulfuron, florasuiam, fluazifop, op-butyl, fluazifOp—methyl, fluazifop-P, fluazifop—P—butyl, fluazolate, flucarbazone, flucarbazone—sodium, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flufenpyr—ethyl, flumetsulam, flumezin, flumiclorac, flumiclorac-pentyi, flumioxazin, opyn, fiuometuron, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, fluoromidine, fluoroniIIofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupropanate~sodium, flupyl'sulfuron, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet—methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, fosamine—ammonium, furyloxyfen, glufosinate, glufosinate-ammonium, glufosinate—P, glufosinate-P-ammonium, glufosinate-P— sodium, glyphosate, glyphosate—diarmnonium, glyphosate-dimethylammonium, glyphosate- isopropylammonium, glyphosate-monoammonium, glyphosate-potassium, satesesquisodium , glyphosate-tn'mesium, halosafen, lfuron, lfuron—methyl, haloxydine, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop—P, haloxyfop—P—etoty], haloxyfop-P—methyl, haloxnyp-sodium, hexachloroacetone, hexaflurate, hexazinone, PCT/U52012/024217 ethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin- ammonium, imazaquin-methyl, imazaquin-sodium, imazethapyr, imazethapyr-ammonium, ulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, iodosulfuron— -sodium, ioxynil, ioxynil octanoate, ioxynil—lithium, ioxynil-sodium, e, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, hlortole, isoxaflutole, isoxapyrifop, ilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-Z— ethylhexyl, MCPA-butotyl, MCPA-butyl, imethylammonium, MCPA-diolamine, MCPA-ethyl, sobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA- olamine, MCPA-potassium, MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB~ethyl, MCPB—methyl, MCPB-sodium, op, op—Z—ethylhexyl, mecoprop— dimethylammonium, mecoprop—diolamine, mecoprop-ethadyl, mecoprop—isoctyl, mecoprop- methyl, mecoprop—P, mecoprop—P—dimethylammonium, mecoprop—P—isobutyl, mecoprop— potassium, mecoprop—P-potassium, mecoprop-sodium, mecoprop-trolamine, medinoterb, medinoterb acetate, cet, mefluidide, mefluidide—diolamine, mefluidide—potassium, mesoprazine, mesosulfuron, mesosulfuron—methyl, mesotrione, metam, metam-ammonium, metamifop, metamitron, metam-potassium, metam-sodium, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metolachlor, metosulam, metoxuron, metn'buzin, metsulfuron, metsulfuron—methyl, molinate, monalide, monisouron, monochloroacetic acid, nuron, monuron, monuron TCA, morfamquat, morfamquat dichloride, MSMA, naproanilide, amide, naptalam, naptalam-sodium, n, nicosulfuron, nipyraclofen, nitralin, nitrofen, uorfen, norflurazon, noruron, OCH, orbencarb, dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxapyrazon-dimolamine, oxapyrazon—sodium, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat, paraquat ride, paraquat dimetilsulfate, pebulate, onic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picloram—Z-ethylhexyl, picloram-isoctyl, picloram-methyl, picloram—olamine, picloram—potassium, picloram-triethylanunonium, picloram-tris(2- hydroxypropyl)ammonium, picolinafen, pinoxaden, piperophos, ium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, primisulfuron—methyl, PCT/U52012/024217 procyazine, prodiamine, azol, profluralin, profoxydim, nazine, nazine— ethyl, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, isulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, proxan-sodiurn, prynachlor, pydanon, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazosulfuroneethyl, pyrazoxyfen, pyiibenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyn'rninobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac—sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, ofop, quizalofop-ethyl, quizalofop-P, quizalofop-P—ethyl, quizalofop-P—tefuryl, rhodethanil, rimsulfuron, saflufenacil, sebuthylazine, secbumeton, sethoxydim, n, simazine, simeton, simetryn, SMA, S—metolachlor, sodium arsenite, sodium azide, sodium chlorate, sulcotn'one, sulfallate, sulfentrazone, sulfometuron, sulfometuron—methyl, sulfosulfuron, sulfuric acid, sulgiycapin, swep, TCA, TCA-ammonium, TCA-Calcium, TCA—ethadyl, TCA- magnesium, TCA—sodium, tebutam, tebuthiuron, tefuryltn'one, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone, thiencarbazone—methyl, thifensull’uron, thifensulfuron-methyl, thiobencarb, tiocarbazil, tioclon'm, topramezone, tralkoxydim, tri-allate, uiasulfuron, triaziflam, tribenuron, tribenuron—methyl, tricamba, tn'clopyr, triclopyr-butotyl, triclopyr—ethyl, triclopyr—tiiethylammonium, hane, trietazine, tn'floxysulfuron, ysulfuron—sodium, tn'fluralin, tn'flusulfuron, triflusulfuron—methyl, trifop, —methyl, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tn'tac, tritosulfuron, vernolate, xylachlor, (collectively these commonly named herbicides are defined as the "Herbicide Group").

BIOPESTICIDES Molecules of Formula One, Two, Three, and Four may also be used in ation (such as in a compositional mixture, or a simultaneous or sequential application) with one or more biopesticides. The term "biopesticide" is used for microbial biological pest control agents that are applied in a similar manner to al pesticides. Commonly these are ial, but there are also examples of fungal l , including derma spp. and Ampelomyces quisqualis (a control agent for grape powdery mildew). Bacillus subtilis are used to control plant pathogens. Weeds and rodents have also been controlled with microbial agents. One nown insecticide example is us thuringiensis, a bacterial disease of Lepidoptera, tera, and Diptera. Because it has little effect on other PCT/U82012/024217 organisms, it is considered more environmentally friendly than synthetic pesticides.

Biological insecticides include products based on: 1. entomopathogenic fungi (e. g. Metarhizium anisopliae); 2. entomopathogenic des (e.g. Steinernemafeltiae); and 3. entomopathogenic viruses (e.g. Cydia pomonella granulovirus).

Other examples of entomopathogenic organisms e, but are not limited to, baculoviruses, bacteria and other prokaryotic organisms, fungi, protozoa and Microsproridia.

Biologically derived insecticides e, but not limited to, rotenone, veratridine, as well as microbial toxins; insect tolerant or resistant plant varieties; and organisms d by inant DNA technology to either produce icides or to convey an insect resistant property to the genetically modified organism. In one embodiment, the molecules of Formula One, Two, Three, and Four may be used with one or more biopesticides in the area of seed treatments and soil amendments. The Manual of trol Agents gives a review of the available biological insecticide (and other biology—based control) products. Copping L.G. (ed.) (2004). The Manual of Biocontrol Agents (formerly the Biopesticide Manual) 3rd Edition. British Crop Production Council (BCPC), Farnham, Surrey UK.

