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Novel Pyrazole And 4,5 Dihydropyrazole Compounds

Abstract: The present invention provides a heterocyclic compound represented by Formula (1): or a salt thereof, wherein R1 and R4 are identical or different and each represents substituted or unsubstituted aryll or a substituted or unsubstituted hetenoaryl group, R2 represents substituted or unsubstituted CM alkyl, R3 represents substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl group, X represents C(=Y), CR5R6, NH, or NR7, Y represents oxygen or sulfur, R5 and R6 are identical or different and each represents hydrogen, or the like, R7 represents CM alkyl, Ci-4 alkylcarbonyl, or Ci-4 alkoxycarbonyl, and the bond represented by: is a single bond or a double bond.

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Patent Information

Application #
Filing Date
12 December 2014
Publication Number
43/2019
Publication Type
INA
Invention Field
CHEMICAL
Status
Email
archana@anandandanand.com
Parent Application
Patent Number
Legal Status
Grant Date
2023-11-06
Renewal Date

Applicants

INSECTICIDES (INDIA) LTD.
401-402 LUSA TOWER, AZADPUR COMMERCIAL COMPLEX, DELHI-110033, INDIA

Inventors

1. Tetsuya Imai
E-423, RIICO Industrial Area, Chopanki (Bhiwadi)-301707, Rajasthan, India
2. Surendra Kumar Kumawat
E-423, RIICO Industrial Area, Chopanki (Bhiwadi)-301707, Rajasthan, India
3. Manish Kumar Singh
E-423, RIICO Industrial Area, Chopanki (Bhiwadi)-301707, Rajasthan, India
4. Ashish Bhatt
E-423, RIICO Industrial Area, Chopanki (Bhiwadi)- 301707, Rajasthan, India
5. Srinivas Venuvenka
E-423, RIICO Industrial Area, Chopanki (Bhiwadi)- 301707, Rajasthan, India
6. Vivek Kumar Pandey
E-423, RIICO Industrial Area, Chopanki (Bhiwadi)- 301707, Rajasthan, India
7. Dhuni Lal Yadav
E-423, RIICO Industrial Area, Chopanki (Bhiwadi)- 301707, Rajasthan, India

Specification

Technical Field The present invention relates to a novel hetero compound and use thereof. Background Art As a result of the long-term use of fungicides, recent years have seen the emergence of fungi that are resistant to chemicals. It has thus become difficult to accomplish control by the use of known fungicides. Under such circumstances, there is a demand for the development of new types of fungicides that are expected to achieve fungicidal activity not only against chemical-sensitive fungi, but also against chemical-resistant fungi. For example, WO 2013/164295 (Patent Literature (PTL) 1) discloses the compound represented by Formula (A) below. PTL 1 discloses that this compound exhibits insecticidal activity. However, FTL 1 nowhere discloses that this compound exhibits fungicidal activity. Summary of Invention Technical Problem An object of the present invention is to provide a heterocyclic compound or a salt thereof that controls a pest Another object of the present invention is to provide a new type of fungicide that exr ib'rts excellent fungicidal activity not only against chemical-sensitive fungi, but also against chemical-resistant fungi. Solution to Problem The present inventors conducted extensive research to achieve the above objects, and succeeded in synthesizing a compound represented by the following Formula (1) or a salt thereof that has fungicidal activity. The present inventors have conducted further research based tin the above findings. The present 'invention has thereby been accomplished. More spedfically, the present invention includes the following embodiments: Item 1: A heterocydic compound represented by Formula (1): or a salt thereof, wherein R1 and R4 are identical or different and each represents substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl group, R2 represents substituted or unsubstituted CM alkyl, R3 represents substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl group, X represents C(=Y), CR5R6, NH, or NR7, Y represents oxygen or sulfur, R5 and R6 are identical or different and each represents hydrogen, hydroxy, thiol, hatogen, CM alkyl, CM haloalkyl, CM alkoxy CM alkyl, CM haloalkoxy CM alkyl, C2-4 alkenyl, CM alkynyl, CM cydoalkyl, CM cydoalkyl CM alkyl, CM alkylcarbonyl, CM alkylcarbonyloxy, CM alkoxy, CM haloalkoxy, CM alkylthio, CM haloalkytthio, CM alkylsulfonyl, CM alkylsulfinyl, arytthio, arylsulfbnyl, arylsulfinyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl CM alkyl, or a substituted or unsubstituted heteroaryl group, R7 represents CM alkyl, CM alkylcarbonyl, or CM alkoxycarbonyl, and the bond represented by: is a single bond or a double bond. Item 2: The heterocydic compound or a salt thereof according to Item 1, wherein R1 represents substituted aryl. Item 3: The heterocydic compound or a salt thereof aooording to Item 1 or 2, wherein R3 represents substituted aryl- The heterocyclic compound or a salt thereof according to any one