|MO NAMAN ATT VI US009924719B2LO HAMA WA MATAI (12 ) United States Patent ( 10 ) Patent No. : US 9 , 924 ,719 B2 Tanabe et al. ( 45 ) Date of Patent: Mar . 27, 2018 (54 ) PYRIDAZINE COMPOUND 200139954 2 / 2001 2003313169 A 11 /2003 (71 ) Applicant: Sumitomo Chemical Company, ?? 201360420 A 4 /2013 Limited , Tokyo ( JP ) WO 2013027660 A1 2 /2013 (72 ) Inventors: Takamasa Tanabe, Takarazuka (JP ) ; OTHER PUBLICATIONS Yoshihiko Nokura , Takarazuka ( JP ) ; Ryota Maehata , Takarazuka ( JP ) ; Vippagunta et al. ( 2001) . * Kohei Orimoto , Takarazuka ( JP ) ; Yuji Int' l Preliminary Report on Patentability dated Apr. 4 , 2017 in Int 'l Nakajima , Takarazuka (JP ) Application No . PCT /JP2015 / 077420 . Int' l Search Report dated Dec. 22 , 2015 in Int' l Application No . (73 ) Assignee : SUMITOMO CHEMICAL PCT/ JP2015 /077420 . STN International, Benzenesulfonamide , N - ( 1 , 1 - dimethylethyl ) - 2 COMPANY, LIMITED , Tokyo ( JP ) [ 6 -( 1 -methylethoxy ) - 3 -pyridazinyl ] -, File Registry [online ] , entered ( * ) Notice : Subject to any disclaimer, the term of this STN : Jun 6 , 2014 , [ retrieved on Dec . 9 , 2015 ], CAS Registry No . patent is extended or adjusted under 35 1609752 - 12 - 6 . U . S .C . 154 (b ) by 0 days . * cited by examiner (21 ) Appl. No. : 15 /515 , 879 ( 22 ) PCT Filed : Sep . 29 , 2015 Primary Examiner — Paul V Ward (74 ) Attorney, Agent, or Firm — Panitch Schwarze ( 86 ) PCT No. : PCT/ JP2015 /077420 Belisario & Nadel LLP $ 371 ( c ) ( 1 ) , ( 2 ) Date : Mar. 30 , 2017 (57 ) ABSTRACT (87 ) PCT Pub. No. : WO2016 /052455 A pyridazine compound represented by formula ( 1 ) : PCT Pub . Date : Apr. 7 , 2016 (65 ) Prior Publication Data US 2017 /0295787 A1 Oct . 19 , 2017 (30 ) Foreign Application Priority Data 0 . N — N (R ) Oct. 3 , 2014 ( JP ) ...... 2014 - 204515 R - 04 (51 ) Int. CI. CO7D 237/ 14 ( 2006 .01 ) AOIN 43 /58 ( 2006 .01 ) C07D 401 /04 ( 2006 . 01 ) (52 ) U .S . CI. wherein Arepresents a nitrogen atom or a CRO, R ' represents CPC ...... AOIN 43/ 58 ( 2013. 01 ) ; CO7D 237/ 14 a C2 - C10 alkyl group having one or more halogen atoms , ( 2013 .01 ) ; C07D 401/ 04 (2013 .01 ) etc . , R2 and R * represent independently of each other a (58 ) Field of Classification Search hydrogen atom , etc ., R4 represents a C1 - C6 chain hydrocar ??? ...... A01N 43 / 58 bon group optionally having one or more halogen atoms, RS See application file for complete search history . represents a C1 - C6 chain hydrocarbon group optionally having one or more halogen atoms, etc ., Rº represents a (56 ) References Cited hydrogen atom , etc . , n represents 0 , 1 , or 2 , and p represents 0 , 1 , or 2 , has an excellent efficacy for controlling harmful FOREIGN PATENT DOCUMENTS arthropods. S591469 A 1 / 1984 JE H1192456 A 4 / 1999 13 Claims, No Drawings US 9 , 924 ,719 B2 PYRIDAZINE COMPOUND more halogen atoms, a C2- C6 alkoxycarbonyl group , a cyano group , or a halogen atom ; CROSS -REFERENCE TO RELATED R4 represents a C1 - C6 chain hydrocarbon group option APPLICATION ally having one or more halogen atoms; 5 R represents a C1 - C6 chain hydrocarbon group option This application is a Section 371 of International Appli - ally having one or more halogen atoms, a phenyl group cation No. PCT/ / JP2015IP2015 /077420 , filedfiled SepSen . 2920 , 20152015 ,which optionally having one or more atoms or groups selected from Group A , a 5 -membered aromatic heterocyclic group was published in the Japanese language on Apr. 7 , 2016 , selected from Group B (wherein said 5 -membered aromatic under International Publication No. WO 2016 / 052455herein A1by, 10 heterocyclic group may optionally have one or more atoms and the disclosure of which is incorporated herein by " or groups selected from Group A ), a 6 -membered aromatic reference . heterocyclic group selected from Group C (wherein said TECHNICAL FIELD 6 -membered aromatic heterocyclic group may optionally have one or more atoms or groups selected from Group A ), The present invention relates to a certain class of 15 a 3 to 7 membered nonaromatic heterocyclic group selected pyridazine compound and use of said compound for con from Group D ( wherein the 3 to 7 membered nonaromatic trolling harmful arthropods . heterocyclic group may optionally have one or more atoms or groups selected from the group consisting of a halogen BACKGROUND ART atom and a C1- C6 alkyl group ), a OR ?, a NR?R " , a NRC 20 (O )RO , a NR $ C ( O )OR , a NR $ C ( O ) NR12R13 , a To date , some compounds for controlling harmful arthro - N = CHNR ' R , a NGS ( O ) , R R " , a S ( O ) R " , a C ( O ) pods have been developed and come into practical use. OR®, a cyano group , or a halogen atom ; Also , a certain class of heterocyclic compound has been Rº represents a hydrogen atom , or a halogen atom ; R ' represents a hydrogen atom , a C1 -C6 alkyl group , a known ( see Patent Document 1 ) . 25 C3 - C6 alkenyl group , a C3 -C6 alkynyl group , a (C1 - C3 CITATION LIST alkyl) - 0 – ( C1- C3 alkyl) group , a ( C1- C3 alkyl) - S ( O ) , (C1 -C3 alkyl) group , a C3 - C7 cycloalkyl group , a (C3 - C7 Patent Document cycloalkyl) -( C1 - C3 alkyl ) group (wherein said C1 - C6 alkyl group , said C3 - C6 alkenyl group , said C3 - C6 alkynyl group , Patent Document 1 : JP 2003 - 313169 A 30 said (C1 - C3 alkyl) - 0 (C1 - C3 alkyl) group , said (C1 - C3 alkyl ) - S ( O ), — (C1 -C3 alkyl) group , said C3 - C7 cycloalkyl SUMMARY OF THE INVENTION group , and said (C3 -C7 cycloalkyl) - ( C1 - C3 alkyl) group may optionally have one or more halogen atoms) , or a Problems to be Solved By Invention phenyl C1 -C3 alkyl group (wherein the phenyl moiety in 35 saide phenyl C1- C3 alkyl group may optionally have one or An object of the present invention is to provide a com more atoms or groups selected from Group A ); pound having an excellent efficacy for controlling harmful R $ represents a hydrogen atom , a C1 - C6 alkyl group arthropods and a method for controlling harmful arthropods optionally having one or more halogen atoms, a C3 - C6 using said compound . alkenyl group optionally having one or more halogen atoms, 40 or a C3 - C6 alkynyl group optionally having one or more Means to Solve Problems halogen atoms; Rº represents a hydrogen atom , a C1 -C6 alkyl group , a [ 1 ] A piridazine compound represented by formula ( 1 ) : C3 - C6 alkenyl group , a C3 - C6 alkynyl group , a (C1 - C3 alkyl ) - 0 (C1 - C3 alkyl) group , a (C1 -C3 alkyl) - S ( O ), — 45 (C1 -C3 alkyl) group , a C3 -C7 cycloalkyl group , a (C3 - C7 ( 1) cycloalkyl) - (C1 - C3 alkyl) group (wherein said C1- C6 alkyl group , said C3 -C6 alkenyl group , said C3 - C6 alkynyl group , said (C1 - C3 alkyl) - 0 — (C1 - C3 alkyl) group , said (C1 - C3 alkyl ) - S ( O ) , (C1 - C3 alkyl) group , said C3 - C7 cycloalkyl N — N ( Rº , 50 group , and said (C3 - C7 cycloalkyl ) - (C1 - C3 alkyl) group R1 - 04 may optionally have one or more halogen atoms) , a cyano C1 - C6 alkyl group , a phenyl C1- C3 alkyl group (wherein the phenyl moiety R2 R3 in said phenyl C1 -C3 alkyl group may optionally have one 55 or more atoms or groups selected from Group A ) , or wherein , a ( 5 or 6 membered heteroaryl) C1- C3 alkyl group A represents a nitrogen atom or a CR " ; (wherein the 5 or 6 membered heteroaryl moiety in said ( 5 R ! represents a C2 -C10 alkyl group , a C3 -C10 alkenyl or 6 membered heteroaryl) C1 -C3 alkyl group may option group , a C3 -C10 alkynyl group , a (C1 - C5 alkyl) -0 (C2 - ally have one or more atoms or groups selected from Group C5 alkyl) group , a (C3 - C5 alkenyl) - 0 (C2 - C5 alkyl) 60 A ); group , a ( C3 - C5 alkynyl) - 0 — (C2 -C5 alkyl) group , a (C1 - R1° represents a hydrogen atom , a C1 -C6 alkyl group , a C5 alkyl) - S ( O ) m ( C2 - C5 alkyl) group , a ( C3 - C5 alkenyl) - C3 -C6 alkenyl group , a C3 - C6 alkynyl group , a C3 - C7 S ( O ) m - ( C2 - C5 alkyl) group , a (C3 - C5 alkynyl) - S ( O ) m - cycloalkyl group , a (C3 - C7 cycloalkyl) - (C1 - C3 alkyl) group ( C2 - C5 alkyl) group , or a (C1 - C5 alkyl) - C ( O ) - (C1 - C5 (wherein said C1 -C6 alkyl group , said C3 - C6 alkenyl group , alkyl ) group (wherein R ' has one or more halogen atoms) ; 65 said C3- C6 alkynyl group , said C3- C7 cycloalkyl group , and R2 and R² represent independently of each other a hydro - said (C3 - C7 cycloalkyl) - ( C1- C3 alkyl) group may option gen atom , a C1 - C6 alkyl group optionally having one or ally have one or more halogen atoms) , or a phenyl C1 -C3 US 9 , 924 ,719 B2 alkyl group (wherein the phenyl moiety in said phenyl -continued C1- C3 alkyl group may optionally have one or more atoms B - 8 or substituents selected from Group A ) ; R " represents a C1 - C6 alkyl group optionally having one or more halogen atoms, a C3 - C6 alkenyl group optionally 5 ZA having one or more halogen atoms, a C3 - C6 alkynyl group optionally having one or more halogen atoms, a C3 - C7 B - 9 cycloalkyl group optionally having one or more halogen atoms, a ( C3 -C7 cycloalkyl) - (C1 - C3 alkyl) group optionally having one or more halogen atoms (wherein said (C3 -C7 cycloalkyl) - ( C1- C3 alkyl) group may optionally have one or 10 B - 10 more halogen atoms ), or a phenyl C1 - C3 alkyl group (wherein the phenyl moiety in said phenyl C1- C3 alkyl group may optionally have one or more atoms or groups selected from Group A ) ; Group C : R12 and R13 represent independently of each other a 15 C1 - C6 alkyl group optionally having one or more halogen C - 1 atomsato ; R14 represents a hydrogen atom , a C1 - C6 alkyl group optionally having one or more halogen atoms, a C2 -C6 alkylcarbonyl group optionally having one or more halogen 20 atoms, or a C2 -C6 alkoxycarbonyl group optionally having C - 2 one or more halogen atoms ; n represents 0 , 1 , or 2 ; m represents 0 , 1 , or 2 ; p represents 0 , 1 , 2 , or 3 (wherein when p represents 2 or 35 C - 3 3 , a plurality of Rºmay be identical or different ) ; x represents 0 or 1 ; y represents 0 , 1 , or 2 ; Group A : a group consisting of a C1 -C6 alkyl group C - 4 optionally having one or more halogen atoms, a C1 - C6 30 alkoxy group optionally having one or more halogen atoms, a C1 - C6 alkylsulfanyl group optionally having one or more halogen atoms, a C1 - C6 alkylsulfinyl group optionally hav ing one ormore halogen atoms, a C1 - C6 alkylsulfonyl group ?C - 5 optionally having one or more halogen atoms, a cyano 25 group , and a halogen atom ;

?C - 6 Group B : B - 1 40

C - 7 N B -2 45 C - 8 B - 3

? 50 B - 4 C - 9

? B - 5 55 Group D : D - 1

B - 6 - D D - 2 doccóco B - 7 D - 3 US 9 ,924 , 719 B2

-continued [ 9 ] An N -oxide compound represented by formula ( 1- N ): D - 4 (1 - N ) 5 R4N D - 5 (0 ) 01 - N (R5 ) RIN - 07 D - 6 10 R2N R3

