USOO949 1944B2

(12) United States Patent (10) Patent No.: US 9,491,944 B2 Zhang et al. (45) Date of Patent: Nov. 15, 2016

(54) PESTICIDAL COMPOSITIONS AND 7,774,978 B2 8/2010 Ding et al. RELATED METHODS 7,803,832 B2 9/2010 Critcher et al. 7.910,606 B2 3/2011 Nazare et al. 7,923,573 B2 4/2011 Tamaki et al. (71) Applicant: DOW AGROSCIENCES LLC, 8,163,756 B2 4/2012 Flynn et al. Indianapolis, IN (US) 8,198.308 B2 6/2012 Steurer et al. 8,222,280 B2 7/2012 Liu et al. (72) Inventors: Yu Zhang, Carmel, IN (US); Tony K. 8,350,044 B2 1/2013 Trullinger Trullinger, Westfield, IN (US); Ricky 22 R: ck $38: Bisschneider A61K 45,06 Hunter, Westfield, IN (US); Ann M. wk - a ...... 424/417 Buysse, Carmel, IN (US) 8,853.246 B2 10/2014 Trullinger 9,006,446 B2 4/2015 Trullinger (73) Assignee: Dow AgroSciences LLC, Indianapolis, 9,137,998 B2 9/2015 Niyaz IN (US) 2002fOO 13326 A1 1/2002 Tiebes et al. 2003. O153464 A1 8/2003 Nakamura et al. 2003/0213405 A1 11/2003 Harada et al. (*) Notice: Subject to any disclaimer, the term of this 2004/0082629 A1 4, 2004 E. patent is extended or adjusted under 35 2005, OO38059 A1 2/2005 Mueller et al. U.S.C. 154(b) by 56 days. (Continued) (21) Appl. No.: 14/517,619 FOREIGN PATENT DOCUMENTS (22) Filed: Oct. 17, 2014 EP OO97323 1, 1984 EP O2O5O24 12, 1986 (65) Prior Publication Data EP O248315 12/1987 EP O425948 5, 1991 US 2015/O 111735A1 Apr. 23, 2015 EP 1273582 1, 2003 EP 1321463 6, 2003 EP 1329160 T 2003 Related U.S. Application Data JP 153273 7, 1987 (60) Provisional application No. 61/894,348, filed on Oct. E. 3. 33.6 22, 2013. (Continued) (51) Int. Cl. AOIN 43/647 (2006.01) OTHER PUBLICATIONS CO7D 40/04 (2006.01) CO7D 40/4 (2006.01) PCT International Search Report; PCT/US2014/06 1078; dated Jan. (52) U.S. Cl. Rif Wien Opinion: PCT/US2014/06 1078; dated Jan. 15, 2015 CPC ...... A0IN 43/647 (2013.01); C07D 401/04 p s s k - (2013.01); C07D 401/14 (2013.01) (58) Field of Classification Search Primary Examiner — Jane C Oswecki CPC. A01N 43/647; C07D 401/04: CO7D 401/14 (74) Attorney, Agent, or Firm — Carl D. Corvin; Magelby See application file for complete search history. Cataxinos & Greenwood (56) References Cited (57) ABSTRACT U.S. PATENT DOCUMENTS A pesticidal composition comprises a pyridine triazole com 4,080,457 A 3, 1978 Harrison et al. pound of formula I or any agriculturally acceptable salt 4,260,765 A 4, 1981 Harrison et al. 4,474,599 A * 10/1984 Rogers ...... AON 43,647 thereof, wherein R. R. R. R. Rs. Z, and X are as described 504/230 herein. A method of controlling pests comprises applying the 4,536,506 A 8, 1985 Marcoux et al. pesticidal composition near a population of pests. 5,625,074 A 4/1997 Daum et al. 5,631,380 A 5, 1997 Haas et al. 5,652,372 A 7, 1997 Muller et al. 5,693,657 A 12/1997 Lee et al. 5,750,718 A 5, 1998 Muller et al. R4 N2N. 5,817,677 A 10, 1998 Linz et al. / Z 5,854.264 A 12/1998 Anthony et al. R3 N N 5,854,265 A 12/1998 Anthony 5,869,681 A 2f1999 Muller et al. Rs 6,218,418 B1 4/2001 Pevarello et al. 2 6,274,536 B1 8, 2001 Nebel et al. R R 6,548,525 B2 4/2003 Galemmo, Jr. et al. 6,720,427 B2 4/2004 Sanner et al. (O), 6,878,196 B2 4/2005 Harada et al. 6,916,927 B2 7/2005 Bunnage et al. 7,192,906 B2 3/2007 Hirohara et al. 7,196,104 B2 3/2007 Askew, Jr. et al. 7,319, 108 B2 1/2008 Schwink et al. 38 Claims, No Drawings US 9,491,944 B2 Page 2

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A61K 45/06 WO 2012O35O11 3, 2012 504,100 WO 2012052412 4/2012 WO 2012O61290 5, 2012 WO 2012070114 5, 2012 FOREIGN PATENT DOCUMENTS WO 2012 102387 8, 2012 WO 2012108511 8, 2012 JP O3212864 T 2003 WO 2012168361 12/2012 JP 2004051628 2, 2004 WO 2012175474 12/2012 JP 2004292703 10, 2004 WO 2013OOO931 1, 2013 JP 2012188418 10, 2012 WO 2013001094 1, 2013 JP 2013075871 4/2013 WO 2013.010946 1, 2013 JP 2013O82699 5, 2013 WO 201306.2980 5, 2013 JP 2013O82704 5, 2013 WO 2013156431 10, 2013 JP 2013 107867 6, 2013 WO 2013156433 10, 2013 JP 2013 1296.51 T 2013 WO 2013,162715 10, 2013 JP 2013 1296.53 T 2013 WO 2013,162716 10, 2013 WO 9413644 6, 1994 WO 9736897 10, 1997 * cited by examiner US 9,491,944 B2 1. 2 PESTICIDAL COMPOSITIONS AND "Aryl means and includes an aromatic compound with or RELATED METHODS without any Substitution. Non-limiting examples may include phenyl or naphthyl. CROSS REFERENCE TO RELATED "Alkoxy' means and includes an alkyl group containing APPLICATION at least one carbon-oxygen single bond. Non-limiting examples may include methoxy, ethoxy, propoxy, butoxy, This application claims the benefit of U.S. Provisional cyclopropoxy, cyclobutoxy, or cyclopentoxy. Patent Application Ser. No. 61/894,348, filed Oct. 22, 2013, “Alkenyloxy' means and includes an alkenyl containing the disclosure of which is hereby incorporated herein in its at least one carbon-oxygen single bond. Non-limiting entirety by this reference. 10 examples may include allyloxy, butenyloxy, pentenyloxy, hexenyloxy, heptenyloxy, octenyloxy, nonenyloxy, or dece TECHNICAL FIELD nyloxy “Alkynyloxy' means and includes an alkynyl containing This disclosure relates to the field of compounds having at least one carbon-oxygen single bond. Non-limiting pesticidal utility against pests in Phyla Nematoda, Arthro 15 examples may include pentynyloxy, hexynyloxy, heptyny poda, and/or Mollusca, processes to produce Such com loxy, octynyloxy, nonynyloxy, or decynyloxy. pounds and intermediates used in Such processes. These “Cycloalkoxy' means and includes a cycloalkyl contain compounds may be used, for example, as nematicides, ing at least one carbon-oxygen single bond. Non-limiting acaricides, insecticides, miticides, and/or molluscicides. examples may include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cycloocty BACKGROUND loxy, cyclodecyloxy, norbornyloxy, or bicyclo2.2.2]octy loxy. Controlling pest populations is essential to human health, “Cyclohaloalkyl means and includes a monocyclic or modern agriculture, food storage, and hygiene. There are polycyclic, Saturated Substituent comprising carbon, halo more than ten thousand species of pests that cause losses in 25 gen, and hydrogen. Non-limiting examples may include agriculture and the world-wide agricultural losses amount to 1-chlorocyclopropyl, 1-chlorocyclobutyl, or 1-dichlorocy billions of U.S. dollars each year. Accordingly, there exists clopentyl. a continuous need for new pesticides and for methods of “Cycloalkenyloxy' means and include a cycloalkenyl producing and using such pesticides. further consisting of a carbon-oxygen single bond. Non 30 limiting examples may include cyclobutenyloxy, cyclopen DISCLOSURE tenyloxy, cyclohexenyloxy, cycloheptenyloxy, cycloocteny loxy, cyclodecenyloxy, norbornenyloxy, or bicyclo2.2.2 Definitions octenyloxy. The examples given in the definitions are non-exhaustive “Alkylthio’ means and includes an alkyl group containing and must not be construed as limiting the present disclosure. 35 at least one carbon-sulfur single bond. It is understood that a substituent should comply with "Haloalkylthio’ means and includes an alkyl group con chemical bonding rules and steric compatibility constraints taining at least one carbon-sulfur single bond and halogen in relation to the particular molecule to which it is attached. atOm. “Alkyl means and includes an acyclic, Saturated, "Halo’ or “halogen' means and includes fluorine, chlo branched or unbranched hydrocarbon. Non-limiting 40 rine, bromine, or iodine. examples may include methyl, ethyl, propyl, isopropyl. "Haloalkyl means and includes an alkyl group Substi 1-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 2-methylbutyl, tuted with at least one halogen atom. 1,1-dimethylpropyl, hexyl, heptyl, octyl, nonyl, or decyl. "Haloalkoxy' means and includes an alkoxy group Sub “Cycloalkyl means and includes a monocyclic or poly stituted with at least one halogen atom. cyclic Saturated hydrocarbon. Non-limiting examples may 45 “Heteroatom' means and includes sulfur (S), oxygen (O), include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or nitrogen (N) atom. cycloheptyl, cyclooctyl, cyclodecyl, norbornyl, bicycle “Heteroalkyl means and includes an alkyl containing at 2.2.2]octyl, or decahydronapthyl. least one Sulfur (S), oxygen (O), or nitrogen (N) atom. “Alkenyl' means and includes an acyclic, branched or “Heterocyclyl means a cyclic substituent that may be unbranched hydrocarbon containing at least one carbon 50 fully saturated, partially unsaturated, or fully unsaturated, carbon double bond. Non-limiting examples may include where the cyclic structure contains at least one carbon and ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, at least one heteroatom, where said heteroatom is nitrogen, octenyl, nonenyl, or decenyl. Sulfur, or oxygen. In the case of Sulfur, that atom can be in “Cycloalkenyl means and includes a monocyclic or other oxidation states such as a Sulfoxide and Sulfone. polycyclic hydrocarbon containing at least one carbon 55 Examples of aromatic heterocyclyls include, but are not carbon double bond. Non-limiting examples may include limited to, benzofuranyl, benzoisothiazolyl, benzoisox cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, azolyl, benzoxazolyl, benzothienyl, benzothiazolyl, cinnoli or cyclodecenyl. nyl, furanyl, imidazolyl, indazolyl, indolyl, isoindolyl, iso “Alkynyl' means and includes acyclic, branched or quinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, unbranched hydrocarbon containing at least one carbon 60 oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, carbon triple bond. Non-limiting examples may include pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, ethynyl, propargyl, butynyl, pentynyl, hexynyl, heptynyl, quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, octynyl, nonynyl, or decynyl. thienyl, triazinyl, and triazolyl. Examples of fully saturated “Cycloalkynyl' means and includes a monocyclic or heterocyclyls include, but are not limited to, piperazinyl, polycyclic hydrocarbon containing at least one carbon 65 piperidinyl, morpholinyl, pyrrolidinyl, oxetanyl, tetrahydro carbon triple bond. Non-limiting examples may include furanyl, tetrahydrothienyl and tetrahydropyranyl. Examples cycloheptynyl, cyclooctynyl, or cyclodecynyl. of partially unsaturated heterocyclyls include, but are not US 9,491,944 B2 3 4 limited to, 1.2.3,4-tetrahydroquinolinyl, 4.5-dihydro-OX Co-Co aryl, or C-Coheterocyclyl, wherein each of which azolyl. 4,5-dihydro-1H-pyrazolyl. 4,5-dihydro-isoxazolyl, may be unsubstituted or substituted with R: and 2,3-dihydro-1,3,4-oxadiazolyl. Additional examples Rs is selected from hydrogen, F, Cl, Br, I, CN, NO, include the following: substituted or unsubstituted C-C alkyl, substituted or unsubstituted C-C alkenyl, substituted or unsubstituted C-C alkoxy, C-C cycloalkyl, Substituted or unsubsti tuted C-C aryl, substituted or unsubstituted C-C het An A erocyclyl, OR, C(=X)R, C(=X)OR, C(=X)N S - (R), N(R), N(R)C(=X)R. SR, S(O), OR, or thietanyl \, | 10 RS(O),R, wherein Rs, when Substituted, has one or more thietanyl- thietanyl substituents selected from F, Cl, Br, I, CN, NO, C-C alkyl, oxide dioxide C-C alkenyl, C-C haloalkyl, C-C haloalkenyl, C-C, haloalkyloxy, C-C haloalkenyloxy, C-Co cycloalkyl, C-C cycloalkenyl, C-Cohalocycloalkyl, C-Chalocy “Pesticidally effective amount’ means and includes an 15 cloalkenyl, OR, S(O), OR, Co-Co aryl, or C-C het amount of active material that causes an adverse effect to the erocyclyl, wherein each of which may be unsubstituted or at least one insect, wherein the adverse effect may include substituted with R: deviations from natural development, killing, regulation, or Z is Z1. Z2. Zs. Z4. Zs. Z6. Z7 O Zs: the like. "Control” or grammatical variations thereof means and includes regulating the number of living insects or regulat Z ing the number of viable eggs of the insects. R10 “Synergistic effect” or grammatical variations thereof means and includes a cooperative action encountered in a 25 combination of two or more active agents in which the combined activity of the two or more active agents exceeds the Sum of the activity of each active agent alone. R6 Rs Pesticidal Compounds R7 In one particular embodiment, a pesticidal composition 30 Z2 comprises a pyridine triazole compounds of formula I, or : N R8 any agriculturally acceptable salt thereof: Y N N R7 35 R N2, R6 R3 N / Z Z3 N Rs Rs 2 40 R R (O), N N R6 wherein: 45 Z4 R. R. and Ra are independently selected from hydrogen, Rs F, Cl, Br, I, substituted or unsubstituted C-C alkyl, or substituted or unsubstituted C-C haloalkyl, wherein each 21 NN R. R. and Ra, when substituted, has one or more substitu ents selected from F, Cl, Br, I, CN, NO, C-C alkyl, C-C, 50 N ls alkenyl, C-Chaloalkyl, C-C cycloalkyl, or C-Cohalo R6 N R cycloalkyl where each of which may be unsubstituted or Z5 substituted with R: Ro R is selected from hydrogen, F, Cl, Br, I, CN, NO, substituted or unsubstituted C-C alkyl, substituted or 55 unsubstituted C-C alkenyl, substituted or unsubstituted N C-C alkoxy, Substituted or unsubstituted C-Co S R cycloalkyl, substituted or unsubstituted C-C haloalkyl, Substituted or unsubstituted Co-Co aryl, Substituted or R6 unsubstituted C-Co heterocyclyl, OR, C(=X)R. 60 Z6 C(=X)OR, C(=X)N(R), N(R), N(R)C(=X) Ro R. SR, S(O), OR, or RS(O),R, wherein R, when substituted, has one or more substituents selected from F, Cl, : N Rs Br, I, CN, NO, C-C alkyl, C-C alkenyl, C-Chaloalkyl, C-C haloalkenyl, C-C haloalkyloxy, C-C haloalkeny 65 2 loxy, C-C cycloalkyl, C-Co cycloalkenyl, C-Co halo R6 N R cycloalkyl, C-Co halocycloalkenyl, OR, S(O), OR, US 9,491,944 B2 5 6 -continued Co-Co aryl, or C-Coheterocyclyl, wherein each of which Z7 may be unsubstituted or substituted with R: Ro R is selected from hydrogen, F, Cl, Br, I, CN, NO, : Rs —OR, Substituted or unsubstituted C-C alkyl, Substi 21 tuted or unsubstituted C-C alkenyl, substituted or unsub stituted C-C alkoxy, Substituted or unsubstituted C-Co N N cycloalkyl, Substituted or unsubstituted C-Co halocy R6 cloalkyl, Substituted or unsubstituted C-C cycloalkenyl, R7 Substituted or unsubstituted Co-Co aryl, Substituted or Z8 10 unsubstituted C-C heterocyclyl, C(=X)R, C(=X) : N Rs 2 OR, C(=X)N(R), N(R), N(R)C(=X)R, SR, S(O), OR, or RS(O),R, wherein Ro, when substituted, N has one or more substituents selected from F, Cl, Br, I, CN, 1S NO, C-C alkyl, C-C alkenyl, C-C haloalkyl, C-C, 15 haloalkenyl, C-C haloalkyloxy, C-C haloalkenyloxy, R Cs-Co cycloalkyl, C-C cycloalkenyl, C-Co halocy cloalkyl, C-C halocycloalkenyl, Oxo, OR, S(O).R. R is selected from hydrogen, F, Cl, Br, I, CN, NO, OR, Co-Co aryl, or C-Coheterocyclyl, wherein each of which substituted or unsubstituted C-C alkyl, substituted or may be unsubstituted or substituted with R: unsubstituted C-C alkenyl, substituted or unsubstituted Ro is selected from hydrogen, F, Cl, Br, I, CN, NO, C-C alkoxy, Substituted or unsubstituted C-Co OR, substituted or unsubstituted C-C alkyl, substituted cycloalkyl, Substituted or unsubstituted C-C halocy or unsubstituted C-C alkenyl, substituted or unsubstituted cloalkyl Substituted or unsubstituted C-Co cycloalkenyl, C-C alkoxy, Substituted or unsubstituted C-Co Substituted or unsubstituted Co-Co aryl, Substituted or 25 cycloalkyl, Substituted or unsubstituted C-Co halocy unsubstituted C-C heterocyclyl, C(=X)R. C(=X) cloalkyl Substituted or unsubstituted C-C cycloalkenyl, OR, C(=X)N(R), N(R), N(R)C(=X)R, SR, Substituted or unsubstituted Co-Co aryl, Substituted or S(O), OR, or RS(O).R, wherein R6, when substituted, unsubstituted C-Co heterocyclyl, C(=X)R. C(=X) has one or more substituents selected from F, Cl, Br, I, CN, OR, C(=X)N(R), N(R), N(R)C(=X)R, SR, NO, C-C alkyl, C-C alkenyl, C-C haloalkyl, C-C, 30 S(O), OR, or RS(O).R, wherein Ro, when substituted, haloalkenyl, C-C haloalkyloxy, C-C haloalkenyloxy, has one or more substituents selected from F, Cl, Br, I, CN, Cs-Co cycloalkyl, C-Co cycloalkenyl, C-Co halocy NO, C-C alkyl, C-C alkenyl, C-C haloalkyl, C-C, cloalkyl, C-C halocycloalkenyl, Oxo, OR, S(O).R. haloalkenyl, C-C haloalkyloxy, C-C haloalkenyloxy, Co-Co aryl, or C-Co heterocyclyl, wherein each of which Cs-Co cycloalkyl, C-C cycloalkenyl, C-Co halocy may be unsubstituted or substituted with R: 35 cloalkyl, C-C halocycloalkenyl, Oxo, OR, S(O).R. R, is selected from hydrogen, F, Cl, Br, I, CN, NO, OR, Co-Co aryl, or C-Coheterocyclyl, wherein each of which substituted or unsubstituted C-C alkyl, substituted or may be unsubstituted or substituted with R: unsubstituted C-C alkenyl, substituted or unsubstituted R is selected from hydrogen, F, Cl, Br, I, CN, NO, C-C alkoxy, Substituted or unsubstituted C-Co substituted or unsubstituted C-C alkyl, substituted or cycloalkyl, Substituted or unsubstituted C-C halocy 40 unsubstituted C-C alkenyl, substituted or unsubstituted cloalkyl Substituted or unsubstituted C-Co cycloalkenyl, C-C alkoxy, Substituted or unsubstituted C-C alkeny Substituted or unsubstituted C-C aryl, Substituted or loxy, Substituted or unsubstituted C-C cycloalkyl, substi unsubstituted C-C heterocyclyl, C(=X)R. C(=X) tuted or unsubstituted C-C cycloalkenyl, Substituted or OR, C(=X)N(R), N(R), N(R)C(=X)R, SR, unsubstituted Co-Co aryl, Substituted or unsubstituted S(O), OR, or RS(O),R, wherein Rz, when substituted, 45 C-C heterocyclyl, substituted or unsubstituted S(O)C- has one or more substituents selected from F, Cl, Br, I, CN, C alkyl, or substituted or unsubstituted N(C-C alkyl). NO, C-C alkyl, C-C alkenyl, C-C haloalkyl, C-C, wherein R, when substituted, has one or more substituents haloalkenyl, C-C haloalkyloxy, C-C haloalkenyloxy, selected from F, Cl, Br, I, CN, NO, C-C alkyl, C-C, C-C cycloalkyl, C-C cycloalkenyl, C-Co halocy alkenyl, C-C haloalkyl, C-C haloalkenyl, C-C, cloalkyl, C-Co halocycloalkenyl, Oxo, OR, S(O).R. 50 haloalkyloxy, C-C haloalkenyloxy, C-Co cycloalkyl, Co-Co aryl, or C-Co heterocyclyl, wherein each of which Cs-Co cycloalkenyl, Cs-Cohalocycloalkyl, Cs-Cohalocy may be unsubstituted or substituted with R: cloalkenyl, OC-C alkyl, OC-C haloalkyl, S(O)C- Rs is selected from hydrogen, F, Cl, Br, I, CN, NO, OR, Calkyl, S(O), OC-C alkyl, Co-Co aryl, or C-Cohetero substituted or unsubstituted C-C alkyl, substituted or cyclyl; unsubstituted C-C alkenyl, substituted or unsubstituted 55 X=O or S: C-C alkoxy, Substituted or unsubstituted C-Co n is 0, 1, or 2; and cycloalkyl, Substituted or unsubstituted C-Co halocy X is 0 or 1. cloalkyl Substituted or unsubstituted C-Co cycloalkenyl, In another embodiment, and in any combination with any Substituted or unsubstituted Co-Co aryl, Substituted or of the previous or following embodiments, R, R2, and R. unsubstituted C-C heterocyclyl, C(=X)R. C(=X) 60 are H. OR, C(=X)N(R), N(R), N(R)C(=X)R, SR, In another embodiment, and in any combination with any S(O), OR, or RS(O),R, wherein Rs, when substituted, of the previous or following embodiments, R is selected has one or more substituents selected from F, Cl, Br, I, CN, from H, F, Cl, Br, or I, preferably, H or F. NO, C-C alkyl, C-C alkenyl, C-C haloalkyl, C-C, In another embodiment, and in any combination with any haloalkenyl, C-C haloalkyloxy, C-C haloalkenyloxy, 65 of the previous or following embodiments, Rs is hydrogen. Cs-Co cycloalkyl, C-C cycloalkenyl, C-Co halocy In another embodiment, and in any combination with any cloalkyl, C-Co halocycloalkenyl, Oxo, OR, S(O).R. of the previous or following embodiments, Z is Zs. US 9,491,944 B2 7

