WO1994000427A1 - Process for the preparation of disulfides from thiols - Google Patents

Process for the preparation of disulfides from thiols Download PDF

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Publication number
WO1994000427A1
WO1994000427A1 PCT/CA1993/000055 CA9300055W WO9400427A1 WO 1994000427 A1 WO1994000427 A1 WO 1994000427A1 CA 9300055 W CA9300055 W CA 9300055W WO 9400427 A1 WO9400427 A1 WO 9400427A1
Authority
WO
WIPO (PCT)
Prior art keywords
thiols
disulfides
catalyst
preparation
selenium
Prior art date
Application number
PCT/CA1993/000055
Other languages
French (fr)
Inventor
Omar Chaudhry
Original Assignee
Omar Chaudhry
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 Omar Chaudhry filed Critical Omar Chaudhry
Priority to EP93903748A priority Critical patent/EP0649403A1/en
Priority to AU34883/93A priority patent/AU3488393A/en
Publication of WO1994000427A1 publication Critical patent/WO1994000427A1/en

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Classifications

    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0573—Selenium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds

Definitions

  • the present Invention relates to a process for the preparation of disulfides by oxidizing thiols in the presence of a catalyst in aqueous solution.
  • These catalysts include CuCl 2 , FeCl 3 , and Na 2 SeO 3 .
  • the preparation of disulfides as a result of the oxidation of alkylthlols with O 2 in the presence of cuprous chloride has been described in an article by D.W. Giles, J.A. Cha and P.K. Lim in Chemical Engineering Science,Vol.41,No.12, pp.3129-3140, 1986.
  • the present invention provides a process for the preparation of disulfides in aqueous solution by oxidizing thiols with molecular oxygen in the presence of a catalyst in the
  • the catalyst is elemental selenium which is solubilized by complexing with sulfides according to the equation
  • the thiol containing molecule that was used is mercaptoethanol which was deprotonated using sodium hydroxide solution
  • the equilibrium constant was found to be 0.36. Saturation was achieved after approximately 2 hours of vigorous stirring. If oxygen is passed through the solution containing HOCH 2 CH 2 SSe- anlons, the HOCH 2 CH 2 SSe-anions are rapidly oxidized to the disulfide HOCH 2 CH 2 SSCH 2 CH 2 OH with a yield exceeding 95%.
  • PROPERTY OR PRIVILEGE IS CLAIMED IS DEFINED AS FOLLOWS:

Abstract

The process oxidizes thiols to disulfides using elemental selenium as a catalyst. Elemental selenium complexes with the thiol to form the species RSSe- which is rapidly oxidized by molecular oxygen to the disulfide RSSR.

Description

Description
Process for the preparation of disulfides from thiols
The present Invention relates to a process for the preparation of disulfides by oxidizing thiols in the presence of a catalyst in aqueous solution.
Several catalysts are known to catalyze the oxidation of thiols to disulfides according to the equation
Figure imgf000003_0001
These catalysts include CuCl2, FeCl3 , and Na2SeO3 . The preparation of disulfides as a result of the oxidation of alkylthlols with O2 in the presence of cuprous chloride has been described in an article by D.W. Giles, J.A. Cha and P.K. Lim in Chemical Engineering Science,Vol.41,No.12, pp.3129-3140, 1986.
The present invention provides a process for the preparation of disulfides in aqueous solution by oxidizing thiols with molecular oxygen in the presence of a catalyst in the
temperature range in which water is a liquid.
Figure imgf000003_0002
The catalyst is elemental selenium which is solubilized by complexing with sulfides according to the equation
Figure imgf000003_0003
The thiol containing molecule that was used is mercaptoethanol which was deprotonated using sodium hydroxide solution
HOCH2CH2SH + NaOH→HOCH2CH2S-Na+ + H2O (4)
The deprotonated mercaptoethanol complexes with selenium according to the equilibrium
Figure imgf000004_0001
The equilibrium constant for the above equilibrium is given by the equation
Figure imgf000004_0003
The equilibrium constant was found to be 0.36. Saturation was achieved after approximately 2 hours of vigorous stirring. If oxygen is passed through the solution containing HOCH2CH2SSe- anlons, the HOCH2CH2SSe-anions are rapidly oxidized to the disulfide HOCH2CH2SSCH2CH2OH with a yield exceeding 95%.
Selenium catalyzes the oxidation of thiols according to the equations
Figure imgf000004_0002
As the HOCH2CHaSSe-anlons are oxidized, the solubilized selenium precipitates out of solution in the form of grey selenium.
Eventually, all the solubilized selenium precipitates out of solution. Example
0.5g of selenium and 50ml of water was placed in a 250ml flask. 0.5ml of mercaptoethanol was added to the flask. The mercaptoethanol was deprotonated by adding 71.68ml of 0.1N NaOH to the flask. The solution was stirred with a magnetic stirring bar until equilibrium was reached after 2 hours. Oxygen was passed through the solution for 10 minutes using a fritted glass attachment to oxidize mercaptoethanol to the disulfide HOCH2CH2SSCH2CH2OH.
THE EMBODIMENT OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED IS DEFINED AS FOLLOWS:
1. A process for preparing dlsulfides in aqueous solution by
oxidizing thiols with oxygen in the presence of a catalyst characterized in that the catalyst is elemental selenium.
2. A process according to claim 1 in which the thiols have the formula R-SH wherein R is hydrogen, an alkyl group or other organic moieties.
3. A process according to claim 1 or 2 in which sodium hydroxide is added.

