WO2007020964A1 - Procede de fabrication d'un compose 4-halogenopyrocatechine - Google Patents

Procede de fabrication d'un compose 4-halogenopyrocatechine Download PDF

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Publication number
WO2007020964A1
WO2007020964A1 PCT/JP2006/316149 JP2006316149W WO2007020964A1 WO 2007020964 A1 WO2007020964 A1 WO 2007020964A1 JP 2006316149 W JP2006316149 W JP 2006316149W WO 2007020964 A1 WO2007020964 A1 WO 2007020964A1
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WO
WIPO (PCT)
Prior art keywords
producing
chloromethylenedioxybenzene
halocatechol
compound
content
Prior art date
Application number
PCT/JP2006/316149
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English (en)
Japanese (ja)
Inventor
Shigeyoshi Nishino
Akira Nakamura
Hiroyuki Oda
Yoji Omata
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
Application filed by Ube Industries, Ltd. filed Critical Ube Industries, Ltd.
Priority to CN2006800297717A priority Critical patent/CN101243030B/zh
Priority to JP2007531017A priority patent/JP5338072B2/ja
Publication of WO2007020964A1 publication Critical patent/WO2007020964A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring

Definitions

  • the present invention relates to a novel method for producing a 4-halocatechol compound.
  • the 4-halocatechol compound is a useful compound as a raw material for pharmaceuticals, agricultural chemicals, etc. and as a synthetic intermediate.
  • the present invention also relates to high-purity 4-chloromethylenedioxybenzene and a process for producing the same.
  • High purity 4-chloromethylenedioxybenzene is a useful compound as a raw material for pharmaceuticals and agricultural chemicals and as a synthetic intermediate.
  • reaction system is complicated, and gases such as chlorine gas, hydrogen chloride gas, sulfur dioxide disulfide, and other highly toxic and corrosive gases are generated.
  • gases such as chlorine gas, hydrogen chloride gas, sulfur dioxide disulfide, and other highly toxic and corrosive gases are generated.
  • it is disadvantageous as an industrial 4-halocatechol compound manufacturing method.
  • Patent Document 1 International Application WO02 / 16352A1 Pamphlet
  • Non-patent document 1 Synlett, 221 (2003)
  • Non-Patent Document 2 Adv. Synth. Catal., 346, 77 (2004)
  • An object of the present invention is to solve the above-mentioned problems and to obtain a 4-nitrocatechol compound in high yield by a simple method under mild conditions, which is industrially suitable. It is to provide a method for producing a 4-nocatechol compound.
  • the subject of the present invention is also a residual raw material such as methylenedioxybenzene and a by-product such as 4,5-dichloromethylenedioxybenzene, which are most suitable for use as raw materials for pharmaceuticals' agricultural chemicals and synthetic intermediates.
  • the object is to provide a high-purity 4-chloromethylenedioxybenzene containing substantially no impurities and a process for producing the same.
  • the present invention relates to a general formula (1):
  • R 1 and IT represent the same or different hydrocarbon groups
  • R 3 , R 4 and R 5 represent a group not participating in the reaction, wherein R 1 and R 2 may be bonded to each other to form a ring,
  • x represents a halogen atom.
  • R 2 , R 3 , R 4 , R 5 and X are as defined above,
  • the present invention is also characterized in that the content power of methylenedioxybenzene is 0.5% by mass or less and the content of 4,5-dichloromethylenedioxybenzene is 0.5% by mass or less. -Relates to chloromethylenedioxybenzene.
  • the present invention further relates to a process for producing high-purity 4-chloromethylenedioxybenzene, which is obtained by reacting methylenedioxybenzene with a chlorinating agent and then purifying it by distillation.
  • a 4-halocatechol compound can be obtained in a high yield with a simple method under mild conditions. Can provide a manufacturing method.
  • methylenedioxybenzene as a residual raw material and 4,5-dichloromethylenedioxybenzene as a by-product which are most suitable for use as raw materials for pharmaceuticals' agricultural chemicals and synthetic intermediates, etc.
