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(12) United States Patent (10) Patent No.: US 6,274,536 B1 Nebel Et Al

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(12) United States Patent (10) Patent No.: US 6,274,536 B1 Nebel Et Al USOO62745.36B1 (12) United States Patent (10) Patent No.: US 6,274,536 B1 Nebel et al. (45) Date of Patent: Aug. 14, 2001 (54) PYRAZOLE DERIVATIVES AS HERBICIDES Tetrahedron Lett. 36(49), 8917 (1995); idem. 31(14), 1965 (1990). (75) Inventors: Kurt Nebel, Hochwald; Alain De Bull. Soc. Chim. Fr. 1953, 1001, in French language (the Mesmaeker, Kaenerkinden, both of english language abstract is also enclosed). (CH); Jirgen Schaetzer, Rheinfelden Heterocycles 30(2), 875 (1990). (DE) Can. J. Chem. 31, 457 (1953). (73) Assignee: Syngenta Crop Protection, Inc., J. Chem. Soc. 1939, 1858. Greensboro, NC (US) J. Het. Chem. 25, 511 (1988); idem. 22, 268 (1985). J. prakt. Chem. 330, 293 (1988); idem. 334, 119 (1992). (*) Notice: Subject to any disclaimer, the term of this Chem. Ber. 62,2732 (1929) (the english language abstract patent is extended or adjusted under 35 is also enclosed). U.S.C. 154(b) by 0 days. Chem. Heterocycl. Compd. (Engl. Transl.) 1988, 658. (21) Appl. No.: 09/380,678 Pharmazie 45,731 (1990) (the english language abstract is also enclosed). (22) PCT Filed: Mar. 19, 1998 (List continued on next page.) (86) PCT No.: PCT/EP98/O1611 Primary Examiner Jane Fan S371 Date: Sep. 7, 1999 (74) Attorney, Agent, or Firm William A. Teoli, Jr. S 102(e) Date: Sep. 7, 1999 (57) ABSTRACT (87) PCT Pub. No.: WO98/42698 Compounds of the following formula I PCT Pub. Date: Oct. 1, 1998 (30) Foreign Application Priority Data (I) Mar. 21, 1997 (CH) ..................................................... 695/97 (51) Int. Cl. .......................... A01N 43/40; CO7D 401/04 (52) U.S. Cl. ....................... 504/252; 504/246; 546/275.4; 546/276.1; 54.6/113; 54.6/115 (58) Field of Search .............................. 546/275.4, 276.1; 504/252 (56) References Cited wherein U.S. PATENT DOCUMENTS W is a group 2,742,476 4/1956 Bernstein et al. (W1) 2,809,971 10/1957 Bernstein et al. 3,047,579 7/1962. Witman. 4,526,895 7/1985 Jarreau et al. ....................... 514/341 5,032,165 7/1991 Miura et al. ........................... 546/22 FOREIGN PATENT DOCUMENTS O 361 114 4/1990 (EP). (W2) WO 92/O2509 2/1992 (WO). WO 92/06962 4/1992 (WO). S(O) R, or WO95/33728 12/1995 (WO). WO 96/O1254 1/1996 (WO). 97/00246 1/1997 (WO). OTHER PUBLICATIONS (W3) Org. Synth. 4,828 (1963); idem. 3,619 (1955). B. Iddon and H. Suschitzky in “Polychloroaromatic Com pounds”, Editor H. Suschitzky, Plenum Press, London 1974, p. 197. Quart. Rev. 10, 395 (1956). J. Am. Chem. Soc. 85,958 (1963); idem. 73,3681 (1951); idem. 72, 4362 (1950). J. Am. Chem. 26, 428 (1961); idem. 35,2517 (1970); idem. wherein all variables are as defined in the Specification and 32, 4040 (1967); idem. 19, 1633 (1954); idem. 54, 4330 the pyrazoleN-oxides, agrochemically acceptable Salts and (1989). Stereisomers thereof useful as herbisdes. Tetrahedron 37, 187 (1981); idem. 1991, 7091. Org. Prep. Proced. Int. 9(1), 5-8 (1977). 