of Items 1 to 3, wherein R4 represents a substituted or unsubstituted heteroaryl group. Item 5: The heterocyclic compound or a salt thereof according to any one of Items 1 to 4, wherein R4 is substituted or unsubstituted pyridyl. Item 6: A pest-controlling agent containing the heterocyclic compound or a sait thereof of any one of Items 1 to 5. Item 7: A fungicide containing the heterocyclic compound or a salt thereof of any one of Items 1 to 5. Advantageous Effects of Invention The heterocyclic compound or a salt thereof aooording to the present invention achieves an excellent fungicidal effect on fungal plant pathogens. Additionally, the heterocyclic compound or a salt thereof according to the present invention is useful as a new type of fungicide that exhibits excellent fungicidal activity not only against chemical-sensitive fungi, but also against chemical-resistant fungi. Description of Embodiments Heterocyclic compound or a salt thereof The present invention is directed to a compound represented by Formula (1): R2 N=n' »3 or a salt thereof (hereinafter sometimes referred to as "compound (1) of the present invention" or "compound (1)"), wherein R1 and R4 are identical or different and each represents substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl group, R3 represents substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl group, X represents C(=Y), CR5R6, NH, or NR7, Y represents oxygen or sulfur, R5 and R6 are identical or different and each represents hydrogen, hydroxy, thiol, halogen, CM alkyl, CM haloalkyl, CM alkoxy CM alkyl, CM haloalkoxy CM alkyl, G-4 alkenyl, CM alkynyl, G* cydoalkyl, C3-8 cydoalkyl CM alkyl, CM alkylcarbonyl, CM alkylcarbonyloxy, CM alkoxy, CM haloalkcxy, CM alkylthio, CM haloalkylthio, CM alkylsulfonyl, CM alkylsulfinyl, arylthio, arylsulfonyl, arylsulfinyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl CM alkyl, or a substituted or unsubstituted heteroaryl group, R7 represents CM alkyl, CM alkylcarbonyl, or CM alkoxycarbonyl, and the bond represented by: is a single bond or a double bond. The following shows spedfic examples of each group as used in this specification. Examples of aryl indude, but are not particularly limited to, phenyl, 1-naphthyl, 2-naphthyl, and the like. Examples of a heteroaryl group indude, but are not particularly limited to, thienyl, furyl, pymolyl, oxazolyl, isoxazolyl, thiazolyl, pyrazolyl, imidazolyl, oxadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, thiadiazolyl, pyrimidinyl, triazinyl, indolyl, isoindolyl, quinazolyl, carbazolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzisothiazolyl, benzimidazolyl, indazolyl, quinolyl, isoquinolyl, pyridoindolyl, benzofuranyl, and the like. These heteroaryl groups indude those substituted at any substitutable position with an oxo or thioketone group. These heteroaryl groups may optionally be substituted at any substitutable position with 1 to 5 (preferably 1 to 3) substituents. Examples of CM alkyl indude, but are not particularly limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and like CM straight-chain or branched-chain alkyl. Examples of halogen indude, but are not particularly limited to, fluorine, chlorine, bromine, iodine, and the like. Examples of CM haloalkyl indude, but are not particularly limited to, fluoromethyl, choromethyl, bromomethyl, iodomethyl, difljjorometiiyi, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl 2-chloroethyl, 2,2,2-trifluoroethyI, pentafluoroethyl, 1-fluoropropyl, 2-chloropropyl, 3-fluoropropyl, 3-chloropropyl, 3,3,3-trifluoropropyl, 1-fluorobutyl, 1-chlorobutyl, 4-fluorobutyl, 4,4,4-trifluorobutyl, and like CM straight-chain or branched-chain alkyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms. Examples of CM alkoxy CM alkyl indude, but are not particularly limited to, methoxyimethyl, ethoxymethyl, n-propoxymetfiyl, isopropoxymethyl, n-butoxymethyl, sec-butoxymethyl, 2-methoxyethyl, and like alkoxyalkyl in which CM straight-chain or branched-chain alkyl is substituted with CM straight-chain or branched-chain alkoxy. Examples of CM haloalkoxy CM alkyl indude, but are not particularly limited to, fluoromethoxymethyl, chloromethoxymethyl, bromomethoxymethyl, iodomethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, 2,2,2-trifluoromethoxymethyl, and like straight-chain or branched-chain alkoxyalkyl substituted with 1 to 9, preferably 1 to 5, halogen atoms. Examples of CM alkenyi indude, but are not particularly limited to, vinyl, allyl, 2-butenyl, 3-butenyl, 1-methylallyl, and the like. Examples of CM alkynyl indude, but are not particularly limited to, ethynyl, 1-propynyl, l-methyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and the like. Examples of CM cydoalkyl indude, but are not particularly limited to, cydopropyl, cydobutyl, cydopentyl, cydohexyl, cydoheptyl, cydooctyl, and