  • a high-purity 4-chloromethylenedioxybenzene and a process for producing the same which are substantially free of impurities. Lead these compounds to pharmaceuticals, pesticides, etc.
  • WO 02/163521 A1 can be referred to.
  • the catechol compound used in the reaction of the present invention is represented by the general formula (1).
  • R 1 and R 2 represent a hydrogen atom or a hydrocarbon group which may be the same or different, and examples of the hydrocarbon group include a methyl group, an ethyl group, and a propyl group.
  • Alkyl group having 1 to 10 carbon atoms such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclo A cycloalkyl group having 3 to 8 carbon atoms such as a heptyl group or a cyclooctyl group; an aralkyl group in which an aryl group is bonded to an alkyl group having 1 to 6 carbon atoms such as a phenethyl group or a phenylpropyl group; a full group And aryl groups having 6 to 20 carbon atoms such as p-tolyl group, naphthyl group and anthryl group.
  • R 1 and R 2 may be bonded to each other to form a ring.
  • the ring formed by bonding include a methylenedioxy ring and an ethylenedioxy ring containing an alkylene group having 1 to 3 carbon atoms. And propylenedioxy ring.
  • R 1 and R 2 are bonded to each other to form a methylene group are particularly preferable.
  • R 3 , R 4 and R 5 each represent a group not involved in the reaction. Specifically, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a halogen atom, It represents a hydroxyl group, an alkoxyl group, an alkylthio group, a nitro group, a cyano group, a carboxylic group, an amino group or a carboxyl group.
  • alkyl group examples include, for example, 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, and a decyl group.
  • alkyl group examples include various isomers.
  • cycloalkyl group examples include cycloalkyl groups having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. .
  • aralkyl group examples include an aralkyl group in which an aryl group is bonded to an alkyl group having 1 to 6 carbon atoms such as a benzyl group, a phenethyl group, or a phenylpropyl group. It is done. These groups include various isomers.
  • aryl group examples include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a P-tolyl group, a naphthyl group, and an anthryl group. These groups include various foreign substances.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkoxyl group examples include an alkoxyl group having 1 to 10 carbon atoms such as a methoxyl group, an ethoxyl group, and a propoxyl group. These groups include various isomers.
  • alkylthio group examples include alkylthio groups having 1 to 10 carbon atoms such as a methylthio group, an ethylthio group, and a propylthio group. These groups include various isomers.
  • the 1,3-diha-5,5-dimethylhydantoin used in the reaction of the present invention is represented by the general formula (2).
  • X is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferable.
  • the amount of 1,3-diha-5,5-dimethylhydantoin used is preferably 0.4 to 1.3 mol, more preferably 0.45 to 1.15 mol, per 1 mol of the catechol compound.
  • the solvent used preferably in the presence of a solvent is not particularly limited as long as it does not inhibit the reaction.
  • a solvent for example, water; formic acid, acetic acid, propionic acid
  • Carboxylic acids such as methanol, ethanol, isopropyl alcohol, t -butyl alcohol, etc .
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ -dimethylacetate
  • Sulfoxides such as dimethyl sulfoxide
  • Sulfones such as sulfolane
  • -Tolyls such as acetonitrile and propio-tolyl
  • Ethers such as jetyl ether, diisopropyl
  • the amount of the solvent used is preferably 0.5 to 100 ml, more preferably 1 to 50 ml, relative to catechol compound lg.
  • the reaction of the present invention is carried out, for example, by a method of mixing a catechol compound, 1,3-diha-5,5-dimethylhydantoin and a solvent and reacting them with stirring.
  • the reaction temperature at that time is preferably ⁇ 20 to 200 ° C., more preferably 0 to 120 ° C., and the reaction pressure is not particularly limited.