D - 7 wherein 15 Q1 represents a N - O or a nitrogen atom , N - R14 O2 represents a N + 0 , a CRÓN , or a nitrogen atom , wherein at least one of Q ' and Q2 represents an N + _ 0 " ; D - 7 7 RONPON represents a hydrogen atom , or a halogen atom ; RIN represents a C2- C10 haloalkyl group ; R2N and R3N represent independently of each other a hydrogen atom , a C1 - C3 alkyl group optionally having one or more halogen atoms, or a halogen group ; R4N represents a C1- C6 alkyl group optionally having one ????? or more halogen atoms; (hereinafter , a pyridazine compound represented by formula R5N represents a C1- C6 alkyl group optionally having one ( 1 ) is refered to as “ the compound of the present invention ” ) . 23 or more halogen atoms; and [2 ] The compound according to [1 ], wherein A represents q represents 0 or 1 CRO . (hereinafter , refered to as “ N - oxide compound ” ) . [ 3 ] The compound according to [ 1 ] , wherein A represents a [ 10 ] A composition for controlling a harmful arthropod , comprising the compound according to any one of [ 1 ] to nitrogen atom . 30 [9 ], and an inert carrier . [ 4 ] The compound according to any one of [ 1 ] to [3 ], [ 11 ] A method for controlling a harmful arthropod , com wherein R4 represents a C1- C6 alkyl group optionally prising applying an effective amount of the compound having one or more halogen atoms. according to any one of [ 1 ] to [ 9 ] to a harmful arthropod [ 5 ] The compound according to any one of [ 1 ] to [3 ], or a habitat where a harmful arthropod lives . wherein R + represents an ethyl group . 35 [ 6 ] The compound according to any one of [ 1] to [3 ], Effect of Invention wherein Rl represents a C2- C10 haloalkyl group ; The present compound has an excellent control efficacy R2 and R3 represent independently of each other a hydro against harmful arthropods and is thus useful as an active gen atom , a C1- C3 alkyl group optionally having one or 4010 ingredient of an agent for controlling harmful arthropods . more halogen atoms, or a halogen atom ; MODE FOR CARRYING OUT THE INVENTION R * represents a C1- C6 alkyl group optionally having one or more halogen atoms; The group ( s ) as described herein is / are explained as Rrepresents a C1- C6 alkyl group optionally having one follows by means of examples. The expression of “ optionally having one or more atoms or more halogen atoms; and or groups selected from Group A ” as used herein represents p represents 0 or 1 . that when two or more atoms or groups selected from Group [ 7 ] The compound according to any one of [ 1 ] to [ 3 ] , A are present , these atoms or groups selected from Group A wherein may be identical to or different from each other. Rl represents a C2- C10 haloalkyl group ; 50 The expression of “ optionally having one or more halogen R2 and Ry represent each a hydrogen atom ; atoms” as used herein represents that when two or more halogen atoms are present , these halogen atoms may be R4 represents a C1 - C6 alkyl group optionally having one identical to or different from each other . or more halogen atoms; The expression of “ having one or more halogen atoms” as R $ represents a C1- C6 alkyl group optionally havingng undone 5555 used herein represents that when two or more halogen atoms or more halogen atoms; and are present, the halogen atoms may be identical to or p represents 0 or 1 . different from each other . [ 8 ] The compound according to any one of [ 1 ] to [ 3 ], The term of " heterocyclic group ” as used herein repre wherein sents a group containing one or more atoms selected from Rl represents a C3 - C6 alkyl having four or more fluorine 60 the group consisting of a nitrogen atom , an oxygen atom , and a sulfur atom as a ring constituent atom other than a atoms; carbon atom , and includes an aromatic heterocyclic group R and R3 represent each a hydrogen atom ; and a non - aromatic heterocyclic group . R4 represents an ethyl group ; Examples of the term of " aromatic heterocyclic group ” as Rrepresents a C1- C6 alkyl group optionally having one 65 used herein include , or more halogen atoms; and a 5 -membered aromatic heterocyclic group such as 2 - fu p represents 0 or 1. ryl group , 3 -furyl group , 2 -thienyl group , 3 - thienyl group , US 9 , 924 , 719 B2 3 - pyrazolyl group , 4 - pyrazolyl group , 5 - pyrazolyl group , 2 - ( trifluoromethylsulfinyl ) ethyl group , 2 - ( trifluoromethyl 1 -pyrrolyl group , 1 -pyrazolyl group , 1 - imidazolyl group and sulfonyl) ethyl group , 2 - ( 2 , 2 , 2 - trifluoroethylthio )ethyl 1 , 2 , 4 - triazol- 1 - yl group ; and group , 2 - ( 2 , 2 , 2 -trifluoroethanesulfinyl ) ethyl group , and a 6 -membered aromatic heterocyclic group in which a 2 -( 2 ,2 ,2 - trifluoroethanesulfonyl) ethyl group . carbon atom of the heterocyclic group is attached to the rest 5 The term of “ (C1 - C5 alkyl) - S ( O ) , ( C2- C5 alkyl) of the molecule , such as 2 -pyridyl group , 3 -pyridyl group , group ” as used herein includes, for example , 2 - methylthio ) and 4 -pyridyl group . ethyl group , and 2 - (methylsulfonyl ) ethyl group . Examples of the term of “ non - aromatic heterocyclic group ” as used herein include aziridin - 1 - yl group , azetidin The term of “ (C1 - C3 alkyl) - S ( O ), (C1 - C3 alkyl) group 1 -yl group , pyrrolidin - 1 -yl group , 3 ,3 , 4 ,4 - tetrafluoropyrro - 10 optionally having one or more halogen atoms” as used lidin - 1 -yl group , tetrahydrofuran -2 - yl group , tetrahydro herein represents a group having one ormore halogen atoms furan - 3 -yl group , piperidin - 1- yl group , morpholin - 4 -yl in the C1 - C3 alkyl moiety and / or C1- C3 alkyl moiety , and group , thiomorpholin - 4 - yl group , and azepan - 1 -yl group . includes , for example , methylthiomethyl group , trifluorom The term of “ 5 or 6 membered heteroaryl” as used herein ethylthiomethyl group , methanesulfinylmethyl group , trif represents a 5 -membered aromatic heterocyclic group or a 15 luoromethanesulfonylmethyl group , methanesulfonylmethyl 6 -membered aromatic heterocyclic group . group , 2 - (methylthio Jethyl group , and ethylthiomethyl Examples of the term of “ C2 - C10 alkyl group ” as used group . herein include ethyl group , isopropyl group , propyl group The term of “ (C1 -C3 alkyl) - S ( O ), (C1 - C3 alkyl) group ” and butyl group . as used herein includes , for example , methylthiomethyl Examples of the “ C2 - C10 haloalkyl group ” as used herein 20 group , methanesulfinylmethyl group , methanesulfonylm include 2- fluoroethyl group , 2, 2 - difluoroethyl group , 2 ,2 ,2 - ethyl group , 2 - methylthio )ethyl group , and ethylthiomethyl trifluoroethyl group , 2 , 2 , 2 - trichloroethyl group , pentafluo group . roethyl group , heptafluoroisopropyl group , 2 ,2 , 3, 3 -tetrafluo The term of “ (C3 -C5 alkenyl) - S (O )m (C2 - C5 alkyl) ropropyl group , 2 , 2, 3 ,3 ,3 - pentafluoropropyl group , and 2 , 2 , group having one or more halogen atoms” as used herein 3 , 4 , 4 , 4 -hexafluoroburyl group . represents a group having one or more halogen atoms in the Examples of the term of “ C3 - C10 alkenyl group ” as used C3 - C5 alkenyl moiety and / or C2- C5 alkyl moiety , and herein include 2 -propenyl group , and 3 -butenyl group . includes , for example , 2 - ( 3 , 3 - difluoro - 2 - propenylthio )ethyl Examples of the term of “ C3 - C10 haloalkenyl group ” as group . used herein include 3 , 3 - difluoro - 2 - propenyl group , 3 , 3 - dif - The term of " (C3 - C5 alkenyl )- S ( O ) m (C2 - C5 alkyl) luoro - 2 - propenyl group , and 4 , 4 - difluoro - 3 - butenyl group . 30 group ” as used herein includes, for example , 2 - ( 2 - propenyl Examples of the term of “ C3 -C10 alkynyl group ” as used thio ) ethyl group . herein include 2 - propynyl group , and 2 -butynyl group . The term of “ (C3 -C5 alkynyl) - S (O ) m (C2 - C5 alkyl) Examples of the term of “ C3 -C10 haloalkynyl group ” as group having one or more halogen atoms” as used herein used herein include 3 - chloro - 2 - propynyl group , 3 - fluoro - 2 represents a group having one or more halogen atoms in the propynyl group , and 4 , 4 , 4 - trifluoro - 2 - butynyl group . 35 C3 -C5 alkynyl moiety and /or C2 - C5 alkyl moiety , and The term of “ (C1 - C5 alkyl) - 0 ( C2 - C5 alkyl) group includes , for example , 2 -( 4 , 4 , 4 -trifluoro - 2 -butynylthio ) ethyl having one or more halogen atoms” as used herein repre group. sents a group having one or more halogen atoms in the The term of “ (C3 -C5 alkynyl ) - S ( O ) ( C2 - C5 alkyl) C1- C5 alkyl moiety and / or C2 -C5 alkyl moiety , and group ” as used herein includes, for example , 2 - ( 2 -butynyl includes , for example , 2 - ( 2 , 2 , 2 - trifluoroethoxyethyl group , 40 thio ) ethyl group . and 1, 1, 1- trifluoro -3 -methoxypropan - 2 -yl group. The term of “ (C1 - C5 alkyl) - C ( O ) - (C1 - C5 alkyl) group Examples of the term of “ (C1 - C5 alkyl ) - 0 (C2 - C5 having one or more halogen atoms” as used herein repre alkyl) group " as used herein includes 2 -methoxyethyl group sents a group having one or more halogen atoms in either and 2 - ethoxyethyl group . one of the C1- 05 alkylmoieties or both of the C1 - C5 alkyl The term of “ (C3 - C5 alkenyl) - 04 ( C2 - C5 alkyl) group 45 moieties, and includes, for example , ( 3, 3 ,3 - trifluoro - 2 -oxo having one or more halogen atoms” as used herein repre propyl group . sents a group having one or more halogen atoms in the The term of “ ( C1 - 05 alkyl) - C ( O ) - (C1 - C5 alkyl ) group " C3 -C5 alkenyl moiety and / or C2- C5 alkyl moiety , and as used herein includes , for example , 2 -oxopropyl group , includes, for example , 2 - ( 3 , 3 - difluoro - 2 -propenyloxy ) ethyl and 3 , 3 -dimethyl - 2 -oxobutyl group . group . 50 Examples of the term of “ C1 -C6 chain hydrocarbon group The term of “ ( C3 - C5 alkenyl) - 0 ( C2- C5 alkyl) group ” optionally having one or more halogen atoms” as used as used herein includes , for example , 2 - ( 2 -propenyl ) oxy - herein include ethyl group . a C1- C6 alkyl group optionally having one or more The term of “ (C3 - C5 alkynyl ) -0 (C2 - C5 alkyl) group halogen atoms such as methyl group , ethyl group , propyl having one or more halogen atoms” as used herein repre - 55 group , isopropyl group , butyl group , isobutyl group , sec sents a group having one or more halogen atoms in the butyl group , tert -butyl group , pentyl group , neopentyl group , C3 - C5 alkynyl moiety and / or C2- C5 alkyl moiety , and hexyl group , trifluoromethyl group , truchloromethyl group , includes, for example , 2 - ( 4 , 4 ,4 - trifluoro - 2 -butynyloxy ) ethyl 2 - fluoroethyl group , 2 , 2 -difluoroethyl group , 2 , 2 , 2 - trifluo group . roethyl group and pentafluoroethyl group ; The term of “ (C3 -C5 alkynyl ) - 0 (C2 - C5 alkyl) group ” 60 a C2 - C6 alkenyl group optionally having one or more as used herein includes , for example , 2 - ( 2 - butyloxy ) ethyl halogen atoms such as vinyl group , 1 - propenyl group , group . 2 -propenyl group , 1 -methylvinyl group , 2 -methyl - 1 -prope The term of “ (C1 -C5 alkyl )- S (O )m — (C2 - C5 alkyl) group nyl group , 1- butenyl group , 2 -butenyl group , 3- butenyl having one or more halogen atoms” as used herein repre - group , 1- pentenyl group , 1- hexenyl group , 1 , 1 -difluoroallyl sents a group having one or more halogen atoms in the 65 group and pentafluoroallyl group ; and C1- C5 alkyl moiety and /or C2 -C5 alkyl moiety , and a C2 - C6 alkynyl group optionally having one or more includes , for example , 2 - ( trifluoromethylthio ) ethyl group , halogen atoms such as ethynyl group , propargyl group , US 9 , 924 ,719 B2 10 2 - butynyl group , 3 -butynyl group , 1 -pentynyl group , moiety in said ( 5 or 6 membered heteroaryl) C1 -C3 alkyl 1 -hexynyl group and 4 ,4 , 4 -trifluoro -2 -butynyl group . group may optionally have one or more atoms or groups Examples of the “ phenyl group optionally having one or selected from Group A )” as used herein include, for more atomsor groups selected from Group A ” as used herein example , a C1- C3 alkyl group having one 5 -membered include phenyl group , 2 - fluorophenyl group , 4 - fluorophenyl 5 aromatic heterocyclic group such as ( 1 -methylpyrrol - 3 - yl ) group , 2 , 3 -difluorophenyl group , 2 , 3 ,4 ,5 , 6 -pentafluorophe nyl group , 4 -chlorophenyl group , 4 -bromophenyl group , methyl group , ( oxazol - 2 - yl) methyl group , ( tetrahydrofuran 4 - iodophenyl group , 4 - ( trifluoromethyl) phenyl group , 4 -( tri 3 - yl) methyl group , (tetrahydrofuran - 2 - yl) methyl group , fluoromethoxyphenyl group , 4 - ( trifluoromethylsulfanyl) 2 - ( 1 , 2 , 4 - triazol- 1 - yl) ethyl group and ( 2 - chlorothiazol- 5 - yl ) phenyl group , 4 - cyanophenyl group , 4 - (methylsulfinyl ) phe - 10 methyl group ; and nyl group , and 4 -( methylsulfonyl ) phenyl group . a C1- C3 alkyl group having one 6 -membered aromatic Examples of the “ 5 -membered aromatic heterocyclic heterocyclic group such as (pyridin -2 - yl)methyl group , group selected from Group B (wherein said 5 -membered (pyridin -4 -yl ) methyl group , (pyrimidin - 2 -yl ) methyl group , aromatic heterocyclic group may optionally have one or (pyrimidin - 4 -yl ) methyl group , 2 -( 2 -chloropyridin - 5 -yl ) more atoms or groups selected from Group A )" ” as usedused 15 anyethyl groupgroup and [2 - ( trifluoromethyl) pyridin - 2 -yl ] methyl herein include pyrrol- 1 - yl group , 2 - chloropyrrol- 1 - yl group , group . pyrazol- 1 - yl group , 3 - ( trifluoromethyl) pyrazol - 1 - yl group , Examples of the term of “ C2- C6 alkoxycarbonyl group ” 4 - chloroimidazol - 1 - yl group , 1 , 2 , 4 - triazol - 1 - yl group , as used herein include methoxycarbonyl group , and ethoxy 3 -methoxy - 1 , 2 ,4 - triazol- 1 - yl group , 3 -methylthio - 1 , 2 , 4 -tri - carbonyl group . azol- 1 -yl group , 1 , 2 , 3 - triazol- 1 -yl group , oxazol- 2 - yl group , 20 The term of " ( C1- C3 alkyl) - 0 (C1 - C3 alkyl) group thiazol- 2 -yl group , 1 ,3 ,4 -oxadiazol - 2 -yl group, 1 ,3 ,4 - thiadi- optionally having one or more halogen atoms” as used azol- 2 -yl group , and 1 , 2 , 4 -oxadiazol - 3 - yl group . herein represents a group having one or more halogen atoms Examples of the “ 6 -membered aromatic heterocyclic in either one of the C1 - C3 alkyl moieties or both of the group selected from Group C (wherein said 6 -membered C1- C3 alkyl moieties , and includes , for example , aromatic heterocyclic group may optionally have one or 25 methoxymethyl group , ethoxymethyl group , and more atoms or groups selected from Group A ) ” as used 2 - methoxy Jethyl group . herein include pyridin - 2 - yl group , pyridin - 3 - yl group , pyri Examples of the term of “ C1- C6 alkoxyl group optionally din - 4 - yl group , 4 - trifluoromethylpyridin - 2 - yl group , 2 - chlo having one or more halogens” as used herein include trif ropyridin - 5 - yl group, pyrimidin - 2 - yl group, pyrazin - 2 - yl luoromethoxy group , and 2 , 2 , 2 - trifluoroethoxy group . group , pyrimidin - 4 - yl group , pyridazin - 3 - yl group , pyrimi- 30 1 din -5 - yl group , and pyridazin - 4 - yl group . The term of " halogen atom ” as used herein represents Examples of the term of “ 3 to 7 membered nonaromatic fluorine atom , chlorine atom , bromine atom , and iodine heterocyclic group selected from Group D (wherein said 3 to atom . 7 membered nonaromatic heterocyclic group optionally has Examples of the compound of the present invention one or more atoms or groups selected from the group 3526 include the following compounds. consisting of a halogen atom and a C1 -C6 alkyl group ) ” as A compound represented by formula ( 1) , wherein R4 used herein include , for example , aziridin - 1 - vl group , aze - represents a C1- C6 alkyl group or a C1 -C6 haloalkyl group ; tidin - 1 -yl group , pyrrolidin - 1 -yl group , 3 ,3 , 4, 4 -tetrafluoro A compound represented by formula ( 1 ), wherein R + pyrrolidin - 1 - yl group , piperidin - 1 - yl group , 4 , 4 - dimethylpi- represents a C1- C6 alkyl group ; peridin - 1 - yl group , and azepan - 1 -yl group . 40 A compound represented by formula ( 1 ), wherein R + Examples of the term of “ C3 -C7 cycloalkyl group option represents a C1 -C6 haloalkyl group ; ally having one or more halogen atoms” as used herein A compound represented by formula (1 ), wherein R + include cyclopropyl group , 2 , 2 -difluorocyclopropan - 1 -yl represents a C2- C6 alkyl group ; group , cyclobutanyl group , cyclopentanyl group , cyclohexyl A compound represented by formula ( 1) , wherein R4 group , and cycloheptanyl group . 45 represents a C2 -C6 haloalkyl group ; Examples of the term of “ C3 - C7 cycloalkyl group ” as A compound represented by formula ( 1 ) , wherein R + used herein include cyclopropyl group , cyclopentanyl represents a methyl group , an ethyl group , a propyl group , group , cyclohexyl group , and cycloheptanyl group . an isopropyl group , a trifluoromethyl group , or a 2 , 2 ,2 The term of “ ( C3 - C7 cycloalkyl) - (C1 - C3 alkyl) group trifluoroethyl group ; ( wherein the (C3 -C7 cycloalkyl) - (C1 - C3 alkyl ) group may 50 A compound represented by formula (1 ), wherein R * optionally have one or more halogen atoms” as used herein represents an ethyl group ; represents a group having one or more halogen atoms in the compound represented by formula ( 1 ) , wherein n rep C3- C7 cycloalkylmoiety , and includes, for example , cyclo - resents 0 , 1 , or 2 ; propylmethyl group , 2 -( cyclopropyl ) ethyl group, (2 ,2 -dif A compound represented by formula (1 ), wherein repre luorocyclopropyl) methyl group , and cyclopentylmethyl 55 sents 0) ; group . A compound represented by formula ( 1 ), wherein n rep Examples of the " (C3 - C7 cycloalkyl) - ( C1 -C3 alkyl ) resents 1 ; group ” as used herein include cyclopropylmethyl group , compound represented by formula ( 1 ) , wherein repre 2 -( cyclopropyl) ethyl group , and cyclopenthylmethyl group . sents 2 ; Examples of the term of “ phenyl C1 - C3 alkyl group 60 A compound represented by formula ( 1 ) , wherein p rep (wherein the phenyl moiety in said phenyl C1- C3 alkyl resents 0 , 1 , 2 , or 3 ; group may optionally have one or more atoms or groups A compound represented by formula ( 1 ) , wherein p rep selected from Group A ) " include benzyl group , 2 - fluoroben resents 0 or 1 ; zyl group , 4 -chlorobenzyl group , 4 - ( trifluoromethyl) benzyl A compound represented by formula ( 1 ), wherein p rep group , and 2 - [ 4 - ( trifluoromethyl) phenyl ] ethyl group . 65 resents 0 ; Examples of the term of “ ( 5 or 6 membered heteroaryl) A compound represented by formula ( 1 ) , wherein R2 and C1 -C3 alkyl group (wherein the 5 or 6 membered heteroaryl Rº represent independently of each other a hydrogen atom , US 9 ,924 ,719 B2 12 a C1 -C6 alkyl group optionally having one or more halogen A compound represented by formula (1 ), wherein R ! atoms, a C2 -C6 alkoxycarbonyl group , a cyano group , or a represents a C2 -C10 chain hydrocarbon group having one or halogen atom ; more halogen atoms ; A compound represented by formula ( 1 ) , wherein R2 and A compound represented by formula ( 1 ) , wherein R R * represent independently of each other a hydrogen atom , 5 represents a C2 -C10 haloalkyl group , a C3 -C10 haloalkenyl a C1- C6 alkyl group optionally having one or more halogen group , or a C3 -C10 haloalkynyl group ; A compound represented by formula (1 ), wherein R ' atoms, or a halogen atom ; represents a C2- C10 haloalkyl group ; A compound represented by formula ( 1 ) , wherein R2 and representsA compound represented by formula ( 1 ) , wherein R R ” represent independently of each other a hydrogen atom , represents a C2- C10 alkyl group having two or more halo or a C1 - C6 alkyl group optionally having one or more 10 gen atoms; halogen atoms; A compound represented by formula ( 1 ) , wherein R1 A compound represented by formula ( 1) , wherein R2 and represents a C2 -C10 alkyl group having two or more fluo Rrepresent each a hydrogen atom ; rine atoms; A compound represented by formula ( 1 ), wherein A A compound represented by formula ( 1 ), wherein R ' represents a nitrogen atom , or a CR®, and Rº represents a 15 represents a 2 , 2 - difluoroethyl group , a 2 , 2 , 2 - trifluoroethyl hydrogen atom or a halogen atom ; group , 2 ,2 , 2 -trichloroethyl group , 2 , 2 -difluoropropyl group , A compound represented by formula ( 1 ), wherein A 2 ,2 ,3 , 3 -tetrafluoropropyl group , 2 ,2 , 3, 3 ,3 -pentafluoropropyl represents a nitrogen atom , or a CH ; group , 1 , 1, 1, 3 ,3 , 3 -hexafluoro - 2 -propyl group , 2 , 2 -( bistrif A compound represented by formula ( 1 ) , wherein A luoromethyl) - propyl group , 2 , 2 , 3 , 4 ,4 , 4 - hexafluorobutyl represents N ; 20 group , 2 , 2 , 3 , 3 , 4 , 4 , 4 - heptafluorobutyl group , 2 , 2 , 3 , 3 , 4 , 4 ,5 , 5 , A compound represented by formula (1 ), wherein p rep - 5 -nonafluoropentyl group , 2 ,2 ,3 ,3 ,4 ,4 , 5, 5, 6 ,6 ,6 -undecafluo resents 0 or 1 , and when p represents 1 , R represents a rohexyl group , 3 , 3 , 3 - trifluoro - 2 -propyl group , 3 , 3 , 4 , 4 , 4 C1 - C6 chain hydrocarbon group optionally having one or pentafluoro - 2 -butyl group , or 3 , 3 , 4 , 4 , 5 , 5 , 5 -heptafluoro - 2 more halogen atoms, a phenyl group optionally having one or more atoms or groups selected from Group A , a 5 -mem - 25 A compound represented by formula ( 1 ) , wherein Rº bered aromatic heterocyclic group selected from Group B represents a hydrogen atom or a halogen atom ; ( wherein the 5 membered aromatic heterocyclic group may A compound represented by formula ( 1 ), wherein Rº optionally have one or more atoms or groups selected from represents a halogen atom ; Group A ), a 6 membered aromatic heterocyclic group A compound represented by formula ( 1 ), wherein Rº selected from Group C ( wherein the 6 -membered aromatic 30 representsrep a hydrogen atom ; heterocyclic group may optionally have one or more atoms A compound represented by formula ( 1 ), wherein A or groups selected from Group A ) , a 3 to 7 membered represents a nitrogen atom or a CH , R ' represents a C2 -C6 nonaromatic heterocyclic group selected from Group D alkyl group having two or more fluorine atoms, R² and R * (wherein the 3 to 7 membered nonaromatic heterocyclic represent independently of each other a hydrogen atom , a group may optionally have one or more atoms or groups 35 C1- C6 alkyl group optionally having one or more halogen selected from the group consisting of a halogen atom and a atoms, or a halogen group , R * represents a C1 - C6 alkyl C1 - C6 alkyl group ) , a OR ? , a NRSR " , a NR8C ( O ) R19 , a group , and p represents 0 or 1 , and when p represents 1 , R NR $ C (O ) ORII , a NR $ C (O )NR12R13 , a N = CHNR12R13 , a represents a C1 - C6 alkyl group optionally having one or N = S( O ), R ?R13 , a S (O ), R ? ?, a C (O )OR® , a cyano group, or more halogen atoms; a halogen atom ; 40 A compound represented by formula ( 1 ) , wherein A A compound represented by formula ( 1 ) , wherein p rep represents a nitrogen atom or a CH , R ' represents a C2 -C6 resents 0 or 1 , and when p represents 1 , R represents a alkyl group having two or more fluorine atoms, R2 and R3 C1 - C6 chain hydrocarbon group optionally having one or represent independently of each other a hydrogen atom , a more halogen atoms, a 5 membered aromatic heterocyclic C1- C6 alkyl group optionally having one or more halogen group selected from Group B (wherein the 5 membered 4545 atomsanos , or a halogen group , R * represents an ethyl group , and aromatic heterocyclic group may optionally have one or p represents 0 or 1 , and when p represents 1 , R represents more atoms or groups selected from Group A ), a 6 mem a C1 -C6 alkyl group optionally having one or more halogen bered aromatic heterocyclic group selected from Group C atoms; (wherein the 6 membered aromatic heterocyclic group may A compound represented by formula (1 ) , wherein A optionally have one or more atoms or groups selected from so50 represents a nitrogen atom or a CH , R represents a C2 -C10 Group A ), a 3 to membered nonaromatic heterocyclic group alkyl group having two or more fluorine atoms, R² and Rº selected from Group D (wherein the 3 to 7 membered represent a hydrogen atom , R4 represents an ethyl group , and nonaromatic heterocyclic group may optionally have one or p represents 0 or 1, R? represents a C1- C6 alkyl group more atoms or groups selected from the group consistingsting of optionallyop having one or more halogen atoms. a halogen atom and a C1- C6 alkyl group ). a OR ? . a NR8R9 55 A compound represented by formula ( 1 - 1 ): a S ( O ), R ! ? , or a halogen atom ; A compound represented by formula ( 1 ) , wherein p rep resents 0 or 1 , and when p represents 1 , R represents a ( 1 - 1 ) C1- C6 chain hydrocarbon group optionally having one or 24 more halogen atoms, a OR ”, a NR?R ", a S (O ), R ? , or a 60 (O ), S' RS halogen atom ; N - N A compound represented by formula ( 1 ) , wherein p rep resents 0 or 1 , and when p represents 1 , RS represents a R1 - 04 R52 C1- C6 haloalkyl group ; A compound represented by formula ( 1 ), wherein p rep - 65 R2 R3 resents 0 or 1 , and when p represents 1 , R represents a trifluoromethyl group ; US 9 , 924 , 719 B2 13 14 wherein A compound represented by formula ( 1 - 1 ) , wherein R ! R ! represents a C2 - C10 alkyl group , a C3 - C10 alkenyl represents a C2 - C6 alkyl group having two or more fluorine group , a C3 - C10 alkynyl group , a ( C1 -C5 alkyl) - 0 (C2 atoms, R² and R3 represent each a hydrogen atom , R4 C5 alkyl) group , a (C3 - C5 alkenyl ) - 0 (C2 - C5 alkyl) represents an ethyl group , RSI , RS2 , and R $ 3 represent group , a ( C3 - C5 alkynyl) - 0 — (C2 - C5 alkyl) group , a ( C1 - 5 independently of each other a hydrogen atom , or a C1 - C6 C5 alkyl) -S (O )m (C2 -C5 alkyl) group , a (C3 - C5 alkenyl) alkyl group optionally having one or more halogen atoms. S ( O ) m (C2 - C5 alkyl) group , a (C3 - C5 alkynyl) - S ( O ) m - A compound represented by formula ( 1 - 2 ) : ( C2 - C5 alkyl) group , or a (C1 -C5 alkyl) - C ( O ) - (C1 -C5 alkyl) group (wherein R has one or more halogen atoms) ; R2 and R represent independently of each other a hydro - 10 ( 1 - 2 ) gen atom , a C1 - C6 alkyl group optionally having one or more halogen atoms, a C2- C6 alkoxycarbonyl group , a R51 cyano group , or a halogen group ; R + represents a C1 -C6 chain hydrocarbon group option N - N ally having one or more halogen atoms; 15 R - 0 – R$ RSI, R52, and R53 represent independently of each other a hydrogen atom , a C1 -C6 chain hydrocarbon group option ally having one or more halogen atoms, a phenyl group R3 R6 optionally having one or more atoms or groups selected from Group A , a 5 membered aromatic heterocyclic group 20 wherein selected from Group B (wherein the 5 membered aromatic Rl represents a C2- C10 alkyl group , a C3- 010 alkenyl heterocyclic group may optionally have one or more atoms group , a C3- C10 alkynyl group , a ( C1- C5 alkyl) - 0 (C2 or groups selected from Group A ), a 6 membered aromatic C5 alkyl) group , a ( C3 -C5 alkenyl) - 0 (C2 -C5 alkyl) heterocyclic group selected from Group C (wherein the 6 group , a (C3 - C5 alkynyl) - 0 (C2 - C5 alkyl) group , a ( C1 membered aromatic heterocyclic group may optionally have 25 C5 alkyl) - S ( O ) m ( C2 - C5 alkyl) group , a (C3 -C5 alkenyl) one or more atoms or groups selected from Group A ), a 3 to S (O )m — ( C2 - C5 alkyl) group , a (C3 -C5 alkynyl) - S ( O ) m 7 membered nonaromatic heterocyclic group selected from (C2 -C5 alkyl) group , or a (C1 - C5 alkyl - C ( O ) - (C1 - C5 Group D (wherein the 3 to 7 membered nonaromatic het - alkyl) group (wherein R has one or more halogen atoms) ; erocyclic group may optionally have one or more atoms or R and Rº represent independently of each other a hydro groups selected from the group consisting of a halogen atom 30 gen atom , a C1 - C6 alkyl group optionally having one or and a C1 -C6 alkyl group ) , a OR ? , a NRSR°, a NRC (O ) R10 , more halogen atoms, a C2- C6 alkoxycarboxyl group , a a NR $ C (O ) OR11, a NR $ C (O ) NR2R13, a N — CHNR12R13 , cyano group , or a halogen group ; a N = S ( O ), R ! R13, a S ( O ), R12 , a C ( O ) OR®, a cyano group, R represents a C1 -C6 chain hydrocarbon group option or a halogen atom ; ally having one or more halogen atoms; n represents 0 , 1 , or 2 ; 35 R represents a C1 - C6 chain hydrocarbon group option m represents 0 , 1 , or 2 ; ally having one or more halogen atoms, a phenyl group x represents 0 or 1 ; and optionally having one or more atoms or groups selected y represents 0 , 1 , or 2 . from Group A , a 5 membered aromatic heterocyclic group A compound represented by formula ( 1 - 1 ) , wherein selected from Group B (wherein the 5 membered aromatic R ' represents a C2 -C10 haloalkyl group ; 40 heterocyclic group may optionally have one or more atoms R2 and Rº represent independently of each other a hydro or groups selected from Group A ) , a 6 membered aromatic gen atom , a C1- C6 alkyl group optionally having one or heterocyclic group selected from Group C (wherein the 6 more halogen atoms, or a halogen group ; membered aromatic heterocyclic group may optionally have R * represents a C1 - C6 alkyl group optionally having one one or more atoms or groups selected from Group A ), a 3 to or more halogen atoms; 45 7 membered nonaromatic heterocyclic group selected from R51 , R52 , and R53 represent independently of each other a Group D (wherein the 3 to 7 membered nonaromatic het hydrogen atom , a C1 - C6 chain hydrocarbon group option - erocyclic group may optionally have one or more atoms or ally having one or more halogen atoms, a 5 membered groups selected from the group consisting of a halogen atom aromatic heterocyclic group selected from Group B and a C1- C6 alkyl group ), a OR ? , a NR?R " , a NR8C ( O )R19 , ( wherein the 5 membered aromatic heterocyclic group may 50 a NR $ C ( O ) OR11 , a NR $ C ( O ) NR12R13 , a N = CHNRI2R13, optionally have one or more atoms or groups selected from aN S ( O ), R2R13 , a S ( O ), R ! ? , a C ( O ) OR®, a cyano group , Group A ) , a 6 membered aromatic heterocyclic group or a halogen atom ; selected from Group C (wherein the 6 membered aromatic Rº represents a hydrogen atom , or a halogen atom ; heterocyclic group may optionally have one or more atoms n represents 0 , 1 , or 2 ; or groups selected from Group A ), a 3 to 7 membered 55 m represents 0 , 1 , or 2 ; nonaromatic heterocyclic group selected from Group D x represents 0 or 1 ; and (wherein the 3 to 7 membered nonaromatic heterocyclic y represents 0 , 1 , or 2 . group may optionally have one or more atoms or groups A compound represented by formula ( 1 - 2 ) , wherein selected from the group consisting of a halogen atom and a Rl represents a C2 -C10 haloalkyl group ; C1 - C6 alkyl group ) , a OR " , a NRØR ” , a S ( O ), R ! ? , or a 60 R² and Rº represent independently of each other a hydro halogen atom ; gen atom , a C1 -C6 alkyl group optionally having one or A compound represented by formula ( 1 - 1) , wherein R more halogen atoms, or a halogen group ; represents a C2 - C10 haloalkyl group , R² and Rº represent R + represents a C1 - C6 alkyl group optionally having one each a hydrogen atom , R + represents an ethyl group , R " , or more halogen atoms; RS2 , and R53 represent independently of each other a hydro - 65 RI, RS2 , and R53 represent independently of each other a gen atom , or a C1- C6 alkyl group optionally having one or hydrogen atom , a C1 - C6 chain hydrocarbon group option more halogen atoms; ally having one or more halogen atoms, a 5 membered US 9 ,924 ,719 B2 15 16 aromatic heterocyclic group selected from Group B A compound represented by formula ( 1 - N ), wherein ( wherein the 5 membered aromatic heterocyclic group may optionally have one or more atoms or groups selected from Q ' represents a N + _ 0 " ; Group A ), a 6 membered aromatic heterocyclic group Q ? represents a nitrogen atom or a CH ; selected from Group C (wherein the 6 membered aromatic 5 RIN represents a C2 - C10 haloalkyl group; heterocyclic group may optionally have one or more atoms R2N and R3N represent each a hydrogen atom ; or groups selected from Group A ) , a 3 to 7 -membered nonaromatic heterocyclic group selected from Group D R4N represents an ethyl group ; and ( wherein the 3 to 7 membered nonaromatic heterocyclic q represents 0 or 1 , wherein when q represents 1 , RIN group may optionally have one or more atoms or groupsins 10 represents a C1 - C6 alkyl group optionally having one or selected from the group consisting of a halogen atom and a more halogen atoms. C1 - C6 alkyl group ) , a OR ” , a NR?R " , a S ( O ) , R ? , or a A compound represented by formula ( 1 - N ) , wherein halogen atom ; and Q represents an N + - 0 " ; Rº represents a hydrogen atom , or a halogen atom ; A compound represented by formula (1 - 2 ), wherein R ' 15 Q² represents a nitrogen atom ; represents a C2 - C10 haloalkyl group , R2 and R3 represent RIN represents a C2- C10 haloalkyl group ; each a hydrogen atom , R4 represents an ethyl group , RSI, R2N and R3M represent each a hydrogen atom ; R® , and R represent independently of each other a hydro - R4N represents an ethyl group ; and gen atom , or a C1- C6 alkyl group optionally having one or 20 g represents 0 or 1 . wherein when a represents 1 . RON more halogen atoms, and Rº represents a hydrogen atom ; represents a C1- C6 alkyl group optionally having one or A compound represented by formula ( 1 - 2 ) , wherein R ? more halogen atoms. represents a C2 - C6 alkyl group having two or more fluorine atoms, R² and R3 represent each a hydrogen atom , R + A compound represented by formula ( 1 -N1 ) : represents an ethyl group , RSI, R52 , and R $ 3 represent 25 independently of each other a hydrogen atom , or a C1 - C6 alkyl group optionally having one or more halogen atoms, ( 1 - N1 ) Rº represents a hydrogen atom . Examples of the N -oxide compound include the following O O compounds. 30 N - N (RSM ) A compound represented by formula ( 1 - N ) : RIN - 02

( 1 - N ) R2N RIN 35 (0 )2S wherein ( R ) RIN represents a C2- C10 haloalkyl group ; RIN – 0 – R2N and R3N represent independently of each other a 40 byhydrogen atom , a C1- C3 alkyl group optionally having one R2N RUNR3N or more halogen atoms, or a halogen group ; R4N represents a C1- C6 alkyl group optionally having one wherein or more halogen atoms; Q ' represents a N + _ O - or a nitrogen atom , 45 RSN represents a C1 -C6 alkyl group optionally having one Q2 represents an N + _ 0 , a CRON , or a nitrogen atom , or more halogen atoms; and wherein at least one of Q ' and Q ? represents an N + _ 0 ; RM represents a hydrogen atom , or a halogen atom ; q represents 0 or 1 . RIN represents a C2 -C10 haloalkyl group ; A compound represented by formula ( 1 - N1) , wherein R2N and R3N represent independently of each other a 50 RIN represents a C2 - C10 haloalkyl group ; hydrogen atom , a C1- C3 alkyl group optionally having one R2N and R3N represent each a hydrogen atom : or more halogen atoms, or a halogen group ; R ^ represents a C1- 06 alkyl group optionally having one R4N represents a C1 -C6 alkyl group optionally having one or more halogen atoms; and or more halogen atoms; q represents 0 or 1, wherein when q represents 1 , R5N 55 R represents a C1 - C6 alkyl group optionally having one represents a C1- C6 alkyl group optionally having one or or more halogen atoms; and more halogen atoms. q represents 0 or 1 . A compound represented by formula ( 1 - N ) , wherein Q represents a N + _ 0 ; A compound represented by formula (1 -N1 ) , wherein O2 represents a N + _ 0 , a CH , a CF , or a nitrogen atom ; 60 R " represents a C3 - C6 alkyl group having two or more RIN represents a C2 -C10 haloalkyl group ; fluorine atoms; R2N and R3N represent a hydrogen atom ; R2N and R3M represent each a hydrogen atom ; R4N represents a C1- C6 alkyl group optionally having one or more halogen atoms; and R4N represents an ethyl group ; g represents 0 or 1, wherein when a represents 1, RSN 65 R represents a C1 - C6 alkyl group optionally having one represents a C1 -C6 alkyl group optionally having one or or more halogen atoms; and more halogen atoms. q represents 0 or 1 . US 9 ,924 ,719 B2 18 A compound represented by formula ( 1 -N2 ) : wherein R1M represents a C2- C10 haloalkyl group;

5 R2M and R3N represent independently of each other a hydrogen atom , a C1 -C3 alkyl group optionally having one ( 1 -N2 ) or more halogen atoms, or a halogen group ; PA R4N represents a C1- C6 alkyl group optionally having one 10 DOM or more halogen atoms; RIN - 07 RSN represents a C1 - C6 alkyl group optionally having one or more halogen atoms; 27-9 RIN 15 q represents 0 or 1 ; and RÓN represents a hydrogen atom , or a halogen atom . A compound represented by formula ( 1 - N3) , wherein 20 RIN represents a C2 -C10 haloalkyl group ; wherein RIN represents a C2 -C10 haloalkyl group ; R2N and R3N represent each a hydrogen atom ; R2N and R3N represent independently of each other a R ^ ^ represents a C1- C6 alkyl group optionally having one hydrogen atom , a C1- C3 alkyl group optionally having one or more halogen atoms; or more halogen atoms, or a halogen group ; R4N represents a C1- C6 alkyl group optionally having one RSN represents a C1- C6 alkyl group optionally having one or more halogen atoms; or more halogen atoms; R5N represents a C1- C6 alkyl group optionally having one 30 q represents 0 or 1 ; and or more halogen atoms; and q represents 0 or 1. R6N represents a hydrogen atom , or a fluorine atom . A compound represented by formula ( 1 -N2 ) , wherein A compound represented by formula ( 1 -N3 ) , wherein RIN represents a C2- C10 haloalkyl group; 3535 R2N and R3N represent each a hydrogen atom ; RIN represents a C3 -C6 alkyl group having two or more R4N represents a C1- C6 alkyl group optionally having one fluorine atoms; or more halogen atoms; R2N and RBN represent each a hydrogen atom ; 40 RSN represents a C1- C6 alkyl group optionally having one * R4N represents an ethyl atom ; or more halogen atoms; and q represents 0 or 1 . RSN represents a C1- C6 alkyl group optionally having one or more halogen atoms; and A compound represented by formula ( 1 -N2 ) , wherein 45 RIN represents a C3- C6 alkyl group having two or more q represents 0 or 1 . fluorine atoms; R2N and R3N represent a hydrogen atom ; Next, a process for preparing the present compound is R ^ ^ represents an ethyl group ; described . RSN represents a C1- C6 alkyl group optionally having one 50 The present compound and the immediate compound can or more halogen atoms; and be prepared , for example , according to the following (Pro q represents 0 or 1. A compound represented by formula ( 1 -N3 ) : cesse 1 ) to (Process 12) . 55 (1 - N3 ) Process 1 R4N The present compound ( 1b ) represented by formula ( 1) (O )2S 60 wherein n is 1 (hereinafter , referred to as “ Present compound N - N (ROM ( 1b )” ) and the present compound ( 1c ) wherein n is 2 RIN – 0 – (hereinafter , referred to as “ Present compound ( 1c )” ) may be prepared by reacting the present compound (1a ) wherein n R3N RON is 0 ( hereinafter , referred to as “ Present compound ( 1a ) ” ) with an oxidizing agent. US 9, 924 ,719 B2 20

OSS NN 2 N - N (R )p - L ( R ) R - 04 DI- 0

(la ) E

N - VN OS ( R ') p R1 - 04 =

R3 ( 1c ) wherein the symbols are the same as those defined in the aqueous solution of a base such as sodium hydrogen car formula ( 1 ) bonate . The resulting organic layer is dried and concentrated First , a process for preparing Present compound (1b ) from to give Present compound ( 1b ). The obtained Present com Present compound ( la ) is described . pound ( 1b ) may be further purified with a chromatography, The reaction is usually carried out in the presence of a and recrystallization , etc . solvent. Next, a process for preparing Present compound ( 1c ) from Examples of the solvent to be used in the reaction include Present compound ( 1b ) is explained . halogenated aliphatic hydrocarbons (hereinafter , collec - 35 The reaction is usually carried out in the presence of a tively referred to as “ halogenated aliphatic hydrocarbons” ) solvent. such as dichloromethane and chloroform ; nitriles (hereinaf - Examples of the solvent to be used in the reaction include ter, collectively referred to " nitriles” ) such as acetonitrile ; halogenated aliphatic hydrocarbons, nitriles, alcohols , acetic alcohols ( hereinafter, collectively referred to as " alcohols” ) acid , water , and mixed solvents thereof. such as methanol and ethanol; acetic acid ; water ; and mixed 40 Examples of the oxidizing agent to be used in the reaction solvents thereof. include mCPBA and hydrogen peroxide. Examples of the oxidizing agent to be used in the reaction When hydrogen peroxide is used as the oxidizing agent, includes sodium periodate , m - chloroperoxybenzoic acid a base or a catalyst may be added as needed . (hereinafter , referred to as “ mCPBA ” ) , and hydrogen per - Examples of the base to be used include sodium carbon oxide. 45 ate . When hydrogen peroxide is used as the oxidizing agent , Examples of the catalyst to be used include sodium a base or a catalyst may be added as needed . tungstate . Examples of the base to be used in the reaction include In the reaction , the oxidizing agent is used usually within sodium carbonate . a range of 1 to 4 molar ratio ( s ) as opposed to 1 mole of Examples of the catalyst to be used in the reaction include 50 Present compound ( 1b ). Preferably , the oxidizing agent is tungstic acid , and sodium tungstate . used within a range of 1 to 2 molar ratio ( s ) as opposed to 1 In the reaction , the oxidizing agent is used usually within mole of Present compound ( 1b ) . a range of 1 to 1 . 2 molar ratio ( s ) , as opposed to 1 mole of In the reaction , the base is used usually within a range of Present compound ( 1a ). 0 .01 to 1 molar ratio ( s ) as opposed to 1 mole of Present In the reaction , the base is used usually within a range of 55 compound ( 1b ) . 0 .01 to 1 molar ratio ( s) , as opposed to 1 mole of Present In the reaction , the catalyst is used usually within a range compound ( la ) . of 0 .01 to 0 . 5 molar ratios as opposed to 1 mole of Present In the reaction , the catalyst is used usually within a range compound ( 1b ) . of 0 .01 to 0 . 5 molar ratios , as opposed to 1 mole of Present reaction temperature in the reaction is usually within a compound ( 1a ). 60 range of - 20 to 120° C . A reaction period in the reaction is A reaction temperature in the reaction is usually within a usually within a range of 0 .1 to 12 hours . range of - 20 to 80° C . A reaction period in the reaction is When the reaction is completed , the reaction mixture is usually within a range of 0 .1 to 12 hours. extracted with an organic solvent, and the organic layer is When the reaction is completed , the reaction mixture is optionally washed with an aqueous solution of a reducing extracted with organic a solvent, and the organic layer is 65 agent such as sodium sulfite and sodium thiosulfate , and an optionally washed with an aqueous solution of a reducing aqueous solution of a base such as sodium hydrogen car agent such as sodium sulfite and sodium thiosulfate , and an bonate . The resulting organic layer is dried and concentrated US 9 ,924 ,719 B2 21 22 to give Present compound ( 1c ). The obtained Present com wherein V represents a halogen atom , and the other symbols pound ( 1c ) may be further purified with a chromatography, are the same as those defined in the formula ( 1 ) . and recrystallization , etc . Also , Present compound ( 1c ) may be prepared in one step The reaction is usually carried out in the presence of a ( one - spot ) by reacting Present compound ( la ) with an 5 solvent. oxidizing agent. Examples of the solvent to be used in the reaction include The reaction is usually carried out in the presence of a ethers (hereinafter , referred to as “ ethers ” ) such as tetrahy solvent. drofuran (hereinafter , referred to as “ THF " ) , ethyleneglycol Examples of the solvent to be used in the reaction include dimethyl ether, methyl tert -butyl ether, and 1 , 4 - dioxane ; halogenated aliphatic hydrocarbons , nitriles , alcohols , acetic 10 aromatic hydrocarbons (hereinafter , referred to as " aromatic acid , water, and mixed solvents thereof. hydrocarbons " ) such as toluene and xylene; nitrils ; polar Examples of the oxidizing agent to be used in the reaction aprotic solvents (hereinafter , referred to as “ polar aprotic include mCPBA and hydrogen peroxide . solvents ” ) such as N , N - dimethylformamide (hereinafter , When hydrogen peroxide is used as oxidizing agent, a referred to as “ DMF ' ) , N -methyl pyrrolidone (hereinafter , base or a catalyst may be added as needed . 15 referred to as “ NMP” ) and dimethyl sulfoxide (hereinafter , Examples of the base to be used include sodium carbon referred to “ DMSO " ) ; water ; and mixed solvents thereof. ate . Examples of the base to be used in the reaction include Examples of the catalyst to be used include tungstate , and alkali metal carbonates (hereinafter , referred to as " alkali sodium tungstate , etc . metal carbonates ” ) such as sodium carbonate and potassium In the reaction , the oxidizing agent is used usually within 20 carbonate ; and alkali metal hydrides ( hereinafter, referred to a range of 2 to 5 molar ratios as opposed to 1 mole of Present as “ alkali metal hydrides” ) such as sodium hydride . compound ( 1a ) . In the reaction , Compound ( R1) is usually used within a In the reaction , the base is used usually within a range of range of in 1 to 10 molar ratio ( s ) as opposed to 1 mole of 0 .01 to 1 molar ratio ( s ) as opposed to 1 mole of Present ComCompound (M1 ) . Preferably , Compound (R1 ) is used within compound ( la ). 25 a range of in 1 . 0 to 1 . 1 molar ratio ( s ) , and the base is used In the reaction , the catalyst is used usually within a range within a range of 1 to 2 molar ratio ( s ) as opposed to 1 mole of 0 .01 to 0 . 5 molar ratios as opposed to 1 mole of Present of Compound (M1 ) . compound (la ). A reaction temperature in the reaction is usually within a A reaction temperature in the reaction is usually within a range of - 20 to 150° C . A reaction period in the reaction is range of - 20 to 120° C . A reaction period in the reaction is 30 usually within a range of 0 . 5 to 24 hours . usually within a range of 0 . 1 to 12 hours . When the reaction is completed , the reaction mixture is When the reaction is completed , the reaction mixture is extracted with an organic solvent , and the organic layer is extracted with an organic solvent, and the resulting organic optionally washed with an aqueous solution of a reducing layer is worked up such as drying and concentration to give agent such as sodium sulfite and sodium thiosulfate , and an 35 Present compound ( la ) . The obtained Present compound aqueous solution of a base such as sodium hydrogen car ( la ) may be further purified with a chromatography , and bonate . The resulting organic layer is dried and concentrated recrystallization , etc. to give Present compound ( 1c ) . The obtained Present com In the reaction , V is preferably a fluorine atom or a pound ( 1c ) may be further purified with a chromatography, chlorine atom . and recrystallization , etc . 40 Process 3 Process 2 Present compound ( 1 ) may be prepared by reacting a Present compound ( la ) may be prepared by reacting a compound represented by formula (M2 ) (hereinafter , compound represented by formula (M1 ) (hereinafter , referred to as “ Compound (M2 ) ” ) with a compound repre referred to as “ Compound (M1 ) ” ) with a compound repre sented by formula (R2 ) (hereinafter , referred to as “ Com sented by formula (R1 ) (hereinafter , referred to as “ Com - 45 pound (R2 ) ” ) in the presence of a base . pound (R1 ) " ) in the presence of a base .

