2) United States Patent Tsukamoto et al. US007964531B2 US 7,964,531 B2 *Jun. 21, 2011 (10) Patent No.: 4s) Date of Patent: (54). 3 PHENOXY-4-PYRIDAZINOL DERIVATIV ‘AND HERBICIDAL COMPOSITION CONTAINING THE SAME (75) lnventors: Yoshihisa Tsukamoto, Shige (1) Hiroyuki Komai, Shiga (JP), Jun Kadotani, Shiga (IP) Kiyoshi Koi, Shiga (IP): Shigeru Mio, Shiga JP) ideo Takeshiba, Tokyo UP) Assignee: Mitsul Chemleals Agro, Ine, Tokyo (P) (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 USC. 154(b) by 0 days This patent is subject to a temninal dis claimer. (21) Appl. Nos 120883,324 (22) Filed: Aug. 18,2009 6) Prior Publication Data US 201010081555.A1 Feb, 18,2010 Related US. Application Data (6) Contiavation of application No. 10/487,013, fled as application No, PCT/JP02/08278 on Aug. 14, 2002, ‘now Pat. No, 7.608.563, 60) Foreign Application Priority Data Avg. 17, 2001 (UP) Mar.25, 2002 (UP) 2001-248014 2002-082219 (51) Int.ct ADIN 43/58 (200601) co7D 40512 (2005.01), 07D 23716 (200601) (52) US.C. -... SOM/I37; 504/238; 544/238; 584/240 (58) Field of Classification Search 504/137, 504/225, 238; S4/114, 238, 239, 240 See application file for complete search history J (56) Referenees Ci US. PATENT DOCUMENTS: 4.661496 A 411987 ‘Takes etal SSS9080 A 91996 Southet ‘7608563 B2* 102009 Teukamod otal... SO422S FOREIGN PATENT DOCUMENTS. Be 0.470856 AL ® os264575 A. 21992 11998 (OTHER PUBLICATIONS PM, Harington et al, “Synthesis and Hesbicial Activity of ypsin, Journal of ricultural and Food Chemisty, vl 43,No. 3. pp 804-808 (1995), Teniomi oma ctl ,"Pyridarine Novel nramolecular Coa Aiton of 3-Chioo-6<2-allylphenoxypytizines", Chem. Pharm Bull, 1972, vo. 20, No, 10, pp. 2191-2203, Dold E-Ames ea, “tl -)Benzodioninopyiazines”, Journal of the Chemica Soc Peskin Transaction], 1978, No. 6p. S38 The Pesticide Mamet, 11 Edition, CDS. Tomlin editor pp. L110 112.pp. 1049 1 1050, and pp, 1084 fo 1088 (1997 The Pesticide Manual, 12° Fiton, DS. Torin, elitr, pp. 6 S64, pp. 642-644 and pp 846-849 (2000), * cited by examiner Kamal A Saved Kristin Bianchi Holtz Holtz Goodman & Primary Examiner Assistant Examiner (74) Auornes, Agent, or Firm Chick PC on ABSTRACT A compound represented by the formula O, o, x [wherein RR represents a hydrogen atom, 2 halogen atom, alkyl group, ee represents @ hydrogen atom, » halogen stom, alkyl group, ete RY, RY, RY R® and R” cach independently represent a fnydrogen atom, a halogen atom, a substitutable alkyl soup, a substitutable alkenyl group, alkynyl group, a substitutable eycloalky! group, ete, or R°, R*, RE RP and R” may forma ing which may be substituted, which is formed by the adjacent two of them with earbon atoms to which the respective substituents are bonded, ‘mand n each independently represent Oor 1. sal thereof, an ester derivative thereof and an agricultural chemical containing the same as an efletive ingredient, and «herbicidal composition containing the compound and a secondlierbicidally ative compound asefectve ingredients 34 Claims, No DrawingsUS 7,964,531 B2 1 3-PHENONY-+-PYRIDAZINOL DERIVATIVES AND HERBICIDAL COMPOSITION CONTAINING THE SAME (CROSS-REFERENCE TO RELATED. "APPLICATIONS ‘This application is a Continuation application of applica- tion Ser. No, 10/487,013 filo Feb. 27, 2004 (U'S. Pa No. 7,608,563), which is the United States national phase apli- cation under 35 USC 371 of International application PCT! 4370208278 fled Aug. 14, 2002. The entire contents of each ‘of Ser. No, 10/487,013 and PCT/1P0208278 are incorporated by reference herein, ‘TECHNICAL FIELD ‘The present invention relates toa 3-phenoxy-4-pyridazinol ‘compound is salt, its ester derivative and agricultural chemi- cal containing the same as an effective ingredient, and a herbicidal composition containing 3-phenoxy-4-pyridazinol ‘compound and a second herbicidally active compound as, cefletve ingredients. BACKGROUND ART In Chemical Pharmaceutical Bulletin, 1972, vo. 20, No 10, pp. 2191-2208, 3-2-llylphenoxy)-6-chloro-4-methoxy~ pytidavine has been disclosed but 3-phenoxy-4-pyridazinol ‘compound having a hydroxyl group a the 4-position ofthe pytidazine has not heen disclosed, and there is no description about a herbicide, ‘In Journal ofthe Chemical Society: Perkin Transaction I, 1975, No. 6, pp. $34-538, 3-(shydroxyphenoxy)-4-meth- ‘oxypyridazine and 6-chloro-3-(2-hydroxyphenoxy}-4-meth- “oxypyridazine has been diselosed but a 3-phenoxy-4-py- Fidazinol_ compound having a hydroxyl group at the 4-position ofthe pyridazine has not been disclosed, and there is no description about a herbicide. In US. Pat. No. 5,559,080, a 3-(phenoxy which may be substtuted)pyrdazine compound having 2 haloalkyl-phe- roxy group atthe 4-posiion ofthe pyridazine has been dis- ‘closed but a 3-phenoxy-4-pyridazinol compound having 3 hydroxyl group atthe 4-position of the pyrdazine has not been disclosed, Also, inthe 3(phenoxy which may be sub- stituted) pyrazine compound having