WO2005063664A1 - Procede de transformation de phenol en hydroquinone et en quinones - Google Patents

Procede de transformation de phenol en hydroquinone et en quinones Download PDF

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Publication number
WO2005063664A1
WO2005063664A1 PCT/IN2003/000452 IN0300452W WO2005063664A1 WO 2005063664 A1 WO2005063664 A1 WO 2005063664A1 IN 0300452 W IN0300452 W IN 0300452W WO 2005063664 A1 WO2005063664 A1 WO 2005063664A1
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WIPO (PCT)
Prior art keywords
phenol
catalyst
hydroquinone
oxidant
heated
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PCT/IN2003/000452
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English (en)
Inventor
Gajaran Kundalik Dewkar
Vinay Vijayraj Thakur
Sanjeevani Amrit Pardhay
Arumugam Sudalai
Sukumar Devotta
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Council Of Scientific & Industrial Research
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Priority to PCT/IN2003/000452 priority Critical patent/WO2005063664A1/fr
Priority to AU2003304661A priority patent/AU2003304661A1/en
Publication of WO2005063664A1 publication Critical patent/WO2005063664A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
    • C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring

Definitions

  • the present invention relates to a process for the conversion of phenol to hydroquinone and quinones. More particularly this invention relates to a process for the oxidation of phenol to a mixture of 1,4-benzoquinone and hydroquinone using aq. hydrogen peroxide as the oxidant in the presence of titanium superoxide as a reusable catalyst in a liquid phase condition.
  • aq. hydrogen peroxide as the oxidant in the presence of titanium superoxide as a reusable catalyst in a liquid phase condition.
  • European patent [EP C07C039-08, C07C037-60, C07C037-82] claims 55% catechol, 34% hydroquinone by hydroxylation of preheated phenol with propionic acid using ion- exchange resin.
  • a Chinese patent [CN 1167012] reports that the hydroxylation of phenol with aq. H 2 O 2 has been achieved in low conversion by using nano metal oxide particles and a microporous ion exchanged resin.
  • German patent DE 2658545 describes phenol hydroxylation using H 3 PO 4 and HClO 4 as catalyst in the presence of benzaldehye to give hydroquinone and catechol.
  • German patent DE 26330302 describes phenol hydroxylation with H 2 O 2 in CF 3 SO 3 H containing a small amount of H 3 PO 4 giving 51% hydroquinone and 23.7% catechol.
  • Oxidation of phenol with Y-zeolites containing transition metals such as Cu, Mn, Fe, Cr, etc. makes use of expensive cyclic ligands for effective conversion of phenol to hydroquinone; separation of these cyclic ligands is also tedious.
  • H 3 PO 4 , and HClO 4 which are corrosive and environmentally hazardous, are used for the oxidation of phenol.
  • MnO 2 is used as the oxidant in presence of aniline; here again the process is homogeneous wherein the separation of product becomes difficult.
  • Co-Schiff base complexes are also used under the homogeneous conditions.
  • the ligands have to be prepared using multi step reaction sequences.
  • the present invention provides a heterogeneous catalytic process for the oxidation of phenols which comprises treating a solution of the phenol with an oxidant in the presence of Ti-superoxide (1) heterogeneous catalyst subsequently treating the mixture with water (5 ml) atlOO °C and then terminating the reaction by bringing the reaction mixture to room temperature, extracting the product by conventional methods like solvent extraction and purifying by conventional methods to obtain the oxidized phenol.
  • the strength of the oxidant H O 2 is in the range of 10-90%, preferably around 30-50%.
  • the oxidant comprises 10 - 50% of aq. H 2 O 2 .
  • the oxidant comprises 30% of aq. H O 2 .
  • the phenol solution comprises a solution of phenol in a solvent, which may be selected from a range of organic solvents such as, but are not limited to, acetonitrile, acetone, methanol and acetic acid. Water also can be used as the solvent.
