Method for preparing catechol and hydroquinone

• US 3,920,756 A
• Filed: 03/13/1974
• Issued: 11/18/1975
• Est. Priority Date: 03/23/1973
• Status: Expired due to Term

• Current Assignee: Katsuzo Harada, Koichi Yamamoto, Kou Hoshide, Shigeki Nagai, Shigenori Kawazoe, Susumu Tahara, Yurio Hayashi
• Original Assignee: Katsuzo Harada, Koichi Yamamoto, Kou Hoshide, Shigeki Nagai, Shigenori Kawazoe, Susumu Tahara, Yurio Hayashi
• Inventors: Tahara, Susumu, Nagai, Shigeki, Hayashi, Yurio, Hoshide, Kou, Kawazoe, Shigenori, Harada, Katsuzo, Yamamoto, Koichi
• Primary Examiner(s): Morgenstern, Norman P.
• Application Number:
  US05/450,751
• Time in Patent Office: 615 Days
• Field of Search: 260/621G 252/431R,431C,431N
• US Class Current: 568/771
• CPC Class Codes: C07C 37/60 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
• CPC Class Codes: C07C 39/08 Dihydroxy benzenes; Alkylated derivatives thereof
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

A mixture of catechol and hydroquinone is prepared by oxidizing phenol in an aqueous medium with hydrogen peroxide at a pH of 6.0 or lower in the presence of a catalyst consisting of at least one organic metal coordinate compound which is prepared from a salt of a metal selected from the class consisting of iron, copper, chromium and cobalt and an organic ligand compound selected from the class consisting of aromatic chelating compounds, heterocyclic monodentate coordinating compounds, heterocyclic polydentate chelating compounds and aliphatic chelating compounds, when one of the coordinate bonding groups in the aliphatic chelating compound is the carbonyl group, the remaining coordinate atoms or groups are other than the carbonyl group, and isolating the resulting catechol and hydroquinone from the oxidation admixture.

Claims

1. A METHOD FOR PREPARING CATECHOL AND HYDROQUINONE, COMPRISING THE STEPS OF:

OXIDIZING PHENOL WITH 10 TO 100 PERCENT BY MOLE BASED ON THE AMOUNT BY MOLE OF SAID PHENOL, OF HYDROGEN PEROXIDE IN AN AQUEOUS MEDIUM AT A TEMPERATURE OF 10*-80*C. AT A PH NOT HIGHER THAN 6.0 IN THE PRESENCE OF A CATALYST CONSISTING OF AT LEAST ONE ORGANIC METAL COORDINATE COMPOUND WHICH CONSISTS OF AT LEAST ONE ORGANIC LIGAND COMPONENT COORDINATE-BONDED WITH AT LEAST ONE METAL ATOM COMPONENT SELECTED FROM THE GROUP CONSISTING OF IRON, COPPER, CHROMIUM, AND COBALT AND SELECTED FROM THE GROUP CONSISTING OF (A) ANY AROMATIC CHELATING COMPOUND SELECTED FROM THE GROUP CONSISTING OF CATECHOL, SALICYLIC ALDEHYDE, SALICYLIC ACID, THIOSALICYLIC ACID, O-AMINOPHENOL, SAICYLIC AMIDE, O-NITROPHENOL, ANTHRANILIC ACID, ORTHANILIC ACID, O-PHENOL SULFONIC ACID, AND A-NITROSO-BNAPHTHOL, (B) A HETEROCYCLIC MONODENTATE COORDINATING COMPOUND SELECTED FROM THE GROUP CONSISTING OF PYRIDINE, PICOLINES, LUTIDINES AND QUINOLINE, (C) A HETEROCYCLIC POLYDENTATE COORDINATE COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF NICOTINIC ACID, NICOTINIC AMIDE, ISOCINCHOMERONIC ACID, A-THIOPHENIC ACID, O-PHENANTHROLINE, 2-MERCAPTOPYRIDINE, 2-AMINOTHIAZOLE, 8-HYDROXYQUINOLINE, MERCAPTOBENZOTHIAZOLE AND E-CAPROLACTAM, AND (D)ALIPHATIC CHELATING COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF ETHYLENE DIAMINE, D,L-A-ALANINE, D,L-B-ALANINE, 2,2'"'"''"'"',2"-TRIHYDROXYETHYLAMINE, THIOGLYCOLLIC ACID, THIOACETAMIDE, THIOUREA, 2,3-DIMERCAPTO-1PROPANOL, ETHYLENEDIAMINETETRAACETIC ACID, DIMETHYLGLYOXIME, 2-HYDROXYETHYLAMINE, ETHYLENE CYANOHYDRIN, OXAMIDE, DIETHYLENE GLYCOL, GLUTAMIC ACID, LYSINE, METHIONINE, GLYCINE AND ARGININE, SAID CATALYST BEING IN AN AMOUNT OF ONE-THIRTY TO 100 PERCENT BY MOLE CALCULATED IN TERMS OF SAID METAL COMPONENT CONTAINED THEREIN, BASED ON THE AMOUNT BY MOLE OF SAID PHENOL, AND ISOLATING THE RESULTING CATECHOL AND HYDROQUINONE FROM SAID OXIDATION MIXTURE.

2. A method according to claim 1 wherein said catalyst is a chelate of copper sulfate pentahydrate and catechol.

3. A method according to claim 1 wherein said catalyst is a chelate prepared from copper sulfate pentahydrate and D,L- Beta -alanine.

4. A method according to claim 1 wherein said catalyst is a chelate prepared from chromium sulfate heptahydrate and catechol.

5. A method according to claim 1 wherein said catalyst is copper nicotinate.

6. A method according to claim 1 wherein said catalyst is copper- Alpha -thiophenate.

7. A method according to claim 1 wherein said catalyst is a chelate prepared from copper sulfate pentahydrate and a member selected from the group consisting of o-Phenanthroline, nicotinic amide, ethylene diamine, pyridine, thiosalicylic acid, D,L- Alpha -alanine, and epsilon -caprolactam.

8. A method according to claim 1 wherein said catalyst is a chelate prepared from iron sulfate heptahydrate and catechol.

9. A method according to claim 1 wherein said catalyst is a chelate prepared from iron sulfate heptahydrate and a member selected from the group consisting of Beta -alanine, o-phenanthroline, isocinchomeronic acid, nicotinic acid, nicotinic amide, Alpha -thiophenic acid, and 2,2'"'"''"'"',2'"'"''"'"''"'"''"'"'-trihydroxyethylamine.

10. A method as claimed in claim 1, wherein said oxidation is carried out at a pH of 1 to 5.

11. A method as claimed in claim 1, wherein said oxidation temperature is from 20 to 70*C at the start thereof.

12. A method as claimed in claim 1, wherein the isolation of catechol and hydroquinone is effected by extracting with an organic solvent for catechol and hydroquinone.

13. A method as claimed in claim 12, wherein said extracting organic solvent is selected from the class consisting of methyl isobutyl ketone, n-butyl acetate and isopropyl ether.