US008895.035B2

(12) United States Patent (10) Patent No.: US 8,895,035 B2 Fukumoto et al. (45) Date of Patent: Nov. 25, 2014

(54) ALKOXYIMINO DERIVATIVE AND PEST (2013.01); A0IN 43/08 (2013.01); A0IN 43/10 CONTROL AGENT (2013.01); A0IN 43/20 (2013.01); A0IN 43/40 (2013.01); A0IN 43/50 (2013.01); A0IN 43/56 (75) Inventors: Shunichirou Fukumoto, Shizuoka (JP); (2013.01); A0IN 43/653 (2013.01); A0IN Daisuke Shikama, Shizuoka (JP); Keiji 43/713 (2013.01); A0IN 43/78 (2013.01); Toriyabe, Shizuoka (JP); Toshihiro A0IN 43/82 (2013.01); C07C 259/02 Nagata, Shizuoka (JP); Masaaki (2013.01); A0IN 43/84 (2013.01); C07D Komatsu, Shizuoka (JP): Takeshi 249/10 (2013.01); C07D401/12 (2013.01); Matsuda, Shizuoka (JP); Yuki Nakano, C07D 403/12 (2013.01); C07D 413/06 Tokyo (JP) (2013.01); C07D 413/12 (2013.01); C07D (73) Assignees: Kumiai Chemical Industry Co., Ltd, 417/06 (2013.01); C07F 7/10 (2013.01); C07D 403/06 (2013.01); C07D405/12 (2013.01); Tokyo (JP); Ihara Chemical Industry C07D 417/12 (2013.01); A0IN 47/18 Co., Ltd., Tokyo (JP) (2013.01); C07F 7/0812 (2013.01) (*) Notice: Subject to any disclaimer, the term of this USPC ...... 424/400: 514/63: 514/236 patent is extended or adjusted under 35 (58) Field of Classification Search U.S.C. 154(b) by 0 days. CPC ...... A01N 37/50: A01N 43/56 (21) Appl. No.: 13/806,317 USPC ...... 424/400: 514/63, 236 See application file for complete search history. (22) PCT Filed: Jun. 21, 2011 (86). PCT No.: PCT/UP2011/OO3522 (56) References Cited S371 (c)(1), (2), (4) Date: Dec. 21, 2012 U.S. PATENT DOCUMENTS (87) PCT Pub. No.: WO2011/161945 4,358.408 A 11/1982 Kruger et al. 5,411,990 A 5/1995 Tsuji et al. PCT Pub. Date: Dec. 29, 2011 (Continued) (65) Prior Publication Data US 2013/O1 O2568 A1 Apr. 25, 2013 FOREIGN PATENT DOCUMENTS (30) Foreign Application Priority Data AU A-9 1777.82 12/1982 GB 1443555. A 7, 1976 Jun. 24, 2010 (JP) ...... 2010-143577 (Continued) (51) Int. Cl. AOIN 43/54 (2006.01) Primary Examiner — Johann R Richter AOIN 55/00 (2006.01) Assistant Examiner — Yanzhi Zhang AOIN 37/50 (2006.01) (74) Attorney, Agent, or Firm — Bacon & Thomas, PLLC AOIN 43/08 (2006.01) AOIN 43/10 (2006.01) (57) ABSTRACT AOIN 43/20 (2006.01) AOIN 43/40 (2006.01) The present invention provides a novel alkoxyimino deriva AOIN 43/50 (2006.01) tive or a salt thereof, as well as to a pest control agent con AOIN 43/56 (2006.01) taining the derivative or salt thereofas an active ingredient, AOIN 43/653 (2006.01) which shows an excellent pest control effect on a wide range AOIN 43/73 (2006.01) of pests in the agricultural and horticultural field and is also AOIN 43/78 (2006.01) capable of controlling resistant pests. The novel alkoxyimino AOIN 43/82 (2006.01) derivative is characterized by being represented by general C07C 259/02 (2006.01) formula I AOIN 43/84 (2006.01) Chemicial formula 1 CO7D 249/10 (2006.01) CO7D 40/12 (2006.01) CO7D 403/2 (2006.01) X CO7D 413/06 (2006.01) CO7D 413/2 (2006.01) R11 O NN 2 2 No1 CO7D 417/06 (2006.01) C07F 7/10 (2006.01) CO7D 403/06 (2006.01) CO7D 405/2 (2006.01) (in the formula, X, R, R and Q are as defined in the speci C07D 417/12 (2006.01) fication) and the post control agent is characterized by con AOIN 47/8 (2006.01) taining as an active ingredient the alkoxyimino derivative or a C07F 7/08 (2006.01) salt thereof. (52) U.S. Cl. CPC ...... A0IN 55/00 (2013.01); A0IN37/50 16 Claims, No Drawings US 8,895,035 B2 Page 2

(56) References Cited JP 521361.20. A 11, 1977 JP 58110569. A T 1983 U.S. PATENT DOCUMENTS JP 6-40811 A 2, 1994 JP 11-512446. A 10, 1999 6,130,247 A 10/2000 Bayer et al. JP 2000506902 A1 6, 2000 6.225,349 B1* 5/2001 Bayer et al...... 514,538 JP 2001-513782. A 9, 2001 2004/0023806 A1* 2/2004 Ziegler et al...... 504,244 JP 2003-516384 A 5, 2003 WO 971 1065 A1 3, 1997 FOREIGN PATENT DOCUMENTS WO 01,36399 A1 5, 2001 JP 49-55833 5, 1974 * cited by examiner US 8,895,035 B2 1. ALKOXYMNO DERVATIVE AND PEST CONTROL AGENT Formula 1 TECHNICAL FIELD

The present invention relates to a novel alkoxyimino R11 OnNN 2 2 N No1 derivative or a salt thereof, as well as to a pest control agent containing the derivative or salt thereof as an active ingredi ent. 10 in the formula, BACKGROUND ART X is a hydrogen atom, a halogen atom, a cyano group, a C-C alkyl group, a C-C alkenyl group, a C-C alkynyl For example, the following patent literature 1 or patent group, a C-C cycloalkyl group, a C-C cycloalkyl C-C, literature 2 is already known as a literature regarding com 15 alkyl group, a C-C haloalkyl group, a C-C alkylthio pounds similar to the alkoxyimino derivative of the present group, a C-C alkylsulfinyl group, a C-C alkylsulfonyl invention. group, a C-C alkylthio C-C alkyl group, a C-C alkyl The patent literature 1 discloses a hydroximoylazole sulfinyl C-C alkyl group, a C-C alkylsulfonyl C-C, derivative. However, this derivative is restricted to com alkyl group, a C-C alkoxy group, a C-C alkoxy C-C, pounds having a carbamic acid ester structure, and the litera alkyl group, a thiocarbamoyl group, a RRNC(=O) group, ture does not disclose the alkoxyimino derivative of the a R'R''N group, a C-C alkoxycarbonyl group, a carboxyl present invention. group, a RO(HN=)C group, a RON=(R')C group, a The patent literature 2 discloses a hydroximoyl derivative. R''S(O—)C group, a R'R''NSONH group, a hydroxy However, this derivative is restricted to O-acyl derivatives, 25 C-C alkyl group, a cyano C-C alkyl group, a C-C, and the literature does not disclose the alkoxyimino derivative alkylcarbonyl group, a phenyl group which may be substi of the present invention. tuted with substituent(s) selected from substituent group C. PRIOR ART LITERATURES shown later, or a heterocyclic ring group of 1 to 9 carbon 30 atoms, having 1 to 5 hetero atoms which may be the same or Patent Literatures different and which are selected from oxygen atom, sulfur atom and nitrogen atom (the group may be substituted with 1 Patent literature 1: DE-3150984 to 5 substituent(s) selected from halogenatoms, C-C alkyl Patent literature 2: JP-1995-41704 group, C-C haloalkyl group, C-C alkoxy group, oxo 35 group or cyano group), SUMMARY OF THE INVENTION R" is a C-Clo alkyl group, a C-C alkenyl group, a C-C alkynyl group, a C-C cycloalkyl group, a C-C, Task to be Achieved by the Invention cycloalkyl C-C alkyl group, a C-C haloalkyl group, a C-C haloalkenyl group, a C-C haloalkynyl group, a 40 It is desired that pest control agents such as insecticide, C-C alkylthio C-C alkyl group, a C-C alkylsulfinyl acaricide and the like, used to useful crops are safe to man and C-C alkyl group, a C-C alkylsulfonyl C-C alkyl group, livestock, are Small in influence to environment, and exhibit a a C-C alkoxy C-C alkyl group, a C-C haloalkoxy sufficient effect to pests at a low dose. Use of insecticides and C-C alkyl group, a C-C alkoxyimino C-C alkyl group, acaricides for past many years has generated resistant pests, 45 a tri (C-C alkyl)silyl C-C alkyl group, a cyano C-C, making it difficult to control pests completely with conven alkyl group, a gem-di (C-C alkoxy) C-C alkyl group, a tional chemicals. hydroxy C-C alkyl group, an amino C-C alkyl group (the The task of the present invention is to provide an excellent group may be substituted with R'' and R'), a phenyl group which may be substituted with substituent(s) selected from pest control agent which solves the above-mentioned prob 50 lems of conventional pest control agents. the Substituent group C, a phenyl C-C alkyl group which may be substituted with substituent(s) selected from the sub Means for Achieving the Task stituent group C, a phenyl C-C alkenyl group which may be substituted with substituent(s) selected from the substituent In order to develop a pest control agent having the above 55 group C, a phenoxy C-C alkyl group which may be substi mentioned advantageous features, the present inventors Syn tuted with substituent(s) selected from the substituent group thesized various alkoxyimino derivatives and studied physi C., a heterocyclic ring group of 1 to 9 carbon atoms, having 1 ological activities thereof. As a result, it was found that an to 5 hetero atoms which may be the same or different and alkoxyimino derivative represented by the general formula II which are selected from oxygen atom, Sulfur atom and shown below shows a high effect to pests and resistant pests. 60 nitrogen atom (the group may be substituted with 1 to 5 The finding has led to the completion of the present invention. Substituent(s) selected from halogen atoms, C-C alkyl The present invention has a scope characterized as shown group, C-Chaloalkyl group, C-C alkoxy group, or cyano below. group), a C-C alkyl group Substituted with a heterocyclic (1) An alkoxyimino derivative characterized by being repre 65 ring of 1 to 9 carbonatoms, having 1 to 5 hetero atoms which sented by the following general formula I or an agricul may be the same or different and which are selected from turally acceptable salt thereof. oxygen atom, Sulfur atom and nitrogen atom (the group may US 8,895,035 B2 3 4 be substituted with 1 to 5 substituent(s) selected from halogen alkylene chain may contain one oxygenatom, Sulfur atom or atoms, C-C alkyl group, C-C haloalkyl group, C-C, nitrogenatom and also may be substituted with halogenatom, alkoxy group, oxo group or cyano group), or a C-C alkenyl C-C alkyl group and oxo group, group substituted with a heterocyclic ring of 1 to 9 carbon RandR are each a hydrogenatom, a C-C alkyl group, atoms, having 1 to 5 hetero atoms which may be the same or a C-C haloalkyl group, or a C-C alkoxycarbonyl group, different and which are selected from oxygen atom, sulfur R" is a RRN group or Q, and atom and nitrogen atom (the group may be substituted with 1 R'' is a C-C alkyl group. Substituent Group C. to 5 substituent(s) selected from halogen atoms, C-C alkyl Halogenatom, C-C alkyl group, C-Chaloalkyl group, group, C-C haloalkyl group, C-C alkoxy group, or a 10 C-C alkoxy group, C-C haloalkoxy group, C-C, cyano group, alkoxycarbonyl group, nitro group, and cyano group when the heterocyclic ring group contains nitrogen atom, (2) An alkoxyimino derivative oran agriculturally acceptable the nitrogen atom may be oxidized to form N-oxide, R is a C-C alkyl group, a C-C alkenyl group, a C-C, salt thereof, set forth in (1), wherein alkynyl group, a C-C cycloalkyl group, a C-C haloalkyl 15 X is a hydrogen atom, a halogen atom, a cyano group, a group, a C-C haloalkenyl group, a C-C haloalkynyl C-C alkyl group, a C-C cycloalkyl group, a C-C, group, a C-C alkylthio C-C alkyl group, a C-C alkyl haloalkyl group, a C-C alkylthio group, a C-C alkylsulfi Sulfinyl C-C alkyl group, a C-C alkylsulfonyl C-C, nyl group, a C-C alkylsulfonyl group, a C-C alkoxy alkyl group, a C-C alkoxy C-C alkyl group, a C-C, group, a thiocarbamoyl group, a RRNC(=O) group, a haloalkoxy C-C alkyl group, a cyano C-C alkyl group, or RRN group, a C-C alkoxycarbonyl group, a carboxyl a phenyl C-C alkyl group which may be substituted with group, a RO(HN=)C group, a RON=(R')C group, a the Substituent group C. R'S(O—)C group, a R'R''NSONH group, a hydroxy Q is a heterocyclic ring group represented by the following C-C alkyl group, a cyano C-C alkyl group, a C-C, formula O-1 or formula O-2. alkylcarbonyl group, a phenyl group which may be substi 25 tuted with substituent(s) selected from the substituent group C, or a heterocyclic ring group of 1 to 9 carbon atoms, having formula 2) 1 to 5 hetero atoms which may be the same or different and which are selected from oxygen atom, Sulfur atom and Q-1 nitrogen atom (the group may be substituted with 1 to 5 30 Substituent(s) selected from halogen atoms, C-C alkyl N group, C-C haloalkyl group, C-C alkoxy group, oxo group or cyano group), KN- # -R)pi R" is a C-Clo alkyl group, a C-C alkenyl group, a Q-2) C-C alkynyl group, a C-C cycloalkyl group, a C-C, 35 cycloalkyl C-C alkyl group, a C-C haloalkyl group, a C-C haloalkenyl group, a C-C alkylthio C-C alkyl S. group, a C-C alkoxy C-C alkyl group, a C-C, ( IT-R3 ), haloalkoxy C-C alkyl group, a tri (C-C alkyl)silyl C-C, alkyl group, a cyano C-C alkyl group, a gem-di (C-C, 40 alkoxy) C-C alkyl group, a hydroxy C-C alkyl group, an or a halogen atom, amino C-C alkyl group (the group may be substituted with in the formula Q-1, W is a nitrogen atom or a methine R'' and R'), a phenyl group which may be substituted with grOup, Substituent(s) selected from the Substituent group C, a phenyl the nitrogen atom(s) of the heterocyclic ring group of for C-C alkyl group which may be substituted with substitu mula Q-1 and formula Q-2) may be oxidized to form N-ox 45 ent(s) selected from the Substituent group C, a phenyl C-C, ide, alkenyl group which may be substituted with substituent(s) in the formula Q-1 and formula Q-2), R is a halogen selected from the substituent group C, a phenoxy C-C alkyl atom, a cyano group, a nitro group, a hydroxyl group, a group which may be substituted with substituent(s) selected mercapto group, a C-C alkyl group, a C-C haloalkyl from the Substituent group C, a heterocyclic ring group of 1 to group, a C-C alkoxy group, a C-C alkylthio group, a 50 9 carbonatoms, having 1 to 5 hetero atoms which may be the C-C alkylsulfinyl group, a C-C alkylsulfonyl group, a same or different and which are selected from oxygen atom, formyl group, or a hydroxyimino C-C alkyl group, Sulfur atom and nitrogen atom (the group may be substituted in the formula Q-1 and formula Q-2, n is 0, 1 or 2 when with 1 to 5 substituent(s) selected from halogenatoms, C-C, W is a nitrogen atom and 0, 1, 2 or 3 when W is a methine alkyl group, C-C haloalkyl group, C-C alkoxy group, or grOup, 55 cyano group), or a C-C alkyl group Substituted with a R. R. R. R7, R. R. R'' and R' are each a hydrogen heterocyclic ring of 1 to 9 carbon atoms, having 1 to 5 hetero atom, a C-C alkyl group, a C-C alkoxy group, a C-C, atoms which may be the same or different and which are alkoxy C-C alkyl group, a C-C alkylcarbonyl group, a selected from oxygen atom, Sulfur atom and nitrogen atom C-C alkoxycarbonyl group, a C-C haloalkyl group, a (the group may be substituted with 1 to 5 substituent(s) C-C cycloalkyl group, a C-C cycloalkyl C-C alkyl 60 selected from halogen atoms, C-C alkyl group, C-C, group, a C-C alkylsulfonyl group, a cyano C-C alkyl haloalkyl group, C-C alkoxy group, oxo group or cyano group, or a phenyl group which may be substituted with group). Substituent(s) selected from the Substituent group C. when the heterocyclic ring group contains nitrogen atom, R and R, R and R7, R'' and R', and R'' and R' may the nitrogen atom may be oxidized to form N-oxide, respectively be combined together to forman C-C, alkylene 65 R is a C-C alkyl group, a C-C alkenyl group, a C-Cs chain and thereby may form, together with the nitrogenatom alkynyl group, a C-C cycloalkyl group, a C-C haloalkyl to which they bond, a 3- to 8-membered ring, wherein the group, a C-C alkoxy C-C alkyl group, a cyano C-C, US 8,895,035 B2 5 6 alkyl group, or a phenyl C-C alkyl group which may be (7) A method for pest control, which is characterized by substituted with the substituent group C, using, in an effective amount, analkoxyimino derivative or Q is a heterocyclic ring group represented by the following an agriculturally acceptable salt thereof, set forth in any of formula O-1 or formula O-2. (1) to (4). 5 (8) A method for pest control according to (7), which com prises using an alkoxyimino derivative or an agriculturally formula 3 acceptable salt thereof as an insecticide. The alkoxyimino derivative or agriculturally acceptable Q-1 salt thereof, of the present invention is a novel compound. The 10 pest control agent containing the compound as an active Nw ingredient shows an excellent control effect to a variety of ( t R3 pests in agricultural and horticultural fields, can control even N if t-R), resistant pests, and is highly effective particularly to Hemi Q-2) pteran pests such as Nilaparvata lugens (brown rice plantho 15 pper), Laodelphax striatella (Small brown planthopper), Sogatella fircifera (white backed rice planthopper), Nepho S. tettix cincticeps (green rice leafhoper), Aphis gossipii (aphid), N- R3 ), Benisia tabaci (white fly) and the like. BEST MODE FOR CARRYING OUT THE or a halogen atom, INVENTION in the formula Q-1, W is a nitrogen atom or a methine grOup, Description is made on the symbols and terms used in the in the formula Q-1 and formula Q-2), R is a mercapto Description. group or a C-C haloalkyl group, 25 In the present invention, pest control agent means pest in the formula Q-1 and formula Q-2, n is 0 or 1, control agents targeted for injurious orthopods, used in agri R. R. R. R7, R. R. R'' and R' are each a hydrogen cultural and horticultural fields, livestock industry, sanitation atom, a C-C alkyl group, a C=C alkoxy group, a C-C, field, etc. (insecticide and acaricide agents for agricultural alkylcarbonyl group, a C-C alkoxycarbonyl group, a and horticultural fields, control agents for internal and exter 30 nal parasites of mammals and birds as livestock or pet animal, C-C haloalkyl group, a C-C cycloalkyl C-C alkyl and control agents for sanitary pests and uncomfortable pests, group, a cyano C-C alkyl group, or a phenyl group which for household use and business use). may be substituted with substituent(s) selected from the sub In the present invention, agricultural chemical means stituent group C. insecticides, acaricides, nematicides, etc. used in agricultural R and R, R and R7, R'' and R', and R'' and R' may 35 and horticultural fields. respectively be combined together to forman C-C, alkylene Halogen atom refers to fluorine atom, chlorine atom, bro chain and thereby may form, together with the nitrogenatom mine atom or iodine atom. to which they bond, a 3- to 8-membered ring, wherein the C-C alkyl group refers to a straight chain or branched alkylene ring may contain one oxygen atom, Sulfur atom or chain alkyl group of 1 to 6 carbon atoms, unless otherwise nitrogen atom, 40 specified. There can be mentioned, for example, methyl, RandR are each a hydrogenatom, a C-C alkyl group, ethyl, n-propyl, isopropyl. n-butyl, sec-butyl, isobutyl, tert or a C-C alkoxycarbonyl group, butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, R' is a RRN group or Q, and 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl. neo R'' is a C-C alkyl group. pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methyl (3) An alkoxyimino derivative oran agriculturally acceptable 45 pentyl, isohexyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbu tyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2.2- salt thereof, set forth in (1) or (2), wherein Q is a halogen dimethylbutyl, 2,3-dimethylbutyl, 3.3-dimethylbutyl, 1,1,2- atOm. trimethylpropyl, 1.2.2-trimethylpropyl, and 1-ethyl-1- (4) An alkoxyimino derivative oran agriculturally acceptable methylpropyl groups. salt thereof, set forth in (1) or (2), wherein Q is a hetero cyclic ring group represented by the following formula 50 C-C alkyl group refers to a straight chain or branched chain alkyl group of 1 to 8 carbon atoms, unless otherwise Q-1. specified. There can be mentioned, for example, those groups mentioned for the C-C alkyl group; and n-heptyl, 1-meth ylhexyl, 5-methylhexyl, 4.4-dimethylpentyl, n-octyl, 1-me Formula 4 55 thylheptyl, 6-methylhexptyl and 5,5-dimethylhexyl groups. C-C alkyl group refers to a straight chain or branched chain alkyl group of 1 to 10 carbon atoms, unless otherwise specified. There can be mentioned, for example, those groups NS mentioned for the C-C alkyl group; and n-nonyl, isononyl, KN- AIf t-R)pi 60 n-decanyl, isodecanyl, 7.7-dimethyloctyl and n-undecanyl groups. C-C alkenyl group refers to a straight chain or branched (5) A pest control agent characterized by containing, as an chain alkenyl group of 2 to 6 carbon atoms, unless otherwise active ingredient, an alkoxyimino derivative or an agricul specified. There can be mentioned, for example, vinyl, 1-pro turally acceptable salt thereof, set forth in any of (1) to (4). 65 penyl, isopropenyl, 2-propenyl, 1-butenyl, 1-methyl-1-pro (6) A pest control agent according to (5), which is an insec penyl, 2-butenyl, 1-methyl-2-propenyl, 3-butenyl, 2-methyl ticide. 1-propenyl, 2-methyl-2-propenyl, 1,3-butadienyl, US 8,895,035 B2 7 8 1-pentenyl, 1-ethyl-2-propenyl, 2-pentenyl, 1-methyl-1- tioned, for example, chloromethoxy, difluoromethoxy, chlo butenyl, 3-pentenyl, 1-methyl-2-butenyl, 4-pentenyl, 1-me rodifluoromethoxy, trifluoromethoxy and 2.2.2-trifluoroet thyl-3-butenyl, 3-methyl-1-butenyl, 1,2-dimethyl-2-prope hoxy groups. nyl, 1,1-dimethyl-2-propenyl, 2-methyl-2-butenyl, 3-methyl C-C alkylthio group refers, unless otherwise specified, 2-butenyl, 1,2-dimethyl-1-propenyl, 2-methyl-3-butenyl, to a straight chain or branched chain alkyl-Sgroup of 1 to 6 3-methyl-3-butenyl, 1,3-pentadienyl, 1-vinyl-2-propenyl, carbon atoms wherein the alkyl moiety of alkylthio has the 1-hexenyl, 1-propyl-2-propenyl, 2-hexenyl, 1-methyl-1-pen above-mentioned meaning. There can be mentioned, for tenyl, 1-ethyl-2-butenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, example, methylthio and ethylthio groups. 1-methyl-4-pentenyl, 1-ethyl-3-butenyl, 1-(isobutyl) vinyl, C-C alkylsulfinyl group refers, unless otherwise speci 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-2-propenyl, 10 fied, to a straight chain or branched chain alkyl-S(O)—group 1-(isopropyl)-2-propenyl, 2-methyl-2-pentenyl, 3-methyl-3- of 1 to 6 carbonatoms wherein the alkyl moiety of alkylsulfi pentenyl, 4-methyl-3-pentenyl, 1,3-dimethyl-2-butenyl, 1,1- nyl has the above-mentioned meaning. There can be men dimethyl-3-butenyl, 3-methyl-4-pentenyl, 4-methyl-4-pente tioned, for example, methylsulfinyl and ethylsulfinyl groups. nyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-3-butenyl, 1,1,2- C-C alkylsulfonyl group refers, unless otherwise speci trimethyl-2-propenyl, 1.5-hexadienyl, 1-vinyl-3-butenyl and 15 fied, to a straight chain or branched chain alkyl-S(O) - 2.4-hexadienyl groups. group of 1 to 6 carbon atoms wherein the alkyl moiety of C-C alkynyl group refers to a straight chain or branched alkylsulfonyl has the above-mentioned meaning. There can chain alkynyl group of 2 to 6 carbon atoms, unless otherwise be mentioned, for example, methylsulfonyl and ethylsulfonyl specified. There can be mentioned, for example, ethynyl, groups. 1-propynyl, 2-propynyl, 1-butynyl, 1-methyl-2-propynyl, C-C alkylthio C-C alkyl group refers, unless other 2-butynyl, 3-butynyl, 1-pentynyl, 1-ethyl-2-propynyl, 2-pen wise specified, to an alkyl group of 1 to 6 carbon atoms, tynyl, 3-pentynyl, 1-methyl-2-butynyl, 4-pentynyl, 1-me substituted with alkylthio group of 1 to 6 carbon atoms, thyl-3-butynyl, 2-methyl-3-butynyl, 1-hexnynyl, 1-(n-pro wherein the alkyl moiety and the alkyl moiety of alkylthio pyl)-2-propynyl, 2-hexynyl, 1-ethyl-2-butynyl, 3-hexynyl, have the above-mentioned meaning. There can be mentioned, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 4-methyl-1-pen 25 for example, methylthiomethyl and ethylthiomethyl groups. tynyl, 3-methyl-1-pentynyl, 5-hexnynyl, 1-ethyl-3-butynyl, C-C alkylsulfinyl C-C alkyl group refers, unless oth 1-ethyl-1-methyl-2-propynyl, 1-(isopropyl)-2-propynyl, 1.1- erwise specified, to an alkyl group of 1 to 6 carbon atoms, dimethyl-2-butynyl and 2,2-dimethyl-3-butynyl groups. substituted with alkylsulfinyl group of 1 to 6 carbon atoms, C-C cycloalkyl group refers to a cycloalkyl group of 3 to wherein the alkyl moiety and the alkyl moiety of alkylsulfinyl 6 carbon atoms, unless otherwise specified. There can be 30 have each the above-mentioned meaning. There can be men mentioned, for example, cyclopropyl, cyclobutyl, cyclopen tioned, for example, methylsulfinylmethyl and ethylsulfinyl tyl and cyclohexyl groups. methyl groups. C-C cycloalkyl C-C alkyl group refers, unless other C-C alkylsulfonyl C-C alkyl group refers, unless oth wise specified, to a (C-C cycloalkyl)-(C-C alkyl) group erwise specified, to an alkyl group of 1 to 6 carbon atoms, wherein the cycloalkyl moiety and the alkyl moiety have each 35 substituted with alkylsulfonyl group of 1 to 6 carbon atoms, the above-mentioned meaning. There can be mentioned, for wherein the alkyl moiety and the alkyl moiety of alkylsulfo example, cyclopropylmethyl, cyclobutylmethyl, cyclopen nyl have each the above-mentioned meaning. There can be tylmethyl and cyclohexylmethyl groups. mentioned, for example, methylsulfonylmethyl and ethylsul C-C alkoxy group refers, unless otherwise specified, to a fonylmethyl groups. (C-C alkyl)-O-group wherein the alkyl moiety has the 40 C-C alkoxy C-C alkyl group refers, unless otherwise above-mentioned meaning. There can be mentioned, for specified, to an alkyl group of 1 to 6 carbonatoms, Substituted example, methoxy, ethoxy, n-propoxy, isopropXy, n-butoxy, with alkoxy group of 1 to 6 carbon atoms, wherein the alkyl isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy moiety and the alkoxy moiety have each the above-mentioned and isohexyloxy groups. meaning. There can be mentioned, for example, methoxym C-C haloalkyl group refers, unless otherwise specified, 45 ethyl, ethoxymethyl, isopropoxymethyl, pentyloxymethyl, to a straight chain or branched chain alkyl group of 1 to 6 methoxyethyl and butoxyethyl groups. carbonatoms, substituted with 1 to 13, preferably 1 to 5 same Phenoxy C-C alkyl group refers, unless otherwise speci or different halogen atoms. There can be mentioned, for fied, to an alkyl group of 1 to 6 carbonatoms, substituted with example, 2-fluoroethyl, 2.2.2-trifluoroethyl, 3,3,3-trifluoro phenyl-O-group, wherein the alkyl moiety has the above propyl and 2.2.2-trichloroethyl groups. 50 mentioned meaning. There can be mentioned, for example, C-C haloalkenyl group refers, unless otherwise speci phenoxyethyl, 4-trifluoromethylphenoxypropyl and 2-(2- fied, to a straight chain or branched chain alkenyl group of 2 chlorophenoxy)propyl groups. to 6 carbon atoms, substituted with 1 to 11, preferably 1 to 5 C-C haloalkoxy C-C alkyl group refers, unless other same or different halogenatoms. There can be mentioned, for wise specified, to an alkyl group of 1 to 6 carbon atoms, example, 3-chloro-2-propenyl, 2-chloro-2-propenyl, 3.3- 55 Substituted with haloalkoxy group of 1 to 6 carbon atoms, dichloro-2-propenyl and 4.4-difluoro-3-butenyl groups. wherein the haloalkoxy moiety and the alkyl moiety have C-C haloalkynyl group refers, unless otherwise speci each the above-mentioned meaning. There can be mentioned, fied, to a straight chain or branched chain alkynyl group of 2 for example, chloromethoxymethyl, difluoromethoxym to 6 carbon atoms, substituted with 1 to 4 same or different ethyl, chlorodifuloromethoxymethyl, trifluoromethoxym halogen atoms. There can be mentioned, for example, 60 ethyl and 2.2.2-trifluoroethoxymethyl groups. 3-chloro-2-propynyl, 3-bromo-2-propynyl, 3-iodo-2-propy C-C alkoxyimino C-C alkyl group refers, unless oth nyl, 3-chloro-1-propynyl and 5-chloro-4-pentynyl groups. erwise specified, to an alkyl group of 1 to 6 carbon atoms, C-C haloalkoxy group refers, unless otherwise speci substituted with (alkoxy)-N= of 1 to 6 carbon atoms, fied, to a straight chain or branched chain alkyl-O-group of wherein the alkoxy moiety and the alkyl moiety have each the 1 to 6 carbon atoms, substituted with 1 to 11, preferably 1 to 65 above-mentioned meaning. There can be mentioned, for 5 same or different halogen atoms, wherein the haloalkyl example, 2-methoxyiminoethyl, 3-methoxyiminopropyl and moiety has the above-mentioned meaning. There can be men 1-methoxyiminoethyl groups. US 8,895,035 B2 9 10 Hydroxyimino C-C alkyl group refers, unless otherwise Hydroxy C-C alkyl group refers, unless otherwise speci specified, to an alkyl group of 1 to 4 carbonatoms, Substituted fied, to an alkyl group of 1 to 6 carbonatoms wherein the alkyl with HO N=. There can be mentioned, for example, moiety is substituted with hydroxyl group. There can be men hydroxyiminomethyl and hydroxyiminoethyl groups. tioned, for example, 2-hydroxyethyl, 3-hydroxy-n-butyl and Tri (C-C alkyl)silyl C-C alkyl group refers, unless 3-hydroxy-n-propyl groups. otherwise specified, to an alkyl group of 1 to 6 carbon atoms, C-C alkylcarbonyl group refers, unless otherwise speci substituted with tri(C-C alkyl)-Si group, wherein the fied, to alkyl-C(=O)— wherein the alkyl moiety has the alkyl moiety has the above-mentioned meaning. There can be above-mentioned meaning. There can be mentioned, for mentioned, for example, trimethylsilylmethyl group, 2-trim example, acetyl and isobutanoyl groups. ethylsilylethyl group, 3-trimethylsilylpropyl group and 4-tri 10 C-C alkoxycarbonyl group refers, unless otherwise methylsilylbutyl group. specified, to alkoxy-C(=O)—wherein the alkoxy moiety has the above-mentioned meaning. There can be mentioned, for Phenyl C-C alkyl group refers, unless otherwise speci example, methoxycarbonyl and isopropoxycarbonyl groups. fied, to an alkyl group of 1 to 6 carbonatoms, substituted with Amino C-C alkyl group refers, unless otherwise speci phenyl group, wherein the alkyl moiety has the above-men 15 fied, to an alkyl group of 1 to 6 carbonatoms wherein the alkyl tioned meaning. There can be mentioned, for example, ben moiety is substituted with amino group. There can be men Zyl, 1-phenylethyl and 2-phenylethyl groups. tioned, for example, 2-aminoethyl, 3-amino-n-butyl and Phenyl C-C alkenyl group refers, unless otherwise speci 3-amino-n-propyl groups. fied, to an alkenyl group of 2 to 6 carbon atoms, Substituted As the agriculturally acceptable salt, there can be men with phenyl group, wherein the alkyl moiety has the above tioned, for example, a salt of alkali metal (e.g. sodium or mentioned meaning. There can be mentioned, for example, potassium); a salt of alkaline earth metal (e.g. calcium, mag styryl and 3-phenyl-2-propenyl groups. nesium or barium); a salt of transition metal (e.g. manganese, As heterocyclic ring group of 1 to 9 carbon atoms, having copper, Zinc or iron); an ammonium salt (the nitrogen atom 1 to 5 hetero atoms which may be the same or different and may be, as necessary, Substituted with 1 to 4 alkyl groups of 1 which are selected from oxygen atom, Sulfur atom and nitro 25 to 4 carbon atoms and/or one phenyl or benzyl group), pref genatom, there can be mentioned, unless otherwise specified, erably diisopropyl ammonium, tetramethyl ammonium, tet for example, pyridine, pyrimidine, pyrazine, pyridazine, 1.3, rabutyl ammonium, or trimethylbenzyl ammonium; a salt 5-triazine, 1,2,4-triazine, pyrrole, pyrazole, imidazole, 1.3,4- with an inorganic acid (e.g. hydrochloric acid, hydrobromic triazole, 1,2,4-triazole, 1,2,3-triazole, tetrazole, furan, acid, phosphoric acid or Sulfuric acid); and a salt with an oxazole, isoxazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 30 organic acid such as C-C alkylsulfonic acid (e.g. methane thiophene, thiazole, isothiazole, 1.3,4-thiadiazole, 1,2,4-thia Sulfonic acid), aromatic Sulfonic acid (e.g. benzenesulfonic diazole, 1,2,3-thiadiazole, quinoline, indole, benzofuran, acid or toluenesulfonic acid), oxalic acid, maleic acid, benzothiophene, benzoimidazole, benzoxazole, benzisoX fumaric acid, lactic acid, tartaric acid, adipic acid, benzoic azole, benzothiazole, benzisothiazole, oxirane, oxorane and acid or the like. isoxazoline groups. Incidentally, when the heterocyclic ring 35 Next, representative compounds of the present invention group contains nitrogen atom, the nitrogen atom may be compound of the general formula II are shown in Tables 1 to oxidized to form N-oxide. 63. However, the present compound is not restricted thereto. C-C alkyl group Substituted with heterocyclic ring of 1 to The No. of each compound shown in each Table is referred to in the later description. 9 carbonatoms, having 1 to 5 hetero atoms which may be the The compounds included in the present invention contain, same or different and which are selected from oxygen atom, 40 in Some cases, E-isomers and Z-isomers depending upon the Sulfur atom and nitrogenatom, refers, unless otherwise speci kind of substituent. The present invention includes the E-iso fied, to an alkyl group of 1 to 6 carbonatoms, substituted with mers, the Z-isomers, and mixtures of any mixing ratio of heterocyclic ring, wherein the alkyl moiety has the above E-isomer and Z-isomer. Further, the compounds included in mentioned meaning. There can be mentioned, for example, the present invention contain, in some cases, optical isomers (tetrahydrofuran-2-yl)methyl, (4,5-dihydroisoxazol-5-yl) 45 due to the presence of at least one asymmetric carbon atom methyl, (isoxazol-5-yl)methyl and (thiophen-2-yl)methyl and asymmetric Sulfur atom. The present invention includes groups. all optical active compounds, racemic modifications and dias C-C alkenyl group Substituted with heterocyclic ring of tereomerS. 1 to 9 carbon atoms, having 1 to 5 hetero atoms which may be In the present invention, the following expressions refer to the same or different and which are selected from oxygen 50 corresponding groups. atom, Sulfur atom and nitrogenatom, refers, unless otherwise Me: methyl group specified, to an alkyl group of 1 to 6 carbonatoms, Substituted Et: ethyl group with heterocyclic ring, wherein the alkyl moiety has the Pr-n: n-propyl group above-mentioned meaning. There can be mentioned, for Pr-i: isopropyl group example, 5-(tetrahydrofuran-2-yl) vinyl and 3-(4,5-dihy 55 Pr-c: cyclopropyl group droisoxazol-5-yl)-2-propenyl groups. Bu-n: n-butyl group Cyano C-C alkyl group refers, unless otherwise speci Bu-s: Sec-butyl group fied, to an alkyl group of 1 to 6 carbonatoms, substituted with Bu-i: isobutyl group cyano group, wherein the alkyl moiety has the above-men Bu-t: tert-butyl group tioned meaning. There can be mentioned, for example, cya 60 Pen-n: n-pentyl group nomethyl group and 1-cyanobutyl group. Pen-c: cyclopentyl group gem-di (C-C alkoxy) C-C alkyl group refers, unless Pen-i: isopentyl group otherwise specified, to an alkyl group of 1 to 6 carbon atoms Pen-neo: neopentyl group wherein one carbon atom is substituted with two alkoxy Pen-2: 2-pentyl group groups having the above-mentioned meaning. There can be 65 Pen-3: 3-pentyl group mentioned, for example, diethoxymethyl and 2-dimethox Hex-n: n-hexyl group ypropyl groups. Hex-c: cyclohexyl group