  • the phenol is selected from the group consisting of phenol, o-cresol, m-cresol, 2,6-dimethylphenol, 2-butylphenol, 2,6- dibutylphenol, 4-chlorophenol, 4-bromophenol, 4-iodophenol and 2,4-dichlorophenol.
  • the reaction of the phenol with acetic acid and hydrogen peroxide is carried out at a temperature in the range of 50-60 °C and for a time period of 1-10 h.
  • the conversion of the phenol is up to 100% and the selectivity of the catalyst is up to 99%.
  • the present invention provides a new heterogeneous catalytic process for the oxidation of phenols, which comprises treating a solution of phenol in acetic acid with 30% aq. H 2 O 2 in the presence of Ti-superoxide (1) heterogeneous catalyst.
  • Ti-superoxide catalyst was synthesized (Scheme 1) in the laboratory and successfully used for oxidation of amines to nitro compounds [Angew. Chem. Int. Ed. Engl. 2001, 40, 405- 408]
  • the temperature is preferably in the range of 50-60°C and the reaction is preferably carried out for a time period in the range of 1-10 h.
  • the reaction mixture is treated with water (5 ml) at 100°C and then the reaction terminated by bringing the reaction mixture to room temperature.
  • the product can be extracted by any conventional method such as like solvent extraction and the product is then purified by any conventional method to obtain the product (Scheme 2).
  • R H, alk l, alide, etc.
  • Scheme 2 (i) cat. Ti-superoxide (1), 30% H 2 O 2 , AcOH, 50-60 °C; (ii) water, reflux (100 °C).
  • the strength of the oxidant i.e. H 2 O 2 can be in the range 10-90%, and most preferably around 30-50%.
  • the solvent used can be selected from a range of organic solvents such as, but are not limited to, acetonitrile, acetone, methanol and acetic acid. Water also can be used as the solvent.
  • the present invention provides a new heterogeneous catalytic process for the oxidation of phenol to hydroquinone, which avoids the drawbacks as detailed above. More particularly the present invention demonstrates the use of heterogeneous Ti-superoxide (1) as a catalyst for the oxidation of phenol to hydroquinone.
  • Ti-superoxide catalyst was synthesized (Scheme 1) in our laboratory and successfully used for oxidation of amines to nitro compounds [Angew. Chem. Int. Ed. Engl. 2001, 40, 405-408]
  • Ti-superoxide catalyst aq. 50% H 2 O (5.98 g, 0.175 mol) is added slowly to a solution of Ti(O'Pr) 4 (5.0 g, 0.0175 mol) in anhydrous MeOH (50 ml) over 40 minutes under N 2 with stirring at room temperature.
  • the yellow precipitate that formed is collected by filtration on a sintered funnel, washed with anhydrous methanol and dried under reduced pressure (3 mm Hg) at 25 °C for 1 h to afford 3.94 g (98%>) of Ti-superoxide (1) catalyst.
  • the process of the present invention is described herein with reference to examples, which are illustrative only and should not be construed to limit the scope of the present invention in any manner.
  • Example 1 Preparation of 1,4-hydroquinone A mixture of phenol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 10% H O 2 (20 mmol) drop wise over 15 min. and heated for 2 h. After this, water (5 ml) was added and the reaction mixture was heated to reflux for 8 h. The catalyst was recovered by simple filtration and 1,4-hydroquinone formed (20%) was separated by chromatographic purification.
  • Example 2 Preparation of 1,4-hydroquinone A mixture of phenol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 50% H O 2 (20 mmol) drop wise over 15 min. and heated for 1 h. After this, water (5 ml) was added and the reaction mixture was heated to reflux for 7 h. The catalyst was recovered by simple filtration and 1,4-hydroquinone formed (61%) was separated by chromatographic purification.
  • Example 3 Preparation of 1,4-hydroquinone A mixture of phenol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 30% H 2 O 2 (20 mmol) drop wise over 15 min. and heated for 1 h. After this, water (5 ml) was added and the reaction mixture was heated to reflux for 6 h. The catalyst was recovered by simple filtration and 1,4-hydroquinone formed (60%) was separated by chromatographic purification.
