OA16336A

OA16336A - Pesticidal compositions.

Info

Publication number: OA16336A
Application number: OA1201300082
Authority: OA
Inventors: Lawrence C. Creemer; Gary D. Crouse; Thomas C. Sparks; Casandra Lee Mcleod
Original assignee: Dow Agrosciences Llc
Priority date: 2010-08-26
Filing date: 2011-08-25
Publication date: 2015-05-11

Abstract

Molecules having the following structure are disclosed.

Description

The invention disclosed in this document is related to the field of processes to produce molécules that are iiseful as pesticides (e.g., acaricides, insecticides, molluscicides, and nematicides), such molécules, and processes of using such molécules to control 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 world-wide agricultural losse^ amount to billions of U.S. dollars each year.

Termites cause damage to ail kinds of private and public structures. The world-wide termite damage losses amount to billions of U.S. dollars each year.

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

There is an acute neéd for new pesticides. Certain pests are developing résistance to pesticides rn current use. Hundreds of pest species are résistant to one or more pesticides. The development of résistance to some of the older pesticides, such as DDT, the carbamates, and the organophosphates, is wel( known But résistance has even developed to some of the newer pesticides.

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

DEFINITIONS

The examples given ; ¹ in the définition? are-generally non-exhaustive and must not be construed as limiting the invention disclosed jn this document. It is understood that a substituent should comply with chemical bonding rules and steric compatibility constraints in relation to the particular molécule to which it is attached.

Acaricide Group” is defined under the heading “ACARICIDES.

“Al Group is defined after the place in this document where the “Herbicide Group” is {i defined.

t

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. ^{d :} ' “Alkenyloxy means an alkenyl further consisting of a carbon-oxygen single bond, for example, allyloxy, butenyloxy, pentenyloxy, héxenyloxy.

“Alkoxy” means an alkyl further consisting of a carbon-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 tert-butyl,

Alkynyl” means an acyclic, unsaturated (at least one carbon-carbon triple bond), branched or unbranched, substituent consisting ' of carbon and hydrogen, for example, ethynyl, propargyl, butynyl, and pentynyl. ^tL ’ “Alkynyloxy means an alkynyl further consisting of a carbon-oxygen single bond, ?

for example, pentynyloxy, hexynyloxy, heptynyloxy, and octynyloxy.

“Aryl means a cyclic, aromatic substituent(Consisting of hydrogen and carbon, for example, phenyl, naphthyl, énd biphenyl,, “Cycloalkeny! means a mohocycliô or polycyclic, unsaturated (at least one carboncarbon double bond) substituent consisting ^! pf-î carbon and hydrogen, for example, cyclobutenyl, cyclopentenyl,_; cyclohexenyl, , ' norbomenyl, bicyclo[2,2.2]octenyl, tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.

“Cycloalkenyloxy means a cycloalkenyl further consisting of a carbon-oxygen single bond, for examplb, cyclobutenyloxy, cyclopentenyloxy, norbornenyloxy, and bicyclo[2.2.2]octenyloxy.

Cycloalkyl” mean^ a monocyclic or polycyclic, saturated substituent consisting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, bicyclo[2,2.2]octyl, and decqhydronaphthyl. ;.·

I “Cycloalkoxy mearis a cycloalkyl further cpnsisting of a carbon-oxygen single bond, for example, cyclopropÿloxy, cyclobutyloxy, cyclopentyloxy, norbomyloxy, and bicyclo[2.2,2]octyloxy.

u f

- ; i/ j Τ<ι: .ΐί , ·.

Fungicide Group is defined under the heading “FUNGICIDES.

Halo means fluoro, chloro^bromo, and iodo.^:!

Haloalkoxy” means an alkoxy furthçr consisting of, from one to the maximum or different, halos, for example, fluoromethoxy, trifluoromethoxy, chlorbmethoxy, trichloromethoxy, 1,1,2,2-tetrafluoroethoxy, and ii possible number of identical 2,2-difluoropropoxy, pentafluoroethoxy.

Haloalkyl” means a^i alkyl further consisting of, from one to the maximum possible number of, identical or different, halos, for example, fluoromethyl, trifluoromethyl, 2,2difluoropropyl, chloromethyl, trichloromethyl, and 1.;i,2,2-tetrafluoroethyl,

Herbicide Group” ts defined under the heading HERBICIDES.” “Heterocyclyl” means a cyclic substituent that may be fully saturated, partially unsaturated, or fully unsaturated, where the cyclic structure contai ns at least one carbon and at least one heteroatom, whëre said heteroatom'is‘nitrogen, sulfur, or oxygen. Examples of aromatic heterocyclyls inclüde, but are not limited to, benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl cinnolinyl, furanyl, indazolyl, indolyl, imidazolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyî, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, 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 tetrahydropyranyl. Examples of partially unsaturated heterocyclyls .include, but are not limited to, 1,2,3,4tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl, 4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, i

and 2,3-dihydro-[1,3,4]-oxadiazolyl. , “Insecticide Group” is defined under the heading “INSECTICIDES.”

Nematicide Group is defined under ithe heading NEMATIC1DES”

Synergist Group is defined under the.heading “SYNERGISTIC MIXTURES AND SYNERGISTS” ' .'· î

DETAILED DESCRIPTION OF THE INVENTION

This document discloses molécules having the following formula (“Formula One’’):

wherein:

(a)

An is ¹ (1) furany, phenyl, pyridazinyl; pyridyl, pyrimidinyl, thienyl, or (2) substituted furanyl, ; , Substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, or substituted thienyl, wherein said subs :itüted - furanyl; S substituted phenyl, substituted pyridazinyl, substituted pyridyl, substitüted pyrimidinyl, and substituted thienyl, hâve one or more

substituents independently selected from H, OH, F, Cl, Br, I, CN, NO₂, C_rCe alkyl, C_rC₆ haloalkyl, C_vC_e hydroxyalkyl, C₃-C_e cycloalkyl, C₃-C₀ halocycloalkyl, C₃-C_e hydroxycycloalkyl, C₃-C_s cycloalkoxy, C₃-C₀ halocycloalkoxy, C₃-C_e hydroxycycloalkoxy, CiC₆ alkoxy, Ci-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(=O)_n(C₁-C₀ alkyl), S(=O)_n(CrCe haloalkyl), 0502(0,-06 alkyl), OSOs^-Cg haloalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (C_r

C₆ alkyl)NR_xR_y, 0(=0)(0,-06 alkyl), 0(=0)0(0,-C_s alkyl), C(=O)(C,-C₆ haloalkyl), C(=0)0(C,-C_e haloalkyl), C(=O)(C₃-C₀ cycloalkyl), C(=O)O(C₃-C₆ cycloalkyl), C(=O)(C₂-C_ealkenyl), 0(=0)0(0₂-0₆ alkenyl), -.{Ci-Ca alky 1)01((¾-C₀ alkyl), (C,-C_e alkyl)S(Ci-C₆ alkyl), C(=O)(Ci-C₆ alkyl)C(=O)O(Ôi-C₆ alkyl), phényl/phénoxy, substituted phenyl and substituted phenoxy (wherein such substituted phenyl and substituted phenoxy hâve one or more substituents independently selected from H, OH, F, Cl, Br, I, CN, N0₂, C,-C₆ alkyl, C,-C_ehaloalkyl, Ci-C₆ hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆hydroxycycloalkyl, C₃-C_s cycloalkoxy, C₃-C₀ halocycloalkoxy, C₃-C_e hydroxycycloalkoxy, 0,C_e alkoxy, C,-C₆ haloalkoxy, C₂-C₀ alkenyl, C₂-C₆ alkynyl, S(=O)_n(C₁-C₆ alkyl), S(=O)_n(C₁-C₆ haloalkyl), OSO₂(C_rC₆ alkyl), OSO₂(Ci-C₆ haloalkyl), C(=O)H, C(=0)0H, C(=O)NR_xR_y, (C_rC₀ alkyl)NR_xR_y, Ο(=Ο)(Ο)-Ο₀. alkyl), 0(=0)0(0,-0^ alkyl), C(=0)(CrC_e haloalkyl), C(=0)0(Ci-C_e haloalkyl), C(=O)(C₃-C₆ cycloalkyl),,/C(=O)O(C₃-C₈ cycloalkyl), C(=O)(C₂-C_ealkenyl), C(=O)O(C₂-C₀ alkenyl), (Çi-Ce alkyl)O(ÇrC_e alkyl), (Ci-C₀ alkyl)S(Ci-C₆ alkyl), C(=O)(Ci-C₆ alkyl)C(=O)O(C₁-C₀ alkyl) phenyl, and phenoxy);

(b) Het is a 5 br 6 membered, ‘saturated or unsaturated, heterocyclic ring, containing one or more heteroatoms independently selected from nitrogen, sulfur, or oxygen, and where An and Ar₂ are not ortho to each othçr (but may be meta or para, such as, for a five membered ring they are 1,3 and for a 6' membered ring thesy are either 1,3 or 1,4), and where said heterocyclic ring may also be substituted with one or more substituents independently selected from H, OH, F, Cl, Br, I, CN, N0₂, oxo, C-i-Ce alkyl, Ci-C₀ haloalkyl,

Ci-C₀ hydroxyalkyl, C₃-C_s cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₀ hydroxycycloalkyl, C₃-C_scycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, CrCe alkoxy, CrC₆ haloalkoxy, C₂-C_e alkenyl, Ο₂-Ο₆ alkynyl, S(=O)_n(Ci-Ce alkyl), S(=O)_n(Ci-C_e haloalkyl), OSO₂(Ci-C₆ alkyl), OSO₂(Ci-C_e haloalkyl),, C(=0)H, C(=O)OH, C(=O)NR_xR_y, (CrCe alkyl)NR_xR_y, 0(=0)(0,-Ce alkyl), C(=O)O(CrC₆ alkyl), C(=O)(C_rC₀ haloalkyl), 0(=0)0(0,-0_βhaloalkyl), C(=O)(C₃-C₆ cycloalkyl), C(=O)O(,C^-Çe cycloalkyl), C(=O)(C₂-C_S alkenyl), Ο(=Ο)Ο(Ο₂-Ο₀ alkenyl), (Ο,τΟβ alkyQO^-Ce aljryl^/ÇrCe alkyl)S(C,-Ce alkyl), C(=O)(C₁-C₆alkyl)C(=O)O(C₁-C₆ alkyl), phenyl, phenoxy, substituted phenyl and substituted phenoxy (wherein such substituted phenyl and substituted phenoxy hâve one or more substituents independently selected from H, pH, F, Cl, Br^J_;,, CN, NO₂, Ci-C_e alkyl, C_rC_e haloalkyl, C-i-Ce hydroxyalkyl, C₃-C₆ cycloalkyl, Ç₃-C_6!i halocycloalkyl, < C₃-;C₀ hydroxycycloalkyl, C₃-C₆halocycloalkoxy, CrÇ_0! .hydroxycycloalkoxy, CrC₀ alkoxy, Ο,-Ο_β halocy.cloplkyl, : C₃-;C₀ hydroxycycloalkyl, C₃-C₆ cycloalkoxy, 0₃-0₆

i haloalkoxy, C₂-C_B alkenyl, |C₂-C₆'alkynyl, S(=O)_n(Ci-Ce alkyl), S(=O)_n(Ci-C₆ haloalkyl), OSOzCCrCe alkyl), OSO^-Ce haloalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (C_rC₆alkyl)NR_xR_y, C(=O)(Ci-C₅ alkyl), C(=O)O(C_rC₆ alkyl), 0(=0)(0,-Ce haloalkyl), 0(=0)0(0,-06 haloalkyl), C(=O)(C₃-C₆ cycloalkyl), C(=O)O(C₃-C₆ cycloalkyl), C(=O)(C₂-C_e alkenyl),

C(=O)O(C₂-C_e alkenyl), (C,-C_B alkyl)O(C,-C_e alkyl), (Ο,-Ο_δ alkyl)S(C_rCe alkyl), 0(=0)(0,-06 alkyl)C(=O)O(C,-C₆ alkyl), phenyl, and phenoxy);

(c) Ar₂ is (1) furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl, thienyl, or (2) substituted furanyl, substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, or substituted thienyl, wherein said substituted furanyl; 'substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, and substituted thienyl, hâve one or more substituents independently selected from H, OH,’ F, Cl, Br, I, CN, N0₂, C,-C₆ alkyl, C,-C_shaloalkyl, C,-C₆ hydroxyalkyl, Ο₃-Ο₆ cycloalkyl, Ο₃-Ο₆ halocycloalkyl, C₃-C₆hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C_e halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, 0,C_e alkoxy, C,-C₆ haloalkoxy, C₂-C_e alkenyl, C₂-C₆ alkynyl, S(=O)_n(C,-C₆ alkyl), S(=0)_n(C₁-C_shaloalkyl), OSO₂(Ci-C_e alkyl), 030₂(0,-0₆ haloalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (0,C₆ alkyl)NR_xR_y, 0(=0)(0,-06 alkyl), 0(=0)0(0,-06 alkyl), 0(=0)(0,-Ce haloalkyl), C(=O)O(C,-C_e haloalkyl), 0(=0)(0₃-0₆ cycloalkyl), C(=O)O(C₃-C₆ cycloalkyl), C(=0)(C₂-C₆alkenyl), C(=0)0(C₂-C₆ alkenyl), (C,-C₆ alkyl)p(C,-C₆ alkyl), (C,-C₆ alkyl)S(C,-C₆ alkyl), C(=0)(Ci-C₆ alkyl)C(=O)O(Ci-Ce alkyl), phenyl, phenoxy, substituted phenyl and substituted phenoxy (wherein such substituted phenyl and (substituted phenoxy hâve one or more substituents independently selected from H, OH, F, Cl, Br, I, CN, N0₂, C,-C₆ alkyl, C,-C₆haloalkyl, 0,-0₆ hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C_shydroxycycloalkyl, C₃-C₆ cycloalkoxy, ,C₃-Ce halocycloalkoxy, C₃-C_e hydroxycycloalkoxy, 0,C₆ alkoxy, 0,-0₆ haloalkoxy, C₂-C_e,alkenyl, C₂-C₆ alkynyl, S(=O)_n(C_rC₀ alkyl), S(=O)_n(Ci-C₆haloalkyl), OSO₂(Ci-C₆ alkyl), OSO₂(C_rC₆ haloalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (0,C₆ alkyl)NR_xR_y, C(=O)(C,-Ce alkyl), C(=0)O(C,-C₆ alkyl), C(=O)(C₁-C₆ haloalkyl), 0(=0)0(0,-06 haloalkyl), C(=O)(C₃-C₆ cycloalkyl), C(=O)O(C₃-C₆ cycloalkyl), 0(=0)(0,-06 haloalkyl), C(=0)(C₂-C_B alkenyl), 0(=0)0(0₂-0_Β alkenyl), (Ci-Ce aIkyl)0(01-Ce alkyl), (C,-C_Balkyl)S(C,-C₆ alkyl), 0(=0)(0,-0₆ alkyl)C(=O)O(C,-C_e alkyl), phenyl, and phenoxy);

(d) JisCRj,Rj₂;

i (e) L is a single bond;

(f) KîsNRk,; I (g) Q is O; ] ^; ‘ .· A (h) R1 is H, OH, F, Cl, Br, I, oxo, Ο,-Οβ alkyl, 0,-0₆ haloalkyl, Ο,-Ο_θ alkoxy, C₃-Ce cycloalkoxy, 0,-0₆ haloalkoxy, C₂-C₆ alkenylosty, (C,-C_B alkyl)O(C,-C_s alkyl), (Ci-C₆