a haloalkylphenoxy group at the 4-postion of the pyridazine, an oxygen atom bonded to the 4-position of the pyridazine is bonded by a benzene ring, and its herbicidal activity was insufficient. Also, at present, a number of herbicides have boen practi- cally used asa herbicide fora paddy field, and widely been used for general purpose asa single agent and 2 mixed agent However, there are many kinds of paddy field weeds, and germination an growth period ofthe respective weeds are not uniform, in particular, occurence of perennial weeds ranges fora long-period oftime. Thus itis extremely dificult to prevent from and kill ll woods with onetime spread of herbicide. Accordingly, as a herbicide, an appearance of a ‘chemical which can kill many kinds of weeds including annual weeds and perennial weeds, that i, which has a wide ‘weed-klling spectrum, is effective for already grown weeds, preventing and killing elfects of weesof which ean be main- ‘ained for a certain period of time, and has high safety 0 paddy rice has earnestly been desire. Aso, a8 upland herbicides, a aumber of herbicides have now been commerially available and practically used, but there are many kinds of weeds to be prevented, and aceur- 4s © 2 rence thereof ranges for a Tong petiod of time, so that a herbicide which has higher herbicidal effects, has broad ‘weed-Killing speetrum, and causes no chemical damage 10 crops has been desired One ofthe effctive ingredient ofthe herbicidal composi tion ofthe present invention (hereinafter refered to a8 a second herbicidally active compound), 4-(2.4-dichlouben- 2y)-1Sedimethy-S-pyrazly-p-tolvenesulfonate (herein. ater referred to as Compound A. General name: Pyrazate, 244-(2.4ichlorbeazoy!)1 3-timethylyrazo-S-ylexy] acetophenone [hereinafter refered to as Compound B, Cen- eral name: Pyrazoxyfen} 2-(4424-dichloro-m-ioluoyl)l,3- dimethylpyrol-5sloxy]--methy-acetophenone [hereinafter refered to as Compound C. General name: Ben- zofenap], Seeyclopropy! 1 2oxazal4-yl ae.cctriftor-2- rmesyl-p-toy! ketone hereinafter reared as Compound D. General name: Isoxaflutole}, 2-(2-chloro-4-mesylbenz0y!) eyclohexan-1.3-tione [hereinafter refered to as Compound , General name; sulctrione}, 2(4mesyl-2-nitrobei0y!) eyclohexan-1,3sHione [herinalerrefemed t0 as Compound F, General name: mesotrioa} and 4chloro-2ethysulfo~ nyl)phenyl S-cyclopropyl-tisoxamlyl Ketone [hereinafter referred to as Compound G. General name: Isxachlorole] are each conventionally known herbicidal compound, and each deseribed in The Pesticide Manual 1th Edition, pp. 104910 1050 Tid, pp. 105410 1085, hid. pp. 11110112. The Pesticide Mann 12h Flition p. 56% Ibid. p, $48, Tip. 02 and EP 470 856 (1990), These compounds have high effec against annual broa-eaved weeds anda part of peren- nial woods, bu ther effects against rice plant weeds ora part of perennial weeds are not necessarily suffice, DISCLOSURE OF THE INVENTION The present inventors have eamestly. studied about pyridazine derivatives having a pienoxy group atthe -posi- tion thereof, and asa result, they have found that a compound having @ hydroxyl group atthe 4-positon ofthe pyridazine ring shows substantially no chemical damage against paddy rice, and shows excellent herbicidal activity against a wide range of weeds in a paddy fled witha low dosage to aecom- plish the present invention. Moreover, they have found that similar herbicidal activities are possessed by an ester deriva- tive thereof in which a bonding between an oxygen stom at the 4-position of the pyrazine ring and an acyl group is cleaved in a soil or ina plant body to be converted into a ‘compound in which a hydrogen atom binds to the oxygen ‘tom, whereby accomplished the present invention. Also, the present inventors have continved to search on & herbicide which can completely prevent and remove various kinds of weeds with one time spread, has extremely high safety to paddy rice or upland rops, and has extremely low ‘oxieity against hamans and animals for the purpose of wver- ‘coming the above-mentioned problems involved in the con- ventional herbicides suchas socond herbicidally active com pounds A, B,C, D,E, Fand G,andas result they have foun that by formulating the above-mentioned 3-phenoxy-4-py- ridazinol derivatives andthe sovond herbicidally active com- pound as effective ingredients, 2 weed-Killing spectrum can be enlarged, and serious weeds can be prevented aad Killed with a smaller amount of effective ingredients by their syn- emtstc action, whereby accomplished the present invention “The present invention relates to-@ compound represented by the formal:US 7,964,531 B2 H a RoR R RS xe o tox Oy [ovheren R? represents hydrogen atom, abalogenatom, aC, ‘0 C, alkyl group, aC, to C, haloalkyl group, a C, to Cy fused with benzene ring. The substivent is a substituent selected from the substituent Group B.)”is“a3- to 6-meme tered heterocyctic group which contains one