US 201402881 84A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0288.184 A1 Fukumoto et al. (43) Pub. Date: Sep. 25, 2014

(54) GYLOXIME DERIVATIVE AND PEST Publication Classification CONTROL AGENT (51) Int. Cl. (71) Applicants: KUMIAI CHEMICAL INDUSTRY AOIN 37/52 (2006.01) CO.,LTD., Tokyo (JP); IHARA AOIN37/18 (2006.01) CHEMICAL INDUSTRY CO.,LTD., (52) U.S. Cl. Tokyo (JP) CPC ...... A0IN37/52 (2013.01); A0IN37/18 (72) Inventors: Shunichirou Fukumoto, Shizuoka (JP); (2013.01) Daisuke Shikama, Shizuoka (JP); USPC ...... 514/626; 564/256; 564/198: 564/189: Toshihiro Nagata, Shizuoka (JP); 564/191; 514/640; 514/613 Katsuya Kato, Shizuoka (JP); Kei Kawamoto, Shizuoka (JP); Masaaki (57) ABSTRACT Komatsu, Tokyo (JP); Takeshi The present invention provides a glyoxime derivative display Matsuda, Tokyo (JP); Seisuke Ito, ing excellent pesticidal effect or a salt thereof and a pesticide Tokyo (JP) containing the same as an active ingredient. This pesticide is characterized by containing as an active ingredient, a gly (73) Assignees: IHARACHEMICAL INDUSTRY oxime derivative expressed by the general formula II (in CO.,LTD., Tokyo (JP); KUMIAI which X represents a cyano group or a carbamoyl group, R' CHEMICAL INDUSTRY CO.,LTD., represents a C-C alkyl group, a C-C cycloalkyl C-C, Tokyo (JP) alkyl group, etc., and IV represents a hydrogenatom, a C-Cs alkyl group, a C-C cycloalkyl C-C alkyl group, etc.) oran (21) Appl. No.: 14/360,527 agriculturally acceptable salt thereof. (22) PCT Filed: Nov. 19, 2012 (86). PCT No.: PCT/UP2012/007400

S371 (c)(1), N R2 (2), (4) Date: May 23, 2014 R11 O NN 2 21 no-1 (30) Foreign Application Priority Data Nov.30, 2011 (JP) ...... 2011-261804 US 2014/0288.184 A1 Sep. 25, 2014

GYLOXIME DERVATIVE AND PEST CONTROL AGENT formula 1

TECHNICAL FIELD X 0001. The present invention relates to a novel glyoxime 2 derivative or a salt thereof, as well as to a pest control agent R -ON Na 2 N No1 R characterized by containing the derivative or salt thereofas an active ingredient. BACKGROUND ART {in the formula, 0002 For example, Patent Literature 1 is already known as X is a cyano group or a carbamoyl group, a literature regarding compounds similar to the glyoxime R" is a C-Cs alkyl group, a C-C alkenyl group, a C-C, derivative of the present invention. alkynyl group, a C-C cycloalkyl group, a C-C cycloalkyl 0003 Glyoxime derivatives are disclosed in the Patent C-C alkyl group, a C-Chaloalkyl group, a C-C alkoxy Literature 1. However, they are restricted to those glyoxime C-C alkyl group, a cyano C-C alkyl group or a phenyl derivatives in which the Substituent on one oxygen is a Sulfo C-C alkyl group which may be substituted by at least one nyl group (e.g. methanesulfonyl group), and no glyoxime substituent selected from the below-shown substituent group derivative according to the present invention is disclosed. C. and Further in the literature, there is no disclosure on the control R is a hydrogenatom, a C-Cs alkyl group, a C-C alkenyl effect of the glyoxime derivatives on pests. group, a C-C alkynyl group, a C-C cycloalkyl group, a C-C cycloalkyl C-C alkyl group, a C-C haloalkyl PRIOR ART LITERATURE group, a C-C alkoxy C-C alkyl group, a cyano C-C, alkyl group or a phenyl C-C alkyl group which may be Patent Literature substituted by at least one substituent selected from the 0004 Patent literature 1: EP-795551 below-shown Substituent group C. SUMMARY OF THE INVENTION Substituent Group C. 0010 a halogen atom, a C-C alkyl group, a C-C, Task to Be Achieved by the Invention haloalkyl group, a C-C alkoxy group, a C-Chaloalkoxy 0005. It is desired that the pest control agents used for group, a nitro group or a cyano group. useful crops are applied to Soil or foliage at a low chemical or an agriculturally acceptable salt thereof. dose and yet exhibit a sufficient pest control effect. With the increasing requirements for the safety of chemical Substances (2) A glyoxime derivative represented by the general formula and the effect on environment, it is also desired to develop a safer pest control agent. Further, in recent years, the use over many years, of pest control agents (e.g. insecticides and miti cides) have caused the appearance of pests resistant to these formula 2) pest control agents, making difficult the complete control of pests. Also, the use of highly toxic pest control agents has caused problems regarding, for example, the safety to pest control agent operator. 0006 Under such a situation, the task of the present inven tion is to solve the above-mentioned problems of conven tional pest control agents and provide a pest control agent Superior in Safety, control effect, etc. 0007 Means for Achieving the Task {in the formula, 0008. In order to develop a pest control agent having the X" is a cyano group or a carbamoyl group, above-mentioned preferred properties, the present inventors R" is a C-Cs alkyl group, a C-C alkenyl group, a C-C, synthesized various glyoxime derivatives and investigated alkynyl group, a C-C cycloalkyl group, a C-C cycloalkyl their physiological activities. As a result, it was found that the C-C alkyl group, a C-Chaloalkyl group, a C-C alkoxy glyoxime derivatives represented by the general formula I C-C alkyl group, a cyano C-C alkyl group or a phenyl shown below show a control effect to pests and resistant pests C-C alkyl group which may be substituted by at least one and show a very high control (insecticidal) effect particularly substituent selected from the below-shown substituent group to Hemipteran pests represented by Nilaparvata lugens, Lao C. and delphax striatella, Nephotettix cincticeps, Aphis gossypii, etc. I0011) R' is a hydrogen atom, a C-C alkyl group, a The finding has led to the completion of the present invention. C-C alkenyl group, a C-C alkynyl group, a C-C, 0009. The present invention has a scope characterized as cycloalkyl group, a C-C cycloalkyl C-C alkyl group, a shown below C-Chaloalkyl group, a C-C alkoxy C-C alkyl group, a (1) A pest control agent characterized by containing, as an cyano C-C alkyl group or a phenyl C-C alkyl group active ingredient, a glyoxime derivative represented by the which may be substituted by at least one substituent selected general formula II from the below-shown Substituent group C. US 2014/0288.184 A1 Sep. 25, 2014

Substituent Group C. hexyl, 4.4-dimethylpentyl, n-octyl, 1-methylheptyl, 6-meth 0012 a halogen atom, a C-C alkyl group, a C-C, ylheptyl and 5,5-dimethylhexyl groups. haloalkyl group, a C-C alkoxy group, a C-C haloalkoxy 0020. In the present invention, C-C alkenyl group refers group, a nitro group or a cyano group, to, unless otherwise specified, a straight chain or branched or an agriculturally acceptable salt thereof. chain alkenyl group of 2 to 6 carbon atoms. There can be (3) A pest control agent according to (1), which is an insec mentioned, for example, vinyl, 1-propenyl, isopropenyl, ticide. 2-propenyl, 1-butenyl, 1-methyl-1-propenyl, 2-butenyl, (4) A method for pest control which uses the glyoxime deriva 1-methyl-2-propenyl, 3-butenyl, 2-methyl-1-propenyl, tive or agriculturally acceptable salt thereof, according to (2), 2-methyl-2-propenyl, 1,3-butadienyl, 1-pentenyl, 1-ethyl-2- at an effective amount. propenyl, 2-pentenyl, 1-methyl-1-butenyl, 3-pentenyl, 1-me (5) A method for pest control according to (4), which uses the thyl-2-butenyl, 4-pentenyl, 1-methyl-3-butenyl, 3-methyl-1- glyoxime derivative or agriculturally acceptable salt thereof, butenyl, 1,2-dimethyl-2-propenyl, 1,1-dimethyl-2-propenyl, as an insecticide. 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1,2-dimethyl-1- propenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,3-pen Effect of the Invention tadienyl, 1,3-butadien-2-yl, 1-hexenyl, 1-propyl-2-propenyl, 2-hexenyl, 1-methyl-1-pentenyl, 1-ethyl-2-butenyl, 3-hex 0013 The present invention shows an excellent control enyl, 4-hexenyl, 5-hexenyl, 1-methyl-4-pentenyl, 1-ethyl-3- effect to a variety of pests in agricultural and horticultural butenyl, 4-methyl-1-penten-2-yl, 1-ethyl-1-methyl-2-prope fields, can control even resistant pests, and are highly effec nyl, 1-ethyl-2-methyl-2-propenyl, 4-methyl-1-penten-3-yl, tive particularly to Hemipteran pests represented by Nilapar 2-methyl-2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pen vata lugens, Laodelphax striatella, Sogatella fircifera, tenyl, 1,3-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, Nephotettix cincticeps, Aphis gossypii, Bemisia tabaci. etc. 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,2-dimethyl-3- butenyl, 1,3-dimethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, MODE FOR CARRYING OUT THE INVENTION 1.5-hexadienyl, 1.4-pentadien-2-yl, and 2.4-hexadienyl 0014 Explanation is made on the symbols and terms used groups. in the present Description. 0021. In the present invention, C-C alkynyl group refers 0015. In the present invention, pest control agent means to, unless otherwise specified, a straight chain or branched insecticides, miticides, nematicides, etc. used in agricultural chain alkynyl group of 2 to 6 carbon atoms. There can be and horticultural fields, (e.g. livestock and pets), mentioned, for example, ethynyl, 1-propynyl, 2-propynyl, households or disinfection. 1-butynyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, 0016. In the present invention, halogen atom refers to a 1-pentynyl, 1-ethyl-2-propynyl, 2-pentynyl, 3-pentynyl, fluorine atom, a chlorine atom, a bromine atom or an iodine 1-methyl-2-butynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-me atOm. thyl-3-butynyl, 1-hexynyl, 1-(n-propyl)-2-propynyl, 2-hexy 0017. In the present invention, C-C alkyl group refers nyl, 1-ethyl-2-butynyl, 3-hexynyl, 1-methyl-2-pentynyl, to, unless otherwise specified, a straight chain or branched 1-methyl-3-pentynyl, 4-methyl-1-pentynyl, 3-methyl-1-pen chain alkyl group of 1 to 6 carbon atoms. There can be tynyl, 5-hexynyl, 1-ethyl-3-butynyl, 1-ethyl-1-methyl-2-pro mentioned, for example, methyl, ethyl, n-propyl, isopropyl. pynyl, 4-methyl-1-pentyn-3-yl, 1,1-dimethyl-2-butynyl and n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbu 2,2-dimethyl-3-butynyl groups. tyl, 2-methylbutyl, isopentyl, 1-ethylpropyl, 1,1-dimethyl 0022. In the present invention, C-C cycloalkyl group propyl, 1,2-dimethylpropyl. neopentyl, n-hexyl, 1-methyl refers to, unless otherwise specified, a cycloalkyl group of 3 pentyl, 2-methylpentyl, 3-methylpentyl, isohexyl, to 6 carbon atoms. There can be mentioned, for example, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethyl cyclopropyl, cyclobutyl, cyclopenty1 and cyclohexyl groups. butyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethyl 0023. In the present invention, C-C cycloalkyl C-C, butyl, 3.3-dimethylbutyl, 1,1,2-trimethylpropyl, 1.2.2-trim alkyl group refers to, unless otherwise specified, a (C-C, ethylpropyl, and 1-ethyl-1-methylpropyl groups. cycloalkyl)-(C-C alkyl)group wherein the cycloalkyl moi 0018. In the present invention, C-C alkyl group refers ety and the alkyl moiety have each the above-mentioned to, unless otherwise specified, a straight chain or branched meaning. There can be mentioned, for example, cyclopropy chain alkyl group of 1 to 8 carbon atoms. There can be lmethyl, cyclobutylmethyl, cyclopentylmethyl and cyclo mentioned, for example, those groups mentioned for the C-C alkyl group; and n-heptyl, 1-methylhexyl, 5-methyl hexylmethyl groups. hexyl, 4.4-dimethylpentyl, n-octyl, 1-methylheptyl, 6-meth 0024. In the present invention, C-C alkoxy group refers ylhexptyl and 5,5-dimethylhexyl groups. to, unless otherwise specified, a (C-C alkyl)-O-group 0019. In the present invention, C-C alkyl group refers wherein the alkyl moiety has the above-mentioned meaning. to, unless otherwise specified, a straight chain or branched There can be mentioned, for example, methoxy, ethoxy, chain alkyl group of 3 to 8 carbon atoms. There can be n-propoxy, isopropXy, n-butoxy, isobutoxy, tert-butoxy, pen mentioned, for example, n-propyl, isopropyl. n-butyl, sec tyloxy, isopentyloxy, hexyloxy and isohexyloxy groups. butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methyl 0025. In the present invention, C-C haloalkyl group butyl, isopentyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dim refers to, unless otherwise specified, a straight chain or ethylpropyl. neopentyl, n-hexyl, 1-methylpentyl, branched chain alkyl group of 1 to 6 carbonatoms, Substituted 2-methylpentyl, 3-methylpentyl, isohexyl, 1-ethylbutyl, with 1 to 13, preferably 1 to 5 same or different halogen 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dim atoms. There can be mentioned, for example, difluoromethyl, ethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3.3-dim 2-fluoroethyl, 2,2-difluoroethyl, 2.2.2-trifluoroethyl, 2.2.2- ethylbutyl, 1,1,2-trimethylpropyl, 1.2.2-trimethylpropyl. trichloroethyl, 3,3,3-trifluoropropyl, 2.2.3,3,3-pentafluoro 1-ethyl-1-methylpropyl, n-heptyl, 1-methylhexyl, 5-methyl propyl and 1.1.2.3.3.3-hexafluoropropyl groups. US 2014/0288.184 A1 Sep. 25, 2014