the like. Examples of C3-8 cydoalkyl CM alkyl indude, but are not particularly limited to, cydopropylmethyl, cydobutylethyl, and the like. Examples of CM alkylcarbonyl indude, but are not particularly limited to, methylcarbonyl (acetyl), ethylcarbonyl (propionyl), n-propylcarbonyl (butyryl), isopropylcarbonyl (isobutyryl), n-butylcarbonyl (valeryl), isobutylcarbbnyl (isovaleryl), sec-butylcarbonyl, tert-butylcarbonyl, and like CM straight-chain or branched-chain alkylcarbonyl groups. Examples of CM alkoxycarbonyl indude, but are not particularly limited to, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, and like CM straight-chain or branched-chain alkoxycarbonyl Examples of CM alkylcarbonyloxy indude, but are not particularly limited to, methylcarbonyloxy (acetyloxy), ethylcarbonyloxy (propionyloxy), n-propylcarbonyloxy, (butyryloxy), isopropylcarbonylo:-R3 "R4 H (2) (3) (1B.1} (wherein^1, R2,,R3, and R^are^as defined above, and the wavy lines represent optical isomers.) In the reaction of compound (2) and compound (3), the proportions of these compounds used are not particularly limited, and may be suitably selected from a wide range. The latter is usually used in an amount of about 1 to 5 moles per mole of the former, and preferably about an equimolar amount with respect to the latter. The reaction above is performed after a step (a chlorination step) in which compound (2) is chlorinated to produce a chloride of compound (2). After the chlorination step, the chloride of compound (2) is reacted with compound (3) to produce compound (1B-1). In the chlorination step, a chlorinating agent may be used. Examples of such a chlorinating agent indude, but are not particularly limited to, chlorine, phosphorus oxychloride (POCb), and the like. These chlorinating agents may be used alone or in a combination of two or more. The chlorinating agent is usually used in an amount of 1 mole or more, preferably 1 to 10 moles, and more preferably 1 to 8 moles, per mole of compound (2). When, for example, phosphorus oxychloride, which can also function as a solvent, is used as a chlorinating agent, the excess of phosphorus oxychloride, after the completion of the chlorination step, may be removed under reduced pressure so as to be used in the subsequent reaction. Examples of the base used in the step for reacting compound (2) or a chlorination product of compound (2) with compound (3) indude, but are not particularly limited to, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and like alkali metal carbonate salts;tsodium hydroxide, potassium hydroxide, and like alkali metal hydroxides; sodium hydride, potassium hydride, and like alkali metal hydrides, and other inorganic bases; sodium methoxide, sodium ethoxide, potassium tert-butoxide, and like alkali metal alkoxides; and triethylamine, pyridine, and other organic bases. These bases may be used alone, or in a combination of two or more. The base may be used in a stoichiometric amount or more than the stoichiometric amount, with respect to compound (2). Specifically, the base is preferably used in an amount of 1 to 5 moles, and more preferably 1 to 3 moles, per mole of compound (2). When used, triethylamine, pyridine, or like organic base may be used in large excess to serve also as a reaction solvent The above reaction may be carried out in a suitable solvent or in the absence of a solvent. When the reaction is carried out in a solvent, usable solvents for the reaction are not limited insofar as they are inert i to m&reaction. ^Examples^fisolvenfe indude'n-hexane, cydohexane, n-heptane, and like aliphatic or alicyclic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and like aromatic hydrocarbons; methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, and like halogenated hydrocarbons; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane, and like ethers; N,N-dimethylformamide (DMF), and like amides; dimethylsulfoxide, and like sulfoxides; and the like. These solvents may be used alone or in a combination of two or more, as required. The reaction temperature of the above reaction is usually in, although not limited, the range of -20°C to the boiling point of the solvent used. The reaction is preferably performed under reflux of the solvent The reaction time varies according to, for example, the reaction temperature. The reaction is usually completed in about 0.5 to about 24 hours. Reaction Scheme 2 As shown in Reaction Scheme 2, a dihydropyrazole compound represented by Formula (1B-2) or a salt ' thereof (hereinafter referred to as "compound (1B-2)") is prepared by reducing compound (1B-1) in a solvent Reaction Scheme 2 R2 -R3 Reducing agent — ^- N= R1'% R2 >-R3 O^R^ Solvent X HO "R4 (1B-1) (11 3-2) (wherein R1, R2, R3, and R4 are as defined above, and the wavy lines represent optical isomers.) Reaction Scheme 3 As shown in Reaction Scheme 3, a pyrazole compound represented by Formula (1A-2) or a salt thereof (hereinafter referred to as "compound (1A-2)"), or a compound (1B-2) is prepared by reducing compound (1A-1) in a solvent. Reaction Scheme 3 R2 R2 R2 R M R3 ^eduo^n^ R1 K ^ R M R3 O^R4 • S°IVent HO^R4 0r HO--V HX (1M)--1Z, - I.