US 8,895,035 B2 55 56 TABLE 63-continued R. R. R. R. R. R. R', R'' and the substituent group C. have each the above-mentioned meaning, Compound No. R X R2 R" is a hydrogen atom, a halogen atom, a cyano group, a VII-183 CH-C=CH CONH, Pr-n nitro group, a C-C alkyl group, a C-Chaloalkyl group, a VII-184 CH2C=CCH CONH, Pr-n VII-185 Bu-i Me Et C-C alkoxy group, a C-C alkylthiogroup, a C-C alkyl VII-186 Pr- Me Et sulfinyl group, a C-C alkylsulfonyl group, or formyl group, VII-187 Pr- Me Et and VII-188 Pr- Me Et VII-189 Pr- Me Et E" is an leaving group such as chlorine atom, bromine VII-190 Pr- Me Et 10 atom, iodine atom, methanesulfonyl group, methanesulfony VII-191 Pr- CF Me loxy group, trifluoromethanesulfonyloxy group or the like. A compound Ia-II can be produced by reacting a com The present compound represented by the general formula pound Ib-I with a compound II in a solvent in the presence I can be produced by the production methods shown below. of a base. When W is a nitrogenatom, a compound Ic-I can However, the production is not restricted to these methods. 15 be produced in the same manner. In the following, for example, "a compound represented by In the reaction, the use amount of the compound II is general formula I-II”, “a compound represented by formula appropriately selected ordinarily in a range of 1 to 5 equiva I-II' and “a compound I-II' mean the same compound. lents relative to 1 equivalent of the compound Ib-I, and is Production Method 1 preferably 1 to 2 equivalents. Of the present compounds represented by the general for As the solvent used in the reaction, there can be mentioned, mula I, a compound represented by Ia-II or Ic-I can be for example, an ether Such as diethyl ether, 1,2-dimethoxy produced, for example, by the following method. ethane, tetrahydrofuran or the like; an amide such as N.N- dimethylacetamide, N,N-dimethylformamide, 1,3-dimethyl 25 2-imidazolidinone, N-methyl-2-pyrrolidinone or the like; a Formula 5 sulfur compound such as dimethylsulfoxide, sulfolane or the like; a nitrile Such as acetonitrile, propionitrile or the like; an w1k f5 aliphatic hydrocarbon Such as hexane, heptane or the like; an XI (Rian 18 ( aromatic hydrocarbon Such as benzene, toluene, Xylene or the On 2 N R2 II) like; a halogenated hydrocarbon Such as 1,2-dichloroethane, R11 NN 2 No1 chlorobenzene or the like; or a mixture thereof. The use El amount of the solvent is ordinarily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 mol of the compound Ib-I. Ib-I 35 As the base usable in the reaction, there can be mentioned, XI XI for example, an inorganic base such as alkali metal hydroxide On 2 N R2 On 2 N R2 (e.g. sodium hydroxide or potassium hydroxide), alkali metal R11 NN 2 No1 R11 NN 2 No1 carbonate (e.g. sodium carbonate or potassium carbonate), alkali metal bicarbonate (e.g. sodium hydrogencarbonate or W N k 40 potassium hydrogencarbonate) or the like; a metal hydride (R3a)n 1Wk / (Rs.1. f Such as sodium hydride, potassium hydride or the like; and an organic base Such as triethylamine, 1,8-diazabicyclo5.4.0- 7-undecene or the like. The use amount of the base is appro 45 priately selected ordinarily in a range of 1 to 10 equivalents in the above, relative to 1 equivalent of the compound Ib-II, and is prefer R", R, W and n have each the above-mentioned meaning, ably 1 to 5 equivalents. X' is a hydrogenatom, a cyanogroup, a C-Cs alkyl group, The temperature of the reaction is ordinarily any desired a C-C alkenyl group, a C-Cs alkynyl group, a C-C, temperature from -20° C. to the reflux temperature of the cycloalkyl group, a C-C cycloalkyl C-C alkyl group, a 50 reaction system and is preferably a temperature of -10°C. to C-C haloalkyl group, a C-C alkylthio group, a C-C, 1000 C. alkylthio C-C alkyl group, a C-C alkylsulfinyl C-C, The time of the reaction differs depending upon the reac alkyl group, a C-C alkylsulfonyl C-C alkyl group, a tion temperature, the Substrate of reaction, the amount of C-C alkoxy group, a C-C alkoxy C-C alkyl group, a 55 reaction, etc. but is ordinarily 1 to 48 hours. thiocarbamoyl group, a RRNCO group, a RRN group, a After the completion of the reaction, there are conducted C1-C5 alkoxycarbonyl group, a carboxyl group, a R' operations such as pouring of reaction mixture into water, (HN=)C group, RON=(R')C group, a R''S(O—)C extraction by organic solvent, and Subsequent concentration, group, a phenyl group which many be substituted with the whereby the compound Ia-II, or the compound Ia-II and the Substituent group C, or a heterocyclic ring group of 1 to 9 60 compound Ic-I can be obtained. The isolated compounds carbon atoms, having 1 to 5 hetero atoms which may be the Ia-II and Ic-I can be purified as necessary by column chro same or different and which are selected from oxygen atom, matography, recrystallization, etc. Sulfur atom and nitrogen atom (the group may be substituted Production Method 2 with 1 to 5 substituent(s) selected from halogenatoms, C-C, 65 Of the present compounds represented by the general for alkyl group, C-Chaloalkyl group, C-C alkoxy group, or mula I, a compound represented by formula Ia-III can be cyano group), produced, for example, by the following method. US 8,895,035 B2 58 As the nitrous acid ester used in the reaction, there can be Formula 6 mentioned tert-butyl nitrite, amyl nitrite, etc. The use amount NH of the nitrous acid ester is appropriately selected ordinarily in 2 NaNO, Aqueous HX? a range of 1.0 to 5.0 equivalents relative to 1 equivalent of the 1nO 2 N n1 R2 Solution or compound Ia-II, and is preferably 1.1 to 2.0 equivalents. RI N 21 O Nitrous acid ester, CuX. As the solvent usable in the reaction, there can be men He tioned an ether (e.g. diethyl ether, 1,2-dimethoxyethane or w/ tetrahydrofuran), an aromatic hydrocarbon (e.g. benzene, s toluene or Xylene), a nitrile (e.g. acetonitrile or propionitrile), (R3a pi \ S. 10 or a mixture thereof. The amount of the solvent is ordinarily Ia-II 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 mol of X2 the compound Ia-II. The temperature of the reaction is ordinarily any desired On 2 N R2 R11 NN a no-1 15 temperature from -50° C. to the reflux temperature of the reaction system and is preferably a temperature of -10°C. to w1 N 1000 C. The time of the reaction differs depending upon the reac ( R3a W- Nf tion temperature, the Substrate of reaction, the amount of reaction, etc. but is ordinarily 1 to 24 hours. After the completion of the reaction, there are conducted operations such as pouring of reaction mixture into water, (in the above, R. R. R. W. and n have each the above extraction by organic solvent, and Subsequent concentration, mentioned meaning; and X is a halogen atom, preferably a whereby the compound Ia-III can be isolated. The isolated 25 compound Ia-III can be purified as necessary by column chlorine atom or a bromine atom.) chromatography, etc. A compound Ia-III can be produced by reacting a com Production Method 3 pound Ia-II with sodium nitrite (NaNO) in an aqueous Of the present compounds represented by the general for hydrogen halide solution. mula I, the compound represented by formula Ia-III can The amount of sodium nitrite used in the reaction may be 30 also be produced, for example, by the following method. appropriately selected ordinarily in a range of 1.0 to 5.0 equivalents relative to 1 equivalent of the compound Ia-III and is preferably 1.1 to 2.0 equivalents. Formula 7 The hydrogen halide content in the aqueous hydrogen O halide solution, used in the present invention, is ordinarily 2 to 35 O N R2 200 equivalents relative to 1 mol of the compound Ia-II, and 1n n1 the amount of the aqueous solution is preferably 50 to 100 R1 N 2 O Halogenating agent liters. A solvent may be added as necessary. -e- As the solvent usable in the reaction, there can be men w1 tioned, for example, an aliphatic carboxylic acid (e.g. acetic 40 f acid or trifluoroacetic acid) or an ether (e.g. 1,2-dimethoxy (R3a 1\ . ethane or tetrahydrofuran). The amount of the solvent is ordi III narily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 X2 mol of the compound Ia-III. The temperature of the reaction is ordinarily any desired 45 R11 OnNN 2 2 N No1 R2 temperature from -50° C. to the reflux temperature of the reaction system and is preferably a temperature of -10°C. to 100° C. w/ The time of the reaction differs depending upon the reac 50 (R3a)\ . tion temperature, the Substrate of reaction, the amount of reaction, etc. but is ordinarily 1 to 24 hours. After the completion of the reaction, there are conducted operations such as filtration of reaction mixture or pouring of (in the above, R. R. R. X. Wand n have each the above reaction mixture into water, extraction by organic solvent, 55 mentioned meaning.) and Subsequent concentration, whereby the compound Ia A compound Ia-III can be produced by reacting a com III can be isolated. The isolated compound Ia-III may be pound III with a halogenating agent in a solvent. purified as necessary by column chromatography, etc. As the halogenating agent usable in the reaction, there can The compound Ia-III can also be produced by reacting be mentioned, for example, phosphorus pentachloride, thio the compound Ia-II with a nitrous acid ester in a solvent in 60 nyl chloride, or carbon tetrachloride or carbon tetrabromide the presence of a copper halide (II). in the presence of triphenylphosphine. The use amount of the As the copper halide (II) used in the reaction, there can be halogenating agent is appropriately selected in a range of 1.0 mentioned copper bromide (II), copper chloride (II), etc. The to 20.0 mols relative to 1.0 mol of the compound III, and is use amount of the copper halide (II) is appropriately selected preferably 1.0 to 6.0 mols. ordinarily in a range of 1.0 to 5.0 equivalents relative to 1 65 As the solvent usable in the reaction, there can be men equivalent of the compound Ia-II, and is preferably 1.1 to tioned, for example, an aromatic hydrocarbon (e.g. benzene 2.0 equivalents. or toluene), a halogenated hydrocarbon (e.g. chloroform or US 8,895,035 B2 59 60 carbon tetrachloride), or a nitrile (e.g. acetonitrile or propi alkali metal bicarbonate (e.g. sodium hydrogencarbonate or onitrile). The amount of the solvent is ordinarily 0.1 to 50 potassium hydrogencarbonate) or the like. liters, preferably 0.2 to 10 liters relative to 1 mol of the The use amount of the base is appropriately selected ordi compound III. narily in a range of 1 to 10 equivalents relative to 1 equivalent The temperature of the reaction is ordinarily any desired of the compound Ia-IV), and is preferably 0.1 to 2 equiva temperature from -50° C. to the reflux temperature of the lents. reaction system and is preferably a temperature of 0° C. to The temperature of the reaction is ordinarily any desired 100° C. temperature from -50° C. to the reflux temperature of the The time of the reaction differs depending upon the reac reaction system and is preferably a temperature of 0° C. to tion temperature, the Substrate of reaction, the amount of 10 1000 C. reaction, etc. but is ordinarily 1 to 48 hours. The time of the reaction differs depending upon the reac After the completion of the reaction, there are conducted tion temperature, the Substrate of reaction, the amount of operations such as concentration of reaction mixture or pour reaction, etc. but is ordinarily 1 to 48 hours. ing of reaction mixture into water, extraction by organic Sol 15 After the completion of the reaction, there are conducted vent, and Subsequent concentration, whereby the compound operations such as pouring of reaction mixture into water, Ia-III can be isolated. The isolated compound Ia-III can be extraction by organic solvent, and Subsequent concentration, purified as necessary by column chromatography, recrystal whereby the compound Ia-V can be isolated. The isolated lization, etc. compound Ia-V can be purified as necessary by column Production Method 4 chromatography, recrystallization, etc. Of the present compounds represented by the general for Production Method 5 mula II, a compound represented by formula Ia-V can be Of the present compounds represented by the general for produced, for example, by the following method. mula I, a compound represented by formula Ia-VII can be produced, for example, by a method of the following reaction 25 formula. Formula 8 CN O 2 N R2 Aqueous H2O2 Formula 9 RI 1N N 21 No1 Solution CN -e- 30 N 1nOn 2 N n1 R2 NH2OH / R1 N 21 No IV W -e- (R3a 1\, . w/ f Ia-IV) 35 HN O (R3a 1\ . Ia-IV) HN NOH R11 OnYN 2 2 N No1 R2 40 On 2 N R2 w/ 5 R11 NN 2 No1 (R3a)\pi { w/ Ia-V 45 (R3a)\pi . (in the above, R. R. R. W. and n have each the above Ia-VI) mentioned meaning.) A compound Ia-V can be produced by reacting a com (in the above, R. R. R. W. and n have each the above pound Ia-IV with an aqueous hydrogen peroxide solution in 50 mentioned meaning.) the presence of a base. A compound Ia-VII can be produced by reacting a com The use amount of the aqueous hydrogen peroxide Solution pound Ia-IV) with a compound IV in a solvent. The com is appropriately selected in a range of 1.0 to 20.0 mols relative pound IV may be a salt (e.g. hydrochloride or Sulfate) and, to 1 mol of the compound Ia-IV), and is preferably 1.0 to 6.0 in that case, the reaction may be conducted in the presence of mols. 55 a base. A solvent may be used as necessary in the reaction. As the The amount of the compound IV used in the reaction is Solvent usable, there can be mentioned, for example, an alco appropriately selected ordinarily in a range of 1 to 5 equiva hol (e.g. methanol, ethanol or propanol), a halogenated lents relative to 1 equivalent of the compound Ia-IV), and is hydrocarbon (e.g. chloroform or dichloromethane), a Sulfur preferably 1 to 2 equivalents. compound (e.g. dimethylsulfoxide or Sulfolane), or a mixture 60 As the solvent usable in the reaction, there can be men thereof. The amount of the solvent is ordinarily 0.1 to 50 tioned, for example, water, an alcohol (e.g. methanol, ethanol liters, preferably 0.2 to 3 liters relative to 1 mol of the com or propanol), an amide (e.g. N,N-dimethylacetamide, N.N- pound Ia-IV). dimethylformamide, 1,3-dimethyl-2-imidazolidinone or As the base usable in the reaction, there can be mentioned, N-methyl-2-pyrrolidinone), a Sulfur compound (e.g. dim for example, an inorganic base such as alkali metal hydroxide 65 ethyl sulfoxide or sulfolane), or a mixture thereof. The (e.g. sodium hydroxide or potassium hydroxide), alkali metal amount of the solvent is ordinarily 0.1 to 50 liters, preferably carbonate (e.g. sodium carbonate or potassium carbonate), 0.2 to 3.0 liters relative t 1 mol of the compound Ia-IV). US 8,895,035 B2 61 62 As the base usable in the reaction, there can be mentioned, As the solvent and base usable in the reaction, there can be for example, an acetic acid base (e.g. sodium acetate or potas mentioned the same solvents and compounds as mentioned in sium acetate); an inorganic base such as alkali metal hydrox the production method 5. The amount of the solvent is ordi ide (e.g. sodium hydroxide or potassium hydroxide), alkali narily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 metal carbonate (e.g. sodium carbonate or potassium carbon ate), alkali metal bicarbonate (e.g. sodium hydrogencarbon mol of the compound IV. ate or potassium hydrogencarbonate) or the like; an alcohol The use amount of the base is appropriately selected ordi metal salt (e.g. sodium methoxide, Sodium ethoxide or potas narily in a range of 1 to 3 equivalents relative to 1 equivalent sium tert-butoxide); oran organic base (e.g. pyridine, triethy of the compound VII, and is preferably 1 to 2 equivalents. lamine or 1,8-diazabicyclo5.4.0-7-undecene). The use The temperature of the reaction is ordinarily any desired amount of the base is appropriately selected in a range of 1 to 10 temperature from -50° C. to the reflux temperature of the 3 equivalents relative to 1 equivalent of the compound IV. reaction system and is preferably a temperature of -10°C. to and is preferably 1 to 2 equivalents. 1000 C. The temperature of the reaction is ordinarily any desired The time of the reaction differs depending upon the reac temperature from room temperature to the reflux temperature of the reaction system and is preferably a temperature of 50° 15 tion temperature, the Substrate of reaction, the amount of C. to 100° C. reaction, etc. but is ordinarily 1 to 48 hours. The time of the reaction differs depending upon the reac After the completion of the reaction, there are conducted tion temperature, the Substrate of reaction, the amount of operations such as concentration of reaction mixture or pour reaction, etc. but is ordinarily 1 to 24 hours. ing of reaction mixture into water, extraction by organic Sol After the completion of the reaction, there are conducted vent, and Subsequent concentration, whereby the compound operations such as concentration of reaction mixture or pour Ia-II can be isolated. The isolated compound Ia-II can be ing of reaction mixture into water, extraction by organic Sol purified as necessary by column chromatography, etc. vent, and Subsequent concentration, whereby the compound (Step 1-b) Ia-VII can be isolated. The isolated compound Ia-VII can be A compound Ia-VII can be produced by reacting the purified as necessary by column chromatography, etc. 25 compound IV with a compound IV in a solvent. The com Production Method 6 pound IV may be a salt (e.g. hydrochloride or Sulfate) and, Of the present compounds represented by the general for in that case, the reaction may be conducted in the presence of mula II, a compound represented by formula Ia-II can be a base. produced, for example, by a method of the following reaction The amount of the compound IV used in the reaction is formula. 30 appropriately selected ordinarily in a range of 1 to 5 equiva lents relative to 1 equivalent of the compound IV and is preferably 1 to 2 equivalents. Formula 10 As the solvent and base usable in the reaction, there can be mentioned the same solvents and compounds as mentioned in NHOR 35 the production method 5. The amount of the solvent is ordi VI) NH narily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 2 1 (Stepp 1-a) Ya 2 2 mol of the compound IV. When a base is used, the use amount of the base is appro N-so-N ------N priately selected ordinarily in a range of 1 to 3 equivalents W W 40 relative to 1 equivalent of the compound IV, and is prefer (R3a)3 s (R3a)3a ably 1 to 2 equivalents. IV Ia-II The temperature of the reaction is ordinarily any desired temperature from room temperature to the reflux temperature NHOH R-El of the reaction system and is preferably a temperature of 50° (Step 1-by V VII/(Step 2) 45 C. to 100° C. The time of the reaction differs depending upon the reac NH2 tion temperature, the Substrate of reaction, the amount of reaction, etc. but is ordinarily 1 to 48 hours. HONNN 2 21N No1 R2 After the completion of the reaction, there are conducted 50 operations such as concentration of reaction mixture or pour ing of reaction mixture into water, extraction by organic Sol w/ vent, and Subsequent concentration, whereby the compound (Ria),3a 4f Ia-VIII can be isolated. The isolated compound Ia-VII can Ia-VII be purified as necessary by column chromatography, etc. 55 (Step 2) A compound Ia-II can be produced by reacting the com (in the above, R. R. R. W., n and E' have each the above pound Ia-VII with a compound VIII in a solvent in the mentioned meaning.) presence of a base. (Step 1-a) The amount of the compound VIII used in the reaction is A compound Ia-II can be produced by reacting a com 60 appropriately selected ordinarily in a range of 0.5 to 5 equiva pound IV with a compound VII in a solvent in the presence lents relative to 1 equivalent of the compound Ia-VII and is of a base. The base VII may be a salt (e.g. hydrochloride or preferably 1.0 to 2 equivalents. sulfate). As the solvent and base usable in the reaction, there can be The amount of the compound VII used in the reaction is mentioned the same solvents and compounds as mentioned in appropriately selected ordinarily in a range of 1 to 10 equiva 65 the production method 1. The amount of the solvent is ordi lents relative to 1 equivalent of the compound IV, and is narily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 preferably 2 to 5 equivalents. mol of the compound Ia-VII. US 8,895,035 B2 63 64 The use amount of the base is appropriately selected ordi The temperature of the reaction is ordinarily any desired narily in a range of 1 to 20 equivalents relative to 1 equivalent temperature from -50° C. to the reflux temperature of the of the compound Ia-VII, and is preferably 1 to 10 equiva reaction system and is preferably a temperature of -10°C. to lents. 1000 C. The temperature of the reaction is ordinarily any desired The time of the reaction differs depending upon the reac temperature from -50° C. to the reflux temperature of the tion temperature, the Substrate of reaction, the amount of reaction system and is preferably a temperature of -10°C. to reaction, etc. but is ordinarily 1 to 48 hours. 100° C. After the completion of the reaction, there are conducted The time of the reaction differs depending upon the reac operations such as concentration of reaction mixture or pour tion temperature, the Substrate of reaction, the amount of 10 ing of reaction mixture into water, extraction by organic Sol reaction, etc. but is ordinarily 1 to 48 hours. vent, and Subsequent concentration, whereby the compound After the completion of the reaction, there are conducted IX can be isolated. The isolated compound IX can be operations such as pouring of reaction mixture into water, purified as necessary by column chromatography, etc. (Step 4) extraction by organic solvent, and Subsequent concentration, 15 whereby the compound Ia-II can be isolated. The isolated A compound IV can be produced by reacting the com compound Ia-II can be purified as necessary by column pound IX with a dehydrating agent in a solvent. chromatography, etc. As the solvent usable in the reaction, there can be men Production Method 7 tioned, for example, an ether (e.g. diethyl ether, 1.2- A compound represented by general formula IV can be dimethoxyethane or tetrahydrofuran), a nitrile (e.g. acetoni produced, for example, by the following method. trile or propionitrile), an aromatic hydrocarbon (e.g. benzene, toluene or pyridine), or a halogenated hydrocarbon (e.g. 1.2- dichloroethane or chlorobenzene). The amount of the solvent Formula 11 is ordinarily 0.1 to 50 liters, preferably 0.2 to 10 liters relative O 25 to 1 mol of the compound IX. N R2 As the dehydrating agent usable in the reaction, there can Y1O 21 No 1 Ammonia be mentioned, for example, phosphorus pentoxide, phospho (Step 3) rus pentachloride, phosphorus oxychloride, triphosgene, tri N fluoroacetic anhydride, acetic anhydride, or thionyl chloride. W. 30 The use amount of the dehydrating agent is appropriately \ N (Rian selected ordinarily in a range of 1 to 10 equivalents relative to VIII) 1 equivalent of the compound IX and is preferably 1 to 5 O equivalents. Dehydrating The temperature of the reaction is ordinarily any desired N R2 agent temperature from -50° C. to the reflux temperature of the HN 2 nNo 1 -e-(Step 4) 35 reaction system and is preferably a temperature of -10°C. to 1000 C. N The time of the reaction differs depending upon the reac W. tion temperature, the Substrate of reaction, the amount of \ N (Rian 40 reaction, etc. but is ordinarily 1 to 48 hours. IX After the completion of the reaction, there are conducted 2 operations such as pouring of reaction mixture into water, extraction by organic solvent, and Subsequent concentration, s's -R whereby the compound IV can be isolated. The isolated N compound IV can be purified as necessary by column chro W. 45 matography, recrystallization, etc. \ Ni-R3a), Production Method 8 IV A compound represented by general formula VIII can be produced, for example, by the following method. (in the above, R, R", W and n have each the above-men 50 tioned meaning, and Y is a C-C alkyl group.) (Step 3) Formula 12 A compound IX can be produced by reacting a compound O O VIII with ammonia in a solvent. N N R2 The amount of ammonia used in the reaction is appropri 55 Y1O 21 YOH R2-El Ylo 2 No1 ately selected ordinarily in a range of 1 to 10 equivalents relative to 1 equivalent of the compound VIII and is prefer N XI N ably 1 to 5 equivalents. W. W. As the solvent usable in the reaction, there can be men \ (Ren \ (Ren tioned, for example, water, an ether (e.g. diethyl ether, 1.2- 60 dimethoxyethane or tetrahydrofuran), an amide (e.g. N.N- X) VIII dimethylacetamide, N,N-dimethylformamide, 1,3-dimethyl 2-imidazolidinone or N-methyl-2-pyrrolidinone), a sulfur (in the above, R. R. W. Y', n and E' have each the above compound (e.g. dimethyl Sulfoxide or Sulfolane), an alcohol mentioned meaning.) (e.g. methanol, ethanol or propanol), or a mixture thereof. 65 A compound VIII can be produced by reacting a com The amount of the solvent is ordinarily 0.1 to 50 liters relative pound XI with a compound XI in a solvent in the presence to 1 mol of the compound VIII, preferably 0.2 to 3.0 liters. of a base. US 8,895,035 B2 65 66 The amount of the compound XI used in the reaction is As the base usable in the reaction, there can be mentioned, appropriately selected ordinarily in a range of 1.0 to 5.0 for example, an inorganic base (e.g. potassium carbonate, equivalents relative to 1 equivalent of the compound XI and Sodium hydride or Sodium hydroxide), and an organic base is preferably 1.1 to 2.0 equivalents. e.g. 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU). The use As the solvent and base usable in the reaction, there can be amount of the base is appropriately selected in a range of 0.01 mentioned the same solvents and compounds as mentioned in to 100 mols relative to 1 mol of the compound VIII and is the production method 1. The amount of the solvent is ordi preferably 0.1 to 10 mols. narily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 As the acid usable in the reaction, there can be mentioned, mol of the compound DX. for example, an inorganic acid (e.g. hydrochloric acid, hydro The use amount of the base is appropriately selected ordi 10 bromic acid or Sulfuric acid) and an organic acid (e.g. acetic narily in a range of 1 to 20 equivalents relative to 1 equivalent of the compound XI, and is preferably 1 to 10 equivalents. acid or trifluoroacetic acid). The use amount of the acid may The temperature of the reaction is ordinarily any desired be 1 mol to a large excess relative to 1 mol of the compound temperature from -50° C. to the reflux temperature of the VIII and is preferably 1 to 100 mols. reaction system and is preferably a temperature of -10°C. to 15 As the solvent usable in the reaction, there can be men 100° C. tioned, for example, an alcohol (e.g. methanol or ethanol), an The time of the reaction differs depending upon the reac ether (e.g. tetrahydrofuran), a ketone (e.g. acetone or methyl tion temperature, the Substrate of reaction, the amount of isobutyl ketone), an amide (e.g. N,N-dimethylformamide or reaction, etc. but is ordinarily 1 to 48 hours. N,N-dimethylacetamide), a Sulfur compound (e.g. dimethyl After the completion of the reaction, there are conducted Sulfoxide or Sulfolane), acetonitrile, water, or a mixture operations such as pouring of reaction mixture into water, thereof. The use amount of the solvent is 0.01 to 100 liters, extraction by organic solvent, and Subsequent concentration, preferably 0.1 to 10 liters relative to 1 mol of the formula whereby the compound VIII can be isolated. The isolated VIII. compound VIII can be purified as necessary by column The temperature of the reaction is selected ordinarily from chromatography, etc. 25 a range from -20°C. to the boiling point of the inert solvent Incidentally, the compound XI can be produced, for and is preferably a temperature of 0°C. to 100° C. example, based on the method described in Journal of the The time of the reaction differs depending upon the reac Chemical Society Perkin Transactions 1, pp. 2235-2239, tion temperature, the Substrate of reaction, the amount of (1987). reaction, etc. but is ordinarily 10 minutes to 48 hours. Production Method 9 30 (Step 6) A compound represented by formula III can be produced, A compound III can be produced by reacting the com for example, by the following method. pound DXIII with a compound VII in a solvent using a con densing agent. The compound VII may be a salt (e.g. hydro chloride or Sulfate) and, in that case, the reaction may be Formula 13 35 conducted in the presence of a base. O The amount of the compound VII used in the reaction is N R2 appropriately selected ordinarily in a range of 1.0 to 5 equiva Y1O 2 No1 lents relative to 1 equivalent of the compound XIII and is N Hydrolysis preferably 1.0 to 2 equivalents. 40 As the condensing agent, there can be mentioned dicyclo W / f (Step 5) hexylcarbodiimide (DCC), N-(3-dimethylaminopropyl)-N'- \ S(R3a), ethylcarbodiimide hydrochloride (EDC or WSC), N,N-car N bonyldiimidazole, 2-chloro-1,3-dimethylimidazolium VIII O chloride, 2-chloro-1-pyridinium iodide, etc. The use amount 45 of the condensing agent is appropriately selected ordinarily in N R2 a range of 1 to 20 equivalents relative to 1 equivalent of the HO 2 No1 R-ONH compound XIII and is preferably 1.0 to 10 equivalents. VI) N Condensing agent As the base usable in the reaction, there can be mentioned, -e- for example, an acetic acid base (e.g. sodium acetate or potas W I (Step 6) 50 sium acetate), a metal salt of alcohol (e.g. sodium methoxide, \ {s(R), p Sodium ethoxide or potassium tert-butoxide), or an organic XII) base (e.g. pyridine, triethylamine or 1,8-diazabicyclo5.4.0- O 7-undecene). When a base is used, the use amount of the base is appropriately selected ordinarily in a range of 1 to 20 RON N 2 N- No -R 55 equivalents relative to 1 equivalent of the compound VII and H is preferably 1 to 10 equivalents. N As the solvent usable in the reaction, there can be men W. tioned, for example, an ether (e.g. diethyl ether, 1.2- dimethoxyethane or tetrahydrofuran), an amide (e.g. N.N- 60 dimethylacetamide, N,N-dimethylformamide, 1,3-dimethyl 2-imidazolidinone or N-methyl-2-pyrrlidinone), a sulfur compound (e.g. dimethylsulfoxide or Sulfolane), an aromatic (in the above, R', R. R. W.Y. and n have each the above hydrocarbon (e.g. benzene, toluene or Xylene), a halogenated mentioned meaning.) hydrocarbon (e.g. chloroform or dichloromethane), a nitrile (Step 5) 65 (e.g. acetonitrile or propionitrile), or a mixture thereof. The A compound XIII can be produced by hydrolyzing a com amount of the solvent is ordinarily 0.1 to 50 liters, preferably pound VIII in a solvent in the presence of an acid or a base. 0.2 to 3.0 liters relative to 1 mol of the compound XII. US 8,895,035 B2 67 68 The temperature of the reaction is ordinarily any desired whereby the compound Ia-VIII can be isolated. The isolated temperature from -50° C. to the reflux temperature of the compound Ia-VIII can be purified as necessary by column reaction system and is preferably a temperature of -10°C. to chromatography, etc. 100° C. Production Method 11 The time of the reaction differs depending upon the reac Of the present compounds represented by the general for tion temperature, the Substrate of reaction, the amount of mula I, a compound represented by formula Ia-IX can be reaction, etc. but is ordinarily 1 to 48 hours. produced, for example, by a method of the following reaction After the completion of the reaction, there are conducted formula. operations such as pouring of reaction mixture into water, 10 extraction by organic solvent, and Subsequent concentration, Formula 15 whereby the compound III can be isolated. The isolated HN NOH compound III can be purified as necessary by column chro matography, etc. RO N R2 Production Method 10 n 4 ano1 Y2C(OYi) Of the present compounds represented by the general for 15 DXV mula II, a compound represented by formula Ia-VIII can be N He produced, for example, by the following method. W. \ N, (R3a), Ia-VI) Formula 14 Y2 O Y-El III RO N R2 O n n1 )W -\ N 21 No YSO4 NaN N XIV 25 W. RO-NN 2 2- N No1 R2 \ N, (Rian III N Y No 30 W.\ is(R'), RO-NN 2 2 N No1 R2 Ia-VI) 35 (in the above, R', R. R. W., n and Y have each the above w/ f mentioned meaning, and Y is a C-C alkyl group.) A compound Ia-IX can be produced by reacting a com pound Ia-VI) with a compound XV in the presence of a Ia-VIII catalytic amount of an acid. 40 The amount of the compound XVI used in the reaction is (in the above, R. R. R. Y', W., n and E' have each the appropriately selected ordinarily in a range of 1 to 5 equiva above-mentioned meaning.) lents relative to 1 equivalent of the compound Ia-VII and is A compound Ia-VIII can be produced by reacting a com preferably 1 to 2 equivalents. The compound DXVI may be pound III with a compound XIII or a compound XIV in used also as a solvent. a solvent in the presence of a base. 45 A solvent may be used in the reaction. The solvent The amount of the compound DXIII or the compound includes, for example, an alcohol (e.g. methanol, ethanol or DXIV used in the reaction is appropriately selected ordinarily propanol) and a sulfur compound (e.g. dimethylsulfoxide or in a range of 1.0 to 5.0 equivalents relative to 1 equivalent of sulfolane). The amount of the solvent is ordinarily 0.1 to 50 the compound III and is preferably 1.1 to 2 equivalents. liters, preferably 0.2 to 3.0 liters relative to 1 mol of the As the solvent and base usable in the reaction, there can be 50 compound Ia-VI. mentioned the same solvents and compounds as mentioned in As the acid usable in the reaction, there can be mentioned, the production method 1. The amount of the solvent is ordi for example, an inorganic acid (e.g. Sulfuric acid), a Sulfonic narily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 acid (e.g. p-toluenesulfonic acid), a Lewis acid (e.g. boron mol of the compound III. trifluoride) or an acetic acid (e.g. trifluoroacetic acid). The use amount of the base is appropriately selected ordi 55 The temperature of the reaction is ordinarily any desired narily in a range of 1 to 20 equivalents relative to 1 equivalent temperature from room temperature to the reflux temperature of the compound III, and is preferably 1 to 10 equivalents. of the reaction system and is preferably a temperature of 50° The temperature of the reaction is ordinarily any desired C. to 140° C. temperature from -50° C. to the reflux temperature of the The time of the reaction differs depending upon the reac reaction system and is preferably a temperature of -10°C. to 60 tion temperature, the Substrate of reaction, the amount of 100° C. reaction, etc. but is ordinarily 1 to 48 hours. The time of the reaction differs depending upon the reac After the completion of the reaction, there are conducted tion temperature, the Substrate of reaction, the amount of operations such as pouring of reaction mixture into water, reaction, etc. but is ordinarily 1 to 48 hours. extraction by organic solvent, and Subsequent concentration, After the completion of the reaction, there are conducted 65 whereby the compound Ia-IX) can be isolated. The isolated operations such as pouring of reaction mixture into water, compound Ia-IX can be purified as necessary by column extraction by organic solvent, and Subsequent concentration, chromatography, etc. US 8,895,035 B2 69 70 Production Method 12 The time of the reaction differs depending upon the reac Of the present compounds represented by the general for tion temperature, the Substrate of reaction, the amount of mula I, a compound represented by formula Ia-XII can be reaction, etc. but is ordinarily 1 to 48 hours. produced, for example, by a method of the following reaction After the completion of the reaction, there are conducted formula. operations such as concentration of reaction mixture or pour ing of reaction mixture into water, extraction by organic Sol vent, and Subsequent concentration, whereby the compound Formula 16 Ia-X can be isolated. The isolated compound Ia-X can be CN purified as necessary by column chromatography, etc. 10 (Step 8) ROn 21Ne,N no-1 R2 HN N-1Ns. A compound Ia-XI can be produced by reacting the com pound Ia-X with an oxidizing agent in a solvent. N DXVI As the solvent usable in the reaction, there can be men w1 f (Step 7) tioned, for example, water, an aromatic hydrocarbon (e.g. \ N -(R3a), 15 benzene, toluene or Xylene), a halogenated hydrocarbon (e.g. chloroform or dichloromethane), or a mixture thereof. The Ia-IV) amount of the solvent is ordinarily 0.1 to 50 liters, preferably 0.2 to 10 liters relative to 1 mol of the compound Ia-X. Sn 2N As the oxidizing agent usable in the reaction, there can be mentioned, for example, potassium permanganate, manga nese dioxide, nickel peroxide, or 2,3-dichloro-5,6-dicyano ROn 4 2 N No1 R2 Oxidizing agent -e- p-benzoquinone (DDQ). The use amount of the oxidizing (Step 8) agent is appropriately selected ordinarily in a range of 1 to 10 N equivalents relative to 1 equivalent of the compound Ia-X W. 25 and is preferably 1 to 5 equivalents. \ N S(R3an The temperature of the reaction is ordinarily any desired temperature from -50° C. to the reflux temperature of the Ia-X reaction system and is preferably a temperature of -10°C. to 1000 C. N Na 30 The time of the reaction differs depending upon the reac tion temperature, the Substrate of reaction, the amount of R"O 2 N R2 reaction, etc. but is ordinarily 1 to 48 hours. NN 2 No1 After the completion of the reaction, there are conducted operations such as pouring of reaction mixture into water, N 35 extraction by organic solvent, and Subsequent concentration, W. whereby the compound Ia-XII can be isolated. The isolated \ N, (Rian compound Ia-XII can be purified as necessary by column Ia-XI chromatography, recrystallization, etc. Production Method 13 40 Of the present compounds represented by the general for (in the above, R. R. R. W. and n have each the above mentioned meaning.) mula II, a compound represented by formula IIa-XIII can be (Step 7) produced, for example, by a method of the following reaction A compound Ia-X can be produced b reacting a com formula. pound Ia-IV with a compound XVI in a solvent. The Formula 17 compound XVI may be a salt (e.g. hydrochloride or sulfate). 45 CN The amount of the compound XVI used in the reaction is appropriately selected ordinarily in a range of 1 to 10 equiva ROn 4 21N No1 R2 AZide compound lents relative to 1 equivalent of the compound Ia-IV and is -- preferably 2 to 5 equivalents. N As the solvent usable in the reaction, there can be men / tioned, for example, water, an ether (e.g. diethyl ether, 1.2- 50 dimethoxyethane or tetrahydrofuran), an alcohol (e.g. metha W Ni 3 nol, ethanol or propanol), an aromatic hydrocarbon (e.g. \ {i(R) benzene, toluene or Xylene), or a halogenated hydrocarbon Ia-IV) (e.g. chloroform or dichloromethane). The amount of the NN solvent is ordinarily 0.1 to 50 liters, preferably 0.2 to 3.0 liters 55 relative to 1 mol of the compound Ia-IV). in 2 \ A base may be used in the reaction. As the base, there can be mentioned, for example, a metal salt of alcohol (e.g. Sodium methoxide, Sodium ethoxide or potassium tert-butox R'OSNN a 2 NNo1 R2 ide), an acetic acid base (e.g. sodium acetate or ammonium acetate), or an organic base (e.g. pyridine or triethylamine). 60 The use amount of the base is appropriately selected ordi N narily in a range of 1 to 3 equivalents relative to 1 equivalent of the compound Ia-IV and is preferably 1 to 2 equivalents. WRe) The temperature of the reaction is ordinarily any desired Ia-XII) temperature from -50° C. to the reflux temperature of the 65 reaction system and is preferably a temperature of -10°C. to (in the above, R. R. R. W. and n have each the above 100° C. mentioned meaning.) US 8,895,035 B2 71 72 A compound Ia-XIII can be produced by reacting a com The amount of the compound III used in the reaction is pound Ia-IV with an azide compound. appropriately selected ordinarily in a range of 1 to 5 equiva The amount of the azide compound used in the reaction is lents relative to 1 equivalent of the compound Ib-III and is appropriately selected ordinarily in a range of 1 to 5 equiva preferably 1 to 2 equivalents. As the base usable in the reaction, there can be mentioned lents relative to 1 equivalent of the compound Ia-IV and is the same compounds as mentioned in the production method preferably 1 to 2 equivalents. 1. The use amount of the base is appropriately selected in a As the azide compound usable in the reaction, there can be range of 1.0 to 20.0 mols relative to 1 mol of the compound mentioned, for example, a trialkyl metal (e.g. trimethyltin Ib-III and is preferably 1.0 to 6.0 mols. azide or trimethylsilicon azide), or sodium azide. The reac As the solvent usable in the reaction, there can be men tion may be conducted in the presence of a Lewis acid (e.g. 10 tioned the same solvents as mentioned in the production Zinc bromide or aluminum chloride) or a tin compound (e.g. method 1. The use amount of the solvent is ordinarily 0.1 to 50 dibutyltin oxide). liters relative to 1 mol of the compound Ib-III and is prefer As the solvent usable in the reaction, there can be men ably 0.2 to 3.0 liters. tioned, for example, an ether (e.g. 1,4-dioxane or tetrahydro The temperature of the reaction is ordinarily any desired furan), an alcohol (e.g. methanol, ethanol or propanol), an 15 temperature from -20° C. to the reflux temperature of the amide (e.g. N,N-dimethylacetamide, N,N-dimethylforma reaction system and is preferably a temperature of -10°C. to mide, 1,3-dimethyl-2-imidazolidinone or N-methyl-2-pyrro 1000 C. lidinone), an aromatic hydrocarbon (e.g. benzene, toluene or The time of the reaction differs depending upon the reac Xylene), or a halogenated hydrocarbon (e.g. 1,2-dichloroet tion temperature, the Substrate of reaction, the amount of hane or chlorobenzene). The amount of the solvent is ordi reaction, etc. but is ordinarily 1 to 48 hours. narily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative t 1 After the completion of the reaction, there are conducted mol of the compound Ia-IV). operations such as pouring of reaction mixture into water, The temperature of the reaction is ordinarily any desired extraction by organic solvent, and Subsequent concentration, temperature from room temperature to the reflux temperature whereby the compound Ia-XIII can be isolated. The isolated of the reaction system and is preferably a temperature of 50° compound Ia-XIII can be purified as necessary by column C. to 140° C. 25 chromatography, recrystallization, etc. The time of the reaction differs depending upon the reac Production Method 15 tion temperature, the Substrate of reaction, the amount of Of the present compounds represented by the general for reaction, etc. but is ordinarily 1 to 24 hours. mula I, a compound represented by Ia-XIV can be pro After the completion of the reaction, there are conducted duced, for example, by a method of the following reaction operations such as pouring of reaction mixture into water, 30 formula. extraction by organic solvent, and Subsequent concentration, whereby the compound Ia-XIII can be isolated. The isolated compound Ia-XIII can be purified as necessary by column Formula 19 chromatography, etc. N- A (R3)n Production Method 14 35 / Of the present compounds represented by the general for ( N x, Y-SNa mula II, a compound represented by formula Ia-XIII can be produced, for example, by a method of the following reaction R la OS 4. ano- R la HoDXVII formula. Formula 18 40 w/ ( R3a W Nf Ia-XIII 45 SY1 R1aO NN2 2 N No1 R1a N 50

