USOO9131694B2 (12) United States Patent (10) Patent No.: US 9,131,694 B2 Niyaz et al. (45) Date of Patent: Sep. 15, 2015 (54) INSECTICIDAL PYRIDINE COMPOUNDS 5,723.450 A 3/1998 Reuschling et al. 5,994,373 A 1 1/1999 Olesen (71) Applicant: pyroscience, LLC, Indianapolis, 6,878,7266,004,977 AB2 12/19994/2005 KurysG. etet al.al. 7,087.616 B2 8, 2006 Fischer et al. 7,119,098 B2 10/2006 Nagarajan et al. (72) Inventors: Noormohamed M. Niyaz, Indianapolis, 7,238,697 B2 7/2007 Bretschneider et al. IN (US); Francis E. Tisdell, Carmel, IN 7,371,759 B2 5/2008 Ahmad et al. (US); Gerald B. Watson, Zionsville, IN (US); James M. Renga, Indianapolis, IN FOREIGN PATENT DOCUMENTS SIR.US); William C. H. C.Yap Lo, Zionsville Fishers. IN N (US): GS, DE 10/2008/OOO872 11, 2008 e is savs s EP 1273580 A1 1/2003 EP 1775293 A1 4/2007 (73) Assignee: Dow AgroSciences LLC, Indianapolis, EP 17831 14 A1 5/2007 IN (US) WO 2005/063736 7/2005 WO 2009,025823 A1 1, 2009 (*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. U.S. Appl. No. 12/799,478, filed Apr. 26, 2010, Niyaz et al. European Patent Office. Patent Cooperation Treaty International (21) Appl. No.: 14/070,254 Search Report and Written Opinion of the International Searching Authority. PCT Patent Application No. PCT/US2010/001232. Jul. (22) Filed: Nov. 1, 2013 28, 2010. Allan, J.R. Paton, A.D. Preparation, structural characterisation, ther (65) Prior Publication Data mal and electrical studies of Some first row transition metal com US 2014/O141975 A1 May 22, 2014 plexes of 2,3-bis(2-pyridyl)pyrazine. Thermochimica Acta, 214 s (1993), pp. 227-233. Related U.S. Application Data Katritzky, A.R., Jiang, J.; Greenhill, J.V. 1.2- and 1,3- Monoazabisylides as Novel Synthones. Journal of Organic Chemis (62) Division of application No. 12/799,478, filed on Apr. try, 1993, vol. 58, pp. 1987-1988. 26, 2010, now Pat. No. 8,604,199. Heirtzler, F.; Neuburger, M.; Kulike, K. Insights on the synthesis and organisational phenomena of twisted pyrazine-pyridine hybrids. J. (60) Provisional application No. 61/172,958, filed on Apr. Chem. Soc., Perkin Trans. 1, 2002. p. 809-820. 27, 2009. Sumengen, D. The Preparation of 3, 4-Diaryl Furoxans and 3.5- diaryl-1,2,4-Oxadiazol-4-Oxides. Chimica Acta Turcica 13 (1985), (51) Int. Cl. pp. 3939-402. CO7D 413/4 (2006.01) Colonna, M., Risaliti, A. Recerche Sugli azocomosti AOIN 43/76 (2006.01) N-eterociclici. Nota VIII. Reazione con difenilchetene ed AOIN 43/40 (2006.01) autossidazione degli addotti da azoici simmetrici. Gassetta Chimica AOIN 55/00 (2006.01) Italia's Chimica, Italiana, Rome; Italy, vol. 90, Jan. 1, 1960, CO7D 40/4 (2006.01) RefNional Preliminary Report on Patentability, PCT/US2010/ (52) U.S. Cl. 001232, Apr. 26, 2010, Dow AgroSciences, LLC. CPC ................ A0IN 43/76 (2013.01); A0IN 43/40 Dorwald, Side Reactions in Organic Synthesis, 2005, Wiley: VCH (2013.01); A0IN 55/00 (2013.01); C07D Weinheim Preface, pp. 1-15 & Chapter 8, pp. 279-308. 401/14 (2013.01); C07D 413/14 (2013.01) (58) Field of Classification Search Primary Examiner — Patricia L. Morris CPC ..................................................... CO7D 413/14 (74) Attorney, Agent, or Firm — Carl D. Corvin; Maschoff USPC ........................................... 546/256; 514/333 Brennan See application file for complete search history. (57) ABSTRACT (56) References Cited The invention disclosed in this document is related to the field of pesticides and their use in controlling pests. Novel pyridine U.S. PATENT DOCUMENTS compounds for use in controlling pests are disclosed. 4.474,599 A 10/1984 Rogers et al. 5,084,459 A 1/1992 Uneme et al. 11 Claims, No Drawings US 9, 131,694 B2 1. INSECTICIDAL PYRIDINE COMPOUNDS Formula (I) CROSS REFERENCE TO RELATED APPLICATIONS The present application is a divisional of U.S. patent appli cation Ser. No. 12/799,478 filed 26 Apr. 2009, now U.S. Pat. No. 8,604,199, which claims priority to U.S. Provisional Patent Application No. 61/172,958 filed 27 Apr. 2009. The contents of these applications are incorporated herein by ref erence in their entirety. 10 FIELD OF THE INVENTION wherein A1, A2, and A3, are each independently C or N, with the The inventions disclosed in this document are related to the proviso that A1 and A2 are not simultaneously N: field of pesticides and their use in controlling pests. 