Zs Scheme 2 Ro R4 N2N : R I OH 21 8 R3 N / / N + Z-B Hope N Rs OH N R 2 R N R 2-2 R6 10 2-1 R4 N2N In another embodiment, and in any combination with any R3 N / Z of the previous or following embodiments, R and R, are N independently selected from hydrogen, Substituted or unsub 15 Rs stituted C-C haloalkyl and Rs and R are hydrogen. 2 While some embodiments have been described herein, R N R other embodiments and combinations of the described embodiments with other embodiments may be possible. In one embodiment, the pyridine triazole compounds of Pesticidally Acceptable Acid Addition Salts, Salt Deriva formula I may be prepared, as shown in Scheme 1, by tives, Solvates, Ester Derivatives, Polymorphs, Isotopes, reacting the triazole compound 1-1 (prepared as described in Radionuclides and Stereoisomers Bioorganic & Medicinal Chemistry 2008, 16, 9817) with an In some embodiments, the pyridine triazole compounds of formula I may be formulated into pesticidally acceptable aryl/heterocyclic halide 1-2 in the presence of a catalyst and 25 acid addition salts. By way of a non-limiting example, an a base in a polar aprotic solvent Such as dioxane, at a amine function can form salts with hydrochloric, hydrobro temperature of from about -78° C. to about 120° C. Non mic, Sulfuric, phosphoric, acetic, benzoic, citric, malonic, limiting examples of the catalysts may include bis-(triph salicylic, malic, fumaric, oxalic, Succinic, tartaric, lactic, enylphosphine) palladium (II) dichloride (Pd(PPh)C1) gluconic, ascorbic, maleic, aspartic, benzenesulfonic, meth and copper(I) iodide (CuI). Non-limiting examples of the 30 anesulfonic, ethanesulfonic, hydroxymethanesulfonic, base may include a salt such as cesium fluoride (CSF). hydroxyethanesulfonic, and trifluoroacetic acids. Addition ally, by way of a non-limiting example, an acid function can form salts including those derived from alkali or alkaline Scheme 1 earth metals and those derived from ammonia and amines. 35 Examples of preferred cations include Sodium, potassium, R4 N2N and magnesium. Sn(Bu)3 In some embodiments, the pyridine triazole compounds of R3 NU/ formula I may be formulated into salt derivatives. By way of N -- Z-Br -e- a non-limiting example, a salt derivative can be prepared by Rs 1-2 2 40 contacting a free base with a Sufficient amount of the desired R N R acid to produce a salt. A free base may be regenerated by treating the salt with a suitable dilute aqueous base Solution 1-1 Such as dilute aqueous Sodium hydroxide (NaOH), potas sium carbonate, ammonia, and Sodium bicarbonate. As an 45 example, in many cases, a pesticide. Such as 2,4-D, is made more water-soluble by converting it to its dimethylamine R4 N2N. salt. Z In further embodiments, the pyridine triazole compounds R3 N / of formula I may be formulated into stable complexes with N 50 a solvent, such that the complex remains intact after the Rs non-complexed solvent is removed. These complexes are 2 often referred to as “solvates.” However, it is particularly R N R desirable to form stable hydrates with water as the solvent. In some embodiments, the pyridine triazole compounds of 55 formula I may be made into ester derivatives. These ester derivatives can then be applied in the same manner as the In another embodiment, the pyridine triazole compounds invention disclosed in this document is applied. of formula I may be prepared, as shown in Scheme 2, by In some embodiments, the pyridine triazole compounds of reacting 4-iodo-triazole compound 2-1 (prepared as formula I may be made as various crystal polymorphs. described in Bioorganic & Medicinal Chemistry 2008, 16, 60 Polymorphism is important in the development of agro 9817) with an aryl/heterocyclic boronic acid compound chemicals since different crystal polymorphs or structures of (2-2) in the presence of a catalyst and a base in a Suitable the same molecule can have vastly different physical prop Solvent system, Such as a mixture of 1,4-dioxane and water, erties and biological performances. at a temperature of from about 25° C. to about 120° C. In further embodiments, the pyridine triazole compounds Non-limiting examples of the catalyst may include 65 of formula I may be made with different isotopes. Of Pd(PPh3)2Cl and non-limiting examples of the base may particular importance are molecules having H (also known include Sodium carbonate (Na,CO). as deuterium) in place of H. US 9,491,944 B2 10 In some embodiments, the pyridine triazole compounds of mula I may include 1,2-dichloropropane, abamectin, formula I may be made with different radionuclides. Of acephate, acetamiprid, acethion, acetoprole, acrinathrin, particular importance are molecules having C or ''C. acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, In some embodiments, the pyridine triazole compounds of allethrin, allosamidin, allyxycarb, alpha-cypermethrin, formula I may exist as one or more stereoisomers. Thus, 5 alpha-ecdysone, O/p/co-endosulfan, amidithion, aminocarb, certain molecules can be produced as racemic mixtures. It amiton, amiton oxalate, amitraz, anabasine, athidathion, will be appreciated by those skilled in the art that one azadirachtin, azamethiphos, azinphos-ethyl, azinphos Stereoisomer may be more active than the other stereoiso methyl, azothoate, barium hexafluorosilicate, barthrin, ben mers. Individual stereoisomers may be obtained by known diocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cyper selective synthetic procedures, by conventional synthetic 10 methrin, bifenthrin, bioallethrin, bioethanomethrin, procedures using resolved starting materials, or by conven biopermethrin, bistrifluron, borax, boric acid, bromfenvin tional resolution procedures. Certain molecules disclosed in fos, bromocyclen, bromo-DDT, bromophos, bromophos this document can exist as two or more isomers. The various ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocar isomers include geometric isomers, diastereomers, and boxim, butonate, butoxycarboxim, cadusafos, calcium enantiomers. Thus, the molecules disclosed in this document 15 arsenate, calcium polysulfide, camphechlor, carbanolate, include geometric isomers, racemic mixtures, individual carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, stereoisomers, and optically active mixtures. It will be carbophenothion, carbosulfan, cartap, cartap hydrochloride, appreciated by those skilled in the art that one isomer may chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, be more active than the others. The structures disclosed in chlordimeform, chlordimeform hydrochloride, chlorethoxy the present disclosure are drawn in only one geometric form 20 fos, chlorfenapyr, chlorfenvinphos, chlorfluaZuron, chlo for clarity, but are intended to represent all geometric forms rmephos, chloroform, chloropicrin, chlorphoxim, chlorpra of the molecule. Zophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, Pesticidal Compositions chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, In one particular embodiment, a pesticidal composition cloethocarb, closantel, clothianidin, copper acetoarsenite, comprises a pyridine triazole compounds of formula I, or 25 copper arsenate, copper naphthenate, copper oleate, couma any agriculturally acceptable salt thereof phos, coumithoate, crotamiton, crotoxyphos, crufomate, In some embodiments, a pesticidal composition com cryolite, cyanofenphos, cyanophos, cyanthoate, cyantra prises a pyridine triazole compounds of formula I or any niliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, agriculturally acceptable salt thereof, and a phytologically cypermethrin, cyphenothrin, cyromazine, cythioate, DDT. acceptable inert carrier (e.g., Solid carrier, or liquid carrier). 30 decarbofuran, deltamethrin, demephion, demephion-O. In one embodiment, the pesticidal composition may fur demephion-S, demeton, demeton-methyl, demeton-O. ther comprise at least one additive selected from surfactant, demeton-O-methyl, demeton-S, demeton-S-methyl, deme a stabilizer, an emetic agent, a disintegrating agent, an ton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous antifoaming agent, a Wetting agent, a dispersing agent, a earth, diazinon, dicapthon, dichlofenthion, dichlorvos, binding agent, dyes, or fillers. 35 dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenZuron, In some embodiments, the pesticidal compositions may dilor, dimefluthrin, dimefox, dimetan, dimethoate, dime be in the form of solid. Non-limiting examples of the solid thrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, forms may include power, dust or granular formulations. dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, In other embodiments, the pesticidal compositions may be dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, in the form of liquid formulation. Examples of the liquid 40 DNOC, DNOC-ammonium, DNOC-potassium, DNOC-so forms may include, but not limited to, dispersion, Suspen dium, doramectin, ecdysterone, emamectin, emamectin ben Sion, emulsion or Solution in appropriate liquid carrier. Zoate, EMPC, empenthrin, endosulfan, endothion, endrin, In further embodiments, the pesticidal compositions may EPN, epofenonane, eprinomectin, esdépallethrine, esfenva be in the form of liquid dispersion, wherein the pyridine lerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate triazole compounds of formula I may be dispersed in water 45 methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene or other agriculturally suitable liquid carrier. dibromide, ethylene dichloride, ethylene oxide, etofenprox. In yet further embodiments, the pesticidal compositions etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlo may be in the form of solution in an appropriate organic rphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, solvent. In one embodiment, the spray oils, which are widely fenoxacrim, fenoxycarb, fempirithrin, fenpropathrin, fensul used in agricultural chemistry, may be used as an organic 50 fothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, floni Solvent for the pesticidal compositions. camid, flubendiamide (additionally resolved isomers The pesticidal composition may be used in conjunction thereof), flucofuron, flucycloxuron, flucythrinate, flufen (such as, in a compositional mixture, or a simultaneous or erim, flufenoxuron, flufenprox, fluvalinate, fonofos, sequential application) with one or more compounds having formetanate, formetanate hydrochloride, formothion, form acaricidal, algicidal, avicidal, bactericidal, fungicidal, her 55 paranate, formparanate hydrochloride, foSmethilan, fospi bicidal, insecticidal, molluscicidal, nematicidal, rodentici rate, fosthietan, fufenozide, furathiocarb, furethrin, gamma dal, and/or virucidal properties. cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, Furthermore, the pesticidal composition may be used in HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, conjunction (such as, in a compositional mixture, or a HHDN, hydramethylnon, hydrogen cyanide, hydroprene, simultaneous or sequential application) with one or more 60 hyduincarb, imidacloprid, imiprothrin, indoxacarb, compounds that are antifeedants, bird repellents, chemoste iodomethane, IPSP, isazofoS, isobenzan, isocarbophos, iso rilants, herbicide Safeners, insect attractants, insect repel drin, isofenphos, isofenphos-methyl, isoprocarb, isoprothi lents, mammal repellents, mating disrupters, plant activa olane, isothioate, isoxathion, ivermectin, jasmolin I, jasmo tors, plant growth regulators, and/or synergists. lin II, jodfenphos, juvenile hormone I, juvenile hormone II, Insecticides juvenile hormone III, kelevan, kinoprene, lambda-cyhalo Non-limiting examples of insecticides that may be used in thrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, combination with the pyridine triazole compounds of for lufenuron, lythidathion, malathion, malonoben, mazidox, US 9,491,944 B2 11 12 mecarbam, mecarphon, menazon, meperfluthrin, mephosfo mula I may include 1,3-dichloropropene, benclothiaz, lan, mercurous chloride, mesulfenfos, metaflumizone, meth dazomet, dazomet-sodium, DBCP, DCIP, diamidafos, flu acrifos, methamidophos, methidathion, methiocarb, metho ensulfone, fosthiazate, furfural, imicyafos, isamidofos, isa crotophos, methomyl, methoprene, methothrin, Zofos, metam, metam-ammonium, metam-potassium, methoxychlor, methoxyfenozide, methyl bromide, methyl metam-Sodium, phosphocarb, or thionaZin. isothiocyanate, methylchloroform, methylene chloride, Fungicides metofluthrin, metolcarb, metoxadiaZone, mevinphos, mex Non-limiting examples of fungicides that may be used in acarbate, milbemectin, milbemycin Oxime, mipafox, mirex, combination with the pyridine triazole compounds of for moloSultap, monocrotophos, monomehypo, monosultap, mula I may include (3-ethoxypropyl)mercury bromide, morphothion, moxidectin, naftalofos, naled, naphthalene, 10 2-methoxyethylmercury chloride, 2-phenylphenol, 8-hy nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, droxyquinoline Sulfate, 8-phenylmercurioxyquinoline, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton acilbenzolar, acilbenzolar-S-methyl, acy petacs, acypetacs methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene, copper, acypetacs-zinc, aldimorph, allyl alcohol, ametoctra parathion, parathion-methyl, penfluron, pentachlorophenol, din, amisulbrom, ampropylfos, anilazine, aureofungin, aza permethrin, phenkapton, phenothrin, phenthoate, phorate, 15 conazole, azithiram, azoxystrobin, barium polysulfide, phosalone, phosfolan, phosmet, phosnichlor, phosphami benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, don, phosphine, phoxim, phoxim-methyl, pirimetaphos, bentaluron, benthiavalicarb, benthiavalicarb-isopropyl, ben pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium Zalkonium chloride, benzamacril, benzamacril-isobutyl, arsenite, potassium thiocyanate, pp'-DDT, prallethrin, pre benZamorf, benZohydroxamic acid, bethoxazin, binapacryl, cocene I, precocene II, precocene III, primidophos, profeno biphenyl, bitertanol, bithionol, bixafen, blasticidin-S, Bor fos, profluralin, profluthrin, promacyl, promecarb, propa deaux mixture, boScalid, bromuconazole, bupirimate, Bur phos, propetamphos, propoXur, prothidathion, prothiofos, gundy mixture, buthiobate, butylamine, calcium polysulfide, prothoate, protrifenbute, pymetrozine, pyraclofos, pyraflu captafol, captan, carbamorph, carbendazim, carboxin, car prole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, propamid, carvone, Cheshunt mixture, chinomethionat, pyrethrins, pyridaben, pyridalyl pyridaphenthion, pyri 25 chlobenthiazone, chloraniformethan, chloranil, chlorfena fluguinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxy Zole, chlorodinitronaphthalene, chloroneb, chloropicrin, fen, quassia, quinallphos, quinallphos-methyl, quinothion, chlorothalonil, chlorquinox, chloZolinate, climbazole, clotri rafoxanide, resmethrin, rotenone, ryania, Sabadilla, Schra mazole, copper acetate, copper carbonate, basic, copper dan, Selamectin, Silafluofen, silica gel, Sodium arsenite, hydroxide, copper naphthenate, copper oleate, copper oxy Sodium fluoride, Sodium hexafluorosilicate, Sodium thiocya 30 chloride, copper silicate, copper Sulfate, copper Zinc chro nate, Sophamide, spinetoram, spinosad, Spiromesifen, spiro mate, cresol, cufraneb, cuprobam, cuprous oxide, cyaZof tetramat, sulcofuron, Sulcofuron-sodium, sulfluramid, sul amid, cyclafuramid, cycloheximide, cyflufenamid, fotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau cymoxanil, cypendazole, cyproconazole, cyprodinil, fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, dazomet, dazomet-sodium, DBCP, debacarb, decafentin, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP. 35 dehydroacetic acid, dichlofluanid, dichlone, dichlorophen, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, dichloZoline, diclobutraZol, diclocymet, diclomeZine, tetramethrin, tetramethylfluthrin, Aeto-cypermethrin, thia diclomeZine-sodium, dicloran, diethofencarb, diethyl pyro cloprid, thiamethoxam, thicrofos, thiocarboxime, thiocy carbonate, difenoconazole, diflumetorim, dimethirimol, clam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, dimethomorph, dimoxystrobin, diniconazole, diniconazole thiosultap, thiosultap-disodium, thiosultap-monosodium, 40 M. dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyri transpermethrin, triarathene, triazamate, triaZophos, trichlo thione, disulfiram, ditalimfos, dithianon, DNOC, DNOC rfon, trichlorimetaphos-3, trichloronat, trifenofos, triflu ammonium, DNOC-potassium, DNOC-sodium, dode muron, trimethacarb, triprene, vamidothion, Vaniliprole, morph, dodemorph acetate, dodemorph benzoate, dodicin, XMC, xylylcarb, Zeta-cypermethrin, or Zolaprofos. 45 dodicin-Sodium, dodine, draZOXolon, edifenphos, epoxicon Acaricides azole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, Non-limiting examples of acaricides that may be used in ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmer combination with the pyridine triazole compounds of for cury acetate, ethylmercury bromide, ethylmercury chloride, mula I may include acequinocyl, amidoflumet, arsenous ethylmercury phosphate, etridiazole, famoxadone, fenami oxide, azobenzene, azocyclotin, benomyl, benoxafos, ben 50 done, fenaminosulf, fenapanil, fenarimol, fenbuconazole, Zoximate, benzyl benzoate, bifenazate, binapacryl, bro fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil. mopropylate, chinomethionat, chlorbenside, chlorfenethol, fenpropidin, fenpropimorph, fentin, fentin chloride, fentin chlorfenson, chlorfensulphide, chlorobenzilate, chlorome hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flu buform, chloromethiuron, chloropropylate, clofentezine, metover, flumorph, fluopicolide, fluopyram, fluoroimide, cyenopyrafen, cyflumetofen, cyhexatin, dichlofluanid, dico 55 fluotrimazole, fluoxastrobin, fluquinconazole, flusilaZole, fol, dienochlor, diflovidazin, dinobuton, dinocap, dinocap-4. flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberida diphenyl Sulfone, disulfiram, dofenapyn, etoxazole, fenaza Zole, furalaxyl, furametpyr, furcarbanil, furconazole, furcon quin, fenbutatin oxide, fenothiocarb, fenpyroximate, fenson, azole-cis, furfural, furmecyclox, furophanate, glyodin, gris fentrifanil, fluacrypyrim, fluaZuron, flubenzimine, fluenetil, 60 eofulvin, guazatline, halacrinate, hexachlorobenzene, flumethrin, fluorbenside, hexythiazox, mesulfen, MNAF, hexachlorobutadiene, hexaconazole, hexylthiofos, hydrarga nikkomycins, proclonol, propargite, quintiofos, spirodi phen, hymexaZol, imazalil, imazalil nitrate, imazalil Sulfate, clofen, Sulfiram, Sulfur, tetradifon, tetranactin, tetrasul, or imibenconazole, iminoctadine, iminoctadine triacetate, imi thioquinox. noctadine trial besilate, iodomethane, ipconazole, iproben Nematicides 65 fos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, iso Non-limiting examples of nematicides that may be used in tianil, isovaledione, kasugamycin, kresoxim-methyl, combination with the pyridine triazole compounds of for mancopper, mancoZeb, mandipropamid, maneb, mebenil. US 9,491,944 B2 13 14 mecarbinzid, mepanipyrim, mepronil, meptylidinocap, mer ametridione, ametryn, amibuzin, amicarbazone, amidosul curic chloride, mercuric oxide, mercurous chloride, metal furon, amino cyclopyrachlor, amino cyclopyrachlor-methyl, axyl, metalaxyl-M, metam, metam-ammonium, metam-po amino cyclopyrachlor-potassium, aminopyralid, aminopyra tassium, metam-Sodium, metaZOXolon, metconazole, lid-potassium, aminopyralid-tris(2-hydroxypropyl)ammo methasulfocarb, methfuroxam, methyl bromide, methyl iso nium, amiprofoS-methyl, amitrole, ammonium sulfamate, thiocyanate, methylmercury benzoate, methylmercury dicy anilofos, anisuron, asulam, asulam-potassium, asulam-So andiamide, methylmercury pentachlorophenoxide, metiram, dium, atraton, atrazine, azafenidin, azim Sulfuron, azipro metominostrobin, metrafenone, metSulfovax, milineb, tryne, barban, BCPC, beflubutamid, benazolin, benazolin myclobutanil, mycloZolin, N-(ethylmercury)-p-toluenesul dimethylammonium, benazolin-ethyl, benazolin-potassium, phonanilide, nabam, natamycin, nitrostyrene, nitrothal-iso 10 bencarbazone, benfluralin, benfuresate, bensulfuron, bensul propyl, nuarimol, OCH, Octhillinone, ofurace, orysastrobin, furon-methyl, bensulide, bentaZone, bentazone-sodium, oxadixyl, oxine-copper, Oxpoconazole, Oxpoconazole benzadox, benzadox-ammonium, benzfendizone, benzip fumarate, oxycarboxin, pefurazoate, penconazole, pency ram, benzobicyclon, benzofenap, benzofluor, benzoylprop, curon, penflufen, pentachlorophenol, penthiopyriad, phenyl benzoylprop-ethyl, benzthiazuron, bicyclopyrone, bifenox, mercuriurea, phenylmercury acetate, phenylmercury chlo 15 bilanafos, bilanafos-Sodium, bispyribac, bispyribac-Sodium, ride, phenylmercury derivative of pyrocatechol, borax, bromacil, bromacil-lithium, bromacil-sodium, bro phenylmercury nitrate, phenylmercury Salicylate, phosdi mobonil, bromobutide, bromofenoxim, bromoxynil, bro phen, phthalide, picoxystrobin, piperalin, polycarbamate, moxynil butyrate, bromoxynil heptanoate, bromoxynil polyoxins, polyoxorim, polyoxorim-zinc, potassium azide, octanoate, bromoxynil-potassium, brompyrazon, butachlor, potassium polysulfide, potassium thiocyanate, probenazole, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, prochloraz, procymidone, propamocarb, propamocarb butralin, butroxydim, buturon, butylate, cacodylic acid, hydrochloride, propiconazole, propineb, produinazid, pro cafenstrole, calcium chlorate, calcium cyanamide, camben thiocarb, prothiocarb hydrochloride, prothioconazole, pyra dichlor, carbasulam, carbetamide, carboxazole, carfentra carbolid, pyraclostrobin, pyraclostrobin, pyrametostrobin, Zone, carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril, 25 chloramben, chloramben-ammonium, chloramben-di pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxy olamine, chloramben-methyl, chloramben-methylammo chlor, pyroxyfur, quinacetol, quinacetol Sulfate, quinaZamid, nium, chloramben-sodium, chloranocryl, chlorazifop, chlo quinconazole, quinoxyfen, quintoZene, rabenzazole, Salicy razifop-propargyl, chlorazine, chlorbromuron, chlorbufam, lanilide, sedaxane, silthiofam, Simeconazole, sodium azide, chloreturon, chlorfenac, chlorfenac-sodium, chlorfenprop, Sodium orthophenylphenoxide, sodium pentachlorophenox 30 chlorfemprop-methyl, chlorflurazole, chlorflurenol, chlo ide, Sodium polysulfide, spiroxamine, Streptomycin, Sulfur, rflurenol-methyl, chloridazon, chlorimuron, chlorimuron Sultropen, TCMTB, tebuconazole, tebufloquin, tecloftalam, ethyl, chlornitrofen, chloropon, chlorotoluron, chloroxuron, tecnaZene, tecoram, tetraconazole, thiabendazole, thiadif chloroxynil, chlorprocarb, chlorpropham, chlorSulfuron, luor, thicyofen, thifluzamide, thiochlorfenphim, thiomersal, chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, chlor thiophanate, thiophanate-methyl, thioquinox, thiram, tia 35 thiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisa dinil, tioxymid, tolclofos-methyl, tolylfluanid, tolylmercury nilide, clethodim, cliodinate, clodinafop, clodinafop-propar acetate, triadimefon, triadimenol, triamiphos, triarimol, tri gyl, clofop, clofop-isobutyl, clomaZone, clomeprop, azbutil, triazoxide, tributyltin oxide, trichlamide, tricycla cloprop, cloproxydim, clopyralid, clopyralid-methyl, clopy Zole, tridemorph, trifloxystrobin, triflumizole, triforine, triti ralid-olamine, clopyralid-potassium, clopyralid-tris(2-hy conazole, uniconazole, uniconazole-P. validamycin, 40 droxypropyl)ammonium, cloranSulam, cloranSulam-methyl, Valifenalate, VincloZolin, Zarilamid, Zinc naphthenate, Zineb, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, Ziram, or Zoxamide. cumyluron, cyanamide, cyanatryn, cyanaZine, cycloate, Herbicides cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyhalo Non-limiting examples of herbicides that may be used in fop-butyl, cyperquat, cyperquat chloride, cyprazine, cypra combination the pyridine triazole compounds of formula I 45 Zole, cypromid, daimuron, dalapon, dalapon-calcium, may include 2.3.6-TBA, 2.3.6-TBA-dimethylammonium, dalapon-magnesium, dalapon-Sodium, dazomet, dazomet 2.3.6-TBA-sodium, 2,4,5-T 2,4,5-T-2-butoxypropyl. 2,4,5- Sodium, delachlor, desmedipham, desmetryn, di-allate, T-2-ethylhexyl, 2,4,5-T-3-butoxypropyl. 2,4,5-TEB, 2,4,5-T- dicamba, dicamba-dimethylammonium, dicamba-di butometyl, 2,4,5-T-butotyl, 2,4,5-T-butyl, 2,4,5-T-isobutyl, olamine, dicamba-isopropylammonium, dicamba-methyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl. 2,4,5-T-methyl, 2,4,5-T- 50 dicamba-olamine, dicamba-potassium, dicamba-Sodium, pentyl, 2,4,5-T-sodium, 2.4.5-T-triethylammonium, 2.4.5-T- dicamba-trolamine, dichlobenil, dichloralurea, dichlormate, trolamine, 2,4-D, 2,4-D-2-butoxypropyl. 2,4-D-2-ethyl dichlorprop, dichlorprop-2-ethylhexyl, dichlorprop-butotyl, hexyl, 2,4-D-3-butoxypropyl. 2,4-D-ammonium, 2,4-DB, dichlorprop-dimethylammonium, dichlorprop-ethylammo 2,4-DB-butyl, 2,4-DB-dimethylammonium, 2,4-DB-isoctyl, nium, dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl, 2,4-D- 55 P. dichlorprop-P-dimethylammonium, dichlorprop-potas butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium, sium, dichlorprop-sodium, diclofop, diclofop-methyl, 2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4- dicloSulam, diethamquat, diethamquat dichloride, diethatyl, DEP, 2,4-D-ethyl, 2,4-D-heptylammonium, 2,4-D-isobutyl, diethatyl-ethyl, difenopenten, difenopenten-ethyl, difenox 2,4-D-isoctyl, 2,4-D-isopropyl. 2,4-D-isopropylammonium, uron, difenZoquat, difenZoquat metilsulfate, diflufenican, 2,4-D-lithium, 2,4-D-meptyl, 2,4-D-methyl, 2,4-D-octyl, 60 diflufenZopyr, diflufenZopyr-sodium, dimefuron, dimepiper 2,4-D-penty1, 2,4-D-potassium, 2,4-D-propyl. 2,4-D-So ate, dimethachlor, dimethametryn, dimethenamid, dimeth dium, 2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-tri enamid-P, dimexano, dimidazon, dinitramine, dinofenate, ethylammonium, 2,4-D-tris(2-hydroxypropyl)ammonium, dinoprop, dinosam, dinoseb, dinoseb acetate, dinoseb-am 2,4-D-trolamine, 3,4-DA, 3,4-DB, 3,4-DP, 4-CPA, 4-CPB, monium, dinoseb-diolamine, dinoseb-sodium, dinoseb-tro 4-CPP. acetochlor, acifluorfen, acifluorfen-methyl, acifluor 65 lamine, dinoterb, dinoterb acetate, diphacinone-sodium, fen-Sodium, aclonifen, acrolein, alachlor, allidochlor, diphenamid, dipropetryn, diduat, diduat dibromide, disul, alloxydim, alloxydim-Sodium, allyl alcohol, alorac, disul-sodium, dithiopyr, diuron, DMPA, DNOC, DNOC US 9,491,944 B2 15 16 ammonium, DNOC-potassium, DNOC-sodium, DSMA, methyl isothiocyanate, methyldymron, metobenzuron, EBEP eglinazine, eglinazine-ethyl, endothal, endothal-di metolachlor, metoSulam, metoxuron, metribuzin, metSulfu ammonium, endothal-dipotassium, endothal-disodium, ron, metSulfuron-methyl, molinate, monalide, monisouron, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsul monochloroacetic acid, monolinuron, monuron, monuron furon, ethametsulfuron-methyl, ethidimuron, ethiolate, etho TCA, morfamduat, morfamquat dichloride, MSMA, naproa fumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, nilide, napropamide, naptalam, naptalam-Sodium, neburon, etinofen, etnipromid, etobenzanid, EXD, fenasulam, feno nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, prop, fenoprop-3-butoxypropyl, fenoprop-butometyl, feno norflurazon, noruron, OCH, orbencarb, ortho-dichloroben prop-butotyl, fenoprop-butyl, fenoprop-isoctyl, fenoprop Zene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, methyl, fenoprop-potassium, fenoxaprop, fenoxaprop-ethyl, 10 oxapyrazon, oxapyrazon-dimolamine, Oxapyrazon-Sodium, fenoxaprop-P, fenoxaprop-P-ethyl, fenoxasulfone, fentera oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, para col, fenthiaprop, fenthiaprop-ethyl, fentraZamide, fenuron, quat, paraquat dichloride, paraquat dimetilsulfate, pebulate, fenuron TCA, ferrous Sulfate, flamprop, flamprop-isopropyl. pelargonic acid, pendimethalin, penoXSulam, pentachloro flamprop-M, flamprop-methyl, flamprop-M-isopropyl. phenol, pentanochlor, pentoxaZone, perfluidone, pethox flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, 15 amid, phenisopham, phenmedipham, phenmedipham-ethyl, fluazifop-butyl, fluazifop-methyl, fluazifop-P, fluazifop-P- phenobenzuron, phenylmercury acetate, picloram, picloram butyl, fluazolate, flucarbazone, flucarbazone-sodium, fluc 2-ethylhexyl, picloram-isoctyl, picloram-methyl, picloram etosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr. olamine, picloram-potassium, picloram-triethylammonium, flufenpyr-ethyl, flumetsulam, flumezin, flumiclorac, flumi picloram-tris(2-hydroxypropyl)ammonium, picolinafen, clorac-pentyl, flumioxazin, flumipropyn, fluometuron, fluo pinoxaden, piperophos, potassium arsenite, potassium azide, rodifen, fluoroglycofen, fluoroglycofen-ethyl, fluoromidine, potassium cyanate, pretilachlor, primisulfuron, primisulfu fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupro ron-methyl, procyazine, prodiamine, profluaZol, profluralin, panate, flupropanate-sodium, flupyrsulfuron, flupyrsulfu profoxydim, proglinazine, proglinazine-ethyl, prometon, ron-methyl-sodium, fluridone, flurochloridone, fluroxypyr. prometryn, propachlor, propanil, propaquizafop, propazine, fluroxypyr-butometyl, fluroxypyr-meptyl, flurtamone, flu 25 propham, propisochlor, propoxycarbazone, propoxycarba thiacet, fluthiacet-methyl, fomesafen, fomesafen-Sodium, Zone-sodium, propyrisulfuron, propyZamide, prosulfalin, foramsulfuron, fosamine, fosamine-ammonium, furyloxy prosulfocarb, prosulfuron, proxan, proXan-Sodium, fen, glufosinate, glufosinate-ammonium, glufosinate-P. glu prynachlor, pydanon, pyraclonil, pyraflufen, pyraflufen fosinate-P-ammonium, glufosinate-P-Sodium, glyphosate, ethyl, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazo glyphosate-diammonium, glyphosate-dimethylammonium, 30 Sulfuron-ethyl, pyrazoxyfen, pyribenzoxim, pyributicarb, glyphosate-isopropylammonium, glyphosate-monoammo pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, nium, glyphosate-potassium, glyphosate-sesquisodium, gly pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithio phosate-trimesium, halosafen, halosulfuron, halosulfuron bac-Sodium, pyroxasulfone, pyroxSulam, quinclorac, quin methyl, haloxydine, haloxyfop, haloxyfop-etotyl, merac, quinoclamine, quinonamid, quizalofop, quizalofop haloxyfop-methyl, haloxyfop-Phaloxyfop-P-etotyl, haloxy 35 ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P- fop-P-methyl, haloxyfop-sodium, hexachloroacetone, tefuryl, rhodethanil, rimsulfuron, saflufenacil, hexaflurate, hexaZinone, imazamethabenZ, imazameth Sebuthylazine, secbumeton, Sethoxydim, siduron, simazine, abenZ-methyl, imaZamox, imaZamox-ammonium, imazapic, simeton, simetryn, SMA, S-metolachlor, Sodium arsenite, imazapic-ammonium, imazapyr, imazapyr-isopropylammo Sodium azide, Sodium chlorate, Sulcotrione, Sulfallate, nium, imaZaquin, imaZaquin-ammonium, imaZaquin 40 SulfentraZone, Sulfometuron, Sulfometuron-methyl, Sulfos methyl, imazaquin-sodium, imazethapyr, imazethapyr-am ulfuron, Sulfuric acid, Sulglycapin, Swep, TCA, TCA-am monium, imaZoSulfuron, indanofan, indaziflam, iodobonil. monium, TCA-calcium, TCA-ethadyl, TCA-magnesium, iodomethane, iodosulfuron, iodosulfuron-methyl-Sodium, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotri ioxynil, ioxynil octanoate, ioxynil-lithium, ioxynil-Sodium, one, tepraloxydim, terbacil, terbucarb, terbuchlor, terbume ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, 45 ton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thi isomethiozin, isonoruron, isopolinate, isopropalin, isopro aZafluron, thiazopyr, thidiazimin, thidiaZuron, turon, isouron, isoxaben, isoxachlortole, isoxaflutole, isox thiencarbazone, thiencarbazone-methyl, thifensulfuron, apyrifop, karbutilate, ketospiradox, lactofen, lenacil, lin thifensulfuron-methyl, thiobencarb, tiocarbazil, tioclorim, uron, MAA, MAMA, MCPA, MCPA-2-ethylhexyl, MCPA toprameZone, tralkoxydim, tri-allate, triasulfuron, triaziflam, butotyl, MCPA-butyl, MCPA-dimethylammonium, MCPA 50 tribenuron, tribenuron-methyl, tricamba, triclopyr, triclopyr diolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl, butotyl, triclopyr-ethyl, triclopyr-triethylammonium, tri MCPA-isopropyl, MCPA-methyl, MCPA-olamine, MCPA diphane, trietazine, trifloxysulfuron, trifloxysulfuron-so potassium, MCPA-sodium, MCPA-thioethyl, MCPA-trola dium, trifluralin, triflusulfuron, triflusulfuron-methyl, trifop, mine, MCPB, MCPB-ethyl, MCPB-methyl, MCPB-sodium, trifop-methyl, trifopsime, trihydroxytriazine, trimeturon, tri mecoprop, mecoprop-2-ethylhexyl, mecoprop-dimethylam 55 propindan, tritac, tritosulfuron, Vernolate, or Xylachlor. monium, mecoprop-diolamine, mecoprop-ethadyl, meco Biopesticides prop-isoctyl, mecoprop-methyl, mecoprop-P, mecoprop-P- The pyridine triazole compounds of formula I may also be dimethylammonium, mecoprop-P-isobutyl, mecoprop used in combination (such as in a compositional mixture, or potassium, mecoprop-P-potassium, mecoprop-sodium, a simultaneous or sequential application) with one or more mecoprop-trolamine, medinoterb, medinoterb acetate, 60 biopesticides. The term “biopesticide' is used for microbial mefenacet, mefluidide, mefluidide-diolamine, mefluidide biological pest control agents that are applied in a similar potassium, mesoprazine, mesosulfuron, mesosulfuron manner to chemical pesticides. Commonly these are bacte methyl, mesotrione, metam, metam-ammonium, metamifop, rial, but there are also examples of fungal control agents, metamitron, metam-potassium, metam-Sodium, metazach including Trichoderma spp. and Ampelomyces quisqualis (a lor, metazosulfuron, metflurazon, methabenzthiazuron, 65 control agent for grape powdery mildew). Bacillus subtilis methalpropalin, methazole, methiobencarb, methioZolin, are used to control plant pathogens. Weeds and rodents have methiuron, methometon, methoprotryne, methyl bromide, also been controlled with microbial agents. One well-known US 9,491,944 B2 17 18 insecticide example is Bacillus thuringiensis, a bacterial 18. 