USOO9434684B2

(12) United States Patent (10) Patent No.: US 9.434,684 B2 Wasa et al. (45) Date of Patent: Sep. 6, 2016

(54) OXIME-SUBSTITUTED AMIDE COMPOUND FOREIGN PATENT DOCUMENTS AND PEST CONTROL AGENT EP 1 256 569 A1 11, 2002 (71) Applicant: Nissan Chemical Industries, Ltd., EP 1 428 817 A1 6, 2004 Chiyoda-ku (JP) (Continued) (72) Inventors: Motoyoshi Iwasa, Funabashi (JP); OTHER PUBLICATIONS Keisuke Tsuji, Funabashi (JP); JP2004035439; English Machine Translation from EPO, Feb. Mitsutaka Tomizawa, Funabashi (JP); 2004. Takeshi Mita, Funabashi (JP); Hidehito Kuwahara, Shiraoka (JP); Miho Asahi, (Continued) Shiraoka (JP); Hotaka Imanaka, Primary Examiner — Andrew D. Kosar Shiraoka (JP) Assistant Examiner — Daniel Carcanague (73) Assignee: Nissan Chemical Industries, Ltd., (74) Attorney, Agent, or Firm — Oblon, McClelland, Maier Chiyoda-ku (JP) & Neustadt, L.L.P. (57) ABSTRACT (*) Notice: Subject to any disclaimer, the term of this To provide a novel pesticide, especially a fungicide and a patent is extended or adjusted under 35 nematocide. U.S.C. 154(b) by 0 days. An oxime-Substituted amide compound represented by the (21) Appl. No.: 14/.414,173 formula (I) or its salt, and a pesticide containing it: (22) PCT Filed: Jul. 12, 2013 (I) W R2 R3 (86). PCT No.: PCT/UP2013/069207 S 371 (c)(1), (2) Date: Jan. 12, 2015 (87) PCT Pub. No.: WO2014/010737 PCT Pub. Date: Jan. 16, 2014 wherein G' is a structure represented by G-1 or the like, G (65) Prior Publication Data is a structure represented by G°-2 or the like: US 2015/0210630 A1 Jul. 30, 2015 (30) Foreign Application Priority Data G-1 Jul. 12, 2012 (JP) ...... 2012-156398 XI Feb. 4, 2013 (JP) ...... 2013-O19666 X May 16, 2013 (JP) ...... 2013-103989 (51) Int. Cl. CD7C 2.5L/48 (2006.01) X4 X2 AOIN 37/18 (2006.01) X3 (Continued) G2-2 (52) U.S. Cl. Y2 CPC ...... C07C 251/48 (2013.01); A0IN 37/18 Y Y3 N (Continued) (58) Field of Classification Search 2 CPC ...... A01N 43/10; A01N 47/12: A01N 43/60; N Y4 A01N 43/84: A01N 43/56: A01N 43/76; A01N 43/713; A01N 37/20: A01N 43/78: W is an oxygen atom or the like, X is a halogen atom, A01N 43/40: A01N 43/80; C07C 251/48; methyl, trifluoromethyl or the like, each of X, X, X and C07C 251/52; C07D 213/42; C07D 213/61; X is independently a hydrogen atom, a halogen atom or the C07D 213/82: C07D 333/38; C07D 407/12: like, each of Y and Y is independently a halogen atom, CO7D 409/12 cyano, methyl, trifluoromethyl, C-C alkynyl or the like, USPC ...... 514/617: 546/262 each of Y and Y is independently a hydrogen atom, a See application file for complete search history. halogen atom or the like, R is C-C alkyl, C-Chaloalkyl, (C-C)alkyl substituted with R', C-C cycloalkyl, C-C, (56) References Cited alkenyl or the like, each of R and R is independently a hydrogen atom, methyl or the like, R is a hydrogen atom or U.S. PATENT DOCUMENTS the like, R is C-C cycloalkyl, phenyl, phenyl substituted 6,403,600 B1 6, 2002 Maurer et al. with (Z) or the like, Z is a halogen atom or the like, and m 6,864,289 B1 3/2005 Tohnishi et al. is an integer of 1, 2 or 3. (Continued) 30 Claims, No Drawings US 9.434,684 B2 Page 2

(51) Int. Cl. A0IN 47/12 (2013.01); A0IN 55/00 AOIN 37/34 (2006.01) (2013.01); C07C 251/52 (2013.01); C07C AOIN 4I/It (2006.01) 255/64 (2013.01); C07C317/32 (2013.01); AOIN 4I/2 (2006.01) C07C321/28 (2013.01); C07D 213/42 AOIN 43/10 (2006.01) (2013.01); C07D 213/53 (2013.01); C07D CD7C 255/64 (2006.01) 213/61 (2013.01); C07D 213/65 (2013.01); C07C 317/32 (2006.01) C07D 213/82 (2013.01); C07D 24I/24 C07C32L/28 (2006.01) (2013.01); C07D 333/38 (2013.01); C07D C it. R 401/12 (2013.01); C07D 405/12 (2013.01); CO7D 213/82 3:08: C07D407/12 (2013.01); C07D 409/12 CO7D 24I/24 (2006.015 (2013.01); C07D 413/12 (2013.01); C07D AOIN 43/40 (2006.015 417/12 (2013.01); C07F 7/0814 (2013.01) CO7D 333/38 (2006.01) C07D 407/12 (2006.01) (56) References Cited CO7D 409/2 (2006.01) U.S. PATENT DOCUMENTS C07C 251/52 (2006.01) CO7D 213/42 (2006.01) 2004/0254237 A1* 12/2004 Nakamura et al...... 514,460 CO7D 213/6 (2006.01) 2009,0163545 A1 6/2009 Goldfarb AOIN 37/20 (2006.01) 2012. O157476 A1 6, 2012 Hebeisen et al. 39ty 7.75 3.08: FOREIGN PATENT DOCUMENTS AOIN 43/73 (2006.01) JP 2001-1587.64 6, 2001 AOIN 43/76 (2006.01) JP 2002-523397 T 2002 AOIN 43/78 (2006.01) JP 2004-35439 2, 2004 A0IN 43/80 (2006.01) E. 20:52. A 3. AOIN 43/84 (2006.01) WO O1, 55.136 A1 8/2001 AOIN 47/12 (2006.01) WO WO 2006.016708 A1 2/2006 AOIN 55/00 (2006.01) WO WO 2008/081011 A1 T 2008 CO7D 40/12 (2006.01) WO 2009/127722 A1 10/2009 WO 2011, 151369 A1 122O11 C07D 405/12 (2006.01) WO 2011/151370 A1 12/2011 C f/ 3:08: WO 2012/08O144 A1 6, 2012 (52) s",c.08 (2006.01) OTHER PUBLICATIONS CPC ...... (2013.01); A0IN 37/20 (2013.01); A0IN Chemical Abstracts STN REGISTRY database record for RN 37/34 (2013.01); A0IN 41/10 (2013.01); 343374-29-8 entered on Jun. 26, 2001.* A0IN 41/12 (2013.01): A0IN 43/10 International Search Report issued Sep. 24, 2013, in PCT/JP2013/ (2013.01); A0IN 43/40 (2013.01); A0IN 069207, filed Jul 12, 2013. 43/56 (2013.01); A0IN 43/60 (2013.01); Extended European Search Report issued Dec. 15, 2015 in Patent A0IN 43/713 (2013.01); A0IN 43/76 Application 13816560.0. (2013.01); A0IN 43/78 (2013.01); A0IN 43/80 (2013.01); A0IN 43/84 (2013.01); * cited by examiner US 9,434,684 B2 1. 2 OXIME-SUBSTITUTED AMIDE COMPOUND However, recently, control of pests with conventional AND PEST CONTROL AGENT pesticides has become difficult in more and more cases, as pathogens or parasites acquire resistance to them over many TECHNICAL FIELD years of their use. Problems of the high toxicity of some conventional pesticides and of the disturbance of the eco system by some conventional pesticides which remain in the The present invention relates to a novel oxime-substituted environment for a long period are becoming apparent. Under amide compound or its salt, and a pesticidal composition these circumstances, development of novel pesticides not containing the compound as an active ingredient. only having excellent pesticidal activity on pathogens and parasites but also having high pesticidal properties such as BACKGROUND ART 10 low toxicity and low persistence and of an effective con trolling method is always expected. Heretofore, with respect to oxime-substituted amide com pounds, N-(2-(methoxyimino)-2-phenylethyl-4-(trifluo Solution to Problem romethyl)nicotinamide and 3-iodo-N'-[2-(methoxyimino)- 2-phenylethyl-N'-(2-methyl-4-1.2.2.2-tetrafluoro-1- 15 The present inventors have conducted extensive studies to achieve the above object and as a result, found that a novel (trifluoromethyl)ethylphenylphthalic acid diamide are oxime-substituted amide compound represented by the fol known to have insecticidal activity (for example, Patent lowing formula (I) is a very useful compound which is Documents 1 and 2). excellent in pesticidal activities, especially in antifungal and Further, 2-chloro-N-2-(4-chlorophenyl)-2-(methoxy nematicidal activities, and has little harmful effect on non imino)ethylbenzamide, N-2-(4-chlorophenyl)-2- target organisms such as , mammals, , useful (methoxyimino)ethyl-2,4-dichlorobenzamide and the like insects and natural enemies, and accomplished the present are known to alter the lifespan of eukaryotic organisms invention. (Patent Document 3). That is, the present invention relates to an oxime-substi Further, certain pyrazole-4-carboxamide derivatives are 25 tuted amide compound represented by the formula (I), or its known to have fungicidal activity (for example, Patent N-oxide or salt: Documents 4 to 7). However, the oxime-substituted amide compound of the present invention is not disclosed at all, and its usefulness as (I) a pesticide has not been known. 30 PRIOR ART DOCUMENTS

Patent Documents 35 Patent Document 1: JP-A-2004-035439 Patent Document 2: WO2001/021576 Patent Document 3: U.S. Patent Application Publication No. wherein G' is a structure represented by any one of G-1 to 2009/O163545 G-51: Patent Document 4: WO2001-055.136 40 Patent Document 5: WO2009-127722 Patent Document 6: WO2011-151369 G-1 Patent Document 7: WO2O11-151370 XI X DISCLOSURE OF INVENTION 45

Technical Problem X4 X2 Infection or parasitism of pests such as pathogens and X3 parasites causes, in a case where the hosts are plants such as 50 Gl-2 grain, fruits, or ornamental plants, a decrease in XI the quality of agricultural crops and a remarkable decrease in the yield, and in Some cases, serious damages such as X death of the plants, and inflicts heavy economic losses not N only on the producers but also on the consumers. Thus, to 55 effectively control such pests is a very important object to X4 2N achieve efficient and stable production of agricultural crops. Further, in a case where the hosts are such as X3 companion creatures/pets or livestock/poultry, to effectively G-3 XI control Such pests is an important object also for the purpose 60 of maintaining health of the target animals and further, in a case where the target animals are livestock or poultry, for the N1 N purpose of stably producing safe food or high quality general merchandise Such as wool, feathers or leathers. X4 afn From such a viewpoint, heretofore, development of pesti 65 cides targeted at pathogens or parasites has advanced, and X3 various effective pesticides have been put into practical use.

US 9,434,684 B2 11 12 –OCHCHS –SCHCHS , —CH-CH=CH-, -continued N(R)N–CH , –OCH-CH=CH-, D-9 CH=CHCH-CH , CH=CHCH-N , (Z) CH=CHN-CH , CH NCH N O —N=CHCH=N to form a 5-membered ring or a 6-membered ring together with the carbon atoms attached to Y', Y, Y and Y, wherein hydrogen atoms on the respec D-10 tive ring-constituting carbon atoms may optionally be Sub (Z) stituted with a halogen atom, cyano, nitro, C-C alkyl or C-C haloalkyl, 10 and further, when G' is a structure represented by G-1, G-9, G-10, G-12, G-13, G-16 to G-20, G-22 to G-24, D-11 G-26, G-27, G-30, G-32, G-35, G-38, G - 40 or G-42 to G-50, Y and Y, Y- and Y, or Y and Y, together may 15 form OCH=CH-, - SCH=CH N(R) CH=CH-, OCH=N SCH=N or N(R) CH=N to form a 5-membered ring together with the D-12 carbon atoms attached to Y', Y, Y and Y, wherein hydrogen atoms on the respective ring-constituting carbon atoms may optionally be substituted with a halogen atom, cyano, nitro, C-C alkyl or C-C haloalkyl, D-1 to D-38 are aromatic heterocyclic rings represented D-13 by the following structural formulae, respectively: 25

D-1

D-14 30 D-2

D-15 D-3 35

D-16 D-4 40

45 D-17 D-5

50 D-18 D-6

55 D-7 D-19

60 D-8

65 US 9,434,684 B2 13 14 -continued -continued D-21 D-33 - C D-22 D-34 (Z 10

- CN D-23 D-35 15

-E N D-24 D-36 % 2 N D-25 -E 25 D-37

D-26 30 D-38

D-27 35

E-1 to E-22 are saturated heterocyclic rings represented by the following structural formulae, respectively: D-28 40

E-1 2x (R),

D-29 45 E-2 (R7)