  • reaction of the present invention is particularly useful for producing a 4-halocatechol compound such as 4-halomethylenedioxybenzene from a weakly strong alcohol compound such as methylenedioxybenzene. This is an advantageous method.
  • the following methylenedioxy O carboxymethyl content force 0.1 0/0 of benzene, and 4,5-content of dichloromethylene di O carboxymethyl benzene preferably not more than 0.1 mass% instrument further preferred details, at a content of methylene di O carboxymethyl benzene 0.01 0/0 or less, and the content of 4,5-dichloro-methylenedioxy O carboxymethyl benzene is 0.01 0/0 or less.
  • the high purity 4-chloromethylenedioxybenzene of the present invention can be obtained by distillation purification after reacting a chlorinating agent with methylenedioxybenzene.
  • the distillation purification method is, for example, at least selected from the group consisting of Sulzer One Pack (registered trademark), Paul Ring, Merapack (registered trademark), Meracarbon (registered trademark), and Mellajour (registered trademark).
  • One kind of packing is carried out by a method such as distillation purification by packing one or more in the distillation column of a distillation apparatus.
  • the filler is preferably filled with two or more theoretical plates. There are no particular restrictions on the temperature or pressure during distillation purification.
  • chlorinating agent examples include sulfuryl chloride, 1,3-dichloro-5,5-dimethylhydantoin, trichloroisocyanuric acid, t-butyl hypochlorite, and the like. 3,3-Dichloro-5,5-dimethylhydantoin is used. These chlorinating agents may be used alone or in combination of two or more.
  • the amount of the chlorinating agent used is preferably 0.
  • the amount is 4 to 1.3 mol, more preferably 0.45 to 1.15 mol.
  • the reaction of methylenedioxybenzene and chlorinating agent is preferably carried out in the presence of a solvent, and is not particularly limited as long as it does not inhibit the reaction.
  • a solvent Water; carboxylic acids such as formic acid, acetic acid and propionic acid; alcohols such as methanol, ethanol, isopropyl alcohol and t-butyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Amides such as formamide, ⁇ , ⁇ -dimethylacetamide, ⁇ -methylpyrrolidone; Ureas such as ⁇ , ⁇ '-dimethylimidazolidinone; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Acetonitrile, Propio -Tolyls such as -tolyl; jetyl ether, diisopropyl ether, tetrahydrofuran,
  • the amount of the solvent used is preferably 0.5 to 100 ml, more preferably 1 to 50 ml based on methylenedioxybenzene lg.
  • the reaction between the methylenedioxybenzene and the chlorinating agent is performed by, for example, a method of mixing methylenedioxybenzene, a chlorinating agent and a solvent and reacting them while stirring.
  • the reaction temperature at that time is preferably ⁇ 20 to 200 ° C., more preferably 0 to 120 ° C., and the reaction pressure is not particularly limited.
  • reaction solution was cooled to room temperature, 245 ml of hexane and 245 ml of water were added to the reaction solution and stirred, and then the organic layer was separated.
  • the obtained organic layer was washed with a 10% aqueous sodium hydroxide solution and a 10% aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and then the concentrated solution was distilled under reduced pressure (85 ° C, 1067 to 1333 Pa) to obtain 227.3 g of 4_chloromethylenedioxybenzene as an colorless liquid (isolation yield) 72.6%).
  • reaction solution was cooled to room temperature, and 200 g (1.0 mol) of 20% aqueous sodium hydroxide solution was added to the reaction solution and stirred. Next, the reaction solution was filtered to separate the organic layer, and then the organic layer was distilled under reduced pressure (93 ° C., 1200 Pa) to obtain 71.2 g of 4-bromomethylenedioxybenzene as a colorless liquid (isolated product). Rate; 70.8%).