1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2, disease of Lepidoptera, Coleoptera, and Diptera. Because it 3,5,6,7-hexahydro-imidazo[1,2-alpyridin-5-ol; has little effect on other organisms, it is considered more 19. 4-4-chlorophenyl-(2-butylidine-hydrazono)methyl) environmentally friendly than synthetic pesticides. Biologi phenyl mesylate; and cal insecticides include products based on: 5 20. N-ethyl-2,2-dichloro-1-methylcyclopropanecarbox 1. entomopathogenic fungi (e.g. Metarhizium aniisopliae): amide-2-(2,6-dichloro-C.C.C.-trifluoro-p-tolyl)hydra 2. entomopathogenic nematodes (e.g. Steinernema ZO. feltiae); and The pyridine triazole compounds of formula I may also be 3. entomopathogenic viruses (e.g. Cydia pomonella used in combination (such as in a compositional mixture, or granulovirus). 10 a simultaneous or sequential application) with one or more Other examples of entomopathogenic organisms include, compounds in the following groups: algicides, antifeedants, but are not limited to, baculoviruses, bacteria and other avicides, bactericides, bird repellents, chemosterilants, her prokaryotic organisms, fungi, protozoa and Microsproridia. bicide Safeners, insect attractants, insect repellents, mammal Biologically derived insecticides include, but not limited to, repellents, mating disrupters, molluscicides, plant activators, rotenone, Veratridine, as well as microbial toxins; insect 15 plant growth regulators, rodenticides, or virucides. tolerant or resistant plant varieties; and organisms modified Synergistic Mixtures and Synergists by recombinant DNA technology to either produce insecti The pyridine triazole compounds of formula I may be cides or to convey an insect resistant property to the geneti used in combination with at least one other insecticides to cally modified organism. In one embodiment, the molecules form a synergistic mixture where the mode of action of Such of Formula One may be used with one or more biopesticides compounds compared to the mode of action of the pyridine in the area of seed treatments and soil amendments. The triazole compounds of formula I are the same, similar, or Manual of Biocontrol Agents gives a review of the available different. Examples of modes of action may include, but are biological insecticide (and other biology-based control) not limited to: acetylcholinesterase inhibitor; sodium chan products. Copping L. G. (ed.) (2004). The Manual of Bio nel modulator; chitin biosynthesis inhibitor; GABA-gated control Agents (formerly the Biopesticide Manual) 3rd Edi 25 chloride channel antagonist; GABA and glutamate-gated tion. British Crop Production Council (BCPC), Farnham, chloride channel agonist; acetylcholine receptor agonist; Surrey UK. METI inhibitor; Mg-stimulated ATPase inhibitor; nicotinic Other Active Compounds acetylcholine receptor, Midgut membrane disrupter, oxida The pyridine triazole compounds of formula I may also be tive phosphorylation disrupter, or ryanodine receptor used in combination (such as in a compositional mixture, or 30 (RyRs). a simultaneous or sequential application) with one or more Additionally, the pyridine triazole compounds of formula of the following: I may be used in combination with at least one of fungicides, 1. 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1- acaricides, herbicides or nematicides to form a synergistic aZaspiro4.5 dec-3-en-2-one; mixture. 2. 3-(4-chloro-2,4-dimethyl 1, 1'-biphenyl-3-yl)-4-hy 35 Furthermore, the pyridine triazole compounds of formula droxy-8-Oxa-1-azaspiro4.5dec-3-en-2-one; I may be used in combination with other active compounds, 3. 4-(6-chloro-3-pyridinyl)methylmethylamino-2 such as the compounds under the heading “OTHER (5H)-furanone; ACTIVE COMPOUNDS,” algicides, avicides, bactericides, 4. 4-(6-chloro-3-pyridinyl)methylcyclopropylamino-2 molluscicides, rodenticides, Virucides, herbicide Safeners, (5H)-furanone; 40 adjuvants, and/or Surfactants to form a synergistic mixture. 5. 3-chloro-N2-(1S)-1-methyl-2-(methylsulfonyl)ethyl Moreover, the following compounds are known as Syner N1-2-methyl-4-1.2.2.2-tetrafluoro-1-(trifluorom gists and may be used in combination with the pyridine ethyl)ethylphenyl-1,2-benzenedicarboxamide: triazole compounds of formula I: piperonylbutoxide, pipro 6. 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfona tal, propyl isome, Sesamex, Sesamolin, Sulfoxide, and tribu mide; 45 fos. 7. 2-cyano-N-ethyl-3-methoxy-benzenesulfonamide: Formulations 8. 2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzene A pesticide is rarely Suitable for application in its pure Sulfonamide; form. It is usually necessary to add other Substances so that 9. 2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfona the pesticide can be used at the required concentration and mide; 50 in an appropriate form, permitting ease of application, 10. 2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzene handling, transportation, storage, and maximum pesticide Sulfonamide; activity. Thus, pesticides are formulated into, for example, 11. 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-ben baits, concentrated emulsions, dusts, emulsifiable concen Zenesulfonamide; trates, fumigants, gels, granules, microencapsulations, seed 12. 2-cyano-3-difluoromethoxy-N,N-dimethylbenzene 55 treatments, Suspension concentrates, Suspoemulsions, tab Sulfon-amide; lets, water Soluble liquids, water dispersible granules or dry 13. 3-(difluoromethyl)-N-2-(3.3-dimethylbutyl)phenyl flowables, wettable powders, and ultra low volume solu 1-methyl-1H-pyrazole-4-carboxamide: tions. For further information on formulation types see 14. N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro “Catalogue of Pesticide Formulation Types and International C.C.C.-trifluoro-p-tolyl) hydraZone; 60 Coding System Technical Monograph n°2, 5th Edition by 15. N-ethyl-2,2-dichloro-1-methylcyclopropane-carbox CropLife International (2002). amide-2-(2,6-dichloro-C.C.C.-trifluoro-p-tolyl) hydra Pesticides are applied most often as aqueous Suspensions Zone nicotine; or emulsions prepared from concentrated formulations of 16. O-(E-)-2-(4-chloro-phenyl)-2-cyano-1-(2-trifluo Such pesticides. Such water-soluble, water-Suspendable, or romethylphenyl)-vinylS-methyl thiocarbonate; 65 emulsifiable formulations are either Solids, usually known as 17. (E)-N1-(2-chloro-1,3-thiazol-5-ylmethyl)-N2 wettable powders, or water dispersible granules, or liquids cyano-N1-methylacetamidine; usually known as emulsifiable concentrates, or aqueous US 9,491,944 B2 19 20 Suspensions. Wettable powders, which may be compacted to Pesticide baits are formed when the pesticide is mixed form water dispersible granules, comprise an intimate mix with food or an attractant or both. When the pests eat the bait ture of the pesticide, a carrier, and Surfactants. The concen they also consume the pesticide. Baits may take the form of tration of the pesticide is usually from about 10% to about granules, gels, flowable powders, liquids, or Solids. They can 90% by weight. The carrier is usually selected from among be used in pest harborages. the attapulgite clays, the montmorillonite clays, the diato Fumigants are pesticides that have a relatively high vapor maceous earths, or the purified silicates. Effective surfac pressure and hence can exist as a gas in Sufficient concen tants, comprising from about 0.5% to about 10% of the trations to kill pests in soil or enclosed spaces. The toxicity wettable powder, are found among Sulfonated lignins, con of the fumigant is proportional to its concentration and the densed naphthalenesulfonates, naphthalenesulfonates, alky 10 exposure time. They are characterized by a good capacity for Ibenzenesulfonates, alkyl sulfates, and non-ionic Surfactants diffusion and act by penetrating the pest's respiratory system Such as ethylene oxide adducts of alkyl phenols. or being absorbed through the pest’s cuticle. Fumigants are Emulsifiable concentrates of pesticides comprise a con applied to control stored product pests under gas proof venient concentration of a pesticide, such as from about 50 sheets, in gas sealed rooms or buildings or in special to about 500 grams per liter of liquid dissolved in a carrier 15 chambers. that is either a water miscible solvent or a mixture of Pesticides can be microencapsulated by Suspending the water-immiscible organic solvent and emulsifiers. Useful pesticide particles or droplets in plastic polymers of various organic solvents include aromatics, especially Xylenes and types. By altering the chemistry of the polymer or by petroleum fractions, especially the high-boiling naphtha changing factors in the processing, microcapsules can be lenic and olefinic portions of petroleum Such as heavy formed of various sizes, solubility, wall thicknesses, and aromatic naphtha. Other organic Solvents may also be used, degrees of penetrability. These factors govern the speed with Such as the terpenic solvents including rosin derivatives, which the active ingredient within is released, which in turn, aliphatic ketones Such as cyclohexanone, and complex alco affects the residual performance, speed of action, and odor hols such as 2-ethoxyethanol. Suitable emulsifiers for emul of the product. sifiable concentrates are selected from conventional anionic 25 Oil Solution concentrates are made by dissolving pesticide and non-ionic Surfactants. in a solvent that will hold the pesticide in solution. Oil Aqueous Suspensions comprise Suspensions of water Solutions of a pesticide usually provide faster knockdown insoluble pesticides dispersed in an aqueous carrier at a and kill of pests than other formulations due to the solvents concentration in the range from about 5% to about 50% by themselves having pesticidal action and the dissolution of weight. Suspensions are prepared by finely grinding the 30 the waxy covering of the integument increasing the speed of pesticide and vigorously mixing it into a carrier comprised uptake of the pesticide. Other advantages of oil solutions of water and surfactants. Ingredients, such as inorganic salts include better storage stability, better penetration of crev and synthetic or natural gums may also be added, to increase ices, and better adhesion to greasy Surfaces. the density and Viscosity of the aqueous carrier. It is often Another embodiment is an oil-in-water emulsion, wherein most effective to grind and mix the pesticide at the same 35 the emulsion comprises oily globules which are each pro time by preparing the aqueous mixture and homogenizing it vided with a lamellar liquid crystal coating and are dispersed in an implement such as a sand mill, ball mill, or piston-type in an aqueous phase, wherein each oily globule comprises at homogenizer. least one compound which is agriculturally active, and is Pesticides may also be applied as granular compositions individually coated with a monolamellar or oligolamellar that are particularly useful for applications to the soil. 40 layer comprising: (1) at least one non-ionic lipophilic Sur Granular compositions usually contain from about 0.5% to face-active agent, (2) at least one non-ionic hydrophilic about 10% by weight of the pesticide, dispersed in a carrier Surface-active agent and (3) at least one ionic Surface-active that comprises clay or a similar Substance. Such composi agent, wherein the globules having a mean particle diameter tions are usually prepared by dissolving the pesticide in a of less than 800 nanometers. Further information on the Suitable solvent and applying it to a granular carrier which 45 embodiment is disclosed in U.S. patent publication has been pre-formed to the appropriate particle size, in the 20070027034 published Feb. 1, 2007, having patent appli range of from about 0.5 to about 3 mm. Such compositions cation Ser. No. 1 1/495,228. For ease of use, this embodiment may also be formulated by making a dough or paste of the will be referred to as “OIWE. carrier and compound and crushing and drying to obtain the For further information consult “Insect Pest Manage desired granular particle size. 50 ment 2nd Edition by D. Dent, copyright CAB International Dusts containing a pesticide are prepared by intimately (2000). Additionally, for more detailed information consult mixing the pesticide in powdered form with a suitable dusty “Handbook of Pest Control The Behavior, Life History, agricultural carrier, Such as kaolin clay, ground Volcanic and Control of Household Pests” by Arnold Mallis, 9th rock, and the like. Dusts can suitably contain from about 1% Edition, copyright 2004 by GIE Media Inc. to about 10% of the pesticide. They can be applied as a seed 55 Other Formulation Components dressing or as a foliage application with a dust blower Generally, when the pyridine triazole compounds of for machine. mula I or any agriculturally acceptable salt thereof, are used It is equally practical to apply a pesticide in the form of in a formulation, such formulation can also contain other a solution in an appropriate organic solvent, usually petro components. These components include, but are not limited leum oil. Such as the spray oils, which are widely used in 60 to, (this is a non-exhaustive and non-mutually exclusive list) agricultural chemistry. wetters, spreaders, Stickers, penetrants, buffers, sequestering Pesticides can also be applied in the form of an aerosol agents, drift reduction agents, compatibility agents, anti composition. In Such compositions the pesticide is dissolved foam agents, cleaning agents, and emulsifiers. A few com or dispersed in a carrier, which is a pressure-generating ponents are described forthwith. propellant mixture. The aerosol composition is packaged in 65 A wetting agent is a Substance that when added to a liquid a container from which the mixture is dispensed through an increases the spreading or penetration power of the liquid by atomizing valve. reducing the interfacial tension between the liquid and the US 9,491,944 B2 21 22 Surface on which it is spreading. Wetting agents are used for Surfactants are sometimes used, either alone or with other two main functions in agrochemical formulations: during additives such as mineral or vegetable oils as adjuvants to processing and manufacture to increase the rate of wetting of spray-tank mixes to improve the biological performance of powders in water to make concentrates for soluble liquids or the pesticide on the target. The types of Surfactants used for Suspension concentrates; and during mixing of a product 5 bioenhancement depend generally on the nature and mode of with water in a spray tank to reduce the wetting time of action of the pesticide. However, they are often non-ionics wettable powders and to improve the penetration of water Such as: alkyl ethoxylates; linear aliphatic alcohol ethoxy into water-dispersible granules. Examples of wetting agents lates; aliphatic amine ethoxylates. used in wettable powder, Suspension concentrate, and water A carrier or diluent in an agricultural formulation is a 10 material added to the pesticide to give a product of the dispersible granule formulations are: Sodium lauryl Sulfate; required strength. Carriers are usually materials with high Sodium dioctyl sulfoSuccinate; alkyl phenol ethoxylates; and absorptive capacities, while diluents are usually materials aliphatic alcohol ethoxylates. with low absorptive capacities. Carriers and diluents are A dispersing agent is a Substance which adsorbs onto the used in the formulation of dusts, wettable powders, granules surface of particles and helps to preserve the state of 15 and water-dispersible granules. dispersion of the particles and prevents them from reaggre Organic solvents are used mainly in the formulation of gating. Dispersing agents are added to agrochemical formu emulsifiable concentrates, oil-in-water emulsions, Suspoe lations to facilitate dispersion and Suspension during manu mulsions, and ultra low Volume formulations, and to a lesser facture, and to ensure the particles redisperse into water in extent, granular formulations. Sometimes mixtures of Sol a spray tank. They are widely used in wettable powders, vents are used. The first main groups of solvents are aliphatic Suspension concentrates and water-dispersible granules. paraffinic oils such as kerosene or refined paraffins. The Surfactants that are used as dispersing agents have the second main group (and the most common) comprises the ability to adsorb strongly onto a particle Surface and provide aromatic solvents such as Xylene and higher molecular a charged or Steric barrier to reaggregation of particles. The weight fractions of C9 and C10 aromatic solvents. Chlori most commonly used surfactants are anionic, non-ionic, or 25 nated hydrocarbons are useful as cosolvents to prevent mixtures of the two types. For wettable powder formula crystallization of pesticides when the formulation is emul tions, the most common dispersing agents are sodium ligno sified into water. Alcohols are sometimes used as cosolvents Sulfonates. For Suspension concentrates, very good adsorp to increase solvent power. Other solvents may include tion and stabilization are obtained using polyelectrolytes, vegetable oils, seed oils, and esters of vegetable and seed Such as Sodium naphthalene Sulfonate formaldehyde con 30 oils. densates. Tristyrylphenol ethoxylate phosphate esters are Thickeners or gelling agents are used mainly in the also used. Non-ionics such as alkylarylethylene oxide con formulation of suspension concentrates, emulsions and sus densates and EO-PO block copolymers are sometimes com poemulsions to modify the rheology or flow properties of the bined with anionics as dispersing agents for Suspension liquid and to prevent separation and settling of the dispersed concentrates. In recent years, new types of very high 35 particles or droplets. Thickening, gelling, and anti-settling molecular weight polymeric Surfactants have been devel agents generally fall into two categories, namely water oped as dispersing agents. These have very long hydropho insoluble particulates and water-soluble polymers. It is pos bic “backbones' and a large number of ethylene oxide sible to produce Suspension concentrate formulations using chains forming the "teeth of a “comb' surfactant. These clays and silicas. Examples of these types of materials, high molecular weight polymers can give very good long 40 include, but are not limited to, montmorillonite, bentonite, term stability to Suspension concentrates because the hydro magnesium aluminum silicate, and attapulgite. Water phobic backbones have many anchoring points onto the soluble polysaccharides have been used as thickening-gell particle Surfaces. Examples of dispersing agents used in ing agents for many years. The types of polysaccharides agrochemical formulations are: sodium lignoSulfonates; most commonly used are natural extracts of seeds and Sodium naphthalene Sulfonate formaldehyde condensates; 45 seaweeds or are synthetic derivatives of cellulose. Examples tristyrylphenol ethoxylate phosphate esters; aliphatic alco of these types of materials include, but are not limited to, hol ethoxylates; alkyl ethoxylates; EO-PO block copoly guar gum, locust bean gum, carrageenam; alginates; methyl mers; and graft copolymers. cellulose; sodium carboxymethyl cellulose (SCMC); An emulsifying agent is a Substance which stabilizes a hydroxyethyl cellulose (HEC). Other types of anti-settling Suspension of droplets of one liquid phase in another liquid 50 agents are based on modified starches, polyacrylates, poly phase. Without the emulsifying agent the two liquids would vinyl alcohol and polyethylene oxide. Another good anti separate into two immiscible liquid phases. The most com Settling agent is Xanthan gum. monly used emulsifier blends contain alkylphenol or ali Microorganisms can cause spoilage of formulated prod phatic alcohol with twelve or more ethylene oxide units and ucts. Therefore preservation agents are used to eliminate or the oil-soluble calcium salt of dodecylbenzenesulfonic acid. 55 reduce their effect. Examples of such agents include, but are A range of hydrophile-lipophile balance (“HLB) values not limited to: propionic acid and its sodium salt; Sorbic acid from 8 to 18 will normally provide good stable emulsions. and its sodium or potassium salts; benzoic acid and its Emulsion stability can sometimes be improved by the addi Sodium salt; p-hydroxybenzoic acid sodium salt; methyl tion of a small amount of an EO-PO block copolymer p-hydroxybenzoate; and 1,2-benzisothiazolin-3-one (BIT). Surfactant. 60 The presence of Surfactants often causes water-based A solubilizing agent is a Surfactant which will form formulations to foam during mixing operations in produc micelles in water at concentrations above the critical micelle tion and in application through a spray tank. In order to concentration. The micelles are then able to dissolve or reduce the tendency to foam, anti-foam agents are often solubilize water-insoluble materials inside the hydrophobic added either during the production stage or before filling part of the micelle. The types of surfactants usually used for 65 into bottles. Generally, there are two types of anti-foam solubilization are non-ionics, Sorbitan monooleates, Sorbitan agents, namely silicones and non-silicones. Silicones are monooleate ethoxylates, and methyl oleate esters. usually aqueous emulsions of dimethyl polysiloxane, while US 9,491,944 B2 23 24 the non-silicone anti-foam agents are water-insoluble oils, 1-MCP). Furthermore, such molecules may be used during Such as octanol and nonanol, or silica. In both cases, the times when pest activity is low, such as before the plants that function of the anti-foam agent is to displace the Surfactant are growing begin to produce valuable agricultural com from the air-water interface. modities. Such times include the early planting season when "Green’ agents (e.g., adjuvants, Surfactants, solvents) can pest pressure is usually low. reduce the overall environmental footprint of crop protection The pyridine triazole compounds of formula I can be formulations. Green agents are biodegradable and generally applied to the foliar and fruiting portions of plants to control derived from natural and/or Sustainable sources, e.g. plant pests. The molecules will either come in direct contact with and animal sources. Specific examples are: vegetable oils, the pest, or the pest will consume the pesticide when eating seed oils, and esters thereof, also alkoxylated alkyl polyg 10 lucosides. leaf fruit mass, or extracting sap, that contains the pesticide. For further information, see "Chemistry and Technology The pyridine triazole compounds of formula I can also be of Agrochemical Formulations' edited by D. A. Knowles, applied to the soil, and when applied in this manner, root and copyright 1998 by Kluwer Academic Publishers. Also see stem feeding pests can be controlled. The roots can absorb “Insecticides in Agriculture and Environment—Retrospects 15 a molecule taking it up into the foliar portions of the plant and Prospects” by A. S. Perry, I. Yamamoto, I. Ishaaya, and to control above ground chewing and sap feeding pests. R. Perry, copyright 1998 by Springer-Verlag. Generally, with baits, the baits are placed in the ground Pesticidal Activities where, for example, termites can come into contact with, The disclosed pesticidal compositions may be used, for and/or be attracted to, the bait. Baits can also be applied to example, as nematicides, acaricides, pesticides, insecticides, a Surface of a building, (horizontal, Vertical, or slant Surface) miticides, and/or molluscicides. where, for example, ants, termites, cockroaches, and flies, In one particular embodiment, a method of controlling can come into contact with, and/or be attracted to, the bait. pests comprises applying a pesticidal composition compris Baits can comprise a pyridine triazole compounds of for ing a pyridine triazole compounds of formula I or any mula I. agriculturally acceptable salt thereof near a population of 25 The pyridine triazole compounds of formula I can be pests. encapsulated inside, or placed on the Surface of a capsule. The pyridine triazole compounds of formula I are gener The size of the capsules can range from nanometer size ally used in amounts from about 0.01 grams per hectare to (about 100-900 nanometers in diameter) to micrometer size about 5000 grams per hectare to provide control. Amounts (about 10-900 microns in diameter). from about 0.1 grams per hectare to about 500 grams per 30 Because of the unique ability of the eggs of Some pests to hectare are generally preferred, and amounts from about 1 resist certain pesticides, repeated applications of the pyri gram per hectare to about 50 grams per hectare are generally dine triazole compounds of formula I may be desirable to more preferred. control newly emerged larvae. The area to which a pyridine triazole compounds of Systemic movement of pesticides in plants may be uti formula I is applied can be any area inhabited (or maybe 35 lized to control pests on one portion of the plant by applying inhabited, or traversed by) a pest, for example: where crops, (for example by spraying an area) the pyridine triazole trees, fruits, cereals, fodder species, vines, turf and orna compounds of formula I to a different portion of the plant. mental plants, are growing; where domesticated animals are For example, control of foliar-feeding insects can be residing; the interior or exterior Surfaces of buildings (such achieved by drip irrigation or furrow application, by treating as places where grains are stored), the materials of construc 40 the Soil with for example pre- or post-planting soil drench, tion used in building (Such as impregnated wood), and the or by treating the seeds of a plant before planting. soil around buildings. Particular crop areas to use a molecule Seed treatment can be applied to all types of seeds, of Formula One include areas where apples, corn, Sunflow including those from which plants genetically modified to ers, cotton, soybeans, canola, wheat, rice, Sorghum, barley, express specialized traits will germinate. Representative oats, potatoes, oranges, alfalfa, lettuce, Strawberries, toma 45 examples include those expressing proteins toxic to inver toes, peppers, crucifers, pears, tobacco, almonds, Sugar tebrate pests, such as Bacillus thuringiensis or other insec beets, beans and other valuable crops are growing or the ticidal toxins, those expressing herbicide resistance. Such as seeds thereof are going to be planted. It is also advantageous “Roundup Ready seed, or those with "stacked' foreign to use ammonium Sulfate with a 3-(thiazol-2-yl)pyridine genes expressing insecticidal toxins, herbicide resistance, 1-oxide compound when growing various plants. 