£r£: = 1~1 2-1 (1A-2) (1B-2) (wherein R1, R2, R3, and R4 are as defined above, and the wavy lines represent optical isomers.) In the reduction reaction in Reaction Scheme 2 or Reaction Scheme 3 above, a reducing agent may be used. Examples of such a reducing agent include, but are not particularly limited to:- boron compounds, and the like. Examples of boron compounds include sodium borohydride, potassium borohydride, and like alkali metal borohydride compounds; sodium triacetoxyborohydride; sodium cyanoborohydride; and the like. These reducing agents may be used alone or in a combination of two or more. The reducing agent is used in an amount of preferably 1 to 3 moles, and more preferably 1.5 to 2.5 moles, per mole of compound (1B-1) or compound (1A-1). Examples of solvents include, but are not particularly limited to, methanol, ethanol, isopropanol, and like lower alcohols; diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, and like ether-based solvents; benzene, toluene, and like aromatic hydrocarbon-based solvente; and the like. Of these solvents, Iowa alcohols are preferable, and 2-propanol is more preferable. These solvents may be used alone or in a combination of two or more. The reaction temperature of the above reaction is usually in, although not limited, the range of -10°C to the boiling point of the solvent used. The reaction is preferably performed at room temperature. The reaction time varies according to, for example, the reaction temperature. The reactbn is usually completed in about 0.5 to about 24 hours. Reaction Scheme 4 As shown in Reaction Scheme 4, a pyrazole compound represented by Formula (lA-li) (haeinafter referred to as "compound (1A-1)") is prepared by oxidizing compound (1B-1) in a solvent. Reaction Scheme 4 R2 R2 ' \. Oxidizing agent .; R1'NV^R3 " ~^— R1'N^R3 O^R4 (1A-1) Solvent O^R4 (1B-1) (wherein R1, R2, R3, and R4 are as defined above, and the wavy lines represent optica) isomers.) ;l\n oxidizing agent mayle-used for-the oxidation above. Examples of such an oxidizing agent include, but are not particularly limited to, lead compounds, such as lead oxide (PbCk, Pt>304), lead tetraacetate (Pb(OAc)4), lead trifluoroacetate (Pb(OCOCF3>t); copper compounds, such as copper chloride, copper acetate, copper benzoate, copper carbonate, and copper nitrate; iron compounds, such as iron chloride, iron acetate, iron sulfate, and iron nitrate; manganese compounds, such as manganese chloride, manganese acetate, manganese oxide; zinc compounds, such as zinc chloride and z'ric acetate; and the like. These oxidizing agents may be used alone or in a combination of two or more. The amount of the oxidizing agent used is not particularly limited. The oxidizing agent used is usually 1 mole or more, preferably 1 to 3 moles, and more preferably 1.5 to 2.5 moles, per mole of compound (1B-1)- Examples of solvents include n-hexane, cydohexane, n-heptane, and like aliphatic or alicydic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and like aromatic hydrocarbons; methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride^ and like halogenated hydrocarbons; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane, and like ethers; N,N-dimethylfbrrnamide (DMF), and like amides; dimethyteulfbxide, and like sulfoxides; and the like. These solvents may be used alone or in a combination of two or more. The reaction temperature of the above reaction is usually in, although not limited, the range of -10°C to the boiling point of the solvent used. The reaction is preferably performed at room temperature. The reaction time varies according to, for example, the reaction temperature. The reaction is usually completed in about 0.5 to about 24 hours. Reaction Scheme 5 As shown in Reaction Scheme 5, a pyrazole compound represented by Formula (lA'-l) (hereinafter referred to as "compound (1A'-1)") is prepared by reacting an amino compound represented by Formula (4) (hereinafter referred to as "compound (4)") with a compound represented by Formula (5) (hereinafter referred to as "compound (5)") in a solvent in the presence of a catalyst and a base. Reaction Scheme 5 R2 Z-R4 Catalst, Base R2 R1'NVAR3 + Solvent R1'N^^R3 NH2 (5) HNL A R4 i: ^f 12 -^-a - — i^ '■ § (1A'-1) . (wherein R1, R2, R3, and R4 are as defined above, and Z represents a leaving group) Examples of the leaving group represented by Z include chlorine, bromine, iodine, and like halogen atoms; and substituted or unsubstituted alkyl