N (0 ) = s N - - (R )p R4 - SH 50 R - V1 R - 04 | HN _ N . 2 (R5 ) , (R1 ) (R2 ) P3R ? 55 (M1 ) 55 R R3 za(M2 ) RY S N - N (O ) = (R ) 60 N - N RI — 0 – ((RºR ) ) ,p + R1R - 040 T R R3 BB( 1a ) 65 BY US 9, 924 ,719 B2 23 24 -continued -continued comment R ! (0 ) = s (On = S NN - A (RRS R ).p , 5 N — N (RS ) 04 l R1 - 04

'R3 (B1 ) 10 East wherein Vl represents a halogen atom , a methylsulfonyloxy wherein V2 represents a halogen atom or a methylsulfonyl group , a trifluoromethylsulfonyloxy group , a nonafluorobu - group, and the other symbols are the same as those defined tanesulfonyloxy group , or a para- toluenesulfonyloxy group , 15 in the formula ( 1 ) . and the other symbols are the same as those defined in the The reaction is usually carried out in the presence of a formula ( 1 ) . solvent. The reaction is usually carried out in the presence of a Examples of the solvent to be used in the reaction include solvent. ethers , aromatic hydrocarbons, nitrils , polar aprotic solvents , Examples of the solvent to be used in the reaction include watwater , and mixed solvents thereof. ethers , halogenated aliphatic hydrocarbons, aromatic hydro Examples of the base to be used in the reaction include carbons , polar aprotic solvents , and mixed solvents thereof. alkali metal carbonates , and alkali metal hydrides. In the reaction , Compound (R3 ) is usually used within a Examples of the base to be used in the reaction include 25 range of in 1 to 100 molar ratio ( s ), and the base is used organic bases (hereinafter , referred to as “ organic bases ” ) within a range of 1 to 10 molar ratio ( s ), as opposed to 1 mole such as triethylamine, diisopropylethylamine , pyridine and of Compound (M3 ) . Preferably , Compound (R3 ) is used 4 -dimethylaminopyridine ; alkali metal hydrides ; or alkali within a range of in 1 . 0 to 1 . 5 molar ratio ( s ) , and the base metal carbonates . is used within a range of 1 . 0 to 2 .0 molar ratio ( s ), as opposed In the reaction , Compound (R2 ) is usually used within a 30 to 1 mole of Compound (M3 ) . range of in 1 to 10 molar ratio ( s ) , and the base is used within A reaction temperature in the reaction is usually within a a range of 0 . 1 to 5 molar ratio ( s ), as opposed to 1 mole of range of - 20 to 150° C . A reaction period in the reaction is Compound (M2 ) . usually within a range of 0 . 5 to 24 hours . A reaction temperature in the reaction is usually within a zo When the reaction is completed , the reaction mixture is range of - 20 to 120° C . A reaction period in the reaction is extracted with an organic solvent, and the resulting organic usually within a range of 0 . 1 to 24 hours . layer is worked up such as drying and concentration to give Present compound ( 1 ) . The obtained Present compound ( 1 ) In the reaction , the compound represented by formula may be further purified with a chromatography, and recrys ( B1) may be produced as a by -product . 40 tallization , etc . When the reaction is completed , the reaction mixture is In the reaction , V2 is preferably a chlorine atom , or a extracted with an organic solvent, and the resulting organic methylsulfonyl group . layer is concentrated ; the reaction mixture is added to water, and the resulting solid is collected through filtration ; or the Process 5 solid in the reaction mixture is collected through filtration to 45 Compound (M1 ) may be prepared by reacting a com obtain Present compound ( 1 ) . The obtained Present com - " pound represented by formula (M4 ) (hereinafter , referred to pound ( 1 ) may be further purified with a chromatography, as “ Compound (M4 ) ” ) with a compound represented by formula (R2 ) (hereinafter , referred to as “ Compound (R2 ) " ) and recrystallization , etc . in the presence of a base . Process 4 Present compound ( 1 ) may be prepared by reacting a 50 compound represented by formula (M3 ) (hereinafter , referred to as “ Compound (M3 ) ” ) with a compound repre HN (RS ) p RS - v ! sented by formula (R3 ) (hereinafter , referred to as “ Com ON pound (R3 ) ” ) in the nresence of a base . 55 (R2 ) R3 (M3 ) (On = S N - NM S (RS ) , R - OH N - N ( R ) , V2 (R3 ) RSROM -- 04

R3 R2 R3 (M3 ) (M1 ) US 9 , 924 ,719 B2 25 26 -continued Examples of the solvent to be used in the reaction include R ! ethers , aromatic hydrocarbons, polar aprotic solvents , water , N - N and mixed solvents thereof. (RS ), Examples of the metal catalyst to be used in the reaction 5 include palladium catalysts such as tetrakis ( triphenylphos phine )palladium ( 0 ), 1, 1' - bis ( diphenylphosphino ) ferrocene 'R3 palladium ( II ) dichloride , tris (dibenzylideneacetone )dipalla dium ( 0 ) and palladium (II ) acetate ; nickel catalysts such as (B2 ) bis (cyclooctadiene ) nickel ( 0 ) and nickel( II ) chloride ; and 10 cocopper) catalyst such as copper (I ) iodide and copper( I ) wherein the symbols are the same as those defined in the chloride . formula (1 ). In the reaction , a ligand , a base and an inorganic haloge The reaction may be carried out according to the similar nated compound may be added as needed . method to that described in Process 3 by using Compound 155 Examples of the ligand to be used in the reaction include (M4 ) instead of Compound (M2 ) . triphenylphosphine, Xantphos , 2 ,2 '- bis (diphenylphoshino ) In the reaction , a compound represented by formula ( B2 ) 1, 1' - binaphthyl , 1, 1 ' - bis (diphenylphoshino ) ferrocene, 2 - (di may be produced as a by - product . cyclohexylphosphino )- 2 ' , 4 ' , 6 '- triisopropylbiphenyl , 2 -dicy Process 6 20 clohexylphosphino - 2' , 6 '- dimethoxybiphenyl , 1 ,2 -bis Compound (M1 ) may be prepared by reacting a com - (diphenylphosphino ) ethane, 2 , 2 -bipyridine , pound represented by formula (M6 ) (hereinafter , referred to as “ Compound (M6 ) ” ) with a compound represented by 2 - aminoethanol , 8 -hydroxyquinoline , and 1 , 10 -phenanthro formula (M7 ) (hereinafter , referred to as “ Compound (M7 ) ” ) line , etc . in the presence of a metal catalyst . Examples of the base to be used in the reaction include alkali metal hydrides, alkali metal carbonates , or organic bases . Examples of the inorganic halogenated compounds to be 30 used in the reaction include alkali metal fluorides such as N - N potassium fluoride and sodium fluoride ; and alkali metal R1 - 07 03V L ( R ) chlorides such as lithium chloride and sodium chloride. + M In the reaction , Compound (M7 ) is usually used within a 35 range of 1 to 10 molar ratio (s ) , the metal catalyst is usually R2 P3 (M7 ) used within a range of 0 .01 to 0 .5 molar ratios, the ligand is (M6 ) usually used within a range of 0 .01 to 1 molar ratio ( s ), the base is usually used within a range of 0 . 1 to 5 molar ratios, 40 and the inorganic halogenated compound is usually used N — N within a range of 0 . 1 to 5 molar ratios , as opposed to 1 mole R ? — 0 – of Compound (M6 ). 45 A reaction temperature in the reaction is usually within a range of - 20 to 200° C . A reaction period in the reaction is usually within a range of 0 . 1 to 24 hours . (M1 ) When the reaction is completed , to the reaction mixtures is added water, and the reaction mixture is then extracted 50 with an organic solvent, and the resulting organic layer is concentrated ; the reaction mixture is added to water, and the wherein V? represents a halogen atom , M represents 9- bo resulting solid is collected through filtration ; or the solid in rabicyclo [ 3 .3 . 1 ]nona - 9 -yl group , — B (OH )2 , 4 , 4 ,5 ,5 - tetram ethyl- 1 , 3 , 2 - dioxaborolan - 2 - yl group , SnBuz, ZnCl, 55 methe reaction mixture is collected through filtration to obtain - MgCl, or MgBr; and the other symbols are the same as Present compound (M1 ) . The obtained Present compound those defined above. (M1 ) may be further purified using a chromatography, and Compound ( M6 ) may be prepared according to a similar method to that described in US patent application publica recrystallization , etc . tion No . 2010 /0261727 . 60 In the reaction , V3 is preferably a chlorine atom , a Compound (M7 ) may be prepared according to a similar bromine atom , or an iodine atom . method to that described in International Publication No . Process 7 03 / 024961 or Organic Process Research & DevelopMent, A compound of Compound (M2 ) wherein n is 0 (M2a ), a 2004 , 8, 192 -200 . compound of Compound (M2 ) wherein n is 1 (M2b ) , and a The reaction is usually carried out in the presence of a compound of Compound (M2 ) wherein n is 2 (M2c ) may be solvent . prepared according to a method described as follows. US 9 , 924 ,719 B2 27 28

HN - N (Rp R4 — SH HN - N . (RS ) (R1 ) 0 = 2 R3 R ? (M4 ) a potom(M2a )

0 R4 OES HN - N (R ) HN - NN . = ( R5) ,

R3 R R3R3 ( M2c) (M2b ) wherein V represents a halogen atom , and the other symbolsbols 25 -continued are the same as those defined in the formula ( 1 ) . First, a process for preparing Compound (M2a ) from (0 ) , = Compound (M4 ) is described . HN Compound (M2a ) may be prepared according to the 30 ( R ) method described in Process 2 using Compound (M4 ) instead of Compound (M1 ) . Next, a process for preparing Compound (M2b ) from P3 Compound (M2a ) and Compound (M2c ) from Compound 35 (M2 ) (M2b ) is described . wherein R represents a hydrogen atom , a methyl group, or Compound (M2b ) may be prepared according to the an ethyl group , and the other symbols are the same as those method described in Process 1 using Compound (M2a ) - defined above . 40 Compound (M8 ) may be prepared according to a similar instead of Compound ( la ). method to that described in Journal of American Chemical Compound (M2c ) may be prepared according to the Society , 2012 , 134 (6 ) , 2906 - 2909 , or International Publica tion No. 2014 / 010990 . method described in Process 1 using Compound (M2b ) The reaction is usually carried out in the presence of a instead of Compound ( 1b ) . 45 solvent. Examples of the solvent to be used in the reaction include Process 8 methanol, ethanol, ethers, polar aprotic solvents , water , and Compound (M2 ) may be prepared by reacting a com - mixed solvents thereof. pound represented by formula (M8 ) (hereinafter , referred to Examples of the base to be used in the reaction include 50 alkali metal hydroxides (hereinafter , referred to as “ alkali as “ Compound (M8 ) ” ) with a compound represented by » metal hydroxides ” ) such as sodium hydroxide and potassium formula (M4 ) (hereinafter , referred to as “ Compound (M4 ) ' ) hydroxide, alkali metal carbonates, or alkalimetal hydrides. in the presence of a base or an acid , and reacting the obtained Examples of the acid to be used in the reaction include compound with hydrazine . organic carbonic acids such as acetic acid and formic acid , 55 and mineral acids such as hydrochloric acid and sulfuric acid . In the reaction , Compound (R4 ) is usually used within a range of 1 to 10 molar ratio ( s ) , the base is usually used within a range of 1 to 10 molar ratios , the acid is usually (0 ) , = s 60 used within a range of 1 to 10 molar ratio ( s ) , and hydrazine (R pt) H2N - NH2 is usually used within a range of 1 to 10 molar ratios , as R2 opposed to 1 mole of Compound (M8 ) . A reaction temperature in the reaction is usually within a 73 yho range of - 20 to 150° C . A reaction period in the reaction is R3 65 usually within a range of 0 .5 to 24 hours . (M8 ) ( R4 ) When the reaction is completed , the reaction mixture is extracted with an organic solvent, and the organic layer is US 9 ,924 ,719 B2 30 worked up such as drying and concentration to give Com - continued pound (M2 ) . The obtained Compound (M2 ) may be further purified with a chromatography, and recrystallization , etc . Process 9 (0 , = s A compound of Compound (M3 ) wherein n is 1 (M3b ), 5 (Rº ) p and a compound of Compound (M3 ) wherein n is 2 (M3c ) V4 may be prepared by reacting a compound of Compound (M3 ) wherein n is 0 (M3a ) with an oxidizing agent. R3 (M3d ) Me - S - OM N - N (R (On = dhmenS R3 ON- N (R ) (M3a ) Me

=o

= R R3 N - N Me( ) 12. 25 wherein V4 represents a chlorine atom or a bromine atom , R3 M ' represents sodium , and the other symbols are the same as those defined above . (M3b ) First , a process for preparing Compound (M3d ) from 30 Compound (M2 ) is described . Compound (M3d ) may be prepared by reacting Com pound (M2 ) with a halogenating agent. The reaction is usually carried out in the presence of a 35 Solven Ó - (RS ) Examples of the solvent to be used in the reaction include A ethers , halogenated hydrocarbons , and aliphatic hydrocar bons. Examples of the halogenating agent to be used in the 40 reaction include thionyl chloride , phosphorus oxychloride, (M3c ) and phosphorus oxybromide, etc . In the reaction , a catalyst may be added as needed . Examples of the catalyst to be used in the reaction include wherein the symbols are the same as those defined above. DA Compound (M3b ) may be prepared according to the 45 . In the reaction , the halogenating agent is usually used method described in Process 1 using Compound (M3a ) within a range of 1 to 10 molar ratio ( s ), and the catalyst is instead of Compound (1a ). usually used within a range of 0 .01 to 0 . 1 molar ratio ( s ) , as Compound (M3c ) may be prepared according to the opposed to 1 mole of Compound (M2 ) . Further, in the method described in Process 1 using Compound (M3b ) reaction , thionyl chloride and phosphorus oxychloride in the instead of Compound ( 1b ) . 50 state of liquid may be used as a solvent. Process 10 A reaction temperature in the reaction is usually within a A compound of Compound (M3 ) wherein V2 is a chlorine range of - 20 to 150° C . A reaction period in the reaction is atom or a bromine atom (M3d ) , and a compound of Com usually within a range of 0 . 5 to 24 hours . pound (M3 ) wherein V2 is a methylsulfonyl (M3e ) may be When the reaction is completed , to the reaction mixture is prepared according to a method described as follows. 55 added water after evaporating an excess of the halogenating agent under reduced pressure , and then the obtained mixture is extracted with an organic solvent , and the organic layer is worked up such as drying and concentration to give Com (O ) = S pound (M3d ) . The obtained Compound (M3d ) may be HN _ N 60 further purified with a chromatography , and recrystalliza ( R ) tion , etc . Next, a process for preparing Compound (M3e ) from Compound (M3d ) is described . Compound (M3e ) may be prepared by reacting Com R3 65 pound (M3d ) with sodium methanesulfinate . (M2 ) The reaction is usually carried out in the presence of a solvent. US 9 , 924 ,719 B2 31 32 Examples of the solvent to be used in the reaction include Examples of the acid to be used in the reaction include polar aprotic solvents . mineral acids such as hydrochloric acid , boron halides such In the reaction , a catalyst may be added as needed . Examples of the catalyst to be used in the reaction include as boron trichloride and boron tribromide, and metal chlo quaternary ammonium salts such as tetrabutylammonium 5 rides such as titanium chloride and aluminium chloride . chloride , etc . m 5 In the reaction , the acid is usually used within a range of In the reaction , sodium methanesulfinate is usually used 0 . 1 to 10 molar ratio ( s ) as opposed to 1 mole of Compound within a range of 1 to 10 molar ratio ( s ), and the catalyst is (M -9 ) . In the reaction , when the mineral acid is used as an usually used within a range of 0 . 01 to 0 . 5 molar ratio ( s ) , as acid , the mineral acid can be also used as a solvent. opposed to 1 mole of Compound (M3d ) . A reaction temperature in the reaction is usually within a A reaction temperature in the reaction is usually within a range of - 20 to 150° C . A reaction period in the reaction is range of - 20 to 150° C . A reaction period in the reaction is usually within a range of 0 . 1 to 24 hours . usually within a range of 0 . 5 to 24 hours. When the reaction is completed , to the reaction mixture is When the reaction is completed , the reaction mixture is added water, and the reaction mixture is then extracted with extracted with an organic solvent, and the organic layer is is an organic solvent, and the resulting organic layer is con worked up such as drying and concentration to give Com - 15 pound (M3e ) . The obtained Compound (M3 ) may be centrated ; the reaction mixture is added to water , and the further purified with a chromatography, and recrystalliza resulting solid is collected through filtration ; or the solid in tion , etc . the reaction mixture is collected through filtration to give Process 11 Present compound (M4 ) . The obtained Present compound Compound (M4 ) may be prepared according to a method 20 (M4 ) may be further purified with a chromatography, and described as follows . recrystallization , etc . A compound of Compound (M8 ) wherein n is 0 (M8a ) , a N - N compound of Compound (M8 ) wherein n is 1 (M8b ) , and a ll compound of Compound (M8 ) wherein n is 2 (M8c ) may be R04 í 13 25 prepared according to a method described as follows. R2 R3 R4 (M10 ) (M7 ) 30 O . N - N (Rº ) p R4 — SH O . (RS ) (R1 ) RO

R3 35 P3 (M9 ) ( M11 ) (M8a ) HN _ N Rp( 40

+ (RS (M4 ) 45 wherein R * represents a methyl group and an ethyl group , and the other symbols are the same as those defined above . Compound , (M10 ) may be prepared according to a similar (M8c ) (M8b ) method to that described in US patent application publica tion No . 2010 /0261727 . First, a process for preparing a compound represented by wherein the symbols are the same as those defined above. formula (M9 ) (hereinafter , referred to as “ Compound (M9 ) ” ) Compound (M11 ) is a known compound , or may be is described . prepared according to a known method or a similar method Compound (M9 ) may be prepared according to the to that described in International Publication No . 2014 / method described in Process 6 using a compound repre - 55 010990 . sented by formula (M10 ) (hereinafter , referred to as “ Com - First , a process for preparing Compound (M8a ) from a pound (M10 ) ” ) instead of Compound (M6 ) . compound represented by formula (M11 ) (hereinafter , Next, a process for preparing Compound (M4 ) from referred to as “ Compound (M11 ) '' ) is described . Compound (M9 ) is described . Compound (M8a ) may be prepared according to the Compound (M4 ) may be prepared by reacting Compound 60 method described in Process 2 using Compound (M11 ) (M9 ) in the presence of an acid . instead of Compound (M1 ). The reaction is usually carried out in the presence of a Next, a process for preparing Compound (M8b ) from solvent. Compound (M8a ) and Compound (M8c ) from Compound Examples of the solvent to be used in the reaction include (M8b ) is described . halogenated aliphatic hydrocarbons, aromatic hydrocarbons, 65 Compound (M8b ) may be prepared according to the nitrils , alcohols , acetic acid , water, and mixed solvents method described in Process 1 using Compound (M8a ) thereof. instead of Compound (la ). US 9 ,924 ,719 B2 33 34 Compound (M8c ) may be prepared according to the Examples of the catalyst to be used in the reaction include method described in Process 1 using Compound (M8b ) tungstic acid , and sodium tungstate . instead of Compound ( 1b ) . In the reaction , the oxidizing agent is used usually within Process 13 a range of 1 to 20 molar ratio ( s ) as opposed to 1 mole of An N -oxide compound represented by formula (N11 ) 5 Present compound ( 18N ). (hereinafter , referred to as “ N - oxide compound (N11 ) ” ) , an N - oxide compound represented by formula (N12 ) (herein In the reaction , the catalyst is used usually within a range after , referred to as “ N -oxide compound (N12 )” ), and an of 0 .01 to 0 . 5 molar ratio ( s ) as opposed to 1 mole of Present N - oxide compound represented by formula (N13 ) (herein compound ( 18N ) . after . referred to as “ N -oxide compound (N13 ) ” ) may be 10 A reaction temperature in the reaction is usually within a prepared by reacting the present compound represented by range of - 20 to 80° C . A reaction period in the reaction is formula ( 1dN ) (hereinafter , referred to as “ Present com usually within a range of 0 . 1 to 24 hours . pound ( 10N )" ) with an oxidizing agent. When the reaction is completed , the reaction mixture is extracted with an organic solvent, and the organic layer is optionally washed with an aqueous solution of a reducing O RAN agent such as sodium sulfite and sodium thiosulfate , and an aqueous solution of a base such as sodium hydrogen car N - N (ROM ) bonate . The resulting organic layer is dried and concentrated RIN - 07 to give any one of N -oxide compound (N11 ) , N -oxide N compound (N12 ) , or N -oxide compound (N13 ), or the R2N RIN (10N ) mixture of N -oxide compounds ( N11 )- (N13 ). Any one of the R4N 25 obtained N - oxide compound (N11 ) , N - oxide compound R41 (N12 ) , or N -oxide compound (N13 ) , or the mixture of N -oxide compounds (N11 ) -( N13 ) may be further purified N - N (RM ) RIN - O with a chromatography , and recrystallization , etc . 30 Process 14 R21 R3N An N -oxide compound represented by formula (N15 ) (N11 ) ( hereinafter, referred to as “ N -oxide compound (N15 )" ) may R41 be prepared by reacting the present compound represented a 35 by formula ( 1eN ) ( hereinafter , referred to as “ Present com N - N = (RS ) pound ( leN )” ) with an oxidizing agent. RIN - 04 40 RAN R21 RIN O s (N12 ) O= N EN? AV (RSM 5M) , O 85 RINRIN – 0 – N - N (R5M RIARIN – 0 – R2N R3N RON (len ) N R4N 50 R2N R3NR3N Ó 0 ( 0 )2S (N13 ) N - N (RS wherein the symbols are the same as those defined above . RIN – 0 – The reaction is usually carried out in the presence of a 55 solvent. R2N RIN Examples of the solvent to be used in the reaction include RON halogenated aliphatic hydrocarbons, nitriles , alcohols , acetic ( N15 ) acid , water, and mixed solvents thereof. Examples of the oxidizing agent to be used in the reaction 60 wherein the symbols are the same as those defined above . includes sodium periodate , m - chloroperoxybenzoic acid ( hereinafter, referred to as “mCPBA ” ), and hydrogen per The reaction may be carried out according to the method oxide . en per described in Reference Process 1 using Present compound When hydrogen peroxide is used as the oxidizing agent, (len ) instead of Present compound ( 18N ) . a catalyst may be added as needed . 65 Process 15 Examples of the base to be used in the reaction include The N -oxide compound may be prepared according to a sodium carbonate . method described as follows. US 9 , 924 ,719 B2 35 36 35 A present compound represented by formula ( 1 - 1 ) : R4N

( 1 - 1 ) N - N ( RSM ) (O ). . s N - N R2N RIN R1 - 04 RS2 (M3f ) 10 R2 R3 R53 wherein R² and R3 represent each a hydrogen atom , and 15 R1, R4, n , R51 , R52 , and R53 represent any one combination R4N indicated in Table 1 to Table 10 . TABLE 1 ( R™ ) p 20 R1 R4 n R51 R52 253 CF2HCH CH3CH2 CH2CF2 CH2CH R2N R3N CF2CH CH2CH2 CC12CH2 CH2CH (M3N ) 25 CF HCF , CH2CH2 CHCIFCF , CH3CH2 RIN - OH CF2CH . CH CH3CH2 (R3N ) CF HCF CH2 CH3CH2 CF CF CH2 CH3CH2 CBrF CF2 CH3CH2 CF CFHCF ) CH3CH2 30 CH , CF- CH CH3CH2 CF2CH ( CH3) CH3CH2 CF3C ( CH3) 2 CH3CH2 CH (CH3 ) 2CH (CF3 ) CH3CH2 R4N ( CF3) , CH CH3CH2 CH2CH2CH ( CF3) CH2CH , 35 CF CCI, CH2 CH3CH2 CF3CF2CH ( CH3) CH3CH2 01_ N (RSM CF3CF2CH (CH2CH3 ) CH3CH2 RIN - 07

40 NNNNNNNNNNNNNNNNNNNN R2N RIN TABLE 2 ( 1- 1 ) RI R4 n R51 R52 R53 C (CH3 ) ( CF3) 2CH2 CH2CH2 2 H H CF3CFHCF2CH2 CH2CH wherein the symbols are the same as those defined above . 45 CF3( CF2 )2CH2 CH , CH , CBFF CF - CH - CH , CH2CH2 First, a process for preparing a compound represented by CF2CFHCF , CH (CH3 ) CH3CH2 formula (M3N ) (hereinafter , referred to as “ Compound CF2CH = CHCH , CH3CH2 CF3( CF2 ) 3CH2 CH3CH2 (M3N ) ” ) is described . Compound (M3N ) may be prepared CF3 (CF2 ) ACH CH2CH2 by reacting a compound represented by formula (M3f D ) 50 CF3( CF ) CH , CH , CH3CH2 (hereinafter , referred to as “ Compound (M3f ) " ) with an CF (CF3 ) 2CF2CF2CH2CH2 CH2CH2 CF H (CF2 ) 3CH2 CH3CH2 oxidizing agent. CF _ H (CF2 ) SCH , CH2CH2 The reaction may be carried out according to the method CF3??? ( CF2 ) 2CH2CH2CH2 CH3CH2 described in Reference Process 1 using Compound (M3f ) CF??? CF (CH ) SCH CH2CH2 CF3??? ( CF2 ) . CH2CH2CH2 CH2CH2 instead of Present compound ( 10N ) . 55 CF3( CF2) 2CH ( CHACH , CH, CH , Next, a process for preparing N -oxide compound ( 1 - N ) is CF3( CF2) 3CH2CH2 CH3CH2 described . N -oxide compound ( 1 - N ) may be prepared by CF ( CF3) 2CH ( CH2) 4CH2 CH3CH2 2 H H reacting Compound (M3N ) with a compound represented by formula (R3N ) (hereinafter , referred to as “ Compound NNNNNNNNNNNNNNNNNN (R3N ) " ) in the presence of an oxidizing agent. TABLE 3 The reaction may be carried out according to the method described in Process 4 using Compound (M3N ) instead of RI R4 R51 R52 R53 Compound (M3 ) and Compound (R3N ) instead of Com CF2OCFHCF2 CH2CH2 2 ?H ? H CH3OCH CF2CH2 CH3CH2 H pound (R3 ) . 65 CF CHOCH CF2CH2 CH3CH2 H Next, specific examples of the present compound are CH FCF2CH2 CH2CH2CH3CH2 H H shown as follows. HHH US 9, 924 ,719 B2 38 TABLE 3 -continued TABLE 6 - continued R ? R4 n R51 R52 R53 RI R4 n R51 R52 R53