Ia-XIV) (in the above, R', R. W. Y' and n have each the above mentioned meaning.) A compound Ia-XIV can be produced by reacting a com pound Ia-XIII with a compound XVIII in a solvent. The amount of the compound DXVIII used in the reaction is 60 appropriately selected ordinarily in a range of 1.0 to 5.0 equivalents relative to 1.0 equivalent of the compound Ia XIII and is preferably 1.0 to 1.2 equivalents. (in the above, R", W, X and n have each the above-men As the solvent usable in the reaction, there can be men tioned meaning, and R' is a C-C alkyl group.) tioned the solvents mentioned in the production method 1. A compound Ia-XIII can be produced by reacting a com 65 The amount of the solvent is ordinarily 0.1 to 50 liters relative pound Ib-II with a compound III in a solvent in the pres to 1 mol of the compound Ia-XIII and is preferably 0.2 to 3.0 ence of a base. liters. US 8,895,035 B2 73 74 The temperature of the reaction is ordinarily any desired (in the above, R. R. R. W. and n have each the above temperature from -20° C. to the reflux temperature of the mentioned meaning.) reaction system and is preferably a temperature of -10°C. to A compound Ia-XVI can be produced by reacting a com 100° C. pound Ia-V with a Sulfurizing agent. The time of the reaction differs depending upon the reac 5 tion temperature, the Substrate of reaction, the amount of The amount of the Sulfurizing agent used in the reaction is reaction, etc. but is ordinarily 1 to 48 hours. appropriately selected ordinarily in a range of 1 to 5 equiva After the completion of the reaction, there are conducted lents relative to 1 equivalent of the compound Ia-V and is operations such as pouring of reaction mixture into water, preferably 1 to 2 equivalents. extraction by organic solvent, and Subsequent concentration, 10 As the Sulfurizing agent usable in the reaction, there can be whereby the compound Ia-XIV can be isolated. The isolated mentioned a Lawesson’s reagent, 2.4-bis(4-methoxyphenyl)- compound Ia-XIV can be purified as necessary by column 1.3.2.4-dithiadiphophetane-2,4-disulfide, diphosphorus pen chromatography, recrystallization, etc. tasulfide, etc. Production Method 16 As the solvent usable in the reaction, there can be men Of the present compounds represented by the general for 15 tioned, for example, an ether (e.g. diethyl ether, 1.2- mula II, a compound represented by Ia-XVI can be pro dimethoxyethane or tetrahydrofuran), a nitrile (e.g. acetoni duced, for example, by a method of the following reaction trile or propionitrile), an aromatic hydrocarbon (e.g. benzene, formula. toluene, Xylene or pyridine), or a halogenated hydrocarbon (e.g. 1,2-dichloroethane or chlorobenzene). The amount of the solvent is ordinarily 0.1 to 50 liters, preferably 0.2 to 3.0 Formula 20 liters relative to 1 mol of the compound Ia-V. O NH2 The temperature of the reaction is ordinarily any desired temperature from room temperature to the reflux temperature R"Onn a N n1 R2 of the reaction system and is preferably a temperature of 20° N 2 O Sulfurizing 25 C. to 140° C. agent N Her The time of the reaction differs depending upon the reac tion temperature, the Substrate of reaction, the amount of (R)n-W...Y N reaction, etc. but is ordinarily 1 to 24 hours. Ia-V 30 After the completion of the reaction, there are conducted S NH2 operations such as pouring of reaction mixture into water, extraction by organic Solvent, and Subsequent concentration, whereby the compound Ia-XVI can be isolated. The isolated RONNN 2 2 N No1 R2 compound Ia-XVI can be purified as necessary by column 35 chromatography, etc. -N Production Method 17 (R)n-WRe)...Y N Of the present compounds represented by the general for mula II, a compound represented by Ia-XVIII can be pro Ia-XV duced, for example, by a method of the following reaction formula.

Formula 21 HN OYi CN HC-alcohol (YOH) RON 2 N R2 1 (Step 9-a) N RON 2 N R2 Hydrolysis No1 He se- No1 (Step 10) N N W 5 N. Alcohol metal salt (YOM) 1. WW 5 (R)n (Step 9-b) (R)n Ia-XV Ia-XVI)

O OYi

R'O 2 N R2 NN 21 No1 y (Reyn-WR3a Nf Ia-XVII US 8,895,035 B2 75 76 (in the above, R. R. R. W.Y. and n have each the above The temperature of the reaction is ordinarily any desired mentioned meaning, and Misan alkali metal Such as Sodium, temperature from -50° C. to the reflux temperature of the potassium or the like.) reaction system and is preferably a temperature of -10°C. to (Step 9-a) 1000 C. A compound Ia-XVI can be produced by reacting a com 5 The time of the reaction differs depending upon the reac pound Ia-IV, hydrogen chloride and a C-C alcohol tion temperature, the Substrate of reaction, the amount of (YOH) such as methanol, ethanol or the like. reaction, etc. but is ordinarily 1 to 48 hours. The amount of the hydrogen chloride used in the reaction is After the completion of the reaction, there are conducted appropriately selected ordinarily in a range of 1 to 10 equiva operations such as pouring of reaction mixture into water, lents relative to 1 equivalent of the compound Ia-IV and is 10 extraction by organic solvent, concentration and drying, preferably 1 to 5 equivalents. The use amount of the alcohol whereby the compound Ia-XVIII can be isolated. The iso is ordinarily 0.1 to 50 liters, preferably 0.2 to 10 liter relative lated compound Ia-XVIII can be purified as necessary by to 1 mol of the compound Ia-IV). column chromatography, recrystallization, etc. Production Method 18 The temperature of the reaction is ordinarily any desired 15 temperature from -50° C. to the reflux temperature of the Of the present compounds represented by the general for reaction system and is preferably a temperature of -10°C. to mula II, a compound represented by formula IIa-XVIII can 100° C. be produced by a method of the following reaction formula. The time of the reaction differs depending upon the reac tion temperature, the Substrate of reaction, the amount of Formula 22 reaction, etc. but is ordinarily 1 to 48 hours. O OYi After the completion of the reaction, the reaction mixture HNRRS may be concentrated and the concentrate perse may be used in the Subsequent reaction. However, it is also possible to ROSn N a 21 N No1 R2 HerXVIII conduct operations such as pouring of reaction mixture into 25 water, extraction by organic solvent, concentration and dry ing, whereby the compound Ia-XVII can be isolated. The w1 isolated compound Ia-XVII can be purified as necessary by f column chromatography, recrystallization, etc. (Ra) 1& (Step 9-b) 30 Ia-XVII) The compound Ia-XVI may also be produced by reacting O NRRS the compound Ia-IV with a C-C alcohol metal salt (Y'OM) such as sodium methoxide, sodium ethoxide or the R'O- a N R2 like, in a C-C alcohol (YOH) such as methanol, ethanol or NN 2 No1 the like. 35 The amount of the alcohol metal salt used in the reaction is w1 appropriately selected ordinarily in a range of a catalytic W f amount to 10 equivalents relative to 1 equivalent of the com (R-18 ( pound Ia-IV and is preferably 0.1 to 5 equivalents. Ia-XVIII The amount of the alcohol used in the reaction is ordinarily 40 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 mol of the compound Ia-IV). (in the above, R. R. R. R. R. W.Y. and n have each the The temperature of the reaction is ordinarily any desired above-mentioned meaning.) temperature from -50° C. to the reflux temperature of the A compound Ia-XVIII can be produced by reacting a reaction system and is preferably a temperature of -10°C. to 45 compound Ia-XVIII with a compound DXVIII in a solvent in 100° C. the presence of a Lewis acid. The compound XVIII may be The time of the reaction differs depending upon the reac a salt (e.g. hydrochloride or Sulfate). tion temperature, the Substrate of reaction, the amount of The amount of the compound XVIII used in the reaction reaction, etc. but is ordinarily 1 to 48 hours. is appropriately selected ordinarily in a range of 1 to 10 After the completion of the reaction, the reaction mixture 50 equivalents relative to 1 equivalent of the compound Ia may be concentrated and the concentrate perse may be used XVIII and is preferably 2 to 5 equivalents. in the Subsequent reaction. However, it also possible to con As the solvent usable in the reaction, there can be men duct operations such as pouring of reaction mixture into tioned, for example, an ether (e.g. 1,4-dioxane, 1.2- water, extraction by organic solvent, concentration and dry dimethoxyethane or tetrahydrofuran), an aromatic hydrocar ing, whereby the compound Ia-XVII can be isolated. The 55 bon (e.g. benzene, toluene or Xylene), or a halogenated isolated compound Ia-XVII can be purified as necessary by hydrocarbon (e.g. chloroform or dichloromethane). The column chromatography, recrystallization, etc. amount of the solvent is ordinarily 0.1 to 50 liters, preferably (Step 10) 0.2 to 3.0 liters relative to 1 mol of the compound Ia-XVIII. A compound Ia-XVIII can be produced by reacting the As the Lewis acid usable in the reaction, there can be compound Ia-XVII in a solvent in the presence of an acid 60 mentioned an aluminum (e.g. trimethyl aluminum or alumi (e.g. hydrochloric acid or Sulfuric acid). num chloride). The use amount of the Lewis acid is appropri As the solvent usable in the reaction, there can be men ately selected ordinarily in a range of 1 to 3 equivalents tioned, for example, an ether (e.g. diethyl ether, 1.2-dietoxy relative to 1 equivalent of the compound Ia-XVIII and is ethane or tetrahydrofuran), an alcohol (e.g. methanol, ethanol preferably 1 to 2 equivalents. or propanol), or water. The amount of the solvent is ordinarily 65 In the reaction, the compound XVIII may be used in an 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 mol of excess, or a base may be used in place of the Lewis acid. As the compound Ia-XVI. the base, there can be mentioned, for example, an inorganic US 8,895,035 B2 77 78 base Such as alkali metal hydroxide (e.g. sodium hydroxide or The amount of the compound XIX used in the reaction is potassium hydroxide), alkali metal carbonate (e.g. sodium appropriately selected ordinarily in a range of 1 to 10 equiva carbonate or potassium carbonate), alkali metal bicarbonate lents relative to 1 equivalent of the compound Ia-XVIII and (e.g. sodium hydrogencarbonate or potassium hydrogencar is preferably 2 to 5 equivalents. bonate) or the like; a metal salt of alcohol (e.g. sodium meth- 5 As the solvent usable in the reaction, there can be men oxide or Sodium ethoxide); or an organic base (e.g. pyridine, tioned, for example, an aromatic hydrocarbon (e.g. benzene, triethylamine or 1,8-diazabicyclo[5.4.0-7-undecene). The toluene or Xylene), and a halogenated hydrocarbon (e.g. chlo use amount of the base is appropriately selected ordinarily in roform or dichloromethane). The amount of the solvent is a range of 1 to 3 equivalents relative to 1 equivalent of the ordinarily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative compound Ia-XVIII and is preferably 1 to 2 equivalents. 10 to 1 mol of the compound Ia-XVII. As the solvent usable in the reaction, there can be men As the Lewis acid usable in the reaction, there can be tioned, for example, an alcohol (e.g. methanol, ethanol or mentioned an aluminum compound (e.g. trimethyl aluminum propanol), an ether (e.g. 1,4-dioxane, 1,2-dimethoxyethane or aluminum chloride). The use amount of the Lewis acid is or tetrahydrofuran), an aromatic hydrocarbon (e.g. benzene, appropriately selected ordinarily in a range of 1 to 3 equiva toluene or Xylene), or a halogenated hydrocarbon (e.g. chlo 15 lents relative to 1 equivalent of the compound Ia-XVIII and roform or dichloromethane). The amount of the solvent is is preferably 1 to 2 equivalents. ordinarily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative The temperature of the reaction is ordinarily any desired to 1 mol of the compound Ia-XVIII. temperature from -50° C. to the reflux temperature of the The temperature of the reaction is ordinarily any desired 20 reaction system and is preferably a temperature of -10°C. to temperature from -50° C. to the reflux temperature of the 1000 C. reaction system and is preferably a temperature of -10°C. to The time of the reaction differs depending upon the reac tion temperature, the Substrate of reaction, the amount of 100° C. reaction, etc. but is ordinarily 1 to 48 hours. The time of the reaction differs depending upon the reac After the completion of the reaction, there are conducted tion temperature, the substrate of reaction, the amount of 25 operations such as concentration of reaction mixture or pour reaction, etc. but is ordinarily 1 to 48 hours. ing of reaction mixture into water, extraction by organic Sol After the completion of the reaction, there are conducted vent, and Subsequent concentration, whereby the compound operations such as concentration of reaction mixture or pour Ia-XIX can be isolated. The isolated compound Ia-XIX ing of reaction mixture into water, extraction by organic Sol 30 can be purified as necessary by column chromatography, etc. vent, and Subsequent concentration, whereby the compound Production Method 20 Ia-XVIII can be isolated. The isolated compound Ia Of the present compounds represented by the general for XVIII can be purified as necessary by column chromatogra mula II, a compound represented by formula Ia-XXI can be phy, etc. produced, for example, by a method of the following reaction Production Method 19 formula. Of the present compounds represented by the general for 35 mula II, a compound represented by formula IIa-XIX can be produced, for example, by a method of the following reaction Formula 24 formula. NH2 40 R'On 2 N R2 NN 21 No1 El-R6 Formula 23 N XX O OYi W p (R3a)n-W d naN a N No1 R2 HSYXIX 45 -> Ia-II NHR6

RONNN 2 21 N No1 R2 50 Ia-XVII O SY1 y (R*n\R3a {f n21 Nen-'N R2 ss Ia-XX N (in the above, R. R. R. R. W., n and E' have each the above-mentioned meaning.) (R)n- 4 A compound Ia-XXI can be produced by reacting a com pound Ia-II with a compound DXXI in a solvent in the Ia-XIX) 60 presence of a base. The amount of the compound XXI used in the reaction is (in the above, R. R. R. W. Y', Y and n have each the appropriately selected ordinarily in a range of 1.0 to 5.0 above-mentioned meaning.) equivalents relative to 1.0 equivalent of the compound Ia-III A compound Ia-XIX can be produced by reacting a com- 65 and is preferably 1.1 to 2.0 equivalents. pound Ia-XVIII with a compound XIX in a solvent in the As the solvent and base usable in the reaction, there can be presence of a Lewis acid. mentioned the same solvents and compounds as mentioned in US 8,895,035 B2 79 80 the production method 1. The amount of the solvent is ordi Sulfur atom and nitrogen atom (the group may be substituted narily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 with 1 to 5 substituent(s) selected from halogenatoms, C-C, mol of the compound Ia-III. alkyl group, C-C haloalkyl group, C-C alkoxy group or The use amount of the base is appropriately selected ordi cyano group), narily in a range of 1 to 20 equivalents relative to 1 equivalent R is a halogen atom, a mercapto group, a C-C alkyl of the compound Ia-II and is preferably 1 to 10 equivalents. group, a C-Chaloalkyl group, a C-C alkylthio group, or The temperature of the reaction is ordinarily any desired a formyl group, and temperature from -50° C. to the reflux temperature of the R. R7 and the substituent group C. have each the above reaction system and is preferably a temperature of -10°C. to mentioned meaning. 100° C. 10 (Step 11) The time of the reaction differs depending upon the reac A compound XXIII can be produced by reacting a com tion temperature, the Substrate of reaction, the amount of pound Ia-XXII with an alkyl lithium compound DXXI in a reaction, etc. but is ordinarily 1 to 24 hours. solvent. After the completion of the reaction, there are conducted 15 The amount of the compound XXII used in the reaction is operations such as pouring of reaction mixture into water, appropriately selected ordinarily in a range of 1.0 to 5.0 extraction by organic solvent, and Subsequent concentration, equivalents relative to 1 equivalent of the compound Ia-XXII whereby the compound Ia-XXI can be isolated. The isolated and is preferably 1.1 to 2.0 equivalents. compound Ia-XXI can be purified as necessary by column As the solvent usable in the reaction, there can be men chromatography, etc. tioned, for example, an ether such as diethyl ether, 1.2- Production Method 21 dimethoxyethane, tetrahydrofuran or the like. The amount of Of the present compounds represented by the general for the solvent is ordinarily 0.1 to 50 liters, preferably 0.2 to 3.0 mula II, a compound represented by formula IIa-XXIII can liters relative to 1 mol of the compound Ia-XXII. be produced, for example, by a method of the following The temperature of the reaction is ordinarily any desired reaction formula. 25 temperature from -100° C. to the reflux temperature of the reaction system and is preferably a temperature of-70° C. to OO C. Formula 25 X3 The time of the reaction differs depending upon the reac tion temperature, the Substrate of reaction, the amount of R'O- a N R2 reaction, etc. but is ordinarily 1 to 24 hours. NN 21 No1 After the completion of the reaction, no purification is N Y2-Li conducted and the reaction mixture containing the compound / I DXXIII is used perse in the next reaction. W\ N (StepN 11) (Step 12) 35 A compound Ia-XXIII can be produced by reacting the Ia-XXI reaction mixture containing the compound XXIII with an X3 electrophilic agent in a solvent. 2 As the electrophilic agent usable in the reaction, there can "Sane-N-N O Electrophilic 40 be mentioned, for example, a halogen (e.g. chlorine or bro -N Li agent mine), a halogenated C-C alkyl (e.g. methyl iodide or ethyl bromide), a halogenated C-C haloalkyl (e.g. 1-chloro-2- W y (Step 12) bromoethane or hexachloroethane), a diC-C alkyl disulfide -N (e.g. dimethyl disulfide or diethyl disulfide), sulfur, or N.N- DXXII 45 dimethylformamide. The use amount of the electrophilic X3 agent is appropriately selected in a range of 1.0 to 5.0 mols RO- 2 N R2 relative to 1.0 mol of the compound XXIII and is preferably NN 21 No1 1.1 to 2.0 mols. The temperature of the reaction is ordinarily any desired N R3b 50 temperature from -100° C. to the reflux temperature of the reaction system and is preferably a temperature of-70° C. to W\ { - OO C. IaXXII The time of the reaction differs depending upon the reac 55 tion temperature, the Substrate of reaction, the amount of in the above, reaction, etc. but is ordinarily 1 to 24 hours. R", R. WandY have each the above-mentioned meaning, After the completion of the reaction, there are conducted X is a hydrogenatom, a cyanogroup, a C-Cs alkyl group, operations such as pouring of reaction mixture into water, a C2-Cs alkenyl group, a C-C alkynyl group, a C-Cs extraction by organic solvent, and Subsequent concentration, cycloalkyl group, a C-C cycloalkyl C-C alkyl group, a 60 whereby the compound Ia-XXIII can be isolated. The iso C-Cs haloalkyl group, a C-C alkylthio group, a C-C, lated compound Ia-XXIII can be purified as necessary by alkylthio C-C alkyl group, a C-C alkoxy group, a C-Cs column chromatography, etc. alkoxy C-C alkyl group, a RRN group, a C-C alkoxy Production Method 22 carbonyl group, a phenyl group which may be substituted Of the present compounds represented by the general for with Substituent group C, or a heterocyclic ring group of 1 to 65 mula II, a compound represented by formula Ib-III can be 9 carbonatoms, having 1 to 5 hetero atoms which may be the produced, for example, by a method of the following reaction same or different and which are selected from oxygen atom, formula. US 8,895,035 B2