OTHER ACTIVE COMPOUNDS Molecules of Formula One, Two, Three, and Four may also be used in combination (such as in a compositional e, or a simultaneous or sequential application) with one or more of the following: 1. 3—(4—chloro-2,6—dimethylphenyl)—4—hydroxy—8—oxa—1—azaspiro[4,5]dec—3—en—2~one; 2. 3—(4’ ~chloro-2,4—dimethyl[ 1,1 ’-biphenyl]—3-y1)hydroxy-8~oxaazaspiro[4,5]dec- 3—en-2—one; 3. 4-[[(6-chloropyridinyl)methyl]methylamino]-2(5H)-furanone; 4. 4~[[(6-chloro—3-pyridinyl)methyl]cyclopropylamino]-2(5H)—furanone; . 3 -chloro-N2- [(1S)- l—methyl(methylsulfonyl)ethyl]-Nl -[2—methyl-4— [ 1 ,2,2,2- tetrafluoro-l-(trifluoromethyl)ethy1]phenyl]-1,2—benzenedicarboxamide; 6. 2-cyano-N-ethylfluoromethoxy—benenesulfonamide; 7. 2-cyano-N—ethylmethoxy-benzenesulfonamide; 8. 2-cyanodifluoromethoxy-N-ethyl—4—fluoro-benzenesulfonamide; 9. 2-cyanofluoromethoxy—N—ethyl—benzenesulfonamide; . o-6—fluoromethoxy-N,N-dimethyl-benzenesulfonamide; l 1. 2-cyano-N-ethylfluoromethoxy-N-methyl-benzenesulfonamide; PCT/U52012/024217 12. 2-cyanodifluoromethoxy—N,N-dimethylbenzenesulfon-amide; 13. 3—(difluoromethyl)-N—[2—(3,3-dimethy1butyl)phenyl]-l—methyl-1H—pyrazole-4— carboxarnide; 14. N—ethy1—2,2-dimethylpropionamide(2,6-dichlvro-d,d,a-trifluoro-p-tolyl) hydrazone; . N-ethyl-2,2-dichloromethylcyclopropane-carboxamide(2,6-dichloro-a,0t,a- trifluoro-p-tolyl) hydrazone nicotine; 16. O- { (E-)-[2-(4-chloro-phenyl)cyano-1—(2-trifluoromethylphenyl)-vinyl] } S-methyl rbonate; 17. (E)-N1-[(2-chloro-1,3-thiazol-5—y]methyl)]—N2-cyano-N1-methylacetamidine; 18. 1-(6-chloropyridin—3-ylmethy1)—7—methyl—8—nitro- 1 ,2,3,5 ,6 ,7—hexahydro-imidazo[ 1 ,2— a]pyn'dinol; 19. 4-[4—chlorophenyl-(2~butylidine«hydrazono)methyl)]phenyl mesylate; and . l—2,2-dichloro—1emethylcyclopropanecarboxamide(2,6—dichloro— alpha,alpha~trifluoro-p-tolyl)hydrazone.

Molecules of Formula One, Two, Three, and Four may also be used in combination (such as in a compositional mixture, or a simultaneous or sequential application) with one or more compounds in the following groups: algicides, antifeedants, avicides, bactericides, bird repellents, terilants, ide safeners, insect tants, insect repellents, mammal repellents, mating disrupters, cicides, plant tors, plant growth regulators, rodenticides, and/or virucides (collectively these commonly named groups are defined as the "Al Group"). It should be noted that compounds falling within the AI Group, Insecticide Group, Fungicide Group, Herbicide Group, Acaricide Group, or Nematicide Group might be in more than one group, because of multiple activities the compound has. For more information consult the "COMPENDIUM OF PESTICIDE COMMON NAMES" located at htt ://www.alanwood.net/ esticides/indexhtml. Also consult "THE PESTICIDE MANUAL" 14th Edition, edited by C D S Tomlin, copyright 2006 by British Crop Production Council, or its prior or more recent editions.

SYNERGISTIC MIXTURES AND SYNERGISTS Molecules of a One, Two, Three, and Four may be used with the compounds in the Insecticide Group to form synergistic mixtures where the mode of action of such compounds compared to the mode of action of the molecules of Formula One, Two, Three, and Four are the same, similar, or different. Examples of modes of action include, but are not limited to: acetylcholinesterase inhibitor; sodium channel tor; chitin biosynthesis inhibitor; GABA-gated chloride channel antagonist; GABA and glutamate-gated chloride channel agonist; choline receptor agonist; MET I inhibitor; Mg-stimulated ATPase inhibitor; nicotinic acetylcholine or; Midgut membrane disrupter; oxidative phosphorylation disrupter, and ryanodine receptor (RyRs). Additionally, molecules of Formula One, Two, Three, and Four may be used with compounds in the Fungicide Group, Acaricide Group, ide Group, or Nematicide Group to form synergistic es.

Furthermore, molecules of Formula One, Two, Three, and Four may be used with other active compounds, such as the compounds under the heading "OTHER ACTIVE COMPOUNDS", algicides, avicides, bactericides, molluscicides, rodenticides, virucides, herbicide safeners, adjuvants, and/or surfactants to form istic es. Generally, weight ratios of the molecules of Formula One, Two, Three, and Four in a synergistic mixture with another compound are from about 10:1 to about 1:10, preferably from about 5:1 to about 1:5, and more preferably from about 3:1, and even more preferably about 1:1. onally, the following compounds are known as synergists and may be used with the molecules sed in Formula One: nyl butoxide, piprotal, propyl isome, sesamex, sesamolin, sulfoxide, and tribufos (collectively these synergists are d as the "Synergists Group").

FORMULATIONS A pesticide is rarely suitable for application in its pure form. It is usually necessary to add other substances so that the pesticide can be used at the required concentration and in an appropriate form, permitting ease of ation, handling, transportation, storage, and m pesticide activity. Thus, pesticides are formulated into, for example, baits, concentrated emulsions, dusts, emulsifiable concentrates, fumigants, gels, granules, microencapsulations, seed treatments, suspension concentrates, suspoemulsions, tablets, water soluble liquids, water dispersible granules or dry flowables, wettable powders, and ultra low volume solutions. For further information on formulation types see "Catalogue of ide Formulation Types and International Coding System" Technical Monograph n°2, 5th Edition by CropLife International (2002).

Pesticides are applied most often as aqueous suspensions or ons prepared from concentrated formulations of such pesticides. Such soluble, water-suspendable, or emulsifiable formulations are either solids, usually known as wettable powders, or water dispersible granules, or liquids usually known as emulsifiable concentrates, or aqueous suspensions. Wettable powders, which may be compacted to form water dispersible granules, se an intimate mixture of the pesticide, a r, and surfactants. The concentration of PCT/U52012/024217 the pesticide is usually from about 10% to about 90% by weight. The carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, are found among sulfonated lignins, sed naphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants such as ethylene oxide adducts of alkyl phenols.