0026. In the present invention, C-C haloalkyl group example, formic acid, acetic acid, methanesulfonic acid, refers to, unless otherwise specified, a straight chain or 4-toluenesulfonic acid and trifluoromethanesulfonic acid. branched chain alkyl group of2 to 6 carbonatoms, Substituted 0035) Next, representative examples of the compounds with 1 to 13, preferably 1 to 5 same or different halogen included in the glyoxime derivative of the above general atoms. There can be mentioned, for example, 2-fluoroethyl, formula, of the present invention, are shown in Tables 1 to 12. 2,2-difluoroethyl, 2.2.2-trifluoroethyl, 2.2.2-trichloroethyl, However, the compounds included in present invention is not 3,3,3-trifluoropropyl, 2.2.3,3,3-pentafluoropropyl and 1.1.2, restricted thereto. The No. of each compound shown in each 3.3.3-hexafluoropropyl groups. Table is referred to in the later description. 0027. In the present invention, C-C haloalkoxy group 0036 Incidentally, the compounds included in the present refers to, unless otherwise specified, a (C-C haloalkyl)-O- glyoxime derivative contain, in Some cases, geometrical iso group wherein the haloalkyl moiety has the above-mentioned mers of E-form and Z-form, depending upon the kinds of meaning. There can be mentioned, for example, chlo substituents. The present invention includes the E-isomers, romethoxy, difluoromethoxy, chlorodifluoromethoxy, trif the Z-isomers, and the mixtures of any mixing ratio of E-iso luoromethoxy, 2,2-difluoroethoxy and 2.2.2-trifluoroethoxy mer and Z-isomer. groups. 0037. In the present Description, the following expres 0028. In the present invention, C-C alkoxy C-C alkyl sions in Tables refer to corresponding groups. group refers to, unless otherwise specified, a (C-C alkoxy)- 0038 Me: methyl group (C-C alkyl)-group, wherein the alkyl moiety and the alkoxy 0039 Et: ethyl group moiety have each the above-mentioned meaning. 0040 Pr-n: n-propyl group 0029. There can be mentioned, for example, methoxym 0041) Pr-i: isopropyl group ethyl, ethoxymethyl, isopropoxymethyl, pentyloxymethyl, 0042 Pr-c: cyclopropyl group 2-methoxyethyl, 2-ethoxyethyl and 2-butoxyethyl groups. 0043 Bu-n: n-butyl group 0030. In the present invention, phenyl C-C alkyl group 0044 Bu-s: sec-butyl group refers to, unless otherwise specified, an alkyl group of 1 to 6 0045 Bu-i: isobutyl group carbon atoms, Substituted with phenyl group, wherein the 0046 Bu-t: tert-butyl group alkyl moiety has the above-mentioned meaning. There can be 0047 Pen-n: n-pentyl group mentioned, for example, benzyl, 1-phenylethyl and 2-phenyl 0048 Pen-c: cyclopentyl group ethyl groups. 0049 Pen-i: isopentyl group 0031. Incidentally, the phenyl C-C alkyl group may be 0050 Pen-neo: neopentyl group substituted with at least one substituent selected from the 0051 Pen-2: 1-methylbutyl group Substituent group C. 0.052 Pen-3: 1-ethylpropyl group 0032. In the present invention, cyano C-C alkyl group 0053 Hex-n: n-hexyl group refers to, unless otherwise specified, an alkyl group of 1 to 6 0054 Hex-c: cyclohexyl group carbon atoms, Substituted with cyano group, wherein the 0055 Also, for example, the following expressions have alkyl moiety has the above-mentioned meaning. There can be corresponding meanings. mentioned, for example, cyanomethyl group and 1-cyanobu 0056 5-CF: substituted with trifluoromethyl group at tyl group. 5-position 0033. As the compounds included in the glyoxime deriva 0057. 3-C1-5-CF: substituted with chlorine atomat3-po tive of general formula II and the glyoxime derivative of sition and with trifluoromethyl group at 5-position general formula II, there can be mentioned those com 0.058 2,6-(C1): substituted with chlorine atom at 2- and pounds in which the above-mentioned substituents are com 6-positions bined. However, the following compounds are preferred in view of their pesticidal effects. Compounds in which X is a cyano group, R' is an n-propyl TABLE 1 group, an isopropyl group or an n-butyl group, and R is CN hydrogen, an n-propyl, or an isopropyl group. Compounds in which X is a carbamoyl group, R is an n-pro R111. OnNN 2 2 NNo1 R2 pyl group or an isopropyl group, and R is hydrogen, an n-propyl group or an isopropyl group. NH2 Compounds in which X is a cyano group, R is a 2-propynil Compond group or a 2-propenyl group, andR is ann-propyl group oran No. RI R2 isopropyl group. 1-001 Me H 0034. The agriculturally acceptable salt refers to a salt of 1-0O2 Et H any compound included in the glyoxime derivative of the 1-0O3 Pr-n H above general formula, of the present invention, and contain 1-004 Pr- H ing hydroxyl group, amino group or the like in the structure, 1-OOS Bu-n H 1-OO6 Bu-i H with a metal or an organic base, or with a mineral acid or an 1-007 Bu-s H organic acid. As the metal, there can be mentioned alkali 1-008 Bu-t H metals (e.g. sodium and potassium) and alkaline earth metals 1-009 Pen-n H (e.g. magnesium and calcium). As the organic base, there can 1-010 Pen-i. H 1-011 Pen-neo H be mentioned, for example, triethylamine and diisopropy 1-012 Pen-2 H lamine. As the mineral acid, there can be mentioned, for 1-013 Pen-3 H example, hydrochloric acid hydrobromic acid and Sulfuric 1-014 Hex-n H acid. As the organic acid, there can be mentioned, for

US 2014/0288.184 A1 Sep. 25, 2014

TABLE 9 TABLE 11 Compond Compond No. R No. RI R2 2-113 CH-CH=CH Pr 2-055 Pen-n E 2-114 CHC=CH Pr 2-0S6 Pen-i. E 2-115 CH2C=CCH Pr 2-057 Pen-neo E 2-116 Pr 2-117 Pr Pen-i. 2-058 Pen-2 E 2-118 Pr CHPr-c 2-0.59 Pen-3 E 2-119 Pr CHCF 2-06O Hex-n E 2-120 Pr CHCHOCHCH 2-061 CH2CH2C(Me) E 2-121 Pr CH-C=CH 2-062 Pen-c E 2-122 Pr CH-C=CCH 2-063 Hex-c E 2-123 Pr Bu-t 2-124 Pr 2-064 CH-Pr-c E 2-125 Pr 2-06S CH-Bu-c E 2-126 Pr 2-066 CHPen-c E 2-127 Pr 2-067 CH-CH=CH- E 2-128 Pr 2-068 CH-C=CH E 2-129 2-130 2-069 CH2C=CCH E 2-131 CHPh 2-070 Me Pr-n 2-132 CHCHOCHCH 2-071 Et Pr-n 2-133 CHPen-c 2-072 Pr-n Pr-n 2-134 Pen-c 2-073 Pr- Pr-n 2-13S CH-Pr-c 2-136 2-074 Bu-n Pr-n CFCHFCF 2-137 CHF, 2-075 Bu-i Pr-n 2-138 H 2-076 Bu-s Pr-n 2-139 CHCF Pr-n 2-077 Bu-t Pr-n 2-140 CH2(CH2)6CH H 2-078 Pen-n Pr-n 2-141 CHPh H 2-079 Pen-i. Pr-n 2-08O Pen-neo Pr-n 2-081 Pen-2 Pr-n TABLE 12 2-082 Pen-3 Pr-n 2-083 Hex-n Pr-n Compond No. R R2 2-142 HPh CHCF 2-143 HPh Me TABLE 10 2-144 HPh CHCFCF 2-145 HPh(3-CN) CHCFCF Compond 2-146 HPh(3-NO) CHCFCF No. RI R2 2-147 HPh Et 2-148 HPh Pr-n 2-084 CH2CH2C(Me) Pr-n 2-149 HPh Bu-n 2-085 Pen-c Pr-n 2-1SO HPhC2,6-CH) CH-CH=CH 2-086 Hex-c Pr-n 2-151 HPh(3-OCF) CH-CH=CH, 2-087 CHPr-c Pr-n 2-152 H2CH2OCH2CH CH-CH=CH 2-088 CH-Bu-c Pr-n 2-153 HCN CH-CH=CH 2-089 CHPen-c Pr-n 2-154 H-CH=CHCH H 2-O90 CH-CH=CH- Pr-n 2-155 CH=CHCH Pr-n 2-091 CHC=CH Pr-n 2-156 H-CH=CH Bu-n 2-092 CH2C=CCH Pr-n 2-157 H-CH=CH Pen-n 2-093 Me Pr 2-158 H-CH=CH Hex-n 2-094 Et Pr 2-159 HCH=CH, CHPh 2-09S Pr-n Pr 2-160 HC=CH Bu-n 2-096 Pr- Pr 2-161 HC=CH CHPh 2-097 Bu-n Pr 2-162 HCFCF Pr-n 2-098 Bu-i Pr 2-163 HCFCF Pr 2-099 Bu-s Pr 2-164 HPh(4-OCH) CHCF 2-1OO Bu-t Pr 2-16S HPh(4-CI) CHCF 2-101 Pen-n Pr 2-166 HPhC2,6-Cl2) CHCF 2-102 Pen-i. Pr 2-167 HPh(3-CF) CHCF 2-103 Pen-neo Pr 2-168 H2CF CHCF 2-104 Pen-2 Pr 2-105 Pen-3 Pr 2-106 Hex-n Pr 2-107 CH2CH2C(Me) Pr 0059. The glyoxime derivative represented by the general 2-108 Pen-c Pr formula, of the present invention can be produced by the 2-109 Hex-c Pr production methods shown below. However, the production is 2-110 CHPr-c Pr not restricted by these methods. 2-111 CH-Bu-c Pr 2-112 CHPen-c Pr 0060. In the following, for example, “compound repre sented by the general formula III. compound represented by formula III and “compound III' have the same meaning. US 2014/0288.184 A1 Sep. 25, 2014

Production Method 1 0066. As the base usable in the reaction, there can be mentioned, for example, inorganic bases such as alkali metal 0061. Of the glyoxime derivatives represented by the gen hydroxides (e.g. sodium hydroxide and potassium hydroxy eral formula, the compound represented by the general for ide), alkali metal carbonates (e.g. sodium carbonate and mula VII can be produced, for example, by the following potassium carbonate), alkali metal bicarbonates (e.g. sodium method. hydrogencarbonate and potassium hydrogencarbonate) and the like; metal hydrides such as sodium hydride, potassium hydride and the like; and organic bases such as triethylamine, Formula 3 1,8-diazabicyclo5.4.0-7-undecene and the like. The use CN R-E CN amount of the base is appropriately selected ordinarily in a HO, 2 N III On 2 N range of 1 to 10 equivalents relative to 1 equivalent of the NN a NOH - (Step 1-1) - R11 NN a YOH compound II and is preferably 1 to 5 equivalents. 0067. The reaction temperature of the reaction is ordi NH2 NH2 narily any temperature from -20°C. to the reflux temperature II) IV of the reaction system and is preferably -10°C. to 100° C. R-E 3 0068. The reaction time of the reaction differs depending III R-E upon the reaction temperature, the Substrate of reaction, the V amount of reaction, etc., but is ordinarily 1 to 48 hours. (R = R3) IV 0069. After the completion of the reaction, there are con (Step 2) (StepStep 1-21-2) ducted operations such as poring of water into reaction mix CN ture, extraction with organic solvent, concentration and the like, whereby the compound IV can be isolated. The iso On 2 N R3 lated compound IV can be purified as necessary by column R11 NN 2 No1 chromatography, recrystallization, etc. NH2 VI) (Step 1-2) 0070 The compound VII can be produced by reacting the I0062 (In the formula, R' has the same meaning as given compound IV with a compound IV in an appropriate Sol above; R is a C-Cs alkyl group, a C-C alkenyl group, a vent in the presence of an appropriate base. C-C alkynyl group, a C-C cycloalkyl group, a C-C, 0071. The amount of the compound IV used in the reac cycloalkyl C-C alkyl group, a C-C haloalkyl group, a tion is appropriately selected ordinarily in a range of 1 to 5 C-C alkoxy C-C alkyl group, a cyano C-C alkyl group, eluivalents relative to 1 equivalent of the compound IV and or a phenyl C-C alkyl group which may be substituted with is preferably 1 to 2 equivalents. at least one substituent selected from the Substituent group a; 0072. As the solvent and base usable in the reaction, there and E is a leaving group Such as chlorine atom, bromine atom, can be mentioned the same solvents and bases as mentioned iodine atom, methanesulfonyl group, methanesulfonyloxy in the (step 1-1). The use amount of the solvent is ordinarily group, trifluoromethanesulfonyloxy group or the like). 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 mol of the compound IV. The use amount of the base is appropri (Step 1-1) ately selected ordinarily in a range of to 10 equivalents rela tive to 1 equivalent of the compound IV and is preferably 1 0063. The compound IV can be produced by reacting a to 5 equivalents. compound II with a compound III in an appropriate Sol 0073. The reaction temperature of the reaction is ordi vent in the presence of an appropriate base. Incidentally, the narily any temperature from -20°C. to the reflux temperature compound III can be produced based on the method of the reaction system and is preferably -10°C. to 100° C. described in Journal of Organic Chemistry, 2000, Vol 65, No. 0074 The reaction time of the reaction differs depending 4, pp. 1139-1143. upon the reaction temperature, the Substrate of reaction, the 0064. The amount of the compound III used in the reac amount of reaction, etc., but is ordinarily 1 to 48 hours. tion is appropriately selected ordinarily in a range of 1 to 5 0075. After the completion of the reaction, there are con equivalents relative to 1 equivalent of the compound II and ducted operations such as poring of water into reaction mix is preferably 1 to 2 equivalents. ture, extraction with organic solvent, concentration and the 0065. As the solvent usable in the reaction, there ca be like, whereby the compound VI can be isolated. The iso mentioned, for example, ethers such as diethyl ether, 1.2- lated compound VI can be purified as necessary by column dimethoxyethane, tetrahydrofuran and the like; amides Such chromatography, recrystallization, etc. as N,N-dimethylacetamide, N,N-dimethylformamide, 1,3- dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidinone and (Step 2) the like; Sulfur compounds such as dimethyl sulfoxide, Sul folane and the like; nitriles such as acetonitrile, propionitrile 0076. When R—R, the compound VII can be produced and the like; aliphatic hydrocarbons such as hexane, heptane in one step without via the compound IV by reacting the and the like; aromatic hydrocarbons such as benzene, toluene, compound II with a compound III in an appropriate Sol Xylene and the like; halogenated hydrocarbons such as 1.2- vent in the presence of an appropriate base. dichloroethane, chlorobenzene and the like; water, and mixed 0077. The amount of the compound III used in the reac solvents thereof. The use amount of the solvent is ordinarily tion is appropriately selected ordinarily in a range of 2 to 10 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 mol of eluivalents relative to 1 equivalent of the compound III and is the compound II. preferably 2 to 5 equivalents. US 2014/0288.184 A1 Sep. 25, 2014