6 Claims, No Drawings US 6,274,536 B1 Page 2 OTHER PUBLICATIONS “Methoden der Organischen Chemie” (Houben-Weyl), vol. J. Chem. Soc., Perkin Trans I 1976, 201; idem. 1987, 1159. E 8b, Georg Thieme Verlag Stuttgart, 1994, p. 399ff, idem. Liebigs Ann. Chem. 1978, 1491 (english language abstract vol. E 7B, Georg Thieme Verlag Stuttgart 1992, p. 286 ff also enclosed). Helv. Chim. Acta 73, 1679 (1990) (english language abstract (english language abstracts of each are enclosed). also enclosed). II Farmaco-Ed. Sc. 37, 22 (1982). Sov. Prog. Chem. (Engl. Transl.) 42, 65 (1976). J. Chem. Res. (Miniprint) II, 3368 (1986) (english language abstract also enclosed). * cited by examiner US 6,274,536 B1 1 2 PYRAZOLE DERVATIVES AS HERBICIDES Rs is hydrogen, halogen, C-C alkyl, C-Chaloalkyl, cyano, nitro, amino, NHC(O)-, NHC(S)-, This application is a 371 of PCT/EP98/01611 filed Mar. C-C alkylcarbonyl, C-C alkoxy carbonyl, 19, 1998. C-Chalo alkylcarbonyl, C-C alkenylcarbonyl, The present invention relates to novel, herbicidally active 5 C-C alkyl-CH(OH), OHC , HOC(O), CIC(O), Substituted pyridone derivatives, to a process for the prepa HON=CH-, C-C alkoxy-N=CH-, ration thereof, to compositions comprising those C-Chaloalkenylcarbonyl or C-C alkynylcarbonyl, compounds, and to the use thereof in the control of weeds, R is hydrogen, fluorine, chlorine, bromine or methyl, especially in crops of useful plants, for example, cereals, R is hydrogen, halogen, methyl, halomethyl, nitro, amino, maize, rice, cotton, Soybean, rape, Sorghum, Sugar cane, hydroxy, OHC-, HOC(O)-, cy an O, Sugar beet, Sunflowers, vegetables, plantation crops and C-C alkoxycarbonyl or halomethoxy, fodder plants, or in the inhibition of plant growth. Phenyl X is O, S, RN= or RON=; pyrazole compounds having herbicidal activity are known R is hydroxy, C-C alkoxy, Ca-Calkenyloxy, and are described, for example, in EP-A-0361114, U.S. Pat. C-C alky nyloxy, C-Chalo alkoxy, C-C- No. 5,032,165, WO 92,02509, WO 92,06962, WO haloalkenyl oxy, C-C alkoxy - C - Calkyl, 95/33728, WO 96/O1254 and WO 97/00246. 15 C-C alkenyloxy-C-C alkyl, C-C alkynyloxy Surprisingly, it has now been found that Substituted C-C alkyl, C-C alkoxy-C-Calkoxy-C-C alkyl, pyridono-pyrazole derivatives have excellent herbicidal and B-C-C alkoxy, R (R) N-, C-C alkyl, growth-inhibiting properties. C-C alkenyl, C-C alkynyl, C-Chaloalkyl, The present invention accordingly relates to compounds C - Chaloalkenyl, C - Cecy cloalkyl, of formula I 20 C-Chalocycloalkyl, B-C-C alkyl, OHC-, C-C alkylcarbonyl, C-C alkylcarbonyloxy, (I) C-Chalo alkylcarbonyl, C-C alkenylcarbonyl, R11 C-C alkoxy carbonyl, C-C alkyl-S(O)2-, C-Chaloalkyl-S(O) , (C-Calkyl)-N-N=CH-, R12 / \ W, 25 C - Calkyl N V D-CH-, O s X1 R13 O CH 3O wherein B-CH=N-, (CH) N-CH=N-, (C-C shy droxyalkyl)-CH-, (B- C-C hydroxyalkyl)-CH-, (B-C-Chaloalkyl)- W is a group CH-, (hydroxy-C-C alkyl)-O- or (B- (W1) 35 C-C hydroxyalkyl)-O-, R B is cyano, OHC-, HOC(O), C-C alkylcarbonyl, O n C-C alkoxycarbonyl, C-C alkenyloxycarbonyl, R2, C-C alkynyloxycarbonyl, benzyloxycarbonyl, benzy