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United States Patent (19) (11) 4,072,584 Cipris Et Al

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United States Patent (19) (11) 4,072,584 Cipris Et Al United States Patent (19) (11) 4,072,584 Cipris et al. (45) Feb. 7, 1978 (54) ELECTROCHEMICAL PRODUCTION OF Berichte, Verh. der Naturforsch, Ges. (Basel), vol. 19, ORGANCTHOLS p. 37, (1908) Fichter. Primary Examiner-R. L. Andrews (75) Inventors: Divna Cipris, Morristown, N.J.; Dirk Attorney, Agent, or Firm-Robert J. North; Jay P. Pouli, Williamsville, N.Y. Friedenson 73) Assignee: Allied Chemical Corporation, Morris 57 ABSTRACT Township, N.J. A process is described for the electrochemical reduc tion of organic disulfides in the presence of halide ion to 21 Appl. No.: 753,051 form the corresponding thiols, which comprises using a 22 Filed: Dec. 21, 1976 stable solid cathode selected from the group consisting of the disulfides and diselenides of titanium, vanadium, Int, Cl’......................................... C25B3/04 51 molybdenum, tantalum, tungsten, niobium and zirco 52 U.S. C. .................................................. 2O4/73 R nium, wherein the cathode does not undergo substantial 58 Field of Search ..................... 204/59 R, 72, 73 R, disintegration during the reduction. 204/77 The organic thiol products are useful as intermediates in the manufacture of organic pigments, as polymerization 56) References Cited activators and as polymerization modifiers in the manu PUBLICATIONS facture of rubber. ECS Abstracts No. 149, pp. 364-367. Berichte, vol. 42, p. 4308 (1905) Fichter. 15 Claims, No Drawings 4,072,584. 1. 2 The reason is that in order to effectively reduce sulfonyl ELECTROCHEMICAL PRODUCTION OF halide completely to thiol, the intermediate sulfinic acid ORGANICTHOLS formed in step 1 requires a moderately high electrode potential for reduction to the intermediate disulfide in BACKGROUND OF THE INVENTION step 2, as illustrated in the above reaction sequence. 1. Field of the Invention Furthermore, the cathode must be resistant to attack by This invention relates to the. electrochemical reduc halide ion since halide ion is produced in the reduction tion of organic disulfides in the presence of halide ion of sulfonylhalide to sulfinic acid. In the electrochemical using certain stable solid cathodes to form the corre production of disulfides to thiols, the cathode also has to sponding thiols, useful as intermediates in the manufac O be resistant to attack by halide ion, especially chloride ture of organic pigments and as polymerization activa ion, because the preferred electrolyte for the catholyte tors and polymerization modifiers in the manufacture of is hydrochloric acid, rather than sulfuric acid or other rubber. The organic disulfides are formed preferably in known electrolytes, since it increases the solubility of situ by starting with an organic sulfonyl halide. the disulfide in the reaction solvent. 2. Brief Description of the Prior Art 15 Electrochemical reduction of unsubstituted ben Thus a method is needed by the art for the electro zenedisulfides and benzenesulfonyl halides to thiols chemical reduction of organic disulfides, derived pref using a liquid mercury cathode is known in the art, as erably from organic sulfonyl halides, to thiols in the exemplified in G. M. Nichols, The Electrochemical presence of halide ion, using stable solid cathodes, Society Meeting, New York, 1969, extended Abstracts 20 which does not require hazardous reagents, and in No. 149, page 364. However, the use of liquid mercury which substantial disintegration of the cathodes and in an industrial process has the disadvantages of being heavy metal pollution do not occur. extremely heavy and difficult to handle and tending to SUMMARY create potential water pollution problems. The use of solid lead and nickel cathodes in the elec 25 In accordance with the present invention, there is trochemical reduction of organic sulfonyl halides to provided a process for the electrochemical reduction of thiols is known in the prior art and is exemplified in organic disulfides to thiols in the presence of halide ion Fichter and bernoulli, Berichte, Volume 42, page 4308 which comprises passing a direct electric current be (1905), and Fichter, Verh. der Naturforsch, Ges. (Ba tween (1) a stable solid cathode selected from the group sel), Volume 19, page 37 (1908). However, use of these 30 consisting of the disulfides and diselenides of titanium, cathodes, although being preferable to the use of a liq vanadium, molybdenum, tantalum, tungsten, niobium uid mercury cathode, are disadvantageous because haz and zirconium, immersed in a catholyte containing the ardous and toxic titanium chloride salts must be used organic disulfide and halide ion, and (2) an anode im with the nickel cathode to obtain appreciable yields of mersed in an anolyte. thiols; and we have found that the lead cathode, even 35 The process further comprises forming the disulfide though producing good yields of thiols, undergoes dis in situ by starting with a catholyte containing an or integration during reduction in the presence of halide ganic sulfonyl halide. ion, especially chloride ion. Thus, a continuous or batch DETAILED DESCRIPTION OF THE type of plant process based on either of these methods is INVENTION AND THE PREFERRED economically unattractive. 