0078. As the solvent and base usable in the reaction, there 0087. As the base usable in the reaction, there can be can be mentioned the same solvents and bases as mentioned mentioned, for example, inorganic bases such as alkali metal in the (step 1-1). The use amount of the solvent is ordinarily hydroxides (e.g. sodium hydroxide and potassium hydroxy 0.1 to 50 liters, preferably 0.2 to 3.0 liters relative to 1 mol of ide), alkali metal carbonates (e.g. sodium carbonate and the compound II. The use amount of the base is appropri potassium carbonate), alkali metal bicarbonates (e.g. sodium ately selected ordinarily in a range of to 20 equivalents rela hydrogencarbonate and potassium hydrogencarbonate) and tive to 1 equivalent of the compound III and is preferably 2 to the like. The use amount of the base is appropriately selected 10 equivalents. ordinarily in a range of 0.1 to 10 equivalents relative to 1 007.9 The reaction temperature of the reaction is ordi equivalent of the compound VIII and is preferably 0.1 to 2 narily any temperature from -20°C. to the reflux temperature equivalents. of the reaction system and is preferably -10°C. to 100° C. I0088 As the catalyst usable in the reaction, there can be 0080. The reaction time of the reaction differs depending mentioned, for example, quaternary ammonium salts such as upon the reaction temperature, the Substrate of reaction, the tetra-n-butylammoniumhydrogensulfate, tetra-nbutylammo nium bromide, tetra-n-butylammonium chloride and the like. amount of reaction, etc., but is ordinarily 1 to 48 hours. The use amount of the catalyst is appropriately selected ordi 0081. After the completion of the reaction, there are con narily in a range of 0.01 to 0.5 equivalent relative to 1 equiva ducted operations such as poring of water into reaction mix lent of the compound VIII and is preferably 0.01 to 0.1 ture, extraction with organic solvent, concentration and the equivalent. like, whereby the compound VI can be isolated. The iso I0089. The reaction temperature of the reaction is ordi lated compound VII can be purified as necessary by column narily any temperature from -50° C. to the reflux temperature chromatography, recrystallization, etc. of the reaction system and is preferably 0°C. to 100° C. 0090 The reaction time of the reaction differs depending Production Method 2 upon the reaction temperature, the Substrate of reaction, the 0082) Of the glyoxime derivatives represented by the gen amount of reaction, etc., but is ordinarily 1 to 48 hours. eral formula, the compound represented by the general for 0091 After the completion of the reaction, there are con mula VIII can be produced, for example, by the following ducted operations such as poring of water into reaction mix method. ture, extraction with organic solvent, concentration and the like, whereby the compound VIII can be isolated. The iso lated compound VIII can be purified as necessary by col Formula 4 umn chromatography, recrystallization, etc. 0092. The pest control agent of the present invention is CN characterized by containing, as an active ingredient, a gly oxime derivative represented by the general formula II or an R11 NN 21 No1 Aqueous H2O2 solution agriculturally acceptable salt thereof. The present pest control agent is representatively an insecticide. NH2 0093. Of the glyoxime derivatives represented by the gen VII eral formula II, the glyoxime derivatives represented by the HN O general formula II are novel compounds; and they and, as necessary, salts thereof are preferably used for pest control, On 2 N R2 particularly as insecticide. R11 NN 2 No1 0094. The present pest control agent may as necessary contain an additive component (carrier) ordinarily used in NH2 agricultural chemical formulations. VIII 0.095 As the additive component, there can be mentioned a carrier (e.g. Solid carrier or liquid carrier), a surfactant, a binder or a tackifier, a thickening agent, a coloring agent, a I0083 (In the formula, R' and R have the same meanings spreader, a sticker, an anti-freeze, a solidification inhibitor, a as given above.) disintegrator, a decomposition inhibitor, etc. As necessary, 0084. The compound VIII can be produced by reacting a there may be used other additive components such as antisep compound VIII with an aqueous hydrogen peroxide Solution tic, vegetable chip and the like. in the presence of an appropriate base. An appropriate catalyst 0096. These additive components may be used in one kind may be added in the production. or in combination of two or more kinds. The above additive 0085. The use amount of the aqueous hydrogen peroxide components are explained below. solution is appropriately selected in a range of 1.0 to 20.0 0097. As the solid carrier, there can be mentioned, for mols relative to 1 mol of the compound VIII and is preferably example, mineral carriers such as pyrophyllite clay, kaolin 1.0 to 6.0 mols. clay, silicastone clay, talc, diatomaceous earth, Zeolite, ben I0086. In the reaction, a solvent may be used as necessary. tonite, acid clay, active clay, Attapulgus clay, Vermiculite, As the solvent usable, there can be mentioned, for example, perlite, pumice, white carbon (e.g. synthetic silicic acid or alcohols such as methanol, ethanol propanol and the like; synthetic silicate), titanium dioxide and the like; vegetable halogenated hydrocarbons such as chloroform, dichlo carriers such as wood flour, corn culm, walnut shell, fruit romethane and the like; Sulfur compounds such as dimethyl stone, rice hull, sawdust, wheat bran, soybean flour, powder sulfoxide, sulfolane and the like; water; and mixtures thereof. cellulose, starch, dextrin, saccharide and the like; inorganic The amount of the solvent is ordinarily 0.1 to 50 liters, pref salt carriers such as calcium carbonate, ammonium Sulfate, erably 0.2 to 3 liters relative to 1 mol of the compound VIII. Sodium Sulfate, potassium chloride and the like; and polymer US 2014/0288.184 A1 Sep. 25, 2014 carriers such as polyethylene, polypropylene, polyvinyl chlo diaminoethylbetaine or alkyldimethylbenzylbetaine), amino ride, polyvinyl acetate, ethylene-vinyl acetate copolymer, acid type (e.g. dialkylaminoethylglycine or alkyldimethyl urea-aldehyde resin and the like. benzylglycine) and the like. 0100. As the binder and tackifier, there can be mentioned, 0098. As the liquid carrier, there can be mentioned, for for example, carboxymethyl cellulose or a salt thereof, dex example, monohydric alcohols such as methanol, ethanol, trin, water-soluble starch, Xanthane gum, guar gum, Sucrose, propanol, isopropanol, butanol, cyclohexanol and the like; polyvinylpyrrolidone, gum arabi, polyvinyl alcohol, polyvi polyhydric alcohols such as ethylene glycol, diethylene gly nyl acetate, Sodium polyacrylate, polyethylene glycol having col, propylene glycol, hexylene glycol, polyethylene glycol, an average molecular weight of 6,000 to 20,000, polyethylene polypropylene glycol, glycerine and the like; polyhydric oxide having an average molecular weight of 100,000 to alcohol derivatives such as propylene-type glycol ether and 5,000,000, and natural phospholipid (e.g. cephalinic acid or the like; ketones such as acetone, methyl ethyl ketone, methyl lecithin). isobutyl ketone, disobutyl ketone, cyclohexanone, isophor 0101. As the thickening agent, there can be mentioned, for one and the like; ethers such as ethyl ether, dioxane, cello example, water-soluble polymers such as Xanthan gum, guar solve, dipropyl ether, tetrahydrofuran and the like: aliphatic gum, carboxymethyl cellulose, polyvinylpyrrolidone, car hydrocarbons such as normal paraffin, naphthene, isoparaf boxyvinyl polymer, acrylic polymer, starch derivative, fin, kerosene, mineral oil and the like; aromatic hydrocarbons polysaccharide and the like; and inorganic fine powders such Such as toluene, Co-Co alkylbenzene, Xylene, solvent naph as high-purity bentonite, white carbon and the like. tha, alkylnaphthalene, high-boiling aromatic hydrocarbon 0102. As the coloring agent, there can be mentioned, for and the like; halogenated hydrocarbons such as dichloroet example, inorganic pigments such as iron oxide, titanium hane, chloroform, carbon tetrachloride and the like; esters oxide, Prussian Blue and the like; and organic dyes Such as Such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate, Alizarine dye, azo dye, metal phthalocyanine dye and the dioctyl phthalate, dimethyl adipate and the like; lactones Such like. as Y-butyrolactone and the like; amides Such as dimethylfor 0103) As the spreader, there can be mentioned, for example, silicone-based surfactant, cellulose powder, dex mamide, diethylformamide, dimethylacetamide, N-alkylpyr trin, processed starch, polyaminocarboxylic acid chelate rolidinone and the like: nitriles such as acetonitrile and the compound, crosslinked polyvinylpyrrolidone, maleic acid like: Sulfur compounds such as dimethyl sulfoxide and the and styrene, methacrylic acid copolymer, half ester between like; vegetable oils such as soybean oil, rapeseed oil, cotton polyhydric alcohol polymer and dicarboxylic acid anhydride, seed oil, coconut oil, castor oil and the like; and water. and water-soluble salt of polystyrenesulfonic acid. 0099. As to the surfactant, there is no particular restriction. 0104. As the sticker, there can be mentioned, for example, However, the surfactant preferably gels or swells in water. Surfactant (e.g. sodium dialkylsulfoSuccinate, polyoxyethyl There can be mentioned, for example, non-ionic Surfactants ene alkyl ether, polyoxyethylene alkylphenyl ether, or poly Such as Sorbitan fatty acid ester, polyoxyethylene Sorbitan oxyethylene fatty acid ester), paraffin, terpene, polyamide fatty acid ester, Sucrose fatty acid ester, polyoxyethylene fatty resin, polyacrylic acid salt, polyoxyethylene, wax, polyvinyl acid ester, polyoxyethylene resin acid ester, polyoxyethylene alkyl ether, alkylphenol-formalin condensate, and synthetic fatty acid diester, polyoxyethylene alkyl ether, polyoxyethyl resin emulsion. enealkylphenyl ether, polyoxyethylene dialkylphenyl ether, 0105. As the anti-freeze, there can be mentioned, for polyoxyethylene alkylphenyl ether-formalin condensate, example, polyhydric alcohol (e.g. ethylene glycol, diethyl polyoxyethylene polyoxypropylene block polymer, alkyl lene glycol, propylene glycol, or glycerine). polyoxyethylene polypropylene block polymer ether, poly 0106. As the solidification inhibitor, there can be men oxyethylene alkyl amine, polyoxyethylene fatty acid amide, tioned, for example, polysaccharide (e.g. starch, alginic acid, polyoxyethylene fatty acid bisphenyl ether, polyalkylene mannonse orgalactose), polyvinylpyrrolidone, white carbon, benzyl phenyl ether, polyoxyalkylene styryl phenyl ether, ester gum and petroleum resin. acetylene diol, polyoxyalkylene-added acetylene diol, poly 0107 As the disintegrator, there can be mentioned, for oxyethylene ether type silicone, ester type silicone, fluorine example, sodium tripolyphosphate, sodium hexametaphos containing Surfactant, polyoxyethylene castor oil, polyoxy phate, Stearic acid metal salt, cellulose powder, dextrin, meth ethylene hardened castor oil and the like; anionic Surfactants acrylic acid ester copolymer, polyvinylpyrrolidone, polyami Such as alkyl Sulfate, polyoxyethylene alkyl ether Sulfate, nocarboxylic acid chelate compound, Sulfonated Styrene polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene isobutylene-maleic anhydride copolymer, and styryl phenyl ether sulfate, alkylbenzenesulfonic acid salt, starchpolyacrylonitrile graft copolymer. ligninsulfonic acid salt, alkylsulfo Succinic acid salt, naphtha 0108. As the decomposition inhibitor, there can be men lenesulfonic acid salt, alkylnaphthalenesulfonic acid salt, tioned, for example, desiccants such as Zeolite, quick lime, naphthalenesulfonic acid-formalin condensate salt, alkyl magnesium oxide and the like; antioxidants such as phenol naphthalenesulfonic acid-formalin condensate salt, fatty acid type, amine type, Sulfur type, phosphoric acid type and the salt, polycarboxylic acid salt, N-methyl-fatty acid sarcosi like; and ultraviolet absorbents such as Salicylic acid type, nate, resin acid salt, polyoxyethylene alkyl ether phosphate, benzophenone type and the like. polyoxyethylene alkylphenyl ether phosphate and the like: 0109 When the present pest control agent contains the cationic Surfactants including alkyl amine salts such as lau above-mentioned additive components, their contents based rylamine hydrochloride, stearylamine hydrochloride, oley on mass are selected in a range of ordinarily 5 to 95%, pref lamine hydrochloride, Stearylamine acetate, Stearylamino erably 20 to 90% in the case of carrier, ordinarily 0.1 to 30%, propylamine acetate, alkyl trimethyl ammonium chloride, preferably 0.5 to 10% in the case of surfactant, and ordinarily alkyl dimethyl benzalkonium chloride and the like; and 0.1 to 30%, preferably 0.5 to 10% in the case of other addi ampholytic Surfactants such as betaine type (e.g. dialkyl tives. US 2014/0288.184 A1 Sep. 25, 2014

