Spectral Evidence for the One-Step Three-Electron Oxidation of Phenylsufinylacetic Acid and Oxalic Acid by Cr(VI)

Perumal Subramaniam, Natesan Thamil Selvi

Department of Chemistry, Govindammal Aditanar College for Women, Tiruchendur, India.
Research Department of Chemistry, Aditanar College of Arts and Science, Tiruchendur, India.

DOI: 10.4236/ajac.2013.410A1003                

Abstract

The co-oxidation of a mixture of phenylsulfinylacetic acid (PSAA) and oxalic acid (OxH₂) by Cr(VI) in 20% acetonitrile-80% water (v/v) medium follows third order kinetics, first order, each with respect to PSAA, OxH₂ and Cr(VI). The reaction involves nucleophilic attack of sulfur atom of PSAA on chromium of the oxidizing species, Cr(VI)-OxH₂ to form a ternary complex, Cr(VI)-OxH₂-PSAA followed by a one-step three-electron reduction of Cr(VI) to Cr(III) and simultaneous oxidation of both the substrates. The reaction is catalysed by Mn²⁺ ion while retarded by Al³⁺ ion. Electron releasing substituents in the meta- and para-positions of the phenyl ring of PSAA enhance the rate of co-oxidation while electron withdrawing substituents retards the reaction. The Hammett plots at different temperatures exhibit excellent correlation with negative ρ values. The reaction series obey isokinetic relationship and the observed isokinetic temperature is lying below the experimental range of temperature.

Keywords

Phenylsulfinylacetic Acid; Oxalic Acid; Co-Oxidation; Nucleophilic Attack of Sulfur; Three-Electron Transfer; Substituent Effect