-El O D-30 50 E-3 -El(R7) 55 D-31 E-4

60

D-32

65

US 9,434,684 B2 23 24 nitrogen atom attached to R’ and R, wherein the alkylene R’ is a hydrogen atom, C-Cs alkyl, (C-Cs)alkyl option chain may contain an oxygen atom, Sulfur atom or nitrogen ally substituted with R. C-C cycloalkyl, (C-C)cy atom, and may optionally be substituted with a halogen cloalkyl optionally substituted with R, E-2 to E-6, E-8, atom, a C-C alkyl group, a C-C alkoxy group, a —CHO E-14 to E-21, C-C alkenyl, (C-Cs)alkenyl optionally group, a C-C alkylcarbonyl group or a C-C alkoxycar substituted with R. C.-Cs alkynyl, (C-Cs)alkynyl option bonyl group, ally substituted with R, C(O)R’, C(O)C(O)R', R" is a hydrogen atom, C-C alkyl, C-C haloalkyl, C(O)OR, C(O)C(O)OR, C(O)SR, C(O)N C-C cycloalkyl, C-Cs halocycloalkyl, C-C alkenyl, (R')R', C(S)R, C(S)OR, C(S)SR, C(S)N C-C haloalkenyl, C-C alkynyl, C-C haloalkynyl, (R2)R. s —S (O).R., —S (O)N(R2)R. s Si(R) 10 (R')R'', -P(O)(OR), P(S)(OR), phenyl, phenyl —S(O),R or -S(O)N(R)R, or may form the after substituted with (Z), D-1, D-2, D-4 to D-6, D-8 to D-10, mentioned ring together with R. D-12 to D-19, D-21, D-23, D-25, D-27 or D-30 to D-38, or R is a hydrogen atom, C-C alkyl, C-C haloalkyl, may form the after-mentioned ring together with R', C-C alkenyl, C-C haloalkenyl, C-C alkynyl or C-C, R" is a hydrogen atom, C-C alkyl, C-C haloalkyl, haloalkynyl, 15 C-C cycloalkyl (C-C)alkyl, C-C alkoxy(C-C)alkyl, or R may form, together with R', a C-Cs alkylene C-C alkylthio(C-C)alkyl, cyano(C-C)alkyl, C-C, chain to form a 5- to 6-membered ring together with the cycloalkyl, C-C alkenyl, C-C alkynyl, C-C haloalkyl nitrogen atom attached to R* and R, wherein the alkylene carbonyl, C-C alkoxycarbonyl, C-C alkoxy, C-C alkyl chain may contain an oxygen atom, Sulfur atom or nitrogen sulfonyl, phenyl or phenyl substituted with (Z), atom, and may optionally be substituted with a halogen or R' may form, together with R', a C-Cs alkylene atom, a C-C alkyl group, a C-C haloalkyl group, a C-C, chain to form a 3- to 7-membered ring together with the alkoxy group, a —CHO group, a C-C alkylcarbonyl group, nitrogen atom attached to R and R', wherein the alkylene a C-C alkoxycarbonyl group, an oxo group or a thioxo chain may contain an oxygen atom, Sulfur atom or nitrogen grOup, atom, and may optionally be substituted with a halogen R" is a hydrogen atom, C-C alkyl, C-C haloalkyl, 25 atom, a C-C alkyl group, a C-Chaloalkyl group, a C1-C4 C-Cs cycloalkyl, phenyl or phenyl Substituted with (Z), or alkoxy group, a —CHO group, a C-C alkylcarbonyl group, may form the after-mentioned ring together with R", a C-C alkoxycarbonyl group, a phenyl group, a phenyl R" is a hydrogen atom, C-C alkyl, C-C alkoxy, group Substituted with (Z), an oxo group or a thioxo group, C-C alkylthio or di(C-C alkyl)amino, R" is C-Cs alkyl, (C-Cs)alkyl optionally substituted or R* may form, together with R', a C-C alkylene 30 with R. C-C cycloalkyl, (C-C)cycloalkyl optionally chain to form a 4- to 6-membered ring together with the substituted with R, E-2 to E-6, E-8, E-14 to E-21, C-Cs carbon atom attached to R* and R", wherein the alkylene alkenyl, (C-C)alkenyl optionally substituted with R. chain may contain an oxygen atom, Sulfur atom or nitrogen C-C alkynyl, (C-C)alkynyl optionally substituted with atom, and may optionally be substituted with a halogen R, C(O)R, C(O)C(O)R', C(O)OR', C(O)C atom, a C-C alkyl group, a C-C haloalkyl group, a 35 (O)OR, C(O)SR, C(O)N(R)R, C(S)R’, —CHO group, a C-C alkylcarbonyl group or a C-C, C(S)OR, C(S)SR, C(S)N(R')R', SH, C-C, alkoxycarbonyl group, alkylthio, C-Cs haloalkylthio, phenylthio, phenylthio Sub R" is C-C2 alkyl, C-C2 haloalkyl, C-C2 alkoxy(C- stituted with (Z), -P(O)(OR), -P(S)(OR), phenyl, C.)alkyl, cyano(C-C)alkyl, C-C alkoxycarbonyl(C- phenyl substituted with (Z), D-9, D-10, D-12, D-14 to C.)alkyl, phenyl(C-C)alkyl, phenyl (C-C)alkyl substi 40 D-17, D-30 or D-32 to D-35, tuted with (Z), C-C alkenyl, C-C haloalkenyl, C-C2 R is a hydrogen atom, C-C alkyl, C-C haloalkyl, alkynyl, C-C haloalkynyl, C-C alkylcarbonyl, C-C, C-C cycloalkyl(C-C)alkyl, C-C alkoxy(C-C)alkyl, alkoxycarbonyl, -C(O)ON=C(CH)SCH, C(O) C-Cs haloalkoxy(C-C)alkyl, C-Cs alkylthio(C-C) ON=C(SCH)C(O)N(CH), phenyl or phenyl substituted alkyl, C-C haloalkylthio(C-C)alkyl, C-C alkylsulfonyl with (Z), or may form the after-mentioned ring together 45 (C-C)alkyl, C-Cs haloalkylsulfonyl(C-C)alkyl, phenyl with R7, (C-C)alkyl, phenyl (C-C)alkyl Substituted with (Z). R’ is C-C alkyl, C-C haloalkyl, C-C alkoxy(C- C-C cycloalkyl, phenyl or phenyl substituted with (Z), C alkyl), cyano (C-C)alkyl, C-C alkoxycarbonyl(C- R is C-Cs alkyl, (C-Cs)alkyl optionally substituted C.)alkyl, phenyl(C-C)alkyl, phenyl (C-C)alkyl substi with R. C-C cycloalkyl, (C-C)cycloalkyl optionally tuted with (Z), C-C alkenyl, C-C haloalkenyl, C-C2 50 substituted with R, E-2 to E-6, E-8, E-14 to E-21, C-Cs alkynyl, C-C haloalkynyl, phenyl or phenyl Substituted alkenyl, (C-C)alkenyl optionally substituted with R. with (Z), C-C alkynyl, (C-C)alkynyl optionally Substituted with or R may form, together with R', a C-C, alkylene R, phenyl, phenyl substituted with (Z), D-1, D-2, D-4 to chain to form a 5- to 8-membered ring together with the D-6, D-8 to D-10, D-12 to D-19, D-21, D-23, D-25, D-27 or nitrogen atom attached to R'' and R', wherein the alkylene 55 D-30 to D-38, chain may contain an oxygen atom or Sulfur atom, and may R is a hydrogen atom, C-C alkyl, (C-C)alkyl option optionally be substituted with a C-C alkyl group or a ally substituted with R. C.-Cs cycloalkyl, (C-Cs)cy C-C alkoxy group, cloalkyl optionally substituted with R, E-2 to E-6, E-8, R is a halogen atom, cyano, nitro, Ca-Cs cycloalkyl, E-14 to E-21, C-C alkenyl, (C-C)alkenyl optionally C-Cs halocycloalkyl, C-C alkoxy, C-C haloalkoxy, 60 substituted with R. C.-Cs alkynyl, (C-C)alkynyl option C-C alkylthio, C-C haloalkylthio. C-C alkylsulfinyl, ally substituted with R, phenyl, phenyl substituted with C-C haloalkylsulfinyl, C-C alkylsulfonyl, C-C, (Z), D-1 to D25 or D-27 to D-38, or may form the haloalkylsulfonyl, C-C alkylamino, di(C-C alkyl)amino, after-mentioned ring together with R. C-C alkoxycarbonyl, C-C haloalkoxycarbonyl, —C(O) R is a hydrogen atom, C-C alkyl, (C-C)alkyl option NH, C-C alkylaminocarbonyl, di(C-C alkyl)aminocar 65 ally substituted with R. C-C alkenyl, C-C haloalkenyl, bonyl, —C(S)NH, phenyl, phenyl substituted with (Z), or C-C alkynyl, C-C haloalkynyl, phenyl or phenyl Substi D-1 to D-38, tuted with (Z), US 9,434,684 B2 25 26 or R may form, together with R', a C-Cs alkylene group, a C-C alkylcarbonyl group, a C-C alkoxycarbonyl chain to form a 3- to 6-membered ring together with the group, a phenyl group or a phenyl group Substituted with nitrogen atom attached to R and R, wherein the alkylene (Z), chain may contain an oxygen atom, Sulfur atom or nitrogen R" is C-C alkyl or C-C haloalkyl, atom, and may optionally be substituted with a halogen R" is cyano, C-C cycloalkyl, C-C halocycloalkyl, atom, a C-C alkyl group, a C-C alkoxy group, a —CHO E-5, E-6, E-14, E-15, C-C alkoxy, C-C haloalkoxy, group, a C-C alkylcarbonyl group, a C-C alkoxycarbonyl phenoxy, phenoxy Substituted with (Z), C-C alkylthio. group, a phenyl group, a phenyl group substituted with (Z), C-Chaloalkylthio, phenylthio, phenylthio substituted with or an OXO group, (Z), C-C alkylsulfonyl, C-C haloalkylsulfonyl, phenyl R is a hydrogen atom, C-Cs alkyl, (C-Cs)alkyl option 10 sulfonyl, phenylsulfonyl substituted with (Z), N(R') ally substituted with R. C-C cycloalkyl, (C-C)cy R", C-C alkylcarbonyl, C-C haloalkylcarbonyl, C-C, cloalkyl optionally substituted with R, E-2 to E-6, E-8, alkoxycarbonyl, C-C alkylaminocarbonyl, di(C-C alkyl) E-14 to E-21, C-C alkenyl, (C-Cs)alkenyl optionally aminocarbonyl, tri(C-C alkyl)silyl phenyl, phenyl Substi substituted with R. C-C alkynyl, (C-C)alkynyl option tuted with (Z) or D-1 to D-38, ally substituted with R. C(O)R’, C(O)C(O)R', 15 R" is a hydrogenatom, C-C alkyl, C-C alkylcarbonyl, C(O)OR, C(O)C(O)OR, C(O)SR, C(O)N C-C haloalkylcarbonyl, C-C alkoxycarbonyl, phenylcar (R')R', C(S)R’, C(S)OR, C(S)SR, C(S)N bonyl or phenylcarbonyl substituted with (Z), (R2)R. s —S (O).R', —S (O)N(R')R. s —Si (R14) R" is a hydrogen atom or C-C alkyl, (R')R'', P(O)(OR:), or P(S)(OR), m is an integer of 1, 2, 3, 4 or 5. R7 is C-C alkyl, (C-C)alkyl optionally substituted n is an integer of 0, 1, 2, 3 or 4. with R. C.-Cs cycloalkyl, (C-Cs)cycloalkyl optionally p is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9. substituted with R, E-2 to E-6, E-8, E-14 to E-21, C-Cs r is an integer of 0, 1 or 2, and alkenyl, (C-C)alkenyl optionally substituted with R. t is an integer of 0 or 1. C-Cs alkynyl, (C-Cs)alkynyl optionally Substituted with 25 Further, the present invention relates to all stereoisomers R, C(O)R, C(O)C(O)R, C(O)OR, C(O)C thereof, its intermediate, and a pesticide containing it as an (OOR), C(O)SR-9, C(O)N(R)R, C(S)R’, active ingredient. C(S)OR, C(S)SR, C(S)N(R')R', SH, C-C, alkylthio, C-C haloalkylthio, phenylthio, phenylthio Sub Advantageous Effects of Invention 30 stituted with (Z), -P(O)(OR), or -P(S)(OR), The compound of the present invention represented by the R is a halogen atom, cyano, nitro, Cs-Cs cycloalkyl, formula (I) and the pesticide containing the compound as an C-C halocycloalkyl, E-5, E-6, E-9, E-10, E-12, E-14, E-15, active ingredient have excellent controlling effect on pests, E-18, E-19, E-21, OH, OR', OC(O)R’, OC(O) especially fungi and nematodes in agricultural fields or OR, OC(O)N(R')R'', OC(S)N(R')R, SH, 35 Zootechnical/hygienic fields, and have Sufficient controlling S(O), R, SC(O)R, SC(O)OR, SC(O)N(R') effect on pests which have acquired resistance to conven R', SC(S)N(R')R', N(R')R', N(R')C(O)R, tional pesticides. Further, they have little harmful effect on N(R')C(O)SR, N(R')C(O)N(R')R, N(R')C non-target organisms such as plants, mammals, fishes, useful (S)N(R')R', N(R')S(O).R, C(O)R, C(O)OH, insects and natural enemies, show low persistence and are C(O)OR, C(O)SR, C(O)N(R')R', C(O)C 40 environmentally friendly. (OOR), C(S)SR, C(S)N(R')R', Si(R')(R') Thus, the present invention can provide useful novel R', -P(O)(OR), P(S)(OR), P(phenyl), -P(O) pesticides. (phenyl), phenyl, phenyl Substituted with (Z), or D-1 to D-38, DESCRIPTION OF EMBODIMENT(S) R is a hydrogen atom, C-C alkyl, C-C haloalkyl, 45 (C-C)alkyl optionally substituted with R', C.-C The oxime-substituted amide compounds of the present cycloalkyl, C-C halocycloalkyl, E-5, E-6, E-14, E-15, invention represented by the formula (I) can have geometri C-Cs alkenyl, C-Cs haloalkenyl, cycloalkenyl, Cs-Co cal isomers such as E-isomers and Z-isomers, and the halocycloalkenyl, C-C alkynyl, C-C haloalkynyl, phe present invention covers both E-isomers and Z-isomers and nyl, phenyl substituted with (Z), or D-1 to D-38, 50 mixtures containing them in any ratios. The compounds of R" is C-C alkyl, C-C haloalkyl, (C-C)alkyl option the present invention can have optically active isomers due ally substituted with R', C-C cycloalkyl, E-5, E-6, C-Cs to the presence of one or more asymmetric carbon atoms alkenyl, C-Cs haloalkenyl, C-Cs alkynyl or phenyl, depending on the types of Substituents in them, and the R' is a hydrogen atom, C-C alkyl, C-C haloalkyl, present invention covers any optically active isomers and (C-C)alkyl optionally substituted with R', C.-C 55 any racemates. cycloalkyl, E-5, E-6, E-14, C-C alkenyl, C-C haloalk As a halogen atom herein, a fluorine atom, a chlorine enyl, C-C alkynyl, phenyl, phenyl Substituted with (Z). atom, a bromine atom or an iodine atom may be mentioned. D-1 to D-25 or D-27 to D-38, or may form the after Herein, the expression "halo' also means such a halogen mentioned ring together with R', atOm. R" is a hydrogen atom, C-C alkyl, C-C haloalkyl, 60 In the specific description of the substituents herein, the C-C cycloalkyl, C-C alkenyl or C-C alkynyl, expression “n-” denotes “normal”, “i-” “iso', 's-” “second or R' may form, together with R', a C-Cs alkylene ary”, “tert-” “tertiary”, and “Ph” “phenyl”. chain to form a 3- to 6-membered ring together with the The expression "C-C, alkyl herein means a linear or nitrogen atom attached to R' and R', wherein the alkylene branched hydrocarbon group containing from a to b carbon chain may contain an oxygen atom, Sulfur atom or nitrogen 65 atoms such as a methyl group, an ethyl group, a n-propyl atom, and may optionally be substituted with a halogen group, an i-propyl group, a n-butyl group, an i-butyl group, atom, a C-C alkyl group, a C-C alkoxy group, a —CHO a S-butyl group, a tert-butyl group, a pentyl group, a 1-eth US 9,434,684 B2 27 28 ylpropyl group, a 2.2-dimethylpropyl group or a hexyl in the molecule, in which hydrogen atom(s) on carbon group, and those within the designated carbon number range atom(s) are optionally substituted with halogen atom(s) are selected. which may be identical with or different from one another if The expression "C-C, haloalkyl herein means a linear two or more halogen atoms are present, Such as a 2-fluoro or branched hydrocarbon group containing from a to b vinyl group, a 2-chlorovinyl group, a 1,2-dichlorovinyl carbon atoms in which hydrogen atom(s) on carbon atom(s) group, a 2,2-dichlorovinyl group, a 2-fluoro-2-propenyl are optionally Substituted with halogen atom(s) which may group, a 2-chloro-2-propenyl group, a 3-chloro-2-propenyl be identical with or different from one anotheriftwo or more group, a 3.3-difluoro-2-propenyl group, a 2,3-dichloro-2- halogen atoms are present, such as a fluoromethyl group, a propenyl group, a 3.3-dichloro-2-propenyl group, a 2.3.3- chloromethyl group, a bromomethyl group, an iodomethyl 10 group, a difluoromethyl group, a dichloromethyl group, a trifluoro-2-propenyl group, a 2,3,3-trichloro-2-propenyl trifluoromethyl group, a chlorodifluoromethyl group, a group, a 1-(trifluoromethyl)ethenyl group, a 4.4-difluoro-3- trichloromethyl group, a bromodifluoromethyl group, a butenyl group, a 3,4,4-trifluoro-3-butenyl group, a 2.4.4.4- 1-fluoroethyl group, a 2-fluoroethyl group, a 2-chloroethyl tetrafluoro-2-butenyl group or a 3-chloro-4,4,4-trifluoro-2- group, a 2-bromoethyl group, a 2.2-difluoroethyl group, a 15 butenyl group, and those within the designated carbon atom 2.2.2-trifluoroethyl group, a 2-chloro-2,2-difluoroethyl range are selected. group, a 2.2.2-trichloroethyl group, a 2-bromo-2,2-difluoro The expression "C-C, cycloalkenyl herein means a ethyl group, a 1.1.2.2-tetrafluoroethyl group, a 2-chloro-1, cyclic unsaturated hydrocarbon group containing from a to 1.2-trifluoroethyl group, a pentafluoroethyl group, a 2.2- b carbon atoms and containing one or more endo- or difluoropropyl group, a 3.3,3-trifluoropropyl group, a exo-double bonds in the form of a 3- to 10-membered 3-bromo-3,3-difluoropropyl group, a 2,2,3,3-tetrafluoropro monocyclic or polycyclic ring which may optionally be pyl group, a 2.2.3,3,3-pentafluoropropyl group, a 1.1.2.3.3. Substituted with an alkyl group as long as the number of 3-hexafluoropropyl group, a heptafluoropropyl group, a 2.2, carbon atoms does not exceed the designated carbon number 2-trifluoro-1-(methyl)ethyl group, a 2.2.2-trifluoro-1- range. Such as a 1-cyclopentenyl group, a 2-cyclopentenyl (trifluoromethyl)ethyl group, a 1.2.2.2-tetrafluoro-1- 25 group, a 1-cyclohexenyl group, a 2-cyclohexenyl group or a (trifluoromethyl)ethyl group, a 2.2.3.4.4.4-hexafluorobutyl bicyclo[2.2.1-5-hepten-2-yl group, and those within the group, a 2.2.3.3.4.4.4-heptafluorobutyl group or a nonafluo designated carbon atom range are selected. robutyl group, and those within the designated carbon num The expression "C-C, halocycloalkenyl herein means a ber range are selected. cyclic unsaturated hydrocarbon group containing from a to The expression "C-C, cycloalkyl herein means a cyclic 30 b carbon atoms and containing one or more endo- or hydrocarbon group containing from a to b carbon atoms in exo-double bonds in the form of a 3- to 10-membered the form of a 3- to 10-membered monocyclic or polycyclic monocyclic or polycyclic ring which may optionally be ring which may optionally be substituted with an alkyl group Substituted with an alkyl group as long as the number of as long as the number of carbon atoms does not exceed the carbon atoms does not exceed the designated carbon number designated carbon number range. Such as a cyclopropyl 35 range, in which hydrogen atom(s) on carbon atom(s) in the group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl ring moiety and/or in the side chain are optionally Substi group, a 2.2-dimethylcyclopropyl group, a cyclobutyl group, tuted with halogen atom(s) which may be identical with or a cyclopentyl group or a cyclohexyl group, and those within different from one another if two or more halogenatoms are the designated carbon number range are selected. present, Such as a 2-fluoro-1-cyclopentenyl group, a The expression "C-C, halocycloalkyl herein means a 40 2-chloro-1-cyclopentenyl group, a 3-chloro-2-cyclopentenyl cyclic hydrocarbon group containing from a to b carbon group or a 2-fluoro-1-cyclohexenyl group, and those within atoms in the form of a 3- to 10-membered monocyclic or the designated carbon atom range are selected. polycyclic ring which may optionally be substituted with an The expression "C-C, alkylidene' herein means a linear alkyl group as long as the number of carbon atoms does not or branched hydrocarbon group containing from a to b exceed the designated carbon number range, in which 45 carbon atoms which attaches by a double bond. Such as a hydrogen atom(s) on carbon atom(s) in a ring moiety and/or methylidene group, an ethylidene group, a propylidene in a side chain are optionally substituted with halogen group or a 1-methylethylidene group, and those within the atom(s) which may be identical with or different from one designated carbon number range are selected. another if two or more halogen atoms are present, Such as a The expression "C-C, alkynyl herein means a linear or 2,2-difluorocyclopropyl group, a 2,2-dichlorocyclopropyl 50 branched unsaturated hydrocarbon group containing from a group, a 2.2-dibromocyclopropyl group, a 2.2-difluoro-1- to b carbon atoms and having one or more triple bonds in the methylcyclopropyl group, a 2.2-dichloro-1-methylcyclopro molecule Such as an ethynyl group, a 1-propynyl group, a pyl group, a 2.2-dibromo-1-methylcyclopropyl group or a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 2.2.3,3-tetrafluorocyclobutyl group, and those within the 3-butynyl group, a 1-methyl-2-propynyl group, a 2-pentynyl designated carbon atom range are selected. 55 group or a 3-hexynyl group, and those within the designated The expression "C-C, alkenyl herein means a linear or carbon atom range are selected. branched unsaturated hydrocarbon group containing from a The expression “C-C, haloalkynyl herein means a lin to b carbon atoms and having one or more double bonds in ear or branched unsaturated hydrocarbon group containing the molecule Such as a vinyl group, a 1-propenyl group, a from a to b carbon atoms and having one or more triple 2-propenyl group, a 1-methylethenyl group, a 1-butenyl 60 bonds in the molecule, in which hydrogen atom(s) on carbon group, a 2-butenyl group, a 1-methyl-1-propenyl group, a atom(s) are optionally substituted with halogen atom(s) 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group or which may be identical with or different from one another if a 3-methyl-2-butenyl group, and those within the designated two or more halogen atoms are present, such as a 2-chlo carbon atom range are selected. roethynyl group, a 2-bromoethynyl group, a 2-iodoethynyl The expression "C-Chaloalkenyl herein means a linear 65 group, a 3-chloro-2-propynyl group or a 3-bromo-2-propy or branched unsaturated hydrocarbon group containing from nyl group or a 3-iodo-2-propynyl group, and those within the a to b carbon atoms and having one or more double bonds designated carbon number range are selected. US 9,434,684 B2 29 30 The expression "C-C, alkoxy herein means an alkyl nyl group or a tert-butylsulfonyl group, and those within the O— group in which the alkyl is a previously mentioned designated carbon atom range are selected. alkyl group containing from a to b carbon atoms, such as a The expression “C-C, haloalkylsulfonyl herein means a methoxy group, an ethoxy group, a n-propyloxy group, an haloalkyl-S(O) - group in which the haloalkyl is a previ i-propyloxy group, a n-butyloxy group, an i-butyloxy group, ously mentioned haloalkyl group containing from a to b a S-butyloxy group, a tert-butyloxy group, a pentyloxy group carbon atoms, such as a difluoromethylsulfonyl group, a or a hexyloxy group, and those within the designated carbon trifluoromethylsulfonyl group, a chlorodifluoromethylsulfo atom range are selected. nyl group, a bromodifluoromethylsulfonyl group, a 2.2.2- The expression "C-C, haloalkoxy” herein means a trifluoroethylsulfonyl group, a 1.1.2.2-tetrafluoroethylsulfo haloalkyl-O-group in which the haloalkyl is a previously 10 nyl group or a 2-chloro-1,1,2-trifluoroethylsulfonyl group, mentioned haloalkyl group containing from a to b carbon and those within the designated carbon atom range are atoms, such as a difluoromethoxy group, a trifluoromethoxy selected. group, a chlorodifluoromethoxy group, a bromodifluo The expression "C-C, alkylamino' herein means an romethoxy group, a 2-fluoroethoxy group, a 2-chloroethoxy amino group in which either hydrogen atom is replaced by group, a 2.2.2-trifluoroethoxy group, a 1.1.2.2,-tetrafluo 15 a previously mentioned alkyl group containing from a to b roethoxy group, a 2-chloro-1,1,2-trifluoroethoxy group or a carbon atoms, such as a methylamino group, an ethylamino 1.1.2.3.3.3-hexafluoropropyloxy group, and those within the group, a n-propylamino group, an i-propylamino group, a designated carbon atom range are selected. n-butylamino group, an i-butylamino group or a tert-buty The expression "C-C, alkenyloxy' herein means an lamino group, and those within the designated carbon atom alkenyl-O- group in which the alkenyl is a previously range are selected. mentioned alkenyl group containing from a to b carbon The expression “di(C-C, alkyl)amino' herein means an atoms, such as a 2-propenyloxy group, a 2-butenyloxy amino group in which both hydrogen atoms are replaced by group, a 2-methyl-2-propenyloxy group or a 3-methyl-2- previously mentioned alkyl groups containing from a to b butenyloxy group, and those within the designated carbon carbon atoms which may be identical with or different from atom range are selected. 25 each other, Such as a dimethylamino group, an ethyl(methyl) The expression "C-C, alkylthio’ herein means an alkyl amino group, a diethylamino group, a di(n-propyl)amino S— group in which the alkyl is a previously mentioned alkyl group or a di(n-butyl)amino group, and those within the group containing from a to b carbon atoms, such as a designated carbon atom range are selected. methylthio group, an ethylthio group, a n-propylthio group, The expression "C-C, alkylimino' herein means an an i-propylthio group, a n-butylthio group, an i-butylthio 30 alkyl-N-group in which the alkyl is a previously mentioned group, a S-butylthio group or a tert-butylthio group, and alkyl group containing from a to b carbon atoms, such as a those within the designated carbon atom range are selected. methylimino group, an ethylimino group, a n-propylimino The expression "C-C, haloalkylthio’ herein means a group, an i-propylimino group, a n-butylimino group, an haloalkyl-S— group in which the haloalkyl is a previously i-butylimino group or a S-butylimino group, and those mentioned haloalkyl group containing from a to b carbon 35 within the designated carbon atom range are selected. atoms, such as a difluoromethylthio group, a trifluorometh The expression "C-C, alkoxyimino' herein means an ylthio group, a chlorodifluoromethylthio group, a bromodi alkoxy-N-group in which the alkoxy is a previously men fluoromethylthio group, a 2.2.2-trifluoroethylthio group, a tioned alkoxy group containing from a to b carbon atoms, 1.1.2.2-tetrafluoroethylthio group, a 2-chloro-1,1,2-trifluo Such as a methoxyimino group, an ethoxyimino group, a roethylthio group, a pentafluoroethylthio group, a 1.1.2.3.3. 40 n-propyloxyimino group, an i-propyloxyimino group or a 3-hexafluoropropylthio group, a heptafluoropropylthio n-butyloxyimino group, and those within the designated group, a 1.2.2.2-tetrafluoro-1-(trifluoromethyl)ethylthio carbon atom range are selected. group or a nonafluorobutylthio group, and those within the The expression "C-C, alkylcarbonyl herein means an designated carbon atom range are selected. alkyl-C(O)— group in which the alkyl is a previously The expression “C-C, alkylsulfinyl herein means an 45 mentioned alkyl group containing from a to b carbon atoms, alkyl-S(O)— group in which the alkyl is a previously Such as an acetyl group, a propionyl group, abutyryl group, mentioned alkyl group containing from a to b carbon atoms, an isobutyryl group, a Valeryl group, an isovaleryl group, a Such as a methylsulfinyl group, an ethylsulfinyl group, a 2-methylbutanoyl group or a pivaloyl group, and those n-propylsulfinyl group, an i-propylsulfinyl group, a n-butyl within the designated carbon atom range are selected. Sulfinyl group, an i-butylsulfinyl group, a S-butylsulfinyl 50 The expression “C-C, haloalkylcarbonyl herein means group or a tert-butylsulfinyl group, and those within the a haloalkyl-C(O)—group in which the haloalkyl is a pre designated carbon atom range are selected. viously mentioned haloalkyl group containing from a to b The expression “C-C, haloalkylsulfinyl herein means a carbon atoms, such as a fluoroacetyl group, a chloroacetyl haloalkyl-S(O)— group in which the haloalkyl is a previ group, a difluoroacetyl group, a dichloroacetyl group, a ously mentioned haloalkyl group containing from a to b 55 trifluoroacetyl group, a chlorodifluoroacetyl group, a bro carbon atoms, such as a difluoromethylsulfinyl group, a modifluoroacetyl group, a trichloroacetyl group, a penta trifluoromethylsulfinyl group, a chlorodifluoromethylsulfi fluoropropionyl group, a heptafluorobutanoyl group or a nyl group, a bromodifluoromethylsulfinyl group, a 2.2.2- 3-chloro-2,2-dimethylpropanoyl group, and those within the trifluoroethylsulfinyl group or a nonafluorobutylsulfinyl designated carbon atom range are selected. group, and those within the designated carbon atom range 60 The expression “C-C, cycloalkylcarbonyl herein means are selected. a cycloalkyl-C(O)— group in which the cycloalkyl is a The expression "C-C, alkylsulfonyl herein means an previously mentioned cycloalkyl group containing from a to alkyl-S(O) - group in which the alkyl is a previously b carbon atoms. Such as a cyclopropylcarbonyl group, a mentioned alkyl group containing from a to b carbon atoms, cyclobutylcarbonyl group, a cyclopentylcarbonyl group, a Such as a methylsulfonyl group, an ethylsulfonyl group, a 65 2,2-dimethylcyclopropylcarbonyl group or a cyclohexylcar n-propylsulfonyl group, an i-propylsulfonyl group, a n-bu bonyl group, and those within the designated carbon atom tylsulfonyl group, an i-butylsulfonyl group, a S-butylsulfo range are selected. US 9,434,684 B2 31 32 The expression "C-C, alkoxycarbonyl herein means an The expression "C-C, haloalkylsulfonyloxy' herein alkyl-O C(O)— group in which the alkyl is a previously means a haloalkylsulfonyl-O- group in which the mentioned alkyl group containing from a to b carbon atoms, haloalkylsulfonyl is a previously mentioned haloalkylsulfo Such as a methoxycarbonyl group, an ethoxycarbonyl group, nyl group containing from a to b carbon atoms, such as a a n-propyloxycarbonyl group, an i-propyloxycarbonyl difluoromethylsulfonyloxy group, a trifluoromethylsulfony group, a n-butoxycarbonyl group, an i-butoxycarbonyl loxy group, a chlorodifluoromethylsulfonyloxy group or a group or a tert-butoxycarbonyl group, and those within the bromodifluoromethylsulfonyloxy group, and those within designated carbon atom range are selected. the designated carbon atom range are selected. The expression "C-C, haloalkoxycarbonyl herein The expression Such as "C-C, cycloalkyl (C-C)alkyl. means a haloalkyl-O-C(O)—group in which the haloalkyl 10 is a previously mentioned haloalkyl group containing from “hydroxy(C-C)alkyl, "C-C, alkoxy(C-C)alkyl, "C- a to b carbon atoms, such as a chloromethoxycarbonyl Chaloalkoxy(C-C)alkyl, "C-C, alkylthio(C-C)alkyl. group, a 2-chloroethoxycarbonyl group, a 2.2-difluoroeth "C-C, haloalkylthio(C-C)alkyl, "C-C, alkylsulfinyl oxycarbonyl group, a 2.2.2-trifluoroethoxycarbonyl group (C-C)alkyl, "C-C, haloalkylsulfinyl (C-C)alkyl, “C- or a 2.2.2-trichloroethoxycarbonyl group, and those within 15 C, alkylsulfonyl(C-C)alkyl”, “C-C, haloalkylsulfonyl the designated carbon atom range are selected. (C-C)alkyl, "C-C, alkylamino(C-C)alkyl, "di(C-C, The expression "C-C, alkylaminocarbonyl herein alkyl)amino(C-C)alkyl, "cyano(C-C)alkyl, "C-C, means a carbamoyl group in which either hydrogen atom is alkoxycarbonyl(C-C)alkyl, "C-C, haloalkoxycarbonyl replaced by a previously mentioned alkyl group containing (C-C)alkyl, "phenyl (C-C)alkyl or “phenyl (C-C) from a to b carbon atoms, such as a methylcarbamoyl group, alkyl substituted with (Z), herein means a previously an ethylcarbamoyl group, a n-propylcarbamoyl group, an mentioned alkyl group containing from d to e carbon atoms i-propylcarbamoyl group, a n-butylcarbamoyl group, an in which hydrogen atom(s) on carbon atom(s) are optionally i-butylcarbamoyl group, a S-butylcarbamoyl group or a Substituted with previously mentioned optional C-C, tert-butylcarbamoyl group, and those within the designated cycloalkyl group, C-C, alkoxy group, C-C, haloalkoxy carbon atom range are selected. 