+

WO2003064377A1 - 2-formylaminobenzamides-4,5 substitues et methodes de production et de conversion desdits composes - Google Patents

2-formylaminobenzamides-4,5 substitues et methodes de production et de conversion desdits composes Download PDF

Info

Publication number
WO2003064377A1
WO2003064377A1 PCT/JP2003/000562 JP0300562W WO03064377A1 WO 2003064377 A1 WO2003064377 A1 WO 2003064377A1 JP 0300562 W JP0300562 W JP 0300562W WO 03064377 A1 WO03064377 A1 WO 03064377A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
substituted
group
formylaminobenzamide
general formula
Prior art date
Application number
PCT/JP2003/000562
Other languages
English (en)
Japanese (ja)
Inventor
Masashi Shirai
Toshio Furuya
Original Assignee
Ube Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2002019583A external-priority patent/JP4281280B2/ja
Priority claimed from JP2002077880A external-priority patent/JP4296747B2/ja
Application filed by Ube Industries, Ltd. filed Critical Ube Industries, Ltd.
Publication of WO2003064377A1 publication Critical patent/WO2003064377A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having carbon atoms of carboxamide groups, amino groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C07D239/72—Quinazolines; Hydrogenated quinazolines
    • C07D239/86—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in position 4
    • C07D239/88—Oxygen atoms