N 2-N loxycarbonyl mono- to tri-Substituted at the phenyl ring R1 40 by halogen, C-C alkyl or by C-Chaloalkyl, (W2) benzylthio-C(O), benzylthio-C(O)- mono- to tri Substituted at the phenyl ring by halogen, C-C alkyl or R by C-Chaloalkyl, C-Chaloalkoxycarbonyl, S(O)n-R4 or C-Calkylthio-C(O), R(R)NC(O), phenyl, phe 45 nyl mono- to tri-Substituted by halogen, C-C alkyl or by N -N C-Chaloalkyl, C-C-alkyl-S(O)-, C-C alkyl-S R1 (O)-, C-Calkylthio, C-C cycloalkyl, C-Calkoxy, (W3) C-Calkenylthio or C-Calkynylthio; R Ro is hydrogen, C-Calkyl, C-Calkenyl, C-Calkynyl, R5; 50 C2 - Chalo alkyl, cyano, R - (R) N-, C-C alkoxycarbonyl, C-C alkenyloxycarbonyl, C-C alkynyloxycarbonyl, C-Chaloalkoxycarbonyl, 2-N N OHC , C-Calkylcarbonyl, C-Chaloalkylcarbonyl, R1 C-Calkyl-S(O)-, C-Chaloalkyl-S(O)-, phenyl, 55 phenyl mono- to tri-Substituted by halogen, C-C alkyl or R is hydrogen, C-C alkyl, C-Chaloalkyl, cyano by C-Chaloalkyl, phenyl-C-C alkyl, or phenyl C-C alkyl, C- or C-alkenyl, C- or C-haloalkenyl, C C-Calkyl mono- to tri-Substituted at the phenyl ring by or C-alkynyl or C-Cacycloalkyl, halogen, C-C alkyl or by C-Chaloalkyl, R is hydrogen, C-C alkyl, C-Chaloalkyl, C-Calkenyl, R and R are each independently hydrogen, C-C alkyl, C-Chaloalkenyl, C-C alkynyl, C-C alkyl-S(O)- 60 C-C alkenyl, C-C alkynyl, C-C-haloalkyl, or C-Chaloalkyl-S(O) ; C-Chaloalkenyl, C-C cycloalkyl, C-Calkoxy R is hydrogen, C-C alkyl, C-Chaloalkyl, C-Calkenyl, C-C alkyl, OHC-, C-C alkyl carbonyl, C-Chaloalkenyl, C-C alkynyl, halogen, cyano, NHC C-Chaloalkylcarbonyl, C-C alkyl-S(O)- or (S)-, nitro or amino; C-Chaloalkyl-S(O)-; n is 0, 1 or 2, 65 R2 and R2 are each independently as defined for R; R is hydrogen, C-C alkyl, C-Chaloalkyl, C-Calkenyl, Rs is hydrogen, C-Calkyl, C-Calkenyl, C-Calkynyl, C-Chaloalkenyl, C-Calkynyl or C-Cacycloalkyl, C-Chaloalkyl, C-Chaloalkenyl, C-C alkoxy US 6,274,536 B1 3 4 C-C alkyl, benzyl, C-C alkyl-S(O)2- or and also to the pyrazole N-oxides, agrochemically accept C-Chaloalkyl-S(O)-; able Salts and Stereoisomers of those compounds of formula R and R27 are each independently hydrogen, C-C alkyl, I. C-C alkenyl, C-C alkynyl, C-Chalo alkyl, In the above definitions, halogen is to be understood as C-Chaloalkenyl, phenyl, phenyl mono- to tri meaning iodine or, preferably, fluorine, chlorine or bromine. Substituted by halogen, C-C alkyl or by C-Chaloalkyl, The alkyl, alkenyl and alkynyl groups in the Substituent benzyl, or benzyl mono- to tri-substituted at the phenyl definitions may be Straight-chain or branched, this applying ring by halogen, C-C alkyl or by C-Chaloalkyl, or also to the alkyl, alkenyl and alkynyl moiety of the X and R together form a group =N-Y- wherein Y is alkylcarbonyl, hydroxyalkyl, cyanoalkyl, alkoxyalkyl, bonded to the ring nitrogen atom; alkoxyalkoxyalkyl, alkylthio, alkylthio-C(O)-, alkylsulfonyl, alkylaminocarbonyl, dialkylaminocarbonyl, B-alkyl and HOC(O)-alkyl groups. Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, Sec butyl, isobutyl, tert-butyl and the various isomers of pentyl and hexyl.
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