25 group, C-C, alkylthio group, C-C, haloalkylthio group, The expression “C-C, haloalkylaminocarbonyl herein C-C, alkylsulfinyl group, C-C, haloalkylsulfinyl group, means a carbamoyl group in which either hydrogen atom is C-C, alkylsulfonyl group, C-C, haloalkylsulfonyl group, replaced by a previously mentioned haloalkyl group con C-C, alkylamino group, di(C-C, alkyl)amino group, C taining from a to b carbon atoms, such as a 2-fluoroethyl C, alkoxycarbonyl group, C-C, haloalkoxycarbonyl group, carbamoyl group, a 2-chloroethylcarbamoyl group, a 2.2- 30 hydroxy group, cyano group, phenyl group or phenyl group difluoroethylcarbamoyl group O a 2.2.2- trifluoroethylcarbamoyl group, and those within the Substituted with (Z), and those within the designated car designated carbon atom range are selected. bon atom range are selected. The expression “di(C-C, alkyl)aminocarbonyl herein The expression such as “hydroxy(C-C)cycloalkyl or means a carbamoyl group in which both hydrogen atoms are 35 "C-C, alkoxy(C-C)cycloalkyl herein means a previously replaced by previously mentioned alkyl groups containing mentioned cycloalkyl group containing from d to e carbon from a to b carbon atoms which may be identical with or atoms in which hydrogen atom(s) on carbon atom(s) are different from each other, such as an N,N-dimethylcarbam optionally substituted with previously mentioned optional oyl group, an N-ethyl-N-methylcarbamoyl group, an N.N- C-C, alkoxy group(s) or hydroxy group(s), and those diethylcarbamoyl group, an N,N-di(n-propyl)carbamoyl 40 within the designated carbon atom range are selected. group or an N,N-di(n-butyl)carbamoyl group, and those The expression “phenyl(C-C)alkynyl herein means a within the designated carbon atom range are selected. previously mentioned alkynyl group containing from a to b The expression “di(C-C, alkyl)aminosulfonyl herein carbon atoms in which hydrogen atom(s) on carbon atom(s) means a sulfamoyl group in which both hydrogen atoms are are optionally substituted with phenyl group(s), and those replaced by previously mentioned alkyl groups containing 45 within the designated carbon atom range are selected. from a to b carbon atoms which may be identical with or The expression Such as "(C-C) alkyl optionally Substi different from each other, such as an N,N-dimethylsulfa tuted with R', “(C-C) alkyl optionally substituted with moyl group, an N-ethyl-N-methylsulfamoyl group, an N.N- R", "(C-C) alkyl optionally substituted with R'”, “(C- diethylsulfamoyl group, an N,N-di(n-propyl)sulfamoyl C) alkyl optionally substituted with R", "(C-C) alkyl group or an N,N-di(n-butyl)sulfamoyl group, and those 50 optionally substituted with R" or “(C-C) alkyl optionally within the designated carbon atom range are selected. substituted with R“” herein means a previously mentioned The expression “tri(C-C, alkyl)silyl herein means a alkyl group containing from a to b carbon atoms in which silyl group replaced by previously mentioned alkyl groups hydrogen atom(s) on carbon atom(s) are optionally Substi containing from a to b carbon atoms which may be identical tuted with optional R. R. R. R, R or R, and those with or different from one another, such as a trimethylsilyl 55 within the designated carbon atom range are selected. When group, a triethylsilyl group, a tri(n-propyl)silyl group, an there are two or more Rs, R's, R's, Rs. Rs or ethyldimethylsilyl group, a n-propyldimethylsilyl group, a R’s on a (C-C) alkyl group, each R. R. R. R. R. n-butyldimethylsilyl group, an i-butyldimethylsilyl group or or R' may be identical with or different from one another. a tert-butyldimethylsilyl group, and those within the desig The expression Such as "(C-C) cycloalkyl optionally nated carbon atom range are selected. 60 substituted with R", "(C-C) cycloalkyl optionally substi The expression "C-C, alkylsulfonyloxy” herein means tuted with R or “(C-C) cycloalkyl optionally substi an alkylsulfonyl-O-group in which the alkylsulfonyl is a tuted with R" herein means a previously mentioned previously mentioned alkylsulfonyl group containing from a cycloalkyl group containing from a to b carbon atoms in to b carbon atoms, such as a methylsulfonyloxy group, an which hydrogen atom(s) on carbon atom(s) in the ring ethylsulfonyloxy group, a n-propylsulfonyloxy group or an 65 moiety and/or in the side chain are optionally substituted i-propylsulfonyloxy group, and those within the designated with optional R, R or R, and those within the designated carbon atom range are selected. carbon atom range are selected. When there are two or more US 9,434,684 B2 33 34 R's, R's or R's on a (C-C) cycloalkyl group, each R', thiomorpholine-1-oxide, thiomorpholine-1,1-dioxide, per R or R may be identical with or different from one hydropyrimidine-2-one, piperazine, homopiperidine, another. homopiperidin-2-one, heptamethyleneimine or the like, and The expression Such as "(C-C) alkenyl optionally Sub those within the designated carbon atom range are selected. stituted with R", "(C-C) alkenyl optionally substituted 5 The expression such as 'R' may form, together with R', with R" or “(C-C) alkenyl optionally substituted with a C-C alkylene chain to form a 3- to 7-membered ring R” herein means a previously mentioned alkenyl group together with the nitrogen atom attached to R' and R', containing from a to b carbon atoms in which hydrogen wherein the alkylene chain may contain an oxygen atom, atom(s) on carbon atom(s) are optionally Substituted with sulfur atom or nitrogenatom”, “R” may form, together with optional R, R or R, and those within the designated 10 carbon atom range are selected. When there are two or more R’, a C-C alkylene chain to form a 3- to 7-membered ring Rs. Rs or R's on a (C-C) alkenyl group, each R, together with the nitrogen atom attached to R' and R. R or R may be identical with or different from one wherein the alkylene chain may contain an oxygen atom, another. sulfur atom or nitrogenatom”, “R” may form, together with The expression Such as "(C-C) alkynyl optionally Sub 15 R’, a C-C, alkylene chain to form a 5- to 8-membered ring stituted with R', “(C-C) alkynyl optionally substituted together with the nitrogen atom attached to R' and R. with R" or “(C-C) alkynyl optionally substituted with wherein the alkylene chain may contain an oxygen atom or R” herein means a previously mentioned alkynyl group sulfur atom' or “R” may form, together with R', a C-C, containing from a to b carbon atoms in which hydrogen alkylene chain to form a 3- to 6-membered ring together atom(s) on carbon atom(s) are optionally Substituted with with the nitrogen atom attached to R' and R', wherein the optional R. R. or R, and those within the designated alkylene chain may contain an oxygen atom, Sulfur atom or carbon atom range are selected. When there are two or more nitrogen atom' is specifically exemplified by aziridine, Rs. Rs or R's on a (C-C) alkynyl group, each R, aZetidine, pyrrolidine, oxazolidine, thiazolidine, imidazoli R or R may be identical with or different from one dine, piperidine, morpholine, thiomorpholine, thiomorpho another. 25 line-1-oxide, thiomorpholine-1,1-dioxide, piperazine, The expression “R may form, together with R', a C-Cs homopiperidine, heptamethyleneimine or the like, and those alkylene chain to form a 3- to 6-membered ring together within the designated carbon atom range are selected. with the carbon atom attached to R and R, wherein the The expression such as “R” may form, together with R', alkylene chain may contain an oxygen atom, Sulfur atom or a C-C alkylene chain to form a 5- to 7-membered ring nitrogen atom' is specifically exemplified by a cyclopropane 30 together with the carbon atom attached to R* and R', ring, a cyclobutane ring, a cyclopentane ring, a tetrahydro wherein the alkylene chain may contain an oxygen atom or furan ring, a tetrahydrothiophene ring, a pyrrolidine ring, a sulfur atom” or "R" may form, together with R', a C-C, cyclohexane ring, a tetrahydropyran ring, a tetrahydrothio alkylene chain to form a 4- to 6-membered ring together pyran ring, a piperidine ring, a cycloheptane ring, an with the carbon atom attached to R* and R', wherein the OXepane ring, a thiepane ring, an azepane ring or the like, 35 alkylene chain may contain an oxygen atom, Sulfur atom or and those within the designated carbon atom range are nitrogen atom' is specifically exemplified by cyclopentyl selected. idene, tetrahydrofuran-3-ylidene, tetrahydrothiophen-3- The expression such as “R” may form, together with R', ylidene, cyclohexylidene, tetrahydropyran-3-ylidene, tetra a C-C alkylene chain to form a 3- to 7-membered ring hydropyran-4-ylidene, tetrahydrothiopyran-3-ylidene, together with the nitrogen atom attached to R and R. 40 tetrahydrothiopyran-4-ylidene or the like, and those within wherein the alkylene chain may contain an oxygen atom, the designated carbon atom range are selected. Sulfur atom or nitrogen atom, and may optionally be Sub As the preferred range of the substituent represented by stituted with an oxo group or a thioxo group”, “Rand R' G' in the compounds which fall within the present invention, together may form a C-C alkylene chain to form a 5- to the following sets may, for example, be mentioned. 6-membered ring together with the nitrogen atom attached to 45 G-I: G-1 wherein X is a bromine atom, an iodine atom, R* and R, wherein the alkylene chain may contain an methyl, difluoromethyl or trifluoromethyl, and X, X, X* oxygen atom, Sulfur atom or nitrogen atom, and may option and X are hydrogen atoms). ally be substituted with an oxo group or a thioxo group'. G'-II: G-1 wherein X" is a chlorine atom, and X, X, “R” may form, together with R', a C-C alkylene chain to X and X are hydrogen atoms. form a 3- to 7-membered ring together with the nitrogen 50 G'-III: G-2 wherein X" is a halogen atom, methyl or atom attached to R and R', wherein the alkylene chain trifluoromethyl, and X, X and X are hydrogen atoms). may contain an oxygen atom, Sulfur atom or nitrogen atom, G-IV: G-3 wherein X is a halogen atom or trifluorom and may optionally be substituted with an oxo group or a ethyl, and X, X and X’ are hydrogen atoms). thioxo group” or “R may form, together with R', a C-C, G-V: G-7 wherein X is trifluoromethyl, and X and X* alkylene chain to form a 3- to 6-membered ring together 55 are hydrogen atoms. with the nitrogen atom attached to R and R, wherein the G-VI: G-11 wherein X is a halogen atom, methyl or alkylene chain may contain an oxygen atom, Sulfur atom or trifluoromethyl, and X and X’ are hydrogen atoms). nitrogen atom, and may optionally be substituted with an G-VII: G-12 wherein X" is a halogen atom or trifluo oxo group' is specifically exemplified by aziridine, aZeti romethyl, and X and X are hydrogen atoms. dine, aZetidin-2-one, pyrrolidine, pyrrolidin-2-one, oxazoli 60 G-VIII: G-16 wherein X is trifluoromethyl, X and X* dine, oxazolidin-2-one, oxazolidine-2-thione, thiazolidine, are hydrogen atoms, and R is methyl). thiazolidin-2-one, thiazolidine-2-thione, imidazolidine, imi G-IX: G-27 wherein X is difluoromethyl or trifluo dazolidin-2-one, imidazolidine-2-thione, piperidine, piperi romethyl, X is a hydrogen atom, and R is methyl). din-2-one, piperidine-2-thione, 2H-3,4,5,6-tetrahydro-1,3- G-X: G-33 wherein X is difluoromethyl or trifluorom oxazin-2-one, 2H-3,4,5,6-tetrahydro-1,3-oxazine-2-thione, 65 ethyl, and X is methyl). morpholine, 2H-3,4,5,6-tetrahydro-1,3-thiazin-2-one, 2H-3, G-XI: G-1 wherein X is nitro, and X, X, X and X 4.5,6-tetrahydro-1,3-thiazine-2-thione, thiomorpholine, are hydrogen atoms. US 9,434,684 B2 35 36 G-XII: G-1 wherein X is trifluoromethyl, X and X G-XLI: G-31 wherein X is trifluoromethyl, and X is are hydrogen atoms, X is a halogen atom, and X is a a halogen atom or methyl. hydrogen atom. G'-XLII: G-32 wherein X is a halogen atom, difluo G-XIII: G-9 wherein X is methyl or trifluoromethyl, romethyl or trifluoromethyl, and X is a hydrogen atom or X is a hydrogen atom, and X is methyl. methyl. G'-XIV: G-27 wherein X" is a halogen atom or trifluo G'-XLIII: G-33 wherein X" is a halogen atom, methyl, romethyl, X is a halogen atom, and R is methyl). difluoromethyl or trifluoromethyl, and X is a hydrogen G-XV: G-32 wherein X and X’ are methyl). atom, a halogen atom, C-C alkyl, C-C haloalkyl, C-C, G-XVI: G-50 wherein X is trifluoromethyl, and r is 0. cycloalkyl, C-C alkoxy or —NH. 10 G-XLIV: G-41 and G-43 wherein X is trifluorom G'-XVII: G-1 wherein X" is a fluorine atom, cyano, ethyl. C-C alkoxy, C-C haloalkoxy, C-C alkylthio or phenyl, G-XLV: G-45, G-46, G-49 and G-51 wherein X is and X, X, X and X are hydrogen atoms). methyl or trifluoromethyl. G'-XVIII: G-1 wherein X" is a halogen atom, methyl or G-XLVI: G-50 wherein X is methyl or trifluorom trifluoromethyl, X is a hydrogen atom or a halogen atom, 15 ethyl, and r is an integer of from 0 to 2. X and X’ are hydrogen atoms, and X is a hydrogen atom Among them, as the scope of the Substituent represented or a halogen atom. by G', more preferred are G-I to G-XVI, G-XXIX, G-XIX: G-2 wherein X is a halogen atom, X is a G-XXX, G-XXXII to G-XXXVII and G-XLII, particu hydrogen atom, X is trifluoromethyl, and X is a hydrogen larly preferred are G-I to G-X. atom. As the preferred range of the substituent represented by G-XX: G-4 wherein X is trifluoromethyl, and X, X G’ in the compounds which fall within the present invention, and X are hydrogen atoms. the following sets may, for example, be mentioned. G-XXI: G-8 wherein X" is a halogen atom or methyl, G-I: G-1 wherein Y is a halogen atom, Y is a and X and X’ are hydrogen atoms). hydrogen atom, Y is a halogen atom or methyl, and Y and G-XXII: G-9 wherein X is trifluoromethyl, X is a 25 Y are hydrogen atoms). hydrogen atom, and X is phenyl). G-II: G-2 wherein Y is a halogen atom, Y is a G'-XXIII: G-13 wherein X" is a halogen atom, and X hydrogen atom or a halogen atom, Y is a halogen atom, and X’ are hydrogen atoms). cyano, trifluoromethyl, C-C haloalkoxy, —C(R')= G-XXIV: G-20 wherein X is trifluoromethyl, and X NOR', C-C alkynyl, cyclopropylethynyl, trimethylsilyl is a hydrogen atom. 30 ethynyl or phenylethynyl, Y is a hydrogen atom or a G-XXV: G-30 wherein X is trifluoromethyl, and X is halogen atom, R' is methyl, and R' is methyl or ethyl). methyl). G-III: G-1 wherein Y and Y are hydrogen atoms, Y G-XXVI: G-33 wherein X and X’ are trifluoromethyl is a halogen atom or methyl, and Y and Y are hydrogen atoms. G-XXVII: G-44 wherein X is trifluoromethyl, and R 35 G°-IV: G-1 wherein Y is a hydrogen atom, Y and Y is C-C alkyl. together may form —CH=CHCH=CH- to form a G-XXVIII: G-1 wherein X is C-C alkyl, C-C, 6-membered ring together with the carbon atoms attached to haloalkyl, C-C cycloalkyl, Ca haloalkylthio. —NH2 or Y° and Y, and Y and Y are hydrogen atoms). D-3, X, X, X and X are hydrogen atoms, and n is 0. G-V: G-1 wherein Y is a halogen atom, methyl, G-XXIX: G-2 wherein X is difluoromethyl, and X, 40 trifluoromethyl or methoxy, Y is a hydrogen atom or a X and X are hydrogen atoms). halogen atom, Y is a hydrogen atom, a halogen atom, G-XXX: G-3 wherein X is methyl, and X, X and X* methyl, trifluoromethyl, C-C alkoxy, —C(R')=NOR'', are hydrogen atoms. C-C alkenyl, phenyl or D-7. Y is a hydrogen atom or a G-XXXI: G-5 wherein X is trifluoromethyl, and X* halogen atom, Y is a hydrogen atom or a halogen atom, Z and X are hydrogen atoms). 45 is trifluoromethyl, R' is methyl, R' is methyl or ethyl, and G'-XXXII: G-7 wherein X" is a halogen atom or n is 1. methyl, and X and X’ are hydrogen atoms. G-VI: G-2 wherein Y is a halogen atom, Y is a G-XXXIII: G-8 wherein X is trifluoromethyl, and X hydrogen atom, Y is methyl, C-C alkoxy, C-C alkenyl, and X’ are hydrogen atoms). (C-C)alkynyl substituted with R. D-3 or D-7. Y is a G-XXXIV: G'-9 and G-12 wherein X is difluorom 50 hydrogen atom, R is a halogen atom, C-C cycloalkyl, ethyl, and X and X are hydrogen atoms). —OH, trimethylsilyl or phenyl, and n is 0. G-XXXV: G-10 and G-13 wherein X is difluorom G-VII: G-2 wherein Y is a halogen atom, Y is cyano, ethyl or trifluoromethyl, and X and X’ are hydrogenatoms). Y is a halogen atom, and Y is a hydrogen atom). G-XXXVI: G-11 wherein X is difluoromethyl, and X G-VIII: G-6 wherein Y and Y are halogen atoms, and and X’ are hydrogen atoms. 55 Y is a hydrogen atom). G-XXXVII: G-16 wherein X is difluoromethyl or G°-IX: G°-9 wherein Y is a halogen atom, Y is a trifluoromethyl, X and X’ are hydrogen atoms, and R is hydrogenatom or a halogen atom, and Y is a halogen atom). C-C alkyl. G-X: G°-10 wherein Y is a halogen atom, Y is a G-XXXVIII: G'-19 and G-23 wherein X is difluo hydrogen atom or a halogen atom, and Y is a hydrogen romethyl or trifluoromethyl, and X is a hydrogen atom). 60 atom. G-XXXIX: G-27 wherein X is a halogen atom, C-C, G-XI: G-1 wherein Y and Y are hydrogen atoms, Y alkyl, C-C haloalkyl or C1-C4 alkoxy, X is a hydrogen is C-C alkyl, C-C haloalkyl, C-C haloalkoxy, phenoxy atom, a fluorine atom or a chlorine atom, and R is C-C, or phenyl, and Y and Y are hydrogen atoms. alkyl). G-XII: G°-1 wherein Y is a hydrogen atom, Y’ is a G'-XL: G-27 wherein X" is C-C alkyl or C-C, 65 halogen atom or C-C alkoxy, Y is a hydrogen atom or a haloalkyl, X is a hydrogen atom, and R is C1-C4 alkyl, halogen atom, Y is a hydrogen atom, a halogen atom or C-C haloalkyl or C-C cycloalkyl. trifluoromethyl, and Y is a hydrogen atom). US 9,434,684 B2 37 38 G-XIII: G-1 wherein Y is a halogen atom, E-9 or tuting carbon atoms may optionally be substituted with a —C(R')—NOR'', Y is a hydrogenatom, or Y may form, halogenatom or methyl, and Y and Y are hydrogenatoms. together with Y', -CH=CHCH=CH- to form a 6-mem G-XXII: G-1 wherein Y is a halogen atom, methyl or bered ring together with the carbonatoms attached to Y and methoxy, Y is a hydrogen atom, Y is a hydrogen atom, a Yi, Y is a hydrogen atom, a halogen atom, cyano, C-C, halogen atom, methyl or trifluoromethyl, Y is a halogen alkylthio, C-C alkylsulfinyl, C-C alkylsulfonyl, —C(O) atom, methyl or methoxy, or Y may form, together with Y, R', M-7, phenyl substituted with (Z), D-3 or D-7. Y is a —OCHO or —OCH2CH2O to form a 5-membered hydrogen atom or trifluoromethyl, Y is a hydrogen atom, Z. ring or a 6-membered ring together with the carbon atoms is trifluoromethoxy, R' is a hydrogen atom or C-C alkyl, attached to Y and Y, wherein hydrogen atoms on the R'' is C-C alkyl, R'' is methyl, m is 1, n is 0, and p is an 10 respective ring-constituting carbon atoms may optionally be integer of from 0 to 2. substituted with a halogen atom or methyl, and Y is a G-XIV: G-2 wherein Y is a hydrogen atom, a halogen hydrogen atom. atom, trifluoromethyl or methoxy, Y is a hydrogenatom, Y G-XXIII: G-1 wherein Y is a halogenatom, methyl or is a halogen atom, C-C haloalkyl, C-C alkoxymethyl, 15 trifluoromethyl, Y is a hydrogenatom or a halogenatom, Y —OR or D-22, Y is a hydrogen atom or methoxy, R is is a hydrogen atom, a halogen atom, C-C alkyl, trifluo phenyl or phenyl Substituted with (Z), Z is a halogen atom, romethyl or methoxy, Y is a hydrogen atom, and Y is a m is 1, and n is 0. halogen atom or methyl. G-XV: G’-3 wherein Y is a halogen atom, each of Y G-XXIV: G’-2 wherein Y is cyano, nitro, difluo and Y is independently a hydrogen atom or a halogen atom, romethoxy, trifluoromethoxy or methylthio. Y is a hydro and Y is a hydrogen atom). gen atom, Y is a halogen atom, C-C alkyl or trifluorom G-XVI: G°-11 wherein Y is a halogen atom, Y is ethyl, and Y is a hydrogen atom). C-C alkoxy, and R is methyl. G-XXV: G-2 wherein Y is a halogen atom, methyl or G-XVII: G’-12 wherein Y is trifluoromethyl, Y is a trifluoromethyl, Y is cyano, methyl, C1-C4 alkoxy, C-C, hydrogen atom, and R is methyl). 25 haloalkoxy or C-C alkylthio. Y is a halogen atom, methyl G-XVIII: G-17 wherein Y and Y are halogenatoms. or trifluoromethyl, and Y is a hydrogen atom. G-XIX: G°-1 wherein Y is a hydrogen atom, Y’ is a G-XXVI: G-2 wherein Y is a halogen atom, methyl or hydrogen atom, a halogen atom, methyl, trifluoromethyl, trifluoromethyl, Y is a hydrogen atom, Y is a halogen C-C alkoxy, C1-C4 haloalkoxy or phenoxy, Y is a hydro atom, cyano, nitro, methyl, difluoromethyl, trifluoromethyl, gen atom, a halogen atom, cyano, nitro, C-C alkyl, C-C, 30 C-C alkoxy, C-C haloalkoxy, C-C alkylthio. —N(R) haloalkyl, C-C cycloalkyl, C-C alkoxy, C-C, R, C(R')—NOR'', M-3, C(O)NH, C(S)NH, haloalkoxy or C-C haloalkylthio, or Y may form, together —SON(CH), C-C alkynyl, (C-C)alkynyl substituted with Y?, —OCHO , –OCHCHO or with R, D-11, D-28 or D-29, Y is a hydrogen atom, R is —CH=CHCH=CH to form a 5-membered ring or a a halogen atom, C-C cycloalkyl, hydroxy(C-C)cy 6-membered ring together with the carbon atoms attached to 35 cloalkyl, C-C alkenyl, C-C cycloalkenyl, -OH, C-C, Y and Y, wherein hydrogen atoms on the respective alkoxy, C-Chaloalkoxy, C-C alkylthio, C-C alkylsulfi ring-constituting carbon atoms may optionally be substi nyl, alkylsulfonyl, -Si(R')(R')R'', phenyl, phenyl sub tuted with a halogen atom or methyl, Y is a hydrogen atom, stituted with (Z), D-1, D-2, D-4, D-12 or D-32, RandR a halogen atom, methyl or trifluoromethyl, and Y is a together may form a C-C alkylene chain to form a 5- to hydrogen atom. 40 6-membered ring together with the nitrogenatom attached to G-XX: G-1 wherein Y is a halogen atom, methyl or R and R, wherein the alkylene chain may contain an trifluoromethyl, Y is a hydrogen atom, Y is cyano, nitro, oxygen atom or sulfur atom, R' is a hydrogen atom or OR7, S(O), R7, C(R')—NOR'', C(O)NH, C-C alkyl, R' is C-C alkyl, R'' is C-C alkyl or phenyl, —C(S)NH2, C-C alkynyl or (C-C)alkynyl substituted each of R'' and R'' is independently a C-C alkyl, R'' is with R. Y and Y are hydrogen atoms, R is a halogen 45 C-C alkyl, Z is a halogen atom or C-C alkyl, m is an atom, C-C cycloalkyl, -OH, C-C alkoxy, C-C alkyl integer of 1 or 2, n is 0, and p is an integer of from 0 to 2. thio, C-C alkylsulfinyl, C-C alkylsulfonyl or - Si(R'') G-XXVII: G-3 wherein Y is a halogen atom or (R')R'', R’ is C-C haloalkyl, C-C haloalkenyl, C-C, methyl, Y is a halogen atom, methyl, trifluoromethyl or haloalkynyl, phenyl or phenyl substituted with (Z) R' is methoxy, Y is a halogen atom or cyano, and Y is a a hydrogen atom or C-C alkyl, R' is C-C alkyl, R'' is 50 hydrogen atom. C-C alkyl or phenyl, each of R'' and R'' is indepen G-XXVIII: G-4 wherein Y is a halogen atom or dently C-C alkyl, Z is a halogen atom, m is 1, and r is an methyl, Y is a hydrogen atom, Y is a halogen atom or integer of from 0 to 2. methoxy, and Y is a hydrogen atom). G-XXI: G-1 whereinY' is a halogenatom, C-C alkyl, G-XXIX: G-5 wherein Y is a halogen atom, methyl, C-C haloalkyl, C-C alkoxymethyl, C-C alkoxy, C-C, 55 difluoromethyl or trifluoromethyl, Y is a hydrogen atom, haloalkoxy, phenoxy or C-C alkylthio. Y is a hydrogen and Y is a halogen atom, methyl, trifluoromethyl or atom, methyl or methoxy, or Y may form, together with Y', methoxy. —OCHO or —OCH2CH2O to form a 5-membered G-XXX: G°-6 wherein each of Y and Y is indepen ring or a 6-membered ring together with the carbon atoms dently a halogen atom or methyl, and Y is a hydrogen atom attached to Y and Y, wherein hydrogen atoms on the 60 or methyl. respective ring-constituting carbon atoms may optionally be G-XXXI: G-7 wherein Y', Y and Y are halogen substituted with a halogen atom or methyl, Y is a hydrogen atoms. atom, a halogen atom, cyano, nitro, methyl or trifluorom G-XXXII: G-9 wherein Y is a halogen atom or ethyl, or Y may form, together with Y. —OCHO or methyl, Y is a hydrogenatom, a halogenatom or methyl, Y —OCHCHO to form a 5-membered ring or a 6-mem 65 is a halogen atom, or Y may form, together with Y, bered ring together with the carbon atoms attached to Y and —CH=CHCH=CH to form a 6-membered ring together Y, wherein hydrogen atoms on the respective ring-consti with the carbon atoms attached to Y and Y, wherein US 9,434,684 B2 39 40 hydrogen atoms on the respective ring-constituting carbon —C(O)R' or - C(O)CR'', R' is a hydrogen atom, C-C, atoms may optionally be substituted with a halogen atom. alkyl or cyclopropyl, R' is C-C alkyl or C-C haloalkyl, G-XXXIII: G-10 wherein Y is methyl, Y is a hydro and p is 0. gen atom, a halogen atom or methyl, and Y is a hydrogen R-VIII: (C-C)alkyl optionally substituted with R' atom. wherein R' is a halogen atom, C-C halocycloalkyl, G-XXXIV: G-10 wherein Y is a hydrogen atom or a C-C alkoxy, C-C haloalkoxy or C-C alkylthio. halogen atom, Y is a halogen atom, Y is a halogen atom, R-IX: (C-C)alkyl optionally substituted with R' or Y may form, together with Y. —CHCHCHCH or wherein R' is a halogen atom, E-2 to E-4, E-6, E-8, M-3, —CH=CHCH=CH to form a 6-membered ring together C(R)—NOR, C(O)NH, or C(S)NH R is with the carbon atoms attached to Y and Y, wherein 10 —C(O)R' or - C(O)CR'', R' is a hydrogen atom, C-C, hydrogen atoms on the respective ring-constituting carbon alkyl or cyclopropyl, R' is C1-C4 alkyl or C-C haloalkyl, atoms may optionally be substituted with a halogen atom. R7 is C-C alkyl, R is a hydrogen atom or methyl, R is G-XXXV: G’-14 wherein Y is methyl, and Y is C-C alkyl or C-C haloalkyl, p is an integer of from 0 to trifluoromethyl. 2, and r is an integer of from 0 to 2. 15 R'-X: (C-C)alkyl optionally substituted with R' G-XXXVI: G-16 and G™-17 wherein Y is methyl, and wherein R' is a halogen atom, phenyl substituted with Y is a halogen atom or trifluoromethyl). (Z), D-2, D-4, D-6, D-8, D-9, D-12, D-14, D-15 or D-17, Among them, as the scope of the Substituent represented R" is methyl, Z is a halogen atom, methyl, ethyl, trifluo by G', more preferred are G--I to G°-X, G°-XX, romethyl, difluoromethoxy, methylthio, methylsulfinyl, G-XXVIII, G-XXIX and G°-XXX, particularly preferred methylsulfonyl, trifluoromethylsulfinyl or trifluoromethyl are G-I and G-II. Sulfony, when m and n are 2, the respective Z's may be In the compounds which fall within the present invention, identical with or different from each other, m is an integer of the substituent represented by W may be an oxygen atom or 1 or 2, and n is an integer of from 0 to 2. a Sulfur atom, and W is preferably an oxygen atom. Among them, as the scope of the Substituent represented As the preferred range of the substituent represented by 25 by R', more preferred are R'-I to R'-IV, particularly pre R" in the compounds which fall within the present invention, ferred are R-I and R-II. the following sets may, for example, be mentioned. As the preferred range of the substituent represented by R-I: C-C alkyl, (C-C)alkyl substituted with R' R’ in the compounds which fall within the present invention, wherein R' is C-C cycloalkyl or trimethylsilyl), C-C, the following sets may, for example, be mentioned. cycloalkyl, C-C alkenyl and C-C alkynyl. 30 R-I: A hydrogen atom. R'-II: C-C haloalkyl, (C-C)alkyl substituted with R' R-II: Methyl wherein R is phenyl, phenyl substituted with (Z), or R-III Ethyl. D-32, Z is a halogen atom, cyano, nitro, methyl, trifluorom R-IV: C-C alkyl and phenyl. ethyl or trifluoromethoxy, when m is an integer of at least 2, R-V: Fluoromethyl and trifluoromethyl. the respective Z's may be identical with or different from 35 R-VI: Methoxymethyl, methylthiomethyl, methylsulfi one another, m is an integer of from 1 to 3, and n is 1, and nylmethyl and methylsulfonylmethyl. C-C haloalkenyl. R-VII: Cyclopropyl and cyclobutyl. R-III: (C-C)alkyl substituted with R' wherein R is Among them, as the scope of the Substituted represented cyano, E-5, C-C alkoxy, C-C alkylthio. —C(R)= by R, more preferred are R-I to R-III and R-V, particu NOR, D-5 or D-10, R is methyl, R is methyl or ethyl, 40 larly preferred are R-I and R-II. Z is a halogen atom or methyl, n is an integer of 0 or 1, and As the scope of the substituent represented by R in the p is 0, and phenyl. compounds which fall within the present invention, the R-IV: (C-C)alkyl substituted with R' wherein R' is following sets may, for example, be mentioned. phenyl Substituted with (Z), or D-32, Z is a halogen atom, R-1: A hydrogen atom. C-C alkyl, methoxy, trifluoromethylthio or phenyl, when 45 R-II: Methyl. m and n are 2, the two Z's may be identical with or different R-III: R forms a cyclopropyl ring together with R. from each other, and when there are two neighboring Z’s, the R-IV: R forms, together with R', a C-C alkylene chain two neighboring Z's may form —CH=CH-CH=CH to to form a 4- to 6-membered ring together with the carbon form a 6-membered ring together with the carbon atoms atom attached to R and R. attached to the Z’s, m is an integer of 1 or 2, and n is an 50 R-V: C-C alkyl. integer of from 0 to 2. R-VI: R form, together with R', a C-Cs alkylene chain R-V: (C-C)alkyl substituted with R' wherein R is to form a 3- to 6-membered ring together with the carbon E-9, —C(R')—NOR, M-4, C-C alkoxycarbonyl, C-C, atom attached to R and R, wherein the alkylene chain haloalkylaminocarbonyl or D-1, R’ is a hydrogen atom or contains an oxygen atom or Sulfur atom. C-C alkyl, R is C-C alkyl, Z is methyl or trifluorom 55 Among them, as the scope of the Substituent represented ethyl, n is 1, and p is 0, E-2 wherein p is O and E-14 by R, more preferred are R-I to R-III, and particularly wherein p is 0. preferred is R-I. R'-VI: C-C halocycloalkyl and C-C haloalkynyl. As the scope of the substituent represented by R' in the R-VII: E-3 wherein p is 0, and r is an integer of from 0 compounds which fall within the present invention, the to 2), E-4 wherein R' is C(O)R' or C(O)OR'', R' 60 following sets may, for example, be mentioned. is a hydrogen atom, C-C alkyl or cyclopropyl, R' is C-C, R-I: A hydrogen atom. alkyl or C-C haloalkyl, and p is 0, E-5 wherein p is 0. R-II: C-C alkylcarbonyl. E-6 wherein p is 0, and r is an integer of from 0 to 2, E-8 R-III: C-C alkoxycarbonyl. wherein R' is –C(O)R' or -C(O)OR'', R' is a hydro R-IV: C-C haloalkylthio. gen atom, C-C alkyl or cyclopropyl, R' is C-C alkyl or 65 R-V: C-C alkyl, (C-C)alkyl substituted with R' C-C haloalkyl, and p is 0, E-15 wherein p is 0, and r is wherein R' is cyano or C-C alkoxyl, cyclopropyl, allyl an integer of from 0 to 2), and E-17 wherein R' is and propargyl.