Formula 26 XI RONH2 H Halogenating R"O- n 2 Oyl He-XXIV RONn a N n1 R2 He-agent R'Onn 2 N n1 R2 N (Step 13) N O (Step 14) N 2 No O O X2 XXIII) DXXV Ib-III)

Hydrolysis RONH XXIV Condensing agent XI ROSNN a OH O DXXVIII

(in the above, R', R, X, X and Y have each the above The amount of the compound XXIV used in the reaction mentioned meaning.) 25 is appropriately selected ordinarily in a range of 1.0 to 5 (Step 13) equivalents relative to 1 equivalent of the compound XX A compound XXVI can be produced by reacting a com VIII and is preferably 1.1 to 2 equivalents. pound DXXIII with a compound XXIV in a solvent in the As the condensing agent and solvent usable in the reaction, presence of a Lewis acid. there can be mentioned the same compounds and solvents as The amount of the compound XXIV used in the reaction 30 mentioned in the production method 9. The use amount of the is appropriately selected ordinarily in a range of 1 to 10 condensing agent is appropriately selected ordinarily in a equivalents relative to 1 equivalent of the compound XXIII range of 1 to 20 equivalents relative to 1 equivalent of the and is preferably 2 to 5 equivalents. compound XXVIII and is preferably 1.2 to 10 equivalents. As the solvent and Lewis acid usable in the reaction, there The amount of the solvent is ordinarily 0.1 to 50 liters, pref 35 erably 0.2 to 3.0 liters relative to 1 mol of the compound can be mentioned the same solvents and compounds as men XXVIII. tioned in the production method 18. The amount of the sol The temperature of the reaction is ordinarily any desired vent is ordinarily 0.1 to 50 liters, preferably 0.2 to 3.0 liters temperature from -50° C. to the reflux temperature of the relative to 1 mol of the compound XXIII. reaction system and is preferably a temperature of -10°C. to The use amount of the Lewis acid is appropriately selected 40 1000 C. ordinarily in a range of 1 to 3 equivalents relative to 1 equiva The time of the reaction differs depending upon the reac lent of the compound XXIII and is preferably 1 to 2 equiva tion temperature, the Substrate of reaction, the amount of lents. reaction, etc. but is ordinarily 1 to 24 hours. In the reaction, a base may be used in place of the Lewis After the completion of the reaction, there are conducted acid. As the base, there can be mentioned the same com 45 operations such as pouring of reaction mixture into water, pounds as mentioned in the production method 18. The use extraction by organic solvent, and Subsequent concentration, amount of the base is appropriately selected ordinarily in a whereby the compound XXVI can be isolated. The isolated range of 1 to 3 equivalents relative to 1 equivalent of the compound XXVI can be purified as necessary by column compound XXIII and is preferably 1 to 2 equivalents. chromatography, etc. The temperature of the reaction is ordinarily any desired 50 (Step 14) temperature from -50° C. to the reflux temperature of the A compound Ib-III can be produced by reacting the com reaction system and is preferably a temperature of -10°C. to pound XXV with a halogenating agent in a solvent. 100° C. As the halogenating agent usable in the reaction, there can The time of the reaction differs depending upon the reac be mentioned the same compounds as mentioned in the pro tion temperature, the Substrate of reaction, the amount of 55 duction method 3. The use amount of the halogenating agent reaction, etc. but is ordinarily 1 to 48 hours. is appropriately selected in a range of 1.0 to 20.0 mols relative After the completion of the reaction, there are conducted to 1.0 mol of the compound DXXVI and is preferably 1.0 to 6.0 operations such as concentration of reaction mixture or pour mols. ing of reaction mixture into water, extraction by organic Sol As the solvent usable in the reaction, there can be men vent, and Subsequent concentration, whereby the compound 60 tioned the same solvents as mentioned in the production DXXVI can be isolated. The isolated compound XXVI can be method 3. The amount of the solvent is ordinarily 0.1 to 50 purified as necessary by column chromatography, etc. liters, preferably 0.2 to 3.0 liters relative to 1.0 mol of the The compound DXXVI can also be produced by hydrolyz compound XXV. ing the compound XXIII in the presence of an acid or a base The temperature of the reaction is ordinarily any desired to obtain a compound XXVIII and reacting the compound 65 temperature from -50° C. to the reflux temperature of the DXXVIII with a compound DXXIV in a solvent in the pres reaction system and is preferably a temperature of 0° C. to ence of a condensing agent. 1000 C. US 8,895,035 B2 83 84 The time of the reaction differs depending upon the reac base is appropriately selected ordinarily in a range of 2 to 10 tion temperature, the Substrate of reaction, the amount of equivalents relative to 1 equivalent of oxalyldichloride and is reaction, etc. but is ordinarily 1 to 48 hours. preferably 2 to 5 equivalents. After the completion of the reaction, there are conducted The temperature of the reaction is ordinarily any desired operations such as concentration of reaction mixture or pour temperature from -20° C. to the reflux temperature of the ing of reaction mixture into water, extraction by organic Sol reaction system and is preferably a temperature of -10°C. to vent, and Subsequent concentration, whereby the compound 1000 C. Ib-III can be isolated. The isolated compound Ib-III can be purified as necessary by column chromatography, recrystal The time of the reaction differs depending upon the reac lization, etc. 10 tion temperature, the Substrate of reaction, the amount of Incidentally, the compound XXIII can be produced, for reaction, etc. but is ordinarily 1 to 48 hours. example, based on the method described in Journal of After the completion of the reaction, there are conducted Medicinal Chemistry, pp. 4608 to 4612 (1992) or Journal of operations such as pouring of reaction mixture into water, Organic Chemistry, pp. 496 to 500 (2001). 15 extraction by organic solvent, and Subsequent concentration, Production Method 23 whereby the compound XXVIII can be isolated. The isolated Of the present compounds represented by the general for compound DXXVIII can be purified as necessary by column mula II, a compound represented by formula Ib-III can be chromatography, recrystallization, etc. produced, for example, by a method of the following reaction (Step 16) formula. A compound Ib-II can be produced by reacting the com pound XXVIII with a halogenating agent in a solvent. Formula 27 As the halogenating agent usable in the reaction, there can O RONH be mentioned the same compounds as mentioned in the pro C DXXVI) 25 duction method 3. The use amount of the halogenating agent C (Step 15) is appropriately selected in a range of 1.0 to 20.0 mols relative to 1.0 mol of the general formula XXVIII and is preferably O 1.0 to 6.0 mols. O As the solvent usable in the reaction, there can be men 30 RON N R" HerHalogenating agent tioned the same solvents as mentioned in the production N O (Step 16) method 3. The amount of the solvent is ordinarily 0.1 to 50 O liters, preferably 0.2 to 3.0 liters relative to 1 mol of the DXXVII) compound XXVIII. X2 The temperature of the reaction is ordinarily any desired 35 temperature from -50° C. to the reflux temperature of the R1aO NN 2 2 N No1 R1a reaction system and is preferably a temperature of 0° C. to 1000 C. X2 The time of the reaction differs depending upon the reac 40 tion temperature, the Substrate of reaction, the amount of reaction, etc. but is ordinarily 1 to 48 hours. (in the above, R'' and X have each the above-mentioned After the completion of the reaction, there are conducted meaning.) operations such as concentration of reaction mixture or pour (Step 15) ing of reaction mixture into water, extraction by organic Sol A compound XXVIII can be produced by reacting oxalyl 45 vent, and Subsequent concentration, whereby the compound dichloride with a compound XXVII in a solvent in the pres Ib-III can be isolated. The isolated compound Ib-III can be ence of a base. purified as necessary by column chromatography, recrystal The amount of the compound XXVI used in the reaction lization, etc. is appropriately selected ordinarily in a range of 2 to 5 equiva Production Method 24 lents relative to 1 equivalent of oxalyl dichloride and is pref 50 erably 2.0 to 3.0 equivalents. Of the present compounds represented by the general for As the solvent usable in the reaction, there can be men mula I, a compound represented by formula Ia-II can also tioned, for example, an ether (e.g. diethyl ether, 1.2- be produced, for example, by a method of the following dimethoxyethane or tetrahydrofuran), a nitrile (e.g. acetoni reaction formula. trile or propionitrile), an aliphatic hydrocarbon (e.g. hexane 55 or heptane), an aromatic hydrocarbon (e.g. benzene, toluene or Xylene), a halogenated hydrocarbon (e.g. 1.2-dichloroet Formula 28 hane or chlorobenzene), or a mixture thereof. The amount of X the solvent is ordinarily 0.1 to 50 liters, preferably 0.2 to 3.0 Ph On 2 N R2 liters relative to 1 mol of oxalyl dichloride. 60 N1 NN 2 No1 As the base usable in the reaction, there can be mentioned, Catalytic for example, an inorganic base Such as alkali metal carbonate N reduction w1 -e- (e.g. sodium carbonate or potassium carbonate); alkali metal I (Step 17) bicarbonate (e.g. sodium hydrogencarbonate or potassium \ N (R3a), hydrogencarbonate); a metal hydride (e.g. sodium hydride or 65 potassium hydride); or an organic base (e.g. triethylamine or Ia-XXIII 1,8-diazabicyclo5.4.0-7-undecene). The use amount of the US 8,895,035 B2 85 86 -continued The use amount of the base is appropriately selected ordi X narily in a range of 0.5 to 20 equivalents relative to 1 equiva lent of the compound XXIX and is preferably 1 to 10 HOnn 2 N 1. R2 equivalents. N 2. No R-El The temperature of the reaction is ordinarily any desired N VII temperature from -50° C. to the reflux temperature of the W / (Step 18) reaction system and is preferably a temperature of -10°C. to \ N (R3a), 1000 C. XXIX) The time of the reaction differs depending upon the reac X 10 tion temperature, the Substrate of reaction, the amount of reaction, etc. but is ordinarily 1 to 24 hours. On 2 N R2 After the completion of the reaction, there are conducted R1 NN 2 No1 operations such as pouring of reaction mixture into water, extraction by organic solvent, and Subsequent concentration, -N 15 whereby the compound Ia-II can be isolated. The isolated W. compound Ia-II can be purified as necessary by column chromatography, etc. The pest control agent of the present invention is charac terized by containing, as an active ingredient, analkoxyimino derivative represented by the general formula I or an agri (in the above, R. R. X, W, E and n have each the above culturally acceptable salt thereof. The present pest control mentioned meaning.) agent is representatively an insecticide. (Step 17) The present pest control agent may as necessary contain an A compound XXIX can be produced by reacting a com additive component (carrier) ordinarily used in agricultural pound Ia-XXIII with hydrogen in a solvent in the presence 25 chemical formulations. of a catalyst. As the additive component, there can be mentioned a car As the catalyst used in the reaction, there can be mentioned, rier (e.g. Solid carrier or liquid carrier), a Surfactant, a binder for example, palladium, palladium hydroxide, or a catalyst or a tackifier, a thickening agent, a coloring agent, a spreader, obtained by loading palladium or palladium hydroxide on a sticker, an anti-freeze, a Solidification inhibitor, a disinte active carbon. 30 grator, a decomposition inhibitor, etc. As necessary, there The amount of the catalyst used in the reaction is appro may be used other additive components such as antiseptic, priately selected ordinarily in a range of 0.01 to 0.1 equivalent vegetable chip and the like. relative to 1 equivalent of Ia-XXIII and is preferably 0.02 to These additive components may be used in one kind or in 0.05 equivalent. combination of two or more kinds. As the solvent usable in the reaction, there can be men 35 The above additive components are explained. tioned, for example, an ether (e.g. diethyl ether, 1,4-dioxane As the Solid carrier, there can be mentioned, for example, or tetrahydrofuran), an alcohol (e.g. methanol or ethanol), an mineral carriers such as pyrophyllite clay, kaolin clay, silica acetic acid ester (e.g. ethyl acetate or butyl acetate), or acetic stone clay, talc, diatomaceous earth, Zeolite, bentonite, acid acid. The amount of the solvent is ordinarily 0.1 to 50 liters, clay, active clay, Attapulgus clay, Vermiculite, perlite, pum preferably 0.2 to 3.0 liters relative to 1 mol of Ia-XXIII. 40 ice, white carbon (e.g. synthetic silicic acid or synthetic sili The temperature of the reaction is ordinarily any desired cate), titanium dioxide and the like; vegetable carriers such as temperature from -50° C. to the reflux temperature of the wood flour, corn culm, walnut shell, fruit stone, rice hull, reaction system and is preferably a temperature of 0° C. to sawdust, wheat bran, soybean flour, powder cellulose, starch, 100° C. dextrin, Saccharide and the like; inorganic salt carriers such as The time of the reaction differs depending upon the reac 45 calcium carbonate, ammonium sulfate, sodium sulfate, potas tion temperature, the Substrate of reaction, the amount of sium chloride and the like; and polymer carriers such as reaction, etc. but is ordinarily 1 to 48 hours. polyethylene, polypropylene, polyvinyl chloride, polyvinyl After the completion of the reaction, there are conducted acetate, ethylene-vinyl acetate copolymer, urea-aldehyde operations such as concentration of reaction mixture or pour resin and the like. ing of reaction mixture into water, extraction by organic Sol 50 As the liquid carrier, there can be mentioned, for example, vent, and Subsequent concentration, whereby the compound monohydric alcohols such as methanol, ethanol, propanol, DXXIX can be isolated. The isolated compound XXIX can isopropnanol, butanol, cyclohexanol and the like; polyhydric be purified as necessary by column chromatography, recrys alcohols such as ethylene glycol, diethylene glycol, propy tallization, etc. lene glycol, hexylene glycol, polyethylene glycol, polypro (Step 18) 55 pylene glycol, glycerine and the like; polyhydric alcohol A compound Ia-II can be produced by reacting the com derivatives such as propylene-type glycol ether and the like; pound XXIX with VIII in a solvent in the presence of a ketones such as acetone, methyl ethylketone, methyl isobutyl base. ketone, disobutyl ketone, cyclohexanone, isophorone and the The amount of the compound VIII used in the reaction is like; ethers such as ethyl ether, dioxane, cellosolve, dipropyl appropriately selected ordinarily in a range of 1.0 to 5.0 60 ether, tetrahydrofuran and the like: aliphatic hydrocarbons equivalents relative to 1 equivalent of the compound DXXIX Such as normal paraffin, naphthene, isoparaffin, kersene, min and is preferably 1.0 to 2.0 equivalents. eral oil and the like; aromatic hydrocarbons such as toluene, As the solvent and base usable in the reaction, there can be Co-Co alkylbenzene, Xylene, solvent naphtha, alkylnaphtha mentioned the same solvents and compounds as mentioned in lene, high-boiling aromatic hydrocarbon and the like; halo the production method 1. The use amount of the solvent is 65 genated hydrocarbons such as dichloroethane, chloroform, ordinarily 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative carbon tetrachloride and the like; esters such as ethyl acetate, to 1 mol of the compound XXIX. diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, US 8,895,035 B2 87 88 dimethyl adipate and the like; lactones Such as Y-butyrolac crosslinked polyvinylpyrrolidone, maleic acid and styrene, tone and the like; amides such as dimethylformamide, dieth methacrylic acid copolymer, half ester between polyhydric ylformamide, dimethylacetamide, N-alkylpyrrolidinone and alcohol polymer and dicarboxylic acid anhydride, and water the like: nitriles such as acetonitrite and the like; sulfur com soluble salt of polystyrenesulfonic acid. pounds such as dimethylsulfoxide and the like; vegetable oils As the Sticker, there can be mentioned, for example, Sur Such as Soybean oil, rapeseed oil, cottonseed oil, coconut oil, factant (e.g. sodium dialkylsulfoSuccinate, polyoxyethylene castor oil and the like; and water. alkyl ether, polyoxyethylene alkylphenyl ether, or polyoxy As to the surfactant, there is no particular restriction. How ethylene fatty acid ester), paraffin, terpene, polyamide resin, ever, the surfactant preferably gels or swells in water. There polyacrylic acid salt, polyoxyethylene, wax, polyvinyl alkyl can be mentioned, for example, non-ionic Surfactants such as 10 ether, alkylphenol-formalin condensate, and synthetic resin sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid emulsion. ester, Sucrose fatty acid ester, polyoxyethylene fatty acid As the anti-freeze, there can be mentioned, for example, ester, polyoxyethylene resin acid ester, polyoxyethylene fatty polyhydric alcohol (e.g. ethylene glycol, diethylene glycol, acid diester, polyoxyethylene alkyl ether, polyoxyethylene propylene glycol, or glycerine). alkylphenyl ether, polyoxyethylene dialkylphenyl ether, 15 As the solidification inhibitor, there can be mentioned, for polyoxyethylene alkylphenyl etherformalin condensate, example, polysaccharide (e.g. starch, alginic acid, mannonse polyoxyethylene polyoxypropylene block polymer, alkyl or galactose), polyvinylpyrrolidone, white carbon, ester gum polyoxyethylene polypropylene block polymer ether, poly and petroleum resin. oxyethylene alkyl amine, polyoxyethylene fatty aci amide, As the disintegrator, there can be mentioned, for example, polyoxyethylene fatty acid bisphenyl ether, polyalkylene Sodium tripolyphosphate, sodium hexametaphosphate, benzyl phenyl ether, polyoxyalkylene styryl phenyl ether, Stearic acid metal salt, cellulose powder, dextrin, methacrylic acetylene diol, polyoxyalkylene-added acetylene diol, poly acid ester copolymer, polyvinylpyrrolidone, polyaminocar oxyethylene ether type silicone, ester type silicone, fluorine boxylic acid chelate compound, Sulfonated Styreneisobuty containing Surfactant, polyoxyethylene castor oil, polyoxy lene-maleic anhydride copolymer, and starchpolyacryloni ethylene hardened castor oil and the like; anionic Surfactants 25 trile graft copolymer. Such as alkyl Sulfate, polyoxyethylene alkyl ether Sulfate, As the decomposition inhibitor, there can be mentioned, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene for example, desiccants such as Zeolite, quick lime, magne styryl phenyl ether Sulfate, alkylbenzenesulionic acid salt, sium oxide and the like; antioxidants such as phenol type, ligninsulfonic acid salt, alkylsulfo Succinic acid salt, naphtha amine type, Sulfur type, phosphoric acid type and the like; and lenesulfonic acid salt, alkylnaphthalenesulfonic acid salt, 30 ultraviolet absorbents such as Salicylic acid type, benzophe naphthalenesulfonic acid-formalin condensate salt, alkyl none type and the like. naphthalenesulfonic acid-formalin condensate salt, fatty acid When the present pest control agent contains the above salt, polycarboxylic acid salt, N-methyl-fatty acid sarcosi mentioned additive components, their contents based on mass nate, resin acid salt, polyoxyethylene alkyl ether phosphate, are selected in a range of ordinarily 5 to 95%, preferably 20 to polyoxyethylene alkylphenyl ether phosphate and the like: 35 90% in the case of carrier, ordinarily 0.1 to 30%, preferably cationic Surfactants including alkyl amine salts such as lau 0.5 to 10% in the case of surfactant, and ordinarily 0.1 to 30%, rylamine hydrochloride, stearylamine hydrochloride, oley preferably 0.5 to 10% in the case of other additives. lamine hydrochloride, Stearylamine acetate, Stearylamino The present pest control agent is used in any formulation propylamine acetate, alkyl trimethyl ammonium chloride, selected from dust formulation, dust-granule mixture, gran alkyl dimethyl benzalkonium chloride and the like; and 40 ule, wettable powder, water-soluble concentrate, water dis ampholytic Surfactants such as betaine type (e.g. dialkyl persible granule, tablet, Jumbo, emulsifiable concentrate, oil diaminoethylbetaine or alkyldimethylbenzylbetaine), amino formulation, Solution, flowable concentrate, emulsion, acid type (e.g. dialkylaminoethylglycine or alkyldimethyl microemulsion, Suspoemulsion, ultra-low Volume formula benzylglycine) and the like. tion, microcapsule, Smoking agent, aerosol, baiting agent, As the binder and tackifier, there can be mentioned, for 45 paste, etc. example, carboxymethyl cellulose or a salt thereof, dextrin, In actual use of the formulation, the formulation can be water-soluble starch, Xanthane gum, guar gum, Sucrose, poly used perse or after dilution with a diluent (e.g. water) in a vinylpyrrolidone, gum arabi, polyvinyl alcohol, polyvinyl given concentration. The application of the formulations con acetate, Sodium polyacrylate, polyethylene glycol having an taining the present compound or of its dilution product can be average molecular weight of 6,000 to 20,000, polyethylene 50 conducted by a method ordinarily used. Such as dispersion oxide having an average molecular weight of 100,000 to (e.g. spraying, misting, atomizing, powder dispersion, gran 5,000,000, and natural phospholipid (e.g. cephalinic acid or ule dispersion, on-water-Surface dispersion, or inbox disper lecithin). sion), in-soil application (e.g. mixing or drenching), on-sur As the thickening agent, there can be mentioned, for face application (e.g. coating, dust coating or covering). example, water-soluble polymers such as Xanthan gum, guar 55 immersion, poison bait, Smoking and the like. It is also pos gum, carboxymethyl cellulose, polyvinylpyrrolidone, car sible to mix the above-mentioned active ingredient with a boxyvinyl polymer, acrylic polymer, starch derivative, livestock feed in order to prevent the infestation and growth of polysaccharide and the like; and inorganic fine powders such injurious pest, particularly injurious insect in the excreta of as high-purity bentonite, white carbon and the like. livestock. As the coloring agent, there can be mentioned, for 60 The proportion of the active ingredient in the present pest example, inorganic pigments such as iron oxide, titanium control agent is appropriately selected so as to meet the neces oxide, Prussian Blue and the like; and organic dyes Such as sity. The active ingredient is appropriately selected, for Alizarine dye, azo dye, metal phthalocyanine dye and the example, in the following range. like. Indust formulation, dust-granule mixture, etc. As the spreader, there can be mentioned, for example, 65 0.01 to 20% (mass), preferably 0.05 to 10% (mass) silicone-based Surfactant, cellulose powder, dextrin, pro In granule, etc. cessed starch, polyaminocarboxylic acid chelate compound, 0.1 to 30% (mass), preferably 0.5 to 20% (mass) US 8,895,035 B2 89 90 In wettable powder, water dispersible granule, etc. 3. Sodium channel modulators 1 to 70% (mass), preferably 5 to 50% (mass) (3A) Pyrethroids/Pyrethrins: acrinathrin, allethrin (in In water-soluble concentrate, Solution, etc cludes d-cis-trans and d-trans), bifenthrin, bioallethrin, bio 1-95% (mass), preferably 10 to 80% (mass) allethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, In emulsifiable concentrate, etc. cyfluthrin (includes beta-), cyhalothrin (includes gamma- and 5 to 90% (mass), preferably 10 to 80% (mass) lambda-), cypermethrin (includes alpha-, beta-, theta- and In oil formulation, etc. Zeta-), cyphenothrin includes (IR)-trans-isomers, delta 1 to 50% (mass), preferably 5 to 30% (mass) methrin, empenthrin, esfenvalerate, etofemproX, fempropath In flowable concentrate, etc. rin, fenvalerate, flucythrinate, flumethrin, tauflu valinate (in 5 to 60% (mass), preferably 10 to 50% (mass) 10 cludes tau-), halfenproX, imiprothrin, metofluthrin, In emulsion, microemulsion, Suspoemulsion, etc. permethrin, phenothrin includes (IR)-trans-isomer, pral 5 to 70% (mass), preferably 10 to 60% (mass) lethrin, profluthrin, pyrethrine, resmethrin, RU15525 (code In tablet, baiting agent, paste, etc. number), silafluofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin, ZX18901 (code number), fluvalinate, tetram 1 to 80% (mass), preferably 5 to 50% (mass) 15 ethylfluthrin, meperfluthrin; In Smoking agent, etc. (3B) DDT/Methoxychlor: DDT, methoxychlor 0.1 to 50% (mass), preferably 1 to 30% (mass) 4. Nicotinic acetylcholine receptor agonist/antagonist In aerosol, etc. 0.05 to 20% (mass), preferably 0.1 to 10% (mass) (4A) Neonicotinoids: acetamiprid, clothianidin, dinotefu The formulation is sprayed after dilution in an appropriate ran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; concentration, or applied directly. (4B) Nicotine: nicotine-sulfate When the present pest control agent is used after dilution 5. Nicotinic acetylcholine receptor allosteric activators with a diluent, the concentration of active ingredient is gen Spinosyns: spinetoram, spinosad erally 0.1 to 5,000 ppm. When the formulation is used perse, 6. Chloride channel activators the application amount thereof per unit area is 0.1 to 5,000 g Avermectins, Milbemycins: abamectin, emamectin ben per 1 ha in terms of active ingredient compound; however, the 25 Zoate, lepimectin, milbemectin, ivermectin, polynactins application amount is not restricted thereto. 7. Juvenile hormone mimics Incidentally, the present pest control agent is sufficiently diofenolan, hydroprene, kinoprene, methothrin, fenoxy effective when using the present compound alone as an active carb, pyriproxyfen ingredient. However, in the present pest control agent, there 8. Miscellaneous non-specific (multi-site) inhibitors may be mixed or used in combination, as necessary, fertilizers 30 1,3-dichloropropene, DCIP, ethylene dibromide, methyl and agricultural chemicals such as insecticide, acaricide, bromide, chloropicrin, sulfuryl fluoride nematicide, Synergist, fungicide, anti-viral agent, attractant, 9. Antifeedant herbicide, plant growth-controlling agent and the like. In this pymetrozine, flonicamid, pyrifluquinazon case, a higher effect is exhibited. 