CH _ CICF2CH2 CH3CH2 H H CBrF ,CF2 CH3CH2 CF3??? CH , BrCF2CH2 CH3CH2 5 CF3CFHCF2 CH3CH2 ??? CH OCH ( CF2) 2CH2 CH2CH2 CH , CÁCH , CH2CH2 1??? CF3CH2OCH ( CF2) 2CH2 CH2CH2 CF2CH (CH3 ) CH3CH2 1??? CH F ( CF2) 2CH CH3CH2 CF3C (CH3 ) 2 CH3CH2 1??? CH _ CI( CF2) 2CH2 CH3CH2 CH ( CH3) 2CH (CF3 ) CH2CH2 ??? CH , Br( CF2) 2CH2 CH3CH2 (CF3 ) 2CH CH3CH2 1??? 1 CH2OCH ( CF2) 3CH2 CH3CH2 10 CH3CH2CH (CF3 ) CH3CH2 ??? 1 CF2CH OCH ( CF2 )3CH2 CH3CH2 CF3CCl2CH2 CH2CH2 0.99 ??? 1 CH OCH ( CF2) 3CH2 CH2CH2 CFCF - CH( CH3) . CH2CH2 CF3??? CF ,CH , OCH ( CF2) 2CH2 CH2CH , CF3??? CH , F ( CF2) 3CH2 CH3CH2 CF3CF2CH (CH2CH3 ) CH3CH2 CH2Cl( CF2 ) 3CH2 CH3CH2 NNNNNNNNNNN CH , Br( CF2) 3CH2 CH3CH2 15 CH3OCH (CF2 ) ACH CH3CH2 CF2CH OCH (CF2 ) ACH2 CH3CH2 TABLE 7 R ! R4 R51 R52 R53

NNNNNNNNNNNNNNNN ??? C (CH3 ) ( CF3) 2CH2 CH2CH2 TABLE 4 20 CF2CFHCF CH CH2CH2 ??? CF3( CF )2CH2 CH3CH2 ??? R1 R4 R51 R52 R53 CBrF2CF2CH2CH2 CH2CH2 65550??? CF2CFHCF2CH ( CH3) CH2CH ??? CH , F (CF2 )ACH , CH2CH 2 ? ? CF2CH = CHCH CH2CH2 ??? CH2Cl( CF2 ) 4CH2 CH3CH2 2 . ? ? CF3( CF2) 3CH2 CH2CH CF3??? CH , Br ( CF2) ACHZ CH2CH2 25. CF3 (CF2 ) ACH , CH3CH2 ??? CF CF ,OCFHCF , CH3CH2 CF3( CF2) 3CH2CH2 CH3CH2 CF3??? CF3CF CF ,OCFHCF2 CH3CH2 CF ( CF3) 2CF2CF2CH2CH2 CH3CH2 CF3??? CF3CF CF2OCF (CF3 ) CH2 CH3CH2 CF2H ( CF2) 3CH2 CH3CH2 CF3??? CF3CH2OCH CH2 CH2CH2 CF H ( CF ) ) = CH2 CH2CH2 CF3??? CH2SCH CF2CH CH3CH2 CF3( CF2) 3CH2CH2CH2 CH3CH , ??3??? CH2S ( O ) CH CF2CH2 CH3CH2 30 CF3CF2( CH2 ) . CH CH2CH CF??? CH2S ( O ) 2CH2CF2CH2 CH3CH2 CF3??? ( CF2) , CH2CH2CH2 CH3CH2 CF??? CF2CH . SCH CF2CH , CH2CH2 CF3LLL ???( CF2) 3CH2 ( CH2) 2CH2 CH2CH2 CF3??? CF ,CH S (O ) CH CF2CH2 CH3CH2 CF3???( CF2) . CH2CH2 CH2CH2 CF3??? CF3CH2S ( O )2CH2CF2CH2 CH2CH2 CF (CF3 )2CH2 ( CH2) 4CH2 CH2CH H CF3??? CF2SCH CF2CH2 CH3CH2 CF2OCFHCF2 CH2CH , H CF3??? CF3S ( O )CH CF2CH2 CH2CH2 CH2OCH CF2CH2 CH2CH2 H CFz??? CF3S ( O ) 2CH2CF2CH2 CH3CH2 35 CF3SCH (CF2 ) 2CH2 CH2CH CF3S ( O ) CH2 (CF2 ) 2CH2 CH2CH2 CH2CH NNNNNNNNNNNNNNNNNNNN CF3S( O )2CH ( CF2) 2CH2 CF3SCH ( CF2) 3CH2 CH3CH2 2 ? ? TABLE 8 40 R ? R4 R51 R52 R53 CF3CH2OCH CF2CH2 CH3CH2 H CF31??? NNNNNNNNNNNNNNNNNNNN 1 TABLE 5 CH FCF2CH2 CH3CH2 CF3??? 1 CH CICF2CH2 CH2CH2 ??? R1R R4 R51 R52 R53 CH , BrCF2CH2 CH2CH CF???? CH OCH (CF ) , CH , CH2CH CF??? 1 CF3S ( O )CH (CF2 ) 3CH2 CH2CH2 H H H CF3CH2OCH (CF2 ) 2CH2 CH?CH , ??? ? ? CF3S (O )2CH ( CF2) 3CH2 CH2CH2 CH _ F ( CF _ ) , CH CH2CH CF3??? CF3SCH (CF2 ) ACH CH2CH2 CH _ CI (CF2 ) 2CH2 CH3CH2 ??? 1 CF3S ( O ) CH (CF2 ) ACHZ CH2CH2 CH , Br ( CF2 ) CH CH3CH2 ??? 1 CF3S ( O ) 2CH2( CF24CH2 CH2CH2 CH3OCH (CF2 ) 3CH2 CH2CH2 ??? 1 CF3CH2SCH2CH2 CH2CH2 HHH CF3CH OCH ( CF2) 3CH2 CH3CH2 ??? CF2CH S ( O ) CH , CH , CH3CH2 50 CH3OCH2( CF2) 3CH2 CH2CH2 1??? CF3CH2S (O )2CH2CH2 CH3CH2 CF3CH2OCH2( CF2 ) 3CH2 CH3CH2 1??? CF3SCH CH2 CH3CH2 CH F ( CF2 )3CH2 CH3CH2 1??? 1 CF3S ( O ) CH2CH2 CH2CH2 CH CI( CF2) 3CH2 CH2CH2 ??? 1 CF3S ( O ) 2CH2CH2 CH3CH2 ? ? CH Br( CF2 ) 3CH2 CH2CH2 ??? CH ,OCH (CF2 ) ACH CH3CH2 1??? o1 NNNNNNNNNNN ??? CF2CH OCH2( CF2 ) ACH2 CH3CH2 CH , F (CF2 ) . CH CH2CH2 CE??? 1 TABLE 6 CH2Cl( CF2 ) 4CH2 CH3CH2 CF3??? R ! R4 n R51 R52 R53 CE CF2HCH2 CH3CH2 ??? TABLE 9FINNNNNNNNNNNNNNNNNNNN CH2CF CH3CH2 ??? CF3CH2 CH3CH2 ??? R ! R4 n R51 R52 R53 CCl2CH2 CH3CH2 000 ??? CF HCF2 CH3CH2 ??? CH Br( CF2) 4CH2 CH2CH2 H CFz??? 1 HHHHH-R CHCIFCF CH2CH2 00 ??? CF2CF2OCFHCF2 CH2CH , ??? T CF3CH2CH2 CH3CH2 ??? CF2CF CF2OCFHCF2 CH2CH 2 O ??? T CF2HCF2CH2 CH3CH2 ??? 65 CF CF CF ,OCF (CF3 ) CH CH3CH2 O ??? 1 CF3CF2CH2 CH3CH2 TTTTTTTTT??? CF3CH2OCH2CH2 CH3CH2 2 O ??? US 9, 924 ,719 B2 39 40 TABLE 9 - continued A present compound represented by formula ( 1 -2 ): R ? R4 n R51 R52 R53 ( 1 - 2 ) CH2SCH CF2CH2 CH3CH2 ??? 5 CH3S ( O )CH CF2CH2 CH3CH2 CF3??? H CH3S (O ) 2CH2CF2CH2 CH3CH2 ??? (O ) . CF3CH SCH , CF _CH , CH2CH2 ??? N - N CF3CH _ S ( O ) CH CF2CH2 CH3CH2 ??? CF3CH S ( O )2CH2CF2CH2 CH3CH2 CF3??? R1 - 04 R32 CF2SCH CF _ CH CH2CH2 ??? 1010 CF3S ( O )CH2CF2CH2 CH3CH2 ??? CF3S ( O ) 2CH2CF2CH2 CH3CH2 ??? R2 R3 R6 R53 CFZSCH ( CF2) 2CH2 CH2CH2 ??? CF3S ( O ) CH2 (CF2 ) 2CH2 CH3CH2 CF3??? CF3S ( O )2CH2 ( CF2) 2CH2 CH3CH2 ??? wherein R2 and R3 represent each a hydrogen atom , R CF2SCH (CF2 ) 2CH CH2CH2 CF3??? H 15 represents a hydrogen , and R ', R4, n , RSI, R " ? , and R33 CF3S ( O ) CH2( CF2 ) 3CH2 CH3CH2 2 ??? represent any one combination indicated in Table 1 to Table CF3S( O )2CH2 ( CF2 ) 3CH2 CH3CH2 2 ??? 10 . The present compound represented by formula ( 1- 2 ) NNNNNNNNNNNNNNN ???????????????TTTTTTTTTTTTTTT wherein R2 represents a methyl group , R² represents a TABLE 10 20 hydrogen group , R represents a hydrogen , and R ' , R4, n , R ” , R52, and R ” represent any one combination indicated RI R4 R51 R52 R53 in Table 1 to Table 10 . CF2SCH ( CF2) ACH CH3CH2 H CFzH??? The present compound represented by formula ( 1 - 2 ) CF3S ( O ) CH (CF2 ) ACH , CH3CH2 H CFz??? H wherein R ? represents a trifluoromethyl group , R represents CF3S ( O )2CH2 ( CF2) 4CH2 CH2CH2 ??? 25 a hydrogen group , Rº represents a hydrogen , and R ' , R4, n , CF3CH2SCH2CH2 CH3CH2 ??? RSI , R32, and R33 represent any one combination indicated CF3CH2S ( O )CH2CH2 CH3CH2 ??? CF3CH2S ( O ) 2CH2CH2 CH2CH2 ??? in Table 1 to Table 10 . CFZSCH CH2 CH2CH2 ??? The present compound represented by formula ( 1 - 2 ) CFJS ( O ) CH- CH , CH3CH2 ??? wherein R represents a chlorine group , Rº represents a CF3S (O )2CH2CH2 CH3CH2 NNNNNNNNN SSSSSSSS??? 30 hydrogen group , Rº represents a hydrogen , and R ' , R4, n , RSI , RS ? , and R33 represent any one combination indicated in Table 1 to Table 10 . The present compound represented by formula ( 1 - 1 ) The present compound represented by formula ( 1 - 2 ) wherein R2 represents a methyl group , R3 represents a wherein R2 represents a fluorine group , Rº represents a hydrogen group , and R ', R4, n , RSI , R52, and R33 represent 35 hydrogen group , Rº represents a hydrogen , and R ', R4, n , any combination indicated in Table 1 to Table 10 . RSI, RS , and R33 represent any one combination indicated The present compound represented by formula ( 1 - 1 ) in Table 1 to Table 10 . wherein R2 represents a trifluoromethyl group , Rº represents The present compound represented by formula ( 1 - 2 ) a hydrogen group , and R ' , R * , n ,RI , RS ? , and R ” represent wherein R2 represents a hydrogen group , R² represents a any combination indicated in Table 1 to Table 10 . 40 methyl group , R? represents a hydrogen , and R ' , R4, n , RSI, The present compound represented by formula12 ( 11 - 1 ) R32, and R33 represent any one combination indicated in Table 1 to Table 10 . wherein R ? represents a chlorine group , R represents a The present compound represented by formula ( 1 - 2 ) hydrogen group , and R ', R4, n , RSI , R52 , and R33 represent wherein R ? represents a chlorine group , R represents a any combination indicated in Table 1 to Table 10 . 45 trifluoromethyl group , R? represents a hydrogen , and R1, R4, The present compound represented by formula ( 1 - 1 ) n , R51, R52 , and R53 represent any one combination indicated wherein R² represents a fluorine group , R3 represents a in Table 1 to Table 10. hydrogen group , and R ' , R4, n , RSI, R52, and R53 represent The present compound represented by formula ( 1 - 2 ) any combination indicated in [ Table 1 to Table 10 . wherein R2 represents a hydrogen group , Rº represents a The present compound represented by formula ( 1 - 1 ) 50 chlorine group , Rº represents a hydrogen , and R ' , R *, n , R ” , R32, and R33 represent any one combination indicated in wherein R² represents a hydrogen group , R3 represents a Table 1 to Table 10 . methyl group , and R ' , R4, n , RSI , RS2 , and RS represent any The present compound represented by formula (1 -2 ) combination indicated in Table 1 to Table 10 . wherein R² represents a hydrogen group , R represents a The present compound represented by formula (1 - 1) 55 fluorine group , R represents a hydrogen , and R ', R4, n , R ” , wherein R2 represents a chlorine group , R represents a R52 , and R represent any one combination indicated in Table trifluoromethyl group , and R ' , R4, n , RSI , RS? , and R $ 3 1 to Table 10 . represent any combination indicated in Table 1 to Table 10 . The present compound represented by formula ( 1 - 2 ) wherein R ? represents a methyl group , R represents a The present compound represented by formula ( 1is - 1a ) 60 hydrogen group , R? represents a fluorine atom , and R ' , R4, wherein R² represents a hydrogen group , R3 represents a 60 n , RSI, R52 , and R53 represent any one combination indicated chlorine group , and R ', R4, n , RSI, R52 , and R53 represent in Table 1 to Table 10 . any combination indicated in Table 1 to Table 10 . The present compound represented by formula ( 1 - 2 ) The present compound represented by formula (1 - 1) wherein R2 represents a trifluoromethyl group , Rº represents wherein R2 represents a hydrogen group , Rº represents a 65 a hydrogen group , R? represents a fluorine atom , and R ' , Rº, fluorine group , R ', R4, n , RSI , RS2 , and R $ 3 represent any n R51, R52 , and R53 represent any one combination indicated combination indicated in Table 1 to Table 10 . in Table 1 to Table 10 . US 9 ,924 ,719 B2 41 42 The present compound represented by formula ( 1 - 2 ) TABLE 11 -continued wherein R2 represents a chlorine group , R represents a hydrogen group , Rº represents a fluorine atom , and R ', R4, RLY RAN R51 R520 R53N n , RSI , R32 , and R53 represent any one combination indicated in Table 1 to Table 10 . 5 CH2CH2CH (CF3 ) CH3CH2 H The present compound represented by formula ( 1 - 2 ) CF3CCl2CH2 CH2CH H H H wherein R represents a fluorine group , R² represents a CF3CF2CH (CH3 ) CH2CH2 H H H hydrogen group , Ro represents a fluorine atom , and R ' , R4, CF3CF2CH (CH2CH3 CH3CH2 H H H n ,RSI , RS2 , andR3 represent any one combination indicated in Table 1 to Table 10 . 10 The present compound represented by formula ( 1 - 2 ) wherein R² represents a hydrogen atom , R3 represents a TABLE 12 methyl group , Rº represents a fluorine , and R ' , R4, n , RSI , RIN R4N RSIN R52N R53N R52, and R $ 3 represent any one combination indicated in | 15 C ( CH ( CF, ACH , CH2CHCH3CH2 H H H Table 1 to Table 10 . CF CFHCF CH CH3CH2CH3CH2 HHH The present compound represented by formula ( 1 - 2 ) CF ( CF . ), CH , CH3CH2 H H H wherein R² represents a chlorine group , Rº represents a CBrF2CF2CH2CH2 CH3CH2 CF3CFHCF2CH ( CH3) CH3CH2 trifluoromethyl group , R? represents a fluorine atom , and R ', CF3 (CF2 ) 2CH2 CH2CH2 R * , n , Rº , Rº , and R ” represent any one combination 20 CECESS . CH , CH3CH2 indicated in Table 1 to Table 10 . CF3 ( CF2) 2CH2CH2 CH3CH2 The present compound represented by formula ( 1 - 2 ) CF (CF3 ) CF CF2CH2CH2 CH3CH2 CF H (CF2 ) 3CH2 CH2CH2 wherein R ? represents a hydrogen group , Rº represents a CF , H ( CF2 ) = CH2 CH2CH2 chlorine group , R? represents a fluorine atom , and R ' , R4, n , CF3( CF2 )3CH2CH2CH2 CH3CH2 RS1, R32, and R53 represent any one combination indicated 25 CF3CF (CH2 ) CH2 CH2CH in Table 1 to Table 10 . CF3( CF2) sCH2CH2CH2 CH3CH2 CF3 (CF2 ) 3CH2CH2 ) 4CH2 CH3CH2 The present compound represented by formula ( 1 - 2 ) CF3( CF2 ) 3CH2CH2 CH3CH2 wherein R ? represents a hydrogen group , R3 represents a CF( CF ) CH ( CH2) CH , CH2CH2 fluorine group , R? represents a fluorine atom , and R ! , R4, n , CH FCF2CH2 CH3CH2 RSI, RS2, and R $ 3 represent any one combination indicated 30 CH CICF2CH2 CH2CH2 in Table 1 to Table 10 . CH _ BrCF2CH2 CH2CH2CH3CH2 H H H Next , specific examples of the N -oxide compound are shown as follows. A present compound represented by formula (1 -N11 ): TABLE 13 35 RIN R4N RIIN R52N R53N ( 1 -N11 ) CH , F (CF ) , CH CH2CH2 R4N CH2Cl ( CF ) - CH CH3CH2 RSIN CH , Br ( CF2 )2CH2 CH2CH2 0 ( 0 ) 2S CH F (CF2 ) 3CH2 CH3CH2 N - N 40 CH _ CI( CF2) 3CH2 CH3CH2 CH , Br ( CF2 ) 3CH2 CH3CH2 RIN - 07 R $2N CH _ F ( CF2) 4CH CH3CH2 CH2Cl (CF )ACH CH3CH2 CH _ Br (CF2 )4CH2 CH3CH2 R 53N R2 R30 45 wherein R2N and R3N represent each a hydrogen atom , and TABLE 14 RIN , R4N , RSIN , R52N , and R53N represent any one combi nation indicated in Table 11 to Table 16 . RIN RAN RSINR5IN R52NB52N . R53N 50 CF HCH CH2CH CF3??? TABLE 11 CH3CF2 CH3CH2 ??? CF2CH2 CH3CH2 CF3??? RIN RAN RSIN R52N R53N CCl2CH2 CH3CH2 CF3??? CF HCF ) CH2CH CF3??? CF2HCH2 CH2CH2 CHCIFCF2 CH2CH CF3??? CH2CF2 CH2CH2 55 CF2CH . CH CH2CH2 CF3??? CF3CH2 CH3CH2 CF HCF2CH2 CH2CH2 CF3??? CCl2CH2 CH3CH2 CF3CF2CH2 CH3CH2 CF3??? CF HCF2 CH2CH2 CBrF CF CH2CH ??? CHCIFCF2 CH2CH2 CF2CFHCF2 CH2CH2 ??? CF2CH . CH CH3CH2 CH2CF ,CH , CH2CH ??? CF HCF2CH2 CH2CH2 60 CF3CH (CH3 ) CH3CH2 ??? CF % CF , CH , CH2CH2 CFAC( CH3 ) 2 CH3CH2 ??? CBrF CF2 CH3CH2 CH (CH3 ) 2CH (CF3 ) CH3CH2 ??? CF3CFHCF2 CH3CH2 ( CF3 ) 2CH CH3CH2 CF3??? CH3CF2CH2 CH3CH2 CH3CH2CH ( CF3) CH3CH2 ??? CF2CH (CH3 ) CH2CH2 CF2CCI, CH , CH2CH2 CF3??? CF3C (CH3 ) 2 CH3CH2 CF2CF2CH (CH3 ) CH2CH2 CF3??? CH ( CH3) 2CH (CF3 ) CH3CH2 CF3CF2CH (CH2CH3 ) CH3CH2 CF3??? H ( CF3) 2CH CH3CH2 HHHHHHHHHHHH US 9, 924 ,719 B2 43 44 TABLE 15 group , RIN , R4N , RSIN , R52N , and R $ 3N represent any one combination indicated in Table 11 to Table 16 . RIN RAN RSIN R520 R53N A compound represented by formula ( 1 -N12 ) : C ( CH3) (CF3 ) 2CH2 CH3CH2 H CFCF3??? H CF3CFHCF2CH2 CH3CH2 ??? 5 CF3 ( CF2) 2CH2 CH2CH2 ??? ( 1 -N12 ) CBrF2CF2CH2CH2 CH2CH2 ??? RAN ??? CF3CFHCF2CH ( CH3) CH3CH2 D51N CF3( CF2) 3CH2 CH2CH2 OOOOOO ??? (O ) s CF3 (CF2 )4CH CH2CH ??? N - N CF3 (CF2 ) 3CH2CH2 CH3CH2 ??? 10 CF( CF , ) CFACF - CH - CH2 CH2CH2 ??? RIN - O R 52N CFH( CF , CH , CH2CH2 ??? CF, H ( CF ) CH , CH3CH2 ??? CF3 (CF2 ) 3CH2CH2CH2 CH3CH2 ??? CF3CF2 (CH2 ) CH CH3CH2 ??? R2 R3N Ó R53N CF3( CF2 ) CH _ CH2CH2 CH2CH2 TTTTT??? 15 CF3( CF2) 3CH2 ( CH2)4CH2 CH2CH2 ??? CF3( CF2 )5CH2CH2 CH3CH2 ??? wherein R2N and R3N represent each a hydrogen atom , and CF (CF3 ) 2CH (CH2 ) 4CH2 CH2CH2 ??? RIN , R4N , RSIN , R52N , and R $ 3N represent any one combi CH , FCF2CH2 CH2CH2 ??? CH CICF2CH2 CH3CH2 ??? nation indicated in Table 11 to Table 16 . CH _ BrCF2CH2 CH2CH2 ??? The compound represented by formula ( 1- N12 ) wherein R2M represents a methyl group , R3N represents a hydrogen 00000000000000 group , and RIN , R4N , RSIN , R52N , and R53N represent any one combination indicated in Table 11 to Table 16 . TABLE 16 The compound represented by formula ( 1- N12 ) wherein RIN R4N RSIN R52N R53N 25 R20 represents a trifluoromethyl group , R3M represents a hydrogen group , and RIN , R4N , RSIN , R52N , and R53N CH , F (CF2 ) 2CH2 CH3CH2 ??? CH _ CI( CF2) 2CH2 CH3CH2 1??? represent any one combination indicated in Table 11 to Table CH Br( CF2 ) 2CH2 CH3CH2 1??? 16 . CH F (CF2 ) 3CH2 CH3CH2 CE??? The compound represented by formula ( 1 - N12 ) wherein CH , CI( CF ) 3CH2 CH3CH2 CF??? CH , Br( CF2) 3CH2 CH3CH2 CF??? 30 R2N represents a chlorine group , R3N represents a hydrogen CH , F (CF2 ) 4CH2 CH3CH2 ??? group , and RIN , R4N , RSIN , R52 » , and RSN represent any CH , CI( CF2 ) 4CH2 CH3CH2 1??? one combination indicated in Table 11 to Table 16 . CH , Br( CF ) _ CH2 CH2CH2 ? CF3??? The compound represented by formula ( 1 -N12 ) wherein R2N represents a fluorine group , R3N represents a hydrogen The compound represented by formula ( 1 -N11 ) wherein 35 group , and RIN , R4N , RIIN , R52N , and R53N represent any R2N represents a methyl group , R3N represents a hydrogen one combination indicated in Table 11 to Table 16 . group , and R ' N , R ^ ^ , R » N , RP2 , and Rºn represent any The compound represented by formula ( 1 -N12 ) wherein one combination indicated in Table 11 to Table 16 . R2N represents a hydrogen group , R3N represents a methyl The compound represented by formula ( 1 -N11 ) wherein group , and RIN , R4N , R5IN , R52N , and R33N represent any R2N represents a trifluoromethyl group , RS represents a 40 one combination indicated in Table 11 to Table 16 . hydrogen group , and RIN , R4N , RSIN , R52N , and RS3N The compound represented by formula ( 1- N12 ) wherein represent any one combination indicated in Table 11 to Table R2N represents a chlorine group , R3N represents a trifluo 16 . romethyl group , and RIN , R4N , RSIN , R52N , and R53N rep The compound represented by formula ( 1- N11 ) wherein resent any one combination indicated in Table 11 to Table R2N represents a chlorine group , R3N represents a hydrogen + 16 . group , and RIN , R4N , RSIN , R52N , and R53N represent any The compound represented by formula ( 1 -N12 ) wherein one combination indicated in Table 11 to Table 16 . R2M represents a hydrogen group, R3N represents a chlorine The compound represented by formula ( 1 - N11 ) wherein group , and RIN , R4N , RSIN , R32M , and R53N represent any R2 represents a fluorine group , R3N represents a hydrogen so one combination indicated in Table 11 to Table 16 . group , and RIN , R4N , RSIN , R52N , and R53N represent any The compound represented by formula ( 1- N12 ) wherein one combination indicated in Table 11 to Table 16 . R2N represents a hydrogen group , R3N represents a fluorine The compound represented by formula ( 1 -N11 ) wherein group , R " , R , R , Rº , and R ” represent any one R2N represents a hydrogen group , RBN represents a methyl combination indicated in Table 11 to Table 16 . group , and RIN , R4N , RSIN , R520 , and R53N represent any 55 AA compound represented by formula ( 1 -N13 ): one combination indicated in Table 11 to Table 16 . The compound represented by formula ( 1- N11 ) wherein R2N represents a chlorine group , R3N represents a trifluo ( 1 -N13 ) romethyl group , and RIN , R4N , RSIN , R52N , and R53N rep resent any one combination indicated in Table 11 to Table 60 COMPX RSIN 16 . N - N The compound represented by formula ( 1 - N11) wherein R2N represents a hydrogen group , R3N represents a chlorine RIN - O - R 52N group , and RIN , R4N , RSIN , R520 , and R53N represent any one combination indicated in Table 11 to Table 16 . 65 RN R3N RON R53N The compound represented by formula ( 1 -N11 ) wherein R2N represents a hydrogen group , R3 represents a fluorine US 9 , 924 , 719 B2 45 46 wherein R2M and R3N represent each a hydrogen atom , group , R6N represent a fluorine atom , and RIN , R4N , RSIN , R6N represent a hydrogen atom , and RIN , R4N , RSIN , R52N , R52N , and R53N represent any one combination indicated in and R53N represent any one combination indicated in Table Table 11 to Table 16 . 11 to Table 16 . The compound represented by formula ( 1 -N13 ) wherein The compound represented by formula ( 1 -N13 ) wherein 5 R20 represents a chlorine group , R3N represents a trifluo R2N represents a methyl group , R3N represents a hydrogen romethyl group , RÓN represent a fluorine atom , and RIN , group , R6N represent a hydrogen atom , and RIN , R4N , RSIN , R4N , RSIN , R52N , and R53N represent any one combination R52N and R53N represent any one combination indicated in indicated in Table 11 to Table 16 . Table 11 to Table 16 . The compound represented by formula (1 -N13 ) wherein The compound represented by formula ( 1 -N13 ) wherein R2N represents a hydrogen group , R3 represents a chlorine R2N represents a trifluoromethyl group , R3N represents a group , R N represent a fluorine atom , and RIN , R4N , RSIN , hydrogen group , RØN represent a hydrogen atom , and RIN , RS2N , and R33M represent any one combination indicated in R4N , RSIN , R520 , and R53N represent any one combination Table 11 to Table 16 . indicated in Table 11 to Table 16 . The compound represented by formula ( 1 -N13 ) wherein The compound represented by formula ( 1 -N13 ) wherein R2N represents a hydrogen atom , R3N represents a fluorine R2N represents a chlorine group , R3N represents a hydrogen group , RÓN N represent a fluorine atom , RIN , R4N , RSIN , group , RÓN represent a hydrogen atom , and RIN , R4N , RSIN , RS2N , and R $3N represent any one combination indicated in R52N , and R33M represent any one combination indicated in Table 1 to Table 10 . Table 11 to Table 16 . 20 Examples of the harmful arthropod on which the com The compound represented by formula (1 -N13 ) wherein pound of the present invention has a control efficacy include R2N represents a fluorine group , R3N represents a hydrogen harmful insects and harmful mites . Specific examples of group , RON represent a hydrogen atom , and RIN , R4N , RSIN , such harmful arthropod are as follows. RS2N , and R $ 3M represent any one combination indicated in Hemiptera Pests : Table 11 to Table 16 . 25 Delphacidae ( for example , Laodelphax striatellus , The compound represented by formula ( 1 -N13 ) wherein Nilaparvata lugens, Sogatella furcifera , or Peregrinus R2N represents a hydrogen group , R3N represents a methyl maidis ). group , R N represent a hydrogen atom , and RIN , R4N , RSIN , Deltocephalidae ( for example , Nephotettix cincticeps, R52N and R33M represent any one combination indicated in Nephotettix virescens, Nephotettix nigropictus (Rice green Table 11 to Table 16 . The compound represented by formula ( 1 -N13 ) wherein leafhopper ), Recilia dorsalis , Empoasca onukii, Empoasca R2N represents a chlorine group , R3N represents a trifluo fabae , Dalbulus maidis , Mahanarva posticata (Sugarcane romethyl group , RÓN represent a hydrogen atom , and RIN , froghopper ), Mahanarva fimbriolota (Sugarcane root R4N , RSIN , R $ 23 , and RS3N represent any one combinationRIN spittlebug) , Cofana spectra, Nephotettix nigropictus , or indicated in Table 11 to Table 16 . Recilia dorsalis ) , The compound represented by formula ( 1 -N13 ) wherein Aphididae ( for example , Aphis gossypii , Myzus persicae , R2N represents a hydrogen group , R3N represents a chlorine Brevicoryne brassicae, Aphis spiraecola , Macrosiphum group , RÓN represent a hydrogen atom , and RIN , R4N , RSIN euphorbiae, Aulacorthum solani, Rhopalosiphum padi, Tox R > 2N , and R53N represent any one combination indicated in qptera citricidus , Hyalopterus pruni, Aphis glycines Mat Table 11 to Table 16 . 40 sumura , Rhopalosiphum maidis , Tetraneura nigriabdomina The compound represented by formula (1 -N13 ) wherein lis , Viteus vitifoliae, Daktulosphaira vitifoliae (Grape R2N represents a hydrogen group , R3N represents a fluorine Phylloxera ), Phylloxera devastatrix Pergande (Pecan phyl group ,RN represent a hydrogen atom , and RIN , R4N , RSN , loxera ), Phylloxera notabilis pergande (Pecan leaf phyllox R52N , and R $ 3N represent any one combination indicated in era ) , or Phylloxera russellae Stoetzel (Southern pecan leaf Table 11 to Table 16 . 45 phylloxera ) , The compound represented by formula ( 1 -N13 ) wherein Pentatomidae ( for example , Scotinophara lurida , Scotin R2 represents a methyl group , R represents a hydrogen ophara coarctata (Malayan rice black bug ) , Nezara anten group , Rº represent a fluorine atom , and RIN , R4 , RSIN , nata , Eysarcoris parvus, Ralyomorpha mista , Nezara R52N , and R $ 3N represent any one combination indicated in viridula , Euschistus heros ( Brown stink bug) , Nezara Table 11 to Table 16 . 50 The compound represented by formula ( 1 -N13 ) wherein viridula (Southern green stink bug ), Piezodorus guildinii R2N represents a trifluoromethyl group , R3N represents a (Red banded stink bug ), Scaptocoris castanea (Burrower hydrogen group , RM represent a fluorine atom , and RIN , brown bug ), Oebalus pugnax , or Dichelops melacanthus) , R4N , RSIN , R520 , and R $ 3N represent any one combination Alydidae ( for example , Riptortus clavetus, Leptocorisa indicated in Table 11 to Table 16 . chinensis , Leptocorisa acuta , or Leptocorisa spp . ) , The compound represented by formula ( 1 -N13 ) whereinin Miridae ( for example , Trigonotylus caelestialium , Steno R2N represents a chlorine group , R3N represents a hydrogen tus rubrovittatus, Lygus lineolaris , or Blissus leucopterus group , R N represent a fluorine atom , and RIN , R4N , RSIN , leucopterus (Chinchi bug ) ) , R52N , and R53N represent any one combination indicated in Aleyrodidae ( for example , Trialeurodes vaporariorum , [ Table 11 to Table 16 . 60 Bemisia tabaci, Dialeurodes citri, or Aleurocanthus The compound represented by formula ( 1 -N13 ) wherein spiniferus ), R2N represents a fluorine group , R3N represents a hydrogen Coccoidea ( for example , Aonidiella aurantii , Comstock group , R6N represent a fluorine atom , and RIN , R4N , RSIN , aspis perniciosa , Unaspis citri, Ceroplastes rubens, Icerya R $ 2N , and R53N represent any one combination indicated in purchasi , Planococcus Kraunhiae , Pseudococcus longispi Table 11 to Table 16 . 65 nis , Pseudaulacaspis Pentagona , or Brevennia rehi) , The compound represented by formula ( 1 -N13 ) wherein Psyllidae ( for example , Diaphorina citri, Psylla pyrisuga , R2N represents a hydrogen group , R3M represents a methyl Bactericerca cockerelli ), US 9 , 924 ,719 B2 47 48 Tingidae ( for example , Stephanitis nasi ), Chloropidae ( for example , Chlorops oryzae ), Cimicoidea ( for example , Cimex lectularius ) , Tephritidae ( for example , Dacus cucurbitae , or Ceratitis Quesada gigas (Giant Cicada ) ; capitata ), and the others . Ephydridae ( for example , Hydrellia philippina , or Lepidoptera Pests : 5 Hydrellia sasakii ) , Pyralidae ( for example , Chilo suppressalis , Chilo poly Drosophilidae , chrysus (Darkheaded stm borer ) , Tryporyza incertulas , Phoridae (for example, Megaselia spiracularis ), Chilo polychrysus , Scirpophaga innotata , Scirpophaga Psychodidae ( for example , Clogmia albipunctata ), incertulas ( Yellow stem borer ) , Sesamia inferens ( Pink borer ) , Rupela albinella , Cnaphalocrocis medinalis , Maras - 10 Sciaridae, mia patnalis , Marasmia exigna , Notarcha derogata , Plodia Cecidomyiidae ( for example , Mayetiola destructor , or interpunctella , Ostrinia furnacalis, Hellula undalis , Pedia Orseolia oryzae ) , sia teterrellus, Nymphula depunctalis , Marasmia spp ., Diopsidae ( for example , Diopsis macrophthalma ) , Hydraecia immanis (Hop vine borer ), Ostrinia nubilalis Tipulidae ( for example , Tipula oleracea (Common crane ( European corn borer ) . Elasmopalpus lignosellus ( Lesser 15 fly ) , or Tipula paludosa ( European cranefly ) ) ; cornstalk borer ), Epinotia aporema (Bean Shoot Borer ), and the others. Diatraea saccharalis ( Sugarcane borer ) , Telchin licus (Giant Coleoptera Pests : Sugarcane borer) ), Chrysomelidae ( for example , Diabrotica virgifera vir Noctuidae ( for example , Spodoptera litura , Spodoptera gifera, Diabrotica undecimpunctata howardi, Diabrotica exigua , Pseudaletia separata , Mamestra brassicae, Sesamia 20 barberi, Diabrotica virgifera zeae , Diabrotica balteata inferens, Spodoptera mauritia , Spodoptera frugiperda , LeConte , Diabrotica speciosa , Diabrotica speciosa ( Cucur Spodoptera exempta , Agrotis Ipsilon , Plusia nigrisigna , bit Beetle ) , Cerotoma trifurcata , Oulema melanopus, Aula Pseudoplusia includens (Soybean looper) , Trichoplusia cophora femoralis , Phyllotreta striolata , Leptinotarsa spp . , Heliothis spp . ( for example, Heliothis virescens) , Heli - decemlineata , Oulema oryzae, Colaspis brunnea , Chaetoc coverpa spp . ( for example , Helicoverpa armigera ) , Anticar - 25 nema pulicaria , Epitrix cucumeris , Dicladispa armigera , sia gammatalis (Velvetbean caterpillar ), or Alabama argil Stenolophus lecontei (Seedcorn beetle ), or Clivinia impres lacea ( Cotton leafworm ) ) , sifrons (Slender seedcorn beetle ) ) , Pieridae (for example , Pieris rapae ) , Scarabaeidae ( for example , Anomala cuprea , Anomala Adokisofiesu genus , Tortricidae ( for example , Grapholita molesta , Legumini- 30 rufocuprea , Popillia japonica , Rhizotrogus majalis (Euro vora glycinivorella , Matsumuraeses azukivora , Adoxophyes pean Chafer) , Bothynus gibbosus ( Carrot beetle ) , Colaspis orana fasciata , Adoxophyes honmai, Homona magnanima, brunnea (Grape Colaspis ) , Myochrous denticollis ( southern Archips fuscocupreanus , or Cydia pomonella ), Corn leaf beetle ), Holotrichia spp ., or Phyllophaga spp . ( for Gracillariidae ( for example , Caloptilia theivora , or Phyl example , Phyllophaga crinita ) ) , lonorycter ringoneella ) , 35 Erirhinidae ( for example , Sitophilus zeamais, Echinocne Carposinidae ( for example , Carposina niponensis , Ecdy - musm squameus, Lissorhoptrus oryzophilus, or Sphenophorus tolopha aurantiana ( Citrus fruit borer) ), venatus) , Lyonetiidae ( for example , Leucoptera coffeela ( Coffee Curculionidae ( for example , Anthonomus grandis , Sphe Leaf miner ), or Lyonetia spp .) ), nophorus callosus ( Southern Corn Billbug ) , Sternechus sub Lymantriidae ( for example , Lymantria spp . , or Euproctis 40 signatus (Soybean stalk weevil) , or Sphenophorus spp . ( for spp . ) , example , Sphenophorus levis ) ), Yponomeutidae ( for example , Plutella xylostella ) , Epilachna ( for example , Epilachna vigintioctopunctata ), Gelechiidae ( for example , Pectinophora gossypiella , or Scolytidae ( for example , Lyctus brunneus , or Tomicus Phthorimaea operculella ) , piniperda ), Arctiidae ( for example , Hyphantria cunea ) ; 45 Bostrichidae , and the others . Ptinidae , Thysanoptera Pests : Cerambycidae ( for example , Anoplophora malasiaca , or Thysanopterae ( for example , Frankliniella occidentalis , Migdolus fryanus ) , Thrips parmi, Scirtothrips dorsalis , Thrips tabaci, Franklin Elateridae (Agriotes sp ., Aelous sp ., Anchastus sp ., Mel iella intonsa, Frankliniella occidentalis , Haplothrips acu - 50 anotus sp ., Limonius sp ., Conoderus sp ., Ctenicera sp .) ( for leatus, Stenchaetothrips biformis ) ; example ,Melanotus okinawensis , Agriotes ogurae fuscicol and the others . lis , or Melanotus legatus ), Diptera Pests : Staphylinidae (for example , Paederus fuscipes ), House mosquitoes (Culex spp .) ( for example , Culex pipi Hypothenemus hampei (Coffee Barry Borer ); ens pollens , Culex tritaeniorhynchus , or Culex quinquefas - 55 and the others. ciatus ), Orthoptera Pests : Aedes spp . (for example , Aedes aegypti , or Aedes albopic - Locusta migratoria , Gryllotalpa africana , Dociostaurus tus ) , maroccanus , Chortoicetes terminifera , Nomadacris septem Anopheles spp . ( for example , Anopheles sinensis ), fasciata , Locustana pardalina ( Brown Locust) , Anacridium Chironomidae , 60 melanorhodon ( Tree Locust ), Calliptamus italicus ( Italian Muscidae ( for example , Musca domestica , or Muscina Locust ), Melanoplus differentialis ( Differential grasshop stabulans) , per ), Melanoplus bivittatus (Twostriped grasshopper) , Mel Anthomyiidae ( for example , Delia platura , Delia antiqua , anoplus sanguinipes (Migratory grasshopper ) , Melanoplus or Tetanops myopaeformis ), femurrubrum (Red -Legged grasshopper ), Camnula pellu Agromyzidae ( for example , Agromyza oryzae , Hydrellia 65 cida (Clearwinged grasshopper ), Schistocerca gregaria , griseola , Liriomyza sativae , Liriomyza trifolii, or Chromato - Gastrimargus musicus ( Yellow -winged locust ) , Austracris myia horticola ) , guttulosa (Spur - throated locust ) , Oxya yezoensis, Oxya US 9 ,924 ,719 B2 49 50 japonica, Patanga succincta , Grylloidea ( for example , emulsifiable concentrates, oil solutions, dust formulations, Acheta domesticus, Teleogryllus emma, or Anabrus simplex granules, wettable powders , flowables , microcapsules , aero (Mormon cricket ) ) ; sols, smoking agents, poison baits , resin formulations , and the others . shampoo formulations , paste - like formulations , foams, car Hymenoptera Pests : 5 bon dioxide formulations and tablets and the others . Such Tenthredinidae ( for exmaple , Athalia rosae , or Athalia formulations may be processed into mosquito repellent japonica ), coils , electric mosquito repellent mats , liquid mosquito Solenopsis spp ., formulations, smoking agents , fumigants , sheet formula Attini spp . ( for example , Atta capiguara (Brown leaf tions, spot- on formulations or formulations for oral treat cutting ant) ) ; 10 ment. Also , the agent for controlling harmful arthropods of and the others . the present invention may be mixed with other pesticides, Blattariae Pests : miticides , nematicides , fungicides , plant growth regulators , Blattella germanica , Periplaneta fuliginosa , Periplaneta herbicides , and synergists . americana, Periplaneta brunnea , Blatta orientalis , and the The agent for controlling harmful arthropods of the pres others . 15 ent invention comprises usually 0 .01 to 95 % by weight of Isoptera Pests : the present compound . Reticulitermes speratus, Coptotermes formosanus, Incisi . Examples of the solid carrier to be used in the formulation termes minor, Cryptotermes domesticus, Odontotermes for include fine powders or granules of clays ( for example , mosanus, Neotermes koshunensis, Glyptotermes satsumen - kaolin clay , diatomaceous earth , bentonite , Fubasami clay , sis , Glyptotermes nakajimai, Glyptotermes fuscus, 20 or acid white clay ) , synthetic hydrated silicon oxides , talcs, Glyptotermes kodamai, Glyptotermes kushimensis, Hodoter ceramics , other inorganic minerals ( for example , sericite , mopsis japonica, Coptotermes guangzhoensis, Reticuli quartz , sulfur, active carbon , calcium carbonate , or hydrated termes miyatakei, Reticulitermes flaviceps amamianus, silica ) or chemical fertilizers (for example , ammonium sul Reticulitermes sp . , Nasutitermes takasagoensis , Pericaprit - fate , ammonium phosphate , ammonium nitrate , urea , or ermes nitobei, Sinocapritermes mushae , or Cornitermes 25 ammonium chloride) and the others ; as well as synthetic clicumulans ; resins ( for example , polyester resins such as polypropylene , and the others . polyacrylonitrile , polymethylmethacrylate and polyethylene Acarina Pests: terephthalate ; nylon resins ( for example , nylon - 6 , nylon - 11 Tetranychidae ( for example , Tetranychus urticae, Tet- and nylon -66 ) ; polyamide resins; polyvinyl chloride, poly ranychus kanzawai, Panonychus citri , Panonychus ulmi, 30 vinylidene chloride, vinyl chloride - propylene copolymers , Oligonychus spp. , or Brevipalpus phoenicis (Southern Tur- and the others ) . key spider mites) ), Examples of the liquid carrier include water , alcohols ( for Eriophyidae ( for example , Aculops pelekassi, Phyllocop - example , methanol, ethanol, isopropyl alcohol, butanol, truta citri, Aculops lycopersici, Calacarus carinatus, Aca - hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phylla theavagrans, Eriophyes chibaensis , or Aculus 35 or phenoxy ethanol) ; ketones (for example , acetone , methyl schlechtendali ) , ethyl ketone, or cyclohexanone) ; aromatic hydrocarbons ( for Tarsonemidae ( for example , Polyphagotarsonemus latus) , example , toluene , xylene , ethyl benzene , dodecyl benzene , Tenuipalpidae ( for Example , Brevipalpus phoenicis ), phenyl xylyl ethane, or methylnaphthalene ); aliphatic hydro Tuckerellidae ; carbons ( for example , hexane, cyclohexane, kerosene, or Ixodidae ( for Example , Haemaphysalis longicornis, Hae - 40 light oil) ; esters ( for example , ethyl acetate , butyl acetate , maphysalis flava , Dermacentor taiwanicus, Dermacentor isopropyl myristate , ethyl Oleate , diisopropyl adipate , variabilis , Ixodes ovatus, Ixodes persulcatus, Ixodes scapu diisobutyl adipate , or propylene glycol monomethyl ether laris , Amblyomma americanum , Boophilus microplus, or acetate ) ; nitriles ( for example , acetonitrile , or isobutyroni Rhipicephalus sanguineus ), trile ) ; ethers ( for example , diisopropyl ether , 1 , 4 - dioxane , Acaridae ( for example , Tyrophagus putrescentiae, or 45 ethyleneglycol dimethyl ether, diethyleneglycol dimethyl Tyrophagus similis ), ether , diethylene glycol monomethyl ether, propylene glycol Pyroglyphidae ( for example , Dermatophagoides farinae , monomethyl ether , dipropylene glycol monomethyl ether, or or Dermatophagoides ptrenyssnus ); 3 -methoxy - 3 -methyl - 1 -butanol ) ; acid amides ( for example , Cheyletidae ( for example , Cheyletus eruditus, Cheyletus DMF, or N , N -dimethylacetamide ) ; halogenated hydrocar malaccensis , or Cheyletus moorei) ; 50 bons ( for example , dichloromethane, trichloroethane , or Sarcoptidae ( for example , Octodectes cynotis , or Sacrop carbon tetrachloride ) ; sulfoxides (for example , dimethyl tes scabiei) , sulfoxide ); propylene carbonate ; and vegetable oils ( for Demodex folliculorum (for example , Demodex canis ), example , soybean oil , or cottonseed oil ) . Listrophoridae , Examples of the gaseous carrier include fluorocarbon , Oribatid mites, 55 butane gas , LPG ( liquefied petroleum gas ) , dimethyl ether, Dermanyssidae ( for example , Ornithonyssus bacoti, and carbon dioxide gas. Ornithonyssus sylvairum , or Dermanyssus gallinae) , Examples of the surfactant include nonionic surfactants Trombiculid mites ( for example , Leptotrombidium aka such as polyoxyethylenated alkyl ethers , polyoxyethyl mushi) , enated alkyl aryl ethers and polyethylene glycol fatty acid and the others . 60 esters ; and anionic surfactants such as alkyl sulfonates , The agent for controlling harmful arthropods of the pres - alkylbenzene sulfonates and alkyl sulfates. ent invention comprises the present compound and an inert Examples of the other auxiliary agent for formulation active carrier . The agent for controlling harmful arthropods include a binder , a dispersant, a colorant and a stabilizer. is usually prepared by mixing the present compound with an Specific examples include casein , gelatin , polysaccharides inert active carrier such as solid carrier , liquid carrier and 65 ( for example , starch , gum arabic , cellulose derivatives, and gaseous carrier, and if necessary , adding surfactants and the alginic acid ) , lignin derivatives, bentonite , water - soluble other auxiliary agents for formulation , to formulate into synthetic polymers ( for example , polyvinyl alcohol, poly US 9 ,924 ,719 B2 51 52 vinyl pyrrolidone , and polyacrylic acids) , PAP (acidic iso with water in such a way that a concentration of the active propyl phosphate ) , BHT ( 2 ,6 -di - tert -butyl - 4 -methylphenol ) , ingredient is within a range from 0 . 1 to 10 ,000 ppm , and BHA ( a mixture of 2 - tert -butyl - 4 -methoxyphenol and 3 - tert then sparging it. In the case of being formulated into oil butyl- 4 -methoxyphenol ) . solutions, aerosols , smoking agents , poison baits and the Examples of a base material of the resin formulation 5 others, the formulation is used as itself without diluting it . include polyvinyl chloride polymers , polyurethane and the When the agent for controlling harmful arthropods of the others , and a plasticizer such as phthalate esters ( for present invention is used for controlling external parasites of example , dimethyl phthalate , dioctyl phthalate ), adipic acid livestock such as cows, horses , pigs, sheep , goats and esters and stearic acid may be added to the base material, if chickens, and small animals such as dogs , cats , rats and necessary. The resin formulation can be prepared by mixing 10 mice , the pest control agent of the present invention can be the present compound with the above- mentioned base mate applied to the animal by a known method in the veterinary rial, kneading the mixture , followed by molding it by field . Specifically , when systemic control is intended , the injection molding , extrusion molding or pressure molding pest control agent of the present invention is administered to and the like . The resultant resin formulation can be subjected the animal as a tablet , a mixture with feed or a suppository , to further molding or cutting procedure and the like , if 15 or by injection ( including intramuscular, subcutaneous , necessary , to be processed into shapes such as a plate , film , intravenous and intraperitoneal injections ). On the other tape , net or string shape . The resin formulation can be hand , when non -systemic control is intended , the pest con processed into animal collars , animal ear tags, sheet prod - trol agent of the present invention is applied to the animal by ucts , trap strings , gardening supports , and other products . means of spraying of the oil solution or aqueous solution , Examples of a base material for the poison bait include 20 pour -on or spot- on treatment , or washing of the animal with bait ingredients such as grain powder, vegetable oil, saccha - a shampoo formulation , or by putting a collar or ear tag ride and crystalline cellulose , and if necessary , with addition made of the resin formulation to the animal. In the case of of antioxidants such as dibutylhydroxytoluene and nordihy - administering to an animal body, the dose of the present droguaiaretic acid , preservatives such as dehydroacetic acid , compound is usually within a range from 0 . 1 to 1 , 000 mg per accidental ingestion inhibitors for children and pets such as 25 1 kg of an animal body weight. a chili powder, insect attraction fragrances such as cheese flavor, onion flavor and peanut oil. EXAMPLES The method for controlling harmful arthropods of the present invention is conducted by applying an effective The following examples including Preparation examples , amount of the present compound to a harmful arthropod 30 Formulation examples and Test examples serve to illustrate directly and / or a habitat thereof ( for example, plant bodies, the present invention in more detail, which should not intend soil, an interior of a house, and animal bodies ). In the to limit the present invention . method for controlling harmful arthropods of the present First, regarding the preparation of the present compound , invention , the present compound is usually used in the form Preparation examples are shown as follows. of a harmful arthropod controlling agent. 35 When an agent for controlling harmful arthropods of the Preparation Example 1 ( 1 ) present invention is used for controlling harmful arthropods in an agricultural field , the application dose as an amount of Eighty ( 80 ) ml of the mixture of 3 - chloro - 6 -methoxy the present compound is usually within a range from 1 to pyridazine 17 g , 2 - fluoro - 4 - ( trifluoromethyl) phenylboron 10 ,000 g per 10 , 000 m2. The emulsifiable concentrate , the 40 acid pynacol ester 12 g , tetrakis ( triphenylphosphine )palla wettable powder , or the flowable formulation etc . of an agent dium ( 0 ) 2 . 3 g , 2M solution of sodium carbonate 50 ml, and for controlling harmful arthropods of the present invention 1 ,2 -dimethoxyethane (hereinafter , referred to as “ DME ” ) 80 is usually applied by diluting it with water in such a way that ml was stirred at 80° C . for 5 hours. The reaction mixture a concentration of the active ingredient of the present was allowed to stand to room temperature and to the mixture invention is within a range from 0 .01 to 10 , 000 ppm . The 45 was added water , and the mixture was extracted with ethyl granular formulation , or the dust formulation etc . , is usually acetate , and dried over anhydrous sodium sulfate . The applied as itself without diluting it . mixture was concentratated under reduced pressure , and the These formulations and diluents of the formulations with resulting residue was then subjected to a silica gel column water may be directly sprayed to a harmful arthropod or a chromatography to give Intermediate compound ( 1 - 1 ) 4 . 81 plant such as a crop to be protected from a harmful arthro - 50 g . pod , or applied to a soil in a cultivated area to control a harmful arthropod that inhabits the soil . Also , a resin formulation processed into sheet shape or string shape may be wrapped around a crop , stretched near N - N a crop , spread on a plant foot soil , or the like . 55 When the agent for controlling harmful arthropods of the present invention is used to control harmful arthropods that live inside a house , the application dose as an amount of the present compound is usually within a range from 0 . 01 to H -NMR (CDC12 ) 8 : 8 .28 ( 1H , dd ), 7 . 90 ( 1H , dd ) , 7 .58 1 ,000 mg per 1 m² of an area to be treated , in the case of 60 (1H , d ), 7 .47 ( 1H , d ), 7. 09 (1H , d ), 4 .21 (3H , s ). using it on a planar area. In the case of using it spatially , the application dose as an amount of the present compound is Preparation Example 1 ( 2 ) usually within a range from 0 .01 to 500 mg per 1 m of the space to be treated . When the agent for controlling harmful To the reaction mixure of the Intermediate compound arthropods of the present invention is formulated into emul- 65 (1 - 1 ) 4 .8 g and NMP 40 ml, ethanethiol 1 .6 ml and sodium sifiable concentrates , wettable powders , flowables or the hydride (60 % , oily ) 0 . 99 g were added under ice - cooling , others , the formulation is usually applied after diluting it and the mixture was stirred at room temperature for 2 hours . US 9 ,924 ,719 B2 53 54 To the reaction mixtures was added water, and the mixtures 'H -NMR (CDC13 ) 8: 11. 74 (1H , s ), 8. 41 ( 1H , s ), 8 .01 (1H , were extracted with ethyl acetate and dried over anhydrous d ), 7 .62 ( 1H , d ), 7 .42 ( 1H , d ), 7 .06 (1H , d ), 3 . 30 ( 2H , 9 ) , 1 . 30 sodium sulfate . The obtained organic layer was concentrated (3H . t ) . under reduced pressure to give an Intermediate compound ( 1 - 2 ). 5 Preparation Example 1( 5 ) H3C To the mixure of the Intermediate ( 1 - 4 ) 0 . 30 g , cesium carbonate 0 . 35 g , and NMP 4 ml, 2 , 2 , 2 - trifluoroethyl non 10 afluorobutane sulfonate 0 .37 g were added at room tempera ture , and the mixture was stirred at room temperature for 2 H3C hours . To the obtained reaction mixture was added water, CF3 and the mixture was extracted with ethyl acetate and dried over anhydrous sodium sulfate . After the organic layer was 15 concentrated under reduced pressure , the obtained residue H - NMR (CDC1z ) 8 : 7 .72 ( 1H , d ), 7 .68 - 7 .63 ( 2H , m ) , was subjected to a silica gel column chromatography to give 7 . 55 ( 1H , d ), 7 .05 ( 1H , d ), 4 .21 ( 3H , s ) , 2 . 89 ( 2H , 9 ), 1. 25 Present compound 1 0 . 02 mg and By- product 1 0 .31 g . (3H , t ). Preparation Example 1( 3) 20 Present Compound 1 To the mixure of a full amount of the Intermediate compound ( 1 - 2 ) obtained in Preparation example 1 ( 2 ) and chloroform 40 ml, mCPBA (purity 65 % or more ) 8 . 9 g was H3C added under ice - cooling , and the mixture was stirred at room 25 temperature for one day . To the reaction mixtures was added 10 % aqueous sodium thiosulfate solution , and the mixtures were extracted with chloroform . The organic layer was FzC6 N - NY washed with saturated aqueous sodium hydrocarbonate solution , dried over anhydrous sodium sulfate, and concen - 30 -CF3 trated under reduced pressure . The obtained residue was subjected to a silica gel column chromatography to give Intermediate compound ( 1 - 3 ) 3. 3 g . H -NMR (CDC13 ) 8 : 8 . 46 ( 1H , s ) , 8 .02 ( 1H , d ), 7 .65 - 7 . 59 (2H , m ), 7 .27 ( 1H , d ), 5 .00 ( 2H , q ), 3 .43 ( 2H , q ) , 1. 30 (3H , HC 35 t) . By- Product 1