sulfonate, substituted or unsubstituted aryl sulfonate, and the like. Specific examples of compound (5) include substituted or unsubstituted aryl halide, substituted or unsubstituted heteroaryl halide, and the like, with substituted or unsubstituted aryl halide and substituted or unsubstjtutEd pyridyl halide being preferable. Compound (5) is usually used in an amount of 1 mole or more, preferably 1 to 10 moles, and more preferably 1 to 5 moles, per mole of compound (4). Examples of bases include, but are not particularly limited to, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, and like alkali metal carbonate salts; sodium hydroxide, potassium hydroxide, and like alkali metal hydroxides; sodium hydride, potassium hydride, and like alkali metal hydrides, and other inorganic bases; sodium methoxide, sodium ethoxide, potassium tert-butoxide, and like alkali metal alkoxides; and triethylamine, N,N-diisoprbpylethylamine, pyridine, l,8-diazabicydo[5.4.0]undec-7-ene (DBU), and other organic bases. These bases may be used alone or in a combination of two or more. The base may be used in a stoichiometric amount or more than the stoichiometric amount, with respect to compound (4). Specifically, the base is preferably used in an amount of 1 to 5 moles, and more preferably 1 to 3 moles, per mole of compound (4). The reaction may be performed in the presence of a catalyst. Examples of the catayst include metal catalysts (e.g., metal and metal salts), copper salt complexes (e.g., a oopper salt complex of copper iodide with N,N'-dimethyl-ethylenediamine, proline, or bipyridyl), palladium complexes (e.g., tris(dibenzylidene-acetone)dipalladium (0), palladium acetate, and complexes of xantphos), and the like. The amount of the catalyst used is not particularly limited. The catalyst is usually used in an amount of 0.001 to 1 mole, preferably 0.01 to 0.5 moles, and more preferably 0.05 to 0.3 moles, per mole of compound (4). Examples of solvents indude n-hexane, cydohexane, n-heptane, and like aliphatic or alicydic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and like aromatic hydrocarbons; methylene. chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, and like halogenated hydrocarbons; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane, and like ethers; M,N-dimethylformamide (DMF), and like amides; dimethylsulfoxide and'like sulfoxides; acatonitrile; and the like. These solvents may be used alone or in a combination of two or more. The reaction temperature of the above reaction is usually in, although not limited, the range of -10°C to the boiling point of the solvent used. The reaction is preferably performed under reflux. The reaction time varies according to, for example, the reaction temperature. The reaction is usually completed in about 0.5 to about 24 hours. Reaction Scheme 6 As shown in Reaction Scheme 6, a pyrazole compound represented by Formula (lA'-2) (hereinafter referred to as "compound (1A-2)") is prepared by reacting compound (lA'-l) with a compound 1 represented by Formula (6) (hereinafter referred to as "compound (6)") in a solvent, whether in the presence of a base or not R1'NN^R3 + Z_R7 ^R4 (6) ' (1A'-1) (1A'-2) (wherein R1, R2, R3, R4, and R7 are as defined above, and Z represents a leaving group.) Reaction Scheme 6 R2 Base R2 R1'NN^R3 Solvent T R?%4 Examples of the leaving group represented by Z of compound (6) indude chlorine, bromine, iodine, and like halogen atoms; and substituted or unsubsrjtuted alkyl sulfonate, substituted or unsubstituted aryl sulfonate, and the like. Spedfic examples of compound (6) indude methyl halide, ethyl halide, acetyl halide, methoxycarbonyl halide, and the like. HISDornf&Snd (6) is:.usually3useeEin ari amount 611 mole or more, preferably 1 to 10 moles, and more preferably 1 to 5 moles, per mole of compound (1A'-1). Examples of bases include, but are not particularly limited to, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, and like alkali metal carbonate salts; , sodium hydroxide, potassium hydroxide, and like alkali metal hydroxides; sodium hydride, potassium hydride, and like alkali metal hydrides, and other inorganic bases; sodium methoxide, sodium ethoxide, potassium tert-butoxide, and like alkali metal alkoxides; and triethylamine, N,N-diisopropylethylamine, pyridine, l,8-diazabicydo[5.4.0]undec-7-ene (DBU), and other organic bases. These bases may be used alone or in a combination of two or more. The base may be used in a stoichiometric amount or more than the stoichiometric amount, with respect to compound (lA'-l). Specifically, the base is preferably used in an amount of 1 to 5 moles, and more preferably 1 to 3 moles, per mole of compound (lA'-l). Examples of solvents include n-hexane, cydohexane, n-heptane, and like aliphatic or alicydic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and