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	[1] G. F. Vandegrift and J. Rocek, “Catalysis in Oxidation Reactions. II. The Oxalic Acid Catalyzed Oxidation of Iodide,” Journal of American Chemical Society, Vol. 98, No. 6, 1976, pp. 1371-1376. http://dx.doi.org/10.1021/ja00422a015
[2]	R. F. Hintze and J. Rocek, “Catalysis in Oxidation Reactions. 3. The Oxalic Acid Catalyzed Chromic Acid Oxidation of Tris(1,10-phenanthroline)iron(II),” Journal of American Chemical Society, Vol. 99, No. 1, 1977, pp. 132-137. http://dx.doi.org/10.1021/ja00443a025
[3]	T. Satyanarayana, N. R. Anipindi, V. Subbiah and M. W. Pandit, “The Oxalic Acid Catalysed Oxidation of Bis(2,4, 6-tripyridyl-1,3,5-triazine)-iron(II) by Chromium(VI) in Acetate Buffer,” Transition Metal Chemistry, Vol. 18, No. 1, 1993, pp. 93-95. http://dx.doi.org/10.1007/BF00136060
[4]	S. P. Meenakshisundaram, M. Gopalakrishnan, S. Nagarajan and N. Sarathi, “Oxalic Acid Catalyzed Chromium(VI) Oxidation of Some 2-Amino-4,6-diarylpyrimidines,” Catalysis Communications, Vol. 8, No. 4, 2007, pp. 713-718. http://dx.doi.org/10.1016/j.catcom.2006.08.033
[5]	G. Rajarajan, N. Jayachandramani, S. Manivarman, J. Jayabharathi and V. Thanikachalam, “Kinetics and Mechanism of the Oxidation of Some Substituted Aldonitrones by Quinolinium Cholorochromate in Aqueous DMF Medium in the Absence and Presence of Oxalic Acid,” Journal of the Serbian Chemical Society, Vol. 74, No. 2, 2009, pp. 171-182. http://dx.doi.org/10.2298/JSC0902171R
[6]	D. C. Gaswick and J. H. Krueger, “Kinetics and Mechanism of the Chromium(VI)-iodide Reaction,” Journal of American Chemical Society, Vol. 91, No. 9, 1969, pp. 2240-2244. http://dx.doi.org/10.1021/ja01037a010
[7]	I. Baldea and G. Niac, “Reaction between Chromate and Thiosulfate. II. Kinetics of Tetrathionate Formation,” Inorganic Chemistry, Vol. 9, No. 1, 1970, pp. 110-114. http://dx.doi.org/10.1021/ic50083a023
[8]	K. A. Muirhead and G. P. Haight, “Kinetics and Mechanism of the Oxidation of Thiocyanate Ion by Chromium (VI),” Inorganic Chemistry, Vol. 12, No. 5, 1973, pp. 1116-1120. http://dx.doi.org/10.1021/ic50123a028
[9]	M. A. Olatunji and A. McAuly, “Metal-Ion Oxidations in Solution. Part XII. Oxidation of Thiourea and NN′-ethylenethiourea by Chromium(VI) in Perchlorate Media,” Journal of the Chemical Society, Dalton Transactions, 1975, No. 8, pp. 682-688. http://dx.doi.org/10.1039/dt9750000682
[10]	L. F. Sala, C. Palopoli, V. Alba and S. Signorella, “A Secondary Reaction in the Oxidation of L-Methionine by Chromium(VI) in Acidic Medium,” Polyhedron, Vol. 12, No. 18, 1993, pp. 2227-2234. http://dx.doi.org/10.1016/S0277-5387(00)88261-3
[11]	F. Hasan and J. Rocek, “Cooxidation of isopropyl alcohol and oxalic acid by chromic acid, One-step three-electron oxidation,” Journal of American Chemical Society, Vol. 94, No. 9, 1972, pp. 3181-3187.
[12]	A. K. Das, A. Roy, B. Saha and M. Das, “Cooxidation of Formic Acid and Oxalic Acid by Chromium(VI) in Aqueous Acid Media: A Kinetic Study,” Journal of Chemical Research, No. 8, 2001, pp. 334-335.
[13]	R. Srinivasan and A. N. M. Kasim, “Cooxidation of Aromatic Anils and Oxalic Acid by Chromic Acid in Aqueous Acetic Acid Medium,” Asian Journal of Chemistry, Vol. 21, No. 9, 2009, pp. 6909-6914.
[14]	K. A. Basheer Ahamed, “Cooxidation of Anilides and Oxalic Acid by Chromic Acid: A One-Step, Three-Electron Oxidation,” International Journal of Chemical Kinetics, Vol. 33, No. 1, 2001, pp. 21-28. http://dx.doi.org/10.1002/1097-4601(20010101)33:1<21::AID-KIN3>3.0.CO;2-R