H3C H3C N - N 40

- CF3 O F3C N - N " H -NMR (CDC13 ) 8 : 8 .45 ( 1H , s) , 8 .00 ( 1H , d ), 7 .60 ( 1H , d ), 7 . 53 ( 1H , d ), 7 . 12 ( 1H , d ), 4 . 21 (3H , s ), 3 . 46 ( 2H , q ) , 1 .29 45 CF3 (3H , t) . Preparation Example 1 ( 4 ) H -NMR (CDC13 ) 8 : 8 . 40 ( 1H , s ), 8 .02 ( 1H , d ) , 7 .61 ( 1H , The mixture of the Intermediate compound ( 1 - 3 ) 3 . 3 g and 50 d ) , 7 .37 ( 1H , d ) , 7 . 05 ( 1H , d ) , 4 .81 ( 2H , q ) , 3 . 19 (2H , q ) , 1 .28 concentrated hydrochloric acid 25 mL was heated to reflux (3H , t ) . for 1 hour. The obtained mixture was allwed to stand to room The present compound was prepared according to the temperature , and thereto was added water . The precipitated method described in Preparation example 1 (5 ) using the solid was filtered and the filtrate was concentrated under compound represented by Formula R ? _ OSO ,CFz instead reduced pressure to give an Intermediate compound ( 1 - 4 ) 55 of 2 . 2 . 2 - trifluoroethyl nonafluorobutane sulfonate . and is 2 . 9 g . shown in Table 17 .