US 9,434,684 B2 45 46 TABLE 1-continued Chive (Allium Schoenoprasum var. foliosum). Oriental garlic (Allium tuberosum), Scallion (Alliumxwakegi), etc., the fam G R2 G2 RI ily Asparagaceae such as Asparagus (Asparagus officinalis). Gl-XXXVII R2- G2 R etc., the family Arecaceae subfamily Arecoideae such as Gl-XXXVII R2- G2 R Coconut palm (Cocos nucifera), Oil palm (Elaeis quineen Gl-XXXVII R2- G2 R-II sis), etc., the family Arecaceae the Subfamily Coryphoideae G-XXXVII R2- G2 R-II Gl-XXXVIII R2- G2 R Such as Date palm (Phoenix dactylifera), etc., the family G-XXXIX R2- G2 R Bromeliaceae such as Pineapple (Ananas Comosus), etc., the G-XL R2- G2 R family Poaceae subfamily Ehrhartoideae such as Rice G-XLI R2- G2 R 10 (Oryza sativa), etc., the family Poaceae subfamily Pooideae G-XLI R2- G2 R G-XLII R2- G2- R Such as Bent grass (Agrostis spp.), Blue grass (Poa spp.), G-XLII R2- G2- R-II Barley (Hordeum vulgare). Wheat (Triticum aestivum, T. G-XLII R2- G2 R durum), Rye (Secale cereale), etc., the family Poaceae G-XLII R2- G2 R Subfamily Chloridoideae Such as Bermuda grass (Cynodon G-XLII R2- G2 R-II G-XLII R2- G2 R-II 15 dactylon), Grass (Zoysia spp.), etc., the family Poaceae G-XLIII R2- G2 R Subfamily Panicoideae Such as Sugarcane (Saccharum offi G-XLIII R2- G2 R cinarum), Sorgum (Sorghum bicolor), Corn (Zea mays), etc., G-XLIII R2- G2 R the family Musaceae such as Banana (Musa spp.), etc., the G-XLIV R2- G2 R G-XLV R2- G2 R family Zingiberaceae Such as Myoga (Zingiber mioga), Gl-XLVI R2- G2 R Ginger (Zingiber officinale), etc. Plants of the group belonging to the family Nelumbonaceae such as Lotus root (Nelumbo nucifera), etc., Some of the compounds of the present invention repre the family Fabaceae such as Peanut (Arachis hypogaea), sented by the formula (I) can be converted, by ordinary Chickpea (Cicer arietinum), Lentil (Lens culinaris), Pea methods, to acid addition salts with hydrogen halides Such 25 (Pisum sativum), Broad bean (Vicia faba), Soybean (Glycine as hydrofluoric acid, hydrochloric acid, hydrobromic acid max), Common bean (Phaseolus vulgaris), Adzuki bean and hydroiodic acid, with inorganic acids Such as nitric acid, (Vigna angularis), Cowpea (Vigna unquiculata), etc., the Sulfuric acid, phosphoric acid, chloric acid and perchloric family Cannabaceae Such as Hop (Humulus lupulus), etc., acid, with Sulfonic acids such as methanesulfonic acid, the family Moraceae such as Fig Tree (Ficus carica), ethanesulfonic acid, trifluoromethanesulfonic acid, benze 30 Mulberry (Morus spp.), etc., the family Rhamnaceae such as nesulfonic acid and p-toluenesulfonic acid, with carboxylic Common jujube (Ziziphus jujuba), etc., the family Rosaceae acids such as formic acid, acetic acid, propionic acid, subfamily Rosoideae such as Strawberry (Fragaria), Rose trifluoroacetic acid, fumaric acid, tartaric acid, oxalic acid, (Rosa spp.), etc., the family Rosaceae subfamily Maloideae maleic acid, malic acid, Succinic acid, benzoic acid, man Such as Japanese loquat (Eriobotrya japonica), Apple delic acid, ascorbic acid, lactic acid, gluconic acid and citric 35 (Malus punila), European Pear (Pyrus communis), Nashi acid, with amino acids such as glutamic acid and aspartic Pear (Pyrus pyrifolia var. culta), etc., the family Rosaceae acid. Subfamily Prunoideae Such as Peach (Amygdalus persica), Some of the compounds of the present invention repre Apricot (Prunus armeniaca), Cherry (Prunus avium), Prune sented by the formula (I) can be converted, by ordinary (Prunus domestica), Almond (Prunus dulcis), Japanese methods, to metal salts with alkali metals such as lithium, 40 Apricot (Prunus mume), Japanese Plum (Prunus Salicina), Sodium and potassium, with alkaline earth metals such as Cerasus speciosa, CerasusXyedoensis Somei-yoshino, calcium, barium and magnesium, with metals such as alu etc., the family Cucurbitaceae such as Winter melon (Beni minum. incasa hispida), Watermelon (Citrullus lanatus), Bottle The pesticides herein mean fungicides and parasiticides gourd (Lagenaria Siceraria var. hispida), Luffa (Lufa cylin for controlling harmful pathogens and parasites which 45 drica), Pumpkin (Cucurbita spp.), Zucchini (Cucurbita infect/parasitize plants or animals. pepo), Bitter melon (Momordica charantia var. pavel), Plants herein mean grain, fruits and vegetables, cultivated Muskmelon (Cucumis melo), Oriental pickling melon (Cu as food for human, feed crop for livestock and poultry, cumis melo var. conomon), Oriental melon (Cucumis melo ornamental plants of which appearances are enjoyed, or var. makuwa), Cucumber (Cucumis sativus), etc., the family Tracheophyta Such as planting of parks, streets and the like, 50 Fagaceae Such as Japanese Chestnut (Castanea crenata), and specifically, the following plants may, for example, be etc., the family Juglandaceae Such as Walnut (Juglans spp.), mentioned, but the present invention is not restricted thereto. etc., the family Anacardiaceae such as Cashew (Anacardium Plants of the order Pinales belonging to the family occidentale), Mango (Mangifera indica), Pistachio (Pistacia Pinaceae such as Japanese Red Pine (Pinus densiflora), vera), etc., the family Rutaceae subfamily Rutoideae such as Scots Pine (Pinus Sylvestris), Japanese Black Pine (Pinus 55 Japanese pepper (Zanthoxylum piperitum), etc., the family thunbergii), etc. Rutaceae subfamily Aurantioideae such as Bitter orange Plants of the group Magnoliids belonging to the family (Citrus aurantium), Lime (Citrus aurantifolia), Hassaku Piperaceae such as pepper (Piper nigrum), etc., the family orange (Citrus hassaku), Yuzu (Citrus junos), Lemon (Cit Lauraceae such as Avocado (Persea americana), etc. rus limon), Natsumikan (Citrus natsudaidai), Grapefruit Plants of the group monocots belonging to the family 60 (Citrusxparadisi), Orange (Citrus sinensis), KaboSu (Citrus Araceae such as Konjac (Amorphophallus koniac), Eddoe sphaerocarpa), Sudachi (Citrus Sudachi), Mandarin Orange (Colocasia esculenta), etc., the family Dioscoreaceae Such (Citrus tangerina), Satsuma (Citrus unshiu), Kumquat (For as Chinese yam (Dioscorea batatas), Japanese yam (Di tunella spp.), etc., OsCorea japonica), etc., the family Alliaceae Such as Leek the family Such as Horseradish (Armoracia (Allium ampeloprasum var. porrum), Onion (Allium cepa). 65 rusticana), Mustard ( iuncea), Takana (Brassica Rakkyo (Allium chinense), Welsh onion (Allium fistulosum), juncea var. integrifolia), Rapeseed (Brassica napus), Cau Garlic (Allium sativum), Chives (Allium Schoenoprasum), liflower (Brassica oleracea var. botrytis), Cabbage (Bras US 9,434,684 B2 47 48 sica oleracea var. Capitata), Brussels sprout (Brassica olera griseus), etc., the family Muridae such as Mongolian gerbil cea var. gemmifera), Broccoli (Brassica oleracea var. (Meriones unguiculatus), House mouse (Mus musculus), italica), Green pak choi (Brassica raga var. Chinensis), Black rat (Rattus rattus), etc., the family Sciuridae such as Nozawana (Brassica raga var. hakabura), Napa cabbage Chipmunk (Tamias Sibiricus), etc., the family Camelidae ( var. nippo-oleifera), Potherb Mustard (Bras Such as Dromedary (Camelus dromedarius), Bactrian camel sica raga var. nipposinica), Napa cabbage (Brassica rapa (Camelus bactrianus), Alpaca (Vicuqna pacos), Llama var. pekinensis), leaf (Brassica raga var. perviridis), (Lama glama), etc., the family Suidae Such as Pig (Sus Turnip (Brassica rapa var. rapa), Garden rocket (Eruca scrofa domesticus), etc., the family Cervidae Such as Rein vesicaria), Daikon (Raphanus sativus var. longipinnatus), deer (Rangifer tarandus), Red deer (Cervus elaphus), etc., Wasabi (Wasabia japonica), etc., the family Caricaceae Such 10 the family Bovidae such as Yak (Bos grunniens), Cattle (Bos as Papaya (Carica papaya), etc., the family Malvaceae Such taurus), Water buffalo (Bubalus armee), Goat (Capra hir as Okra (Abelmoschus esculentus), Cotton (Gossypium cus). Sheep (Ovis aries), etc., the family Felidae such as Cat spp.), Cacao (Theobroma cacao), etc., the family Vitaceae (Felis silvestris catus), etc., the family Canidae such as Dog Such as Grape (Vitis spp.), etc., the family Amaranthaceae (Canis lupus familiaris), Red fox (Vulpes vulpes), etc., the Such as Sugar beet (Beta vulgaris ssp. vulgaris var. 15 family Mustelidae such as European mink (Mustela altissima), Table beet (Beta vulgaris ssp. vulgaris var. vul lutreola), American mink (Mustela vison), Ferret (Mustela garis), Spinach (Spinacia oleracea), etc., the family Polygo putorius firo), etc., the family Equidae Such as Donkey naceae Such as Buckwheat (Fagopyrum esculentum), etc., (Equus asinus), Horse (Equus cabalus), etc., the family the family Ebenaceae such as Kaki Persimmon (Diospyros Macropodidae Such as Red kangaroo (Macropus rufius), etc. kaki), etc., the family Theaceae scuh as Tea plant (Camellia Animals of the class Ayes belonging to the family Stru Sinensis), etc., the family Actinidiaceae such as Kiwifruit thionidae such as Ostrich (Struthio camelus), etc., the family (Actinidia deliciosa, A. chinensis), etc., the family Ericaceae Rheidae such as American rhea (Rhea americana), etc., the such as Blueberry (Vaccinium spp.), Cranberry (Vaccinium family Dromaiidae such as Emu (Dromaius novaehollan spp.), etc., the family Rubiaceae Such as Coffee plants diae), etc., the family Phasianidae Such as Ptarmigan (Lago (Coffea spp.), etc., the family Lamiaceae Such as Lemon 25 pus muta), Wild turkey (Meleagris gallopavo), Japanese balm (Melissa officinalis), Mint (Mentha spp.), Basil (Oci quail (Coturnix japonica), Chicken (Gallus gallus domesti mum basilicum), Shiso (Perilla frutescens var. Crispa), Per cus), Common pheasant (Phasianus colchicus), Golden illa frutescens var. frutescens, Common Sage (Salvia offi pheasant (Chrysolophus pictus), Indian peafowl (Pavo Cris cinalis), Thyme (Thymus spp.), etc., the family Pedaliaceae tatus), etc., the family Numididae Such as Helmeted guinea Such as Sesame (Sesamum indicum), etc., the family 30 fowl (Numida meleagris), etc., the family Anatidae such as Oleaceae such as Olive (Olea europaea), etc. the family Mallard (Anas platyrhynchos), Domesticated duck (Anas Convolvulaceae such as Sweet potato (Ipomoea batatas), platyrhynchos var. domesticus), Spot-billed duck (Anas etc., the family Solanaceae Such as Tomato (Solanum lyco poecilorhyncha), Greylag goose (Anser anser), Swan goose persicum), Eggplant (Solanum melongena), Potato (Sola (Anser cygnoides), Whooper Swan (Cygnus Cygnus), Mute num tuberosum), Chili pepper (Capsicum annuum), Bell 35 Swan (Cygnus Olor), etc., the family Columbidae Such as pepper (Capsicum annuum var. grossum), Tobacco (Nico Rock dove (Columba livia), Oriental turtle dove (Streptope tiana tabacum), etc., the family Apiaceae Such as Celery lia Orientalis), European turtle dove (Streptopelia turtur), (Apium graveolens var. dulce), Coriander (Coriandrum sati etc., the family Cacatuidae Such as Sulphur-crested cockatoo vum), Japanese honeywort (Cryptotaenia Canadensis Subsp. (Cacatua galerita), Galah (Eolophus roseicapilla), Cocka japonica), Carrot (Daucus carota Subsp. sativus), Parsley 40 tiel (Nymphicus hollandicus), etc., the family Psittacidae (Petroselium crispum), Italian parsley (Petroselinum nea Such as Rosy-faced lovebird (Agapornis roseicollis), Blue politanum), etc., the family Araliaceae Such as Udo (Aralia and-yellow macaw (Ara ararauna), Scarlet Macaw (Ara cordata), Aralia elata, etc., the family Subfamily macao), Budgerigar (Melopsittacus undulatus), African grey Carduoideae such as Artichoke (Cynara scolymus), etc., the parrot (Psittacus erithacus), etc., the family Sturnidae Such family Asteraceae subfamily Asteraceae Such as Chicory 45 as Common hill myna (Gracula religiosa), etc., the family (Cichorium intybus), Lettuce (Lactuca sativa), etc., the Estrildidae Such as Red avadavat (Amandava amandava), family Asteraceae subfamily Asteraceae such as Florists Zebra finch (Taeniopygia guttata), Bengalese finch (LOn daisy (Dendranthema grandiflorum), Crown daisy (Glebio chura striata var. domestica), Java sparrow (Padda nis coronaria), Sunflower (Helianthus annuus), Fuki (Peta Oryzivora), etc., the family Fringillidae Such as Domestic sites japonicus), Burdock (Arctium lappa), etc. 50 canary (Serinus canaria domestica), European goldfinch Animals herein mean human, companion creatures/pets, (Carduelis carduelis), etc. livestock/poultry, and vertebrate such as research/laboratory Animals of the class Reptilia belonging to the family animals, and specifically, the following animals may, for Chamaeleonidae such as Veiled chameleon (Chamaeleo example, be mentioned, but the present invention is not calyptratus), etc., the family Iguanidae such as Green iguana restricted thereto. 55 (Iguana iguana), Carolina anole (Anolis Carolinensis), etc., Animals of the class Mammalia belonging to the family the family Varanidae such as Nile monitor (Varanus niloti Cebidae Such as Tufted capuchin (Cebus apella), etc., the cus), Water monitor (Varanus Salvator), etc., the family family Cercopithecidae such as Crab-eating macaque Scincidae Such as Solomon islands skink (Corucia zebrata), (Macaca fascicularis), Rhesus macaque (Macaca mulata), etc., the family Colubridae such as Beauty rat Snake (Elaphe etc., the family Homimidae such as Chimpanzee (Pan 60 taeniura), etc., the family Boidae such as Boa constrictor troglodytes), Human (Homo sapiens), etc., the family Lep (Boa constrictor), etc., the family Pythonidae such as Indian oridae such as European rabbit (Oryctolagus cuniculus), python (Python molurus), Reticulated python (Python etc., the family Chinchillidae such as Long-tailed chinchilla reticulatus), etc., the family Chely dridae such as Common (Chinchilla lanigera), etc., the family Caviidae such as Snapping turtle (Chelvdra serpentina), etc., the family Emy Guinea pig (Cavia porcellus), etc., the family Cricetidae 65 didae Such as Diamondback terrapin (Malaclemy's terrapin), Such as Golden hamster (Mesocricetus auratus), Djungarian Pond slider (Trachemys scripta), etc., the family Geoemy hamster (Phodopus sungorus), Chinese hamster (Cricetulus didae Such as Japanese pond turtle (Mauremys japonica), US 9,434,684 B2 49 50 etc., the family Testudimidae such as Central Asian tortoise Alternaria alternata, A. brassicae, A. brassicicola, A. citri, (Agrionemy's horsfieldii), etc., the family Trionychidae Such A. dauci, A. helianthi, A. japonica, A. kikuchiana, A. mali, A. as Soft-shelled turtle (Pelodiscus sinensis), etc., the family panax, A. porri, A. radicina, A. Solani, etc.), Bipolaris spp. Alligatoridae Such as American alligator (Alligator missis (e.g. Bipolaris Sorghicola, etc.), Cochliobolus spp. (e.g. sippiensis), Black caiman (Melanosuchus niger), etc., the Cochliobolus heterostrophus, C. lunatus, C. miyabeanus, family Crocodylidae such as Siamese crocodile (Crocodylus etc.), Curvularia spp. (e.g. Curvularia geniculata, C. ver Siamensis), etc. ruculosa, etc.), Drechslera spp., Pleospora spp. (e.g. Pleo Animals of the class belonging to the spora herbarum, etc.), Pyrenophora spp. (e.g. Pyrenophora family Cyprimidae Such as Carp (Cyprinus carpio), Goldfish graminea, P. teres, etc.), Setosphaeria spp. (e.g. Setospha (Carassius auratus auratus), Zebrafish (Danio rerio), etc., 10 eria turcica, etc.), Stemphylium spp. (e.g. Stemphylium the family such as Kuhli ( kuhlii), botryosum, S. lycopersici, S. Solani, S. vesicarium, etc.), etc., the family Characidae such as Red piranha (Pygocen Fusicladium spp., Venturia spp. (e.g. Venturia carpophila, V. trus nattereri), Neon tetra (Paracheirodon innesi), etc., the Inaequalis, V nashicola, V. pirina, etc.), Didymella spp. (e.g. family Salmonidae such as Maraena whitefish (Coregonus Didymella bryoniae, D. fabae, etc.), Hendersonia spp., lavaretus maraena), Coho Salmon (Oncorhynchus kisutsh), 15 Phoma spp. (e.g. Phoma erratica var. mikan, P. exiqua var. Rainbow trout (Oncorhynchus mykiss), Chinook salmon exiqua, P. wasabiae, etc.), Pyrenochaeta spp. (e.g. Pyreno (Oncorhynchus tshawytscha), Atlantic salmon (Salmo Chaeta lycopersici, etc.), Stagonospora spp. (e.g. Stagono salar), Brown trout (Salmo trutta), etc., the family Percich spora sacchari, etc.). Botryosphaeria spp. (e.g. Botryospha thyidae such as Spotted sea bass (Lateolabrax maculatus), eria berengeriana f. sp. piricola, B. dothidea, etc.), etc., the family such as Sea goldie ( Dothiorella spp., Fusicoccum spp., Guignardia spp., Lasio squamipinnis), Longtooth (Epinephelus bruneus), diplodia spp. (e.g. Lasiodiplodia theobromae, etc.), Macro Convict grouper (Epinephelus Septemfasciatus), etc., the phoma spp., Macrophomina spp., Neofisicoccum spp., Phyl family Centrarchidae Such as Bluegill (Lepomis macrochi losticta spp. (e.g. Phyllosticta Zingiberis, etc.), rus), etc., the family Carangidae such as White trevally Schizothyrium spp. (e.g. Schizothyrium pomi, etc.), (Pseudocaranx dentex), Greater amberjack (Seriola 25 Acrospermum spp., Leptosphaerulina spp., Aspergillus spp., dumerili), Japanese amberjack (Seriola quinqueradiata), Penicillium spp. (e.g. Penicillium digitatum, P italicum, P etc., the family Sparidae Such as Red Sea bream (Pagrus sclerotigenum, etc.), Microsporum spp., Trichophyton spp. major), etc., the family Cichlidae such as Nile tilapia (Ore (e.g. Trichophyton mentagrophytes, T. rubrum, etc.). Histo ochromis niloticus), Angelfish (Pterophyllum scalare), etc., plasma spp., Blumeria spp. (e.g. Blumeria graminis f. sp. the family Scombridae such as Pacific bluefin tuna (Thunnus 30 hordei. B. g. f. sp. tritici, etc.), Erysiphe spp. (e.g. Erysiphe Orientalis), etc., the family Tetraodontidae such as Japanese betae, E. cichoracearum, E. C. Var. cichoracearum, E. hera pufferfish (Takifugu rubripes), etc. clei, E. pisi, etc.), Golovinomyces spp. (e.g. Golovinomyces Pathogens herein mean microorganisms which cause cichoracearum var. latisporus, etc.), Leveillula spp. (e.g. plant diseases and infections, and specifically, the Leveillula taurica, etc.), Microsphaera spp., Oidium spp. following microorganisms may, for example, be mentioned, 35 (e.g. Oidium neolycopersici, etc.), Phyllactinia spp. (e.g. but the present invention is not restricted thereto. Phyllactinia kakicola, P. mali, P. moricola, etc.), Podospha Fungi of the phylum Ascomycota, Such as Taphrina spp. era spp. (e.g. Podosphaera fisca, P. leucotricha, P. pannosa, (e.g. Taphrina deformans, T. pruni, etc.), Pneumocystis spp., P tridactyla var. tridactyla, P. xanthii, etc.), Sphaerotheca Geotrichum spp., Candida spp. (e.g. Candida albicans, C. spp. (e.g. Sphaerotheca aphanis var. aphanis, S. fitliginea, SOrbosa, etc.), Pichia spp. (e.g. Pichia kluyveri, etc.), 40 etc.), Uncinula spp. (e.g. Uncinula necator, U. n. Var. Geotrichum spp., Capnodium spp., Fumago spp., Hypocap necator, etc.), Uncinuliella spp. (e.g. Uncinuliella simulans nodium spp., Cercospora spp. (e.g. Cercospora apii, C. var. Simulans, U. S. Var. tandae, etc.), Blumeriella spp. (e.g. asparagi, C. beticola, C. capsici, C. carotae, C. kaki, C. Blumeriella jaapi, etc.), Cylindrosporium spp., Diplocar kikuchii, C. Zonata, etc.), Cercosporidium spp., Cladospo pon spp. (e.g. Diplocarpon mali, D. mespili, D. rosae, etc.), rium spp. (e.g. Cladosporium colocasiae, C. cucumerinum, 45 Gloeosporium spp. (e.g. Gloeosporium minus, etc.), C. variabile, etc.), Davidiella spp., Didymosporium spp., Marssonina spp., Tapesia spp. (e.g. Tapesia acuformis, T. Heterosporium spp. (e.g. Heterosporium allii, etc.), vallundae, etc.), Lachnum spp., Scleromitrula spp., Botryo Mycosphaerella spp. (e.g. Mycosphaerella arachidis, M. tinia spp. (e.g. Botryotinia fickeliana, etc.). Botrytis spp. berkeleyi, M. cerasella, M. fijiensis, M. fragariae, M. (e.g. Botrytis allii, B. byssoidea, B. cinerea, B. elliptica, B. graminicola, M. nawae, M. pinodes, M. pomi, M. Zingiberis, 50 fabae, B. squamosa, etc.), Ciborinia spp., Grovesinia spp., etc.), Mycovellosiella spp. (e.g. Mycovellosiella fulva, M. Monilia munecola, Monilinia spp. (e.g. Monilinia fructi nattrassii, etc.), Paracercospora spp. (e.g. Paracercospora cola, M. fructigena, M. laxa, M. mali, M. vaccini-corym egenula, etc.), Phaeoisariopsis spp., Phaeoranularia spp., bosi, etc.), Sclerotinia spp. (e.g. Sclerotinia borealis, S. Pseudocercospora spp. (e.g. Pseudocercospora abelmoschi, homoeocarpa, S. minor; S. Sclerotiorum, etc.), Valdensia P filligena, P. vitis, etc.), Pseudocercosporella spp. (e.g. 55 spp. (e.g. Valdensia heterodoxa, etc.), Claviceps spp. (e.g. Pseudocercosporella capselae, etc.), Ramichloridium spp., Claviceps sorghi, C. Sorghicola, etc.), Epichloe spp., Ephelis Ranularia spp., Septogloeum spp., Septoria spp. (e.g. Sep japonica, Villosiclava virens, Hypomyces spp. (e.g. Hypo toria albopunctata, S. apicola, S. chrysanthemella, S. myces Solani f.sp. mori, H. S. f. sp. pisi, etc.), Trichoderma helianthi, S. obesa, etc.), Sphaerulina spp., Aureobasidium spp. (e.g. Trichoderma viride, etc.), Calonectria spp. (e.g. spp., Kabatiella spp., Plowrightia spp., Stigmina spp., Elsi 60 Calonectria ilicicola, etc.), Candelospora spp., Cylindro noe spp. (e.g. Elsinoe ampelina, E. araliae, E. fawcettii, carpon spp., Cylindrocladium spp., Fusarium spp. (e.g. etc.). Sphacelona spp. (e.g. Sphacelona Caricae, etc.). Fusarium arthrosporioides, F. Crookwellense, F. culmorum, As Cochyta spp. (e.g. Ascochyta pisi, etc.). CorynespOra spp. F. cuneirostrum, F. Oxysporum, F. O. f. sp. adzukicola, F. O. (e.g. CorynespOra Cassicola, etc.), Leptosphaeria spp. (e.g. f. sp. alli, F. o. f. sp. asparaqi, F. o. f. sp. batatas, F. O. f. Leptosphaeria coniothyrium, L. maculans, etc.), Sacchari 65 sp. Cepae, F. o. f.sp. colocasiae, F. o. f.sp. conglutinans, F. cola spp., Phaeosphaeria spp., Ophiosphaerella spp., Seto O. f. sp. cubense, F. O. f. sp. cucumerinum, F. O. f. sp. fabae, phoma spp., Helminthosporium spp., Alternaria spp. (e.g. F. o. f. sp. fragariae, F. o. f. sp. lactucae, F. o. f. sp. US 9,434,684 B2 51 52 lagenariae, F. o. f. sp. lycopersici, F. o. f. sp. melongenae, Exobasidium spp. (e.g. Exobasidium reticulatum, E. vexans, F. o. f. sp. melonis, F. o. f. sp. melumbinicola, F. o. f. sp. etc.), Microstroma spp., Tilletia spp. (e.g. Tilletia caries, T. niveum, F. o. f. sp. radicis-lycopersici, F. o. f. sp. raphani, controversa, T. laevis, etc.). Itersonilia spp. (e.g. Itersonilia F. o. f.sp. spinaciae, F sporotrichioides, F. Solani, F. S. f.sp. perplexans, etc.), Cryptococcus spp., Bovista spp. (e.g. cucurbitae, F. S. f. sp. eumartii, F. S. f. sp. pisi, F. S. f. sp. 5 Bovista dermoxantha, etc.), Lycoperdon spp. (e.g. Lycoper radicicola, etc.), Gibberella spp. (e.g. Gibberella avenacea, don curtisii, L. perlatum, etc.), Conocybe spp. (e.g. Cono G. baccata, G. fijikuroi, G. Zeae, etc.), Haematonectria spp., cybe apala, etc.), Marasmius spp. (e.g. Marasmius Oreades, Nectria spp., Ophionectria spp., Caldariomyces spp., etc.), Armilaria spp., Helotium spp., Lepista spp. (e.g. Myrothecium spp., Trichothecium spp., Verticillium spp. Lepista subnuda, etc.), Sclerotium spp. (e.g. Sclerotium (e.g. Verticillium albO-atrum, V. dahliae, V. longisporum, 10 cepivorum, etc.), Tiphula spp. (e.g. Tiphula incarnata, T. etc.), Ceratocystis spp. (e.g. Ceratocystis ficicola, C. fim ishikariensis var. ishikariensis, etc.), Athelia spp. (e.g. Athe briata, etc.). Thielaviopsis spp. (e.g. Thielaviopsis basicola, lia rolfsii, etc.), Ceratobasidium spp. (e.g. Ceratobasidium etc.), Adisciso spp., Monochaetia spp., Pestalotia spp. (e.g. cornigerum, etc.), Ceratorhiza spp., Rhizoctonia spp. (e.g. Pestalotia eriobotrifolia, etc.), Pestalotiopsis spp. (e.g. Rhizoctonia Solani, etc.), Thanatephorus spp. (e.g. Thanate Pestalotiopsis fitnerea, P. longiseta, P. neglecta, P theae, 15 phorus cucumeris, etc.), Laetisaria spp., Waitea spp., Fomi etc.), Physalospora spp., Nemania spp., Nodulisporium spp., tiporia spp., Ganoderma spp., Chondrostereum purpureum, Rosellinia spp. (e.g. Rosellinia necatrix, etc.), Mono Phanerochaete spp., etc. graphella spp. (e.g. Monographella nivalis, etc.), Ophios Fungi of the phylum Chitridiomycota such as Olpidium toma spp., Cryphonectria spp. (e.g. Cryphonectria para spp., etc. sitica, etc.), Diaporthe spp. (e.g. Diaporthe citri, D. Fungi of the phylum Blastocladiomycota Such as Physo kyushuensis, D. nomurai, D. tanakae, etc.), Diaporthopsis derma spp., etc. spp., Phomopsis spp. (e.g. Phomopsis asparaqi, Pfukushii, Fungi of the phylum Mucoromycotina Such as Choane P. obscurans, P. vexans, etc.), Cryptosporella spp., Discula phora spp., Choanephoroidea cucurbitae, Mucor spp. (e.g. spp. (e.g. Discula theae-simensis, etc.), Gnomonia spp., Mucor fragilis, etc.), Rhizopus spp. (e.g. Rhizopus arrhizus, Coniella spp., Coryneum spp., Greeneria spp., Melanconis 25 R. Chinensis, R. Oryzae, R. Stolonifer var. Stolonifer, etc.), spp., Cytospora spp., Leucostoma spp., Valsa spp. (e.g. etc. Valsa ceratosperma, etc.), Tubakia spp., Monosporascus Protists of the phylum Cercozoa such as Plasmodiophora spp., Clasterosporium spp., Gaeumannomyces spp. (e.g. spp. (e.g. Plasmodiophora brassicae, etc.), Spongospora Gaeumannomyces graminis, etc.), Magnaporthe spp. (e.g. subterranea f. sp. subterranea, etc. Magnaporthe grisea, etc.), Pyricularia spp. (e.g. Pyricu 30 Microorganisms of the phylum Heterokontophyta class laria Zingiberis, etc.), Monilochaetes infiscans, Colletotri Oomycetes Such as Aphanomyces spp. (e.g. Aphanomyces chum spp. (e.g. Colletotrichum acutatum, C. capsici, C. cochlioides, A. raphani, etc.), Albugo spp. (e.g. Albugo cereale, C. destructivum, C. fragariae, C lindemuthianum, macrospora, A. Wasabiae, etc.), Bremia spp. (e.g. Bremia C. nigrum, C. Orbiculare, C. spinaciae, etc.), Glomerella lactucae, etc.), Hyaloperonospora spp., Peronosclerospora spp. (e.g. Glomerella cinquilata, etc.), Khuskia Oryzae, Phyl 35 spp., Peronospora spp. (e.g. Peronospora alliariae-wasabi, lachora spp. (e.g. Phyllachora ponigena, etc.), Ellisembia P. chrysanthemi-coronaria, P. destructor, Pfarinosa f. sp. spp., Briosia spp., Cephalosporium spp. (e.g. Cephalospo spinaciae, P. manshurica, P. parasitica, P. sparsa, etc.), rium gramineum, etc.), Epicoccum spp., Gloeocercospora Plasmopara spp. (e.g. Plasmopara halstedii, P. nivea, P Sorghi, Mycocentrospora spp., Peltaster spp. (e.g. Peltaster viticola, etc.), Pseudoperonospora spp. (e.g. PseudoperOno fructicola, etc.), Phaeocytostroma spp., Phialophora spp. 40 spora cubensis, etc.), Sclerophthora spp., Phytophthora spp. (e.g. Phialophora gregata, etc.), Pseudophloeosporella (e.g. Phytophthora cactorum, P capsici, P. citricola, P dioscoreae, Pseudoseptoria spp., Rhynchosporium spp. (e.g. citrophthora, P. cryptogea, P fragariae, P infestans, P Rhynchosporium secalis, etc.), Sarocladium spp., Coleop melonis, P. nicotianae, P. palmivora, P. porri, P. Sojae, P homa spp., Helicoceras Oryzae, etc. Fungi of the phylum syringae, P vignae f.sp. adzukicola, etc.), Pythium spp. (e.g. Basidiomycota, Such as Septobasidium spp. (e.g. Septoba 45 Pythium afertile, P aphanidermatum, P apleroticum, P sidium bogoriense, S. tanakae, etc.), Helicobasidium spp. aristosporum, P arrhenomanes, P. buismaniae, P debarya (e.g. Helicobasidium longisporum, etc.), Coleosporium spp. num, P. graminicola, P horinouchiense, P irregulare, P. (e.g. Coleosporium plectranthi, etc.), Cronartium spp., Pha iwayamai, P. myriotylum, P. Okanoganense, P. paddicum, P kopsora spp. (e.g. Phakopsora