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United States Patent Office Patented Apr 3,376,313 United States Patent Office Patented Apr. 2, 1968 2 which is employed. The organic radicals of the (SFO) 3,376,313 PROCESS OF PREPARNG ORGANC containing organic compound do not become part of the DSULFDES FROM THOLS disulfide produced in the reaction. Therefore, a wide Thomas J. Wa:Eace, Elizabeth, N.J., assignor to Esso variety of organic compounds containing an (SFO) Research and Engineering Company, a corporation of moiety can be used. Suitable exemplary classes of (SFO) Delaware containing organic compounds which can be employed No Drawing. Filed Nov. 15, 1963, Ser. No. 323,897 include, but are not limited to, the following: organic 19 Claims. (C. 260-327) Sulfoxides; organic sulfones; organic disulfoxides; organic sulfinates; organic thiosulfinates; etc. The following 30 (SFO) containing organic compounds can be listed as ABSTRACT OF THE DISCLOSURE exemplary of those suitable for use in accordance with Organic sulfides are prepared by reacting an organic this invention: phenyl methyl sulfoxide; tetramethylene thiol with an organic compound containing the (SFO) sulfoxide; dimethyl sulfoxide; diethyl sulfoxide; di-n- moiety, the mole ratio of thiol to SFO containing com propyl sulfoxide; cyclohexyl methyl sulfoxide; di-iso 5 propyl sulfoxide; di-n-butyl sulfoxide; benzyl methyl sul pound being about 1:1 when it is desired to form cyclic foxide; dibenzylsulfoxide; phenyl methyl sulfone; dibenz disulfides and about 2:1 when it is desired to form acyclic yl sulfone; tetramethylene sulfone; dimethyl sulfone; di disulfides. The organic disulfides produced are useful as ethyl sulfone; di-n-propyl sulfone; di-iso-propyl sulfone; additives in cosmetic products and depilatory creams. di-n-butyl sulfone; cyclohexyl methyl sulfone; dimethyl -mastessurasam 20 disulfoxide; diethyl disulfoxide; dimethyl sulfinate; dieth This invention is directed to a novel process of prepar yl sulfinate; methyl ethyl sulfinate; dimethyl thiosulfinate; ing organic disulfides which comprises contacting an or diethyl thiosulfinate; methyl ethyl thiosulfinate; etc. ganic thiol with an organic compound containing the It has been discovered that while any organic (S=O) (S=O) moiety. The reactions contemplated herein are containing compound, especially any of the classes of usually conducted in essentially inert atmospheres and compounds listed hereinabove, can be used to selectively preferably in the absence of extraneous oxygen. oxidize the organic thiols to their corresponding organic According to a preferred embodiment of this invention, disulfides, all such (S=O) containing organic compounds the organic thiol and the organic (SFO) containing com are not equally effective in this regard. Preferably, an pounds are reacted in the presence of an organic amine, organic (SFO) containing compound is employed which preferably a primary, secondary or tertiary aliphatic has two organic groups joined to the same sulfur atom amine having from 4 to 12 carbon atoms. The use of an which is doubly bonded to an oxygen atom, viz., the or amine catalyst, especially C4 to C12 aliphatic amines, ganic Sulfoxides and sulfones. Of the organic sulfoxides lowers the temperature of reaction, increases the yield of and sulfones, it has been discovered that those having and selectivity to the disulfide, and greatly increases the both of the organic substituents as aliphatic substituents rate of reaction anywhere from approximately 80 to ap 3 5 yield the best results in preferentially oxidizing the organic proximately 250-fold, and even higher. Acid catalysts, thiols to their corresponding disulfides. The order of as e.g.,acetic acid and other organic acids also have a cata cending selectivity of the organic sulfoxides and sulfones lytic effect, but much less than that of the aliphatic in terms of their comparative ability to preferentially oxi amines. dize organic thiols to their corresponding disulfides is as The temperatures of reaction can range from room tem 40 follows: diaryl, alkyl-aryl, diaralkyl and dialkyl, with di perature or even below up to about 140 C. and even alkyl sulfoxides and sulfones being the most selective and higher. diaryl sulfoxides and sulfones being the least selective on Usually when preparing aromatic disulfides in accord a comparative basis. ance with this invention, the reaction temperatures range Consequently, insofar as obtaining selective oxidation from about room temperature to about 60° C., and from 45 of the organic thiols to their corresponding organic di about 90 to 150° C. when preparing aliphatic disulfides. sulfides is concerned, the preferred organic sulfoxides are When amine catalysts are employed, reaction tempera those having the formula: tures usually range from about 40 to 70° C. for pre O paring aliphatic disulfides from aliphatic thiols. The re actions are conducted at atmospheric pressure in closed 50 R--R system reactor vessels so that the pressures developed wherein R is selected from the group consisting of alkyl, during reaction are the autogenous reaction pressures aralkyl and alkaryl. caused by