15 X and Y are independently C or N: Zand T are each independently C(R6) (where R6 could be BACKGROUND the same or different), C—O, C=NR7, NR7, O, S(O)n' (n'=0-2); Pests cause millions of human deaths around the world n=0, 1, 2 and 3 (X, Y, T and Z together form a 3- or 4- or 5 each year. Furthermore, there are more than ten thousand or 6-membered heteroaryl or a fully or partially saturated species of pests that cause losses in agriculture. These agri heterocyclic ring); cultural losses amount to billions of U.S. dollars each year. R1 is (provided that A1 is not N) H, CN, CHO, SCN, Termites cause damage to various structures such as homes. NO, F, Cl, Br, I, substituted or unsubstituted C1-C4-alkyl, These termite damage losses amount to billions of U.S. dol substituted or unsubstituted halo-C1-C4-alkyl, substituted or lars each year. As a final note, many stored food pests eat and 25 unsubstituted C1-C4-alkoxy, substituted or unsubstituted adulterate stored food. These stored food losses amount to halo-C1-C4-alkoxy, substituted or unsubstituted C1-C4-thio billions of U.S. dollars each year, but more importantly, alkyl, substituted or unsubstituted halo-C1-C4-thioalkyl, deprive people of needed food. substituted or unsubstituted C3-C7-cycloalkyl, substituted or There is an acute need for new pesticides. Insects are devel unsubstituted C2-C4-alkenyl, C2-C4-alkynyl, substituted or oping resistance to pesticides in current use. Hundreds of 30 unsubstituted C1-C4-acylalkyl, C1-C4-acyloxy, C1-C4 insect species are resistant to one or more pesticides. The alkoxycarbonyl, C1-C4-alkoxy-amino, C1-C4-alkyl-S(O) development of resistance to some of the older pesticides, —NH, substituted or unsubstituted aryl, substituted or unsub Such as DDT, the carbonates, and the organophosphates, is stituted heterocyclyl, wherein the substituents are one or well known. But resistance has even developed to some of the more of the following F, C1, Br, OH, CN, NO, CHO,-SCN, newer pesticides. Therefore, a need exists for new pesticides 35 S(O)n-C1-C4-alkyl (where n=0-2). C1-C4-alkyl, halo-C1 and particularly for pesticides that have new modes of action. C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4 alkoxy, C1-C4-thioalkyl, halo-C1-C4-thioalkyl, C1-C4 SUMMARY alkylacyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl, C1-C4 alkoxy-imino, hydroxy-imino, C1-C4-alkyl-S(O)—NH, This invention concerns compounds useful for the control 40 (C1-C4-trialkyl)Si; of insects, especially useful for the control of aphids and other R2 is (provided that A2 is not N) H, CN, CHO, SCN, Sucking insects. More specifically, the invention concerns NO, F, C1, Br, I, substituted or unsubstituted C1-C4-alkyl, compounds of formula I: substituted or unsubstituted halo-C1-C4-alkyl, substituted or unsubstituted C1-C4-alkoxy, substituted or unsubstituted 45 halo-C1-C4-alkoxy, substituted or unsubstituted C1-C4-thio alkyl, substituted or unsubstituted halo-C1-C4-thioalkyl, substituted or unsubstituted C3-C7-cycloalkyl, substituted or unsubstituted C2-C4-alkenyl, C2-C4-alkynyl, substituted or unsubstituted C1-C4-acylalkyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl, C1-C4-alkoxy-amino, C1-C4-alkyl-S(O) —NH, substituted or unsubstituted aryl, substituted or unsub stituted heterocyclyl, wherein the substituents are one or more of the following F, C1, Br, OH, CN, NO, CHO,-SCN, S(O)n-C1-C4-alkyl (where n=0-2). C1-C4-alkyl, halo-C1 wherein A1, A2, A3, X,Y,Z, T, n, R1, R2, R3, R4, R5, R6 and 55 C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4 R7 are as defined herein. alkoxy, C1-C4-thioalkyl, halo-C1-C4-thioalkyl, C1-C4 The invention also provides new processes for preparing alkylacyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl, C1-C4 compounds of formula I as well as new compositions and alkoxy-imino, hydroxy-imino, C1-C4-alkyl-S(O)—NH, methods of use, which will be described in detail hereinafter. (C1-C4-trialkyl)Si; Further embodiments, forms, aspects, features, and details of 60 R3 is CN, NO, F, Cl, Br, I, substituted or unsubstituted the present invention shall become apparent from the descrip halo-C1-C4-alkyl, or unsubstituted C3-C7-cycloalkyl, sub tions contained herein. stituted or unsubstituted halo-C1-C4-alkoxy, substituted or unsubstituted halo-C1-C4-thioalkyl substituted or unsubsti DETAILED DESCRIPTION tuted halo-C2-C4-alkenyl, substituted or unsubstituted five 65 membered heteroaryl, wherein the substituents are one or The compounds of this application have the following more of the following F, Cl, Br, OH, CN, NO, CHO,-SCN, molecular structure: S(O)n-C1-C4-alkyl (where n=0-2). C1-C4-alkyl, halo-C1 US 9, 131,694 B2 3 4 C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4 unsubstituted C1-C4-acylalkyl, C1-C4-acyloxy, C1-C4 alkoxy, C1-C4-thioalkyl, halo-C1-C4-thioalkyl, C1-C4 alkoxycarbonyl, C1-C4-alkyl-S(O)—NH, substituted or alkylacyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl, C1-C4 unsubstituted aryl, substituted or unsubstituted heterocyclyl, alkoxy-imino, hydroxy-imino, C1-C4-alkyl-S(O)—N: wherein the substituents are one or more of the following F.