50 nutrition-enhancement, drought resistance, or any other ben Controlling pests generally means that pest populations, eficial traits. Furthermore, such seed treatments with the pest activity, or both, are reduced in an area. This can come pyridine triazole compounds of formula I may further about when: pest populations are repulsed from an area; enhance the ability of a plant to better withstand stressful when pests are incapacitated in or around an area; or pests growing conditions. This results in a healthier, more vigor are exterminated, in whole, or in part, in or around an area. 55 ous plant, which can lead to higher yields at harvest time. Of course, a combination of these results can occur. Gen Generally, about 1 gram of the pyridine triazole compounds erally, pest populations, activity, or both are desirably of formula I to about 500 grams per 100,000 seeds is reduced more than fifty percent, preferably more than 90 expected to provide good benefits, amounts from about 10 percent. Generally, the area is not in or on a human; grams to about 100 grams per 100,000 seeds is expected to consequently, the locus is generally a non-human area. 60 provide better benefits, and amounts from about 25 grams to The pyridine triazole compounds of formula I may be about 75 grams per 100,000 seeds is expected to provide used in mixtures, applied simultaneously or sequentially, even better benefits. alone or with other compounds to enhance plant vigor (e.g. It should be readily apparent that the pyridine triazole to grow a better root system, to better withstand stressful compounds of formula I may be used on, in, or around plants growing conditions). Such other compounds are, for 65 genetically modified to express specialized traits, such as example, compounds that modulate plant ethylene receptors, Bacillus thuringiensis or other insecticidal toxins, or those most notably 1-methylcyclopropene (also known as expressing herbicide resistance, or those with "stacked' US 9,491,944 B2 25 26 foreign genes expressing insecticidal toxins, herbicide resis The disclosed pesticidal composition comprising a pyri tance, nutrition-enhancement, or any other beneficial traits. dine triazole compounds of formula I may be used to control The pyridine triazole compounds of formula I may be a wide variety of pests. used for controlling endoparasites and ectoparasites in the As a non-limiting example, in one or more embodiments, veterinary medicine sector or in the field of non-human 5 the method of the present disclosure may be used to control animal keeping. The pyridine triazole compounds of for one or more members of Lyrioniza sativae, Calliothrips mula I are applied, such as by oral administration in the form phaseoli, Paratrioza cockerel, Spodoptera exigua, Myzus of for example, tablets, capsules, drinks, granules, by der persicae, Nilaparvata lugens, Bemisia tabaci, and Myzus mal application in the form of, for example, dipping, spray persicae. ing, pouring on, spotting on, and dusting, and by parenteral 10 In additional embodiments, the method of the present administration in the form of for example, an injection. disclosure may be used to control one or more members of The pyridine triazole compounds of formula I may also be at least one of Phylum Arthropoda, Phylum Nematoda, employed advantageously in livestock keeping, for example, Subphylum Chelicerata, Subphylum Myriapoda, Subphy cattle, sheep, pigs, chickens, and geese. They may also be lum Hexapoda, Class Insecta, Class Arachnida, and Class employed advantageously in pets such as, horses, dogs, and 15 Symphyla. In at least some embodiments, the method of the cats. Particular pests to control would be fleas and ticks that present disclosure may be used to control one or more are bothersome to such animals. Suitable formulations are members of at least one of Class Insecta and Class Arach administered orally to the animals with the drinking water or nida. feed. The dosages and formulations that are Suitable depend In further embodiments, the method of the present dis on the species. closure may be used to control members of the Order The pyridine triazole compounds of formula I may also be Coleoptera (beetles) including, but not limited to, Acanthos used for controlling parasitic worms, especially of the intes celides spp. (weevils), Acanthoscelides Obtectus (common tine, in the animals listed above. bean weevil), Agrilus planipennis (emerald ash borer), Agri The pyridine triazole compounds of formula I may also be otes spp. (wireworms). Anoplophora glabripennis (Asian employed in therapeutic methods for human health care. 25 longhorned beetle), Anthonomus spp. (weevils), Anthono Such methods include, but are limited to, oral administration mus grandis (boll weevil), Aphidius spp., Apion spp. (wee in the form of, for example, tablets, capsules, drinks, gran vils), Apogonia spp. (grubs), Ataenius spretulus (Black ules, and by dermal application. Turfgrass Ataenius), Atomaria linearis (pygmy mangold Pests around the world have been migrating to new beetle), Aulacophore spp., Bothy noderes punctiventris (beet environments (for Such pest) and thereafter becoming a new 30 root weevil), Bruchus spp. (weevils), Bruchus pisorum (pea invasive species in Such new environment. The pyridine weevil), Cacoesia spp., Callosobruchus maculatus (South triazole compounds of formula I may also be used on such ern cow pea weevil), Carpophilus hemipteras (dried fruit new invasive species to control them in Such new environ beetle), Cassida vittata, Cerosterna spp., Cerotoma spp. ment. (chrysomelids), Cerotoma trifurcata (bean leaf beetle), Ceu The pyridine triazole compounds of formula I may also be 35 torhynchus spp. (weevils), Ceutorhynchus assimilis (cab used in an area where plants, such as crops, are growing (e.g. bage seedpod weevil), Ceutorhynchus napi (cabbage curcu pre-planting, planting, pre-harvesting) and where there are lio), Chaetocnema spp. (chrysomelids), Colaspis spp. (Soil low levels (even no actual presence) of pests that can beetles), Conoderus scalaris, Conoderus stigmosus, Cono commercially damage such plants. The use of Such mol trachelus menuphar (plum curculio), Cotinus initidis (Green ecules in Such area is to benefit the plants being grown in the 40 June beetle), Crioceris asparagi (asparagus beetle), Cryp area. Such benefits, may include, but are not limited to, tolestes ferrugineus (rusty grain beetle), Cryptolestes pusil improving the health of a plant, improving the yield of a lus (flat grain beetle), Cryptolestes turcicus (Turkish grain plant (e.g. increased biomass and/or increased content of beetle), Ctenicera spp. (wireworms), Curculio spp. (wee valuable ingredients), improving the vigor of a plant (e.g. vils), Cyclocephala spp. (grubs), Cylindrocpturus adspersus improved plant growth and/or greener leaves), improving 45 (Sunflower stem weevil), Deporaus marginiatus (mango the quality of a plant (e.g. improved content or composition leafcutting weevil), Dermestes lardarius (larder beetle), of certain ingredients), and improving the tolerance to Dermestes maculates (hide beetle), Diabrotica spp. (chry abiotic and/or biotic stress of the plant. somelids), Epilachna varivestis (Mexican bean beetle), Before a pesticide can be used or sold commercially, Such Faustinus cubae, Hylobius pales (pales weevil), Hypera spp. pesticide undergoes lengthy evaluation processes by various 50 (weevils), Hypera postica (alfalfa weevil), Hyperdoes spp. governmental authorities (local, regional, state, national, and (Hyperodes weevil), Hypothenemus hanpei (coffee berry international). Voluminous data requirements are specified beetle), Ips spp. (engravers), Lasioderma serricorne (ciga by regulatory authorities and must be addressed through data rette beetle), Leptinotarsa decemlineata (Colorado potato generation and Submission by the product registrant or by a beetle), Liogeny's fiscus, Liogenys suturalis, Lissorhoptrus third party on the product registrants behalf, often using a 55 Oryzophilus (rice water weevil), Lyctus spp. (wood beetles/ computer with a connection to the World WideWeb. These powder post beetles), Maecolaspis joliveti, Megascelis spp., governmental authorities then review Such data and if a Melanotus communis, Melligethes spp., Melligethes aeneus determination of safety is concluded, provide the potential (blossom beetle), Melolontha melolontha (common Euro user or seller with product registration approval. Thereafter, pean cockchafer), Oberea brevis, Oberea linearis, Oryctes in that locality where the product registration is granted and 60 rhinoceros (date palm beetle), Oryzaephilus mercator (mer Supported, such user or seller may use or sell Such pesticide. chant grain beetle), Oryzaephilus Surinamensis (Sawtoothed A pyridine triazole compounds of formula I can be tested grain beetle), Otiorhynchus spp. (weevils), Oulema melano to determine its efficacy against pests. Furthermore, mode of pus (cereal leaf beetle), Oulema Oryzae, Pantomorus spp. action studies can be conducted to determine if said mol (weevils), Phyllophaga spp. (May/June beetle), Phyl ecule has a different mode of action than other pesticides. 65 lophaga cuyabana (chrysomelids), Phynchites spp., Popillia Thereafter, such acquired data can be disseminated, such as japonica (Japanese beetle), Prostephanus truncates (larger by the internet, to third parties. grain borer), Rhizopertha dominica (lesser grain borer), US 9,491,944 B2 27 28 Rhizotrogus spp. (European chafer), Rhynchophorus spp. Pseudacy.sta perseae, Scaptocoris castanea, and Triatoma (weevils), Scolytus spp. (wood beetles), Shenophorus spp. spp. (bloodsucking conenose bugs/kissing bugs). (Billbug), Sitona lineatus (pea leaf weevil), Sitophilus spp. In additional embodiments, the method of the present (grain weevils), Sitophilus granaries (granary weevil), Sito disclosure may be used to control members of the Order philus Oryzae (rice weevil), Stegobium paniceum (drugstore 5 Homoptera (aphids, scales, whiteflies, leaflhoppers) includ beetle), Tribolium spp. (flour beetles), Tribolium castaneum ing, but is not limited to, Acrythosiphon pisum (pea aphid), (red flour beetle), Tribolium confilsum (confused flour Adelges spp. (adelgids), Aleurodes proletella (cabbage beetle), Trogoderma variabile (warehouse beetle), and whitefly), Aleurodicus disperses, Aleurothrixus floccosus Zabrus tenebioides. (woolly whitefly), Aluacaspis spp., Amrasca biguitella bigu In other embodiments, the method of the present disclo 10 tella, Aphrophora spp. (leafhoppers), Aonidiella aurantii sure may also be used to control members of the Order (California red scale), Aphis spp. (aphids), Aphis gossypii Dermaptera (earwigs). (cotton aphid), Aphis pomi (apple aphid), Aulacorthum In additional embodiments, the method of the present Solani (foxglove aphid), Bemisia spp. (whiteflies), Bemisia disclosure may be used to control members of the Order argentifolii, Bemisia tabaci (sweetpotato whitefly), Brachy Dictyoptera (cockroaches) including, but is not limited to, 15 colus noxius (Russian aphid), Brachycorynella asparagi Blattella germanica (German cockroach), Blatta Orientalis (asparagus aphid), Brevennia rehi, Brevicoryne brassicae (oriental cockroach), Parcoblatta pennylvanica, Periplaneta (cabbage aphid), Ceroplastes spp. (Scales), Ceroplastes americana (American cockroach), Periplaneta austral rubens (red wax scale), Chionaspis spp. (scales), Chry oasiae (Australian cockroach), Periplaneta brunnea (brown somphalus spp. (scales), Coccus spp. (scales), Dysaphis cockroach), Periplaneta fuliginosa (Smokybrown cock plantaginea (rosy apple aphid), Empoasca spp. (leafhop roach), Pyncoselus suninamensis (Surinam cockroach), and pers), Eriosoma lanigerum (woolly apple aphid), Icerya Supella longipalpa (brownbanded cockroach). purchasi (cottony cushion scale), Idioscopus initidulus In further embodiments, the method of the present dis (mango leafhopper), Laodelphax striatellus (Smaller brown closure may be used to control members of the Order planthopper), Lepidosaphes spp., Macrosiphum spp., Mac Diptera (true flies) including, but is not limited to, Aedes 25 rosiphum euphorbiae (potato aphid), Macrosiphum grana spp. (mosquitoes), Agromyza frontella (alfalfa blotch leaf rium (English grain aphid), Macrosiphum rosae (rose miner), Agromyza spp. (leaf miner flies), Anastrepha spp. aphid), Macrosteles quadrilineatus (aster leafhopper), Mah (fruit flies), Anastrepha suspensa (Caribbean fruit fly), anarva frimbiolata, Metopolophium dirhodium (rose grain Anopheles spp. (mosquitoes), Batrocera spp. (fruit flies), aphid), Mictis longicornis, Myzus spp., Myzus persicae Bactrocera cucurbitae (melon fly), Bactrocera dorsalis (ori 30 (green peach aphid), Nephotettix spp. (leafhoppers), Nepho ental fruit fly), Ceratitis spp. (fruit flies), Ceratitis capitata tettix cinctipes (green leafhopper), Nilaparvata lugens (Mediterranean fruit fly), Chrysops spp. (deer flies), Coch (brown planthopper), Parlatoria pergandii (chaff scale), liomyia spp. (screwworms), Contarinia spp. (Gall midges), Parlatoria Ziziphi (ebony Scale), Peregrinus maidis (corn Culex spp. (mosquitoes), Dasineura spp. (gall midges), delphacid), Philaenus spp. (spittlebugs), Phylloxera vitifo Dasineura brassicae (cabbage gall midge), Delia spp., Delia 35 liae (grape phylloxera), Physokermes piceae (spruce bud platura (seedcorn maggot), Drosophila spp. (vinegar flies), scale), Planococcus spp. (mealybugs), Pseudococcus spp. Fannia spp. (filth flies), Fannia canicularis (little house fly), (mealybugs), Pseudococcus brevipes (pine apple mealy Fannia scalaris (latrine fly), Gasterophilus intestinalis bug), Ouadraspidiotus perniciosus (San Jose scale), (horse botfly), Gracillia perseae, Haematobia irritans (horn Rhapalosiphum spp. (aphids), Rhapalosiphum maida (corn fly), Hyllemyia spp. (root maggots), Hypoderma lineatum 40 leaf aphid), Rhapalosiphum padi (oat bird-cherry aphid), (common cattle grub), Liriomyza spp. (leafminer flies), Saissetia spp. (Scales), Saissetia oleae (black scale), Schiza Liriomyza brassica (serpentine leafminer), Mellophagus Ovi phis graminum (greenbug), Sitobion avenae (English grain nus (sheep ked), Musca spp. (muscid flies), Musca autum aphid), Sogatella fircifera (white-backed planthopper). The nalis (face fly), Musca domestica (house fly), Oestrus Ovis rioaphis spp. (aphids), Toumeyella spp. (scales), Toxoptera (sheep botfly), Oscinella frit (frit fly), Pegomyia betae (beet 45 spp. (aphids), Trialeurodes spp. (whiteflies), Trialeurodes leafminer), Phorbia spp., Psila rosae (carrot rust fly), vaporariorum (greenhouse whitefly), Trialeurodes Rhagoletis cerasi (cherry fruit fly), Rhagoletis pomonella abutiloneus (bandedwing whitefly). Unaspis spp. (scales), (apple maggot), Sitodiplosis mosellana (orange wheat blos Unaspis vanonensis (arrowhead scale), and Zulia entreri som midge), Stomoxys calcitrans (stable fly), Tabanus spp. ana. In at least Some embodiments, the method of the (horse flies), and Tipula spp. (crane flies). 50 present disclosure may be used to control Myzus persicae. In other embodiments, the method of the present disclo In other embodiments, the method of the present disclo sure may be used to control members of the Order Hemip sure may be used to control members of the Order Hyme tera (true bugs) including, but is not limited to, Acrosternum noptera (ants, wasps, and bees) including, but not limited to, hilare (green Stink bug), Blissus leucopterus (chinch bug), Acromyrrmex spp., Athalia rosae, Atta spp. (leafcutting Calocoris norvegicus (potato mirid), Cimex hemipterus 55 ants), Camponotus spp. (carpenter ants), Diprion spp. (saw (tropical bed bug), Cimex lectularius (bed bug), Dagbertus flies), Formica spp. (ants), Iridomyrmex humilis (Argentine fasciatus, Dichelops furcatus, Dysdercus suturellus (cotton ant), Monomorium ssp., Monomorium minumum (little black stainer), Edessa meditabunda, Eurygaster maura (cereal ant), Monomorium pharaonis (Pharaoh ant), Neodiprion bug), Euschistus heros, Euschistus servus (brown Stink bug), spp. (sawflies), Pogonomyrmex spp. (harvester ants), Helopeltis antonii, Helopeltis theivora (tea blight plantbug), 60 Polistes spp. (paper wasps), Solenopsis spp. (fire ants), Lagynotomus spp. (Stink bugs), Leptocorisa Oratorius, Lep Tapoinoma sessile (odorous house ant), Tetranomorium spp. toCOrisa varicornis, Lygus spp. (plant bugs), Lygus hesperus (pavement ants), Vespula spp. (yellow jackets), and Xvlo (western tarnished plant bug), Maconellicoccus hirsutus, copa spp. (carpenter bees). Neurocolpus longirostris, Nezara viridula (Southern green In certain embodiments, the method of the present dis Stink bug), Phytocoris spp. (plant bugs), Phytocoris Califor 65 closure may be used to control members of the Order nicus, Phytocoris relativus, Piezodorus guildingi, Poecilo Isoptera (termites) including, but not limited to, Copto capsus lineatus (fourlined plant bug), Psallus vaccinicola, termes spp., Coptotermes curvignathus, Coptotermes US 9,491,944 B2 29 30 frenchii, Coptotermes formosanus (Formosan Subterranean (rice caseworm), Operophthera brumata (winter moth), termite), Cornitermes spp. (nasute termites), Cryptotermes Ostrinia nubilalis (European corn borer), Oxydia vesulia, spp. (drywood termites), Heterotermes spp. (desert Subter Pandemis cerasana (common currant tortrix), Pandemis ranean termites), Heterotermes aureus, Kalotermes spp. heparana (brown apple tortrix), Papilio demodocus, Pecti (drywood termites), Incistitermes spp. (drywood termites), nophora gossypiella (pink bollworm), Peridroma spp. (cut Macrotermes spp. (fungus growing termites), Margini worms), Peridroma Saucia (variegated cutworm), Perileu termes spp. (drywood termites), Microcerotermes spp. (har coptera coffeella (white coffee leafminer), Phthorimaea vester termites), Microtermes obesi, Procornitermes spp., operculella (potato tuber moth), Phyllocnisitis citrella, Phyl Reticulitermes spp. (Subterranean termites), Reticulitermes lonorycter spp. (leafminers), Pieris rapae (imported cab banyulensis, Reticulitermes grassei, Reticulitermes flavipes 10 bageworm), Plathypena scabs, Plodia interpunctella (Indian (eastern Subterranean termite), Reticulitermes hageni, Reticulitermes hesperus (western Subterranean termite), meal moth), Plutella xylostella (diamondback moth), Poly Reticulitermes Santonensis, Reticulitermes speratus, Reticu chrosis viteana (grape berry moth), Prays endocarps, Prays litermes tibialis, Reticulitermes virginicus, Schedorhino Oleae (olive moth), Pseudaletia spp. (noctuid moths), Pseu termes spp., and Zootermopsis spp. (rotten-wood termites). 15 daletia unipunctata (armyworm), Pseudoplusia includens In additional embodiments, the method of the present (soybean looper), Rachiplusia nu, Scirpophaga incertulas, disclosure may be used to control members of the Order Sesamia spp. (stemborers), Sesamia inferens (pink rice stem Lepidoptera (moths and butterflies) including, but not lim borer), Sesamia nonagrioides, Setora initens, Sitotroga cere ited to, Achoea janata, Adoxophyes spp., Adoxophyes Orana, alella (Angoumois grain moth), Sparganothis pilleriana, Agrotis spp. (cutworms), Agrotis ipsilon (black cutworm), Spodoptera spp. (armyworms), Spodoptera exigua (beet Alabama argillacea (cotton leafworm), Amorbia cuneana, armyworm), Spodoptera fiugiperda (fall armyworm), Amyelosis transitella (navel orangeworm), Anacamptodes Spodoptera oridania (Southern armyworm), Synanthedon defectaria, Anarsia lineatella (peach twig borer). Anomis spp. (root borers), Thecla basilides, Thermisia gemmatalis, Sabulifera (jute looper), Anticarsia gemmatalis (velvetbean Tineola bisselliella (webbing clothes moth), Trichoplusia ni caterpillar), Archips argyrospilla (fruittree leafroller), 25 (cabbage looper), Tuta absoluta, Yponomeuta spp., Zeuzera Archips rosana (rose leafroller), Argyrotaenia spp. (tortricid coffeae (red branch borer), and Zeuzera pyrina (leopard moths), Argyrotaenia citrana (orange tortrix), Autographa moth). In at least some embodiments, the method of the gamma, Bonagota Cranaodes, Borbo cinnara (rice leaf present disclosure may be used to control Spodoptera folder), Bucculatrix thurberiella (cotton leafperforator), exigua. Caloptilia spp. (leaf miners), Capua reticulana, Carposina 30 niponensis (peach fruit moth), Chilo spp., Chlumetia trans The method of the present disclosure may be used to also versa (mango shoot borer), Choristoneura rosaceana control members of the Order Mallophaga (chewing lice) (obliquebanded leafroller), Chrysodeixis spp., Cnaphalo including, but not limited to, Bovicola Ovis (sheep biting cerus medinalis (grass leafroller), Colias spp., Conpomor louse), Menacanthus stramineus (chicken body louse), and pha cramerella, Cossus Cossus (carpenter moth), Crambus 35 Menopon gallinea (common hen louse). spp. (Sod webworms), Cydiafinebrana (plum fruit moth), In additional embodiments, the method of the present Cydia molesta (oriental fruit moth), Cydia nignicana (pea disclosure may be used to control members of the Order moth), Cydia pomonella (codling moth), Darna diducta, Orthoptera (grasshoppers, locusts, and crickets) including, Diaphania spp. (stem borers), Diatraea spp. (stalk borers), but not limited to, Anabrus simplex (Mormon cricket), Diatraea saccharalis (Sugarcane borer), Diatraea grani 40 Gryllotalpidae (mole crickets), Locusta migratoria, Mel Osella (Southwester corn borer), Earias spp. (bollworms), anoplus spp. (grasshoppers), Microcentrum retinerve (angu Earias insulata (Egyptian bollworm), Earias vitella (rough larwinged katydid), Pterophylla spp. (kaydids), chistocerca northern bollworm), Ecdytopopha aurantianum, Elasmopal gregaria, Scudderia fircata (forktailed bush katydid), and pus lignosellus (lesser cornstalk borer), Epiphysias postrut Valanga nigricorni. tana (light brown apple moth), Ephestia spp. (flour moths), 45 In other embodiments, the method of the present disclo Ephestia cautella (almond moth), Ephestia elutella (tobbaco sure may be used to control members of the Order Phthi moth), Ephestia kuehniella (Mediterranean flour moth), raptera (Sucking lice) including, but not limited to, Hae Epimeces spp., Epinotia aporema, Erionota thrax (banana matopinus spp. (cattle and hog lice), Linognathus Ovillus skipper), Eupoecilia ambiguella (grape berry moth), Euxoa (sheep louse), Pediculus humanus capitis (human body auxiliaris (army cutworm), Feltia spp. (cutworms), Gortyna 50 louse), Pediculus humanus humanus (human body lice), and spp. (stemborers), Grapholita molesta (oriental fruit moth), Pthirus pubis (crab louse). Hedylepta indicata (bean leaf webber), Helicoverpa spp. In particular embodiments, the method of the present (noctuid moths), Helicoverpa armigera (cotton bollworm), disclosure may be used to control members of the Order Helicoverpa zea (bollworm/corn earworm), Heliothis spp. Siphonaptera (fleas) including, but not limited to, Cteno (noctuid moths), Heliothis virescens (tobacco budworm), 55 Hellula undalis (cabbage webworm), Indarbela spp. (root cephalides canis (dog flea), Ctenocephalides felis (cat flea), borers), Keiferia lycopersicella (tomato pinworm), Leuci and Pulex irritans (human flea). nodes Orbonalis (eggplant fruit borer), Leucoptera malifo In additional embodiments, the method of the present liella, Lithocollectis spp., Lobesia botrana (grape fruit disclosure may be used to control members of the Order moth), Loxagrotis spp. (noctuid moths), Loxagrotis albi 60 Thysanoptera (thrips) including, but not limited to, costa (western bean cutworm), Lymantria dispar (gypsy Frankliniella fusca (tobacco thrips), Frankliniella occiden moth), Lyonetia clerkella (apple leaf miner), Mahasena talis (western flower thrips), Frankliniella Shultzei, corbetti (oil palm bagworm), Malacosoma spp. (tent cater Frankliniella williamsi (corn thrips), Heliothrips haemor pillars), Mamestra brassicae (cabbage armyworm), Maruca rhaidalis (greenhouse thrips), Riphiphorothrips cruentatus, testulalis (bean pod borer), Metisa plana (bagworm), 65 Scirtothrips spp., Scirtothrips citri (citrus thrips), Scirto Mythinna unipuncta (true armyworm), Neoleucinodes thrips dorsalis (yellow tea thrips), Taeniothrips rhopalan elegantalis (Small tomato borer), Nymphula depunctalis tennalis, and Thrips spp. US 9,491,944 B2 31 32 The method of the present disclosure may be used to also bage, carrot, cauliflower, daikon, eggplant, green beans, control members of the Order Thysanura (bristletails) lettuce, macadamia, papaya, peppers, Sweet potatoes, toma including, but not limited to, Lepisma spp. (silverfish) and toes, watercress, and Zucchini, among other plants. GPA also Thermobia spp. (firebrats). attacks many ornamental crops such as carnation, chrysan In further embodiments, the method of the present dis themum, flowering white cabbage, poinsettia, and roses. closure may be used to control members of the Order Acari GPA has developed resistance to many pesticides. (mites and ticks) including, but not limited to, Acarapsis Cabbage seedlings grown in 3-inch pots, with 2-3 small woodi (tracheal mite of honeybees), Acarus spp. (food (3-5 cm) true leaves, were used as test substrate. The mites), Acarus siro (grain mite), Aceria mangiferae (mango seedlings were infested with 20-50 GPA (wingless adult and bud mite), Aculops spp., Aculops lycopersici (tomato russet 10 nymph stages) one day prior to chemical application. Four mite), Aculops pelekasi, Aculus pelekassi, Aculus Schlech pots with individual seedlings were used for each treatment. tendali (apple rust mite), Amblyomma americanum (lone Test compounds (2 mg) were dissolved in 2 mL of acetone/ star tick), Boophilus spp. (ticks), Brevipalpus obovatus methanol (1:1) solvent, forming stock solutions of 1000 ppm (privet mite), Brevipalpus phoenicis (red and black flat test compound. The stock solutions were diluted 5x with mite), Demodex spp. (mange mites), Dermacentor spp. (hard 15 0.025% Tween 20 in H2O to obtain the solution at 200 ppm ticks), Dermacentor variabilis (american dog tick), Der test compound. A hand-held aspirator-type sprayer was used matophagoides pteronyssinus (house dust mite), Eotetrany for spraying a solution to both sides of cabbage leaves until cus spp., Eotetranychus carpini (yellow spider mite), Epi runoff Reference plants (solvent check) were sprayed with timerus spp., Eriophyes spp., Ixodes spp. (ticks), the diluent only containing 20% by volume of acetone/ Metatetranycus spp., Notoedres cati, Oligonychus spp., Oli methanol (1:1) solvent. Treated plants were held in a holding gonychus coffee, Oligonychus ilicus (Southern red mite), room for three days at approximately 25° C. and ambient Panonychus spp., Panonychus citri (citrus red mite), relative humidity (RH) prior to grading. Evaluation was Panonychus ulmi (European red mite), Phylocoptruta conducted by counting the number of live aphids per plant oleivora (citrus rust mite), Polyphagotarisonemun latus under a microscope. Percent control was measured by using (broad mite), Rhipicephalus sanguineus (brown dog tick), 25 Abbott’s correction formula (W. S. Abbott, “A Method of Rhizoglyphus spp. (bulb mites), Sarcoptes scabiei (itch Computing the Effectiveness of an Insecticide. J. Econ. mite), Tegolophus perseaflorae, Tetranychus spp., Tetrany Entomol. 18 (1925), pp. 265-267) as follows chus urticae (twospotted spider mite), and Varroa destructor (honey bee mite). Corrected 96 Control=100*(X-Y)/X In additional embodiments, the method of the present 30 where disclosure may be used to control members of the Order X=No. of live aphids on solvent check plants and Nematoda (nematodes) including, but not limited to, Aph Y=No. of live aphids on treated plants. elen.choides spp. (foliar nematodes), Belonolaimus spp. The results are indicated in the table entitled “TABLE 2. (sting nematodes), Criconemella spp. (ring nematodes), Biological Data for Green Peach Aphid (GPA) (MYZUPE) Dirofilaria immitis (dog heartworm), Dity lenchus spp. (stem 35 and Sweetpotato Whitefly-crawler (WF) (BEMITA) (see and bulb nematodes), Heterodera spp. (cyst nematodes), Table section). Heterodera zeae (corn cyst nematode), Hirschmanniella spp. (root nematodes), Hoplolaimus spp. (lance nematodes), Example B Meloidogyne spp. (root knot nematodes), Meloidogyne incognita (root knot nematode). Onchocerca volvulus 40 Insecticidal Test for Sweetpotato Whitefly-Crawler (hook-tail worm), Pratylenchus spp. (lesion nematodes), (WF) (Bemisia tabaci) (BEMITA) in Foliar Spray Radopholus spp. (burrowing nematodes), and Rotylenchus Assay reniformis (kidney-shaped nematode). In at least some embodiments, the method of the present The sweetpotato whitefly (Bemisia tabaci) has been disclosure may be used to control at least one insect in one 45 reported as a serious pest of cultivated crops world-wide. It or more of the Orders Lepidoptera, Coleoptera, Homoptera, has an extremely wide host range attacking more than 500 Hemiptera, Thysanoptera, Isoptera, Orthoptera, Diptera, species of plants from 63 plant families. Weeds often serve Hymenoptera, and Siphonaptera, and at least one mite in the as alternate hosts of crop pests. Direct feeding damage is Order Acari. caused by the piercing and Sucking sap from the foliage of 50 plants. This feeding causes weakening and early wilting of DETAILED DESCRIPTION the plant and reduces the plant growth rate and yield. Indirect damage results by the accumulation of honeydew Insecticidal Testing produced by the whiteflies. Honeydew serves as a substrate for the growth of black sooty mold on leaves and fruit Example A 55 reducing photosynthesis and lessens the market value of the plant or yield. Damage is also caused when Sweetpotato Bioassay for Green Peach Aphid (Myzus persicae) whitefly vectors plant viruses. The sweetpotato whitefly is (GPA) (MYZUPE) considered the most common and important whitefly vector of plant viruses worldwide. The green peach aphid (Myzus persicae) is the most 60 Cotton plants (Gossypium hirsutum) grown in 3-inch pots, significant aphid pest of peach trees, causing decreased with 1 small (4-5 cm) true leaves, were used as test substrate. growth, shriveling of the leaves, and the death of various The plants were infested with 200-400 whitefly eggs 4-5 tissues. It is also hazardous because it acts as a vector for the days prior to chemical application. Four pots with individual transport of plant viruses, such as potato virus Y and potato plants were used for each treatment. Test compounds (2 mg) leafroll virus to members of the nightshade/potato family 65 were dissolved in 1 mL of acetone solvent, forming stock Solanaceae, and various mosaic viruses to many other food solutions of 2000 ppm test compound. The stock solutions crops. GPA attacks such plants as broccoli, burdock, cab were diluted 10x with 0.025% Tween 20 in H2O (diluents) US 9,491,944 B2 33 34 to obtain the solution at 200 ppm test compound. A hand EXAMPLES held aspirator-type sprayer was used for spraying a solution to both sides of cotton leaves until runoff. Reference plants These examples are for illustration purposes and are not (solvent check) were sprayed with the diluent only contain to be construed as limiting the disclosure to only the ing 10% by volume of acetone solvent. Treated plants were embodiments disclosed in these examples. held in a holding room for 9 days at approximately 25°C. and ambient relative humidity (RH) prior to grading. Evalu Starting materials, reagents, and solvents that were ation was conducted by counting the number of live 3-4 obtained from commercial sources were used without fur nymph stage per plant under a microscope. Percent control ther purification. Anhydrous solvents were purchased as 10 SURE/SEALTM from Aldrich and were used as received. was measured by using Abbott’s correction formula (W. S. Melting points were obtained using a Thomas Hoover Abbott, “A Method of Computing the Effectiveness of an Unimelt capillary melting point apparatus or an OptiMelt Insecticide.” J. Econ. Entomol. 18 (1925), pp. 265-267) as Automated Melting Point System from Stanford Research follows. Systems and are uncorrected. Examples using "room tem 15 perature' were conducted in climate controlled laboratories Corrected 96 Control=100*(X-Y)/X with a temperature ranging from about 20° C. to about 24° where C. Chemical compounds were given their known names, X=No. of live nymphs on solvent check plants and named according to naming programs within ISIS Draw, Y=No. of live nymphs on treated plants. ChemDraw or ACD Name Pro. If such programs were The results are indicated in the table entitled “Table 2. unable to name the chemical compound, the chemical com Biological Data for Green Peach Aphid (MYZUPE) and pound was named using conventional naming rules. "H Sweetpotato Whitefly-crawler (WF) (BEMITA)' (see Table NMR spectral data were in ppm (Ö) and were recorded at section). 300, 400 or 600 MHz. ''C NMR spectral data were in ppm Insecticidal Testing (8) and were recorded at 75, 100 or 150 MHz. 'F NMR TABLE 2 shows the pesticidal activities of the disclosed 25 pesticidal compounds against green peach aphid (GPA) and spectral data were in ppm (8) and were recorded at 376 sweetpotato whitefly-crawler (WF). The mortality efficiency MHz, unless otherwise stated. of the pesticidal compounds against GPA and WF insects was determined after treatment. The mortality efficiency of Example 1 the disclosed pesticidal compounds against GPA and WF 30 insects was rated as shown in TABLE 1. Preparation of 2-1-(pyridin-3-yl)-1H-1,2,3-triazol 4-yl)-6-(trifluoromethyl) pyridine Compound F7 TABLE 1. Mortality Rating for Green Peach Aphid and Whitefly 35