10. Mite growth inhibitors Below are shown examples of the known insecticide com pounds, acaricide compounds, nematicide compounds and 35 clofentezine, diflovidazin, hexythiazox, etoxazole synergist compounds, which may be mixed or used in com 11. Microbial disruptors of insect midgut membranes bination. BT agent: Bacillus sphaericus, Bacillus thuringiensis 1. Acetylcholinesterase inhibitors Subsp. aizawai, Bacillus thuringiensis Subsp. israelensis, (1A) Carbamates: alanycarb, aldicarb, aldoxycarb, bendio Bacillus thuringiensis Subsp. kurstaki, Bacillus thuringiensis carb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, 40 subsp. tenebrionis, Bt crop proteins (Cry1Ab, Cry1Ac, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetan Cry1 Fa, Cry2Ab, mCry3A, Cry3 Ab, Cry3Bb, Cry34/ ate, furathiocarb, isoprocarb, methiocarb, methomyl, metol 35Ab1), Bacillus popilliae, Bacillus subtillis carb, oxamyl, pirimicarb, propoXur, thiodicarb, thiofanox, 12. Inhibitors of mitochondrial ATP synthase triazamate, trimethacarb. XMC, xylylcarb: diafenthiuron; (1B) Organophosphates: acephate, azamethiphos, azin 45 Organotin miticides: azocyclotin, cyhexatin, fenbutatin phosethyl, azinphos-methyl, cadusafos, chlorethoxyfos, oxide; chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos propargite, tetradifon methyl, coumaphos, cyanophos, demotion-5-methyl, diami 13. Uncouplers of oxidative phosphorylation via disruption dafos, diazinon, dichlorvos, dicrotophos, dimethoate, dim of the proton gradient ethylvinphos, dioxabenzofos, disulfoton, DSP, EPN, ethion, 50 chlorfeinapyr, DNOC ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, 14. Nicotinic acetylcholine receptor channel blockers fenthion, fonofos, fosthiazate, fosthietan, heptenophos, isa Nereistoxin analogues: benSultap, cartap, thiocyclam, midofos, isaZophos, isofenphos-methyl, isopropyl O-(meth thiosultap oxyaminothiophosphoryl)salicylate, isoxathion, malathion, 15. Inhibitors of chitin biosynthesis, type 0 mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, Oxydemeton-methyl, 55 Benzoylureas: bistrifluoron, chlorfluaZuron, diflubenzu Oxydeprofos, parathion, parathion-methyl, phenthoate, phor ron, flucycloXuron, flufenoXuron, hexaflumuron, lufenuron, ate, phosalone, phosmet, phosphamidon, phoxim, pirimi novaluron, noviflumuron, teflubenzuron, triflumuron, fluaZu phos-methyl, profenofos, propaphos, propetamphos, prothio O fos, pyraclofos, pyridaphenthion, quinallphos, Sulfotep, 16. Inhibitors of chitin biosynthesis, type 1 tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiome 60 buprofezin ton, thionazin, triaZophos, trichlorfon, Vamidothion, dichlo 17. Moulting disruptor, Dipteran fenthion, imicyafos, isocarbophos, meSulfenfos, fluprazofoS cyromazine 2. GABA-gated chloride channel antagonists 18. Ecdysone receptor agonist (ecdysis acceleration) (2A) Cyclodiene organochlorines: chlordane, endosulfan, Diacylhydrazines: chromafenozide, halofenozide, meth gamma-BCH: 65 oxyfenozide, tebufenozide (2B) Phenylpyrazoles: acetoprol, ethiprole, fipronil, pyraf 19. Octopamine receptor agonist luprole, pyriprole, RZI-02-003 (code number) amitraz US 8,895,035 B2 91 92 20. Mitochondrial complex III electron transport inhibitors 3. Respiratory inhibitors cyflumetofen, hydramethylnon, acequinocyl, fluacrypy Pyrimidinamines: diflumetorim; rim, cyenopyrafen Carboxamides: benodanil, flutolanil, mepronil, fluopyram, 21. Mitochondrial complex I electron transport inhibitors fenfuram, carboxin, oxycarboxin, thifluZamide, bix METI acaricides and insecticides: fenazaquin, fenpyroxi afen, furametpyr, isopyrazam, penflufen, penthiopyrad, mate, pyridaben, pyrimidifen, tebufenpyrad, tolfenpyrad sedaxane, boscalid; Other: rotenone Methoxy-acrylates: azoxystrobin, enestroburin, picox 22. Sodium channel blockers yStrobin, pyraoxystrobin; indoxacarb, metaflumizone Methoxy-carbamates: pyraclostrobin, pyrametostrobin; 23. Inhibitors of lipid synthesis 10 Oxyimino acetates: kresoxim-methyl, trifloxystrobin; Tetronic and Tetramic acid derivatives: spirodiclofen, Oxyimino-acetamides: dimoxystrobin, metominostrobin, spiromesifen, Spirotetramat orysastrobin; 24. Mitochondrial complex IV electron transport inhibitors Oxazolidine-diones: famoxadone; aluminium phosphide, phosphine, Zinc phosphide, calcium 15 Dihydro-dioxazines: fluoxastrobin: cyanide Imidazolinones: fenamidone; 25. Neuronal inhibitors (unknown mode of action) Benzyl-carbamates: pyribencarb: bifenazate Cyano-imidazoles: cyaZofamid; 26. Aconitase inhibitors Sulfamoyl-triazoles: amisulbrom: Sodium fluoroacetate Dinitrophenyl crotonates: binapacryl, methyldinocap, 27. Synergists dinocap: piperonyl butoxide, DEF 2,6-Dinitro-anilines: fluaZinam, 28. Ryanodine receptor modulators Pyrimidinone hydrazones: ferimZone; chlorantraniliprole, flubendiamide, cyantraniliprole Triphenyl tin compounds: TPTA, TPTC, TPTH: 29. Compounds with unknown mode of action 25 Thiophene-carboxamides: silthiofam; azadirachtin, amidoflumet, benclothiaz, benzoximate, bro Triazolo-pyrimidylamines: ametoctradin mopropylate, chinomethionat, CL900167 (code number), 4. Amino acid and protein synthesis inhibitors cryolite, dicofol, dicyclanil, dienochlor, dinobuton, fenbuta Anilino-pyrimidines: cyprodinil, mepanipyrim, tin oxide, fenothiocarb, fluensulfone, flufenerim, fulsulfa pyrimethanil; mide, karanjin, metham, methoprene, methoxyfenozide, 30 Enopyranuronic acid antibiotic: blasticidin-S, mildiomy methyl isothiocyanate, pyridalyl, pyrifluquinazon, Sulcofu cin; ron-sodium, Sulfluramid, Sulfoxaflor Hexopyranosyl antibiotic: kasugamycin; 30. Entomopathogenic fungi, nematode-pathogenic microor Glucopyranosyl antibiotic: Streptomycin; ganisms 35 Tetracycline antibiotic: oxytetracycline Beauveria bassiana, Beauveria tenella, Verticillium leca 5. Signal transduction inhibitors nii, Pacilimyces tenuipes, Paecilomyces fumosoroceus, Beau Aryloxyquinoline: quinoxyfen; veria brongniartii, Monacrosporium phymatophagum, Pas Quinazolines: produinazid; teuriapenetrans Phenylpyrroles: fempiclonil, fludioxonil; 31. Sex pheromone 40 Dicarboxylmides: chloZolinate, iprodione, procymidone, (Z)-11-hexadecenal, (Z)-11-hexadecenyl acetate, litlure Vinclozolin A, litlure-B, Z-13-eicosene-10-one, (Z.E)-9,12-tetradecadi 6. Lipid synthesis and membrane integrity inhibitors enyl acetate, (Z)-9-tetradecen-1-ol, (Z)-11-tetradecenyl Phosphoro-thiolates: edifenphos, iprobenfos, pyrazophos: acetate, (Z)-9,12-tetradecadienyl acetate, (Z.E)-9,11-de Dithiolanes: isoprothiolane; tradecadienyl acetate 45 Aromatic hydrocarbons: biphenyl, chloroneb, dicloran, Below are shown examples of the known fungicide or quintoZenes, tecnaZene, tolclofoS-methyl, disease damage control agent compounds which may be 1,2,4-Thiadiazoles: etridiazole mixed or used in combination. Carbamates: iodocarb, propamocarb-hydrochloride, pro 1. Nucleic acid biosynthesis inhibitors thiocarb: Acylalanines: benalazyl, benalazyl-M, furalaxyl, metal 50 Cinnamic acid amides: dimethomorph, flumorph; axyl, metalaxyl-M; Valineamide carbamates: benthiavalicarb-isopropyl. Oxazolidinones: oxadixyl: iprovalicarb, valifenalate: Butyrolactones: cloZylacon, ofurace; Mandelic acid amides: mandipropamid; Hydroxy-(2-amino)pyrimidines: bupirimate, dimethiri Bacillus subtilis and the fungicidal lipopeptides produced: 55 Bacillus subtilis (strain: QST 713) mol, ethirimol; 7. Inhibitors of sterol biosynthesis in membranes Isoxazoles: hymexaZol; piperazines: triforine; Isothiazolones: octhillinone; Pyridines: pyrifenox; Carboxylic acids: oxolinic acid Pyrimidines: fenarimol, nuarimol; 2. Mitosis and cell division inhibitors 60 Imidazoles: imazalil, Oxpoconazole-fumarate, pefura Benzoimidazoles: benomyl, carbendazim, fuberidazole, Zoate, prochloraz, triflumizole; thiabendazole; Triazoles: azaconazole, bitertanol, bromuconazole, cypro Thiophanates: thiophanate, thiophanate-methyl; conazole, difenoconazole, diniconazole, diniconazole N-phenylcarbamates: diethofencarb: M, epoxiconazole, etaconazole, fenbuconazole, flu Toluamides: Zoxamide; 65 quinconazole, flusilaZole, flutriafol, hexaconazole, Phenylureas: pencycuron; imibenconazole, ipconazole, metconazole, myclobuta Pyridinylmethylbenzamides: fluopicolide nil, penconazole, propiconazole, prothioconazole, sim US 8,895,035 B2 93 94 econazole, tebuconazole, tetraconazole, triadimefon, B. Acetolactic synthase (ALS) inhibitors triadimenol, triticonazole, furconazole, furconazole-cis, (B-1) Imidazolinones: imazamethabenZ-methyl, quinconazole; imaZamox, imazapic (includes salts with amine, etc.), imaza Morpholines: aldimorph, dodemorph, fempropimorph, tri pyr (includes salts with isopropylamine, etc.), imaZaquin, demorph; 5 imazathapyr; Piperidines: fempropidin, piperalin; (B-2) Pyrimidinyloxy benzoate: bispyribac-sodium, Spiroketal amines: Spiroxamine; pyribenZoxim, pyriftalid, pyriminobac-methyl, pyrithiobac Hydroxyanilides: fenhexamid: Sodium, pyrimisulfan; Thiocarbamates: pyributicarb: (B-3) Sulfonylaminocarbonyl-triazolinones: flucarba Allylamines: naftifine, terbinafine 10 Zonesodium, thiencarbazone (includes sodium salt, methyl 8. Glucan synthesis inhibitors ester, etc.), propoxycarbazone-sodium, procarbazone-so Glucopyranosyl type antibiotic: validamycin; dium; Peptidylpyridine nucleotide compound: polyoxin (B-4) Sulfonylureas: amidosulfuron, azimsulfuron, ben 9. Melanine synthesis inhibitors Sulfuron-methyl, chlorimuron-ethyl, chlorSulfuron, cinosul Isobenzo-furanones: phthalide; 15 furon, cycloSulfamuron, ethametSulfuron-methyl, ethoxysul Pyrrolo-quinolines: pyroquilon; furon, flaZaSulfuron, fluipyrsulfuron-methyl-Sodium, Triazolobenzo-thiazoles: tricyclazole; foramsulfuron, halosulfuron-methyl, imaZosulfuron, Carboxamides: carpropamid, diclocymet; iodosulfulon-methyl-Sodium, mesosulfuron-methyl, thifen Propionamides: fenoxanil sulfuron-methyl, triasulfuron, tribenuron-methyl, triflox 10. Host plant defence inducers ysulfuron-sodium, triflusulfuron-methyl, tritosulfuron, Benzo-thiadiazoles: acilbenzolar-5-methyl: orthosulfamuron, propgirisulfuron, metazosulfuron, fluceto Benzoisothiazoles: probenazole; sulfuron; Thiadiazole-carboxamides: tiadinil, isotianil (B-5) Triazolopyrimidines: cloransulam-methyl, diclosu Natural compound: laminarin lam, florasulam, flumetSulam, metoSulam, penoXSulam, 11. Compounds with unknown mode of action 25 pyroxSulam, Copper compound: copper hydroxide, copper dioctanoate, C1. Photosynthesis at photosystem II inhibitors (1) copper oxychloride, copper Sulfate, cuprous oxide, (C1-1) Phenyl-carbamates: desmedipham, phenme oxine-copper, Bordeaux mixture, copper nonyl phenol dipham; Sulphonate; (C1-2) Pyridazinones: chloridazon, brompyrazon: Sulfur compound: sulfur, 30 (C1-3) Triazines: ametryn, atrazine, cyanazine, desm Dithiocarbamates: ferbam, mancoZeb, maneb, metiram, etryne, dimethametryn, eglinazine-ethyl, prometon, prom propineb, thiram, Zineb, Ziram, cufraneb: etryn, propazine, simazine, simetryn, terbumeton, terbuthy Phthalimides: captan, folpet, captafol: lazine, terbutryn, trietazine; Chloronitriles: chlorothalonil; (C1-4) Triazinones: metamitron, metribuzin, Sulfamides: dichlofluanid, tolylfluanid; 35 (C1-5) Triazolinones: amicarbazone: Guanidines: guazatline, iminoctadine-albesilate, iminocta (C1-6) Uracils: bromacil, lenacil, terbacil; dine-triacetate, dodine; C2. Photosynthesis at photosystem II inhibitors (2) Other compound: anilazine, dithianon, cymoxanil, fosetyl (C2-1) Amides: pentanochlor, propanil; (alminium, calcium, Sodium), phosphorus acid and (C2-2) Ureas: chlorbromuron, chlorotoluron, chloroxuron, salts, tecloftalam, triazoxide, flusulfamide, diclomeZine, 40 dimefuron, diuron, ethidimuron, fenuron, fluometuron, iso methasulfocarb, ethaboxam, cyflufenamid, proturon, isouron, linuron, methabenzthiaZuron, metobromu metrafenone, potassium bicarbonate, Sodium bicarbon ron, metoxuron, monolinuron, neburon, Siduron, tebuthiuron, ate, BAF-045 (code number), BAG-010 (code number), metobenzuron; benthiazole, bronopol, carvone, chinomethionat, C3. Photosynthesis at photosystem II inhibitors (3) dazomet, DBEDC, debacarb, dichlorophen, difenzo 45 (C3-1) Benzothiadiazones: bentazone: quat-methyl Sulfate, dimethyl disulfide, diphenylamine, (C3-2) Nitriles: bromofenoxim, bromoxynil (includes ethoxyquin, flumetover, fluoroimide, flutianil, fluxapy esters of butyric acid, octanoic acid, heptanoic acid, etc.), roXad, furancarboxylic acid, metam, nabam, natamycin, ioxynil; nitrapyrin, nitrothalisopropyl, o-phenylphenol, oxazi (C3-3) Phenylpyrazines: pyridafol, pyridate; nylazole, oxyquinoline Sulfate, phenazine oxide, poly 50 D. Photosystem-1-electron acceptors carbamate, pyriofenone, S-2188 (code number), silver, (D-1) Bipyridyliums: diguat, paraquat dichloride; SYP-Z-048 (code number), tebufloquin, tolnifanide, E. Protoporphyrinogen oxidase (PPO) inhibitors trichlamide, mineral oils, organic oils Below are shown (E-1) Diphenylethers: acifluorfen-sodium, bifenox, chi examples of the known herbicidal compounds and plant omethoxyfen, ethoxyfen-ethyl, fluoroglycofen-ethyl, frame growth-controlling compounds which may be mixed or 55 safen, lactofen, oxyfluorfen: used in combination. (E-2) N-phenylphthalimides: cinidon-ethyl, flumiciorac A1. Acetyl CoA carboxylase (ACCase) inhibitors pentyl, flumioxazin, chlorphthalim, (A1-1) Aryloxyphenoxy propionate: clodinafop-propar (E-3) OXydiazoles: oxadiargyl, oxadiaZon; gyl, cyhalofop-butyl, diclofop-methyl, diclofop-P-methyl, (E-4) Oxazolidinediones: pentoxaZone; fenoxaprop-P-ethyl, fluazifop-butyl, fluazifop-P-butyl, 60 (E-5) Phenylpyrazoles: fluazolate, pyraflufen-ethyl: haloxyflop, haloxyflop-etotyl, haloxyfop-P, metamifop, pro (E-6) Pyrimidinediones: benzfendizone, butafenacil, paquizafop, quizalofop-ethyl, quizalofop-P-ethyl, quizalo saflufenacil; fop-P-tefuryl, fenthiaprop-ethyl: (E-7) Thiadiazoles: fluthiacet-methyl, thidiazimin: (A1-2) Cyclohexandiones: alloxydim, butroxydim, (E-8) Triazolinones: azafenidin, carfentraZone-ethyl, clethodim, cycloxydim, profoxydim, Sethoxydim, tepraloxy 65 SulfentraZone, bencarbazone; dim, tralkoxydim; (E-9) Other compound: flufenpyr-ethyl, profluaZol, pyre (A1-3) Phenylpyrazolines: aminopyralid, pinoxaden; clonil, SYP-298 (code number), SYP-300 (code number); US 8,895,035 B2 95 96 F1. Inhibitors of carotenoid biosynthesis at the phytoene (N-3) Phosphorodithioates: bensulide; desaturase step (PDS) (N-4) Thiocarbamates: butylate, cycloate, dimepiperate, (F1-1) Pyridazinones: norflurazon: EPTC, esprocarb, molinate, orbencarb, pebulate, prosulfo (F1-2) Pyrimidinecarboxamides: diflufenican, picolin carb, thiobencarb, tiocarbazil, tri-allate, Vernolate afen; O. Synthetic auxins (F1-3) Other compound: beflubutamid, fluridone, fluoro (O-1) Benzoic acids: chloramben, 2.3.6-TBA, dicamba chloridone, flurtamone; (includes salts of amine, diethylamine, isopropylamine, dig F2. 4-Hydroxyphenylpyruvate dioxygenase (HPPD) inhibi lycolamine, Sodium, lithium, etc.); tOrs (O-2) Phenoxycarboxylic acids: 2,4,5-T 2,4-D (includes (F2-1) Callistemones: mesotrione: 10 salts of amine, diethylamine, triethanolamine, isopropy (F2-2) Isoxazoles: pyrasulfotole, isoxaflutole, isoxachlor lamine, sodium, lithium, etc.), 2,4-DB, clomeprop, dichlor tole; prop, dichlorprop-P, MCPA, MCPA-thioethyl, MCPB (in (F2-3) Pyrazoles: benzofenap, pyrazolynate, pyrazoxyfen; cludes Sodium salt, ethylester, etc.), mecoprop (includes salts (F2-4) Ttiketones: sulcotrione, tefuryltrion, tembotrione, of Sodium, potassium, isopropylamine, trietanolamine, dim pyrasulfotole, toprameZone, bicyclopyrone; 15 ethylamine, etc.), mecoprop-P; F3. Carotinoid biosynthesis inhibitors (unknown target) (O-3) Pyridine carboxylic acids: clopyralid, fluoroxypyr. (F3-1) Diphenylethers: acionifen; picloram, triclopyr, triclopyr-butotyl; (F3-2) Isoxazolidinones: clomazone: (O-4) Quinoline carbXylic acids: quinclorac, quinmerac: (F3-3) Triazoles: amitrole; (O-5) Other compound: benazolin; G. EPSP synthase inhibitors (aromatic amino acid biosynthe P. Auxin transport inhibitors sis inhibitors) (P-1) Phthalamates: naptalam (includes salts with sodium, (G-1) Glycines: glyphosate (includes salts of Sodium, etc.); amine, propylamine, ispropylamine, dimethylamine, trime (P-2) Semicarbazones: diflufenzopyr; sium etc.); 25 Z. Compounds with unknown mode of action H. Glutamine synthetase inhibitors flamprop-M (includes methyl, ethyl and isopropyl esters), (H-1) Phosphinic acids: bilanafos, glufosinate (includes flamprop (includes methyl, ethyl and isopropyl esters), chlo salts of amine, Sodium, etc.); rflurenol-methyl, cinmethylin, cumyluron, daimuron, meth I. Dihydropteroate (DHP) inhibitors yldymuron, difenZoquat, etobenzanid, fosamine, pyributi 30 carb, oxaziclomefone, acrolein, AE-F-150954 (code (I-1) Carbamates: asulam; number), aminocyclopyrachlor, cyanamide, heptamaloxylo K1. Microtubule assembly inhibitors glucan, indaziflam, triaziflam, quinoclamine, endothal-diso (K1-1) BenZamides: propyZamide, tebutam; dium, phenisopham Plant growth-controlling agent: 1-meth (K1-2) Benzoic acids: chlorthal-dimethyl: ylcyclopropene, 1-naphthylacetamide, 2,6- (K1-3) Dinitroanilines: benfluralin, butralin, dinitramine, 35 diisopropylnaphthalene, 4-CPA, benzylaminopurine, ethal fluralin, fluchloralin, oryzalin, pendimethalin, prodi ancymidol, aviglycine, carvone, chiormeduat, cloprop, amine, trifluralin; cloxyfonac, cloxyfonac-potassium, cyclanilide, cytokinins, (K1-4) Phosphoroamidates: amiprofos-methyl, butamifos; daminozide, dikegulac, dimethipin, ethephon, ethylchloZate, (K1-5) Pyridines: dithiopyr, thiazopyr; flumetralin, flurenol, flurprimidol, forchlorfenuron, gibberel K2. Inhibitors of mitosis/microtubule organization 40 lin acid, inabenfide, indole acetic acid, indole butyric acid, (K2-1) Carbamates: carbetamide, chlorpropham, maleic hydrazide, mefluidide, mepiduat chloride, n-decanol, propham, Swep, karbutilate: paclobutraZol, prohexadione-calcium, prohydrojasmon, K3. Very-long-chain fatty acids (VLCFAs) inhibitors (cell sintofen, thidiaZuron, triacontanol, trinexapac-ethyl, uni division inhibitors) conazole, uniconazole-P. (K3-1) Acetamides: diphenamid, napropamide, naproanil 45 Below are shown examples of the known chemical injury ide; reducing compounds which may be mixed or used in combi (K3-2) Chloroacetamides: acetochlor, alachlor, butachlor, nation. butenachlor, diethatyl-ethyl, dimethachlor, dimethenamid, benoxacor, furilazole, dichlormid, dicyclonone, DKA-24 dimethenamid-P. metaZachlor, metolachior, pethoxamid, (N1,N2-diallyl-N2-dichloroacetylglycineamide), AD-67 pretilachlor, propachlor, propisochlor, S-metholachlor, the 50 (4-dichloroacetyl-1-oxa-4-azaspiro4.5 decane), PPG-1292 nylchlor; (2,2-dichloro-N-(1,3-dioxan-2-ylmethyl)-N-(2-propenyl)ac (K3-3) Oxyacetamides: flufenacet, mefenacet: etamide), R-29148 (3-dichloroacetyl-2.2.5-trimethyl-1,3- (K3-4) Tetrazolinones: fentraZamide: oxazoline), cloquintcet-methyl, 1.8-Naphthalic Anhydride, (K3-5) Other compound: anilofos, bromobutide, cafens mefenpyrdiethyl, mefenpyr, mefenpyr-ethyl, fenchlorazole O trole, indanofan, piperophos, fenoxasulfone, pyroxasulfone, 55 ethyl, fenclorim, MG-191 (2-dichloromethyl-2-methyl-1,3- ipfencarbazone; dioxane), cyometrinil, flurazole, fluxofenim, isoxadifen, L. Cellulose synthesis inhibitors isoxadifenethyl, mecoprop, MCPA, daimuron, 2,4-D, MON (L-1) Benzamides: isoxaben; 4660 (code number), oxabetrinil, cyprosulfamide and TI-35 (L-2) Nitriles: dichiobenil, chlorthiamid: (code number) (L-3) Triazolocarboxamides: flupoxame: 60 The pest targeted by the present invention refers to pest of M. Uncouplers (Membrane disruptors) Orthoptera, Thysanoptera, Hemiptera, Coleoptera, Diptera, (M-1) Dinitrophenols: dinoterb, DNOC (includes salts of Lepidoptera, Hymenoptera, Collembola, Thysanura, Blat amine, sodium, etc.); todea, Isoptera, Psocoptera, Mallophaga, Anoplura, plant N. Lipid synthesis inhibitors (excluding ACCase inhibitors) feeding mites, plant parasitic nematodes, plant parasitic mol (N-1) Benzofurans: benfuresate, ethofumesate: 65 lusc pests, other crop pests, nuisance pests, sanitary insects, (N-2) Halogenated carboxylic acids: dalapon, flupropan parasites, etc. AS examples of such pests, the following organ ate, TCA (includes salts of sodium, calcium, ammonia, etc.); ism species can be mentioned. US 8,895,035 B2 97 98 As the Orthopteran pest, there can be mentioned, for Dermestidae: Anthrenus verbasci, etc., example, Bostrichidae: Heterobostrychus hamatipennis, etc., Tettigoniidae: Ruspolia lineosa, etc., Anobiidae: Stegobium paniceum, etc., Gryllidae: Teleogryllus emma, etc., Ptinidae: Pitinus clavipes, etc., Gryllotalpidae: Gryllotalpa orientalis, Trogositidae: Tenebroides manritanicus, etc., Locustidae: Oxya hyla intricate, Locusta migratoria, Mel Cleridae: Necrobia rufipes, anoplus sanguinipes, etc., Nitidulidae: Carpophilus hemipterus, etc., Pyrgomorphidae: Atractomorpha lata, Silvanidae: Ahasverus advena, etc., Acrididae: Euscyrtus japonicus Laemophloeidae: cryptolestes ferrugineus, etc., Tridactylidae: Xva japonicus, etc. 10 As the Thysanopteran pests, there can be mentioned, for Coccinellidae: Epilachna varivestis, Henosepilachna vig example, intioctopunctata, etc., Thripidae: Frankliniella intonsa, Frankliniella occidenta Tenebrionidae: Tenebrio molitor, tribolium Castaneum, lis, Scirtothrips dorsalis, Thrips palmi, Thrips tabaci, etc., etc., Phlaeothripidaes: Ponticulothrips diospyrosi, Haplothrips 15 Meloidae: Epicauta gorhami, etc., aculeatus, etc. Cerambycidae: Anoplophora glabripennis, Xylotrechus As the Hemipteran pest, there can be mentioned, for pyrroderus, Monochamus alternatus, etc., example, Bruchidae: Callosobruchus chinensis, etc., Cicadidae: Mogannia minuta, etc., Chrysomelidae: Leptinotarsa decemlineata, Diabrotica Cercopidae: Aphorphora intermedia, etc., virgifera, Phaedon brassicae, Phyllotreta striolata, etc., Membracidae: Machaerotypus Sibiricus, etc., Brentidae: Cylas formicarius, etc., Deltcephalidae: Arboridia apicalis, Empoasca Onuki, Curculionidae: Hypera postica, Listroderes costirostris, Nephotettix cincticeps, Recilia dorsalis, etc., Euscepes postfasciatus, etc., Cixiidae: Pentastiridius apicalis, etc., Erirhinidae: Echinocnemus bipunctatus, Lissorhoptrus Delphacidae: Laodelphax striatellus, Nilaparvata lugens, 25 Oryzophilus, etc., Sogatella furcifera, etc., Rhynchophoridae: Sitophilus zeanais, Sphenophrus vane Meenoplidae: Nisia nervosa, etc., tuS, etc., Derbidae: Kamendaka saccharivora, etc., Limnoriidae: Tomicus piniperda, etc., Cixidia Okuni. Achilus flammeus, etc., Platypodidae: Crossotarsus niponicus, etc., Ricamidae: Orosanga japonicus, etc., 30 Lyctidae: Lyctus brunneus, etc. Flatidae: Mimophantia maritima, etc., As the Diptera pest, there can be mentioned, for example, Psyllidae: Cacopsylia pyrisuga, etc., Tipulidae: Tipila aino, etc., Calophyidae: Calophya mangiferae, etc., Bibionidae: Plecia nearctica, etc., Phylloxeridae: Daktulosphaira vitifoliae, etc., Fungivoridae: Exechia Shiitakevora, etc., Chemidae: Adelges laricis, 35 Lycoriidae: Pnyxiascabiei, etc., Adelgidae: Adelges tsugae, etc., Cecidomyiidae: Asphondylia vulsinai, Mayetiola destruc Aphididae: Acyrthosiphon pisum, Aphis gossypii, Aphis tor, etc., spiraecola, Lipaphis erysimi, Myzuspersicae, Culicidae: Aedes aegypti, Culex pipiens pallens, etc., Aphrastasia tsugae: Schizaphis graminum, Rhopalosi Simuliidae: Simulin takahasii, etc., phum padi, etc., 40 Chironomidae: Chironomus Oryzae, etc., Aleyrodidae: Aleurocanthus spiniferus, Bemisia tabaci, Tabanidae: Chrysops suavis, Tabanus trigonus, etc., Bemisia argentifolii, Trialeurodes vaporariorum, etc., Syrphidae: Eumerus Strigatus, etc., Margarodidae: Drosicha corpulenta, Icerya purchasi, etc., Trypetidae: Bactrocera dorsalis, Euphranta japonia, Cer Pseudococcidae: Dysmicoccus brevipes, Planococcus atitis Capitata, etc., citri, Pseudococcus Comstocki, etc., 45 Agromyzidae: Liriomyza trifolii, Chromatomyia horti Coccidae: Ceroplastes ceriferus, etc., Cola, etc., Aclerdidae: Aclerda takahasii, etc., Chloropidae: Meromyza nigriventris, etc., Diaspididae: Aonidella aurantii, Diaspidiotus perniciosus, Drosophilidae: Drosophila Suzuki, Drosophila melano Unaspis vanonensis, etc., gaster, etc., Miridae: Lygus hesperus, Trigonotylus Caelestialium, etc., 50 Ephydridae: Hydrellia griseola, etc., Tingitidae: Stephanitis pyrioides, Stephanitis nashi, etc., Hippoboscidae: Hippobosca equina, etc., Pentatomidae: Eysarcoris aeneus, Lagynotomus elonga Scatophagidae: Parallelpmma Sasakawae, etc., tus, Nezara viridula, Plautia crissota, etc., Anthomyiidae: Delia antiqua, Delia platura, etc., Plataspidae: Megacopta Cribaria, etc., Fanniidae: Fannia canicularis, etc., Lygaeidae: Cavelerius saccharivorus, etc., 55 Muscidae: Musca domestica, Stomoxys calcitrans, etc., Malcidae: Malicus japonicus, etc., Sarcophagidae: Sarcophaga peregrina, etc., Pyrrhocoridae: Dysdercus cingulatus, etc., Gasterophilidae: Gasterophilus intestinalis, etc., Alydidae: Leptocorisa acuta, Leptocorisa chinensis, etc., Hypodermatidae: Hypoderma lineatum, etc., Coreidae: Anacanthocoris stricornis, etc., Oestridae: Oestrus ovis, etc. Rhopalidae: Rhopalus maculatus, etc., 60 As the Lepidoptera pest, there can be mentioned, for Cimicidae: Cimex lectularius, etc. example, As the Coleoptera pests, there can be mentioned, for Hepialidae: Endoclita excrescens, etc., example, Heliozelidae: Antispilla ampelopsia, etc., Scarabaeidae: Anomara cuprea, Anomara rufocuprea, Cossidae: Zeuzera leuconotum, etc., Popillia japonica, Oryctes rhinoceros, etc., 65 Tortricidae: Archips fiascocupreanus, Adoxophyes Orana Elateridae: Agriotes Ogurae, Melanotus Okinawensis, Mel fasciata, Grapholita molesta, Homona magnanima, Legu anotos fortnunifortnumi, etc., minivora glycinivorella, Cydia pomenella, etc., US 8,895,035 B2 99 100 Cochylidae: Eupoecilia ambiguella, etc., As the Order Mallophaga pest, there can be mentioned, for Psychidae: Bambalina sp., Eumeta minuscule, etc., example, Tineidae: Nemapogon granella, Tinea translucens, etc., Menoponidae: Lipeurus caponis, etc., Nepticulidae: Bucculatrix pyrivOrella, etc., Trichodectidae: Damalinia bovis, etc. Lyonetiidae: Lyonetia clerkella, etc., As the Order Anoplura pest, there can be mentioned, for Gracilariidae: Caloptilia theivora, Phyllonorycter ringo example, niella, etc., Haematopinidae: Haematopinus suis, etc., Phyllocnistidae: Phyllocnistis citrella, etc., Pediculine: Pediculus humanus, etc., Acrolepiidae: Acrolepiopsis sapporensis, etc., Linognathidae: Linognathus setosus, etc., Yponomeutidae: Plutella xylostella, Yponomeuta Orienta 10 Pthiridae: public louse, etc. As the Plant-feeding mites, there can be mentioned, for lis, etc., example, Argyresthidae: Argyresthia conjugella, etc., Eupodidae: Penthaleus major, etc., Aegeriidae: Nokona regalis, etc., Tarsonemidae: Phytonemus pallidus, Polyphagotarson Gelechiidae: Phthorimaea operculella, Sitotroga cere 15 emus latus, etc., alella, Pectinophora gossypiella, etc., Pyemotidae: Siteroptes sp., etc., Carposinidae: Carposina Sasaki, etc., Tenuipalpidae: Brevipalpus lewisii, etc., Zygaenidae: Illiberispruni, etc., Tuckerellidae: Tuckerella pavoniformis, etc., Heterogeneidae: Monema flavescens, etc., Tetranychidae: Eotetranychusboreus, Panonychus citri, Crambidae: Ancylolonia japonica, Chile suppressalis, Panonychus ulmi, Tetranychus urticae, Tetranychus kanza Cnaphalocrosis medinalis, Ostrinia furnacalis, Ostrinia Wai, etc., nubilalis, etc., Nalepellidae: Trisetacus pini, etc., Pyralidae: Cadra cautella, Galleria mellonella, etc., Eriophyidae: Aculops pelekassi, Epitrimerus pyri, Phyllo Pterophoridae: Nippoptilia vitis, etc., coptruta oleivola, etc., Papilionidae: Papilio xuthus, etc., 25 Diptilomiopidae: Diptacus crenatae, etc., Pieridae: Pieris rapae, etc., Acaridae: Aleuroglyphus Ovatus, Trophagus putrescen Hesperiidae: Parnara guttata guttata, etc., tiae, Rhizoglyphus robini, etc. Geometridae: Ascotis selenaria, etc., As the Plant-parasitic nematodes, there can be mentioned, Lasiocampidae: Dendrolimus spectabilis, Malacosoma for example, neuStrium testaceum, etc., 30 Longidoridae: Xiphinema index, etc., Sphingidae: Agrius convolvuli, etc., Trichodoridae: Paratrichodorus minor, etc., Rhabditidae: Rhabditella sp., etc., Lymantriidae: Arna pseudoconspersa, Lymantria dispar, Tylenchidae: Agilenchussp., etc., etc., Tylodoridae: Cephalenchus sp., etc., Arctiidae: Hyphantria cunea, etc., 35 Anguinidae: Nothotylenchus acris, Dity lenchus destruc Noctuidae: Agrotis ipsilon, Autographa nigrisigna, Heli tor, etc., coverpa armigera, Helicoverpa zea, Heliothis virescens, Hoplolainidae: Rotylenchulus reniformis, Helicotylenchus Spodoptera exigua, Spodoptera litura, etc. dihystera, etc., As the Hymenoptera pest, there can be mentioned, for Paratylenchidae: Paratylenchus curvitatus, etc., example, 40 Meloidogynidae: Meloidogyne incognita, Meloidogyne Argidae: Arge pagana, etc., hapla, etc., Tenthredinidae: Apethymus kuri, Athaliarosae ruficornis, Heteroderidae: Globodera rostochiensis, Heterodera gly etc., Cines, etc., Cynipidae: Dryocosmus kuriphilus, etc., Telotylenchidae: Tilenchorhynchus claytoni etc., Vespidae: Vespa simillima xanthoptera, etc., 45 Psilenchidae: Psilenchus sp., etc., Formicidae: Solenopsis invicta, etc., Criconematidae: Criconenoides sp., etc., Megachilidae: Megachile nipponica, etc. Tylenchulidae: Tvlenchulus semipenetrans, etc., As the Order Collembola pest, there can be mentioned, for Sphaeronematidae: Sphaeronema cameliae, etc., example, Pratylenchidae: Sphaeronema cameliae, Radopholus cit 50 rophilus, Radopholus similis, Nacobbus aberrans, Pratylen Sminthuridae: Bourletiellahortensis, etc. chus penetrans, Pratylenchus coffeae, etc., As the Order Thysanura pest, there can be mentioned, for Iotonchiidae: Totonchium ungulatum, etc., example, Aphelenchidae: Aphelenchus avenae, etc., Lepismatidae: Lepisma saccharina, Ctenoiepisma villosa, Aphelenchoididae: Aphelenchoides besseyi, Aphelen etc. 55 choides fragariae, etc., As the Blattodea pest, there can be mentioned, for example, Palasitaphelenchidae: Bursaphelenchus xylophilus, etc. Blattidae: Periplaneta americana, As the plant parasitic mollusc pests, there can be men Blattellidae: Blattella germanica, etc. tioned, for example, As the Order Isoptera pest, there can be mentioned, for Pilidae: Pomacea canaliculata, etc., example, 60 Veronicellidae: Leavicaulis alte, etc., Kalotermitidae: Incisitermes minor, etc., Achatinidae: Achatina fillica, etc., Rhinotermitidae: Coptotermes formosanus, etc., Philomycidae: Meghimatium bilineatum, etc., Termitidae: Odontotermes formosanus, etc. Succineidae: Succinealauta, etc., As the Order Psocoptera pest, there can be mentioned, for Didcidae: Discus pauper, etc., example, 65 Zonitidae: Zonitoides vessoensis, etc., Trogiidae: Trogium pulsatorium, etc., Limacidae: Limax flavus, Deroceras reticulatum, etc., Liposcelidaidae: Liposcelis corrodens, etc. Hehelicarionidae: Parakaliella harimensis, etc., US 8,895,035 B2 101 102 Bradybaenidae: Acusta despecta Sieboldiana, Bradybaena hexane=1/1), to obtain 1.12 g (yield: 97%) of 2-cyano-2- similaris, etc. isopropoxyimino-N-isopropoxyacetamide. As other pests such as injurious animals, uncomfortable Incidentally, ethyl 2-cyano-2-isopropoxyiminoacetate was animals, sanitary insects, livestock insects, parasites and the produced based on a method described in Journal of Medici like, there can be mentioned, for example, 5 nal Chemistry, pp. 4608-4612 (1992). Acari Macronysshidae: Ornithonyssus Sylvialum, etc., Varroidae: Varroa jacobsoni, etc., 'H-NMR data (CDC1/TMS 8 (ppm)): Dermanyssidae: Dermanyssus gallinae, etc., 1.29 (6H, d), 1.40 (6H, d), 4.24 (1H, qq), 4.69 (1H, qq), Macronyssidae: Ornithonyssus Sylvialum, etc., 8.74 (1H, s) Ixodidae: Boophilus microplus, Rhipicephalussanguineus, 10 (2) To 5 ml of an acetonitrile solution containing 0.40 g (1.88 Haemaphysalis longicornis, etc., mmol) of the 2-cyano-2-isopropoxyimino-N-isopropoxy Sarcoptidae: Sarcoptes scabiei, etc., acetamide obtained in above (1) were added 1.48 g (5.64 Isopoda Armadillididae: Armadillidium vulgare, etc., mmol) of triphenylphosphine and 1.73 g (11.25 mmol) of Decapoda Astacidae: Procambarus clarkii, etc., carbon tetrachloride, followed by stirring for 4 hours under Porcellionidae: Armadillidium vulgare, etc., 15 heating and refluxing. The reaction mixture was cooled to Chilopoda pests: Scutigeromorpha Sutigeridae. There room temperature, followed by extraction with ethyl uonema tuberculata, Scolopendromorpha Scolopendra sub acetate. The extract solution was washed with an aqueous pinipes etc., saturated sodium chloride solution and dried over anhy Diplopodapests: Polydesmida Paradoxosomatidae Oxidus drous magnesium sulfate. The solvent was distilled off gracilis etc., under reduced pressure. The residue was purified by silica Araneae Latrodectus hasseltii. Theridiadae hasseltii, etc., gel column chromatography (elutant:ethyl acetate/hex Clubionidae: Chiracanthium japonicum, etc., ane=1/2), to obtain 0.21 g (yield: 49%) of 1-chloro-2- Order Scorpionida: Androctonus Crassicauda, etc., cyano-1,2-diisopropoxyiminoethane. Parasitic roundworm: Ascaris lumbricoides, Syphacia sp., 'H-NMR data (CDC1/TMS 8 (ppm)): Wucherebia bancrofti, etc., 25 Parasitic flatworm: Distomum sp., Paragonimus wester 1.37 (6H, d), 1.39 (6H, d), 4.62 (1H, qq), 4.70 (1H, qq.) manii, Metagonimus yokokawai, Schistosoma japonicum, (3) To 5 ml of an N,N-dimethylformamide solution contam Taenia solium, Taeniarhynchus saginatus, Echinococcus sp., ing 0.21 g (0.906 mmol) of the 1-chloro-2-cyano-1,2-di Diphyllobothrium latum, etc. isopropoxyiminoethane obtained in above (2) were added The pest control agent of the present invention exhibits 30 0.10 g (1.45 mmol) of 1,2,4-triazole and 0.13 g (0.941 excellent control effect to the above-mentioned pests. Fur mmol) of potassium carbonate, followed by stirring at 90° ther, the present pest control agent exhibits control effect also C. for 2 hours. The reaction mixture was cooled to room to the above-mentioned pests, etc. which already have resis temperature, followed by extraction with ethylacetate. The tances to existing pest control agents. Furthermore, the extract solution was washed with an aqueous saturated present control agent can be applied to plants which already 35 Sodium chloride Solution and dried over anhydrous mag have resistances to insects, diseases, herbicides, etc., owing to nesium sulfate. The solvent was distilled offunder reduced genetic recombination, artificial mating, etc. pressure. The residue was purified by silica gel column Next, there are described the production methods, formu chromatography (elutant:ethyl acetate/hexane-1/1), to lation methods and applications of the present compound, in obtain 0.22 g (yield: 92%) of a title compound. detail by way of Examples. However, the present invention is 40 'H-NMR data (CDC1/TMS 8 (ppm)): in no way restricted by these Examples. 1.33 (6H, d), 1.35 (6H, d), 4.54-4.71 (2H, m), 8.08 (1H, s), There are also described the production methods of the 8.66 (1H, s) intermediates for production of the present compound.