^:Λ ! ^! F alkyl)O(C,-C₆ alkoxy), 00=0:.00, alkyl), 'Oe'lOMCs-Co cycloalkyl), OC(=O)(C,-C_e haloalkyl), OC(=O)(C₂-C₆ alkenyl),or NR_xR_y; ’ ’ ' (î) R2 is H, OH, F, Cl, Br, I, oxo, C,-C_B alkyl, 0,-0₆ haloalkyl, C,-C_e alkoxy, C₃-C_scycloalkoxy, 0,-0_Β haloalkoxy, C₂-C₆ alkenyloxy, (C_rC₆ alkyl)O(Ci-C_e alkyl), (Cj-C₆5 alkyl)O(C,-C_B alkoxy), 00(=0)(0,-0₆ alkyl), OC(=O)(C₃-C₆ cycloalkyl), OC(=O)(C₁-C_Shaloalkyl), OC(=O)(C₂-C₆ alkenyl),or NR_xR_y;

(j) R3 is H, OH, F, Cl, Br, I, oxo, C_rC_B alkyl, C,-Ce haloalkyl, C--C₅ alkoxy, C₃-C_ecycloalkoxy, C_rCe haloalkoxy, C₂-C_e alkenyloxy, (C_rC₆ alkyl)O(C,-C_e alkyl), (0,-0_Βalkyl)O(C,-C_e alkoxy), OC(=O)(C,-C₆ alkyl), bC(=O)(C₃-C₆ cycloalkyl), 00(=0)(0,-06 10 haloalkyl), 0C(=0)(C₂-C₆ alkenyl),or NR_xR_y;

(k) R4 is H, C,-C₆ alkyÊ 0,-0₆ haloàlk^, 0,-0₆ alkoxy, 0,-0₆ haloalkoxy, C₂-C₆alkenyloxy, (C_rC₆ alkyl)O(Ci-Ce alkyl); and ^f (l) Rjl, Rj2i and R_Ki, are independently selected from H, OH, F, Cl, Br, I, CN, N0₂, Ο,-Ο_β alkyl, C,-C₆ haloalkyl, 0,-0₆ hydroxyalkyl, C₃-C_s cycloalkyl, C₃-C_e halocycloalkyl,

C₃-C₆ hydroxycycloalkyl, Ç₃-C_B cycloalkoxy, ₍ C₃-C₆ halocycloalkoxy, C₃-C_e hydroxycycloalkoxy, C,-C₆ alkoxy, 0,-0₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C_e alkynyl, S(=O)_n(C,C₆ alkyl), S(=O)_n(C_rC₆ haloalkyl), OSO₂(C_rC₆ alkyl), QSO₂(C,-C_e haloalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (CrÇe alkyl)NR_xR_y, C(=O)(C,-C_B alkyl), 0(=0)(0,-0₆ alkyl)C(=O)O(C₁-C₆ alkyl), C(=O)O(C,-C₆ alkyl), 0(=0)(0,-06 haloalkyl), C(=O)O(C,-C_B haloalkyl), C(=O)(C₃-C_B cycloalkyl), C(=O)O(C₃-C₆ cycloalkyl), C(=O)(C₂-C_B alkenyl), C(=O)O(C₂-C_B alkenyl), (C,-C₆ alkyl)O(C,-C_e alkyl), (C,-C_s alkyl)S(C,-C_B alkyl), C(=O)(C_rC₆alkyl)C(=O)O(C,-C_e alkyl), 0(=0)(0,-C₆ alkyl)C(=O)OH, phenyl, phenoxy, wherein each alkyl, haloalkyl, hydroxyalkyl, cycloalkyl, halocycloalkyl hydroxycycloalkyl, cycloalkoxy, halocycloalkôxy, -hydroxycycloalkoxy, alkoxy, haloalkoxy, 25 alkenyl, alkynyl, phenyl, and phenoxy are j optionally substituted with one or more substituents independently selected from OH, .F, Cl, Br, I, CN, NO₂, oxo, Ci-C₆ alkyl, C,-C_Bhaloalkyl, C,-C₆ hydroxyalkyl,, C₃-C_e ,cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C_shydroxycycloalkyl, C₃-C_B cycloalkoxy, C₃-C_B halpçycloalkoxy, C₃-C_B hydroxycycloalkoxy, Ο,Οβ alkoxy, 0,-0_Β haloalkoxy, C₂-C_Bi'alkenyl, C^C^alkynyl,· S(=O)_n(Ci-C₆ alkyl), S(=O)n(C₁-Ce 30 haloalkyl), OSO₂(C,-C_e alkyj), OSO₂(G_rC_B haloalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (0,C₆ alkyl)NR_xR_y, 0(=0)(0,-0« alkyl), C(=O)O(Ç,-C_B alkyl), 0(=0)(0,-Ce haloalkyl), 0(=0)0(0,-06 haloalkyl), 0(=0)(C₃-C₆ cycloalkyl), C(=O)O(C₃-C_B cycloalkyl), 0(=0)(0₂-0_Βalkenyl), C(⁼O)O(C2^-CB alkenyl), (Ci-Cg alkyl )0(C,-C_B alkyl), (Ci-Ce alkyl)S(C,-C_B alkyl), C(=0)(C,-Ce alkyl)C(=O)O(0i-C_e alkyl), phenyl, and phenoxy;

(m) n= 0, 1, or2;Îand (n) R_x and R_y are independently selected from H, C,-C_B alkyl, C,-C₆ haloalkyl, 0,C₆ hydroxyalkyl, C₃-C_B cyploalkyl, C₃-C₆ halocycloalkyl, C₃-C_e hydroxycycloalkyl, C₃-C₆ ^; ' 'AA cycloalkoxy, C₃-C_e halocyçloalkoxy, C₃-C₆ hydroxycycloalkoxy, C_rC_e alkoxy, C,-C_ehaloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(=O)_n(C,-C₆ alkyl), S(=O)_n(C,-C_e haloalkyl), OSO₂(Ci-C₆ alkyl), OSO₂(C,-C₆ haloalkyl),. ,C(=O)H, C(=O)OH, C(=O)(C,-C₆ alkyl), 0(=0)0(0,-06 alkyl), C(=O)(ÇrÇ,6._; haloalkyl), ‘ C(=O)O(C,-C₆ haloalkyl), C(=O)(C_rC₆cycloalkyl), C(=O)O(C₃-C_B cycloalkyl), 0(=0)(0^06 alkenyl), C(=O)O(C₂-C₆ alkenyl), (C,-C₆alkyl)O(C,-C₆ alkyl), (C,-C₆ alkyl)S(C,-C_e alkyl), Ç(=O)(C,-C₆ alkyl)C(=0)O(C,-C₆ alkyl), phenyl, and phenoxy.

In another embodiment Ar, is a substituted phenyl. In another embodiment Ar, is a substituted phenyl having a C,-C₆ haloalkoxy substituent.

In another embodiment Het is a triazolyl.

In another embodiment Ar₂ is a phenyl.

In another embodiment Rj, and R_J2 are H

In another embodiment R_K, is H, C(=O)(Ci;Ce alkyl), C(=O)(CrC_e alkyl)C(=O)O(C_rC₆ alkyl), 0(=0)(0,-0_Θ alkyl)C(=O)OH.

PREPARATION OF PYRANOSE-INTERMEDIATES ' i

A wide variety of pyranoses (in different structural forms, for example, D and L) can be used to make the compounds of this invention. For example, the following non-exhaustive

A*·' · â; 'tf list of pyranoses may be used: ribose, arabînpse; xylose, lyxose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, psicose, fructose, sorbose, tagatose, fucose, mycarose, quinovose, oleandrose, rhamnose, and paratose.

In general, pyranose-intermediates can be prepared by methods previously described in the chemical literature and in Çrouse et al., U.S. Patent Application Publication 2009/0209476 A1, the entire disclosure of which is expressly incorporated by reference herein.

PREPARATION OF TRIARYL-INTERMEDIATES

Compounds of this invention are prepared by linking the above-described pyranoses to a triaryl intermediate, Ar,-Het-Ar₂, by means of a .covalent linker J[L]KQ (defined above). A wide variety of triaryl precurscrs can be used, to préparé compounds of this invention, provided that they contain ! a suitable functional group on Ar₂. Suitable functional groups include an amino, oxoalkyljformyl, or carboxylic acid group. These triaryl-intermediates can be prepared by methods previously described in the chemical literature and in Crouse et al., U.S. Patent Application Publication 2009/0209476 A1, the entire disclosure of which is expressly incorporated by réference herein.

i . · r . , i

PREPARATION OF OXIMÉ-LINKED COMPOUNDS

Oxime-linked compounds can be prepared from the corresponding aryl aldéhydes or i

ketones by reaction with thè corresponding 2-hydroxylamino sugar, in an organic solvent such as methyl alcohol (MeOH) or ethyl alcohol (ÉtôH), at températures between 0 and 100 ^cc. ··': Λ

I

PREPARATION OF HYDROXYLAMINE-LINKED COMPOUNDS

Hydroxylamine-linked compounds can be prepared from the corresponding oximelinked compounds via réduction using pyridine borane complex in an organic solvent such as EtOH. Altematively, the compounds can be generated in a two-step procedure from the 5 aldéhyde or ketone by reaction with the 2-hydroxylamino sugar, followed by réduction using pyridine borane complex in an organic solvent such as EtOH, at températures between 0 and 100 °C.

R2

pyridine borane complex

HCl, EtOH

R2

CHO

R

R2

EtOH

2. pyridine borane complex, HCl

R2

Elaboration of the hydroxylamine-linked compounds can be done in a variety of ways, such as formation of the sait using hydrochloric acid in dioxane in a solvent such as diethyl ether (Et₂O); acylation of the nitrogen with an acid chloride or anhydride in the i: ' presence of a base, such as pyridine; or alkylation/of the nitrogen with an alkyl halide in the presence of a base, such as diisopropylethylamine (DIEA) or potassium carbonate, in an organic solvent such as tetrahydrofuran (THF).

R2

4.0 M HCl in dioxane, Et,O . ‘..L *

R2

R3

R4 acetyl chloride, pyridine or succinic anhydride, pyridine

R2

2. CHJ. K₂CO,. THF, reflux

1. CH₃I, DIEA, THF, reflux

R2

Acylation of the nitrôgen can also be effected in a multistep process involving the acylation of the 2-hydroxyla(nino sugar and réduction of the aldéhyde to the corresponding alcohol, followed by réaction; with carbon tetrabromide to provide the corresponding bromide.

The bromide and acylated hydroxylamino sugar are then allowed to react in the presence of

» a base, such as sodium hydride, in an organic solvent, such as THF, to afford the acylated material.

D1EA, CH₂CI;

methyl chlormalonate

1. NaBH₄, EtOH

ÇHO R

2. PPh₃, CBq, THF

3. NaH, THF,

O

EXAMPLES

The examples are for illustration purposes ànd 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 further purification. Anhydrous solvents were purchased as Sure/Seal™ from Aldrich and were used as received. Melting points were obtained on a Thomas Hoover Unimelt capillary melting point apparatus or an OptiMelt Automated Melting Point System from Stanford Research Systems and are uncorrected. Molécules are given their known names, named according to naming programs within ISIS Draw, ChemDraw or ACD Name Pro. If such programs are unable to nàme a molécule, the molécule is named ’j using conventional naming rules. ¹H NMR spectrahdata are in ppm (δ) and were recorded at 300, 400 or 600 MHz, and ¹³C NMR spectral data are in ppm (□) and were recorded at 75, 100 or 150 MHz, unless otherwise stated.

Examples 1-9 illustrate the préparation of additional molécules useful in making various embodiments of this invention.

Example 1 : Préparation of O-((2S,3R,4R,5S,6S)-4-ethoxy-3,5-dimethoxy-6-methyltetrahydropyran-2-yl)-N-{4-[1-(4-pentafluoroethyloxy-phenyl)-1H-[1,2,4]triazol-3-yl]benzyl}-hydroxylamine (Compound 1)

ί,.; .

F

To a solution of 4-[1-(4-pentafluoroethyloxy-phenyl)-1 H-[1,2,4]triazol-3-yl]benzaldehyde 0-((2S,3R,4R,5S,6S)-4-ethoxy-3,5-dimethoxy-6-methyl-tetrahydropyran-2-yl)oxime (P-1; 257 milligrams (mg), 0.429 millimoles (mmol)) in 190 proof ethyl alcohol (EtOH;

10 milliliters (mL)) at room température was added pyridine borane complex (200 microliters (□L), 1.99 mmol) in one portion. 3 N Hydrochloric acid (HCl; 1.4 mL) was then added dropwise. When the addition was complété, the mixture stirred at room température for 23 hours (h). The mixture was then diluted with EtOH/water (H₂O) and treated with saturated sodium bicarbonate (NaHCO₃). The resulting aqueous mixture was extracted with ethyl acetate (EtOAc; 2X). The organic extracts were .‘combined, dried, washed with brine and dried with anhydrous sodium sulfate (Na₂SO₄). The solvent was evaporated at room température under vacuum. The resulting crude material was purified by silica gel chromatography (eluting with 50% EtOAc in Hexane). The title product (164 mg, 63%) was isolated as a white sticky solid: ¹H NMR (300 MHz, CDCl₃) δ 8.60 (s, 1H), 8.22-8.16 (m, 2H),

7.87-7.80 (m, 2H), 7.50 (d, J = 8.2 Hz, 2H), 7.46-7.38 (m, 2H), 6.04 (s, 1H), 5.01 (d, J = 1.4

Hz, 1H), 4.18 (s, 2H), 3.84-3.28 (m, 12H), 3.11 (dd, J = 12.0, 6.5 Hz, 1H), 1.30 (ddd, J = 20.9, 10.3, 4.6 Hz, 6H); ESIMS m/z 603 (M+H).

Example 2: (2S,3S,4R,5R,6S)-4,5-Dimethoxy-2-methyl-6-(N-{4-[1-(420 pentafluoroethyloxy-phenyl)-1H-[1,2,4]triazol-3-yl]-benzyl}aminooxy)-tetrahydroyran3-ol (Compound 2)

The title material was made as in Example 1 starting from 4-(1-(4pentafluoroethyloxy-phenyO-IH-fl.Z^triazol-'S-yll-benzaldehyde O-((2S,3R,4R,5S,6S)-5 1 r / ¹J ! : ’ ¹ hydroxy-3,4-dimethoxy-6-methyl-tetrahydropÿrah-2-ÿl)-oxime (P-2; 173 mg, 0.30 mmol). The j _μ desired product (113 mg, 66%) was isolated as a colorless glass: mp 50-58 °C; ¹H NMR (300 MHz, COCI₃) δ 8.61 (d, J= 5.1 Hz, 1H), 8.30-8.Ί3 (m, 2H), 7.93-7.76 (m, 2H), 7.51 (d, J = 8.3 Hz, 2H), 7.41 (d, J = 9.0 Hz, 2H), 6.10 (s] 1H), 5.07 (d, J= 1.5 Hz, 1H), 4.18 (d, J = 6.9 Hz, 2H), 3.76-3.12 (m, 10H), 2.44 (s, 1H), 1.48-1.28 (m, 3H); ESIMS m/z 576 (M+2H), 575 30 (M+H).