Definitions

  • the present invention relates to a 4,5-substituted-2-formylaminonovenzamide compound useful as a synthetic intermediate for pharmaceuticals, a method for industrially and efficiently producing the compound, and a method for industrially and efficiently producing the compound. , 7-substituted-quinazolin-4-ones. Background art
  • a conventional method for producing 4,5-substituted-2-formylamino novenzamide is disclosed in Acta Chim. Acad. Sci. Hung., 94, 233 (1977).
  • acetic acid-formic acid mixed anhydride used as a formylating agent in the above-mentioned conventional method is extremely unstable with respect to moisture, and this method is disadvantageous as an industrial production method.
  • the above-mentioned document discloses a method of converting 4,5-methylenedioxy-2-formylaminobenzamide to a 4,5-methylenedioxyquinazolin-4-one by heating it at a high temperature of 245 to 250 ° C. Is described. However, this method requires the above high temperature of 245 to 250 ° C., and therefore, it was difficult to carry out this method as an industrial conversion method.
  • the present invention provides a 4,5-substituted-2-formylaminobenzamide compound having a substituted or unsubstituted hydrocarbonoxy group at the 4 and 5 positions, a method for industrially and efficiently producing the compound, and It is intended to provide a method for converting a compound into a ring.
  • the 4,5-substituted-2-formylaminobenzamide compound of the present invention has the following general formula (1):
  • R 1 and R 2 each independently represent a hydrogen atom, and an unsubstituted alkynole having at least one substituent, a cycloanolequinole, an anorekeninole, Represents a member selected from the group consisting of an aranoquinone, an arynole, and an asinole group, wherein the substituent is an alkyl, cycloalkyl, alkenyl, heterocyclic alkenyl, aryl, acryl, alkoxycarbonyl, aryloxycanoleboninole Selected from alkyl, cyano, hydroxy, alkoxy, aryloxy, mercapto, thioalkoxy, and thioaryloxy groups, and halogen atom.
  • R 1 and R 2 each independently represent a methyl, ethyl, or 2-methoxyl group.
  • the 4,5-substituted-2-formylaminobenzamide compound of the present invention is preferably selected from the following formula (2):
  • the 4,5-substituted-2-formylaminobenzamide compound of the present invention has the following formula (3):
  • the 4,5-substituted-2-formylaminobenzamide compound of the present invention has the following formula (4): And 4,5-diethoxy-2-formylaminobenzamide compounds.
  • the 4,5-substituted-2-formylaminobenzamide compound of the present invention has the following formula (5):
  • R 1 and R 2 are each independently of each other. Represents a hydrogen atom and one member selected from an unsubstituted and at least one substituent selected from the group consisting of anolequinole, cycloalkyl, alkenyl, aralkyl, aryl, and acyl; and the substituent is an alkyl group.
  • Cycloalkyl alkenyl, heterocyclic alkenyl, aryl, acynore, anorecoxycanololeponyl, arixoxycanolebonyl, alkyl halide, cyano, hydroxy, alkoxy, arylioxy, mercapto, Selected from thioalkoxy, thioaryloxy, and halogen atoms.
  • R 1 and R 2 are as defined above
  • the reaction is performed in an organic solvent.
  • R 1 and R 2 in the general formulas (1) and (6) are each independently methyl or ethyl. , And a 2-methoxyl group.
  • the reaction between the 4,5-substituted-2-aminobenzamide of the general formula (6) and formic acid is 10 to 10%.
  • the reaction is carried out at a temperature of 50 ° C.
  • the 4,5-substituted-2-amide of the general formula (6) is preferably used.
  • the organic solvent used in the reaction with formic acid is-a tritol compound, an ether compound, a ketone compound, a halogenated aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, a haegenated aromatic hydrocarbon compound,
  • the compound is selected from a compound, a sulfoxide compound, and a urea compound.
  • the method for converting a 4,5-substituted-2_formylaminobenzamide compound of the present invention comprises a 4,5-substituted-2-formylaminonovenzamide represented by the general formula (1) of the present invention.
  • the compound is subjected to a cyclization reaction in the presence of a basic substance to obtain a compound represented by the following general formula (7):
  • the basic substance may be an alkali metal hydroxide, an alkaline earth metal hydroxide, or an alkali metal carbonate. And alkali metal bicarbonates, and alkali metal alkoxides.
  • the cyclization reaction is performed in a liquid reaction medium.
  • the cyclization reaction is carried out at a temperature of 0 to 100 ° C. Is preferred.
  • the 4,5-substituted-2-formylaminobenzamide compounds of the general formula (1) of the present invention are the same as the 4,5-substituted-2-aminobenzamides substituted by the general formula (6). And formic acid in an organic solvent.
  • R 1 and R 2 each independently represent a hydrogen atom and an unsubstituted and at least one alkynole and cycloanolequinolene having a substituent.
  • Anoleckeninole, aralkynole, aryl, and an acyl group wherein the substituent is an alkyl, cycloalkyl, alkenyl, heterocyclic alkenyl, aryl, ashinole, anorecoxycanololepo Selected from the group consisting of alkylene, halogenated alkyl, cyano, hydroxy, anorecoxy, aryloxy, menolecapto, thioalkoxy, and thioaryloxy groups, and halogen atom.