nitrogen atom, ‘oxygenatom orsulfur atom asa heteroatom, and may contain further I 10 2 nitrogen atoms)” which may be subsiuted by te same or different 110 3 substtvent(s) selected from the roup consisting ofthe above-mentioned “halogen atom”; the above-mentioned “C, 10C,alky group” and the above-men- tioned "C, t0C; haoalks group”, orbya hydroxy group, the shove-mentioned “pbenylsulfonyl group which may be sub- stitmted (The substituent isa substituent selected from the substituent Group A.)" or the above-mentioned “i(C, to C, alkyDsulfamoy! group”, ormay be fused with a benzene ring, preferably “a 3- to G-membered hetemeyclic group which ‘contains one nitrogen atom, oxyzen atom or sll atom asa hetero afom, and may contain father one nitrogen atom” ‘which may be substituted by the same or diferent I- to 2 substituent) selected from the group consisting ofa oorine atom, achlorine atom, abromineatom, aC, oC alkyl group ‘and "aC, 10 alkyl group substituted bythe same or differ ‘ent | t03 substituents) selected from the group consisting of ‘fluorine atom, achlorin tom anda bromine atom, or may be substituted by a hydroxy] group, “a phenysulfony! group ‘which may be substituted by the same or different 1 10 3 substituent(s) selected from the group consisting ofa fvorine atom, achorine toma bromine atom, aC, toC alk group, “aC; toC alkyl group substitute by the same or different 1 to 3 substtuen() selected from the group consisting of @ fluorine atom, acilorine tom anda bromine atom, 8 C, 10 ‘C,cyeloalky group, cyano group anda tri, to C,alky}) sill group” or “a sulfamoyl group to which the same oF diffrent 2C, tC; ally groups are bonded”, ormay be fed with a benzene ring. more preferably an azirine, oxiranyl, ‘oxetanyl, pymolyl, fury, thiensl, pyrazlyl thizols, pyridyl, benzimidazolyl or benzothiazo}yl each of which may be substituted by the same I to 2 substitent(s) selected fromthe group consisting oa chlarineatom, abromine stom, methyl group thy! group and trifluoromethyl group, oF may be substituted by a hydroxyl group, phenylslfonyl group, tolylsulfony group or dimethylsullamey] group tl further preferbly a thieny, pyrazoly, thiszolyl group which may be substituted by the Same oF different Iw 2 substituents) » 0 16 selected fom the sroup consstngofa chlorine atom, methy sroup and triflvoromethy! group. Inthe present invention, “the (C, to C, alkoxy) C, to Cy alkoxy group” isan alkoxy proup having Ito Gcarbon atoms to which an alkoxy group having 1 to 6 carbon atoms is bonded, and for example, it may be a methoxymethoxy, ethoxymethory,_propoxymethoxy, butoxymethoxy, s-bi- toxymethoxy, Fbutoxymethoxy, penyloxymethoxy, hexy- Joxymethoxy, methoryethoxy, ethoxyethony, propoxy- ehony, butoxyethory, methoxypropoxy,methoxybutony, rmethoxypentyloxy or methoxyhexyloxy aroup, preferably an alkoxy group having Ito 3 carbon stoms to which an alkoxy aroup having Ito 3 carbon atoms is substited, more pet erably & methoxyethoxy, ethoxyethoxy or ethoxymethoxy group. Inthe preset invention, “a phenoxy group which may be substituted (The substituents hydroxy] group orapyrdazi- ryloxy group substituted bya substituents) select irom the sroup consisting of halogen stom and a C1 to C6 alkoxy ‘roup.)"is phenoxy group which may be substituted by one hydroxy group,ora phenoxy group substituted hy apyridazi- rayloxy aroup which is substituted by the same or diferet 1 to 3 substtuent(s) selected from the group consisting ofthe shove-mentioned “halogen stom and the above-mentioned "C, to Cy alkoxy group”, preferably a hydroxyphenoxy troup, ora phenoxy group substituted by a pyridazinylony ‘sroup which is substituted by the same or different 1 10 2 Substivent(s)selete fom te group consisting fi rine atom, a chlorine atom, a bromine atom and C, to Cy alkoxy troup, more preferably a phenoxy group substituted by a pyridazinyloxy group which is substituted by each one of @ chlorine atom, and a methoxy or ethoxy group. Inthe preseat inveation, “the So 6-memberedheteroey- cloxy group which may be substituted (the hetereyele eon- ‘aias one nitrogen atom, oxygen atom or sur atom in the ring. and may contain furer 1 or 2 nitrogen atom(s). The substituent is a substituent selected from the substituent Group "is “a S- to 6-membered heterooycloxy group ‘which contains one nitrogen atom, oxygen atom or sulfur stom asa heteroatom, and may contain further to 2itrogen atoms)" which may be substituted by the same or different 1 to 2 substituen(s) selected from the soup consisting ofthe above-mentioned “halogen atom, the above-mentioned "C, tC alkyl group”, the above-mentioned “C) to C Cy alkytsly group.) or the sibstituted pyrazasfoxy aroup (The substituents benzoyl group substituted by two chlo- Fine atoms, and two C,t0C, alkyl groups.) more preferably a chlorine atom, a bromine atom, teiflo- romethy] group ora eyano aroup, sill further preferably a chlorine atom ora bromine atom, panicularly