« *

Example 3: Préparation of /V-(4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]benzyl}-O-((2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydro-pyran-2-yl)hydroxylamine (Compound 3)

A solution of 4-[1-(4-trifluorômethoxÿphenylj-1H-[1,2,4]triazoi-3-yl]-benzaldehyde (P3; 203 mg, 0,610 mmol) and 0-((2S,3R₎4R,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydropyran-2-yl)-hydroxylamine (P-4; 179 mg, 0.81 mmol) in EtOH (20 mL) was heated to reflux under N₂ for 16 h. The mixture was then cooled to room température and pyridine borane complex (200 CL, 1.99 mmol) was added, followed by the dropwise addition of 3 N HCl (2 mL, 6.0 mmol). The mixture was allowed to stir at room température for 28 h and was then evaporated at room température under vacuum to a smaller volume. The concentrated mixture was diluted with EtOAc and washed with saturated NaHCO₃. The aqueous solution was extracted with more EtOAc. The organic fractions were combined, washed with brine, dried with anhydrous Na₂SO₄, and. evaporated at room température under vacuum. The resulting crude material was purified by silica gel chromatography (eluting with 50% EtOAc in Hexane to 100% EtOAc in a single step). The title product (223 mg, 68% from P-3) as a white glass: ¹H NMR (300 MHz, CDCI₃) δ 8.^9 (s, 1 H), 8.2-8.14 (m, 2H), 7.89-7.75 (m, 2H), 7.58-7.34 (m, 4H), 6.08 (d, J = 15.0 Hz, 1H), 5.01,(dd, J = 13.5, 6.1 Hz, 1H), 4.16 (d, J= 9.4 ί ¹ ^: -ï ·

Hz, 2H), 3.71-3.41 (m, 8H), 3.42-3.24 (m, 4H); 3_f10 (t, J = 9.4 Hz, 1H), 1.61 (d, J = 19.8 Hz, 1H), 1.38-1.24 (m, 3H); ¹³C NMR (101 MHz, ÇDÇI₃) δ 163.15, 148.37, 141.60, 138.97, 135.51, 129.64, 129.30, 126.65, 122.37, 121.66, 121.20, 119.10, 99.78, 82.04, 80.98, 76.20, 68.35, 60.83, 58.63, 57.61,56.52, 50.59, 17.81.; ESIMS m/z 539 (M+H).

Example 4: Préparation of Λ/-(4-[1-(4-ίπίΙυοΓθΓηθΐ1ΊθχγρηβηγΙ)-1Η-[1,2,4]1ΓΪ3ζοΙ-3-γΙ]benzyl}-O-((2S,3F?,4f?,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl)hydroxylamîne hydrochloride (Compound 4)

A solution of A/-{4-[1-(4-trifluoro^,mëtbo,xyphenyl)-1H-[1,2l4]triazol-3-yl]-benzyl}-O((2S,3R,4R,5S,6S)-3,4,5-trimethoxÿ-6-méthÿl-tetrah.ydropyran^j2-yl)-hydroxylamine (3; 87.5 mg, 0.162 mmol) in diethyl ether (Et2O; 8.75mL.) was treated by the dropwise addition of HCl (4 M in dioxane) until no more solid precipitated. The resulting suspension was spun in a

centrifuge and the solvent was decanted. The solid was slurried with fresh Et₂O, centrifuged and the solvent was decanted. The resulting solid was dried by évaporation at room température under vacuum to give the title product (70 mg, 75%) as a white solid: mp 107121 °C;¹H NMR (300 MHz, CD₃OD) δ 9.46 (d, J = 2.8 Hz, 1H), 8.37-8.17 (m, 2H), 8.15-7.96 (m, 2H), 7.73 (d, J = 8.3 Hz, 2H), 7.63-7.41 (m, 2H), 5.45 (d, J = 2.4 Hz, 1H), 4.75-4.58 (m, r

2H), 3.83-3.24 (m, 17H), 3.11 (dd, J =9.2, 8.3 Hz, 1 H), 1.25 (d, J =6.2 Hz, 3H), 1.18 (td, J = 7.2, 2.8 Hz, 2H); ES1MS m/z 539 (M+H, base).,

- 7' r/ . iii. i

Example 5: O-((2S,3R,4R,5S,6S)-4-Ethoxy-3,5-dimethoxy-6-methyl-tetrahydropyran-2yl)-N-{4-[1-(4-pentafluoroethyloxy-phenyl)-1H-[1,2,4]triazol-3-yl]-benzyl}hydroxylamine hydrochloride (Compound 5)

The title compound was made as in Example 3 starting from O-((2S,3R,4R,5S,6S)-4ethoxy-3,5-dimethoxy-6-methyl-tetrahydropyran-2-yj)-/V-{4-[1-(4-pentafluoroethyloxy-phenyl)1/7-[1,2,4]triazol-3-yl]-benzyl}-hydroxylamine (105 mg, 0.17 mmol). The title product (110 mg, 100%) was isolated as a white solid: mp 115-119 °C; ¹H NMR (400 MHz, CD₃OD) δ 9.44 (d, J = 7.1 Hz, 1H), 8.28 (d, J= 8.3 Hz, 2H), 8.16-7.96 (m, 2H), 7.74 (d, J= 8.3 Hz, 2H), 7.55 (d, J= 9.0 Hz, 2H), 5.47 (d, J = 2.2 Hz, 1H), 4.69 (s, 2H), 3.82-3.25 (m, 12H), 3.14 (d, J = 9.1 Hz, 1H), 1.38-1.20 (m, 6H); ESIMS m/z 603 (M+H. base). ' ’ / -:i; _?r

Example 6: Préparation of N-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]benzyl}-N-((2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yloxy)acetamide (Compound 6)

A solution of A/-{4-[1-(4-trifiuorom'èthoxyphenyl)-1/7-[1,2,4]triazol-3-yl]-benzyl}-0((2S,3R₎4R,5S,6S)-3,4,5-trimethoxy-6-methÿl-teÎrahydropyran-2-yl)-hydroxylamine (3; 94.4 ’ . f mg, 0.175 mmol) in pyridine (2 mL) was treated with acetyl chloride (70 üL, 0.98 mmol), and the mixture was allowed to stir at room température for 2.5 h. The mixture was then evaporated at room température under vacuum to a smaller volume. The concentrate was diluted with EtOAc and washed with 1 N HCl. The, aqueous layer was extracted 3 times with

Z ³ , r . ï Λ;.

ï · 1 .

EtOAc. The organic fractions were combined and dried with anhydrous MgSO₄. The solvent was then evaporated at room température under vacuum. The resulting crude material was purified by silica gel chromatography (eluting with 50% EtOAc in Hexane going to 90% EtOAc in Hexane in a single step). The title product (96.8 mg, 95%) was isolated as a colorless semi-solid: ¹H NMR (300 MHz, CDCI3) δ 8.56 (s, 1H), 8.16 (d, J = 8.4 Hz, 2H), 7.87-7.69 (m, 2H), 7.39 (d, J - 8.1 Hz, 4H), 5.19 (dd, J = 9.3, 6.6 Hz, 2H), 4.71 (d, J = 16.1 Hz, 1H), 3.70-3.28 (m, 12H), 3.12 (dd, J = 9.2, 7.9 Hz, 1H), 2.24 (s, 3H), 1.60 (s, 1H); ¹³C NMR (101 MHz, CDCI3) δ 163.17, 141.89, Ί35.74, '129.76, 128.21, 126.89, 122.44, 121.26, 81.74, 79.82, 73.74, 69.61,60.33, 58.86, 58.10’2ÎJ05, 18.12; ESIMS m/z 581 (M+H).

Example 7: Préparation of N-Methyl-N-{4-[1-(4-trifluoromethoxyphenyl)-1H- [1,2,4]triazol-3-yl]-benzyl}-O-((2S,3R,4/?,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl)-hydroxylamine (Compound 7) 'η ΐ

To a solution of A/-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]-benzyl}-O((2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl)-hydroxylamine (3; 205 mg, 0.38 mmol) in tetrahydrofuran (THF; 10 mL) was added diisopropylethylamine (DIEA;

300 üL, 1.7 mmol) followed by methyl iodide (250.QL, 4.0 mmol). This solution was heated to reflux. After 1 h, due to apparent précipitation of quaternized DIEA, anhydrous potassium carbonate (K₂CO₃) was added to the mixture albpg with methyl iodide (200 üL, 3.2 mmol), and the suspension was allowed to stir at reflux an additional 21 h. The mixture was then cooled to room température, diluted with H₂O and extracted with EtOAc (2X). The organic fractions were combined, washed with brine, dried with anhydrous Na₂SO₄ and evaporated

·. ^: Y. :

at room température under vacuum. The resulting crude material was purified by silica gel i . ·’ chromatography (eluting with 60%‘EtOAc in Hexarie). The title product (131 mg, 63%) was isolated as a pale yellow solid: mp 93-100 °C; ¹H NMR (400 MHz, CDCI₃) δ 8.63 (d, J = 4.1 Hz, 1H), 8.16 (d, J-8.3 Hz, 2H), 7.88-7.75 (m, 2H), 7.52 (t, J- 10.7 Hz, 2H), 7.39 (t, J= 9.5 Hz, 2H), 4.37 (d, J = 13.2 Hz, 2H), 3.98-2.89 (m, 15H), 1.25 (dd, J = 24.7, 6.2 Hz, 3H); ESIMS m/z 553 (M+H).

Example 8: Préparation of /V-{4-[1-(4-trifluorornethoxypheiiyl)-1H-[1,2,4]triazol-3-yl]benzyl}-N-((2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yloxy)succinamic acid (Compound 8) , r

-14. f

A λ

i

To a solution of A/-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]-benzyl}-0((2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl)-hydroxylamine (3; 140 mg, 0.26 mmol) in pyridine (5 mL) was added succinic anhydride (large excess), and the mixture stirred at room température for 3.5 h. The mixture was diluted with EtOAc and washed with 1 N HCl. The aqueous fraction was extracted with EtOAc (2X). The organic fractions were combined, washed with brine, dried with anhydrous MgSO₄ and evaporated at room température under vacuum.¹ The resulting Crude material was purified by silica gel chromatography (eluting with 80% EtOAc in Hexane going to 100% EtOAc over a short gradient). The title product (64 mg, 39%) was isolated as a white solid: mp 61-75 °C; ¹H NMR (300 MHz, CDCI₃) δ 8.63 (s, 1H), 8.16 (d, J = 8.3 Hz, 2H), 7.93-7.68 (m, 2H), 7.40 (d, J = 8.4 Hz, 4H), 5.40-5.10 (m, 2H), 4.76 (d, J= 1.6.1 Hz, 1 H). 3.73-3.25 (m, 13H), 3.15 (dd, J = 9.1, 7.9 Hz, 1H), 3.04-2.60 (m, 4H), 1.27 (dd, J = 9.8, 4.3 Hz, 3H); ESIMS m/z 639 (M+H), 638 (M+). .

Example 9: Préparation of N-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]benzyl}-W-((2S,3R,4R,5S_f6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yloxy)malonamic acid methyl ester (Compound 9)

Step A: Préparation of N-((2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydro!

pyran-2-yloxy)-malonamic acid methyl ester (P-5) ,

To a solution of O-^S.S^R.SS.eSkS^^trimethoxy-S-methyl-tetrahydropyran^yl)-hydroxylamine (P-4; 157 mg, 0.71 mmoljjn diôhloromethane (CH2CI2; 8 mL) was added DIEA (230 nL, 1.3 mmol) followed by a solutiôn of methyl chloromalonate (137 mg, 1.0 mmol) dissolved in CH2CI2 (2 mL). This mixture was allowed to stir at room température for 4 h. The mixture was then diluted with CH2CI2 and washed with 1 N HCl. The aqueous fraction was extracted with CH₂CI₂; The organic fractions were combined, dried with anhydrous Na_zSO₄ and evaporated at|room température under vacuum. The resulting crude material was purified by silica gel Chromatography (eluting· with 75% EtOAc in Hexane). The title

A

H · product (132 mg, 58%) was isolated as a colorless-oil: ¹H NMR (300 MHz, CDCI₃) δ 10.009.38 (m, 1H), 5.06 (d, J= 55.9 Hz, 1H), 4.02-2.92 (m, 18H), 1.39 (t, J = 20.4 Hz, 3H); ¹³C

NMR (101 MHz, CDCI₃) δ 189.13, 101.59, 81.56,77.24, 75.39, 69.66, 59.26, 57.89, 52.86,

39.75, 26.47, 17.85; ESIMS m/z 320 (M-H).

Step B: Préparation of {4-[1-(4-trifluorometh9xyphenyl)-1H-[1,2,4]triazol-3-yl]-phenyl}methanol (P-6)

To a solution of 4-[1-(4-trifluoromethoxyphenyl)-1/-/-[1,2_]4]triazol-3-yl]-benzaldehyde 10 (P-3; 2.59 g, 7.79 mmol) in EtOH (120 mL), sodium borohydride (725.8 mg, 19.18 mmol) was added as a solid în portions at room température. After the addition was complété, the mixture was stirred at room température for 90 minutes (min). The mixture was then diluted n ' with EtOAc and washed with H₂O. The aqueousfraction was extracted with EtOAc. The organic fractions were combined, dried over anhydrous MgSO₄, and evaporated at room 15 température under vacuum. The crude material was absorbed to silica gel with EtOAc and eluted with 50% EtOAc in hexane, The title product (2.43 g, 93%) was isolated as a white solid: mp 112-114 °C; ¹H NMR (300 MHz, CDCI₃) δ 8.55 (s, 1H), 8.29-8.12 (m, 2H), 7.917.69 (m, 2H), 7.43 (ddd, J = 9.0,. 5.7, 4.5 Hz, 4H), ^.78 (d, J = 6.0 Hz, 2H), 2.07 (t, J = 6.0 Hz, 1 H); ESIMS m/z 336 (M+H).

:

Step C: Préparation of 3-(4-bromomethylphenyl)-1-(4-trifluoromethoxyphenyl)-1ft- [1,2,4]triazole (P-7)

To a solution of (4-[1-(4-trifluoror)nethoxyphenyl)-1 H-[1,2,4]triazol-3-yl]-phenyl}25 methanol (P-6; 5.033 g, 15.01 mmol) in THF (1Q0 mL,) was added triphenylphosphine (6.009 g, 22.91 mmol). Carbon tetrabromide (7.704 g,; 23/23 mmol) dissolved in THF (20 mL) was then added dropwise at room température. The mixture was allowed to stir at room température for 23 h. It was then filtered through Celite, and the solvent was evaporated at room température under vacuum. The icrude ?.material was purified by silica gel 30 chromatography, eluting with 50% .EtOAc/^eXiajpe.'Ooing to 70% EtOAc/hexane and then 100% EtOAc in a two-step gradient, The title product (4.61 g, 77%) was isolated as a beige solid: mp 124-126 °C; ¹H NMR (300 MHz, CDC|₃) δ 8.59 (s, 1H), 8.25-8.13 (m, 2H), 7.89- 1616336

7.72 (m, 2H), 7.60-7.47 (m, 2H), 7.47-7.34 (m, ,2H), 4.57 (s, 2H); ESIMS m/z 400 (M+2H), 399 (M+H). . ;

' - <* , Γ '

Step D: Préparation of W-{4-[1-(4-trifluorômethoxyphenyl)-1H-[1,2,4]triazol-3-yl]5 benzyl}-/V-((2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yloxy) malonamic acid methyl ester (Compound 9)

To a solution of N-((2S,3R.4R_:5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2ί yloxy)-malonamic acid methyl ester (P-5; 108 mg, 0.34 mmol) in dry THF (3 mL) was added

60% NaH (14.4 mg, 0.36 mmol) giving gas évolution. To this mixture was added 3-(4bromomethylphenyl)-1-(4-trifluoromethoxyphenyl)-1W-[1,2_]4]triazole (P-7; 106 mg, 0.26 ï mmol), and the resulting mixture was heated to 50 °C for 21 h. The mixture was then allowed to cool to room température and diluted with EtOAc and washed with H₂O. The aqueous fraction was extracted with EtOAc. The organic fractions were combined, washed with brine, 15 dried with anhydrous Na₂SO₄ and evaporatëd at room température under vacuum. The resulting crude material was purified by silica^gél. chromatography (eluting with 100% ^{1 1} 'f - '¹

Hexane going to 50% EtOAc in Hexane over 15 min and then going to 100% EtOAc over an additional 20 min). The title product (56 mg, 34%) was isolated as a colorless glass: ¹H NMR (300 MHz, CDCIs) δ 8.58 (s, 1H), 8.17 (d, J = 8.4 Hz, 2H), 7.90-7.70 (m, 2H), 7.41 (dd, J = 20 9.9, 8.4 Hz, 4H), 5.42-5.09 (m, 2H), 4.76 (d, J = 15.9 Hz, 1H), 3.83-3.05 (m, 18H), 1.41-1.20 ] (m, 3H); ¹³C NMR (151 MHz, CDCI₃) δ 167.80, 148.87, 141.93, 137.72, 135.95, 130.20,

128.71, 127.19, 122.81, 121.66, 119.95, 105.05, 82.11, 81.97, 79.79, 76.81, 70.28, 70.04, 60.48, 59.63, 59.20, 58.37, 52.76, 41.66, 30.10, 18.58; ESIMS m/z 639 (M+H).