Emulsifiable concentrates of pesticides comprise a convenient concentration of a pesticide, such as from about 50 to about 500 grams per liter of liquid dissolved in a carrier that is either a water le solvent or a mixture of water-immiscible organic solvent and emulsifiers. Useful organic solvents include aromatics, especially s and petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as the terpenic solvents including rosin derivatives, aliphatic s such as cyclohexanone, and complex alcohols such as 2—ethoxyethanol. le emulsifiers for emulsifiable concentrates are chosen from conventional anionic and non-ionic surfactants. s sions comprise suspensions of water—insoluble pesticides dispersed in an aqueous carrier at a concentration in the range from about 5% to about 50% by weight.

Suspensions are prepared by finely grinding the pesticide and vigorously mixing it into a carrier comprised of water and surfactants. ients, such as nic salts and synthetic or natural gums may also be added, to se the density and viscosity of the aqueous carrier. It is often most effective to grind and mix the pesticide at the same time by preparing the aqueous mixture and homogenizing it in an ent such as a sand mill, ball mill, or piston—type homogenizer.

Pesticides may also be applied as granular compositions that are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about % by weight of the pesticide, dispersed in a carrier that comprises clay or a similar substance. Such itions are usually prepared by dissolving the pesticide in a suitable solvent and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. Such compositions may also be ated by making a dough or paste of the carrier and nd and crushing and drying to obtain the d granular particle size.

Dusts containing a pesticide are prepared by intimately mixing the pesticide in ed form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic PCT/U82012/024217 rock, and the like. Dusts can suitably contain from about 1% to about 10% of the pesticide.

They can be applied as a seed dressing or as a foliage application with a dust blower machine.

It is equally practical to apply a pesticide in the form of a solution in an appropriate organic solvent, usually petroleum oil, such as the spray oils, which are widely used in agricultural chemistry.

Pesticides can also be applied in the form of an aerosol composition. In such compositions the pesticide is dissolved or dispersed in a carrier, which is a pressure- generating propellant mixture. The aerosol composition is packaged in a container from which the mixture is dispensed through an atomizing valve.

Pesticide baits are formed when the pesticide is mixed with food or an tant or both. When the pests eat the bait they also e the pesticide. Baits may take the form of granules, gels, flowable powders, liquids, or solids. They can be used in pest harborages.

Fumigants are pesticides that have a relatively high vapor re and hence can exist as a gas in sufficient concentrations to kill pests in soil or enclosed spaces. The toxicity of the fumigant is proportional to its concentration and the re time. '[hey are characterized by a good capacity for diffusion and act by penetrating the pest’s respiratory system or being ed through the pest’s e. Fumigants are applied to control stored product pests under gas proof sheets, in gas sealed rooms or buildings or in special chambers.

Pesticides can be microencapsulated by ding the pesticide particles or ts in plastic polymers of s types. By altering the chemistry of the polymer or by changing factors in the processing, microcapsules can be formed of various sizes, solubility, wall thicknesses, and degrees of penetrability. These factors govern the speed with which the active ingredient within is released, which in turn, affects the residual performance, speed of action, and odor of the product.

Oil solution concentrates are made by dissolving pesticide in a solvent that will hold the ide in solution. Oil solutions of a pesticide usually provide faster knockdown and kill of pests than other formulations due to the solvents themselves having pesticidal action and the dissolution of the waxy ng of the integument increasing the speed of uptake of the pesticide. Other ages of oil solutions include better storage stability, better penetration of crevices, and better adhesion to greasy surfaces.

Another embodiment is an oil-in—water emulsion, wherein the emulsion comprises oily globules which are each provided with a lamellar liquid crystal coating and are dispersed in an aqueous phase, n each oily globule comprises at least one compound which is agriculturally active, and is dually coated with a monolamellar or oligolamellar layer WO 09292 comprising: (1) at least one non-ionic lipophilic surface-active agent, (2) at least one non- ionic hydrophilic surface-active agent and (3) at least one ionic surface-active agent, wherein the globules having a mean particle diameter of less than 800 nanometers. r information on the embodiment is disclosed in US. patent pubhcation 20070027034 published February 1, 2007, having Patent Application serial number 11/495,228. For ease of use, this embodiment will be referred to as "OIWE".

For further ation consult "Insect Pest Management" 2nd Edition by D. Dent, copyright CAB International (2000). Additionally, for more ed information consult "Handbook of Pest Control — The Behavior, Life History, and l of Household Pests" by Arnold Mallis, 9th Edition, copyright 2004 by GIE Media Inc.

OTHER FORMULATION COMPONENTS Generally, when the molecules disclosed in Formula One are used in a formulation, such formulation can also contain other ents. These components include, but are not limited to, (this is a non-exhaustive and non—mutually exclusive list) wetters, Spreaders, stickers, penetrants, s, tering agents, drift reduction agents, compatibility agents, anti-foam agents, cleaning agents, and emulsifiers. A few components are described forthwith.

A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in emical formulations: during sing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble s or suspension concentrates; and during mixing of a t with water in a spray tank to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible es. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations are: sodium lauryl sulfate; sodium dioctyl su i....i .

(D(I) (7 ('3 p.. :3 $9 9-9 ('0 ; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates.

A dispersing agent is a nce which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from reaggregating. Dispersing agents are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles redisperse into water in a spray tank. They are widely used in le powders, suspension concentrates and water-dispersible granules. Surfactants that are used as dispersing agents have the ability to PCT/U32012/024217 adsorb strongly onto a particle surface and provide a charged or steric r to reaggregation of particles. The most commonly used tants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersing agents are sodium lignosulfonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulfonate formaldehyde condensates. Tristyrylphenol ethoxylate phosphate esters are also used. Non-ionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersing agents for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersing agents.

These have very long hydrophobic ‘backbones’ and a large number of ne oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long—term stability to suspension concentrates because the hobic backbones have many anchoring points onto the particle surfaces. Examples of dispersing agents used in agrochemical formulations are: sodium lignosulfonates; sodium naphthalene sulfonate formaldehyde condensates; Histyrylphenol ethoxylate phosphate esters; aliphatic alcohol lates; alkyl ethoxylates; EO-PO block copolymers; and graft copolymers.

An emulsifying agent is a substance which stabilizes a suspension of droplets of one liquid phase in another liquid phase. Without the emulsifying agent the two liquids would separate into two ible liquid phases. The most commonly used emulsifier blends contain alkylphenol or aliphatic alcohol with twelve or more ethylene oxide units and the oil— soluble calcium salt of dodecylbenzenesulfonic acid. A range of hile-lipophile e ("HLB") values from 8 to 18 will normally provide good stable emulsions. Emulsion ity can sometimes be ed by the addition of a small amount of an EO-PO block copolymer tant.