like aromatic hydrocarbons; methylene chbride, 1,2-dichloroethane, chloroform, carbon tetrachloride, and like halogenated hydrocarbons; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane, and like ethers; NIN-dimethylformamide (DMF), and like amides; dimethylsulfoxide and like sulfoxides; acetonitrile; and the like. These solvents may be used alone or in a combination of two or more. The reaction temperature of the above reaction is usually in, although not limited, the range of -10°C to the boiling point of the solvent used. The reaction is preferably performed under reflux. The reaction time varies according to, for example, the reaction temperature. The reaction is usually completed in about 0.5 to about 24 hours. Compound (2), compound (3), compound (4), and compound (5), used as starting materials in Reaction Scheme 1 or Reaction Scheme 5 above are known compounds or compounds easily prepared by a known method. Each compound (1) obtained after the completion of the reactions shown in Reaction Scheme 1 to Reaction Scheme 6 may be easily isolated from the reaction mixture and-purified by known isolation and purification techniques, such as filtration, solvent extraction, distillation, recrystallization, and column chromatography. When compound (1) has regioisomers, each regioisomer may be separated by a usual separation step, such as silica gel chromatography. Pest-Controlling Agent Compound (1) of the present invention may be used as an active ingredient of a pest-controlling agent. Examples of pest-controlling agents indude agents (fungiddes or viruddes) for controlling plant diseases that cause problems in the agricultural and horticultural fields; agents (agricultural and horticultural insectidde, mitiddes, nematiddes, or soil insectiddes) for controlling pests, mites, nematode, or soil pests that all cause problems in the agricultural and horticultural fields; animal-ectoparasite-controlling agents (e.g., pulidde, ixodidde, and pedivuliddeon), and the like. For use as an active ingredient of a pest-controlling agent, it is possible to use compound (1) of the present invention as is with no additional components. However, it is usually preferable to use the compound by combining with a solid carrier, liquid carrier, or gaseous carrier (propellant), and optionally with a surfactant and other adjuvants for pharmaceutical preparation, and formulating the resulting mixture into various forms such as oil solutions, emulsions, wettable powders, flowable preparations, granules, dusts, aerosols, fumigants, or the like, according to known preparation methods. Compound (1) of the present invention is usually contained in these formulations in a proportion of 0.01 to 95 wt%, and preferably 0.1 to 50 wt%. Examples of solid carriers usable in the formulations indude solid carriers in a fine powder or granular form, such as day (e.g., kaolin day, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, Fubasami day, and add day), talc, ceramic, other inorganic minerals (e.g., celite, quartz, sulfur, active carbon, caldum carbonate, and hydrated silica), and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride); and the like. Examples of liquid earners indude water, alcohols (e.g., methanol and ethanol), ketones (e.g., acetone and methylethylketone), aromatic hydrocarbons (e.g., benzene, toluene, xylene, ethylbenzene, and methylnaphthalene), aliphatic hydrocarbons (e.g., hexane, cydohexane, kerosene, and light oil), esters (e.g., ethyl aoatate and butyl acetate), nitriles (e.g., acetonitrile and isobutyronitrile), ethers (e.g., diisopropyl ether and dioxane), add amides (e.g., N,Akiimethylformamide and /V,Akiimethylacetamide), halogenated hydrocarbons (e.g., dichloromethane, trichloroethane, and carbon tetrachloride), dimethylsulfoxide, soybean oil, cottonseed oil, and like vegetable oils, and the like. Examples of gaseous earners include butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas, and the like. Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl aryl ethers, polyoxyethylene adducts thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, and the like. Examples of adjuvants for pharmaceutical preparation include fixing agents, dispersaits, stabilizers, and the like. Examples of the fixing agents and dispersants include casein, gelatin, polysaccharides (e.g., starch, gum arabic, cellulose derivatives, and alginic acid), lignin derivatives, bentonite, sugars, and water-soluble synthetic polymers (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acids). Examples of stabilizers include PAP (acidic isopropyl phosphate), BHT (2,6-di-^f butyl-4-methyIphenol), BHA (mixture of 2-te^-butyl-4methoxyphenol and 3-fer£butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty adds, and fatty acid esters, and the like. For the pest-controlling