artemisiae, P. nishidana, P paroeCandrum, P. periplocum, P. spinosum, P sulcatum, P pachyrhizi, etc.), Physopella spp. (e.g. Physopella ampelop 50 sylvaticum, P. ultimum var. ultimum, P. vanterpoolii, P sidis, etc.), Kuehneola spp. (e.g. Kuehneola japonica, etc.), vexans, P. volutum, etc.), etc. Phragmidium spp. (e.g. Phragmidium fisiiforme, P. mucro Gram-positive bacteria of the phylum Actinobacteria such natum, P rosae-multiflorae, etc.), Gymnosporangium spp. as Clavibacter spp. (e.g. Clavibacter michiganensis Subsp. (e.g. Gymnosporangium asiaticum, G. yamadae, etc.), Puc michiganensis, etc.), Curtobacterium spp., Leifsonia spp. cinia spp. (e.g. Puccinia allii, P. brachypodii var. poae 55 (e.g. Leifsonia xyli Subsp. xyli, etc.), Streptomyces spp. (e.g. memoralis, P. coronata, P. c. Var. coronata, P Cynodontis, P Streptomyces ipomoeae, etc.), etc. graminis, P. g. Subsp. graminicola, P hordei, P horiana, P Gram-positive bacteria of the phylum Firmicutes such as Kuehnii, P. melanocephala, P. recondita, P Striiformis var. Clostridium sp., etc. Striiformis, P tanaceti var. tanaceti, P tokvensis, P. Zoysiae, Gram-positive bacteria of the phylum Tenericutes such as etc.), Uromyces spp. (e.g. Uromyces phaseolivar. azukicola, 60 Phytoplasma, etc. U. p. var. phaseoli, Uromyces viciae-fabae var. viciae-fabae, Gram-negative bacteria of the phylum Proteobacteria etc.), Naohidemyces vaccinii, Nyssopsora spp., Leucotelium Such as Rhizobium spp. (e.g. Rhizobium radiobacter, etc.), spp., Tranzschelia spp. (e.g. Tranzschelia discolor, etc.), Acetobacter spp., Burkholderia spp. (e.g. Burkholderia Aecidium spp., Blastospora spp. (e.g. Blastospora similacis, andropogonis, B. cepacia, B. gladioli, B. glumae, B. plan etc.), Uredo spp., Sphacelotheca spp., Urocystis spp., Spor 65 tarii, etc.), Acidovorax spp. (e.g. Acidovorax avenae Subsp. isorium spp. (e.g. Sporisorium scitamineum, etc.), Ustilago avenae, A. a. Subsp. citrulli, A. konjaci, etc.), Herbaspirillum spp. (e.g. Ustilago maydis, U. nuda, etc.). Entvloma spp., spp., Ralstonia spp. (e.g. Ralstonia Solanacearum, etc.). US 9,434,684 B2 53 54 Xanthomonas spp. (e.g. Xanthomonas albilineans, X. arbo dosphaera fusca), Powdery mildew (Podosphaera leucotri ricola pv. pruni, X. axonopodis pv. vitians, X. Campestris pv. cha), Powdery mildew (Podosphaera pannosa, Uncinuliella campestris, X. C. pv. cucurbitae, X. c. pv. glycines, X. C. pv. simulans var. Simulans, U. S. Var. tandae), Powdery mildew mangiferae indicae, X. c. pv. nigromaculans, X. c. pv. vesi (Podosphaera xanthii), Powdery mildew (Sphaerotheca catoria, X. citri Subsp. citri, X. Oryzae pv. Oryzae, etc.), 5 aphanis var. aphanis), Powdery mildew (Sphaerotheca Pseudomonas spp. (e.g. Pseudomonas cichorii, P. fluore fiuliginea), Powdery mildew (Uncinula necator, U. n. Var. scens, P. marginalis, P. m. pv. marginalis, P. Savastanoi pv. necator), Blotch (Diplocarpon mali), Black spot (Diplocar glycinea, P. Syringae, P. S. pv. actinidiae, P. S. pv. eriobot pon rosae), Gray mold neck rot (Botrytis allii), Gray mold, rvae, P. S. pv. helianthi, P. S. pv. lachrymans, P. S. pv. Botrytis light (Botrytis cinerea), Leaf blight (Botrytis maculicola, P. S. pv. mori, P. s. morsprunorum, P. S. pv. 10 cinerea, B. byssoidea, B. squamosa), Chocolate spot (Botry spinaciae, P. S. pv. Syringae, P. S. pv. theae, P viridiflava, tis cinerea, B. elliptica, B. fabae), Brown rot (Monilinia etc.), Rhizobacter spp., Brenneria spp. (e.g. Brenneria nigri fructicola, M. fructiqena, M. laxa), Blossom blight (Mo fluens, etc.), Dickeya spp. (e.g. Dickeya dianthicola, D. zeae, nilinia mali), Dollar spot (Sclerotinia homoeocarpa), Cot etc.), Erwinia spp. (e.g. Erwinia amylovora, E. rhapontici, tony rot, Sclerotinia rot, Stem rot (Sclerotinia sclerotiorum), etc.), Pantoea spp., Pectobacterium spp. (e.g. Pectobacte 15 False Smut (Villosiclava virens), Root necrosis (Calonectria rium atrosepticum, P. Carotovorum, P. wasabiae, etc.), etc. ilicicola), Fusarium light (Fusarium crookwellense, F. cul AS specific examples the plant diseases and animal infec morum, Gibberella avenacea, G. Zeae, Monographella niva tions caused by infection/proliferation of Such pathogens, lis), Fusarium light (Fusarium culmorum, Gibberella ave the following plant diseases and animal infections may, for nacea, G. Zeae), Dry rot (Fusarium oxysporum, F. Solani f. example, be mentioned, but the present invention is not 20 sp. radicicola), Brown rot (Fusarium oxysporum, F. Solani restricted thereto. f. sp. pisi, F. S. f. sp. radicicola), Fusarium wilt (Fusarium Plant Diseases: Oxysporum f.sp. adzukicola), Fusarium asal rot (Fusarium Leaf curl (Taphrina deformans), Plum pockets (Taphrina Oxysporum f.sp. alli, F. Solani f. sp. radicicola), Stem rot pruni), Leaf spot (Cercospora asparaqi), Cercospora leaf (Fusarium oxysporum f. sp. batatas, F. Solani), Dry rot spot (Cercospora beticola). Frogeye leaf spot (Cercospora 25 (Fusarium oxysporum f.sp. colocasiae), Yellows (Fusarium capsici), Angular leaf spot (Cercospora kaki), Purple stain Oxysporum f.sp. conglutinans), Panama disease (Fusarium (Cercospora kikuchii), Brown Leaf spot (Mycosphaerella Oxysporum f. sp. cubense), Fusarium wilt (Fusarium arachidis), Cylindrosporium leaf spot (Mycosphaerella Oxysporum f.sp. fragariae), Root rot (Fusarium oxysporum cerasella, Blumeriella jaapi), Speckled leaf blotch (My f. sp. lactucae), Fusarium wilt (Fusarium oxysporum f.sp. cosphaerella praminicola), Circular leaf spot (Mycosphaer 30 lagenariae, F. O.f. sp. niveum), Fusarium wilt (Fusarium ella nawae), Mycosphaerella light (Mycosphaerella Oxysporum f. sp. lycopersici), Fusarium wilt (Fusarium pinodes), Leaf spot (Mycosphaerella zinqiberis), Leaf mold Oxysporum f.sp. melonis), Yellows (Fusarium oxysporum f. (Mycovellosiella filva), Leaf mold (Mycovellosiella nat sp. raphani), Fusarium wilt (Fusarium oxysporum f. sp. trassii), Cercospora leaf mold (Pseudocercospora filligena), Spinaciae), Isariopsis leaf spot (Pseudocercospora vitis), Leaf spot 35 “Bakanae disease (Gibberella fujikuroi), Verticillium lack (Pseudocercosporella capselae), Leaf spot (Septoria chry spot (Verticillium albo-atrum, V. dahliae), Verticillium wilt Santhemella), Leaf blight (Septoria obesa), Anthracnose (Verticillium dahliae), Ceratocystis canker (Ceratocystis (Elsinoe ampelina), Spot anthracnose (Elsinoe araliae), ficicola), Black rot (Ceratocystis fimbriata), Gray blight Scab (Elsinoe fawcettii), Leaf spot (Ascochyta pisi), Coryne (Pestalotiopsis longiseta, P theae). Endothia canker (Cry spora leaf spot (Corynespora cassicola), Stem canker (Lep 40 phonectria parasitica), Melanose (Diaporthe citri), Stem tosphaeria Coniothyrium), Leaf spot (Alternaria alternata), blight (Phomopsis asparagi), Phomopsis canker (Phomopsis Leaf blight (Alternaria dauci), Black spot (Alternaria kiku fiukushi), Brown spot (Phomopsis vexans), Anthracnose chiana), Alternaria lotch (Alternaria mali). Alternaria leaf (Discula theae-simensis), Valsa canker (Valsa cera spot (Alternaria porri), Target spot (Bipolaris Sorghicola), tosperma), Blast (Magnaporthe grisea), Crown rot (Col Southern leaf blight (Cochliobolus heterostrophus), Brown 45 letotrichum acutatum, C. fragariae, Glomerella cingulata), spot (Cochliobolus miyabeanus), Tip blight (Pleospora her Bitter rot (Colletotrichum acutatum, Glomerella cingulata), barum), Stripe (Pyrenophora graminea), Net blotch Anthracnose (Colletotrichum acutatum, Glomerella Cingu (Pyrenophora teres), Leaf blight (Setosphaeria turcica), lata), Anthracnose (Colletotrichum acutatum), Ripe rot Northern leafblight (Setosphaeria turcica), Leaf spot (Stem (Colletotrichum acutatum, Glomerella Cingulata), Anthra phyllium botryosum), Scab (Venturia carpophila), Scab (Ven 50 cnose (Colletotrichum acutatum), Anthracnose (Colletotri turia linaequalis), Scab (Venturia nashicola), Gummy stem chum lindemuthianum), Anthracnose (Colletotrichum blight (Didymella bryoniae), Leaf spot (Phoma exigua var. orbiculare), Anthracnose (Glomerella cingulata), Anthra exigua), Streak (Phoma wasabiae), Ring rot (Botryospha cnose (Glomerella cingulata), Anthracnose (Glomerella cin eria berengeriana f. sp. piricola), Soft rot (Botryosphaeria gulata), Brown stem rot (Phialophora gregata), Leaf spot dothidea, Lasiodiplodia theobromae, Diaporthe sp.), Com 55 (Pseudophloeosporella dioscoreae), Scald (Rhynchospo mon green mold (Penicillium digitatum), Blue mold (Peni rium secalis), cillium italicum), Powdery mildew (Blumeria graminis f.sp. Rust (Phakopsora nishidana), Rust (Phakopsora pachy hordei), Powdery mildew (Blumeria qraminis f.sp. tritici), rhizi), Rust (Kuehneola japonica, Phragmidium fusiforme, Powdery mildew (Erysiphe betae, Leveillula taurica, P. mucronatum, P. rosae-multiflorae), Rust (Gymnosporan Oidium sp., Podosphaera xanthii), Powdery mildew (Ery 60 gium asiaticum), Rust (Gymnosporangium yamadae), Rust siphe cichoracearum, Leveillula taurica, Sphaerotheca (Puccinia allii), Rust (Puccinia horiana), Brown rust (Puc fiuliqinea), Powdery mildew (Erysiphe heraclei), Powdery cinia recondita), Rust (Puccinia tanaceti var. tanaceti), Rust mildew (Erysiphe pisi), Powdery mildew (Leveillula tau (Uromyces viciae-fabae var. viciae-fabae), Smut (Sporiso rica, Oidium neolycopersici, Oidium sp.), Powdery mildew rium scitamineum), Smut (Ustilago maydis), Loose Smut (Leveillula taurica), Powdery mildew (Oidium sp., 65 (Ustilago nuda), Net blister blight (Exobasidium reticula Podosphaera xanthii), Powdery mildew (Oidium sp.), Pow tum), Blister blight (Exobasidium vexans), Stem rot, South dery mildew (Phyllactinia kakicola), Powdery mildew (Po ern blight (Athelia rolfsii), Root and stem rot (Ceratoba US 9,434,684 B2 55 56 sidium cornigerum, Rhizoctonia Solani), (Rhizoctonia verrucosum). Histoplasmosis (Histoplasma capsulatum), Solani), Damping-off (Rhizoctonia Solani), Damping-off Cryptococcosis (Cryptococcus neoformans). (Rhizoctonia Solani), Bottom rot (Rhizoctonia Solani), Parasites herein mean plant-parasitic nematodes parasit Brown patch, Large patch (Rhizoctonia Solani), Sheath izing plants, animal-parasitic nematodes parasitizing ani blight (Thanatephorus cucumeris), Root rot/Leaf blight 5 mals, Acanthocephala, Platyhelminthes, Protozoa and the (Thanatephorus cucumeris), Rhizopus rot (Rhizopus stolo like, and specifically, the following parasites may, for nifer var. Stolonifer), Clubroot (Plasmodiophora brassicae), example, be mentioned, but the present invention is not Aphanomyces root rot (Aphanomyces cochlioides), White restricted thereto. rust (Albugo macrospora), Downy mildew (Bremia lactu Nematodes of the order Enoplida such as Giant kidney cae), Downy mildew (Peronospora chrysanthemi-coro 10 worm (Dioctophyma renale), Thread worms (Capillaria narii), Downy mildew (Peronospora destructor), Downy annulata), Cropworm (Capillaria contorta), Capillary liver mildew (Peronospora farinosa f. sp. spinaciae), Downy worm (Capillaria hepatica), Capillaria perforans, Capil mildew (Peronospora manshurica), Downy mildew (Per laria philippinensis, Capillaria suis, Whipworm (Trichuris onospora parasitica), Downy mildew (Peronospora discolor), Whipworm (Trichuris ovis), Pig whipworm (Tri sparsa), Downy mildew (Plasmopara halstedii), Downy 15 churis suis), Human whipworm (Trichuris trichiura), Dog mildew (Plasmopara nivea), Downy mildew (Plasmopara whipworm (Trichuris vulpis), Pork worm (Trichinella spi viticola), Downy mildew (Pseudoperonospora cubensis), ralis), etc. Phytophthora root rot (Phytophthora cactorum), Brown rot Nematodes of the order Rhabditida such as Intestinal (Phytophthora capsici), Phytophthora rot (Phytophthora threadworm (Strongyloides papillosus), Strongyloides plani capsici), Phytophthora light (Phytophthora capsici), Phy ceps, Pig threadworm (Strongyloides ransOmi). Threadworm tophthora rot (Phytophthora cryptogea), Late blight (Phy (Strongyloides stercoralis), Micronema spp., etc. tophthora infestans), White powdery rot (Phytophthora Nematodes of the order Strongylida such as Hookworm palmivora), Leaf blight (Phytophthora porri), Phytophthora (Ancylostoma braziliense), Dog hookworm (Ancylostoma root and stem rot (Phytophthora soiae), Phytophthora stem caninum), Old World hookworm (Ancylostoma duodenale), rot (Phytophthora vignae f. sp. adzukicola), Damping-off 25 Cat hookworm (Ancylostoma tubaeforme), The Northern (Pythium aphanidermatum, P. myriotylum, P. paroecan hookworm of dogs (Uncinaria Stenocephala), Cattle hook drum, P. ultimum var. ultimum), Root rot (Pythium aris worm (Bunostomum phlebotomum), Small ruminant hook tosporum), Browning root rot (Pythium arrhenomanes, P worm (Bunostomum trigonocephalum), New World hook graminicola), Damping-off (Pythium buismaniae, P. myrio worm (Necator americanus), Cyathostomum spp., tylum), Root rot (Pythium myriotylum), Root rot (Pythium 30 Cylicocyclus spp., Cylicodontophorus spp., Cylicostephanus myriotylum, P. ultimum var. ultimum), Brown blotted root rot spp., Strongylus asini, Strongylus edentatus, Blood worm (Pythium sulcatum), Bacterial canker (Clavibacter michi (Strongylus equinus), Blood worm (Strongylus vulgaris), ganensis Subsp. michiganensis), Scab (Streptomyces spp.), Large-mouthed bowel worm (Chabertia ovina), Nodular Crown gall (Rhizobium radiobacter), Bacterial stripe (Bur worm (Oesophagostomum brevicaudatum), Nodule worm kholderia andropogonis), Soft rot (Burkholderia cepacia, 35 (Oesophagostomum columbianum), Nodule worm (Oesoph Pseudomonas marginalis marginalis, Erwinia rhapontici), agostomum dentatum), Nodular worm (Oesophagostomum Bacterial grain rot (Burkholderia gladioli, B. glumae), Bac georgianum), Nodular worm (Oesophagostomum maplesto terial fruit blotch (Acidovorax avenae subsp. citrulli), Bac nei). Nodular worm (Oesophagostomum quadrispinulatum), terial leaf blight (Acidovorax konjaci), Bacterial wilt (Ral Nodular worm (Oesophagostomum radiatum), Nodular stonia Solanacearum), Bacterial shot hole (Xanthomonas 40 worm (Oesophagostomum venulosum), Syngamus Skriabi arboricola pv. pruni, Pseudomonas Syrinqae pv. Syringae, nomorpha, Gapeworm (Syngamus trachea), Swine kidney Brenneria nigrifluens), Bacterial leaf spot (Xanthomonas worm (Stephanurus dentatus), Cattle bankrupt worm (Coo arboricola a. pruni), Bacterial spot (Xanthomonas axonopo peria. Oncophora), Red Stomach worm (Hyostrongylus rubi dis a vitians), Black rot (Xanthomonas campestris pv. dus), Stomach hair worm (Trichostrongylus axei), Tricho campestris), Bacterial pustule (Xanthomonas Campestris pv. 45 strongylus colubriformis, Oriental trichoStrongylus glycines), Bacterial spot (Xanthomonas campestris pv. (Tricho strongylus Orientalis), Red Stomach worm (Haemon nigromaculans), Bacterial spot (Xanthomonas campestris chus contortus), Cattle stomach worm (Mecistocirrus digi pV. vesicatoria), Citrus canker (Xanthomonas citri Subsp. tatus), Brown stomach worm (Ostertagia Ostertaqi), Com citri), (Pseudomonas Cichorii, P. marginalis a. marginalis, mon lungworm (Dictyocaulus filaria), Bovine lungworm Erwinia sp.), Bacterial rot (Pseudomonas cichorii, P. mar 50 (Dictyocaulus viviparus). Thin-necked intestinal worm ginalis a. marginalis, P viridiflava), Bacterial blossom (Nematodirus filicollis), Swine lungworm (Metastrongylus blight (Pseudomonas marginalis pv. marginalis, P. syringae elongatus), Lungworm (Filaroides hirthi), Lungworm pV. syringae, P viridiflava), Bacterial canker (Pseudomonas (Crenosoma aerophila), Fox lungworm (Crenosoma vulpis), syringae pv. actinidiae), Canker (Pseudomonas Syringaea. Rat lung worm (Angiostrongylus cantonensis), French heart eriobotryae), Bacterial spot (Pseudomonas syringae lachry 55 worm (Angiostrongylus vasorum), Protostrongylus spp., etc. mans), Bacterial black spot (Pseudomonas Syringae pv. Nematodes of the order Aphelenchida such as Rice white maculicola), Bacterial canker (Pseudomonas Syringae pv. tip nematode (Aphelenchoides besseyi), Strawberry foliar morsprunorum, Erwinia sp.), Bacterial shoot blight nematode (Aphelen.choides fragariae), Chrysanthemum (Pseudomonas Syrigae a... theae), Bacterial Soft rot (Dickeya foliar nematode (Aphelenchoides ritzemabosi), Pine wood sp., Pectobacterium carotovorum), Fire blight (Erwinia 60 nematode (Bursaphelenchus xylophilus), etc. amylovora), Soft rot (Pectobacterium carotovorum), Bacte Nematodes of the order Tylenchida such as White potato rial soft rot (Pectobacterium carotovorum). cyst nematode (Globodera pallida), Potato cyst nematode Animal Diseases: (Globodera rostochiensis), Cereal cyst nematode (Het Pneumocystis pneumonia (Pneumocystis irovecii), Candidi erodera avenae), Soybean cyst nematode (Heterodera gly asis (Candida albicans), Aspergillosis (Aspergillus filmiqa 65 cines), Sugarbeet cyst nematode (Heterodera Schachtii), tus), Trichophytosis (Microsporum canis, M. gypseum, Clover cyst nematode (Heterodera trifolii), Peanut root-knot Trichophyton mentagrophytes, T. rubrum, T. tonsurans, T. nematode (Meloidogyne arenaria), Northern root-knot US 9,434,684 B2 57 58 nematode (Meloidogyne hapla), Southern root-knot nema Trematodes of the order Strigeidida such as Pharyngos tode (Meloidogyne incognita), Javanese root-knot nematode tomum cordatum, Blood fluke (Schistosoma haematobium), (Meloidogyne iavanica), Apple root-knot nematode (Melo Blood fluke (Schistosoma japonicum), Blood fluke (Schis idogyne mali), Coffee root-lesion nematode (Pratylenchus tosoma mansoni), etc. coffeae), (Pratylenchus drenatus), Tea root-lesion nematode Trematodes of the order Echinostomida such as Echinos (Pratylenchus loosi), California root-lesion nematode (Pra toma cinetorchis, Echinostoma hortense, Giant liver fluke tylenchus neglectus), Cobb's root-lesion nematode (Praty (Fasciola gigantica), Common liver fluke (Fasciola lenchus penetrans), Walnut root-lesion nematode (Pratylen hepatica), Fasciolopsis buski, Homalogaster paloniae, etc. chus vulnus), Citrus burrowing nematode (Radopholus Trematodes of the order Plagiorchiida such as Dicrocoe citrophilus), Banana burrowing nematode (Radopholus 10 lium chinensis, Lancet liver fluke (Dicrocoelium dendriti similis), etc. cum), African lancet fluke (Dicrocoelium hospes), Eury Nematodes of the order Oxyurida such as Pinworm (En trema coelomaticum, Pancreatic fluke (Eurytrena terobius vermicularis), Equine pinworm (Oxyuris equi), pancreaticum), Paragonimus miyazakii, Paragonimus Ohi Rabbit pinworm (Passalurus ambiguus), etc. rai, Lung fluke (Paragonimus westermani), etc. Nematodes of the order Ascaridida such as Pig round 15 Trematodes of the order Opisthorchiida such as Amphime worm (Ascaris suum), Horse roundworm (Parascaris equo rus spp., Chinese liver fluke (Clonorchis sinensis), Cat liver rum), Dog roundworm (Toxascaris leonina), Dog intestinal fluke (Opisthorchis felineus), Southeast Aasian liver fluke roundworm (Toxocara canis), Feline roundworm (Toxocara (Opisthorchis viverrini), Pseudamphistomum spp., cati), Large cattle roundworm (Toxocara vitulorum), Anisa Metorchis spp., Parametorchis spp., Intestinal fluke (Het kis spp., Pseudoterranova spp., Caecal worm (Heterakis erophyes heterophyes), MetaqOnimus yokokawai, Pygidiop gallinarum), Chicken roundworm (Ascaridia galli), etc. Sis Summa, etc. Nematodes of the order Spirurida such as Guinea worm Amebas Such as Entamoeba histolytica, E. invadens, etc. (Dracunculus medimensis), Gnathostoma doloresi, Gina Piroplasmida Sporozoa Such as Babesia biqemina, Babe thostoma hispidum, Gnathostoma nipponicum, Reddish-co sia bovis, Babesia caballi, Babesia canis, Babesia felis, loured worm (Gnathostoma spinigerum), Dog Stomach 25 Babesia gibsoni, Babesia ovata, Cytaux zoon felis, Theileria worm (Physaloptera canis), Cat Stomach worm (Physallop annulata, Theileria mutans, Theileria Orientalis, Theileria tera felidis, P. praeputialis), Feline/canine stomach worm parva, etc. (Physaloptera rara), Eye worm (Thelazia Calipaeda), Haemosporida sporozoa Such as Haemoproteus mansoni, Bovine eyeworm (Thelazia rhodesi), Large mouth stomach Leucocytozoon caulleryi, Plasmodium falciparum, Plasmo worm (Draschia megastoma). Equine stomach worm (Ha 30 dium malariae, Plasmodium ovale, Plasmodium vivax, etc. bronema microstoma), Stomach worm (Habronema mus Eucoccidiorida Sporozoa Such as Caryospora spp., Eime cae), Gullet worm (Gongylonema pulchrum). Thick stom ria acervulina, Eimeria bovis, Eimeria brunet, Eimeria ach worm (Ascarops strongylina), Parafilaria (Parafilaria maxima, Eimeria necatrix, Eimeria ovinoidalis, Eimeria bovicola), Parafilaria multipapillosa, Stephanofilaria Oki Stiedae, Eimeria tenella, Isospora canis, Isospora felis, nawaensis, Bancroft filarial (Wuchereria bancrofti), Brugia 35 Isospora suis, Tizzeria alleni, Tizzeria anseris, Tizzeria malayi, Neck threadworm (Onchocerca cervicalis), perniciosa, Wenyonella anatis, Wenyonella gagari, Cryp Onchocerca gibsoni, Cattle filarial worm (Onchocerca gut tosporidium canis, Cryptosporidium felis, Cryptosporidium turosa). Onchocerca volvulus, Bovine filarial worm (Setaria hominis, Cryptosporidium meleaqridis, Cryptosporidium digitata), Peritoneal worm (Setaria equina), Setaria labi muris, Cryptosporidium parvum, Sarcocystis canis, Sarco atopapillosa, Setaria marshalli, Dog heartworm (Dirofilaria 40 cystis cruzi, Sarcocystis felis, Sarcocystis hominis, Sarco immitis), African eye worm (Loa loa), etc. cystis miescheriana, Sarcocystis neurona, Sarcocystis Microorganisms of the phylum Acanthocephala Such as tenella, Sarcocystis ovalis, Toxoplasma gondii, Hepatozoon Moniliformis moniliformis, Giant thorny-headed worm canis, Hepatozoon felis, etc. (Macracanthorhynchus hirudinaceus), etc. Vestibuliferida Ciliata such as Balantidium coli, etc. Cestodes of the order Pseudophyllidea such as tape 45 Trichomonadida flagellata such as Histomanas melea worm (Diphyllobothrium latum), Diphyllobothrium gridis, Pentatrichomonas hominis, Trichomonas tenax, etc. nihonkaiense, Manson tapeworm (Spirometra erinaceieuro Diplomonadida flagellata Such as Giardia intestinalis, paei). Diplogonoporus grandis, etc. Giardia muris, Hexamita meleagridis, Hexamita parva, etc. Cestodes of the order Cyclophyllidea such as (Mesoces Kinetoplastida flagellata Such as Leishmania donovani, toides lineatus), Chicken tapeworm (Raillietina Cesticillus), 50 Leishmania infantum, Leishmania maior, Leishmania Fowl tapeworm (Raillietina echinobothrida), Chicken tape tropica, Trypanosoma bruceigambiense, Trypanosoma bru worm (Raillietina tetragona), Canine tapeworm (Taenia cei rhodesiense, Trypanosoma Cruzi, Trypanosoma equipe hydatiqena), Canine tapeworm (Taenia multiceps), Sheep rdum, Trypanosoma evansi, etc. measles (Taenia ovis), Dog tapeworm (Taenia pisiformis), Useful insects herein mean insects useful for human life Beef tapeworm (Taenia Saginata), Tapeworm (Taenia seria 55 by utilizing their products, or useful to make agricultural lis), Pork tapeworm (Taenia solium), Feline tapeworm (Tae work efficient e.g. by using them for pollination of orchard nia taeniaeformis), Hydatid tapeworm (Echinococcus trees/vegetables, and specifically, Japanese honeybee (Apis granulosus), Small fox tapeworm (Echinococcus multilocu cerana japonica), Western honey bee (Apis mellifera), laris), Echinococcus oligarthrus, Echinococcus vogeli, Rat Bumblebee (Bombus consobrinus wittenburgi, B. diversus tapeworm ( diminuta), Dwarf tapeworm (Hy 60 diversus, B. hypocrita hypocrita, B. ignitus, B. terrestris), menolepis mana), Double-pored dog tapeworm (Dipylidium Hornfaced bee (Osmia cornifions), Silkworm (Bombyx caninum), Amoebotaenia sphenoides, Choanotaenia infin mori) may, for example, be mentioned, but the present dibulum, Metroliasthes Coturnix, Equine tapeworm (Anop invention is not restricted thereto. locephala magna), Cecal tapeworm (Anoplocephala perfo Natural enemies herein mean organisms which kill spe liata), Dwarf equine tapeworm (Paranoplocephala 65 cific organisms particularly specific organisms damaging manillana), Common tapeworm (Moniezia benedeni), agricultural crops by predation or parasitism or which inhibit Sheep tapeworm (Moniezia expansa), Stilesia spp., etc. propagation of Such organisms, and specifically, the follow US 9,434,684 B2 59 60 ing organisms may, for example, be mentioned, but the carbonate, potassium carbonate, Sodium hydrogen carbon present invention is not restricted thereto. ate, sodium acetate, triethylamine, ethyl diisopropylamine, Parasitic wasps belonging to the family Braconidae Such N-methylmorpholine, pyridine or 4-(dimethylamino)pyri as Dacnusa Sasakawai, Dacnusa Sibirica, Aphidius cole dine in an amount of from 1 to 3 equivalents per 1 equivalent mani, Apanteles glomeratus, etc., the family Aphelimidae 5 of the compound represented by the formula (II), within a Such as Aphelinus albipodus, Aphelinus asychis, Aphelinus temperature range of from 0°C. to the refluxing temperature gossypii, Aphelinus maculatus, Aphelinus varipes, Encarsia of the reaction mixture for from 30 minutes to 24 hours, to formosa, Eretnocerus eremicus, Erethnocerus mundus, etc., obtain a compound of the present invention represented by and the family Eulophidae such as Chrysocharis pentheus, the formula (Ia) wherein G', R', R and Rare the same as Neochrysocharis formosa, Diglyphus isaea, Hemiptarsenus 10 defined above which is a compound of the formula (I) varicornis, etc.; Aphidophagous gall midge (Aphidoletes wherein W is an oxygen atom, and R is a hydrogen atom. aphidimyza); Seven-spot ladybird (Coccinella Septempunc Some of the compounds represented by the formula (III) tata); Asian lady beetle (Harmonia axyridis); Predatory used in this process are known compounds, and some of beetle (Propylea japonica); Anthocorid predatory bugs 15 them are commercially available. The rest of them can be belonging to the family Anthocoridae such as Orius minutus, synthesized in accordance with known methods disclosed in Orius nagaii, Orius Sauteri, Minute pirate bug (Orius Strigi collis), etc.; Predatory mirids belonging to the family Miri the literature, for example, by a method in accordance with dae such as Pilophorus typicus, Nesidiocoris tenuis, etc.; the method disclosed in J. Med. Chem., 1991, vol. 34, p. Predatory thrips belonging to the family Aeolothripidae such 1630, etc., in which a corresponding known carboxylic acid as Franklinothrips vespiformis, etc.; Green lacewing is reacted with a halogenating agent such as thionyl chloride, belonging to the family Chrysopidae Such as Dichochrysa phosphorus pentachloride or oxalyl chloride, a method in formosanus, Chrysoperla nipponensis, etc.; Predatory mites accordance with the method disclosed in Tetrahedron Let belonging to the family Phytoseiidae Such as Neoseiulus ters, 2003, vol. 44, p. 4819, J. Med. Chem., 1991, vol. 34, Californicus, Ambly seius cucumeris, Amblyseius degener p. 222, etc., in which a corresponding known carboxylic acid ans, Amblyseius Swirskii, Phytoseiulus persimilis, etc.; Wolf 25 is reacted with an organic acid halide Such as pivaloyl spider (Pardosa pseudoannulata); Crab spider (Misumenops chloride or isobutyl chloroformate in the presence of a base tricuspidatus). if necessary, or a method disclosed in J. Org. Chem., 1989, The compounds of the present invention represented by Vol. 54, p. 5620, etc., in which a corresponding known the formula (I) can be produced, for example, by the carboxylic acid is reacted with carbonyl diimidazole, sulfo following processes. 30 nyl diimidazole or the like.