A solubilizing agent is a surfactant which will form micelles in water at concentrations above the critical micelle concentration. The micelles are then able to dissolve or solubilize water-insoluble materials inside the hydrophobic part of the micelle. The types of surfactants usually used for solubilization are non—ionics, sorbitan monooleates, sorbitan monooleate ethoxylates, and methyl oleate esters.

Surfactants are sometimes used, either alone or with other additives such as mineral or vegetable oils as adjuvants to spray-tank mixes to improve the biological performance of the pesticide on the . The types of surfactants used for bioenhancement depend generally on the nature and mode of action of the pesticide. However, they are often nics such as: alkyl ethoxylates; linear aliphatic alcohol lates; aliphatic amine ethoxylates.

W0 2012/109292 A carrier or diluent in an ltural formulation is a material added to the pesticide to give a product of the required strength. Caniers are usually materials with high absorptive capacities, while ts are y materials with low absorptive capacities. Carriers and diluents are used in the formulation of dusts, wettable powders, granules and water— dispersible granules.

Organic solvents are used mainly in the formulation of emulsifiable concentrates, oil— in-water emulsions, suspoemulsions, and ultra low volume formulations, and to a lesser , granular formulations. Sometimes mixtures of solvents are used. The first main groups of solvents are tic paraffinic oils such as kerosene or refined paraffins. The second main group (and the most common) comprises the ic solvents such as xylene and higher molecular weight fractions of C9 and C10 aromatic solvents. Chlorinated hydrocarbons are useful as cosolvents to t crystallization of pesticides when the formulation is emulsified into water. Alcohols are sometimes used as cosolvents to increase solvent power. Other solvents may include vegetable oils, seed oils, and esters of vegetable and seed oils. ners or gelling agents are used mainly in the formulation of suspension trates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets.

Thickening, gelling, and anti—settling agents generally fall into two categories, namely water— insoluble particulates and water—soluble polymers. It is possible to e suspension concentrate formulations using clays and silicas. es of these types of materials, include, but are not limited to, montmorillonite, bentonite, magnesium aluminum silicate, and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds or are tic derivatives of cellulose. Examples of these types of als include, but are not limited to, guar gum; locust bean gum; carrageenam; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl .ellulose (HEC). Other types of anti—settling agents are based on modified starches, polyacrylates, nyl alcohol and polyethylene oxide. Another good anti—settling agent is n gum.

Microorganisms can cause spoilage of formulated products. Therefore preservation agents are used to eliminate or reduce their effect. Examples of such agents include, but are not d to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxybenzoic acid sodium salt; methyl p— hydroxybenzoate; and l,2-benzisothiazolinone (BIT).

PCT/U82012/024217 The ce of surfactants often causes water-based ations to foam during mixing operations in production and in application through a spray tank In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into s. Generally, there are two types of anti—foam agents, namely silicones and liconesl Silicones are y aqueous emulsions of dimethyl polysiloxane, while the non-silicone anti—foam agents are insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the tant from the air-water interface.

"Green" agents (e.g., adjuvants, surfactants, solvents) can reduce the overall environmental footprint of crop protection ations. Green agents are biodegradable and generally derived from natural and/or sustainable sources, e. g. plant and animal sources.

Specific examples are: vegetable oils, seed oils, and esters f, also alkoxylated alkyl polyglucosides.

For further information, see "Chemistry and Technology of Agrochemical ations" edited by DA. Knowles, copyright 1998 by Kluwer Academic Publishers.

Also see "Insecticides in Agriculture and Environment — Retrospects and Prospects" by AS Perry, I. Yamamoto, I. Ishaaya, and R. Perry, copyright 1998 by er—Verlag.

PESTS In general, the molecules of Formula One, Two, Three, and Four may be used to control pests e. g. beetles, earwigs, cockroaches, flies, aphids, scales, whiteflies, leafhoppers, ants, wasps, termites, moths, butterflies, lice, grasshoppers, locusts, crickets, fleas, thrips, bristletails, mites, ticks, nematodes, and symphylans.

In another embodiment, the Molecules of Formula One, Two, Three, and Four may be used to control pests in the Phyla Nematoda and/or Arthropoda.

In r embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests in the Subphyla Chelicerata, Myriapoda, and/or Hexapoda.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests in the Classes of Arachnida, Symphyla, and/or Insecta.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to l pests of the Order Anoplura. A non-exhaustive list of particular genera includes, but is not limited to, Haematopinus spp., Hoplopleura spp., Linognathus spp., Pediculus spp., and Polyplax spp. A non-exhaustive list of ular species includes, but is not limited to, Haematopinus asini, opinus suis, Linognathus setosus, Linognathus ovillus, Pediculus humanus s, Pediculus humanus humanus, and Pthirus pubis.

In another embodiment, the molecules of a One, Two, Three, and Four may be used to l pests in the Order Coleoptera. A non-exhaustive list of particular genera includes, but is not limited to, Acanthoscelides spp., Agriotes spp., Anthonomus spp., Apion spp., Apogonia spp., Aulacophora spp., Bruchus spp., Cerosterna spp., Cerotoma spp., Ceutorhynchus spp., Chaetocrzema spp., Colaspis spp., Ctenicera spp., io spp., Cyclocephala spp., Diabrotica spp., Hypera spp., Ips spp., Lyctus spp., Megascelis spp., Meligethes spp., Otiorhynchus spp., Pantomorus spp., Phyllophaga spp., treta spp., Rhizotrogus spp., Rhynchizes spp., Rhynchophorus spp., Scolytus spp., Sphenophorus spp., Sitophilus spp., and Tribolium spp. A non—exhaustive list of particular species es, but is not d to, Acanthoscelides obtectus, Agrilus planipennis, Anoplophora glabripennis, Anthonamus grmdis, Areniu‘s sprelulus, Atomaria linearis, Bothynoderes punctiventris, s pisorum, obruchus maculazus, Carpophilus hemiptems, Cassida vittaza, Cerotoma trifitrcata, Ceutorhynchus assimilis, Ceutorhynchus napi, Conoderus scalaris, Conoderus stigmosus, achelus nenuphar, Cotinis nitida, ris asparagi, Cryptolestes ferrugineus, Cryptolestes pusillus, Cryptolestes turcicus, Cylindrocopturus adspersus, Deporaus marginatus, Dermestes lardarius, Dermestes maculatus, Epilachna varivestis, Faustinus cubae, Hylobius pales, Hypera a, Hypothenemus hampei, Lasioderma serricorne, Leptinotarsa decemlineata, Liogenys fuscus, Liogenys suturalis, Lissorhoptrus oryzophilus, Maecolaspis joliveti, Melanolus communis, Meligethes aeneus, ntha melolontha, Oberea brevis, Oberea is, Oryctes rhinoceros, Oryzaephilus mercator, Oryzaephilus surinamensis, Oulema melanopus, Oulema oryzae, Phyllophaga cuyabana, Papillia japonica, Prostephanus truncatus, Rhyzopertha d0minica,, Sizona lineatus, ilus ius, Sitaphilus oryzae, Sitophilus zeamais, ium paniceum, Tribolium eum, Tribolium confusum, Trogoderma variabile, and Zabrus tenebrioides.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Order tera.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Order Blattaria. A non-exhaustive list of particular species includes, but is not limited to, Blattella germanica, Blatta orientalis, Parcoblatta pennsylvanica, Periplaneta americana, Periplaneta australasiae, Periplaneta brunnea, Periplanetafiliginosa, Pycnoscelus surinamensis, and Supella longipalpa.