[15]	S. Meenakshisundaram and R. Sockalingam, “Enhanced Reactivity in the Quinolinium Fluorochromate Cooxidation of Some Cycloalkanones and Oxalic Acid,” Bulletin of the Chemical Society of Japan, Vol. 74, No. 6, 2001, pp. 1043-1049. http://dx.doi.org/10.1246/bcsj.74.1043
[16]	G. Vanangamudi and S.Srinivasan, “Kinetic Studies on the Oxidation of Some Para and Meta-Substituted Cinnamic Acids by Pyridinium Bromochromate in the Presence of Oxalic Acid (A Co-Oxidation Study),” E-Journal of Chemistry, Vol. 6, No. 3, 2009, pp. 920-927. http://dx.doi.org/10.1155/2009/242743
[17]	C. Srinivasan, P. Pandarakutty Jegatheesan, S. Rajagopal and N. Arumugam, “Substituent Effects in Cooxidation: Cr(VI)-Oxalic Acid-Sulfoxides Systems,” Canadian Journal of Chemistry, Vol. 65, No. 10, 1987, pp. 2421-2424. http://dx.doi.org/10.1139/v87-403
[18]	A. K. Das, B. Saha, and M. Islam, “Micellar Effect on the Catalytic Cooxidation of Dimethyl Sulfoxide and Oxalic Acid by Chromium(VI) in Aqueous Acid Media: A Kinetic Study,” Progress in Reaction Kinetics and Mechanism, Vol. 30, No. 3, 2005, pp. 215-226. http://dx.doi.org/10.3184/007967405779134047
[19]	G. Mangalam and S. Meenakshisundaram, “Cooxidation of S-Phenylmercaptoacetic Acid and Oxalic Acid with Pyridinium Chlorochromate,” Polish Journal of Chemistry, Vol. 72, No. 3, 1998, pp. 582-586.
[20]	V. Sumangala, B. Poojary, N. Chidananda, T. Arulmoli and S. Shenoy, “Synthesis, Characterization, Antimicrobial and Antioxidant Activity of Some Disubstituted [1,3, 4]-Oxadiazoles Carrying 4-(Methylsulfonyl/sulfinyl)benzyl Moieties,” Journal of Chemical and Pharmaceutical Research, Vol. 4, No. 3, 2012, pp. 1661-1669.
[21]	N. J. Gogan, M. J. Newlands and B.-Y. Tan, “Ambident Ligands.1. Phenylsulfinylacetic Acid,” Canadian Journal of Chemistry, Vol. 50, No. 19, 1972, pp. 3202-3206. http://dx.doi.org/10.1139/v72-510
[22]	M. Janczewski, T. Najda and T. Jablonska Pikus, “Effect of Molecular Structure on Optical Properties of Sulfoxide Systems. [Phenyl-and (m-bromophenyl)-sulfinyl]acetic Acids and Some of Their Derivatives. Part I,” Polish Journal of Chemistry, Vol. 56, 1982, pp. 1297-1312.
[23]	A. A. Jaxa-Chamiec, P. G. Sammes and P. D. Kennewell, “A New Route to 5-Substituted Resorcinols and Related Systems,” Journal of the Chemical Society, Perkin Transactions 1, 1980, pp. 170-175. http://dx.doi.org/10.1039/p19800000170
[24]	Q. B. Cass, A. A. Jaxa-Chamiec and P. G. Sammes, “Preparation and Rearrangement of Some Conjugated Phenylsulfinylacetate Derivatives,” Journal of the Chemical Society, Chemical Communications, Vol. 24, 1981, pp. 1248-1250. http://dx.doi.org/10.1039/c39810001248
[25]	T. Allmendinger, “Ethyl Phenylsulfinyl Fluoroacetate, a New and Versatile Reagent for the Preparation of α-Fluoro-α,β-Unsaturated Carboxylic Acid Esters,” Tetrahedron, Vol. 47, No. 27, 1991, pp. 4905-4914. http://dx.doi.org/10.1016/S0040-4020(01)80956-X
[26]	K.-S. Lee, “Tert-Butyl 3-Oxo-4-(phenylsulfinyl)-2-(triphenyl-λ5-phosphanylidene)butanoate: A New Reagent for the Efficient Synthesis of Triphenylphosphorane Ylide Precursors to Vicinal Tricarbonyls from Alkyl Halides,” Bulletin of the Korean Chemical Society, Vol. 32, No. 9, 2011, pp. 3477-3479. http://dx.doi.org/10.5012/bkcs.2011.32.9.3477
[27]	D. Walker and J. Leib, “The Acid-Catalysed Cleavage of Phenylsulfinylacetic Acid,” Canadian Journal of Chemistry, Vol. 40, No. 7, 1962, pp. 1242-1248. http://dx.doi.org/10.1139/v62-192
[28]	W. J .Kenney, J. A. Walsh and D. A. Davenport, “An Acid-Catalyzed Cleavage of Sulfoxides,” Journal of American Chemical Society, Vol. 83, No. 19, 1961, pp 4019-4022. http://dx.doi.org/10.1021/ja01480a016