0110. The present pest control agent is used in any formu 0.126 Below are shown examples of the known insecticide lation selected from dust formulation, dust-granule mixture, compounds, acaricide compounds, nematicide compounds granule, wettable powder, water-soluble concentrate, water and synergist compounds, which may be mixed or used in dispersible granule, tablet, Jumbo, emulsifiable concentrate, combination. However, other Such compounds may be mixed oil formulation, Solution, flowable concentrate, emulsion, or used in combination. microemulsion, Suspoemulsion, ultra-low Volume formula tion, microcapsule, Smoking agent, aerosol, baiting agent, 1. Acetylcholinesterase Inhibitors paste, etc. I0127 (1A) Carbamates: alanycarb, aldicarb, aldoxycarb, 0111. In actual use of the formulation, the formulation can bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, be used perse or after dilution with a diluent (e.g. water) in a carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, given concentration. The application of the formulations con formetanate, furathiocarb, isoprocarb, methiocarb, meth taining the present compound or of its dilution product can be omyl, metolcarb, oxamyl, pirimicarb, propoXur, thiodicarb, conducted by a method ordinarily used, such as dispersion thiofanox, triazamate, trimethacarb. XMC, xylylcarb: (e.g. spraying, misting, atomizing, powder dispersion, gran I0128 (1B) Organophosphates: acephate, azamethiphos, ule dispersion, on-water-Surface dispersion, or in-box disper azinphosethyl, azinphos-methyl, cadusafos, chlorethoxyfos, sion), in-soil application (e.g. mixing or drenching), on-sur chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifosm face application (e.g. coating, dust coating or covering). ethyl, coumaphos, cyanophos, demotion-5-methyl, diami immersion, poison bait, Smoking and the like. It is also pos dafos, diazinon, dichlorvos, dicrotophos, dimethoate, dim sible to mix the above-mentioned active ingredient with a ethylvinphos, dioxabenzofos, disulfoton, DSP, EPN, ethion, livestock feed in order to prevent the infestation and growth of ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, injurious pest, particularly injurious in the excreta of fenthion, fonofos, fosthiazate, fosthietan, heptenophos, isa livestock. midofos, isaZophos, isofenphos-methyl, isopropyl O-(meth 0112 The proportion of the active ingredient in the present oxyaminothio-phosphoryl)salicylate, isoxathion, malathion, pest control agent is appropriately selected so as to meet the mecarbam, methamidophos, methidathion, mevinphos, necessity. The active ingredient is appropriately selected, for monocrotophos, naled, omethoate, Oxydemeton-methyl, example, in the following range. In dust formulation, dust Oxydeprofos, parathion, parathion-methyl, phenthoate, phor granule mixture, etc. ate, phosalone, phosmet, phosphamidon, phoxim, pirimi 0113 0.01 to 20% (mass), preferably 0.05 to 10% (mass) phos-methyl, profenofos, propaphos, propetamphos, prothio In granule, etc. fos, pyraclofos, pyridaphenthion, quinallphos, sulfotep, 0114 0.1 to 30% (mass), preferably 0.5 to 20% (mass) In tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiome wettable powder, water dispersible granule, etc. ton, thionazin, triaZophos, trichlorfon, Vamidothion, dichlo 0115 1 to 70% (mass), preferably 5 to 50% (mass) In fenthion, imicyafos, isocarbophos, mesulfenfos, fluprazofoS water-soluble concentrate, solution, etc 1-95% (mass), pref erably 10 to 80% (mass) In emulsifiable concentrate, etc. 2. GABA-Gated Chloride Channel Antagonists 0116 5 to 90% (mass), preferably 10 to 80% (mass) In oil I0129 (2A) Cyclodiene organochlorines: chlordane, formulation, etc. endosulfan, gamma-BCH; 0117. 1 to 50% (mass), preferably 5 to 30% (mass) In 0.130 (2B) Phenylpyrazoles: acetoprol, ethiprole, fipronil, flowable concentrate, etc. pyrafluprole, pyriprole, RZI-02-003 (code number), 0118 5 to 60% (mass), preferably 10 to 50% (mass) In flufiprole emulsion, microemulsion, Suspoemulsion, etc. 0119) 5 to 70% (mass), preferably 10 to 60% (mass) In 3. Sodium Channel Modulators tablet, baiting agent, paste, etc. 0120 1 to 80% (mass), preferably 5 to 50% (mass) In I0131 (3A) Pyrethroids/Pyrethrins: acrinathrin, allethrin Smoking agent, etc. (includes d-cis-trans and d-trans), bifenthrin, bioallethrin, 012 1 0.1 to 50% (mass), preferably 1 to 30% (mass) In bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, aerosol, etc. cyfluthrin (includes beta-), cyhalothrin (includes gamma- and lambda-), cypermethrin (includes alpha-, beta-, theta- and 0122 0.05 to 20% (mass), preferably 0.1 to 10% (mass) Zeta-), cyphenothrin includes (1R)-trans-isomers, delta 0123. The formulation is sprayed after dilution in an methrin, empenthrin, esfenvalerate, etofemproX, fempropath appropriate concentration, or applied directly. rin, fenvalerate, flucythrinate, flumethrin, tauflu valinate (in 0.124 When the present pest control agent is used after cludes tau-), halfenproX, imiprothrin, metofluthrin, dilution with a diluent, the concentration of active ingredient permethrin, phenothrin includes (1R)-transisomer, pral is generally 0.1 to 5,000 ppm. When the formulation is used lethrin, profluthrin, pyrethrine, resmethrin, RU15525 (code per se, the application amount thereof per unit area is 0.1 to number), silafluofen, tefluthrin, tetramethrin, tralomethrin, 5,000 g per 1 ha in terms of active ingredient compound; transfluthrin, ZX18901 (code number), fluvalinate, tetram however, the application amount is not restricted thereto. ethylfluthrin, meperfluthrin, heptafluthrine; 0.125 Incidentally, the present pest control agent is suffi (0132 (3B) DDT/Methoxychlor: DDT, methoxychlor ciently effective when using the present compound alone as an active ingredient. However, in the present pest control 4. Nicotinic Acetylcholine Receptor Agonist/Antagonist agent, there may be mixed or used in combination, as neces sary, fertilizers and agricultural chemicals such as insecticide, 0.133 (4A) Neonicotinoids: acetamiprid, clothianidin, acaricide, nematicide, Synergist, fungicide, anti-viral agent, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thia attractant, herbicide, plant growth-controlling agent and the methoxam; like. In this case, a higher effect is exhibited. 0.134 (4B) Nicotine: nicotine-sulfate US 2014/0288.184 A1 Sep. 25, 2014

5. Nicotinic Acetylcholine Receptor Allosteric Activators 20. Mitochondrial Complex III Electron Transport Inhibitors 0135 Spinosyns: Spinetoram, Spinosad 0151 hydramethylnon, aceduinocyl, fluacrypyrim, pyriminostrobin 6. Chloride Channel Activators 0.136 Avermectins, Milbemycins: abamectin, emamectin 21. Mitochondrial Complex II Electron Transport Inhibitors benzoate, lepimectin, milbemectin, ivermectin, polynactins 0152 cyflumetofen, cyenoprafen, pyflubumide 7. Juvenile Hormone Mimics 22. Mitochondrial Complex I Electron Transport Inhibitors 0.137 diofenolan, hydroprene, kinoprene, methothrin, 0153 METI acaricides and insecticides: fenazaquin, fen fenoxycarb, pyriproxyfen pyroximate, pyridaben, pyrimidifen, tebufenpyrad, tolfen pyrad 8. Miscellaneous Non-Specific (Multi-Site) Inhibitors 0154) Other: rotenone 0138 1,3-dichloropropene, DCIP, ethylene dibromide, 23. Sodium Channel Blockers methyl bromide, chloropicrin, sulfuryl fluoride 0.155 indoxacarb, metaflumizone 9. Antifeedant 24. Inhibitors of Lipid Synthesis 0139 pymetrozine, flonicamid 0156 Tetronic and Tetramic acid derivatives: spirodi 10. Mite Growth Inhibitors clofen, spiromesifen, spirotetramat 25. Mitochondrial Com plex IV Electron Transport Inhibitors 0140 clofentezine, diflovidazin, hexythiazox, etoxazole 0157 aluminium phosphide, phosphine, Zinc phosphide, calcium cyanide 11. Microbial Disruptors of Insect Midgut Membranes 0141 BT agents: Bacillus sphaericus, Bacillus thuring 26. Neuronal Inhibitors (Unknown Mode of Action) iensis Subsp. aizawai, Bacillus thuringiensis Subsp. israelen 0158 bifenazate sis, Bacillus thuringiensis Subsp. kurstaki, Bacillus thuring iensis subsp. tenebrionis, Bt crop proteins (Cry1Ab, Cry1Ac, 27. Aconitase Inhibitors Cry1 Fa, Cry2Ab, mCry3A, Cry3 Ab, Cry3Bb, Cry34/ 35Ab1), Bacillus popilliae, Bacillus subtillis 0159 sodium fluoroacetate 28. Synergists 12. Inhibitors of Mitochondrial ATP Synthase (0160 piperonylbutoxide, DEF 0142 diafenthiuron; 0143 Organotin miticides: azocyclotin, cyhexatin, fenb 29. Ryanodine Receptor Modulators utatin oxide; 0144 propargite, tetradifon 13. Uncouplers of Oxidative 0.161 chlorantraniliprole, flubendiamide, cyantraniliprole Phosphorylation Via Disruption of the Proton Gradient 30. Compounds with Unknown Mode of Action (0162 azadirachtin, amidoflumet, benclothiaz, benzoxi (0145 chlorfeinapyr, DNOC mate, bromopropylate, chinomethionat, CL900167 (code 14. Nicotinic Acetylcholine Receptor Channel Blockers number), cryolite, dicofol, dicyclanil, dienochlor, dinobuton, fenbutatin oxide, fenothiocarb, fluensulfone, flufenerim, full 0146 Nereistoxin analogues: benSultap, cartap, thiocy Sulfamide, karanjin, metham, methoprene, methoxyfenozide, clam, thiosultap methyl isothiocyanate, pyridalyl pyrifluquinazon, Sulcofu ron-sodium, sulfluramid, sulfoxaflor, flupyradifurone, flom 15. Inhibitors of Chitin Biosynthesis, Type 0 etoquin, IKI-3106 (code number), afidopyropen, rescalure, 0147 Benzoylureas: bistrifluoron, chlorfluaZuron, NA-85 (code number) diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, 31. Entomopathogenic Fungi, Nematode-Pathogenic lufenuron, novaluron, noviflumuron, teflubenzuron, triflu Microorganisms muron, fluaZuron (0163 Beauveria bassiana, Beauveria tenella, Verticillium 16. Inhibitors of Chitin Biosynthesis, Type 1 Buprofezin lecanii, Pacilimyces tenuipes, Paecilomyces filmOsOroceus, Beauveria brongniartii, Monacrosporium phymatophagum, 17. Moulting Disruptor, Dipteran Pasteuriapenetrans 0148 cyromazine 32. Sex Pheromone 18. Ecdysone Receptor Agonist (Ecdysis Acceleration) 0164 (Z)-11-hexadecenal, (Z)-11-hexadecenyl acetate, litlure-A, litlure-B, Z-13-eicosene-10-one, (Z.E)-9,12-tet 0149 Diacylhydrazines: chromafenozide, halofenozide, radecadienyl acetate, (Z)-9-tetradecen-1-ol, (Z)-11-tetrade methoxyfenozide, tebufenozide cenyl acetate, (Z)-9,12-tetradecadienyl acetate, (Z.E)-9,11 19. Octopamine Receptor Agonist detradecadienyl acetate 0.165 Below are shown examples of the known fungicide 0150 amitraz or disease damage control agent compounds which may be US 2014/0288.184 A1 Sep. 25, 2014

mixed or used in combination. However, other such com 5. Signal Transduction Inhibitors pounds may be mixed or used in combination. 0203 Aryloxyquinoline: quinoxyfen; 0204 Quinazolines: produinazid: 1. Nucleic Acid Biosynthesis Inhibitors 0205 Phenylpyrroles: fempiclonil, fludioxonil; 0166 Acylalanines: benalazyl, benalazyl-M, furalaxyl, 0206 Dicarboxylmides: chlozolinate, iprodione, pro metalaxyl, metalaxyl-M; cymidone, VincloZolin 0167 Oxazolidinones: oxadixyl; 0168 Butyrolactones: clozylacon, ofurace; 6. Lipid Synthesis and Membrane Integrity Inhibitors 0169 Hydroxy-(2-amino)pyrimidines: bupirimate, dime 0207 Phosphoro-thiolates: edifenphos, iprobenfos, pyra thirimol, ethirimol; Zophos: 0170 Isoxazoles: hymexazol; 0208 Dithiolanes: isoprothiolane; 0171 Isothiazolones: octhillinone: 0209 Aromatic hydrocarbons: biphenyl, chloroneb, 0172 Carboxylic acids: oxolinic acid dicloran, quintoZenes, tecnaZene, tolclofoS-methyl; 0210 1,2,4-Thiadiazoles: etridiazole 2. Mitosis and Cell Division Inhibitors 0211 Carbamates: iodocarb, propamocarb-hydrochlo (0173 Benzoimidazoles: benomyl. carbendazim, ride, prothiocarb: fuberidazole, 0212 Cinnamic acid amides: dimethomorph, flumorph; 0.174 thiabendazole; 0213 Valineamide carbamates: benthiavalicarb-isopro 0.175. Thiophanates: thiophanate, thiophanate-methyl: pyl, iprovalicarb. Valifenalate; 0176 N-phenylcarbamates: diethofencarb: 0214. Mandelic acid amides: mandipropamid; 0177 Toluamides: Zoxamide: 0215 Bacillus subtilis and the fungicidal lipopeptides 0.178 Phenylureas: pencycuron; produced: Bacillus subtilis (strain: QST 713) (0179 Pyridinylmethylbenzamides: fluopicolide 7. Inhibitors of Sterol Biosynthesis in Membranes 3. Respiratory Inhibitors 0216 piperazines: triforine; 0180 Pyrimidinamines: diflumetorim; 0217 Pyridines: pyrifenox; 0181 Carboxamides: benodanil, flutolanil, mepronil, flu 0218. Pyrimidines: fenarimol, nuarimol; opyram, fenfuram, carboxin, oxycarboxin, thifluZamide, bix 0219. Imidazoles: imazalil, oxpoconazole-fumarate, afen, furametpyr, isopyrazam, penflufen, penthiopyrad, pefurazoate, prochloraZ, triflumizole; sedaxane, boScalid, fluxapyroxad, isofetamid, benzovindif 0220 Triazoles: azaconazole, bitertanol, bromuconazole, lupyr; cyproconazole, difenoconazole, diniconazole, diniconazole 0182 Methoxy-acrylates: azoxystrobin, enestroburin, M, epoxiconazole, etaconazole, fenbuconazole, fluquincona picoxystrobin, pyraoxystrobin, coumoxystrobin, enxas Zole, flusilaZole, flutriafol, hexaconazole, imibenconazole, trobin, flufenoxystrobin; ipconazole, metconazole, myclobutanil, penconazole, propi 0183 Methoxy-carbamates: pyraclostrobin, pyrameto conazole, prothioconazole, Simeconazole, tebuconazole, tet strobin, triclopyricarb: raconazole, triadimefon, triadimenol, triticonazole, furcona 0184 Oxyimino acetates: kresoxim-methyl, triflox Zole, furconazole-cis, quinconazole; ystrobin: 0221 Morpholines: aldimorph, dodemorph, fenpropi 0185. Oxyimino-acetamides: dimoxystrobin, metominos morph, trobin, orysastrobin, fenaminstrobin; 0222 tridemorph; 0186 Oxazolidine-diones: famoxadone: 0223 Piperidines: fempropidin, piperalin; 0187 Dihydro-dioxazines: fluoxastrobin; 0224 Spiroketal amines: spiroxamine; 0188 Imidazolinones: fenamidone; 0225 Hydroxyanilides: fenhexamid; 0189 Benzyl-carbamates: pyribencarb; 0226. Thiocarbamates: pyributicarb: 0190. Cyano-imidazoles: cyazofamid: 0227 Allylamines: naftifine, terbinafine 0191 Sulfamoyl-triazoles: amisulbrom; 0.192 Dinitrophenyl crotonates: binapacryl, methyldi 8. Glucan Synthesis Inhibitors nocap, dinocap: 0228 Glucopyranosyl type antibiotic: validamycin; 0193 2,6-Dinitro-anilines: fluazinam; 0229 Peptidylpyridine nucleotide compound: polyoxin 0194 Pyrimidinone hydrazones: ferimzone: (0195 Triphenyl tin compounds: TPTA, TPTC, TPTH: 9. Melanine Synthesis Inhibitors 0196. Thiophene-carboxamides: silthiofam; 0230 Isobenzo-furanones: phthalide; 0.197 Triazolo-pyrimidylamines: ametoctradin 0231. Pyrrolo-quinolines: pyroquilon; 0232 Triazolobenzo-thiazoles: tricyclazole; 4. Amino Acid and Protein Synthesis Inhibitors 0233 Carboxamides: carpropamid, diclocymet: 0198 Anilino-pyrimidines: cyprodinil, mepanipyrim, 0234 Propionamides: fenoxanil pyrimethanil; 0199 Enopyranuronic acid antibiotic: blasticidin-S, mil 10. Host Plant Defence Inducers diomycin; 0235 Benzo-thiadiazoles: acibenzolar-5-methyl: 0200 Hexopyranosyl antibiotic: kasugamycin; 0236 BenZoisothiazoles: probenazole; 0201 Glucopyranosyl antibiotic: streptomycin; 0237. Thiadiazole-carboxamides: tiadinil, isotianil 0202 Tetracycline antibiotic: oxytetracycline 0238 Natural compound: laminarin US 2014/0288.184 A1 Sep. 25, 2014

