United States Patent (19) 11 Patent Number: 5,034,393 Hackler et al. (45) Date of Patent: Jul. 23, 1991 54 FUNGICIDALUSE OF OTHER PUBLICATIONS PYRIDOPYRIMIDINE, PTERIDINE, PYRIMIDOPYRIMIDINE, Sankyo Co., Chemical Abstracts, vol. 94: 1068f and PYRIMIDOPYRIDAZINE, AND attached 10th collected index, p. 46420CS. PYRIMIDO-1,2,4-TRIAZINE DERIVATIVES E. C. Taylor et al., 82 J.A.C.S. 5711-5718 (1960). S. Nishikawa et al., 50 Agric. Biol. Chem., 2243-2249 75) Inventors: Ronald E. Hackler, Indianapolis; (1986). Glen P. Jourdan, Morristown, both S. Nishikawa et al., 50 Agric. Biol. Chenn., 495-497 of Ind. (1986). H. Iwamura et al., 28 J. Med. Chem, 577-583 (1985). Derwent Abst. 86-001 168/01 (1986) abstracting EP (73) Assignee: Dowelanco, Indianapolis, Ind. 165,572A. Derwent Abst. 80-70448C/40 (1980) abstracting JP (21) Appl. No.: 385,840 55108806. (22 Filed: Jul. 27, 1989 Primary Examiner-Mukund J. Shah Assistant Examiner-M. V. Grumbling 51) Int. Cl. ............................................. A01N 43/90 Attorney, Agent, or Firm-Donald R. Stuart 52 U.S. Cl. .................................... 514/258; 514/249; 57 ABSTRACT 514/248; 514/63; 514/278; 544/257; 544/258; Fungicidal compositions contain as active ingredient a 544/256; 544/238; 544/279 4-substituted-pyrido3,2-dipyrimidine, -pyrido4,3- (58) Field of Search ................. 514/249, 258, 248, 63, d)pyrimidine, -pyrido3,4-dpyrimidine, pyrido 2,3- 514/278; 546/345; 544/257, 258, 256, 238,279 dlpyrimidine, -pteridine, -pyrimido-4,5-d)pyrimidine, -pyrimido-4,5-cpyridazine, -pyrimido5,4-d)pyrimi (56) References Cited dine, -pyrimido5,4-c)pyridazine, pyrimido-4,5- U.S. PATENT DOCUMENTS d)pyridazine, or -pyrimido5,4-e-1,2,4-triazine, for ex ample 4-2-(4-chlorophenyl)ethoxypyrido2,3- 4, 101,554 7/1989 Tobin ........................... 260/290 HC d)pyrimidine. FOREIGN PATENT DOCUMENTS 920267 5/1959 United Kingdom ................ 544/257 40 Claims, No Drawings 5,034,393 1 2 (C3-C4) branched alkyl, phenyl, or substituted phenyl, FUNGICIDALUSE OF PYRIDOPYRIMIDINE, and optionally substituted with (C1-C4) alkyl, (C2-C4) PTERIDINE, PYRIMIDOPYRIMIDINE, alkenyl or -alkynyl, branched (C3-C7) alkyl, C3-C7) PYRIMIDOPYRIDAZINE, AND cycloalkyl or -cycloalkenyl, halo, hydroxy, or acetyl, PYRIMIDO-1,2,4-TRIAZINE DERIVATIVES 5 and Z is FIELD OF THE INVENTION (a) a C1-C12 saturated or unsaturated hydrocarbon This invention provides new compounds that have chain, straight chain or branched optionally including a excellent plant fungicide activity. Some of the com hetero atom selected from O, S, SO, SO2, or SiR20R21, pounds have also demonstrated insecticidal and mitici 10 dal activity. The invention also provides compositions where R20 and R2 are as defined above and optionally and combination products that contain a compound of substituted with halo, halo (C1-C4) alkoxy, hydroxy, the invention as active ingredient, as well as providing (C3-C8) cycloalkyl or cycloalkenyl, or (C1-C4) acyl; fungicidal, miticidal, and insecticidal methods. (b) (C3-Cs) cycloalkyl or cycloalkenyl, optionally There is an acute need for new fungicides, insecti 15 substituted with (C1-C4) alkyl, (C1-C4) alkoxy, halo cides, and miticides, because target pathogens are rap (C1-C4) alkyl, halo (C1-C4) alkoxy, halo, hydroxy, or idly developing resistance to currently used pesticides. (C1-C4) acyl; Widespread failure of N-substituted azole fungicides to (c) a phenyl group of the formula (2) control barley mildew was observed in 1983, and has been attributed to the development of resistance. At 20 least 50 species of fungi have developed resistance to (2) the benzimidazole fungicides. The field performance of DMI (demethylation inhibitor) fungicides, which are now widely relied on to protect cereal crops from pow dery mildew, has declined since they were introduced 25 in the 1970's. Even recently introduced fungicides, like the acylalanines, which initially exhibited excellent con trol of potato late blight and grape downy mildew in the where field, have become less effective because of widespread R6 to R10 are independently H, halo, I, (C1-C10) alkyl, resistance. Similarly, mites and insects are developing 30 resistance to the miticides and insecticides in current (C3-C8) alkenyl or -alkynyl, branched (C3-C6) alkyl, use. Resistance to insecticides in arthropods is wide -alkenyl, or -alkynyl, (C3-C8) cycloalkyl or -cycloalke spread, with at least 400 species resistant to one or more nyl, halo (C1-C7) alkyl, (C1-C7) alkoxy, (C-C7) alkyl insecticides. The development of resistance to some of thio, halo (C1-C7) alkoxy, phenoxy, substituted phe the older insecticides, such as DDT, the carbamates, 35 noxy, phenylthio, substituted phenylthio, phenyl, sub and the organophosphates, is well known. But resis stituted phenyl, NO2, acetoxy, OH, CN, SiR11R2R3, tance has even developed to some of the newer pyre OSiR 11R12R13, NR14R15, S(O)R16, or SOR17 where throid insecticides and miticides. Therefore a need ex Ril, R12, and R3 are independently (C1-C4) alkyl, ists for new fungicides, insecticides, and miticides. (C3-C4) branched alkyl, phenyl, or substituted phenyl, 40 R“ and R1s are independently H, (C1-C4) alkyl, or SUMMARY OF THE INVENTION (C3-C4) acyl, and R6 and R 7 are (C1-C10) alkyl, This invention provides compounds of the formula phenyl, or substituted phenyl; (1): (d) a furyl group of formula (3) 45 X-Y-Z (1) (3) 2. N O s N 2. 