preferably a chlorine atom, (0) Inte present invention, R? is preferably a hydrogen ‘atom, a forine stom, a chlorine atom, a bromine atom, an iodine atom, aC, to, alkyl group. a (C, tC, alkoxy) C, 10 Calls group, a benzoyl group whieh may be substituted {The substituent is the same or different 1 to 2 substituent(s) Selected rom the group consisting fa horine atom, a chlo- rine atom, a bromine atom, 3, t0C, alkyl group, tC haloalkyl group (The halogen atom is the same or diferet 1 to 3 halogen atom(s) selected from the group consisting of a fluorine stom, a chlorine atom anda bromine atom), acyelo- propyl group a cyano group and a tr(C, 40 Cy alkylslyl anup}aC; tC, alkoxycarbonyl group, a phenoxy group ‘which may be substituted {The substituent isthe same or different | to 2 substitven() selected from the group con- sisting ofa oorie atom. achlorin atom, a bromine atom, & C,toCalky group, aC, to haloalkyl group (The halogen ‘atom is the same or different Ito 3 halogen atom(s) selected from the group consisting ofa urine atom, achlorine atom ana bromine ston.) aeyclopropy group, aeyano group and ‘tri; to Cy alkyl)styl group}, 2 phenslthio group which may be substituted {The substituent isthe same or diferent 1 to 2 substtvent(s) selecied from the group consisting of @ fluorine atom, a chorine atom, a bromine atom, 2 C, to Cy aly] group, aC, tC halalky group (The halogen stom i the amor diffrent I 13 halogen atoms) elected fom the ‘grup consisting ofa fhvorine atom, a chlorine atom and a bromine atom.) a eyelopropyl group, a eyano group and a tri(C, 1 C, alkyDsily group.) or a t(C, t0 C, alkyDslyl eroup, more preferably a hydrogen atom, fluorine atom, a chk rineatom,a bromine atom, aniodine atom, amethy| group, an ‘ethoxyearbonyl group ora trimethylsilyl group, still further preferably a hydrogen atom, (6) In the present invention, R®, R*, R, R® and R each independently epreset preferably « hydevgen atom, a fuo- x0 ” 4s 24 rineatom, a chlorine atom, abromine atom, an iodine atom, @ C10 C. alkyl zoup which may be substittod (The subst eat isthe same or different Ito 3 substituents) selected from the goup consisting ofa forine atom, a chlorine atom and a bromine atom, oF a C, to C, exeloalkyl group, a C, 10 Cy alkylthio group or aC, to, alkoxyimino proup.),aC't0C, alkenyl group, aC, tC, alkynyl group, aC; toC eyelalkyl _roup which may be substituted (The substituent isthe same o different 1 0 3 substituent) selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, aC, 10 Cy alky! group, aC to C,eyeloaligl group, cyano group, a, 10, alkoxy group and aC, t0C, alkylthio gtbup.).a Cs toC;bieyeloalkyl group, cyano group,aC 10 C,alkylarbonyl group, a C30 C, alkoxycarbonyl group, @ phenyl group which may be substituted {The substituent isa ffoorne atom, a chlorine atom, a bromine atom, a C, oC, alkyl group oF aC, oC haloalkyl group (Ue halogen stom isthe same or different | to 3 halogen atoms) selected from the group consisting ofa orn atom, a chlorine atom and a bromine stom.)}. a $+ to membered heterocyclic group ‘Which may be substitute {the hetereyeleeontainsone nit gen atom, oxygen atom or sulfur atom in the ring, and may contain further 1 or nitrogen atom). The substituent isthe same or different | 2substtven() selected from the group consisting of a fluorine stom, a chlorine atom, a bromine atom, aC, to, alky] group and aC, 0 C, haloalky! group (The halogen atom is the same or different 110 3 halogen ‘ans) selected from the group consisting of uorine stom, chlorine stom anda bromine atom). anit group, aC, 0 Callony group, aC, tC, haalkoxy group (The halogen som s the same or cifereat | to 3 halogen stom(s) selected {rom the group consisting of a Murine atom, chlorine stom and a bromine stom), a phenoxy group which may be sub- sttued (The subsient is « pyridainylony group substi tuted by a substtvent(s) selected fom the group consisting of «fluorine atom, a chlorine atom, 2 bromine stom a C, to Cy alkoxy group. )oraC tC alkylthio group, or R'E RE and area groun(s) whichisfare formed by the adjacent wo of them with carbon atoms to which the respective substitu eats are bonded, and include a group represented by CH.CH | —CHsCH,CH,—, —CH(CH)CHsCHs— ze 5 AV7 AW. NacitSy Boe ‘more preferably each independently representa hytinogen atom, a fluorine atom, a chlorine atom, a bromine atom, an ‘ine atom, aC, to C, alkyl group which may be substtited (The substituent is 1 t0 3 fluorine tomy), ora eyclopropy! group.) aC, t0C, eycoalkyl group which may be substituted (The substituent isthe same { to 2 substituent selected from the group consisting ofa Muorine tom, a eborine stom, @ bromine atom, aC, to C, alkyl group, a cyclopropyl group and a C, to C; alkoxy group.) a eyano group, C, 1 Cs alkoxyearbony group, anit group, , to alkoxy group oF teifuoromethoxy group, or R°, RY, RE, RE and R’ are a roup(s) which ivare formed By the adjacent two of them ‘with carbon atoms