% Control (or Mortality) Rating N2N. o 80-100 A. More than O-Less than 80 B Not Tested C 40 No activity noticed in this bioassay D F 2 CN to F F TABLE 2 45 A stirred solution of 3-(4-(tributylstannyl)-1H-1,2,3-tri Biological Data for Green Peach Aphid (MYZUPE) and azol-1-yl)pyridine (0.396 g. 0.910 mmol) (prepared accord Sweetpotato Whitefly-crawler (BEMITA ing to Bioorganic & Medicinal Chemistry 2008, 9817) in Insect species 1,4-dioxane (8.00 mL) was charged with 2-bromo-6-(trif luoromethyl)pyridine (0.248 g, 1.10 mmol), CuI (0.0510 g, GPA 50 No. 200 ppm 200 ppm 0.270 mmol), and Pd(PPh)C1 (0.0630 g, 0.0900 mmol) sequentially at room temperature (about 22° C.) under a nitrogen atmosphere. The reaction mixture was evacuated and backfilled with nitrogen gas two or three times, and was 55 heated to reflux (about 100° C.) for 4 hours. The reaction mixture was cooled and diluted with ethyl acetate (EtOAc, 20 mL), shaken well with 5% aqueous potassium fluoride (KF) solution (3x50 mL), and passed through a CELITE(R) bed. The organic layer was washed with brine solution (2x25 60 mL), dried over anhydrous Sodium sulfate (Na2SO4), and concentrated under reduced pressure. The crude residue was purified by flash column chromatography (0-50% EtOAc/ The following examples serve to explain embodiments of hexanes with 1% triethylamine as coeluent) to afford the title the present invention in more detail. These examples should 65 compound F7 as a solid (0.085 g, 32% yield). not be construed as being exhaustive or exclusive as to the The following compounds were prepared according to the Scope of this invention. procedures describes in Example 1: US 9,491,944 B2 35 36 (Pd-PEPPSI-IPr) precatalyst (0.0200 g, 0.0300 mmol) suc N2N o cessively at room temperature under a nitrogen atmosphere. The reaction mixture was evacuated and backfilled with nitrogen gas two or three times, and was heated at reflux for 4 hours. The reaction mixture was cooled to room tempera ture, diluted with EtOAc (20 mL), shaken well with 5% N aqueous KF solution (3x50 mL), and passed through a CELITER) bed. The organic layer was washed with brine 2-Chloro-6-1-(pyridin-3-yl)-1H-1,2,3-triazol-4-ylpyri solution (2x25 mL), dried over anhydrous NaSO, and dine (F10) was isolated in 34% yield. 10 concentrated under reduced pressure. The crude residue was purified by flash column chromatography (0-100% EtOAc/ hexanes with 1% triethylamine as coeluent) to afford the N o compound (F12) as a solid (0.0820 g. 44%). 15 The following compound was prepared according to the procedures disclosed in Example 2: O-CH 5-Methyl-2-1-(pyridin-3-yl)-1H-1,2,3-triazol-4-ylpyri dine (F4), isolated in 40% yield.