the reactants, themselves. Suitable preferred organic sulfoxides and sulfones The preparation of organic disulfides according to this which can be listed as exemplary of those included by invention can be performed at acid, neutral or basic pH the above formula: dimethyl sulfoxide; diethyl sulfoxide; with or without solvents, which can be either organic or tetramethylene sulfoxide; cyclohexyl methyl sulfoxide; di inorganic. Of course, when a solvent is employed, an inert benzyl sulfoxide; benzyl methyl sulfoxide; diisopropyl solvent should be used, viz., one which does not interfere sulfoxide; di-n-butyl sulfoxide; dimethyl sulfone; tetra with the oxidation of thiols to disulfides. Examples of methylene sulfone; cyclohexyl methyl sulfone; dibenzyl suitable inert solvents are toluene, Xylene, cetane, dimeth 60 sulfone; etc. ylformamide, sulfur dioxide, etc. Usually the disulfide When it is desired to form linear (acyclic) disulfides, synthesis is conducted at a pH ranging from about 4 to organic monothiols are reacted with a suitable (SFO) 14. The employment of an aliphatic amine catalyst usual organic compound, e.g., an organic sulfoxide, employing ly results in a basic pH during reaction. approximately a 2:1 mole ratio of organic monothiol to Both linear and cyclic disulfides can be prepared in 65 organic sulfoxide. The reaction stoichiometry is shown accordance with the process of this invention. The present in Equation 1 below: invention is based upon the discovery that organic com Equation 1 pounds containing the (SFO) moiety selectively oxidize organic thiols (organic mercaptans) to their correspond In essence the organic monothiol is oxidized to the cor ing disulfides. The specific organic disulfide produced is 70 responding organic disulfide, and the organic sulfoxide is independent of the (SFO) containing organic compound reduced to the corresponding monosulfide with the elimi 3,376,313 4. 3 It has been discovered that the preparation of organic nation of water. Of course, a mixed organic disulfide can disulfides in accordance with this invention is general both be prepared readily by employing a mixture of organic insofar as the organic thiol and the organic (SFO) con monothiols, but the mole ratio of organic thiol to organic pounds are concerned. Thus, in the preparation of acyclic (SFO) containing compound is still maintained at 2:1. organic disulfides in accordance with this invention, the The production of a mixed organic disulfide, viz., one organic monothiol can be alkyl or mixed alkyl; aryl or having different organic R groups is illustrated in Equa mixed aryl; alkaryl or mixed alkaryl; aralkyl or mixed tion 2 below. aralkyl; alkylaryl; alkyl-alkaryl; alkyl-araikyl; aryl Equation 2 alkaryl; aryl-aralkyl; and alkaryl-alkyl. R-SH -- R'SO - R-S-S-R -- R'S -- HO Suitable organic dithiols which can be employed in the R-SE 10 practice of this invention to produce cyclic organic di sulfides by (S=O) selective oxidation include those in As noted from Equation 2, the mixed disulfide produced the following exemplary classes of organic dithiols: alkyl has two different organic groups, R1 and R. dithiols; esp. C. to Ca alkyl dithiols; alkyl trithiols; aryl Moreover, the organic (SFO) containing compound dithiols; alkaryl dithiols and aralkyl dithiols wherein the can have a plurality of different organic radicals. For alkyl moiety has at least two carbon atoms. Of course, in example, a mixed organic sulfoxide can be used to oxidize cases where the alkyl moiety has more than two carbon either a single organic monothiol, a mixture of organic atoms, e.g., three or four carbon atoms or more, a trithiol, monothiols or an organic dithiol. Equation 3 below illus tetrathiol, etc. can be used in place of the dithiol. Further, trates the products obtained by reaction of a mixed or it is also clear that polymeric dithiols can be oxidized by ganic sulfoxide with a mixture of different organic mono 20 this technique provided that a suitable molar ratio of thiols. sulfoxide to thiol group is employed, viz., one (SFO) Equation 3 group per two (SH) groups. Ri-SH. R. The alkyl groups of the organic thiols can be substi tuted or unsubstituted C, to Cao aliphatic alkyls, espe -- DS-o - R-S-S-R -- R-S-R' + H2O cially C to C aliphatic alkyls. The aryl group (or R-SI R' groups) of the organic thiols can be substituted or uri substituted, homo or heterocyclic rings containing at least When the present invention is employed to produce one benzene ring with monocyclic or polycyclic, especially cyclic disulfides, an organic dithiol is reacted with an mono- and di-benzene rings containing, aryl groups. The (SFO) containing organic compound, e.g., an organic alkaryl and aralkyl groups of the organic thiols can be Sulfoxide, employing approximately a 1:1 mole ratio of substituted or unsubstituted groups having combinations dithiol to sulfoxide. Equation 4 below, stoichiometrically of the alkyl and aryl groups set forth hereinabove. illustrates the preparation of a cyclic disulfide in accord The following organic thiols can be listed as exemplary : ance with this invention.
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