to whieh the respective substitwents are bonded, and include group represented byUS 7,964,531 B2 25 —CH,CH,CH;—, —CH(CH, CHCl Och,Cii, 5 “OCH=CH or & Soper S, provide that Ris not a hydrogen atom, sill farther preferably each independently represent a hydrogen atom, a forine atom, chlorine stom, a bromine atom, an dine atom, C, to Cy alkyl group, & Cy 10 Cy ‘eyeloalkyl group which may be substnted (The substituents the same Ito 2substitvent() selected from the group con- sisting ofchlorineatom anda, toC, alkyl group. ‘souporaC, toCalkoxy group, or R*, R°,R® and R’ are 8 group(s) which ivare formed by the adiacent two of them ‘wit carbon atoms to which the respective substituents are tonded, and include group represented by —CH,CH,CH,—or—OCH=CIi— provided that Ris not a hydrogen som, particularly preferably each independently represent a hydrogen atom. fhorine atom, a chlorine atom, ‘bromine atom, an iodine atom, a methyl group, an ethyl nop. anisopropyl group, aeyelopropy group which may be substituted (The substituents are two chlorine toms.) or a methoxy group, or R?, RS, RY, Rand R” area group(s) which isfare formed by the adjacent two of them with carbon atoms to which the respective substituents are bonded, nd include a ‘ou represented by —CH,CH,CH,—, provided that Ris not a hydrogen atom, ‘most preferably R* isa fluorine atom, a blorne atom, a bromine atom, an iodine atom, a methyl group, an ethyl ‘aroup, an isopropyl group, a eyelopropy group oF a methoxy rou cébyand R” isa hydrogen atom, aforine atom, @ hlorine atom, a bromine atom, an iodine atom, a methyl oup, an ey group, an isopropy! group, a cyclopropyl xoup or methony group, and R*, Rand R° each indepen- ‘ently representa hydrogen atom or a methyl group. (4) Inthe present invention, mand nare preferably both 0. “The compound (1) ofthe present invention is preferably a ‘compound wherein (a) Ris hydrogen atom, a foorine atom, a chlorine atom, bromine atom, aC, toC alkyl group, aC, to haloalkyl sroup (The halogen stom is 10 3 florine atoms), a cyclopropyl group, to alkenyl group, cyano areup, CoC alkylearbouyl group, adi(C, tC ally}earbam- yl group, a phenyl group which may be substituted (The substituent isthe same or diferent 1 to 2 substituents) selected from the group consisting ofa fluorine atom, & chlorine atom, abromineatom, aC, 1oCalkyl group, aC 10 C; haloalkyl group (The halogen atom i the same or different 1 103 halogen atom(s) select from the group consisting ofa fori atom, a chlorine stom and 8 bro- mine atom}, a eyelopropyl group, a eyano group and a ‘i(C, 10 C, alkylsilyl group.}, a faryl group, a thieny! group, aC, to Cy alkoxy group, a phenoxy group which ‘may be substituted {The substtuentisthe same or different 110 2 subtitvent() selected from the group consisting of afivorineatom,achlorineatom,a bromine stom,aC, oC, allyl group, 1 C; haloalkyl group (The halogen tom §s 110 3 vorine atoms), a eyclopropy! group a eyano sroup and a t(C, t0 C, alkysiyl group. } or the subst- tuted pyrazolyloxy group (The substituent is a benzoyl roup substituted by two chlorine toms and two C to Cs allyl groups), 26 (1b)? sa hydrogen alom, a urine stom, a chlorine stom, «bromine atom, an iodine atom, aC, 10C, ally group, (C, Cy alkoxy) C, 10 Cy alkyl group, a benzoyl group Which may be substituted {The substituent i the same or different Ito 2 substituent) selected from the group con- sisting ofa forine tom, chlorine atom, bromine atom, aC, to Cy alkyl group, aC, to Cy haloalkyl group (The halogen atom is the same or different 110 3 halogen atoms) slecied from the group consisting ofa fluorine ‘om, a chlorine atom and bromine atom.) aeyelapropyl aroup.a cyano groupanda s(C, 10 C, alkyl group), 8C, to Cyalkoxyearbony] group, phenoxy group whieh ‘may be substiuted [The sbstituentsthe sume or different 1 to 2 substiven() selected from the group consisting of afluorineatom,achlorine atom, abromine tom, aC, t0C alk! group, a, 10, haloalkyl group (The halogen atom is the same or diffrent Ito 3 halogen atoms) selected fom the aroup consisting of a forine atom, a chlorine ‘tom and bromine atom.) eyclopropyl group, eyano sroup and a t(C, to C,alkyDsilyl group J, a phenythio troup which may be substited {The substituent is the same or different 1 2 substituents) selected fom the group consisting of @ Mvorine atom, a chlorine tom, a bromine atom, a, to, alkyl group, aC, 10, haloalfyt sroup (The halogen atom isthe same or diferent 1 to 3 halogen atoms) selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom), a eyelopropyl group, a eyano group and atr(C, tC, alky}) silyl group) oratn(C, t9C alkyl goup, 5 (le) RY, RY, R°, R® and R” eich independently represent a ” 4s so © hydrogen tom, fluorine atom, achorine stom, abromine som, aniodine atom, aC, t0C, alkyl goup which may be substituted (The substituent is the same or different 1.3 sustituen()selectod from the group consisting fa uo- Fac atom, a