ί j i t

I ' ] 25 Example 10: Bioassays om Beet Armyworm (“BAW”) and Corn Earworm (“CEW”)

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 économie concern upon asparagus, cotton, 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, asparagus, i cabbage, cantaloupe, collards, eowpeas, cucurpHers, eggplant, lettuce, lima beans, melon,

I ' ¹

£ okra, peas, peppers, potatoes, pumpkin, snap beans, spinach, squash, sweet potatoes, and watermelon, among other plants, CEW is also known to be résistant to certain insecticides.

Consequently, because of the above factors control of these pests is important.

Furthermore, molécules that control these pests are useful in controlling other pests.

Certain molécules disclosed in this document were tested against BAW and CEW using procedures described in the following examples. In the reporting of the results, the BAW & CEW Rating Table” was used (See Table Section), ; ^: J · ]

i > .'

I

Bioassays on BAW (Spodoptera exigua)

Bioassays on BAW were conducted using a 128-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 pg/cm² of the test compound 5 (dissolved in 50 pL of 90:10 acetone-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 ^eC, 14:10 light-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activîty in the eight wells was then averaged. The results are indicated in the table entitled “Table 1 (See Table Section).

.

• · f , i r? :

Bioassays on 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 15 (dissolved in 50 pL of 90:10 acetone-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 light-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activîty in the eight wells was then averaged. The results are indicated in the table entitled “Table 1” (See Table Section).

Example 11 : Bioassays on 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 transport of plant viruses, such as potato virus Y and potato leafroll virus 25 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, carrot, cauliflower, daikon, eggplant, green beans, Jettuce, macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress, apd zucchini, among other plants. GPA also attacks many ornamental crops such as carnation;.chrysanthempm, flowering white cabbage, poinsettia, 30 and roses. GPA has developed résistance to many pesticides.

Certain molécules disclosed in this document were tested against 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 35 used as test substrate. The seedlings were infested with 20-50 GPA (wingless adult and nymph stages) one day prior to chemical application. Four pots with individual seedlings

I were used for each treatment. Test compounds (2 mg) were dissolved in 2 mL of

19i

Jl !

acetone/methanol (1:1) solvent, forming stock solutions of 1000 ppm test compound. The stock solutions were diluted 5X with 0.025% Tween 20 in H₂O 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 containing 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 relative humidity (RH) prior to grading. Evaluation was conducted by counting the number of live aphids per plant under a microscope. Percent Control was measured by using Abbott’s correction formula (W.S. Abbott, “A Method of Computing the Effectiveness of an Insecticide J. Econ. Entomol. 18(1925), pp.265-267)_L as follows.

Corrected % Control = 100 * (X - Y) IX where

X = No. of live aphids on solvent check plants and

Y ~ No. of live aphids on treated plants

The results are indicated in the table entitled “Table 1” (See Table Section).

• : ‘ - · ’ '¹ ί ' l - i :

PESTICIDALLY ACCEPTABLE ACID ADDITION SALTS, SALT DERIVATIVES, SOLVATES, ESTER DERIVATIVES, POLYMORPHS, ISOTOPES AND RADIONUCLIDES

Molécules of Formula One may be formulated into pesticidally acceptable acid addition 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, oxalic, succinic, tartane, 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 alkaline earth metals and those derived from ammonia and amines. Examples of preferred^ cations include sodium, potassium, and magnésium. , _; > η.·

Molécules of Formula One may be formulated into sait dérivatives. By way of a nonlimiting example, a sait dérivative can be prepared. by contacting a free base with a sufficient amount ofthe desired acid to produce a sait. Afree base may be regenerated by treating the sait 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 sait..

Molécules of Formula ^One may be formulated into stable complexes with a solvent, such that the complex remains intact after the non-complexed solvent is removed. These ’-20À ί i i

I t complexes are often referred to as solvatés. However, it is particularly désirable to form | stable hydrates with water as the solvent. ‘ j

Molécules of Formula One may be .made into ester dérivatives. These ester dérivatives can then be applied in the same manner as the invention disclosed in this document is applied.

Molécules of Formula One may /be made as various crystal polymorphs. Poiymorphism is important in the development? of agrochemicals since different crystal i polymorphs or structures of the sarhe'moleculè ’Çan hâve vastly different physical properties and biological performances.

Molécules of Formula One. may be made with different isotopes. Of particular importance are molécules having ²H (also known as deuterium) in place of ’H.

Molécules of Formula One may be made with different radionuclides. Of particular importance are molécules having ¹⁴C.

STEREOISOMERS

Molécules of Formula One may exist as one or more stereoisomers. Thus, certain molécules 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 stereoisomers may be obtained by known sélective synthetic procedures, by conventional synthetic procedures using resolved starting,·, materials, or by conventional résolution procedures. . · _}< :·£, _ÿi \ /. .

À

INSECTICIDES

Molécules of Formula One 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 insecticides - 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, 5 acetoprole, acrinathrin, acrylonitrile, alanycarb,_i;aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, atpha-cypermethrin, a/pfta-ecdysone, a/pha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azînphos-ethyl,. azinphos-methyt, azothoate, barium hexaf lu orosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, 10 bioallethrîn, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, 15 chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, 20 coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, , decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demetqp-njethyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dial if os, 25 diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, _: dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, dlimonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, 30 ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, ,esdepalléthrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl,. ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene ojçide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, 35 fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronîl, flometoquin, flonicamid,Jlubendiamide (additionally resolved isomers thereof), flucofuron, flucycloxuron, ΑυογίΜπη^β,.; flufenerim, flufenoxuron, flufenprox,

-22 / i

flupyradifurone, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthietan, fufenozide, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, 5 hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphosmethyl, isoprocarb, isoprothiolane, isothioate, isôxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvénile hormone I, juvénile hormbne 11, juvénile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, 10 lufenuron, lythidathion, malathion, malonoben, ma'zidox, mecarbam, mecarphon, menazon, meperfluthrin, mephosfolan, mercurous chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb,. biethocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, ^methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metoflüthrin· metolcarb, metoxadiazone, mevinphos, 15 mexacarbate, milbemectin, milbemycin oxime; mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, 20 phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphôs, pirimicarb, pirimiphos-ethyl, pirimiphosmethyl, potassium arsenite, potassium thiocyanate, pp’-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos; profenofos, profluralin, profluthrin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, 25 protrifenbute, pymetrozine, pyraclofos, pyrafluprple, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben,·, pyridalyl./pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla^ schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium . hexafluorosilicate, sodium thiocyanate, 30 sophamîde, spinetoram, spinosad,. spiromesifen, spirotetramat, sulcofuron, sulcofuronsodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, iheta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, 35 thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultapdisodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate,, _; tnazophos, trichlorfon, trichlormetaphos-3, î23· l

/ trichloronat, trifenofos, triflumuron, trimethacarlô, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, , and zolaprofo^ (collectively these commonly named insecticides are defined as the “Insecticide Group”).

ACARICIDES

Molécules of Formula One 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 acaricides - acequinocyl, amidoflumet, arsenous oxide, azobenzene, azocyclotin, benomyl, benoxafos, benzoximate, benzyl benzoate, bifenazate, binapacryl, bromopropylate, chinomethionat, chlorbenside, chlorfenethol, chlorfenson, chlorfensulphide, chlorobenzilate, chloromebuform, chlorometbiuron, chloropropylate, 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, fenothiocarb, fenpyroximate, fenson, fentrifanil, ifluacrypyrim, fluazuron, flubenzimine, fluenetil, flumethrin, fluorbenside, hexythiazo^_i._îimpsulfen, MNAF, nikkomycins, proclonol, propargite, quintiofos, spirodiclofen, sulfirarp, .sulfur, tetradifon, tetranactin, tetrasul, and thioquinox (collectively these commonly named acaricides are defined as the “Acaricide Group).

NEMATICIDES

Molécules of Formula One 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, isamidofos, isazofos, metam, metam-ammonium, metam-potassium, metam-sodium, phosphocarb, and thionazin (collectively these commonly named nematicides are defined as the “Nematicide Group)

FUNGICIDES ?

Molécules of Formula One 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 fungicides - (3-ethoxypropyl) mercury bromide, 2-methoxyethylmercury chloride, 2phenylphenol, 8-hydroxyquinoline sulfate, 8-phenylmercurioxyquinoline, acibenzolar, acibenzolar-S-methyl, acypetacs, acypetacs-copper, acypetacs-zinc, aldimorph, allyl alcohol, ametoctradin, amisulbrom, ampropylfos, anilazine, aureofungin, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benthiavalicarb-isopropyl, benzalkonium chloride, benzamacril,

-•2416336 benzamacril-isobutyl, benzamorf, benzohydroxamic acid, bethoxazin, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S, Bordeaux mixture, boscalid, bromuconazole, bupirimate, Burgundy mixture, buthiobate, butylamine, calcium polysulfide, captafol, captan, carbamorph, carbendazim, carboxin, carpropamid, carvone, Cheshunt mixture, chinomethionat, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chlorodinitronaphthalene, chloroneb, chloropicrin, chlorpthalonil, chlorquinox, chlozolinate, climbazole, clotrimazole, copper acetate, 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, 10 cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, dazomet-sodium, DBCP, debacarb, decafentin, dehydroacetic acid, dichlofluanid, dichlone, dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomezine, diclomezine-sodium, dicloran, diethofencarb, diethyl pyrocarbonate, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinicoriazole-M, dinobuton, dinocap, dinocap-4, 15 dinocap-6, dînocton, dinopenton, dinosulfon, dlnoterbon, diphenylamine, dipyrithione, disulfîram, ditalimfos, dithianon, DNOC, DNOC/ammonium, DNOC-potassium, DNOCsodium, dodemorph, dodemorph acetate, dodemorph benzoate, dodicin, dodicin-sodium, dodine, drazoxolon, edîfenphos, epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate, 20 ethylmercury bromide, ethylmercury chloride, /ethylmercury phosphate, etridiazole, famoxadone, fenamidone, fenamiriosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonll, fenpropidin, fenpropimorph, fentin, fentin chloride, fentin hydroxide, ferbam,_; ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, 25 flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, fol pet, formaldéhyde, fosetyl, fosetylaluminium, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furconazole-cls, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene, hexaconazole, hexylthiofos, hydrargaphen, hymexazol, imazalil, imazalil nitrate, imazalil i sulfate, imibenconazole, iminoctadine, 30 iminoctadine triacetate, iminoctadine trialbesilate, iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazapi, isotianil, isovaledione, kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid, mepanipyrim, mepronil, meptyldinocap, merçuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, . rrietam, rnetafn-.ammonium, metam-potassium, metam35 sodium, metazoxolon, metconazole₍ methaSulfqdarb, methfuroxam, methyl bromide, methyl isothiocyanate, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, metiram, metominostrobin, metrafenone, metsulfovax, milneb,

-25 16336 myclobutanil, myclozolin, N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin, nitrostyrene, nitrothal-iso propyl, nuarimol, OCH, octhilinone, ofurace, orysastrobin, oxadixyl, oxine-copper, oxpoconazole, oxpoconazole fuma rate _; oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, penthiopyrad, phenylmercuriurea, 5 phenylmercury acetate, phenylmercury chloride, phenylmercury dérivative of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, phosdiphen, phthalide, picoxystrobin, piperalin, polycarbamate, polyoxins, polyoxorim, polyoxorim-zinc, potassium azide, potassium polysulfide, potassium_f thiocyanate·,.. probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride,.j;· pfopiconazole, propineb, 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, sedaxane, silthiofam, simeconazole, sodium azide, sodium 15 orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, spiroxamine, streptomycin, sulfur, sultropen, TCMTB, tebucoqazole, tebufloquin, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiochlorfenphim, thiomersal, thiophanate, thiophanate-methyl, thioquinpx, thiram, tiadinil, tioxymid, tolclofosmethyl, tolylfluanid, tolylmercury acetate, triadirpefon, triadimenol, triamiphos, triarimol, 20 triazbutil, triazoxide, tributyltin oxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, uniconazole-P, validamycin, valifenalate, vinclozolin, zarilamîd, zinc naphthenate, ;zineb_V: ziram, zoxamide (collectively these commonly named fongicides are defined as the Fungicide Group”),

HERBICIDES

Molécules of Formula One 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-dimethylammonium, 2,3,6-TBA-sodium, 2,4,5-T,

2.4.5- T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl, 2,4,5-T-3-butoxypropyl, 2,4,5-TB, 2,4,5-T30 butometyl, 2,4,5-T-butotyl, 2,4,5-T-butyl, 2,4,5-Trisobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl,

2.4.5- T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium, 2,4,5-T-triethylammonium, 2,4,5-T-trolamine, j/·¹’

2.4- D, 2,4-D-2-butoxy propyl, 2,4-D-2-ethylhexyl, ·2,4-D-3-butoxypropyl, 2,4-D-ammonium,

2.4- DB, 2,4-DB-butyl, 2,4-DB-dimethylammoniurn_; 2,4-DB-isoctyl, 2,4-DB-potassium, 2,4DB-sodium, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium,

2,4-D-diolamine, 2,4-D-dodeçylammonium, 2,4-DEB, 2,4-DEP, 2,4-D-ethyl, 2,4-Dheptylammonium, 2,4-D-isobutyl_f ^,4-D-isocty^ 2!,4-D-isopropyl, 2,4-D-isopropylammonium, • ’.Z v