11. Compounds with Unknown Mode of Action iodosulfulon-methyl-Sodium, mesosulfuron-methyl, thifen 0239 Copper compound: copper hydroxide, copper dio sulfuronmethyl, triasulfuron, tribenuron-methyl, trifloxysul ctanoate, copper oxychloride, copper Sulfate, cuprous oxide, furonsodium, triflusulfuron-methyl, tritosulfuron, orthosul oxine-copper, Bordeaux mixture, copper nonyl phenol Sul famuron, propyrisulfuron, metazosulfuron, flucetosulfuron; phonate; 0255 (B-5) Triazolopyrimidines: cloransulam-methyl, 0240 Sulfur compound: sulfur, dicloSulam, florasulam, flumetSulam, metoSulam, penoXSu 0241 Dithiocarbamates: ferbam, mancozeb, maneb, lam, pyroxSulam; metiram, propineb, thiram, Zineb, Ziram, cufraneb; 0242 Phthalimides: captan, folpet, captafol; C1. Photosynthesis at Photosystem II Inhibitors (1) 0243 Chloronitriles: chlorothalonil; 0256 (C1-1) Phenyl-carbamates: desmedipham, phenme 0244 Sulfamides: dichlofluanid, tolylfluanid; dipham; 0245 Guanidines: guazatline, iminoctadine-albesilate, 0257 (C1-2) Pyridazinones: chloridazon, brompyrazon: iminoctadine-triacetate, dodine; 0258 (C1-3) Triazines: ametryn, atrazine, cyanazine, des 0246. Other compound: anilazine, dithianon, cymoxaniil, metryne, dimethametryn, eglinazine-ethyl, prometon, prom fosetyl (alminium, calcium, sodium), phosphorus acid and etryn, propazine, Simazine, simetryn, terbumeton, terbuthy salts, tecloftalam, triaZoxide, flusulfamide, diclomeZine, lazine, terbutryn, trietazine; methasulfocarb, ethaboxam, cyflufenamid, metrafenone, 0259 (C1-4) Triazinones: metamitron, metribuzin; potassium bicarbonate, sodium bicarbonate, BAF-045 (code 0260 (C1-5) Triazolinones: amicarbazone: number), BAG-010 (code number), benthiazole, bronopol, 0261 (C1-6) Uracils: bromacil, lenacil, terbacil; carvone, chinomethionat, dazomet, DBEDC, debacarb, dichlorophen, difenzoquat-methyl sulfate, dimethyl disul C2. Photosynthesis at Photosystem II Inhibitors (2) fide, diphenylamine, ethoxyquin, flumetover, fluoroimide, flutianil, furancarboxylic acid, metam, nabam, natamycin, 0262 (C2-1) Amides: pentanochlor, propanil; nitrapyrin, nitrothal-isopropyl, o-phenylphenol, oxazinyla 0263) (C2-2) Ureas: chlorbromuron, chlorotoluron, Zole, oxyquinoline Sulfate, phenazine oxide, polycarbamate, chloroXuron, dimefuron, diuron, ethidimuron, fenuron, flu pyriofenone, fenpyraZamine, silver, pyrisoxazole, tebuflo ometuron, isoproturon, isouron, linuron, methabenzthiaZu quin, tolnifanide, trichlamide, mineral oils, organic oils, tol ron, metobromuron, metoxuron, monolinuron, neburon, procarb, oxathiapiprolin siduron, tebuthiuron, metobenzuron; 0247 Below are shown examples of the known herbicidal compounds and plant growth-controlling compounds which C3. Photosynthesis at Photosystem II Inhibitors (3) may be mixed or used in combination. However, the com 0264 (C3-1) Benzothiadiazones: bentazone; pounds are not restricted to these examples. 0265 (C3-2) Nitriles: bromofenoxim, bromoxynil (in cludes esters of butyric acid, octanoic acid, heptanoic acid, A1. Acetyl CoA Carboxylase (ACCase) Inhibitors etc.), ioxynil; 0266 (C3-3) Phenylpyrazines: pyridafol, pyridate; 0248 (A1-1) Aryloxyphenoxy propionate: clodinafop propargyl, cyhalofop-butyl, diclofop-methyl, diclofop-P-me D. Photosystem-1-Electron Acceptors thyl, fenoxaprop-P-ethyl, fluazifop-butyl, fluazifop-P-butyl, haloxyflop, haloxyflop-etotyl, haloxyfop-P, metamifop, pro 0267 (D-1) Bipyridyliums: diguat, paraquat dichloride; paquizafop, quizalofop-ethyl, quizalofop-P-ethyl, quizalo E. Protoporphyrinogen oxidase (PPO) inhibitors fop-P-tefuryl, fenthiaprop-ethyl: 0268 (E-1) Diphenylethers: acifluorfen-sodium, bifenox, 0249 (A1-2) Cyclohexandiones: alloxydim, butroxydim, chlomethoxyfen, ethoxyfen-ethyl, fluoroglycofen-ethyl, clethodim, cycloxydim, profoxydim, Sethoxydim, tepraloxy fomesafen, lactofen, oxyfluorfen: dim, tralkoxydim; 0269 (E-2) N-phenylphthalimides: cinidon-ethyl, flumi 0250 (A1-3) Phenylpyrazolines: Aminopyralid, Pinoxa cloracpentyl, flumioxazin, chlorphthalim, den; 0270 (E-3) Oxydiazoles: oxadiargyl, oxadiazon: 0271 (E-4) Oxazolidinediones: pentoxazone: B. Acetolactic Synthase (ALS) Inhibitors 0272 (E-5) Phenylpyrazoles: fluazolate, pyraflufen-ethyl: 0251 (B-1) Imidazolinones: imazamethabenz-methyl, 0273 (E-6) Pyrimidinediones: benzfendizone, imaZamox, imazapic (includes salts with amine, etc.), imaza butafenacil, saflufenacil; pyr (includes salts with isopropylamine, etc.), imaZaquin, 0274 (E-7) Thiadiazoles: fluthiacet-methyl, thidiazimin: imazathapyr; 0275 (E-8) Triazolinones: azafenidin, carfentraZone 0252 (B-2) Pyrimidinyloxy benzoate: bispyribac-so ethyl, SulfentraZone, bencarbazone; dium, pyribenzoxim, pyriftalid, pyriminobac-methyl, 0276 (E-9) Other compound: flufenpyr-ethyl, profluaZol, pyrithiobacsodium, pyrimisulfan, triafamone; pyraclonil, SYP-298 (code number), SYP-300 (code num 0253 (B-3) Sulfonylaminocarbonyl-triazolinones: flucar ber): baZonesodium, thiencarbazone (includes Sodium salt, methyl ester, etc.), propoxycarbazone-sodium, procarbazone-so F1. Inhibitors of Carotenoid Biosynthesis at the Phytoene dium, iofensulfuran-Sodium; Desaturase Step (PDS) 0254 (B-4) Sulfonylureas: amidosulfuron, azimsulfuron, (0277 (F1-1) Pyridazinones: norflurazon: bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cino 0278 (F1-2) Pyrimidinecarboxamides: diflufenican, Sulfuron, cyclosulfamuron, ethametSulfuron-methyl, ethox picolinafen; ySulfuron, flaZaSulfuron, flupyrsulfuron-methyl-Sodium, (0279 (F1-3) Other compound: beflubutamid, fluridone, foramsulfuron, halosulfuron-methyl, imaZoSulfuron, fluorochloridone, flurtamone; US 2014/0288.184 A1 Sep. 25, 2014 14

0280 F2. 4-Hydroxyphenylpyruvate dioxygenase M. Uncouplers (Membrane Disruptors) (HPPD) inhibitors 0281 (F2-1) Callistemones: mesotrione; (0305 (M-1) Dinitrophenols: dinoterb, DNOC (includes 0282 (F2-2) Isoxazoles: pyrasulfotole, isoxaflutole, isox salts of amine, Sodium, etc.); achlortole; 0283 (F2-3) Pyrazoles: benzfenap, pyrazolynate, pyra N. Lipid Synthesis Inhibitors (Excluding ACCase Inhibitors) ZOxyfen, toprameZone; 0306 (N-1) Benzofurans: benfuresate, ethofumesate: 0284 (F2-4) Ttiketones: sulcotrione, tefuryltrion, tembot 0307 (N-2) Halogenated carboxylic acids: dalapon, flu rione, pyrasulfotole, bicyclopyrone; propanate, TCA (includes salts of sodium, calcium, ammo nia, etc.); F3. Carotinoid Biosynthesis Inhibitors (Unknown Target) (0308 (N-3) Phosphorodithioates: bensulide; 0285 (F3-1) Diphenylethers: aclonifen; 0309 (N-4) Thiocarbamates: butylate, cycloate, dimepip 0286 (F3-2) Isoxazolidinones: clomazone: erate, EPTC, esprocarb, molinate, orbencarb, pebulate, pro (0287 (F3-3) Triazoles: amitrole; sulfocarb, thiobencarb, tiocarbazil, tri-allate, vernolate G. EPSP Synthase Inhibitors (Aromatic Amino Acid O. Synthetic Auxins Biosynthesis Inhibitors) 0310 (O-1) Benzoic acids: chloramben, 2.3.6-TBA, 0288 (G-1) Glycines: glyphosate (includes salts of dicamba (includes salts of amine, diethylamine, isopropy Sodium, amine, propylamine, ispropylamine, dimethylamine, lamine, diglycolamine, sodium, lithium, etc.); trimesium etc.); 0311 (O-2) Phenoxycarboxylic acids: 2,4,5-T 2,4-D (in cludes salts of amine, diethylamine, triethanolamine, isopro H. Glutamine Synthetase Inhibitors pylamine, Sodium, lithium, etc.), 2,4-DB, clomeprop, dichlo 0289 (H-1) Phosphinic acids: bilanafos, glufosinate (in rprop, dichlorprop-P, MCPA, MCPA-thioethyl, MCPB cludes salts of amine, Sodium, etc.); (includes Sodium salt, ethylester, etc.), mecoprop (includes salts of Sodium, potassium, isopropylamine, trietanolamine, I. Dihydropteroate (DHP) Inhibitors dimethylamine, etc.), mecoprop-P; 0312 (O-3) Pyridine carboxylic acids: clopyralid, flu 0290 (1-1) Carbamates: asulam; oroxypyr, picloram, triclopyr, triclopyr-butotyl; K1. Microtubule Assembly Inhibitors 0313 (O-4) Quinoline carbxylic acids: quinclorac, quin 0291 (K1-1) Benzamides: propyZamide, tebutam; merac, 0292 (K1-2) Benzoic acids: chlorthal-dimethyl: 0314 (O-5) Other compound: benazolin; 0293 (K1-3) Dinitroanilines: benfluralin, butralin, dinit ramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, P. Auxin Transport Inhibitors prodiamine, trifluralin; 0315 (P-1) Phthalamates: naptalam (includes salts with 0294 (K1-4) Phosphoroamidates: amiprofos-methyl, Sodium, etc.); butamifos; 0316 (P-2) Semicarbazones: diflufenzopyr; 0295 (K1-5) Pyridines: dithiopyr, thiazopyr; Z. Compounds with Unknown Mode of Action flamprop-M (includes methyl, ethyl and isopropyl esters), flamprop (in K2. Inhibitors of Mitosis/Microtubule Organization cludes methyl, ethyl and isopropyl esters), chlorflurenol-me 0296 (K2-1) Carbamates: carbetamide, chlorpropham, thyl, cinmethylin, cumyluron, daimuron, methyldymuron, propham, Swep, karbutilate: difenZoquat, etobenzanid, fosamine, pyributicarb, oxazi clomefone, acrolein, AEF-150944 (code number), aminocy K3. Very-Long-Chain Fatty Acids (VLCFAs) Inhibitors (Cell clopyrachlor, cyanamide, heptamaloxyloglucan, indaziflam, Division Inhibitors) triaziflam, quinoclamine, endothaldisodium, phenisopham, 0297 (K3-1) Acetamides: diphenamid, napropamide, SL-573 (code number), SW-065 (code number) naproanilide; 0317 Plant growth-controlling agent: 1-methylcyclopro 0298 (K3-2) Chloroacetamides: acetochlor, alachlor, pene, 1-naphthylacetamide, 2,6-diisopropylnaphthalene, butachlor, butenachlor, diethatyl-ethyl, dimethachlor, 4-CPA, benzylaminopurine, ancymidol, aviglycine, carvone, dimethenamid, dimethenamid-P, metaZachlor, metolachlor, chlormeduat, cloprop, cloxyfonac, cloxyfonac-potassium, pethoxamid, pretilachlor, propachlor, propisochlor, S-meth cyclanilide, cytokinins, daminozide, dikegulac, dimethipin, olachlor, thenylchlor; ethephon, ethychlozate, flumetralin, flurenol, flurprimidol, forchlorfenuron, gibberellin acid, inabenfide, indole acetic 0299 (K3-3) Oxyacetamides: flufenacet, mefenacet: acid, indole butyric acid, maleic hydrazide, mefluidide, mepi 0300 (K3-4) Tetrazolinones: fentrazamide: quat chloride, n-decanol, paclobutraZol, prohexadionecal 0301 (K3-5) Other compound: anilofos, bromobutide, cium, prohydrojasmon, Sintofen, thidiaZuron, triacontanol, cafenstrole, indanofan, piperophos, fenoxasulfone, pyroxas trinexapac-ethyl, uniconazole, uniconazole-P 4-oxo-4-(2- ulfone, ipfencarbazone; phenylethyl)aminobutyric acid (chemical name, CAS regis L. Cellulose Synthesis Inhibitors tration No.: 1083-55-2) 0318 Below are shown examples of the known chemical 0302 (L-1) Benzamides: isoxaben; injury-reducing compounds which may be mixed or used in 0303 (L-2) Nitriles: dichlobenil, chlorthiamid: combination. However, the compounds are not restricted to 0304 (L-3) Triazolocarboxamides: flupoxame: these examples. US 2014/0288.184 A1 Sep. 25, 2014 15