PCT/U82012/024217 In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to l pests of the Order Diptera. A haustive list of particular genera includes, but is not limited to, Aedes spp., za spp., Anastrepha spp., Anopheles spp., cera Chrysops spp., Cochliomyia spp., Contarirzia spp., Ceratitis spp., spp., Culex spp., Dasineura spp., Delia spp., Drosophila spp., Fannia spp., ia spp., Liriomyza spp. A non-exhaustive list of spp., Musca spp., Phorbia spp., s spp., and Tipula ular species includes, but is not d to, za frontella, Anastrepha suspensa, Anastrepha Zudens, Anastrepha , Bactrocera cucurbz‘tae, cera dorsalis, Bactrocera invadens, Bactrocera zonata, Ceratitis capitata, Dasineura brassicae, Delia platura, Fannia canicularis, Fannia scalaris, Gasterophilus intestinalis, Gracillia perseae, Haematobia irritans, Hypoderma lineatum, Liriomyza brassicae, agus ovinus, Musca autumnalis, Musca domestica, OeStrus ovis, Oscinella frit, Pegomya betae, Psila rosae, Rhagoletis cerasi, Rhagoletis pomonella, Rhagoletis mendax, Sitodiplosis mosellana, and Stomoxys rans.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Order Hemiptera. A non—exhaustive list of particular genera includes, but is not limited to, Adelges spp., Aulacaspis spp., Aphrophora spp., Aphis spp., Bemisia Ceroplastes spp., Chionaspis spp., Chrysomphalus spp., Coccus spp., spp., Empoasca spp., Lepidosaphes spp., Lagynotomus spp., Lygus spp., Macrosiphum spp., Nephotettix spp., Nezara spp., Philaenus spp., Phytocoris spp., Piezodorus spp., Planococcus spp., Pseudococcus spp., Rhopalosiphum spp., Saissetia spp., Therioaphis spp., Toumeyella spp., Toxoptera spp., Trialeurodes spp., ma spp. and Unaspis spp. A non-exhaustive list of particular species es, but is not limited to, Acrosternum hilare, Acyrthosiphon pisum, des ella, Aleurodicus dispersus, Aleurothrixus floccosus, Amrasca biguttula biguttula, Aonidiella aurantii, Aphis gossypii, Aphis glycines, Aphis pomi, Aulacorthum solani, Bemisia argentifolii, Bemisia tabaci, Blissus leucopterus, Brachycorynella asparagi, Brevennia rehi, Brevicoryne brassicae, Calocoris norvegicus, Ceroplastes rubens, Cimex hemipterus, Cimex lectularius, Dagbertus fasciatus, Dichelops furcatus, his noxia, Diaphorina citri, Dysaphis plantaginea, Dysdercus suturellus, Edessa meditabunda, Eriosoma lanigerum, Eurygaster maura, Euschistus heros, Euschistus servus, Helopeltis am‘onii, Helopeltis theivora, Icerya purchasi, ldioscopus nitidulus, Laodelphax striatellus, Leptocorisa oratorius, Leptocorisa varicornis, Lygus hesperus, Maconellicoccus hirsutus, Macrosiphum euphorbiae, iphum granarium, Macrosiphum rosae, Macrosteles quadrilineatus, Mahanarva frimbiolata, Metopolophium PCT/U52012/024217 dirhodum, Mictis longicornz's, Myzus persicae, Nephotettix cinctipes, Neurocolpus longirostris, Nezara viridula, Nilaparvata lugens, Parlatoria pergandii, Parlamria ziziphi, inus maidis, Phylloxera vitifoliae, Physokermes piceae,, Phytocoris califomicus, Phytocoris relativus, Piezodorus guildinii, Poecilocapsus lineatus, s vaccinicola, Pseudacysta perseae, Pseudococcus brevipes, Quadraspidiotus perniciosus, Rhopalosiphum maidis, osiphum padi, Saissetia oleae, Scaptocoris castanea, phis graminum, Sitobion , Sogatella furcifera, Trialeurodes vaporariorum, Trialeurodes oneus, s yanonensis, and Zulz'a riana.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Order ptera. A non-exhaustive list of particular genera includes, but is not limited to, Acromyrmex spp., Atta spp., Camponotus spp., Diprion spp., Formica spp., Monomarium spp., Neodiprion spp., Pogonomyrmex spp., Polistes spp., Vesmla spp., and Xylov‘a s*p. A non-"Xhaustive list of particular species includes, but is not limited to, Alhalia rosae, Atta texana, Iridomyrmex s, Monomorium minimum, Monomorium pharaonis, Solenopsis a, psis geminata, Solenopsis a, Solenopsis richtery, Solenopsis xyloni, and Tapinoma sessile.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to l pests of the Order Isoptera. A non-exhaustive list of particular genera includes, but is not d to, Coptotermes spp, Cornitermes spp., Cryptotermes spp., Heterotermes spp., Kalotermes sppl, Incisizermes spp., Macrotermes spp., Marginitermes spp., Microcerot‘ermes sppl, Procomitermes spp., Reticulitermes spp., Schedorhinotermes spp., and Zootermopsis spp. A non—exhaustive list of particular species includes, but is not limited to, Coptotermes curvignathus, Coptotermes frenchi, Coptotermes formosanus, Heterotermes aureus, ermes obesi, Reticulitermes banyulensis, Reticulitermes grassei, NU1 Reticulitermes flavipes, Reticulitermes hageni, Reticulitermes hesperus, Reticulitermes santonensis, Reticulitermes speratus, Reticulitermes tibialis, and Reticulz‘termes virginicus.