2,4-D-lithium, 2,4-D-meptyl, 2,4-D-methyl, 2,,4-0-0^1, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-26 propyl, 2,4-D-sodium, 2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2₁4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 3,4-DA, 3,4-DB, 3,4-DP, 4-CPA, 4CPB, 4-CPP, acetochlor, acifluorfen, acifluorfen-methyl, acifluorfen-sodium, aclonifen, acrolein, alachlor, allidochlor, alloxydim, alloxydim-sodium, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, . amidosulfuron, aminocyclopyrachlor, aminocyclopyrachlor-methyl, aminocyclopyrachlor-potassium, aminopyralid, aminopyralidpotassium, aminopyralid-tris(2-hydroxypropyl)amrnonium, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisurorï, âSulàm,- asulam-potassium, asulam-sodium, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, benazolin-dimethylammonium, ! ‘benazolin-ethyl, benazolin-potassium, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, bentazone-sodium, : benzadôx, benzadox-ammonium, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofiuor, benzoylprop, benzoylprop-ethyl, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribacsodium, borax, bromacil, bromacil-lithium, bromacil-sodium, bromobonil, bromobutide, bromofenoxim, bromoxynil, , bromoxynil butyrate, bromoxynil heptanoate, bromoxynil octanoate, bromoxynil-potassium, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, càmbendichlor, carbasulam, carbetamide, carboxazole, carfentrazone, carfentrazone-ethyl, CDEA, CE PC, chlomethoxyfen, chloramben, chloramben-ammonium, chloramben-diolamine, chloramben-methyl, chloramben-methylammonium, chlcramben-sodium. chloranocryl, chlorazifop, chlorazifoppropargyl, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenacsodium, chlorfenprop, chlorfenprop-methyl, chlorflurazole, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, ή chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorprocarb, chlorproplpm, çhlorsulfuron, chlorthal, chlorthaldimethyl, chlorthal-monomethyl, chlorthiamid_ti;_: çwiidon-ethyl,. cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clodtnafop-propargyl, clofop, clofop-isobutyl, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl, clopyralidolamine, clopyralid-potassium, çlopyralid-tris(2-hydroxypropyl)ammonium_I cloransulam, cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanamide, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyperquat chloride, cyprazine, cyprazoie, cypromid, daimuron, dalapon, dalapon-calcium, dalapop-magnesium, dalapon-sodium, dazomet, dazomet-sodium, delachlor, desmedipham, de^pnetryn, di-allate, dicamba, dicambadimethylammonium, dicamba-diolamine, dicamb^-isopropylammonium, dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba-sodium, dicamba-trolamine, dichlobenil,

i i r iΓ ί

dichloralurea, dichlormate, dichlorprop, dichlorprop-2-ethylhexyl, dichlorprop-butotyl, dichlorprop-dimethylammonium, dichlorprop-ethylammonium, dichlorprop-isoctyl,t 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,!

i dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dihoprop, dinosam, dinoseb, dinoseb acetate, dinoseb-a mm onium, dinoseb-diolamine, dinoseb-sodium, dinoseb-trolamine, dinoterb, 10 dinoterb acetate, dîphacinone-sodium, dipheriamfà, dipropetryn, diquat, diquat dibromide, disul, disul-sodium, dithiopyr, diuron, DMPA, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, DSMA, EBEP, eglinazine, eglinazine-ethyl, endothal, endothal-diammonium, endothal-dipotassium, endothal-disodium, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethidimuron, ethiolate, ethofumesate, ethoxyfen, 15 ethoxyfen-ethyl, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoprop-3-butoxypropyl, fenoprop-butometyl, fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl, fenoprop-methyl, fenoprop-potassium, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fenoxasulfone, fenteracol, fenthiaprop, fenthiaprop-ethyl, fentrazamide, fenuron, fenuron TCA, ferrous sulfate, flamprop, flamprop-isopropyl, flamprop20 M, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-butyl, fluazifop-methyl, fluazifop-P, fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flufenpyr-ethyl, flumetsulam, flumezin, flümiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron, fluorodjfen, fluoroglycçfen, fluoroglycofen-ethyl, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropaçil, flupropanate, flupropanate-sodium, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, fJurochloridone, fluroxypyr, fluroxypyrbutometyl, fluroxypyr-meptyl, flurtamone, fluthiacpt, fluthiacet-methyl, fomesafen, fomesafensodium, foramsulfuron, fosamine, fosamine-ammonium, furyloxyfen, glufosinate, glufosinateammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-diammonium, glyphosate-dimethylammonium, glyphosate-isopropylammonium, glyphosate-monoammonium, glyphosate-potassium, glyphosate-sesquisodium, glyphosatetrimesium, halosafen, halosulfuron, halosulfuron-methyl, haloxydine, haloxyfop, haloxyfopetotyl, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-etotyl, haloxyfop-P-methyl, haloxyfopsodium, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamethabenz35 methyl, imazamox, imazamox-ammonium, . imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium. imazaquin-methyl, imazaquin-sodium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan,

indaziflam, iodobonil, iodomethane, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, ioxynil, ioxynil octanoate, ioxynil-lithium, ioxynil-sodium, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, .s'·,, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, ΜΑΜΑ, MCPA, MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl, _f ' j. » J ' ) i .

MCPA-diméthylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA-olamine, MCPA-potassium, MCPA-sodium, MCPAthioethyl, MCPA-trolamine, MCPB, MCPB-ethyl, MCPB-methyl, MCPB-sodium, mecoprop, mecoprop-2-ethylhexyl, mecoprop-dimethylammonium, mecoprop-diolamine, mecopropethadyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-P, mecoprop-P-dimethylammonium, mecoprop-P-isobutyl, mecoprop-potassium, mecoprop-P-potassium, mecoprop-sodium. mecoprop-trolamine, medinoterb, medinoterb acetate, mefenacet, mefluidide, mefluididediolamine, mefluidide-potassium, mesoprazine, mesosulfuron, mesosulfuron-methyl, mesotrione, metam, metam-ammonium, metamifop, metamitron, metam-potassium, metamsodium, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiurôn, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfùron, metsulfuron-methyl, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monufon, mônuron TCA, morfamquat, morfamquat ' .^! '' ¹ !

dichloride, MSMA, naproanilide, napropamicfe,, naptalam, riaptalam-sodium, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene, orthosu Ifamuron, oryzalin, oxadiargyl, oxadiazon, l

oxapyrazon, oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat, paraquat dichloride, paraquat dimetilsulfate, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmediphamethyl, phenobenzuron, phenylmercury acetate,· picloram, picloram-2-ethylhexyl, picloramisoctyl, picloram-methyl, picloram-olamine, piçloram-potassium, picloram-triethylammonium, pi cloram-tris(2-hydroxypropyl) ammonium, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, .pretilachlor, primisulfuron, primisulfuronmethyl, procyazine, prodiamine, profluazol, _; profluralin, profoxydim, proglinazine, proglinazine-ethyl, prometon, prometryn, prppaçhlpr, propanil, propaquizafop, propazine, propham, propisochlor, propoxyçarbazone, ; propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfùron, proxan, proxan-sodium, prynachlor, pydanon, pyraclonil, pyraflufen, pyraflufen-ethÿl, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalîd, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, rhodethanil, rimsulfuron, saflufenacil, sebuthylazine, secbùriiëton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, S-metolachlor, sodiüm arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCAmagnesium, TCA-sodium, tebutam, tebuthiuron. tbfuryltrionë, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbüthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, tri-allate, triasulfuron, triazifîam, tribenuron, tribenuron-methyl, tricamba, triclopyr, triclopyr-butotyl, triclopyr-ethyl, triclopyr-triethylammonium, tridiphane, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, triflusulfuron, triflusulfuron-methyl, trifop, trifop-methyl, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, xylachlor, (collectively these commonly named herbicides are defined as the “Herbicide Group).

' f · \.

.? ^! f ?î. :

BIOPESTICIDES

Molécules of Formula One may also be used in combination (such as in a compositional mixture, or a simultaneous .br sequential application) with one or more biopesticides. The term “biopesticide” is used for microbial biologieal pest control agents that are applied in a similar manner to chemical pesticides. Commonly these are bacterial, but there are also examples of fungal control agents, including Trichoderma spp. and Ampelomyces quisqualis (a control agent for grape powdery mildew). Bacillus subtilis are used to control plant pathogens. Weeds and rodents hâve also been controlled with microbial agents. One well-known insecticide example is Bacillus thuringiensis, a bacterial disease of Lepidoptera, Coleoptera, and Diptera. Because it has little effect on other organisms, it is considered more environmentally friendly than synthetic pesticides. Biologieal insecticides include products based on:

1. entomopathogenic fungi (e.g. Metarhizium anisopliae);

2. entomopathogenic nematodes (e.g. tyeinemema feltiae); and

3. entomopathogenic viruses (e.g. Cydia pomonella granulovirus).

Other examples of entomopathogenic organisms include, but are not limited to, baculoviruses, bacteria and other prokaryoticorganisms, fungi, protozoa and Microsproridia.. Biologically derived insecticides include, but not limited to, rotenone, veratridine, as well as microbial toxins; insect tolérant or résistant plant varieties; and organisms modified by recombinant DNA technology to either produçe insecticides or to convey an insect résistant property to the genetically modified organism. in one embodiment, the molecuies of Formula One may be used with one or more biopesticides in the area of seed treatments and soit amendments. The Manual of Biocontrol 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. _s.

t ‘ i

OTHER ACTIVE COMPOUNDS

Molécules of Formula One may also be used in combination (such as in a 10 compositional mixture, or a simultaneous or sequential application) with one or more of the . - ; . t following:

1. 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxÿ-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;

2. 3-(4’-chloro-2,4-dimethyl[1,1’-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3en-2-one;

3. 4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5/-/)-furanone;

4. 4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5W)-furanone,

5. 3-chloro-/V2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-A/1-[2-methyl-4-[1,2,2,2tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide;

6. 2-cyano-/V-ethyl-4-fluoro-3-methoxy-benenesu)fonamide,

7. 2-cyano-A/-ethyl-3-methoxy-benzenesulfonamide;

ΐ Al ’ ·

8. 2-cyano-3-difiuoromethoxy-A/-ethyl-4-fluoro-benzenesulfonamide;

- · J

9. 2-cyano-3-fluoromethoxy-A/-ethyl-benzenesulfonamide;

10. 2-cyano-6-fluoro-3-methoxy-/V,/\/-dimethyl-benzenesulfonamide;

11. 2-cyano-N-ethyl-6-fluoro-3-methoxy-A/-methyl-benzenesulfonamide:

12. 2-cyano-3-difluoromethoxy-A/,N-dimethÿlbênèenesulfon-amide;

13. 3-(difluoromethyl)-N-[2-(3,3-dimethyibutyi)phenyl]-1 -methyl-1 /-/-pyrazole-4carboxamide;

14. A/-ethyl-2,2-dimethy)propionamide-2-(2,6-dichloro-a,a,a-trifluoro-p-tolyl) hydrazone;

15. N-ethyl-2,2-dichloro-1-fnethylcyclopropane-carboxamicle-2-(2_]e’dichloro-a,a,a- trifluoro-p-tolyl) hydrazone nicotine;

16. 0-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1 -(2-trifluo romethy Iph eny l)-vi ny I]} S-methyl thiocarbonate;

17. (E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine;

18. 1 -(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitrp;1,2,3,5,6,7-hexahydro-imidazo[1,2-

a]pyridin-5-ol; V ^; · 7

i ¹ ί

i ι 19. 4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl mesylate; and

20. N-Ethyl-2,2-dichloro-1rmethylcyc!opropanecarboxamide-2-(2,6-dichloroa/p/îa,a/pfia,a/pha-trifluoro-p-tolyl)hydrazone.

Molécules of Formula One 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, bactéricides, bird repellents, chemosterilants, herbicide safenersjnsect attractants, insect repellents, mammal repellents, mating disrupters, molluscicides, plant activators, plant growth regulators, rodenticides, and/or virucides (collectively these cotnmonly named groups are defîned as the

AI Group). It should be noted that compounds falling within the Al 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 http.7/www.alanwood.net/pesticides/index.html. Also consult “THE Pesticide Manual 14th

SYNERGISTIC MIXTURES AND SYNERGISTS

Molécules of Formula One 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 molécules of Formula One are the same, similar, or different. Examples of modes of action include, but are not limited to: acetylcholinesterase inhibitor; sodium channel modulator; chitin biosynthesis inhibitor; GABA-gated chloride channel antagonist; GABA and glutamate-gated chloride? channel agonist; acétylcholine receptor agonist; MET I inhibitor; Mg-stimulated ATPase inhibitor; nicotinic acétylcholine receptor; Midgut membrane disrupter; oxidative phosphorylation disrupter, and ryanodine receptor (RyRs). Additionally, molécules of Formula Op^may, be used with compounds in the Fungicide Group, Acaricide Group, Herbicide Group, or Nematicide Group to form synergistic mixtures. Furthermore, molécules pf Formula One may be used with other active compounds, such as the compounds under the heading OTHER ACTIVE COMPOUNDS”, algicides, avicides, bactéricides, molluscicides, rodenticides, virucides, herbicide safeners, adjuvants, and/or surfactants to form synergistic mixtures. Generally, weight ratios of the molécules of Formula One 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. Addjtionally, the following compounds are known as synergists and may be used with the moleçqles disclosed in Formula One: piperonyl

butoxide, piprotal, propyl isome, sesamex, sesamolin, sulfoxide, and tribufos (collectively these synergists are defined as the Synergists Group”).

r j 31· ‘ji? _ . ,

FORMULATIONS _;i<

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 application, handling, transportation, storage, and maximum pesticide activity. Thus, pesticides are formulated into, for example, baits, concentrated émulsions, dusts, emulsifiable concentrâtes, fumigants, gels, granules, microencapsulations, seed treatments, suspension concentrâtes, 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 Pesticide 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 émulsions prepared from concentrated formulations of such pesticides. Such water-soluble, water-suspendable, or emulsifiable formulations are either solids, usually known as wettable powders, or water * ·} il·/ dispersible granules, or liquids usually known as emulsifiable concentrâtes, or aqueous suspensions. Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the pesticide, a carrier, and surfactants. The concentration of the pesticidejs 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, condensed naphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants such as ethylene oxide adduqts of alkyl phénols.

Emulsifiable concentrâtes 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 miscible solvent or a mixtqre of water-immiscible organic solvent and emulsifiers. Useful organic solvents include aromatics, especially xylenes and petroleum fractions, especially the high-boiling naphthalenic arpd olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents. may also be used, such as the terpenic solvents including rosin dérivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrâtes are chosen from conventional anionic and non-ionic surfactants.

Aqueous suspensions 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.

-33ί I ! r

Suspensions are prepared by finely grinding the pesticide and vigorously mixing it into a carrier comprised of water and surfactants, ingrédients, such as inorganic salts and synthetic or natural gums may also be added, to increase 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 jm’plement such as a sand mill, bail mill, or piston-type homogenizer. J , '' .♦' ·

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 10% by weight of the pesticide, dispersed in a carrier that comprises clay or a similar substance. Such compositions 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 formulated by making a dough or paste of the carrier and cornpound and crushing and drying to obtain the desired granular particle size,

Dusts containing a pesticide are prepared by intimately mixing the pesticide in powdered form with a suitable dusty agriculture! carrier, such as kaolin clay, ground volcanic rock, and the like. Dusts can suitàbly contain from_fabout 1% to about 10% of the pesticide. They can be applied as a seed dressing or as^j a toilage application with a dust blower machine. ._; , ' ^L r- )

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. _Γ

Pesticides can also be applied in the form of an aérosol composition. In such compositions the pesticide is dissolved or dispersed in a carrier, which is a pressuregenerating propellant mixture. The aérosol 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 attractant or both. When the pests eat the bait they also consume the pesticide. Baits may take the form of granules, gels, flowable powders, Iiquids, or solids. They can be used in pest harborages.

Fumigants are pesticides that have a relatively high vapor pressure and hence can exist as a gas in sufficient concentrations to kill pests in soi! or enclosed spaces. The toxicity of the fumigant is proportional to its concentration and the exposure time. They are characterized by a good capacity for diffusion and act by penetrating the pest’s respiratory ^:.ί· i system or being absorbed through the pest’s,cuticte. Fumigants are applied to control stored product pests under gas proof sheets, in ga§_; sealed rooms or buildings or in spécial chambers.