0319 benoxacor, furilazole, dichlormid, dicyclonone, 0349 : Acyrthosiphon pisum, Aphis gossypii, DKA(N.N2-diallyl-N2-dichloroacetylglycineamide), Aphis spiraecola, Lipaphis erysimi, Myzuspersicae, Schiza AD-67 (4-dichloroacetyl-1-Oxa-4-azaspiro4.5 decane), phis graminum, Rhopalosiphum padi, etc., PPG-1292 (2,2-dichloro-N-(1,3-dioxan-2-ylmethyl)-N-(2- 0350 Aleyrodidae: Aleurocanthus spiniferus, Bemisia propenyl)acetamide), R-29148 (3-dichloroacetyl-2.2.5-trim tabaci, Bemisia argentifolii, Trialeurodes vaporariorum, etc., ethyl-1,3-oxazoline), cloquintcet-mexyl, 1.8-Naphthalic 0351 : Drosicha corpulenta, Icerya pur Anhydride, mefenpyrdiethyl, mefenpyr, mefenpyr-ethyl, Chasi, etc., fenchlorazole-O-ethyl, fenclorim, MG-191 (2-dichlorom 0352) Pseudococcidae: Dysmicoccus brevipes, Planococ ethyl-2-methyl-1,3-dioxane), cyometrinil, flurazole, flux cus citri, Pseudococcus comstocki, etc., ofenim, isoxadifen, isoxadifenethyl, mecoprop, MCPA, 0353 : Ceroplastes ceriferus, etc., daimuron, 2,4-D, MON 4660 (code number), oxabetrinil, 0354 : Aclerda takahasii, etc., cyprosulfamide, lower alkyl-substituted benzoic acid, TI-35 0355 : Aonidella aurantii, Diaspidiotus perni (code number), N-(2-methoxybenzolyl)-4-(methylami ciosus, Unaspis vanonensis, etc., nocarbonyl)aminobenzenesulfonamide (chemical name, 0356. : Lygus hesperus, Trigonotylus caelestia CAS registration No.: 129531-12-0) lium, etc., 0320. The pest control agent of the present invention 0357 Tingitidae: Stephanitis pyrioides, Stephanitis nashi, shows an excellent control effect to pests of Orthoptera, Thys etc., anoptera, , Coleoptera, Diptera, , 0358 : Eysarcoris aeneus, Lagynotomus Hymenoptera, Collembola, Thysanura, Blattodea, Isoptera, elongatus, Nezara viridula, Plautia crSSota, etc., Psocoptera, Mallophaga, Anoplura, plant-feeding mites, 0359 : Megacopta cribaria, etc., plant parasitic nematodes, plant parasitic mollusc pests, other 0360 : Cavelerius saccharivorus, etc., crop pests, nuisance pests, sanitary , parasites, etc. As 0361 Malcidae: Malcus japonicus, etc., examples of Such pests, the following organism species can 0362 . Dysdercus cingulatus, etc., be mentioned. 0363 : Leptocorisa acuta, Leptocorisa chinen 0321. As the Orthopteran pest, there can be mentioned, for sis, etc., example, 0364 : Anacanthocoris stricornis, etc., 0322 Tettigoniidae: Ruspolia lineosa, etc., 0365 : Rhopalus maculatus, etc., 0323 Gryllidae: Teleogryllus emma, etc., 0366 : Cimex lectularius, etc. 0324 Gryllotalpidae: Gryllotalpa orientalis, 0367. As the Coleopterapests, there can be mentioned, for 0325 Locustidae: Oxya hyla intricate, Locusta migrato example, ria, Melanoplus sanguinipes, etc., 0368 Scarabaeidae: Anomara cuprea, Anomara rufocu 0326 Pyrgomorphidae: Atractomorphalata, prea, Popillia japonica, Oryctes rhinoceros, etc., 0327 Acrididae: Euscyrtus japonicus 0369 Elateridae: Agriotes Ogurae, Melanotus Okinawen 0328 Tridactylidae: Xya japonicus, etc. sis, Melanotos fortnumi, etc., 0329. As the Thysanopteran pests, there can be men 0370 Dermestidae: Anthrenus verbasci, etc., tioned, for example, 0371 Bostrichidae: Heterobostrychus hamatipennis, etc., 0330. Thripidae: Frankliniella intonsa, Frankliniella 0372 Anobiidae: Stegobium paniceum, etc., occidentalis, Scirtothrips dorsalis, Thrips palmi, Thrips 0373) Ptimidae: Pitinus clavipes, etc., tabaci, etc., 0374 Trogositidae: Tenebroides manritanicus, etc., 0331 Phlaeothripidaes: Ponticulothrips diospyrosi, Hap 0375 Cleridae: Necrobia rufipes, lothripsaculeatus, etc. 0376 Nitidulidae: Carpophilus hemipterus, etc., 0332. As the Hemipteran pest, there can be mentioned, for Silvanidae: Ahasverus advena, etc., example, 0377 Laemophloeidae: cryptolestes ferrugineus, etc., 0333 Cicadidae: Mogannia minuta, etc., 0378 Coccinellidae: Epilachna varivestis, Henosepil 0334 : Aphorphora intermedia, etc., achna vigintioctopunctata, etc., 0335 Membracidae: Machaerotypus sibiricus, etc., 0379 Tenebrionidae: Tenebrio molitor, tribolium casta 0336 Deltcephalidae: Arboridia apicalis, Empoasca neum, etc., onukii. 0380 Meloidae: Epicauta gorhami, etc., 0337 Nephotettix cincticeps, Recilia dorsalis, etc., (0381 Cerambycidae: Anoplophora glabripennis, 0338 : Pentastiridius apicalis, etc., : Xylotrechus pyrroderus, Monochamus alternatus, etc., Laodelphax striatellus, Nilaparvata lugens, Sogatella fir 0382 Bruchidae: Callosobruchus chinensis, etc., Chry cifera, etc., somelidae. Leptinotarsa decemlineata, Diabrotica virgifera, 0339 Meenoplidae: Nisia nervosa, etc., Phaedon brassicae, Phyllotreta striolata, etc., 0383 Brentidae: Cylas formicarius, etc., 0340 : Kamendaka saccharivora, etc., 0384 Curculionidae: Hypera postica, List roderes 0341 Cixidia okunii: Achilus flammeus, etc., costirostris, Euscepes postfasciatus, etc., 0342 Ricamidae: Orosanga japonicus, etc., 0385 Erirhimidae: Echinocnemus bipunctatus, Lissor 0343 : Mimophantia maritima, etc., hoptrus Oryzophilus, etc., 0344) : Cacopsylla pyrisuga, etc., (0386 Rhynchophoridae: Sitophilus zeanais, Sphe 0345 Calophyidae: mangiferae, etc., nophrus venattiS, etc., 0346 : Daktulosphairavitifoliae, etc., 0387 Limnoriidae: Tomicus piniperda, etc., 0347 Chemidae: Adelges laricis, 0388 Platypodidae: Crossotarsus niponicus, etc., 0348 : Adelges tsugae, etc., 0389 Lyctidae: Lyctus brunneus, etc. US 2014/0288.184 A1 Sep. 25, 2014

0390. As the Diptera pest, there can be mentioned, for 0437. Pterophoridae: Nippoptilia vitis, etc., example, 0438 Papilionidae: Papilio xuthus, etc., 0391 Tipulidae: Tipila aino, etc., 0439 Pieridae: Pieris rapae, etc., 0392 Bibionidae: Plecia nearctica, etc., 0440 Hesperiidae: Parnara guttata guttata, etc., 0393 Fungivoridae: Exechia shiitakevora, etc., 0441 Geometridae: Ascotis selenaria, etc., 0394 Lycoriidae: Pnyxiascabiei, etc., 0442 Lasiocampidae: Dendrolimus spectabilis, Malaco 0395 Cecidomyiidae: Asphondylia y usimai, Mayetiola Somaneustrium testaceum, etc., destructor, etc., 0443) Sphingidae: Agrius convolvuli, etc., 0396 Culicidae: Aedes aegypti, Culex pipiens pallens, 0444 Lymantriidae: Arna pseudoconspersa, Lymantria etc., dispar, etc., 0397) Simuliidae: Simulim takahasii, etc., 0445 Arctiidae: Hyphantria cunea, etc., 0398 Chironomidae: Chironomus oryzae, etc., 0446 Noctuidae: Agrotis ipsilon, Autographa nigrisigna, 0399 Tabanidae: Chrysops suavis, Tabanus trigonus, etc., Helicoverpa armigera, Helicoverpa zea, Heliothis virescens, 0400 Syrphidae: Eumerus strigatus, etc., 0447 Spodoptera exigua, Spodoptera litura, etc. 04.01 Trypetidae: Bactrocera dorsalis, Euphranta 0448. As the Hymenoptera pest, there can be mentioned, japonia, Ceratitis Capitata, etc., for exmaple, 0402 Agromyzidae: Liriomyza trifolii, Chromatomyia 0449 Argidae: Arge pagana, etc., horticola, etc., 0450 Tenthredimidae: Apethymus kuri, Athaliarosae rufi 0403. Chloropidae: Meromyza nigriventris, etc., cornis, etc., 0404 Drosophilidae: Drosophila Suzuki, Drosophila 0451 Cynipidae: Dryocosmus kuriphilus, etc., melanogaster, etc., 0452 Vespidae: Vespa simillimaxanthoptera, etc., 04.05 Ephydridae: Hydrellia griseola, etc., 0453 Formicidae: Solenopsis invicta, etc., 0406 Hippoboscidae: Hippobosca equina, etc., 0454 Megachilidae: Megachile nipponica, etc. 04.07 Scatophagidae: Parallelpmma sasakawae, etc., 0455 As the Order Collembola pest, there can be men 0408 Anthomyiidae: Delia antiqua, Delia platura, etc., tioned, for example, 04.09 Fanniidae: Fannia canicularis, etc., 0456 Sminthuridae: Bourletiellahortensis, etc. 0410 Muscidae: Musca domestica, Stomoxys calcitrans, 0457. As the Order Thysanura pest, there can be men etc., tioned, for example, 0411 Sarcophagidae: Sarcophaga peregrina, etc., 0458 Lepismatidae: Lepisma saccharina, Ctenolepisma 0412 Gasterophilidae: Gasterophilus intestinalis, etc., villosa, etc. 0413 Hypodermatidae: Hypoderma lineatum, etc., 0459. As the Blattodea pest, there can be mentioned, for 0414 Oestridae: Oestrus ovis, etc. example, 0415. As the Lepidoptera pest, there can be mentioned, for 0460 Blattidae: Periplaneta americana, example, 0461 Blattellidae: Blattella germanica, etc. 0416 Hepialidae: Endoclita excrescens, etc., 0462. As the Order Isoptera pest, there can be mentioned, 0417. : Antispila ampelopsia, etc., for example, 0418 Cossidae: Zeuzera leuconotum, etc., 0463 Kalotermitidae. Incisitermes minor, etc., Rhinoter 0419 Tortricidae: Archips fiascocupreanus, Adoxophyes mitidae. Coptotermes formosanus, etc., Orana fasciata, Grapholita molesta, Homona magnanima, 0464 Termitidae: Odontotermes formosanus, etc. Leguminivora glycinivorella, Cydia pomenella, etc., 0465. As the Order Psocoptera pest, there can be men 0420 Cochylidae: Eupoecilia ambiguella, etc., tioned, for example, 0421 Psychidae: Bambalina sp., Eumeta minuscula, etc., 0466 Trogiidae: Trogium pulsatorium, etc., 0422 Tineidae: Nemapogon granella, Tinea translucens, 0467 Liposcelidaidae: Liposcelis corrodens, etc. etc., 0468. As the Order Mallophaga pest, there can be men 0423 Nepticulidae: Bucculatrix pyrivorella, etc., tioned, for example, 0424 Lyonetiidae: Lyonetia clerkella, etc., 0469 Menoponidae: Lipeurus caponis, etc., 0425 Gracilariidae: Caloptilia theivora, Phyllonorycter 0470 Trichodectidae: Damalinia bovis, etc. ringoniella, etc., 0471. As the Order Anoplura pest, there can be mentioned, 0426 Phyllocnistidae: Phyllocnistis citrella, etc., for example, 0427 Acrolepiidae: Acrolepiopsis sapporensis, etc., 0472 Haematopimidae: Haematopinus suis, etc., 0428 Yponomeutidae: Plutella xylostella, Yponomeuta 0473 Pediculine: Pediculus humanus, etc., orientalis, etc., 0474 Linognathidae: Linognathus setosus, etc., 0429 Argyresthidae: Argyresthia conjugella, etc., 0475 Pthiridae: public louse, etc. 0430 Aegeriidae: Nokona regalis, etc., 0476. As the Plant-feeding mites, there can be mentioned, 0431 Gelechiidae: Phthorimaea operculella, Sitotroga for example, cerealella, Pectinophora gossypiella, etc., 0477 Eupodidae: Penthaleus major, etc., 0432 Carposimidae: Carposina Sasakii, etc., 0478 Tarsonemidae: Phytonemus pallidus, Polyphago 0433 Zygaenidae: Illiberispruni, etc., tarisonemus latus, etc., 0434 Heterogeneidae: Monema flavescens, etc., 0479 Pyemotidae: Siteroptes sp., etc., 0435 Crambidae: Ancylolomia japonica, Chilo suppres 0480 Tenuipalpidae: Brevipalpus lewisi, etc., salis, Cnaphalocrosis medinalis, Ostrinia furnacalis, 0481 Tuckerellidae: Tuckerella pavoniformis, etc., Ostrinia nubilalis, etc., 0482 Tetranychidae: Eotetranychusboreus, Panonychus 0436 Pyralidae: Cadra cautella, Galleria mellonella, citri, Panonychus ulmi, Tetranychus urticae, Tetranychus etc., kanzawai, etc., US 2014/0288.184 A1 Sep. 25, 2014