2-Methoxy-6-1-(pyridin-3-yl)-1H-1,2,3-triazol-4-yl) pyridine (F5) was isolated in 40% yield.

N2N o 25

% Br 30 Example 3

2-Bromo-6-1-(pyridin-3-yl)-1H-1,2,3-triazol-4-ylpyri Preparation of 3-(4-(3-(trifluoromethoxy)phenyl)- dine (F9) was isolated in 32% yield. 1H-1,2,3-triazol-1-yl)pyridine Compound F6 35

NaleN

40

N U C F 2-1-(Pyridin-3-yl)-1H-1,2,3-triazol-4-yl)-5-(trifluorom N sk F ethyl)pyridine (F8) was isolated in 36% yield. 45 F Example 2 A stirred solution of 3-(4-iodo-1H-1,2,3-triazol-1-yl)pyri Preparation of 2-methyl-6-(1-(pyridin-3-yl)-1H-1.2. dine (0.15g, 0.55 mmol) in 1,4-dioxane (6.0 mL) and water 3-triazol-4-yl)pyridine Compound F12 50 (6.0 mL) was charged with (3-(trifluoromethoxy)phenyl) boronic acid (0.12 g, 0.60 mmol), NaCO (29 mg 0.27 mmol), and Pd(PPh3)Cl. (21 mg, 0.03 mmol) sequentially at room temperature under a nitrogen atmosphere. The 55 reaction flask was evacuated and backfilled with nitrogen ry-/s gas two or three times, and was heated at reflux for 4 hours. The reaction mixture was diluted with water (20 mL) and extracted with EtOAc (2x50 mL). The combined organic % CH layer was washed with brine solution (2x25 mL), dried over 60 anhydrous Na2SO4, and concentrated under reduced pres A stirred solution of 3-(4-(tributylstannyl)-1H-1,2,3-tri sure. The crude residue was purified by flash column chro azol-1-yl)pyridine (0.348 g. 0.800 mmol) in 1,4-dioxane (10 matography (0-100% EtOAc/hexanes with 1% triethylamine mL) was charged with 2-bromo-6-methylpyridine (0.165 g, as coeluent) to afford the title compound (F6) as a solid (0.12 0.960 mmol), CsP (0.243 g, 1.60 mmol), 4 A molecular 65 g, 65%). sieves (0.100 g), and 1,3-bis(2,6-diisopropylphenyl)-imida The following compounds were prepared according to the Zol-2-ylidene)-(3-chloropyridyl)palladium(II) dichloride procedures disclosed in Example 3:

US 9,491,944 B2 41 42 -continued

ESIMS No. Structure (m/z) H NMR F12 2N. Off- 238.1 H NMR (300 MHz, CDC1) 8 N NS White (IM + H') 9.12 (d, J = 2.4 Hz, 1H), 8.73 Solid (dd, J = 4.8, 1.2 Hz, 1H), 8.66 N N \ (s, 1H), 8.24-8.21 (m, 1H), N 8.05 (d, J = 11.4 Hz, 1H), 7.71 (t, d, J = 7.8 Hz, 1H), 7.55 4 CH 3 7.51 (m, 1H), 7.15 (d, J = 7.8 Hz, 1H), 2.60 (s, 3H) F13 2N Off- 291.0 H NMR (400 MHz, CDC1) 8 N White (IM + H') 9.10 (s, 1H), 8.77 (s, 1H), 8.34 / Solid (s, 1H), 8.24-8.22 (m, 1H), N N 8.18 (s, 1H), 8.15 (d, J = 7.6 Hz, 1H), 7.68-7.55 (m, 3H) 2 N F F F

Example 4 -continued P2 Preparation of 2-(6-(1-(pyridin-3-yl)-1H-1,2,3-tri- 25 % \ azol-4-yl)pyridin-2-yl)pyrimidine Compound P1 N S. N2 N N