Process B Process A

R2 R3 35 M R2 R3 HNO-R C X (V) O HN OrrR4 O — n -- N ao -e-base (IV) 40 R2 R3 C (III) (II) R2 R3 R4 N C 45 -o GD1 NNi || N “ao (I)

50 1 Equivalent of a compound represented by the formula (Ia) (IV) wherein G', G'. W. R. R. and R are the same as defined above is reacted with from 1 to 3 equivalents of a A compound represented by the formula (II) wherein G', compound represented by the formula (V) wherein R' is the R", Rand Rare the same as defined above or its salt (such same as defined above or its salt (such as a hydrochloride as a hydrochloride or a hydrobromide) is reacted with a 55 or a hydrobromide), if necessary in a solvent Such as compound represented by the formula (III) wherein G' is benzene, toluene, methanol, ethanol, tetrahydrofuran, acetic the same as defined above, and J is a chlorine atom, a acid, pyridine, water or a mixture of two or more of them in bromine atom, a C-C alkylcarbonyloxy group (such as a any ratio, if necessary in the presence of a base such as pivaloyloxy group), a C-C alkoxycarbonyloxy group (Such Sodium hydroxide, potassium hydroxide, sodium carbonate, as an isobutyloxycarbonyloxy group), an azolyl group (Such 60 potassium carbonate, Sodium hydrogen carbonate, Sodium as an imidazol-1-yl group) or the like, if necessary in a acetate, triethylamine or pyridine in an amount of from 1 to Solvent Such as benzene, toluene, dichloromethane, chloro 4 equivalents per 1 equivalent of the compound represented form, 1,2-dichloroethane, diethyl ether, tert-butyl methyl by the formula (IV), or with hydrochloric acid, sulfuric acid ether, tetrahydrofuran, 1,4-dioxane, ethyl acetate, N,N-dim or the like as a catalyst in an amount of from 0.1 to 1 ethylformamide, N,N-dimethylacetamide, acetonitrile, 65 equivalent per 1 equivalent of the compound represented by water or a mixture of two or more of them in an any ratio, the formula (IV), within a temperature range of from room if necessary in the presence of a base such as sodium temperature to the refluxing temperature of the reaction US 9,434,684 B2 61 62 mixture for from 1 to 48 hours to obtain a compound of the like as a catalyst in an amount of from 0.01 to 1 equivalent present invention represented by the formula (I) wherein per 1 equivalent of the compound represented by the for G', G. W. R. R. Rand Rare the same as defined above). mula (VI), within a temperature range of from room tem perature to the refluxing temperature of the reaction mixture for from 1 to 24 hours to obtain a compound of the present invention represented by the formula (I) wherein G. G. W. Process C R", R, R and R are the same as defined above). The compounds represented by the formula (VII) used in HNOH this process are known compounds, and some of them are 10 commercially available. The rest of them can be synthesized in accordance with known methods disclosed in the litera ture regarding known compounds.

15 Processs D

25

(I) 30

1 Equivalent of a compound represented by the formula (IV) wherein G', G'. W. R. R. and R are the same as defined above and from 1 to 3 equivalents of hydroxylam ine or its salt (Such as a hydrochloride or a sulfate) are 35 reacted, if necessary in a solvent such as methanol, ethanol, (I) 1,4-dioxane, acetonitrile, pyridine, water or a mixture of two or more of them in any ratio, if necessary in the presence of A compound represented by the formula (VIII) wherein a base Such as Sodium hydroxide, potassium hydroxide, 40 G, G', W. R. R. and R are the same as defined above is Sodium carbonate, potassium carbonate, Sodium hydrogen reacted, for example, with sodium nitrite by a method in carbonate, Sodium acetate, ethyldiisopropylamine or pyri accordance with J. Org. Chem..., 2004, vol. 69, p. 8997, etc., dine in an amount of from 1 to 4 equivalents per 1 equivalent with tin(II) chloride-phenylmercaptain by a method in accor of the compound represented by the formula (IV), within a dance with Tetrahedron, 1990, vol. 46, p. 587, etc., or with temperature range of from room temperature to the refluxing 45 carbon disulfide by a method in accordance with J. Org. temperature of the reaction mixture for from 1 to 24 hours Chem., 1983, vol. 48, p. 2766, etc., to obtain a compound to obtain a compound represented by the formula (VI) represented by the formula (VI) wherein G', G. W. R. R. wherein G', G. W. R. R. and R are the same as defined and R are the same as defined above). above. 1 Equivalent of the obtained compound represented The compound represented by formula (VI) thus obtained by the formula (VI) and from 1 to 10 equivalents of a 50 may be reacted with a compound represented by the formula compound represented by the formula (VII) wherein R' is (VII) wherein R' and Jare the same as defined above in the same as defined above, J is a chlorine atom, a bromine the same manner as in process C to obtain a compound of the atom, an iodine atom, a C-C alkylsulfonate group (such as present invention represented by the formula (I) wherein a methanesulfonyloxy group), a C-C haloalkylsulfonate G', G. W. R. R. Rand Rare the same as defined above). group (Such as a trifluoromethanesulfonyloxy group) or the 55 like are reacted, if necessary in an atmosphere of an inert gas Such as nitrogen or argon, if necessary in a solvent Such Process E as benzene, toluene, dichloromethane, chloroform, tetrahy drofuran, acetone, acetonitrile, N,N-dimethylformamide, dimethylsulfoxide, water or a mixture of two or more of 60 C J3-R. them in any ratio, if necessary in the presence of a base Such (IX) as Sodium hydride, Sodium methoxide, Sodium ethoxide, Sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate or triethylamine in an amount of from 1 to 3 equivalents per 1 equivalent of the 65 compound represented by the formula (VI), if necessary (Ia) with tetrabutylammonium bromide, potassium iodide or the US 9,434,684 B2 63 64 -continued -continued i R2 R3 C NNl, NNl, R N o R N

(Ib) (Ic) 10

1 Equivalent of a compound of the present invention 1 Equivalent of a compound of the present invention represented by the formula (Ia) wherein G', G, R', R and represented by the formula (Ib) wherein G', G. R. R. R. Rare the same as defined above which is a compound of and Rare the same as defined abovel which is a compound the formula (I) wherein W is an oxygen atom and R is a 15 of the formula (I) wherein W is an oxygen atom, and from hydrogen atom, is reacted with from 1 to 10 equivalents of 1 to 10 equivalents of a sulfidizing agent such as phosphorus a compound represented by the formula (IX) wherein R is pentasulfide, phosphorus pentasulfide-HMDO (hexamethyl the same as defined above except for a hydrogen atom, and disiloxane) or Lawesson’s Reagent (2,4-bis(4-methoxyphe J is a favorable leaving group such as a chlorine atom, a nyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide) are reacted, bromine atom, an iodine atom, a C-C alkylcarbonyloxy if necessary in a solvent such as benzene, toluene, chlo group (such as a pivaloyloxy group), a C-C alkylsulfonate robenzene, dichloromethane, chloroform, 1,2-dimethoxy (such as a methanesulfonyloxy group), a C-C haloalkyl ethane, tetrahydrofuran, 1.4-dioxane or HMPA, if necessary Sulfonate group (such as a trifluoromethanesulfonyloxy in the presence of a base Such as Sodium hydrogen carbon group), an arylsulfonate group (such as a benzenesulfony 25 ate, triethylamine or pyridine in an amount of from 1 to 4 loxy group or a p-toluenesulfonyloxy group), an azolyl equivalents per 1 equivalent of the compound represented by group (such as an imidazol-1-yl group) or the like, if the formula (Ib), within a temperature range of from room necessary in a polar solvent Such as tert-butyl methyl ether, temperature to the refluxing temperature of the reaction mixture for from 10 minutes to 50 hours, or in pyridine as tetrahydrofuran, 1.4-dioxane, acetonitrile or N,N-dimethyl 30 a base in an amount Sufficient as a solvent within a tem formamide, if necessary in the presence of a base Such as perature range of from 80°C. to the refluxing temperature of sodium hydride, potassium tert-butoxide, potassium hydrox the reaction mixture for from 1 to 3 hours, to obtain a ide, potassium carbonate, triethylamine or pyridine in an compound of the present invention represented by the for amount of from 1 to 3 equivalents per 1 equivalent of the mula (Ic) wherein G, G, R', R, R and R are the same compound represented by the formula (Ia), within a tem 35 as defined above which is a compound of the formula (I) perature range of from 0 to 90° C. for from 10 minutes to 24 wherein W is a sulfur atom. hours to obtain a compound of the present invention repre In processes A to F, the reaction mixture after a reaction sented by the formula (Ib) wherein G', G', R, R and R can be worked up by an ordinary procedure Such as direct are the same as defined above, and R is the same as defined 40 concentration, a procedure Such that the reaction mixture is above except for a hydrogen atom which is a compound of dissolved in an organic solvent, washed with water and the formula (I) wherein W is an oxygen atom. concentrated, or a procedure such that the reaction mixture Some of the compounds represented by the formula (IX) is poured into ice water, extracted with an organic solvent used in this process are known compounds, and some of and concentrated, to obtain the desired oxime-substituted them are commercially available. The rest of them can be 45 amide compound. If purification is needed, the desired synthesized in accordance with known methods disclosed in oXime-substituted amide compound may be isolated or the literature regarding known compounds, for example, the purified by an optional purification method such as recrys method disclosed in Chem. Pharm. Bull., 1986, vol. 34, p. tallization or fractionation by column chromatography, thin layer chromatography or liquid chromatography. 540 and 2001, vol. 49, p. 1102, J. Am. Chem. Soc., 1964, 50 vol. 86, p. 4383, J. Org. Chem., 1983, vol. 48, p. 5280, Org. The compound represented by the formula (II) used in Synth., 1988, collective vol. 6, p. 101, Synlett, 2005, p. process A may be synthesized, for example, by reaction 2847, Synthesis, 1990, p. 1159, JP05/125017, EP0,051,273, schemes 1 to 3. GB2,161,802 or the like. 55 Reaction Scheme 1 Process F O R2 R3 NK C n 60 Nl, -asP2S5 R2 R3 R N “-o J4 X O

65 O (Ib) (X) US 9,434,684 B2 66 -continued Some of the compounds represented by the formula (X) O R2 R3 used in this process are known compounds, and some of them are commercially available. The rest of them can be N.XG) C. -H.N-R Y - synthesized in accordance with known methods disclosed in O the literature regarding known compounds. O

(XI) Reaction Scheme 2 O R2 R3 10 HNO-R R2 R3 N H2NNH2 -- N t J4 X-O-N - o " 15 O R1 (XII) (X) R2 R3 O

HN NK N o X2 R3 -O HerO (II) 25 N ho 1 Equivalent of a compound represented by the formula R1 (X) wherein G, Rand R are the same as defined above, (XIII) and J is a chlorine atom, bromine atom, an iodine atom or 30 O R2 R3 the like and from 1 to 1.5 equivalents of potassium phthal imide are reacted, in a solvent such as toluene, dichlo HNNH romethane, tetrahydrofuran, 1.4-dioxane, acetone, N,N-di methylformamide, N,N-dimethylacetamide O N dimethylsulfoxide, if necessary in the presence of from 0.1 35 O * to 2 equivalents of a base Such as sodium carbonate, RI potassium carbonate or sodium hydrogen carbonate, if nec (XII) essary with from 0.1 to 1 equivalent of tetrabutylammonium iodide, tributylhexadecylphosphonium bromide, crown 40 ether (18-Crown-6) or the like as a catalyst, within a R2 R3 -O temperature range of from room temperature to the refluxing ^ N temperature of the reaction mixture for from 0.5 to 24 hours 1o to obtain a compound represented by the formula (XI) 45 wherein G. Rand Rare the same as defined above). The RI obtained compound represented by the formula (XI) is (II) reacted with a compound represented by the formula (V) wherein R' is the same as defined above under the same A compound represented by the formula (X) wherein G, conditions as in process B to obtain a compound represented 50 R. R. and J are the same as defined above and the by the formula (XII) wherein G, R, R and R are the compound represented by the formula (V) wherein R' is the same as defined above. same as defined above are reacted under the same condi Then, the compound represented by the formula (XII) is tions as in process B to obtain a compound represented by reacted with hydrazine monohydrate or aqueous hydrazine 55 the formula (XIII) wherein G. R', R, R and J are the in an amount of from 1 to 4 equivalents per 1 equivalent of same as defined above, and the obtained compound repre the compound represented by the formula (XII), if necessary sented by the formula (XIII) is reacted with potassium in a solvent such as toluene, dichloromethane, chloroform, phthalimide in the same manner as in reaction scheme 1 to methanol, ethanol, tetrahydrofuran, 1.4-dioxane, water or a obtain a compound represented by the formula (XII) mixture of two or more of them in any ratio, if necessary in 60 an atmosphere of an inert gas such as nitrogen or argon, wherein G. R. R. and Rare the same as defined above. within a temperature range of from room temperature to the Then, the compound represented by the formula (XII) is refluxing temperature of the reaction mixture for from 1 to reacted with hydrazine monohydrate or aqueous hydrazine 24 hours to obtain a compound represented by the formula 65 in the same manner as in reaction scheme 1 to obtain a (II) wherein G', R, R and R are the same as defined compound represented by the formula (II) wherein G, R', above. R, and R are the same as defined above). US 9,434,684 B2 67 68 is the same as defined above are reacted under the same Reaction Scheme 3 conditions as in process B to obtain a compound represented by the formula (XVIII) wherein G. R. R. Rand Rare the same as defined above. The obtained compound repre sented by the formula (XVIII) is deprotected under known reaction conditions with respect to the substituent R to (XIV) obtain a compound represented by the formula (II) wherein R2 R3 G. R. R. and Rare the same as defined above or its salt (such as a hydrochloride, a hydrobromide, a trifluoroacetate R No1 C NN X 1 J5 10 or a p-toluenesulfonate). H The compound represented by the formula (IV) used in O processes B and C may be synthesized, for example, by reaction scheme 4 or 5.

M 15 (XV) Reaction Scheme 4 HNO-R O R2 R3 O R2 R3 R C No1 'XNN C (G) - Y - X H Grs R4 O O (III) (XIX) (XVII) R2 R3 25 EX -G) R C No1 NN R2 R3C -O Gry H -e- R O N -o (IVb) 30 RI A compound represented by the formula (III) wherein G' (XVIII) and J are the same as defined abovel and a compound represented by the formula (XIX) wherein G', R and R' are the same as defined above, and R is a hydrogen atom, R2 R3 -O 35 a C-C alkyl group or the like or its salt (such as a hydrochloride, a hydrobromide, a trifluoroacetate or a ^ N p-toluenesulfonate) are reacted under the same conditions as “-o in process A to obtain a compound represented by the formula (IVb) wherein G', G, Rand R are the same as 40 defined above, and R is a hydrogen atom, a C-C alkyl (II) group or the like which is a compound of the formula (IV) wherein W is an oxygen atom. A known compound represented by the formula (XIV) wherein G is the same as defined above, and J is a hydrogen atom, a chlorine atom, a bromine atom, an iodine 45 Reaction Scheme 5 atom or the like is reacted with an alkyllithium, a Grignard reagent or the like in accordance with a method disclosed in Tetrahedron Lett., 2002, vol.43, p. 8223 and 2005, vol. 46, p. 8587, J. Org. Chem., 2006, vol. 71, p. 9861, etc., to prepare a compound represented by the formula (XV) wherein G’ is the same as defined above, and M is Li, R4 O MgCl, MgBr, Mgl or the like, and the prepared compound (XX) represented by the formula (XV) and a compound repre sented by the formula (XVI) wherein R and R are the R2 R3 -O same as defined above, R is a tert-butyl group, a benzyl 55 group or the like, and J is a dimethylamino group, a C X J5 (XV) N-methylmethoxyamine group, a piperidin-1-yl group, a NN c1 benzotriazol-1-yl group or the like are reacted to obtain a R4 O compound represented by the formula (XVII) wherein G, (XXI) R, R and R are the same as defined above). 60 O R2 R3 Some of the compounds represented by the formula (XVI) are known compounds, and some of them are commercially available. The rest of them can be synthesized in accordance with known methods disclosed in the literature regarding known compounds. 65 Then, the compound represented by the formula (XVII) and a compound represented by the formula (V) wherein R' US 9,434,684 B2 69 70 A compound represented by the formula (XX) wherein G. R. R. and Rare the same as defined above is reacted Reaction Scheme 7 for example by a method disclosed in J. Med. Chem., 2004, vol. 47, p. 6884, Bioorganic & Med. Chem. Lett., 2012, vol. HN-R 22, p. 5485, etc. to prepare a compound represented by the (XXIV) C formula (XXI) wherein G', R. R. R. and Jare the same C N Ho- n H He as defined above, and the obtained compound represented R4 by the formula (XXI) is reacted with a compound repre (III) (XXV) sented by the formula (XV) wherein G' and Mare the same as defined above in the same manner as in reaction scheme 10 3 to obtain a compound represented by the formula (IVb) ON wherein G', G, R and Rare the same as defined above, (XXVII) and R is a hydrogen atom, a C-C alkyl group or the like C n 1NJ7 -e- which is a compound of the formula (IV) wherein W is an 15 OXygen atom. R4 Some of the compounds represented by the formula (XX) (XXVI) used in this process are known compounds, and some of them are commercially available. The rest of them can be C synthesized in accordance with known methods disclosed in Gr --O the literature regarding known compounds. R4 NO Some of the compounds represented by the formula (V) (VIIIb) used in process B are known compounds, and some of them are commercially available. The rest of them can be syn 25 That is, a compound represented by the formula (III) thesized, for example, as follows. wherein G' and J are the same as defined above and a compound represented by the formula (XXIV) wherein R' is a hydrogenatom, a C-C alkyl group or the like or its salt Reaction Scheme 6 (such as a hydrochloride) are reacted under the same con O 30 ditions as in process A to obtain a compound represented by J6- RI the formula (XXV) wherein G' is the same as defined (XXII) N-OH above, and R is a hydrogenatom, a C-C alkyl group or the like. 35 The primary amines represented by the formula (XXIV) O used in this process are known compounds, and some of them are commercially available. The rest of them can be O synthesized in accordance with known methods disclosed in RI the literature regarding known primary amines. / N-O 40 Then, the obtained compound represented by the formula (XXV) is reacted, for example, in accordance with a method HNNH2 disclosed in WO2007/026965, Tetrahedron Lett., 1994, vol. O - HNO-R 35, p. 7107, WO2006/067103, J. Org. Chem., 1987, vol. 52, (XXIII) (V) p. 5475, etc. to obtain a compound represented by the 45 formula (XXVI) wherein G' is the same as defined above, R" is a hydrogen atom, a C-C alkyl group or the like, and That is, N-hydroxyphthalimide and a compound repre J" is a chlorine atom, a C-C alkylcarbonyloxy group (such sented by the formula (XXII) wherein R' is the same as as an acetoxy group), a C-C alkylsulfonate group (Such as defined above, and J is a chlorine atom, a bromine atom, an a methanesulfonyloxy group) or an arylsulfonate group iodine atom or hydroxy group are reacted, for example, in 50 (such as a benzenesulfonyloxy group). accordance with a method disclosed in J. Med. Chem..., 2008, The obtained compound represented by the formula vol. 51, p. 4601, WO2008/055013, etc. to obtain a com (XXVI) and a compound represented by the formula pound represented by the formula (XXIII) wherein R' is the (XXVII) wherein G’ is the same as defined above are same as defined above, and the obtained compound repre reacted, for example, in accordance with a method disclosed sented by the formula (XXIII) is reacted with hydrazine 55 monohydrate or aqueous hydrazine under the same condi in Bull. Chem. Soc. Jpn., 2004, vol. 77, p. 2219, Tetrahedron tions as in reaction scheme 1 to obtain a compound repre Lett., 2006, vol. 47, p. 3501, J. Org. Chem., 2004, vol. 69, sented by the formula (V) wherein R' is the same as defined p. 8997, etc. to obtain a compound represented by the above. formula (VIIIb) wherein G' and G' are the same as defined 60 above, and R is a hydrogenatom, a C-C alkyl group or the Some of the compounds represented by the formula like which is the compound of the formula (VIII) wherein (XXII) used in this process are known compounds, and some W is an oxygen atom, and R and R are hydrogen atoms. of them are commercially available. The rest of them can be The compound represented by the formula (XIX) may be synthesized in accordance with known methods disclosed in produced by deprotecting a compound represented by the the literature regarding known compounds. 65 formula (XVII) obtainable by reaction scheme 3 by a known The compound represented by the formula (VIII) used in method or may be synthesized, for example, by any of process D may be synthesized, for example, as follows. reaction schemes 8 to 11. US 9,434,684 B2 71 72 dance with a method disclosed in J. Org. Chem., 1986, vol. Reaction Scheme 8 51, p. 3374, etc., if necessary in a solvent such as toluene, methanol, tetrahydrofuran, acetone, N,N-dimethylforma mide, acetonitrile, dimethylsulfoxide, water or a mixture of two or more of them in any ratio, if necessary with methyl trioctylammonium chloride, potassium iodide or the like as a catalyst, within a temperature range of from 0 to 50° C. for from 0.5 to 18 hours to obtain a compound represented by X-O AN/. the formula (XXIX) wherein G, Rand Rare the same as 10 defined above. The obtained compound represented by formula (XXIX) is hydrogenated in a solvent such as methanol, ethanol, diethyl ether, water or a mixture of two or more of them in any ratio in the presence of palladium or a platinum catalyst, if necessary with hydrochloric acid or \\X-O - I - y O 15 the like, in an atmosphere of hydrogen under 1 to 10 atm at room temperature for from 0.5 to 24 hours; is reacted with l ! | HN a reducing agent such as tin(II) chloride in a solvent Such as dichloromethane, methanol, ethanol or ethyl acetate within (XXVIII) (XIXa) a temperature range of from room temperature to 60° C. for from 3 to 18 hours; or is reacted with triphenylphosphine A compound represented by the formula (X) wherein G, and water in a solvent such as tetrahydrofuran, water or a R. R. and J are the same as defined above and hexam mixture of the two in any ratio within a temperature range ethylenetetramine are reacted, for example, in accordance of from 0°C. to room temperature for from 0.5 to 24 hours, with a method disclosed in J. Heterocyclic Chem., 1987, vol. to obtain a compound (XIXa) wherein G. Rand Rare the 24, p. 297 etc., if necessary in a solvent such as toluene, 25 same as defined above which is a compound of the formula dichloromethane, chloroform, ethanol, diethyl ether, tetra (XIX) wherein R is a hydrogenatom. Further, after comple hydrofuran, acetone, ethyl acetate, acetonitrile, water or a tion of the reaction if necessary, the compound of the mixture of two or more of them in any ratio, if necessary formula (XIXa) may be treated with hydrochloric acid, with sodium iodide or the like, within a temperature range hydrobromic acid, trifluoroacetic acid, p-toluenesulfonic of from room temperature to the refluxing temperature of the 30 acid or the like to obtain a salt thereof. reaction mixture for from 1 to 24 hours to obtain a quater nary ammonium salt represented by the formula (XXVIII) wherein G, R, R and J are the same as defined above). Reaction Scheme 10 The obtained quaternary ammonium salt represented by the formula (XXVIII) is hydrolyzed in a solvent such as metha 35 y Ho nol, ethanol, acetonitrile, water or a mixture of two or more R2 R3 NaN of them in any ratio, in the presence of an acid catalyst Such CHO as hydrochloric acid or hydrobromic acid within a tempera J4 XG)C Y ture range of from room temperature to the refluxing tem O perature of the reaction mixture for from 0.5 to 48 hours to 40 obtain a hydrochloride or hydrobromide of a compound (X) represented by the formula (XIXa) wherein G', RandR O R2 R3 are the same as defined above which is a compound of the H formula (XIX) wherein R is a hydrogenatom. Further, after H1NNEX-O C He- R/X G) completion of the reaction, by neutralization with a base 45 HN C Such as sodium hydroxide or potassium hydroxide, a free H1 so O I amine may be isolated. (XXX) (XIXa)