chlorine ao anda bromine atom, or C19 Cyeyclallyl group. aC 0 alkylthio grouporaC oC, alkoxyimino group ).a CC, alkenyl group, aC, t0 C, alkyl group, Ct C,eyelolky group which may’ be substituted (The substituent is the same or different 13 Subtituen() selected from the group consisting of a fuo- sineatom, achlrine stom, abromine atom, C, toCalky group. aC, to C, cyeloaliy group, cyano group, aC, 10 Galkoxy group andaC, oC alkylthio group ),aCt0C bicyeToallyl group, acyano group C10 Callisearbony stoup,a C, to C, alkoxycarbonyl group, a phenyl groop ‘hich may’ he substitnted (The substituent isa Ruorine stom, a chlorine atom, a bromine atom, aC, 10 C, alk stoup or C, fC, ala] group (The halogen atom is the same or diferent 110 3 halogen atoms) selected fom the group consisting ofa fvorne atom, achlorineatomand bromine atom.) },a5-to6-membere heeroeyeli group which may he substituted {the hetereeyele contains one nitrogen aio, oxygen atom or sulfur atom inthe rng nd ‘may contain furer I or 2 nitrogen atoms). The subsite cat isthe same or different 1 to 2 subttuent(s) selected from the group consisting of 2 fuorne atom, « chlorine stom, abromineatom, 3, toCalkylgroupandaC oC, haloalkyl group (Thehslogen atom the same o diferent 1 3 halogen atom) selected from the group consisting ofa ihorinestom,a chlorine stom anda bromine atom), 8 nitro group, aC, tC, alkoxy group, aC, to C, halatkoxy group (The halogen atom isthe same or diler ent to 3 halogen stom(s) selected from the group consis ing ofa fhurine atom, a chlorine atom and a bromine stom.) pheaoxy group which may be substituted (The substituent isa pytidazinylony group substi by a sb- sttuent() selected from the group consisting ofa MuorineUS 7,964,531 B2 7 atom, a chlorine atom, a bromine atom ora to C, alkoxy agroup.)orC, toC, alkylthio group, or RY, RE, Rand R™ ‘area group(s) which isfare formed by the adjacent wo of them with carbon atoms to which the respective substi- ents are bonded, and inelude a group represented by —CH,CH,CH, —CH(CHS) —CH,CH,CH,CH,—. CH=CH —OCH.CH.. © —OCH=CH, —OCH=C(CH)—, —SCH=CH—, —N=CH— —OCH,O-,—OCH,CH,O—, (1d) mand nare both 0, more preferably a compound wherein (2a) R'isachlorine atom, a bromine stom, tifluoromethy roup ora eyano group, (25)? sa hydogen atom, a Moorne stom, cline atom, 1 bromine atom, an iodine atom, a methyl group, an ethoxyearbonyl group o a trimethysily! aroup, (@e) R°, R*, RY, R® and R” each independently represent a hydrogen stom, fuorinestom, chlorine atom, a bromine atom, an ine atom, aC, Cally group which may be substituted (The substituent is 1 to3fuorine atom), ora cyclopropyl group) @ C, 10 C, eyeloalky! group which ray be substituted (The substituent is the same 1 t 2 substituent selected from the group consisting ofa Morne atom, a chlorine atom, «bromine atom, a C, to alkyl sroup,a cyclopropyl group and aC, to, alkoxy group.) sa eyano group, aC, 10 C, alkoxyearbony! group, a nitro group, 2 Cy to Cy alkoxy group or 3 tilluoromethoxy ‘group, or R®, R4, R°, R® and R” area group(s) which is/are formed bythe adjacent two of them with carbon atoms to hich the respective substituents re bonded, and includea rou represented by —CH,CHsCH=—, —CH(CHL) provided that R®is nota hydrogen stom, (2d) mand nare both 0, sill rhe preferably a compound wherein (Ga) Risa chlorine stom or a bromine atom, (Gb) R? is ahydrogen atom, (Ge) RY, R4, RY, R® and R” each independently represent @ hydrogen stom, fluorine atom, a chlorine tom, a bromine tom, an jadine atom, C, 0 C, alkyl group, a C10 Cy cxcloalky] group which may be substituted (The substi ent isthe same | 102 substiuent(s) selected from the zoup consisting ofa chlorine atom and aC, to, ak] group.) ‘eyano group oraC, to Cs alkoxy arp, oF "| R™ RE? and R” are a group() which sae formed bythe adjacent {wo of them with carbon atoms to which the respective substituents are bonded, and include a group represented by —CH_CH.CH.—or OCI provided tht R° isnot abydogen atom, 28 (G4) mand nare both 0, particulary preferably a compound wherein (4a) Risa chlorine stom, (4b) R? is ahhydeogen atom, 5 (de) RY, RY, RE, RY and R” each independently represent a hydrogen tom, afnorineatom, achlorineatom,abromine atom, an iodine stom, a methyl group, an ethyl group. an ‘isopropyl group, a cyclopropyl group which may be sub- stituted (The substituents are two chlorine atoms.) or a methoxy group, or R°, R*,R®, R° and R” are a groups) which ilare formed by the adjacent to of them with carbon atoms to which the respective substituents are bonded, and include group represented by —CH,CH,CH,—, provided that R? is not @ hydrogen atom, (44) mand nae both. Representative compounds of the present invention are «exemplified inthe fllowing Table 1, bathe present invention isnot limited by these compounds. Inthe following, in R? to R’,“H" means thatll the RR, RE, R® and R” are hydrogen atoms, in R?toR7,“2-C1" means that Risa chlorine