H3C CH3

N - N N - NON = HO - CF3 . -CF3 US 9, 924 ,719 B2 55 56 TABLE 17 Preparation Example 2 (2 ) Present compound No. To the suspension of sodium hydride (60 % , oily ) 57 g and CF CF CH2 DMF 560 mL , ethanethiol 100 mL was added dropwise WN CF3CHFCF2CH2 5 under ice - cooling . To the mixtures , a mixed solution of the Intermediate compound ( 4 - 1 ) 204 g and DMF 190 mL were added dropwise under ice - cooling . The obtained reaction Present compound 2 ; + H - NMR (CDC13 ) 8 : 8 . 46 ( 1H , s ) , mixtures were stirred under ice - cooling for 1 hour, and 8 .02 ( 1H , d ) , 7 .63 ( 1H , d ), 7 .61 ( 1H , d ) , 7 .27 (1H , d ) , 5 .08 thereto was added iced water. The precipitated solid was (2H , t ) , 3 . 43 ( 2H , q ) , 1 .30 (3H , t ). 10 filtered and washed with water . The obtained solid was Present compound 3 ; ' H - NMR ( CDC13 ) 8 : 8 . 46 ( 1H , s ) , dissolved in ethyl acetate , and the solution was washed with 8 .02 ( 1H , d ) , 7 .63 ( 1H , d ) , 7 .61 ( 1H , d ), 7 . 24 ( 1H , d ) , brine , and then the organic layer was dried with sodium 5 . 28 - 5 . 06 ( 1H , m ), 5 . 04 -4 . 95 (2H , m ) , 3 .42 ( 2H , q ), 1 . 30 sulfate . After the organic layer was concentrated under (3H , t) . reduced pressure , the obtained solid was washed with The by -product prepared with the present compound is 15 hexane to give the Intermediate compound ( 4 - 2 ) 160 g . shown in Table 18 . CH3 CH ; 20

N - NON = C3 25 CH3 H -NMR ( CDC13 ) d: 8. 40 (1H , dd ) , 7 .69 ( 1H , dd ), 7. 37 TABLE 18 ( 1H , dd ) , 2 . 92 (2H , q ) , 2 .72 (3H , s ) , 1 .40 (3H , t ) . By- product No . R1 30 Preparation Example 2 ( 3 ) CF CF , CH , ??? CF CHFCF, CH , To the mixure of the Intermediate compound ( 4 - 2 ) 5 .4 g , glyoxylic acid monohydrate 2. 8 g and methanol 90 ml, sodium hydroxide 2 . 4 g and methanol 60 mL were added By -product 2 ; + H -NMR (CDC13 ) 8 : 8 . 40 ( 1H , s ) , 8 . 02 3533 dropwise under ice - cooling. The reaction mixture was ( 1H , d ), 7 .61 ( 1H , d ), 7 . 38 ( 1H , d ) , 7 .04 ( 1H , d ) , 4 . 84 ( 2H , stirred at 60° C . for 2 hours . The obtained reaction mixture t ) , 3 . 17 (2H , q ) , 1 . 27 (3H , t ) . was allowed to stand to room temperature , and thereto were By - product 3 ; ' H -NMR (CDC13 ) 8 : 8 .41 ( 1H , s ), 8 .02 sequentially added acetic acid 11 mL and hydrazine mono ( 1H , d ), 7 .61 ( 1H , d ) , 7 . 38 (1H , d ), 7 .05 ( 1H , d ) , 5 . 18 - 5 .01 hydrate 2 . 3 g . The obtained mixtures were allowed to stand ( TH , m ) , 4 . 90 - 4 .69 ( 2H , m ), 3 . 19 (2H , D ) , 1 . 28 (3H , t ) . 40 to room temperature , followed by thereto was added satu rated ammonium chloride solution , and the mixture was Preparation Example 2 ( 1 ) extracted with chloroform . The obtained organic layer was dried over sodium sulfate and concentrated under reduced To 3 - chloropyridine - 2 -carbonitrile 54 g , and THF 300 pressure . The obtained residue was subjected to a silica gel mL , 1M THF solution of methyl magnesium bromide 500 45 column chromatography to givegive the Intermediate compound mg was added dropwise under ice - cooling. The obtained (4 - 3) 3 .8 g. reaction mixtures were stirred under ice -cooling for 2 hours . The obtained reaction mixtures were added to 2N hydro chloric acid under ice - cooling , and stirred for 30 minutes . To CH3 the mixtures was added IN sodium hydroxide solution to adjust to pH 8 , and the mixtures were extracted with ethyl acetate . The obtained organic layer was washed with brine N — N and dried over anhydrous sodium sulfate . The organic layer ?? . was concentrated to give the Intermediate compound ( 4 - 1 ) 55 58 g. H -NMR (CDC12 ) 8 : 10 .60 ( 1H , brs ), 8 . 43 ( 1H , dd ), 8 . 13 (1H , d ) , 7 .71 ( 1H , dd ) , 7 . 29 ( 1H , dd ) , 7 .05 ( 1H , d ), 2 .95 ( 2H , 2q. ) , 1. 35 (3H , t) . 60 O = Preparation Example 2 ( 4 ) To the mixure of the Intermediate compound ( 4 - 3 ) 2 . 0 g CH3 and toluene 9 ml, DMF and phosphorus oxychloride 1 .6 mL 65 were added sequentially . The mixtures were stirred at 100° ' H -NMR (CDC13 ) d : 8 .55 ( 1H , dd ), 7 . 80 ( 1H , dd ) , 7 . 38 C . for 2 hours . The obtained mixtures were allowed to stand ( 1H , dd ), 2 .70 ( 3H , s) . to room temperature and then concentrated under reduced US 9 ,924 ,719 B2 57 58 pressure . The obtained residue was diluted with chloroform H -NMR (CDC1z ) 8 : 8 . 98 ( 1H , dd ) , 8 .57 (1H , dd ), 8 .37 and to themixtures were added water under ice -cooling . The ( 1H , d ) , 8 . 25 ( 1H , d ), 7 . 72 ( 1H , dd ) , 3 . 90 (2H , q ) , 3 . 48 ( 3H , obtained mixtures were extracted with chloroform , washed s ) , 1 . 43 (3H , t ) . with water and brine , and then dried over sodium sulfate . The obtained organic layer was concentrated under reduced 5 Preparation Example 2 ( 7 ) pressure to give the Intermediate compound ( 4 - 4 ) 2 . 2 g . To the mixure of the Intermediate compound ( 4- 6 ) 0. 2 g , cesium carbonate 0 .23 g , and NMP 2 mL , 2 , 2 , 2 - trichlo - CH3 roethanol 0 . 1 g was added at room temperature , and the mixtures were stirred at room temperature for 1 hours , followed by at 50° C . for 30 minutes . The reaction mixtures were allowed to stand to room temperature , and thereto was added water, and the mixtures were then extracted with ethyl acetate and dried over sodium sulfate . After the mixture was 15 concentrated under reduced pressure , the obtained residue 1H -NMR (CDC12 ) 8 : 8 .48 ( 1H , dd ), 8 . 25 ( 1H , d ), 7 .79 was subjected to a silica gel column chromatography to give ( 1H , dd ), 7 .63 ( 1H , d ) , 7 .34 ( 1H , dd ) , 2 . 95 ( 2H , q ) , 1 . 33 (3H , Present compound 4 0 . 19 g . t ) . Preparation Example 2 (5 ) 20 To the mixure of the Intermediate compound (4 - 4 ) 2 . 2 g and chloroform 43 ml, mCPBA ( 75 % ) 4 . 2 g was added under ice - cooling . The reaction mixtures were stirred at room temperature for 24 hours . To the mixtures, sodium Cl3C N - ?ONU= BO sulfite 11 g and saturated sodium hydrogen carbonate solu - 25 tion were added , and the mixtures weres extracted with chloroform . The obtained organic layer was dried over sodium sulfate and concentrated under reduced pressure . The obtained residue was subjected to a silica gel column H -NMR (CDC12 ) 8 : 8. 92 ( 1H , dd ), 8 .53 ( 1H , dd ), 7 .95 chromatography to give the Intermediate compound ( 4 -5 ) 30 (1H , d ), 7 .63 (1H , dd ) , 7 .34 (1H , d ), 5 .28 (2H , s) , 3 .88 (2H , 2 .2 g . q ) , 1 .40 (3H , t ) . The present compound was prepared according to the method described in Preparation example 2 ( 7 ) using the - CH3 compound represented by Formula R1 - OH instead of 2 , 2 , 35 2 - trichloroethanol and shown in Table 19 . N - N

40 i H - NMR (CDC1z ) 8 : 8 .93 ( 1H , dd ), 8 . 54 ( 1H , dd ) , 7 . 95 N - N ( 1H , d ), 7. 71 (1H , d ), 7 .66 ( 1H , dd ), 3 .89 (2H , q) , 1. 41 (3H ,

Preparation Example 2 ( 6 ) 45 To the mixure of the Intermediate compound ( 4 - 5 ) 3 .0 g , tetrabutylammonium chloride 880 mg and DMF 26 mL , TABLE 19 sodium methanesulfinate 1 . 6 g was added at room tempera ture . The mixtures were stirred at 100° C . for 5 hours . The 50 Present obtained mixtures were allowed to stand to room tempera compound No . Ri ture and thereto was added water, and the mixtures were then CF3CH2 extracted with ethyl acetate . The obtained organic layer was CF3CH2CH2 dried over sodium sulfate and concentrated under reduced CF3CH2CH2CH2 pressure . The obtained residue was subjected to a silica gel 65 DESou CF3CH2CH2CH2CH2 column chromatography to give the Intermediate compound FzC CH3 ( 4 -6 ) 3 .0 g. F CH3 1 ACH CF ,HCH CF3CH2OCH2CH2 CF3CF CF2CH2 05 NEN CF , CFACF CF, CH , CF , CFCF5CF CH - CH CF3CF CF CF CF2CH2 CF (CF3 ) 2CF2CF _ CH _ CH2 US 9, 924 ,719 B2 60 TABLE 19 -continued Present compound 21; + H -NMR (CDC13 ) 8 : 8 .91 ( 1H , dd ) , 8 .52 ( 1H , dd ) , 7 . 87 ( 1H , d ), 7 .61 (1H , dd ), 7 . 16 ( 1H , d ) , Present 4 .91 ( 2H , t ), 3 . 88 ( 2H , 9 ), 2 . 74 ( 2H , tt) , 1 .40 (3H , t) . compound No . Present compound 22 ; ' H -NMR (CDC1z ) 8 : 8 .92 ( 1H , 5 dd ) , 8 .53 (1H , dd ) , 8 .01 (1H , d ), 7 .64 ( 1H , dd ), 7 .38 ( 1H , d ) , 6 . 86 ( 1H , dd ) , 3 .82 ( 2H , 9 ) , 1 . 39 ( 3H , t ). Present compound 23 ; ' H -NMR (CDC1 ) d : 8 .91 ( 1H , dd ) , 8 .52 ( 1H , dd ) , 7 .91 (1H , t ) , 7 .62 ( 1H , dd ), 7 .22 ( 1H , d ) , 6 . 12 - 6 .03 ( 1H , m ), 3 . 93 - 3 .79 (2H , m ) , 1 .63 ( 3H , d ) , 1. 39 ñ (3H , t ). Present compound 24 ; 1H -NMR (CDC12 ) 8 : 8 . 91 ( 1H , dd ) , 8 .52 (1H , dd ) , 7 . 90 ( 1H , t ) , 7 .62 ( 1H , dd ) , 7 . 20 (1H , d ) , k 6 . 23 ( 1H , m ), 3 . 85 (2H , m ) , 1 .67 ( 3H , d ) , 1 . 39 (3H , t ) . F Present compound 25 ; H -NMR (CDC1z ) 8 : 8 .91 (1H , IF dd ), 8 .52 ( 1H , dd ) , 7 . 90 ( 1H , d ) , 7 .62 ( 1H , dd ) , 7 . 22 ( 1H , d ) , CH3CH 15 4 .89 (2H , s) , 3 .88 (2H , 9 ), 1. 59 ( 3H , d ), 1 .40 (3H , t) . Present compound 26 ; ' H -NMR ( CDC13 ) d : 8 . 91 ( 1H , dd ) , 8 . 52 (1H , dd ) , 7 .91 ( 1H , t ) , 7 .61 ( 1H , dd ) , 7 . 23 ( 1H , d ) , ñ LISA 6 . 17 - 6 .09 ( 1H , m ) , 3 . 91 - 3 .77 (2H , m ) , 2 . 12 - 1 . 88 (2H , m ) , 1 . 38 ( 3H , t ) , 1 . 09 ( 3H , t ) . Fzc 20 H302 Preparation Example 3 ( 1 ) F3C The Intermediate compound ( 7 - 1 ) was prepared accord a ing to the method described in Preparation example 2 ( 7) H3C 25 using the compound represented by 1 -hydroxy - acetone instead of 2 , 2 , 2 - trichloroethanol. F3C — HC Present compound 5 ; ' H - NMR (CDC13 ) 8 : 8 .92 (1H , dd ), 30 8 . 53 ( 1H , dd ), 7 . 94 ( 1H , d ) , 7 .63 ( 1H , dd ), 7 . 29 ( 1H , d ), 5 .01 ??? ( 2H , q) , 3 .87 (2H , q ), 1. 40 (3H , t) . N - N 0 Present compound 6 ; ' H - NMR ( CDC13 ) 8 : 8 . 91 (1H , dd ) , 8 .52 ( 1H , dd ), 7 . 87 ( 1H , d ) , 7 .61 ( 1H , dd ), 7 . 17 ( 1H , d ), 4 . 83 35 (2H , t ), 3 .89 ( 2H , 9 ) , 2 .79 - 2 .66 (2H , m ), 1 . 40 ( 3H , t ) . Present compound 10 ; ' H -NMR (CDC13 ) d : 8 .91 ( 1H , dd ) , 8 .52 ( 1H , dd ) , 7 .86 (1H , d ) , 7 .61 ( 1H , dd ) , 7 . 14 (1H , d ) , H -NMR (CDC12 ) 8 : 8 .91 ( 1H , dd ), 8 .51 ( 1H , dd ) , 7 . 90 4 .65 (2H , t ). 3 .89 (21 . g ) . 2 . 42 - 2 .28 (2H . m ) . 2 . 19 - 2 . 10 (2H . ( 1H , d ) , 7 .61 ( 1H , dd ) , 7 .29 ( 1H , d ), 5 . 20 (2H , S ) , 3 . 85 ( 2H , m ) , 1 .39 (3H , t ) . an q ), 2 .28 (3H , s ), 1. 38 (3H , t) . Present compound 12 ; ' H - NMR (CDC13 ) 8 : 8 . 91 ( 1H , dd ) , 8 . 51 ( 1H , dd ) , 7 . 84 ( 1H , d ) , 7 .60 ( 1H , dd ) , 7 . 13 ( 1H , d ) , Preparation Example 3 ( 2 ) 4 .61 ( 2H , t ), 3 .90 ( 2H , q ) , 2 . 27 - 2 . 13 (2H , m ) , 2 .00 - 1 . 92 (2H , To the mixure of the Intermediate compound ( 7 - 1 ) 110 m ) , 1 . 86 - 1 . 76 (2H , m ), 1 .39 (3H , t ). mg , and chloroform 2 mL , bis ( 2 -methoxyethyl )aminosulfur Present compound 14 ; ' H -NMR (CDC13 ) 8 : 8 .91 (1H , 45 trifluoridetriflud 150 mg was added dropwise under ice - cooling . dd ) , 8 . 52 ( 1H , dd ) , 7 . 90 ( 1H , d ), 7 .62 ( 1H , dd ) , 7 .20 ( 1H , d ) , The mixtures were stirred at room temperature for 6 . 5 hours . 6 . 19 ( 1H , m ), 3 . 93 - 3 .77 ( 2H , m ), 1 .66 (3H , d ) , 1 .39 (3H , t ) . The obtained mixtures were added to saturated aqueous Present compound 15 ; " H -NMR (CDC1z ) d : 8 . 91 ( 1H , sodium hydrocarbonate solution and extracted with ethyl dd ), 8. 52 ( 1H , dd ) , 7 .90 (1H , d ), 7 .62 ( 1H , dd) , 7. 23 ( 1H , d ) , acetate . The obtained organic layers were washed with brine, 6 .22 ( 1H , tt ), 4 .81 (2H , dt) , 3 .87 (2H , q ) , 1. 40 (3H , t) . 50 followed by dried over sodium sulfate and concentrated Present compound 16 ; + H -NMR (CDC1 , ) 8 : 8 . 91 ( 1H , under reduced pressure . The obtained residue was subjected dd ), 8 .51 ( 1H , dd ) , 7 . 86 ( 1H , d ), 7 .60 ( 1H , dd ), 7 . 19 ( 1H , d ) , to a silica gel column chromatography to give 3 - ( 2 , 2 4 . 80 - 4 .77 (2H , m ), 4 . 08 ( 2H , t ), 3 .97 (2H , 9 ), 3 . 88 ( 2H , q ) , difluoropropoxy ) - 6 - ( 3 - ethanesulfonylpyridin - 2 -yl ) 1 . 39 (3H , t ) . se pyridazine (hereinafter , referring to as “ Present compound Present compound 17; ' H -NMR ( CDC13 ) d : 8 . 92 ( 1H , » 7 " ) 31 mg. dd ) , 8 .53 ( 1H , dd ), 7 . 94 (1H , d ), 7 .62 (1H , dd ), 7 .29 ( 1H , d ), 5 . 13 (2H , t ) , 3 .87 (2H , q ) , 1 .40 (3H , t ) . Present compound 18; ' H -NMR ( CDC13 ) d: 8. 92 (1H , H3C dd ) , 8 . 53 ( 1H , dd ), 7 . 94 ( 1H , d ), 7 .63 ( 1H , dd ) , 7 . 27 ( 1H , d ) , 60 5 . 14 (2H , t ) , 3 .87 (2H , q ) , 1 .40 (3H , t ) . H3C Present compound 19 ; ' H -NMR (CDC12 ) 8 : 8 . 91 ( 1H , N — N dd) , 8 . 52 ( 1H , dd ) , 7 . 87 ( 1H , d ) , 7 .61 ( 1H , dd ), 7 . 16 ( 1H , d ) , F 4 . 92 (2H , t ), 3 .88 ( 2H , q ) , 2 .78 - 2 .68 ( 2H , m ) , 1 .40 (3H , t ). F 0 Present compound 20 ; ' H -NMR (CDC1z ) 8 : 8 . 92 ( 1H , 65 dd ) , 8 .53 ( 1H , dd ), 7 . 94 (1H , d ), 7 .62 (1H , dd ), 7 .29 ( 1H , d ), 5 . 14 (2H , t ), 3 . 87 (2H , q ), 1. 40 (3H , t ). US 9 ,924 ,719 B2 62 ' H -NMR (CDC1z ) 8 : 8 .92 ( 1H , dd ), 8 .52 ( 1H , dd ) , 7 .91 ( 1H , d ) , 7 .62 ( 1H , dd ), 7 . 25 (1H , d ) , 4 .76 ( 2H , t ), 3 . 89 (2H , q ) , 1 .81 (3H , t ) , 1 . 40 ( 3H , t) . Preparation Example 4 (1 ) 5 N N The Intermediate compound ( 8 - 1 ) was prepared accord ing to the method described in Preparation example 2 ( 5 ) using the Intermediate compound ( 4 - 3 ) instead of the Inter mediate compound (4 -4 ) . 10 TABLE 20 CH3 Present compoun No . RI

N 15 9 CF3CF2CH2 N - 11 CF3CHFCF2CH2 ?? . Present compound 9 ; H - NMR (CDC13 ) 8 : 8 .92 (1H , dd ) , 8 .53 ( 1H , dd ) , 7 . 94 ( 1H , d ), 7 .63 ( 1H , dd ), 7 .29 (1H , d ), 5 .08 810 20 ( 2H , t ), 3 . 87 ( 2H , q ) , 1 . 40 (3H , t ) . H -NMR (CDC13 ) d : 12. 07 ( 1H , s ), 8 . 90 ( 1H , dd ) , 8 . 49 Present compound 11 ; ' H -NMR (CDC1z ) 8 : 8 .92 ( 1H , ( 1H , dd ) , 7 .80 ( 1H , d ), 7 .61 ( 1H , dd ), 7. 11 ( 1H , d ), 3. 67 (2H , dd ), 8 .53 ( 1H , dd ) , 7 . 95 ( 1H , d ) , 7 .63 ( 1H , dd ) , 7 . 27 ( 1H , d ) , q ) , 1 .39 (3H , t ). 5 .28 -5 .06 (1H , m ), 5 .05 - 4 . 96 (2H , m ), 3 .87 ( 2H , 9 ), 1. 40 ( 3H , t ) . Preparation Example 4 ( 2 ) 25 The by- product prepared with the present compound Present compound 8 and the by -product 8 were prepared described in Table 20 is shown in Table 21 . according to the method described in Preparation example 1 ( 5 ) using the Intermediate compound ( 8 - 1 ) instead of the CH3 Intermediate compound ( 1 - 4 ) and 2 , 2 , 3 , 3 , 3 -pentafluoropro pyl trifluoromethane sulfonate instead of 2 , 2 , 2 - trifluoroethyl 30 nonafluorobutane sulfonate .

CH3 35

VN TABLE 21 40 Side product No. F CF2CF CH 11 CF3CHFCF2CH2 1H -NMR (CDC1 , ) 8 : 8 . 92 ( 1H , dd ), 8 .53 ( 1H , dd ) , 7 . 93 45 By -product 9 ; ' H -NMR (CDC1z ) 8 : 8 . 92 ( 1H , dd ), 8 . 50 ( 1H , d ) , 7 .63 ( 1H , dd ) , 7 .27 ( 1H , d ) , 6 .21 - 5 . 90 ( 1H , m ) , 5 .01 (1H , dd ) , 7 .74 ( 1H , d ) , 7 .64 ( 1H , dd ) , 7 . 10 ( 1H , d ) , 4 . 86 (2H , ( 2H , t ) , 3 . 88 ( 2H , q ) , 1 . 40 ( 3H , t ) . t ) , 3 .54 (2H , q ) , 1 . 38 (3H , t ) . By -Product 8 By -product 11; ' H -NMR (CDC1 , ) 8 : 8 . 92 ( 1H , dd ), 8. 49 (1H , dd ) , 7 . 73 ( 1H , d ) , 7 .64 ( 1H , dd ), 7 . 11 ( 1H , d ) , 5 . 21 - 5 . 00 so ( 1H , m ) , 4 . 93 - 4 .69 (2H , m ) , 3 .54 (2H , q ) , 1 .38 (3H , t ) . F Preparation Example 5 ( 1 ) CH3 F To the mixure of 5 . 0 g of 3 - ethylsulfanyl - 5 - ( trifluorom ethyl) pyridine - 2 - carbonic acid prepared according to the F N?N . 55 process described in WO 2013 /018928 , N ,O -dimethylhy O droxyamine hydrochloride salt 1 . 9 g , and acetonitrile 100 mL , 1 - ethyl- 3 -( 3 - dimethylaminopropyl) carbodiimide hydrochloride salt 4 .6 g , 1 -hydroxybenzotriazole 0 . 27 g , and triethylamine 5 . 5 mL were sequentially added at room H - NMR (CDC13 ) 8 : 8 .91 ( 1H , dd ) , 8 . 49 ( 1H , dd ), 7 .73 60 temperature . The reaction mixtures were stirred at room (1H , d ), 7 .63 ( 1H , dd ), 7 . 10 ( 1H , d ) , 6 . 13 - 5 .82 ( 1H , m ) , 4 .78 temperature for 1 hour, thereto was added water, and the ( 2H , t ) , 3 . 56 (2H , q ) , 1 . 38 ( 3H , t ) . mixtures were extracted with ethyl acetate . The obtained The present compound was prepared according to the organic layer was washed with water and brine, followed by method described in Preparation example 4 ( 2 ) using the dried over sodium sulfate and concentrated under reduced compound represented by Formula R ? OSO CFz instead 65 pressure . The obtained residue was subjected to a silica gel of 2 , 2 , 3 , 3 , 3 - pentafluoropropyl trifluoromethane sulfonate column chromatography to give the Intermediate compound and is shown in Table 20 . ( 5 - 1) 4 .8 g . US 9 , 924 ,719 B2 63 64 added saturated sodium hydrogen carbonate solution under - CH3 ice -cooling , and the mixtures were then extracted with MTBE . The obtained organic layer was washed with brine , followed by dried over anhydrous sodium sulfate and con centrated under reduced pressure . The obtained residue was CF3 subjected to a silica gel column chromatography to give the Intermediate compound ( 5 - 4 ) 1 . 73 g . H3C CH2 10 Ets H -NMR (CDC13 ) 8 : 8. 67 ( 1H , s ), 7 .90 ( 1H , s ), 3. 58 (3H , NEN s ), 3. 41 (3H , s) , 3 .00 (2H , q ), 1. 34 ( 3H , t) . 01

Preparation Example 5 (2 ) 15 To the mixure of the Intermediate compound ( 5 - 1 ) 0 .60 g H -NMR (CDC1z ) 8 : 8 .69 ( 1H , s ) , 8 .34 ( 1H , d ) , 7 .94 ( 1H , and tetrahydrofuran 8 mL , 1M THF solution ofmethylmag - s ) , 7 .68 ( 1H , d ), 3 . 00 (2H , q ) , 1 . 38 (3H , t ) . nesium bromide 2 . 5 mL was added under ice -cooling . The reaction mixtures were stirred at room temperature for 2 0 Preparation Example 5 ( 5 ) hours , thereto was added 2N hydrochloric acid , and the mixtures were extracted with ethyl acetate . The obtained organic layer was washed with water and brine, followed by The Intermediate compound (5 - 5 ) was prepared accord dried over anhydrous sodium sulfate and concentrated under ing to the method described in Preparation example 2 (5 ) reduced pressure . The obtained residue was subjected to a , using the Intermediate compound ( 5 - 4 ) instead of the Inter silica gel column chromatography to give the Intermediate* 25 mediate compound (4 - 4 ). compound ( 5 - 2 ) 3 . 7 g . - CH3

- CH3 30 N - N

wT3 - CF3 H3C 35 * H -NMR (CDC13 ) 8 : 9 . 18 ( 1H , d ) , 8 . 78 ( 1H , d ) , 8 .01 ( 1H , 1H - NMR (CDC1 , ) 8 : 8 .62 ( 11 . d ), 7 .84 ( 1H . d ), 2 .96 (2H . d ) , 7 .76 ( 1H , d ) , 3 . 96 ( 2H , 9 ) , 1 . 45 ( 3H , t ) . q ), 2 .74 (3H , s) , 1. 42 (3H , t) . Preparation Example 5 (6 ) Preparation Example 5 (3 ) 40 To the mixure of the Intermediate compound ( 5 - 5 ) 0 . 24 The Intermediate compound ( 5 - 3 ) was prepared accord pentafluoropropanol 0 . 10 mL was added at room tempera ing to the method described in Preparation example 2 ( 3 ) ture. The reaction mixtures were stirred at 60° C . for 1 hour. using the Intermediate compound ( 5 - 2 ) instead of the Interaler 45 After the obtained mixtures were allowed to stand to room mediate compound ( 4 - 2 ) . temperature , thereto was added water, and themixtures were extracted with ethyl acetate . The obtained organic layer was washed with water and brine , followed by dried over anhy CH3 drous sodium sulfate and concentrated under reduced pres 50 sure . The obtained residue was subjected to a silica gel N — N column chromatography to give Present compound 28 . ?? - CF3 CH3 55 F3C ' H -NMR (CDC13 ) 8 : 10 .94 (1H , br s) , 8. 64 ( 1H , d ), 8 .21 ( 1H , d ), 7 .85 ( 1H , d) , 7 .08 (1H , d ), 2 .99 (2H , q ), 1. 39 (3H , Face TED t e CH3 Preparation Example 5 ( 4 ) 60 To 2 . 7 g of the Intermediate compound (5 - 3 ), phosphorus 'H -NMR (CDC1z ) 8 : 9. 16 (1H , s ), 8 . 77 (1H , s) , 8. 01 ( 1H , oxychloride 10 mL was added , and the mixtures were stirred d ) , 7. 32 ( 1H , d ) , 5 .10 (2H , t) , 3 . 96 ( 2H , 9 ) , 1 .44 (3H , t) . at 100° C . for 6 hours . After it was confirmed that TLC The present compound was prepared according to the indicated the consumption of the Intermediate compound 3 , 65 method described in Preparation example 5 (6 ) using the the mixtures were concentrated under reduced pressure with compound represented by Formula R - OH instead of 2 , 2 , 3 , an evaporator , followed by to the obtained residue was 3 , 3 - pentafluoropropanol and is shown in Table 22 . US 9, 924 ,719 B2 65 66 TABLE 22 CH3 Present compound No. R ! F?? 31 CF HCF2CH2 CF3CHFCF2CH2 55 N - N Present compound 31 ; 1H - NMR (CDC1z ) d : 9 . 16 ( 1H , s ) , 8 .77 ( 1H , s ), 8 . 00 ( 1H , d ), 7 . 30 ( 1H , d ) , 6 . 18 - 5 . 93 (1H , m ) , 5 .03 (2H , t ) , 3 . 96 (2H , 9 ) , 1 . 44 ( 3H , t ) . Present compound 32 : 1H -NMR (CDCI ) 8 : 8 .68 ( 11 s ) 10 “ H -NMR (CDC13 ) d : 8 .46 ( 1H , dd ), 8 . 32 ( 1H , d ), 7 . 78 8 . 39 (1H , d ), 7 .92 (1H , s ), 7 .24 ( 1H , S ), 5 .07 ( 3H , m (1H , dd ) , 7 .32 ( 1H , dd ), 7 .24 (1H , d ) , 5 . 12 ( 2H , t) , 2 . 96 (2H , 4 .15 -4 .08 (1H , q ), 1. 39 ( 3H , t ). q ) , 1 . 35 ( 3H , t ). Preparation Example 6 Preparation Example 9 15 Present compound 39 was prepared according to the To the mixure of 790 mg of Present compound 27, and method described in Preparation example 5 ( 6 ) using the chloroform 7 mL , 75 % mCPBA 510 mg was added under Intermediate compound ( 5 - 4 ) instead of the Intermediate ice - cooling . The mixtures were stirred under ice - cooling for compound ( 5 - 5 ) . 0 . 5 hours . To the obtained reaction mixtures , saturated 20 sodium hydrogen carbonate solution was added , and the mixtures were extracted with chloroform . The obtained CH3 organic layer was washed with brine , followed by dried over anhydrous sodium sulfate and concentrated under reduced N - N pressure. The obtained residue was subjected to a silica gel 25 column chromatography to give 780 mg of Present com ÉF O pound 29 .

H -NMR (CDC1z ) 8 : 8 .68 ( 1H , d ) , 8 . 40 ( 1H , d ) , 7 . 93 ( 1H , - CH3 d ), 7 .28 ( 1H , d ), 5 .17 - 5 .11 (2H , m ), 3 .01 (2H , q ), 1. 39 (3H , 30 F3C SS t) . N - N Preparation Example 7 Present compound 40 was prepared according to the 35 method described in Preparation example 5 ( 6 ) using the Intermediate compound ( 5 - 4 ) intead of the Intermediate H -NMR (CDC1 , ) 8 : 8 . 78 ( 1H , dd ) , 8 .68 ( 1H , dd ), 8 .60 compound ( 5 - 5 ) and 2 , 2 , 3 , 3 -tetrafluoropropanol instead of (1H , d ), 7 .64 ( 1H , dd ), 7 .30 (1H , d ) , 5 .21 -5 .02 (2H , m ), 2 ,2 , 3 , 3, 3 -pentafluoropropanol . 3 . 54 - 3 .42 ( 1H , m ), 3 . 06 - 2 . 95 ( 1H , m ), 1 . 41 (3H , t ) . 40 Preparation Example 10 F The mixture of N -oxide 3 0 .45 g , paradium carbon 50 mg, F ammonium formate 0 .66 g , and methanol 3 mlwas stirred at N — N 45 room temperature for 10 minutes . The mixtures was warmed F to 60° C . and heated to stir for 2 hours. The obtained FO - CF3 mixtures were allowed to stand to room temperature , thereto was added water, and the mixtures were extracted with ethyl to acetate . The obtained organic layer was washed with brine , followed by dried over anhydrous sodium sulfate and con 1H - NMR (CDC13 ) 8 : 8 .68 (1H , d ), 8 .38 ( 1H , d ), 7. 92 (1H , 50 centrated under reduced pressure . The obtained residue was d ), 7 .25 (1H , d ), 6 .05 (1H , tt ), 5. 10 - 5. 03 (2H , m ), 3 .01 (2H , subjected to a silica gel column chromatography to give 200 q ) , 1 .39 (3H , t ) . mg of Present compound 30 . Preparation Example 8 55 To the mixure of 1. 0 g of Intermediate ( 4 -4 ), cesium CHZ carbonate 1 . 8 g , and NMP 7 mL , 2 , 2 , 3 , 3 , 3 -pentafluoropro F3C panol 1 . 6 mL was added at room temperature . The mixtures N - N were heated and stirred at 70° C . for 47 hours . After the F obtained mixtures were allowed to stand to room tempera - 60 É 0 ture, thereto was added water , and the mixtures were then extracted with ethyl acetate . The obtained organic layer was washed with water and brine , followed by dried over anhy HansCH3 drous sodium sulfate and concentrated under reduced pres sure . The obtained residue was subjected to a silica gel 65 ' H - NMR ( CDC13 ) d : 8 . 94 (1H , dd ), 8 . 48 ( 1H , dd ), 7 .65 column chromatography to give 1. 3 g of Present compound (1H , dd ), 7. 10 ( 1H , m ), 5 .03 (2H , dt) , 3 .46 (2H , q ), 2 .22 (3H , 27 . t ), 1 .31 ( 3H , t ). US 9 , 924 ,719 B2 67 68 Preparation Example 11( 1 ) under reduced pressure . The obtained residue was subjected to a silica gel column chromatography to give 0 .51 g of the The solution of the Intermediate compound (4 - 2) 0 . 5 g Intermediate compound ( 11- 3 ). and THF 3 mL was cooled to -78° C . , and to the solution , LDA 2 . 7 mL ( 1 . 1 M THF solution ) was added dropwise . 5 After stirring for 1 hour, to the mixtures, ethyl trifluoropy - CH3 ruvate 0 .53 mL was added , and the mixtures were stirred for 30 minutes . To the obtained mixtures , saturated ammonium chloride solution was added at room temperature , and the N - N mixtures were extracted with MTBE . The obtained organic 10 layer was washed with brine , followed by dried over anhy drous sodium sulfate and concentrated under reduced pres sure . The obtained residue was subjected to a silica gel FicF column chromatography to give 0 . 74 g of the Intermediate 15 compound ( 11 - 1 ) . H -NMR (CDC13 ) 8 : 8 . 65 ( 1H , s ), 8 .51 ( 1H , dd ) , 7 . 83 ( 1H , dd ) , 7 . 39 ( 1H , dd ), 2 .99 (2H , q ) , 1 .35 (3H , t ) .

