US008461164B2 (12) United States Patent (10) Patent No.: US 8.461,164 B2 Brewster et al. (45) Date of Patent: Jun. 11, 2013 (54) PTERIDINES AND THEIR USE AS Primary Examiner — Douglas MWillis AGROCHEMICALS (74) Attorney, Agent, or Firm — C. W. Amett; Faegre Baker Daniels LLP (75) Inventors: William K. Brewster, Indianapolis, IN (US); David A. Demeter, Fishers, IN (57) ABSTRACT (US); W. Randal Erickson, Carmel, IN (US); Christian T. Lowe, Westfield, IN The present disclosure relates to 1- or 2-(4-(aryloxy)-phenyl) (US); Carla J. R. Klittich, Zionsville, ethylamino-, oxy- or Sulfanyl)pteridines and 1- or 2-(4-(het IN (US); Jaime S. Nugent, Brownsburg, eroaryloxy)-phenyl)ethylamino-, oxy- or Sulfanyl)pteridines IN (US); Brent J. Rieder, Greenfield, IN and their use as agrochemicals and animal health products. (US); Thomas L. Siddall, Zionsville, IN More specifically, the invention provides new compounds of (US); Chenglin Yao, Westfield, IN (US); the formula (I-A): Carla N. Yerkes, Crawfordsville, IN (US); Yuanming Zhu, Carmel, IN (US) I-A (73) Assignee: Dow AgroSciences, LLC., Indianapolis, IN (US) -- Sey (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 R N U.S.C. 154(b) by 0 days. n CC). 2 2 (21) Appl. No.: 12/551,008 X2 N N els X3 (22) Filed: Aug. 31, 2009 wherein: R is H, CH, phenyl, or a heterocycle comprising a (65) Prior Publication Data 5 or 6 membered single ring or a fused ring system compris ing at least one 5 or 6 membered heterocycle optionally US 2011 FOO54173 A1 Mar. 3, 2011 substituted with H, halo, lower alkyl, lower alkoxy, benzy (51) Int. Cl. loxy, lower alkenyl, lower alkynyl, haloalkyl, haloalkoxy, A 6LX3/59 (2006.01) NO, CN, lower alkoxycarbonyl, lower alkylcarbonyl, lower (52) U.S. Cl. alkyl-SO and aldoximes and lower alkyloximes, optionally USPC ........................................ 514/262.1; 544/257 Substituted on oxygen by lower alkyl. Z is H, a C-C single bond, CH, NH, O, S, CN, CHO, OCH, CHCHO, or (58) Field of Classification Search OCHCH: m is 4; p is 0 or 1; q is an integer from 0 to 2: R' USPC ........................................ 514/262.1544/257 is independently H, halo, lower alkyl, lower alkenyl, lower See application file for complete search history. alkynyl, hydroxy, lower alkoxy, haloalkyl, haloalkoxy, NO, (56) References Cited CN, lower alkylcarbonyl, lower alkoxycarbonyl, mercapto, lower alkylthio, aldoximes and lower alkyloximes, optionally U.S. PATENT DOCUMENTS substituted on oxygen by lower alkyl: Y is a C C single 5,034,393 A * 7/1991 Hackler et al. ............. 514,262.1 bond, C(R)O or C(R); n is 2. * cited by examiner 9 Claims, No Drawings US 8,461,164 B2 1. 2 PTERIDINES AND THEIR USE AS X is H, halogen or lower alkyl; and AGROCHEMICALS X is H. halogen or lower alkyl: with the proviso that when Y is C(R.), R, and R', may be FIELD OF THE INVENTION taken together to form 5 The present disclosure relates to 1- or 2-(4-(aryloxy)-phe nyl)ethylamino-, oxy- or Sulfanyl)pteridines and 1- or 2-(4- R (heteroaryloxy)-phenyl)ethylamino-, oxy- or Sulfanyl)pte SA ridines and their use as agrochemicals and animal health XI products. 10 R N BACKGROUND AND SUMMARY N1 SN 2-R, The present disclosure provides novel organic compounds 2 als that may demonstrate activity as pesticides, meaning that they X2 N N X3 may control fungi, insects, mites, and/or animal parasites. 15 The disclosure also provides novel pesticide methods and The invention also provides new compounds of formula compositions utilizing the novel compounds. (I-B): More specifically, the invention provides new compounds of the formula (I-A): I-B R, I-A R, -- Y R'm 25 R N XI C N n N N X 1. R X2 N 2 Nals 2 als 30 X2 N N X3 wherein: R is H, CH, haloalkyl, phenyl, or a heterocycle comprising wherein: a 5 or 6 membered single ring or a fused ring system com R is H, CH, phenyl, or a heterocycle comprising a 5 or 6 prising at least one 5 or 6 membered heterocycle optionally membered single ring or a fused ring system comprising at 35 substituted with H, halo, lower alkyl, lower alkoxy, benzy least one 5 or 6 membered heterocycle optionally substituted loxy, lower alkenyl, lower alkynyl, haloalkyl, haloalkoxy, with H, halo, lower alkyl, lower alkoxy, benzyloxy, lower NO, CN, lower alkoxycarbonyl, lower alkylcarbonyl, lower alkenyl, lower alkynyl, haloalkyl, haloalkoxy, NO, CN, alkyl-SO aldoximes and lower alkyloximes, optionally sub lower alkoxycarbonyl, lower alkylcarbonyl, lower alkyl-SO. stituted on oxygen by lower alkyl; and aldoximes and lower alkyloximes, optionally Substituted 40 Z is H, a C-C single bond, CH, NH, O, S, CN, CHO, on oxygen by lower alkyl. OCH, CHCHO, or OCHCH: Z is