Oxidation of thiols employing cobalt molybdate/triethylamine catalyst

• US 4,288,627 A
• Filed: 02/12/1980
• Issued: 09/08/1981
• Est. Priority Date: 02/12/1980
• Status: Expired due to Term

• Current Assignee: Phillips Petroleum Company (ConocoPhillips)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Kubicek, Donald H.
• Primary Examiner(s): Daus, Donald G.
• Assistant Examiner(s): Eakin, M. C.
• Application Number:
  US06/120,812
• Time in Patent Office: 574 Days
• Field of Search: 568/26
• US Class Current: 568/26
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 2231/70 Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
• CPC Class Codes: B01J 31/0237 Amines
• CPC Class Codes: B01J 31/1616 Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts catalysts comprising molecular sieves B01J29/00
• CPC Class Codes: B01J 31/26 containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
• CPC Class Codes: B01J 31/28 of the platinum group metals, iron group metals or copper
• CPC Class Codes: B01J 31/34 of chromium, molybdenum or tungsten
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 319/24 by reactions involving the formation of sulfur-to-sulfur bonds
• CPC Class Codes: C07C 321/14 of an acyclic saturated carbon skeleton
• CPC Class Codes: C07C 321/22 Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of rings other than six-membered aromatic rings

Abstract

A thiol is oxidized to a corresponding disulfide employing a supported cobalt molybdate catalyst in combination with a liquid tertiary amine. 2-propanethiol is converted to diisopropyl disulfide with conversions of the order of 94% and selectivities of the order of 98%.

Claims

1. A process for the conversion of a thiol represented by the formula ##STR2## wherein R, R¹, and R² can be hydrogen, alkyl, or cycloalkyl containing from 1 to 20 carbon atoms, R and R¹ taken together can be an alkylene radical having from 5 to 10 carbon atoms to a corresponding disulfide which comprises subjecting the same to oxidation conditions including air or oxygen-containing gas in the presence of a cobalt oxide molybdenum oxide catalyst on a support and a liquid tertiary amine represented by the formula

View Dependent Claims (2, 3, 4, 5, 6, 7)

2. A process according to claim 1 wherein the catalyst contains from about 3 to about 4 weight percent cobalt oxide and about 12 to about 18 weight percent molybdenum oxide on a suitable support.

3. A process according to claim 2 wherein the molybdenum oxide and cobalt oxide is on a support selected from alpha-alumina, gamma-alumina, alumina-silica, charcoal, silica, magnesium oxide, silica-carbon, and mixtures thereof.

4. A process according to claim 1 wherein the catalyst has the following approximate weight percent composition:

space="preserve" listing-type="tabular">______________________________________ Cobalt oxide 3-4 Molybdenum oxide 15-16 Sodium oxide 0.4 Iron oxide 0.05 Alumnia (support) balance ______________________________________

5. A process according to claim 1 wherein the thiol is at least one selected from

6. A process according to claim 1 wherein the tertiary amine is at least one selected from

trimethylamine

triethylamine

tri-n-propylamine

tri-n-butylamine

tri-n-pentylamine

tri-n-hexylamine

methyldiethylamine

ethyldipropylamine

ethyldimethylamine

7. A process according to claim 1 wherein the cobalt molybdate catalyst, including support, is employed in the range of from about 0.1 g to about 1 g and the tertiary amine is in the range of from about 1 to about 10 mL employed to convert from about 25 to about 100 mL of the thiol.