  • the alkyl group preferably has 1 to 10 carbon atoms
  • a methyl group an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and the like.
  • These groups include various isomers.
  • the cycloalkyl group preferably has 3 to 10 carbon atoms, and more preferably, for example, a cyclopropyl group, a cyclopentinole group, a cyclopentinole group, a cyclohexyl / re group , Cycloheptyl group, cyclooctyl group and the like.
  • the alkenyl group preferably has 2 to 10 carbon atoms, and is more preferably selected from, for example, a butyl group, an aryl group, a propinole group, a butageninole group, and the like. Each of these groups includes various isomers.
  • the aralkyl group preferably has 7 to 20 carbon atoms, and is more preferably selected from, for example, a benzyl group, a phenethyl group, a phenylpropyl group and the like. These groups each include various isomers.
  • the aryl group preferably has 6 to 20 carbon atoms, and is more preferably selected from, for example, a ferr group, a P-trinole group, a naphthyl group, an anthranyl group and the like. Each of these groups includes various isomers.
  • the acetyl group preferably has 2 to 20 carbon atoms, and more preferably, for example, acetyl, propionyl, acryloyl, piperoyl, cyclohexylcarbonyl, benzoyl Group, naphthyl group, toluoyl group and the like. Each of these groups includes various isomers.
  • the aryl group, aryl group and acyl group may have a substituent.
  • the substituent include a substituent bonded via a carbon atom, a substituent bonded via an oxygen atom, a substituent bonded via a sulfur atom, and a halogen atom.
  • Examples of the substituent bonded through the carbon atom include an alkyl group, preferably: an alkyl group having 10 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, Pentyl group, hexyl group and the like; cycloalkyl group, preferably cycloalkyl group having 3 to 10 carbon atoms, for example, cyclopropyl group, cyclobutyl group, cyclopentinole group, cyclohexylene group, An alkenyl group, preferably an alkenyl group having 2 to 10 carbon atoms, for example, a vinyl group, an aryl group, a propenyl group, a cyclopropenyl group, a cyclobutenyl group, A pentenyl group, etc .; a heterocyclic alkenyl group, preferably a pyrrolidyl group, a pyrrolyl
  • the substituent bonded via the oxygen atom is a hydroxyl group; an alkoxy group, preferably an alkoxy group having 1 to 10 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, Pentyloxy group, hexyloxy group, heptyloxy group, benzyloxy group and the like; aryloxy group, preferably an aryloxy group having 6 to 20 carbon atoms, for example, phenoxy group, tolyloxy group, naphthyloxy group and the like. Each of these groups includes various isomers.
  • Examples of the substituent bonded via the sulfur atom include a mercapto group; a thioalkoxy group, preferably a thioalkoxy group containing 1 to 10 carbon atoms, for example, a thiomethoxy group and a thioethoxy group.
  • a thioaryloxy group preferably a thioaryloxy group having 6 to 20 carbon atoms, such as a thioenoxyl group, a thiotoluyloxyl group, a thionaphthyloxyl group or the like; It is.
  • Each of these groups includes various isomers.
  • the halogen atom for the substituent is selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the amount of formic acid used in the formylation reaction in the method of the present invention is preferably 1 to 50 mol, more preferably 2 to 50 mol of the 4,5-substituted-2-aminobenzamide compound. ⁇ 30mol.
  • the formic acid may be used in the form of an aqueous solution.
  • the formylation reaction of the method of the present invention is performed in the presence of an organic solvent.
  • the organic solvent used in the method of the present invention is not particularly limited as long as it does not inhibit the reaction. Examples thereof include nitrile compounds such as acetonitrile and propionitrile; tetrahydrofuran; 1,4-Zoki Ether compounds such as sun; ketone conjugates such as acetone and methylethylketone; and haguchi-genated aliphatic hydrocarbon compounds such as dichloromethane, black mouth form, carbon tetrachloride, and dichloroethane.
  • Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as benzene and dichlorobenzene; ⁇ , ⁇ -dimethylformamide, ,, ⁇ -dimethylacetamide, ⁇ Amide compounds such as -methylpyrrolidone; sulfoxide compounds such as dimethylsulfoxide; and urea compounds such as ⁇ , ⁇ '-dimethylimidazolidinone.
  • nitrile compounds, ether compounds, ketone compounds, halogenated aliphatic hydrocarbon compounds, and aromatic hydrocarbon compounds are used, and more preferably, nitrile compounds, ether compounds, and ketone compounds are used. It is more preferable to use a nitrile compound.
  • These compounds for organic solvents may be used alone or in combination of two or more.
  • the amount of the organic solvent to be used can be appropriately set in consideration of the uniformity of the reaction solution, the stirring property, and the like.
  • the amount of the organic solvent is based on the raw material 4,5-substituted-2-aminobenzamide compound lg. It is preferable to use 1 to 30 g, and more preferably 1 to 15 g.