[29]	A. B. P. Lever, “Inorganic Electronic Spectroscopy,” 2nd Edition, Elsevier, Amsterdam, 1984.
[30]	S. Signorella, M. Rizzotto, V. Daier, M. I. Franscaroli, C. Palopoli, D. Martino, A. Boussekou and L. F. Sala, “Comparative Study of Oxidation by Chromium(V) and Chromium(VI),” Journal of the Chemical Society, Dalton Transactions, No. 8, 1996, pp. 1607-1611. http://dx.doi.org/10.1039/dt9960001607
[31]	R. E Hamm, R. L. Johnson, R. H. Perkins and R. E. Davis, “Complex Ions of Chromium. VIII. Mechanism of Reaction of Organic Acid Anions with Chromium(III),” Journal of American Chemical Society, Vol. 80, No. 17, 1958, pp. 4469-4471. http://dx.doi.org/10.1021/ja01550a008
[32]	Kabir-ud-Din, K. Hartani and Z. Khan, “Effect of Micelles on the Oxidation of Oxalic Acid by Chromium(VI) in the Presence and Absence of Manganese(II),” Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 193, No. 1-3, 2001, pp. 1-13. http://dx.doi.org/10.1016/S0927-7757(01)00475-7
[33]	A. K. Das, D. Mondal, D. Kar and M. Das, “Micellar Effect on the Reaction of Picolinic Acid Catalysed Chromium(VI) Oxidation of Dimethyl Sulfoxide in Aqueous Acidic Media: A Mechanistic Study,” International Journal of Chemical Kinetics, Vol. 33, No. 3, 2001, pp. 173-181.http://dx.doi.org/10.1002/1097-4601(200103)33:3<173::AID-KIN1011>3.0.CO;2-I
[34]	S. Meenakshisundaram and R. Vinothini, “Kinetics and Mechanism of Oxidation of Methionine by Chromium (VI): Edta Catalysis,” Croatica Chemica Acta, Vol. 76, No. 1, 2003, pp. 75-80.
[35]	K. Pitchumani, V. Subramanian, P. P. Jegatheesan and C. Srinivasan, “Kinetics and Mechanism of Oxidation of N-Substituted Phenothiazines by Chromium(VI),” Proceedings of the Indian Academy of Sciences, Chemical Sciences, Vol. 104, No. 1, 1992, pp. 67-76.
[36]	C. Karunakaran, S. Karuthapandian and S. Suresh, “Kinetic Evidence of a Common Mechanism in the Oxidations of Diethyl Sulfide by Dichromates and Halaochromates of Heterocyclic Bases,” International Journal of Chemical Kinetics, Vol. 35, No. 1, 2003, pp. 1-8.
[37]	R. C. Petersen, J. H. Markgraf and S. D. Ross, “Solvent Effects in the Decomposition of 1,1’-Diphenylazoethane and 2,2’-Azobis-(2-methylpropionitrile),” Journal of American Chemical Society, Vol. 83, No. 18, 1961, pp. 3819-3823. http://dx.doi.org/10.1021/ja01479a021
[38]	O. Exner, “The Enthalpy-Entropy Relationship,” Progress in Physical Organic Chemistry, Vol. 10, 1973, pp. 411-482. http://dx.doi.org/10.1002/9780470171899.ch6
[39]	K. B. Wiberg, “Oxidation in Organic Chemistry, Part A,” Academic Press, New York, 1965.
[40]	G. Cainelli and G. Cardillo, “Chromium Oxidations in Organic Chemistry,” Springer, Berlin, 1984. http://dx.doi.org/10.1007/978-3-642-69362-5
[41]	N. E. Brasch, D. A. Buckingham, B. A. Evans and C. R. Clark, “17O NMR Study of Chromium(VI) Ions in Water,” Journal of American Chemical Society, Vol. 118, No. 34, 1996, pp. 7969-7980. http://dx.doi.org/10.1021/ja960843j
[42]	L. S. Levitt, “The Common Basis of Organic Oxidations in Acidic Solution,” Journal of Organic Chemistry, Vol. 20, No. 10, 1955, pp. 1297-1310. http://dx.doi.org/10.1021/jo01127a001
[43]	C. Srinivasan, A. Chellamani and S. Rajagopal, “Mechanism of the Oxidation of Alkyl Aryl and Diphenyl Sulfides by Chromium(VI),” Journal of Organic Chemistry, Vol. 50, No. 8, 1985, pp. 1201-1205. http://dx.doi.org/10.1021/jo00208a011
[44]	S. K. Crossno, L. H. Kalbus and G. E. Kalbus, “Determinations of Carbon Dioxide by Titration: New Experiments for General, Physical, and Quantitative Analysis Courses,” Journal of Chemical Education, Vol. 73, No. 2, 1996, pp. 175-176. http://dx.doi.org/10.1021/ed073p175