20 Preparation Example 11( 4 ) To the solution of the Intermediate compound ( 11 -3 ) 0 .26 EtO2C g and NMP 3 mL , 2 , 2 , 3 , 3 , 3 -pentafluoroalcohol 0 . 11 mL and cesium carbonate 0 . 36 g were added , and the mixtures were HÓ CF3 then heated and stirred at 70° C . for 2 hours . To the obtained reaction mixtures, saturated ammonium chloride solution H - NMR (CDC13 ) 8 : 8 .41 ( 1H , dd ) , 7 .69 ( 1H , dd ), 7 .40 was added at room temperature , and the mixtures were ( 1H , dd ), 4 . 56 (1H , br s ) , 4 .45 - 4 .32 (2H , m ) , 4 . 16 - 4 .08 ( 2H , extracted with MTBE . The obtained organic layer was m ) , 2 . 92 ( 2H , 9 ) , 1 . 39 ( 3H , t ) , 1 . 30 ( 3H , t ) . 30 washed with brine, followed by dried over anhydrous sodium sulfate and concentrated under reduced pressure . Preparation Example 11( 2 ) The obtained residue was dissolved in chloroform 5 mL , and To the solution of the Intermediate compound ( 11 - 1 ) 0 .74 thereto was added 75 % mPBA 0 .41 g under ice - cooling , and g and ethanol 10 mL , 12 N hydrochloric acid 0 . 10 mL and 35 the mixtures were stirred for 1 hour. To the obtained reaction hydrazine monohydrate 0 .21 mL was added dropwise . After mixtures , saturated sodium hydrogen carbonate solution and stirring at 80° C . for 10 hours, the mixtures were concen trated under reduced pressure with an evaporator. The sodium thiosulfate solution were added at room temperature , obtained residue was subjected to a silica gel column and the mixtures were then extracted with chloroform . The chromatography to give 0 . 25 g of the Intermediate com - 40 obtained organic layer was washed with brine, followed by pound ( 11 - 2 ). dried over anhydrous sodium sulfate and concentrated under reduced pressure . The obtained residue was subjected to a silica gel column chromatography to give 0 . 20 g of Present CH ; compound 34 . 45 N — N CH3 HO F3C 50 N — N F3C F

L ' H -NMR ( CDC13 ) 8 : 10 .71 ( 1H , s ) , 8 . 55 (1H , s ), 8 .45 ( 1H , dd ), 7 .74 ( 1H , dd ), 7. 33 ( 1H , dd ), 2. 97 (2H , q ), 1. 37 (3H , t) . 55 Preparation Example 11 ( 3 ) H -NMR (CDC13 ) 8: 8 .95 (1H , dd ), 8. 56 ( 1H , dd ), 8 . 22 To 0 .579 g of the Intermediate compound ( 11 - 2 ), phos - ( 1H , s ), 7 .70 -7 .66 ( 1H , m ), 5 .21 - 5 . 15 ( 2H , m ), 3 .88 ( 2H , q ), phorus oxychloride 10 mL was added , and the mixtures were 1 . 43 (3H , dt ) . stirred 100° C . for 6 hours. After it was confirmed that TLC 60 indicated the consumption of the Intermediate compound ( 11 - 2 ) , the mixtures were concentrated under reduced pres Preparation Example 12 sure with an evaporator, and to the obtained residue was added saturated sodium hydrogen carbonate solution under Present compound 33 was prepared according to the ice - cooling , and the mixtures were extracted with MTBE . 65 method described in Preparation example 11 ( 4 ) using 2 , 2 , The obtained organic layer was washed with brine, followed 3 , 3 - tetrafluoropropanol instead of 2 , 2 , 3 , 3 , 3 -pentafluoropro by dried over anhydrous sodium sulfate and concentrated panol. US 9 , 924 ,719 B2 70 H -NMR (CDC1z ) 8 : 10. 70 (1H , s) , 8 .43 ( 1H , dd ), 7 .93 CH3 ( 1H , 9 ), 7 .71 (1H , dd ), 7 .28 (1H , dd ) , 2 .94 (2H , q) , 2 .29 (3H , d ), 1 .34 (3H , t ) . N - N 5 F É O Preparation Example 13 ( 3) To the Intermediate compound ( 13- 2 ) 2. 0 g and phospho FC rus oxychloride 9 mL , toluene 30 mL was added , and the 10 mixtures were stirred at 100° C . for 4 hours . After it was H -NMR ( CDC12 ) 8 : 8 .96 -8 .94 ( 1H , m ), 8 .56 (1H , dd ), confirmed that TLC indicated the consumption of Interme 8 .21 ( 1H , s ) , 7 .67 ( 1H , dd ) , 6 . 19 - 5 .91 ( 1H , m ), 5 . 11 ( 2H , t ) , diate (13 -2 ) , the mixtures weres concentrated under reduced 3 . 93 - 3 . 85 ( 2H , m ), 1. 43 ( 3H , t ) . pressure with an evaporator, and to the obtained residue was Preparation Example 13 ( 1 ) added saturated sodium hydrogen carbonate solution under ice -cooling , and the mixtures were extracted with MTBE . The solution of the Intermediate compound ( 4 - 2 ) 5 . 0 g and THF 25 mL was cooled to - 78° C ., and thereto was The obtained organic layer was washed with brine, followed added LDA 27 mL ( 1 . 1 M THF solution ) . After stirring for 20 by dried over anhydrous sodium sulfate and concentrated 30 minutes, to the mixtures was added ethyl pyruvate 6 . 1 under reduced pressure . The obtained residue was subjected mL , and the mixtures were stirred for 30 minutes. To the to a silica gel column chromatography to give 1. 9 g of the obtained reaction mixtures , saturated ammonium chloride Intermediate compound ( 13 - 3 ) . solution was added at room temperature , and the mixtures were extracted with MTBE . The obtained organic layer was 25 washed with brine , followed by dried over anhydrous sodium sulfate and concentrated under reduced pressure . CH3 The obtained residue was subjected to a silica gel column chromatography to give 4 .2 g of the Intermediate compound N - N ( 13 - 1 ) . 30 CI

CH3 H3C 35 H -NMR (CDC12 ) 8 : 8. 47 ( 1H , dd ), 8. 10 ( 1H , d ), 7 .79 EtO2C ( 1H , dd ) , 7 .33 ( 1H , dd ) , 2 . 95 ( 2H , q ) , 2 . 49 ( 3H , d ) , 1 .33 ( 3H , t). HOCHZ 40 Preparation Example 13 ( 4 ) ' H -NMR (CDC13 ) 8 : 8 .40 ( 1H , dd ), 7. 69 (1H , dd ), 7 .38 ( 1H , dd ), 4 .29 ( 1H , s) , 4 . 23 (2H , 9 ), 3. 86 (1H , d ), 3 .61 (1H , To the solution of Intermediate (13 -3 ) 0 . 92 g and NMP d ), 2 .91 ( 2H , q ), 1. 52 (3H , s ), 1. 39 ( 3H , t) , 1. 30 -1 .22 (3H , mL , 2 , 2 , 3 , 3 -tetrafluoropropanol 0 .46 mL and cesium car m ) . bonate 1 .57 g were added , and the mixtures were then heated Preparation Example 13( 2 ) to 70° C . and stirred for 4 hours . To the obtained mixtures, saturated ammonium chloride solution was added at room To the solution of the Intermediate compound ( 13 - 1 ) 4 . 2 g and ethanol 55 mL , 2 N hydrochloric acid 2 . 0 mL and 50 temperature , and the mixtures were extracted with MTBE . hydrazine monohydrate 1 .36 mL were added dropwise . The The obtained organic layer was washed with brine, followed mixtures were stirred at60° C . for 10 hours and concentrated by dried over anhydrous sodium sulfate and concentrated under reduced pressure with an evaporator. The obtained under reduced pressure. The obtained residue was dissolved residue was subjected to a silica gel column chromatography in chloroform 20 mL , thereto was added mCPBA 1 . 7 g under to give 2 . 1 g of the Intermediate compound ( 13 - 2 ) . ice -cooling , and the mixtures were stirred for 1 hour. To the obtained reaction mixtures , saturated sodium hydrogen car - CH3 bonate solution and sodium thiosulfate solution were added at room temperature , and the mixtures were extracted with N chloroform . The obtained organic layer was washed with HO brine , followed by dried over anhydrous sodium sulfate and concentrated under reduced pressure . The obtained residue was subjected to a silica gel column chromatography to give H2C 65 0 . 25 g of Present compound 37 and 0 . 73 g of Present compound 35 . US 9, 924 ,719 B2 71 72 Present1 Compound 37 930 * Present Compound 36 CH3 O CH

NN N - N F

L 10 TasHzC TasHC H - NMR (CDC13 ) d : 8 .45 ( 1H , dd ) , 8 . 08 ( 1H , d ) , 7 .77 ' H -NMR (CDC13 ) 8 : 8 .91 ( 1H , dd ), 8 .52 (1H , dd ), 7 .74 ( 1H , dd ), 7 .31 (1H , dd ), 6 .03 ( 1H , tt ), 5 .04 ( 2H , ddd ), 2. 95 13 (1H , s ), 7 .62 (1H , dd ), 5 . 06 (2H , t) , 3 .89 (2H , q ) , 2. 35 (3H , (2H , q ), 2 .34 (3H , d ), 1. 34 (3H , t) . s ), 1. 40 (3H , t) . Preparation Example 15 Present Compound 35 20 To the solution of Present compound 9 500 mg and chloroform 2 . 5 mL , 75 % mCPBA 610 mg was added under ice -cooling , and the mixtures were stirred for 24 hours . To the obtained reaction mixtures , saturated sodium hydrogen carbonate solution and sodium sulfite solution were added at 25 room temperature , and the mixtures were extracted with chloroform . The obtained organic layer was washed with - CH3 brine , followed by dried over anhydrous sodium sulfate and concentrated under reduced pressure . The obtained residue N - N was subjected to a silica gel column chromatography to give 30 230 mg of N -oxide 1 , and 300 mg of N - oxide 2 . F N -Oxide 1

35 OACH ;

' H -NMR ( CDC13 ) d : 8 . 91 ( 1H , s ) , 8 . 52 ( 1H , dd ), 7 . 73 ( 1H , s ) , 7 .62 ( 1H , dd ) , 6 . 03 ( 1H , tt ), 5 . 00 (2H , t ), 3 . 89 ( 2H , 40 q ), 2 .35 (3H , d ) , 1 .40 (3H , t ) . " H -NMR (CDC13 ) 8 : 8 . 94 ( 1H , dd ), 8 . 39 ( 1H , dd ), 7 .73 ( 1H , d ), 7 .67 (1H , dd ), 6 . 95 ( 1H , d ) , 4 .99 - 4 .76 (2H , m ), mentePreparation Example 14 3 .64 - 3 .50 (2H , m ), 1. 39 ( 3H , t ). 45 N -Oxide 2 Present compound 38 and Present compound 36 were prepared according to the method described in Preparation example 13 ( 4 ) using 2 , 2 , 3 , 3 , 3 - pentafluoropropanol instead of 2 ,2 ,3 , 3 -tetrafluoropropanol . 50 Present Compound 38 1

-CH3 55 F3C 1H -NMR (CDC1z ) 8 : 8 .50 ( 1H , dd ), 7 . 91 (1H , dd ), 7 .74 N — N ( 1H , d ), 7 .61 ( 1H , dd ) , 6 . 96 ( 1H , d ), 4 . 86 ( 2H , t ) , 3 . 30 - 3 . 24 SENSE( 2H , m ) , 1 . 31 COM( 3H , t ) . 2. 100 , Preparation Example 16 ( 1 ) H3C To the dispersion of sodium hydride ( 60 % , oily ) 3 .44 g and DMF 50 mL , ethylmercaptan 6 mL was added dropwise ' H -NMR (CDC13 ) d : 8 . 45 ( 1H , dd ) , 8 .09 ( 1H , d ), 7 . 77 65 under ice bath . After stirring under ice - cooling for 15 (1H , dd ) , 7 .31 (1H , dd ) , 5 . 11 ( 2H , td ) , 2 .95 ( 2H , q ) , 2 .35 ( 3H , minutes, to the reaction mixtures was added 12 g of 1 - ( 3 d ), 1 .34 ( 3H , t ) . chloropyridin - 2 - yl) propan - 1 - one . The reaction mixtures US 9 ,924 ,719 B2 73 74 were stirred at room temperature for 2 hours . To the obtained reaction mixtures , saturated sodium hydrogen carbonate CH3 solution was added at room temperature , and the mixtures were extracted with MTBE . The obtained organic layer was washed with water and brine , followed by dried over anhy - 5 N - N drous sodium sulfate and concentrated under reduced pres HO sure. The obtained residue was subjected to a silica gel column chromatography to give 14 g of the Intermediate CH3 compound ( 16 - 1 ). 10 H -NMR (CDC1z ) 8 : 8 .48 ( 1H , dt) , 7 .74 ( 1H , d ), 7 . 33 ( 1H , - CH3 ddd ), 6 .86 (1H , t ), 2 .89 ( 2H , q ) , 2 . 06 ( 3H , br s ), 1 . 28 ( 3H ,