agent of the present invention, it is preferable to use compound (1) as is, or by diluting it with water or the like. The pest-controlling agent of the present invention may be used by mixing with, for example, other pest-controlling agents, such as known insecticides, nematodes, acaricides, fungicides, herbicides, plant-growth-controlling agents, synergists, soil conditioners, animal feeds, and the like, or it may be used simultaneously with these agents without mixing. The amount of the pest-controlling agent of the invention is not limited, and may be suitably selected from a wide range aocording to various conditions such as the concentration of active ingredient, the form of preparation, type of disease or pest to be treated, type of plant, severity of disease, time for application, method of application, chemicals to be used in combination (insecticide, nematia'de, miticide, fungicide, herbicide, plant growth control agent, synergist, soil conditioner, etc.), and amount and type of fertilizer. When used as a fungicide, compound (1) of the present invention is usually used in an amount of 0.01 to 500 g/100 m2, and preferably 1 to 200 g/100 m2. I^WheffuSed aI;a^mitidde?!c&mf>ound '(4) 6r%i§ present invention is usually used in an amount of 0.1 to 500 g/100 m2, and preferably 1 to 200 g/100 m2. When the emulsion, wettable powder, flowable preparation, or the like is used by diluting with water, the concentration is 0.1 to 1,000 ppm, and preferably 1 to 500 ppm. The granules, dusts, or the like can be used as is without dilution. The amount or concentration of application of the compound may be suitably increased or decreased according to the type of formulation, time of application, place of application, methoc of application, type of insect, severity of damage, and the like. Compound (1) of the present invention is characterized by having a particularly excellent fungicidal activity and a broad spectrum of activity. The compound may be used for controlling plant diseases ascribed to various fungal pathogens or resistant fungal pathogens. Examples of such fungal pathogens include those that cause cucumber gray mold, rice plant blast, rice plant sheath blight, apple powder/ mildew, apple Altemaria blotch, persimmon powdery mildew, grape powdery mildew, barley powdery mildew, wheat powdery mildew, cucumber powdery mildew, cucumber gray mold, tomato late blight, strawberry powdery mildew, tobaooo powdery mildew, and the like. Compound (1) of the present invention is effectively used as an agricultural and horticultural insecticide, mfticide, nematicide, or a soil insecticide. Specifically, compound (1) of the present invention is effective for controlling pests, such as green peach aphids, cotton apNds, and like aphids; diamondback moths, cabbage armyworms, common cutworms, codling moths, bollworms, tobacco budworms, gypsy moths, rice leafrollers, smaller tea tortrix moths, Colorado potato beeties, cucurtjit leaf beetles:, boll weevils, plant hoppers, leafhoppers, scales, bugs, whiteflies, thrips, grasshoppers, anthomyiid flies, scarabs, black cutworms, cutworms, ants, and agricultural pest insects; slugs, snails, and like gastropods; rat mite, cockroaches, houseflies, house mosquitoes, and like hygiene-harming insects; angoumois grain moths, adzuki bean weevils, red flour beetles, mealworms, and like stored-grain insects; casemaking dothes moths, black carpet beeties, subterranean termites, and like dothes-harming insects and house- and household-harming insects; and the like, mites, such as two-spotted spider mites, carmine spider mites, ■ citrus red mites, Kanzawa spider mites, European red mites, broad mites, pink dtrus rjst mites, bulb mites, and like plant-parasitic mites; Tyrvphagus putrescentiae, Dermatophagoides farinae, Chelacampsis moorei, arid like house dust mites; and the like, and soil pests, such as root-knot nematodes, cyst nematodes, root-lesion nematodes, white-tip nematode, strawberry bud nematode, pne wood nematode, and like plant parasitic nematodes; pill bugs, sow bugs, and like isopods; and the like. The pest-controlling agent of the present invention is also effective for controlling vaious pests resistant to chemicals such as organophosphorus agents, carbamate agents, synthetic pyrethroid agents, and neonicorjnoid agent. Examples The present invention is described in more detail with reference to the following Examples; however, the present invention is not limited to these Examples. Production Example 1: Production of N'-(2-chlorophenyl)aoetohydrazide To a cooled solution of l-(chlorophenyl)hydrazine (3.0 g, 21.12 mmol, 1 equiv.) in dichloromethane (40 ml), was slowly added triethyl amine (6.41 g, 63.36 mmol, 3 equiv.) followed by acetc anhydride (2.59 g, 25.35 mmol, 1.2 equiv.). The resulting mixture was then stirred at room