EXAMPLES 45 Example 2 Example 1 Production of 1-1,2-diisopropoxyimino-2-(1H-tetra Zol-5-yl)ethyl)-1H-1,2,4-triazole (present compound Production of 1-(2-cyano-1,2-diisopropoxyiminoet No. I-213) hyl)-1H-1,2,4-triazole (present compound No. I-50) 50 To 5 ml of a toluene solution containing 0.40 g (1.51 mmol) (1) To 5 ml of a dichloromethane Solution containing 1.0 g of 1-(2-cyano-1,2-diisopropoxyiminoethyl)-1H-1,2,4-triaz (5.43 mmol) of ethyl 2-cyano-2-isopropoxyiminoacetate ole were added 0.35 g (3.03 mmol) of trimethylsilylazide and was added 0.73 g (6.54 mmol) of O-isopropylhy 0.38 g (1.51 mmol) of di-n-butyltin oxide, followed by stir droxyamine hydrochloride, followed by cooling to -20°C. 55 ring for 3 hours under heating and refluxing. The reaction Thereto was added 4.34 ml (6.08 mmol) of a trimethylalu mixture was cooled to room temperature, followed by extrac minum (1.4 M/L) hexane solution. The mixture was heated tion with ethyl acetate. The extract solution was washed with to room temperature and stirred for 20 hours. The reaction an aqueous Saturated Sodium chloride solution and dried over mixture was cooled to -20°C., and 3.88 ml (5.43 mmol) of anhydrous magnesium sulfate. The solvent was distilled off a triethylaluminum hexane solution, followed by stirring at 60 under reduced pressure. The residue was purified by silica gel room temperature for 6 hours. To the reaction mixture was column chromatography (elutant:ethyl acetate/hexane-1/0). added water, with ice-cooling. Extraction was conducted The crystal obtained was washed with isopropyl ether to using ethyl acetate. The organic layer was washed with an obtain 0.23 g (yield: 47%) of a title compound. aqueous Saturated Sodium chloride Solution and dried over anhydrous magnesium Sulfate. The solvent was distilled 65 'H-NMR data (CDC1/TMS 8 (ppm)): off under reduced pressure. The residue was purified by 1.43 (6H, d), 1.49 (6H, d), 4.66 (1H, qq), 4.84 (1H, qq), silica gel column chromatography (elutant:ethyl acetate/ 7.85 (1H, s), 9.34 (1H, s), 13.59 (1H, s) US 8,895,035 B2 103 104 Example 3 Example 1 were added 0.46g (6.62 mmol) of hydroxylamine hydrochloride and 0.54 g (6.58 mmol) of sodium acetate, Production of 1-(2-carbamoyl-1,2-diisopropoxyimi followed by stirring at 50° C. for 3 hours. The solvent in the noethyl)-1H-1,2,4-triazole (present compound No. reaction mixture was distilled offunder reduced pressure. The I-73) resulting crystal was washed with water and isopropyl ether, to obtain 0.91 g (yield: 48%) of 1-2-(N-hydroxyamidino)-2- To 2 ml of a dimethyl Sulfoxide solution containing 4.0 g isobutyloxyimino-1-isopropoxyiminoethyl)-1H-1,2,4-triaz (15.1 mmol) of 1-(2-cyano-1,2-diisopropoxyiminoethyl)- ole. 1H-1,2,4-triazole were added, with ice-cooling, 3.5 ml of hydrogen peroxide water and 2.30 g (16.6 mmol) of potas H-NMR data (CDC1/TMS 8 (ppm)): sium carbonate, followed by stirring at room temperature for 0.99 (6H, d), 1.37 (6H, d), 2.01-2.17 (1H, m), 4.11 (2H, d), 10 hours. The resulting crystal was washed with water and 4.60 (1H, qq), 5.60 (2H, s), 7.48 (1H, s), 7.93 (1H, s), 9.13 isopropyl ether in this order, to obtain 3.28 g (yield: 77%) of (1H, s) a title compound. (2) 0.02 g (0.11 mmol) of p-toluenesulfonic acid monohy H-NMR data (CDC1/TMS 8 (ppm)): drate was added to 5 ml of a triethyl orthoformate solution 1.38 (12H, d), 4.53-4.70 (2H, m), 6.35 (1H, s), 7.39 (1H, s), 15 containing 0.35 g (1.12 mmol) of the 1-2-(N-hydroxya 7.95 (1H, s), 9.20 (1H, s) midino)-2-isobutyloxyimino-1-isopropoxyiminoethyl 1H-1,2,4-triazole obtained in above (1), followed by stir Example 4 ring at 150° C. for 3 hours. The reaction mixture was Production of 1-2-(4,5-dihydro-1,3-thiazolin-2-yl)- cooled to room temperature and poured into water. The 1,2-diisopropoxyiminoethyl)-1H-1,2,4-triazole mixture was subjected to extraction with ethyl acetate. The (present compound No. I-214) and 1-1,2-disopro extract solution was washed with an aqueous saturated poxyimino-2-(thiazol-2-yl)ethyl)-1H-1,2,4-triazole Sodium chloride Solution and dried over anhydrous mag (present compound No. I-215) nesium sulfate. The solvent was distilled offunder reduced pressure. The residue was purified by silica gel column (1) 0.22 g (2.91 mmol) of 2-aminoethanethiole was added to 25 chromatography (elutant:ethyl acetate/hexane-1/2), to 5 ml of a methanol solution containing 0.70 q (2.65 mmol) obtain 0.23 g (yield: 64%) of a title compound. of 1-(2-cyano-1,2-diisopropoxyiminoethyl)-1H-1,2,4- H-NMR data (CDC1/TMS 8 (ppm)); triazole and 0.22 g (2.91 mmol) of ammonium acetate, 0.98 (6H, d), 1.37 (6H, d), 2.04-2.18 (1H, m), 4.21 (2H, d), followed by stirring at room temperature for 16 hours. The 4.61 (1H, qq), 7.89 (1H, s), 8.71 (1H, s), 9.12 (1H, s) reaction mixture was poured into water, followed by 30 extraction with ethyl acetate. The extract solution was Example 6 washed with an aqueous saturated sodium chloride solu tion and dried over anhydrous magnesium sulfate. The Production of 1,2-diisopropoxyimino-1,2-bis(1H-1, solvent was distilled off under reduced pressure. The resi due was purified by silica gel column chromatography 2,4-triazol-1-yl)ethane (present compound No. (elutantiethyl acetate/hexane-2/1), to obtain 0.47 g (yield: 35 I-212) 55%) of 1-2-(4,5-dihydro-1,3-thiazolin-2-yl)-1,2-diiso propoxy minoethy -1H-1,2,4-triazole. (1) To 40 ml of a tetrahydrofuran solution containing 8.79g. H-NMR data (CDC1/TMS 8 (ppm)): (78.78 mmol) of O-isopropylhydroxylamine hydrochlo 1.37 (6H, d), 1.39 (6H, d), 3.18 (2H, t), 4.05 (2H, t), ride were added, with ice-cooling, 21.78 g (157.59 mmol) 4.52-4.68 (2H, m), 9.92 (1H, s), 9.18 (1H, s) 40 of potassium carbonate and 5.00 g (39.39 mmol) of oxalyl (2) To 5 ml of a toluene solution containing 0.27 g (0.832 chloride, followed by stirring at room temperature for 15 mmol) of the 1-2-(4,5-dihydro-1,3-thiazolin-2-yl)-1,2-di hours. The reaction mixture was poured into water, fol isopropoxyiminoethyl)-1H-1,2,4-triazole obtained in lowed by extraction with ethyl acetate. The extract solution above (1) were added 5 ml of water, 0.01 g (0.031 mmol) of was washed with an aqueous Saturated Sodium chloride tetra-n-butyl ammonium bromide and 0.39 g (2.47 mmol) of potassium permanganate, followed by stirring at room 45 Solution and dried over anhydrous magnesium Sulfate. The temperature for 2 days. To the reaction mixture was added solvent was distilled off under reduced pressure to obtain an excess amount of sodium thiosulfate, followed by stir 3.39 g (yield: 42%) of N,N'-diisopropoxyoxamide. ring for 30 minutes. The solid was removed, followed by H-NMR data (CDC1/TMS 8 (ppm)): extraction with ethyl acetate. The organic layer was 1.29 (12H, d), 4.22 (2H, qq), 9.59 (2H, s) washed with an aqueous Saturated sodium chloride solu 50 (2) 2.04 g (9.79 mmol) of phosphorus pentachloride was tion and dried over anhydrous magnesium sulfate. The added to 5 ml of a dichloromethane solution containing 1.0 solvent was distilled off under reduced pressure. The resi g (4.9 mmol) of the N,N'-diisopropoxyoxamide obtained due was purified by silica gel column chromatography in above (1), followed by stirring at room temperature for 4 (elutantiethyl acetate/hexane=1/1) to obtain 0.15 g (yield: hours. The reaction mixture was poured into ice water, 56%) of a title compound. 55 followed by extraction with isopropyl ether. The extract 'H-NMR data (CDC1/TMS 8 (ppm)): Solution was washed with an aqueous saturated Sodium 1.41 (6H, d), 1.49 (6H, d), 4.64 (1H, qq), 4.79 (1H, qq), chloride solution and dried over anhydrous magnesium 7.54 (1H, d), 7.82 (1H, d), 7.84 (1H, s), 9.36 (1H, s) sulfate. The solvent was distilled off under reduced pres Example 5 Sure. The residue was purified by silica gel column chro 60 matography (elutant:ethyl acetate/hexane-1/4) to obtain Production of 1-2-isobutoxyimino-1-isopropoxy 0.19 g (yield: 16%) of 1,2-dichloro-1,2-diisoprpoxyimino imino-2-(1,2,4-oxadiazol-2-yl)ethyl-1H-1,2,4-triaz ethane. ole (present compound No. I-209) 'H-NMR data (CDC1/TMS 8 (ppm)): 1.35 (12H, d), 4.59 (2H, qq) (1) To 10 ml of an ethanol solution containing 1.68 g 65 (3) To 5 ml of an N,N-dimethylformamide solution contain (6.04 mmol) of the 1-2-cyano-2-isobutoxyimino-1-iso ing 0.19 g (0.788 mmol) of the 1,2-dichloro-1,2-diiso propoxyiminoethyl-1H-1,2,4-triazole produced based on prpoxyiminoethane obtained in above (2) were added 0.16 US 8,895,035 B2 105 106 g (2.36 mmol) of 1,2,4-triazole and 0.33 g (2.36 mmol) of hours. To the reaction mixture were added hexane and an potassium carbonate, followed by stirring at 100° C. for 14 aqueous Saturated sodium hydrogencarbonate solution, for hours. The reaction mixture was cooled to room tempera phase separation. The aqueous layer was made acidic with ture and poured into water, followed by extraction with diluted hydrochloric acid, followed by extraction with ethyl acetate. The extract solution was washed with an 5 ethyl acetate. The organic layer was dried over anhydrous aqueous Saturated Sodium chloride Solution and dried over magnesium sulfate. The solvent was distilled off under anhydrous magnesium Sulfate. The solvent was distilled reduced pressure to obtain 9.7 g (yield: 86%) of 2-isopro off under reduced pressure. The residue was purified by poxyimino-2-1H-1,2,4-triazol-1-ylacetic acid. silica gel column chromatography (elutant:ethyl acetate/ H-NMR data (CDC1/TMS 8 (ppm)): hexane=1/1) to obtain 0.20 g (yield: 83%) of a title com 10 1.40 (6H, d), 4.74 (1H, sep), 8.18 (1H, s), 8.99 (1H, s) pound. (3) To 50 ml of a dichloromethane solution containing 5.5g 'H-NMR data (CDC1/TMS 8 (ppm)): (28 mmol) of the 2-isopropoxyimino-2-1H-1,2,4-triazol 1.43 (12H, d), 4.68 (2H, qq), 7.81 (2H, s) 9.25 (2H, s) 1-ylacetic acid obtained in above (2) were added 3.9 g (33 Example 7 15 mmol) of O-isopropylhydroxyamine hydrochloride, 3.4g (34 mmol) of N-methylmorpholine and 8.0 g (42 mmol) of Production of 1-(2-methylthio-1,2-diisopropoxyimi N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydro noethyl)-1H-1,2,4-triazole (present compound No. chloride (WSC), followed by stirring at room temperature I-228) for 12 hours. The reaction mixture was poured into diluted hydrochloric acid, followed by extraction with dichlo Sodium thiomethoxide was added to 5 ml of a tetrahydro romethane. The extract solution was dried over anhydrous furan Solution (which was under heating and refluxing) con magnesium sulfate. The solvent was distilled off under taining 0.35 g (1.14 mmol) of the 1,2-diisopropoxyimino-1, reduced pressure. The resulting crystal was washed with 2-bis(1H-1,2,4-triazol-1-yl)ethane produced in Example 6, diisopropyl ether to obtain 3.9 g (yield: 55%) of N-isopro with confirming a reaction by thin-layer chromatography. 25 poxy-2-isopropoxyimino-2-(1H-1,2,4-triazol-1-yl)aceta Then, stirring was conducted for 5 hours. The reaction mix mide. ture was cooled to room temperature and poured into water, 'H-NMR data (CDC1/TMS 8 (ppm)): followed by extraction with ethyl acetate. The extract solution 1.28-140 (12H, m), 1.37 (3H, t), 4.29 (1H, sep), 4.58 (1H, was washed with an aqueous Saturated Sodium chloride solu sep), 8.08 (1H, s), 8.82 (1H, s), 9.66 (1H, s) tion and dried over anhydrous magnesium Sulfate. The Sol 30 (4) To 20 ml of an acetonitrile solution containing 0.74 g (2.9 vent was distilled offunder reduced pressure. The residue was mmol) of the N-isopropoxy-2-isopropoxyimino-2-(1H-1, purified by silica gel column chromatography (elutantiethyl 2,4-triazol-1-yl)acetamide obtained in above (3) were acetate/hexane=1/2) to obtain 0.17 g (yield: 52%) of a title compound. added 2.3 g (8.8 mmol) of triphenylphosphine and 2.7 g (18 mmol) of carbon tetrachloride, followed by stirring for 12 H-NMR data (CDC1/TMS 8 (ppm)): 35 hours under heating and refluxing. The reaction mixture 1.31 (6H, d), 1.39 (6H, d), 2.14 (3H, s), 4.50 (1H, qq), 4.63 was subjected to distillation under reduced pressure. The (1H, qq), 8.05 (1H, s), 9.23 (1H, s) resulting residue was purified by silica gel column chro Example 8 matography (elutantiethyl acetate/hexane=1/8) to obtain 40 0.47 g (yield: 59%) of a title compound. Production of 1-(2-chloro-1,2-diisopropoxyiminoet H-NMR data (CDC1/TMS 8 (ppm)): hyl)-1H-1,2,4-triazole (present compound No. I-4) 1.31 (6H, s), 1.35 (6H, d), 4.51 (1H, sep), 4.61 (1H, sep), 8.06 (1H, s), 8.77 (1H, s) (1) 14 g (82 mmol) ofisopropyl iodide and 13 g (94 mmol) of potassium carbonate were added to 100 ml of an N.N- 45 Example 9 dimethylformamide solution containing 14 g (76 mmol) of ethyl 2-hydroxyimino-2-1H-1,2,4-triazol-1-ylacetate, fol Production of 1-(1,2-diisopropoxyimino-2-methoxy lowed by stirring at room temperature for 5 hours. The ethyl)-1H-1,2,4-triazole (present compound No. reaction mixture was poured into water, followed by I-165) extraction with ethyl acetate. The extract solution was 50 dried over anhydrous magnesium sulfate and concentrated 0.22 g (1.55 mmol) of iodomethane was added, with ice under reduced pressure. The resulting residue was purified cooling, to 5 ml of an N,N-dimethylformamide solution con by silica gel column chromatography (elutant:ethyl taining 0.22 g (1.59 mmol) of potassium carbonate and 0.4g acetate/hexane=1/8) to obtain 9.0 g (yield: 52%) of ethyl (1.57 mmol) of the N-isopropoxy-2-isopropoxyimino-2- 2-isopropoxyimino-2-1H-1,2,4-triazol-1-ylacetate. 55 (1H-1,2,4-triazol-1-yl)acetamide produced in Example 8. Incidentally, ethyl 2-hydroxyimino-2-1H-1,2,4-triazol-1- followed by stirring at room temperature for 20 hours. The ylacetate was produced based on a method described in Jour reaction mixture was poured into water, followed by extrac nal of the Chemical Society Perkin Transactions 1, pp. tion with ethyl acetate. The extract solution was washed with 2235-2239 (1987). an aqueous Saturated Sodium chloride solution and dried over H-NMR data (CDC1/TMS 8 (ppm)): 60 anhydrous magnesium sulfate. The solvent was distilled off 1.36 (6H, d), 1.37 (3H, t), 4.43 (2H, q), 4.63 (1H, sep), 8.06 under reduced pressure. The residue was purified by silica gel (1H, s), 8.79 (1H, s) column chromatography (elutantiethyl acetate/hexane-1/2) (2) To 60 ml of a 1,4-dioxane solution containing 13 g (57 to obtain 0.12 g (yield: 29%) of a title compound. mmol) of the ethyl 2-isopropoxyimino-2-1H-1,2,4-triazol H-NMR data (CDC1/TMS 8 (ppm)): 1-ylacetate obtained in above (1) was added 2.9 g (69 65 0.97 (6H, d), 1.38 (6H, d), 2.01-2.16 (1H, m), 2.05 (3H, s), mmol) of lithium hydroxide monohydrate dissolved in 15 4.00 (2H, d), 4.61 (1H, qq), 7.93 (1H, s), 8.24 (1 h, s), 9.22 ml of water, followed by stirring at room temperature for 12 (13, s) US 8,895,035 B2 107 108 Example 10 Example 13 Production of 1-(2-isopropoxyimino-2-thiocarbam Production of 1-(2-isopropoxyimino-2-N,N-dimeth oyl-1-methoxyiminoethyl)-1H-1,2,4-triazole (present ylcarbamoyl-1-methoxyiminoethyl)-1H-1,2,4-triaz compound No. II-224) ole (present compound No. II-226) 0.77 g (1.9 mmol) of Lawesson’s reagent was added, at 4.4 ml (4.4 mmol) of a trimethylaluminum (1 mol/l) hexane room temperature, to a tetrahydrofuran (8 ml) solution con Solution was drop-wise added, at room temperature, into a taining 0.40 g (1.6 mmol) of 1-(2-carbamoyl-2-isopropoxy 1,2-dichloroethane (7ml) suspension of 0.36 g (4.4 mmol) of imino-1-methoxyiminoethyl)-1H-1,2,4-triazole, followed by 10 dimethylamine hydrochloride, followed by stirring at 80°C. stirring at 40°C. for 2 hours and then at 60° C. for 3 hours. The for 30 minutes. To the reaction mixture was added, at 60°C., reaction mixture was cooled to room temperature. Thereto a 1,2-dichloroethane (3 ml) solution containing 0.30 g (1.1 was added diisopropyl ether. The mixture was washed with mmol) of the 1-(2-isopropoxyimino-2-methoxycarbonyl-1- water and an aqueous saturated Sodium chloride solution and dried over anhydrous sodium sulfate. The solvent was dis methoxyiminoethyl)-1H-1,2,4-triazole produced in Example tilled off. The resulting residue was purified by silica gel 15 12, followed by stirring for 1.5 hours. The reaction mixture column chromatography (elutantiethyl acetate/hexane-1/2) was cooled to room temperature and then diluted with iso to obtain 0.25 g (yield: 58%) of a title compound as a yellow propyl ether. Thereto was added a small amount of water, powder. followed by stirring. The resulting precipitate was removed by filtration. The solvent was distilled off. The resulting H-NMR data (CDC1/TMS 8 (ppm)): reside was purified by silica gel column chromatography 1.24 (6H, d), 4.15 (3H, s), 4.52(1H, sep), 7.72 (1H, s), 7.94 (elutantiethyl acetate/hexane=2/1) to obtain 0.30 g (yield: (1H, s), 8.10 (1H, s), 9.24 (1H, s) 97%) of a title compound as a yellow oily matter. H-NMR data (CDC1/TMS 8 (ppm)): Example 11 1.23 (6H, d), 3.02 (3H, s), 3.05 (3H, s), 4.07 (3H, 4.42(1H, 25 sep), 8.06 (1H, s), 8.57 (1H, s) Production of 2-isopropoxyimino-3-methoxyimino 3-1H-1,2,4-triazol-1-ylpropanecarboxymidic acid Example 14 methyl ester (present compound No. II-223) Production of S-ethyl 2-isopropoxyimino-3-meth 1.6 g (8.4 mmol) of a sodium methoxide 28% methanol 30 oxyimino-3-(1H-1,2,4-triazol-1-yl)propanethioate Solution was drop-wise added, with ice-cooling, into a metha (present compound No. II-222 nol (50 ml) solution containing 5.0 g (21 mmol) of 1-(2- cyano-2-isopropoxyimino-1-methoxyiminoethyl)-1H-1,2,4- To 8ml of 1,2-dichloroethane was added 7.5 ml (7.5 mmol) triazole, followed by stirring for 2 hours with ice-cooling. To of a trimethylaluminum (1 mol/l) hexane solution. Thereinto the reaction mixture was added a small amount of an aqueous 35 was drop-wise added 0.47 g (7.5 mmol) of ethanethiol at citric acid solution, followed by extraction with ethyl acetate. room temperature, followed by stirring for 30 minutes. To this The extract solution was washed with an aqueous Saturated mixed solution was added, at room temperature, a 1,2-dichlo Sodium bicarbonate Solution and an aqueous Sodium chloride roethane solution containing 0.50 g (1.9 mmol) of the 1-(2- solution and dried over anhydrous sodium sulfate. The sol isopropoxyimino-2-methoxycarbonyl-1-methoxyiminoet vent was distilled off. The resulting residue was purified by silica gel column chromatography (elutantiethyl acetate/hex 40 hyl)-1H-1,2,4-triazole produced in Example 12, followed by ane=1/2) to obtain 2.5 g (yield: 44%) of a title compound as stirring for 1.5 hours. The reaction mixture was diluted with a yellow oily matter. isopropyl ether. Thereto was added a small amount of water, followed by stirring. The resulting precipitate was removed H-NMR data (CDC1/TMS 8 (ppm)): by filtration. The solvent was distilled off. The resulting resi 1.36 (6H, d), 3.61 (3H, s), 4.14 (3H, s), 4.60(1H, sep), 7.97 45 due was purified by silica gel column chromatography (elut (1H, s), 8.92 (1H, s), 9.08 (1H, s) antiethyl acetate/hexane=1/2) to obtain 0.56 g (yield: 98%) of a title compound as a yellow oily matter. Example 12 H-NMR data (CDC1/TMS 8 (ppm)): 1.34 (6H, d), 2.99 (2H, q), 4.12 (3H, s), 4.54 (1H, sep), 7.99 Production of 1-(2-isopropoxyimino-2-methoxycar 50 (1H, s), 8.88 (1H, s) bonyl-1-methoxyiminoethyl)-1H-1,2,4-triazole (present compound II-221) Example 15 12 ml of a 3 mol/l hydrochloric acid was added, with Production of 1-(2-amino-1,2-diisoprooxyiminoet ice-cooling, to 20 ml of a methanol solution containing 2.5g 55 hyl)-1H-1,2,4-triazole (present compound No. I-119) (9.3 mmol) of the 2-isopropoxyimino-3-methoxyimino-3- 1H-1,2,4-triazol-1-ylpropanecarboxymidic acid methyl ester (1) 12.13 g (213.68 mmol) of a 30% aqueous ammonia solu produced in Example 11, followed by stirring for 40 minutes. tion was added, in ice-cooling, to 40 ml of a methanol Water was added to the reaction mixture, followed by extrac solution containing 24.17 g (106.84 mmol) of the ethyl tion with ethyl acetate. The extract solution was washed with 60 2-isopropoxyimino-2-1H-1,2,4-triazol-1-ylacetate pro an aqueous Saturated Sodium bicarbonate Solution and an duced in Example 8 (1), followed by stirring for 3 hours. aqueous Sodium chloride Solution and dried over anhydrous The solvent in the reaction mixture was distilled off under sodium sulfate. The solvent was distilled off to obtain 2.4g reduced pressure. The resulting residue was dissolved in 40 (yield: 95%) of a title compound as a colorless oily matter. ml of a dichloromethane solution. To the solution were 'H-NMR data (CDC1/TMS 8 (ppm)): 65 added, in ice-cooling, 16.90 g (213.65 mmol) of pyridine 1.26 (6H, d), 3.86 (3H, s), 4.10 (3H, s), 4.46 (1H, sep), 8.05 and 24.68 g (117.51 mmol) of trifluoroacetic anhydride, (1H, s), 8.67 (1H, s) followed by stirring for 4 hours. The reaction mixture was US 8,895,035 B2 109 110 subjected to extraction with ethyl acetate. The extract solu under reduced pressure to obtain 14.81 g (yield: 83%) of tion was washed with an aqueous Saturated Sodium chlo 1-(2-amino-2-hydroxyimino-1-isopropoxyiminoethyl)- ride Solution and dried over anhydrous magnesium Sulfate. 1H-1,2,4-triazole. The solvent was distilled off under reduced pressure. The H-NMR data (CDC1/TMS 8 (ppm)): residue was purified by silica gel column chromatography 5 1.30 (6H, d), 4.54 (1H, qq), 5.05 (2H, s), 7.98 (1H, s), 8.08 (elutantiethyl acetate/hexane=2/1) to obtain 19.14 g (yield: (1H, s), 8.44 (1H, s) 100%) of 1-(1-cyano-1-isopropoxyiminomethyl)-1H-1,2, (2) 0.59 g (63.3 wt.%, 15.56 mmol) of sodium hydride was 4-triazole. added, in ice-cooling, to 30 ml of an N,N-dimethylforma H-NMR data (CDC1/TMS 8 (ppm)): mide solution containing 3.00 g (14.14 mmol) of the 1-(2- 1.45 (6H, d), 4.74 (1H, qq), 8.10 (1H, s), 9.14 (1H, s) 10 amino-2-hydroxyimino-1-isopropoxyiminoethyl)-1H-1, (2) To 5 ml of an ethanol solution containing 0.4 g (2.23 2,4-triazole obtained in above (1) and 2.13 g (15.55 mmol) mmol) of the 1-(1-cyano-1-isopropoxyiminomethyl)-1H of isobutyl bromide, followed by stirring at room tempera 1,2,4-triazole obtained in above (1) were added 0.46 g ture for 2 hours. The reaction mixture was poured into (3.33 mmol) of potassium carbonate and 0.37 g (3.32 water, followed by extraction with ethyl acetate. The mmol) of O-isopropylhydroxyamine hydrochloride, fol 15 extract solution was washed with an aqueous saturated lowed by stirring for 5 hours under heating and refluxing. Sodium chloride Solution and dried over anhydrous mag The reaction mixture was returned to room temperature, nesium sulfate. The solvent was distilled offunder reduced followed by extraction with ethyl acetate. The organic pressure. The residue was purified by silica gel column layer was washed with an aqueous Saturated Sodium chlo chromatography (elutant:ethyl acetate/hexane-2/1) to ride Solution and dried over anhydrous magnesium Sulfate. obtain 2.71 g (yield: 72%) of a title compound. The solvent was distilled off under reduced pressure. The H-NMR data (CDC1/TMS 8 (ppm)): residue was purified by silica gel column chromatography 0.89 (6H, d), 1.29 (6H, d), 1.88-199 (1H, m), 3.77 (2H, d), (elutantiethyl acetate/hexane=1/2) to obtain 0.09 g (yield: 4.52 (1H, qq), 4.97 (2H, s), 8.07 (1H, s), 8.39 (1H, s) 16%) of a title compound. H-NMR data (CDC1/TMS 8 (ppm)): 25 Example 18 1.19 (6H, d), 1.29 (6H, d), 4.22 (1H, qq), 4.51 (1H, qq), 4.92 (2H, s), 8.07 (1H, s), 8.38 (1H, s) Production of 1-2-N-acetylamino-2-isobutyloxy imino-1-isopropoxyiminoethyl)-1H-1,2,4-triazole Example 16 (present compound No. I-217) 30 Production of 1-(2-bromo-1,2-diisopropoxyiminoet 0.58 g (7.39 mmol) of acetylchloride was added to 5 ml of hyl)-1H-1,2,4-triazole (Present compound No. I-142) a toluene solution containing 0.4 g (1.49 mmol) of the 1-(2- amino-2-isobutoxyimino-1-isopropoxyiminoethyl)-1H-1.2. An aqueous solution consisting of 0.04 g (0.58 mmol) of 4-triazole produced in Example 17, followed by stirring at Sodium nitrite and 3 ml of water was added, in ice-cooling, to 35 100° C. for 10 hours. The reaction mixture was cooled to a solution obtained by adding 5 ml of water and 0.5 ml of 47% room temperature, followed by extraction with ethyl acetate. hydrobromic acid to 0.13 g (0.51 mmol) of the 1-(2-amino The extract solution was washed with an aqueous Saturated 1.2-diisoprooxyiminoethyl)-1H-1,2,4-triazole produced in Sodium chloride Solution and dried over anhydrous magne Example 15, followed by stirring. After 4 hours, the reaction sium sulfate. The solvent was distilled off under reduced mixture was subjected to extraction with ethyl acetate. The 40 pressure. The residue was purified by silica gel column chro organic layer was washed with an aqueous saturated sodium matography (elutantiethyl acetate/hexane=2/1) to obtain 0.34 chloride solution and dried over anhydrous magnesium Sul g(yield: 74%) of a title compound. fate. The solvent was distilled offunder reduced pressure. The 'H-NMR data (CDC1/TMS 8 (ppm)): residue was purified by silica gel column chromatography 0.97 (6H, d), 1.38 (6H, d), 2.01-2.16 (1H, m), 2.05 (3H, s), (elutantiethyl acetate/hexane=1/2) to obtain 0.11 g (yield: 45 4.00 (2H, d), 4.61 (1H, qq), 7.93 (1H, s), 8.24 (1H, s), 9.22 68%) of a title compound. (1H, s) 'H-NMR data (CDC1/TMS 8 (ppm)) 1.32 (6H, d), 1.36 (6H, d), 4.50-4.67 (2H, m), 8.05 (1H, s), Example 19 8.82 (1H, s) 50 Production of 1-2-N-methoxycarbonylamino-2- Example 17 isobutyloxyimino-1-isopropoxyiminoethyl)-1H-1.2. 