0483 Nalepellidae: Trisetacus pini, etc., 0529 Decapoda Astacidae Procambarus clarkii, etc., 0484 Eriophyidae: Aculops pelekassi, Epitrimerus pyri, 0530 Porcellionidae: Porcellionides pruinosus, etc., Phyllocoptruta oleivola, etc., 0531 Chilopoda pests: Scutigeromorpha Sutigeridae 0485 Diptilomiopidae: Diptacus crenatae, etc., Thereuonema tuberculata, Scolopendromorpha Scolopendra 0486 Acaridae: Aleuroglyphus ovatus, Tyrophagus Subpinipes etc., putrescentiae, Rhizoglyphus robini, etc. 0532. Diplopoda pests: Polydesmida Paradoxosomatidae, 0487. As the Plant-parasitic nematodes, there can be men Oxidus gracilis etc., tioned, for example, 0533 AraneaeLatrodectus hasseltii: Theridiadae has 0488 Longidoridae: Xiphinema index, etc., seltii, etc., 0489 Trichodoridae: Paratrichodorus minor, etc., 0534 Clubionidae: Chiracanthium japonicum, etc., 0490 Rhabditidae: Rhabditella sp., etc., 0535. Order Scorpionida Androctonus crassicauda, etc., 0491 Tylenchidae: Aglenchussp., etc., 0536 Parasitic roundworm: Ascaris lumbricoides, Sypha 0492 Tylodoridae: Cephalenchus sp., etc., cia sp., Wucherebia bancrofti, etc., 0493 Anguimidae: Nothotylenchus acris, Dity lenchus 0537 Parasitic flatworm: Distomum sp., Paragonimus destructor, etc., westermanii, Metagonimus yokokawai, Schistosoma japoni 0494 Hoplolaimidae: Rotylenchulus reniformis, Heli cum, Taenia solium, Taeniarhynchus saginatus, Echinococ cotylenchus dihystera, etc., cus sp., Diphyllobothrium latum, etc. 0495 Paratylenchidae: Paratylenchus curvitatus, etc., 0538. The pest control agent of the present invention 0496 Meloidogynidae: Meloidogyne incognita, Meloid exhibits a control effect also to the above-mentioned pests, Ogyne hapla, etc., etc. which already have resistances to existing pest control 0497. Heteroderidae: Globodera rostochiensis, Het agents. Further, the present pest control agent can be applied erodera glycines, etc., to plants which already have resistances to insects, diseases, 0498 Telotylenchidae: Tylenchorhynchus claytoni etc., herbicides, etc., owing to genetic recombination, artificial 0499 Psilenchidae: Psilenchus sp., etc., mating, etc. 0500 Criconematidae: Criconenoides sp., etc., 0539 Next, there are described the production methods, 0501) Tylenchulidae: Tilenchulus semipenetrans, etc., formulation methods and applications of the present com 0502 Sphaeronematidae: Sphaeronema camelliae, etc., 96 pound, in detail by way of Examples. However, the present 0503 Pratylenchidae: Radopholus citrophilus, Radopho invention is in no way restricted by these Examples. lus similis, Nacobbus aberrans, 0504 Pratylenchus penetrans, Pratylenchus coffeae, etc., EXAMPLES 0505 Iotonchiidae: Iotonchium ungulatum, etc., 0506 Aphelenchidae: Aphelenchus avenae, etc., Example 1 0507 Aphelenchoididae: Aphelenchoides besseyi, Aph elen.choides fragariae, etc., Production of 0508 Palasitaphelenchidae: Bursaphelenchus xylophilus, 3-amino-2,3-bis(isopropoxyimino)propionitrile etc. (compound No. 1-096) 0509 As the plant parasitic mollusc pests, there can be 0540 (1) 2.52 g (14.8 mM) of 2-iodopropane was added to mentioned, for example, an N,N-dimethylformamide solution (30 ml) of 2.00 g (15.6 0510 Pilidae: Pomacea canaliculata, etc., mM) of 3-amino-2,3-bis(hydroxyimino)propionitrile. The 0511 Veronicellidae: Leavicaulis alte, etc., mixture was cooled to 0°C. 2.05 g (14.8 mM) of potassium 0512 Achatimidae: Achatina fulica, etc., carbonate was added, followed by stirring at room tempera 0513 Philomycidae: Meghimatium bilineatum, etc., ture for 16 hours. The reaction mixture was poured into water, 0514. Succineidae: Succinealauta, etc., followed by extraction with ethyl acetate. The organic layer 0515 Didcidae: Discus pauper, etc., obtained was washed with a saturated aqueous sodium chlo 0516 Zonitidae: Zonitoides yessoensis, etc., ride solution, dried over anhydrous magnesium sulfate, and 0517 Limacidae: Limax flavus, Deroceras reticulatum, filtered to remove inorganic matter. The solvent was distilled etc., offunder reduced pressure. The resulting residue was purified 0518. Hehelicarionidae: Parakaliella harimensis, etc., by silica gel column chromatography (ethyl acetete:hex 0519 Bradybaenidae: Acusta despecta sieboldiana, ane=1:2) to obtain 1.36 g (yield: 51%) of 3-amino-3-hy Bradybaena similaris, etc. droxyimino-2-isopropoxyiminopropionitrile (compound No. 0520. As otherpests such as injurious animals, uncomfort 1-004). able animals, sanitary insects, livestock insects, parasites and (0541 H-NMR data (CDC1/TMS 8 (ppm)): the like, there can be mentioned, for example, (0542 1.38 (6H, d), 4.63 (1H, sept), 5.02 (2H, bs), 8.54 0521 Acari Macronysshidae Ornithonyssus Sylvialum, (1H, bs) etc 0543. Incidentally, the 3-amino-2,3-bis(hydroxyimino) 0522 Varroidae: Varroa jacobsoni, etc., propionitrile was produced based on the method described in 0523 Dermanyssidae: Dermanyssus gallinae, etc., Journal of Organic Chemistry, 2000, Vol. 65, No. 4, pp. 0524 Macronyssidae: Ornithonyssus Sylvialum, etc., 11391143. 0525 Ixodidae Boophilus microplus, Rhipicephalussan (2) 1.35 g (30.9 mM) of 55% sodium hydride was suspended guineus, in 20 ml of N,N-dimethylformamide. Thereinto was drop 0526 Haemaphysalis longicornis, etc., wise added, in ice-cooling, an N,N-dimethylformamide solu 0527 Sarcoptidae: Sarcoptes scabiei, etc., tion (10 ml) of 5.00 g (29.4 mM) of the 3-amino-3-hydroxy 0528 Isopoda Armadillididae Armadillidium vulgare, imino-2-isopropoxyiminopropionitrile obtained in (1). etc., Stirring was conducted at room temperature for 15 minutes. US 2014/0288.184 A1 Sep. 25, 2014

Thereinto was dropwise added, in ice-cooling, 3.98 g (32.4 Example 4 mM) of isopropyl bromide. Stirring was conducted at room temperature for 2 hours. The reaction mixture was poured Production of 3-amino-2,3-bis(2.2.2-trifluoroethoxy into water. Extraction with ethyl acetate was conducted. The imino)propionitrile (compound No. 1-168) organic layer obtained was washed with a saturated aqueous 0552) 1.81 g (7.81 mM) of 2.2.2-trifluoroethyl trifluo Sodium chloride Solution, dried over anhydrous magnesium romethanesulfonate was added to an N,N-dimethylforma sulfate, and filtered to remove inorganic matter. The solvent mide solution (20 ml) of 1.00 g (7.81 mM) of 3-amino-2,3- was distilled off under reduced pressure. The resulting resi bis(hydroxyimino)propionitrile. The mixture was cooled to due was purified by silica gel column chromatography (ethyl 0°C. Thereto was added 1.08 g (7.81 M) of potassium car acetate:hexane=1:4) to obtain 6.12 g (yield: 98%) of the title bonate. Stirring was conducted at room temperature for 3 compound. hours. The mixture was cooled to 0°C. Thereto were added (0544 'H-NMR data (CDC1/TMS 8 (ppm)): 1.81 g (7.81 mM) of 2.2.2-trifluoroethyl trifluoromethane (0545) 1.28 (6H, d), 1.36 (6H, d), 4.41 (1H, sept), 4.60 (1H, sulfonate and 0.34 g (7.8 mM) of 55% sodium hydride. Stir sept), 4.81 (2H, bs) ring was conducted at room temperature for 2 hours. The reaction mixture was poured into water. Extraction with ethyl Example 2 acetate was conducted. The organic layer obtained was washed with a saturated aqueous Sodium chloride solution, dried over anhydrous magnesium sulfonate, and filtered to Production of 3-amino-2-isopropoxyimino-3-pro remove inorganic matter. The solvent was distilled off under poxyiminopropionitrile (compound No.: 1-073) reduced pressure. The resulting residue was purified by silica 0546. To an N N-dimethylformamide solution (16 ml) gel column chromatography (ethyl acetate:hexane-1:2) to of 1.36 g (7.99 mM) of the 3-amino-3-hydroxyimino-2-iso obtain 1.51 g (yield: 66%) of the title compound. propoxyiminopropionitrile obtained in (1) of Example 1 was 0553 'H-NMR data (CDC1/TMS 8 (ppm)): added 1.09 g (8.86 mM) of 1-bromopropane. The mixture 0554 4.52 (2H, q), 4.70 (2H, q), 4.99 (2H, bs) was cooled to 0°C. Thereto was added 0.35 g (8.0 mM) of 55% sodium hydride. Stirring was conducted at room tem Example 5 perature for 3 hours. The reaction mixture was poured into water. Extraction with ethyl acetate was conducted. The Production of 3-amino-3-hydroxyimino-2-isopro organic layer obtained was washed with a saturated aqueous poxyiminopropanamide (compound No. 2-004) Sodium chloride Solution, dried over anhydrous magnesium 0555. To a mixed solution of methanol (1.5 ml) and dim sulfate, and filtered to remove inorganic matter. The solvent ethylsulfoxide (0.5 ml), of 0.50 g (2.94 mM) of the 3-amino was distilled off under reduced pressure. The resulting resi 3-hydroxyimino-2-isopropoxyiminopropionitrile obtained due was purified by silica gel column chromatography (ethyl in (1) of Example 1 were added, at room temperature, 0.73 g acetate:hexane=1:2) to obtain 1.61 g (yield: 95%) of the title (6.4 mM) of a 30% aqueous hydrogen peroxide solution and compound. 0.02 g (0.14 mM) of potassium carbonate. Stirring was con (0547 'H-NMR data (CDC1/TMS 8 (ppm)): ducted at room temperature for 4 hours. Excessive hydrogen peroxide was treated with an aqueous Sodium thiosulfate 0548 0.95 (3H, t), 1.36 (6H, d), 1.37-1.77 (2H, m), 4.10 solution. The solvent was distilled off under reduced pres (2H, t), 4.60 (1H, sept), 4.84 (2H, bs) sure. Water was added to the residue and extraction with ethyl acetate was conducted. The organic layer was washed with a Example 3 saturated aqueous sodium chloride solution, dried over anhy drous magnesium sulfate, and filtered to remove inorganic Production of matter. The solvent was distilled off under reduced pressure. 3-Amino-2,3-Bis(Propoxyimino)Propionitrile The resulting crude crystal was washed with a 1:2 mixed (compound No. 1-072) solution of diisopropyl ether and n-hexane to obtain 0.35g (yield: 63%) of the title compound. 0549. 7.2 g (58.6 mM) of 1-bromopropane was added to an 0556 'H-NMR data (CDC1/TMS 8 (ppm)): 1.29 (6H, d), N,N-dimethylformamide solution (50 ml) of 3.00 g (23.4 4.43 (1H, sept), 4.88 (2H, bs), 6.73 (2H, bs), 10.20 (1H, bs) mM) of 3-amino-2,3-bis(hydroxyimino)propionitrile. The mixture was cooled to 0°C. 22.0 g (159 mM) of potassium Example 6 carbonate was added. Stirring was conducted at 90° C. for 3 hours. The reaction mixture was returned to room tempera Production of ture and poured into water. The mixture was subjected to 3-amino-2,3-bis(isopropoxyimino)propanamide extraction with ethyl acetate. The organic layer obtained was (compound No. 2-096) washed with a saturated aqueous Sodium chloride solution, dried over anhydrous magnesium Sulfate, and filtered to 0557. To a methanol solution (140 ml) of 29.0 g (137 mM) remove inorganic matter. The solvent was distilled off under of 3-amino-2,3-bis(isopropoxyimino)propionitrile were reduced pressure. The resulting residue was purified by silica added, at room temperature, 47 g (415 mM) of a 30% aqueous gel column chromatography (ethyl acetate:hexane-1:2) to hydrogen peroxide Solution, 1.5 g (15 mM) of Sodium car obtain 2.54 g (yield: 51%) of the title compound. bonate and 2.3 g (7.1 mM) of tetrabutylammonium bromide. Stirring was conducted at room temperature for 4 hours. 0550 'H-NMR data (CDC1/TMS 8 (ppm)): Since the raw materials remained, further 24 g (212 mM) of a 0551 0.93-1.01 (6H, m), 1.67-1.84 (4H, m), 4.11 (2H, t), 30% aqueous hydrogen peroxide Solution was added, fol 4.31 (2H, t), 4.83 (2H, bs) lowed by stirring at room temperature for 3 hours. Excessive US 2014/0288.184 A1 Sep. 25, 2014