In another ment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Order Lepidoptera. A non-exhaustive list of particular genera includes, but is not limited to, hyes spp., Agrotis spp., Argyrotaenia spp., Cacoecia spp., Caloptilia spp., Chilo spp., Chrysodeixis spp., Colias spp., Crambus spp., Diaphania spp., Diatraea spp., Earias spp., Ephestia spp., Epimecis spp., Feltia spp., Gortyna spp., Helicoverpa spp., Heliothis spp., Indarbela spp., Lithocolletis spp., loxagrotis spp., Malacosoma spp., Peridroma spp., Phyllonorycter spp., Pseudaletia spp., Sesamia spp., Spodoptera spp., Synamhedon spp., and Yponomeuta spp. A non-exhaustive list of particular species includes, but is not limited to, Achaea janata, Adoxophyes orana, Agrotis n, Alabama argillacea, Amorbia cuneana, Amyelois transitella, Anacamptoa’es defectarz'a, Anarsia lineatella, Anomis sabulifera, Anticarsia gemmatalis, s argyrospila, Archips rosana, Argyrotaem'a citrana, Autographa gamma, Bonagota cranaodes, Borbo a, Bucculatrix thurberz'ella, Capua reticulana, Carposina ensis, Chlumetia transversa, Choristoneura rosaceana Cnaphalocrocis medinalis, Conopomorpha cramerella, Cossus cossus, Cya'ia caryana, Cydiafimebrana, Cya'ia molesta, Cya’z'a nigricana, Cydia pomonella, Darna didacta, Diatraea saccharalis, Diatraea grandiosella, Earias insulana, Earias vittella, Ecdytolopha aurantianum, Elasmopalpus ligaosellus, Ephestia cautella, Ephestia la, Ephestia ella, ia a, Epiphyas postvittana, Erionota thrax, Eupoecz'lia ambiguella, Euxoa auxiliaris, lita molesta, Hedylepta indicata, verpa armigera, Helicoverpa zea, Heliothis virescens, Hellula undalis, Keiferia lycopersicella, Leucinades orbonalis, Leucoptera cofleella, Leucoptera liella, Lobesia botrana, Loxagrotis albicosta, ria dispar, Lyonetia clerkella, Mahasena corbetti, Mamestra brassicae, Maruca testulalis, Metisa plana, Mythimna unipuncta, Nealeucinodes elegantalis, Nymphula depunctalis, Operophtera brumata, Ostrim’a nubilalis, Oxydia vesulia, Pandemis cerasana, Pandemis heparana, o demodocus, Pectinophora gassypiella, Peria’roma saucia, ucoptera coffeella, Phthorimaea operculella, Phyllocriistis Citrella, Pieris rapae, Plathypena scabra, Plodia unctella, Plutella xylostella, Polychrosis viteana, Prays endocarpa, Prays oleae, Pseudaletia unipuncta, Pseudoplusia includens, Rachiplusia nu, Scirpophaga ulas, Sesamia inferens, Sesamia nonagrioides, Setora nitens, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera exigua, Spodoptera frugiperda, Spodoptera eridania, Theda basilides, Tineola bisselliella, Trichoplusia 711', Tara absoluta, Zeuzera e, and Zeuzera pyrina.

In r embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Order haga. A non—exhaustive list of particular genera includes, but is not limited to, Anaticola spp., Bovicola spp., Chelopistes spp., Gonioa'es spp., Menacanthus spp., and Trichodectes spp. A non-exhaustive list of particular species includes, but is not limited to, Bovicola bovis, Bovicola caprae, Bovicola ovis, Chelopistes ridis, Goniodes dissimilis, Goniodes gigas, Menacanthus stramineus, Menopon ae, and Trichodectes canis.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Order Orthoptera. A non-exhaustive list of particular genera es, but is not limited to, Melanoplus spp., and Pterophylla spp. A non-exhaustive list of WO 09292 PCT/U52012/024217 particular species es, but is not limited to, Anabrus simplex, Gryllotalpa africana, Gryllotalpa australis, Gryllotalpa brachyptera, talpa hexadactyla, Locusta migratoria, Microcentrum rve, ocerca gregaria, and Scudderia furcata.

In r embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Order Siphonaptera. A non-exhaustive list of particular species includes, but is not limited to, Ceratophyllus ae, Ceratophyllus niger, Ctenocephalides canis, Ctenocephalidesfelis, and Pulex irritans.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Order Thysanoptera. A non-exhaustive list of particular genera includes, but is not limited to, Caliothrips spp., Frankliniella spp., Scirtothrips spp., and Thrips spp. A non-exhaustive list of particular sp. includes, but is not limited to, Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, iniella williamsi, Heliothrips ‘lis, Rr’zipiphorothrips cruem‘atus, Scirtothrips citri, Scirrothrips dorsalis, and Taeniothrips rhopalantennaiis, Thrips hawaiiensis, Thrips nigropilosus, Thrips orientalis, Thrips tabaci.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Order Thysanura. A haustive list of particular genera includes, but is not limited to, Lepisma spp. and Thermobia spp.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Order Acarina. A non—exhaustive list of particular genera includes, but is not limited to, Acarus spp., s spp., Boophilus spp., Demodex spp., Dermacentor spp., Epitrimerus spp., Eriophyes spp., Ixodes spp., ychus spp., Panonychus spp., Rhizoglyphus spp., and Tetranychus spp. A non—exhaustive list of particular species includes, but is not limited to, is woodi, Acarus siro, Aceria mangiferae, Aculops lycopersici, Aculus pelekassi, Aculus schlechtendali, Amblyomma anum, Brevipalpus obovatus, Brevipalpus phoenicis, Dermacentor variabilis, Dermatophagoides pteronyssinus, Eatetranychus carpini, Notoedres can} Oligonychus cofleae, Oligonychus ilicis, Panonychus citri, Panonychus ulmi, coptruta oleivora, Polyphagotarsonemus latus, Rhipicephalus sanguineus, Sarcoptes scabiei, Tegolophus perseaflorae, Tetranychus e, and Varroa destructor.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pest of the Order Symphyla. A non-exhaustive list of particular sp. includes, but is not limited to, Scutigerella immaculata.

In another embodiment, the molecules of Formula One, Two, Three, and Four may be used to control pests of the Phylum Nematoda. A non-exhaustive list of particular genera includes, but is not limited to, Aphelenchoides spp., Belonolaimus spp., Criconemella spp., Ditylenchus spp., Heteroa’era spp., Hirschmanniella spp., Hoplolaimus spp., Meloidogyne spp., Pratylenchus spp., and Radopholus spp. A non-exhaustive list of particular sp. includes, but is not limited to, Dirofilaria immitis, Heterodera zeae, Meloidogyne incognita, Meloidogyne javanica, Onchocerca valvulus, Radopholus similis, and Rotylenchulus reniformis.

For additional information consult "HANDBOOK OF PEST L — THE BEHAVIOR, LIFE HISTORY, AND CONTROL OF HOUSEHOLD PEsrs" by Arnold Mallis, 9th Edition, copyright 2004 by GIE Media Inc.

APPLICATIONS Molecules of Formula One, Two, Three, and Four are generally used in amounts from about 0.01 grams per hectare to about 5000 grams per hectare to provide control. Amounts from about 0.1 grams per hectare to about 500 grams per hectare are generally preferred, and amounts from about 1 gram per hectare to about 50 grams per hectare are generally more preferred.