N ty 30 N \C Z N N S. N N2 N N / s N N \ Z 35 2 N P3 C To (1-(pyridin-3-yl)-1H-1,2,3-triazol-4-yl)boronic acid in " N Z an appropriate reaction vessel may be added 2-(6-bro- \ mopyridin-2-yl)pyrimidine (from about 1 eq to about 1.5 eq) leN SN in a solvent, Such as 1,4-dioxane at a concentration between - NS about 0.01 M to about 1 M. Then, a base such as Na,CO N / (from about 1 eq to about 5 eq) and a catalyst Such2- -3as 4s N \ Z N Pd(PPh) (from about 0.01 eq to about 0.5 eq) may be added. The reaction may be stirred at a temperature of from % about 50° C. to about 150° C. until the reaction was determined to be completed. Following completion of the 50 reaction, the product may be obtained using standard organic While this invention has been described in certain chayhis of EE an Pitt, ding t embodiments, the present invention can be further modified the CNNE" E.A. pp. g O within the spirit and scope of this disclosure. This applica 55 tion is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. C P1 Further, this application is intended to cover Such departures % from the present disclosure as come within known or N \ 60 customary practice in the art to which this invention pertains N2N. N SN and which fall within the limits of the appended claims. NS N N / \ Z We claim: 1. A pesticidal composition, comprising a pyridine triaz N 2 65 ole compound of formula I, or any agriculturally acceptable salt thereof: US 9,491,944 B2 43 44 -continued I Z2 R4 NN : N R8 R 3 N 21 Z NY N N R 2 Rs R R R6 (O), Z3 10 Rs wherein: (a) R. R. and Ra are independently hydrogen, F, Cl, Br, I, substituted or unsubstituted C-C alkyl, or substi tuted or unsubstituted C-C haloalkyl, 15 wherein each R. R. and Ra, when substituted, has one or NR6 more substituents selected from F, Cl, Br, I, CN, NO, Z4 C-C alkyl, C-C alkenyl, C-C haloalkyl, C-Co Rs cycloalkyl, or C-C halocycloalkyl, where each of which is unsubstituted or substituted with R: a NN (b) R is hydrogen, F, Cl, Br, I, CN, NO, substituted or unsubstituted C-C alkyl, substituted or unsubstituted R6 Sn N ls R7 C-C alkenyl, Substituted or unsubstituted C-C, Z5 alkoxy, Substituted or unsubstituted C-C cycloalkyl, R9 substituted or unsubstituted C-C haloalkyl, substi 25 tuted or unsubstituted C-C aryl, Substituted or unsubstituted C-Co heterocyclyl, OR, C(=X)R. N C(=X)R. C(=X)N(R), N(R), N(R)C N R (=X)R, SR, S(O).OR, or RS(O).R. 30 wherein R, when substituted, has one or more substitu R6 ents selected from F, Cl, Br, I, CN, NO, C-C alkyl, Z6 C-C alkenyl, C-C haloalkyl, C-C haloalkenyl, Ro C-C haloalkyloxy, C-C haloalkenyloxy, C-Co : Rs cycloalkyl, C-Co cycloalkenyl, C-Co halocy 35 N cloalkyl, C-Co halocycloalkenyl, OR, S(O), OR, C-C aryl, or C-C heterocyclyl, wherein each of 2 which is unsubstituted or substituted with R: R6 N R Z7 (c) Rs is hydrogen, F, Cl, Br, I, CN, NO, substituted or Ro unsubstituted C-C alkyl, substituted or unsubstituted 40 C-C alkenyl, Substituted or unsubstituted C-C, : Rs alkoxy, C-Co cycloalkyl, Substituted or unsubstituted 21 C-C aryl, substituted or unsubstituted C-C het N erocyclyl, OR, C(=X)R, C(=X)OR, C(=X) R6 S N(R), N(R), N(R)C(=X)R. SR, 45 S(O), OR, or RS(O).R. R7 wherein Rs, when substituted, has one or more substitu Z8 ents selected from F, Cl, Br, I, CN, NO, C-C alkyl, 21 C-C alkenyl, C-C haloalkyl, C-C haloalkenyl, 50 C-C haloalkyloxy, C-C haloalkenyloxy, C-Co R6 N N cycloalkyl, C-Co cycloalkenyl, C-Co halocy cloalkyl, C-C halocycloalkenyl, OR, S(O), OR, R Co-Co aryl, or C-C heterocyclyl, wherein each of which is unsubstituted or substituted with R: 55 (e) R. is hydrogen, F, Cl, Br, I, CN, NO, OR, substi (d) Z is Z, Z2, Zs, Z4, Zs. Zo. Z7 or Zs: tuted or unsubstituted C-C alkyl, substituted or unsubstituted C-C alkenyl, Substituted or unsubsti tuted C-C alkoxy, Substituted or unsubstituted C-Co cycloalkyl, Substituted or unsubstituted C-Cohalocy 60 cloalkyl Substituted or unsubstituted C-Co cycloalk enyl, Substituted or unsubstituted C-C aryl. Substi tuted or unsubstituted C-Co heterocyclyl, C(=X) R. C(=X)OR, C(=X)N(R), N(R), N(R)C (=X)R, SR, S(O), OR, or RS(0),R, 65 wherein R, when Substituted, has one or more Substitu ents selected from F, Cl, Br, I, CN, NO, C-C alkyl, C-C alkenyl, C-C haloalkyl, C-C haloalkenyl, US 9,491,944 B2 45 46 C-C haloalkyloxy, C-C haloalkenyloxy, C-Co Co-Co aryl, Substituted or unsubstituted C-Co het cycloalkyl, C-C cycloalkenyl, C-C halocy erocyclyl,C(=X)R. C(=X)OR, C(=X) cloalkyl, C-Co halocycloalkenyl, Oxo, OR, N(R), N(R), N(R)C(=X)R. SR, S(O).R. Co-Co aryl, or C-Coheterocyclyl, wherein S(O), OR, or RS(O),R, each of which is unsubstituted or substituted with R: (f) R, is selected from hydrogen, F, Cl, Br, I, CN, NO, wherein Ro, when Substituted, has one or more Substitu OR, substituted or unsubstituted C-C alkyl, substi ents selected from F, Cl, Br, I, CN, NO, C-C alkyl, tuted or unsubstituted C-C alkenyl, substituted or C-C alkenyl, C-C haloalkyl, C-C haloalkenyl, unsubstituted C-C alkoxy, Substituted or unsubsti C-C haloalkyloxy, C-C haloalkenyloxy, C-Co tuted C-Co cycloalkyl, Substituted or unsubstituted 10 cycloalkyl, C-Co cycloalkenyl, C-Co halocy Cs-Co halocycloalkyl Substituted or unsubstituted cloalkyl, C-Co halocycloalkenyl, oxo, OR, Cs-Co cycloalkenyl, Substituted or unsubstituted S(O).R. Co-Co aryl, or C-Coheterocyclyl, wherein Co-Co aryl, Substituted or unsubstituted C-Co het each of which is unsubstituted or substituted with R. erocyclyl, C(=X)R, C(=X)OR, C(=X) (j) R is hydrogen, F, Cl, Br, I, CN, NO, substituted or N(R), N(R), N(R)C(=X)R. SR, 15 unsubstituted C-C alkyl, substituted or unsubstituted S(O), OR, or RS(O).R. C-C alkenyl, Substituted or unsubstituted C-C, wherein R-7, when substituted, has one or more substitu alkoxy, Substituted or unsubstituted C-C alkenyloxy, ents selected from F, Cl, Br, I, CN, NO, C-C alkyl, C-C alkenyl, C-C haloalkyl, C-C haloalkenyl, Substituted or unsubstituted C-C cycloalkyl, Substi C-C haloalkyloxy, C-C haloalkenyloxy, C-Co tuted or unsubstituted C-Co cycloalkenyl, Substituted cycloalkyl, C-C cycloalkenyl, C-C halocy or unsubstituted Co-Co aryl, Substituted or unsubsti cloalkyl, C-Co halocycloalkenyl, Oxo, OR, tuted C-Co heterocyclyl. Substituted or unsubstituted S(O),R, C-C aryl, or C-Coheterocyclyl, wherein S(O)C-C alkyl, or substituted or unsubstituted N(C- each of which is unsubstituted or substituted with R: C alkyl). (g) Rs is hydrogen, F, Cl, Br, I, CN, NO, OR, substi 25 wherein R, when Substituted, has one or more Substitu tuted or unsubstituted C-C alkyl, substituted or ents selected from F, Cl, Br, I, CN, NO, C-C alkyl, unsubstituted C-C alkenyl, Substituted or unsubsti C-C alkenyl, C-C haloalkyl, C-C haloalkenyl, tuted C-C alkoxy, Substituted or unsubstituted C-Co C-C haloalkyloxy, C-C haloalkenyloxy, C-Co cycloalkyl, Substituted or unsubstituted C-Cohalocy cycloalkyl, C-C cycloalkenyl, C-C halocy cloalkyl substituted or unsubstituted C-C cycloalk 30 cloalkyl, C-Cohalocycloalkenyl, OC-C alkyl, OC enyl, Substituted or unsubstituted Co-Co aryl, Substi C haloalkyl, S(O)C-Calkyl, S(O), OC-C alkyl, tuted or unsubstituted C-C heterocyclyl, C(=X) Co-Co aryl, or C-Co heterocyclyl, R. C(=X)OR, C(=X)N(R), N(R), N(R) C(=X)R, SR, S(O), OR, or RS(O),R, (k) X=O or S: wherein Rs, when substituted, has one or more substitu 35 (1) n is 0, 1, or 2: ents selected from F, Cl, Br, I, CN, NO, C-C alkyl, C-C alkenyl, C-C haloalkyl, C-C haloalkenyl, (m) x is 0 or 1; and C-C haloalkyloxy, C-C haloalkenyloxy, C-Co (n) with the following provisos: cycloalkyl, C-Co cycloalkenyl, C-Co halocy (1) that when Z is Z, then at least one of R and Rio cloalkyl, C-Co halocycloalkenyl, Oxo, OR, 40 is not hydrogen, S(O).R. Co-Co aryl, or C-Coheterocyclyl, wherein each of which is unsubstituted or substituted with R: (h) R is hydrogen, F, Cl, Br, I, CN, NO. —OR, substituted or unsubstituted C-C alkyl, substituted or unsubstituted C-C alkenyl, Substituted or unsubsti 45 tuted C-C alkoxy, Substituted or unsubstituted C-Co cycloalkyl, Substituted or unsubstituted C-C halocy cloalkyl, Substituted or unsubstituted C-C cycloalk enyl, Substituted or unsubstituted C-C aryl. Substi tuted or unsubstituted C-Co heterocyclyl, C(=X) 50 R. C(=X)OR, C(=X)N(R), N(R), N(R) C(=X)R, SR, S(O), OR, or RS(O),R, wherein Ro, when Substituted, has one or more Substitu ents selected from F, Cl, Br, I, CN, NO, C-C alkyl, (2) that when Z is Z, then at least two of Re, R, and C-C alkenyl, C-C haloalkyl, C-C haloalkenyl, 55 Rs are not hydrogen, C-C haloalkyloxy, C-C haloalkenyloxy, C-Co cycloalkyl, C-Co cycloalkenyl, C-Co halocy cloalkyl, C-Co halocycloalkenyl, Oxo, OR, S(O).R. Co-Co aryl, or C-Coheterocyclyl, wherein each of which is unsubstituted or substituted with R: 60 (i) Rio is selected from hydrogen, F, Cl, Br, I, CN, NO, OR, substituted or unsubstituted C-C alkyl, substi tuted or unsubstituted C-C alkenyl, substituted or unsubstituted C-C alkoxy, Substituted or unsubsti tuted C-Co cycloalkyl, Substituted or unsubstituted 65 Cs-Co halocycloalkyl Substituted or unsubstituted (3) that when Z is Z, then at least one of R, and Rs is Cs-Co cycloalkenyl, Substituted or unsubstituted not hydrogen, US 9,491,944 B2 47 48 butometyl, 2,4,5-T-butotyl, 2,4,5-T-butyl, 2,4,5-T-isobutyl, Z3 2,4,5-T-isoctyl, 2,4,5-T-isopropyl. 2,4,5-T-methyl, 2,4,5-T- Rs pentyl, 2,4,5-T-sodium, 2.4.5-T-triethylammonium, 2.4.5-T- trolamine, 2,4-D, 2,4-D-2-butoxypropyl. 2,4-D-2-ethyl hexyl, 2,4-D-3-butoxypropyl. 2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium, 2,4-DB-isoctyl, N N 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl, 2,4-D- butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium, 2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4- 10 DEP, 2,4-D-ethyl, 2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl. 2,4-D-isopropylammonium, (4) that when Z is Zs, then at least one of Rs and R is 2,4-D-lithium, 2,4-D-meptyl, 2,4-D-methyl, 2,4-D-octyl, not hydrogen, 2,4-D-penty1, 2,4-D-potassium, 2,4-D-propyl. 2,4-D-So dium, 2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-tri 15 ethylammonium, 2,4-D-tris(2-hydroxypropyl)ammonium, Z5 2,4-D-trolamine, 2iP, 2-methoxyethylmercury chloride, R9 2-phenylphenol, 3,4-DA, 3,4-DB, 3,4-DP, 4-aminopyridine, 4-CPA, 4-CPA-potassium, 4-CPA-sodium, 4-CPB, 4-CPP. 21 4-hydroxyphenethyl alcohol, 8-hydroxyquinoline Sulfate, 8-phenylmercurioxyquinoline, abamectin, abscisic acid, N N R ACC, acephate, acequinocyl, acetamiprid, acethion, acetochlor, acetophos, acetoprole, acilbenzolar, acilbenzolar R6 S-methyl, acifluorfen, acifluorfen-methyl, acifluorfen-so dium, aclonifen, acrep, acrinathrin, acrolein, acrylonitrile, 25 acy petacs, acy petacs-copper, acypetacs-Zinc, alachlor, (5) that when Z is Zs, then at least one of R and R, is alanycarb, albendazole, aldicarb, aldimorph, aldoxycarb, not hydrogen. aldrin, allethrin, allicin, allidochlor, allosamidin, alloxydim, alloxydim-sodium, allyl alcohol, allyxycarb, alorac, alpha cypermethrin, alpha-endosulfan, ametoctradin, ametridione, 30 ametryn, amibuzin, amicarbazone, amicarthiazol, amidi thion, amidoflumet, amidosulfuron, aminocarb, aminocyc : es Rs lopyrachlor, aminocyclopyrachlor-methyl, aminocyclopyra N chlor-potassium, aminopyralid, aminopyralid-potassium, 1S aminopyralid-tris(2-hydroxypropyl)ammonium, amiprofos R 35 methyl, amiprophos, amisulbrom, amiton, amiton oxalate, amitraz, amitrole, ammonium sulfamate, ammonium C.-naphthaleneacetate, amobam, ampropylfos, anabasine, 2. A composition according to claim 1, wherein R. R. ancymidol, anilazine, anilofos, anisuron, anthraquinone, and R are H. antu, apholate, aramite, arsenous oxide, asomate, aspirin, 3. A composition according to claim 1, wherein R is 40 asulam, asulam-potassium, asulam-Sodium, athidathion, selected from H, F, Cl, Br, or I. atraton, atrazine, aureofungin, aviglycine, aviglycine hydro 4. A composition according to claim 1, wherein Rs is chloride, azaconazole, azadirachtin, azafenidin, azamethip hydrogen. hos, azimsulfuron, azinphos-ethyl, azinPhos-methyl, azipro 5. A composition according to claim 1, wherein Z is Za, tryne, azithiram, azobenzene, azocyclotin, azothoate, Zs. Or Z7. 45 azoxystrobin, bachmedesh, barban, barium hexafluorosili 6. A composition according to claim 1, wherein Z is Zs, cate, barium polysulfide, barthrin, BCPC, beflubutamid, and wherein RandR, both simultaneously are hydrogen, or benalaxyl, benalaxyl-M, benazolin, benazolin-dimethylam substituted or unsubstituted C-C haloalkyl. monium, benazolin-ethyl, benazolin-potassium, bencarba 7. The composition of claim 1, further comprising: Zone, benclothiaz, bendiocarb, benfluralin, benfuracarb, (a) one or more compounds having acaricidal, algicidal, 50 benfuresate, benodanil, benomyl, benoxacor, benoxafos, avicidal, bactericidal, fungicidal, herbicidal, insecti benquinox, benSulfuron, benSulfuron-methyl, bensulide, cidal, molluscicidal, nematicidal, rodenticidal, or viru bensultap, bentaluron, bentaZone, bentaZone-sodium, ben cidal properties; or thiavalicarb, benthiavalicarb-isopropyl, benthiazole, bentra (b) one or more compounds that are antifeedants, bird nil, benzadox, benzadox-ammonium, benzalkonium chlo repellents, chemosterilants, herbicide Safeners, insect 55 ride, benzamacril, benzamacril-isobutyl, benzamorf, attractants, insect repellents, mammal repellents, mat benzfendizone, benzipram, benzobicyclon, benzofenap, ing disrupters, plant activators, plant growth regulators, benZofluor, benzohydroxamic acid, benzoximate, benzoyl or synergists; or prop, benzoylprop-ethyl, benzthiazuron, benzyl benzoate, (c) both (a) and (b). benzyladenine, berberine, berberine chloride, beta-cyflu 8. The composition of claim 1, further comprising one or 60 thrin, beta-cypermethrin, bethoxazin, bicyclopyrone, more compounds selected from: (3-ethoxypropyl)mercury bifenazate, bifenox, bifenthrin, bifujunzhi, bilanafos, bromide, 1.2-dichloropropane, 1,3-dichloropropene, bilanafos-Sodium, binapacryl, bingqingxiao, bioallethrin, 1-methylcyclopropene, 1-naphthol. 2-(octylthio)ethanol, bioethanomethrin, biopermethrin, bioresmethrin, biphenyl, 2,3,5-tri-iodobenzoic acid, 2,3,6-TBA, 2,3,6-TBA-dimeth bisazir, bismerthiazol, bispyribac, bispyribac-sodium, bistri ylammonium, 2.3.6-TBA-lithium, 2.3,6-TBA-potassium, 65 fluron, bitertanol, bithionol, bixafen, blasticidin-S, borax, 2.3.6-TBA-sodium, 2,4,5-T 2,4,5-T-2-butoxypropyl. 2,4,5- Bordeaux mixture, boric acid, boscalid, brassinolide, T-2-ethylhexyl, 2,4,5-T-3-butoxypropyl. 2,4,5-TEB, 2,4,5-T- brassinolide-ethyl, brevicomin, brodifacoum, brofenvaler US 9,491,944 B2 49 50 ate, brofluthrinate, bromacil, bromacil-lithium, bromacil cuprous oxide, curcumenol, cyanamide, cyanatryn, sodium, bromadiolone, bromethalin, bromethrin, bromfen cyanazine, cyanofenphos, cyanophos, cyanthoate, cyantra Vinfos, bromoacetamide, bromobonil, bromobutide, niliprole, cyaZofamid, cybutryne, cyclafuramid, cyclanilide, bromocyclen, bromo-DDT, bromofenoxim, bromophos, cyclethrin, cycloate, cycloheximide, cycloprate, cyclopro bromophos-ethyl, bromopropylate, bromothalonil, bro thrin, cycloSulfamuron, cycloxydim, cycluron, cyenopyra moxynil, bromoxynil butyrate, bromoxynil heptanoate, bro fen, cyflufenamid, cyflumetofen, cyfluthrin, cyhalofop, moxynil octanoate, bromoxynil-potassium, brompyrazon, cyhalofop-butyl, cyhalothrin, cyhexatin, cymiazole, cymi bromuconazole, bronopol, bucarpolate, bufencarb, bumin azole hydrochloride, cymoxanil, cyometrinil, cypendazole, afos, bupirimate, buprofezin, Burgundy mixture, buSulfan, cypermethrin, cyperquat, cyperquat chloride, cyphenothrin, butacarb, butachlor, butafenacil, butamifos, butathiofos, 10 cyprazine, cyprazole, cyproconazole, cyprodinil, cypro butenachlor, butethrin, buthidazole, buthiobate, buthiuron, furam, cypromid, cyprosulfamide, cyromazine, cythioate, butocarboxim, butonate, butopyronoxyl, butoxycarboxim, daimuron, dalapon, dalapon-calcium, dalapon-magnesium, butralin, butroxydim, buturon, butylamine, butylate, dalapon-Sodium, daminozide, dayoutong, dazomet, cacodylic acid, cadusafos, cafenstrole, calcium arsenate, dazomet-sodium, DBCP, d-camphor, DCIP, DCPTA, DDT, calcium chlorate, calcium cyanamide, calcium polysulfide, 15 debacarb, decafentin, decarbofuran, dehydroacetic acid, calvinphos, cambendichlor, camphechlor, camphor, capta delachlor, deltamethrin, demephion, demephion-O, deme fol, captan, carbamorph, carbanolate, carbaryl, carbasulam, phion-S, demeton, demeton-methyl, demeton-O, demeton carbendazim, carbendazim benzenesulfonate, carbendazim O-methyl, demeton-S, demeton-S-methyl, demeton-S-meth sulfite, carbetamide, carbofuran, carbon disulfide, carbon ylsulphon, desmedipham, desmetryn, tetrachloride, carbophenothion, carbosulfan, carboxazole, d-fanshiluquebinguzhi, diafenthiuron, dialifos, di-allate, carboxide, carboxin, carfentraZone, carfentraZone-ethyl, car diamidafos, diatomaceous earth, diazinon, dibutyl phthalate, propamid, cartap, cartap hydrochloride, carvacrol, carvone, dibutyl Succinate, dicamba, dicamba-diglycolamine, CDEA, cellocidin, CEPC, ceralure, Cheshunt mixture, chi dicamba-dimethylammonium, dicamba-diolamine, nomethionat, chitosan, chlobenthiaZone, chlomethoxyfen, dicamba-isopropylammonium, dicamba-methyl, dicamba chloralose, chloramben, chloramben-ammonium, chloram 25 olamine, dicamba-potassium, dicamba-Sodium, dicamba ben-diolamine, chloramben-methyl, chloramben-methylam trolamine, dicapthon, dichlobenil, dichlofenthion, dichlo monium, chloramben-sodium, chloramine phosphorus, fluanid, dichlone, dichloralurea, dichlorbenzuron, chloramphenicol, chloraniformethan, chloranil, chloranoc dichlorflurenol, dichlorflurenol-methyl, dichlormate, dichlo ryl, chlorantraniliprole, chlorazifop, chlorazifop-propargyl. rmid, dichlorophen, dichlorprop, dichlorprop-2-ethylhexyl, chlorazine, chlorbenside, chlorbenzuron, chlorbicyclen, 30 dichlorprop-butotyl, dichlorprop-dimethylammonium, chlorbromuron, chlorbufam, chlordane, chlordecone, dichlorprop-ethylammonium, dichlorprop-isoctyl, dichlo chlordimeform, chlordimeform hydrochloride, chlorempen rprop -methyl, dichlorprop-P, dichlorprop-P-2-ethylhexyl, thrin, chlorethoxyfos, chloreturon, chlorfenac, chlorfenac dichlorprop-P-dimethylammonium, dichlorprop-potassium, ammonium, chlorfenac-Sodium, chlorfenapyr, chlorfena dichlorprop-sodium, dichlorvos, dichlozoline, diclobutrazol, Zole, chlorfenethol, chlorfenprop, chlorfenson, 35 diclocymet, diclofop, diclofop-methyl, diclomeZine, chlorfensulphide, chlorfenvinphos, chlorfluaZuron, chlorflu diclomeZine-sodium, dicloran, dicloSulam, dicofol, dicou razole, chlorfluren, chlorfluren-methyl, chlorflurenol, chlo marol, dicresyl dicrotophos, dicyclanil, dicyclonon, diel rflurenol-methyl, chloridazon, chlorimuron, chlorimuron drin, dienochlor, diethamquat, diethamcquat dichloride, ethyl, chlormephos, chlormeduat, chlormeduat chloride, diethatyl, diethatyl-ethyl, diethofencarb, dietholate, diethyl chlomidine, chlornitrofen, chlorobenzilate, chlorodini 40 pyrocarbonate, diethyltoluamide, difenacoum, difenocon tronaphthalenes, chloroform, chloromebuform, chlorome azole, difenopenten, difenopenten-ethyl, difenoXuron, difen thiuron, chloroneb, chlorophacinone, chlorophacinone-so Zoquat, difenZoquat metilsulfate, difethialone, diflovidazin, dium, chloropicrin, chloropon, chloropropylate, diflubenzuron, diflufenican, diflufenzopyr, diflufenzopyr chlorothalonil, chlorotoluron, chloroxuron, chloroxynil, Sodium, diflumetorim, dikegulac, dikegulac-Sodium, dilor, chlorphonium, chlorphonium chloride, chlorphoxim, chlo 45 dimatif dimefluthrin, dimefox, dimefuron, dimepiperate, rpraZophos, chlorprocarb, chlorpropham, chlorpyrifos, chlo dimetachlone, dimetan, dimethacarb, dimethachlor, dimeth rpyrifos-methyl, chlorquinox, chlorSulfuron, chlorthal, chlo ametryn, dimethenamid, dimethenamid-P, dimethipin, dime rthal-dimethyl, chlorthal-monomethyl, chlorthiamid, thirimol, dimethoate, dimethomorph, dimethrin, dimethyl chlorthiophos, chloZolinate, choline chloride, chromafenoz carbate, dimethyl phthalate, dimethylvinphos, dimetilan, ide, cinerin I, cinerin II, cinerins, cinidon-ethyl, cinmethylin, 50 dimexano, dimidazon, dimoxystrobin, dinex, dinex-diclex cinosulfuron, ciobutide, cisanilide, cismethrin, clethodim, ine, dingjuneZuo, diniconazole, diniconazole-M, dinit climbazole, cliodinate, clodinafop, clodinafop-propargyl. ramine, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, cloethocarb, clofencet, clofencet-potassium, clofentezine, dinofenate, dinopenton, dinoprop, dinosaur, dinoseb, dino clofibric acid, clofop, clofop-isobutyl, clomaZone, clom Seb acetate, dinoseb-ammonium, dinoseb-diolamine, dino eprop, cloprop, cloproxydim, elopyralid, clopyralid-methyl, 55 seb-sodium, dinoseb-trolamine, dinosulfon, dinotefuran, clopyralid-olamine, clopyralid-potassium, clopyralid-tris(2- dinoterb, dinoterb acetate, dinoterbon, diofenolan, diox hydroxypropyl)ammonium, cloquintocet, cloquintocet abenzofos, dioxacarb, dioxathion, diphacinone, diphaci mexyl, cloranSulam, cloranSulam-methyl, closantel, cloth none-sodium, diphenamid, diphenyl Sulfone, diphenylam ianidin, clotrimazole, cloxyfonac, cloxyfonac-Sodium, ine, dipropalin, dipropetryn, dipyrithione, diduat, diduat CMA, codlelure, colophonate, copper acetate, copper 60 dibromide, disparlure, disul, disulfiram, disulfoton, disul acetoarsenite, copper arsenate, copper carbonate, basic, cop sodium, ditalimfos, dithianon, dithicrofos, dithioether, dith per hydroxide, copper naphthenate, copper oleate, copper iopyr, diuron, d-limonene, DMPA, DNOC, DNOC-ammo oxychloride, copper silicate, copper Sulfate, copper Zinc nium, DNOC-potassium, DNOC-sodium, dodemorph, chromate, coumachlor, coumafuryl, coumaphos, coumate dodemorph acetate, dodemorph benzoate, dodicin, dodicin tralyl, coumithoate, coumoxystrobin, CPMC, CPMF, CPPC, 65 hydrochloride, dodicin-sodium, dodine, dofenapyn, domini credazine, cresol, crimidine, crotamiton, crotoxyphos, cru calure, doramectin, drazoxolon, DSMA, dufulin, EBEP, fomate, cryolite, cue-lure, cufraneb, cumyluron, cuprobam, EBP, ecdysterone, edifenphos, eglinazine, eglinazine-ethyl, US 9,491,944 B2 51 52 emamectin, emamectin benzoate, EMPC, empenthrin, endo carbanil, furconazole, furconazole-cis, furethrin, furfural, Sulfan, endothal, endothal-diammonium, endothal-dipotas furilazole, furmecyclox, furophanate, furyloxyfen, gamma sium, endothal-disodium, endothion, endrin, enestroburin, cyhalothrin, gamma-HCH, genit, gibberellic acid, gibberel EPN, epocholeone, epolfenonane, epoxiconazole, epri lins, gliftor, glufosinate, glufosinate-ammonium, glufosi nomectin, epronaz, EPTC, erbon, ergocalciferol, erluixian nate-P. glufosinate-P-ammonium, glufosinate-P-Sodium, caoan, esdépallethrine, esfenvalerate, esprocarb, etacelasil, glyodin, glyoxime, glyphosate, glyphosate-diammonium, etaconazole, etaphos, etem, ethaboxam, ethachlor, ethafflu glyphosate-dimethylammonium, glyphosate-isopropylam ralin, ethametSulfuron, ethametSulfuron-methyl, ethap monium, glyphosate-monoammonium, glypho sate-potas rochlor, ethephon, ethidimuron, ethiofencarb, ethiolate, sium, glypho sate- sesquisodium, glyphosate-trimesium, ethion, ethiozin, ethiprole, ethirimol, ethoate-methyl, etho 10 glyphosine, gossyplure, grandlure, griseofulvin, guaZatine, fumesate, ethohexadiol, ethoprophos, ethoxyfen, ethoxyfen guazatline acetates, halacrinate, halfenproX, halofenozide, ethyl, ethoxyquin, ethoxysulfuron, ethychloZate, ethyl for halosafen, halosulfuron, halosulfuron-methyl, haloxydine, mate, ethyl C.