  • Example 4 (Synthesis of 4 bromoveratrol (4 bromo 1,2 dimethoxybenzene)) 13.8 g (100 mmol) of veratrol under argon atmosphere in a 100 ml glass flask equipped with stirrer and thermometer Then, 21.0 g (350 mmol) of acetic acid was cooled to a temperature of 10-20 ° C. Then, after 30 minutes, 17.2 g (60 mmol) of 1,3-dibromo-5,5-dimethylhydantoin was added little by little, and then reacted at 10 to 20 ° C. for 1 hour. After completion of the reaction, 25 ml of toluene was added and the mixture was stirred at 10 to 20 ° C.
  • the filtrate was divided into four parts, the first fraction was added to a mixed solvent of toluene (50 ml) _water (25 ml), the target product was extracted into a toluene layer, and acetic acid was removed into the aqueous layer. 25 ml of water was added to the obtained toluene extract, and subsequently combined with the second fraction of the filtrate, and then the extraction operation was carried out in the same manner to obtain a toluene extract. Repeat the same procedure for the remaining two fractions, and then separate all the filtrates.
  • the resulting toluene extract is twice with 25 ml of water, once with 20 ml of saturated aqueous sodium hydrogen carbonate solution, and finally. And washed once with 35 ml of saturated saline.
  • the obtained Toru When the extracted solution was analyzed by high performance liquid chromatography (absolute quantification method), it contained 19.8 g (yield 91.6%) of 4 bromoveratrol. After concentrating the toluene extract, the resulting concentrate (crude 4 bromoveratrol) was distilled under reduced pressure (5 mmHg, bp 99-100 ° C) to obtain 15.8 g of 4 bromoveratrol as a pale yellow liquid ( Isolated yield 72.9%).
  • the reaction solution was cooled to room temperature, and 1000 g (6.25 mol) of 25% aqueous sodium hydroxide solution was added to the reaction solution and stirred.
  • the organic layer was distilled under reduced pressure (84 ° C, 1067-1200Pa) using a distillation apparatus packed with 3 pieces of Sulzer Pack (55mmH x 2.5mm) in a distillation column, and then a colorless liquid
  • 420.7 g of 4-chloromethylenedioxybenzene purified by distillation was obtained (isolation yield; 67.2%).
  • the obtained 4-chloromethylenedioxybenzene was analyzed by high performance liquid chromatography (absolute quantitative method).
  • 4-chloromethylenedioxybenzene contained 4-chloromethylenedioxybenzene with respect to 4-chloromethylenedioxybenzene.
  • methylenedioxy O carboxymethyl benzene residual feedstock 0.17 mass 0/0
  • the by-product 4,5-Jikurorome Chi range O carboxymethyl benzene contained only 0.35 wt 0/0.
  • the reaction solution was cooled to room temperature, 120 ml of hexane and 120 ml of water were added to the reaction solution and stirred, and then the organic layer was separated.
  • the obtained organic layer was washed with 10% aqueous sodium hydroxide solution 100 g (0.25 mol) and 10% aqueous sodium chloride solution 100 g (0.25 mol), and then dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the concentrate was distilled under reduced pressure (86 ° C, 1333 Pa) using a distillation apparatus packed with three Sulzer packs (55 mmH x 2.5 mm ⁇ ) in a distillation column, and colorless. As a liquid, 97.
  • Example 8 (Synthesis of high purity 4-chloromethylenedioxybenzene by distillation purification of crude 4-chloromethylenedioxybenzene) 0.96 mass methylenedioxy O carboxymethyl benzene residual feedstock 0/0, Suruza one pack byproducts 4,5 Jikuroromechi range O carboxymethyl benzene 1.84 mass 0/0 containing crude 4-chloromethylene-di O carboxymethyl benzene 594.86g (55mmH x 2.5mm) 4_chloromethylenedioxybenzene distilled and purified as a colorless liquid by vacuum distillation (80-81 ° C, 933-1066Pa) using a distillation apparatus packed with 2 pieces in a distillation column 365.59g was obtained.
  • the present invention relates to a novel method for producing a 4-halocatechol compound.
  • the 4-halocatechol compound is a useful compound as a raw material for pharmaceuticals, agricultural chemicals, etc. and as a synthetic intermediate.
  • the present invention also relates to high-purity 4-chloromethylenedioxybenzene and a process for producing the same.
  • High purity 4-chloromethylenedioxybenzene is a useful compound as a raw material for pharmaceuticals and agricultural chemicals and as a synthetic intermediate.

