WO2012173842A2 - Procédé de purification pour du para-méthallylpyrocatéchol - Google Patents

Procédé de purification pour du para-méthallylpyrocatéchol Download PDF

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Publication number
WO2012173842A2
WO2012173842A2 PCT/US2012/041032 US2012041032W WO2012173842A2 WO 2012173842 A2 WO2012173842 A2 WO 2012173842A2 US 2012041032 W US2012041032 W US 2012041032W WO 2012173842 A2 WO2012173842 A2 WO 2012173842A2
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WO
WIPO (PCT)
Prior art keywords
methyl
methallylpyrocatechol
para
grams
benzodioxazole
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2012/041032
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English (en)
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WO2012173842A3 (fr
Inventor
Leonard A. MCMULLEN
Junan JI
Luwei Liu
Krishna RAGHAVAN
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FMC Corp
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FMC Corp
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Filing date
Publication date
Application filed by FMC Corp filed Critical FMC Corp
Priority to CN201280010957.3A priority Critical patent/CN103562169B/zh
Publication of WO2012173842A2 publication Critical patent/WO2012173842A2/fr
Publication of WO2012173842A3 publication Critical patent/WO2012173842A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to a process for the purification of para- methallylpyrocatechol and to the preparation of flavor and fragrance compounds from para-methallylpyrocatechol.
  • catechol-based processes for preparing 2,3-dihydro-2,2-dimethyl-7- hydroxybenzofuran an intermediate to the insecticide/nematicide, carbofuran, catechol is reacted with methallyl chloride to produce 2-methallyloxyphenol and ortho-methallylpyrocatechol.
  • the phenol/pyrocatechol mixture is subjected to thermal rearrangement and cyclization forming 2,3-dihydro-2,2-dimethyl-7- hydroxybenzofuran.
  • a by-product of this thermal rearrangement and cyclization process is para-methallylpyrocatechol, formed in a weight % of about 25% to about 30%, which does not cyclize to form 2,3-dihydro-2,2-dimethyl-7- hydroxybenzofuran, has no commercial use, and is discarded as a waste material. It would be most beneficial to find a commercial process to purify para- methallylpyrocatechol from the reaction tars and use it for the preparation of useful products.
  • the present invention provides a process for the purification of para- methallylpyrocatechol and the use of para-methallylpyrocatechol as an intermediate to certain flavor and fragrance compounds.
  • the present invention provides a process for the purification of para- methallylpyrocatechol and the use of para-methallylpyrocatechol as an intermediate to certain flavor and fragrance compounds.
  • catechol-based processes for preparing 2,3-dihydro-2,2-dimethyl-7- hydroxybenzofuran an intermediate to the insecticide/nematicide, carbofuran, catechol is reacted with methallyl chloride to produce 2-methallyloxyphenol (MOP) and ortho-methallylpyrocatechol (3-MAC), Step 1 below.
  • MOP 2-methallyloxyphenol
  • 3-MAC ortho-methallylpyrocatechol
  • the phenol/pyrocatechol mixture is subjected to Clasien thermal rearrangement and cyclization forming 2,3- dihydro-2,2-dimethyl-7-hydroxybenzofuran (7-Hydroxy), Step 2 below.
  • a byproduct of this thermal rearrangement and cyclization process is para- methallylpyrocatechol (4-MAC), formed in a weight % of about 25% to about 30%, which does not cyclize to form 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran, has no commercial use, and is discarded as a waste material.
  • 4-MAC para- methallylpyrocatechol
  • Step 2 MOP and 3- MAC are placed into an autoclave along with xylene and a catalytic amount of aluminum isopropoxide. The mixture is heated for about four hours, the autoclave is then cooled and the reaction mixture diluted and stirred with a 2% aqueous sodium sulfate solution. The mixture is allowed to separate and the organic phase is removed.
  • the xylene is removed from the organic phase by distillation under reduced pressure leaving an oily residue. This residue is subjected to distillation, collecting the fraction at 99°C to 100°C at 2.5-3 mmHg, which is 7-Hydroxy. The remaining residue (Crude 4-MAC) would usually be treated as a waste material.
  • the process of the present invention to purify para-methallylpyrocatechol comprises:
  • the para-methallylpyrocatechol obtained by the process of this invention has a purity of at least 95%.
  • the present invention provides a method of preparation of certain flavors and fragrances using para-methallylpyrocatechol as an intermediate.
  • Heliotropin the common name for l,3-benzodioxazole-5-carboxaldehyde, is an aromatic aldehyde that has a floral odor commonly described as being similar to that of vanillin and cherry. It is used as flavoring and in perfume.
  • Para- methallylpyrocatechol can be used as a starting material in the process to prepare heliotropin as described in Scheme 1 below.
  • Step A the reaction of 4-MAC and methylene chloride in the presence of a base in a solvent produces 5-(2-methyl-2-propen-l-yl)-l,3- benzodioxazole, Compound 1.
  • the base can be an aqueous or nonaqueous hydroxide, for example potassium or sodium hydroxide or an organic base, for example l,8-diazabicyclo[5.4.0]undec-7-ene.
  • the solvent can be dimethyl sulfoxide, triethyl amine, an alcohol such as butanol, 1 ,4-dioxane, water or an ether such as bis(2-methoxyethyl) ether, depending on the base used.
  • Step B heating Compound 1 with a base in the presence of a glycol forms 5-(2-methyl-l-propene-l-yl)-l,3-benzodioxazole, Compound 2.
  • the base is preferably a hydroxide, for example potassium hydroxide.
  • the glycol is a polyethylene glycol (PEG 300), is added to catalyze the isomerization of Compound 1 to Compound 2.
  • Solvents such as water or an alcohol, for example, n- butanol can be present.
  • Step C oxidation of Compound 2 in the presence of an acid solvent produces heliotropin.
  • the oxidant is potassium chromate and the acid solvent is sulfuric acid.
  • Step A Compound 1 is treated with an oxidant in a solvent to prepare 3-(l,3-benzodioxol-5-yl-methyl)-3-methyl-2-oxirane, Compound 3.
  • the oxidant is preferably 3-chloroperbenzoic acid and the preferred solvent is methylene chloride.
  • Step B Compound 3 and a catalyst are stirred in a solvent to yield helional.
  • Preferred catalyst/ solvent combinations are zinc chloride/1, 4-dioxane; boron trifluridediethyl etherate/1, 4-dioxane; copper (II) tetrafluoroborate/ methlyene chloride; indium (III) chloride/tetrahydrofuran; and bismuth (III) 1,1,1- trifluoromethane sulfonic acid/methylene chloride.
  • para- methallylpyrocatechol can be made using para- methallylpyrocatechol as a starting material.
  • these include: protocatechuic aldehyde, the common name for 3,4-dihydroxybenzaldehyde, which is a phenolic aldehyde, a compound released from cork stoppers into wine and can be used as a precursor in the synthesis of; vanillin (4-hydroxy-3-methoxybenzaldehyde), ethyl vanillin (4-hydroxy-3-ethoxybenzadehyde), veratric aldehyde (3,4- dimethoxybenzaldehyde), veratric alcohol (3,4-dimethoxybenzyl alcohol), and veratric acid (3,4-dimethoxybenzoic acid).
  • Para-methallylpyrocatechol can also be used as a starting material for the preparation of certain pharmaceuticals such as epinephrine, dopamine and L-DOPA.
  • ambient temperature means a temperature of about 15°C to about 20°C.
  • Remaining water was removed by azeotropic distillation under a pressure of 55 mmHg, leaving 338 grams of a xylene solution containing 2- methallyloxyphenol (MOP) and ortho-methallylpyrocatechol (3-MAC).
  • MOP 2- methallyloxyphenol
  • 3-MAC ortho-methallylpyrocatechol
  • the residue was subjected to wiped film distillation collecting the distillate at 99°C to 100°C at 1 mmHg (7-Hydroxy).
  • the residue was subjected to fractional distillation collecting the fraction at 99°C to 100°C at 1 mmHg (7-Hydroxy).
  • the pot residues from the wiped film and fractional distillation were saved for Step C.
  • thermometer, dropping funnel and condenser was added 16 grams of solid potassium hydroxide, 215 grams of dimethyl sulfoxide and 15 grams of water. The mixture was stirred and heated to 92°C. A solution of 20 grams of para- methallylpyrocatechol in 25 grams of dimethyl sulfoxide and 30 grams of methylene chloride was added slowly and after complete addition the mixture was stirred at 95°C for three hours. The mixture was cooled and diluted with 500 grams of water. The mixture was extracted three times with 100 gram portions of methylene chloride. The extracts were combined and washed with 100 grams of an aqueous 1% sodium hydroxide solution followed by three, 25 gram portions of water.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Fats And Perfumes (AREA)