-naphthaleneacetate, ethyl-DDD, ethylene, haloxyflop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop ethylene dibromide, ethylene dichloride, ethylene oxide, P. haloxyfop-P-etotyl, haloxyfop-P-methyl, haloxyfop-so ethylicin, ethylmercury 2,3-dihydroxypropyl mercaptide, 15 dium, HCH, hemel, hempa, HEOD, heptachlor, hepteno ethylmercury acetate, ethylmercury bromide, ethylmercury phos, heptopargil, heterophos, hexachloroacetone, chloride, ethylmercury phosphate, etinofen, etnipromid, eto hexachlorobenzene, hexachlorobutadiene, hexachloro benzanid, etofenproX, etoxazole, etridiazole, etrimfos, euge phene, hexaconazole, hexaflumuron, hexaflurate, hexalure, nol, EXD, famoxadone, famphur, fenamidone, fenamino hexamide, hexazinone, hexylthiofos, hexythiazox, HHDN. Sulf, fenamiphos, fenapanil, fenarimol, fenasulam, holosulf, huancaiwo, huangcaoling, huanjunzuo, hydram fenaZaflor, fenazaquin, fenbuconazole, fenbutatin oxide, ethylnon, hydrargaphen, hydrated lime, hydrogen cyanide, fenchlorazole, fenchlorazole-ethyl, fenchlorphos, fenclorim, hydroprene, hymexaZol, hyduincarb, IAA, IBA, icaridin, fenethacarb, fenfluthrin, fenfuram, fenhexamid, fenitropan, imazalil, imazalil nitrate, imazalil Sulfate, imazamethabenz, fenitrothion, fenjuntong, fenobucarb, fenoprop, fenoprop-3- imazamethabenZ-methyl, imaZamox, imaZamox-ammo butoxypropyl, fenoprop-butometyl, fenoprop-butotyl, feno 25 nium, imaZapic, imaZapic-ammonium, imazapyr, imazapyr prop-butyl, fenoprop-isoctyl, fenoprop-methyl, fenoprop isopropylammonium, imaZaquin, imaZaquin-ammonium, potassium, fenothiocarb, fenoxacrim, fenoxaniil, imaZaquin-methyl, imazaquin-sodium, imazethapyr, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P- imazethapyr-ammonium, imaZoSulfuron, imibenconazole, ethyl, fenoxasulfone, fenoxycarb, fenpiclonil, fempirithrin, imicyafos, imidacloprid, imidaclothiz, iminoctadine, imi fenpropathrin, fenpropidin, fenpropimorph, fenpyraZamine, 30 noctadine triacetate, iminoctadine trialbesilate, imiprothrin, fenpyroximate, fenridazon, fenridazon-potassium, fenrida inabenfide, indanofan, indaziflam, indoxacarb, inezin, iodo Zon-propyl, fenson, fensulfothion, fenteracol, fenthiaprop, bonil, iodocarb, iodomethane, iodosulfuron, iodosulfuron fenthiaprop-ethyl, fenthion, fenthion-ethyl, fentin, fentin methyl, iodosulfuron-methyl-Sodium, iofensulfuron, iofen acetate, fentin chloride, fentin hydroxide, fentraZamide, fen Sulfuron-sodium, ioxynil, ioxynil octanoate, ioxynil-lithium, trifanil, fenuron, fenuron TCA, fenvalerate, ferbam, ferim 35 ioxynil-sodium, ipazine, ipconazole, ipfencarbazone, Zone, ferrous Sulfate, fipronil, flamprop, flamprop-isopropyl. iprobenfos, iprodione, iprovalicarb, iprymidam, ipsdienol, flamprop-M, flamprop-methyl, flamprop-M-isopropyl. ipsenol, IPSP, isamidofos, isaZofoS, isobenzan, isocarbamid, flamprop-M-methyl, flazasulfuron, flocoumafen, flometo isocarbophos, isocil, isodrin, isofenphos, isofenphos quin, flonicamid, florasulam, fluacrypyrim, fluazifop, fluazi methyl, isolan, isomethiozin, isonoruron, isopolinate, iso fop-butyl, fluazifop-methyl, fluazifop-P, fluazifop-P-butyl, 40 procarb, isopropalin, isoprothiolane, isoproturon, isopyra fluazinam, fluazolate, fluaZuron, flubendiamide, flubenz Zam, isopyrimol, isothioate, isotianil, isouron, isovaledione, imine, flucarbazone, flucarbazone-sodium, flucetosulfuron, isoxaben, isoxachlortole, isoxadifen, isoxadifen-ethyl, isox fluchloralin, flucofuron, flucycloxuron, flucythrinate, fludi aflutole, isoxapyrifop, isoxathion, ivermectin, izopamfos, oxonil, fluenetil, fluensulfone, flufenacet, flufenerim, japonilure, japothrins, jasmolin I, jasmolin II, jasmonic acid, flufenican, flufenoxuron, flufenprox, flufenpyr, flufenpyr 45 jiahuangchongzong, jiajizengxiaolin, jiaxiangjunzhi, jie ethyl, flufiprole, flumethrin, flumetover, flumetralin, flumet caowan, jiecaoxi, jodfenphos, juvenile hormone I, juvenile Sulam, flumezin, flumiclorac, flumiclorac-pentyl, flumioX hormone II, juvenile hormone III, kadethrin, karbutilate, azin, flumipropyn, flumorph, fluometuron, fluopicolide, karetazan, karetaZan-potassium, kasugamycin, kasugamycin fluopyram, fluorbenside, fluoridamid, fluoroacetamide, fluo hydrochloride, kejunlin, kelevan, ketospiradox, ketospira rodifen, fluoroglycofen, fluoroglycofen-ethyl, fluoroimide, 50 dox-potassium, kinetin, kinoprene, kresoxim-methyl, kui fluoromidine, fluoronitrofen, fluothiuron, fluotrimazole, flu caoxi, lactofen, lambda-cyhalothrin, latilure, lead arsenate, oxastrobin, flupoxam, flupropacil, flupropadine, flupropan lenacil, lepimectin, leptophos, lindane, lineatin, linuron, ate, flupropanate-sodium, flupyradifurone, flupyrsulfuron, lirimfos, litlure, loopilure, lufenuron, lvdingjunzhi, lVXian flupyrsulfuron-methyl, flupyrsulfuron-methyl-Sodium, caolin, lythidathion, MAA, malathion, maleic hydrazide, fluguinconazole, flurazole, flurenol, flurenol-butyl, flurenol 55 malonoben, maltodextrin, MAMA, mancopper, mancoZeb, methyl, fluridone, flurochloridone, fluroxypyr, fluroxypyr mandipropamid, maneb, matrine, mazidox, MCPA, MCPA butometyl, fluroxypyr-meptyl, flurprimidol, flursulamid, 2-ethylhexyl, MCPA-butotyl, MCPA-butyl, MCPA-dimeth flurtamone, flusilazole, flusulfamide, fluthiacet, fluthiacet ylammonium, MCPA-diolamine, MCPA-ethyl, MCPA methyl, flutianil, flutolanil, flutriafol, fluvalinate, fluxapy isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, roXad, fluxofenim, folpet, fomesafen, fomesafen-Sodium, 60 MCPA-olamine, MCPA-potassium, MCPA-sodium, MCPA fonofos, foramsulfuron, forchlorfenuron, formaldehyde, thioethyl, MCPA-trolamine, MCPB, MCPB-ethyl, MCPB formetanate, formetanate hydrochloride, formothion, form methyl, MCPB-sodium, mebenil, mecarbam, mecarbinzid, paranate, formparanate hydrochloride, fosamine, fosamine mecarphon, mecoprop, mecoprop-2-ethylhexyl, mecoprop ammonium, fosetyl, fosetyl-aluminium, foSmethilan, fospi dimethylammonium, mecoprop-diolamine, mecoprop rate, fosthiazate, fosthietan, frontalin, fuberidazole, 65 ethadyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-P, fucaojing, fucaomi, funaihecaoling, fuphenthiourea, fural mecoprop-P-2-ethylhexyl, mecoprop-P-climethylammo ane, furalaxyl, furamethrin, furametpyr, furathiocarb, fur nium, mecoprop-P-isobutyl, mecoprop-potassium, meco US 9,491,944 B2 53 54 prop-P-potassium, mecoprop-sodium, mecoprop-trolamine, phosdiphen, phosfolan, phosfolan-methyl, phosglycin, medimeform, medinoterb, medinoterb acetate, medlure, phosmet, phosnichlor, phosphamidon, phosphine, phospho mefenacet, mefenpyr, mefenpyr-diethyl, mefluidide, meflui carb, phosphorus, phostin, phoxim, phoxim-methyl, phtha dide-diolamine, mefluidide-potassium, megatomoic acid, lide, picloram, picloram-2-ethylhexyl, picloram-isoctyl, menazon, mepanipyrim, meperfluthrin, mephenate, mephos picloram-methyl, picloram-olamine, picloram-potassium, folan, mepicquat, mepicquat chloride, mepiduat pentaborate, picloram-triethylammonium, picloram-tris(2-hydroxypro mepronil, meptylidinocap, mercuric chloride, mercuric pyl)ammonium, picolinafen, picoxystrobin, pindone, pin oxide, mercurous chloride, merphos, mesoprazine, mesosul done-sodium, pinoxaden, piperalin, piperonylbutoxide, pip furon, mesosulfuron-methyl, mesotrione, meSulfen, eronyl cyclonene, piperophos, piproctanyl, piproctanyl meSulfenfos, metaflumiZone, metalaxyl, metalaxyl-M, met 10 bromide, piprotal, pirimetaphos, pirimicarb, pirimioxyphos, aldehyde, metam, metam-ammonium, metamifop, met pirimiphos-ethyl, pirimiphos-methyl, plifenate, polycar amitron, metam-potassium, metam-Sodium, metaZachlor, bamate, polyoxins, polyoxorim, polyoxorim-zinc, polythi metazosulfuron, metaZOXolon, metconazole, metepa, met alan, potassium arsenite, potassium azide, potassium flurazon, methabenzthiazuron, methacrifos, methalpropalin, cyanate, potassium gibberellate, potassium naphthenate, methamidophos, methasulfocarb, methazole, methfuroxam, 15 potassium polysulfide, potassium thiocyanate, potassium methidathion, methiobencarb, methiocarb, methiopyrisulfu C.-naphthaleneacetate, pp'-DDT, prallethrin, precocene I. ron, methiotepa, methioZolin, methiuron, methocrotophos, precocene II, precocene III, pretilachlor, primidophos, pri methometon, methomyl, methoprene, methoprotryne, misulfuron, primisulfuron-methyl, probenazole, prochloraZ. methoduin-butyl, methothrin, methoxychlor, methoxyfenoz prochloraZ-manganese, proclonol, procyazine, procymi ide, methoxyphenone, methyl apholate, methyl bromide, done, prodiamine, profenofos, profluaZol, profluralin, pro methyl eugenol, methyl iodide, methyl isothiocyanate, fluthrin, profoxydim, proglinazine, proglinazine-ethyl, pro methylacetophos, methylchloroform, methyldymron, meth hexadione, prohexadione-calcium, prohydrojasmon, ylene chloride, methylmercury benzoate, methylmercury promacyl, promecarb, prometon, prometryn, promurit, dicyandiamide, methylmercury pentachlorophenoxide, propachlor, propamidine, propamidine dihydrochloride, pro methylneodecanamide, metiram, metobenzuron, metobro 25 pamocarb, propamocarb hydrochloride, propanil, propa muron, metofluthrin, metolachlor, metolcarb, metominos phos, propaquizafop, propargite, proparthrin, propazine, trobin, metoSulam, metoxadiaZone, metOXuron, propetamphos, propham, propiconazole, propineb, propiso metrafenone, metribuzin, metSulfovax, metSulfuron, metSul chlor, propoXur, propoxycarbazone, propoxycarbazone-so furon-methyl, mevinphos, mexacarbate, mieshuan, milbe dium, propyl isome, propyrisulfuron, propyZamide, produi mectin, milbemycin oxime, milineb, mipafox, mirex, MNAF, 30 nazid, proSuler, prosulfalin, prosulfocarb, prosulfuron, moguchun, molinate, moloSultap, monalide, monisouron, prothidathion, prothiocarb, prothiocarb hydrochloride, pro monochloroacetic acid, monocrotophos, monolinuron, thioconazole, prothiofos, prothoate, protrifenbute, proxan, monosulfuron, monosulfuron-ester, monuron, monuron proXan-sodium, prynachlor, pydanon, pymetrozine, pyrac TCA, morfamquat, morfamquat dichloride, moroxydine, arbolid, pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, moroxydine hydrochloride, morphothion, morzid, moxidec 35 pyraflufen-ethyl, pyrafluprole, pyramat, pyrametostrobin, tin, MSMA, muscalure, myclobutanil, myclozolin, N-(eth pyraoxystrobin, pyrasulfotole, pyrazolynate, pyrazophos, ylmercury)-p-toluenesulphonanilide, nabam, naftalofos, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazothion, pyra naled, naphthalene, naphthaleneacetamide, naphthalic anhy ZOxyfen, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, dride, naphthoxyacetic acids, naproanilide, napropamide, pyribambenz-isopropyl, pyribambenZ-propyl, pyribencarb, naptalam, naptalam-Sodium, natamycin, neburon, niclos 40 pyribenZoxim, pyributicarb, pyriclor, pyridaben, pyridafol. amide, niclosamide-olamine, nicosulfuron, nicotine, nifluri pyridalyl pyridaphenthion, pyridate, pyridinitril, pyrifenox, dide, nipyraclofen, nitenpyram, nithiazine, nitralin, nitrapy pyrifluquinazon, pyriftalid, pyrimethanil, pyrimidifen, rin, nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrimi nitrothal-isopropyl. norbormide, norflurazon, nornicotine, tate, pyrinuron, pyriofenone, pyriprole, pyripropanol, noruron, novaluron, noviflumuron, nuarimol, OCH, 45 pyriproxyfen, pyrithiobac, pyrithiobac-Sodium, pyrolan, octachlorodipropyl ether, octhillinone, ofurace, omethoate, pyroquilon, pyroxasulfone, pyroxSulam, pyroxychlor, orbencarb, orfralure, ortho-dichlorobenzene, orthosulfa pyroxyfur, quassia, quinacetol, quinacetol Sulfate, quinal muron, oryctalure, orysastrobin, oryzalin, osthol, ostramone, phos, quinallphos-methyl, quinaZamid, quinclorac, quincon oXabetrinil, oxadiargyl, oxadiazon, oxadixyl, oXamate, azole, quinmerac, quinoclamine, quinonamid, quinothion, oxamyl, oxapyrazon, oxapyrazon-dimolamine, oxapyrazon 50 quinoxyfen, quintiofos, quintoZene, quizalofop, quizalofop Sodium, oxasulfuron, oxaziclomefone, oxine-copper, OXo ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefu linic acid, Oxpoconazole, Oxpoconazole fumarate, oxycar ryl, quwenzhi, quyingding, rabenzazole, rafoxanide, rebe boxin, oxydemeton-methyl, oxydeprofos, oxydisulfoton, mide, resmethrin, rhodethanil, rhodojaponin-III, ribavirin, oxyfluorfen, oxymatrine, oxytetracycline, Oxytetracycline rimsulfuron, rotenone, ryania, saflufenacil, Saijunmao, hydrochloride, paclobutraZol, paichongding, para-dichlo 55 saisentong, salicylanilide, Sanguinarine, Santonin, Schradan, robenzene, parafluron, paraquat, paraquat dichloride, para Scilliroside, Sebuthylazine, secbumeton, sedaxane, Selamec quat dimetilsulfate, parathion, parathion-methyl, parinol, tin, semiamitraz, semiamitraz, chloride, Sesamex, Sesamolin, pebulate, pefurazoate, pelargonic acid, penconazole, pency Sethoxydim, Shuangjiaancaolin, Siduron, siglure, silafluofen, curon, pendimethalin, penflufen, penfluron, penoXSulam, silatrane, silica gel, silthiofam, Simazine, Simeconazole, pentachlorophenol, pentanochlor, penthiopyrad, pent 60 simeton, simetryn, sintofen, SMA, S-metolachlor, sodium methrin, pentoxazone, perfluidone, permethrin, pethoxamid, arsenite, Sodium azide, Sodium chlorate, Sodium fluoride, phenamacril, phenazine oxide, phenisopham, phenkapton, Sodium fluoroacetate, Sodium hexafluorosilicate, sodium phenmedipham, phenmedipham-ethyl, phenobenzuron, phe naphthenate, Sodium orthophenylphenoxide, Sodium pen nothrin, phenproxide, phenthoate, phenylmercuriurea, phe tachlorophenoxide, Sodium polysulfide, sodium thiocyanate, nylmercury acetate, phenylmercury chloride, phenylmer 65 Sodium C.-naphthaleneacetate, sophamide, spinetoram, cury derivative of pyrocatechol, phenylmercury nitrate, spinosad, spirodiclofen, spiromesifen, Spirotetramat, spiroX phenylmercury salicylate, phorate, phosacetim, phosalone, amine, Streptomycin, streptomycin sesquisulfate, Strych US 9,491,944 B2 55 56 nine, Sulcatol, Sulcofuron, Sulcofuron-sodium, Sulcotrione, 15. The composition of claim 1, wherein the pyridine Sulfallate, SulfentraZone, Sulfiram, Sulfluramid, Sulfo triazole compound comprises a H in place of H. meturon, Sulfometuron-methyl, Sulfosulfuron, Sulfotep, Sul 16. The composition of claim 1, wherein the pyridine foxaflor, sulfoxide, sulfoxime, sulfur, sulfuric acid, sulfuryl triazole compound comprises a 'C in place of a 'C. fluoride, Sulglycapin, Sulprofos, Sultropen, Swep, tau-fluvali 17. The composition of claim 1, further comprising a nate, tavron, tazimcarb, TCA, TCA-ammonium, TCA-cal biopesticide. cium, TCA-ethadyl, TCA-magnesium, TCA-sodium, TDE, 18. The composition of claim 1, further comprising one or tebuconazole, tebufenozide, tebufenpyrad, tebufloquin, more of the following compounds: tebupirimfos, tebutam, tebuthiuron, tecloftalam, tecnaZene, (a) 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1- tecoram, teflubenzuron, tefluthrin, tefuryltrione, tembotri 10 aZaspiro4.5 dec-3-en-2-one; one, temephos, tepa, TEPP tepraloxydim, terallethrin, ter (b) 3-(4-chloro-2,4-dimethyl 1, 1'-biphenyl-3-yl)-4-hy bacil, terbucarb, terbuchlor, terbufos, terbumeton, terbuth droxy-8-Oxa-1-azaspiro4.5dec-3-en-2-one; ylazine, terbutryn, tetcyclacis, tetrachloroethane, (c) 4-(6-chloro-3-pyridinyl)methylmethylamino-2 tetrachlorvinphos, tetraconazole, tetradifon, tetrafluron, 15 (5H)-furanone; tetramethrin, tetramethylfluthrin, tetramine, tetranactin, tet (d) 4-(6-chloro-3-pyridinyl)methylcyclopropylamino rasul, thallium sulfate, thenylchlor, theta-cypermethrin, thi 2(5H)-furanone; abendazole, thiacloprid, thiadifluor, thiamethoxam, thiapro (e) 3-chloro-N2-(1S)-1-methyl-2-(methylsulfonyl) nil, thiazafluron, thiazopyr, thicrofos, thicyofen, thidiazimin, ethyl)-N1-(2-methyl-4-1.2.2.2-tetrafluoro-1-(trifluo thidiaZuron, thiencarbazone, thiencarbazone-methyl, thifen romethyl)ethylphenyl-1,2-benzenedicarboxamide: sulfuron, thifensulfuron-methyl, thifluzamide, thiobencarb, (f) 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfona thiocarboxime, thiochlorfemphim, thiocyclam, thiocyclam mide; hydrochloride, thiocyclam oxalate, thiodiazole-copper, thio (g) 2-cyano-N-ethyl-3-methoxy-benzenesulfonamide; dicarb, thiofanox, thiofluoximate, thiohempa, thiomersal, (h) 2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benze thiometon, thionazin, thiophanate, thiophanate-methyl, thio 25 nesulfonamide; quinox, thiosemicarbazide, thiosultap, thiosultap-diammo (i) 2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfona nium, thiosultap-disodium, thiosultap-monosodium, thio mide; tepa, thiram, thuringiensin, tiadinil, tiaojiean, tiocarbazil, (j) 2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzene tioclorim, tioxymid, tirpate, tolclofoS-methyl, tolfenpyrad, Sulfonamide; tolylfluanid, tolylmercury acetate, toprameZone, tralkoxy 30 (k) 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-ben dim, tralocythrin, tralomethrin, tralopyril, transfluthrin, Zenesulfonamide; transpermethrin, tretamine, triacontanol, triadimefon, triadi (1) 2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesul menol, triafamone, tri-allate, triamiphos, triapenthenol, tri fon-amide; arathene, triarimol, triasulfuron, triaZamate, triazbutil, tri (m) 3-(difluoromethyl)-N-2-(3.3-dimethylbutyl)phenyl aziflam, triazophos, triaZoxide, tribenuron, tribenuron 35 methyl, tribufos, tributyltin oxide, tricamba, trichlamide, 1-methyl-1H-pyrazole-4-carboxamide: trichlorfon, trichlorimetaphos-3, trichloronat, triclopyr, tric (n) N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro lopyr-butotyl, triclopyr-ethyl, triclopyr-triethylammonium, C.C.C.-trifluoro-p-tolyl) hydraZone; tricyclazole, tridemorph, tridiphane, trietazine, trifenmorph, (o) N-ethyl-2,2-dichloro-1-methylcyclopropane-carbox trifenofos, trifloxystrobin, trifloxysulfuron, trifloxysulfuron 40 amide-2-(2,6-dichloro-C.C.C.-trifluoro-p-tolyl) hydra sodium, triflumizole, triflumuron, trifluralin, triflusulfuron, Zone nicotine; triflusulfuron-methyl, trifop, trifop-methyl, trifopsime, tri (p) O-(E-)-2-(4-chloro-phenyl)-2-cyano-1-(2-trifluo forine, trihydroxytriazine, trimedlure, trimethacarb, romethylphenyl)-vinylS-methyl thiocarbonate; trimeturon, trinexapac, trinexapac-ethyl, triprene, tripropin (q) (E)-N1-(2-chloro-1,3-thiazol-5-ylmethyl)-N2 dan, triptolide, tritac, triticonazole, tritosulfuron, trunc-call, 45 cyano-N1-methylacetamidine; uniconazole, uniconazole-P. urbacide, uredepa, Valerate, (r) 1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2, validamycin, Valifenalate, valone, vamidothion, Vangard, 3,5,6,7-hexahydro-imidazo[1,2-alpyridin-5-ol; Vaniliprole, Vernolate, VincloZolin, warfarin, warfarin-potas (s) 4-4-chlorophenyl-(2-butylidine-hydrazono)methyl) sium, warfarin-Sodium, Xiaochongliulin, Xinjunan, Xiwoju phenyl mesylate; and nan, XMC, Xylachlor, Xylenols, Xylylcarb, yishijing, Zaril 50 (t) N-Ethyl-2,2-dichloro-1-methylcyclopropanecarbox amid, Zeatin, Zengxiaoan, Zeta-cypermethrin, Zinc amide-2-(2,6-dichloro-C.C.C.-trifluoro-p-tolyl)hydra naphthenate, Zinc phosphide, Zinc thiazole, Zineb, Ziram, ZO. Zolaprofos, Zoxamide, Zuomihuanglong, C-chlorohydrin, 19. The composition of claim 1, further comprising a C-ecdysone, C.-multistriatin, and C-naphthaleneacetic acid. compound having one or more of the following modes of 9. The composition of claim 1, further comprising an 55 action: acetylcholinesterase inhibitor, sodium channel agriculturally acceptable carrier. modulator; chitin biosynthesis inhibitor; GABA and gluta 10. The composition of claim 1, wherein the pyridine mate-gated chloride channel antagonist; GABA and gluta triazole compound is in the form of a pesticidally acceptable mate-gated chloride channel agonist; acetylcholine receptor acid addition salt. agonist; acetylcholine receptor antagonist, METI inhibitor; 11. The composition of claim 1, wherein the pyridine 60 Mg-stimulated ATPase inhibitor; nicotinic acetylcholine triazole compound is in the form of a salt derivative. receptor, Midgut membrane disrupter, oxidative phospho 12. The composition of claim 1, wherein the pyridine rylation disrupter, and ryanodine receptor (RyRs). triazole compound is in the form a hydrate. 20. The composition of claim 1, further comprising a 13. The composition of claim 1, wherein the pyridine seed. triazole compound is a resolved stereoisomer. 65 21. The composition of claim 1, further comprising a seed 14. The composition of claim 1, wherein the pyridine that has been genetically modified to express one or more triazole compound is in the form a crystal polymorph. specialized traits. US 9,491,944 B2 57 58 22. The composition of to claim 1, wherein the compo 36. The process of claim 24, where the composition sition is encapsulated inside, or placed on the Surface of a further comprises ammonium sulfate. capsule. 37. A method of preparing a pyridine triazole compounds 23. The composition of claim 1, wherein the composition of formula I, comprising: is encapsulated inside, or placed on the Surface of a capsule, reacting a pyridine triazole compounds of formula 1-1 wherein the capsule has a diameter of about 100-900 nano with an aryl or heterocyclic halide of formula 1-2, meters or about 10-900 microns. 24. A process comprising applying a composition of claim 1, to an area to control a pest, in an amount Sufficient to R4 N=N control Such pest. 10 R N 25. The process of claim 24, wherein the pest is selected from beetles, earwigs, cockroaches, flies. aphids, Scales, 2 Rs whiteflies, leafhoppers, ants, wasps, termites, moths, butter R2 N R 1-1 flies, lice, grasshoppers, locusts, crickets, fleas, thrips, 15 bristletails, mites, ticks, nematodes, and Symphylans. R4 NN 26. The process of claim 24, wherein the pest is from the R Phyla Nematoda or Arthropoda. Z-Br -- 3 N 21 Z 27. The process of claim 24, wherein the pest is from the 1-2 Subphyla Chelicerata, Myriapoda, or Hexapoda. 2 Rs 28. The process of claim 24, wherein the pest is from the R N R Class of Arachnida, Symphyla, or Insecta. I 29. The process of claim 24, wherein the pest is from the Order Anoplura, Order Coleoptera, Order Dermaptera, wherein R. R. R. R. Rs. Z, and X are defined as in Order Blattaria, Order Diptera, Order Hemiptera, Order 25 claim 1. Hymenoptera, Order Isoptera, Order Lepidoptera, Order 38. A method of preparing a pyridine triazole compounds Mallophaga, Order Orthoptera, Order Siphonaptera, Order of formula I, comprising: Thysanoptera, Order Thysanura, Order Acarina, or Order reacting 4-iodo-triazole compounds of formula 2-1 with Symphyla. an aryl or heterocyclic boronic acid compounds of 30. The process of claim 24, wherein the pest is MYZUPE 30 formula 2-2, or BEMITA 31. The process of claim 24, wherein an amount of the composition is from about 0.01 grams per hectare to about R4 NN 5000 grams per hectare. R 32. The process of claim 24, wherein an amount of the 35 3 N 2 I -- composition is from about 0.1 grams per hectare to about 2 Rs 500 grams per hectare. R2 N R 33. The process of claim 24, wherein an amount of the 2-1 composition is from about 1 gram per hectare to about 50 R4 NN grams per hectare. 40 34. The process of claim 24, wherein the area is an area pH R N/ where apples, corn, cotton, soybeans, canola, wheat, rice, Z-B - N 2 Z OH Sorghum, barley, oats, potatoes, oranges, alfalfa, lettuce, 2 R Strawberries, tomatoes, peppers, crucifers, pears, tobacco, 2-2 R N R almonds, Sugar beets, or beans, are growing, or the seeds 45 thereof are going to be planted. 35. The process of claim 24, further comprising applying the composition to a genetically modified plant that has been wherein R. R. R. R. Rs. Z, and X are defined as in genetically modified to express one or more specialized claim 1. traits.