-34• . i

Pesticides can be microencapsulated by suspending the pesticide particles or droplets in plastic polymers of various 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 ingrédient within is released, which in> turn, affects the residual performance, speed of action, and odor of the product. _; i

Oil solution concentrâtes are made by dissolving pesticide in a solvent that will hold the pesticide in solution. Oil solutions of a pesticide usually provide faster knockdown and kill of pests than other formulations due to the solv,ents_:themselves having pesticidal action and the dissolution of the waxy covering of the integument increasing the speed of uptake of the pesticide. Other advantages of oil solutions include better storage stability, better pénétration of crevices, and better adhesion to greasy surfaces.

Another embodiment is an oil-in-water émulsion, wherein the émulsion comprises oily globules which are each provided with a lamellar liquid crystal coating and are dispersed in an aqueous phase, wherein each oily globule comprises at least one compound which is agriculturally active, and is individually coated with a monolamellar or oligolamellar layer comprising: (1) at least one non-ionic lipophilie surface-active agent, (2) at least one nonionic hydrophilic surface-active agent and (3) at least one ionic surface-active agent, wherein the globules having a mean particle diameter pf less than 800 nanometers. Further information on the embodiment is disclosed in U.S. patent publication 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 information conduit “Inseçt Pest Management” 2nd Edition by D. Dent, copyright CAB International (2000)., Additionally,^; for more detailed information consult “Handbook of Pest Control - The Behavior, Life Histpry, and Control of Household Pests” by Arnold Mallis, 9th Edition, copyright 2004 by GIE Média Inc.

OTHER FORMULATION COMPONENTS

Generally, when the molécules disclosed in Formula One are used in a formulation, such formulation can also contain other components. These components include, but are not limited to, (this is a non-exhaustive and non-mutually exclusive list) wetters, spreaders, stickers, pénétrants, buffers, sequestering agents, drift réduction 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 pénétration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wettipg agents are used for two main functions in

agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrâtes for soluble liquids or suspension concentrâtes; and during mixing of a product with water in a spray tank to reduce the wetting time of wettable powders and to improve the pénétration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations aré: sodium lauryl sulfate; sodium dioctyl sulfosuccinate; alkyl phénol ethoxylates; and aliphatic alcohol ethoxylates.

A dispersing agent is a substance which àdsorbs onto the surface of partîcles and helps to preserve the state of dispersion of the' partîcles and prevents them from reaggregating. Dispersing agents are added to agrochemical formulations to facilitate dispersion and suspension during manufacturé, and to ensure the partîcles redisperse into water in a spray tank. They are widely uséd in wettable powders, suspension concentrâtes and water-dispersible granules. Surfactants, thakafe used as dispersing agents hâve the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to reaggregatîon of partîcles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersing agents are sodium lignosulfonates. For suspension concentrâtes, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulfonate formaldéhyde condensâtes. Tristyrylphenol ethoxylate phosphate esters are also used. Nonionics such as alkylarylethylene oxide condensâtes and EO-PO block copolymers are sometimes combined with anionics as dispersing agents for suspension concentrâtes. In recent years, new types of very high motecular weight polymeric surfactants hâve been developed as dispersing agents. These hâve, very long hydrophobie ‘backbones’ and a large number of ethylene oxide chains forming the ‘tçeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrâtes because the hydrophobie backbones hâve many anchoring points onto the particle surfaces. Examples of dispersing agents ,psed in agrochemical formulations are: sodium lignosulfonates; sodium naphthalene sulfonate formaldéhyde condensâtes; tristyrylphenol ethoxylate phosphate esters;, aliphatic alcohol ethoxylates; 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 immiscible liquid phases. The most commonly used emulsifier blends contain alkylphenol or aliphatic alcohol with twelve or more ethylene oxide units and the oilsoluble calcium sait of dodecylbenzenesulfonic acid. A range of hydrophile-lipophile balance (“HLB) values from 8 to 18 will normally providç good stable émulsions. Emulsion stability . J.

can sometimes be improved by the addition of a small amount of an EO-PO block copolymer surfactant. u· ' '

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 5 water-insoluble materials inside the hydrophobie 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 minerai or vegetable oils as adjuvants to spray-tank mixès to improve the biological performance of 10 the pesticide on the target. The types of surfactants used for bioenhancement dépend generally on the nature and mode of action of,the pesticide. However, they are often non-

i. ’ · ionics such as: alkyl ethoxylates; linear aliphatiç alcohol ethoxylates; aliphatiç amine ethoxylates.

A carrier or diluent in an agricultural formulation is a material added to the pesticide 15 to give a product of the required strength. Carrier^ are usually materials with high absorptive capacities, while diluents are usually materials with low absorptive capacities. Carriers and diluents are used in the formulation of dusts, wettable powders, granules and waterdispersible granules.

Organic solvents are used mainly in the formulation of emulsifiable concentrâtes, oil20 in-water émulsions, suspoemulsions, and ultra low volume formulations, and to a lesser extent, granular formulations. Sometimes mixtures of solvents are used. The first main groups of solvents are aliphatiç paraffinic oils such as kerosene or refined paraffins. The second main group (and the most common) comprises the aromatic solvents such as xylene and higher molecular weight fractions of C9,and C10 aromatic solvents. Chlorinated 25 hydrocarbons are useful as cosolvents to prevent crystallization of pesticides when the formulation is emulsified into water. Alcohols are sometlmes used as cosolvents to increase ί r solvent power. Other solvents may include vegetable oils, seed oils, and esters of vegetable and seed oils. ;·,ι ·,

’.r·· ’ ' .....i J ; ‘

Thickeners or gelling agents are used .msiinly in the formulation of suspension 30 concentrâtes, émulsions and suspoemulsions tp fpoçiify the rheology or flow properties of the liquid and to prevent séparation and settling qf, the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely waterinsoluble particulates and w^ter-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, 35 include, but are not limited to, montmorillonite, bentonite, magnésium aluminum silicate, and attapulgite. Water-soluble polysaccharides hâve been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of

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seeds and seaweeds or are synthetic dérivatives_:of cellulose. Examples of these types of materials include, but are not limited to, guar/gum; locust bean gum; carrageenam; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC). Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide. Another good anti-settling agent is xanthan gum.

' à-,

Microorganisms can cause spoilage, of formulated products. Therefore préservation agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium sait; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium sait; p-hydroxybenzoic acid sodium sait; methyl phydroxybenzoate; and 1,2-benzisothiazolin-3-one (BIT).

The presence of surfactants often causes water-based formulations 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 bottles. Generally, there are two types of anti-foam agents, namely , il· silicones and non-silicones. Silicones pre usually aqueous émulsions of dimethyl polysiloxane, while the non-silicone anti-foarri agents are water-insoluble oils, such as

J î octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.

“Green agents (e.g., adjuvants, surfactants, solvents) can reduce the overall environmental footprint of crop protection formulations. Green agents are biodégradable and generally derived from natural and/or sustainaple sources, e.g. plant and animal sources. Spécifie examples are: vegetable oils, seed oils, a.nd esters thereof, also alkoxylated alkyl polyglucosides.

For further information, see “Chemistry and Technology of Agrochemical Formulations” edited by D.A. Knowles, copyright 1998 by Kluwer Academie Publishers. Also see “Insecticides in Agriculture and Environment - Rétrospects and Prospects” by A.S. Perry, I. Yamamoto, I. Ishaaya, and R. Perry, copyright 1998 by Springer-Verlag.

PESTS

In general, the molécules of Formula One 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 molécules of.Formula One may be used to control pests ; t i .

in the Phyla Nematoda and/or Arthropoda:

In another embodiment, the molécules of Formula One may be used to control pests in the Subphyla Chelicerata, Myriapoda, and/or Hexapoda.

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In another embodiment, the molécules of Formula One may be used to control pests in the Classes of Arachnide, Symphyla, and/or Insecta.

In another embodiment, the molécules of Formula One may be used to control pests of the Order Anoplura. A non-exhaüstive list of particular généra includes, but is not limited 5 to, Haematopinus spp., Hoplopleura spp., Linognathus spp., Pediculus spp., and Polyplax spp. A non-exhaustive list of particular species includes, but is not limited to, Haematopinus asini, Haematopinus suis, Linognathus setosus, Linognathus ovillus, Pediculus humanus ' i’I, *· capitis, Pediculus humanus humarius, and Pthirus pubis.

In another embodiment, the molécules, of Formula One may be used to control pests 10 in the Order Coleoptera. A non-exhaustive list of particular généra 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., Chaetocnema spp., Colaspis spp., Ctenicera spp., Curcuiio spp., Cyclocephala spp., Diabrotica spp., Hypera spp., Ips spp., Lyctus spp., Megascelis spp., Meligethes spp., 15 Otiorhynchus spp., Pantomorus spp., Phyllophaga spp., Phyllotreta spp., Rhizotrogus spp., Rhynchites spp., Rhynchophorus spp., Scolytus spp-, Sphenophorus spp., Sitophilus spp., and Tribolium spp. A non-exhaustive list of.particular species includes, but is not limited to, Acanthoscelides obtectus, Agrilus \ planipennis, Anôplophora glabripennis, Anthonomus grandis, Ataenius spretulus, Atomaria linear/s, Bothynoderes punctiventris, Bruchus pisorum, 20 Callosobruchus maculatus, Carpophilus hemipterus, Cassida vittata, Cerotoma trifurcata, Ceutorhynchus assimilis, Ceutorhynchus napi, Conoderus scalaris, Conoderus stigmosus, Conotrachelus nénuphar, Cotinis nitida, ^CriQCeris asparagi, Cryptolestes ferrugineus, Cryptolestes pusillus, Cryptolestes turcicus,, Cylindrocopturus adspersus, Deporaus marginatus, Dermestes lardarius, Dermestes maculatus, Epilachna varivestis, Faustinus 25 cubae, Hylobius pales, Hypera postica, Hypothenemus hampei, Lasioderma serricome, Leptinotarsa decemlineata, Liogenys fuscus, Liogenys suturalis, Lissorhoptrus oryzophilus, Maecolaspis joliveti, Melanotus commuais, Meligethes aeneus, Melolontha melolontha, Oberea brevls, Oberea Ünearis, Oryctes rhinocéros, Oryzaephilus mercator, Oryzaephilus surinamensis, Ouléma melanopus, Ouléma oryzae, Phyllophaga cuyabana, Popillia 30 japonica, Prostephanus truncatus, Rhyzopertha dominica,, Sitona lineatus, Sitophilus granarius, Sitophilus oryzae, Sitophilus zearpais, Stegobium paniceum, Tribolium ' ’ 5 7:

castaneum, Tribolium confusum, Trogoderma vpriabile, and Zabrus tenebrioides.

In another embodiment, the molécules of Formula One may be used to control pests of the Order Dermaptera.

In another embodiment, the molécule? of Formula One may be used to control pests of the Order Blattaria. A non-exhaustive lisJïQf. particular species includes, but is not limited to, Blattella germanica, Blatta orientalls, Parcoblatta pennsylvanica, Periplaneta americana,

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Periplaneta australasiae, Periplaneta brunnea, Periplaneta fuliginosa, Pycnoscelus surinamensis, and Supella longipalpa.

In another embodiment, the molécules of Formula One may be used to control pests of the Order Diptera. A non-exhaustive list of particular généra includes, but is not limited to, 5 Aedes spp., Agromyza spp., Anastrepha spp., Anophcles spp., Bactrocera spp., Ceratitis spp., Chrysops spp., Cochliomyia spp., Contarinia'spp., Culex spp., Dasineura spp,, Délia spp., Drosophila spp., Fannia spp._; Hylemyiaspp., Liriomyza spp., Musca spp., Phorbia spp., Tabanus spp., and Tipula spp. A non-exhaustive list of particular species includes, but is not limited to, Agromyza frontella, Anastrepha suspense, Anastrepha ludens, Anastrepha 10 obliqa, Bactrocera cucurbitae, Bactrocera dorsalis, Bactrocera invadens, Bactrocera zonata, Ceratitis capitata, Dasineura brassicae, Délia'ptatura, Fannia canicularis, Fannia sca/aris, Gasterophilus intestinalis, Gracillia perseae, Haematobia irritans, Hypoderma lineatum, Liriomyza brassicae, Melophagus ovinus, Musca autumnaiis, Musca domestica, Oestrus ovis, Oscinella frit, Pegomya betao, Psila rosae, Rhagoletis cerasi, Rhagoletis pomonella, 15 Rhagoletis mendax, Sitodiplosis mosellana, and Stomoxys calcitrans.

In another embodiment, the molécules of Formula One may be used to control pests of the Order Hemiptera. A non-exhaustive list of particular généra includes, but is not limited to, Adelges spp., Aulacaspis spp., Aphrophora spp., Aphis spp,, Bemisia spp., Ceroplastes spp., Chionaspis spp., Chrysomphalus spp., Coccus spp., Empoasca spp., 20 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., Triatoma spp. and Unaspis spp. A non-exhaustive list of particular species includes, but is not_; limited to, Acrostcrnum hilare, Acyrthosiphon 25 pisum, Aleyrodes proletella, Aleurodicus dispersas, Aleurothrixus floccosus, Amrasca biguttuia biguttula, Aonidiella aurantii, Aphis gossypii, Aphis glycines, Aphis pomi, Aulacorthum solani, Bemisia argentifolii, .Bemisia tabaci, Blissus leucopterus, Brachycorynelia asparagi, Brevennia rehi, Brevicoryne brassicae, Calocoris norvegicus, Ceroplastes rubens, Cimex hemipterus, Cimex lectularius, Dagbertus fasciatus, Dichelops 30 furcatus, Diuraphis noxia, Diaphorina citri, Dysaphis plantaginea, Dysdercus suturellus, Edessa meditabunda, Eriosoma lanigerum, Eurygaster maura, Euschistus héros, Euschistus servus, Helopeltis antonii, Helopeltis theivora, Icerya purchasi, Idioscopus nitidulus, Laodelphax striatellus, Leptocorisa oratorius,,, Leptocorisa varicornis, Lygus hesperus, Maconellicoccus hirsutus, Macrosiphum euphorbiae, Macrosiphum granarium, Macrosiphum 35 rosae, Macrosteles quadrilineatus, Mahanarva frimbiolata, Metopolophium dirhodum, Mictis longicornis, Myzus persicae, Nephotettix cinctipes,, Neurocolpus longirostris, Nezara viridula,

J

Nilaparvata lugens, Parlatoria pergandii, Parlatoria ziziphi, Peregrinus maidis, Phylloxéra

' ί; ’ Λ; 'i vitifoliae, Physokermes piceae,, Phytocoris calfëpçnicus,. Phytocoris relativus, PiezodorusI guildinii, Poecilocapsus lineatus, Psallus vaccinïcola, Pseudacysta perseae, Pseudococcusj brevipes, Quadraspidiotus perniciosus, Rhopaldsiphum maidis, Rhopalosiphum padi,i

Sa/ssef/a o/eae, Scaptocoris castanea, Schizaphis graminum, Sitobion avenae, Sogateilai furcifera, Trialeurodes vaporariorum, Trialeurodes abutiloneus, Unaspis yanonensis, andf

i.

Zulia entrerriana.:

In another embodiment, the molécules of Formula One may be used to control pests of the Order Hymenoptera. A non-exhaustive list of particular généra includes, but is notj limited to, Acromyrmex spp., Atta spp., Camponotus spp., Diprion spp., Formica spp.,I

Monomorium spp., Neodiprion spp., Pogonomyrmpx spp., Polistes spp., Solenopsis spp.,i

Vespula spp., and Xylocopa spp. A non-exhaustive list of particular species includes, but isi . 4 i not limited to, Athalia rosae, Atta texana, Iridomyrmex humilis, Monomorium minimum,[

I Monomorium pharaonis, Solenopsis invicta, Solenopsis geminata, Solenopsis molesta,'

I

Solenopsis richtery, Solenopsis xyloni, and Tàpinoma sessile.