4-triazole (present compound No. I-219) Production of 1-(2-amino-2-isobutoxyimino-1-iso propoxyiminoethyl)-1H-1,2,4-triazole (present com 0.06 g (1.40 mmol) of 55% sodium hydride was added, in pound No. I-121) 55 ice-cooling, to 5 ml of an N,N-dimethylacetamide solution containing 0.34 g (1.27 mmol) of the 1-(2-amino-2-isobu (1) 13.94 g (100.86 mmol) of potassium carbonate and 6.50 g toxyimino-1-isopropoxyiminoethyl)-1H-1,2,4-triazole pro (93.54 mmol) of hydroxylamine hydrochloride were added duced in Example 17, followed by stirring at room tempera to 120 ml of a methanol solution containing 15.06 g (84.05 ture for 5 minutes. To the mixture was added, in ice-cooling, mmol) of the 1-(1-cyano-1-isopropoxyiminomethyl)-1H 60 0.13 g (1.40 mmol) of methyl chloroformate, followed by 1,2,4-triazole produced in Example 15 (1), followed by stirring at room temperature for 18 hours. The reaction mix stirring for 2 hours under heating and refluxing. The reac ture was subjected to extraction with ethyl acetate. The tion mixture was cooled to room temperature and adjusted extract solution was washed with an aqueous sodium chloride to pH 4 using 2N HC1. Extraction with ethyl acetate was Solution and dried over anhydrous magnesium sulfate. The conducted. The organic layer was washed with an aqueous 65 solvent was distilled off under reduced pressure. The residue Saturated Sodium chloride solution and dried over anhy was purified by silica gel column chromatography (elutant: drous magnesium sulfate. The solvent was distilled off ethyl acetate/hexane=1/2) to obtain a di-substitution product US 8,895,035 B2 111 112 (1-2-N,N-dimethoxycarbonylamino-2-isobutyloxyimino-1- chromatography (elutant:ethyl acetate/hexane-1/2) to isopropoxyiminoethyl)-1H-1,2,4-triazole). Potassium car obtain 0.83 g (yield: 73%) of 1-(1,2-diisopropoxyimino bonate was added to 5 ml of a methanol solution of the propyl)imidazole (present compound No. I-273). di-substitution product until a pH of about 9 was reached, H-NMR data (CDC1/TMS 8 (ppm)): followed by stirring at 70° C. for 10 hours. The reaction 1.21 (6H, d), 1.28 (6H, d), 2.15 (3H, s), 4.32 (1H, qq), 4.46 mixture was cooled to room temperature, followed by extrac (1H, qq), 7.05 (1H, s), 7.18 (1H, s), 7.77 (1H, s) tion with ethyl acetate. The extract solution was washed with (4) 1.01 ml (1.59 mmol) of n-butyllithium (1.57 mol/l) was an aqueous Saturated Sodium chloride Solution and dried over added, at -60° C., to 5 ml of a tetrahydrofuran solution anhydrous magnesium sulfate. The solvent was distilled off containing 0.40 g (1.59 mmol) of the 1-(1,2-diisopropoxy under reduced pressure. The residue was purified by silica gel iminopropyl)imidazole obtained in above (3), followed by column chromatography (elutantiethyl acetate/hexane-2/1) stirring for 30 minutes. To the mixture was added 0.05 g to obtain 0.18 g (yield: 43%) of a title compound. (1.59 mmol) of a sulfur powder, followed by stirring at H-NMR data (CDC1/TMS 8 (ppm)): -60° C. for 3 hours. The reaction mixture was cooled to 0.96 (6H, d), 1.39 (6H, d), 1.98-2.13 (1H, m), 3.62 (3H, s), room temperature. 2N hydrochloric acid was added and the 3.98 (2H, d), 4.62 (1H, qq), 7.79 (1H, s), 7.95 (1H, s), 9.24 15 mixture was stirred overnight. The reaction mixture was (1H, s) subjected to extraction with ethyl acetate. The extract solu tion was washed with an aqueous saturated Sodium chlo Example 20 ride Solution and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The Production of 1-(1,2-diisopropoxyiminopropyl)-2- residue was purified by silica gel column chromatography mercaptoimidazole (present compound No. V-10) (elutant:ethyl acetate/hexane=1/2). The resulting crystal, was washed with hexane to obtain 0.14 g (yield: 31%) of a (1) To 100 ml of a dichloromethane solution containing 3.00 title compound. g (34.07 mmol) of pyruvic acid were added 7.98 g (71.52 'H-NMR data (CDC1/TMS 8 (ppm)): mmol) of isopropylhydroxylamine hydrochloride and 25 1.18 (6H, d), 1.28 (6H, d), 2.17 (3H, s), 4.27(1H, qq), 4.50 13.71 g (71.52 mmol) of N-(3-dimethylaminopropyl)-N'- (1H, qq), 6.57 (1H, s), 6.71 (1H, s), 11.02 (1H, s) ethylcarbodiimide hydrochloride (WSC). Then, 14.47 g (143.05 mmol) of N-methylmorpholine was added with Example 21 ice-cooling, followed by stirring at room temperature for 20 hours. The reaction mixture was poured into water, 30 Production of 1-(2-n-butoxyimino-2-cyano-1- followed by extraction with ethyl acetate. The extract solu ethoxyiminoethyl)-1H-1,2,4-triazole (present com tion was washed with an aqueous saturated sodium chlo pound No. III-51) ride Solution and dried over anhydrous magnesium Sulfate. The solvent was distilled off under reduced pressure. The (1) There was prepared a mixture consisting of 2.00 g (15.6 residue was purified by silica gel column chromatography 35 mmol) of the methyl 2-cyano-2-hydroxyiminoacetate pro (elutantiethyl acetate/hexane=1/3) to obtain 5.00 g ((yield: duced by a method described in Synthesis, pp. 46-48 73%) of 2-isopropoxyimino-Nisopropoxypropionamide. (1999), 2.35 g (17.2 mmol) of n-butyl bromide, 2.59 g H-NMR data (CDC1/TMS 8 (ppm)): (18.7 mmol) of potassium carbonate and 10 ml of DMF. 1.27 (6H, d), 1.28 (6H, d), 2.02 (3H, s), 4.18 (1H, qq), 4.40 The mixture was stirred at room temperature for 8 hours. (1H, qq), 8.91 (1H, s) 40 The reaction mixture was poured into water, followed by (2) To 20 ml of an acetonitrile solution containing 3.00 g extraction with ethyl acetate. The organic layer was (14.83 mmol) of the 2-isopropoxyimino-N-isopro washed with an aqueous saturated sodium chloride solu poxypropionamide obtained in above (1) were added 7.78 tion and dried over anhydrous magnesium Sulfate. The g (29.66 mmol) of triphenylphosphine and 9.13 g (59.36 solvent was distilled off under reduced pressure to obtain mmol) of carbon tetrachloride, followed by stirring for 4 45 2.05 g (yield: 71%) of methyl 2-n-butoxyimino-2-cy hours under heating and refluxing. The reaction mixture anoacetate. was cooled to room temperature, followed by extraction 'H-NMR data (CDC1/TMS 8 (ppm)): with ethyl acetate. The extract solution was washed with an 0.94 (3H, t), 1.41 (2H, q), 1.74-1.84 (2H, m), 3.96 (3H, s), aqueous Saturated Sodium chloride Solution and dried over 4.53 (2H, t) anhydrous magnesium Sulfate. The solvent was distilled 50 (2) To 20 ml of a 1,4-dioxane solution containing 1.00 g (5.43 off under reduced pressure. The residue was purified by mmol) of the methyl 2-n-butoxyimino-2-cyanoacetate silica gel column chromatography (elutant:ethyl acetate/ obtained in above (1) was added 10 ml of an aqueous hexane=1/2) to obtain 2.63 g (yield: 80%) of 1-chloro-1, solution containing 0.25 g (6.0 mmol) of lithium hydroxide 2-diisopropoxyiminopropane. monohydrate, followed by stirring at room temperature for H-NMR data (CDC1/TMS 8 (ppm)): 55 3 hours. To the reaction mixture were added hexane and an 1.29 (6H, d), 1.33 (6H, s), 2.10 (3H, s), 4.42-4.58 (2H, m) aqueous Saturated sodium hydrogencarbonate solution, for (3) To 5 ml of an N,N-dimethylformamide solution contain phase separation. The aqueous layer was made acidic with ing 1.00 g (4.53 mmol) of the 1-chloro-1,2-diisopropoxy diluted hydrochloric acid, followed by extraction with iminopropane obtained in above (2) were added 0.37 g ethyl acetate. The organic layer was dried over anhydrous (5.43 mmol) of imidazole and 0.75 g (5.43 mmol) of potas 60 magnesium sulfate. The solvent was distilled off under sium carbonate, followed by stirring at 90° C. for 4 hours. reduced pressure to obtain 0.90 g (yield: 98%) of 2-n- The reaction mixture was cooled to room temperature and butoxyimino-2-cyanoacetic acid. pored into water, followed by extraction with ethyl acetate. 'H-NMR data (CDC1/TMS 8 (ppm)): The extract Solution was washed with an aqueous saturated 0.97 (3H, t), 1.42 (2H, q), 1.76-1.86 (2H, m), 4.56 (2H, t) Sodium chloride Solution and dried over anhydrous mag 65 (3) To 20 ml of a dichloromethane solution containing 0.90 g nesium sulfate. The solvent was distilled offunder reduced (5.3 mmol) of the 2-n-butoxyimino-2-cyanoacetic acid pressure. The residue was purified by silica gel column obtained in above (2) were added 0.57 g (5.8 mmol) of US 8,895,035 B2 113 114 Oethylhydroxyamine hydrochloride, 0.59 g (5.8 mmol) of Example 23 N-methylmorpholine and 1.5 g (7.8 mmol) of N-(3-dim ethylaminopropyl)-N'-ethylcarbodiimide hydrochloride Production of 1-2-cyano-1,2-bis(n-propoxyimino) (WSC), followed by stirring at room temperature for 12 ethyl)-1H-1,2,4-triazole (present compound No. hours. The reaction mixture was poured into diluted hydro IV-90) chloric acid, followed by extraction with dichloromethane. The organic layer was dried over anhydrous magnesium (1) There was prepared a mixture consisting of 2.50 g (19.5 sulfate. The solvent was distilled off under reduced pres mmol) of methyl 2-cyano-2-hydroxyiminoacetate, 2.60 g Sure. The resulting residue was purified by column chro (21.1 mmol) of n-propyl bromide, 3.20 g (23.2 mmol) of 10 potassium carbonate and 10 ml of DMF. The mixture was matography (elutant:ethyl acetate/hexane-1/4) to obtain stirred at room temperature for 8 hours. The reaction mix 0.55 g (yield: 49%) of N-ethoxy-2-n-butoxyimino-2-cy ture was poured into water, followed by extraction with anoacetamide. ethyl acetate. The organic layer was washed with an aque H-NMR data (CDC1/TMS 8 (ppm)): ous saturated Sodium chloride solution and dried over 0.97 (3H, t), 1.31 (3H, t), 1.41 (2H, q), 1.72-1.81 (2H, m), 15 anhydrous magnesium sulfate. The solvent was distilled 4.06 (2H, q), 4.44 (2H, t), 8.88 (1H, s) off under reduced pressure to obtain 2.35 g (yield: 71%) of (4) To 20 ml of an acetonitrile solution containing 0.45 g (2.1 methyl 2-cyano-2-n-propoxyiminoacetate. mmol) of the N-ethoxy-2-n-butoxyimino-2-cyanoaceta H-NMR data (CDC1/TMS 8 (ppm)): mide obtained in above (3) were added 2.3 g (8.8 mmol) of 1.00 (3H, t), 1.78-190 (2H, m), 3.97 (3H, s), 4.49 (2H, t) triphenylphosphine and 2.7 g (18 mmol) of carbon tetra (2) 10 ml of an aqueous solution containing 0.41 g (9.8 mmol) chloride, followed by stirring for 3 hours under heating and of lithium hydroxide monohydrate was added to 20 ml of a refluxing. The reaction mixture was concentrated under 1,4-dioxane solution containing 1.50 g (8.81 mmol) of the reduced pressure. The resulting residue was purified by methyl 2-cyano-2-n-propoxyiminoacetate obtained in column chromatography (elutant:ethyl acetate/hexane-1/ above (1), followed by stirring at room temperature for 3 9) to obtain 0.24 g (yield: 48%) of 2-n-butoxyimino-1- 25 hours. To the reaction mixture were added hexane and an chloro-2-cyano-1-ethoxyiminoethane. aqueous Saturated sodium hydrogencarbonate solution, for 'H-NMR data (CDC1/TMS 8 (ppm)): phase separation. The aqueous layer was made acidic with 0.97 (3H, t), 1.40 (3H, t), 1.44 (2H, q), 1.74-1.81 (2H, m), diluted hydrochloric acid, followed by extraction with 4.38-4.47 (4H, m) ethyl acetate. The organic layer was dried over anhydrous (5) There was prepared a mixture consisting of 1.30 g (5.6 30 magnesium sulfate. The solvent was distilled off under mmol) of the 2-n-butoxyimino-1-chloro-2-cyano-1- reduced pressure to obtain 1.28 g (yield: 93%) of 2-cyano ethoxyiminoethane obtained in above (4), 0.76 g (11 2-n-propoxyiminoacetic acid. mmol) of 1,2,4-triazole, 1.50 g (11 mmol) of potassium carbonate and 7 ml of DMF. The mixture was stirred at 70° 'H-NMR data (CDC1/TMS 8 (ppm)): C. for 2 hours. The reaction mixture was cooled to room 1.00 (3H, t), 1.79-191 (2H, m), 4.52 (2H, t) 35 (3) To 20 ml of a dichloromethane solution containing 1.28g temperature and poured into water, followed by extraction (8.20 mmol) of the 2-cyano-2-n-propoxyiminoacetic acid with ethyl acetate. The organic layer was washed with an obtained in above (2) were added 1.00 g (8.96 mmol) of aqueous Saturated Sodium chloride Solution and dried over O-npropylhydroxyamine hydrochloride, 0.91 g (9.0 anhydrous magnesium Sulfate. The solvent was distilled mmol) of N-methylmorpholine and 2.5 g (13 mmol) of off under reduced pressure. The resulting residue was puri 40 N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydro fied by column chromatography (elutant:ethylacetate/hex chloride (WSC), followed by stirring at room temperature ane=1/9) to obtain 1.32 g (yield: 89%) of a title compound. for 12 hours. The reaction mixture was poured into diluted 'H-NMR data (CDC1/TMS 8 (ppm)): hydrochloric acid, followed by extraction with dichlo 0.94 (3H, t), 1.35-146 (5H, m), 1.72 (2H, m), 4.35-4.45 romethane. The organic layer was dried over anhydrous (4H, m), 8.09 (1H, s), 8.66 (1H, s) 45 magnesium sulfate. The solvent was distilled off under reduced pressure. The resulting residue was purified by Example 22 column chromatography (elutant:ethyl acetate/hexane-1/ Production of 1-(2-n-butoxyimino-2-carbamoyl-1- 4) to obtain 0.77 g (yield: 44%) of N-npropoxy-2-cyano ethoxyiminoethyl)-1H-1,2,4-triazole (present com 2-n-propoxyiminoacetamide. 50 H-NMR data (CDC1/TMS 8 (ppm)): pound No. III-74) 0.96-1.03 (6H, m), 1.66-1.87 (4H, m), 3.96 (2H, t), 4.39 To 5 ml of a methanol solution containing 0.98 g (3.7 (2H, t), 8.86 (1H, s) mmol) of the 1-(2-n-butoxyimino-2-cyano-1-ethoxyiminoet (4) 2.2 g (8.4 mmol) of triphenylphosphine and 2.6 g (17 hyl)-1H-1,2,4-triazole produced in Example 17 were added, mmol) of carbon tetrachloride were added to 20 ml of an 55 acetonitrile solution containing 0.59 g (2.8 mmol) of the at room temperature, 60 mg (0.19 mmol) of tetrabutylammo Nn-propoxy-2-cyano-2-n-propoxyiminoacetamide nium bromide, 55 mg (0.40 mmol) of potassium carbonate and 1.7 g (15 mmol) of an aqueous 30 wt.% hydrogen obtained in above (3), followed by stirring for 3 hours peroxide solution, followed by stirring for 10 hours. To the under heating and refluxing. The reaction mixture was reaction mixture was added sodium dithiosulfate, followed concentrated under reduced pressure. The resulting residue by stirring for 10 minutes. The reaction mixture was concen 60 was purified by column chromatography (elutant:ethyl trated under reduced pressure. The resulting crystal was acetate/hexane=1/9) to obtain 0.45 g (yield: 69%) of washed with an aqueous citric acid solution, cold water and 1-chloro-2-cyano-1,2-bis(n-propoxyimino)ethane. isopropyl ether in this order, to obtain 0.64 g (yield: 61%) of 'H-NMR data (CDC1/TMS 8 (ppm)): a title compound. 0.96-1.02 (6H, m), 1.76-1.85 (4H, m), 4.31 (2H, t), 4.40 H-NMR data (CDC1/TMS 8 (ppm)): 65 (2H, t) 0.97 (3H, t), 1.40-1.48 (5H, m), 1.76 (2H, m), 4.35-4.45 (5) There was prepared a mixture consisting of 0.45 g (1.9 (4H, m), 6.16 (1H, s), 7.31 (1H, s), 7.96 (1H, s), 9.18 (1H, s) mmol) of the 1-chloro-2-cyano-1,2-bis(n-propoxyimino) US 8,895,035 B2 115 116 ethane obtained in above (4), 0.20 g (2.9 mmol) of 1,2,4- (2.81 mmol) of potassium carbonate, followed by stirring triazole, 0.53 g (3.8 mmol) of potassium carbonate and 10 at 70° C. for 7 hours. The reaction mixture was cooled to ml of DMF. The mixture was stirred at 40°C. for 12 hours. room temperature and poured into water, followed by The reaction mixture was cooled to room temperature and extraction with ethyl acetate. The organic layer was poured into water, followed by extraction with ethyl washed with an aqueous saturated sodium chloride solu acetate. The organic layer was washed with an aqueous tion and dried over anhydrous magnesium Sulfate. The Saturated Sodium chloride solution and dried over anhy solvent was distilled off under reduced pressure. The drous magnesium sulfate. The solvent was distilled off resulting residue was purified by column chromatography under reduced pressure to obtain 0.40 g (yield: 80%) of a (elutant:ethyl acetate/hexane=1/1) to obtain 0.50 g (yield: title compound. 10 26%) of a title compound. H-NMR data (CDC1/TMS 8 (ppm)): H-NMR data (CDC1/TMS 8 (ppm)): 0.94-1.02 (6H, m), 1.70-1.84 (4H, m), 4.29-4.37 (4H, m), 4.63-4.89 (4H, m), 8.13 (1H, s), 8.75 (1H, s) 8.09 (1H, s), 8.66 (1H, s) The physical properties of the present compounds I pro duced based on the above Examples (including those com Example 24 15 pounds produced in the Examples) are shown in Table 64 to Table 72. Production of 1-2-carbamoyl-1,2-bis(n-propoxy imino)ethyl-1H-1,2,4-triazole (present compound TABLE 64 No. IV-101) Compound Melting point (C.) or To 5 ml of a methanol solution containing 1.06 g (4.0 No. refractive index (n') mmol) of the 1-2-cyano-1,2-bis(n-propoxyimino)ethyl 1 525 4 .505 1H-1,2,4-triazole produced in Example 23 were added, at -S SOO room temperature, 65 mg (0.20 mmol) of tetrabutylammo -6 497 nium bromide, 55 mg (0.40 mmol) of potassium carbonate 25 7 498 and 1.8 g (16 mmol) of an aqueous 30 wt.% hydrogen -8 496 -9 497 peroxide solution, followed by stirring for 10 hours. To the -11 494 reaction mixture was added sodium dithiosulfate, followed -13 495 by stirring for 10 minutes. The reaction mixture was concen -14 495 trated under reduced pressure. The resulting crystal was 30 -15 495 -16 517 washed with an aqueous citric acid solution, cold water and -18 S16 isopropyl ether in this order to obtain 0.73 g (yield: 6.4%) of a -19 514 title compound. -21 515 H-NMR data (CDC1/TMS 8 (ppm)): -22 30-32 35 -29 495 1.00 (6H, t), 1.77-1.84 (4H, m), 4.31 (2H, t), 4.35 (2H, t), -47 S11 6.13 (1H, s), 7.34 (1H, s), 7.96 (1H, s), 9.18 (1H, s) -48 48-51 -49 SO2 Example 25 -SO 498 -S1 SOO -52 498 40 Production of 1-2-cyano-2-(2,2,3,3,3-pentafluoro-n- -53 497 propoxyimino)-1-(2.2.2-trifluoroethoxyimino)ethyl -54 53-54 1H-1,2,4-triazole (present compound No. IV-185) -55 498 -S6 496 -57 492 (1) 0.34 g (0.16 mmol) of 5 wt.% palladium carbon was -58 496 added to 1.70 g (4.83 mmol) of the 1-2-benzyloxyimino 45 -59 496 2-cyano-1-(2.2.2-trifluoroetoxyimino)ethyl)-1H-1,2,4- -60 49SO triazole (present compound No. IV-181) produced based -61 488 -62 515 on Example 1. Thereto was added 10 ml of ethanol in a -64 514 nitrogen current. Hydrogen was added to this mixture at -67 S12 normal pressure at room temperature for 1.5 hours. The 50 -68 517 -69 S22 insoluble was removed by filtration. The filtrate was con -70 82-184 centrated under reduced pressure. The resulting residue -71 79-181 was purified by column chromatography (elutant:ethyl -72 45-147 acetate/hexane=1/1) to obtain 1.26 g (yield: 100%) of 1-2- -73 65-168 cyano-2-hydroxyimino-1-(2.2.2-trifluoroethoxyimino) 55 -74 O9-110 -75 15-117 ethyl)-1H-1,2,4-triazole. -76 97-99 H-NMR data (CDC1/TMS 8 (ppm)): -77 28-131 5.04 (2H, q), 8.36 (1H, s), 9.00 (1H, s) -78 92-93 (2) 1.26 g (4.81 mmol) of the 1-2-cyano-2-hydroxyimino-1- -79 26-127 -8O O7-108 (2.2.2-trifluoroethoxyimino)ethyl)-1H-1,2,4-triazole 60 -81 80-82 obtained in above (1) was dissolved in 10 ml of DMSO. To -82 OO-102 the solution were added 2.49 g (5.77 mmol) of 2,2,3,3,3- -83 OO-101 ptnetafluoro-n-propyl nonafluoro-n-butanesulfonate and -84 93-95 -85 O3-106 0.80 g (5.77 mmol) of potassium carbonate, followed by -87 36-138 stirring at room temperature for 10 hours. To the reaction 65 -90 45-146 mixture were added 1.25 g (2.89 mmol) of 2.2.3,3,3-ptne -91 62-163 tafluoro-n-propylnonafluoro-n-butanesulfonate and 0.40g US 8,895,035 B2 117 118 TABLE 64-continued TABLE 65-continued Compound Melting point (C.) or Compound Melting point (C.) or No. refractive index (n') No. refractive index (n') -92 133-13S 5 -261 1503 -96 490 -262 76-78 -98 489 -263 1...SO2 -110 .505 -264 81-82 -119 SO8 -266 1.512 -121 65-67 -267 1492 -124 SO9 10 -268 10-113 -128 SO4 -269 1517 -129 .505 -270 1.504 -130 68-71 -271 86-88 -131 68-70 -272 39-142 -133 52-54 -273 1495 -134 525 15 -274 65-67 -136 S29 -275 65-168 -142 SO9 -278 25-127 -16S 489 -279 40-142 -28O 95-198 -167 488 -179 SO4 -282 36-139 -283 10-113 -186 144-147 2O -284 94-97 -188 156-158 -285 O8-110 -190 173-176 -286 1516 -199 145-148 -287 11-113 -288 1496 25 -289 70-72 -290 69-172 TABLE 65 -296 1.512 -297 10-112 Compound Melting point (C.) or -298 1521 No. refractive index (no.') -299 95-98 -208 120-123 30 -300 1.534 -209 70-73 -301 12-114 -210 1.506 -211 1. SO3 -212 114-117 -213 163-166 TABLE 66 -214 112-115 35 -215 72-75 Compound Melting point (C.) or -217 118-121 No. refractive index (n') -218 131-134 -219 1.504 -3O2 110-112 -220 1497 -304 121-123 -221 68-71 40 -30S 76-78 -223 93-96 -306 146-149 -224 178-181 -307 S16 -225 118-119 -3O8 169-171 -226 89-90 -309 SOO -228 48-51 -310 99-102 -230 30 -311 S36 -231 479 45 -313 55-58 -233 493 -314 83-86 -234 51-52 -315 111-114 -235 490 -316 S18 -236 468 -318 499 -237 126-128 -319 121-122 -238 462 50 -32O 481 -239 S48 -321 1SO-151 -240 S45 -322 73-76 -241 142-144 -323 .505 -242 S10 -324 54-57 -243 498 -32S S10 -244 SOO 55 -326 96-97 -245 SO3 -327 94-96 -246 492 -329 S11 -247 SO3 -330 131-133 -248 523 -331 SO8 -249 S30 -332 130-132 -2SO S2O -333 550 -251 96-99 60 -334 141-142 -254 552 -33S 72-73 -255 165-168 -3.36 141-142 -2S6 139-140 -337 S45 -257 69-72 -338 162-163 -258 495 -339 541 -259 SO1 65 -340 94-95 -260 492 -341 539 US 8,895,035 B2 119 120 TABLE 66-continued TABLE 67-continued Compound Melting point (C.) or Compound Melting point (C.) or No. refractive index (n') No. refractive index (no.') -342 99-100 5 -58 1...SO3 -343 535 -59 1507 -345 66-69 -346 S290 ise s -347 546O -348 S48O -62 1524 -349 132-13S 10 -63 1.5240 -351 4870 -64 1.529 -352 81-84 -65 1527 -353 59-62 -66 1524 -354 83-86 -67 1531 -355 4890 -68 1536 -356 86-89 15 -70 75-178 -357 5370 -71 74-176 -358 25-126 -72 32-13S -359 433O -73 79-182 -360 17-119 -74 34-137 -361 S130 -75 22-124 g .. 2O -76 S8-161 -77 41-44 -365 S380 -78 O4-107 -367 S48O -79 OS-106 -368 59-162 -369 5140 -8O 56-158 -370 23-126 -81 15-116 -371 77-79 25 -82 22-125 -372 54-57 -83 79-81 -373 23-126 -84 27-129 -374 4470 -85 41-144 -375 17-120 -86 97-100 -376 498O -87 26-129 -377 84-85 30 -88 20-123 -378 S360 -89 OS-107 -379 47OO -90 26-129 -380 123-126 -91 28-131 -381 4930 -121 77-80 -382 78-80 -12S 1516 its, 35 -130 1.512 s 543 -133 10-112 -386 148-150 -18S 80-183 -387 S430 -188 42-144 -388 167-170 C R . s 40 -199 10-113 -391 4940 -2O8 87-88 -392 49SO -214 34-137 -393 69-72 -215 OS-107 -394 57-60 i. .. -395 68-71 45 -223 505 -396 95-98 -397 83-86 -224 33-136 -398 15290 -225 19-122 -226 S11 -227 SOO 50 -235 499 -236 494 TABLE 67 -237 63-66 Compound Melting point (C.) or -238 65-67 No. refractive index (no.') -240 475 -241 154-157 II-4 1516 55 -244 564 II-6 1.508 -245 123-126 II-10 1507 -246 39-42 II-15 1.504 -247 154-157 II-47 89-90 -266 507 II-48 71-73 -267 99-102 II-49 47-SO 60 -268 517 II-SO 1.509 -269 523 II-S1 1.511 -271 82-84 II-52 1.508 II-53 1507 -278 523 II-54 85-88 -279 118-120 II-55 1.508 -28O 542 II-S6 1507 65 -281 153-155 II-57 1...SO3