atom, “Me” represents a meth] group, “EP represents an ethyl group, “PF” represents «propyl 25 stoup, “iPr” represents an isopropyl group, “cP1” represents 8 eyclopropyl group, “Bu” represents a butyl group, “Bu” represents an isobutyl group, “SBu” represents sbutyl sroup, “Bu represents tert-butyl roup, “eB” represents. a eyclobutyl group, “Pea represents a pentyl group, “ePen” represcnis a cyclopentyl group, “neoPen” represents a neo- pentyl group, “HN” represents a hexyl group, “eHIx” rope. sents a eyelohexy! group, in R° to R’, “2-CH,CHCHs3” ‘means that R” and R* area timethylene group and form a ‘S-membered ring together with carbon atoms fo which they are bonded, "—N—OMe" represents a methoxyimino group, represents a carbonyl group together with carbon ston(s) 0 which they are bonded, “SO, (Ph-t-Me)” repre- sents a ptollsulfonyl group “ePe1-F” represents a T-iuo- rocyclopropy] group, “ePrcis-2{CH)s-cis-3” represents _roup represented by » 4s 1, )-CH,CH,” represents group repre: % NAN i / acon “CH(CH,)CH—CH,” represents a group represented by & iN, \/US 7,964,531 B2 29 “CH(OCHL)” represents a group represented by Pro _¢Y \ te 5. “Pyrd” represents a pyrrolidiny! group, “pyre represents. a pyerolyl group, “Pyza"” represen a pyr zolyl group, “Thi” represents thiazolyl group, "Pyzn" rep- resents @pyridaziny! group, “Np” represents a naphihyl group, “I-Ad” represents Iadamantyl group, “loxa” rep- resents an isoxazolyl group, “Tdia" represen a ,2,3thia- diaaolyl group, “Biur” represents a I-beazofurany! group, “Bit represents. I-benzothienyl group, “Bthia” represents 41 3-benzothiazolyl group, “Boxaz" represents a 13-beazo- ° oi SO,/PRANG 2 4 mi SO,(Ph#Ne) 2 “ nok SOsi2h=Ne} 2 “ noi SOuiPh4Ne) 2 4 Boi S0:(Ph# Ne) 5 4 wo SONG “ Bon SO,(Ph#Me) ° % OH SO,/Pm4N) “ 7 ok SOsi2h#Ne “ mi SO;(Ph# Me) 4 BH SO:iPhNe) ° oH SO:IPh2 Ne) “ uo SO,PRANG) 4 2k SOsIPmEN “ Bo Hl “ wou H 4 SoH H 4 “oH H 4 wou H “ wo H 4 oH H “ mH H 4 aH H “ BH H “ MOH H 4 SH H “ 8US 7,964,531 B2 Bie ‘TABLE L-continued RR R 07 Re ont aN re Congo W 2eMe, H Nee i Be tr H 2st, i 2h 35Mey $0,{Ph--Me} 2a ° SO,Pm4N) 2 SOs(Ph#Ne) a SOsIPh# Me) 5 SO:IPh2 Ne) dite SO4(Ph# Ne) der SO,(thene) 2 SO,PmAN Dewcuce,s SO,PR4N) dense SOs(Ph#Ne) 20M $e SO:(Ph Me) 2 SO:IPh2 Me) 2 SO4(Ph Ne) 2 SO,(Pm4NG S0s(2h#NG) SOs(2h=Ne) SOs(Ph=Me} SOs(Ph#Ne) SO, (Phan) SO,PRAN H H H H H H H H H H i i H H H H i i H H H H Hl Hl od H x bs a. H H be a i i inc i H a H H is a i i > le a H x 2 ks cl H H 2 ral H H 2 is a i i 2 is a x x Dept) In H H 2icPrlti) is a H H 2 Inc H H 2 is a H H yee) is H H Dickr1-ih) is a H H HePri-CH.C) Iss cl H H 24ePe-CH) is a H H 2iemcH) Iss H H DePrl-CR| ka cl H H deme-cicr ma x x demcHec) le a H H Deh CH=CH) is a H H Dem-cHt ows)US 7,964,531 B2 Ki TABLE Leconte \-4 ws canyons aa 7H Zebrchae 7 sf toot sees 3 ye on: Peerensonn HE im a tod $ g ¢ io: Q ee io pete $ a ott diecast) ‘ a tot Perici) $ ma i ot Nets $ “US 7,964,531 B2 Bie ‘TABLE L-continued RR R 07 Re ont aN re Congo mo W W eh COm 7 moa x x 2epe-com) “ Boa i H PieP2-C051) “ ma H H 24eh.C0.Me) “ Ba i H PicPr2-COsE) “ moa i i HePe2-CONMe,) “ eo H H Diem CONE) 4 wa H H 2iem2NIG) “ mo H H 2icPr2 SiMe “ mo H H Pra.8Me) 6 2 H H Pr2.NHCOMe) 4 wa i i Deh NHCONME) “ us a H H 22 NHSO,Me) “ Me a i i 2 “ wa i i 2 “ 2 i i 5 6 a H H 2ebe20cry 4 a a H x 2iem20m) “ 2 a H x 2eh2SMe) 4 3 H x 2iemash) “ we H H ctr SP) “ x i i 2yehe2 808) 4 as a Hl Hl Dee S0.Me) 4 ws H x 2eh2S0380) “ » H H DiePr2Me) ‘ wo H H DlckrI Meat) “ ma H H Dckr1-B2Me) 4 ie a i i 2fet2eNy) “ wm a H H dima dF “ ws H H 2aem22ch) “ Me i i Pen) 4 an a H H Me) 6 ia H H eM} 4 m a Hl Hl Deeside) 4 moa H x Dieter Ne) “ moa H x dferrisCih}y63) “ moa i H Pleerinoe CH eaate3) 0 moa i i etree CH lece 3) 4 hs H H 2g 2CHl-tne3) 4 me a H H 2S} ° ma i H Me “ moa H H Deh 23-Mey “ na H H dickra2ee Mey) 4 am H H 4 led i i 4 6 H H det 223 ea “ a H H 2b “ as a H H 4 ae H H 4 in oa H H 4 a H H 2icBor-CO-H) “ aw x x 2eBi1-COMG) a aw a H H 24eB0:-00.Me) “ ma H H 2eputNA) 4 2 a H H even ° moa H H 2H “ bs a H H Decl 4 dws H H eae “US 7,964,531 B2 BLL ‘TABLE L-continued RR R 07 Re ont aN re Congo a W W 2H, 7 a H H 2c, “ a i i ber, “ a x x rec, “ a i i 2c “ cl x x 2eMeciy “ a H H 2-cH Clie 4 a H H 2-CH CHEN “ a H H PctcH=ch, “ o H H doc 4 a H H 20cMe 4 a x x Dewerr o a H H 4 a i i “ a i i “ a i i 4 a H H 4 a H H “ a H H 4 a H H “ a H H “ a i i 4 a Hl Hl 4 a H H “ a H H “ o H H “ a H H 4 a i i “ a H H “ a H H “ moa i i “ m™ a H H 4 Bd H H 4 moa Hl Hl 2on 4 iw H H 20% “ wa H H 20M “ mo i i 200.80 “ mod i i 2008 6 od H H BON, 4 Mw oct x x 2h “ us H x Dime “ ie H H 4 mw a H H ° leone a) are 4H 4H “ Atom D) cl 4H 4H « 1 H H 4 oa H H 4 3 H H ° wa H x 4 sd H H “ Med H H 4 7 H H ° wa H H “ wa H H 4 ma H H “US 7,964,531 B2 4 a ‘TABLE L-continued RR R Re ont aN re Congo a W W Darya) oo wm a x x Dinky) oo ws i H Diy SCF) no wed x x Darr) oo im i H BOpeschy) no ww a W 24S-Byact-SO.NMe,) a6 m a H H 2 oo moa H x 2 oo moa H H 5 