Claims

AMENDED CLAIMS [received by the International Bureau on 26 November 1993 ( 26.11.93 ) ; original claim 2 amended; other claims unchanged (1 page) ]THE EMBODIMENT OF THE INVENTION IN WHICH AN EXCLUSIVEPROPERTY OR PRIVILEGE IS CLAIMED IS DEFINED AS FOLLOWS :
1. A process for preparing dl sulfides in aqueous solution by oxidizing thiols with oxygen in the presence of a catalyst characterized in that the catalyst i s elemental selenium.
2. A process according to claim 1 in which the thlols have the formula R-SH wherein R i s hydrogen or alkyl .
3. A process according to claim 1 or 2 in which sodium hydroxide i s added.
PCT/CA1993/000055 1992-06-29 1993-02-18 Process for the preparation of disulfides from thiols WO1994000427A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP93903748A EP0649403A1 (en) 1992-06-29 1993-02-18 Process for the preparation of disulfides from thiols
AU34883/93A AU3488393A (en) 1992-06-29 1993-02-18 Process for the preparation of disulfides from thiols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA 2072763 CA2072763C (en) 1992-06-29 1992-06-29 Process for the preparation of disulfides from thiols
CA2,072,763 1992-06-29

Publications (1)

Publication Number Publication Date
WO1994000427A1 true WO1994000427A1 (en) 1994-01-06

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA1993/000055 WO1994000427A1 (en) 1992-06-29 1993-02-18 Process for the preparation of disulfides from thiols

Country Status (4)

Country Link
EP (1) EP0649403A1 (en)
AU (1) AU3488393A (en)
CA (1) CA2072763C (en)
WO (1) WO1994000427A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8637578B2 (en) 2003-06-24 2014-01-28 Isis Innovation Limited Reagents and methods for the formation of disulfide bonds and the glycosylation of proteins

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB787914A (en) * 1955-05-03 1957-12-18 Standard Oil Co Improvements in or relating to oxidation of mercaptans
US4721813A (en) * 1986-08-25 1988-01-26 Phillips Petroleum Company Method for the oxidation of mercaptoalkanols to dithiodiglycols

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB787914A (en) * 1955-05-03 1957-12-18 Standard Oil Co Improvements in or relating to oxidation of mercaptans
US4721813A (en) * 1986-08-25 1988-01-26 Phillips Petroleum Company Method for the oxidation of mercaptoalkanols to dithiodiglycols

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL AND ENGINEERING SCIENCE, vol. 41, no. 12, 1986, Oxford, GB, pages 3129 - 3140 D.W. GILES, ET AL.: 'The aerobic and peroxide-induced coupling of aqueous thiols - 1. Kinetic results and engineering significance' cited in the application *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8637578B2 (en) 2003-06-24 2014-01-28 Isis Innovation Limited Reagents and methods for the formation of disulfide bonds and the glycosylation of proteins

Also Published As

Publication number Publication date
AU3488393A (en) 1994-01-24
EP0649403A1 (en) 1995-04-26
CA2072763A1 (en) 1993-12-30
CA2072763C (en) 1994-05-17

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