  • Example 4 Preparation of 1,4-hydroquinone A mixture of phenol (5 mmol) and Ti-superoxide catalyst (250 mg, 40% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 30% H O 2 (20 mmol) drop wise over 15 min. and heated for 1 h. After this, water (5 ml) was added and the reaction mixture was heated to reflux for 6 h. The catalyst was recovered by simple filtration and 1,4-hydroquinone formed (63 %) was separated by chromatographic purification.
  • Example 5 Preparation of 1,4-benzoquinone A mixture of phenol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 30% H 2 O 2 (20 mmol) drop wise over 15 min. and heated for 1 h. The catalyst was recovered by simple filtration and 1,4-benzoquinone formed (88%) was separated by chromatographic purification.
  • Example 6 Preparation of 2-methyl-l,4-benzoquinone A mixture of o-cresol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 30% H 2 O 2 (20 mmol) drop wise over 15 min. and heated for 1 h. The catalyst was recovered by simple filtration and 2-methyl-l,4-benzoquinone formed (96%) was separated by chromatographic purification.
  • Example 7 Preparation of 2-methyl-l,4-benzoquinone A mixture of m-cresol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 30% H 2 O 2 (20 mmol) drop wise over 15 min. and heated for 1 h. The catalyst was recovered by simple filtration and 2-methyl-l,4-benzoquinone formed (99%) was separated by chromatographic purification.
  • Example 8 Preparation of 2,6-dimethyl-l,4-benzoquinone A mixture of 2,6-dimethylphenol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 30% H 2 O 2 (20 mmol) drop wise over 15 min. and heated for
  • Example 9 Preparation of 2-tert-butyl-l,4-benzoquinone A mixture of 2-t-butylphenol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 30% H 2 O 2 (20 mmol) drop wise over 15 min. and heated for
  • Example 10 Preparation of 2,6-di-tert-butyI-l,4-benzoquinone A mixture of 2,6-di-t-butylphenol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 30% H 2 O 2 (20 mmol) drop wise over 15 min. and heated for 3 h. The catalyst was recovered by simple filtration and 2,6-di-tert-butyl-l,4-benzoquinone formed (65%>) was separated by chromatographic purification.
  • Example 11 Preparation of 1,4-benzoquinone A mixture of 4-chlorophenol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 30% H 2 O 2 (20 mmol) drop wise over 15 min. and heated for
  • Example 12 Preparation of 1,4-benzoquinone A mixture of 4-bromophenol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 30% H 2 O 2 (20 mmol) drop wise over 15 min. and heated for 1 h. The catalyst was recovered by simple filtration and 1,4-benzoquinone formed (60%) was separated by chromatographic purification.
  • Example 13 Preparation of 1,4-benzoquinone A mixture of 4-iodophenol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 50-60°C under inert atmosphere. To this reaction mixture was added aq. 30% H 2 O 2 (20 mmol) drop wise over 15 min. and heated for 1 h. The catalyst was recovered by simple filtration and 1,4-benzoquinone formed (75%) was separated by chromatographic purification.
  • Example 14 Preparation of 2-chloro-l,4-benzoquinone A mixture of 2,4-dichlorophenol (5 mmol) and Ti-superoxide catalyst (125 mg, 20% w/w) in acetic acid (5 ml) was heated with stirring at 60-70°C under inert atmosphere. To this reaction mixture was added aq. 30% H 2 O 2 (20 mmol) drop wise over 15 min. and heated for
  • Table 1 Ti-superoxide (1) catalyzed oxidation of phenols to quinines and hydroquinones with aq. 30% H 2 O 2 : a
  • the unique advantage of the present process is that the quinone formed initially after the oxidation of phenol can be converted to hydroquinone by heating with water at 100 °C.
  • Yet another advantage of this process is that the catalyst can be recovered and reused for several times without affecting the catalytic activity and the selectivity of the process.