Abstract

La présente invention concerne un procédé de purification de para-méthallylpyrocatechol et de préparation de composés d'arôme et de parfum à partir du para-méthallylpyrocatéchol.
PCT/US2012/041032 2011-06-13 2012-06-06 Procédé de purification pour du para-méthallylpyrocatéchol Ceased WO2012173842A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201280010957.3A CN103562169B (zh) 2011-06-13 2012-06-06 对-甲代烯丙基邻苯二酚的纯化方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161496292P 2011-06-13 2011-06-13
US61/496,292 2011-06-13

Publications (2)

Publication Number Publication Date
WO2012173842A2 true WO2012173842A2 (fr) 2012-12-20
WO2012173842A3 WO2012173842A3 (fr) 2013-02-28

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CN (1) CN103562169B (fr)
WO (1) WO2012173842A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106673967B (zh) * 2016-11-14 2020-05-22 湖南海利株洲精细化工有限公司 4-(2-甲基烯丙基)-1,2-苯二酚的制备方法
CN111909134B (zh) * 2019-05-07 2024-04-26 北京鼎材科技有限公司 一种化合物及其应用、包含其的有机电致发光器件
CN116554191B (zh) * 2023-05-06 2025-12-05 河南中烟工业有限责任公司 一种香柑内酯的合成方法
CN117486695A (zh) * 2023-11-27 2024-02-02 山东泓瑞医药科技股份公司 一种基于克莱森重排和醚化反应的藜芦酮合成方法
CN118146071B (zh) * 2024-03-07 2024-09-27 江苏三吉利化工股份有限公司 一种4-(2-甲基烯丙基)-1,2-苯二酚的合成工艺

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3008968A (en) * 1958-02-11 1961-11-14 Int Flavors & Fragrances Inc Process for making 2-methyl-3-(3'-4'-methylenedioxyphenyl)-propanal
FR2470768A1 (fr) * 1979-12-07 1981-06-12 Rhone Poulenc Agrochimie Procede de preparation de derives de benzofuranne
US4380654A (en) * 1982-02-18 1983-04-19 Fmc Corporation Process for preparation of 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran
PH26101A (en) * 1987-03-04 1992-02-06 Eisai Co Ltd Benzodioxole derivatives
CN1024098C (zh) * 1988-06-15 1994-03-30 北京燕山石油化工公司京蒸化工技术开发公司 对特丁基邻苯二酚的回收方法

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WO2012173842A3 (fr) 2013-02-28
CN103562169A (zh) 2014-02-05
CN103562169B (zh) 2016-04-20

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