US 8,895,035 B2 129 130 formation examples and may be varied in a wide range. In the Next, the effect of the pest control agent containing the following explanation, parts (part) refer (refers) to mass parts present compound as an active ingredient is shown by Test (mass part). Examples. Test Example 1 Formulation Example 1 Insecticidal Action Test for Aphis gossipii Glover Emulsifiable Concentrate (Cotton Aphid, Melon Aphid) A wettable powder prepared based on Formulation 10 Example 2 was diluted with water so that the concentration of A compound described in Table 1 to Table 51 10 parts active ingredient became 500 ppm. In the resulting liquid Cyclohexanone 30 parts were immersed cucumber seedlings on which the hatchlings Polyoxyethylene alkyl aryl ether 11 parts of Aphis gossipii Glover were parasitic, after which the Calcium alkylbenzenesulfonate 4 parts cucumber seedlings were dried in the air. The resulting Methylnaphthalene 45 parts 15 cucumber seedlings were placed in a thermostat of 25° C. After 3 days, the number of living insects was calculated and The above materials were made into a uniform solution, to the mortality of insect was calculated using the calculation prepare an emulsifiable concentrate. formula of the following Mathematical Expression 1. Insect mortality (%)=1-(number of living insects), (number of tested insects)x100 Mathematical Expression 1 Formulation Example 2 The compounds which gave an insect mortality of 90% or higher in the above test, are shown below. Wettable Powder I-1, I-4, I-5, I-6, I-7, I-8, I-9, I-11, I-13, I-14, I-15, I-18 , I-19, -21, I-22, I-29, I-48, I-49, I-50, I-52, I-54, I-55, I-56, I-57, 25 -58, I-59, I-60, I-61, I-62, I-64, I-67, I-68, I-69, I-71, I-72, -75, I-76, I-78, I-80, I-81, I-87, I-98, I-110, I-120, I-121, A compound described in Table 1 to Table 51 10 parts -124, I-128, I-129, I-130, I-131, I-134, I-136, I-142, I-165, Sodium salt of naphthalenesulfonic acid-formalin condensate 0.5 part I-167, I-179, I-190, I-208, I-209, I-212, I-214, I-215, I-217, Polyoxyethylene alkyl aryl ether 0.5 part I-223, I-224, I-228, I-229, I-230, I-235, I-236, I-239, I-240, Diatomaceous earth 24 parts I-243, I-246, I-247, I-249, I-250, I-257, I-258, I-259, I-260, Clay 65 parts I-267, I-269, I-270, I-271, I-273, I-274, I-281, I-286, I-288, I-289, I-296, I-298, I-300, I-301, I-302, I-305, I-307, I-309, The above materials were mixed and ground to prepare a I-311, I-318, I-319, I-323, I-324, I-331, I-333, I-335, I-339, wettable powder. I-343, I-345, I-347, I-348, I-351, I-355, I-357, I-358, I-359, 35 I-360, I-361, I-363, I-365, I-367, I-369, I-370, I-371, I-372, I-374, I-375, I-376, I-379, I-381, I-383, I-385, I-387, I-393, Formulation Example 3 I-395, I-396, I-397, II-4, II-6, II-10, II-15, II-48, II-49, II-51, II-52, II-53, II-54, II-55, II-56, II-57, II-58, II-59, II-60, II-61, II-62, II-63, II-64, II-65, II-66, II-67, II-68, Dust Formulation II-71, II-72, II-73, II-76, II-77, II-78, II-79, II-80, II-81, 40 II-82, II-83, II-86, II-87, II-88, II-89, II-91, II-130, II-133, II-188, II-190, II-194, II-199, II-208, II-214, II-215, II-221, II-222, II-223, II-224, II-225, II-226, II-235, A compound described in Table 1 to Table 51 2 parts Diatomaceous earth 5 parts II-236, II-240, II-241, II-244, II-246, II-266, II-267, Clay 93 parts II-271, II-278, II-280, II-281, II-284, II-285, II-288, 45 II-289, II-301, II-302, II-303, II-304, II-306, II-309, II-311, II-312, II-313, II-314, II-316, II-317, II-318, The above materials were mixed and ground to prepare a II-319, II-320, II-321, II-322, II-324, II-325, II-326, dust formulation. II-327, II-328, II-329, II-330, II-331, II-332, II-333, II-334, II-335, II-338, II-340, I-342, II-343, II-344, II-345, 50 II-346, II-349, II-351, II-352, II-353, II-355, II-356, Formulation Example 4 II-357, II-359, II-360, II-361, II-365, II-367, II-369, II-371, II-373, II-374, II-375, II-376, II-377, II-378, II-379, III-4, III-48, III-49, III-50, III-51, III-53, III-54, Granule III-55, III-56, III-57, III-58, III-59, III-60, III-61, III-62, 55 III-64, III-65, III-66, III-67, III-68, III-70, III-71, III-72, III-73, III-76, III-77, III-78, III-79, III-80, III-81, III-82, A compound described in Table 1 to Table 51 5 parts III-83, III-84, III-85, III-87, III-88, III-90, III-233, III-238, Sodium salt of lauryl alcohol sulfate 2 parts III-239, III-242, III-262, III-269, III-272, III-273, III-277, Sodium ligninsulfonate 5 parts III-279, III-280, III-281, III-282, III-283, III-284, III-287, Carboxymethyl cellulose 2 parts III-288, III-289, III-290, III-295, III-296, III-297, III-298, Clay 86 parts 60 III-300, III-301, III-302, III-303, III-304, III-305, III-306, III-307, III-308, III-309, IV-1, IV-6, IV-22, IV-30, IV-33, IV-36, IV-37, IV-38, IV-39, IV-79, IV-89, IV-90, IV-91, The above materials were mixed and ground. Thereto was IV-92, IV-95, IV-97, IV-98, IV-99, IV-102, IV-104, IV-107, added 20 parts of water, followed by kneading. The kneaded IV-115, IV-117, IV-119, IV-152, IV-164, IV-170, IV-172, material was passed through an extrusion granulator to obtain 65 IV-176, IV-177, IV-178, IV-179, IV-180, IV-181, V-10, granules of 14 to 32 meshes. The granules were dried to VI-96, VI-199, VI-217, VI-221, VI-222, VI-223, VI-269, prepare a granule. VI-276, VI-291, VI-297 US 8,895,035 B2 131 132 Test Example 2 II-223, II-224, II-225, II-226, II-227, II-232, II-235, II-236, II-238, II-240, II-241, II-244, II-245, II-246, Insecticidal Action Test for Aphis gossipii Glover II-247, II-266, II-267, II-268, II-269, II-271, II-278, (Cotton Aphid, Melon Aphid) II-279, II-280, II-281, II-282, II-283, II-284, II-285, 5 II-286, II-288, II-289, II-301, II-302, II-303, II-304, A wettable powder prepared based on Formulation II-306, II-311, II-312, II-313, II-314, II-316, II-317, Example 2 was diluted with water so that the concentration of II-318, II-319, II-320, II-321, II-322, II-323, II-324, active ingredient became 500 ppm. 5 ml of the resulting II-325, II-326, II-327, II-328, II-329, II-330, II-331, diluted formulation was drenched to the rice-plant foot of II-332, II-333, II-334, II-335, II-336, II-338, II-339, cucumber seedlings on which the hatchlings of Aphis gossipii 10 II-340, II-341, II-342, II-343, II-344, II-345, II-346, Glover were parasitic. The resulting cucumber seedlings II-347, II-348, II-349, II-350, II-351, II-352, II-353, were placed in athermostat of 25°C. After 3 days, the number II-354, II-355, II-356, II-357, II-358, II-359, II-360, of living insects was calculated and the mortality of insect was II-361, II-362, II-365, II-366, II-367, II-368, II-369, calculated using the calculation formula of Mathematical II-370, II-371, II-372, II-373, II-374, II-375, II-376, Expression 1. 15 II-377, II-378, II-379, II-380, II-381, III-4, III-47, III-48, The compounds which gave an insect mortality of 90% or III-49, III-50, III-51, III-52, III-53, III-54, III-55, III-56, higher in the above test, are shown below. III-57, III-58, III-59, III-60, III-61, III-62, III-64, III-65, I-4, I-5, I-55, I-233, II-57, II-63, II-64, II-80, II-301, II-316, III-66, III-67, III-68, III-70, III-71, III-72, III-73, III-74, II-326, II-332, II-334, II-346, II-367, II-371, III-49, III-60, III-75, III-76, III-77, III-78, III-79, III-80, III-81, III-82, III-61, III-64, III-68, III-87, III-281, III-283, III-287, III III-83, III-84, III-85, III-87, III-88, III-89, III-90, III-91, 300, III-304, IV-95 III-233, III-234, III-238, III-239, III-242, III-243, III-262, III-263, III-264, III-266, III-267, III-269, III-270, III-272, Test Example 3 III-273, III-279, III-280, III-281, III-282, III-283, III-284, III-287, III-288, III-289, III-290, III-295, III-296, III-297, Insecticidal Action Test for Nilaparvata lugens Stal III-298, III-299, III-300, III-301, III-302, III-303, III-304, (Brown Rice Planthopper) 25 III-305, III-306, III-307, III-308, III-309, IV-1, IV-4, IV-6, IV-11, IV-14, IV-15, IV-17, IV-18, IV-19, IV-20, IV-21, A wettable powder prepared based on Formulation IV-22, IV-23, IV-25, IV-27, IV-30, IV-32, IV-33, IV-34, Example 2 was diluted with water so that the concentration of IV-35, IV-36, IV-37, IV-38, IV-39, IV-40, IV-42, IV-59, active ingredient became 500 ppm. In the diluted formulation IV-61, IV-62, IV-64, IV-65, IV-74, IV-76, IV-77, IV-78, were immersed sprouting unhulled rice. The immersed rice 30 IV-79, IV-80, IV-86, IV-89, IV-90, IV-91, IV-92, IV-93, was placed in a plastic cup of 60 ml. Into the plastic cup were IV-95, IV-96, IV-97, IV-98, IV-99, IV-100, IV-101, IV-102, released 103-age larvae of Nilaparvata lugens Stål (brown IV-103, IV-104, IV-106, IV-107, IV-108, IV-109, IV-110, rice planthopper). The cup was covered with a cap and placed IV-111, IV-112, IV-113, IV-114, IV-115, IV-116, IV-117, in a thermostat of 25°C. After 6 days, the number of living IV-118, IV-119, IV-120, IV-127, IV-129, IV-130, IV-131, insects was counted and the mortality of insect was calculated 35 IV-133, IV-134, IV-135, IV-146, IV-147, IV-149, IV-164, using the calculation formula of Mathematical Expression 1. IV-165, IV-166, IV-167, IV-168, IV-169, IV-170, IV-171, The compounds which gave an insect mortality of 90% or IV-172, IV-173, IV-176, IV-177, IV-178, IV-179, IV-180, higher in the above test, are shown below. IV-181, IV-182, IV-183, IV-184, IV-185, IV-186, IV-187, I-1, I-4, I-5, I-6, I-7, I-8, I-9, I-11, I-13, I-14,14, I-15. I-16. I-18 V-10, V-181, VI-25, VI-26, VI-27, VI-28, VI-29, VI-30, I-19, I-21, I-22, I-29, I-47, I-48, I-49, I-50, I-51, I-52, I-53, VI-31, VI-32, VI-33, VI-34, VI-37, VI-38, VI-39, VI-41, I-54, I-55, I-56, I-57, I-58, I-59, I-60, I-61, I-62, I-64, I-67, 40 VI-44, VI-45, VI-46, VI-53, VI-63, VI-89, VI-93, VI-96, I-68, I-69, I-70, I-71, I-72, I-73, I-74, I-75, I-76, I-77, I-78, VI-97, VI-99, VI-103, VI-110, VI-153, VI-155, VI-156, I-79, I-80, I-81, I-82, I-83, I-84, I-85, I-87, I-90, I-91, I-92, VI-157, VI-161, VI-163, VI-166, VI-172, VI-173, VI-194, I-96, I-98, I-110, I-119, I-120, I-121, I-124, I-128, I-129, VI-195, VI-196, VI-197, VI-198, VI-199, VI-200, VI-201, I-130, I-131, I-133, I-134, I-136, I-142, I-165, I-167, I-179, VI-202, VI-203, VI-204, VI-205, VI-206, VI-207, VI-209, I-186, I-188, I-190, I-199, I-208, I-209, I-210, I-211, I-212, 45 VI-210, VI-211, VI-213, VI-214, VI-215, VI-217, VI-218, I-213, I-214, I-215, I-217, I-218, I-219, I-220, I-221, I-223, VI-221, VI-222, VI-223, VI-230, VI-232, VI-233, VI-234, I-224, I-225, I-226, I-228, I-229, I-230, I-231, I-233, I-234, VI-235, VI-239, VI-244, VI-246, VI-247, VI-248, VI-250, I-235, I-236, I-237, I-239, I-240, I-241, I-242, I-243, I-244, VI-255, VI-256, VI-257, VI-258, VI-259, VI-260, VI-261, I-245, I-246, I-247, I-249, I-250, I-251, I-254, I-255, I-256, VI-262, VI-263, VI-264, VI-267, VI-268, VI-274, VI-275, I-257, I-258, I-259, I-260, I-261, I-262, I-263, I-264, I-265, 50 VI-277, VI-278, VI-281, VI-282, VI-283, VI-284, VI-286, I-266, I-267, I-268, I-269, I-270, I-271, I-272, I-273, I-274, VI-287, VI-290, VI-292, VI-294, VI-297, VI-300, VI-302, I-275, I-278, I-279, I-281, I-282, I-285, I-286, I-287, I-288, VI-303, VI-304, VI-305, VI-306, VI-307, VI-308, VI-309, I-289, I-290, I-296, I-297, I-298, I-299, I-300, I-301, I-302, VI-310, VI-314, VII-164 I-304, I-305, I-306, I-307, I-308, I-309, I-310, I-311, I-312, I-313, I-315, I-318, I-319, I-321, I-322, I-323, I-324, I-327, 55 Test Example 4 I-331, I-332, I-333, I-335, I-336, I-339, I-343, I-345, I-346, I-347, I-348, I-351, I-353, I-354, I-355, I-357, I-358, I-359, Trial of Systematic Insecticidal Activity Against I-360, I-361, I-365, I-367, I-369, I-370, I-371, I-372, I-373, Brown Planthopper (Nilaparvata lugens) I-374, I-375, I-376, I-377, I-378, I-379, I-380, I-381, I-382, I-383, I-384, I-385, I-386, I-387, I-389, I-390, I-391, I-392, A wettable powder prepared based on Formulation I-393, I-394, I-395, I-396, I-397, I-398, II-4, II-6, II-10, 60 Example 2 was diluted with water so that the concentration of II-15, II-47, II-48, II-49, II-50, II-51, II-52, II-53, II-54, active ingredient became 1,800 ppm. 250 ul of the diluted II-55, II-56, II-57, II-58, II-59, II-60, II-61, II-62, II-63, formulation was poured to the rice-plant foot of 2.5-leaf age II-64, II-65, II-66, II-67, II-68, II-70, II-71, II-72, II-73, rice seedlings planted in a paper pot of 1.5 cm (length)x1.5 II-74, II-75, II-76, II-77, II-78, II-79, II-80, II-81, II-82, cm (width)x3 cm (height). Then, the paper pot was placed in II-83, II-84, II-85, II-86, II-87, II-88, II-89, II-90, II-91, 65 a plastic cup of 700 ml. Into the plastic cup were released 5 II-121, II-125, II-130, II-133, II-185, II-188, II-190, 3-age larvae of Nilaparvata lugens Stål (brown rice plantho II-194, II-199, II-208, II-214, II-215, II-221, II-222, pper). The cup was covered with a cap and placed in a ther US 8,895,035 B2 133 134 mostat of 25°C. After 6 days, the number of living insects was alkynyl group, a C-C cycloalkyl group, a (C-C, counted and the mortality of insect was calculated using the cycloalkyl)-(C-C alkyl) group, a C-C haloalkyl calculation formula of Mathematical Expression 1. group, a C-C alkylthio group, a C-C alkylsulfinyl The compounds which gave an insect mortality of 90% or group, a C-C alkylsulfonyl group, a (C-C alky higher in the above test, are shown below. 5 lthio)-(C-C alkyl) group, a (C-C alkylsulfinyl)- I-4, I-5, I-6, I-7, I-8, I-9, I-11, I-13, I-16, I-18, I-19, I-21, I-22, (C-C alkyl) group, a (C-C alkylsulfonyl)-(C-C, I-48, I-50, I-52, I-53, I-56, I-64, I-71, I-72, I-74, I-75, I-76, alkyl) group, a C-C alkoxy group, a (C-C alkoxy)- I-87, I-90, I-91, I-96, I-98, I-110, I-133, I-142, I-165, (C-C alkyl)group, a thiocarbamoyl group, a RRNC I-167, I-179, I-186, I-190, I-199, I-208, I-218, I-223, I-228, (=O) group, a RRN group, a C-C alkoxycarbonyl I-229, I-230, I-231, I-233, I-236, I-237, I-246, I-273, II-4, group, a carboxyl group, a RO(HN=)C group, a II-6, II-52, II-56, II-61, II-75, II-79, II-81, II-84, II-85, 10 RON=(R')C group, a R''S(O—)C group, a II-199, II-224, II-271, III-4, III-49, III-73, III-75, IV-4, R'R''NSO.NH group, a C-C alkyl group wherein IV-6, IV-25, IV-36, IV-40, IV-101 the alkyl moiety is Substituted with a hydroxyl group, a cyano C-C alkyl group, a C-C alkylcarbonyl group, Test Example 5 a phenyl group which may be substituted with substitu 15 ent(s) selected from a Substituent group C, or a hetero Insecticidal Action Test for Plutella xylostella Linné cyclic ring of 1 to 9 carbon atoms, having 1 to 5 hetero (Diamondback Moth) atoms which may be the same or different and which are Selected from the group consisting of an oxygen atom, A wettable powder prepared based on Formulation Sulfur atom and nitrogen atom, wherein a heterocyclic Example 2 was diluted with water so that the concentration of 20 ring may be substituted with 1 to 5 substituent(s) active ingredient became 500 ppm. In the diluted formulation Selected from the group consisting of halogen atoms, were immersed cabbage leaves, followed by drying in the air. C-C alkyl group, C-C haloalkyl group, C-C, The resulting cabbage leaves were placed in a plastic cup of alkoxy group, oxo group and cyano group: 60 ml. Into the plastic cup were released 10 2-age larvae of R" is a C-Clo alkyl group, a C-C alkenyl group, a Plutella xylostella Linné (diamondback moth). The plastic s C-C alkynyl group, a C-C cycloalkyl group, a cup was covered with a cap and placed in a thermostat of 25° (C-C cycloalkyl)-(C-C alkyl) group, a C-C, C. After 6 days, the number of living insects was counted and haloalkyl group, a C-C haloalkenyl group, a C-C, the mortality of insect was calculated using the calculation formula of Mathematical Expression 1. haloalkynyl group, a (C-C alkylthio)-(C-C alkyl) The compounds which gave an insect mortality of 90% or group, a (C-C alkylsulfinyl)-(C-C alkyl) group, a higher in the above test, are shown below. 30 (C-C alkylsulfonyl)-(C-C alkyl) group, a (C-C, I-378, II-353, II-355, III-78, IV-121, IV-155, VI-25, VI-28, alkoxy)-(C-C alkyl) group, a (C-C haloalkoxy)- VI-33, VI-46, VI-63, VI-110, VI-153, VI-172, VI-196, (C-C alkyl) group, a (C-C alkoxyimino)-(C-C, VI-201, VI-210, VI-215, VI-223, VI-232, VI-233, VI-255, alkyl) group, a (tri(C-C alkyl)silyl)-(C-C alkyl) VI-256, VI-260, VI-265 group, a cyano C-C alkyl group, a (gem-di(C-C, 35 alkoxy)-(C-C alkyl) group, a C-C alkyl group Test Example 6 wherein the alkyl moiety is substituted with a hydroxyl group, an amino C-C alkyl group (the group may be Insecticidal Action Test for Helicoverpa armigera substituted with R'' and R'), a phenyl group which may Hubner (Corn Earworm) be substituted with substituent(s) selected from the 40 group consisting of a halogen atom, C-C haloalkyl A wettable powder prepared based on Formulation group, C1-C alkoxy group, C1-C haloalkoxy group, Example 2 was diluted with water so that the concentration of C-C alkoxycarbonyl group, nitro group, and a cyano active ingredient became 500 ppm. In the diluted formulation group, a phenyl C-C alkyl group which may be Sub were immersed cabbage leaves, followed by drying in the air. The resulting cabbage leaves were placed in a plastic cup of stituted with substituent(s) selected from the group con 60 ml. Into the plastic cup were released 5 hatchlings of 45 sisting of a halogen atom, C-C haloalkyl group, Plutella xylostella Linné (diamondback moth). The plastic C-C alkoxy group, C-C haloalkoxy group, C-C, cup was covered with a cap and placed in a thermostat of 25° alkoxycarbonyl group, nitro group, and a cyano group, a C. After 6 days, the number of living insects was counted and phenyl C-C alkenyl group which may be substituted the mortality of insect was calculated using the calculation with substituent(s) selected from the substituent group formula of Mathematical Expression 1. 50 C, a phenoxy C-C alkyl group which may be substi The compounds which gave an insect mortality of 90% or tuted with substituent(s) selected from the substituent higher in the above test, are shown below. group C, a heterocyclic ring of 1 to 9 carbon atoms, I-374, II-353, III-78, VI-28, VI-46, VI-63, VI-212, VI-215, having 1 to 5 hetero atoms which may be the same or VI-222, VI-223, VI-231 different and which are selected from the group consist The invention claimed is: 55 ing of an oxygen atom, Sulfur atom and nitrogen atom, 1. An alkoxyimino compound of the following general wherein the heterocyclic ring may be substituted with 1 formula I or an agriculturally acceptable salt thereof, to 5 substituent(s) selected from the group consisting of halogen atoms, C-C alkyl group, C-C haloalkyl I X group, C1-C alkoxy group, and cyano group, a C-C, 60 alkyl group substituted with a heterocyclic ring of 1 to 9 On 2 N R2 carbon atoms, having 1 to 5 hetero atoms which may be R11 NN 2 No1 the same or different and which are selected from the group consisting of an oxygen atom, Sulfur atom and nitrogen atom, wherein a heterocyclic ring may be Sub wherein: 65 stituted with 1 to 5 substituent(s) selected from the group X is a hydrogen atom, a halogen atom, a cyano group, a consisting of halogenatoms, C-C alkyl group, C-C, C1-Cs alkyl group, a C-C alkenyl group, a C-C, haloalkyl group, C-C alkoxy group, and cyano group, US 8,895,035 B2 135 136 or a C-C alkenyl group Substituted with a heterocyclic R" is a RRN group or Q: ring may be substituted of 1 to 9 carbon atoms, having 1 R'' is a C-C alkyl group; and to 5 hetero atoms which may be the same or different and Substituent group C. is a which are selected from the group consisting of an oxy halogenatom, C-C alkyl group, C-Chaloalkyl group, gen atom, Sulfur atom and nitrogen atom, wherein a 5 C-C alkoxy group, C-C haloalkoxy group, C-C, heterocyclic ring may be substituted with 1 to 5 substitu alkoxycarbonyl group, nitro group, or cyano group. ent(s) selected from the group consisting of halogen 2. An alkoxyimino compound or an agriculturally accept atoms, C-C alkyl group, C-C haloalkyl group, able salt thereof, set forth in claim 1, wherein C-C alkoxy group, and cyano group; X is a hydrogen atom, a halogen atom, a cyano group, a when the heterocyclic ring contains nitrogen atom, the 10 C-C alkyl group, a C-C cycloalkyl group, a C-C, nitrogenatom may be oxidized to form N-oxide: haloalkyl group, a C-C alkylthio group, a C-C, R is a C-C alkyl group, a C-C alkenyl group, a C-C, alkylsulfinyl group, a C-C alkylsulfonyl group, a alkynyl group, a C-C cycloalkyl group, a C-C, C-C alkoxy group, a thiocarbamoyl group, a RRNC haloalkyl group, a C-C haloalkenyl group, a C-C, (=O) group, a RRN group, a C-C alkoxycarbonyl haloalkynyl group, a (C-C alkylthio)-(C-C alkyl) 15 group, a carboxyl group, a RO(HN=)C group, a group, a (C-C alkylsulfinyl)-(C-C alkyl) group, a RON=(R')C group, a R''S(O—)C group, a (C-C alkylsulfonyl)-(C-C alkyl) group, a (C-C, R'R''NSO.NH group, a C-C alkyl group wherein alkoxy)-(C-C alkyl) group, a (C-C haloalkoxy)- the alkyl moiety is Substituted with a hydroxyl group, a (C-C alkyl) group, a cyano C-C alkyl group, or a cyano C-C alkyl group, a C-C alkylcarbonyl group, phenyl C-C alkyl group which may be substituted a phenyl group which may be substituted with substitu with the Substituent group C.; ent(s) selected from the Substituent group C, or a hetero Q is a heterocyclic ring as set forth by the following for cyclic ring of 1 to 9 carbon atoms, having 1 to 5 hetero mula Q-1 or formula Q-2); atoms which may be the same or different and which are Selected from the group consisting of an oxygen atom, 25 Sulfur atom and nitrogen atom, wherein a heterocyclic Q-1 ring may be substituted with 1 to 5 substituent(s) Selected from the group consisting of halogen atoms, N C-C alkyl group, C-C haloalkyl group, C-C, alkoxy group, oxo group and cyano group, SN- I pi 30 R" is a C-Co to alkyl group, a C-C alkenyl group, a Q-2) C-C alkynyl group, a C-C cycloalkyl group, a (C-C cycloalkyl)-(C-C alkyl) group, a C-C, haloalkyl group, a C-C haloalkenyl group, a (C-C, alkylthio)-(C-C alkyl) group, a (C-C alkoxy C-C, 35 alkyl) group, a (C-C haloalkoxy)-(C-C alkyl) KN-N R’), group, a (tri(C-C alkyl)silyl)-(C-C alkyl) group, a cyano C-C alkyl group, a (gem-di(C-C alkoxy))- or a halogen atom; (C-C alkyl) group, a C-C alkyl group wherein the in the formula Q-1, W is a nitrogen atom or a methine alkyl moiety is substituted with a hydroxyl group, an group; 40 amino C-C alkyl group (the group may be substituted the nitrogenatom(s) of a heterocyclic ring of formula O-1 with R'' and R'), a phenyl group which may be substi and formula Q-2) may be oxidized to form N-oxide: tuted with substituent(s) selected from the group con in the formula (Q-1 and formula (Q-2), R is a mercapto sisting of a halogen atom, C-C haloalkyl group, group, or a C-C haloalkyl group; C-C alkoxy group, C-C haloalkoxy group, C-C, in the formula O-1), n is 0, 1 or 2 when W is a nitrogen 45 alkoxycarbonyl group, nitro group, and a cyano group, a atom and 0, 1, 2 or 3 when W is a methine group: phenyl C-C alkyl group which may be substituted in the formula Q-2, n is 0, 1, 2 or 3: with Substituent(s) selected from the group consisting of R. R. R. R. R. R. R'' and R' are each a hydrogen a halogen atom, C-C haloalkyl group, C-C alkoxy atom, a C-C alkyl group, a C-C alkoxy group, a group, C-Chaloalkoxy group, C-C alkoxycarbonyl (C-C alkoxy)-(C-C alkyl)group, a C-C alkylcar 50 group, nitro group, and a cyano group, a phenyl C-C, bonyl group, a C-C alkoxycarbonyl group, a C-C, alkenyl group which may be substituted with substitu haloalkyl group, a C-C cycloalkyl group, a (C-C, ent(s) selected from the Substituent group C, a phenoxy cycloalkyl)-(C-C alkyl) group, a C-C alkylsulfonyl C-C alkyl group which may be substituted with sub group, a cyano C-C alkyl group, or a phenyl group stituent(s) selected from the Substituent group C, a het which may be substituted with substituent(s) selected 55 erocyclic ring of 1 to 9 carbon atoms, having 1 to 5 from the Substituent group C.; hetero atoms which may be the same or different and R and R, R and R7, R'' and R', and R'' and R' may which are selected from the group consisting of an oxy respectively be combined together to form an C-C, gen atom, Sulfur atom and nitrogen atom, wherein a alkylene chain and thereby may form, together with the heterocyclic ring may be substituted with 1 to 5 substitu nitrogen atom to which they bond, a 3- to 8-membered 60 ent(s) selected from the group consisting of halogen ring, wherein the alkylene chain may contain one oxy atoms, C-C alkyl group, C-C haloalkyl group, gen atom, Sulfur atom or nitrogenatom and also may be C-C alkoxy group, and cyano group, or a C-C alkyl Substituted with halogen atom, C-C alkyl group and group substituted with a heterocyclic ring of 1 to 9 OXO group: carbon atoms, having 1 to 5 hetero atoms which may be RandR are each a hydrogenatom, a C-C alkyl group, 65 the same or different and which are selected from the a C-C haloalkyl group, or a C-C alkoxycarbonyl group consisting of an oxygen atom, Sulfur atom and group; nitrogen atom, wherein the heterocyclic ring may be US 8,895,035 B2 137 138 substituted with 1 to 5 substituent(s) selected from the group consisting of halogen atoms, C-C alkyl group, C-Chaloalkyl group, C-C alkoxy group, and cyano grOup, NN when the heterocyclic ring contains nitrogen atom, the K W 3 nitrogen atom may be oxidized to form N-oxide, N- / -R).) R is a C-C alkyl group, a C-C alkenyl group, a C-C, alkynyl group, a C-C cycloalkyl group, a C haloalkyl group, a C-C alkoxy C-C alkyl group, a 5. A pest control agent characterized by containing, as an 10 active ingredient, the alkoxyimino compound or an agricul cyano C-C alkyl group, or a phenyl C-C alkyl group turally acceptable salt thereof of claim 1. which may be substituted with the substituent group C, 6. The pest control agent of claim 5, wherein said pest Q is a heterocyclic ring as set forth by the following for control agent is formulated as an insecticide. mula Q-1 or formula Q-2). 7. A method for pest control, comprising the step of apply ing an effective amount of the alkoxyimino compound or an 15 agriculturally acceptable salt thereof of claim 1 to a pest in the formula 3 form of dispersion to soil, Surface application or mixing with livestock feed. Q-1 8. The method for pest control of claim 7, wherein said pest is an insect and the alkoxyimino compound or an agricultur NS ally acceptable salt thereof is formulated as an insecticide. 9. The alkoxyimino compound oran agriculturally accept KN- AIf t-R)pi able salt thereof of claim 2, wherein Q is a halogen atom. Q-2) 10. The alkoxyimino compound or an agriculturally acceptable salt thereof of claim 2, wherein Q is a heterocyclic S. 25 ring as set forth by the following formula Q-1. N-N ), or a halogen atom, 30 NN in the formula Q-1, W is a nitrogen atom or a methine grOup, (N -R). in the formula Q-1 and formula Q-2), R is a mercapto group or a C-C haloalkyl group, 35 11. A pest control agent characterized by containing, as an in the formula Q-1 and formula Q-2, n is 0 or 1, active ingredient, the alkoxyimino compound or an agricul R. R. R. R. R. R. R'' and R' are each a hydrogen turally acceptable salt thereof of claim 2. atom, a C-C alkyl group, a C-C alkoxy group, a 12. A pest control agent characterized by containing, as an C-C alkylcarbonyl group, a C-C alkoxycarbonyl active ingredient, the alkoxyimino compound or an agricul group, a C-C haloalkyl group, a C-C cycloalkyl 40 turally acceptable salt thereof of claim 3. C-C alkyl group, a cyano C-C alkyl group, or a 13. A pest control agent characterized by containing, as an phenyl group which may be substituted with substitu active ingredient, the alkoxyimino compound or an agricul ent(s) selected from the Substituent group C, turally acceptable salt thereof of claim 4. R and R, R and R7, R'' and R', and R'' and R' may 14. A method for pest control, comprising the step of apply respectively be combined together to form an C-C, 45 ing an effective amount of the alkoxyimino compound or an alkylene chain and thereby may form, together with the agriculturally acceptable salt thereof of claim 2 to a pest by nitrogen atom to which they bond, a 3- to 8-membered dispersion, in-soil application, Surface application or mixing ring, wherein the alkylene ring may contain one oxygen with livestock feed. atom, Sulfur atom or nitrogen atom, 15. A method for pest control, comprising the step of apply 50 ing an effective amount of the alkoxyimino compound or an RandR are each a hydrogenatom, a C-C alkyl group, agriculturally acceptable salt thereof of claim 3 to a pest by or a C-C alkoxycarbonyl group, dispersion, in-soil application, Surface application or mixing R' is a RRN group or Q, and with livestock feed. R'' is a C-C alkyl group. 16. A method for pest control, comprising the step of apply 3. The alkoxyimino compound oran agriculturally accept 55 ing an effective amount of the alkoxyimino compound or an able salt thereof of claim 1, wherein Q is a halogen atom. agriculturally acceptable salt thereof of claim 4 to a pest by 4. The alkoxyimino compound oran agriculturally accept dispersion, in-soil application, Surface application or mixing able salt thereof of claim 1, wherein Q is a heterocyclic ring as with livestock feed. set forth by the following formula O-1). UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 8,895,035 B2 Page 1 of 1 APPLICATIONNO. : 13/806317 DATED : November 25, 2014 INVENTOR(S) : Shunichirou Fukumoto et al. It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

In the Claims At column 135, line 21: --with the Substituent group O.-- should read: --with substituent(s) selected from the substituent group O.-- At column 135, line 47: --in the formula Q-2), n is 0, 1, 2 or 3:-- should read: --in the formula Q-2), n is 0, 1 or 2:-- At column 137, line 11: --which may be substituted with the substituent group O.-- should read: --which may be substituted with substituent(s) selected from the substituent group O.--

Signed and Sealed this Twenty-fifth Day of August, 2015 74-4-04- 2% 4 Michelle K. Lee Director of the United States Patent and Trademark Office