temperature for 3 hrs. The reaction mixture was then poured into cold water and extracted with dichloromethare. The combined organic layer was washed with distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to get 2.5 g of the crude product The crude product thus obtained was used in the subsequent reaction without any purification. Hi NMR (DMSOd6): 6 9.79 (bs, 1H), 7.37 (bs, 1H), 7.28-7.26 (m, 1H), 7.17-7.13 (m, 1H), 6.76-6.72 (m, 2H), 1.92 (s, 3H). Production Example 2: Production of (E)-3-(4-chlorchfluorophenyl)-l-(pyridin-3-yl)proo-2-en-l-one To a solution of l-(pyridin-3-yl)ethanone (4.00 g, 33.05 mmol, 1 equiv.) and 2-fluoro,4-chlorobenzaldehyde (7.8 g, 49.58 mmol, 1.5 equiv.) in a mixture of THF/water (40/2G ml), was slowly added aqueous NaOH solution (1.3 g, 33.05 mmol, 1.0 equiv., in 10 ml distilled water). The resulting mixture was then stirred at room temperature for 12 hrs. The reaction mixture was then extracted with ethyl acetate. The organic layer was washed with distilled water, dried ova sodium sulfate, filtered, and concentrated under reduced pressure to get a crude product The crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and r>hexane as an eluent to obtain 1.90 g of the title compound. *H NMR (DMSOd6): 5 9.32 (d, J = 1.6 Hz, 1H), 8.85-8.83 (m, 1H), 8.48-8.45 (m, 1H), 8.22 (t, J = 8.4 Hz, 1H), 8.05 (d, J = 15.6 Hz, 1H), 7.80 (d, J = 15.6 Hz, 1H), 7.63-7.58 (m, 2H}, 7.45-7.43 (m, 1H). Example 1: Production of (4-(4-chloro-2-fluorophenyl)-lr(2-chlorophenylM.5-dihydrc)-3-methyl-lH-pyrazol-5Jyl)(pyridin-3-yl) methanone (1B-71) A mixture of N,-(2-chlorophenyl)acetohydrazide (0.88 g, 4.82 mmol, 1.4 equiv.) in phosphorus tt Ixydnioricle (pJOSh, 2^64"g,Il7J20 mmol, 5 equk) was refluxed for 3 hrs under nitrogen atmosphere and volatiles were then removed under reduced pressure. The crude thus obtained was diluted with chloroform (10 ml) and was slowly added triethyl amine (0.696 g, 6.88 mmol, 2.0 equiv.) followed by (E)-3-(4-chloro-fluorophenyl)-l-(pyridin-3-yl)prop-2-en-l-one (0.90 g, 3.44 mmol, 1 equiv.). The reaction mixture was then refluxed for 10 hrs. The reaction mixture was then poured into cold water and extracted with dichloromethane. The combined organic layer was washed with distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to get a crude product The crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane as an eluent to obtain 0.50 g of the title compound. Table 3 shows ^-NMR data of the thus obtained title compound 1B-71. Example 2: Production of (4^4l-(23-yl)methanone (IB-72) A mixture of N'-{4-chlorophenyl)acetohydrazide (0.98 g, 5.36 mmol, 1.4 equiv.) in PGCb (2.94 g, 19.15 mmol, 5 equiv.) was refluxed for 3 hrs under nitrogen atmosphere and volatiles were then removed under reduced pressure. The crude thus obtained was diluted with chloroform (10 ml) and to this was slowly added triethyl amine (0.78 g, 7.66 mmol, 2.0 equiv.) followed by (E)-3<4-chloro-2-fluorophenyl)-l-(pyridin-3-yl)prop-2-en-l-one (1.0 g, 3.83 mmol, 1 equiv.). The resulting mixture was then refluxed for 10 hrs. The reaction mixture was then poured into cooled water and extracted with dichloromethane. The combined organic layer was washed with distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to get a crude product The crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane as an eluent to obtain 0.70 g of the title compound IB-72. Table 3 shows ^-NMR data of the thus obtained title compound IB-72. Example 6: Production of (4-(4

Documents

Application Documents

# Name Date
1 Form 3.pdf 2014-12-16
2 22767-3_Provisiona lSpecification.pdf 2014-12-16
3 GPA-(11-02-2015).pdf 2015-02-11
4 Form-5-(11-02-2015).pdf 2015-02-11
5 Form-1-(11-02-2015).pdf 2015-02-11
6 Correspondence Others-(11-02-2015).pdf 2015-02-11
7 REQUEST FOR CERTIFIED COPY [18-11-2015(online)].pdf 2015-11-18
8 Request For Certified Copy-Online.pdf 2015-11-23
9 Power of Attorney [29-12-2015(online)].pdf 2015-12-29
10 Form 6 [29-12-2015(online)].pdf 2015-12-29
11 Assignment [29-12-2015(online)].pdf 2015-12-29
12 3658-del-2014-GPA-(31-12-2015).pdf 2015-12-31
13 3658-del-2014-Correspondence Others-(31-12-2015).pdf 2015-12-31
14 3658-del-2014-Assignment-(31-12-2015).pdf 2015-12-31
15 Other Patent Document [11-08-2016(online)].pdf 2016-08-11
16 Form 18 [08-03-2017(online)].pdf 2017-03-08
17 Complete specification.pdf 2017-12-08
18 3658-DEL-2014-FER.pdf 2019-10-31
19 3658-DEL-2014-OTHERS [21-04-2020(online)].pdf 2020-04-21
20 3658-DEL-2014-FER_SER_REPLY [21-04-2020(online)].pdf 2020-04-21
21 3658-DEL-2014-CLAIMS [21-04-2020(online)].pdf 2020-04-21
22 3658-DEL-2014-ABSTRACT [21-04-2020(online)].pdf 2020-04-21
23 3658-DEL-2014-PatentCertificate06-11-2023.pdf 2023-11-06
24 3658-DEL-2014-IntimationOfGrant06-11-2023.pdf 2023-11-06

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