15 Preparation Example 16 ( 4 ) To 7. 4 g of the Intermediate compound ( 16 - 3) , phospho rus oxychloride 10 mL was added , and the mixtures were H3C2 stirred at 100° C . for 6 hours. After it was confirmed that TLC indicated the consumption of the Intermediate com pound 3 , the mixtures were concentrated under reduced *H - NMR (CDC12 ) 8 : 8. 39 (1H , dd ), 7 .69 ( 1H , dd ), 7. 36 pressure with an evaporator, and to the obtained residue was ( 1H , dd ) , 3. 22 (2H , q) , 2. 92 (2H , q) , 1. 39 (3H , t) , 1. 21 (3H added saturated sodium hydrogen carbonate solution , and the mixtures were extracted with MTBE . The obtained organic layer was washed with brine, followed by dried over 25 anhydrous sodium sulfate and concentrated under reduced Preparation Example 16 ( 2 ) pressure . The obtained residue was subjected to a silica gel column chromatography to give 5 . 7 g of the Intermediate To 2 N sodium hydroxide 12 mL , glyoxylic acid mono compound ( 16 - 4 ) . hydrate 1 .41 g was added under ice- cooling , and the mix tures were stirred for 10 minutes. To the reaction mixtures , 30 MeOH 12 mL and 1 . 5 g of Intermediate ( 16 - 1 ) were added , CH3 and the mixtures were stirred for 1 hour. After it was confirmed that TLC indicated the consumption of Interme N — N diate ( 16 - 1 ) , to the reaction solution was added 12 N hydrochloric acid , and the mixtures were stirred for 1 hour, 35 and the obtained solid was filtered and dried to give 1 . 3 g of the Intermediate compound ( 16 - 2 ) . CH3 40 H -NMR (CDC1z ) 8 : 8 .95 ( 1H , dd ), 8 . 50 ( 1H , dd ), 7 .68 CH3 (1H , dd ), 7 .52 ( 1H , d ) , 3. 48 (2H , 9 ) , 2 .24 (3H , s ), 1. 31 ( 3H , Preparation Example 16 ( 5 ) 4543 To the solution of the Intermediate compound ( 16 - 4 ) 5 . 7 g and chloroform 150 mL , mCPBA 11 g was added under HO2C CH3CH3 ice -cooling , and the mixtures were stirred for 1 hour. To the obtained reaction mixtures , saturated sodium hydrogen car bonate solution and sodium thiosulfate solution were added 1H -NMR (CDC1 . ) 8 : 8 .46 ( 1H . dd ). 7 .78 ( 11 . dd ) . 7 . 38 30 at room temperature , and the mixtures were extracted with ( 1H , dd ) , 6 . 19 ( 1H , q ), 2 . 93 ( 2H , q ), 2 . 43 ( 3H , d ) , 1 . 33 ( 3H , chloroform . The obtained organic layer was washed with brine , followed by dried over anhydrous sodium sulfate and t) . concentrated under reduced pressure . The obtained residue was subjected to a silica gel column chromatography to give Preparation Example 16 (3 ) 55 2 .3 g of the Intermediate compound ( 16 -5 ) . To the solution of the Intermediate compound ( 16 - 2 ) 0 . 10 g and water 3 mL , sodium sulfite 0 . 06 g was added , and the - CH3 mixtures were stirred at 60° C . for 1 hour . After it was a confirmed that TLC indicated the consumption of the Inter N mediate compound 2 , to the reaction solution were added 12 N hydrochloric acid 1 mL and hydrazine monohydrate 0 .05 mL , and the mixtures were warmed to 90° C . After stirring for 4 hours , the mixtures were slowly stirred under ice - 65 CH cooling, and the formed crystal was filtered and dried to give 84 mg of the Intermediate compound ( 16 - 3 ) . US 9 ,924 ,719 B2 75 'H -NMR (CDC13 ) 8 : 9. 00 ( 1H , dd ), 8 .43 (1H , dd ) , 7. 69 ( 1H , dd ) , 7 . 17 ( 1H , d ) , 3 . 52 - 3 . 33 ( 2H , m ) , 2 . 10 ( 3H , d ) , 1 . 31 CH3 (3H , t) . F Preparation Example 16 ( 6 ) N - N F O - CF3 To the solution of the Intermediate compound ( 16 - 5 ) 0 . 40 g and NMP 5 mL , 2 , 2 , 3 , 3 , 3 -pentafluoropropanol 0 . 2 mL and cesium carbonate 0 .57 g were added , and the mixtures were 10 ' H -NMR (CDC1z ) 8 : 9 . 18 ( 1H , d ), 8 .60 ( 1H , d ) , 7 .73 ( 1H , then heated to 70° C . and stirred for 2 hours . To the obtained d ), 6 . 96 (1H , d ), 6 .13 -5 .87 ( 1H , m ), 4. 83 (2H , dd ) , 3 .63 (2H , reaction mixtures, saturated ammonium chloride solution td ) , 1 . 42 ( 3H , t ) . was added at room temperature , and the mixtures were Next , the formulation examples of the present compound extracted with MTBE . The obtained organic layer was are shown below . The “ parts ” represents “ part by weight” . washed with brine , followed by dried over anhydrous 15 sodium sulfate and concentrated under reduced pressure . Formulation Example 1 The obtained residue was subjected to a silica gel column chromatography to give 0 .45 g of N -oxide 3 . Into a mixture of 35 parts of xylene and 35 parts of DMF, 10 parts of any one of the Present compounds 1 to 40 and the N -oxides 1 to 5 is dissolved , and then 14 parts of polyoxy - CH3 20 ethylene styryl phenyl ether and 6 parts of calcium dode cylbenzene sulfonate are added thereto , followed by mixing FC them to obtain each formulation . N - N F 25 Formulation Example 2 Four( 4 ) parts of sodium lauryl sulfate , 2 parts of calcium CH3 lignin sulfonate , 20 parts of synthetic hydrated silicon oxide fine powder and 54 parts of diatomaceous earth are mixed , and further 20 parts of any one of the Present compounds 1 H -NMR (CDC13 ) 8 : 9 .00 (1H , dd ), 8 .43 (1H , dd ), 7. 70 - 30 to 40 and the N -oxides 1 to 5 is added thereto , followed by 7 .66 ( 1H , m ) , 6 . 82 ( 1H , s ), 4 . 94 - 4 .75 (2H , m ), 3 .44 (2H , m ), mixing them to obtain each wettable powders . 2 .08 (3H , s ) , 1 . 31 (3H , t ) . Formulation Example 3 Preparation Example 17 35 To 2 parts of any one of the Present compounds 1 to 40 and the N - oxides 1 to 5 , 1 part of synthetic hydrated silicon To the solution of Present compound 28 0 .37 g and oxide fine powder , 2 parts of calcium lignin sulfonate , 30 chloroform 5 mL, 75 % mCPBA 0 .22 g was added under parts of bentonite and 65 parts of kaolin clay are added and ice -cooling , and the mixture was then stirred for 1 hour. To mixing . To the mixture is then added an appropriate amount the obtained reaction mixtures, saturated sodium hydrogen 40 of water , and the resulting mixture is further stirred , and carbonate solution and sodium thiosulfate solution were subjected to granulation with a granulator, and forced - air added at room temperature , and the mixtures were extracted drying to obtain each granular formulation . with chloroform . The obtained organic layer was washed with brine , followed by dried over anhydrous sodium sulfate Formulation Example 4 and concentrated under reduced pressure . The obtained 45 residue was subjected to a silica gel column chromatography Into an appropriate amount of acetone , 1 part of any one to give 0 . 25 g of N -oxide 4 . of the Present compounds 1 to 40 and the N -oxides 1 to 5 is dissolved , and then 5 parts of synthetic hydrated silicon oxide fine powder , 0 .3 parts of isopropyl acid phosphate and CH3 50 93 .7 parts of Fubasami clay are added thereto , followed by F?çF3C mixing with stirring thoroughly and removal of acetone N - N from the mixture by evaporation to obtain each powder F formulation . CF3 55 Formulation Example 5 Thirty five (35 ) parts of a mixture of polyoxyethylene H - NMR (CDC1z ) 8 : 9 . 18 ( 1H , d ), 8 .60 ( 1H , d ) , 7 . 74 ( 1H , alkyl ether sulfate ammonium salt and white carbon (weight d ) , 6 .99 ( 1H , d ) , 4 . 98 - 4 .79 (2H , m ) , 3 .63 (2H , m ) , 1 . 42 (3H , ratio of 1 : 1 ) , 10 parts of any one of the Present compounds 60 1 to 40 and the N - oxides 1 to 5 , and 55 parts of water are mixed , followed by finely grounding by a wet grinding Preparation Example 18 method to obtain each flowable formulation . Formulation Example 6 N -oxide compound 5 was prepared according to the 65 method described in Preparation example 17 using Present Into a mixture of 5 parts of xylene and 5 parts of compound 31 instead of Present compound 28 . trichloroethane , 0 .1 parts of any one of the Present com US 9 ,924 ,719 B2 77 78 pounds 1 to 40 and the N - oxides 1 to 5 is dissolved , and the molding die to obtain each rod - shaped molded product resulting mixture is then mixed with 89 . 9 parts of deodor - having a length of 15 cm and a diameter of 3 mm . ized kerosene to obtain each oil solution . Formulation Example 13 Formulation Example 7 5 One- hundred (100 ) mg of any one of the Present com pounds 1 to 40 and the N -oxides 1 to 5 , 68 . 75 mg of lactose , Into 0 . 5 mL of acetone , 10 mg of any one of the Present 237 . 5 mg of corn starch , 43. 75 mg of microcrystalline compounds 1 to 40 and the N - oxides 1 to 5 is dissolved and cellulose , 18 .75 mg of polyvinylpyrrolidone , 28 . 75 mg of the solution is added dropwise to 5 g of a solid feed powder sodium carboxymethyl starch and 25 mg of magnesium for an animal ( solid feed powder for rearing and breeding stearate are mixed , and the resulting mixture is compressed CE - 2 , manufactured by CLEA Japan , Inc . ) , followed by to an appropriate size to obtain each tablet . mixing the resulting mixture uniformly, and then by drying them by evaporation of acetone to obtain each poison bait . Formulation Example 14 Formulation Example 8 15 Twenty - five ( 25 ) mg of any one of the Present compounds 1 to 40 and the N -oxides 1 to 5 , 60 mg of lactose , 25 mg of Into an aerosol can , 0 .1 part of any one of the Present corn starch , 6 mg of carmellose calcium and an appropriate compounds 1 to 40 or the N -oxides 1 to 5 and 49 .9 parts of amount of 5 % of hydroxypropyl methylcellulose are mixed , Neothiozole (Chuo Kasei Co . , Ltd . ) are placed . Aftermount - and the resulting mixture is filled into a hard shell gelatin ing an aerosol valve, 25 parts of dimethylether and 25 parts capsule or a hydroxypropyl methylcellulose capsule to of LPG are filled , followed by shakinghaking andand further mountingmounting obtain each capsule . an actuator to obtain each oily aerosol. Formulation Example 15 Formulation Example 9 25 To 100 mg of any one of the Present compounds 1 to 40 and the N -oxides 1 to 5 , 500 mg of fumaric acid , 2000 mg A mixture of 0 .6 part of any one of the Present compounds of sodium chloride , 150 mg of methyl paraben , 50 mg of 1 to 40 and the N -oxides 1 to 5 , 0 .01 part of BHT ( 2 ,6 - di propyl paraben , 25 , 000 mg of granulated sugar , 13, 000 mg tert- butyl - 4 -methylphenol ) , 5 parts of xylene, 3 . 39 parts of of sorbitol (70 % solution ) , 100 mg of Veegum K (manufac deodorized kerosine and 1 part of an emulsifier {Rheodol 30 tured by Vanderbilt Co .) , 35 mg of perfume, and 500 mg of MO -60 (manufactured by Kao Corporation ) } , and 50 parts coloring agent , distilled water is added so that a final volume of distilled water are filled into an aerosol container , and a is set to be 100 mL , followed by mixing them to obtain each valve part is attached . Then , 40 parts of a propellant (LPG ) suspension for oral administration . is filled therein through the valve under pressure to obtain each aqueous aerosol. 35 Formulation Example 16 Formulation Example 10 Into a mixture of 5 % by weight of polysorbate 85 , 3 % by weight of benzyl alcohol and 30 % by weight of propylene Zero point one ( 0 . 1 ) parts of any one of the Present glycol, 5 % by weight of any one of the Present compounds compounds 1 to 40 and the N -oxides 1 to 5 is mixed into 2 40 1 to 40 and the N -oxides 1 to 5 is dissolved , and phosphate mL of propylene glycol, and the resulting solution is impreg - buffer is added thereto so that a pH of the solution is set to nated into a porous ceramic plate having a size of 4 . 0 be 6 .0 to 6 . 5 , and then water is added as the rest part to cmx4 . 0 cm and a thickness of 1 . 2 cm , to obtain each thermal obtain each solution for oral administration . fumigant. 45 Formulation Example 17 Formulation Example 11 To a mixture of 57 % by weight of fractional distillated Five (5 ) parts of any one of the Present compounds 1 to palm oil and 3 % by weight of polysorbate 85 , 5 % by weight 40 or the N - oxides 1 to 5 , and 95 parts of ethylene -methyl of aluminum distearate is added , and the mixture is heated methacrylate copolymer ( the ratio of the methyl methacry - 50 to disperse it . The resulting mixture is cooled to room late in the copolymer: 10 weight % , Acryft ( registered by temperature , and 25 % by weight of saccharin is dispersed in trademark ) WD 301 , manufactured by Sumitomo Chemical the oil vehicle . Ten ( 10 ) % by weight of any one of the Co . Ltd . ) are melted and kneaded with a closed type pressure Present compounds 1 to 40 and the N -oxides 1 to is divided kneader (manufactured by Moriyama Manufacturing Co ., thereto to obtain each paste for oral administration . Ltd . ) , and the resulting kneaded product is extruded from an 55 extrusion molding machine through a molding die to obtain Formulation Example 18 each rod - shaped molded product having a length of 15 cm and a diameter of 3 mm . Five ( 5 ) % by weight of any one of the Present compounds 1 to 40 and the N -oxides 1 to 5 is mixed with 95 % by weight Formulation Example 12 60 of limestone filler , followed by a wet - granulation of the resulting mixture to obtain each granule for oral adminis Five ( 5 ) parts of any one of the Present compounds 1 to tration . 40 and the N -oxides 1 to 5 , and 95 parts of plasticized polyvinyl chloride resin are melted and kneaded with a Formulation Example 19 closed type pressure kneader (manufactured by Moriyama 65 Manufacturing Co . , Ltd .) , and the resulting kneaded product Into 80 parts of diethylene glycol monoethyl ether, 5 parts is extruded from an extrusion molding machine through a of any one of the Present compounds 1 to 40 and the US 9 ,924 ,719 B2 79 80 N - oxides 1 to 5 is dissolved , and 15 parts of propylene wherein the symbols in the equation represent the following carbonate are added thereto , and the resulting mixture is descriptions . mixed to obtain each spot -on solution . Cb : Number of the test insects before treatment in untreated group ; Formulation Example 20 5 Cai: Number of the surviving insects at the time of the investigation in untreated group ; Into 70 parts of diethylene glycol monoethyl ether, 10 Tb : Number of the test insects before treatment in treated parts of any one of the Present compounds 1 to 40 and the group ; Tai : Number of the surviving insects lived on the leaves N -oxides 1 to 5 is dissolved , and 20 parts of 2 -octyldode 10 at the time of the investigation in treated group ; canol are added thereto , and the resulting mixture is mixed 10 at Here the " untreated group ” represents a group where a to obtain each pour- on solution . test chemical solution which was prepared by diluting a formulation prepared according to the Formulation example Formulation Example 21 5 except for not comprising present compound with the same amount of water as that used in the case of the treated To 0 . 5 parts of any one of the Present compounds 1 to 40 15 group was sprayed . As a result, the treated group that was and the N -oxides 1 to 5 , 60 parts of Nikkol ( registered by treated with each of the test chemical solution comprising trademark ) TEALS -42 (manufactured by Nikko Chemical the Present compound 4 , 5 , 6 , 8 , 9 , 10 , 14 , 15 , 17 , 18 , 19 , 22 , Co . Ltd . : 42 % of aqueous solution of lauryl sulfuric acid 23 , 24 , 25 , 26 , 27 , 29 , 31, 32 , 33 , 34 , 35 , 36 , 37 or 38 , or the triethanol amine ) and 20 parts of propylene glycol are added , N -ovide oxide 2 , the N -oxideovide 33 , the N -oxide 4 , or the N -oxide 5 and the resulting mixture is mixed with stirring thoroughly 20 showed 90 % or greater as the controlling value . to obtain a homogeneous solution , and 19 . 5 parts of water is then added thereto and the resulting mixture is further mixed Test Example 2 with stirring thoroughly to obtain each homogeneous solu tion of shampoo formulation . Each formulation comprising the Present compound 4 , 5 , 35 8 , 9 , 11 , 14 , 17 , 22 , 23 , 24 , 25 , 27 , 28 , 29 , 31 , 32 , 35 , 36 , 37 Formulation Example 22 or 38 , or the N -oxide 1 , the N - oxide 2 , the N -oxide 4 , or the N - oxide 5 prepared by the process according to the Formu Zero point fifteen ( 0 . 15 ) % by weight of any one of the lation example 5 was diluted with water until each concen Present compounds 1 to 40 and the N - oxides 1 to 5 , 95 % by tration of the active ingredient reached 200 ppm to prepare weight of animal feed , as well as 4 .85 % by weight of a 30 each test chemical solution . mixture of dibasic calcium phosphate , diatomaceous earth , Meanwhile , cucumber seedling ( on the developmental aerosol and carbonate (or chalk ) are mixed with stirring stage of the first true leaf) was planted in a plasticcup , and thoroughly to obtain each premix for animal feed . approximately 30 heads of cotton aphid ( Aphis gossypii ) ( all stages of life ) were released onto the leaves of the cucumber, and the seedling was left to stand for 1 day . The test chemical Formulation Example 23 35 solution was sprayed into the seedling in a ratio of 20 mL / seedling . Seven point two ( 7 . 2 ) g of any one of the Present com After 6 days from the spraying , the number of the pounds 1 to 40 and the N -oxides 1 to 5 , and 92 . 8 g of Hosco surviving cotton aphid lived on the leaves was investigated , (registered trademark ) S - 55 (manufactured by Maruishi Pharmaceuticals ) are melted and mixed at 100° C ., and the an andequatio the controlling value was calculated by the following resulting mixture is poured intoa mixeda suppository at 100° moldC ., and , folthe 40 equation . lowed by performing a cooling solidification to obtain each Controlling value ( % ) = { 1 - ( CbxTai ) ( CaixTb ) } x100 suppository . wherein the symbols in the equation represent the following Next, Test examples are used to show an efficacy of the descriptions . Cb : Number of the test insects before treatment in present compounds on controlling harmful arthropods. 45 untreated group ; Cai: Number of the surviving insects lived on the leaves Test Example 1 at the time of the investigation in untreated group ; Tb : Number of the test insects before treatment in treated Each formulation comprising the Present compound 4 , 5 , group ; 6 , 8 , 9 , 10 , 14 , 15 , 17 , 18 , 19 , 22 , 23, 24 , 25 , 26 , 27 , 29 , 31, 50 Tai: Number of the surviving insects lived on the leaves 32 , 33 , 34 , 35 , 36 , 37 or 38 , or the N -oxide 2 , the N -oxide at the time of the investigation in treated group ; 3 , the N - oxide 4 , or the N -oxide 5 prepared by the process Here the " untreated group ” represents a group a test according to the Formulation example 5 was diluted with chemical solution which was prepared by diluting a formu water until each concentration of the active ingredient lation prepared according to the Formulation example 5 reached 500 ppm to prepare each test chemical solution . 55 except for not comprising present compound with the same Meanwhile , cucumber seedling (on the developmental amount of water as that used in the case of the treated group stage of the first true leaf) was planted in a plastic cup , and was sprayed . approximately 30 heads of cotton aphid (Aphis gossypii ) (all As a result , the treated group that was treated with each stages of life ) were released onto the leaves of the cucumber of the test chemical solution comprising the Present com and the seedling was left to stand for 1 day. The test chemical pound 4 , 5 , 8 , 9 , 11, 14 , 17 , 22 , 23 , 24 , 25 , 27 , 28 , 29 , 31 . solution was sprayed into the seedling in a ratio of 20 " 32 , 35 , 36 , 37 or 38 , or the N -oxide 1 , the N -oxide 2 , the mL/ seedling . N -oxide 4 , or the N - oxide 5 showed 90 % or greater as the After 6 days from the spraying, the number of the controlling value . surviving cotton aphrid ( Aphris gossypii ) was investigated and the controlling value was calculated by the following se Test Example 3 equation . Each formulation comprising the Present compound 5 , 6 , Controlling value (% ) = { 1 - (CbxTai )/ ( CaixTb )} x100 8 , 9 , 11, 14 , 17 , 25 , 29 , 31, 35 , 36 , 37 or 38 , or the N -oxide US 9 ,924 ,719 B2 81 82 1 , the N - oxide 2 , or the N - oxide 4 prepared by the process Tb : Number of the test insects before treatment in treated according to the Formulation example 5 was diluted with group ; water until each concentration of the active ingredient Tai: Number of the surviving insects lived on the leaves reached 200 ppm to prepare each test chemical solution . at the time of the investigation in treated group ; Meanwhile , cucumber seedling ( on the developmental 5 Here the " untreated group ” represents a group where a stage of the second true leaf) was planted in a plastic cup , test chemical solution which was prepared by diluting a and 5 mL of each of the above test chemical solution was formulation prepared according to the Formulation example applied to the seedling by irrigation at plant foot, and the 5 except for not comprising present compound with the seedling was left to stand in a greenhouse at 25° C . for days . same amount of water as that used in the case of the treated Approximately 30 heads of cotton aphid (Aphis gossypii ) 10 group was sprayed . ( all stages of life ) were released onto the leaves of the As a result , the treated group that was treated with each cucumber, and the seedling was left to stand for additional of the test chemical solution comprising the Present com 6 days in the greenhouse , followed by the number of the pound 6 , 8 , 14 , 17 , 22 , 23 , 25 , 26 , 27 , 29 , 31 , 32 , 35 , 36 , 37 surviving insects was examined , and then the number of the or 38 , or the N -oxide 4 , or the N -oxide 5 showed 90 % or surviving cotton aphid lived on the leaves of the cucumber 15 greater as the controlling value . was investigated , and the controlling value was calculated by the following equation . Test Example 5 Controlling value ( % )= { 1 - (Cbx Tai) / ( CaixTb) } x100 Each formulation comprising the Present compound 5 , 6 , wherein the symbols in the equation represent the following 20 8 , 9 , 14 , 17 , 22 , 23 , 24 , 25 , 27 , 28 , 29 , 31 , 35 , 36 , 37 or 38 , descriptions . or the N -oxide 1 , or the N -oxide 4 prepared by the process Cb : Number of the test insects before treatment in according to the Formulation example 5 was diluted with untreated group ; water until each concentration of the active ingredient Cai : Number of the surviving insects lived on the leaves reached 200 ppm to prepare each test chemical solution . at the time of the investigation in untreated group ; 25 Rice seedling (on the developmental stage of the second Tb : Number of the test insects before treatment in treated true leaf) was planted in a polyethylene cup , and 10 mL of group ; each of the above test chemical solution was sprayed into the Tai : Number of the surviving insects lived on the leaves seedling . After air -drying the seedling, 20 heads of 3rd to 4th at the time of the investigation in treated group ; instar larvae of brown planthopper (Nilaparvata lugens ) Here the " untreated group ” represents a group where a 30 were released onto the rice leaves , and the seedling was left test chemical solution which was prepared by diluting a to stand at 25° C . in a greenhouse . After 6 days , the number formulation prepared according to the Formulation example of the surviving brown planthopper lived on the rice leaves 5 except for not comprising present compound with the was investigated , and the controlling value was calculated same amount of water as that used in the case of the treated by the following equation . group was sprayed . As a result , the treated group that was treated with each Controlling value ( % ) = { 1 - ( Cbx Tai )/ (CaixTb ) }x100 of the test chemical solution comprising the Present com wherein the symbols in the equation represent the following pounds 5 , 6 , 8 , 9 , 11 , 14 , 17 , 25 , 29 , 31 , 35 , 36 , 37 or 38 , or descriptions . the N -oxide 1 , the N -oxide 2 , or the N -oxide 4 showed 90 % Cb : Number of the test insects before treatment in or greater as the controlling value . 40 untreated group ; Cai: Number of the surviving insects lived on the leaves Test Example 4 at the time of the investigation in untreated group ; Tb : Number of the test insects before treatment in treated Each formulation comprising the Present compound 6 , 8 , group ; 9 , 14 , 17 , 22 , 23 , 25 , 26 , 27, 29, 31, 32 , 35 , 36 , 37 or 38, or 45 Tai: Number of the surviving insects lived on the leaves the N -oxide 4 , or the N - oxide 5 prepared by the process at the time of the investigation in treated group ; according to the Formulation example 5 was diluted with Here the " untreated group ” represents a group where a water until each concentration of the active ingredient test chemical solution which was prepared by diluting a reached 500 ppm to prepare each test chemical solution formulation prepared according to the Formulation example Rice seedling ( on the developmental stage of the second 50 5 except for not comprising present compound with the true leaf) was planted in a polyethylene cup , and 10 mL of same amount of water as that used in the case of the treated each of the above test chemical solution was sprayed into the group was sprayed . seedling . After air -drying the seedling, 20 heads of 3rd to 4th As a result , the treated group that was treated with each instar larvae of brown planthopper (Nilaparvata lugens ) of the test chemical solution comprising the Present com were released onto the rice leaves, and the seedling was left 55 pound 5 , 6 , 8 , 9 , 14 , 17 , 22 , 23, 24 , 25 , 27 , 28 , 29 , 31, 35 , to stand at 25° C . in a greenhouse . After 6 days , the number 36 , 37 or 38 , or the N -oxide 1 , or the N -oxide 4 showed 90 % of the surviving brown planthopper lived on the rice leaves or greater as the controlling value . was investigated , and the controlling value was calculated by the following equation . Test Example 6 60 Controlling value ( % )= { 1 - (CbxTai )/ ( CaixTb )} x100 Each formulation comprising the Present compound 4 , 5 , wherein the symbols in the equation represent the following 6 , 8 ; 9 , 11, 14 , 15 , 17 , 22 , 23 , 25, 28 , 31 , 35 , 36 , 37 or 38 , descriptions. or the N -oxide 1, the N -oxide 4 , or the N - oxide 5 prepared Cb : Number of the test insects before treatment in by the process according to the Formulation example 5 was untreated group ; 65 diluted with water until each concentration of the active Cai: Number of the surviving insects lived on the leaves ingredient reached 200 ppm to prepare each test chemical at the time of the investigation in untreated group ; solution . US 9 ,924 ,719 B2 83 84 Meanwhile , rice seedling (on the developmental stage of 32 , 33 , 34 , 35 , 36 or 38 , or the N -oxide 1, the N -oxide 4 , or the second true leaf at two weeks after seedling ) was planted the N -oxide 5 prepared by the process according to the in a plastic cup , and 5 mL of each of the above test chemical Formulation example 5 was diluted with water until each solution was applied to the seedling by irrigation at plant concentration of the active ingredient reached 200 ppm to foot and the seedling was left to stand at 25° C . in a 5 prepare each test chemical solution . greenhouse for 7 days . Twenty ( 20 ) heads of 3rd to 4th instar Meanwhile , cabbage seedling ( on the developmental larvae of brown planthopper (Nilaparvata lugens) were stage of the third true leaf) was planted in a polyethylene released onto the rice leaves , and the seedling was left to cup , and each of the test chemical solution was sprayed into stand for additional 6 days in the greenhouse , and then the the cabbage seedling in a ratio of 20 mL /cup . After the test number of the surviving brown planthopper lived on the ricen10 chemical solution was dried , the stem and leaf thereof was leaves was investigated , and the controlling value was cut out and then installed into a 50 mL cup . Five ( 5 ) heads calculated by the following equation . of 2nd instar larvae of cabbage moth (Plutella xylostella ) Controlling value (% )= { 1 -( Cbx Tai) / ( CaixTb )} x100 were released into the cup , and the cup was covered with a wherein the symbols in the equation represent the following lid . After the cup was stored at 25° C . for 5 days , the number descriptions . 15 of the dead insects was counted , and the mortality of insects Cb : Number of the test insects before treatment in was calculated by the following equation . untreated group ; Cai : Number of the surviving insects lived on the leaves Morality ( % )= ( 1 - the number of the surviving at the time of the investigation in untreated group ; insects /the number of the test insects )x100 Tb : Number of the test insects before treatment in treated 20 As a result , the treated group that was treated with each group ; of the test chemical solution comprising the Present com Tai : Number of the surviving insects lived on the leaves pound 6 , 8 , 9 , 10 , 11, 14 , 17 , 18, 20 , 22, 23, 24 , 25 , 26 , 27 , at the time of the investigation in treated group ; 28 , 30 , 31, 32 , 33 , 34 , 35 , 36 or 38 , or the N -oxide 1 , the Here the “ untreated group ” represents a group where a N - oxide 4 , or the N - oxide 5 showed 80 % or greater as the test chemical solution which was prepared by diluting a 25 morality of insects . formulation prepared according to the Formulation example 5 except for not comprising present compound with the Test Example 9 same amount of water as that used in the case of the treated group was sprayed . Each formulation comprising the Present compound 5 , 17 , As a result , the treated group that was treatedtreated with eacheach 30 2325 , 26 , 27 , 31, 35 , 36 , 37 or 38 , or the N - oxide 3 , the N -oxide of the test chemical solution comprising the Present com 4 , or the N - oxide 5 prepared by the process according to the Formulation example 5 was diluted with water until the pound 4 , 5 , 6 , 8 , 9 , 11, 14 , 15 , 17 , 22 , 23 , 25 , 28 , 31, 35 , 36 , concentration of the active ingredient reached 500 ppm to 37 or 38 , or the N -oxide 1 , the N - oxide 4 , or the N -oxide 5 prepare a test chemical solution . showed 90 % or greater as the controlling value . The bottom of the polyethylene cup having 5 . 5 cm Test Example 7 35 diameter was matted with the same size of a filter paper, and 0 . 7 mL of the test chemical solution was added dropwise to Each formulation comprising the Present compound 6 , 8 , the filter paper, and 30 mg sucrose as bait was placed in the 9 , 10 , 14 , 15 , 17 , 18 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 31 . 32 . cup uniformly . Ten ( 10 ) heads of female adult housefly 33 , 34 , 35 , 36 , 37 or 38 , or the N - oxide 4 , or the N -oxide 5 10 (Musca domestica ) were released into the polyethylene cup , prepared by the process according to the Formulation and the cup was covered with a lid . After 24 hours , the life example 5 was diluted with water until each concentration of and death of housefly was investigated , and the number of the active ingredient reached 500 ppm to prepare each test dead insects was counted , and the mortality of insects was chemical solution . calculated by the following equation . Meanwhile , cabbage seedling ( on the developmental 45 Mortality of insects ( % ) = (the number of dead stage of the third true leaf) was planted in a polyethylene insects /the number of test insects )x100 cup , and each of the test chemical solution was sprayed into As a result , the treated group that was treated with each the cabbage seedling in a ratio of 20 mL / cup . After the test of the test chemical solution comprising the Present com chemical solution was dried , the stem and leaf thereof was pound 5 , 17 , 25 , 26 , 27 , 31, 35 , 36 , 37 or 38 , or the N - oxide cut out and then installed into a 50 mL cup . Five ( 5 ) heads 50 3 . the N - oxide 4 . or the N - oxide 5 showed 100 % as the of 2nd instar larvae of cabbage moth (Plutella xylostella ) morality of insects. were released into the cup , and the cup was covered with a lid . After the cup was stored at 25° C . for 5 days, the number Test Example 10 of the dead insects was counted , and the mortality of insects was calculated by the following equation . 55 The formulation comprising the Present compounds 4 Morality ( % ) = ( 1 - the number of the dead insects /the prepared by the process according to the Formulation number of the test insects )x100 example 5 was diluted with water until the concentration of As a result, the treated group that was treated with each the active ingredient reached 500 ppm to prepare a test of the test chemical solution of the Present compound 6 , 8 , chemical solution . 9 , 10 , 14 , 15 , 17 , 18 , 20 , 21, 22 , 23 , 24 , 25 , 26 , 27 , 31 , 32 , 60 Zero point seven ( 0 .7 ) mL of the testg chemical solution 33 , 34 , 35, 36 , 37 or 38 , or the N -oxide 4 , or the N -oxide 5 was added to ion -changed water 100 ml ( the concentrataion showed 80 % or greater as the morality of insects. of the active ingredient was 3 . 5 ppm ). Twently ( 20 ) heads of the last instar larvae of female adult house mosquito ( Culex Test Example 8 pipiens pallens ) were released on the leaves , and after 1 day , 65 the life and death of house mosquito was investigated , and Each formulation comprising the Present compound 6 , 8 , the number of dead insects was counted , and the mortality 9 , 10 , 11 , 14 , 17 , 18 , 20 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 30 , 31, of insects was calculated by the following equation . US 9 ,924 ,719 B2 85 86 Mortality of insects ( % )= ( the number of the dead In the test , the following present compounds showed 80 % insects /the number of the test insects ) x100 or greater as the morality of insects . As a result , the treated group that was treated with the test Present compounds : 33, 34 , and 38 chemical solution comprising the Present compound 4 INDUSTRIAL APPLICABILITY showed 95 % or greater as the morality of insects. The present compounds show an excellent control effect against a harmful arthropod . Test Example 11 The invention claimed is : 1 . A pyridazine compound represented by formula (1 ) : Each formulation comprising the Present compound 1 , 2 , - 4 , 5 , 6 , 8 , 9 , 11, 15 , 16 , 17 , 18 , 19 , 20 , 21, 22 , 23 , 24 , 25 , 27 , 28 , 29 , 31, 34 or 35 , or the N -oxide 1, the N -oxide 2 , the N - oxide 4 , or the N -oxide 5 prepared by the process accord ing to the Formulation example 1 was diluted with water 15 (O ), s until each concentration of the active ingredient reached 50 NN (Rº ) ppm to prepare each test chemical solution . R1 - 04 Meanwhile , cucumber seedling (on the developmental stage of the third true leaf) was planted in a polyethylene cup , and each of the test chemical solution was sprayed into 20 the seedling in a ratio of 30 mL /cup . After the test chemical solution was dried , the second leaf thereof was cut out, and wherein , then installed into a 200 mL cup . Ten ( 10 ) heads of the A represents a nitrogen atom or a CR ; second instar larvae of cucurbit leaf beetle (Aulacophora R ' represents a C2- C10 alkyl group , a C3 -C10 alkenyl 25 group , a C3 -C10 alkynyl group , a (C1 - C5 alkyl) femoralis ) were released into the cup , and the cup was 0 — (C2 - C5 alkyl) group , a (C3 -C5 alkenyl) - 0 covered with a lid . After the cup was stored at 25° C . for 5 (C2 - C5 alkyl) group , a (C3 - C5 alkynyl ) - 0 — (C2 -C5 days , the number of the dead insects was counted , and the alkyl ) group, a (C1 - C5 alkyl) - S ( O ) m (C2 -C5 alkyl ) mortality of insects was calculated by the following equa group , a (C3 -C5 alkenyl ) - S ( O ) m ( C2 - C5 alkyl ) tion . 30 group , a (C3 -C5 alkynyl) - S ( O ) m (C2 - C5 alkyl ) group , or a (C1 - C5 alkyl) - C ( O ) ( C1- C5 alkyl ) Morality ( % ) - { the number of the dead insects/ the group , wherein R ' has one or more halogen atoms; number of the test isects } x100 R2 and R * represent independently of each other a hydrogen atom , a C1 - C6 alkyl group optionally As a result , the treated group that was treated with each having one or more halogen atoms, a C2 -C6 alkoxy of the test chemical solution comprising the Present com - 35 carbonyl group , a cyano group , or a halogen atom ; pound 1 , 2 , 4 , 5 , 6 , 8 , 9 , 11 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , R4 represents a C1 - C6 chain hydrocarbon group 23 , 24 , 25 , 27 , 28 , 29 , 31 , 34 or 35 , or the N - oxide 1 , the optionally having one or more halogen atoms; N - oxide 2 , the N -oxide 4 , or the N - oxide 5 showed 85 % or RS represents a C1- C6 chain hydrocarbon group greater as the morality of insects . optionally having one or more halogen atoms, a 40 phenyl group optionally having one or more atoms or Test Example 12 groups selected from Group A , a 5 -membered aro matic heterocyclic group selected from Group B , wherein said 5 -membered aromatic heterocyclic Each 1 mg of any one of the present compounds is group may optionally have one or more atoms or dissolved into the mixed solution of acetone and polyoxy - 45 groups selected from Group A , a 6 -membered aro ethylene sorbitan mono -cocoate ( acetone and polyoxyeth matic heterocyclic group selected from Group C , ylene sorbitan mono - cocoate = 95 : 5 (weight ratio ) ) in a ratio wherein said 6 -membered aromatic heterocyclic of 50 uL of the mixed solution per 1 mg of the present group may optionally have one or more atoms or compound . Thereto is added ion - exchanged water contain groups selected from Group A , a 3 to 7 membered ing 0 .03 % ( v / v ) of Sindain ( registered trademark , manufac - 50 nonaromatic heterocyclic group selected from Group tured by Sumitomo Chemical Company, Limited ) until each D , wherein the 3 to 7 membered nonaromatic het concentration of the present compound reached 200 ppm to erocyclic group may optionally have one or more prepare each diluted solution . atoms or groups selected from the group consisting Corns ( Zea mays ) are sown on a tray overlaid with of a halogen atom and a C1- C6 alkyl group , a OR ” , damped Kim Wipes. After corns are grown for 5 days, the 55 a NR?R " , a NR C (O )R10 , a NR $ C (O )OR11 , a NRC entire seedling of the corn is immersed into the diluted ( O ) NR12R13 , a N = CHNR12R13, a N - S ( O ) R12R13 , solution for 30 seconds . After drying , each two grains of the a S ( O ), R !? , a C ( O ) OR®, a cyano group, or a halogen seedling are installed in a plastic petri dish (90 mm radius ) , atom ; and 10 heads of the second instar larvae of Western corn Rº represents a hydrogen atom , or a halogen atom ; rootworm (Diabrotica virgifera virgifera ) are released onto 60 R ' represents a hydrogen atom , a C1- C6 alkyl group , a the cup and the cup is covered with a lid . After the cup is C3- C6 alkenyl group , a C3 -C6 alkynyl group , a stored at 25° C . for 5 days , the number of the dead insects (C1 - C3 alkyl) - 0 (C1 - C3 alkyl) group , a (C1 - C3 is counted , and the mortality of insects is calculated by the alkyl) -S ( O ) , (C1 - C3 alkyl) group , a C3 -C7 following equation . cycloalkyl group, a (C3 - C7 cycloalkyl) - ( C1 -C3 65 alkyl) group , wherein said C1 - C6 alkyl group , said Morality (% ) = { the number of the deadinsects/ 10 } x C3 - C6 alkenyl group , said C3 - C6 alkynyl group , 100 said ( C1 - C3 alkyl) - 0 (C1 - C3 alkyl) group , said US 9 , 924 ,719 B2 87 88 (C1 - C3 alkyl) - S (O ) , (C1 - C3 alkyl) group , said n represents 0 , 1 , or 2 ; C3 -C7 cycloalkyl group , and said (C3 - C7 cycloalkyl ) - (C1 - C3 alkyl) group may optionally m represents 0 , 1 , or 2 ; have one or more halogen atoms, or a phenyl C1 - C3 p represents 0 , 1 , 2 , or 3 , wherein when p represents 2 alkyl group , wherein the phenyl moiety in said 5 or 3 , a plurality of Rº may be identical or different ; phenyl C1- C3 alkyl group may optionally have one x represents 0 or 1 ; or more atoms or groups selected from Group A ; R $ represents a hydrogen atom , a C1 - C6 alkyl group y represents 0 , 1 , or 2 ; optionally having one or more halogen atoms, a Group A : a group consisting of a C1 - C6 alkyl group C3 - C6 alkenyl group optionally having one or more 10 optionally having one or more halogen atoms, a halogen atoms, or a C3 - C6 alkynyl group optionally C1- C6 alkoxy group optionally having one or more having one or more halogen atoms; halogen atoms, a C1 -C6 alkylsulfanyl group option Rº represents a hydrogen atom , a C1 - C6 alkyl group , a ally having one or more halogen atoms, a C1 - C6 C3 - C6 alkenyl group , a C3 - C6 alkynyl group , a alkylsulfinyl group optionally having one or more (C1 - C3 alkyl) - 0 — (C1 -C3 alkyl) group , a (C1 - C3 15 halogen atoms, a C1- C6 alkylsulfonyl group option alkyl) - S ( O ) , — (C1 -C3 alkyl) group, a C3 -C7 ally having one or more halogen atoms, a cyano cycloalkyl group, a ( C3 - C7 cycloalkyl ) - (C1 -C3 group , and a halogen atom ; alkyl) group , wherein said C1 -C6 alkyl group , said C3 - C6 alkenyl group , said C3 - C6 alkynyl group , said (C1 - C3 alkyl) - 0 (C1 - C3 alkyl) group , said 20 Group B : (C1 - C3 alkyl) - S ( O ) , ( C1- C3 alkyl ) group , said C3 -C7 cycloalkyl group , and said (C3 - C7 B - 1 cycloalkyl) - ( C1- C3 alkyl) group may optionally have one or more halogen atoms, a cyano C1- C6 alkyl group , 25 a phenyl C1- C3 alkyl group , wherein the phenyl moiety B - 2 in said phenyl C1 - C3 alkyl group may optionally have one or more atoms or groups selected from Group A , or a ( 5 or 6 membered heteroaryl) C1 -C3 alkyl group , 30 B - 3 wherein the 5 or 6 membered heteroaryl moiety in said ( 5 or 6 membered heteroaryl) C1 -C3 alkyl group may optionally have one or more atoms or groups B - 4 selected from Group A ; R10 represents a hydrogen atom , a C1- C6 alkyl group , 35 a C3 -C6 alkenyl group , a C3 - C6 alkynyl group , a C3 -C7 cycloalkyl group , a ( C3 -C7 cycloalkyl) -( C1 B - 5 C3 alkyl ) group , wherein said C1 - C6 alkyl group , said C3 - C6 alkenyl group , said C3- C6 alkynyl group , said C3 -C7 cycloalkyl group , and said (C3 - 40 C7 cycloalkyl )- ( C1 -C3 alkyl) group may optionally B - 6 have one or more halogen atoms, or a phenyl C1 - C3 alkyl group , wherein the phenyl moiety in said phenyl C1 -C3 alkyl group may optionally have one or more atoms or substituents selected from Group 45 B - 7 A ; R " represents a C1 -C6 alkyl group optionally having one or more halogen atoms, a C3 - C6 alkenyl group optionally having one or more halogen atoms, a B - 8 C3 - C6 alkynyl group optionally having one or more 50 halogen atoms, a C3 - C7 cycloalkyl group optionally having one or more halogen atoms, a (C3 - C7 cycloalkyl) - (C1 - C3 alkyl) group optionally having B - 9 one or more halogen atoms, wherein said ( C3 - C7 cycloalkyl) - (C1 - C3 alkyl) group may optionally 55 have one or more halogen atoms, or a phenyl C1 - C3 alkyl group , wherein the phenyl moiety in said B - 10 phenyl C1 - C3 alkyl group may optionally have one or more atoms or groups selected from Group A ; R12 and Rls represent independently of each other a 60 C1 - C6 alkyl group optionally having one or more Group C : halogen atoms; R14 represents a hydrogen atom , a C1- C6 alkyl group C - 1 optionally having one or more halogen atoms, a C2 - C6 alkylcarbonyl group optionally having one or 65 more halogen atoms, or a C2 - C6 alkoxycarbonyl group optionally having one or more halogen atoms; US 9, 924 ,719 B2 89 90 -continued -continued D - 7

5 C - 3 2 . The compound according to claim 1 , wherein A rep resents CR C- 4 10 3 . The compound according to claim 1 , wherein A rep resents a nitrogen atom . 4 . The compound according to claim 1 , wherein R4 represents a C1- C6 alkyl group optionally having one or more halogen atoms. C- 5 15 more5 . haloThe compound according to claim 1 , wherein R4 represents an ethyl group . 6 . The compound according to claim 1 , wherein R ' represents a C2 - C10 haloalkyl group ; C -6 20 R2 and Rº represent independently of each other a hydro gen atom , a C1 - C3 alkyl group optionally having one or more halogen atoms, or a halogen atom ; R4 represents a C1 -C6 alkyl group optionally having one or more halogen atoms; N = N 25 R represents a C1- C6 alkyl group optionally having one or more halogen atoms; and p represents 0 or 1 . 7 . The compound according to claim 1 , wherein C - 8 Rrepresents a C2 -C10 haloalkyl group ; 30 R2 and Rº represent each a hydrogen atom ; R * represents a C1- C6 alkyl group optionally having one or more halogen atoms; ZVZZ C - 9 Rrepresents a C1 -C6 alkyl group optionally having one or more halogen atoms; and 35 p represents 0 or 1 . 8 . The compound according to claim 1 , wherein Rl represents a C3 - C6 alkyl having four or more fluorine Group D : atoms; R2 and Rº represent each a hydrogen atom ; D - 1 40 R4 represents an ethyl group ; Rrepresents a C1 -C6 alkyl group optionally having one or more halogen atoms; and D - - 22 p represents 0 or 1 . 9 . A compound represented by formula ( 1 -N ): ? 45 D - 3 ( 1 - N ) D 41 ( O ) , S D - 4 50 = (R5 ) RIN - O

D - 5 R2N RIN

wherein Q ' represents a N + - O or a nitrogen atom , D - 6 Q ? represents a N + _ O , a CRN, or a nitrogen atom , wherein at least one of Q ' and Q represents an N + _ 0 " ; R® represents a hydrogen atom , or a halogen atom ; D - 7 RIN represents a C2- C10 haloalkyl group ; R2N and R3N represent independently of each other a N — R 14 65 hydrogen atom , a C1 -C3 alkyl group optionally ??? having one or more halogen atoms, or a halogen group ; US 9 ,924 ,719 B2 91 R4N represents a C1- C6 alkyl group optionally having one or more halogen atoms; RS represents a C1- C6 alkyl group optionally having one or more halogen atoms; and q represents 0 or 1 . 5 10. A composition for controlling a harmful arthropod , comprising the compound according to claim 1 , and an inert carrier . 11. A method for controlling a harmful arthropod , com prising applying an effective amount of the compound 10 according to claim 1 to a harmful arthropod or a habitat where a harmful arthropod lives . 12 . A composition for controlling a harmful arthropod , comprising the compound according to claim 9 , and an inert carrier . 15 13 . A method for controlling a harmful arthropod , com prising applying an effective amount of the compound according to claim 9 to a harmful arthropod or a habitat where a harmful arthropod lives. * * * * * 20