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

Abstract

L’invention concerne un procédé de fabrication d'un composé 4-halogénopyrocatéchine, caractérisé en ce qu’un composé pyrocatéchine est mis en réaction avec le 1,3-dihalogéno-5,5-diméthylhydantoine. L’invention concerne également un 4-chlorométhylènedioxybenzène de haute pureté, caractérisé en ce que la teneur en méthylènedioxybenzène n’est pas supérieure à 0,5 % en poids, et en ce que la teneur en 4,5-dichlorométhylènedioxybenzène n’est pas supérieure à 0,5 % en poids, ainsi qu’un procédé de fabrication d’un tel 4-chlorométhylènedioxybenzène de haute pureté.
PCT/JP2006/316149 2005-08-17 2006-08-17 Procede de fabrication d'un compose 4-halogenopyrocatechine WO2007020964A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2006800297717A CN101243030B (zh) 2005-08-17 2006-08-17 4-卤代邻苯二酚化合物的制备方法
JP2007531017A JP5338072B2 (ja) 2005-08-17 2006-08-17 ４−ハロカテコール化合物の製法

Applications Claiming Priority (4)

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JP2005236570 2005-08-17
JP2005-236571 2005-08-17
JP2005236571 2005-08-17
JP2005-236570 2005-08-17

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008285473A (ja) * 2008-04-07 2008-11-27 Nippo Kagaku Kk ヨウ素化芳香族化合物の製造方法
CN101121661B (zh) * 2007-09-18 2011-06-01 华东师范大学 β-酮酯和1,3-丙二酸酯类单氯代化合物的制备方法

Citations (4)

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Publication number Priority date Publication date Assignee Title
EP0549263A2 (fr) * 1991-12-27 1993-06-30 Chemagis Ltd. Procédé de préparation de N-alkyl-3,4-dialkyloxyanilines et leur dérivatives
JPH0959197A (ja) * 1995-08-17 1997-03-04 Fuji Photo Film Co Ltd １，３−ジハロ−５，５−ジメチルヒダントインを用いたハロゲン化置換フェノール類の製造方法
JPH11246453A (ja) * 1998-03-04 1999-09-14 Asahi Chem Ind Co Ltd メタクロレイン及びメタノールの回収方法
JP2004506732A (ja) * 2000-08-21 2004-03-04 アストラゼネカ　アクチボラグ キナゾリン誘導体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0549263A2 (fr) * 1991-12-27 1993-06-30 Chemagis Ltd. Procédé de préparation de N-alkyl-3,4-dialkyloxyanilines et leur dérivatives
JPH0959197A (ja) * 1995-08-17 1997-03-04 Fuji Photo Film Co Ltd １，３−ジハロ−５，５−ジメチルヒダントインを用いたハロゲン化置換フェノール類の製造方法
JPH11246453A (ja) * 1998-03-04 1999-09-14 Asahi Chem Ind Co Ltd メタクロレイン及びメタノールの回収方法
JP2004506732A (ja) * 2000-08-21 2004-03-04 アストラゼネカ　アクチボラグ キナゾリン誘導体

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AUERBACH J. ET AL., TETRAHEDRON LETTERS, vol. 34, no. 6, 1993, pages 931 - 934, XP003002198 *
HARAYAMA T. ET AL., HETEROCYCLES, vol. 59, no. 1, 2003, pages 293 - 301, XP003002199 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121661B (zh) * 2007-09-18 2011-06-01 华东师范大学 β-酮酯和1,3-丙二酸酯类单氯代化合物的制备方法
JP2008285473A (ja) * 2008-04-07 2008-11-27 Nippo Kagaku Kk ヨウ素化芳香族化合物の製造方法

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JPWO2007020964A1 (ja) 2009-02-26
CN101243030B (zh) 2012-02-01
CN101243030A (zh) 2008-08-13
JP5338072B2 (ja) 2013-11-13

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