Ihe area to which a molecule of Formula One is applied can be any area ted (or maybe inhabited, or sed by) a pest, for example: where crops, trees, fruits, cereals, fodder species, vines, turf and ornamental plants, are g; where domesticated animals are ng; the or or exterior surfaces of buildings (such as places where grains are stored), the materials of construction used in building (such as impregnated wood), and the soil around buildings. Particular crop areas to use a molecule of Formula One include areas where apples, corn, ers, , soybeans, canola, wheat, rice, sorghum, , oats, potatoes, oranges, alfalfa, lettuce, erries, tomatoes, peppers, crucifers, pears, tobacco, almonds, sugar beets, beans and other valuable crops are growing or the seeds thereof are going to be planted. It is also advantageous to use aluminum sulfate with a molecule of Formula One when growing various plants.

Controlling pests generally means that pest populations, pest activity, or both, are reduced in an area. This can come about when: pest populations are ed from an area; when pests are incapacitated in or around an area; or pests are inated, in whole, or in part, in or around an area. Of course, a ation of these results can occur. Generally, pest populations, activity, or both are desirably reduced more than fifty percent, preferably more PCTfU82012/024217 than 90 percent. Generally, the area is not in or on a human; consequently, the locus is generally a non-human area.

The molecules of Formula One, Two, Three, and Four may be used in es, applied simultaneously or sequentially, alone or with other compounds to enhance plant vigor (e.g. to grow a better root system, to better withstand ful growing conditions). Such other compounds are, for example, nds that modulate plant ne receptors, most notably l-methylcyclopropene (also known as 1—MCP).

The molecules of Formula One, Two, Three, and Four can be applied to the foliar and ng portions of plants to control pests. The les will either come in direct contact with the pest, or the pest will consume the pesticide when eating leaf, fruit mass, or extracting sap, that contains the pesticide. The molecules of Formula One, Two, Three, and Four can also be applied to the soil, and when applied in this manner, root and stem feeding pests can be contrrlled. The roots can absorb a molecule taking it up into the foliar portions of the plant to control above ground chewing and sap feeding pests.

Generally, with baits, the baits are placed in the ground where, for example, termites can come into contact with, and/or be attracted to, the bait. Baits can also be applied to a surface of a building, ontal, al, or slant surface) where, for example, ants, es, cockroaches, and flies, can come into contact with, and/or be attracted to, the bait.

Baits can comprise a molecule of Formula One.

The molecules of Formula One, Two, Three, and Four can be encapsulated inside, or placed on the surface of a capsule. The size of the capsules can range from nanometer size (about 100—900 nanometers in diameter) to micrometer size (about 10—900 microns in diameter).

Because of the unique ability of the eggs of some pests to resist certain pesticides, repeated applications of the molecules of Formula One, Two, Three, and Four may be desirable to control newly emerged larvae.

Systemic movement of pesticides in plants may be utilized to control pests on one portion of the plant by applying (for example by spraying an area) the molecules of Formula One, Two, Three, and Four to a different portion of the plant. For example, control of foliar- feeding insects can be achieved by drip irrigation or furrow application, by ng the soil with for example pre— or post—planting soil drench, or by treating the seeds of a plant before planting.

Seed ent can be applied to all types of seeds, including those from which plants genetically ed to s specialized traits will germinate. Representative examples PCT/U82012/024217 e those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis or other insecticidal toxins, those expressing herbicide resistance, such as "Roundup Ready" seed, or those with "stacked" foreign genes expressing insecticidal toxins, herbicide resistance, nutrition—enhancement, drought resistance, or any other beneficial traits.

Furthermore, such seed treatments with the molecules of Formula One, Two, Three, and Four may further enhance the ability of a plant to better withstand stressful growing conditions.

This results in a healthier, more vigorous plant, which can lead to higher yields at harvest time. Generally, about 1 gram of the molecules of Formula One, Two, Three, and Four to about 500 grams per 100,000 seeds is expected to e good benefits, amounts from about 10 grams to about 100 grams per 0 seeds is expected to provide better ts, and s from about 25 grams to about 75 grams per 100,000 seeds is expected to provide even better benefits.

It should be readily apparent that the molecules of Formula One, Two, Three, and Four may be used on, in, or around plants genetically modified to express specialized traits, such as Bacillus thuringiensis or other insecticidal toxins, or those expressing ide resistance, or those with "stacked" n genes expressing insecticidal toxins, herbicide resistance, nutrition-enhancement, or any other beneficial traits.

The molecules of Formula One, Two, Three, and Four may be used for controlling endoparasites and ectoparasites in the veterinary medicine sector or in the field of non-human animal keeping. The molecules of Formula One, Two, Three, and Four are d, such as by oral administration in the form of, for example, tablets, capsules, drinks, granules, by dermal application in the form of, for example, dipping, spraying, pouring on, spotting on, and dusting, and by eral administration in the form of, for e, an injection.

The molecules of Formula One, Two, Three, and Four may also be employed advantageously in ock keeping, for example, cattle, sheep, pigs, chickens, and geese.

They may also be employed advantageously in pets such as, horses, dogs, and cats. Particular pests to control would be fleas and ticks that are bothersome to such animals. le formulations are administered orally to the animals with the drinking water or feed. The dosages and formulations that are suitable depend on the species.

The molecules of Formula One, Two, Three, and Four may also be used for lling parasitic worms, especially of the intestine, in the s listed above.

The molecules of Formula One, Two, Three, and Four may also be employed in eutic methods for human health care. Such methods include, but are limited to, oral PCT/U82012/024217 administration in the form of, for example, tablets, capsules, drinks, granules, and by dermal application.

Pests around the world have been ing to new environments (for such pest) and thereafter becoming a new invasive species in such new nment. The molecules of a One, Two, Three, and Four may also be used on such new invasive species to control them in such new environment.

The molecules of Formula One, Two, Three, and Four may also be used in an area where plants, such as crops, are growing (e.g. pre-planting, planting, pre-harvesting) and where there are low levels (even no actual presence) of pests that can commercially damage such plants. The use of such molecules in such area is to benefit the plants being grown in the area. Such benefits, may include, but are not limited to, improving the health of a plant, ing the yield of a plant (e. g. increased biomass and/or increased t of valuable ients), improving tiL A "1",". hr: .. ... "A I : A__‘._ _ .A _L M‘Au-r. L - A JI__ <,,r,,,,,, ,. A _ re Vigor U1 :1 plan tang. iiupi ved plant giuwui aru/Ui greener leaves), improving the quality of a plant (e.g. improved content or composition of certain ingredients), and improving the tolerance to abiotic and/0r biotic stress of the plant.