50 A compound represented by the formula (X) wherein G', Reaction Scheme 9 R. R. and J are the same as defined above and diform R2 R3 R2 R3 ylimide sodium salt are reacted, for example, in accordance with a method disclosed in Tetrahedron Lett., 1989, Vol. 30, X-O sis. X-O p. 5285 etc., in a solvent such as N,N-dimethylformamide or r Nr 55 acetonitrile within a temperature range of from room tem O O perature to the refluxing temperature of the reaction mixture (X) (XXIX) for from 2 to 24 hours to obtain a compound represented by the formula (XXX) wherein G, R and Rare the same as defined above. The obtained compound represented by the YO formula (XXX) is hydrolyzed in a solvent such as methanol, ^ O ethanol, 1,4-dioxane, water or a mixture of two or more of them in any ratio with an acid Such as hydrochloric acid (XIXa) within a temperature range of from room temperature to the refluxing temperature of the reaction mixture for from 1 to A compound represented by the formula (X) wherein G', 65 24 hours to obtain a hydrochloride or the like of a compound R, R and J are the same as defined above and sodium represented by the formula (XIXa) wherein G, Rand R' azide or lithium azide are reacted, for example, in accor are the same as defined above which is a compound of the US 9,434,684 B2 73 74 formula (XIX) wherein R is a hydrogenatom. Further, after Y', Yi, Y, Y and Y are the same as defined above which completion of the reaction, by neutralization with a base is a compound of the formula (XXVII) wherein G’ is G-1. Such as sodium hydroxide or potassium hydroxide, a free The compounds represented by the formula (XXXI) used amine may be isolated. are known compounds, and some of them are commercially available. The rest of them can be synthesized from known compounds in accordance with known methods disclosed in Reaction Scheme 11 the literature. HN-R YOX, (XXIV) X.YO 10 Reaction Scheme 13 Y2 O R4 O (X) (XIX) Y2 Y N Y3 15 Y N Y CH, NO, 2 A compound represented by the formula (X) wherein G', base N Y4 R, R and J are the same as defined above and an amine 2 represented by the formula (XXIV) wherein R is a hydro J4 N Y4 NO gen atom, a C-C alkyl group or the like or its salt are (XXXII) (XXVIIb) reacted, if necessary in a solvent Such as toluene, dichlo romethane, methanol, ethanol, diethyl ether, tetrahydro furan, 4-methyl-2-pentanone, ethyl acetate, N,N-dimethyl A compound represented by the formula (XXXII) formamide, acetonitrile, water or a mixture of two or more wherein Y', Y, Y, Y and J are the same as defined of them in any ratio, in an excessive amount of the com above and nitromethane are reacted in accordance with a pound represented by the formula (XXIV) or in the presence 25 known method disclosed in the literature, for example, a of a base such as Sodium hydroxide, potassium carbonate, method disclosed in Heterocycles, 1987, Vol. 26, p. 3259, Sodium carbonate, sodium hydrogen carbonate, triethylam WO2004/096772, etc., if necessary in a solvent such as ine or ethyldiisopropylamine, within a temperature range of tetrahydrofuran or dimethylsulfoxide, if necessary in the from 0° C. to the refluxing temperature of the reaction presence of a base Such as Sodium hydride or potassium 30 tert-butoxide within a temperature range of from 0 to 80°C. mixture for from 1 to 24 hours to obtain a compound for from 1 to 24 hours to obtain a compound of the formula represented by the formula (XIX) wherein G, R and R' (XXVIIb) wherein Y', Y, Y and Y are the same as are the same as defined above, and R is a hydrogen atom, defined above which is a compound of the formula (XXVII) a C-C alkyl group or the like. wherein G’ is G-2. Some of the compounds represented by the formula 35 The compounds represented by the formula (XXXII) used (XXVII) are known compounds, and some of them are in this process are known compounds, and some of them are commercially available. The rest of them may be synthe commercially available. The rest of them can be synthesized sized, for example, by reaction scheme 12 or 13. in accordance with known methods disclosed in the litera 40 ture regarding known compounds. Reaction Scheme 12 In the respective reaction schemes, the compounds after a reaction can be worked up by an ordinary procedure to Y2 Y2 obtain intermediates to be material compounds in processes Y Y3 Y. Y3 A to D. AgNO 45 Further, the respective intermediates produced in such O procedure may be used in the next step reaction without Y4 NaNO/Urea Y4 isolation nor purification. As the oXime-Substituted amide compounds of the present J4 y5 NO Ys invention represented by the formula (I) which can be 50 produced by Such processes, specifically, the following (XXXI) (XXVIIa) compounds of a first group and compounds of a second group may, for example, be mentioned. However, the fol A compound represented by the formula (XXXI) wherein lowing compounds of a first group and compounds of a Y', Y, Y, Y, Y and J are the same as defined above is second group merely exemplify the present invention, and reacted with silver nitrite in accordance with a known 55 the oXime-substituted amide compounds of the present method disclosed in the literature, for example, a method invention are by no means restricted thereto. disclosed in J. Org. Chem., 2004, vol. 69, p. 6907, etc., if Further, combinations of substituents in the compounds of necessary in a solvent Such as benzene, diethyl ether, tert the above respective groups are shown in Tables 2 and 3. In butyl methyl ether, acetonitrile, water or a mixture of two or the Tables, Et denotes ethyl group, n-Pr and Pr-n denote more of them in any ratio, within a temperature range of 60 normal propyl group, i-Pr and Pr-i denote isopropyl group, from 0°C. to room temperature for from 30 minutes to 24 c-Pr and Pr-c denote cyclopropyl group, n-Bu and Bu-n hours, or reacted with sodium nitrite-urea, for example, in denote normal butyl group, i-Bu and Bu-i denote isobutyl accordance with a method disclosed in Tetrahedron, 2009, group, S-Bu and Bu-S denote secondary butyl group, c-Bu vol. 65, p. 1660, etc., if necessary in a solvent such as and Bu-c denote cyclobutyl group, t-Bu and Bu-t denote N,N-dimethylformamide within a temperature range of from 65 tertiary butyl group, Pen denotes pentyl group, c-Pen and -78°C. to room temperature for from 1 to 6 hours, to obtain Pen-c denote cyclopentyl group, Hex denotes hexyl group, a compound represented by the formula (XXVIIa) wherein c-Hex and Hex-c denote cyclohexyl group, Ph denotes US 9,434,684 B2 75 76 phenyl group, 1-Naph denotes 1-naphthyl group, and -continued 2-Naph denotes 2-naphthyl group. Further, in Tables 2 and 3, aromatic heterocyclic rings represented by D-1-1 a to D-35-b have the following struc tures, respectively.

D-1-1a u?y 10 D-1-1b 3 4 W pi 15 O -C)o D-1-2a. (Z) D-1-2b --\ S O 25 2 D-2-1a W \ -C) 30 D-2-1b D-10-1a 3 4 W pi

S 35 o D-2-2a. D-10-1b N -C - 3.W (Z) (Z) D-2-2b S 40 – - D-10-2a. -\ N S 2 D-10-2b 45 o D-3-a -N4 D-4-1b 3 4 50 D-10-3b W pi

N

hi, 55 (Z), (Z) D-5-3b D-11-a 4 t

(),o1 60 D-12-1b (Z) D-6-1b N - 3.W (Z) N 65 US 9,434,684 B2 77 78 -continued -continued D-12-2b D-32-3b

D-12-3a

D-33-1b 10

D-14-1b

15 D-34-1b

D-14-2b

D-15-1b D-34-2b

D-17-b 25

D-22-a 30

D-28-a 35 u3 sn5 (Z) D-29-a 4.

40 For example, the expression “CH(D-5-3b)-3-Cl” means D-32-1a a 3-chloroisoxazol-5-ylmethyl group. In the Tables, aliphatic heterocyclic rings represented by E-2-1 a to E-17-3a have the following structures, respec 45 tively. D-32-1b

E-2-1a

50

D-32-2a. E-2-2a.

55 E-3-2a. D-32-2b

E-3-2b 60

D-32-3a

65 US 9,434,684 B2 79 -continued -continued E-4-1a E-14-3a

RI 6 u E-4-2a. E-15-2a.

10 E-5-1a uC E-15-2b

E-5-2a S 15 -Cl E-15-2c

E-9-1a so E-15-3a E-6-1a

25 u E-6-1b E-15-3b O uC y 30 E-15-3C sa'So

35 E-17-2a. E-6-2a.

N 40 1C. E-17-3a 1 R 16

45 uC O £ O For example, the expression “CH (E-4-1a)CHO” means a E-8-1a 1-formylaZetidin-2-ylmethyl group. 50 In the Tables, partial saturated heterocyclic rings repre sented by M-3-b to M-19-a have the following structures, respectively.

E-8-2a. 55 na R1 E-14-1a

60

E-14-2a.

65 US 9,434,684 B2 81 82 -continued -continued 5 M-7-b O \-(R')7 S - N 31 v / M-9-a S Compounds of First Group (I-1 to I-68)

-->N 10 M-17-a C O

lsON 15 M-19-a s

lsON Br O For example, the expression “CH(M-4-2a)CH' means a 3-methyl-4,5-dihydroisoxazol-5-ylmethyl group. Further, in the Tables, T-1 to T-9 have the following 25 structures, respectively.

T-1 -F 30 T-2 F F 35

F

F T-3 40

OH T-4 45

F F OH 50 T-5

T-6 55

T-7

T-8 US 9,434,684 B2 83 84 -continued -continued

Br

N 21

10 CH3 C N N 15 2

2 N

Br N N 25 21 2 N

F 30 CH N N 2 35

40

N

45

50

55

60

65 US 9,434,684 B2 85 86 -continued -continued R F F ? O 10

Br

15 s

25

30

35

40

s

le 45

I-26

50

55

I-27

60

65 CH3 US 9,434,684 B2 87 88 -continued -continued

1ON 1. O k 10

R2

15

N O k

R2

25 N t O k 30 R2

35 N t O k

40 R2

N 45 O k

R2 50

N N O k 55

R2 60

65

US 9,434,684 B2 91 92 -continued I-63 R F F O R2 Y C s s NN O H N no y5 10 o RI I-64 Y2 F F F Y Y3 N 15 o1 N1 C NN s 2 i || N Y4 N“-o Y 2 Y3 RI I-65 N Y4 F F F y5

C s Y2 s1N1 NN 25 Y Y3 21 N- O H N o R1 N-N 30 I-66 CH3 R2 y5 s1 N1 C NN s Y N- O H N 35 l o 1NNa N11N 4Y3 R1 Y2 Il-67 F Y F F 40 O R2 \ y3 | O O o1 N1 NN Y O N- S H N lo 45 RI I-68 DesY4 F F F 50 Y2 Y s1 N1 C NN N S N S y3 N- H 55 o G-10 R1 Y S y3 Combinations of substituents in the compounds of the 60 above first group are shown in Table 2. In Table 2, the Dx expression (R) or (S) in the column substituent R means that the proportion of the R isomer or the S isomer is at least The expression"-”99 in the columns substituents Yi, Y and 90% in a mixture ratio of optical isomers due to the carbon Y means that there is no corresponding substituent present. atom attached to R. The expression (E) or (Z) in the column substituent R' 65 means that the proportion of the E-isomer or the Z-isomer is The expressions G-1 to G-10 in the column substituent at least 90% in a mixture ratio of oxime geometrical isomers G° mean the following specific structures, respectively. attached to the substituent R'.

US 9,434,684 B2 154 TABLE 2-continued

r r r r

3

3

r r r

C C C C C C C C C C C C

US 9,434,684 B2 167 168 -continued -continued

I-88 US 9,434,684 B2 169 170 -continued -continued I-91

O

Combinations of Substituents in the compounds of a second group are shown in Table 3. TABLE 3 Yi Y2 R

13 i. C

r r r r Br Br Br CF CF CF CF CF

US 9,434,684 B2 183 184 Blastocladiomycota, fungi of the phylum Mucoromycotina, As solid carriers, natural minerals such as quartz, calcite, protists of the phylum Cercozoa, microorganisms of the meerschaum, dolomite, chalk, kaolinite, pyrophyllite, seric phylum Heterokontophyta class Oomycetes, gram-positive ite, halloysite, methahalloysite, kibushi clay, gairome clay, bacteria of the phylum Actinobacteria, gram-positive bacte pottery stone, Zeeklite, allophone, Shirasu, mica, talc, ben ria of the phylum Tenericutes, gram-negative bacteria of the tonite, activated clay, acid clay, pumice, attapulgite, Zeolite phylum Proteobacteria, nematodes of the order Aph and diatomaceous earth, calcined natural minerals such as elenchida and nematodes of the order Tylenchida. The calcined clay, pearlite, Shirasu-balloons, Vermiculite, atta compounds of the present invention have excellent control pulgus clay and calcined diatomaceous earth, inorganic salts ling effect particularly on plant pathogenic fungi belonging Such as magnesium carbonate, calcium carbonate, sodium to the phylum Ascomycota and the phylum Basidiomycota, 10 and plant-parasitic nematodes belonging to the order Aph carbonate, sodium hydrogen carbonate, ammonium sulfate, elenchida and the order Tylenchida at low doses. Sodium sulfate, magnesium Sulfate, diammonium hydrogen Pests against animals may, for example, be fungi of the phosphate, ammonium dihydrogen phosphate and potassium phylum Ascomycota, fungi of the phylum Basidiomycota, chloride, Saccharides Such as glucose, fructose, Sucrose and gram-positive bacteria of the phylum Actinobacteria, gram 15 lactose, polysaccharides such as Starch, cellulose powder positive bacteria of the phylum Firmicutes, gram-positive and dextrin, organic Substances such as urea, urea deriva bacteria of the phylum Tenericutes, gram-negative bacteria tives, benzoic acid and benzoic acid salts, plants such as of the phylum Proteobacteria, nematodes of the order wood flour, powdered cork, corncob, walnut shell and Enoplida, nematodes of the order Rhabditida, nematodes of tobacco stems, fly ash, white carbon (such as hydrated the order Strongylida, nematodes of the order Ascaridida, synthetic silica, anhydrous synthetic silica and hydrous nematodes of the order Spirurida, microorganisms of the synthetic silicate), fertilizers and the like may be mentioned. phylum Acanthocephala, cestodes of the order Pseudophyl As liquid carriers, aromatic hydrocarbons such as Xylene, lidea, cestodes of the order Cyclophyllidea, trematodes of alkyl (Co or Co. etc.) benzene, phenylxylylethane and alkyl the order Strigeidida, trematodes of the order Echinosto (C or C etc.)naphthalene, aliphatic hydrocarbons such as mida, trematodes of the order Plagiorchiida, trematodes of 25 machine oil, normal paraffin, isoparaffin and naphthene, the order Opisthorchiida, amebas, Piroplasmida sporozoa, mixtures of aromatic hydrocarbons and aliphatic hydrocar Haemosporida sporozoa, Eucoccidiorida sporozoa, Vestibu bons such as kerosene, alcohols such as ethanol, isopropa liferida ciliata, Trichomonadida flagellata, Diplomonadida nol, cyclohexanol, phenoxyethanol and benzyl alcohol, flagellata and Kinetoplastida flagellata. Particularly, the polyhydric alcohols such as ethylene glycol, propylene compounds of the present invention have excellent effect to 30 glycol, diethylene glycol, hexylene glycol, polyethylene control internal parasites parasitizing animals of the class glycol and polypropylene glycol, ethers such as propyl Mammalia belonging to the family Cebidae, the family cellosolve, butyl cellosolve, phenyl cellosolve, propylene Cercopithecidae, the family Homimidae, the family Lepori glycol monomethyl ether, propylene glycol monoethyl ether, dae, the family Chinchillidae, the family Caviidae, the propylene glycol monopropyl ether, propylene glycol family Cricetidae, the family Muridae, the family Sciuridae, 35 the family Camelidae, the family Suidae, the family Cervi monobutyl ether and propylene glycol monophenyl ether, dae, the family Bovidae, the family Felidae, the family ketones such as acetophenone, cyclohexanone and Y-buty Canidae, the family Mustelidae, the family Equidae, the rolactone, esters such as fatty acid methyl esters, dialkyl family Macropodidae and the like, especially animal-para Succinates, dialkyl glutamate, dialkyl adipates and dialkyl sitic nematodes belonging to the order Enoplida, the order 40 phthalates, acid amides such as N-alkyl (C, Cs or C Rhabditida, the order Strongylida, the order Aphelenchida, etc.)pyrrolidone, fats and oils such as soybean oil, linseed the order Tylenchida, the order Ascaridida and the order oil, rapeseed oil, coconut oil, cottonseed oil and castor oil, Spirurida, parasitizing mammals of the family Suidae, the dimethyl sulfoxide, water and the like may be mentioned. family Bovidae, the family Felidae, the family Canidae and These solid and liquid carriers may be used alone or in the family Equidae. 45 combinations of two or more. The compounds of the present invention are also effective As Surfactants, nonionic Surfactants such as polyoxyeth on pests which have acquired resistance to conventional ylene alkyl ether, polyoxyethylene alkyl(mono or di)phenyl fungicides or nematicides, and the compounds of the present ether, polyoxyethylene(mono, di or tri)styrylphenyl ether, invention have very useful characteristics such that they polyoxyethylenepolyoxypropylene block copolymers, poly have little harmful effect on non-target animals such as 50 oxyethylene fatty acid (mono or di)ester, Sorbitan fatty acid mammals, fishes, crustaceans, natural enemies and useful ester, polyoxyethylene Sorbitan fatty acid ester, ethylene insects. oxide adducts of castor oil, acetylene glycol, acetylene The compounds of the present invention may be used in alcohol, ethylene oxide adducts of acetylene glycol, ethylene any dosage form Such as a soluble concentrate, an emulsi oxide adducts of acetylene alcohol and alkyl glycosides, fiable concentrate, a wettable powder, a water soluble pow 55 anionic Surfactants such as alkyl Sulfate salts, alkylbenze der, a water dispersible granule, a water Soluble granule, a nesulfonic acid salts, lignin Sulfonate, alkylsulfoSuccinic Suspension concentrate, a concentrated emulsion, a Suspoe acid salts, naphthalenesulfonic acid salts, alkylnaphthalene mulsion, a microemulsion, a dustable powder, a granule, a Sulfonic acid salts, salts of naphthalenesulfonic acid-forma tablet or an emulsifiable gel usually after mixed with an lin condensates, salts of alkylnaphthalenesulfonic acid-for appropriate solid carrier or a liquid carrier, and if necessary, 60 malin condensates, polyoxyethylene alkyl ether Sulfate or with a surfactant, a penetrant, a spreader, a thickener, an phosphate salts, polyoxyethylene(mono or di) alkylphenyl anti-freezing agent, a binder, an anti-caking agent, a disin ether Sulfate or phosphate salts, polyoxyethylene(mono, di tegrant, an antifoaming agent, a preservative, a stabilizer or or tri)Styrylphenyl ether Sulfate or phosphate salts, polycar the like. A formulation in an arbitrary dosage form may be boxylic acid salts (such as polyacrylates, polymaleates and sealed in water-soluble packaging such as a water-soluble 65 copolymers of maleic acid and an olefin) and polystyrene capsule or a water-soluble film, for labor saving or improved Sulfonic acid salts, cationic Surfactants such as alkylamine safety. salts and alkyl quaternary ammonium salts, amphoteric US 9,434,684 B2 185 186 Surfactants such as amino acid types and betaine types, (soaking, bathing or washing) and can be prepared in the silicone surfactants and fluorine Surfactants may be men same manner as an injection fluid. tioned. A pour-on preparation and a spot-on preparation are The amount of these surfactants is usually preferred to be dripped or sprayed to a limited area of the skin so that they from 0.05 to 20 parts by weight per 100 parts by weight of 5 permeate through the skin and act systemically. A pour-on the agent of the present invention, though there is no preparation and a spot-on preparation can be prepared by particular restrictions. These Surfactants may be used alone dissolving, Suspending or emulsifying an active ingredient or in combination of two or more. in an appropriate skin-friendly solvent or solvent mixture. If The suitable application dose of the compounds of the necessary, additives Such as a Surfactant, a colorant, an present invention is generally about from 0.005 to 50 kg per 10 absorbefacient, an antioxidant, a light stabilizer and an hectare (ha) in terms of the active ingredient, though it varies adhesive may be added. depending on the application situation, the application sea As appropriate solvents, water, alkanol, glycol, polyeth son, the application method and the cultivated crop. ylene glycol, polypropylene glycol, glycerin, benzyl alco When the compounds of the present invention are used to hol, phenylethanol, phenoxyethanol, ethyl acetate, butyl control internal parasites in mammals and birds as farm 15 acetate, benzyl benzoate, dipropylene glycol monomethyl animals/poultry and pet animals, the compounds of the ether, diethylene glycol monobutyl ether, acetone, methyl present invention may be administered in an effective ethyl ketone, aromatic and/or aliphatic hydrocarbons, Veg amount together with pharmaceutically acceptable additives etable or synthetic oils, DMF, liquid paraffin, light liquid orally, parenterally by injection (intramuscular, Subcutane paraffin, silicone, dimethylacetamide, N-methylpyrrolidone ously, intravenously or intraperitoneally); percutaneously by or 2.2-dimethyl-4-oxy-methylene-1,3-dioxolane may be dipping, spraying, bathing, Washing, pouring-on and spot mentioned. As absorbefacients, DMSO, isopropyl myristate, ting-on and dusting, or intranasally. The compounds of the pelargonic acid dipropylene glycol, silicone oil, fatty acid present invention may be administered through molded esters, triglycerides and aliphatic alcohols may be men articles Such as chips, plates, bands, collars, ear marks, limb tioned. As antioxidants, sulfites, metabisulfites, ascorbic bands and ID tags. The compounds of the present invention 25 acid, butylhydroxytoluene, butylhydroxyanisole and are administered in an arbitrary dosage form suitable for the tocopherol may be mentioned. administration route. An emulsion may be administered orally, percutaneously The dosage form may be a Solid preparation Such as a or by injection. An emulsion can be prepared by dissolving dust, a granule, a wettable powder, a pellet, a tablet, a ball, an active ingredient in a hydrophobic phase or a hydrophilic a capsule and an molded article containing an active ingre 30 phase and homogenizing the resulting solution with another dient, a liquid preparation Such as an injection fluid, an oral liquid phase together with an appropriate emulsifier, and liquid, a liquid preparation applied to the skin or coelom, a further if necessary with additives such as a colorant, an pour-on preparation, a spot-on preparation, a flowable, an absorbefacient, a protectant, an antioxidant, a light Screen emulsion, and a semisolid preparation Such as an ointment and a thickner. and a gel. 35 As hydrophobic phases (oils), paraffin oil, silicone oil, A Solid preparation may generally be used by oral admin sesame oil, almond oil, castor oil, synthetic triglycerides, istration or by percutaneous or by environmental application ethyl Stearate, di-n-butyryl adipate, hexyl laurate, pelargonic after dilution with water or the like. A solid preparation can acid dipropylene glycol, esters of branched short-chain fatty be prepared by mixing an active ingredient with an appro acids with C-Cls saturated fatty acids, isopropyl myristate, priate vehicle, and with an adjuvant if necessary, and for 40 isopropyl palmitate, esters of C-C Saturated alcohols mulating the mixture into a desired dosage form. As the with caprylic/capric acid, isopropyl Stearate, oleyl oleate, vehicle, an inorganic vehicle Such as a carbonate, a hydrogen decyl oleate, ethyl oleate, ethyl lactate, fatty acid ester carbonate, a phosphate, aluminum oxide, silica or clay or an waxes, dibutyl phthalate, diisopropyl adipate, isotridecyl organic vehicle Such as a saccharide, cellulose, cereal flour alcohol, 2-octyldodecanol, cetylstearyl alcohol and oleyl or starch may, for example, be mentioned. 45 alcohol may be mentioned. An injection fluid may be administered intravenously, As hydrophilic phases, water, propylene glycol, glycerin intramuscularly or Subcutaneously. An injection fluid can be and Sorbitol may be mentioned. prepared by dissolving an active ingredient in an appropriate AS emulsifiers, nonionic Surfactants such as polyoxyeth Solvent and, if necessary, adding additives such as a solu ylated castor oil, polyoxyethylated Sorbitan monoolefinic bilizer, an acid, a base, a buffering salt, an antioxidant and 50 acid, Sorbitan monostearate, glycerin monostearate, poly a protectant. As appropriate solvents, water, ethanol, buta oxyethyl Stearate and alkyl phenol polyglycol ether, ampho nol, benzyl alcohol, glycerin, propylene glycol, polyethyl teric Surfactants such as disodium N-lauryl-3-iminodipropi ene glycol, N-methylpyrrolidone and mixtures thereof, onate and lecithin; anionic Surfactants such as Sodium lauryl physiologically acceptable oils and synthetic oils Sulfate, aliphatic alcohol Sulfate ether, mono/dialkylpolygly suitable for injection may be mentioned. As solubilizers, 55 col orthophosphate monoethanolamine salt; and cationic polyvinylpyrrolidone, polyoxyethylated castor oil, polyoxy Surfactants such as cetyltrimethylammonium chloride may, ethylated sorbitan ester and the like may be mentioned. As for example, be mentioned. protectants, benzyl alcohol, trichlorobutanol, p-hydroxyben As other additives, carboxymethylcellulose, methylcellu Zoic acid esters, n-butanol and the like may be mentioned. lose, polyacrylate, alginate, gelatin, gum arabic, polyvi An oral liquid may be administered directly or after 60 nylpyrrolidone, polyvinyl alcohol, methyl vinyl ether, dilution and can be prepared in the same manner as an maleic anhydride copolymers, polyethylene glycol, waxes injection fluid. and colloidal silica may be mentioned. A flowable, an emulsion or the like may be administered A semisolid preparation is administered by applying or directly or after dilution percutaneously or by environmental spreading onto the skin or introducing into the coelom. A gel application. 65 can be prepared by adding a thickener to a solution prepared A liquid preparation applied to the skin is administered by in the same manner as an injection fluid sufficiently to give dripping, spreading, rubbing, spraying, sprinkling or dipping a transparent viscous Substance like an ointment. US 9,434,684 B2 187 188 Formulation examples of preparations using the com As the others, an anti-drift agent, a stabilizer and the like pounds of the present invention are given below. However, may be mentioned. formulations of the present invention are by no means Next, more specific examples of preparations containing restricted thereto. In the following formulation examples, compounds of the present invention as an active ingredient "parts' means parts by weight. are given below. However, the present invention is by no Wettable Powder means restricted thereto. In the following Formulation Examples, “parts' means Compound of the present invention 0.1 to 80 parts parts by weight. Solid carrier 5 to 98.9 parts 10 Surfactant 1 to 10 parts Others O to 5 parts Formulation Example 1

As the others, an anti-caking agent, a stabilizer and the Wettable Powder like may be mentioned. 15 Emulsifiable Concentrate

Compound of the present invention 0.1 to 30 parts Compound No. 2-132 of the present invention 20 parts Organic solvent 45 to 95 parts Pyrophyllite 74 parts Surfactant 4.9 to 30 parts Sorpol 5039 4 parts Water O to 50 parts (tradename for a mixture of a nonionic Surfactant and an Others O to 10 parts anionic surfactant: manufactured by TOHO Chemical Industry Col., Ltd.) CARPLEX #8OD 2 parts As the others, a spreader, a stabilizer and the like may be (hydrous synthetic silicic acid: tradename manufactured mentioned. 25 by Suspension Concentrate Shionogi & Co., Ltd.)