hydrogen peroxide was treated with an aqueous Sodium thio TABLE 14-continued sulfate solution. The solvent was distilled off under reduced pressure. Water was added to the resulting residue, followed Compound by extraction with ethyl acetate. The organic layer obtained No. Physical Property was washed with a saturated aqueous Sodium chloride solu -119 Reflactive Index (no') 4520 tion, dried over anhydrous magnesium sulfate, and filtered to -121 Reflactive Index (n') SO90 -122 Reflactive Index (n') 5140 remove inorganic matter. The solvent was distilled off under -123 Reflactive Index (n') 4873 reduced pressure. The crystal obtained was washed with a 1:2 -124 Reflactive Index (no') 492S mixed solution of diisopropyl ether and n-hexane to obtain -12S Reflactive Index (n') S100 29.0 g (yield: 92%) of the title compound. -126 Reflactive Index (n') .5225 -127 Reflactive Index (n') 4902 0558 H-NMR data (CDC1/TMS 8 (ppm)): -128 Reflactive Index (no') 4890 0559) 1.24 (6H, d), 1.29 (6H, d), 4.34 (1H, sept), 4.45 (1H, -129 Reflactive Index (n') SO10 -130 Reflactive Index (n') 498O sept), 4.78 (2H, bs), 5.71 (2H, bs) -131 Melting Point (C.) 72-74 0560. Other glyoxime derivatives were produced based on -132 Reflactive Index (no') 5075 the above Examples, and their structural formulas and prop -133 Reflactive Index (n') 5250 -134 Reflactive Index (n') 5273 erties are shown in Table 13 to Table 15 together with those of -13S Reflactive Index (n') 5270 the compounds produced in the above Examples. In these -136 Reflactive Index (no') 4372 tables, symbols have the same meanings as shown previously. -137 Reflactive Index (n') 4.905 Incidentally, compound Nos. are referred in the later descrip -138 Melting Point (C.) 164-167 tion.

TABLE 13 TABLE 1.5 Compound Compound No. Physical Property No. Physical Property -001 Melting Point (C.) 176-179 -140 Melting Point (C.) 99-101 -OO2 Melting Point (C.) 136-139 -141 Melting Point (C.) 173-176 -OO3 Melting Point (C.) 110-113 -142 Reflective Index (n') 15140 -004 Melting Point (C.) 155-157 -143 Melting Point (C.) 54-55 -OOS Melting Point (C.) 106-108 -144 Reflactive Index (n') 14940 -OO6 Melting Point (C.) 135-138 -147 Melting Point (C.) 73-76 -OO7 Melting Point (C.) 153-155 -148 Reflective Index (n') 1.5551 -O1O Melting Point (C.) 129-132 -149 Reflective Index (n') 1.SSO1 -O13 Melting Point (C.) 157-160 -154 Melting Point (C.) 124-127 -014 Melting Point (C.) 107-109 -155 Reflective Index (n') 1.5122 -O16 Melting Point (C.) 151-153 -157 Reflective Index (n') 1...SO43 -O18 Melting Point (C.) 120-121 -159 Reflective Index (n') 1.5660 -O21 Melting Point (C.) 123-124 -160 Reflective Index (n') 15141 -O22 Melting Point (C.) 170-173 -161 Reflective Index (n') 1.5750 -041 Reflective Index (n') 15215 -162 Reflective Index (n') 14402 -OS1 Reflective Index (n') 14975 -164 Melting Point (C.) 81-83 -070 Reflective Index (n') 15101 -16S Melting Point (C.) 76-79 -O71 Reflective Index (n') 1.5025 2-004 Melting Point (C.) 161-164 -O72 Reflective Index (n') 14974 2-051 Melting Point (C.) 106-107 -073 Reflective Index (n') 14973 2-072 Melting Point (C.) 66-69 -O74 Reflective Index (n') 1.4960 2-096 Melting Point (C.) 157-160 -075 Reflective Index (n') 14940 2-116 Melting Point (C.) 140-143 -O76 Reflective Index (n') 1.4960 -O79 Reflective Index (n') 1.4910 -O82 Reflective Index (n') 1.49SO -O84 Reflective Index (n') 1.4875 0561. With respect to compound Nos. 1-120, 1-139, -O85 Reflective Index (n') 15175 1-156, 1-158 and 1-163, their "H-NMR data (CDC1/TMS 8 -087 Reflective Index (n') 15144 (ppm)) are shown below. -O90 Reflective Index (n') 1.S123 Compound No. 1-120:1.22 (3H, t), 1.38 (6H, d), 3.54 (2H, q), 3.73 (2H, t), 4.29 (2H, t), 4.61 (1H, sept), 4.94 (2H, s) Compound No. 1-139: 0.95 (3H, t), 1.67-1.79 (2H, m), 4.13 TABLE 1.4 (2H, t), 4.68 (2H, q), 4.83 (2H, bs) Compound No. Physical Property 0562 Compound No. 1-156: 0.94 (3H, t), 1.35-1.45 (2H, m), 1.65-1.72 (2H, m), 4.16 (2H, t), 4.83 (2H, d), 4.83 (2H, 1-091 Reflactive Index (n') 1.5220 bs), 5.32-5.40 (2H, m), 5.95-6.05 (1H, m) 1-092 Reflactive Index (n') 15242 1-094 Reflactive Index (n') 1.4982 Compound No. 1-158: 0.89 (3H, t), 1.24-1.32 (6H, m), 1.65 1-096 Reflactive Index (n') 14937 1.71 (2H, m), 4.14 (2H, t), 4.83 (2H, d), 4.83 (2H, bs), 5.31 1-098 Reflactive Index (n') 1.4870 5.41 (2H, m), 5.93-6.06 (1H, m) 1-107 Reflactive Index (n') 14886 Compound No. 1-163: 1.29 (6H, d), 4.43 (1H, sept), 4.74-4. 1-110 Reflactive Index (n') 15082 1-116 Reflactive Index (n') 1.4910 80 (4H, m) 1-117 Reflactive Index (n') 14890 0563) Next, there are specifically explained examples of 1-118 Reflactive Index (n') 1.S108 formulating the present pest control agent by using the present glyoxime derivative produced as above or its agricul US 2014/0288.184 A1 Sep. 25, 2014 20 turally acceptable salt. Incidentally, the kinds and proportions Test Example 1 of compounds and additives used in each formulation are not restricted to those shown in the following formation examples Insecticidal action test for Nilaparvata lugens Stal and may be varied in a wide range. In the following explana 0573 (brown rice ) (immersion test) tion, part or parts refer to mass part or mass parts. 0574. A wettable powder prepared based on Formulation Example 2 was diluted with water so that the concentration of Formulation Example 1 Emulsifiable Concentrate active ingredient became 500 ppm. In the diluted liquid was immersed sprouting unhulled rice. The immersed rice was 0564 placed in a plastic cup of 60 ml. Into the plastic cup were released 10 2-age larvae of Nilaparvata lugens Stål (brown A compound described in Table 1 to Table 12 10 parts rice planthopper). The cup was covered with a cap and placed Cyclohexanone 30 parts in a thermostat of 25°C. After 6 days, the number of living Polyoxyethylene alkyl aryl ether 11 parts insects was counted and the mortality of insect was calculated Calcium alkylbenzenesulfonate 4 parts using the calculation formula of Mathematical Expression 1. Methylnaphthalene 45 parts This test was conducted with no repetition. Insect mortality (%)=1-(number of living insects), 0565. The above materials were made into a uniform solu (number of tested insects)x100 Mathematical Expression 1 tion, to prepare an emulsifiable concentrate. 0575. The compound Nos. of the compounds which gave an insect mortality of 90% or higher in the above test, are Formulation Example 2 Wettable Powder shown below. 0576) 1-004, 1-018, 1-041, 1-051, 1-070, 1-071, 1-072, 0566 1-073, 1-074, 1-075, 1-076, 1-079, 1-082, 1-084, 1-085, 1-087, 1-090, 1-091, 1-092, 1-094, 1-096, 1-098, 1-107, A compound described in Table 1 to Table 12 10 parts 1-1 10, 1-116, 1-117, 1-118, 1-119, 1-121, 1-122, 1-123, Sodium salt of naphthalenesulfonic acid-formalin 0.5 part 1-124, 1-127, 1-128, 1-129, 1-130, 1-133, 1-134, 1-135, Condensate 1-136, 1-137, 1-139, 1-142, 1-143, 1-144, 1-147, 1-155, Polyoxyethylene alkyl aryl ether 0.5 part 1-156, 1-157, 1-160, 1-162, 1-163 Diatomaceous earth 24 parts Clay 65 parts Test Example 2 0567 The above materials were mixed and ground to pre Insecticidal Action Test for Plutella xylostella Linné pare a wettable powder. 0577 (diamondback ) (immersion test) 0578. A wettable powder prepared based on Formulation Formulation Example 3 Powder Example 2 was diluted with water so that the concentration of active ingredient became 500 ppm. In the diluted formulation 0568 were immersed cabbage leaves. The resulting cabbage leaves were placed in a plastic cup of 60 ml. Into the plastic cup were released 10 2-age larvae of Plutella xylostella Linné(dia A compound described in Table 1 to Table 12 2 parts Diatomaceous earth 5 parts mondback moth). The plastic cup was covered with a cap and Clay 93 parts placed in a thermostat of 25°C. After 6 days, the number of living insects was counted and the mortality of insect was calculated using the calculation formula of Mathematical 0569. The above materials were mixed and ground to pre Expression 1. This test was conducted with no repetition. pare a powder. 0579. The compound Nos. of the compounds which gave an insect mortality of 90% or higher in the above test, are Formulation Example 4 Granule shown below. 0580 1-005, 1-076, 1-090, 1-091, 1-117, 1-121, 1-122, 0570 1-124, 1-128, 1-156 1-5. (canceled) 6. A pest control agent comprising as an active ingredient, A compound described in Table 1 to Table 12 5 parts a glyoxime derivative represented by the general formula Sodium salt of lauryl alcohol sulfate 2 parts Sodium ligninsulfonate 5 parts I Carboxymethyl cellulose 2 parts X Clay 86 parts 2 R -ON Na 21 N No1 R 0571. The above materials were mixed and ground. Thereto was added 20 parts of water, followed by kneading. The kneaded material was passed through an extrusion granu lator to obtain granules of 14 to 32 meshes. The granules were wherein X is a cyano group or a carbamoyl group, dried to prepare a granule. R" is a C1-C8 alkyl group, a C-C alkenyl group, a C-C, 0572. Next, the effect of the pest control agent of the alkynyl group, a C-C cycloalkyl group, a C-C, present invention is shown by Test Examples. cycloalkyl C-C alkyl group, a C-Chaloalkyl group, US 2014/0288.184 A1 Sep. 25, 2014 21

a C-C alkoxy C-C alkyl group, a cyano C-C alkyl cycloalkyl C-C alkyl group, a C-Chaloalkyl group, group or a phenyl C-C alkyl group which may be a C-C alkoxy C-C alkyl group, a cyano C-C alkyl substituted by at least one substituent selected from a group or a phenyl C-C alkyl group which may be Substituent group C, which consists of a halogenatom, a substituted by at least one substituent selected from a C-C alkyl group, a C-C haloalkyl group, a C-C, Substituent group C, which consists of a halogenatom, a alkoxy group, a C-Chaloalkoxy group, a nitro group C-C alkyl group, a C-C haloalkyl group, a C-C, or a cyano group, alkoxy group, a C-C haloalkoxy group, a nitro group R is a hydrogen atom, a C1-C8 alkyl group, a C-C, or a cyano group alkenyl group, a C-C alkynyl group, a C-C, R is a hydrogen atom, a C1-C8 alkyl group, a C-C, cycloalkyl group, a C-C cycloalkyl C-C alkyl alkenyl group, a C-C alkynyl group, a C-C, group, a C-Chaloalkyl group, a C-C alkoxy C-C, cycloalkyl group, a C-C cycloalkyl C-C alkyl alkyl group, a cyano C-C alkyl group or a phenyl group, a C-Chaloalkyl group, a C-C alkoxy C-C, C-C alkyl group which may be substituted by at least alkyl group, a cyano C-C alkyl group or a phenyl one substituent selected from a Substituent group C. C-C alkyl group which may be substituted by at least or an agriculturally acceptable salt thereof. one Substituent selected from the Substituent group C, or 7. A glyoxime derivative represented by the general an agriculturally acceptable salt thereof. 8. A pest control agent according to claim 6, which is an X insecticide. -On 2 N R2 9. A method for pest control which uses the glyoxime derivative or agriculturally acceptable salt thereof, according to claim 7, at an effective amount. 10. A method for pest control according to claim 9, which wherein X" is a cyano group or a carbamoyl group, uses the glyoxime derivative or agriculturally acceptable salt R" is a C-Cs alkyl group, a C-C alkenyl group, a C-C, thereof, as an insecticide. alkynyl group, a C-C cycloalkyl group, a C-C, k k k k k