Before a pesticide can be used or sold commercially, such pesticide undergoes lengthy evaluation processes by various governmental authorities (local, regional, state, national, and ational). Voluminous data requirements are specified by regulatory authorities and must be addressed through data generation and submission by the product registrant or by a third party on the product registrant's behalf, often using a computer with a connection to the World Wide Web. These governmental authorities then review such data and if a determination of safety is ded, provide the potential user or seller with product registration approval. Thereafter, in that locality where the product registration is granted and supported, such user or seller may use or sell such pesticide.

A molecules according to a One, Two, Three, and Four can be tested to determine its efficacy t pests. Furthermore, mode of action studies can be conducted to determine if said molecule has a different mode of action than other pesticides. Thereafter, such acquired data can be inated, such as by the intemet, to third parties.

The headings in this document are for convenience only and must not be used to ret any portion hereof.

PCT/U82012/024217 TABLE SECTION BAW & CEW Rating Table % l (or Mortality) GPA Rating Table % Control (or Mortality) 80— 100 More than 0 ~ Less than 80 B Not Tested C No activity noticed in this bioassay D PCT/U82012/024217 Table:Bio Results nd % Mortallty % mrta"hW % Mertalltv GPA Number BAW 50 ug/cmz CEW 50 pg/cm 200 ppm .AAAAAAAA D 1000750782#2.d0cx WE

Claims (13)

CLAIM

1. A pesticidal composition comprising a molecule according to Formula One, Two, Three, or Four is R4 \Ar2/NRny, (C1-C6 Rny, C(zoxcl-cé alkyl), C(=O)(C1-C6 alkyl), C(=O)O(C1—C6 alkyl), C(=O)(C1—C6 haloalkyl), C(=O)O(C1-C6 haloalkyl), C(=O)(C3-C6 cycloalkyl), C(=O)O(C3-C6 Cycloalkyl), C(=0)(C2-C6 ll (C2'C6 alkenyl), (C1-C6 a1ky1)O(C1-C6 alkyl), (C1-C6 alkyl)OC(:0)(C1-C6 alkyl), (C1-C6 alky1)S(Cl'C6 , C(:O)(C1"C6 15 C(=O)O(C1—C6 alkyl), phenyl, and phenoxy, wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl, alkynyl, , and selected from phenoxy are optionally substituted with one or more substituents independently OH, F, Cl, Br, 1, CN, N02, oxo, C1—C6 alkyl, C1—C6 haloalkyl, C1—C6 hydroxyalkyl, C3—C6 cycloalkyl, C3-C6 cloalkyl, C3—C6 hydroxycycloalkyl, C3—C6 cycloalkoxy, C3—C6 20 cloalkoxy, C3—C6 hydroxycycloalkoxy, C1-C6 alkoxy, C1—C6 koxy, C2—C6 alkenyl, C2—C6 alkynyl, S(=O)n(C1-C6 alkyl), S(=O)n(C1-C6 haloalkyl), 1—C6 alkyl), OSOZ(C1- C6 haloalkyl), C(=O)NRny, (Cl'Cé a1ky1)NRny, C(=0)(C1~C6 alkyl): C(:O)O(C1'Cs alkyl), C(=O)(C1—C6 haloalkyl), C(=O)O(C1—C6 haloalkyl), C(=O)(C3-C6 cycloalkyl), C(=O)O(C3.C6 cycloalkyl), C(=O)(C2-C6 alkenyl), C(=O)O(C2-C6 l), (C1—C6 alkyl)O(C1-C6 alkyl), 25 (C1—C6 alkyl)S(C1-C6 alkyl), C(=O)(C1-C6 alky1)C(=O)O(C1-C6 alkyl), phenyl, and phenoxy; (i) X1 is S or 0; (j) n= 0, 1, or 2 (each independently); and (k) RX and Ry are independently selected from H, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 hydroxyalkyl, C3-C5 cycloalkyl, C3-C6 cloalkyl, C3—C6 hydroxycycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, S(=O)n(C1-C6 alkyl), S(=O)n(C1-C6 haloalkyl), OSOZ(C1—C6 , OSOZ(C1—C6 haloalkyl), C(=O)H, C(=O)(C1-C6 alkyl), C(=O)O(C1-C6 allql), C(:O)(C1‘C6 0782r2.docx haloalkyl), C(=O)O(C1—C6 haloalkyl), C(ZO)(C3—C6 cycloalkyl), C(SO)O(C3—C6 cycloalkyl), C(=O)(C2-C6 alkenyl), C(=O)O(C2-C6 alkenyl), (C1—C6 alkyl)O(C1-C6 alkyl), (C1-C6 alky1)S(Cr-Ce alkyl), C1'C6 a1ky1)C(=O)O(C1—C6 alkyl), and phenyl. substituted phenyl

2. A pesticidal composition ing to claim 1 wherein said Arl is a selected from wherein said substituted phenyl that has one or more substituents independently C1-C6 haloalkoxy.

3. A pesticidal composition according to claim 1 or 2 wherein said Het is a triazolyl.

4. A pesticidal composition according to claim 3 wherein said Het is a l,2,4-triazoly1_ is a

5. A pesticidal composition according to claim 4 wherein said Het 1,2,4-triazolyl bonded to Arz. with one ring nitrogen atom bonded to Arl and one ring carbon

6. A pesticidal composition according to any one of the ing claims wherein said Arz is a phenyl. wherein said

7. A pesticidal composition according to any one of the ing claims 20 R3 is H.

8. A idal composition according to any one of the preceding claims wherein said R4 is H. 25

9. A pesticidal composition according to any one of claims 1 to 7 wherein said R4 is a phenyl optionally substituted with one or more substituents independently selected from C1- C6 alkyl.

10. A pesticidal composition according to any one of the preceding claims wherein said 30 R5 is Het or phenyl wherein each are optionally substituted with one or more substituents ndently selected from F, C1, C1-C6 alkyl, C1—C6 haloalkyl, C1-C6 alkoxy, or NRny'

11. A idal composition according to any one of the ing claims wherein said R6 is C1-C6 alkyl or phenyl wherein each are optionally substituted with one or more 1000750782_2.docx substituents ndently selected from F, Cl, C1—C6 alkyl, C1—C6 haloalkyl, (334:6 cycloalkyl, C1-C6 alkoxy, Het, or phenyl.

12. A pesticidal composition according to any one of the preceding claims wherein said 5 R7 is (C1-C6 alkyl)OC(=O)(C1-C6 alkyl).

13. A pesticidal composition according to claim 1 wherein said molecule has one of the following ures (Compound 1) - M EE I‘E’V Fig‘Q-‘K: SQ (Compound 2) yfio‘we W35:3: (Compound 3) Egg-71::pg uYQ/flgérim NB}; 15 (Compound 4) fiio‘ngr‘é 5 und 5) ‘EiFO‘Q-V‘k—n 8 (Compound 6) i3 i1 (Compound 7) Fffi}u\j@/