In another embodiment, the. molécules of Formula One may be used to control pests _; yy ÿ of the Order Isoptera. A non-exhaustive list of particular généra includes, but is not limited to, Coptotermes spp., Corn/termes spp., Cryptotermes spp., Heterotermes spp., Kalotermes spp., Incisitermes spp., Macrotermes spp., Marginitermes spp., Microcerotermes spp., 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, ·

Microtermes obesi, Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermes flavipes, Reticulitermes hageni, Reticulitermes hesperus, Reticulitermes santonensis, Reticulitermes speratus, Reticulitermes tibialis, and. Reticulitermes virginicus.

¹ i.

In another embodiment, the molécules of Fprmula One may be used to control pests of the Order Lepidoptera. A non-exhaustive list _;of particular généra includes, but is not limited to, Adoxophyes spp., Agrotis spp,, Argyrotaenia spp., Cacoecia spp., Caloptilia spp., Chilo spp., Chrysodeixis spp., Colias spp., Çrambus spp., Diaphania spp., Diatraea spp., Earias spp., Ephestia spp., Epimecis spp., F;eliia, spp., Gortyna spp., Helicoverpa spp., Heliothis spp., Indarbela spp./ Lithocolletis spp., Loxagrotis spp., Malacosoma spp., Peridroma spp., Phyllonorycter spp.,' Pseudalelia spp., Sesamia spp., Spodoptera spp., Synanthedon spp., and Yponomeuta spp. A ^:non-exhaustive list of particular species includes, but is not limited to_; Achaea janata, Adoxophyes orana, Agrotis ipsilon, Alabama argillacea, Amorbia cuneana, Amyelois transitella, Anacamptodes defectaria, Anarsia lineatella, Anomis sabulifera, Anticarsia gemmatalis, Archips argyrospila, Archips rosana, Argyrotaenia citrana, Autographe gamma, Bonagota cranaodes, Borbo cinnara, Bucculatrix thurberiella, Capua reticulana, Carposina niponensis, Chlumetia transversa, Choristoneura

-4Ér

A rosaceana, Cnaphalocrocis medinalis, Conopomorpha cramerella, Cossus cossus, Cydia ! caryana, Cydia funebrana, Cydia molesta, Cydia nigricana, Cydia pomonella, Dama diducta,

Diatraea saccharalis, Diatraea grandiosella, Eàrias insulana, Earias vittella, Ecdytolopha aurantianum, Elasmopalpus lignosellus, Ephestia cautella, Ephestia elutella, Ephestia kuehniella, Eplnotia aporema, Epiphyas postvittana, Erionota thrax, Eupoecilia ambiguella, Euxoa auxiliaris, Grapholita molesta, Hedylepta indicata, Helicoverpa armigera, Helicoverpa zea, Heliothis virescens, Hellula undalis, Keiferia lycopersicella, Leucinodes orbonalis, Leucoptera coffeella, Leucoptera malifoliella, Lobesia botrana, Loxagrotis albicosta, Lymantria dispar, Lyonetia clerkella, Mahasena corbetti, Mamestra brassicae, Maruca testu/alis, Metisa plana, Mythimna unipuncta, Neoleucinodes elegantalis, Nymphula depunctalis, Operophtera brumata, Ostrinia nubilalis, Oxydia vesulia, Pandemis cerasana, Pandemis heparana, Papilio demodocus, Pectinophora gossypiella, Peridroma saucia, Perileucoptera coffeella, Phthorimaea opercuiellà, Phyllocnistis citrella, Pieris rapae, Plathypena scabra, Plodia interpunctella, Plutella xylostella, Polychrosis viteana, Prays i

endocarpe, Prays oleae, Pseudaletia unipuncta, Pseudoplusia includens, Rachiplusia nu, Scirpophaga incertulas, Sesamia inferens, Sesamia nonagrioides, Setora nitens, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera èxigua, Spodoptera frugiperda, Spodoptera eridania, Thecla basilides, Tineola bisselliëllaJ-Trichoplusia ni, Tuta absoluta, Zeuzera coffeae, and Zeuzera pyrina. . i, ,< _;

In another embodiment, the molécules of>Formula One may be used to control pests of the Order Mallophaga A non-exhaustive list of particular généra includes, but is not limited to, Anaticola spp., Bovicola spp., Chelopistes spp., Goniodes 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 meleagridîs, Goniodes dissimi/is, Goniodes gigas, Menacanthus stramineus, Menopon gallinae, and Trichodectes canis.

In another embodiment, the molécules of Fp.rmula One may be used to control pests of the Order Orthoptera. A non-exhaustive list of particular généra includes, but is not limited to, Melanoplus spp., and Pterophylla spp. A non-exhaustive list of particular species includes, but is not limited to, -Anabrus simplex, Gryllotalpa africana, Gryllotalpa australis, Gryllotalpa brachyptera, Gryllotalpa hexadactyla, > Locusta migratoria, Microcentrum retinerve, Schistocerca gregaria, and Scudderia furcata.

In another embodiment, the molécules pf. Formula One may be used to control pests of the Order Siphonaptera. A non-exhaustive list.of particular species includes, but is not limited to, Ceratophyllus ₍ gallinae, Ceratophyllus niger, Ctenocephalides canis, Ctenocephalides felis, and Pulex irritans.

i

In another embodiment, the molécules of Formula One may be used to control pests of the Order Thysanoptera. A non-exhaustive list of particular généra includes, but îs 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 schuttzei, Frankliniella williamsi, Heliothrips haemorrhoidalis, i J

Rhipiphorothrips cruentatus, Scirtothrips citri, Scirtothrips dorsalis, and Taeniothrips rhopalantennalis, Thrips hawaiiensis. Thrips riigrepilosus, Thrips orientalis, Thrips tabaci.

' i It ' ⁷

In another embodiment, the molécules of Formula One may be used to control pests ; i ' of the Order Thysanura. A non-exhaustive list of particular généra includes, but is not limited to, Lepisma spp. and Thermobia spp.

tn another embodiment, the molécules of Formula One may be used to control pests of the Order Acarina. A non-exhaustive list of particular généra includes, but is not limited to, Acarus spp., Aculops spp., Boophilus spp., Demodex spp., Dermacentor spp., Epitrimerus spp., Eriophyes spp., Ixodes spp., Oligonychus spp., Panonychus spp., Rhizoglyphus spp., and Tetranychus spp. A non-exhaustive list of particular species includes, but is not limited to, Acarapis woodi, Acarus siro, Aceria mangiferae, Aculops lycopersici, Aculus pelekassi, Aculus schlechtendali, Amblyomma americanum, Brevipalpus obovatus, Brevipalpus phoenicis, Dermacentor vanabilis, Dermatophagoides pteronyssinus, Eotetranychus carpini, Notoedres cati, Oligonychus coffeae, Oligonychus ilicis, Panonychus citri, Panonychus ulmi, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Rhipicephalus sanguineus, Sarcoptes scabiei, Tegolophus perseaflorae, Tetranychus urticae, and Varroa destructor.

In another embodiment, the molécules of> Formula One 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 molécules of Formula One may be used to control pests of the Phylum Nematoda A non-exhaustive list of particular généra includes, but is not limited to, Aphelenchoides spp., Belonolaimus spp., Criconemella spp., Ditylenchus spp., Heterodera spp., Hirschmanniella spp., Hoplofaimus 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 volvulus, Radopholus similis, and Rotylenchulus reniformis.

For additional information consult “Hand.book of Pest Control - The Behavior, Life History, and Control of Household Pests” by Arnold Mallis, 9th Edition, copyright 2004 by GIE Media Inc. . · *· / :7 ρ '

APPLICATIONS

J t

-4316336

Molécules of Formula One 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.

The area to which a molécule of Formula One is applied can be any area inhabited (or maybe inhabited, or traversed by) a pest,. for exemple: where crops, trees, fruits, cereals, fodder species, vines, turf and omamental plants, are growing; where domesticated animais are residing; the interior 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 molécule of Formula One include areas where apples, corn, sunflowers, cotton, soybeans, canola, wheat, rice, sorghum, barley, oats, potatoes, oranges, alfalfa, lettuce, strawberries, 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 molécule 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 corne about when; pest populations are repulsed from an area; when pests are incapacitated in or around an area; or pests are exterminated, in whole, or in part, in or around an area. Of course, a combination of these results can occur. Generally, pest populations, activity, or both are desirably reduced more than fifty percent, preferably more than 90 percent. Generally, the area is not in_fôr on a human; consequently, the locus is generally a non-human area. .

The molécules of Formula One may he^sed in mixtures, applied simultaneously or sequentially, alone or with other compounds to enhance plant vigor (e.g. to grow a better root system, to better withstand stressful growing -conditions). Such other compounds are, for example, compounds that modulate plant ethylene receptors, most notably 1methylcyclopropene (also known as 1-MCP).

The molécules of Formula One can be applied to the foliar and fruiting portions of plants to control pests. The molécules will either corne 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 molécules of Formula One can also be applied to the soil, and when applied in this manner, root and stem feeding pests can be controlled. The roots can absorb a molécule 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 piaced in'the ground where, for example, termites can corne into contact with, and/or be attracted to, the bait. Baits can also be applied to a surface of a building, (horizontal,,vertical, or/siant surface) where, for example, ants,

- 44λ termites, cockroaches, and flies, can corne into contact with, and/or be attracted to, the bait.

Baits can comprise a molécule of Formula One.

The molécules of Formula One 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 molécules of Formula One may be désirable to control newly emerged larvae.

Systemic movement of pesticides in plants·' may be utilized to control pests on one 10 portion of the plant by applying (for example by spraying an area) the molécules of Formula One to a different portion of the plant. For example, control of foliar-feeding insects can be achieved by drip irrigation or furrow application, by treating the soil with for example pre- or post-planting soil drench, or by treating the seeds of a plant before planting.

Seed treatment can be applied to air types of seeds, including those from which 15 plants genetically modified to express specialized traits will germinate. Représentative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis or other insecticidal toxins, those expressing herbicide résistance, such as Roundup Ready” seed, or other seed having glyphosate, glufosinate, dicamba, imidazolinones or 2,4-D tolérance, or those with “stacked foreign genes expressing 20 insecticidal toxins, herbicide résistance, nutrition-enhancement, drought résistance, or any other bénéficiai traits. Furthermore, such seed treatments with the molécules of Formula One 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 molécules of Formula One to about 500 grams 25 per 100,000 seeds is expected to provide good benefits, amounts from about 10 grams to about 100 grams per 100,000 seeds is expected to provide better benefits, and amounts from about 25 grams to about 75 grams per_;ip.0i000 seeds is expected to provide even f

better benefits. T’·.

It should be readily apparent that the molécules of Formula One may be used on, in, 30 or around plants genetically modified to express specialized traits, such as Bacillus thuringiensis or other insecticidal toxins, or those expressing herbicide résistance, or those with “stacked foreign genes expressing insecticidal toxins, herbicide résistance, nutritionenhancement, or any other bénéficiai traits.

The molécules of Formula One may be used for controlling endoparasites and 35 ectoparasites in the veterinary medicine sector dr in the field of non-human animal keeping.

The molécules of Formula One are applied, süch as by oral administration in the form of, for example, tablets, capsules, drinks, granules,, by;;,dermal application in the form of, for i- 45 -

[ • ’ ί * ?’ ¹ ' . r example, dipping, spraying, pouring on, spotting on, and dustîng, and by parentéral administration in the form of, for example, an injection.

The molécules of Formula One may also bè employed advantageously in livestock 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 and biting fîtes that are bothersomè to such animais. Suitable formulations are administered orally to the animais with the drinking water or feed. The dosages and formulations that are suitable dépend on the species.

The molécules of Formula One may also be used for controlling parasitic worms, especially ofthe intestine, in the animais listed above.

The molécules of Formula One may also be employed in therapeutic methods for human health care. Such methods include, but are‘limited to, oral administration in the form of, for example, tablets, capsules, drinks, granules? and by dermal application.

Pests around the world hâve been migrating to new environments (for such pest) and thereafter becoming a new invasive species in;such new environment. The molécules of Formula One may also be used on such new invasive species to control them in such new environment. .· . γ f

The molécules of Formula One 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 molécules 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, improving the yield of a plant (e.g. increased biomass and/or increased content of valuable ingrédients), improving the vigor of a plant (e.g. improved plant growth and/or greener leaves), improving the quality of a plant (e.g. improved content or composition of certain ingrédients), and improving the tolérance to abiotic and/or biotic stress of the plant.

Before a pesticide can be used or sold commercially, such pesticide undergoes lengthy évaluation processes by various governfhental authorities (local, régional, state, national, and international). Voluminous data requirements are specified by regulatory authorities and must be addressed through data génération 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 détermination of safety is concluded, provic|e the potential user or seller with product registration approval. Thereafter, in that locality where the product registration is granted and supported, such user or sellermay use or sell such pesticide.

A molécule according to Formula One can be tested to détermine its efficacy against pests. Furthermore, mode of action studies can be conducted to détermine if said molécule -46-

has a different mode of action than other pesticides. Thereafter, such acquired data can be disseminated, such as by the internet, to third parties.