40 It is known in the prior art, as exemplified in Nichols, EMBODEMENTS supra, that electrochemical reduction of organic sulfo This invention involves the reduction of organic di nyl halides to thiols proceeds through at least three sulfides to thiols in the presence of halide ion using a discrete steps involving the intermediates illustrated in solid stable cathode which does not undergo disintegra the reaction sequence below: 45 tion during the reduction. The organic disulfides are preferably prepared in situ by reduction of organic Step Step Step sulfonyl halides. 1 2 3 The reduction of organic disulfides, as well as the RSOX RSOH RSSR RSH reduction of organic sulfonyl halides, can be carried out sulfonyl sulfinic disulfide thiol 50 in the presence of halide ion using a stable solid cathode haide acid . selected from the group consisting of the disulfides and diselenides of titanium, vanadium, molybdenum, tanta where R = aliphatic or aromatic radicals, and X = lum, tungsten, niobium and zirconium. Such cathodes halogen. are moderately high hydrogen overpotential metallic or We have found that the reduction of sulfinic acid to 55 semiconductor cathodes and are suitable for forming disulfide in step 2 occurs at a moderately high electrode organic disulfides from the reduction of organic sulfo potential, whereas the reductions of sulfonyl halide to nyl halides, which requires a moderately high electrode sulfinic acid in step 1 and of disulfide to thiol in step 3 potential value, and for reducing organic disulfides to occur at lower electrode potentials. For the reaction thiols, which requires a lower electrode potential value. requiring a moderately high electrode potential, a cath The term electrode potential is well known in the art ode having a moderately high hydrogen overpotential and refers to the potential which is established at the must be used to generate the required electrode poten solution-electrode interface at equilibrium when a metal tial, whereas, for the reactions requiring lower elec electrode is immersed into an aqueous solution of its trode potentials, cathodes having either moderately ions. There is a tendency for the metal to leave the solid high or low hydrogen overpotentials can be used. 65 phase in the reduced state and enter the liquid phase as Only cathodes having a moderately high hydrogen ions in the oxidized state. The ions already in solution overpotential and resistance to attack by halide ion can will oppose the tendency for the element to form ions, be used for the reduction of sulfonyl halides to thiols. and a reversible equilibrium involving a transfer of 4,072,584 3 4. electrons is ultimately established, The electrode poten in general contain 1 to 20 carbon atoms and contain no tial at equilibrium of the system, E, is given by the other groups which can be reduced under the condi Nernst equation: tions of the reaction, but can contain such groups as bromo, chloro, fluoro, hydroxy, methoxy, ethoxy, 0.0591 oxidized ions propoxy, butoxy and alkyl. The sulfonyl halides are E = E, - via log reduced in employed in producing disulfides in situ which are then further reduced electrochemically to the corresponding where E is the standard electrode potential of the sys thiols. Aliphatic or aromatic sulfonyl halides such as tem when the activity of the ions is unity at 25 C., n is chlorides, bromides, iodides or fluorides can be used, the number of electrons involved per mol of reactant, 10 oxidized ions) is the concentration of oxidized ions in however it is preferred to use the sulfonyl chlorides. solution and reduced ions is the concentration of re Representative examples of aliphatic sulfonylhalides duced ions in the solution. In the case where the re are methane-, decane-, dodecane- and octadecanesulfo duced ions are removed from solution by precipitating nyl chloride. Representative examples of cycloaliphatic out in the zero valence state, reduced ions) is equal to sulfonyl halides are cyclohexane sulfonyl chloride, cy unity. 15 clopentane sulfonyl chloride, 2-methylcyclopentane The term hydrogen overpotential is also well known sulfonyl chloride and 2-chlorocyclopentane sulfonyl in the art and designates the difference in potentials, for chloride. Preferred among the aliphatic sulfonyl chlo a given system, between the actual potential value at rides are those containing 2 to 18 carbon
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