Compound of the present invention 0.1 to 70 parts The above ingredients are mixed and pulverized homog Liquid carrier 15 to 98.89 parts enously to obtain a wettable powder. Surfactant 1 to 12 parts 30 Others 0.01 to 30 parts Formulation Example 2 As the others, an anti-freezing agent, a thickener and the like may be mentioned. Emulsifiable Concentrate Water Dispersible Granule 35

Compound of the present invention 0.1 to 90 parts Solid carrier O to 98.9 parts Compound No.2-124 of the present invention 5 parts Surfactant 1 to 20 parts Xylene 75 parts Others O to 10 parts 40 N-methylpyrrollidone 15 parts Sorpol 2680 5 parts (tradename for a mixture of a nonionic Surfactant and an anionic Surfac As the others, a binder, a stabilizer and the like may be tant: mentioned. manufactured by TOHO Chemical Industry Co., Ltd.) Soluble Concentrate 45 The above ingredients are mixed homogenously to obtain Compound of the present invention 0.01 to 70 parts an emulsifiable concentrate. Liquid carrier 20 to 99.99 parts Others O to 10 parts Formulation Example 3 As the others, an anti-freezing agent, a spreader and the 50 like may be mentioned. Granule Emulsifiable Concentrate

Compound of the present invention 0.01 to 80 parts 55 Solid carrier 10 to 99.99 parts Compound No.2-117 of the present invention 4 parts Others O to 10 parts DBE 36 parts (tradename for a mixture of dimethyl adipate, dimethyl glutarate and dimethyl succinate: manufactured by INVISTA) As the others, a binder, a stabilizer and the like may be Diisobutyl adipate 30 parts mentioned. 60 N-methylpyrrollidone 10 parts Dustable Powder Soprofol BSU 14 parts (tradename for a nonionic Surfactant: manufactured by Rhodia Nicca.Ltd.) Rhodacal 7OBC 6 parts Compound of the present invention 0.01 to 30 parts (tradename for an anionic Surfactant: manufactured by Rhodia Nicca.Ltd.) Solid carrier 65 to 99.99 parts Others O to 5 parts 65 The above ingredients are mixed homogenously to obtain an emulsifiable concentrate. US 9,434,684 B2 189 190 Formulation Example 4 The above ingredients are mixed and pulverized homog enously, then kneaded with a small amount of water, granu Emulsifiable Concentrate lated through an extrusion granulator and dried to obtain a granule. 5 Compound No.2-020 of the present invention 4 parts Formulation Example 8 DBE 11 parts (tradename for a mixture of dimethyl adipate, dimethylglutarate and dimethyl succinate: manufactured by INVISTA) Dustable Powder Diisobutyl adipate 30 parts 10 N-methylpyrrollidone 5 parts Soprofol BSU 14 parts (tradename for a nonionic Surfactant: manufactured by Rhodia Nicca.Ltd.) Rhodacal 7OBC 6 parts (tradename for an anionic Surfactant: manufactured by Rhodia Nicca.Ltd.) CSI: N4 of the present invention o R Propylene glycol 10 parts 15 (tradename for a hydrous synthetic silicic acid: manufactured by Water 20 parts Shionogi & Co., Ltd.) Kaolinite 95 parts The above ingredients are mixed homogenously to obtain Diisopropyl phosphate 1.5 parts an emulsifiable concentrate. 20 The above ingredients are mixed and pulverized homo Formulation Example 5 geneously to obtain a dustable powder. Suspension Concentrate It is applied after diluted with water by a factor of from 1 to 20000 so as to achieve an active ingredient concentra 25 tion of from 0.005 to 50 kg/ha. Compound No.2-136 of the present invention 25 parts AGRISOLS-710 10 parts Formulation Example 9 (tradename for a nonionic Surfactant: manufactured by Kao Corporation) Lunox 1000C 0.5 part (tradename for an anionic surfactant: manufactured by TOHO Chemical 30 Wettable Powder Preparation Industry Co., Ltd.) Xanthan gum 0.2 part Water 64.3 parts Compound No.2-126 of the present invention 25 parts The above ingredients are mixed homogenously and 35 CalciumSodium diisobutylnaphthalenesulfonaten-dodecylbenzenesulfonate 101 partparts wet-pulverized to obtain a Suspension concentration. Alkyl aryl polyglycol ether 12 parts Naphthalenesulfonic acid-formalin condensate Sodium salt 3 parts Formulation Example 6 Silicone emulsion 1 part Silicon dioxide 3 parts Kaolin 45 parts Water Soluble Granule 40 p

Compound No.2-128 of the present invention 75 parts Formulation Example 10 HITENOLNE-15 5 parts (tradename for an anionic Surfactant: manufactured by Dai-ichi Kogyo 45 Seiyaku Co., Ltd.) Water-Soluble Concentrate Preparation WANILLEXN 10 parts (tradename for an anionic Surfactant: manufactured by Nippon Paper Industries Co., LTD.) CARPLEX #8OD . 10 parts. Compound No.2-212 of the present invention 20 parts Co.,(tradename Ltd.) for hydrous synthetic silicic acid: manufactured by Shionogi & 50 Polyoxyethylenelauryl ether 3 parts O. Sodium dioctylsulfosuccinate 3.5 parts Dimethyl sulfoxide 37 parts The above ingredients are mixed and pulverized homog 2-Propanol 36.5 parts enously, then kneaded with a small amount of water, granu lated through an extrusion granulator and dried to obtain a 55 water Soluble granule. Formulation Example 11 Formulation Example 7 Liquid Preparation for Spraying Granule 60

Compound No.2-185 of the present invention 2 parts Compound No.2-120 of the present invention 5 parts Dimethyl sulfoxide 10 parts Bentonite 50 parts 2-Propanol 35 parts Talc 45 parts 65 Acetone 53 parts US 9,434,684 B2 191 192 Formulation Example 12 cases, they may be combined with a plurality of known fungicides, known nematocides, known insecticides, known Liquid Preparation for Percutaneous Administration miticides, known antibiotics or known vermicides simulta neously. The fungicides, nematocides, insecticides, miticides, Ver micides and antibiotics to be used in combination with the Compound No.2-151 of the present invention 5 parts compounds of the present invention include, for example, Hexylene glycol 50 parts the compounds disclosed in e.g. The Pesticidal Manual, 15th Isopropanol 45 parts edition, 2009, having the generic names listed below, but are 10 not necessarily restricted thereto. Fungicides: Such as acilbenzolar-5-methyl, acypetacs, Formulation Example 13 aldimorph, ametoctradin, amisulbrom, amobam, ampropyl fos, anilazine, azaconazole, azoxystrobin, benalaxyl, benal Liquid Preparation for Percutaneous Administration axyl-M, benodanil, benomyl, benthiavalicarb-isopropyl. 15 benthiazole, benzovindiflupyr, biphenyl, bitertanol, bixafen, bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captan, carbendazim, carboxin, carpro Compound No.2-114 of the present invention 5 parts pamid, carvone, cheshunt mixture, chinomethionat, chlo Propylene glycol monomethyl ether 50 parts roneb, chloropicrin, chlorothalonil, chioZolinate, climba Dipropylene glycol 45 parts Zole, copper carbonate, basic, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper Sul fate, copper Sulfate, basic, coumoxystrobin, cresol, Formulation Example 14 cufraneb, cyaZofamid, cyflufenamid, cymoxanil, cyprocon azole, cyprodinil, dazomet, dichlofluanid, dichlorophen, Liquid Preparation for Percutaneous Administration 25 diclobutraZol, diclocymet, diclomeZine, dicloran, diethofen (by Dripping) carb, difenoconazole, diflumetorim, dimethomorph, dimox yStrobin, diniconazole, diniconazole-M, dinobuton, dinocap, dinocap-4, dinocap-6, diphenylamine, dithianon, DNOC, Compound No.2-174 of the present invention 2 parts dodemorph-acetate, dodine, draZOXolon, edifenphos, enes Light liquid paraffin 98 parts 30 trobin, enoxastrobin, epoxiconazole, etaconazole, etha boxam, ethirimol, ethoxyquin, etridiazole, famoxadone, fenamidone, fenaminstrobin, fenarimol, fenbuconazole, fen furam, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fen Formulation Example 15 propidin, fenpropimorph, fenpyraZamine, fentin, ferbam, 35 ferimzone, fluazinam, fludioxonil, flufenoxystrobin, flu Liquid Preparation for Percutaneous Administration morph, fluopicolide, fluopyram, fluoroimide, fluotrimazole, (by Dripping) fluoxastrobin, fluguinconazole, flusilaZole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl aluminium, fuberidazole, furalaxyl, furametpyr, furcon Compound No.2-240 of the present invention 2 parts 40 azole, furmecyclox, guaZatine, hexachlorobenzene, hexa Light liquid paraffin 58 parts conazole, hymexaZol. imazalil, imibenconazole, Olive oil 30 parts iminoctadine-albesilate, iminoctadine-triacetate, ipcon ODO-H 9 parts azole, iprobenfos, iprodione, iprovalicarb, isofetamid, iso Shin-etsu silicone 1 part prothiolane, isopyrazam, isotianil, kasugamycin, kresoxim 45 methyl, laminarin, mancopper, mancoZeb, mandestrobin, For use as agricultural fungicides or nematocides, if mandipropamid, maneb, mepanipyrim, mepronil, metalaxyl, necessary, the compounds of the present invention may be metalaxyl-M, metam, metconazole, methfuroxam, metiram, mixed with other fungicides, other nematocides, insecti metominostrobin, metrafenone, metSulfoVax, milineb, cides, miticides, plant growth regulators, herbicides, syner myclobutanil, nabam, natamycin, nickel bis(dimethyldithio gists, fertilizers, soil conditioners and the like at the time of 50 carbamate), nitrothal-isopropy, nuarimol, ofurace, orysas formulation or application. trobin, oxadixyl, Oxathiapiprolin, oxine copper, Oxpocon Further, for use as internal parasiticides, the compounds azole fumarate, oxycarboxin, pefurazoate, penconazole, of the present invention in effective amounts may be applied pencycuron, penflufen, pentachlorophenol (PCP), penthio alone as active ingredients, or if necessary, they may be pyrad, 2-phenylphenol, phthalide, picoxystrobin, piperalin, mixed with other antibiotics, other vermicides and the like 55 polycarbamate, polyoxins, polyoxorim, potassium azide, at the time of formulation or application. potassium hydrogen carbonate, probenazole, prochloraZ. Particularly, the combined use with other fungicides, procymidone, propamocarb hydrochloride, propiconazole, other nematocides, other antibiotics, other vermicides or the propineb, produinazid, prothioconazole, pyraclostrobin, like is expected to broaden the pesticidal spectrum by the pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb additive or synergistic effect of the other agrochemicals, to 60 methyl, pyrifenox, pyrimethanil, pyriminostrobin, pyri improve the pesticidal effect, to reduce the application cost ofenone, pyrisoxazole, pyroquilon, quinacetol-sulfate, qui by enabling control at lower doses, and further, to prolong noxyfen, quintoZene, sedaxane, silthiofam, Simeconazole, the pesticidal effect for a long period of time. Particularly, Sodium hydrogen carbonate, Sodium hypochlorite, SpiroX the combined use with other fungicides, nematocides, anti amine, Sulfur, tebuconazole, tebufloquin, tecoram, tetracon biotics or vermicides differing in the mechanism of action is 65 azole, thiabendazole, thifluzamide, thiophanate-methyl, thi a very useful controlling method with a view to preventing ram, tiadinil, tolciofos-methyl, tolprocarb, tolylfluanid, the pests from acquiring resistance to pesticides. In Such triadimefon, triadimenol, triazoxide, tributyltin oxide, tric US 9,434,684 B2 193 194 lopyricab, tricyclazole, tridemorph, trifloxystrobin, triflu ride, clorSulon, closantel, coumaphos, cymiaZol, dichloro mizole, triforine, triticonazole, validamycin, Valifenalate, phen, diethylcarbamazine, diminaZene, disophenol, dithi VincloZolin, Zinc naphthenate, Zinc sulfate, Ziram, Zoxamide, aZanine iodide, doxycycline hydrochloride, doramectin, Shiitake mushroom mycelium extracts, Shiitake mushroom emodepside, eprinomectin, febantel, fenbendazole, fluben fruiting body extracts. BCF-082 (experimental name), NNF dazole, furazolidone, glycalpyramide, imidocarb, ivermec 0721 (experimental name) and ZF-9646 (experimental tin, levamisole, mebendazole, mefloquine, melarsamine name). hydrochloride, metronidazole, metyridine, milbemycin Insecticides: Such as abamectin, acephate, acetamiprid, Oxime, monepantel, morantel tartrate, moxidectin, nicarba afidopyropen, afoxolaner, alanycarb, aldicarb, allethrin, Zin, niclosamide, nitroscanate, nitroxynil, omphalotin, oxan aZamethiphos, azinphos-ethyl, azinphos-methyl, bacillus 10 tel pamoate, oxantel tartrate, Oxfendazolee, oxibendazole, thuringiensis, bendiocarb, benfluthrin, benfuracarb, bensul oxyclozanide, pamaquine, phenothiazine, piperazine adi tap, bifenthrin, bioallethrin, bioresmethrin, bistrifluoron, buprofezin, butocarboxim, carbaryl, carbofuran, carbosul pate, piperazine citrate, piperazine phosphate, PNU-97333 fan, cartap, chlorantraniliprole, chlorethoxyfos, chlo (paraherquamide A), PNU-141962 (2-deoxyparaherqu rfenapyr, chlorfenvinphos, chlorfluaZuron, chlormephos, 15 amide), praziquantel, primaquine, propetamphos, propoXur, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, cloth pyrantel pamoate, pyrimethamine, Santonin, Selamectin, Sul ianidin, cyanophos, cyantraniliprole, cyclaniliprole, cyclo fadimethoxine, Sulfadoxine, Sulfamerazine, sulfa prothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma monomethoxine, Sulfamoildapsone, thiabendazole, tinida cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha Zole, toltraZuril, tribromsalan and triclabendazole. cypermethrin, beta-cypermethrin, Zeta-cypermethrin, Antifungal agents: Such as ketoconazole and miconazole cyphenothrin, cyromazine, deltamethrin, diafenthiuron, nitrate. diazinon, dichlorvos, diflubenzuron, dimethoate, dimethyl Antibiotics: Such as amoxicillin, amplicillin, bethoxazin, Vinphos, dinotefuran, diofenolan, disulfoton, emamectin bithionol, bronopol, cefapirin, cefazolin, cefauinome, benzoate, empenthrin, endosulfan, alpha-endosulfan, EPN, ceftiofur, chlortetracycline, clavulanic acid, danofloxacin, esfenvalerate, ethiofencarb, ethiprole, etofenprox, etrimfos, 25 difloxacin, dinitolmide, enrofloxacin, florfenicol, lincomy fenitrothion, fenobucarb, fenoxycarb, fenthion, fenvalerate, cin, lomefloxacin, marbofloxacin, miloxacin, mirosamycin, fipronil, flometoquin, flonicamid, fluaZuron, flubendiamide, nitrapyrin, norfloxacin, octhillinone, ofloxacin, orbifloxacin, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flu oXolinic acid, oxytetracycline, penicillin, Streptomycin, thia fiprole, flumethrin, flupyradifurone, fluralaner, fluvalinate, mphenicol, tiamulin fumarate, tilmicosin phosphate, acetyl tau-fluvalinate, fonofos, furathiocarb, halofenozide, hepta 30 isovaleryltylosin, tylosin phosphate, tulathromycin, valine fluthrin, hexaflumuron, hydramethylnon, imidacloprid, imi mulin, calcinated shell calcium (calcium oxide), prothrin, indoxacarb, indoxacarb-MP isoprocarb, isoxa Talaromyces, Trichoderma and Coniothyrium. thion, lepimectin, lufenuron, malathion, meperfluthrin, metaflumizone, metaldehyde, methacrifos, methamidophos, EXAMPLES methidathion, methomyl, methoprene, methoxychlor, 35 methoxyfenozide, metofluthrin, muscalure, nitenpyram, The present invention will be described in further detail novaluron, noviflumuron, omethoate, Oxydemeton-methyl, by referring to the following specific Examples of synthesis parathion-methyl, permethrin, phenothrin, phenthoate, phor of and tests on the compounds of the present invention. ate, phosalone, phosmet, phoxim, pirimicarb, pirimiphos However, the present invention is by no means restricted methyl, profenofos, prothiofos, pymetrozine, pyraclofos, 40 thereto. pyrethrins, pyridalyl pyrifluquinazon, pyriprole, pyriproxy fen, resmethrin, rotenone, Silafluofen, spinetoram, spinosad, Synthetic Examples spirotetramat, sulfotep, sulfoxaflor, tebufenozide, tefluben Zuron, tefluthrin, terbufos, tetrachlorvinphos, tetramethrin, Synthetic Example 1 d-T-80-phthal thrin (d-tetramethrin), tetramethylfluthrin, 45 thiacloprid, thiamethoxam, thiocyclam, thiodicarb, thio (Z)—N-2-(2,4-dichlorophenyl)-2-(methoxyimino) fanox, thiometon, tolfenpyrad, tralomethrin, transfluthrin, ethyl-2-(trifluoromethyl)benzamide (Compound triazamate, trichlorfon, triflumuron, ME5382 (experimental No. 1-004 of the Present Invention) name), NC-515 (experimental name) and ZDI2501 (experi mental name). 50 Step 1: Preparation of 2-bromo-1-(2,4-dichlorophe Miticides: Such as acequinocyl, acrinathrin, amidoflumet, nyl)ethanone-O-methyloxime amitraz, azocyclotin, benzoximate, bifenazate, bromopropy late, clofentezine, cyenopyrafen, cyflumetofen, dicofol. To 4.00 g of 2-bromo-1-(2,4-dichlorophenyl)ethanone in dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenoth 20 ml of ethanol, 1.25 g of methoxyamine hydrochloride iocarb, fempropathrin, fenpyroximate, fluacrypyrim, 55 was added, and the mixture was stirred at room temperature formetanate, halfenproX, hexythiazox, milbemectin, for 12 hours. After completion of the reaction, the solvent propargite, pyflubumide, pyridaben, pyrimidifen, spirodi was evaporated under reduced pressure, and the resulting clofen, spiromesifen, tebufenpyrad and NA-89 (experimen residue was mixed with 20 ml of water and extracted with tal name). ethyl acetate (20 mlx2). The resulting organic layers were Nematicides: Such as cadusafos, dichlofenthion, ethopro 60 combined, washed with water (20 mlx1) and then dried over phos, fenamiphos, fluenSulfone, fosthiazate, fosthietan, imi saturated aqueous sodium chloride and then anhydrous cyafos, isamidofos, isaZofos, methyl bromide, methyl iso Sodium sulfate, and the solvent was evaporated under thiocyanate, oxamyl, Sodium azide, BYI-1921 reduced pressure to obtain 3.85 g of the desired crude (experimental name) and MAI-08015 (experimental name). product as a pale yellow oil. The oil was used in the next step Vermicides: Such as acriflavine, albendazole, atovaguone, 65 without further purification. azithromycin, bithionol, bromofenofos, cambendazole, H NMR (CDC1, Me Si, 300 MHz) 87.2-7.55 (m, 3H), camidazole, chloroquine, claZuril, clindamycin hydrochlo 4.56 and 4.35 (s. 2H), 4.06 and 4.04 (s, 3H). US 9,434,684 B2 195 196 Step 2: Preparation of N-2-(2,4-dichlorophenyl)-2- of methylmagnesium bromide was added dropwise with (methoxyimino)ethylphthalimide stirring under cooling with ice, and the mixture was stirred at the same temperature for 1 hour. After completion of the To 2.17 g of 2-bromo-1-(2,4-dichlorophenyl)ethanone-O- reaction, the reaction mixture was mixed with 15 ml of methyloxime in 20 ml of N,N-dimethylformamide, 3.03 g of 5 potassium phthalimide and 1.61 g of potassium carbonate concentrated hydrochloric acid and 100 ml of water and were added, and the mixture was stirred at room temperature extracted with ethyl acetate (100 mlx2), the resulting for 18 hours. After completion of the reaction, the reaction organic layers were combined, washed with water (100 mixture was mixed with 40 ml of water and extracted with mlx1) and dried over Saturated aqueous solution chloride ethyl acetate (50 mlx1), the resulting organic layer was and then anhydrous sodium Sulfate, and the solvent was washed with water (20 mlx1) and then dried over saturated 10 evaporated under reduced pressure. The resulting residue aqueous sodium chloride and then anhydrous sodium Sul was dissolved in 40 ml of ethyl acetate and 10 ml of hexane, fate, and the solvent was evaporated under reduced pressure. 20g of silica gel was added, the mixture was stirred at room The resulting residue was purified by silica gel column temperature for 1 hour and then subjected to filtration, and chromatography using ethyl acetate-hexane (with a gradient the solvent was evaporated under reduced pressure. The of from 1:9 to 3:7) as the eluent to obtain 2.10 g of the 15 precipitated solid was washed with 50 ml of hexane to obtain desired product as pale yellow crystals. 17.16 g of the desired product as pale yellow crystals. m.p.: 82.0-85.0° C. "H NMR (CDC1, MeSi, 300 MHz) 88.50 (d. J–2.1 Hz, "H NMR (CDC1, MeSi, 300 MHz) 87.65-7.8 (m, 4H), 1H), 7.82 (d. J–2.1 Hz, 1H), 2.68 (s, 3H). 7.15-7.35 (m, 3H), 4.92 (s. 2H), 4.01 (s, 3H). Step 3: Preparation of 2-amino-1-(2,4-dichlorophe Step 2: Preparation of nyl)ethanone-O-methyloxime 2-bromo-1-(3,5-dichloropyridin-2-yl)ethanone To 316 mg of N-2-(2,4-dichlorophenyl)-2-(methoxy To 5.00 g of 1-(3,5-dichloropyridin-2-yl)ethanone in 75 imino)ethylphthalimide in 10 ml of ethanol, 108 mg of ml of tetrahydrofuran, 9.94 g of trimethylphenylammonium hydrazine monohydrate was added, and the mixture was 25 tribromide was added, and the mixture was stirred at room stirred at 60° C. for 2 hours. After completion of the reaction, temperature for 16 hours. After completion of the reaction, the reaction mixture was allowed to cool to room tempera the precipitated solid was filtered off through celite, and the ture, mixed with 30 ml of water and extracted with ethyl solvent was evaporated under reduced pressure. The result acetate (40 mlx1). The resulting organic layer was dried over ing residue was purified by Silica gel column chromatogra saturated aqueous sodium chloride and then anhydrous 30 phy using ethyl acetate-hexane (with a gradient of from 5:95 Sodium Sulfate, and the solvent was evaporated under to 15:85) as the eluent to obtain 6.64 g of the desired product reduced pressure to obtain 170 mg of the desired crude as a brown oil. product as a colorless oil. The oil was used in the next step H NMR (CDC1, MeSi, 300 MHz) 88.51 (d. J=1.9 Hz, without further purification. 1H), 7.88 (d. J=1.9 Hz, 1H), 4.67 (s. 2H). "H NMR (CDC1, MeSi, 300 MHz) 87.25-7.45 (m, 3H), 35 3.99 (s.3H), 3.82 (s. 2H). Step 3: Preparation of 2-bromo-1-(3,5-dichloropyri Step 4: Preparation of (Z) N-2-(2,4-dichlorophe din-2-yl)ethanone-O-ethyloxime nyl)-2-(methoxyimino)ethyl-2-(trifluoromethyl) benzamide To 3.00 g of 2-bromo-1-(3,5-dichloropyridin-2-yl)etha 40 none in 25 ml of ethanol, 1.09 g of ethoxyamine hydrochlo To a solution of 170 mg of 2-amino-1-(2,4-dichlorophe ride was added, and the mixture was stirred at room tem nyl)ethanone-f-methyloxime and 74 mg of triethylamine in perature for 16 hours. After completion of the reaction, the 5 ml of dichloromethane, 122 mg of 2-(trifluoromethyl) Solvent was evaporated under reduced pressure, the resulting benzoyl chloride was added dropwise, and the mixture was residue was mixed with 50 ml of water and extracted with stirred at room temperature for 1 hour. After completion of 45 the reaction, the reaction mixture was mixed with 10 ml of ethyl acetate (50 mlx2), the resulting organic layers were water and extracted with chloroform (20 mlx1), the resulting combined, washed with water (50 mlx1) and dried over organic layer was dried over Saturated aqueous sodium saturated aqueous sodium chloride and then anhydrous chloride and then anhydrous sodium Sulfate, and the solvent Sodium sulfate, and the solvent was evaporated under was evaporated under reduced pressure. The resulting resi reduced pressure. The resulting residue was purified by due was mixed with 3 ml of diisopropyl ether and crystal 50 silica gel column chromatograph using ethyl acetate-hexane lized to obtain 110 mg of the desired product as white (with a gradient of from 5:95 to 15:85) as the eluent to obtain crystals. 3.03 g of the desired product as a colorless oil. m.p.: 146.0-148.0°C. H NMR (CDC1, MeSi, 300 MHz) 88.50 (d. J=2.1 Hz, "H NMR (CDC1, MeSi, 300 MHz) 87.25-7.7 (m, 6H), 1H), 7.81 (d. J=2.1 Hz, 1H), 4.67 and 4.52 (s. 2H), 4.35 and 7.05-7.15 (m. 1H), 6.31 (bs, 1H), 4.62 (d. J=6.3 Hz, 2H), 55 4.32 (q, J–7.2 Hz, 2H), 1.37 and 1.36 (t, J=7.2 Hz, 3H). 4.02 (s, 3H). Step 4: Preparation of N-2-(3,5-dichloropyridin-2- Synthetic Example 2 yl)-2-(ethoxyimino)ethylphthalimide (Z)—N-2-(3,5-dichloropyridin-2-yl)-2-(ethoxy imino)ethyl-2-(trifluoromethyl)benzamide (Com 60 To 3.00 g of 2-bromo-1-(3,5-dichloropyridin-2-yl)etha pound No. 2-120 of the Present Invention) none-O-ethyloxime in 20 ml of N,N-dimethylformamide, 2.32 g of potassium phthalimide was added, and the mixture Step 1: Preparation of was stirred at room temperature for 12 hours. After comple 1-(3,5-dichloropyridin-2-yl)ethanone tion of the reaction, the reaction mixture was mixed with 50 65 ml of water and extracted with ethyl acetate (100 mlx1), the To 20 g of 3,5-dichloropyridine-2-carbonitrile in 150 ml resulting organic layer was washed with water (50 mlx1) of tetrahydrofuran, 139 ml of a 1Mtetrahydrofuran solution and dried over Saturated aqueous sodium chloride and then