  • a raw material 4,5_-substituted-2-aminobenzamide compound, formic acid and an organic solvent are mixed and reacted in an inert gas atmosphere. And so on.
  • the reaction temperature at that time is preferably 10 to 50 ° C, more preferably 10 to 30 ° C, and the reaction pressure is not particularly limited.
  • the 4,5-substituted-2-formylaminobenzamide compound represented by the general formula (1) of the present invention is a compound of the following formula (2).
  • Nsamide, 5-ethoxy-4-methoxy-2-formylaminobenzenamide of formula (3), 4,5-diethoxy-2-formylaminobenzamide of formula (4), chemical formula Includes 4,5-bis (2-methoxyethoxy)--formylaminobenzamide in (5).
  • Examples of the base used in the cyclization reaction include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and lithium hydroxide; calcium hydroxide, magnesium hydroxide and the like.
  • an alkali metal hydroxide is used, and more preferably, sodium hydroxide is used.
  • the above bases may be used alone or in combination of two or more.
  • the amount of the base to be used in the above cyclization reaction is preferably 1 to 20 mol, more preferably 2 to 10 mol, per 1 mol of the compound of the general formula (1).
  • the cyclization reaction of the compound of the general formula (1) is preferably performed in the presence of a solvent.
  • the solvent used in this case is not particularly limited as long as it does not inhibit the reaction.
  • the solvent used for the cyclization reaction may be water; acetonitrile, propionitrile, etc.
  • Nitril compounds Nitril compounds; ether compounds such as tetrahydrofuran and 1,4-dioxane; ketone compounds such as acetone and methylethylketone; dichloromethane, chloroforme, carbon tetrachloride, dichloroethane Halogenated aliphatic hydrocarbon compounds such as benzene; toluene, xylene and the like; aromatic hydrocarbon compounds such as chlorobenzene and dichlorobenzene; and halogenated aromatic hydrocarbon compounds such as chlorobenzene and dichlorobenzene; N, N-dimethylformamid Amide compounds such as N, N-dimethylacetamide and N-methylpyrrolidone; sulfoxide compounds such as dimethylsulfoxide; N, N, -diamine Horst Midazori can and Mochiiruko urea compounds such Gino down, preferably water, two preparative Lil compounds, er Ter compounds, ketone
  • the cyclization reaction of the compound of the general formula (1) is preferably performed by a method such as mixing and reacting the compound of the general formula (1) with a base and a solvent in an inert gas atmosphere.
  • a method such as mixing and reacting the compound of the general formula (1) with a base and a solvent in an inert gas atmosphere.
  • the reaction temperature at that time is preferably from 0 to 100 ° C, more preferably from 0 to 50 ° C, and the reaction pressure is not particularly limited.
  • the 6,7-substituted quinazolin-4-one compound of the general formula (7) which is the final product of the above cyclization reaction, is subjected to, for example, filtration, extraction, concentration, distillation, recrystallization, and column chromatography. It can be isolated and purified by a general method such as chromatography.
  • 4,5-Dimethoxy-2-formylaminobenzamide is a novel compound identified by the following physical data.
  • Example 6 the same conversion operation as in Example 5 was performed. However, 4,5-substituted-2-formylaminobenzamide having R 1 and R 2 shown in FIG. 2 in the general formula (1) was used as a starting compound for the conversion reaction.
  • FIG. 2 shows the yield of the conversion product.
  • the 4,5-substituted-2-formylaminobenzamide compounds of the general formula (1) according to the present invention are useful as intermediates of various medicines, and the method of the present invention relates to the compound of the general formula (6)
  • the present invention makes it possible to industrially and efficiently produce a compound of the general formula (1) from a 5-substituted-2-aminobenzamide compound and formic acid by a simple process.
  • the compound of the general formula (1) is cyclized in the presence of a base to give a 6,7-substituted-quinazoline-4 compound of the general formula (7), which is useful as a pharmaceutical intermediate. It can be converted to a compound.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des 2-formylaminobenzamides-4,5 substitués de la formule générale (1), qui peuvent être produits par réaction d'un composé de la formule générale (6) avec un acide formique, dans un solvant organique, puis convertis en quinazoline-4-ones 6,7-substitués de la formule générale (7), par cyclisation, en présence d'une base. Dans ladite formule (1), R1 et R2 sont chacun hydrogène, alkyle éventuellement substitué, cycloalkyle, alcényle, aralkyle, aryle, ou acyle, le substituant étant alkyle, cycloalkyle, alcényle, aralkyle, aryle, acyle, alcoxycarbonyle, halogéno, ou analogue.
PCT/JP2003/000562 2002-01-29 2003-01-22 2-formylaminobenzamides-4,5 substitues et methodes de production et de conversion desdits composes WO2003064377A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2002019583A JP4281280B2 (ja) 2002-01-29 2002-01-29 ４，５−ジアルコキシ−２−ホルミルアミノベンズアミドの製法
JP2002-19583 2002-01-29
JP2002-77880 2002-03-20
JP2002077880A JP4296747B2 (ja) 2002-03-20 2002-03-20 ６，７−ジアルコキシキナゾリン−４−オンの製法