H, a C-C single bond, CH, NH, O, S, CN, CHO, m is 4: OCH, CHCHO, or OCHCH: p is 0 or 1: m is 4: q is an integer from 0 to 2: p is 0 or 1; 45 R" is independently H, halo, lower alkyl, lower alkenyl, q is an integer from 0 to 2; lower alkynyl, hydroxy, lower alkoxy, haloalkyl, haloalkoxy, R" is independently H, halo, lower alkyl, lower alkenyl, NO, CN, lower alkylcarbonyl, lower alkoxycarbonyl, mer lower alkynyl, hydroxy, lower alkoxy, haloalkyl, haloalkoxy, capto, lower alkylthio, aldoximes and lower alkyloXimes, NO, CN, lower alkylcarbonyl, lower alkoxycarbonyl, mer optionally substituted on oxygen by lower alkyl; capto, lower alkylthio, aldoximes and lower alkyloximes, 50 Y is a C C single bond, C(R)O or C(R): optionally substituted on oxygen by lower alkyl; n is 2: Y is a C-C single bond, C(R.)O or C(R.); alternatively R', Z, and R may be taken together to form n is 2: a fused 5 or 6 membered heterocycle optionally substituted alternatively R' Z, and R may be taken together to form with H, halo, lower alkyl, lower alkoxy, benzyloxy, lower a fused 5 or 6 membered heterocycle optionally substituted 55 alkenyl, lower alkynyl, haloalkyl, haloalkoxy, NO, CN, with H, halo, lower alkyl, lower alkoxy, benzyloxy, lower lower alkylcarbonyl, lower alkoxycarbonyl and lower alkyl alkenyl, lower alkynyl, haloalkyl, haloalkoxy, NO, CN, SO; lower alkylcarbonyl, lower alkoxycarbonyl and lower alkyl R are independently H or lower alkyl SO; R" is H. halogen, lower alkyl, lower alkoxy or lower R are independently H or lower alkyl: 60 haloalkyl: R is H. halogen, lower alkyl, lower alkoxy or lower Rare independently H or lower alkyl haloalkyl: X is NR, O, and S, where R is selected from H. lower Rare independently H or lower alkyl: alkyl, lower alkylcarbonyl, lower alkoxycarbonyl, hydroxy, X is NR, O, and S, where R is selected from H. lower lower alkoxy, lower alkyl-SO phenyl-SO, or substituted alkyl, lower alkylcarbonyl, lower alkoxycarbonyl, hydroxy, 65 phenyl-SO. lower alkoxy, lower alkyl-SO phenyl-SO, or substituted X is H. halogen or lower alkyl; and phenyl-SO. X is H, halogen or lower alkyl: US 8,461,164 B2 3 4 with the proviso that when Y is C(R), R, and R', may be optionally substituted pyridinyl taken together to form R'm SA XI Nueré 4 2x R NN 1, 10 optionally substituted pyrazinyl X2 N 2 N1. X3 The invention also provides new pesticide methods and R7 compositions utilizing the compounds of formula (I-A) and 15 1 compounds of formula (I-B). The invention includes fungicidal, insecticidal, acaricidal, and anti-parasitic compositions comprising an effective amount of a compound of the present invention in a mixture with an agriculturally acceptable orpharmaceutically accept optionally substituted pyrimidinyl able adjuvant or carrier. The invention also includes methods of controlling a fungus, insect, mite, or parasite comprising applying an effective amount of a compound of the present invention to the fungus, insect or mite, Soil, plant, root, foli 25 age, seed, locus, or animal (for which purpose they may be administered orally, parenterally, percutaneously or topi cally) in which the infestation is to be prevented or cured. DETAILED DESCRIPTION OF THE INVENTION 30 optionally substituted pyridazinyl The compounds of the present invention are directed to compounds of formula (I-A) and (I-B) nSA SN 35 - H 14. 2 I-A 2N !--R - - optionally substituted thiazolyl 40 R N XI C.S. X2 C% % X3 - 45 50 optionally substituted 1,2,3-thiadiazolyl I-B R V 55 f QNS R N XI CN N1 NN NS-R, optionally substituted 1,2,4-thiadiazolyl 60 Wherein p is 1 and R may be an optionally substituted phenyl or a heterocycle comprising a 5 or 6 membered single ring or a fused ring system comprising at least one 5 or 6 membered 65 heterocycle. More specifically, R may be selected from the list including but not limited to: US 8,461,164 B2 5 6 optionally substituted 1,3,4-thiadiazolyl The term “haloalkoxy' refers to lower alkoxy groups sub stituted with one or more halo atoms. The term “substituted phenyl refers to phenyl substituted N -N--R, with lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, lower alkylthio, halo, hydroxy, NO, haloalkyl, haloalkoxy, Q S 3) haloalkylthio, CN, phenyl, substituted phenyl, O-phenyl, O-substituted phenyl, C-C alkanoyloxy, C-C alkoxycar as well as pyridinyl-N-oxide, thienyl, furyl, oxazolyl, isox bonyl, lower alkylcarbonyl, benzyloxy, or and lower alkyl azolyl, isothiazolyl, oxadiazolyl, furazanyl, pyrrolyl pyra 10 SO, and q is an integer from 0 to 2. Zolyl, and imidazolyl, where r is 4 in the case of pyridinyl, 3 The term “fused ring system” refers to two rings joined, as defined in Moss, G.