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

Abstract

La présente invention concerne un procédé permettant de transformer du phénol en hydroquinone et en quinones. Plus particulièrement, cette invention concerne un procédé d'oxydation de phénol dans un mélange de 1,4-benzoquinone et d'hydroquinone au moyen d'un oxydant en présence d'un superoxyde de titane en tant que catalyseur réutilisable en phase liquide.
PCT/IN2003/000452 2003-12-31 2003-12-31 Procede de transformation de phenol en hydroquinone et en quinones WO2005063664A1 (fr)

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PCT/IN2003/000452 WO2005063664A1 (fr) 2003-12-31 2003-12-31 Procede de transformation de phenol en hydroquinone et en quinones
AU2003304661A AU2003304661A1 (en) 2003-12-31 2003-12-31 Process for conversion of phenol to hydroquinone and quinones

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104624240A (zh) * 2015-02-05 2015-05-20 天津大学 一种催化还原苯醌为氢醌的络合物催化剂及其制备方法
US9630899B1 (en) 2015-10-26 2017-04-25 Chang Chun Plastics Co. Ltd. Process for producing hydroquinone and derivates
CN108530268A (zh) * 2017-03-06 2018-09-14 中国科学院成都有机化学有限公司 一种新型阻聚剂甲基氢醌/2-甲基对苯二酚的制备方法

Citations (6)

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Publication number Priority date Publication date Assignee Title
US4396783A (en) * 1980-09-09 1983-08-02 Anic S.P.A. Hydroxylating aromatic hydrocarbons
GB2116974A (en) * 1982-03-19 1983-10-05 Anic Spa Process for hydroxylating aromatic hydrocarbons
EP0314582A1 (fr) * 1987-10-29 1989-05-03 Rhone-Poulenc Chimie Procédé d'hydroxylation de phénols et d'éthers de phénols
US5149888A (en) * 1989-02-28 1992-09-22 Rone-Poulenc Chimie Hydroxylation of phenols/phenol ethers
US5254746A (en) * 1987-10-29 1993-10-19 Rhone-Poulenc Chimie Hydroxylation of phenols/phenol ethers
US5493061A (en) * 1994-12-09 1996-02-20 Council Of Scientific & Industrial Research Process for the conversion of phenol to hydroquinone and catechol

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4396783A (en) * 1980-09-09 1983-08-02 Anic S.P.A. Hydroxylating aromatic hydrocarbons
GB2116974A (en) * 1982-03-19 1983-10-05 Anic Spa Process for hydroxylating aromatic hydrocarbons
EP0314582A1 (fr) * 1987-10-29 1989-05-03 Rhone-Poulenc Chimie Procédé d'hydroxylation de phénols et d'éthers de phénols
US5254746A (en) * 1987-10-29 1993-10-19 Rhone-Poulenc Chimie Hydroxylation of phenols/phenol ethers
US5149888A (en) * 1989-02-28 1992-09-22 Rone-Poulenc Chimie Hydroxylation of phenols/phenol ethers
US5493061A (en) * 1994-12-09 1996-02-20 Council Of Scientific & Industrial Research Process for the conversion of phenol to hydroquinone and catechol

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DEWKAR G K ET AL: "AN EXCEPTIONALLY STABLE TI SUPEROXIDE RADICAL ION: A NOVEL HETEROGENEOUS CATALYST FOR THE DIRECT CONVERSION OF AROMATIC PRIMARY AMINES TO NITRO COMPOUNDS", ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, VERLAG CHEMIE. WEINHEIM, DE, vol. 40, no. 2, 19 January 2001 (2001-01-19), pages 405 - 408, XP000992024, ISSN: 0570-0833 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104624240A (zh) * 2015-02-05 2015-05-20 天津大学 一种催化还原苯醌为氢醌的络合物催化剂及其制备方法
US9630899B1 (en) 2015-10-26 2017-04-25 Chang Chun Plastics Co. Ltd. Process for producing hydroquinone and derivates
CN108530268A (zh) * 2017-03-06 2018-09-14 中国科学院成都有机化学有限公司 一种新型阻聚剂甲基氢醌/2-甲基对苯二酚的制备方法

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