Publications (1)

Publication Number Publication Date
WO2003064377A1 true WO2003064377A1 (fr) 2003-08-07

Family

ID=27667434

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/000562 WO2003064377A1 (fr) 2002-01-29 2003-01-22 2-formylaminobenzamides-4,5 substitues et methodes de production et de conversion desdits composes

Country Status (1)

Country Link
WO (1) WO2003064377A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7705145B2 (en) 2002-09-13 2010-04-27 Astrazeneca Ab Process for the preparation of 4-(3′-chloro-4′-fluoroanilino) -7-methoxy-6-(3-morpholinopropoxy) quinazoline
CN104945332A (zh) * 2014-03-31 2015-09-30 中国科学院广州生物医药与健康研究院 埃罗替尼的制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FETTER J. ET AL.: "Electron deficient heteroaromatic ammonio amidates. Part XIII. N-(3-quinazolinio)amidates, IV.", ACTA CHIMICA ACADEMIAE SCIENTIARUM HUNGARICAE, vol. 94, no. 3, 1977, pages 233 - 260, XP002954476 *
LEMPERT-SRETER M. ET AL.: "Electron deficient heteroaromatic ammonioamediates, XIV. The synthesis and some reactions of 9,10-dimethoxy-2H(1,3,4)-thiadiazino(3,2-c)quinazolin-5-ium-3-olates", ACTA CHIMICA ACADEMIAE SCIENTIARUM HUNGARICAE, vol. 94, no. 4, 1977, pages 391 - 401, XP002954477 *
LEMPERT-SRETER M. ET AL.: "Electron deficient heteroaromatic ammonioamidates. Part 26. N-(quinazolin-3-op)amidates. Part 13. Phototransformations of an N-(quinazolin-2-io)thioamidate and of a 10bH-1,3,4-thiadiazolo(3,2-c)quinazoline, the ring isomer of an N-(quinazolin-3-).....", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1, no. 6, 1984, pages 1143 - 1151, XP002120574 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7705145B2 (en) 2002-09-13 2010-04-27 Astrazeneca Ab Process for the preparation of 4-(3′-chloro-4′-fluoroanilino) -7-methoxy-6-(3-morpholinopropoxy) quinazoline
CN104945332A (zh) * 2014-03-31 2015-09-30 中国科学院广州生物医药与健康研究院 埃罗替尼的制备方法
CN104945332B (zh) * 2014-03-31 2017-10-17 中国科学院广州生物医药与健康研究院 埃罗替尼的制备方法

Similar Documents

Publication Publication Date Title
JP3393891B2 (ja) イミダゾール類の製造方法
JPH06329647A (ja) ２−（４−アルコキシ−３−シアノフェニル）チアゾール誘導体の製造法およびその新規製造中間体
WO2003064377A1 (fr) 2-formylaminobenzamides-4,5 substitues et methodes de production et de conversion desdits composes
JP6884857B2 (ja) フェニルアラニン類化合物の製造方法
WO2003051849A1 (fr) Procede de production de quinazoline-4-one et derive de celle-ci
JP2021088543A (ja) アミドカルボン酸化合物の製造方法、及びアミドアルコール化合物の製造方法、並びにラクトン化合物の製造方法
JP4706320B2 (ja) Ｎ，ｎ−ジメチルアミノアルケノン化合物の製法
WO2006123648A1 (fr) Procede de fabrication de thiophene 3-substitue
JP4639523B2 (ja) ６，７−ジオキシキナゾロン誘導体の製造法
JP4517337B2 (ja) ４−置換キナゾリン化合物の製法
JP4194984B2 (ja) フェニルナフチルイミダゾール化合物
JP3272340B2 (ja) １−［（シクロペント−３−エン−１−イル）メチル］−５−エチル−６−（３，５−ジメチルベンゾイル）−２，４−ピリミジンジオンの製造方法
JP4178793B2 (ja) キナゾリン−４−オン誘導体の製造法
JP4661786B2 (ja) ４−アミノピリミジン化合物の製造法
CN102633728B (zh) 2-氨基嘧啶-4,6-二甲酸的合成方法
JP4281280B2 (ja) ４，５−ジアルコキシ−２−ホルミルアミノベンズアミドの製法
US20250145574A1 (en) Fluoroisoquinoline compound and production method thereof
JP4561635B2 (ja) ４−アルコキシカルボニルテトラヒドロピラン又はテトラヒドロピラニル−４−カルボン酸の製法
JP4296747B2 (ja) ６，７−ジアルコキシキナゾリン−４−オンの製法
WO2005063678A1 (fr) Procede de production d'un derive de l'acide phenylacetique
JP4968602B2 (ja) ベンズアミド誘導体の製造方法
JP3918468B2 (ja) ３，３−ビス（アルコキシカルボニル−メチルチオ）プロピオニトリル及びその製造方法
JP2011190269A (ja) テトラヒドロピラン−４−カルボン酸化合物の製法
JPH0812658A (ja) シドノン類の製造法
JP2002241350A (ja) モノニトロ化芳香族エーテル類の製造法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWE Wipo information: entry into national phase

Ref document number: 1020057010283

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1020057010283

Country of ref document: KR

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载