50 where R8 is H, halo, halomethyl, CN, NO2, (C1-C4) wherein alkyl, (C3-C4) branched alkyl, phenyl, or (C1-C4) alk one or two of A, B, E, or D are N, and the others are Oxy; CR1 or A, E, and D are N and B is CR; where R and (e) a thienyl group of the formula (4) R2 are independently H, halo, (C1-C4) alkyl, (C3-C4) 55 branched alkyl, (C1-C4) alkoxy, halo (C1-C4) alkyl, (4) phenyl, or substituted phenyl; X is O, S, SO, SO2, NR3, or CR“R5, where R3 is H, (C1-C4) alkyl, or (C1-C4) acyl, and R and Rare inde S pendently H, (C1-C4) acyl, (C1-C4) alkyl, (C2-C4) alke nyl or -alkynyl, CN, or OH, or R* and R5 combine to where R8 is as defined in paragraph (d); form a carbocyclic ring containing four to six carbon (f) a group of formula (5) or (6) atoms; Y is a bond or an alkylene chain one to six carbon (5) atoms long, optionally including a carbocyclic ring, and 65 optionally including a hetero atom selected from O, NR3, S, SO, SO2, or SiR20R2, where R3 is as defined sy." above and R20 and R2 are independently (C1-C4) alkyl, 5,034,393 3 4. (l) to (3), in combination with a second insecticide or -continued Initicide. (6) The insecticide and Initicide compositions of the in vention comprise an insect- or mite-inactivating amount of a compound of formula (), including compounds of provisos (1) to (3), in combination with a carrier. Such where R8 is as defined in paragraph (d), J is N or CH, compositions may optionally contain additional active and G is O, NR19, or S, provided that if J is not N then ingredients, such as an additional fungicidal, miticidal, G is NR19, where R19 is H., (C1-C4) alkyl, (C1-C4) acyl, or insecticidal ingredient. phenylsulfonyl, or substituted phenylsulfonyl; 10 The insecticidal or miticidal method of the invention (g) a group selected from comprises applying to the locus to be protected an in optionally substituted naphthyl, dihydronaphthyl, sect- or mite-inactivating amount of a compound of tetrahydronaphthyl, and decahydronaphthyl; formula (1), including compounds of provisos (1) to (3), or of a combination described above. optionally substituted pyridyl; 15 optionally substituted indolyl; DETAILED DESCRIPTION OF THE and 1,3-benzodioxolyl; INVENTION or an acid addition salt of a compound of formula (1); provided that the following compounds are excluded: Throughout this document, all temperatures are 1) pyrido2,3-dipyrimidines of formula (1) wherein X given in degrees Celsius, and all percentages are weight is NR3 and -Y-Z is benzyl, or X is NR3, Y is an 20 percentages unless otherwise stated. alkylene chain containing an O or Saton adjacent to Z, The term "halo' refers to a F, C, or Br atom. The term "(C1-C7) alkoxy' refers to straight or and Z is either unsubstituted phenyl or a substituted branched chain alkoxy groups. phenyl group other than one substituted with The term "(C1-C7) alkylthio" refers to straight and branched (C3-C6) alkyl, 25 halo (C1-C4) alkyl, branched chain alkylthio groups. halo (C1-C4) alkoxy, The term "halo (C1-C7) alkyl" refers to a (C1-C7) phenyl, alkyl group, straight chain or branched, substituted with one or more halo atoms. substituted phenyl, The term "halo (C1-C7) alkoxy' refers to a (C1-C7) phenoxy, 30 alkoxy group substituted with one or more halo groups. substituted phenoxy, The term "halo (C1-C4) alkylthio" refers to a (C1-C4) phenylthio, alkylthio group, straight chain or branched, substituted substituted phenylthio, with one or more halo atoms. SiR11R12R13, or The term "substituted phenyl" refers to phenyl sub OSiR11R12R13; 35 stituted with up to three groups selected from halo, I, 2) pyrido 3,4-dpyrimidines of formula (1) wherein X (C1-C10) alkyl, branched (C3-C6) alkyl, halo (C1-C4) is NR3, Z is unsubstituted phenyl, and R is methyl; and alkyl, hydroxy (C1-C4) alkyl, (C1-C4) alkoxy, halo 3) pyrido3,4-dipyrimidines of formula (1) wherein X (C1-C4) alkoxy, phenoxy, substituted phenoxy, phenyl, is NR3 and -Y-Z is benzyl or isoamyl. substituted phenyl, NO2, OH, CN, (C1-C4) al Proviso (1) excludes compounds that are described as 40 kanoyloxy, or benzyloxy. fungicides in Japanese patent application 55108806 of The terms "substituted naphthyl', 'substituted pyri Sankyo.