no ma H H 2 no ma H H 5 no Me a i i 2 00 ma H H oo im i i oo ma i i oo a1 i i no od H H oo Bo H H oo x H H 0 ws H H oo ie H H no we i i oo wa Hl Hl oo wo H H 06 mo H x 80 ma H H no we H H no ws a i i oo ie H H 2.0CH,cHL0Ne oo moa H H 2oca.cHox oo ie i i dom no wa H H 20h 208) no awa H H oUmLORAaEC-LOR} oo 4a ct x x ser oo 43 a H H 2S oo ww H H 2S0Me oo as a i i 3808 so ae H H 280Me no aoa H H 280 a0 aw oa i i a oo ao oa. H H oo aoa. H H no a2 a H H oo tua i i oo as a H H oo 46 a H H oo aoa H H oo asc H H oo as a H H 00 ana. H H oo aoa H H oo aoa H H ao ea H H 00 aa H H oo a, H H oo aoa H H a0 aoa H H ooUS 7,964,531 B2 4B ‘TABLE L-continued RR R 07 Re ont aN re Congo wa W W 7 aoa H H “ aoa. i i “ aoa H H “ oa i i 6 a a i i “ oa H H 4 aod H H “ aoa. H H “ aoa. H H 6 aoa H H 6 ws oa i i “ “wa H H 4 “soa i i “ “aoa i i “ as a. i i 4 oa H H 4 “oa H H 2 ae 3Me “ 4 a H H 2ascr, “ 42a. H H 230M “ as a H H ver “ 4s cl u u 2Me Br o as a Hl Hl 4 an at H x ° asa. H x “ as oc. H H 2 6 aac H H 5 4 42a x x 2 o 4 oa H H 2 “ feo H H 2 “ is a i i 2 “ ae oc. H H 5 4 aoa H H 2 4 “ec x x 2 o ana. H H 2 “ aoa H H 2 “ na i H 2am, SMe “ a a i i Per SE 4 wm a H H Boe, 4 4% Ch x x Pr 500.Me “ moa H H 222380. “ am oa H H 2h, 30M 4 oa H H dba Fr ° 4 ch u u 2eBu, Me a aed. H H 2am bMe “ 3 al H H DCE OF “ ww oa H H Dery He 4 asc H H 2Cry 3B 4 “6 a H H 2Fy be 4 n at H H DON ° asc x H dens 4 aoa H H 2N, 3 “ aoa H H 2eN SMe 4 soa H H 200.Me, ° 3 H H 2.00:Me, Br ° ‘ua H H 2-C0,Me,}Me 4 as a H H 20, SF “US 7,964,531 B2 45 ‘TABLE L-continued RR R 07 Re ont aN re Congo a W W 20,3 Be 7 a H H 20, Me “ a i i 20M, 3F “ a H H 2-0Me 3.1 “ a i i OMe, 3 6 a H i 30M, OMe “ a H H 2 4 a H H 2 “ a H H 5 “ o H H 2 4 a H H 5 4 a i i Dew.caLcHMes “ a H H Dente c,cai-3 4 a i i 2c(oNe, CH, C3 “ a i i PCH CMe “ a H H POOH HCH 4 a i i 2CHICH CHC 3 6 a H H 2c —-CHic ICH 4 a H H 2emoKcHcH “ a H H 2ck,C=OKH, 3 4 a H H 2CKCLCHOF “ a H H RCNOMOCHLCS “ a u u DOLCE CHS ° a i i 2H, Cas “ a Hl Hl Me CH,CH C83 4 a H H BOKCHCILRILCH EHS 0 6 a H H DCHICH ICH CHC ‘ o H H Ds “ a H H 4 a i i 2HNL03 “ a H H 2-cH,CHMeO3 “ oa H H 2CH=CH-O3, “ imo i i Reve Cik-03 4 ara H H 2ct=CMe_05 4 md H H BeHeH 8 4 Adana) sod 4H 4H 2 NACHRS “ (omer) oc H H ° se i i 6 sa H H 4 soo H H Docwe,ct3| ° ia i i docncHs 4 soo H H Doc MeCie3 “ so H H 20CF,03 4 sao H H ° wed i i 2004/03 4 no H H 20cH,C1,033 “ ssc) H H BOC NS “ wood H H BOC NS 4 so H H 24 4 sod H H 2eLbe 4 52 H H 2acl “ soa H H dae 4 soc H H “ ss od H H 4 56 Cl H H ° ssc H H “ so H H 4 sw H H “US 7,964,531 B2 47 ‘TABLE L-continued RR R 07 Re ont aN re Congo a W W eal 7 ie H H Dende “ se oo i i dinar “ ssc H H imac “ Se i H diteie 6 sao i i doer “ soo H H ama 4 ma H H aaah “ mn a H H 2ePi ee “ ma H H deme 4 moa H H Per eCTs 4 os i i Derscone “ Se H H 2e4NO, 4 in a i i 2oeneoMe “ im a i i doar “ se i i ar 4 so x x Dem Me “ soo H H Der. 4F “ sod x x beret “ eo H H 2k “ as H H ° seo i i 4 seo Hl Hl 4 io H H “ io H H “ so H H 6 2 H H 6 se i i “ Ss C1 H H 2x0, 41 “ Se H H 2ROnd Br “ in i i 2NO, Me 4 oC H H doves 4 so x x 20M C1 o a x x 20M Me “ 2 H H “ “a H H “ om i i “ fs i i 6 a H H 4 fos i i 4 “ a H H “ ‘0 H H 6 ood H H 4 a a i i 4 a H H “ as H H “ a6 H H 4 a7 H H ° ee H H 4 “9 H H ° a a H H 4 aoa H H “ @oa H H 4 a H H 2 Sift ° ea H H 2a cn “ es x x 2Me COs “ aoa H H aves, “49 50 ‘TABLE L-continued RR R Re ont aN re Congo = a W W z oo a a H H 2 oo oo i i 5 no @ oa H H 2 0 =o i i 2 no es a i i 2 oo es a H H 2 oo @ oa H H 2 oo oo H H 5 no ea H H 2 no a H H 5 no “2 cl x x 2 oo a H H 2 oo “a i i 2 oo eo i i 2 oo nc H H 2 06 a oo H H 2 oo oa H H 2 oo @ a H H 2 0 «1 a H x 2 oo ore H H 2 no eM cl H H 2 oo “sa Hl Hl 2 oo “6 H H 2 06 oo H H 2 80 ae H H 2 no oc H H A no esl cl x x 2 oo «a H H 2omsMe oo “a H H paren oo ‘a oo H H 2am, sir no fs H H 2am Seu no ee H H Boesch, a0 68 cl x x Deb OMe oo @ a H H oo a a H H oo mo i i no ma i i no a H H a0 scl x x 2.8, SOME oo a H H 2c SF oo mo H H no ma H H oo a i i oo a H H 2-H Che, SMe oo «a H H POMC, SF ao a H H Dee cl oo oo H H 2 oo as od H H 2 00 oma H H 2 a6 oc H H 5 oo oc H H 2 ao H H 2 00 oc H H 2 oo oa H H 2 06 a H H 2 a0 oa H H » oo US 7,964,531 B2US 7,964,531 B2 st 2 TABLE continued ye X x aN Oe ty & Ww oogot oa 7 7 ORG SI oo oa x x BOONE SMe oo om a x x PeoNe SN oe @ a x x BCE SoM ao cs x x doves 10 ma i i POM Se oe ma x x Powe st a0 ma x x POE ee a0 ie a i i dons oe ie x x dove.scr oo im a x x dove, sex ao 10 cL H H 2 oo a x x a0 oa x x a0 na x x oo he a x x oo sd i i oo ne a x x a0 moa x x oo in a x x oo a x x a0 ma i i a0 ma x x a0 ma x x oo Ma x x 0 md x x 10 ea x x sci oo 2m a W W -CHMeSEr oo Ba x x eon a0 ma x x oo oa x x oe ma x x ao md i i oo ma i i oo Ma x x a0 ma x x oo ma x x oe a x x 0 im a i i oo je a i i ‘0 sa x x a0 je a x x 10 is a x x 1 6etic= cy oe moa H H L6CHOMe oo is a x x econ a0 a i i 1 C1. OMe ae im a x x ao a x x oo ea i i oo sa x x ao yea x x a8 is a x x ao ie a x x a0 isa x x ao io a i i ao ia a x x a0 is a x x ao