The headings in this document are fpr.convenience only and must not be used to interpret any portion hereof,

TABLE SECTION

BAW & CEW Rating Table:
% Control (or Mortality) _;	Rating
50-100 ' i	A
More than 0 - Less than 50	B
Not Tested	C
No activity noticed in this bioassay	D

i i

t· i

i

GPA Rating Table
% Control (or Mortality)	Rating
80-100 ·· · · 'fr	A
More than 0 - Less than 8Q^:	B
Not Tested	C
No activity noticed in this bioassay	D

TABLE, 1. .·

Compound Number	% i Mortality CEW 50 □g/cm2	J ’ % Mortality BAW 50 □g/cm2	% Mortality GPA 200 ppm
1	A	A	B
2	A	A	B
3	A	A	B
4	B	-A	C
5	A	A	D
6	v A	· ·Ά Ίί^! ?.	B
7	A ;	A È	D

-4716336

8	D	D	D
9	A	A	B

Claims

1. A molécule according to Formula One

Formula One¹ wherein:

(a) Ar-ι is (1) furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl, thienyl, or (2) substituted furanyl, substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, or substituted thienyl, wherein said substituted furanyl, substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, and substituted thienyl, hâve one or more substituents independently selected from H, OH, F, Cl, Br, I, CN, NO₂, C_rC_e alkyl, C-i-C₆ haloalkyl, C_rC₆ hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C_ehydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, C_rC_e alkoxy, Ci-C_e haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(=O)_n(C₁-C_e alkyl), S(=O)_n(Ci-C₆ haloalkyl), OSO₂(C_rC₆ alkyl), OSO₂(C_rC_e haloalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (C_rC₆ alkyl)NR_xR_y, C(=O)(C_rC₆ alkyl), 0(=0)0(0^ alkyl), C(=O)(C_rC₆ haloalkyl), C(=O)O(C_rCe haloalkyl), C(=0)(0₃-C₆ cycloalkyl), C(=O)O(C₃-C₆ cycloalkyl), C(=O)(C₂-C_ealkenyl), C(=O)O(C₂-C_e alkenyl), (Ci-C₆ alkyl)O(Ci-C₆ alkyl), (C_rC_e alkyl)S(C_rCe alkyl),

C(=O)(Cf-C₆ alkyl)C(=O)O(C-rC₆ alkyl), phenyl, phenoxy, substituted phenyl and substituted phenoxy (wherein such substituted phenyl and /substituted phenoxy hâve one or more substituents independently selected from H, OH, F, Cl, Br, I, CN, N0₂, CpCe alkyl, Ci-C_ehaloalkyl, C_rC₆ hydroxyalkyl, . C₃-C₆ cycloplkyi, C₃-C_e halocycloalkyl, C₃-C₆hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, CiC_s alkoxy, C_rCe haloalkoxy, C₂-C₆ alkenyl, C₂-C₅ alkynyl, S(=O)_n(C_rC₆ alkyl), 3(=0^(0^06 haloalkyl), OSO₂(C_rC_e alkyl), OSO₂(C_rC₆ haloalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (C_rC₆ alkyl)NR_xR_y, C(=O)(C_rC₆ alkyl), 0(=0)0(0^ alkyl), C(=O)(C_rC_e haloalkyl), C(=O)O(Ci-Ce haloalkyl), C(=O)(C₃-C₆ cycloalkyl), C(=0)0(C₃-C_e cycloalkyl), C(=O)(C₂-C₆alkenyl), C(=O)O(C₂-C₆ alkenyl), (0-ι-0₆ alkyl)O(Ci-C₆ alkyl), (Ci-C_e alkyOSCCrCe alkyl), C(=O)(Ci-C₆ alkyl)C(=O)O(C₁-C₆ alkyl) phenyl, and phenoxy);

(b) Het is a 5 or 6 membered, saturated or unsaturated, heterocyclic ring, containing one or more heteroatoms independently selected from nitrogen, sulfur, or oxygen, and where An and Ar₂ are not ortho to each other (but may be meta or para, such as, for a five membered ring they are 1,3 and for a 6,membered ring they are either 1,3 or 1,4), and where said heterocyclic ring may also be substituted with one or more substituents independently selected from H, OH, F, Cl, Br, I, CN, NO₂, oxo, 0,-0_Β alkyl, C,-C₆ haloalkyl, C,-C₆ hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₃-C₆

5 cycloalkoxy, C₃-C_e halocycloalkoxy, C₃-C_B hydroxycycloalkoxy, C,-C_e alkoxy, Ο,-Ο_Βhaloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(=O)n(C,-C_e alkyl), S(=O)_n(C,-C_e haloalkyl), OSO₂(C_rC_e alkyl), OSO₂(C_rC₆ haloalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (C,-C₆alkyl)NR_xR_y, 0(=0)(0,-06 alkyl), C(=O)O(C,-C₆ alkyl), 0(=0)(0,-06 haloalkyl), C(=0)0(C,-C₆haloalkyl), C(=O)(C₃-C₆ cycloalkyl), C(=O)O(C₃-C_S cycloalkyl), C(=O)(C₂-C₆ alkenyl), 10 C(=O)O(C₂-C_e alkenyl), (C,-C_s alkyl)0(C,-C6 alkyl), (C,-C_B alkyl)S(Ci-C₆ alkyl), C(=O)(C,-C₆alkyl)C(=O)O(Ci-C₆ alkyl), phenyl, phenoxy, substituted phenyl and substituted phenoxy (wherein such substituted phenyl and substituted-phenoxy hâve one or more substituents independently selected from H, OH, F, Cl, Br, I, CN, N0₂, C,-C_B alkyl, C,-C_B haloalkyl, 0,-0_Βhydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₃-C₆15 cycloalkoxy, C₃-C_e halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, C,-C₆ alkoxy, Ο,-Ο_δhaloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(=0)n(C_rC₆ alkyl), 3(=0),,(0,-06 haloalkyl), OSO₂(Ci-C₆ alkyl), OSO₂(C,-Ce haloalkyl), C(=0)H, 0(=0)0H, C(=O)NR_xR_y, (C,-C₆alkyl)NR_xR_y, 0(=0)(0ι-0β alkyl), 0(=0)0(0,-0_δ alkyl), 0(=0)(0,-0₆ haloalkyl), C(=O)O(C,-C₆haloalkyl), C(=O)(C₃-C₆ cycloalkyl), C(=O)O(C₃-C₆ cycloalkyl), C(=O)(C₂-C₆ alkenyl), 20 C(=O)O(C₂-C₆ alkenyl), (C,-C₆ alkyl)O(C,-C_e alkyl), (C,-C_e alky))S(C,-C₆ alkyl), 0(=0)(0,-Ce alkyl)C(=O)O(Ci-C₆ alkyl), phenyl, and phenoxy);

(c) Ar₂ is (1) (2) furanyl, phenyl, pyridazinyl; pyridyl, pyrimidinyl, thienyl, or substituted furanyl, substituted phenyl, substituted pyridazinyl,

25 substituted pyridyl, substituted pyrimidinyl, or substituted thienyl, wherein said substituted furanyl, substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, and substituted thienyl, hâve one or more substituents independently selected from H, 0H, F, Cl, Br, I, CN, N0₂, C,-C_e alkyl, CrC_ehaloalkyl, C,-C_s hydroxyalkyl,, C₃-C₆ cyçloalkyl, C₃-C₆ halocycloalkyl, C₃-C_B30 hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C_B h^lpcyçloalkoxy, C₃-C_B hydroxycycloalkoxy, 0,C₆ alkoxy, C,-C₆ haloalkoxy, C₂-C₆ alkenyl, C_Z-C_B alkynyl, 3(=0),,(0,-06 alkyl), 8(=0),,(0,-06 haloalkyl), 030₂(0,-0₆ alkyl), 0S0₂(C,-C₆ haloalkyl), C(=O)H, C(=O)0H, C(=O)NR_xR_y, (0,C₆ alkyl)NR_xR_y, C(=O)(C,-Ç₆ alkyl), 0(=0)0(0,-0_δ alkyl), 0(=0)(0,-0₆ haloalkyl), C(=O)O(C,-C_B haloalkyl), C(=O)(C₃-C₆ cycloalkyl), C(=O)O(C₃-C₆ cycloalkyl), C(=O)(C₂-C_e35 alkenyl), 0(=0)0(0₂-0δ alkenyl), (C,-C_B alkyl)O(C,-C_s alkyl), (C,-C₆ alky1)S(Ci-Ce alkyl), 0(=0)(0,-0₆ alkyl)C(=O)O(C,-C_B alkyl), phenyl, phenoxy, substituted phenyl and substituted phenoxy (wherein such substituted phenyl and substituted phenoxy hâve one or more !

i substituents independently selected from H, OH, 'F, Cl, Br, I, CN, NO₂, CrC₆ alkyl, C_rCe haloalkyl, C_rC₆ hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C_s hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, C₃C₈ alkoxy, Ci-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(=O)_n(Cj-C₆ alkyl), S(=O)_n(C₁-C_e5 haloalkyl), OSO₂(CrC₆ alkyl), OSO₂(CrC₆ haloalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (C_r

C₆ alkyl)NR_xR_y, C(=O)(C_rC₆ alkyl), C(=0)O(CrC₆ alkyl), C(=O)(C_rC_B haloalkyl), C(=0)0(CrC₆ haloalkyl), C(=O)(C₃-C₆ cycloalkyh/C^OJOiCa-Ce cycloalkyl), C(=O)(C_rC₆haloalkyl), C(=O)(C₂-C₆ alkenyl), C(=0)O(C₂-Ce àlkbnyl), (C_rC₆ alkyl)O(C_rC_e alkyl), (C_rC_ealkyl)S(Ci-C_E alkyl), C(=O)(C<-C₆ alkyl)C(=O)O(CrC₆ alkyl), phenyl, and phenoxy);

10 (d) JisCR^Rjz;

j

I ί· (e) L is a single bond;

(f) K is NR_K1;

(g) Q is O;

(h) R1 is H, OH, F, Cl, Br, I, oxo, C_rC_e alkyl, CrC§ haloalkyl, C--C_s alkoxy, C₃-C_e

15 cycloalkoxy, CrC₆ haloalkoxy, Ç₂-C₆ alkenyloxy, ,(C_rC₆ alkyl)O(C_rC_e alkyl), (CrCe alkyl)O(CrC₆ alkoxy), OC(=O)(Ci-C₆ alkyl), O,C(=O)(C₃-C_Ô cycloalkyl), OC(=O)(CrC₈haloalkyl), OC(=O)(C₂-C₆ alkenyl),or NR_xR_y;

(i) R2 is H, OH, F, Cl, Br, I, oxo, CrÇ₆ alkyl, CrC« haloalkyl, CrC_s alkoxy, C₃-C_ecycloalkoxy, CrC₆ haloalkoxy^ Ç₂-C₆ alkenyloxy, (Ci-C₆. alkyl)O(C_rC_e alkyl), (Ci-C_e

20 alkyl)O(CrC₆ alkoxy), OC(=O)(CrC₀ alkyl), J.OÇ(=O)(C₃-C_S cycloalkyl), OC(=O)(CrC_shaloalkyl), OC(=O)(C₂-C₆ alkenyl),or NR_xR_y; , , (j) R3 is H, OH, F, Cl, Br, I, oxo, Ci-C₆· alkyl, CrC₆ haloalkyl, CrC₆ alkoxy, C₃-C_ecycloalkoxy, CrCe haloalkoxy, C₂-C₆ alkenyloxy, (CrC₆ alkyl)O(C_rC₀ alkyl), (CrC₆alkyl)O(CrC₆ alkoxy), OC(=O)(CrC₆ alkyl), OC(=O)(C₃-C₈ cycloalkyl), OC(=O)(CrC_e

25 haloalkyl), OC(=O)(C₂-C₆ alkenyl),or NR_xR_y;

(k) R4 is H, CrC₆ alkyl, CrC₆ haloalkyl, CrC₆ alkoxy, CrC_e haloalkoxy, C₂-C_ealkenyloxy, (C_rC₆ alkyl)O(CrC₆ alkyl); and (0 Rji> Rj2, and R_Kt, are independently selected from H, OH, F, Cl, Br, I, CN, NO₂, CrC₆ alkyl, C_rC₆ haloalkyl, ÇrC₆ hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, 30 C₃-C₆ hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C_s halocycloalkoxy, C₃-C_e hydroxycycloalkoxy, CrC₆ alkoxy, CrC₆ haloalkoxy, C₂-C_s alkenyl, C_z-C_e alkynyl, S(=O)_n(Cr Ce alkyl), S(=O)_n(CrC_e haloalkyl),, OSO₂(Ci-Ç₆ alkyl), OSO₂(CrC₆ haloalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (CrCe alkyl)NR_xR_y,., C(=O)(CrC₆ alkyl), C(=O)(Ci-C_e alkyl)C(=O)O(CrC₆ alkyl), C(=O)O(CrC₆ , alkyl), _È C(=O)(CrC₆ haloalkyl), C(=O)O(CrC₆

35 haloalkyl), C(=O)(C₃-C_e cycloalkyl), C(=0)O(C₃-C₆ cycloalkyl), C(=O)(C₂-C_e alkenyl), C(=O)O(C₂-C₆ alkenyl), (CrC₆ alkyl)O(CrC_s alkyl), ;(CrC₆ alkyl)S(CrC₆ alkyl), C(=0)(CrC₆alkyl)C(=O)O(CrC₆ alkyl), C(=O)(CrC_e alkyl)C(=O)OH. phenyl, phenoxy, wherein each alkyl, haloalkyl, hydroxyalkyl, cycloalkyl, halocycloalkyl, hydroxycycloalkyl, cycloalkoxy, halocycloalkoxy, hydroxycycloalkoxy, alkoxy, haloalkoxy, alkenyl, alkynyl, phenyl, and phenoxy are ! optionally substituted with one or more substituents independently selected from OH, F,^; CI, Br, I, CN, NO₂, oxo, CrCe alkyl, CrC₆5 haloalkyl, CrCe hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C_a halocycloalkyl, C₃-C_ehydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C_s hydroxycycloalkoxy, C_rC_e alkoxy, CrCe haloalkoxy, C₂-C₆alkenyl, C₂-C₆ alkynyl, S(=O)_n(CrC_e alkyl), S(=O)_n(CrC₆haloalkyl), OSO₂(C_rC_e alkyl), OSO₂(CrC₆ hàlôalkyl), C(=O)H, C(=O)OH, C(=O)NR_xR_y, (C_rC_e alkyl)NR_xR_y, C(=O)(C₁-C₆ alkyl), C(=O)O(C_rC₆ alkyl), C(=O)(CrC₆ haloalkyl), 10 C(=O)O(CrC₆ haloalkyl), C(=O)(C₃-C₆ cycloalkyl), C(=O)O(C₃-C₆ cycloalkyl), C(=O)(C₂-C_aalkenyl), C(=O)O(C₂-C₆ alkenyl), (CrCe alkyl)O(CrC₆ alkyl), (CrC₆ alkyl)S(CrC₆ alkyl), C(=O)(CrC₆ alkyl)C(=O)O(CrC₆ alkyl), phenyl, and phenoxy;

(m) n= 0,1, or 2; and (n) R_x and R_y are independently selected from H, CrC₆ alkyl, CrC₆ haloalkyl, C_r15 C₆ hydroxyalkyl, C₃-C₅ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, CrC_e alkoxy, CrC₆haloalkoxy, C₂-C6 alkenyl, C₂-C₆, alkynyl,t S(rP^(ÇrC_s alkyl), S(=O)_n(CrC₆ haloalkyl), OS0₂(CrC₆ alkyl), OSO₂(CrC₆ haloalkyl), < C(=O)H, C(=O)OH, C(=O)(CrC₆ alkyl), C(=O)O(CrC₆ alkyl), C(=O)(C_rCe haloalkyl), - C(=O)O(CrC_e haloalkyl), C(=O)(C₃-C₆20 cycloalkyl), C(=O)O(C₃-C₆ cycloalkyl), C^OKÇ^Ce. alkenyl), C(=O)O(C₂-C₆ alkenyl), (C_rCe alkyl)O(CrC₆ alkyl), (C_rC₆ aIkyl)S(CrC₆ alkyl), ,Ç(=O)(CrC₈ alkyl)C(=O)O(CrC_e alkyl), phenyl, and phenoxy, <; ·

2. A molécule according to claim 1 having a structure according to Compounds 1-9.

3. A process comprising applying a molécule according to claim 1 to an area to control a pest in an amount suffirent to control such pest.

i

4. A process according to claim 3 wherein said area is an area where apples, corn, 30 cotton, soybeans, canola, wheat, rice, sorghum, barley, oats, potatoes, oranges, alfalfa, lettuce, strawberries, tomatoes, peppers, crucifors,;pears, tobacco, almonds, sugar beets, or beans, are growing, or the seeds thereof are going to be planted

5. A molécule that is a pestiçidally acceptable acid addition sait, a sait dérivative, a 35 solvaté, or an ester derivatîve, of a molécule according to claim 1.

• _{r K} ‘J i f .

A molécule according to claim 1 wherein at least one H is ²H or at least one C is ¹⁴C, - 52·

6.

7. A composition comprising a molécule according to claim 1 and at least one other compound selected from the Insecticide Group, Acaricide Group, Nematicide Group, Fungicide Group, Herbicide Group, Al Group, or Synergist Group.

8. A composition comprising a molécule according to claim 1 and a seed.

9. A composition according to claim 8 wherein said seed has been genetically modified to express one or more specialized traits.

¹⁰

10. A process comprising applying a molécule according to claim 1 to a genetically modified plant that has been genetically modified to express one or more specialized traits.

1’

11. A process comprising: orally administering; or topically applying; a molécule 15 according to claim 1, to a non-human animal, to control endoparasites, ectoparasites, or both.